Influence of exogenous lead pollution on enzyme activities and organic matter degradation in the surface of river sediment.

PubMed

Huang, Danlian; Xu, Juanjuan; Zeng, Guangming; Lai, Cui; Yuan, Xingzhong; Luo, Xiangying; Wang, Cong; Xu, Piao; Huang, Chao

2015-08-01

As lead is one of the most hazardous heavy metals in river ecosystem, the influence of exogenous lead pollution on enzyme activities and organic matter degradation in the surface of river sediment with high moisture content were studied at laboratory scale. The dynamic changes of urease, catalase, protease activities, organic matter content, and exchangeable or ethylenediaminetetraacetic acid (EDTA)-extractable Pb concentration in sediment were monitored during different levels of exogenous lead infiltrating into sediment. At the early stage of incubation, the activities of catalase and protease were inhibited, whereas the urease activities were enhanced with different levels of exogenous lead. Organic matter content in polluted sediment with exogenous lead was lower than control and correlated with enzyme activities. In addition, the effects of lead on the three enzyme activities were strongly time-dependent and catalase activities showed lower significant difference (P < 0.05) than urease and protease. Correlations between catalase activities and EDTA-extractable Pb in the experiment were significantly negative. The present findings will improve the understandings about the ecotoxicological mechanisms in sediment.

Pecan shell-based granular activated carbon for treatment of chemical oxygen demand (COD) in municipal wastewater.

PubMed

Bansode, R R; Losso, J N; Marshall, W E; Rao, R M; Portier, R J

2004-09-01

The present investigation was undertaken to compare the adsorption efficiency of pecan shell-based granular activated carbon with the adsorption efficiency of the commercial carbon Filtrasorb 200 with respect to uptake of the organic components responsible for the chemical oxygen demand (COD) of municipal wastewater. Adsorption efficiencies for these two sets of carbons (experimental and commercial) were analyzed by the Freundlich adsorption model. The results indicate that steam-activated and acid-activated pecan shell-based carbons had higher adsorption for organic matter measured as COD, than carbon dioxide-activated pecan shell-based carbon or Filtrasorb 200 at all the carbon dosages used during the experiment. The higher adsorption may be related to surface area as the two carbons with the highest surface area also had the highest organic matter adsorption. These results show that granular activated carbons made from agricultural waste (pecan shells) can be used with greater effectiveness for organic matter removal from municipal wastewater than a coal-based commercial carbon. Copyright 2004 Elsevier Ltd.

Surface tension prevails over solute effect in organic-influenced cloud droplet activation.

PubMed

Ovadnevaite, Jurgita; Zuend, Andreas; Laaksonen, Ari; Sanchez, Kevin J; Roberts, Greg; Ceburnis, Darius; Decesari, Stefano; Rinaldi, Matteo; Hodas, Natasha; Facchini, Maria Cristina; Seinfeld, John H; O' Dowd, Colin

2017-06-29

The spontaneous growth of cloud condensation nuclei (CCN) into cloud droplets under supersaturated water vapour conditions is described by classic Köhler theory. This spontaneous activation of CCN depends on the interplay between the Raoult effect, whereby activation potential increases with decreasing water activity or increasing solute concentration, and the Kelvin effect, whereby activation potential decreases with decreasing droplet size or increases with decreasing surface tension, which is sensitive to surfactants. Surface tension lowering caused by organic surfactants, which diminishes the Kelvin effect, is expected to be negated by a concomitant reduction in the Raoult effect, driven by the displacement of surfactant molecules from the droplet bulk to the droplet-vapour interface. Here we present observational and theoretical evidence illustrating that, in ambient air, surface tension lowering can prevail over the reduction in the Raoult effect, leading to substantial increases in cloud droplet concentrations. We suggest that consideration of liquid-liquid phase separation, leading to complete or partial engulfing of a hygroscopic particle core by a hydrophobic organic-rich phase, can explain the lack of concomitant reduction of the Raoult effect, while maintaining substantial lowering of surface tension, even for partial surface coverage. Apart from the importance of particle size and composition in droplet activation, we show by observation and modelling that incorporation of phase-separation effects into activation thermodynamics can lead to a CCN number concentration that is up to ten times what is predicted by climate models, changing the properties of clouds. An adequate representation of the CCN activation process is essential to the prediction of clouds in climate models, and given the effect of clouds on the Earth's energy balance, improved prediction of aerosol-cloud-climate interactions is likely to result in improved assessments of future climate change.

Stabilization of surface-immobilized enzymes using grafted polymers

NASA Astrophysics Data System (ADS)

Moskovitz, Yevgeny; Srebnik, Simcha

2004-03-01

Vast research efforts focus on improving the biocompatibility and biofunctionality of surfaces for artificial implants and organs. A relatively successful approach involves grafting of polymer (usually PEG) on the artificial surface, which significantly improves its biocompatibility. In addition, positioning enzymes on or in the vicinity of the surface can significantly enhance bioseparation processes. However, the catalytic activity of the anchored enzyme is often drastically impaired by the nonnatural environment, leading to loss of activity and denaturation. We study protein adsorption and stabilization by grafted polymers using a mean-field lattice model. The model protein is designed as a compact HP with a specific bulk conformation reproducing a catalytic cleft of natural enzymes. Using hydrophilic grafted polymers of tailored length and density, we show that the conformation as well as hydrophobic and active centers of the model enzyme can be restored. This research is inspired by the problem of biocompatibility and biofunctionality of surfaces for artificial implants and organs.

T-Cell Surface Antigens and sCD30 as Biomarkers of the Risk of Rejection in Solid Organ Transplantation.

PubMed

Wieland, Eberhard; Shipkova, Maria

2016-04-01

T-cell activation is a characteristic of organ rejection. T cells, located in the draining lymph nodes of the transplant recipient, are faced with non-self-molecules presented by antigen presenting cells and become activated. Activated T cells are characterized by up-regulated surface antigens, such as costimulatory molecules, adhesion molecules, chemokine receptors, and major histocompatibility complex class II molecules. Surface antigen expression can be followed by flow cytometry using monoclonal antibodies in either cell function assays using donor-specific or nonspecific stimulation of isolated cells or whole blood and without stimulation on circulating lymphocytes. Molecules such as CD30 can be proteolytically cleaved off the surface of activated cells in vivo, and the determination of the soluble protein (sCD30) in serum or plasma is performed by immunoassays. As promising biomarkers for rejection and long-term transplant outcome, CD28 (costimulatory receptor for CD80 and CD86), CD154 (CD40 ligand), and sCD30 (tumor necrosis factor receptor superfamily, member 8) have been identified. Whereas cell function assays are time-consuming laboratory-developed tests which are difficult to standardize, commercial assays are frequently available for soluble proteins. Therefore, more data from clinical trials have been published for sCD30 compared with the surface antigens on activated T cells. This short review summarizes the association between selected surface antigens and immunosuppression, and rejection in solid organ transplantation.

Selection of pecan shell-based activated carbons for removal of organic and inorganic impurities from water.

PubMed

Niandou, Mohamed A S; Novak, Jeffrey M; Bansode, Rishipal R; Yu, Jianmei; Rehrah, Djaafar; Ahmedna, Mohamed

2013-01-01

Activated carbons are a byproduct from pyrolysis and have value as a purifying agent. The effectiveness of activated carbons is dependent on feedstock selection and pyrolysis conditions that modify their surface properties. Therefore, pecan shell-based activated carbons (PSACs) were prepared by soaking shells in 50% (v/v) HPO or 25 to 50% of KOH-NaHCO followed by pyrolysis at 400 to 700°C under a N atmosphere. Physically activated PSACs were produced by pyrolysis at 700°C under N followed by activation with steam or CO at 700 to 900°C. Physicochemical, surface, and adsorption properties of the PSACs were compared with two commercially available activated carbons. The average mass yield of PSACs with respect to the initial mass of the biomass was about 20 and 34% for physically activated and chemically activated carbons, respectively. Acid-activated carbons exhibited higher surface area, higher bulk density, and lower ash content compared with steam- or CO-activated carbons and the two commercial products. Base activation led to the development of biochar with moderate to high surface area with surface charges suitable for adsorption of anionic species. Regardless of the activation method, PSACs had high total surface area ranging from 400 to 1000 m g, better pore size distribution, and more surface charges than commercial samples. Our results also showed that PSACs were effective in removing inorganic contaminants such as Cu and NO as well as organic contaminants such as atrazine and metolachlor. This study showed that pyrolysis conditions and activation had a large influence on the PSAC's surface characteristics, which can limit its effectiveness as a custom sorbent for targeted water contaminants. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Effect of Heterogeneous Chemical Reactions on the Köhler Activation of Aqueous Organic Aerosols.

PubMed

Djikaev, Yuri S; Ruckenstein, Eli

2018-05-03

We study some thermodynamic aspects of the activation of aqueous organic aerosols into cloud droplets considering the aerosols to consist of liquid solution of water and hydrophilic and hydrophobic organic compounds, taking into account the presence of reactive species in the air. The hydrophobic (surfactant) organic molecules on the surface of such an aerosol can be processed by chemical reactions with some atmospheric species; this affects the hygroscopicity of the aerosol and hence its ability to become a cloud droplet either via nucleation or via Köhler activation. The most probable pathway of such processing involves atmospheric hydroxyl radicals that abstract hydrogen atoms from hydrophobic organic molecules located on the aerosol surface (first step), the resulting radicals being quickly oxidized by ubiquitous atmospheric oxygen molecules to produce surface-bound peroxyl radicals (second step). These two reactions play a crucial role in the enhancement of the Köhler activation of the aerosol and its evolution into a cloud droplet. Taking them and a third reaction (next in the multistep chain of relevant heterogeneous reactions) into account, one can derive an explicit expression for the free energy of formation of a four-component aqueous droplet on a ternary aqueous organic aerosol as a function of four independent variables of state of a droplet. The results of numerical calculations suggest that the formation of cloud droplets on such (aqueous hydrophilic/hydrophobic organic) aerosols is most likely to occur as a Köhler activation-like process rather than via nucleation. The model allows one to determine the threshold parameters of the system necessary for the Köhler activation of such aerosols, which are predicted to be very sensitive to the equilibrium constant of the chain of three heterogeneous reactions involved in the chemical aging of aerosols.

Surface sediment quality relative to port activities: A contaminant-spectrum assessment.

PubMed

Yu, Shen; Hong, Bing; Ma, Jun; Chen, Yongshan; Xi, Xiuping; Gao, Jingbo; Hu, Xiuqin; Xu, Xiangrong; Sun, Yuxin

2017-10-15

Ports are facing increasing environmental concerns with their importance to the global economy. Numerous studies indicated sediment quality deterioration in ports; however, the deterioration is not discriminated for each port activity. This study investigated a spectrum of contaminants (metals and organic pollutants) in surface sediments at 20 sampling points in Port Ningbo, China, one of the top five world ports by volume. The spectrum of contaminants (metals and organic pollutants) was quantified following marine sediment quality guidelines of China and USA and surface sediment quality was assessed according to thresholds of the two guidelines. Coupling a categorical matrix of port activities with the matrix of sedimentary contaminants revealed that contaminants were highly associated with the port operations. Ship repair posed a severe chemical risk to sediment. Operations of crude oil and coal loadings were two top activities related to organic pollutants in sediments while port operations of ore and container loadings discharged metals. Among the 20 sampling points, Cu, Zn, Pb, and DDT and its metabolites were the priority contaminants influencing sediment quality. Overall, surface sediments in Port Ningbo had relatively low environmental risks but ship repair is an environmental concern that must be addressed. This study provides a practical approach for port activity-related quality assessment of surface sediments in ports that could be applicable in many world sites. Copyright © 2017 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, W.; Chang, Q.G.; Liu, W.D.

A series of follow-up investigations were performed to produce data for improving the four-indicator carbon selection method that we developed to identify high-potential activated carbons effective for removing specific organic water pollutants. The carbon's pore structure and surface chemistry are dependent on the raw material and the activation process. Coconut carbons have relatively more small pores than large pores; coal and apricot nutshell/walnut shell fruit carbons have the desirable pore structures for removing adsorbates of all sizes. Chemical activation, excessive activation, and/or thermal reactivation enlarge small pores, resulting in reduced phenol number and higher tannic acid number. Activated carbon's phenol,more » iodine, methylene blue, and tannic acid numbers are convenient indicators of its surface area and pore volume of pore diameters < 10, 10-15, 15-28, and > 28 angstrom, respectively. The phenol number of a carbon is also a good indicator of its surface acidity of oxygen-containing organic functional groups that affect the adsorptive capacity for aromatic and other small polar organics. The tannic acid number is an indicator of carbon's capacity for large, high-molecular-weight natural organic precursors of disinfection by-products in water treatment. The experimental results for removing nitrobenzene, methyl-tert-butyl ether, 4,4-bisphenol, humic acid, and the organic constituents of a biologically treated coking-plant effluent have demonstrated the effectiveness of this capacity-indicator-based method of carbon selection.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eric S. Peterson; Jessica Trudeau; Bill Cleary

An active-surface membrane technology was used to separate a die lube manufacturing wastewater stream consisting of various oils, hydrocarbons, heavy metals, and silicones. The ultrafiltration membranes reduced organics from initial oil and grease contents by 20–25X, carbon oxygen demand (COD) by 1.5 to 2X, and total organic carbon (TOC) by 0.6, while the biological oxygen demand (BOD) remained constant. The active-surface membranes were not fouled as badly as non-active-surface systems and the active-surface membrane flux levels were consistently higher and more stable than those of the non-active-surface membranes tested. Field testing demonstrated that the rotary microfilter can concentrate the diemore » lube, i.e. remove the glycerin component, and produce a die lube suitable for recycling. The recycling system operated for six weeks with only seven cleaning cycles and no mechanical or electrical failures. Test data and quality records indicate that the die casting scrap was reduced from 8.4 to 7.8%. There is no doubt that this test yielded tremendous results. This separation process presents significant opportunities that can be evaluated further.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peterson, E. S.; Trudeau, J.; Cleary, B.

An active-surface membrane technology was used to separate a die lube manufacturing wastewater stream consisting of various oils, hydrocarbons, heavy metals, and silicones. The ultrafiltration membranes reduced organics from initial oil and grease contents by 20-25X, carbon oxygen demand (COD) by 1.5 to 2X, and total organic carbon (TOC) by 0.6, while the biological oxygen demand (BOD) remained constant. The active-surface membranes were not fouled as badly as non-active-surface systems and the active-surface membrane flux levels were consistently higher and more stable than those of the non-active-surface membranes tested. Field testing demonstrated that the rotary microfilter can concentrate the diemore » lube, i.e. remove the glycerin component, and produce a die lube suitable for recycling. The recycling system operated for six weeks with only seven cleaning cycles and no mechanical or electrical failures. Test data and quality records indicate that the die casting scrap was reduced from 8.4 to 7.8%. There is no doubt that this test yielded tremendous results. This separation process presents significant opportunities that can be evaluated further.« less

Surface plasmon-mediated energy transfer of electrically-pumped excitons

DOEpatents

An, Kwang Hyup; Shtein, Max; Pipe, Kevin P.

2015-08-25

An electrically pumped light emitting device emits a light when powered by a power source. The light emitting device includes a first electrode, a second electrode including an outer surface, and at least one active organic semiconductor disposed between the first and second electrodes. The device also includes a dye adjacent the outer surface of the second electrode such that the second electrode is disposed between the dye and the active organic semiconductor. A voltage applied by the power source across the first and second electrodes causes energy to couple from decaying dipoles into surface plasmon polariton modes, which then evanescently couple to the dye to cause the light to be emitted.

Functional roles of cell surface peptidases in reproductive organs

PubMed Central

2004-01-01

A number of biologically active peptides have been proposed to regulate function and differentiation of reproductive organs in an autocrine and/or paracrine fashion. Regulation of the local concentrations of these peptides is one of the important factors influencing their physiological effects on target cells. Membrane‐bound cell surface peptidases can activate or inactivate biologically active peptides before peptide factors access their receptors on the cell surface. Aminopeptidase A (EC 3.4.11.7), placental leucine aminopeptidase (EC 3.4.11.3), aminopeptidase‐N/CD13 (EC 3.4.11.2), dipeptidyl peptidases IV/CD26 (EC.3.4.14.5), carboxypeptidase‐M (EC 3.4.17.12), neutral endopeptidase/CD10 (EC 3.4.24.11) and endothelin converting enzyme‐1 (EC 3.4.23) are differentially expressed on the ovary, endometrium and placenta. The inhibition of enzyme activity affects steroid hormone production by granulosa and thecal cells, decidualization of endometrium and migration of extravillous trophoblasts. These findings suggest that membrane‐bound cell surface peptidases are local regulators for cellular growth and differentiation in reproductive organs by controlling extracellular concentration of peptide factors. (Reprod Med Biol 2004; 3: 165 –176) PMID:29662383

Important photosynthetic contribution from the non-foliar green organs in cotton at the late growth stage.

PubMed

Hu, Yuan-Yuan; Zhang, Ya-Li; Luo, Hong-Hai; Li, Wei; Oguchi, Riichi; Fan, Da-Yong; Chow, Wah Soon; Zhang, Wang-Feng

2012-02-01

Non-foliar green organs are recognized as important carbon sources after leaves. However, the contribution of each organ to total yield has not been comprehensively studied in relation to the time-course of changes in surface area and photosynthetic activity of different organs at different growth stages. We studied the contribution of leaves, main stem, bracts and capsule wall in cotton by measuring their time-course of surface area development, O(2) evolution capacity and photosynthetic enzyme activity. Because of the early senescence of leaves, non-foliar organs increased their surface area up to 38.2% of total at late growth stage. Bracts and capsule wall showed less ontogenetic decrease in O(2) evolution capacity per area and photosynthetic enzyme activity than leaves at the late growth stage. The total capacity for O(2) evolution of stalks and bolls (bracts plus capsule wall) was 12.7 and 23.7% (total ca. 36.4%), respectively, as estimated by multiplying their surface area by their O(2) evolution capacity per area. We also kept the bolls (from 15 days after anthesis) or main stem (at the early full bolling stage) in darkness for comparison with non-darkened controls. Darkening the bolls and main stem reduced the boll weight by 24.1 and 9%, respectively, and the seed weight by 35.9 and 16.3%, respectively. We conclude that non-foliar organs significantly contribute to the yield at the late growth stage.

Effect of laser activated bleaching on the chemical stability and morphology of intracoronal dentin.

PubMed

Lopes, Fabiane Carneiro; Roperto, Renato; Akkus, Anna; Akkus, Ozan; Palma-Dibb, Regina Guenka; de Sousa-Neto, Manoel Damião

2018-02-01

To evaluate the effect of the bleaching with 35% hydrogen peroxide either activated or not by a 970nm diode laser on the chemical stability and dentin surface morphology of intracoronary dentin. Twenty-seven slabs of intracoronary dentin specimens (3×3mm) were distributed into three groups (n=9), according to surface treatment: HP - 35% hydrogen peroxide (1×4'), DL - 970nm diode laser (1×30"/0,8W/10Hz), HP+DL - 35% HP activated with 970nm diode laser (1×30"/0,8W/10Hz leaving the gel in contact to the surface for 4' after activation). Three Raman spectra from each fragment were obtained to calculate the mean intensity of peaks of inorganic component (a.u.), organic collagen content (a.u.), and the ratio of inorganic/organic content, before and after treatment. Analyses of the samples by confocal laser microscopy were performed to evaluate the surface roughness, percentage of tubules, perimeter and area percentage of tubules, before and after treatment. Data were analyzed by Kruskal-Wallis, Dunn's, and Wilcoxon test (P<0.05). Data analysis showed that HP+DL did not change the inorganic content peaks 8.31 [29.78] or the inorganic/organic ratio 3.37 [14.67] (P>0.05). Similarly, DL did not affect the chemical stability of the dentin surface (P>0.05). However, HP significantly increased inorganic content peaks 10.87 [22.62], as well as the inorganic/organic ratio 6.25 [27.78] (P<0.05). Regarding the morphological alterations, all surface treatments increase tubules exposure; HP treatment significantly increases perimeter and area percentage; and HP+DL increases surface roughness. Bleaching HP combined with DL offers an improvement in terms of intracoronal dentin surface protection, yielding better maintenance of dentin chemical stability and morphology. Copyright © 2017 Elsevier Ltd. All rights reserved.

Role of Resuspended Sediments in the Transport and Bioaccumulation of Toxic Organic Contaminants in the Nearshore Marine Environment

DTIC Science & Technology

1994-10-11

predictions for the resuspended BRH sediments is not known but would be explained by another pool of sorption stibstrate acting to make up the difference...wo.ad lie in the presence of other active surfaces in addition to the organic carbon; it is possible that sorption onto mineral surfaces may be an...HOCs in the Great Lakes (Baker et al., 1986). Under conditions with a surplus of active sorption sites, the thermodynamic partition coefficient should

Active anatase (0 0 1)-like surface of hydrothermally synthesized titania nanotubes

NASA Astrophysics Data System (ADS)

Chen, Qiang; Mogilevsky, Gregory; Wagner, George W.; Forstater, Jacob; Kleinhammes, Alfred; Wu, Yue

2009-11-01

Using 31P and 13C NMR with DFT calculations we demonstrate the exposed surface of titania nanotubes (TiNTs) is a stable, unterminated anatase (0 0 1)-like surface and is catalytically active under ambient conditions. We find that methanol dissociatively adsorbs on the surface of TiNTs agreeing with the predicted activity of surface dissociation of organic molecules on the crystalline (0 0 1)-anatase surface. We further examined the catalytic activity of anatase power, TiNT, and nanosheets in catalytic hydrolysis of S-[2-(diisopropylamino)ethyl]- O-ethyl methylphosphonothioate (VX) via 31P NMR and demonstrate that titanate-like nanosheets are inactive in the reaction owing to their hydroxylated (0 0 1) surface.

Platinum–nickel frame within metal-organic framework fabricated in situ for hydrogen enrichment and molecular sieving

PubMed Central

Li, Zhi; Yu, Rong; Huang, Jinglu; Shi, Yusheng; Zhang, Diyang; Zhong, Xiaoyan; Wang, Dingsheng; Wu, Yuen; Li, Yadong

2015-01-01

Developing catalysts that provide the effective activation of hydrogen and selective absorption of substrate on metal surface is crucial to simultaneously improve activity and selectivity of hydrogenation reaction. Here we present an unique in situ etching and coordination synthetic strategy for exploiting a functionalized metal-organic framework to incorporate the bimetallic platinum–nickel frames, thereby forming a frame within frame nanostructure. The as-grown metal-organic framework serves as a ‘breath shell' to enhance hydrogen enrichment and activation on platinum–nickel surface. More importantly, this framework structure with defined pores can provide the selective accessibility of molecules through its one-dimensional channels. In a mixture containing four olefins, the composite can selectively transport the substrates smaller than its pores to the platinum–nickel surface and catalyse their hydrogenation. This molecular sieve effect can be also applied to selectively produce imines, which are important intermediates in the reductive imination of nitroarene, by restraining further hydrogenation via cascade processes. PMID:26391605

An ecotoxicological study on tin- and bismuth-catalysed PDMS based coatings containing a surface-active polymer.

PubMed

Pretti, Carlo; Oliva, Matteo; Mennillo, Elvira; Barbaglia, Martina; Funel, Marco; Reddy Yasani, Bhaskar; Martinelli, Elisa; Galli, Giancarlo

2013-12-01

Novel films were prepared by condensation curing reaction of a poly(dimethyl siloxane) (PDMS) matrix with bismuth neodecanoate and dibutyltin diacetate catalysts. An ecotoxicological study was performed on the leachates of the coatings using the bacterium Vibrio fischeri, the unicellular alga Dunaliella tertiolecta, the crustacean Artemia salina and the fish Sparus aurata (larvae) as testing organisms. A copper-based self-polishing commercial paint was also tested as reference. The results showed that the tin-catalysed coatings and the copper paint were highly toxic against at least two of the four test organisms, whereas bismuth-catalysed coatings did not show any toxic effect. Moreover, the same biological assessment was also carried out on PDMS coatings containing a surface-active fluorinated polymer. The toxicity of the entire polymeric system resulted only from the tin catalyst used for the condensation curing reaction, as the bismuth catalysed coatings incorporating the surface-active polymer remained atoxic toward all the tested organisms. © 2013 Elsevier Inc. All rights reserved.

Surface Modified Particles By Multi-Step Michael-Type Addition And Process For The Preparation Thereof

DOEpatents

Cook, Ronald Lee; Elliott, Brian John; Luebben, Silvia DeVito; Myers, Andrew William; Smith, Bryan Matthew

2005-05-03

A new class of surface modified particles and a multi-step Michael-type addition surface modification process for the preparation of the same is provided. The multi-step Michael-type addition surface modification process involves two or more reactions to compatibilize particles with various host systems and/or to provide the particles with particular chemical reactivities. The initial step comprises the attachment of a small organic compound to the surface of the inorganic particle. The subsequent steps attach additional compounds to the previously attached organic compounds through reactive organic linking groups. Specifically, these reactive groups are activated carbon—carbon pi bonds and carbon and non-carbon nucleophiles that react via Michael or Michael-type additions.

Bio-inspired nanocatalysts for the oxygen reduction reaction.

PubMed

Grumelli, Doris; Wurster, Benjamin; Stepanow, Sebastian; Kern, Klaus

2013-01-01

Electrochemical conversions at fuel cell electrodes are complex processes. In particular, the oxygen reduction reaction has substantial overpotential limiting the electrical power output efficiency. Effective and inexpensive catalytic interfaces are therefore essential for increased performance. Taking inspiration from enzymes, earth-abundant metal centres embedded in organic environments present remarkable catalytic active sites. Here we show that these enzyme-inspired centres can be effectively mimicked in two-dimensional metal-organic coordination networks self-assembled on electrode surfaces. Networks consisting of trimesic acid and bis-pyridyl-bispyrimidine coordinating to single iron and manganese atoms on Au(111) effectively catalyse the oxygen reduction and reveal distinctive catalytic activity in alkaline media. These results demonstrate the potential of surface-engineered metal-organic networks for electrocatalytic conversions. Specifically designed coordination complexes at surfaces inspired by enzyme cofactors represent a new class of nanocatalysts with promising applications in electrocatalysis.

Investigation of cloud condensation nuclei properties and droplet growth kinetics of the water-soluble aerosol fraction in Mexico City

NASA Astrophysics Data System (ADS)

Padró, Luz T.; Tkacik, Daniel; Lathem, Terry; Hennigan, Chris J.; Sullivan, Amy P.; Weber, Rodney J.; Huey, L. Greg; Nenes, Athanasios

2010-05-01

We present hygroscopic and cloud condensation nuclei (CCN) relevant properties of the water-soluble fraction of Mexico City aerosol collected upon filters during the 2006 Megacity Initiative: Local and Global Research Observations (MILAGRO) campaign. Application of κ-Köhler theory to the observed CCN activity gave a fairly constant hygroscopicity parameter (κ = 0.28 ± 0.06) regardless of location and organic fraction. Köhler theory analysis was used to understand this invariance by separating the molar volume and surfactant contributions to the CCN activity. Organics were found to depress surface tension (10-15%) from that of pure water. Daytime samples exhibited lower molar mass (˜200 amu) and surface tension depression than nighttime samples (˜400 amu); this is consistent with fresh hygroscopic secondary organic aerosol (SOA) condensing onto particles during peak photochemical hours, subsequently aging during nighttime periods of high relative humidity. Changes in surface tension partially compensate for shifts in average molar volume to give the constant hygroscopicity observed, which implies the amount (volume fraction) of soluble material in the parent aerosol is the key composition parameter required for CCN predictions. This finding, if applicable elsewhere, may explain why CCN predictions are often found to be insensitive to assumptions of chemical composition and provides a very simple way to parameterize organic hygroscopicity in atmospheric models (i.e., κorg = 0.28ɛWSOC). Special care should be given, however, to surface tension depression from organic surfactants, as its nonlinear dependence with organic fraction may introduce biases in observed (and predicted) hygroscopicity. Finally, threshold droplet growth analysis suggests the water-soluble organics do not affect activation kinetics.

Silica decorated on porous activated carbon nanofiber composites for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Kim, So Yeun; Kim, Bo-Hye

2016-10-01

A hybrid of silica decorated on porous activated carbon nanofibers (ACNFs) is fabricated in the form of a web via electrospinning and an activation process as an electrode material for electrochemical capacitors in an organic electrolyte. The introduction of PhSiH3 (PS) into the polyacrylonitrile (PAN) solution induces a porous ACNF structure containing silica nanoparticles (NPs) via the spontaneous sol-gel process of PS by steam in the subsequent physical activation process. These inorganic-organic hybrid composites of porous ACNF containing silica NPs show superior specific capacitance and energy density in electrochemical tests, along with good rate capability and excellent cycle life in an organic electrolyte, which is attributed to the combination of ACNF's high surface area and silica's hydrophilicity. The electrochemical performance decreases with increasing PS concentration, and this trend is consistent with the specific surface area results, which reveal the rapid formation of a double layer.

Enhancing surface plasmon leakage at the metal/semiconductor interface: towards increased light outcoupling efficiency in organic optoelectronics.

PubMed

Kohl, Jesse; Pantina, Joseph A; O'Carroll, Deirdre M

2014-04-07

The light outcoupling efficiency of organic light-emitting optoelectronic devices is severely limited by excitation of tightly bound surface plasmon polaritons at the metal electrodes. We present a theoretical study of an organic semiconductor-silver-SiO(2) waveguide and demonstrate that by simple tuning of metal film thickness and the emission regime of the organic semiconductor, a significant fraction of surface plasmon polariton mode amplitude is leaked into the active semiconductor layer, thereby decreasing the amount of optical energy trapped by the metal. At visible wavelengths, mode leakage increases by factors of up to 3.8 and 88 by tuning metal film thickness and by addition of gain, respectively.

Relationships between Reading Activities and Language Use.

ERIC Educational Resources Information Center

Gordon, Sandra L.; Van Dongen, Richard

1988-01-01

Noting that the ways children encounter and use print in the classroom can be examined as surface and organizing content of curriculum, this article provides descriptions of innovative uses of print in the kindergarten and elementary school classroom. Curriculum "surface content" includes activities, use of classroom space, display, and…

Electride Mediated Surface Enhanced Raman Scattering (SERS)

NASA Technical Reports Server (NTRS)

Anderson, Mark S. (Inventor)

2016-01-01

An electride may provide surface enhanced Raman scattering (SERS). The electride, a compound where the electrons serve as anions, may be a ceramic electride, such as a conductive ceramic derived from mayenite, or an organic electride, for example. The textured electride surface or electride particles may strongly enhance the Raman scattering of organic or other Raman active analytes. This may also provide a sensitive method for monitoring the chemistry and electronic environment at the electride surface. The results are evidence of a new class of polariton (i.e., a surface electride-polariton resonance mechanism) that is analogous to the surface plasmon-polariton resonance that mediates conventional SERS.

Enhanced photocatalytic activity of TiO2 by surface fluorination in degradation of organic cationic compound.

PubMed

Yang, Shi-ying; Chen, You-yuan; Zheng, Jian-guo; Cui, Ying-jie

2007-01-01

Experiments were carried out to investigate the influence of TiO2 surface fluorination on the photodegradation of a representative organic cationic compound, Methylene Blue (MB). The electropositive MB shows poor adsorption on TiO2 surface; its degradation performs a HO-radical-mediated mechanism. In the F-modified system, the kinetic reaction rate enlarged more than 2.5 fold that was attributed mainly to the accumulating adsorption of MB and the increased photogenerated hole available on the F-modified TiO2 surface.

Purification system

NASA Technical Reports Server (NTRS)

Flanagan, David T. (Inventor); Gibbons, Randall E. (Inventor)

1992-01-01

A system for prolonging the life of a granulated activated charcoal (GAC) water treatment device is disclosed in which an ultraviolet light transparent material is used to constrain water to flow over carbon surfaces. It is configured to receive maximum flux from a UV radiation source for the purpose of preventing microbial proliferation on the carbon surfaces; oxidizing organic contaminants adsorbed from the water onto the carbon surfaces and from biodegradation of adsorbed microbial forms; disinfecting water; and oxidizing organic contaminants in the water.

Surfaces of Fluorinated Pyridinium Block Copolymers with Enhanced Antibacterial Activity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krishnan,S.; Ward, R.; Hexemer, A.

2006-01-01

Polystyrene-b-poly(4-vinylpyridine) copolymers were quaternized with 1-bromohexane and 6-perfluorooctyl-1-bromohexane. Surfaces prepared from these polymers were characterized by contact angle measurements, near-edge X-ray absorption fine structure spectroscopy and X-ray photoelectron spectroscopy. The fluorinated pyridinium surfaces showed enhanced antibacterial activity compared to their nonfluorinated counterparts. Even a polymer with a relatively low molecular weight pyridinium block showed high antimicrobial activity. The bactericidal effect was found to be related to the molecular composition and organization in the top 2-3 nm of the surface and increased with increasing hydrophilicity and pyridinium concentration of the surface.

Isolation, screening, and characterization of surface-active agent-producing, oil-degrading marine bacteria of Mumbai Harbor.

PubMed

Mohanram, Rajamani; Jagtap, Chandrakant; Kumar, Pradeep

2016-04-15

Diverse marine bacterial species predominantly found in oil-polluted seawater produce diverse surface-active agents. Surface-active agents produced by bacteria are classified into two groups based on their molecular weights, namely biosurfactants and bioemulsifiers. In this study, surface-active agent-producing, oil-degrading marine bacteria were isolated using a modified Bushnell-Haas medium with high-speed diesel as a carbon source from three oil-polluted sites of Mumbai Harbor. Surface-active agent-producing bacterial strains were screened using nine widely used methods. The nineteen bacterial strains showed positive results for more than four surface-active agent screening methods; further, these strains were characterized using biochemical and nucleic acid sequencing methods. Based on the results, the organisms belonged to the genera Acinetobacter, Alcanivorax, Bacillus, Comamonas, Chryseomicrobium, Halomonas, Marinobacter, Nesterenkonia, Pseudomonas, and Serratia. The present study confirmed the prevalence of surface-active agent-producing bacteria in the oil-polluted waters of Mumbai Harbor. Copyright © 2016 Elsevier Ltd. All rights reserved.

pH-Responsive Mercaptoundecanoic Acid Functionalized Gold Nanoparticles and Applications in Catalysis

PubMed Central

Ansar, Siyam M.; Chakraborty, Saptarshi

2018-01-01

Mercaptoundecanoic acid (MUA) functionalized gold nanoparticles (AuNP-MUA) were synthesized and demonstrated to possess pH-triggered aggregation and re-dispersion, as well as the capability of phase transfer between aqueous and organic phases in response to changes in pH. The pH of aggregation for AuNP-MUA is consistent with the pKa of MUA (pH ~4) in solution, while AuNP-MUA phase transition between aqueous and organic phases occurs at pH ~9. The ion pair formation between the amine group in octadecylamine (ODA), the carboxylate group in MUA, and the hydrophobic alkyl chain of ODA facilitates the phase transfer of AuNP-MUA into an organic medium. The AuNP-MUA were investigated as a reusable catalyst in the catalytic reduction of 4-nitrophenol by borohydride—a model reaction for AuNPs. It was determined that 100% MUA surface coverage completely inhibits the catalytic activity of AuNPs. Decreasing the surface coverage was shown to increase catalytic activity, but this decrease also leads to decreased colloidal stability, recoverability, and reusability in subsequent reactions. At 60% MUA surface coverage, colloidal stability and catalytic activity were achieved, but the surface coverage was insufficient to enable redispersion following pH-induced recovery. A balance between AuNP colloidal stability, recoverability, and catalytic activity with reusability was achieved at 90% MUA surface coverage. The AuNP-MUA catalyst can also be recovered at different pH ranges depending on the recovery method employed. At pH ~4, protonation of the MUA results in reduced surface charge and aggregation. At pH ~9, ODA will form an ion-pair with the MUA and induce phase transfer into an immiscible organic phase. Both the pH-triggered aggregation/re-dispersion and aqueous/organic phase transfer methods were employed for catalyst recovery and reuse in subsequent reactions. The ability to recover and reuse the AuNP-MUA catalyst by two different methods and different pH regimes is significant, based on the fact that nanoparticle-catalyzed reactions may occur under different pH conditions. PMID:29772775

Experts workshop on the ecotoxicological risk assessment of ionizable organic chemicals: Towards a science-based framework for chemical assessment

EPA Science Inventory

There is a growing need to develop analytical methods and tools that can be applied to assess the environmental risks associated with charged, polar, and ionisable organic chemicals, such as those used as active pharmaceutical ingredients, biocides, and surface active chemicals. ...

Potential of coconut shell activated carbon (CSAC) in removing contaminants for water quality improvement: A critical review

NASA Astrophysics Data System (ADS)

Akhir, Muhammad Fitri Mohd; Saad, Noor Aida; Zakaria, Nor Azazi

2017-10-01

Commonly, water contaminations occur due to human-induced conditions such as industrial discharge and urban activities. The widely identified contaminants are heavy metal. The toxicity of those heavy metal elements is high and very poisonous to humans' health and environment even at lower dose or concentration of exposure. Chronic poisoning can cause fatal or defect to one's body or environment. Organic contaminants such as oil and microbial are also found due to decomposition of organic matter. The excellent quality adsorption of contaminants is highly related to surface area, pore size, pore volume, and amount plus type of functional group on surface of CSAC. The higher the surface area and pore volume, the higher adsorption that CSAC have towards contaminants. In comparison to meso-pore and macro-pore, micro-pore is better for trapping and adsorbing water contaminants. The purpose of this article is to critically review the potential of CSAC in increasing adsorption to remove contaminants for water quality improvement. A critical review is implemented using search engine like Science Direct. Alkali-modification is shown to have good adsorption in anion elements and organic matter due to improvement of hydrophobic organic compound (HOC) while acid-modification is good in cation elements adsorption. Strong alkali impregnated solution makes CSAC more hydrophobic and positively charge especially after increasing the impregnation dosage. Strong acid of adsorbate affects the quality of adsorption by reducing the surface area, pore volume and it also breaks the Van der Waals forces between adsorbent and adsorbate. However, the formation of oxygen helps the activated carbon surface to become more hydrophilic and negative charge is produced. It helps the effectiveness of metal adsorption. Therefore, by controlling dosage and types of functional groups on surface of CSAC and the pH of adsorbate, it can contribute to high adsorption of organic and inorganic contaminants in the water.

Possible Niches for Extant Life on Titan in Light of Cassini/Huygens Results

NASA Astrophysics Data System (ADS)

Grinspoon, D. H.; Bullock, M. A.; Spencer, J. R.; Schulze-Makuch, D.

2005-08-01

Results from the first year of the Cassini mission show that Titan has an active surface with few impact craters and abundant hints of cryovolcanism, tectonism, aeolian and fluvial activity (Porco et al., 2005; Elachi et al., 2005). Methane clouds and surface characteristics strongly imply the presence of an active global methane cycle analogous to Earth's hydrological cycle. Astrobiological interest in Titan has previously focused on possible prebiological chemical evolution on a moon with a thick nitrogen atmosphere and rich organic chemistry (Raulin and Owen, 2002). Yet the emerging new picture of Titan has raised prospects for the possibility of extant life. Several key requirements for life appear to be present, including liquid reservoirs, organic molecules and ample energy sources. One promising location may be hot springs in contact with hydrocarbon reservoirs. Hydrogenation of photochemically produced acetylene could provide metabolic energy for near-surface organisms and also replenish atmospheric methane (Schulze-Makuch and Grinspoon, 2005). The energy released could be used by organisms to drive endothermic reactions, or go into heating their surroundings, helping to create their own liquid microenvironments. In environments which are energy-rich but liquid-poor, like the near-surface of Titan, natural selection may favor organisms that use their ``waste heat" to melt their own watering holes. Downward transport of high energy photochemical compounds could provide an energy supply for near-surface organisms which could be used, in part, to maintain the liquid environments conducive to life. We will present the results of thermal modeling designed to test the feasibility of biothermal melting on Titan. C. Porco and the Cassini Imaging Team (2005) Nature 434, 159-168; C. Elachi et al, Science, 308, 970-974; F. Raulin and T. Owen (2002) Space Sci. Rev. 104, 377 - 394.; D. Schulze-Makuch and D. H. Grinspoon (2005) Astrobiology, in press.

Extended Survival of Several Microorganisms and Relevant Amino Acid Biomarkers under Simulated Martian Surface Conditions as a Function of Burial Depth

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Adam; Pratt, L.M.; Vishnivetskaya, Tatiana A

2011-01-01

Recent orbital and landed missions have provided substantial evidence for ancient liquid water on the martian surface as well as evidence of more recent sedimentary deposits formed by water and/or ice. These observations raise serious questions regarding an independent origin and evolution of life on Mars. Future missions seek to identify signs of extinct martian biota in the form of biomarkers or morphological characteristics, but the inherent danger of spacecraft-borne terrestrial life makes the possibility of forward contamination a serious threat not only to the life detection experiments, but also to any extant martian ecosystem. A variety of cold andmore » desiccation-tolerant organisms were exposed to 40 days of simulated martian surface conditions while embedded within several centimeters of regolith simulant in order to ascertain the plausibility of such organisms survival as a function of environmental parameters and burial depth. Relevant amino acid biomarkers associated with terrestrial life were also analyzed in order to understand the feasibility of detecting chemical evidence for previous biological activity. Results indicate that stresses due to desiccation and oxidation were the primary deterrent to organism survival, and that the effects of UV-associated damage, diurnal temperature variations, and reactive atmospheric species were minimal. Organisms with resistance to desiccation and radiation environments showed increased levels of survival after the experiment compared to organisms characterized as psychrotolerant. Amino acid analysis indicated the presence of an oxidation mechanism that migrated downward through the samples during the course of the experiment and likely represents the formation of various oxidizing species at mineral surfaces as water vapor diffused through the regolith. Current sterilization protocols may specifically select for organisms best adapted to survival at the martian surface, namely species that show tolerance to radical-induced oxidative damage and low water activity environments. Additionally, any hypothetical martian ecosystems may have evolved similar physiological traits that allow sporadic metabolism during periods of increased water activity.« less

Supercritical processing as a route to high internal surface areas and permanent microporosity in metal-organic framework materials.

PubMed

Nelson, Andrew P; Farha, Omar K; Mulfort, Karen L; Hupp, Joseph T

2009-01-21

Careful processing of four representative metal-organic framework (MOF) materials with liquid and supercritical carbon dioxide (ScD) leads to substantial, or in some cases spectacular (up to 1200%), increases in gas-accessible surface area. Maximization of surface area is key to the optimization of MOFs for many potential applications. Preliminary evidence points to inhibition of mesopore collapse, and therefore micropore accessibility, as the basis for the extraordinarily efficacious outcome of ScD-based activation.

An interfacial mechanism for cloud droplet formation on organic aerosols

DOE PAGES

Ruehl, C. R.; Davies, J. F.; Wilson, K. R.

2016-03-25

Accurate predictions of aerosol/cloud interactions require simple, physically accurate parameterizations of the cloud condensation nuclei (CCN) activity of aerosols. Current models assume that organic aerosol species contribute to CCN activity by lowering water activity. We measured droplet diameters at the point of CCN activation for particles composed of dicarboxylic acids or secondary organic aerosol and ammonium sulfate. Droplet activation diameters were 40 to 60% larger than predicted if the organic was assumed to be dissolved within the bulk droplet, suggesting that a new mechanism is needed to explain cloud droplet formation. A compressed film model explains how surface tension depressionmore » by interfacial organic molecules can alter the relationship between water vapor supersaturation and droplet size (i.e., the Köhler curve), leading to the larger diameters observed at activation.« less

An interfacial mechanism for cloud droplet formation on organic aerosols

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ruehl, C. R.; Davies, J. F.; Wilson, K. R.

Accurate predictions of aerosol/cloud interactions require simple, physically accurate parameterizations of the cloud condensation nuclei (CCN) activity of aerosols. Current models assume that organic aerosol species contribute to CCN activity by lowering water activity. We measured droplet diameters at the point of CCN activation for particles composed of dicarboxylic acids or secondary organic aerosol and ammonium sulfate. Droplet activation diameters were 40 to 60% larger than predicted if the organic was assumed to be dissolved within the bulk droplet, suggesting that a new mechanism is needed to explain cloud droplet formation. A compressed film model explains how surface tension depressionmore » by interfacial organic molecules can alter the relationship between water vapor supersaturation and droplet size (i.e., the Köhler curve), leading to the larger diameters observed at activation.« less

An interfacial mechanism for cloud droplet formation on organic aerosols.

PubMed

Ruehl, Christopher R; Davies, James F; Wilson, Kevin R

2016-03-25

Accurate predictions of aerosol/cloud interactions require simple, physically accurate parameterizations of the cloud condensation nuclei (CCN) activity of aerosols. Current models assume that organic aerosol species contribute to CCN activity by lowering water activity. We measured droplet diameters at the point of CCN activation for particles composed of dicarboxylic acids or secondary organic aerosol and ammonium sulfate. Droplet activation diameters were 40 to 60% larger than predicted if the organic was assumed to be dissolved within the bulk droplet, suggesting that a new mechanism is needed to explain cloud droplet formation. A compressed film model explains how surface tension depression by interfacial organic molecules can alter the relationship between water vapor supersaturation and droplet size (i.e., the Köhler curve), leading to the larger diameters observed at activation. Copyright © 2016, American Association for the Advancement of Science.

Strong Effects of a Shelfbreak Jet on Microbial Enzyme Activities

NASA Astrophysics Data System (ADS)

Hoarfrost, A.; Balmonte, J. P.; Ziervogel, K.; Ghobrial, S.; Gawarkiewicz, G.; Arnosti, C.

2016-02-01

The activities of extracellular enzymes are critical in initiating microbial cycling of organic carbon, yet the dynamics of heterotrophic enzyme activities in marine environments are still poorly understood. Variations at a given site in rates of activity and the spectrum of organic substrates hydrolyzed may depend upon environmental context. We measured the extracellular enzymatic hydrolysis of 13 high- and low-molecular-weight organic substrates in surface and bottom waters along a closely spaced 4-station transect at 71 W on the North Atlantic continental shelf, in the vicinity of the shelfbreak front. This transect intersects a robust upwelling cell that typically shows high biologic productivity, and is locatable by changes in T/S profiles and chl a concentrations along sharp spatial gradients. At the time of sampling, cold pool waters over the continental shelf were relatively cold, 3.5 Deg. C, compared to 12 Deg. C over the upper continental slope. Satellite thermal imagery indicated that shelf water extended offshore and interacted with a large crest of the Gulf Stream. The surface and bottom waters associated with the upwelling jet were characterized by enzyme activities a factor of 20 more rapid than closer inshore waters, and surface water chl a concentrations that were two to three times higher than the inshore waters. The spectrum of enzyme activities also differed markedly between surface and bottom waters both within the jet and at near-shore stations. Microbial extracellular enzymatic activities were strongly influenced by differences in their environmental context along the continental slope and shelfbreak front. Constraining the factors controlling heterotrophic activity across the diverse marine environment is an important step in understanding microbial controls on carbon cycling.

Spatio-temporal variations in the composition of organic matter in surface sediments of a mangrove receiving shrimp farm effluents (New Caledonia).

PubMed

Aschenbroich, Adélaïde; Marchand, Cyril; Molnar, Nathalie; Deborde, Jonathan; Hubas, Cédric; Rybarczyk, Hervé; Meziane, Tarik

2015-04-15

In order to investigate spatio-temporal variations in the composition and origin of the benthic organic matter (OM) at the sediment surface in mangrove receiving shrimp farm effluents, fatty acid (FA) biomarkers, natural stable isotopes (δ(13)C and δ(15)N), C:N ratios and chlorophyll-a (chl-a) concentrations were determined during the active and the non-active period of the farm. Fatty acid compositions in surface sediments within the mangrove forest indicated that organic matter inputs varied along the year as a result of farm activity. Effluents were the source of fresh particulate organic matter for the mangrove, as evidenced by the unsaturated fatty acid (UFA) distribution. The anthropogenic MUFA 18:1ω9 was not only accumulated at the sediment surface in some parts of the mangrove, but was also exported to the seafront. Direct release of bacteria and enhanced in situ production of fungi, as revealed by specific FAs, stimulated mangrove litter decomposition under effluent runoff condition. Also, microalgae released from ponds contributed to maintain high benthic chl-a concentrations in mangrove sediments in winter and to a shift in microphytobenthic community assemblage. Primary production was high whether the farm released effluent or not which questioned the temporary effect of shrimp farm effluent on benthic microalgae dynamic. This study outlined that mangrove benthic organic matter was qualitatively and quantitatively affected by shrimp farm effluent release and that responses to environmental condition changes likely depended on mangrove stand characteristics. Copyright © 2015 Elsevier B.V. All rights reserved.

The nature and function of microbial enzymes in subsurface marine sediments

NASA Astrophysics Data System (ADS)

Steen, A. D.; Schmidt, J.

2016-02-01

Isotopic and genomic evidence indicates that marine sediments contain populations of active heterotrophic microorganisms which appear to metabolize old, detrital, apparently recalcitrant organic matter. In surface communities, heterotrophs use extracellular enzymes to access complex organic matter. In subsurface sediments, in which microbial doubling times can be on the order of hundreds or thousands of years, it is not clear whether extracellular enzymes could remain stable and active long enough to constitute a 'profitable' stragtegy for accessing complex organic carbon. Here we present evidence that a wide range of extracellular enzyme are active in subsurface sediments from two different environments: the White Oak River, NC, and deep (up to 80 m) sediments of the Baltic Sea Basin recovered from IODP Expedition 347. In the White Oak River, enzymes from deeper sediments appear to be better-adapted to highly-degraded organic matter than enzymes from surface sediments. In the Baltic Sea, preliminary data suggest that enzymes related to nitrogen acquisition are preferentially expressed. By characterizing the extracellular enzymes present in marine sediments, we hope to achieve a better understanding of the mechanisms that control sedimentary organic matter remineralization and preservation.

First Molecular Dynamics simulation insight into the mechanism of organics adsorption from aqueous solutions on microporous carbons

NASA Astrophysics Data System (ADS)

Terzyk, Artur P.; Gauden, Piotr A.; Zieliński, Wojciech; Furmaniak, Sylwester; Wesołowski, Radosław P.; Klimek, Kamil K.

2011-10-01

The results of 84 MD simulations showing the influence of porosity and carbon surface oxidation on adsorption of three organic compounds from aqueous solutions on carbons are reported. Based on a model of 'soft' activated carbon, three carbon structures with gradually changed microporosity were created. Next, different number of surface oxygen groups was introduced. We observe quantitative agreement between simulation and experiment i.e. the decrease in adsorption from benzene down to paracetamol. Simulation results clearly demonstrate that the balance between porosity and carbon surface chemical composition in organics adsorption on carbons, and the pore blocking determine adsorption properties of carbons.

Surface tensions of solutions containing dicarboxylic acid mixtures

NASA Astrophysics Data System (ADS)

Lee, Jae Young; Hildemann, Lynn M.

2014-06-01

Organic solutes tend to lower the surface tension of cloud condensation nuclei, allowing them to more readily activate. The surface tension of various dicarboxylic acid aerosol mixtures was measured at 20 °C using the Wilhelmy plate method. At lower concentrations, the surface tension of a solution with equi-molar mixtures of dicarboxylic acids closely followed that of a solution with the most surface-active organic component alone. Measurements of surface tension for these mixtures were lower than predictions using Henning's model and the modified Szyszkowski equation, by ˜1-2%. The calculated maximum surface excess (Γmax) and inverse Langmuir adsorption coefficient (β) from the modified Szyszkowski equation were both larger than measured values for 6 of the 7 mixtures tested. Accounting for the reduction in surface tension in the Köhler equation reduced the critical saturation ratio for these multi-component mixtures - changes were negligible for dry diameters of 0.1 and 0.5 μm, but a reduction from 1.0068 to 1.0063 was seen for the 4-dicarboxylic acid mixture with a dry diameter of 0.05 μm.

Cloud condensation nucleus activity of internally mixed ammonium sulfate/organic acid aerosol particles

NASA Astrophysics Data System (ADS)

Abbatt, J. P. D.; Broekhuizen, K.; Pradeep Kumar, P.

The ability of mixed ammonium sulfate/organic acid particles to act as cloud condensation nuclei (CCN) has been studied in the laboratory using a continuous flow, thermal-gradient diffusion chamber operated at supersaturations between 0.3% and 0.6%. The organic acids studied were malonic acid, azelaic acid, hexanoic acid, cis-pinonic acid, oleic acid and stearic acid, and the particles were largely prepared by condensation of the organic vapor onto a dry ammonium sulfate core. For malonic acid and hexanoic acid, the mixed particles activated as predicted by a simple Köhler theory model where both species are assumed to be fully soluble and the droplet has the surface tension of water. Three low-solubility species, cis-pinonic acid, azelaic acid and oleic acid, are well modeled where the acid was assumed to be either partially or fully insoluble. Interestingly, although thin coats of stearic acid behaved in a manner similar to that displayed by oleic and cis-pinonic acid, we observed that thick coats led to a complete deactivation of the ammonium sulfate, presumably because the water vapor could not diffuse through the solid stearic acid. We observed no CCN behavior that could be clearly attributed to a lowering of the surface tension of the growing droplet by the presence of the organic constituents, some of which are highly surface active.

Highly sensitive photoelectrochemical biosensor for kinase activity detection and inhibition based on the surface defect recognition and multiple signal amplification of metal-organic frameworks.

PubMed

Wang, Zonghua; Yan, Zhiyong; Wang, Feng; Cai, Jibao; Guo, Lei; Su, Jiakun; Liu, Yang

2017-11-15

A turn-on photoelectrochemical (PEC) biosensor based on the surface defect recognition and multiple signal amplification of metal-organic frameworks (MOFs) was proposed for highly sensitive protein kinase activity analysis and inhibitor evaluation. In this strategy, based on the phosphorylation reaction in the presence of protein kinase A (PKA), the Zr-based metal-organic frameworks (UiO-66) accommodated with [Ru(bpy) 3 ] 2+ photoactive dyes in the pores were linked to the phosphorylated kemptide modified TiO 2 /ITO electrode through the chelation between the Zr 4+ defects on the surface of UiO-66 and the phosphate groups in kemptide. Under visible light irradiation, the excited electrons from [Ru(bpy) 3 ] 2+ adsorbed in the pores of UiO-66 injected into the TiO 2 conduction band to generate photocurrent, which could be utilized for protein kinase activities detection. The large surface area and high porosities of UiO-66 facilitated a large number of [Ru(bpy) 3 ] 2+ that increased the photocurrent significantly, and afforded a highly sensitive PEC analysis of kinase activity. The detection limit of the as-proposed PEC biosensor was 0.0049UmL -1 (S/N!=!3). The biosensor was also applied for quantitative kinase inhibitor evaluation and PKA activities detection in MCF-7 cell lysates. The developed visible-light PEC biosensor provides a simple detection procedure and a cost-effective manner for PKA activity assays, and shows great potential in clinical diagnosis and drug discoveries. Copyright © 2017 Elsevier B.V. All rights reserved.

Predicting adsorption isotherms for aqueous organic micropollutants from activated carbon and pollutant properties.

PubMed

Li, Lei; Quinlivan, Patricia A; Knappe, Detlef R U

2005-05-01

A method based on the Polanyi-Dubinin-Manes (PDM) model is presented to predict adsorption isotherms of aqueous organic contaminants on activated carbons. It was assumed that trace organic compound adsorption from aqueous solution is primarily controlled by nonspecific dispersive interactions while water adsorption is controlled by specific interactions with oxygen-containing functional groups on the activated carbon surface. Coefficients describing the affinity of water for the activated carbon surface were derived from aqueous-phase methyl tertiary-butyl ether (MTBE) and trichloroethene (TCE) adsorption isotherm data that were collected with 12 well-characterized activated carbons. Over the range of oxygen contents covered by the adsorbents (approximately 0.8-10 mmol O/g dry, ash-free activated carbon), a linear relationship between water affinity coefficients and adsorbent oxygen content was obtained. Incorporating water affinity coefficients calculated from the developed relationship into the PDM model, isotherm predictions resulted that agreed well with experimental data for three adsorbents and two adsorbates [tetrachloroethene (PCE), cis-1,2-dichloroethene (DCE)] that were not used to calibrate the model.

Investigating the photostability of carboxylic acids exposed to Mars surface ultraviolet radiation conditions.

PubMed

Stalport, F; Coll, P; Szopa, C; Cottin, H; Raulin, F

2009-01-01

The detection and identification of organic molecules on Mars are of primary importance to establish the existence of a possible ancient prebiotic chemistry or even biological activity. The harsh environmental conditions at the surface of Mars could explain why the Viking probes-the only efforts, to date, to search for organics on Mars-detected no organic matter. To investigate the nature, abundance, and stability of organic molecules that could survive such environmental conditions, we developed a series of experiments that simulate martian surface environmental conditions. Here, we present results with regard to the impact of solar UV radiation on various carboxylic acids, such as mellitic acid, which are of astrobiological interest to the study of Mars. Our results show that at least one carboxylic acid, mellitic acid, could produce a resistant compound-benzenehexacarboxylic acid-trianhydride (C(12)O(9))-when exposed to martian surface radiation conditions. The formation of such products could contribute to the presence of organic matter in the martian regolith, which should be considered a primary target for in situ molecular analyses during future surface missions.

Ultra-thin microporous/hybrid materials

DOEpatents

Jiang, Ying-Bing [Albuquerque, NM; Cecchi, Joseph L [Albuquerque, NM; Brinker, C Jeffrey [Albuquerque, NM

2012-05-29

Ultra-thin hybrid and/or microporous materials and methods for their fabrication are provided. In one embodiment, the exemplary hybrid membranes can be formed including successive surface activation and reaction steps on a porous support that is patterned or non-patterned. The surface activation can be performed using remote plasma exposure to locally activate the exterior surfaces of porous support. Organic/inorganic hybrid precursors such as organometallic silane precursors can be condensed on the locally activated exterior surfaces, whereby ALD reactions can then take place between the condensed hybrid precursors and a reactant. Various embodiments can also include an intermittent replacement of ALD precursors during the membrane formation so as to enhance the hybrid molecular network of the membranes.

Water activity and the challenge for life on early Mars.

PubMed

Tosca, Nicholas J; Knoll, Andrew H; McLennan, Scott M

2008-05-30

In situ and orbital exploration of the martian surface has shown that acidic, saline liquid water was intermittently available on ancient Mars. The habitability of these waters depends critically on water activity (aH2O), a thermodynamic measure of salinity, which, for terrestrial organisms, has sharply defined limits. Using constraints on fluid chemistry and saline mineralogy based on martian data, we calculated the maximum aH2O for Meridiani Planum and other environments where salts precipitated from martian brines. Our calculations indicate that the salinity of well-documented surface waters often exceeded levels tolerated by known terrestrial organisms.

A quantitative speciation model for the adsorption of organic pollutants on activated carbon.

PubMed

Grivé, M; García, D; Domènech, C; Richard, L; Rojo, I; Martínez, X; Rovira, M

2013-01-01

Granular activated carbon (GAC) is commonly used as adsorbent in water treatment plants given its high capacity for retaining organic pollutants in aqueous phase. The current knowledge on GAC behaviour is essentially empirical, and no quantitative description of the chemical relationships between GAC surface groups and pollutants has been proposed. In this paper, we describe a quantitative model for the adsorption of atrazine onto GAC surface. The model is based on results of potentiometric titrations and three types of adsorption experiments which have been carried out in order to determine the nature and distribution of the functional groups on the GAC surface, and evaluate the adsorption characteristics of GAC towards atrazine. Potentiometric titrations have indicated the existence of at least two different families of chemical groups on the GAC surface, including phenolic- and benzoic-type surface groups. Adsorption experiments with atrazine have been satisfactorily modelled with the geochemical code PhreeqC, assuming that atrazine is sorbed onto the GAC surface in equilibrium (log Ks = 5.1 ± 0.5). Independent thermodynamic calculations suggest a possible adsorption of atrazine on a benzoic derivative. The present work opens a new approach for improving the adsorption capabilities of GAC towards organic pollutants by modifying its chemical properties.

Performance enhancement in organic photovoltaic solar cells using iridium (Ir) ultra-thin surface modifier (USM)

NASA Astrophysics Data System (ADS)

Pandey, Rina; Lim, Ju Won; Kim, Jung Hyuk; Angadi, Basavaraj; Choi, Ji Won; Choi, Won Kook

2018-06-01

In this study, Iridium (Ir) metallic layer as an ultra-thin surface modifier (USM) was deposited on ITO coated glass substrate using radio frequency magnetron sputtering for improving the photo-conversion efficiency of organic photovoltaic cells. Ultra-thin Ir acts as a surface modifier replacing the conventional hole transport layer (HTL) PEDOT:PSS in organic photovoltaic (OPV) cells with two different active layers P3HT:PC60BM and PTB7:PC70BM. The Ir USM (1.0 nm) coated on ITO glass substrate showed transmittance of 84.1% and work function of >5.0 eV, which is higher than that of ITO (4.5-4.7 eV). The OPV cells with Ir USM (1.0 nm) exhibits increased power conversion efficiency of 3.70% (for P3HT:PC60BM active layer) and 7.28% (for PTB7:PC70BM active layer) under 100 mW/cm2 illumination (AM 1.5G) which are higher than those of 3.26% and 6.95% for the same OPV cells but with PEDOT:PSS as HTL instead of Ir USM. The results reveal that the chemically stable Ir USM layer could be used as an alternative material for PEDOT:PSS in organic photovoltaic cells.

Hydroxylation of organic polymer surface: method and application.

PubMed

Yang, Peng; Yang, Wantai

2014-03-26

It may be hardly believable that inert C-H bonds on a polymeric material surface could be quickly and efficiently transformed into C-OH by a simple and mild way. Thanks to the approaches developed recently, it is now possible to transform surface H atoms of a polymeric substrate into monolayer OH groups by a simple/mild photochemical reaction. Herein the method and application of this small-molecular interfacial chemistry is highlighted. The existence of hydroxyl groups on material surfaces not only determines the physical and chemical properties of materials but also provides effective reaction sites for postsynthetic sequential modification to fulfill the requirements of various applications. However, organic synthetic materials based on petroleum, especially polyolefins comprise mainly C and H atoms and thus present serious surface problems due to low surface energy and inertness in reactivity. These limitations make it challenging to perform postsynthetic surface sequential chemical derivatization toward enhanced functionalities and properties and also cause serious interfacial problems when bonding or integrating polymer substrates with natural or inorganic materials. Polymer surface hydroxylation based on direct conversion of C-H bonds on polymer surfaces is thus of significant importance for academic and practical industrial applications. Although highly active research results have reported on small-molecular C-H bond activation in solution (thus homogeneous), most of them, featuring the use of a variety of transition metals as catalysts, present a slow reaction rate, a low atom economy and an obvious environmental pollution. In sharp contrast to these conventional C-H activation strategies, the present Spotlight describes a universal confined photocatalytic oxidation (CPO) system that is able to directly convert polymer surface C-H bonds to C-OSO3(-) and, subsequently, to C-OH through a simple hydrolysis. Generally speaking, these newly implanted hydroxyl groups preserve their own reactivity toward other complementary compounds, thus creating a novel base with distinct surface properties. Thanks to this functionalized platform, a wide range of organic, inorganic and metal materials have been attached to conventional organic polymer substrates through the rational engineering of surface molecular templates from small functional groups to macromolecules. It is expected that the proposed novel CPO method and its versatile usages in advanced material applications will offer new opportunities for a variety of scientific communities, especially for those working on surface/interface modulation.

[Effects of intensive management on soil C and N pools and soil enzyme activities in Moso bamboo plantations.

PubMed

Yang, Meng; Li, Yong Fu; Li, Yong Chun; Xiao, Yong Heng; Yue, Tian; Jiang, Pei Kun; Zhou, Guo Mo; Liu, Juan

2016-11-18

In order to elucidate the effects of intensive management on soil carbon pool, nitrogen pool, enzyme activities in Moso bamboo (Phyllostachys pubescens) plantations, we collected soil samples from the soil surface (0-20 cm) and subsurface (20-40 cm) layers in the adjacent Moso bamboo plantations with extensive and intensive managements in Sankou Township, Lin'an City, Zhejiang Province. We determined different forms of C, N and soil invertase, urease, catalase and acid phosphatase activities. The results showed that long-term intensive management of Moso bamboo plantations significantly decreased the content and storage of soil organic carbon (SOC), with the SOC storage in the soil surface and subsurface layers decreased by 13.2% and 18.0%, respectively. After 15 years' intensive management of Masoo bamboo plantations, the contents of soil water soluble carbon (WSOC), hot water soluble carbon (HWSOC), microbial carbon (MBC) and readily oxidizable carbon (ROC) were significantly decreased in the soil surface and subsurface layers. The soil N storage in the soil surface and subsurface layers in intensively managed Moso bamboo plantations increased by 50.8% and 36.6%, respectively. Intensive management significantly increased the contents of nitrate-N (NO 3 - -N) and ammonium-N (NH 4 + -N), but decreased the contents of water-soluble nitrogen (WSON) and microbial biomass nitrogen (MBN). After 15 years' intensive management of Masoo bamboo plantations, the soil invertase, urease, catalase and acid phosphatase activities in the soil surface layer were significantly decreased, the soil acid phosphatase activity in the soil subsurface layer were significantly decreased, and other enzyme activities in the soil subsurface layer did not change. In conclusion, long-term intensive management led to a significant decline of soil organic carbon storage, soil labile carbon and microbial activity in Moso bamboo plantations. Therefore, we should consider the use of organic fertilizer in the intensive mana-gement process for the sustainable management of Moso bamboo plantations in the future.

Mechanisms for trace metal enrichment at the surface microlayer in an estuarine salt marsh

USGS Publications Warehouse

Lion, Leonard W.

1982-01-01

The relative contributions of adsorption to particulate surfaces, complexation with surface-active organic ligands and uptake by micro-organisms were evaluated with respect to their importance in the surface microlayer enrichment (‘partitioning’) of Cd, Pb and Cu. The contributions of each process were inferred from field data in which partitioning of the dissolved and particulate forms of Cd, Pb and Cu, total and dissolved organic carbon, particles and total bacteria were observed. In the South San Francisco Bay estuary, particle enrichment appears to control trace metal partitioning. Trace metal association with the particulate phase and the levels of partitioning observed were in the order Pb > Cu > Cd and reflect the calculated equilibrium chemical speciation of these metals in computer-simulated seawater matrices.

Stabilization and activation of alpha-chymotrypsin in water-organic solvent systems by complex formation with oligoamines.

PubMed

Kudryashova, Elena V; Artemova, Tatiana M; Vinogradov, Alexei A; Gladilin, Alexander K; Mozhaev, Vadim V; Levashov, Andrey V

2003-04-01

Formation of enzyme-oligoamine complexes was suggested as an approach to obtain biocatalysts with enhanced resistance towards inactivation in water-organic media. Complex formation results in broadening (by 20-40% v/v ethanol) of the range of cosolvent concentrations where the enzyme retains its catalytic activity (stabilization effect). At moderate cosolvent concentrations (20-40% v/v) complex formation activates the enzyme (by 3-6 times). The magnitude of activation and stabilization effects increases with the number of possible electrostatic contacts between the protein surface and the molecules of oligoamines (OA). Circular dichroism spectra in the far-UV region show that complex formation stabilizes protein conformation and prevents aggregation in water-organic solvent mixtures. Two populations of the complexes with different thermodynamic stabilities were found in alpha-chymotrypsin (CT)-OA systems depending on the CT/OA ratio. The average dissociation constants and stoichiometries of both low- and high-affinity populations of the complexes were estimated. It appears that it is the low-affinity sites on the CT surface that are responsible for the activation effect.

Solid-support immobilization of a "swing" fusion protein for enhanced glucose oxidase catalytic activity.

PubMed

Takatsuji, Yoshiyuki; Yamasaki, Ryota; Iwanaga, Atsushi; Lienemann, Michael; Linder, Markus B; Haruyama, Tetsuya

2013-12-01

The strategic surface immobilization of a protein can add new functionality to a solid substrate; however, protein activity, e.g., enzymatic activity, can be drastically decreased on immobilization onto a solid surface. The concept of a designed and optimized "molecular interface" is herein introduced in order to address this problem. In this study, molecular interface was designed and constructed with the aim of attaining high enzymatic activity of a solid-surface-immobilized a using the hydrophobin HFBI protein in conjunction with a fusion protein of HFBI attached to glucose oxidase (GOx). The ability of HFBI to form a self-organized membrane on a solid surface in addition to its adhesion properties makes it an ideal candidate for immobilization. The developed fusion protein was also able to form an organized membrane, and its structure and immobilized state on a solid surface were investigated using QCM-D measurements. This method of immobilization showed retention of high enzymatic activity and the ability to control the density of the immobilized enzyme. In this study, we demonstrated the importance of the design and construction of molecular interface for numerous purposes. This method of protein immobilization could be utilized for preparation of high throughput products requiring structurally ordered molecular interfaces, in addition to many other applications. Copyright © 2013 The Authors. Published by Elsevier B.V. All rights reserved.

The surface tension of aqueous solutions of some atmospheric water-soluble organic compounds

NASA Astrophysics Data System (ADS)

Tuckermann, Rudolf; Cammenga, Heiko K.

The surface tensions of aqueous solutions of levoglucosan, 3-hydroxybutanoic acid, 3-hydroxybenzoic acid, azelaic acid, pinonic acid, and humic acid have been measured. These compounds are suggested as model substances for the water-soluble organic compounds (WSOC) in atmospheric aerosols and droplets which may play an important role in the aerosol cycle because of their surface-active potentials. The reductions in surface tension induced by single and mixed WSOC in aqueous solution of pure water is remarkable. However, the results of this investigation cannot explain the strong reduction in surface tension in real cloud and fog water samples at concentrations of WSOC below 1 mg/mL.

Aqueous aerosol SOA formation: impact on aerosol physical properties.

PubMed

Woo, Joseph L; Kim, Derek D; Schwier, Allison N; Li, Ruizhi; McNeill, V Faye

2013-01-01

Organic chemistry in aerosol water has recently been recognized as a potentially important source of secondary organic aerosol (SOA) material. This SOA material may be surface-active, therefore potentially affecting aerosol heterogeneous activity, ice nucleation, and CCN activity. Aqueous aerosol chemistry has also been shown to be a potential source of light-absorbing products ("brown carbon"). We present results on the formation of secondary organic aerosol material in aerosol water and the associated changes in aerosol physical properties from GAMMA (Gas-Aerosol Model for Mechanism Analysis), a photochemical box model with coupled gas and detailed aqueous aerosol chemistry. The detailed aerosol composition output from GAMMA was coupled with two recently developed modules for predicting a) aerosol surface tension and b) the UV-Vis absorption spectrum of the aerosol, based on our previous laboratory observations. The simulation results suggest that the formation of oligomers and organic acids in bulk aerosol water is unlikely to perturb aerosol surface tension significantly. Isoprene-derived organosulfates are formed in high concentrations in acidic aerosols under low-NO(x) conditions, but more experimental data are needed before the potential impact of these species on aerosol surface tension may be evaluated. Adsorption of surfactants from the gas phase may further suppress aerosol surface tension. Light absorption by aqueous aerosol SOA material is driven by dark glyoxal chemistry and is highest under high-NO(x) conditions, at high relative humidity, in the early morning hours. The wavelength dependence of the predicted absorption spectra is comparable to field observations and the predicted mass absorption efficiencies suggest that aqueous aerosol chemistry can be a significant source of aerosol brown carbon under urban conditions.

Titan's Lakes in a Beaker

NASA Astrophysics Data System (ADS)

Hodyss, R. P.

2017-12-01

The surface of Titan presents a complex, varied surfaced, with mountains, plains, dunes, rivers, lakes and seas, composed of a layer of organics over a water ice bedrock. Over the past 10 years, our group at JPL has developed a variety of techniques to study the chemistry of Titan's organic surface under relevant temperature and pressure conditions (90-100 K, 1.5 bar). Dissolution, precipitation, and both covalent and non-covalent chemical processes are examined using Raman and infrared spectroscopy, mass spectrometry, optical microscopy, and synchrotron X-ray powder diffraction. Despite the low temperatures, our experiments are revealing that a rich and active organic chemistry is possible on Titan's surface. Laboratory experiments like these can provide crucial insights into the geological processes occurring Titan's surface, and help explain the wealth of observational data returned by the Cassini/Huygens mission. This type of data is also critical for the development of future missions to Titan.

Field-induced charge transport at the surface of pentacene single crystals: A method to study charge dynamics of two-dimensional electron systems in organic crystals

NASA Astrophysics Data System (ADS)

Takeya, J.; Goldmann, C.; Haas, S.; Pernstich, K. P.; Ketterer, B.; Batlogg, B.

2003-11-01

A method has been developed to inject mobile charges at the surface of organic molecular crystals, and the dc transport of field-induced holes has been measured at the surface of pentacene single crystals. To minimize damage to the soft and fragile surface, the crystals are attached to a prefabricated substrate which incorporates a gate dielectric (SiO2) and four probe pads. The surface mobility of the pentacene crystals ranges from 0.1 to 0.5 cm2/V s and is nearly temperature independent above ˜150 K, while it becomes thermally activated at lower temperatures when the induced charges become localized. Ruling out the influence of electric contacts and crystal grain boundaries, the results contribute to the microscopic understanding of trapping and detrapping mechanisms in organic molecular crystals.

Poly(3,4-ethylenedioxythiophene)-Poly(styrenesulfonate) Interlayer Insertion Enables Organic Quaternary Memory.

PubMed

Cheng, Xue-Feng; Hou, Xiang; Qian, Wen-Hu; He, Jing-Hui; Xu, Qing-Feng; Li, Hua; Li, Na-Jun; Chen, Dong-Yun; Lu, Jian-Mei

2017-08-23

Herein, for the first time, quaternary resistive memory based on an organic molecule is achieved via surface engineering. A layer of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) was inserted between the indium tin oxide (ITO) electrode and the organic layer (squaraine, SA-Bu) to form an ITO/PEDOT-PSS/SA-Bu/Al architecture. The modified resistive random-access memory (RRAM) devices achieve quaternary memory switching with the highest yield (∼41%) to date. Surface morphology, crystallinity, and mosaicity of the deposited organic grains are greatly improved after insertion of a PEDOT-PSS interlayer, which provides better contacts at the grain boundaries as well as the electrode/active layer interface. The PEDOT-PSS interlayer also reduces the hole injection barrier from the electrode to the active layer. Thus, the threshold voltage of each switching is greatly reduced, allowing for more quaternary switching in a certain voltage window. Our results provide a simple yet powerful strategy as an alternative to molecular design to achieve organic quaternary resistive memory.

Protein-scaffold Directed Nanoscale Assembly of T Cell Ligands: Artificial Antigen Presentation with Defined Valency, Density and Ratio.

PubMed

Smith, Mason R; Tolbert, Stephanie V; Wen, Fei

2018-05-07

Tuning antigen presentation to T cells is a critical step in investigating key aspects of T cell activation. However, existing technologies have limited ability to control the spatial and stoichiometric organization of T cell ligands on 3D surfaces. Here, we developed an artificial antigen presentation platform based on protein-scaffold directed assembly that allows fine control over the spatial and stoichiometric organization of T cell ligands on a 3D yeast-cell surface. Using this system, we observed that the T cell activation threshold on a 3D surface is independent of peptide-major histocompatibility complex (pMHC) valency, but instead determined by the overall pMHC surface density. When intercellular adhesion molecule 1 (ICAM-1) was co-assembled with pMHC, it enhanced antigen recognition sensitivity by 6-fold. Further, T cells responded with different magnitudes to varying ratios of pMHC and ICAM-1 and exhibited a maximum response at a ratio of 15% pMHC and 85% ICAM-1, introducing an additional parameter for tuning T cell activation. This protein-scaffold directed assembly technology is readily transferrable to acellular surfaces for translational research as well as large-scale T-cell manufacturing.

Preparation of a new adsorbent from activated carbon and carbon nanofiber (AC/CNF) for manufacturing organic-vacbpour respirator cartridge

PubMed Central

2013-01-01

In this study a composite of activated carbon and carbon nanofiber (AC/CNF) was prepared to improve the performance of activated carbon (AC) for adsorption of volatile organic compounds (VOCs) and its utilization for respirator cartridges. Activated carbon was impregnated with a nickel nitrate catalyst precursor and carbon nanofibers (CNF) were deposited directly on the AC surface using catalytic chemical vapor deposition. Deposited CNFs on catalyst particles in AC micropores, were activated by CO2 to recover the surface area and micropores. Surface and textural characterizations of the prepared composites were investigated using Brunauer, Emmett and Teller’s (BET) technique and electron microscopy respectively. Prepared composite adsorbent was tested for benzene, toluene and xylene (BTX) adsorption and then employed in an organic respirator cartridge in granular form. Adsorption studies were conducted by passing air samples through the adsorbents in a glass column at an adjustable flow rate. Finally, any adsorbed species not retained by the adsorbents in the column were trapped in a charcoal sorbent tube and analyzed by gas chromatography. CNFs with a very thin diameter of about 10-20 nm were formed uniformly on the AC/CNF. The breakthrough time for cartridges prepared with CO2 activated AC/CNF was 117 minutes which are significantly longer than for those cartridges prepared with walnut shell- based activated carbon with the same weight of adsorbents. This study showed that a granular form CO2 activated AC/CNF composite could be a very effective alternate adsorbent for respirator cartridges due to its larger adsorption capacities and lower weight. PMID:23369424

Shrink wrapping redox-active crystals of polyoxometalate open frameworks with organic polymers via crystal induced polymerisation.

PubMed

Takashima, Yohei; Miras, Haralampos N; Glatzel, Stefan; Cronin, Leroy

2016-06-14

We report examples of crystal surface modification of polyoxometalate open frameworks whereby the use of pyrrole or aniline as monomers leads to the formation of the corresponding polymers via an oxidative polymerization process initiated by the redox active POM scaffolds. Guest-exchange experiments demonstrate that the polymers can finely tune the guest exchange rate and their structural integrity is retained after the surface modifications. In addition, the formation of polyoxometalate-based self-fabricating tubes by the dissolution of Keggin-based network crystals were also modulated by the polymers, allowing a new type of hybrid inorganic polymer with an organic coating to be fabricated.

Occurrence of pesticides and contaminants of emerging concern in surface waters: Influence of surrounding land use and evaluation of sampling methods

USDA-ARS?s Scientific Manuscript database

Biologically active compounds originating from agricultural, residential, and industrial sources have been detected in surface waters, which have invoked concern of their potential ecological and human health effects. Automated and grab surface water samples, passive water samples - Polar Organic Co...

Elevated levels of diesel range organic compounds in groundwater near Marcellus gas operations are derived from surface activities.

PubMed

Drollette, Brian D; Hoelzer, Kathrin; Warner, Nathaniel R; Darrah, Thomas H; Karatum, Osman; O'Connor, Megan P; Nelson, Robert K; Fernandez, Loretta A; Reddy, Christopher M; Vengosh, Avner; Jackson, Robert B; Elsner, Martin; Plata, Desiree L

2015-10-27

Hundreds of organic chemicals are used during natural gas extraction via high-volume hydraulic fracturing (HVHF). However, it is unclear whether these chemicals, injected into deep shale horizons, reach shallow groundwater aquifers and affect local water quality, either from those deep HVHF injection sites or from the surface or shallow subsurface. Here, we report detectable levels of organic compounds in shallow groundwater samples from private residential wells overlying the Marcellus Shale in northeastern Pennsylvania. Analyses of purgeable and extractable organic compounds from 64 groundwater samples revealed trace levels of volatile organic compounds, well below the Environmental Protection Agency's maximum contaminant levels, and low levels of both gasoline range (0-8 ppb) and diesel range organic compounds (DRO; 0-157 ppb). A compound-specific analysis revealed the presence of bis(2-ethylhexyl) phthalate, which is a disclosed HVHF additive, that was notably absent in a representative geogenic water sample and field blanks. Pairing these analyses with (i) inorganic chemical fingerprinting of deep saline groundwater, (ii) characteristic noble gas isotopes, and (iii) spatial relationships between active shale gas extraction wells and wells with disclosed environmental health and safety violations, we differentiate between a chemical signature associated with naturally occurring saline groundwater and one associated with alternative anthropogenic routes from the surface (e.g., accidental spills or leaks). The data support a transport mechanism of DRO to groundwater via accidental release of fracturing fluid chemicals derived from the surface rather than subsurface flow of these fluids from the underlying shale formation.

Elevated levels of diesel range organic compounds in groundwater near Marcellus gas operations are derived from surface activities

PubMed Central

Drollette, Brian D.; Hoelzer, Kathrin; Warner, Nathaniel R.; Darrah, Thomas H.; Karatum, Osman; O’Connor, Megan P.; Nelson, Robert K.; Fernandez, Loretta A.; Reddy, Christopher M.; Vengosh, Avner; Jackson, Robert B.; Elsner, Martin; Plata, Desiree L.

2015-01-01

Hundreds of organic chemicals are used during natural gas extraction via high-volume hydraulic fracturing (HVHF). However, it is unclear whether these chemicals, injected into deep shale horizons, reach shallow groundwater aquifers and affect local water quality, either from those deep HVHF injection sites or from the surface or shallow subsurface. Here, we report detectable levels of organic compounds in shallow groundwater samples from private residential wells overlying the Marcellus Shale in northeastern Pennsylvania. Analyses of purgeable and extractable organic compounds from 64 groundwater samples revealed trace levels of volatile organic compounds, well below the Environmental Protection Agency’s maximum contaminant levels, and low levels of both gasoline range (0–8 ppb) and diesel range organic compounds (DRO; 0–157 ppb). A compound-specific analysis revealed the presence of bis(2-ethylhexyl) phthalate, which is a disclosed HVHF additive, that was notably absent in a representative geogenic water sample and field blanks. Pairing these analyses with (i) inorganic chemical fingerprinting of deep saline groundwater, (ii) characteristic noble gas isotopes, and (iii) spatial relationships between active shale gas extraction wells and wells with disclosed environmental health and safety violations, we differentiate between a chemical signature associated with naturally occurring saline groundwater and one associated with alternative anthropogenic routes from the surface (e.g., accidental spills or leaks). The data support a transport mechanism of DRO to groundwater via accidental release of fracturing fluid chemicals derived from the surface rather than subsurface flow of these fluids from the underlying shale formation. PMID:26460018

Removal of bromide and iodide anions from drinking water by silver-activated carbon aerogels.

PubMed

Sánchez-Polo, M; Rivera-Utrilla, J; Salhi, E; von Gunten, U

2006-08-01

The aim of this study is to analyze the use of Ag-doped activated carbon aerogels for bromide and iodide removal from drinking water and to study how the activation of Ag-doped aerogels affects their behavior. It has been observed that the carbonization treatment and activation process of Ag-doped aerogels increased the surface area value ( [Formula: see text] ), whereas the volume of meso-(V(2)) and macropores (V(3)) decreased slightly. Chemical characterization of the materials revealed that carbonization and especially activation process considerably increased the surface basicity of the sample. Original sample (A) presented acidic surface properties (pH(PZC)=4.5) with 21% surface oxygen, whereas the sample that underwent activation showed mainly basic surface chemical properties (pH(PZC)=9.5) with only 6% of surface oxygen. Carbonization and especially, activation process considerable increased the adsorption capacity of bromide and iodide ions. This would mainly be produced by (i) an increase in the microporosity of the sample, which increases Ag-adsorption sites available to halide anions, and (ii) a rise of the basicity of the sample, which produces an increase in attractive electrostatic interactions between the aerogel surface, positively charged at the working pH (pH(solution)

Lanthanum cobaltite perovskite supported on zirconia as an efficient heterogeneous catalyst for activating Oxone in water.

PubMed

Lin, Kun-Yi Andrew; Chen, Yu-Chien; Lin, Tien-Yu; Yang, Hongta

2017-07-01

Zirconia-supported LaCoO 3 perovskite (LaCoO 3 /ZrO 2 (LCZ)) is prepared and adopted for the first time as a heterogeneous catalyst for activating Oxone to degrade organic pollutants. The resulting LCZ exhibits a significantly higher surface area (i.e., 10 times) than bulk LaCoO 3 powder as nanoscale LaCoO 3 particles were easily afforded on the surface of ZrO 2 support. As Rhodamine B (RB) decolorization is selected as a model test to evaluate catalytic activity for activating Oxone, LCZ showed a much higher catalytic activity to activate Oxone than LaCoO 3 even though LCZ contained only 12.5wt% of LaCoO 3 . LCZ-activated Oxone also remained effective for RB decolorization even in the presence of salts and other organic contaminant. The mechanism of RB decolorization by LCZ-activated Oxone was revealed and involved sulfate radical and other reactive oxygen species. The mechanism of Oxone activation by LCZ could be owing to both La 3+ and Co 3+ of LCZ. LCZ was recycled to activate Oxone for RB decolorization over multiple times without loss of catalytic activity. These results demonstrate that LCZ is a promising LaCoO 3 -based nanocomposite as a heterogeneous catalyst for activating Oxone to degrade organic pollutants. Copyright © 2017 Elsevier Inc. All rights reserved.

Vertical Stratification of Peat Pore Water Dissolved Organic Matter Composition in a Peat Bog in Northern Minnesota

NASA Astrophysics Data System (ADS)

Tfaily, Malak M.; Wilson, Rachel M.; Cooper, William T.; Kostka, Joel E.; Hanson, Paul; Chanton, Jeffrey P.

2018-02-01

We characterized dissolved organic matter (DOM) composition throughout the peat column at the Marcell S1 forested bog in northern Minnesota and tested the hypothesis that redox oscillations associated with cycles of wetting and drying at the surface of the fluctuating water table correlate with increased carbon, sulfur, and nitrogen turn over. We found significant vertical stratification of DOM molecular composition and excitation-emission matrix parallel factor analysis components within the peat column. In particular, the intermediate depth zone ( 50 cm) was identified as a zone where maximum decomposition and turnover is taking place. Surface DOM was dominated by inputs from surface vegetation. The intermediate depth zone was an area of high organic matter reactivity and increased microbial activity with diagenetic formation of many unique compounds, among them polycyclic aromatic compounds that contain both nitrogen and sulfur heteroatoms. These compounds have been previously observed in coal-derived compounds and were assumed to be responsible for coal's biological activity. Biological processes triggered by redox oscillations taking place at the intermediate depth zone of the peat profile at the S1 bog are assumed to be responsible for the formation of these heteroatomic PACs in this system. Alternatively, these compounds could stem from black carbon and nitrogen derived from fires that have occurred at the site in the past. Surface and deep DOM exhibited more similar characteristics, compared to the intermediate depth zone, with the deep layer exhibiting greater input of microbially degraded organic matter than the surface suggesting that the entire peat profile consists of similar parent material at different degrees of decomposition and that lateral and vertical advection of pore water from the surface to the deeper horizons is responsible for such similarities. Our findings suggest that molecular composition of DOM in peatland pore water is dynamic and is a function of ecosystem activity, water table, redox oscillation, and pore water advection.

Vertical Stratification of Peat Pore Water Dissolved Organic Matter Composition in a Peat Bog in Northern Minnesota: Pore Water DOM composition in a peat bog

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tfaily, Malak M.; Wilson, Rachel M.; Cooper, William T.

We characterized dissolved organic matter (DOM) composition throughout the peat column at the Marcell S1 forested bog in northern Minnesota and tested the hypothesis that redox oscillations associated with cycles of wetting and drying at the surface of the fluctuating water table correlate with increased carbon, sulfur and nitrogen turn over. We found significant vertical stratification of DOM molecular composition and EEM-PARAFAC components within the peat column. In particular the intermediate depth zone (~ 50 cm) was identified as a zone where maximum decomposition and turnover is taking place. Surface DOM was dominated by inputs from surface vegetation. The intermediate-depthmore » zone was an area of high organic matter reactivity and increased microbial activity with diagenetic formation of many unique compounds, among them polycyclic aromatic compounds (PAC) that contain both nitrogen and sulfur heteroatoms. These compounds have been previously observed in coal-derived compounds and were assumed to be responsible for coal's biological activity. Biological processes triggered by redox oscillations taking place at the intermediate depth zone of the peat profile at the S1 bog are assumed to be responsible for the formation of these heteroatomic PACs in this system. Alternatively these compounds could stem from black carbon and nitrogen derived from fires that have occurred at the site in the past. Surface and deep DOM exhibited more similar characteristics, compared to the intermediate-depth zone, with the deep layer exhibiting greater input of microbially degraded organic matter than the surface suggesting that the entire peat profile consists of similar parent material at different degrees of decomposition and that lateral and vertical advection of pore water from the surface to the deeper horizons is responsible for such similarities. Our findings suggest that molecular composition of DOM in peatland pore water is dynamic and is a function of ecosystem activity, water table and redox oscillation and porewater advection.« less

ELECTROPHYSIOLOGY OF ELECTRIC ORGAN IN GYMNOTUS CARAPO

PubMed Central

Bennett, Michael V. L.; Grundfest, Harry

1959-01-01

The electric organ of G. carapo is formed by linearly arrayed electroplaques which lie in four tubes on each side of the fish. In one tube the electroplaques are innervated on their rostral surfaces, in the others on the caudal. Both surfaces of each electroplaque produce spikes, and either can be excited alone by a suitably oriented externally applied stimulating current. The innervated surface, however, has a lower threshold, and in the normal organ activity, which is a continuous discharge at 35 to 60/sec., it is always fired first by the large neurally evoked postsynaptic potential. The spike of the innervated face then fires the opposite face. The potential recorded external to the innervated face is initially negative and becomes positive when the other face fires. The potential outside the other face is inverted. The p.s.p.'s are electrically inexcitable, have short duration, and are augmented by hyperpolarization. A single electroplaque is innervated by several nerve fibers, which produce summative p.s.p.'s. Homosynaptic facilitation of p.s.p.'s is common. The synapses are cholinoceptive. The organ discharge begins with synchronized activity in the rostrally innervated electroplaques. After a brief interval, the electroplaques in the other three tubes fire. The organ discharge therefore is triphasic, resulting from the summation of the two diphasic components that are oppositely directed and asynchronous. Observations on the sensory role of the organ are included. PMID:13654750

Evaluation of biocidal efficacy of copper alloy coatings in comparison with solid metal surfaces: generation of organic copper phosphate nanoflowers.

PubMed

Gutierrez, H; Portman, T; Pershin, V; Ringuette, M

2013-03-01

To analyse the biocidal efficacy of thermal sprayed copper surfaces. Copper alloy sheet metals containing >60% copper have been shown to exhibit potent biocidal activity. Surface biocidal activity was assessed by epifluorescence microscopy. After 2-h exposure at 20 °C in phosphate-buffered saline (PBS), contact killing of Gram-negative Escherichia coli and Gram-positive Staphylococcus epidermidis by brass sheet metal and phosphor bronze was 3-4-times higher than that by stainless steel. SEM observations revealed that the surface membranes of both bacterial strains were slightly more irregular when exposed to brass sheet metal than stainless steel. However, when exposed to phosphor bronze coating, E. coli were 3-4 times larger with irregular membrane morphology. In addition, the majority of the cells were associated with spherical carbon-copper-phosphate crystalline nanostructures characteristic of nanoflowers. The membranes of many of the S. epidermidis exhibited blebbing, and a small subset was also associated with nanoflowers. Our data indicate that increasing the surface roughness of copper alloys had a pronounced impact on the membrane integrity of Gram-positive and, to a lesser degree, Gram-negative bacteria. In the presence of PBS, carbon-copper-phosphate-containing nanoflowers were formed, likely nucleated by components derived from killed bacteria. The intimate association of the bacteria with the nanoflowers and phosphor bronze coating likely contributed to their nonreversible adhesion. Thermal spraying of copper alloys provides a strategy for the rapid coating of three-dimensional organic and inorganic surfaces with biocidal copper alloys. Our study demonstrates that the macroscale surface roughness generated by the thermal spray process enhances the biocidal activity of copper alloys compared with the nanoscale surface roughness of copper sheet metals. Moreover, the coating surface topography provides conditions for the rapid formation of organic copper phosphate nanocrystals/nanoflowers. © 2012 The Society for Applied Microbiology.

Importance of lateral flux and its percolation depth on organic carbon export in Arctic tundra soil: Implications from a soil leaching experiment

NASA Astrophysics Data System (ADS)

Zhang, Xiaowen; Hutchings, Jack A.; Bianchi, Thomas S.; Liu, Yina; Arellano, Ana R.; Schuur, Edward A. G.

2017-04-01

Temperature rise in the Arctic is causing deepening of active layers and resulting in the mobilization of deep permafrost dissolved organic matter (DOM). However, the mechanisms of DOM mobilization from Arctic soils, especially upper soil horizons which are drained most frequently through a year, are poorly understood. Here we conducted a short-term leaching experiment on surface and deep organic active layer soils, from the Yukon River basin, to examine the effects of DOM transport on bulk and molecular characteristics. Our data showed a net release of DOM from surface soils equal to an average of 5% of soil carbon. Conversely, deep soils percolated with surface leachates retained up to 27% of bulk DOM while releasing fluorescent components (up to 107%), indicating selective release of aromatic components (e.g., lignin and tannin), while retaining nonchromophoric components, as supported by spectrofluorometric and ultrahigh-resolution mass spectroscopic techniques. Our findings highlight the importance of the lateral flux of DOM on ecosystem carbon balance as well as processing of DOM transport through organic active layer soils en route to rivers and streams. This work also suggests the potential role of leachate export as an important mechanism of C losses from Arctic soils, in comparison with the more traditional pathway from soil to atmosphere in a warming Arctic.

Effects of activated carbon surface chemistry and pore structure on the adsorption of trace organic contaminants from aqueous solution

NASA Astrophysics Data System (ADS)

Li, Lei

The objectives were (1) to identify activated pore structure and surface chemistry characteristics that assure the effective removal of trace organic contaminants from aqueous-solution, and (2) to develop a procedure to predict the adsorption capacity of activated carbons from fundamental adsorbent and adsorbate properties. A matrix of activated carbon fibers (ACFs) (with three activation levels and four surface chemistry levels) and three commercially available granular activated carbons (GACs) served as the adsorbents. BET surface area, pore size distribution, elemental composition, point of zero charge and infrared spectroscopy data were obtained to characterize the adsorbents. The adsorption of relative hydrophilic methyl tertiary-butyl ether (MTBE) and relative hydrophobic trichloroethene (TCE) were conducted in both ultrapure water and Sacramento-San Joaquin Delta water. The results showed that an effective adsorbent for the removal of micropollutants from water requires (1) a large volume of micropores with widths that are about 1.5 times larger than the kinetic diameter of the target adsorbate, (2) a micropore size distribution that extends to widths that are approximately twice the kinetic diameter of the target adsorbate to prevent pore blockage by NOM, and (3) a hydrophobic pore surface chemistry with the sum of oxygen and nitrogen contents less than 2 to 3 mmol/g. A procedure based on the Polanyi Potential Theory (PPT) was developed to predict the adsorption capacities of activated carbons from fundamental adsorbent and adsorbate properties. A correlation between the coalescing factor for water adsorption and adsorbent oxygen content was developed. Based on this correlation, the PPT yielded reasonable estimates of aqueous phase adsorption capacities for both relatively polar and non-polar adsorbates on both relatively hydrophobic and hydrophilic activated carbons. With the developed procedure, the adsorption capacities of organic compounds that are partially miscible in water can be predicted from (1) N2 and CO2 adsorption isotherms of a given adsorbent, (2) the adsorbent oxygen content, and (3) the molar volume and parachor of the target adsorbate.

An All-Organic Composite System for Resistive Change Memory via the Self-Assembly of Plastic-Crystalline Molecules.

PubMed

Cha, An-Na; Lee, Sang-A; Bae, Sukang; Lee, Sang Hyun; Lee, Dong Su; Wang, Gunuk; Kim, Tae-Wook

2017-01-25

An all-organic composite system was introduced as an active component for organic resistive memory applications. The active layer was prepared by mixing a highly polar plastic-crystalline organic molecule (succinonitrile, SN) into an insulating polymer (poly(methyl methacrylate), PMMA). As increasing concentrations of SN from 0 to 3.0 wt % were added to solutions of different concentrations of PMMA, we observed distinguishable microscopic surface structures on blended films of SN and PMMA at certain concentrations after the spin-casting process. The structures were organic dormant volcanos composed of micron-scale PMMA craters and disk type SN lava. Atomic force microscopy (AFM), cross-sectional transmission electron microscopy (TEM), scanning electron microscopy (SEM), and energy dispersive X-ray spectrometer (EDX) analysis showed that these structures were located in the middle of the film. Self-assembly of the plastic-crystalline molecules resulted in the phase separation of the SN:PMMA mixture during solvent evaporation. The organic craters remained at the surface after the spin-casting process, indicative of the formation of an all-organic composite film. Because one organic crater contains one SN disk, our system has a coplanar monolayer disk composite system, indicative of the simplest composite type of organic memory system. Current-voltage (I-V) characteristics of the composite films with organic craters revealed that our all-organic composite system showed unipolar type resistive switching behavior. From logarithmic I-V characteristics, we found that the current flow was governed by space charge limited current (SCLC). From these results, we believe that a plastic-crystalline molecule-polymer composite system is one of the most reliable ways to develop organic composite systems as potential candidates for the active components of organic resistive memory applications.

Photodegradation processes in arid ecosystems: controlling factors and potential application in land restoration

NASA Astrophysics Data System (ADS)

Muñoz-Rojas, Miriam; Luna-Ramos, Lourdes; Oyonarte, Cecilio; Sole Benet, Albert

2017-04-01

Water availability plays a fundamental part in controlling biotic processes in arid ecosystems. However, recent evidence suggests that other decisive drivers take part in these processes. Despite low annual rainfall and microbial activity, unexplained high rates of litter decomposition, net nitrogen mineralization, soil enzymatic activity and carbon turnover have been observed in arid ecosystems. These observations have been partly explained by photodegradation, a process that consists of the breakdown of organic matter via solar radiation (UV) and that can increase decomposition rates and lead to changes in the balance of carbon and nutrients between plants, soil and atmosphere. A complete understanding of these mechanisms and its drivers in arid ecosystems remains a critical challenge for the scientific community at the global level. In this research, we conducted a multi-site field experiment to test the effects of photodegradation on decomposition of organic amendments used in ecosystem restoration. The study was carried out during 12 months in two study areas: the Pilbara region in Western Australia (Southern Hemisphere) and the Cabo de Gata Nijar Natural Park, South Spain (Northern Hemisphere). In both sites, four treatments were applied in replicated plots (1x1 m, n=4) that included a control (C) with no soil amendment; organic amendment covering the soil surface (AS); organic amendment incorporated into the soil (AI); and a combination of both techniques, both covering the surface and incorporated into the soil (AS-AI). Different organic amendments (native mulch versus compost) and soil substrates were used at each site according to local practices, but in both sites these were applied to increase soil organic matter up to 2%. At the two locations, a radiometer and a logger with a soil temperature and soil moisture probe were installed to monitor UV radiation and soil conditions for the duration of the trial. Soil microbial activity, soil CO2 efflux, and the organic matter fractions (including total OC and hydro-soluble C) were measured repeatedly during the experiment. At the end of the experiment, levels of the soluble fraction of C, soil CO2 efflux and soil microbial activity were significantly (p< 0.05) higher in those plots amended in the surface in both sites. These increases in the surface reflect a fast C decomposing process that can be directly related to UV radiation, evidencing the critical role of photodegradation on the decomposition of the organic matter. These processes can be critical at global scales as they can contribute to forcing biogechemical cycles; however, responses will vary depending on the type of the substrate and organic amendment.

Preparation and evaluation of coal-derived activated carbons for removal of mercury vapor from simulated coal combustion flue fases

USGS Publications Warehouse

Hsi, H.-C.; Chen, S.; Rostam-Abadi, M.; Rood, M.J.; Richardson, C.F.; Carey, T.R.; Chang, R.

1998-01-01

Coal-derived activated carbons (CDACs) were tested for their suitability in removing trace amounts of vapor-phase mercury from simulated flue gases generated by coal combustion. CDACs were prepared in bench-scale and pilot-scale fluidized-bed reactors with a three-step process, including coal preoxidation, carbonization, and then steam activation. CDACs from high-organicsulfur Illinois coals had a greater equilibrium Hg0 adsorption capacity than activated carbons prepared from a low-organic-sulfur Illinois coal. When a low-organic-sulfur CDAC was impregnated with elemental sulfur at 600 ??C, its equilibrium Hg0 adsorption capacity was comparable to the adsorption capacity of the activated carbon prepared from the high-organicsulfur coal. X-ray diffraction and sulfur K-edge X-ray absorption near-edge structure examinations showed that the sulfur in the CDACs was mainly in organic forms. These results suggested that a portion of the inherent organic sulfur in the starting coal, which remained in the CDACs, played an important role in adsorption of Hg0. Besides organic sulfur, the BET surface area and micropore area of the CDACs also influenced Hg0 adsorption capacity. The HgCl2 adsorption capacity was not as dependent on the surface area and concentration of sulfur in the CDACs as was adsorption of Hg0. The properties and mercury adsorption capacities of the CDACs were compared with those obtained for commercial Darco FGD carbon.

Spatial distribution and vertical migration of (137)Cs in soils of Belgrade (Serbia) 25 years after the Chernobyl accident.

PubMed

Petrović, Jelena; Ćujić, Mirjana; Đorđević, Milan; Dragović, Ranko; Gajić, Boško; Miljanić, Šćepan; Dragović, Snežana

2013-06-01

In this study, the specific activity of (137)Cs was determined by gamma-ray spectrometry in 72 surface soil samples and 11 soil profiles collected from the territory of Belgrade 25 years after the Chernobyl accident. Based on the data obtained the external effective gamma dose rates due to (137)Cs were assessed and geographically mapped. The influence of pedogenic factors (pH, specific electrical conductivity, cation exchange capacity, organic matter content, soil particle size and carbonate content) on the spatial and vertical distribution of (137)Cs in soil was estimated through Pearson correlations. The specific activity of (137)Cs in surface soil samples ranged from 1.00 to 180 Bq kg(-1), with a mean value of 29.9 Bq kg(-1), while in soil profiles they ranged from 0.90 to 58.0 Bq kg(-1), with a mean value of 15.3 Bq kg(-1). The mean external effective gamma dose at 1 m above the ground due to (137)Cs in the soil was calculated to be 1.96 nSv h(-1). Geographic mapping of the external effective gamma dose rates originating from (137)Cs revealed much higher dose rates in southern parts of Belgrade city and around the confluence of the Sava and Danube. Negative Pearson correlation coefficients were found between pH, cation exchange capacity and (137)Cs specific activity in surface soil. There were positive correlations between organic matter and (137)Cs specific activity in surface soil; and between specific electrical conductivity, organic matter, silt content and (137)Cs specific activity in soil profiles.

A novel organic solvent-based coupling method for the preparation of covalently immobilized proteins on gold.

PubMed Central

Parker, M. C.; Patel, N.; Davies, M. C.; Roberts, C. J.; Tendler, S. J.; Williams, P. M.

1996-01-01

A novel organic solvent-based coupling method has been developed for the covalent immobilization of biological material to gold surfaces. The method employs the polar organic solvent anhydrous 2,2,2-trifluoroethanol as the reaction medium and involves dissolution of the protein (catalase) in the solvent allowing protein coupling to proceed under basic conditions in a dry organic environment. The advantage of this method is that protein attachment is favored over hydrolysis of the coupling reagent. We have shown qualitatively and quantitatively that following attachment to the gold surface a significant proportion of the enzyme catalase remains catalytically active (at least 20-31%). PMID:8931151

Hydroisomerization of n-Hexane Using Acidified Metal-Organic Framework and Platinum Nanoparticles.

PubMed

Sabyrov, Kairat; Jiang, Juncong; Yaghi, Omar M; Somorjai, Gabor A

2017-09-13

Exceptionally high surface area and ordered nanopores of a metal-organic framework (MOF) are exploited to encapsulate and homogeneously disperse a considerable amount of phosphotungstic acid (PTA). When combined with platinum nanoparticles positioned on the external surface of the MOF, the construct shows a high catalytic activity for hydroisomerization of n-hexane, a reaction requiring hydrogenation/dehydrogenation and moderate to strong Brønsted acid sites. Characterization of the catalytic activity and acidic sites as a function of PTA loading demonstrates that both the concentration and strength of acidic sites are highest for the catalyst with the largest amount of PTA. The MOF construct containing 60% PTA by weight produces isoalkanes with 100% selectivity and 9-fold increased mass activity as compared to a more traditional aluminosilicate catalyst, further demonstrating the capacity of the MOF to contain a high concentration of active sites necessary for the isomerization reaction.

Electron Spin Resonance (ESR) detection of active oxygen species and organic phases in Martian soils

NASA Technical Reports Server (NTRS)

Tsay, Fun-Dow; Kim, Soon Sam; Liang, Ranty H.

1989-01-01

The presence of active oxygen species (O(-), O2(-), O3(-)) and other strong oxidants (Fe2O3 and Fe3O4) was invoked in interpretations of the Viking biological experiments and a model was also suggested for Martian surface chemistry. The non-biological interpretations of the biological results gain futher support as no organic compounds were detected in the Viking pyrolysis-gas chromatography mass spectrometer (GCSM) experiments at concentrations as low as 10 ppb. Electron spin resonance (ESR) measures the absorption of microwaves by a paramagnetic and/or ferromagnetic center in the presence of an external field. In many instances, ESR has the advantage of detailed submicroscopic identification of the transient species and/or unstable reaction intermediates in their environments. Since the higly active oxygen species (O(-), O2(-), O3(-), and R-O-O(-)) are all paramagnetic in nature, they can be readily detected in native form by the ESR method. Active oxygen species likely to occur in the Martian surface samples were detected by ESR in UV-irradiated samples containing MgO. A miniaturized ESR spectrometer system can be developed for the Mars Rover Sample Return Mission. The instrument can perform the following in situ Martian samples analyses: detection of active oxygen species; characterization of Martian surface chemistry and photooxidation processes; and searching for organic compounds in the form of free radicals preserved in subsoils, and detection of microfossils with Martian carbonate sediments.

Potentiodynamic study of Al-Mg alloy with superhydrophobic coating in photobiologically active/not active natural seawater.

PubMed

Benedetti, Alessandro; Cirisano, Francesca; Delucchi, Marina; Faimali, Marco; Ferrari, Michele

2016-01-01

Superhydrophobic coating technology is regarded as an attractive possibility for the protection of materials in a sea environment. DC techniques are a useful tool to characterize metals' behavior in seawater in the presence/absence of coatings and/or corrosion inhibitors. In this work, investigations concerning Al-5%Mg alloy with and without a sprayed superhydrophobic coating were carried out with potentiodynamic scans in photobiologically active and not active seawater (3 weeks of immersion). In not photobiologically active seawater, the presence of the superhydrophobic coating did not prevent pitting corrosion. With time, the coating underwent local exfoliations, but intact areas still preserved superhydrophobicity. In photobiologically active seawater, on samples without the superhydrophobic coating (controls) pitting was inhibited, probably due to the adsorption of organic compounds produced by the photobiological activity. After 3 weeks of immersion, the surface of the coating became hydrophilic due to diatom coverage. As suggested by intermediate observations, the surface below the diatom layer is suspected of having lost its superhydrophobicity due to early stages of biofouling processes (organic molecule adsorption and diatom attachment/gliding). Polarization curves also revealed that the metal below the coating underwent corrosion inhibiting phenomena as observed in controls, likely due to the permeation of organic molecules through the coating. Hence, the initial biofouling stages (days) occurring in photobiologically active seawater can both accelerate the loss of superhydrophobicity of coatings and promote corrosion inhibition on the underlying metal. Finally, time durability of superhydrophobic surfaces in real seawater still remains the main challenge for applications, where the early stages of immersion are demonstrated to be of crucial importance. Copyright © 2015 Elsevier B.V. All rights reserved.

Survival of Burkholderia pseudomallei on Environmental Surfaces.

PubMed

Shams, Alicia M; Rose, Laura J; Hodges, Lisa; Arduino, Matthew J

2007-12-01

The survival of the biothreat agent Burkholderia pseudomallei on the surfaces of four materials was measured by culture and esterase activity analyses. The culture results demonstrated that this organism persisted for <24 h to <7 days depending on the material, bacterial isolate, and suspension medium. The persistence determined by analysis of esterase activity, as measured with a ScanRDI solid-phase cytometer, was always longer than the persistence determined by culture analysis.

New Electrocatalysts for Direct Oxidation of Organic Fuels

DTIC Science & Technology

2009-06-12

ambient temperature . [28,29] While 13C-NMR provides information on the nature of the adsorbate and the electronic environment at the active surface of...our study to unsupported electrocatalysts that are of greater interest for direct methanol and direct ethanol fuel cells. We have developed a new in...coverage, and type of surface site on the relative adsorption rate and electrooxidative activity of the electrocatalyst. Figure 2 shows sample

Spatial and Temporal Scales of Surface Water-Groundwater Interactions

NASA Astrophysics Data System (ADS)

Boano, F.

2016-12-01

The interfaces between surface water and groundwater (i.e., river and lake sediments) represent hotspots for nutrient transformation in watersheds. This intense biochemical activity stems from the peculiar physicochemical properties of these interface areas. Here, the exchange of water and nutrients between surface and subsurface environments creates an ecotone region that can support the presence of different microbial species responsible for nutrient transformation. Previous studies have elucidated that water exchange between rivers and aquifers is organized in a complex system of nested flow cells. Each cell entails a range of residence timescales spanning multiple order of magnitudes, providing opportunities for different biochemical reactions to occur. Physically-bases models represent useful tools to deal with the wide range of spatial and temporal scales that characterize surface-subsurface water exchange. This contribution will present insights about how hydrodynamic processes control scale organization for surface water - groundwater interactions. The specific focus will be the influence of exchange processes on microbial activity and nutrient transformation, discussing how groundwater flow at watershed scale controls flow conditions and hence constrain microbial reactions at much smaller scales.

Dissolved organic matter in sea spray: a transfer study from marine surface water to aerosols

NASA Astrophysics Data System (ADS)

Schmitt-Kopplin, P.; Liger-Belair, G.; Koch, B. P.; Flerus, R.; Kattner, G.; Harir, M.; Kanawati, B.; Lucio, M.; Tziotis, D.; Hertkorn, N.; Gebefügi, I.

2012-04-01

Atmospheric aerosols impose direct and indirect effects on the climate system, for example, by absorption of radiation in relation to cloud droplets size, on chemical and organic composition and cloud dynamics. The first step in the formation of Organic primary aerosols, i.e. the transfer of dissolved organic matter from the marine surface into the atmosphere, was studied. We present a molecular level description of this phenomenon using the high resolution analytical tools of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and nuclear magnetic resonance spectroscopy (NMR). Our experiments confirm the chemoselective transfer of natural organic molecules, especially of aliphatic compounds from the surface water into the atmosphere via bubble bursting processes. Transfer from marine surface water to the atmosphere involves a chemical gradient governed by the physicochemical properties of the involved molecules when comparing elemental compositions and differentiating CHO, CHNO, CHOS and CHNOS bearing compounds. Typical chemical fingerprints of compounds enriched in the aerosol phase were CHO and CHOS molecular series, smaller molecules of higher aliphaticity and lower oxygen content, and typical surfactants. A non-targeted metabolomics analysis demonstrated that many of these molecules corresponded to homologous series of oxo-, hydroxy-, methoxy-, branched fatty acids and mono-, di- and tricarboxylic acids as well as monoterpenes and sugars. These surface active biomolecules were preferentially transferred from surface water into the atmosphere via bubble bursting processes to form a significant fraction of primary organic aerosols. This way of sea spray production leaves a selective biological signature of the surface water in the corresponding aerosol that may be transported into higher altitudes up to the lower atmosphere, thus contributing to the formation of secondary organic aerosol on a global scale or transported laterally with possible deposition in the context of global biogeocycling.

Golgi sorting regulates organization and activity of GPI-proteins at apical membranes

PubMed Central

Tivodar, Simona; Formiggini, Fabio; Ossato, Giulia; Gratton, Enrico; Tramier, Marc; Coppey-Moisan, Maïté; Zurzolo, Chiara

2014-01-01

Here, we combined classical biochemistry with novel biophysical approaches to study with high spatial and temporal resolution the organization of GPI-anchored proteins (GPI-APs) at the plasma membrane of polarized epithelial cells. We show that in polarized MDCK cells, following sorting in the Golgi, each GPI-AP reaches the apical surface in homo-clusters. Golgi-derived homo-clusters are required for their subsequent plasma membrane organization into cholesterol-dependent hetero-clusters. By contrast, in non-polarized MDCK cells GPI-APs are delivered to the surface as monomers in an unpolarized manner and are not able to form hetero-clusters. We further demonstrate that this GPI-AP organization is regulated by the content of cholesterol in the Golgi apparatus and is required to maintain the functional state of the protein at the apical membrane. Thus, different from fibroblasts, in polarized epithelial cells a selective cholesterol-dependent sorting mechanism in the Golgi regulates both the organization and the function of GPI-APs at the apical surface. PMID:24681536

Isotropic actomyosin dynamics promote organization of the apical cell cortex in epithelial cells.

PubMed

Klingner, Christoph; Cherian, Anoop V; Fels, Johannes; Diesinger, Philipp M; Aufschnaiter, Roland; Maghelli, Nicola; Keil, Thomas; Beck, Gisela; Tolić-Nørrelykke, Iva M; Bathe, Mark; Wedlich-Soldner, Roland

2014-10-13

Although cortical actin plays an important role in cellular mechanics and morphogenesis, there is surprisingly little information on cortex organization at the apical surface of cells. In this paper, we characterize organization and dynamics of microvilli (MV) and a previously unappreciated actomyosin network at the apical surface of Madin-Darby canine kidney cells. In contrast to short and static MV in confluent cells, the apical surfaces of nonconfluent epithelial cells (ECs) form highly dynamic protrusions, which are often oriented along the plane of the membrane. These dynamic MV exhibit complex and spatially correlated reorganization, which is dependent on myosin II activity. Surprisingly, myosin II is organized into an extensive network of filaments spanning the entire apical membrane in nonconfluent ECs. Dynamic MV, myosin filaments, and their associated actin filaments form an interconnected, prestressed network. Interestingly, this network regulates lateral mobility of apical membrane probes such as integrins or epidermal growth factor receptors, suggesting that coordinated actomyosin dynamics contributes to apical cell membrane organization. © 2014 Klingner et al.

Denitrification potential in relation to lithology in five headwater riparian zones.

PubMed

Hill, Alan R; Vidon, Philippe G F; Langat, Jackson

2004-01-01

The influence of riparian zone lithology on nitrate dynamics is poorly understood. We investigated vertical variations in potential denitrification activity in relation to the lithology and stratigraphy of five headwater riparian zones on glacial till and outwash landscapes in southern Ontario, Canada. Conductive coarse sand and gravel layers occurred in four of the five riparian areas. These layers were thin and did not extend to the field-riparian perimeter in some riparian zones, which limited their role as conduits for ground water flow. We found widespread organic-rich layers at depths ranging from 40 to 300 cm that resulted from natural floodplain processes and the burial of surface soils by rapid valley-bottom sedimentation after European settlement. The organic matter content of these layers varied considerably from 2 to 5% (relic channel deposit) to 5 to 21% (buried soils) and 30 to 62% (buried peat). Denitrification potential (DNP) was measured by the acetylene block method in sediment slurries amended with nitrate. The highest DNP rates were usually found in the top 0- to 15-cm surface soil layer in all riparian zones. However, a steep decline in DNP with depth was often absent and high DNP activity occurred in the deep organic-rich layers. Water table variations in 2000-2002 indicated that ground water only interacted frequently with riparian surface soils between late March and May, whereas subsurface organic layers that sustain considerable DNP were below the water table for most of the year. These results suggest that riparian zones with organic deposits at depth may effectively remove nitrate from ground water even when the water table does not interact with organic-rich surface soil horizons.

Surfactant-associated bacteria in the near-surface layer of the ocean.

PubMed

Kurata, Naoko; Vella, Kate; Hamilton, Bryan; Shivji, Mahmood; Soloviev, Alexander; Matt, Silvia; Tartar, Aurélien; Perrie, William

2016-01-12

Certain marine bacteria found in the near-surface layer of the ocean are expected to play important roles in the production and decay of surface active materials; however, the details of these processes are still unclear. Here we provide evidence supporting connection between the presence of surfactant-associated bacteria in the near-surface layer of the ocean, slicks on the sea surface, and a distinctive feature in the synthetic aperture radar (SAR) imagery of the sea surface. From DNA analyses of the in situ samples using pyrosequencing technology, we found the highest abundance of surfactant-associated bacterial taxa in the near-surface layer below the slick. Our study suggests that production of surfactants by marine bacteria takes place in the organic-rich areas of the water column. Produced surfactants can then be transported to the sea surface and form slicks when certain physical conditions are met. This finding has potential applications in monitoring organic materials in the water column using remote sensing techniques. Identifying a connection between marine bacteria and production of natural surfactants may provide a better understanding of the global picture of biophysical processes at the boundary between the ocean and atmosphere, air-sea exchange of greenhouse gases, and production of climate-active marine aerosols.

Surfactant-associated bacteria in the near-surface layer of the ocean

PubMed Central

Kurata, Naoko; Vella, Kate; Hamilton, Bryan; Shivji, Mahmood; Soloviev, Alexander; Matt, Silvia; Tartar, Aurélien; Perrie, William

2016-01-01

Certain marine bacteria found in the near-surface layer of the ocean are expected to play important roles in the production and decay of surface active materials; however, the details of these processes are still unclear. Here we provide evidence supporting connection between the presence of surfactant-associated bacteria in the near-surface layer of the ocean, slicks on the sea surface, and a distinctive feature in the synthetic aperture radar (SAR) imagery of the sea surface. From DNA analyses of the in situ samples using pyrosequencing technology, we found the highest abundance of surfactant-associated bacterial taxa in the near-surface layer below the slick. Our study suggests that production of surfactants by marine bacteria takes place in the organic-rich areas of the water column. Produced surfactants can then be transported to the sea surface and form slicks when certain physical conditions are met. This finding has potential applications in monitoring organic materials in the water column using remote sensing techniques. Identifying a connection between marine bacteria and production of natural surfactants may provide a better understanding of the global picture of biophysical processes at the boundary between the ocean and atmosphere, air-sea exchange of greenhouse gases, and production of climate-active marine aerosols. PMID:26753514

Do insect repellents induce drift behaviour in aquatic non-target organisms?

PubMed

Fink, Patrick; Moelzner, Jana; Berghahn, Ruediger; von Elert, Eric

2017-01-01

Synthetic insect repellents are compounds applied to surfaces to discourage insects, mainly mosquitoes, from landing on those surfaces. As some of these repellents have repeatedly been detected in surface waters at significant concentrations, they may also exert repellent effects on aquatic non-target organisms. In running water systems, aquatic invertebrates actively enter downstream drift in order to avoid unfavourable environmental conditions. We thus tested the hypothesis that the widely used insect repellents DEET (N,N-Diethyl-m-toluamide), EBAAP (3-[N-butyl-N-acetyl]-aminopropionic acid ethyl ester) and Icaridin (1-piperidinecarboxylic acid 2-(2-hydroxyethyl)-1-methylpropyl ester) induce downstream drift behaviour in the aquatic invertebrates Gammarus pulex (Crustacea, Amphipoda) and Cloeon dipterum (Insecta, Ephemeroptera), using a laboratory-scale drift assay. We found no clear increase in the drift behaviour of both invertebrate species across a concentration gradient of eight orders of magnitude and even beyond maximum environmental concentrations for any of the three repellents. We found no evidence for a direct drift-inducing activity of insect repellents on aquatic non-target organisms. Copyright © 2016 Elsevier Ltd. All rights reserved.

A secreted antibacterial neuropeptide shapes the microbiome of Hydra.

PubMed

Augustin, René; Schröder, Katja; Murillo Rincón, Andrea P; Fraune, Sebastian; Anton-Erxleben, Friederike; Herbst, Eva-Maria; Wittlieb, Jörg; Schwentner, Martin; Grötzinger, Joachim; Wassenaar, Trudy M; Bosch, Thomas C G

2017-09-26

Colonization of body epithelial surfaces with a highly specific microbial community is a fundamental feature of all animals, yet the underlying mechanisms by which these communities are selected and maintained are not well understood. Here, we show that sensory and ganglion neurons in the ectodermal epithelium of the model organism hydra (a member of the animal phylum Cnidaria) secrete neuropeptides with antibacterial activity that may shape the microbiome on the body surface. In particular, a specific neuropeptide, which we call NDA-1, contributes to the reduction of Gram-positive bacteria during early development and thus to a spatial distribution of the main colonizer, the Gram-negative Curvibacter sp., along the body axis. Our findings warrant further research to test whether neuropeptides secreted by nerve cells contribute to the spatial structure of microbial communities in other organisms.Certain neuropeptides, in addition to their neuromodulatory functions, display antibacterial activities of unclear significance. Here, the authors show that a secreted neuropeptide modulates the distribution of bacterial communities on the body surface during development of the model organism Hydra.

Potent antitumor activity of a urokinase-activated engineered anthrax toxin

NASA Astrophysics Data System (ADS)

Liu, Shihui; Aaronson, Hannah; Mitola, David J.; Leppla, Stephen H.; Bugge, Thomas H.

2003-01-01

The acquisition of cell-surface urokinase plasminogen activator activity is a hallmark of malignancy. We generated an engineered anthrax toxin that is activated by cell-surface urokinase in vivo and displays limited toxicity to normal tissue but broad and potent tumoricidal activity. Native anthrax toxin protective antigen, when administered with a chimeric anthrax toxin lethal factor, Pseudomonas exotoxin fusion protein, was extremely toxic to mice, causing rapid and fatal organ damage. Replacing the furin activation sequence in anthrax toxin protective antigen with an artificial peptide sequence efficiently activated by urokinase greatly attenuated toxicity to mice. In addition, the mutation conferred cell-surface urokinase-dependent toxin activation in vivo, as determined by using a panel of plasminogen, plasminogen activator, plasminogen activator receptor, and plasminogen activator inhibitor-deficient mice. Surprisingly, toxin activation critically depended on both urokinase plasminogen activator receptor and plasminogen in vivo, showing that both proteins are essential cofactors for the generation of cell-surface urokinase. The engineered toxin displayed potent tumor cell cytotoxicity to a spectrum of transplanted tumors of diverse origin and could eradicate established solid tumors. This tumoricidal activity depended strictly on tumor cell-surface plasminogen activation. The data show that a simple change of protease activation specificity converts anthrax toxin from a highly lethal to a potent tumoricidal agent.

Selection of pecan shell based activated carbons for removal of organic and inorganic impurities from simulated well-water

USDA-ARS?s Scientific Manuscript database

Activated carbons are a byproduct from pyrolysis and have value as a purifying agent. The effectiveness of activated carbons is dependent on feedstock selection and pyrolysis conditions that modify its surface properties. Therefore, pecan shell-based activated carbons (PSACs) were prepared by soakin...

Final Technical Report: Metal—Organic Surface Catalyst for Low-temperature Methane Oxidation: Bi-functional Union of Metal—Organic Complex and Chemically Complementary Surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tait, Steven L.

Stabilization and chemical control of transition metal centers is a critical problem in the advancement of heterogeneous catalysts to next-generation catalysts that exhibit high levels of selectivity, while maintaining strong activity and facile catalyst recycling. Supported metal nanoparticle catalysts typically suffer from having a wide range of metal sites with different coordination numbers and varying chemistry. This project is exploring new possibilities in catalysis by combining features of homogeneous catalysts with those of heterogeneous catalysts to develop new, bi-functional systems. The systems are more complex than traditional heterogeneous catalysts in that they utilize sequential active sites to accomplish the desiredmore » overall reaction. The interaction of metal—organic catalysts with surface supports and their interactions with reactants to enable the catalysis of critical reactions at lower temperatures are at the focus of this study. Our work targets key fundamental chemistry problems. How do the metal—organic complexes interact with the surface? Can those metal center sites be tuned for selectivity and activity as they are in the homogeneous system by ligand design? What steps are necessary to enable a cooperative chemistry to occur and open opportunities for bi-functional catalyst systems? Study of these systems will develop the concept of bringing together the advantages of heterogeneous catalysis with those of homogeneous catalysis, and take this a step further by pursuing the objective of a bi-functional system. The use of metal-organic complexes in surface catalysts is therefore of interest to create well-defined and highly regular single-site centers. While these are not likely to be stable in the high temperature environments (> 300 °C) typical of industrial heterogeneous catalysts, they could be applied in moderate temperature reactions (100-300 °C), made feasible by lowering reaction temperatures by better catalyst control. They also serve as easily tuned model systems for exploring the chemistry of single-site transition metals and tandem catalysts that could then be developed into a zeolite or other stable support structures. In this final technical report, three major advances our described that further these goals. The first is a study demonstrating the ability to tune the oxidation state of V single-site centers on a surface by design of the surrounding ligand field. The synthesis of the single-site centers was developed in a previous reporting period of this project and this new advance shows a distinct new ability of the systems to have a designed oxidation state of the metal center. Second, we demonstrate metal complexation at surfaces using vibrational spectroscopy and also show a metal replacement reaction on Ag surfaces. Third, we demonstrate a surface-catalyzed dehydrocyclization reaction important for metal-organic catalyst design at surfaces.« less

Method of making gold thiolate and photochemically functionalized microcantilevers

DOEpatents

Boiadjiev, Vassil I [Knoxville, TN; Brown, Gilbert M [Knoxville, TN; Pinnaduwage, Lal A [Knoxville, TN; Thundat, Thomas G [Knoxville, TN; Bonnesen, Peter V [Knoxville, TN; Goretzki, Gudrun [Nottingham, GB

2009-08-25

Highly sensitive sensor platforms for the detection of specific reagents, such as chromate, gasoline and biological species, using microcantilevers and other microelectromechanical systems (MEMS) whose surfaces have been modified with photochemically attached organic monolayers, such as self-assembled monolayers (SAM), or gold-thiol surface linkage are taught. The microcantilever sensors use photochemical hydrosilylation to modify silicon surfaces and gold-thiol chemistry to modify metallic surfaces thereby enabling individual microcantilevers in multicantilever array chips to be modified separately. Terminal vinyl substituted hydrocarbons with a variety of molecular recognition sites can be attached to the surface of silicon via the photochemical hydrosilylation process. By focusing the activating UV light sequentially on selected silicon or silicon nitride hydrogen terminated surfaces and soaking or spotting selected metallic surfaces with organic thiols, sulfides, or disulfides, the microcantilevers are functionalized. The device and photochemical method are intended to be integrated into systems for detecting specific agents including chromate groundwater contamination, gasoline, and biological species.

Assembly, Structure, and Functionality of Metal-Organic Networks and Organic Semiconductor Layers at Surfaces

NASA Astrophysics Data System (ADS)

Tempas, Christopher D.

Self-assembled nanostructures at surfaces show promise for the development of next generation technologies including organic electronic devices and heterogeneous catalysis. In many cases, the functionality of these nanostructures is not well understood. This thesis presents strategies for the structural design of new on-surface metal-organic networks and probes their chemical reactivity. It is shown that creating uniform metal sites greatly increases selectivity when compared to ligand-free metal islands. When O2 reacts with single-site vanadium centers, in redox-active self-assembled coordination networks on the Au(100) surface, it forms one product. When O2 reacts with vanadium metal islands on the same surface, multiple products are formed. Other metal-organic networks described in this thesis include a mixed valence network containing Pt0 and PtII and a network where two Fe centers reside in close proximity. This structure is stable to temperatures >450 °C. These new on-surface assemblies may offer the ability to perform reactions of increasing complexity as future heterogeneous catalysts. The functionalization of organic semiconductor molecules is also shown. When a few molecular layers are grown on the surface, it is seen that the addition of functional groups changes both the film's structure and charge transport properties. This is due to changes in both first layer packing structure and the pi-electron distribution in the functionalized molecules compared to the original molecule. The systems described in this thesis were studied using high-resolution scanning tunneling microscopy, non-contact atomic force microscopy, and X-ray photoelectron spectroscopy. Overall, this work provides strategies for the creation of new, well-defined on-surface nanostructures and adds additional chemical insight into their properties.

SHINE transcription factors act redundantly to pattern the archetypal surface of Arabidopsis flower organs.

PubMed

Shi, Jian Xin; Malitsky, Sergey; De Oliveira, Sheron; Branigan, Caroline; Franke, Rochus B; Schreiber, Lukas; Aharoni, Asaph

2011-05-01

Floral organs display tremendous variation in their exterior that is essential for organogenesis and the interaction with the environment. This diversity in surface characteristics is largely dependent on the composition and structure of their coating cuticular layer. To date, mechanisms of flower organ initiation and identity have been studied extensively, while little is known regarding the regulation of flower organs surface formation, cuticle composition, and its developmental significance. Using a synthetic microRNA approach to simultaneously silence the three SHINE (SHN) clade members, we revealed that these transcription factors act redundantly to shape the surface and morphology of Arabidopsis flowers. It appears that SHNs regulate floral organs' epidermal cell elongation and decoration with nanoridges, particularly in petals. Reduced activity of SHN transcription factors results in floral organs' fusion and earlier abscission that is accompanied by a decrease in cutin load and modified cell wall properties. SHN transcription factors possess target genes within four cutin- and suberin-associated protein families including, CYP86A cytochrome P450s, fatty acyl-CoA reductases, GSDL-motif lipases, and BODYGUARD1-like proteins. The results suggest that alongside controlling cuticular lipids metabolism, SHNs act to modify the epidermis cell wall through altering pectin metabolism and structural proteins. We also provide evidence that surface formation in petals and other floral organs during their growth and elongation or in abscission and dehiscence through SHNs is partially mediated by gibberellin and the DELLA signaling cascade. This study therefore demonstrates the need for a defined composition and structure of the cuticle and cell wall in order to form the archetypal features of floral organs surfaces and control their cell-to-cell separation processes. Furthermore, it will promote future investigation into the relation between the regulation of organ surface patterning and the broader control of flower development and biological functions.

SHINE Transcription Factors Act Redundantly to Pattern the Archetypal Surface of Arabidopsis Flower Organs

PubMed Central

Shi, Jian Xin; Malitsky, Sergey; De Oliveira, Sheron; Branigan, Caroline; Franke, Rochus B.; Schreiber, Lukas; Aharoni, Asaph

2011-01-01

Floral organs display tremendous variation in their exterior that is essential for organogenesis and the interaction with the environment. This diversity in surface characteristics is largely dependent on the composition and structure of their coating cuticular layer. To date, mechanisms of flower organ initiation and identity have been studied extensively, while little is known regarding the regulation of flower organs surface formation, cuticle composition, and its developmental significance. Using a synthetic microRNA approach to simultaneously silence the three SHINE (SHN) clade members, we revealed that these transcription factors act redundantly to shape the surface and morphology of Arabidopsis flowers. It appears that SHNs regulate floral organs' epidermal cell elongation and decoration with nanoridges, particularly in petals. Reduced activity of SHN transcription factors results in floral organs' fusion and earlier abscission that is accompanied by a decrease in cutin load and modified cell wall properties. SHN transcription factors possess target genes within four cutin- and suberin-associated protein families including, CYP86A cytochrome P450s, fatty acyl-CoA reductases, GSDL-motif lipases, and BODYGUARD1-like proteins. The results suggest that alongside controlling cuticular lipids metabolism, SHNs act to modify the epidermis cell wall through altering pectin metabolism and structural proteins. We also provide evidence that surface formation in petals and other floral organs during their growth and elongation or in abscission and dehiscence through SHNs is partially mediated by gibberellin and the DELLA signaling cascade. This study therefore demonstrates the need for a defined composition and structure of the cuticle and cell wall in order to form the archetypal features of floral organs surfaces and control their cell-to-cell separation processes. Furthermore, it will promote future investigation into the relation between the regulation of organ surface patterning and the broader control of flower development and biological functions. PMID:21637781

Hydrogen storage studies on palladium-doped carbon materials (AC, CB, CNMs) @ metal-organic framework-5.

PubMed

Viditha, V; Srilatha, K; Himabindu, V

2016-05-01

Metal organic frameworks (MOFs) are a rapidly growing class of porous materials and are considered as best adsorbents for their high surface area and extraordinary porosity. The MOFs are synthesized by using various chemicals like triethylamine, terepthalic acid, zinc acetate dihydrate, chloroform, and dimethylformamide (DMF). Synthesized MOFs are intercalated with palladium/activated carbon, carbon black, and carbon nanomaterials by chemical reduction method for the purpose of enhancing the hydrogen adsorption capacities. We have observed that the palladium doped activated carbon on MOF-5 showed high hydrogen storage capacity. This may be due to the affinity of the palladium toward hydrogen molecule. The samples are characterized by X-ray diffraction, scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) surface area analysis. We have observed a clear decrease in the BET surface area and pore volume. The obtained results show a better performance for the synthesized sample. To our best knowledge, no one has reported the work on palladium-doped carbon materials (activated carbon, carbon black, carbon nanomaterials) impregnated to the metal-organic framework-5. We have attempted to synthesize carbon nanomaterials using indigenously fabricated chemical vapor deposition (CVD) unit as a support. We have observed an increase in the hydrogen storage capacities.

Enhanced visible light-induced photocatalytic activity of surface-modified BiOBr with Pd nanoparticles

NASA Astrophysics Data System (ADS)

Meng, Xiangchao; Li, Zizhen; Chen, Jie; Xie, Hongwei; Zhang, Zisheng

2018-03-01

Palladium nanoparticles well-dispersed on BiOBr surfaces were successfully prepared via a two-step process, namely hydrothermal synthesis of BiOBr followed by photodeposition of palladium. Surface-exposed palladium nanoparticles may improve the harvesting capacity of visible light photons via the surface plasmonic resonance effect to produce extra electrons. Palladium is an excellent electron acceptor, and therefore favours the separation of photogenerated electron/hole pairs. As a result, palladium significantly improves the photocatalytic activity of BiOBr in the removal of organic pollutants (phenol) under visible light irradiation. In addition to as-prepared samples which were comprehensively characterized, the mechanism for the enhancement via the deposition of palladium nanoparticles was also proposed based on results. This work may serve as solid evidence to confirm that surface-deposited palladium nanoparticles are capable of improving photocatalytic activity, and that photodeposition may be an effective approach to load metal nanoparticles onto a surface.

Reuse of spent granular activated carbon for organic micro-pollutant removal from treated wastewater.

PubMed

Hu, Jingyi; Shang, Ran; Heijman, Bas; Rietveld, Luuk

2015-09-01

Spent granular activated carbons (sGACs) for drinking water treatments were reused via pulverizing as low-cost adsorbents for micro-pollutant adsorption from a secondary treated wastewater effluent. The changes of physicochemical characteristics of the spent carbons in relation to the fresh carbons were determined and were correlated to the molecular properties of the respective GAC influents (i.e. a surface water and a groundwater). Pore size distribution analysis showed that the carbon pore volume decreased over a wider size range due to preloading by surface water, which contains a broader molecular weight distribution of organic matter in contrast to the groundwater. However, there was still considerable capacity available on the pulverized sGACs for atrazine adsorption in demineralized water and secondary effluent, and this was particularly the case for the groundwater spent GAC. However, as compared to the fresh counterparts, the decreased surface area and the induced surface acidic groups on the pulverized sGACs contributed both to the lower uptake and the more impeded adsorption kinetic of atrazine in the demineralized water. Nonetheless, the pulverized sGACs, especially the one preloaded by surface water, was less susceptible to adsorption competition in the secondary effluent, due to its negatively charged surface which can repulse the accessibility of the co-present organic matter. This suggests the reusability of the drinking water spent GACs for micro-pollutant adsorption in the treated wastewater. Copyright © 2015 Elsevier Ltd. All rights reserved.

The effect of metal (hydr)oxide nano-enabling on intraparticle mass transport of organic contaminants in hybrid granular activated carbon.

PubMed

Garcia, Jose; Markovski, Jasmina; McKay Gifford, J; Apul, Onur; Hristovski, Kiril D

2017-05-15

The overarching goal of this study was to ascertain the changes in intraparticle mass transport rates for organic contaminants resulting from nano-enabled hybridization of commercially available granular activated carbon (GAC). Three different nano-enabled hybrid media were fabricated by in-situ synthesizing titanium dioxide nanoparticles inside the pores of GAC sorbent, characterized, and evaluated for removal of two model organic contaminants under realistic conditions to obtain the intraparticle mass transport (pore and surface diffusion) coefficients. The results validated the two hypotheses that: (H1) the pore diffusion rates of organic contaminants linearly decrease with decrease in cumulative pore volume caused by increase in metal (hydr)oxide nanoparticle content inside the pores of the hybrid GAC sorbent; and (H2) introduction of metal (hydr)oxide nanoparticles initially increases surface diffusivity, but additional loading causes its decrease as the increase in metal (hydr)oxide nanoparticles content continues to reduce the porosity of the GAC sorbent. Nano-enabled hybridization of commercially available GAC with metal (hydr)oxides has the potential to significantly increase the intraparticle mass transport limitations for organic contaminants. Introduction of metal (hydr)oxide nanoparticles inside the pores of a pristine sorbent causes the pore diffusion rates of organic contaminants to decrease as the cumulative pore volume is reduced. In contrast, the introduction of limited amounts of metal (hydr)oxide nanoparticles appears to facilitate the surface diffusion rates of these contaminants. Copyright © 2017 Elsevier B.V. All rights reserved.

Organic and Hybrid Organic Solid-State Photovoltaic Materials and Devices

DTIC Science & Technology

2014-02-19

hybrids have potential applications in solar cells and may thus provide mobile energy sources for aircraft and soldier technologies. Modeling and...modeling and simulation developed in this project are encouraging further development. 2. Technical Activities Hybrid organic solar cells are an...between surface-modified semiconducting nanoparticles and polymers often contributes to the limited efficiency of hybrid photovoltaic cells and

Influences and interactions of inundation, peat, and snow on active layer thickness

DOE PAGES

Atchley, Adam L.; Coon, Ethan T.; Painter, Scott L.; ...

2016-05-18

Active layer thickness (ALT), the uppermost layer of soil that thaws on an annual basis, is a direct control on the amount of organic carbon potentially available for decomposition and release to the atmosphere as carbon-rich Arctic permafrost soils thaw in a warming climate. Here, we investigate how key site characteristics affect ALT using an integrated surface/subsurface permafrost thermal hydrology model. ALT is most sensitive to organic layer thickness followed by snow depth but is relatively insensitive to the amount of water on the landscape with other conditions held fixed. Furthermore, the weak ALT sensitivity to subsurface saturation suggests thatmore » changes in Arctic landscape hydrology may only have a minor effect on future ALT. But, surface inundation amplifies the sensitivities to the other parameters and under large snowpacks can trigger the formation of near-surface taliks.« less

Hematopoietic organs of Manduca sexta and hemocyte lineages.

PubMed

Nardi, James B; Pilas, Barbara; Ujhelyi, Elizabeth; Garsha, Karl; Kanost, Michael R

2003-10-01

Cells of the moth immune system are derived from organs that loosely envelop the four wing imaginal discs. The immune response in these insects is believed to depend on the activities of two main classes of hemocytes: plasmatocytes and granular cells. The fates of cells that arise from these hematopoietic organs have been followed by immunolabeling with plasmatocyte-specific and granular-cell-specific antibodies. Cells within each hematopoietic organ differ in their coherence and in their expression of two plasmatocyte-specific surface proteins, integrin and neuroglian. Within an organ there is no overlap in the expression of these two surface proteins; neuroglian is found on the surfaces of the coherent cells while integrin is expressed on cells that are losing coherence, rounding up, and dispersing. A granular-cell-specific marker for the protein lacunin labels the basal lamina that delimits each organ but only a small number of granular cells that lie on or near the periphery of the hematopoietic organ. When organs are cultured in the absence of hemolymph, all cells derived from hematopoietic organs turn out to immunolabel with the plasmatocyte-specific antibody MS13. The circulating plasmatocytes derived from hematopoietic organs have higher ploidy levels than the granular cells and represent a separate lineage of hemocytes.

Importance of lateral flux and its percolation depth on organic carbon export in Arctic tundra soil: Implications from a soil leaching experiment: Changes of OC in Arctic Soil Leachate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Xiaowen; Hutchings, Jack A.; Bianchi, Thomas S.

Temperature rise in the Arctic is causing deepening of active layers and resulting in the mobilization of deep permafrost dissolved organic matter (DOM). However, the mechanisms of DOM mobilization from Arctic soils, especially upper soil horizons which are drained most frequently through a year, are poorly understood. Here, we conducted a short-term leaching experiment on surface and deep organic active layer soils, from the Yukon River basin, to examine the effects of DOM transport on bulk and molecular characteristics. Our data showed a net release of DOM from surface soils equal to an average of 5% of soil carbon. Conversely,more » deep soils percolated with surface leachates retained up to 27% of bulk DOM-while releasing fluorescent components (up to 107%), indicating selective release of aromatic components (e.g. lignin, tannin), while retaining non-chromophoric components, as supported by spectrofluorometric and ultra high resolution mass spectroscopic techniques. Our findings highlight the importance of the lateral flux of DOM on ecosystem carbon balance as well as processing of DOM transport through organic active layer soils en route to rivers and streams. This work also suggests the potential role of leachate export as an important mechanism of C losses from Arctic soils, in comparison with the more traditional pathway from soil to atmosphere in a warming Arctic.« less

Alteration of biochar characteristics through Post Production Treatments

NASA Astrophysics Data System (ADS)

Schmidt, Hans-Peter; Kammann, Claudia; Glaser, Bruno

2013-04-01

The application of pure, untreated biochar to temperate soils does not lead to substantial increase in soil fertility and plant growth. Moreover, the application of 10 tonnes or more of biochar per hectare is not economically viable on most farms. To be more efficient in improving soil fertility, increasing SOM and ecosystem services, new methods of using biochar in farm settings need to be developed. To improve the effect of biochar on plant growth, biochar can be enhanced by (1) adding nutrients, (2) inoculating it with beneficial microorganisms, (3) improving its surface reactivity and thus its sorption dynamic, (4) increasing its porous volume, and/or (5) fostering the creation of biochar-mineral-organic complexes. These supplementary biochar enhancements can be achieved through different methods of feedstock blending and biochar post-production treatment which can be classified according to the resulting surface alteration of biochar: 1. Addition of nutrients, MOs, minerals in liquid solution which get soaked into the biochar pores without or with only slight surface alteration, resulting in enriched biochar. 2. Physico-chemical activation (treatment with acids, vapours, toasting with minerals …) resulting in alteration of the surface, pore volume and functional groups. 3. Bio-chemical activation through the interaction of biochar with organic compounds, minerals, nutrients and microorganisms in a biological very active environment, resulting in the complexation of biochar, minerals and organic compounds. Whereas physico-chemical activation is a highly technical process and has to be done by professional biochar producers, bio-chemical activation and enrichment can be done very efficiently by the farmer himself. On-farm enrichment and activation of biochar help to close the organic nutrient cycles of the farm, improving agronomic system efficiency and thus becoming economically viable. Adding biochar to highly labile organic matter like manure, sludge or compost improves decomposition and complexation, and helps to stabilize their nutrients and carbon. The combination of biochar and lacto-acid-bacteria in silage, feed, bedding and liquid manure treatment decreases methane and ammonia emissions, increases the feed-energy balance, and boosts animal health. On every step of this cascading use of biochar in animal husbandry, the biochar becomes more oxidized, more activated and more enriched with nutrients. When finally applied to the soil, biochar acts as carrier for nutrients and thus works to improve soil fertility. Much more research is needed in the field of biochar post-treatment and into each of the different possible farm uses. Nevertheless, sufficient serious research has already been done and published, enabling us to judge the importance of post-treating biochar to improve its agronomic performance and value.

Flash NanoPrecipitation of organic actives via confined micromixing and block copolymer stabilization

NASA Astrophysics Data System (ADS)

Johnson, Brian K.

This dissertation provides a method and the understanding required to produce nanoparticles of organic actives using Flash NanoPrecipitation . The process comprises mixing a solvent phase containing molecularly dissolved amphiphilic block copolymer and an organic active with an anti-solvent. One block of the copolymer precipitates to alter the nucleation and growth of the organic active while the other remains in solution for particle stabilization. A custom built confined impinging jets (CIJ) mixer provides optimum micromixing at the laboratory or full scale within milliseconds. Comparison to other reactor designs is provided. The resulting nanoparticles have functional surfaces tailored to meet the needs of pharmaceutical or specialty chemical formulations. Example beta-carotene nanoparticles with a polyethylene oxide surface are produced at high concentration, high yield, low stabilizer content, and a size suitable for sterile filtration or larger. The technical challenges in nanoparticle production are explained via the characteristic times for mixing, copolymer aggregation, and organic active particle formation. The time for Flash NanoPrecipitation is shown to depend strongly on the time for copolymer aggregation, and control of the organic nucleation versus growth is critical to achieve nanoparticles. Mixing operating lines explain the impact of solubility differences between the colloidal stabilizer and the organic active as function of mixing rate. Techniques to measure the solubility of the copolymer and DeltaG° , DeltaH°, and DeltaS° of micellization are demonstrated. An analytical CIJ mixer is developed by quantifying the characteristic time and physical mechanism of mixing. The methodology described to find an absolute mixing lifetime is also applied to a vortex mixer at a spectrum of flow ratios away from one. Dimensional analysis using the process Damkohler number, defined as the ratio of the mixing to the process time, is applied to precipitation to quantify the induction time through knowledge of the mixing lifetime. Copolymer aggregation without an organic active to kinetically frozen nanoparticles occurs by a "fusion only" mechanism. By analogy to classical precipitation kinetics, the interfacial free energy of a diblock copolymer nanoparticle is determined for the first time. The composite dissertation provides a clear picture of Flash NanoPrecipitation for future research and applications.

The pressure control technology of the active stressed lap

NASA Astrophysics Data System (ADS)

Li, Ying; Wang, Daxing

2010-10-01

The active stressed lap polishing technology is a kind of new polishing technology that can actively deform the lap surface to become an off-axis asphere according to different lap position on mirror surface and different angle of lap. The pressure of the lap on the mirror is an important factor affecting the grinding efficiency of the optics mirror. The active stressed lap technology using dynamic pressure control solution in the process of polishing astronomical Aspheric Mirror with faster asphericity will provide the advantage like high polishing speed and natural smooth, etc. This article puts emphases on the pressure control technology of the active stressed lap technology. It requires that the active stressed lap keeps symmetrical vertical compression on the mirrors in the process of grinding mirrors. With a background of an active stressed lap 450mm in diameter, this article gives an outline of the pressure control organization, analyzes the principle of pressure control and proposes the limitations of the present pressure control organization and the relevant solutions, designs a digital pressure controller with C32-bit RISC embedded and gives the relevant experimental test result finally.

Organic carbon accumulation and preservation in surface sediments on the Peru margin

USGS Publications Warehouse

Arthur, M.A.; Dean, W.E.; Laarkamp, K.

1998-01-01

Concentrations and characteristics of organic matter in surface sediments deposited under an intense oxygen-minimum zone on the Peru margin were studied in samples from deck-deployed box cores and push cores acquired by submersible on two transects spanning depths of 75 to 1000 m at 12??and 13.5??S. The source of organic matter to the seafloor in these areas is almost entirely marine material as confirmed by the narrow range of ??13C of organic carbon obtained in the present study (-20.3 to -21.6???; PDB) and the lack of any relationship between pyrolysis hydrogen index and carbon isotope composition. Organic carbon contents are highest (up to 16%) on the slope at depths between 75 and 350 m in sediments deposited under intermediate water masses with low dissolved oxygen concentrations (< 5 ??mol/kg). Even at these low concentrations of dissolved oxygen, however, the surface sediments that were recovered from these depths are dominantly unlaminated. Strong currents (up to 30 cm/s) associated with the poleward-flowing Peru Undercurrent were measured at depths between 160 and 300 m on both transects. The seafloor in this range of water depths is characterized by bedforms stabilized by bacterial mats, extensive authigenic mineral crusts, and (or) thick organic flocs. Constant advection of dissolved oxygen, although in low concentrations, active resuspension of surficial organic matter, activity of organisms, and transport of fine-grained sediment to and from more oxygenated zones all contribute to greater degradation and poorer initial preservation of organic matter than might be expected under oxygen-deficient conditions. Dissolved-oxygen concentrations ultimately may be the dominant affect on organic matter characteristics, but reworking of fine-grained sediment and organic matter by strong bottom currents and redeposition on the seafloor in areas of lower energy also exert important controls on organic carbon concentration and degree of oxidation in this region.

Bioweathering Potential of Cultivable Fungi Associated with Semi-Arid Surface Microhabitats of Mayan Buildings.

PubMed

Ortega-Morales, Benjamín O; Narváez-Zapata, José; Reyes-Estebanez, Manuela; Quintana, Patricia; De la Rosa-García, Susana Del C; Bullen, Heather; Gómez-Cornelio, Sergio; Chan-Bacab, Manuel J

2016-01-01

Soil and rock surfaces support microbial communities involved in mineral weathering processes. Using selective isolation, fungi were obtained from limestone surfaces of Mayan monuments in the semi-arid climate at Yucatan, Mexico. A total of 101 isolates representing 53 different taxa were studied. Common fungi such as Fusarium, Pestalotiopsis, Trichoderma, and Penicillium were associated with surfaces and were, probably derived from airborne spores. In contrast, unusual fungi such as Rosellinia, Annulohypoxylon, and Xylaria were predominantly identified from mycelium particles of biofilm biomass. Simulating oligotrophic conditions, agar amended with CaCO3 was inoculated with fungi to test for carbonate activity. A substantial proportion of fungi, in particular those isolated from mycelium (59%), were capable of solubilizing calcium by means of organic acid release, notably oxalic acid as evidenced by ion chromatography. Contrary to our hypothesis, nutrient level was not a variable influencing the CaCO3 solubilization ability among isolates. Particularly active fungi (Annulohypoxylon stygium, Penicillium oxalicum, and Rosellinia sp.) were selected as models for bioweathering experiments with limestone-containing mesocosms to identify if other mineral phases, in addition to oxalates, were linked to bioweathering processes. Fungal biofilms were seen heavily covering the stone surface, while a biomineralized front was also observed at the stone-biofilm interface, where network of hyphae and mycogenic crystals was observed. X-ray diffraction analysis (XRD) identified calcite as the main phase, along with whewellite and wedellite. In addition, lower levels of citrate were detected by Attenuated Total Reflectance-Fourier-Transform Infrared Spectroscopy (ATR-FTIR). Overall, our results suggest that a diverse fungal community is associated with limestone surfaces insemi-arid climates. A subset of this community is geochemically active, excreting organic acids under quasi-oligotrophic conditions, suggesting that the high metabolic cost of exuding organic acids beneficial under nutrient limitation. Oxalic acid release may deteriorate or stabilize limestone surfaces, depending on microclimatic dynamics.

Bioweathering Potential of Cultivable Fungi Associated with Semi-Arid Surface Microhabitats of Mayan Buildings

PubMed Central

Ortega-Morales, Benjamín O.; Narváez-Zapata, José; Reyes-Estebanez, Manuela; Quintana, Patricia; De la Rosa-García, Susana del C.; Bullen, Heather; Gómez-Cornelio, Sergio; Chan-Bacab, Manuel J.

2016-01-01

Soil and rock surfaces support microbial communities involved in mineral weathering processes. Using selective isolation, fungi were obtained from limestone surfaces of Mayan monuments in the semi-arid climate at Yucatan, Mexico. A total of 101 isolates representing 53 different taxa were studied. Common fungi such as Fusarium, Pestalotiopsis, Trichoderma, and Penicillium were associated with surfaces and were, probably derived from airborne spores. In contrast, unusual fungi such as Rosellinia, Annulohypoxylon, and Xylaria were predominantly identified from mycelium particles of biofilm biomass. Simulating oligotrophic conditions, agar amended with CaCO3 was inoculated with fungi to test for carbonate activity. A substantial proportion of fungi, in particular those isolated from mycelium (59%), were capable of solubilizing calcium by means of organic acid release, notably oxalic acid as evidenced by ion chromatography. Contrary to our hypothesis, nutrient level was not a variable influencing the CaCO3 solubilization ability among isolates. Particularly active fungi (Annulohypoxylon stygium, Penicillium oxalicum, and Rosellinia sp.) were selected as models for bioweathering experiments with limestone-containing mesocosms to identify if other mineral phases, in addition to oxalates, were linked to bioweathering processes. Fungal biofilms were seen heavily covering the stone surface, while a biomineralized front was also observed at the stone-biofilm interface, where network of hyphae and mycogenic crystals was observed. X-ray diffraction analysis (XRD) identified calcite as the main phase, along with whewellite and wedellite. In addition, lower levels of citrate were detected by Attenuated Total Reflectance-Fourier-Transform Infrared Spectroscopy (ATR-FTIR). Overall, our results suggest that a diverse fungal community is associated with limestone surfaces insemi-arid climates. A subset of this community is geochemically active, excreting organic acids under quasi-oligotrophic conditions, suggesting that the high metabolic cost of exuding organic acids beneficial under nutrient limitation. Oxalic acid release may deteriorate or stabilize limestone surfaces, depending on microclimatic dynamics. PMID:26941725

The effect of fire and permafrost interactions on soil carbon accumulation in an upland black spruce ecosystem of interior Alaska: Implications for post-thaw carbon loss

USGS Publications Warehouse

O'Donnell, J. A.; Harden, J.W.; McGuire, A.D.; Kanevskiy, M.Z.; Jorgenson, M.T.; Xu, X.

2011-01-01

High-latitude regions store large amounts of organic carbon (OC) in active-layer soils and permafrost, accounting for nearly half of the global belowground OC pool. In the boreal region, recent warming has promoted changes in the fire regime, which may exacerbate rates of permafrost thaw and alter soil OC dynamics in both organic and mineral soil. We examined how interactions between fire and permafrost govern rates of soil OC accumulation in organic horizons, mineral soil of the active layer, and near-surface permafrost in a black spruce ecosystem of interior Alaska. To estimate OC accumulation rates, we used chronosequence, radiocarbon, and modeling approaches. We also developed a simple model to track long-term changes in soil OC stocks over past fire cycles and to evaluate the response of OC stocks to future changes in the fire regime. Our chronosequence and radiocarbon data indicate that OC turnover varies with soil depth, with fastest turnover occurring in shallow organic horizons (~60 years) and slowest turnover in near-surface permafrost (>3000 years). Modeling analysis indicates that OC accumulation in organic horizons was strongly governed by carbon losses via combustion and burial of charred remains in deep organic horizons. OC accumulation in mineral soil was influenced by active layer depth, which determined the proportion of mineral OC in a thawed or frozen state and thus, determined loss rates via decomposition. Our model results suggest that future changes in fire regime will result in substantial reductions in OC stocks, largely from the deep organic horizon. Additional OC losses will result from fire-induced thawing of near-surface permafrost. From these findings, we conclude that the vulnerability of deep OC stocks to future warming is closely linked to the sensitivity of permafrost to wildfire disturbance. ?? 2010 Blackwell Publishing Ltd.

Rapid removal of organic micropollutants from water by a porous β-cyclodextrin polymer.

PubMed

Alsbaiee, Alaaeddin; Smith, Brian J; Xiao, Leilei; Ling, Yuhan; Helbling, Damian E; Dichtel, William R

2016-01-14

The global occurrence in water resources of organic micropollutants, such as pesticides and pharmaceuticals, has raised concerns about potential negative effects on aquatic ecosystems and human health. Activated carbons are the most widespread adsorbent materials used to remove organic pollutants from water but they have several deficiencies, including slow pollutant uptake (of the order of hours) and poor removal of many relatively hydrophilic micropollutants. Furthermore, regenerating spent activated carbon is energy intensive (requiring heating to 500-900 degrees Celsius) and does not fully restore performance. Insoluble polymers of β-cyclodextrin, an inexpensive, sustainably produced macrocycle of glucose, are likewise of interest for removing micropollutants from water by means of adsorption. β-cyclodextrin is known to encapsulate pollutants to form well-defined host-guest complexes, but until now cross-linked β-cyclodextrin polymers have had low surface areas and poor removal performance compared to conventional activated carbons. Here we crosslink β-cyclodextrin with rigid aromatic groups, providing a high-surface-area, mesoporous polymer of β-cyclodextrin. It rapidly sequesters a variety of organic micropollutants with adsorption rate constants 15 to 200 times greater than those of activated carbons and non-porous β-cyclodextrin adsorbent materials. In addition, the polymer can be regenerated several times using a mild washing procedure with no loss in performance. Finally, the polymer outperformed a leading activated carbon for the rapid removal of a complex mixture of organic micropollutants at environmentally relevant concentrations. These findings demonstrate the promise of porous cyclodextrin-based polymers for rapid, flow-through water treatment.

Rapid removal of organic micropollutants from water by a porous β-cyclodextrin polymer

NASA Astrophysics Data System (ADS)

Alsbaiee, Alaaeddin; Smith, Brian J.; Xiao, Leilei; Ling, Yuhan; Helbling, Damian E.; Dichtel, William R.

2016-01-01

The global occurrence in water resources of organic micropollutants, such as pesticides and pharmaceuticals, has raised concerns about potential negative effects on aquatic ecosystems and human health. Activated carbons are the most widespread adsorbent materials used to remove organic pollutants from water but they have several deficiencies, including slow pollutant uptake (of the order of hours) and poor removal of many relatively hydrophilic micropollutants. Furthermore, regenerating spent activated carbon is energy intensive (requiring heating to 500-900 degrees Celsius) and does not fully restore performance. Insoluble polymers of β-cyclodextrin, an inexpensive, sustainably produced macrocycle of glucose, are likewise of interest for removing micropollutants from water by means of adsorption. β-cyclodextrin is known to encapsulate pollutants to form well-defined host-guest complexes, but until now cross-linked β-cyclodextrin polymers have had low surface areas and poor removal performance compared to conventional activated carbons. Here we crosslink β-cyclodextrin with rigid aromatic groups, providing a high-surface-area, mesoporous polymer of β-cyclodextrin. It rapidly sequesters a variety of organic micropollutants with adsorption rate constants 15 to 200 times greater than those of activated carbons and non-porous β-cyclodextrin adsorbent materials. In addition, the polymer can be regenerated several times using a mild washing procedure with no loss in performance. Finally, the polymer outperformed a leading activated carbon for the rapid removal of a complex mixture of organic micropollutants at environmentally relevant concentrations. These findings demonstrate the promise of porous cyclodextrin-based polymers for rapid, flow-through water treatment.

Characterization and Modeling Of Microbial Carbon Metabolism In Thawing Permafrost

NASA Astrophysics Data System (ADS)

Graham, D. E.; Phelps, T. J.; Xu, X.; Carroll, S.; Jagadamma, S.; Shakya, M.; Thornton, P. E.; Elias, D. A.

2012-12-01

Increased annual temperatures in the Arctic are warming the surface and subsurface, resulting in thawing permafrost. Thawing exposes large pools of buried organic carbon to microbial degradation, increasing greenhouse gas generation and emission. Most global-scale land-surface models lack depth-dependent representations of carbon conversion and GHG transport; therefore they do not adequately describe permafrost thawing or microbial mineralization processes. The current work was performed to determine how permafrost thawing at moderately elevated temperatures and anoxic conditions would affect CO2 and CH4 generation, while parameterizing depth-dependent GHG production processes with respect to temperature and pH in biogeochemical models. These enhancements will improve the accuracy of GHG emission predictions and identify key biochemical and geochemical processes for further refinement. Three core samples were obtained from discontinuous permafrost terrain in Fairbanks, AK with a mean annual temperature of -3.3 °C. Each core was sectioned into surface/near surface (0-0.8 m), active layer (0.8-1.6 m), and permafrost (1.6-2.2 m) horizons, which were homogenized for physico-chemical characterization and microcosm construction. Surface samples had low pH values (6.0), low water content (18% by weight), low organic carbon (0.8%), and high C:N ratio (43). Active layer samples had higher pH values (6.4), higher water content (34%), more organic carbon (1.4%) and a lower C:N ratio (24). Permafrost samples had the highest pH (6.5), highest water content (46%), high organic carbon (2.5%) and the lowest C:N ratio (19). Most organic carbon was quantified as labile or intermediate pool versus stable pool in each sample, and all samples had low amounts of carbonate. Surface layer microcosms, containing 20 g sediment in septum-sealed vials, were incubated under oxic conditions, while similar active and permafrost layer samples were anoxic. These microcosms were incubated at -2, +3, or +5 °C for 6 months. The pH decreased in all samples (5.5 to 5.9). The proportions of carbon in labile and intermediate turnover pools from permafrost samples decreased during incubation, while microbial biomass carbon increased in all cases. Microcosm samples and original core material were analyzed by 16S rDNA pyrosequencing and showed increased populations of bacteria that ferment simple and complex carbohydrates, as well as acidophilic bacteria. Microbial diversity declined in permafrost samples. Concentrations of CO2 and CH4 were measured monthly by gas chromatography. CO2 production was highest in the surface/near surface incubations (4-14%) while CH4 was undetectable. Active layer sediments produced considerably less CO2 (0.2-0.7%) but CH4 was detected up to 0.25%. Concentrations of CO2 found in the deep permafrost incubations were comparable to those in the active layer, while CH4 was considerably higher ranging from 0.2-0.6%. Overall, the CO2 generation rate (0.02-0.12 μmol/g/month) was roughly 50 times that of methanogenesis (0.002-0.007 μmol/g/month). GHG levels peaked after 4 months, and the decreasing pH suggested that organic acid accumulation could control GHG biogenesis. Surprisingly, increasing temperature and water content did not necessarily increase GHG emission rates or proportions of CO2 and CH4.

The effects of adsorbing organic pollutants from super heavy oil wastewater by lignite activated coke.

PubMed

Tong, Kun; Lin, Aiguo; Ji, Guodong; Wang, Dong; Wang, Xinghui

2016-05-05

The adsorption of organic pollutants from super heavy oil wastewater (SHOW) by lignite activated coke (LAC) was investigated. Specifically, the effects of LAC adsorption on pH, BOD5/COD(Cr)(B/C), and the main pollutants before and after adsorption were examined. The removed organic pollutants were characterized by Fourier transform infrared spectroscopy (FTIR), Boehm titrations, gas chromatography-mass spectrometry (GC-MS), and liquid chromatography with organic carbon detection (LC-OCD). FTIR spectra indicated that organic pollutants containing -COOH and -NH2 functional groups were adsorbed from the SHOW. Boehm titrations further demonstrated that carboxyl, phenolic hydroxyl, and lactonic groups on the surface of the LAC increased. GC-MS showed that the removed main organic compounds are difficult to be degraded or extremely toxics to aquatic organisms. According to the results of LC-OCD, 30.37 mg/L of dissolved organic carbons were removed by LAC adsorption. Among these, hydrophobic organic contaminants accounted for 25.03 mg/L. Furthermore, LAC adsorption was found to increase pH and B/C ratio of the SHOW. The mechanisms of adsorption were found to involve between the hydrogen bonding and the functional groups of carboxylic, phenolic, and lactonic on the LAC surface. In summary, all these results demonstrated that LAC adsorption can remove bio-refractory DOCs, which is beneficial for biodegradation. Copyright © 2016. Published by Elsevier B.V.

Influence of organic films on the evaporation and condensation of water in aerosol

PubMed Central

Davies, James F.; Miles, Rachael E. H.; Haddrell, Allen E.; Reid, Jonathan P.

2013-01-01

Uncertainties in quantifying the kinetics of evaporation and condensation of water from atmospheric aerosol are a significant contributor to the uncertainty in predicting cloud droplet number and the indirect effect of aerosols on climate. The influence of aerosol particle surface composition, particularly the impact of surface active organic films, on the condensation and evaporation coefficients remains ambiguous. Here, we report measurements of the influence of organic films on the evaporation and condensation of water from aerosol particles. Significant reductions in the evaporation coefficient are shown to result when condensed films are formed by monolayers of long-chain alcohols [CnH(2n+1)OH], with the value decreasing from 2.4 × 10−3 to 1.7 × 10−5 as n increases from 12 to 17. Temperature-dependent measurements confirm that a condensed film of long-range order must be formed to suppress the evaporation coefficient below 0.05. The condensation of water on a droplet coated in a condensed film is shown to be fast, with strong coherence of the long-chain alcohol molecules leading to islanding as the water droplet grows, opening up broad areas of uncoated surface on which water can condense rapidly. We conclude that multicomponent composition of organic films on the surface of atmospheric aerosol particles is likely to preclude the formation of condensed films and that the kinetics of water condensation during the activation of aerosol to form cloud droplets is likely to remain rapid. PMID:23674675

Global distribution and surface activity of macromolecules in offline simulations of marine organic chemistry

DOE PAGES

Ogunro, Oluwaseun O.; Burrows, Susannah M.; Elliott, Scott; ...

2015-10-13

Here, organic macromolecules constitute high percentage components of remote sea spray. They enter the atmosphere through adsorption onto bubbles followed by bursting at the ocean surface, and go on to influence the chemistry of the fine mode aerosol. We present a global estimate of mixed-layer organic macromolecular distributions, driven by offline marine systems model output. The approach permits estimation of oceanic concentrations and bubble film surface coverages for several classes of organic compound. Mixed layer levels are computed from the output of a global ocean biogeochemistry model by relating the macromolecules to standard biogeochemical tracers. Steady state is assumed formore » labile forms, and for longer-lived components we rely on ratios to existing transported variables. Adsorption is then represented through conventional Langmuir isotherms, with equilibria deduced from laboratory analogs. Open water concentrations locally exceed one micromolar carbon for the total of protein, polysaccharide and refractory heteropolycondensate. The shorter-lived lipids remain confined to regions of strong biological activity. Results are evaluated against available measurements for all compound types, and agreement is generally quite reasonable. Global distributions are further estimated for both fractional coverage of bubble films at the air-water interface and the two-dimensional concentration excess. Overall, we show that macromolecular mapping provides a novel tool for the comprehension of oceanic surfactant distributions. Results may prove useful in planning field experiments and assessing the potential response of surface chemical behaviors to global change.« less

Influence of organic films on the evaporation and condensation of water in aerosol.

PubMed

Davies, James F; Miles, Rachael E H; Haddrell, Allen E; Reid, Jonathan P

2013-05-28

Uncertainties in quantifying the kinetics of evaporation and condensation of water from atmospheric aerosol are a significant contributor to the uncertainty in predicting cloud droplet number and the indirect effect of aerosols on climate. The influence of aerosol particle surface composition, particularly the impact of surface active organic films, on the condensation and evaporation coefficients remains ambiguous. Here, we report measurements of the influence of organic films on the evaporation and condensation of water from aerosol particles. Significant reductions in the evaporation coefficient are shown to result when condensed films are formed by monolayers of long-chain alcohols [C(n)H(2n+1)OH], with the value decreasing from 2.4 × 10(-3) to 1.7 × 10(-5) as n increases from 12 to 17. Temperature-dependent measurements confirm that a condensed film of long-range order must be formed to suppress the evaporation coefficient below 0.05. The condensation of water on a droplet coated in a condensed film is shown to be fast, with strong coherence of the long-chain alcohol molecules leading to islanding as the water droplet grows, opening up broad areas of uncoated surface on which water can condense rapidly. We conclude that multicomponent composition of organic films on the surface of atmospheric aerosol particles is likely to preclude the formation of condensed films and that the kinetics of water condensation during the activation of aerosol to form cloud droplets is likely to remain rapid.

Washing-resistant surfactant coated surface is able to inhibit pathogenic bacteria adhesion

NASA Astrophysics Data System (ADS)

Treter, Janine; Bonatto, Fernando; Krug, Cristiano; Soares, Gabriel Vieira; Baumvol, Israel Jacob Rabin; Macedo, Alexandre José

2014-06-01

Surface-active substances, which are able to organize themselves spontaneously on surfaces, triggering changes in the nature of the solid-liquid interface, are likely to influence microorganism adhesion and biofilm formation. Therefore, this study aimed to evaluate chemical non-ionic surfactants activity against pathogenic microbial biofilms and to cover biomaterial surfaces in order to obtain an anti-infective surface. After testing 11 different surfactants, Pluronic F127 was selected for further studies due to its non-biocidal properties and capability to inhibit up to 90% of biofilm formation of Gram-positive pathogen and its clinical isolates. The coating technique using direct impregnation on the surface showed important antibiofilm formation characteristics, even after extensive washes. Surface roughness and bacterial surface polarity does not influence the adhesion of Staphylococcus epidermidis, however, the material coated surface became extremely hydrophilic. The phenotype of S. epidermidis does not seem to have been affected by the contact with surfactant, reinforcing the evidence that a physical phenomenon is responsible for the activity. This paper presents a simple method of surface coating employing a synthetic surfactant to prevent S. epidermidis biofilm formation.

Direct Determination of Activities for Microorganisms of Chesapeake Bay Populations

PubMed Central

Tabor, Paul S.; Neihof, Rex A.

1984-01-01

We used three methods in determination of the metabolically active individual microorganisms for Chesapeake Bay surface and near-bottom populations over a period of a year. Synthetically active bacteria were recognized as enlarged cells in samples amended with nalidixic acid and yeast extract and incubated for 6 h. Microorganisms with active electron transport systems were identified by the reduction of a tetrazolium salt electron acceptor. Microorganisms active in uptake of amino acids, thymidine, and acetate were determined by microautoradiography. In conjunction with enumeration of active organisms, a total direct count was made for each sample preparation by epifluorescence microscopy. For the majority of samples, numbers of amino acid uptake-active organisms were greater than numbers of organisms determined to be active by other direct measurements. Within a sample, the numbers of uptake-active organisms (amino acids or thymidine) and electron transport system-active organisms were significantly different for 68% of the samples. Numbers of synthetically active bacteria were generally less than numbers determined by the other direct activity measurements. The distribution of total counts in the 11 samplings showed a seasonal pattern, with significant dependence on in situ water temperature, increasing from March to September and then decreasing through February. Synthetically active bacteria and amino acid uptake-active organisms showed a significant dependence on in situ temperature, independent of the function of temperature on total counts. Numbers of active organisms determined by at least one of the methods used exceeded 25% of the total population of all samplings, and from June through September, >85% of the total population was found to be active by at least one direct activity measurement. Thus, active rather than dormant organisms compose a major portion of the microbial population in this region of Chesapeake Bay. PMID:16346659

Direct determination of activities for microorganisms of chesapeake bay populations.

PubMed

Tabor, P S; Neihof, R A

1984-11-01

We used three methods in determination of the metabolically active individual microorganisms for Chesapeake Bay surface and near-bottom populations over a period of a year. Synthetically active bacteria were recognized as enlarged cells in samples amended with nalidixic acid and yeast extract and incubated for 6 h. Microorganisms with active electron transport systems were identified by the reduction of a tetrazolium salt electron acceptor. Microorganisms active in uptake of amino acids, thymidine, and acetate were determined by microautoradiography. In conjunction with enumeration of active organisms, a total direct count was made for each sample preparation by epifluorescence microscopy. For the majority of samples, numbers of amino acid uptake-active organisms were greater than numbers of organisms determined to be active by other direct measurements. Within a sample, the numbers of uptake-active organisms (amino acids or thymidine) and electron transport system-active organisms were significantly different for 68% of the samples. Numbers of synthetically active bacteria were generally less than numbers determined by the other direct activity measurements. The distribution of total counts in the 11 samplings showed a seasonal pattern, with significant dependence on in situ water temperature, increasing from March to September and then decreasing through February. Synthetically active bacteria and amino acid uptake-active organisms showed a significant dependence on in situ temperature, independent of the function of temperature on total counts. Numbers of active organisms determined by at least one of the methods used exceeded 25% of the total population of all samplings, and from June through September, >85% of the total population was found to be active by at least one direct activity measurement. Thus, active rather than dormant organisms compose a major portion of the microbial population in this region of Chesapeake Bay.

Effects of surface-active organic matter on carbon dioxide nucleation in atmospheric wet aerosols: a molecular dynamics study.

PubMed

Daskalakis, Vangelis; Charalambous, Fevronia; Panagiotou, Fostira; Nearchou, Irene

2014-11-21

Organic matter (OM) uptake in cloud droplets produces water-soluble secondary organic aerosols (SOA) via aqueous chemistry. These play a significant role in aerosol properties. We report the effects of OM uptake in wet aerosols, in terms of the dissolved-to-gas carbon dioxide nucleation using molecular dynamics (MD) simulations. Carbon dioxide has been implicated in the natural rainwater as well as seawater acidity. Variability of the cloud and raindrop pH is assumed in space and time, as regional emissions, local human activities and geophysical characteristics differ. Rain scavenging of inorganic SOx, NOx and NH3 plays a major role in rain acidity in terms of acid-base activity, however carbon dioxide solubility also remains a key parameter. Based on the MD simulations we propose that the presence of surface-active OM promotes the dissolved-to-gas carbon dioxide nucleation in wet aerosols, even at low temperatures, strongly decreasing carbon dioxide solubility. A discussion is made on the role of OM in controlling the pH of a cloud or raindrop, as a consequence, without involving OM ionization equilibrium. The results are compared with experimental and computational studies in the literature.

The prospects for life on Mars - A pre-Viking assessment

NASA Technical Reports Server (NTRS)

Sagan, C.; Lederberg, J.

1976-01-01

The paper considers implications of the Mariner 9 findings for the investigation of Martian biology in the next decade, beginning with the Viking mission. Previous claims for observations of Martian biological activity are reviewed and refuted or reinterpreted. The question is raised of whether there are combinations of environmental temperature and water activity on Mars that are suitable for a conceivable Martian biology. Four possible classes of Martian organisms associated with temperature/water ecological niches in the external environment are proposed: organisms requiring high temperatures and high water activity, those inhabiting niches with low temperatures and high water activity, those inhabiting niches of high temperature and low water activity, and those which can survive under conditions of low temperature and low water activity. It is noted that organisms of the last two classes may extract water from minerals or from ice and may be of large dimensions. The possible surface distribution of Martian organisms is discussed along with future search strategies for life on Mars.

Adsorption of organic compounds onto activated carbons from recycled vegetables biomass.

PubMed

Mameli, Anna; Cincotti, Alberto; Lai, Nicola; Crisafulli, Carmelo; Sciré, Salvatore; Cao, Giacomo

2004-01-01

The removal of organic species from aqueous solution by activated carbons is investigated. The latter ones are prepared from olive husks and almond shells. A wide range of surface area values are obtained varying temperature and duration of both carbonization and activation steps. The adsorption isotherm of phenol, catechol and 2,6-dichlorophenol involving the activated carbons prepared are obtained at 25 degrees C. The corresponding behavior is quantitatively correlated using classical isotherm, whose parameters are estimated by fitting the equilibrium data. A two component isotherm (phenol/2,6-dichlorophenol) is determined in order to test activated carbon behavior during competitive adsorption.

Dragonfly: In Situ Exploration of Titan's Organic Chemistry and Habitability

NASA Astrophysics Data System (ADS)

Turtle, E. P.; Barnes, J. W.; Trainer, M. G.; Lorenz, R. D.

2017-12-01

Titan's abundant complex carbon-rich chemistry, interior ocean, and past presence of liquid water on the surface make it an ideal destination to study prebiotic chemical processes and document the habitability of an extraterrestrial environment. Titan exploration is a high science priority due to the level of organic synthesis that it supports. Moreover, opportunities for organics to have interacted with liquid water at the surface (e.g., in impact melt sheets) increase the potential for chemical processes to progress further, providing an unparalleled opportunity to investigate prebiotic chemistry, as well as to search for signatures of potential water-based or even hydrocarbon-based life. The diversity of Titan's surface materials and environments drives the scientific need to be able to sample a variety of locations, thus mobility is key for in situ measurements. Titan's atmosphere is 4 times denser than Earth's reducing the wing/rotor area required to generate a given amount of lift, and the low gravity reduces the required magnitude of lift, making heavier-than-air mobility highly efficient. Dragonfly is a rotorcraft lander mission proposed to NASA's New Frontiers Program to take advantage of Titan's unique natural laboratory to understand how far chemistry can progress in environments that provide key ingredients for life. Measuring the compositions of materials in different environments will reveal how far organic chemistry has progressed. Surface material can be sampled into a mass spectrometer to identify the chemical components available and processes at work to produce biologically relevant compounds. Bulk elemental surface composition can be determined by a neutron-activated gamma-ray spectrometer. Meteorology measurements can characterize Titan's atmosphere and diurnal and spatial variations therein. Geologic features can be characterized via remote-sensing observations, which also provide context for samples. Seismic sensing can probe subsurface structure and activity. In addition to surface investigations, Dragonfly can perform measurements during flight, including atmospheric profiles and aerial observations of surface geology, which also provide sampling context and scouting for landing sites.

The PROCESS experiment: amino and carboxylic acids under Mars-like surface UV radiation conditions in low-earth orbit.

PubMed

Noblet, Audrey; Stalport, Fabien; Guan, Yuan Yong; Poch, Olivier; Coll, Patrice; Szopa, Cyril; Cloix, Mégane; Macari, Frédérique; Raulin, Francois; Chaput, Didier; Cottin, Hervé

2012-05-01

The search for organic molecules at the surface of Mars is a top priority of the next Mars exploration space missions: Mars Science Laboratory (NASA) and ExoMars (ESA). The detection of organic matter could provide information about the presence of a prebiotic chemistry or even biological activity on this planet. Therefore, a key step in interpretation of future data collected by these missions is to understand the preservation of organic matter in the martian environment. Several laboratory experiments have been devoted to quantifying and qualifying the evolution of organic molecules under simulated environmental conditions of Mars. However, these laboratory simulations are limited, and one major constraint is the reproduction of the UV spectrum that reaches the surface of Mars. As part of the PROCESS experiment of the European EXPOSE-E mission on board the International Space Station, a study was performed on the photodegradation of organics under filtered extraterrestrial solar electromagnetic radiation that mimics Mars-like surface UV radiation conditions. Glycine, serine, phthalic acid, phthalic acid in the presence of a mineral phase, and mellitic acid were exposed to these conditions for 1.5 years, and their evolution was determined by Fourier transform infrared spectroscopy after their retrieval. The results were compared with data from laboratory experiments. A 1.5-year exposure to Mars-like surface UV radiation conditions in space resulted in complete degradation of the organic compounds. Half-lives between 50 and 150 h for martian surface conditions were calculated from both laboratory and low-Earth orbit experiments. The results highlight that none of those organics are stable under low-Earth orbit solar UV radiation conditions.

EMG responses to maintain stance during multidirectional surface translations

NASA Technical Reports Server (NTRS)

Henry, S. M.; Fung, J.; Horak, F. B.; Peterson, B. W. (Principal Investigator)

1998-01-01

To characterize muscle synergy organization underlying multidirectional control of stance posture, electromyographic activity was recorded from 11 lower limb and trunk muscles of 7 healthy subjects while they were subjected to horizontal surface translations in 12 different, randomly presented directions. The latency and amplitude of muscle responses were quantified for each perturbation direction. Tuning curves for each muscle were examined to relate the amplitude of the muscle response to the direction of surface translation. The latencies of responses for the shank and thigh muscles were constant, regardless of perturbation direction. In contrast, the latencies for another thigh [tensor fascia latae (TFL)] and two trunk muscles [rectus abdominis (RAB) and erector spinae (ESP)] were either early or late, depending on the perturbation direction. These three muscles with direction-specific latencies may play different roles in postural control as prime movers or as stabilizers for different translation directions, depending on the timing of recruitment. Most muscle tuning curves were within one quadrant, having one direction of maximal activity, generally in response to diagonal surface translations. Two trunk muscles (RAB and ESP) and two lower limb muscles (semimembranosus and peroneus longus) had bipolar tuning curves, with two different directions of maximal activity, suggesting that these muscle can play different roles as part of different synergies, depending on translation direction. Muscle tuning curves tended to group into one of three regions in response to 12 different directions of perturbations. Two muscles [rectus femoris (RFM) and TFL] were maximally active in response to lateral surface translations. The remaining muscles clustered into one of two diagonal regions. The diagonal regions corresponded to the two primary directions of active horizontal force vector responses. Two muscles (RFM and adductor longus) were maximally active orthogonal to their predicted direction of maximal activity based on anatomic orientation. Some of the muscles in each of the synergic regions were not anatomic synergists, suggesting a complex central organization for recruitment of muscles. The results suggest that neither a simple reflex mechanism nor a fixed muscle synergy organization is adequate to explain the muscle activation patterns observed in this postural control task. Our results are consistent with a centrally mediated pattern of muscle latencies combined with peripheral influence on muscle magnitude. We suggest that a flexible continuum of muscle synergies that are modifiable in a task-dependent manner be used for equilibrium control in stance.

Vertical Stratification of Peat Pore Water Dissolved Organic Matter Composition in a Peat Bog in Northern Minnesota: Pore Water DOM composition in a peat bog

DOE PAGES

Tfaily, Malak M.; Wilson, Rachel M.; Cooper, William T.; ...

2018-01-29

Here, we characterized dissolved organic matter (DOM) composition throughout the peat column at the Marcell S1 forested bog in northern Minnesota and tested the hypothesis that redox oscillations associated with cycles of wetting and drying at the surface of the fluctuating water table correlate with increased carbon, sulfur, and nitrogen turn over. We found significant vertical stratification of DOM molecular composition and excitation-emission matrix parallel factor analysis components within the peat column. In particular, the intermediate depth zone (~ 50 cm) was identified as a zone where maximum decomposition and turnover is taking place. Surface DOM was dominated by inputsmore » from surface vegetation. The intermediate depth zone was an area of high organic matter reactivity and increased microbial activity with diagenetic formation of many unique compounds, among them polycyclic aromatic compounds that contain both nitrogen and sulfur heteroatoms. These compounds have been previously observed in coal-derived compounds and were assumed to be responsible for coal's biological activity. Biological processes triggered by redox oscillations taking place at the intermediate depth zone of the peat profile at the S1 bog are assumed to be responsible for the formation of these heteroatomic PACs in this system. Alternatively, these compounds could stem from black carbon and nitrogen derived from fires that have occurred at the site in the past. Surface and deep DOM exhibited more similar characteristics, compared to the intermediate depth zone, with the deep layer exhibiting greater input of microbially degraded organic matter than the surface suggesting that the entire peat profile consists of similar parent material at different degrees of decomposition and that lateral and vertical advection of pore water from the surface to the deeper horizons is responsible for such similarities. Lastly, our findings suggest that molecular composition of DOM in peatland pore water is dynamic and is a function of ecosystem activity, water table, redox oscillation, and pore water advection.« less

Vertical Stratification of Peat Pore Water Dissolved Organic Matter Composition in a Peat Bog in Northern Minnesota: Pore Water DOM composition in a peat bog

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tfaily, Malak M.; Wilson, Rachel M.; Cooper, William T.

Here, we characterized dissolved organic matter (DOM) composition throughout the peat column at the Marcell S1 forested bog in northern Minnesota and tested the hypothesis that redox oscillations associated with cycles of wetting and drying at the surface of the fluctuating water table correlate with increased carbon, sulfur, and nitrogen turn over. We found significant vertical stratification of DOM molecular composition and excitation-emission matrix parallel factor analysis components within the peat column. In particular, the intermediate depth zone (~ 50 cm) was identified as a zone where maximum decomposition and turnover is taking place. Surface DOM was dominated by inputsmore » from surface vegetation. The intermediate depth zone was an area of high organic matter reactivity and increased microbial activity with diagenetic formation of many unique compounds, among them polycyclic aromatic compounds that contain both nitrogen and sulfur heteroatoms. These compounds have been previously observed in coal-derived compounds and were assumed to be responsible for coal's biological activity. Biological processes triggered by redox oscillations taking place at the intermediate depth zone of the peat profile at the S1 bog are assumed to be responsible for the formation of these heteroatomic PACs in this system. Alternatively, these compounds could stem from black carbon and nitrogen derived from fires that have occurred at the site in the past. Surface and deep DOM exhibited more similar characteristics, compared to the intermediate depth zone, with the deep layer exhibiting greater input of microbially degraded organic matter than the surface suggesting that the entire peat profile consists of similar parent material at different degrees of decomposition and that lateral and vertical advection of pore water from the surface to the deeper horizons is responsible for such similarities. Lastly, our findings suggest that molecular composition of DOM in peatland pore water is dynamic and is a function of ecosystem activity, water table, redox oscillation, and pore water advection.« less

Influence of Selected Organic Micropollutants on Organisms

NASA Astrophysics Data System (ADS)

Włodarczyk-Makuła, Maria

2017-03-01

This article describes the toxicity of organic micropollutants on tested microorganisms. Itis a current issue because organic micropollutants are identified in all elements of environmental (surface water, ground water, soils) and in food products. The organic micropollutants include: polychlorinated dibenzodioxyns PCDD, polychlorinated dibenzofurans PCDF, polychlorinated biphenyls PCB, polycyclic aromatic hydrocarbons PAH, halogenated compounds and by-products of water treatment. Some organic compounds cause hazard for health and human life due to their estrogenic biological activity, carcinogenic, mutagenic or teratogenic activity. The influence on organisms indicators of these compounds based on literature data were presented. The level of TEQ (toxic equivalency) in response to organic chlorine derivatives (PCDDs, PCDF, PCBs) is usually determined by toxic equivalency factor (TEF). The International Agency for Research on Cancer classifies organic micropollutants as carcinogenic to humans (Group 1), possibly carcinogenic (Group 2A) or probably carcinogenic to humans (Group 2B).

[Cell surface peroxidase--generator of superoxide anion in wheat root cells under wound stress].

PubMed

Chasov, A V; Gordon, L Kh; Kolesnikov, O P; Minibaeva, F V

2002-01-01

Development of wound stress in excised wheat roots is known to be accompanied with an increase in reactive oxygen species (ROS) production, fall of membrane potential, release of K+ from cells, alkalization of extracellular solution, changes in respiration and metabolism of structural lipids. Dynamics of superoxide release correlates with changes in other physiological parameters, indicating the cross-reaction of these processes. Activity of peroxidase in extracellular solution after a 1 h incubation and removal of roots was shown to be stimulated by the range of organic acids, detergents, metals, and to be inhibited by cyanide. Superoxide production was sensitive to the addition of Mn2+ and H2O2. Increase in superoxide production correlates with the enhancement of peroxidase activity at the application of organic acids and detergents. The results obtained indicate that cell surface peroxidase is one of the main generators of superoxide in wounded wheat root cells. Different ways of stimulation of the ROS producing activity in root cells is supposed. By controlling superoxide and hydrogen peroxide formation, the cell surface peroxidase can control the adaptation processes in stressed plant cells.

Adsorption of dyes onto carbonaceous materials produced from coffee grounds by microwave treatment.

PubMed

Hirata, Mizuho; Kawasaki, Naohito; Nakamura, Takeo; Matsumoto, Kazuoki; Kabayama, Mineaki; Tamura, Takamichi; Tanada, Seiki

2002-10-01

Organic wastes have been burned for reclamation. However, they have to be recycled and reused for industrial sustainable development. Carbonaceous materials were produced from coffee grounds by microwave treatment. There are many phenolic hydroxyl and carboxyl groups on the surface of carbonaceous materials. The base consumption of the carbonaceous materials was larger than that of the commercially activated carbon. The carbonaceous materials produced from coffee grounds were applied to the adsorbates for the removal of basic dyes (methylene blue and gentian violet) in wastewater. This result indicated that the adsorption of dyes depended upon the surface polar groups on the carbonaceous materials. Moreover, the Freundlich constants of isotherms for the adsorption of methylene blue and gentian violet onto the carbonaceous materials produced from coffee grounds were greater than those for adsorption onto activated carbon or ceramic activated carbon. The interaction was greatest between the surface or porosity of the carbonaceous materials and methylene blue and gentian violet. The microwave treatment would be useful for the carbonization of organic wastes to save energy.

Adsorptive removal of hydrophobic organic compounds by carbonaceous adsorbents: a comparative study of waste-polymer-based, coal-based activated carbon, and carbon nanotubes.

PubMed

Lian, Fei; Chang, Chun; Du, Yang; Zhu, Lingyan; Xing, Baoshan; Liu, Chang

2012-01-01

Adsorption of the hydrophobic organic compounds (HOCs) trichloroethylene (TCE), 1,3-dichlorobenzene (DCB), 1,3-dinitrobenzene (DNB) and gamma-hexachlorocyclohexane (HCH) on five different carbonaceous materials was compared. The adsorbents included three polymer-based activated carbons, one coal-based activated carbon (F400) and multiwalled carbon nanotubes (MWNT). The polymer-based activated carbons were prepared using KOH activation from waste polymers: polyvinyl chloride (PVC), polyethyleneterephthalate (PET) and tire rubber (TR). Compared with F400 and MWNT, activated carbons derived from PVC and PET exhibited fast adsorption kinetics and high adsorption capacity toward the HOCs, attributed to their extremely large hydrophobic surface area (2700 m2/g) and highly mesoporous structures. Adsorption of small-sized TCE was stronger on the tire-rubber-based carbon and F400 resulting from the pore-filling effect. In contrast, due to the molecular sieving effect, their adsorption on HCH was lower. MWNT exhibited the lowest adsorption capacity toward HOCs because of its low surface area and characteristic of aggregating in aqueous solution.

Effect of Organic Capping Layers over Monodisperse Platinum Nanoparticles upon Activity for Ethylene Hydrogenation and Carbon Monoxide Oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuhn, John N.; Tsung, Chia-Kuang; Huang, Wenyu

2009-03-24

The influence of oleylamine (OA), trimethyl tetradecyl ammonium bromide (TTAB), and polyvinlypyrrolidone (PVP) capping agents upon the catalytic properties of Pt/silica catalysts was evaluated. Pt nanoparticles that were 1.5 nm in size were synthesized by the same procedure (ethylene glycol reduction under basic conditions) with the various capping agents added afterward for stabilization. Before examining catalytic properties for ethylene hydrogenation and CO oxidation, the Pt NPs were deposited onto mesoporous silica (SBA-15) supports and characterized by transmission electron microscopy (TEM), H{sub 2} chemisorption, and elemental analysis (ICP-MS). PVP- and TTAB-capped Pt yielded mass-normalized reaction rates that decreased with increasing pretreatmentmore » temperature, and this trend was attributed to the partial coverage of the Pt surface with decomposition products from the organic capping agent. Once normalized to the Pt surface area, similar intrinsic activities were obtained regardless of the pretreatment temperature, which indicated no influence on the nature of the active sites. Consequently, a chemical probe technique using intrinsic activity for ethylene hydrogenation was demonstrated as an acceptable method for estimating the metallic surface areas of Pt. Amine (OA) capping exhibited a detrimental influence on the catalytic properties as severe deactivation and low activity were observed for ethylene hydrogenation and CO oxidation, respectively. These results were consistent with amine groups being strong poisons for Pt surfaces, and revealed the need to consider the effects of capping agents on the catalytic properties.« less

Efficiency of activated carbon to transform ozone into *OH radicals: influence of operational parameters.

PubMed

Sánchez-Polo, M; von Gunten, U; Rivera-Utrilla, J

2005-09-01

Based on previous findings (Jans, U., Hoigné, J., 1998. Ozone Sci. Eng. 20, 67-87), the activity of activated carbon for the transformation of ozone into *OH radicals including the influence of operational parameters (carbon dose, ozone dose, carbon-type and carbon treatment time) was quantified. The ozone decomposition constant (k(D)) was increased by the presence of activated carbon in the system and depending on the type of activated carbon added, the ratio of the concentrations of *OH radicals and ozone, the R(ct) value ([*OH]/[O3]), was increased by a factor 3-5. The results obtained show that the surface chemical and textural characteristics of the activated carbon determines its activity for the transformation of ozone into *OH radicals. The most efficient carbons in this process are those with high basicity and large surface area. The obtained results show that the interaction between ozone and pyrrol groups present on the surface of activated carbon increase the concentration of O2*- radicals in the system, enhancing ozone transformation into *OH radicals. The activity of activated carbon decreases for extended ozone exposures. This may indicate that activated carbon does not really act as a catalyst but rather as a conventional initiator or promoter for the ozone transformation into *OH radicals. Ozonation of Lake Zurich water ([O3] = 1 mg/L) in presence of activated carbon (0.5 g/L) lead to an increase in the k(D) and R(ct) value by a factor of 10 and 39, respectively, thereby favouring the removal of ozone-resistant contaminants. Moreover, the presence of activated carbon during ozonation of Lake Zurich water led to a 40% reduction in the content of dissolved organic carbon during the first 60 min of treatment. The adsorption of low concentrations of dissolved organic matter (DOM) on activated carbon surfaces did not modify its capacity to initiate/promote ozone transformation into *OH radicals.

Dissolved organic carbon leaching from plastics stimulates microbial activity in the ocean.

PubMed

Romera-Castillo, Cristina; Pinto, Maria; Langer, Teresa M; Álvarez-Salgado, Xosé Antón; Herndl, Gerhard J

2018-04-12

Approximately 5.25 trillion plastic pieces are floating at the sea surface. The impact of plastic pollution on the lowest trophic levels of the food web, however, remains unknown. Here we show that plastics release dissolved organic carbon (DOC) into the ambient seawater stimulating the activity of heterotrophic microbes. Our estimates indicate that globally up to 23,600 metric tons of DOC are leaching from marine plastics annually. About 60% of it is available to microbial utilization in less than 5 days. If exposed to solar radiation, however, this DOC becomes less labile. Thus, plastic pollution of marine surface waters likely alters the composition and activity of the base of the marine food webs. It is predicted that plastic waste entering the ocean will increase by a factor of ten within the next decade, resulting in an increase in plastic-derived DOC that might have unaccounted consequences for marine microbes and for the ocean system.

Sediment carbon fate in phreatic karst (Part 1): Conceptual model development

NASA Astrophysics Data System (ADS)

Husic, A.; Fox, J.; Agouridis, C.; Currens, J.; Ford, W.; Taylor, C.

2017-06-01

Recent research has paid increased attention to quantifying the fate of carbon pools within fluvial networks, but few, if any, studies consider the fate of sediment organic carbon in fluviokarst systems despite that karst landscapes cover 12% of the earth's land surface. The authors develop a conceptual model of sediment carbon fate in karst terrain with specific emphasis upon phreatic karst conduits, i.e., those located below the groundwater table that have the potential to trap surface-derived sediment and turnover carbon. To assist with their conceptual model development, the authors study a phreatic system and apply a mixture of methods traditional and novel to karst studies, including electrical resistivity imaging, well drilling, instantaneous velocimetry, dye tracing, stage recording, discrete and continuous sediment and water quality sampling, and elemental and stable carbon isotope fingerprinting. Results show that the sediment transport carrying capacity of the phreatic karst water is orders of magnitude less than surface streams during storm-activated periods promoting deposition of fine sediments in the phreatic karst. However, the sediment transport carrying capacity is sustained long after the hydrologic event has ended leading to sediment resuspension and prolonged transport. The surficial fine grained laminae occurs in the subsurface karst system; but unlike surface streams, the light-limited conditions of the subsurface karst promotes constant heterotrophy leading to carbon turnover. The coupling of the hydrological processes leads to a conceptual model that frames phreatic karst as a biologically active conveyor of sediment carbon that recharges degraded organic carbon back to surface streams. For example, fluvial sediment is estimated to lose 30% of its organic carbon by mass during a one year temporary residence within the phreatic karst. It is recommended that scientists consider karst pathways when attempting to estimate organic matter stocks and carbon transformation in fluvial networks.

Inclusion of Ti and Zr species on clay surfaces and their effect on the interaction with organic molecules

NASA Astrophysics Data System (ADS)

Rangel-Rivera, Pedro; Bachiller-Baeza, María Belén; Galindo-Esquivel, Ignacio; Rangel-Porras, Gustavo

2018-07-01

The interactions between the clay surface and the organic molecules play an important role in the efficient of these materials in adsorption and catalytic processes. These materials are often modified with the inclusion of other catalytic particles for the purpose of enhancing the activity. In this study, commercial clay K10 was modified with the particles inclusion of titanium and zirconium. The solid surfaces were examined by infrared spectroscopy, scanning electron microscopy (SEM) coupled to an energy-dispersive X-ray spectroscopy device (EDS), and X-ray photoelectron spectroscopy (XPS). Temperature programmed desorption of ammonia (TPD-NH3) and propan-2-ol decomposition test reaction were performed to probe the acid properties. The adsorption of acetic acid, ethanol, and propan-2-ol on the surface of each solid and their thermal stability were studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFT). Finally, these materials were used in the esterification of acetic acid with penta-1-ol. The real effect over the incorporation of titanium species and zirconium species on clay surface for interacting with the organic molecules was discussed.

Dew-worms in white nights: High latitude light constrains earthworm (Lumbricus terrestris) behaviour at the soil surface

USDA-ARS?s Scientific Manuscript database

Soil is an effective barrier to light penetration that limits the direct influence of light on belowground organisms. Variation in aboveground light conditions, however, is important to soil-dwelling animals that are periodically active on the soil surface. A prime example is the earthworm Lumbricus...

Efficacy of a Food-grade Mixture of Volatile Compounds to Reduce Salmonella Levels on Food Contact Surfaces

USDA-ARS?s Scientific Manuscript database

Introduction: Volatile organic compounds (VOCs) released from an endophytic fungus, Muscodor crispans, have been shown to have antimicrobial activity against many fungal and bacterial species. These VOCs have been synthesized into a commercial mixture called “B-23”, which may be a useful surface san...

Visible light activated TiO2/microcrystalline cellulose nanocatalyst to destroy organic contaminants in water.

EPA Science Inventory

Hybrid TiO2/microcrystalline cellulose (MC) nanophotocatalyst was prepared in situ by a facile and simple synthesis utilizing benign precursors such as MC and TiCl4. The as-prepared nanocomposite was characterized by XRD, XPS, BET surface area analyzer, UV–vis DRS and TGA. Surfac...

Dynamic pesticide removal with activated carbon fibers.

PubMed

Martín-Gullón, I; Font, R

2001-02-01

Rapid small-scale minicolumn tests were carried out to simulate the atrazine adsorption in water phase with three pelletized pitch-based activated carbon fibers (ACF) and one commercial granular activated carbon (GAC). Initial atrazine solutions were prepared with pretreated ground water. Minicolumn tests showed that the performance of highly activated carbon fibers (surface area of 1700 m2/g) is around 7 times better than the commercial GAC (with surface area at around 1100 m2/g), whereas carbon fibers with medium activation degree (surface area of 1500 m2/g) had a removal efficiency worse than the commercial carbon. The high removal efficiency of the highly activated ACF is due to the wide-opened microstructure of the material, with an appreciable contribution of the low size mesopores, maintaining at these conditions a fast kinetic adsorption rate rather than a selective adsorbent for micropollutants vs. natural organic matter.

Optical properties of chromophoric dissolved organic matter (CDOM) in surface and pore waters adjacent to an oil well in a southern California salt marsh.

PubMed

Bowen, Jennifer C; Clark, Catherine D; Keller, Jason K; De Bruyn, Warren J

2017-01-15

Chromophoric dissolved organic matter (CDOM) optical properties were measured in surface and pore waters as a function of depth and distance from an oil well in a southern California salt marsh. Higher fluorescence and absorbances in pore vs. surface waters suggest soil pore water is a reservoir of CDOM in the marsh. Protein-like fluorophores in pore waters at distinct depths corresponded to variations in sulfate depletion and Fe(II) concentrations from anaerobic microbial activity. These variations were supported by fluorescence indexes and are consistent with differences in optical molecular weight and aromaticity indicators. Fluorescence indices were consistent with autochthonous material of aquatic origin in surface waters, with more terrestrial, humified allochthonous material in deeper pore waters. CDOM optical properties were consistent with significantly enhanced microbial activity in regions closest to the oil well, along with a three-dimensional excitation/emission matrix fluorescence spectrum peak attributable to oil, suggesting anaerobic microbial degradation of oil. Copyright © 2016 Elsevier Ltd. All rights reserved.

Microbial community responses in forest mineral soil to compaction, organic matter removal, and vegetation control

Treesearch

Matt D. Busse; Samual E. Beattie; Robert F. Powers; Felipe G. Sanchez; Allan E. Tiarks

2006-01-01

We tested three disturbance hypotheses in young conifer plantations: H1: soil compaction and removal of surface organic matter produces sustained changes in microbial community size, activity, and structure in mineral soil; H2: microbial community characteristics in mineral soil are linked to the recovery of plant diversity...

Study on detection of terrestrial and marine fractions in marine organic molecules by spectrophoto- and spectrofluorometric methods

NASA Astrophysics Data System (ADS)

Drozdowska, Violetta; Wróbel, Iwona; Piskozub, Jacek

2017-04-01

The sea surface is a highly productive and active interface between the sea and the atmosphere. Sea surface films are created by organic matter from sea and land sources and they dissipate due to loss of material at the sea surface, including microbial degradation, chemical and photo chemical processes, and loss due to absorption and adsorption onto particulates. However the surface microlayer is almost ubiquitous and cover most of the surface of the ocean, even under conditions of high turbulence. Surface active molecules (surfactants) present in the surface microlayer (SML) may modify the number of physical processes taking place there: among others they affect the depth of penetration of solar radiation and gas exchange. Therefore, research on the influence of surfactants on the sea surface properties become an important task, especially in coastal waters and in vicinity of the river mouths. Surfactants comprises a mixture of organic molecules rich in lipids, polymeric and humus whose proportions determine the various properties of the SML. A unique structure of the energy levels of the organic molecules results in a unique spectral distribution of the light intensity absorbed and emitted by the molecules. Hence, the absorption and fluorescence spectra of organic compounds may allow the identification of the sources of organic matter. Additionally, several absorption (E2:E3, S, SR) and fluorescence (fluorescence intensities at peaks: A, C, M, T, the ratio (M+T)/(A+C), HIX) indices help in describing the changes in molecular size and weight as well as composition of organic matter during the humification processes and caused by photobleaching and biodegradation. Investigations included the region of Gulf of Gdańsk, along a transect from the Vistula River outlet to open sea. The fluorescence and absorption measurements of the samples collected from a surface films and a subsurface layer (SS, a depth of 1 m) during three research cruises in Gulf of Gdańsk, the Baltic Sea, as well as hydrophysical studies and meteorological observations allowed to assess (i) the contribution of two terrestrial components (A and C) decreased with increasing salinity ( 1.64% and 1.89 % in SML and 0.78 and 0.71 % in SS, respectively), while the contribution of, in-situ, in the sea produced components (M and T) increased with salinity ( 0.52% and 2.83% in SML and 0.98% and 1.87 % in SS, respectively), (ii) the biggest relative changes of the FDOM component composition, along the transect from the Vistula River outlet to Gdańsk Deep, were recorded for component T, both in SML and SS (about 18.5 % and 12.3 %, respectively), (iii) the ratio E2:E3 points to discrete changes in molecular weight/size, effected by photobleaching, while (iv) HIX index reflects the humification/condensation processes more sensitively and effectively in SS. The organic molecules included in the SML can specifically modify the physical processes associated with the sea surface microlayers. It should be necessary to continue a study on the physical properties of surface microlayer in the future, especially in less urbanized and more natural and pristine region, like Arctic.

Nanoscale observation of organic thin film by atomic force microscopy

NASA Astrophysics Data System (ADS)

Mochizuki, Shota; Uruma, Takeshi; Satoh, Nobuo; Saravanan, Shanmugam; Soga, Tetsuo

2017-08-01

Organic photovoltaics (OPVs) fabricated using organic semiconductors and hybrid solar cells (HSCs) based on organic semiconductors/quantum dots (QDs) have been attracting significant attention owing to their potential use in low-cost solar energy-harvesting applications and flexible, light-weight, colorful, large-area devices. In this study, we observed and evaluated the surface of a photoelectric conversion layer (active layer) of the OPVs and HSCs based on phenyl-C61-butyric acid methyl ester (PCBM), poly(3-hexylthiophene) (P3HT), and zinc oxide (ZnO) nanoparticles. The experiment was performed using atomic force microscopy (AFM) combined with a frequency modulation detector (FM detector) and a contact potential difference (CPD) detection circuit. We experimentally confirmed the changes in film thickness and surface potential, as affected by the ZnO nanoparticle concentration. From the experimental results, we confirmed that ZnO nanoparticles possibly affect the structures of PCBM and P3HT. Also, we prepared an energy band diagram on the basis of the observation results, and analyzed the energy distribution inside the active layer.

Unveiling the composite structures of emissive consolidated p-i-n junction nanocells for white light emission.

PubMed

Lee, Kyu Seung; Shim, Jaeho; Lee, Hyunbok; Yim, Sang-Youp; Angadi, Basavaraj; Lim, Byungkwon; Son, Dong Ick

2018-06-08

Hybrid organic-Red-Green-Blue (RGB) color quantum dots were incorporated into consolidated p(polymer)-i(RGB quantum dots)-n(small molecules) junction structures to fabricate a single active layer for a light emitting diode device for white electroluminescence. The semiconductor RGB quantum dots, as an intrinsic material, were electrostatically bonded between functional groups of the p-type polymer organic material core surface and the n-type small molecular organic material shell surface. The ZnCdSe/ZnS and CdSe/ZnS quantum dots distributed uniformly and isotropically surrounding the polymer core which in turn was surrounded by small molecular organic materials. In the present study, we have identified the mechanisms of chemical synthesis and interactions of the p-i-n junction nanocell structure through modeling studies by DFT calculations. We have also investigated optical, structural and electrical properties along with the carrier transport mechanism of the light emitting diodes which have a single active layer of consolidated p-i-n junction nanocells for white electroluminescence.

Compositions and sorptive properties of crop residue-derived chars

USGS Publications Warehouse

Chun, Y.; Sheng, G.; Chiou, G.T.; Xing, B.

2004-01-01

Chars originating from the burning or pyrolysis of vegetation may significantly sorb neutral organic contaminants (NOCs). To evaluate the relationship between the char composition and NOC sorption, a series of char samples were generated by pyrolyzing a wheat residue (Triticum aestivum L) for 6 h at temperatures between 300 ??C and 700 ??C and analyzed for their elemental compositions, surface areas, and surface functional groups. The samples were then studied for their abilities to sorb benzene and nitrobenzene from water. A commercial activated carbon was used as a reference carbonaceous sample. The char samples produced at high pyrolytic temperatures (500-700 ??C) were well carbonized and exhibited a relatively high surface area (>300 m2/g), little organic matter (20% oxygen). The char samples exhibited a significant range of surface acidity/basicity because of their different surface polar-group contents, as characterized by the Boehm titration data and the NMR and FTIR spectra. The NOC sorption by high-temperature chars occurred almost exclusively by surface adsorption on carbonized surfaces, whereas the sorption by low-temperature chars resulted from the surface adsorption and the concurrent smaller partition into the residual organic-matter phase. The chars appeared to have a higher surface affinity for a polar solute (nitrobenzene) than for a nonpolar solute (benzene), the difference being related to the surface acidity/basicity of the char samples.

Transplantation of transduced chondrocytes protects articular cartilage from interleukin 1-induced extracellular matrix degradation.

PubMed Central

Baragi, V M; Renkiewicz, R R; Jordan, H; Bonadio, J; Hartman, J W; Roessler, B J

1995-01-01

Gene therapy used in the context of delivering a therapeutic gene(s) to chondrocytes offers a new approach for treating chondrocyte-mediated cartilage degradation associated with various human arthropathies including osteoarthritis. In this study, gene delivery to human osteoarthritis chondrocytes in monolayer culture was demonstrated using two adenoviral vectors (Ad.CMVlacZ and Ad.RSVntlacZ) carrying the Escherichia coli beta-galactosidase marker gene, and a third vector (Ad.RSV hIL-1ra) containing the cDNA for human interleukin-1 receptor antagonist. At an moi of 10(3) plaque-forming units/chondrocyte, > 90% of the infected cells stained positive for E. coli beta-galactosidase activity, indicating a high efficiency of transduction. Genetically modified chondrocytes were then transplanted onto the articular surface of osteoarthritic cartilage organ cultures with and without the underlying subchondral bone. Both in situ staining of the cartilage organ cultures for E. coli beta-galactosidase activity and examination by scanning electron microscopy indicated that the transplanted chondrocytes adhered and integrated into the articular surface and continued to express transgenic protein. Chondrocytes transduced with Ad.RSV hIL-1ra and seeded onto the surface of osteoarthritic cartilage secreted high levels of biologically active IL-1 receptor antagonist. The Ad.RSV hIL-1ra-treated cartilage samples were resistant to IL1-induced proteoglycan degradation over 10 d of sustained organ culture. These data demonstrate that transplantation of transduced chondrocytes onto the articular surface protects cartilage from IL-1-induced extracellular matrix degradation. Images PMID:7593634

Differential contributions of archaeal ammonia oxidizer ecotypes to nitrification in coastal surface waters

PubMed Central

Smith, Jason M; Casciotti, Karen L; Chavez, Francisco P; Francis, Christopher A

2014-01-01

The occurrence of nitrification in the oceanic water column has implications extending from local effects on the structure and activity of phytoplankton communities to broader impacts on the speciation of nitrogenous nutrients and production of nitrous oxide. The ammonia-oxidizing archaea, responsible for carrying out the majority of nitrification in the sea, are present in the marine water column as two taxonomically distinct groups. Water column group A (WCA) organisms are detected at all depths, whereas Water column group B (WCB) are present primarily below the photic zone. An open question in marine biogeochemistry is whether the taxonomic definition of WCA and WCB organisms and their observed distributions correspond to distinct ecological and biogeochemical niches. We used the natural gradients in physicochemical and biological properties that upwelling establishes in surface waters to study their roles in nitrification, and how their activity—ascertained from quantification of ecotype-specific ammonia monooxygenase (amoA) genes and transcripts—varies in response to environmental fluctuations. Our results indicate a role for both ecotypes in nitrification in Monterey Bay surface waters. However, their respective contributions vary, due to their different sensitivities to surface water conditions. WCA organisms exhibited a remarkably consistent level of activity and their contribution to nitrification appears to be related to community size. WCB activity was less consistent and primarily constrained to colder, high nutrient and low chlorophyll waters. Overall, the results of our characterization yielded a strong, potentially predictive, relationship between archaeal amoA gene abundance and the rate of nitrification. PMID:24553472

The electrodeposition of multilayers on a polymeric substrate in flexible organic photovoltaic solar cells

NASA Astrophysics Data System (ADS)

Guedes, Andre F. S.; Guedes, Vilmar P.; Souza, Monica L.; Tartari, Simone; Cunha, Idaulo J.

2015-09-01

Flexible organic photovoltaic solar cells have drawn intense attention due to their advantages over competing solar cell technologies. The method utilized to deposit as well as to integrate solutions and processed materials, manufacturing organic solar cells by the Electrodeposition System, has been presented in this research. In addition, we have demonstrated a successful integration of a process for manufacturing the flexible organic solar cell prototype and we have discussed on the factors that make this process possible. The maximum process temperature was 120°C, which corresponds to the baking of the active polymeric layer. Moreover, the new process of the Electrodeposition of complementary active layer is based on the application of voltage versus time in order to obtain a homogeneous layer with thin film. This thin film was not only obtained by the electrodeposition of PANI-X1 on P3HT/PCBM Blend, but also prepared in perchloric acid solution. Furthermore, these flexible organic photovoltaic solar cells presented power conversion efficiency of 12% and the inclusion of the PANI-X1 layer reduced the effects of degradation on these organic photovoltaic panels induced by solar irradiation. Thus, in the Scanning Electron Microscopy (SEM), these studies have revealed that the surface of PANI-X1 layers is strongly conditioned by the dielectric surface morphology.

Porous carbon derived via KOH activation of a hypercrosslinked porous organic polymer for efficient CO{sub 2}, CH{sub 4}, H{sub 2} adsorptions and high CO{sub 2}/N{sub 2} selectivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Modak, Arindam; Bhaumik, Asim, E-mail: msab@iacs.res.in

2015-12-15

Microporous carbon having Brunauer-Emmett-Teller (BET) surface area of 2186 m{sup 2} g{sup −1} and micropore volume of 0.85 cm{sup 3} g{sup −1} has been synthesized via KOH induced high temperature carbonization of a non-conjugated hypercrosslinked organic polymer. Owing to the templating and activation by KOH, we have succeeded in making a microporous carbon from this porous polymer and the resultant carbon material showed high uptake for CO{sub 2} (7.6 mmol g{sup −1}) and CH{sub 4} (2.4 mmol g{sup −1}) at 1 atm, 273 K together with very good selectivity for the CO{sub 2}/N{sub 2} (30.2) separation. Furthermore, low pressure (1more » atm) H{sub 2} (2.6 wt%, 77 K) and water uptake (57.4 wt%, 298 K) ability of this polymer derived porous activated carbon is noteworthy. - Graphical abstract: Microporous carbon with BET surface area of 2186 m{sup 2} g{sup −1} has been synthesized via KOH activation of a porous organic polymer and it showed high uptake for CO{sub 2} (7.6 mmol g{sup −1}), CH{sub 4} (2.4 mmol g{sup −1}) and H{sub 2} (2.6 wt%) at 1 atm together with very good selectivity for CO{sub 2}. - Highlights: • Porous carbon from hypercrosslinked organic polymer. • KOH activated carbon with BET surface area 2186 m{sup 2} g{sup −1}. • High CO2 uptake (7.6 mmol g{sup −1}) and CO{sub 2}/N{sub 2} selectivity (30.2). • Porous carbon also showed high H{sub 2} (2.6 wt%) and H{sub 2}O (57.4 wt%) uptakes.« less

Multilevel organization in hybrid thin films for optoelectronic applications.

PubMed

Vohra, Varun; Bolognesi, Alberto; Calzaferri, Gion; Botta, Chiara

2009-10-20

In this work we report two simple approaches to prepare hybrid thin films displaying a high concentration of zeolite crystals that could be used as active layers in optoelectronic devices. In the first approach, in order to organize nanodimensional zeolite crystals of 40 nm diameter in an electroactive environment, we chemically modify their external surface and play on the hydrophilic/hydrophobic forces. We obtain inorganic nanocrystals that self-organize in honeycomb electroluminescent polymer structures obtained by breath figure formation. The different functionalizations of the zeolite surface result in different organizations inside the cavities of the polymeric structure. The second approach involving soft-litography techniques allows one to arrange single dye-loaded zeolite L crystals of 800 nm of length by mechanical loading into the nanocavities of a conjugated polymer. Both techniques result in the formation of thin hybrid films displaying three levels of organization: organization of the dye molecules inside the zeolite nanochannels, organization of the zeolite crystals inside the polymer cavities, and micro- or nanostructuration of the polymer.

Spatially resolved observation of crystal-face-dependent catalysis by single turnover counting

NASA Astrophysics Data System (ADS)

Roeffaers, Maarten B. J.; Sels, Bert F.; Uji-I, Hiroshi; de Schryver, Frans C.; Jacobs, Pierre A.; de Vos, Dirk E.; Hofkens, Johan

2006-02-01

Catalytic processes on surfaces have long been studied by probing model reactions on single-crystal metal surfaces under high vacuum conditions. Yet the vast majority of industrial heterogeneous catalysis occurs at ambient or elevated pressures using complex materials with crystal faces, edges and defects differing in their catalytic activity. Clearly, if new or improved catalysts are to be rationally designed, we require quantitative correlations between surface features and catalytic activity-ideally obtained under realistic reaction conditions. Transmission electron microscopy and scanning tunnelling microscopy have allowed in situ characterization of catalyst surfaces with atomic resolution, but are limited by the need for low-pressure conditions and conductive surfaces, respectively. Sum frequency generation spectroscopy can identify vibrations of adsorbed reactants and products in both gaseous and condensed phases, but so far lacks sensitivity down to the single molecule level. Here we adapt real-time monitoring of the chemical transformation of individual organic molecules by fluorescence microscopy to monitor reactions catalysed by crystals of a layered double hydroxide immersed in reagent solution. By using a wide field microscope, we are able to map the spatial distribution of catalytic activity over the entire crystal by counting single turnover events. We find that ester hydrolysis proceeds on the lateral {1010} crystal faces, while transesterification occurs on the entire outer crystal surface. Because the method operates at ambient temperature and pressure and in a condensed phase, it can be applied to the growing number of liquid-phase industrial organic transformations to localize catalytic activity on and in inorganic solids. An exciting opportunity is the use of probe molecules with different size and functionality, which should provide insight into shape-selective or structure-sensitive catalysis and thus help with the rational design of new or more productive heterogeneous catalysts.

Strong catalytic activity of iron nanoparticles on the surfaces of reduced olivine

NASA Astrophysics Data System (ADS)

Tucker, William C.; Quadery, Abrar H.; Schulte, Alfons; Blair, Richard G.; Kaden, William E.; Schelling, Patrick K.; Britt, Daniel T.

2018-01-01

It is demonstrated that olivine powders heated to subsolidus temperatures in reducing conditions can develop significant concentrations of 10-50 nm diameter Fe nanoparticles on grain surfaces and that these display strong catalytic activity not observed in powders without Fe nanoparticles. Reduced surfaces were exposed to NH3, CO, and H2, volatiles that may be present on the surfaces of comet and volatile-rich asteroids. In the case of NH3 exposure, rapid decomposition was observed. When exposed to a mixture of CO and H2, significant coking of the mineral surfaces occurred. Analysis of the mineral grains after reaction indicated primarily the presence of graphene or graphitic carbon. The results demonstrate that strong chemical activity can be expected at powders that contain nanophase Fe particles. This suggests space-weathered mineral surfaces may play an important role in the synthesis and processing of organic species. This processing may be part of the weathering processes of volatile-rich but atmosphereless solar-system bodies.

Sequential Reactions of Surface-Tethered Glycolytic Enzymes

PubMed Central

Mukai, Chinatsu; Bergkvist, Magnus; Nelson, Jacquelyn L.; Travis, Alexander J.

2014-01-01

SUMMARY The development of complex hybrid organic-inorganic devices faces several challenges, including how they can generate energy. Cells face similar challenges regarding local energy production. Mammalian sperm solve this problem by generating ATP down the flagellar principal piece by means of glycolytic enzymes, several of which are tethered to a cytoskeletal support via germ cell-specific targeting domains. Inspired by this design, we have produced recombinant hexokinase type 1 and glucose-6-phosphate isomerase capable of oriented immobilization on a nickel-nitrilotriacetic acid modified surface. Specific activities of enzymes tethered via this strategy were substantially higher than when randomly adsorbed. Furthermore, these enzymes showed sequential activities when tethered onto the same surface. This is the first demonstration of surface-tethered pathway components showing sequential enzymatic activities, and it provides a first step toward reconstitution of glycolysis on engineered hybrid devices. PMID:19778729

Correlation between Surface Tension and Water Activity in New Particle Formation

NASA Astrophysics Data System (ADS)

Daskalakis, E.; Salameh, A.

2016-12-01

The impact of aerosol properties on cloud dynamics and the radiative balance of the atmosphere relies on the parametrizations of cloud droplet formation. Such parametrization is based on equilibrium thermodynamics proposed by Köhler in 1936. There is considerable debate in the literature on the importance of factors like the surface tension depression or the water activity decrease for the correct parametrization. To gain fundamental insight into New Particle Formation (NPF), or Cloud Condensation Nuclei (CCN) activation one has to study microscopic properties of aqueous droplets, involving surface and bulk dynamics. The surface tension of droplets can be associated with the effects from Organic Matter (OM), whereas the static dielectric constant of water reflects the structure and dynamics of ions within solutions and can present a measure of water activity. In this study we employ Molecular Dynamics Simulations on aquatic droplets that contain surface active OM (acetaldehyde, methylglyoxal) and salts. We give insight into the dynamics of aquatic droplets with radials of 3.6nm at a level of detail that is not accessible experimentally (J. Phys. Chem. C 2016, 120:11508). We propose that as the surface tension of an aquatic droplet is decreased in the presence of surface-active OM, the water activity is affected as well. This is due to the fact that the water dipoles are oriented based on the salt morphology within the droplet. We suggest that the surface tension depression can be accompanied by the water activity change. This can be associated with the possible effects of surface-active species in terms of salt morphology transitions within an aerosol at the NPF and early particle growth time scales. Based on this study, surface-active OM seems important in controlling (a) the salt morphology transitions within a nucleus during NPF and particle growth and (b) a correlation between surface activity and water activity of ionic aquatic droplets. The latter correlation could be a fundamental property to consider when assessing NPF and the Köhler theory.

Monte-Carlo modelling of nano-material photocatalysis: bridging photocatalytic activity and microscopic charge kinetics.

PubMed

Liu, Baoshun

2016-04-28

In photocatalysis, it is known that light intensity, organic concentration, and temperature affect the photocatalytic activity by changing the microscopic kinetics of holes and electrons. However, how the microscopic kinetics of holes and electrons relates to the photocatalytic activity was not well known. In the present research, we developed a Monte-Carlo random walking model that involved all of the charge kinetics, including the photo-generation, the recombination, the transport, and the interfacial transfer of holes and electrons, to simulate the overall photocatalytic reaction, which we called a "computer experiment" of photocatalysis. By using this model, we simulated the effect of light intensity, temperature, and organic surface coverage on the photocatalytic activity and the density of the free electrons that accumulate in the simulated system. It was seen that the increase of light intensity increases the electron density and its mobility, which increases the probability for a hole/electron to find an electron/hole for recombination, and consequently led to an apparent kinetics that the quantum yield (QY) decreases with the increase of light intensity. It was also seen that the increase of organic surface coverage could increase the rate of hole interfacial transfer and result in the decrease of the probability for an electron to recombine with a hole. Moreover, the increase of organic coverage on the nano-material surface can also increase the accumulation of electrons, which enhances the mobility for electrons to undergo interfacial transfer, and finally leads to the increase of photocatalytic activity. The simulation showed that the temperature had a more complicated effect, as it can simultaneously change the activation of electrons, the interfacial transfer of holes, and the interfacial transfer of electrons. It was shown that the interfacial transfer of holes might play a main role at low temperature, with the temperature-dependence of QY conforming to the Arrhenius model. The activation of electrons from the traps to the conduction band might become important at high temperature, which accelerates the electron movement for recombination and leads to a temperature dependence of QY that deviates from the Arrhenius model.

Tracing organic matter composition and distribution and its role on arsenic release in shallow Cambodian groundwaters

NASA Astrophysics Data System (ADS)

Lawson, Michael; Polya, David A.; Boyce, Adrian J.; Bryant, Charlotte; Ballentine, Christopher J.

2016-04-01

Biogeochemical processes that utilize dissolved organic carbon are widely thought to be responsible for the liberation of arsenic from sediments to shallow groundwater in south and southeast Asia. The accumulation of this known carcinogen to hazardously high concentrations has occurred in the primary source of drinking water in large parts of densely populated countries in this region. Both surface and sedimentary sources of organic matter have been suggested to contribute dissolved organic carbon in these aquifers. However, identification of the source of organic carbon responsible for driving arsenic release remains enigmatic and even controversial. Here, we provide the most extensive interrogation to date of the isotopic signature of ground and surface waters at a known arsenic hotspot in Cambodia. We present tritium and radiocarbon data that demonstrates that recharge through ponds and/or clay windows can transport young, surface derived organic matter into groundwater to depths of 44 m under natural flow conditions. Young organic matter dominates the dissolved organic carbon pool in groundwater that is in close proximity to these surface water sources and we suggest this is likely a regional relationship. In locations distal to surface water contact, dissolved organic carbon represents a mixture of both young surface and older sedimentary derived organic matter. Ground-surface water interaction therefore strongly influences the average dissolved organic carbon age and how this is distributed spatially across the field site. Arsenic mobilization rates appear to be controlled by the age of dissolved organic matter present in these groundwaters. Arsenic concentrations in shallow groundwaters (<20 m) increase by 1 μg/l for every year increase in dissolved organic carbon age compared to only 0.25 μg/l for every year increase in dissolved organic carbon age in deeper (>20 m) groundwaters. We suggest that, while the rate of arsenic release is greatest in shallow aquifer sediments, arsenic release also occurs in deeper aquifer sediments and as such remains an important process in controlling the spatial distribution of arsenic in the groundwaters of SE Asia. Our findings suggest that any anthropogenic activities that alter the source of groundwater recharge or the timescales over which recharge takes place may also drive changes in the natural composition of dissolved organic carbon in these groundwaters. Such changes have the potential to influence both the spatial and temporal evolution of the current groundwater arsenic hazard in this region.

A Colloidal Route to Detection of Organic Molecules Based on Surface-Enhanced Raman Spectroscopy Using Nanostructured Substrate Derived from Aerosols

NASA Astrophysics Data System (ADS)

Gen, Masao; Kakuta, Hideo; Kamimoto, Yoshihito; Wuled Lenggoro, I.

2011-06-01

A detection method based on the surface-enhanced Raman spectroscopy (SERS)-active substrate derived from aerosol nanoparticles and a colloidal suspension for detecting organic molecules of a model analyte (a pesticide) is proposed. This approach can detect the molecules of the derived from its solution with the concentration levels of ppb. For substrate fabrication, a gas-phase method is used to directly deposit Ag nanoparticles on to a silicon substrate having pyramidal structures. By mixing the target analyte with a suspension of Ag colloids purchased in advance, clotianidin analyte on Ag colloid can exist in junctions of co-aggregated Ag colloids. Using (i) a nanostructured substrate made from aerosol nanoparticles and (ii) colloidal suspension can increase the number of activity spots.

Warming Effects on Enzyme Activities are Predominant in Sub-surface Soils of an Arctic Tundra Ecosystem over 6-Year Field Manipulation

NASA Astrophysics Data System (ADS)

Kang, H.; Seo, J.; Kim, M.; Jung, J. Y.; Lee, Y. K.

2017-12-01

Arctic tundra ecosystems are of great importance because they store a large amount of carbon as un-decomposed organic matter. Global climate change is expected to affect enzyme activities and heterotrophic respiration in Arctic soils, which may accelerate greenhouse gas (GHG) emission through positive biological feedbacks. Unlike laboratory-based incubation experiments, field measurements often show different warming effects on decomposition of organic carbon and releases of GHGs. In the present study, we conducted a field-based warming experiment in Cambridge Bay, Canada (69°07'48″N, 105°03'36″W) by employing passive chambers during growing seasons over 6 years. A suite of enzyme activities (ß-glucosidase, cellobiohydrolase, N-acetylglucosaminidase, leucine aminopeptidase and phenol oxidase), microbial community structure (NGS), microbial abundances (gene copy numbers of bacteria and fungi), and soil chemical properties have been monitored in two depths (0-5 cm and 5-10 cm) of tundra soils, which were exposed to four different treatments (`control', `warming-only', `water-addition only', and both `warming and water-addition'). Phenol oxidase activity increased substantially, and bacterial community structure and abundance changed in the early stage (after 1 year's warming manipulation), but these changes disappeared afterwards. Most hydrolases were enhanced in surface soils by `water-addition only' over the period. However, the long-term effects of warming appeared in sub-surface soils where both `warming only' and `warming and water addition' increased hydrolase activities. Overall results of this study indicate that the warming effects on enzyme activities in surface soils are only short-term (phenol oxidase) or masked by water-limitation (hydrolases). However, hydrolases activities in sub-surface soils are more strongly enhanced than surface soils by warming, probably due to the lack of water limitation. Meanwhile, negative correlations between hydrolase activities and humic fraction of DOC appeared following the sudden increase in phenol oxidase after 1 year's manipulation, suggesting that `enzyme latch' hypothesis is partially responsible for the control of hydrolases in the ecosystem.

Enhancement of room temperature ferromagnetism in tin oxide nanocrystal using organic solvents

NASA Astrophysics Data System (ADS)

Sakthiraj, K.; Hema, M.; Balachandra Kumar, K.

2017-10-01

The effect of organic solvents (ethanol & ethylene glycol) on the room temperature ferromagnetism in nanocrystalline tin oxide has been studied. The samples were synthesized using sol-gel method with the mixture of water & organic liquid as solvent. It is found that pristine SnO2 nanocrystal contain two different types of paramagnetic centres over their surface:(i) surface chemisorbed oxygen species and (ii) Sn interstitial & oxygen vacancy defect pair. The magnetic moment induced in the as-prepared samples is mainly contributed by the alignment of local spin moments resulting from these defects. These surface defect states are highly activated by the usage of ethylene glycol solvent rather than ethylene in tin oxide nanostructure synthesis. Powder X-ray diffraction, transmission electron microscope imaging, energy dispersive spectrometry, Fourier transformed infrared spectroscopy, UV-vis absorption spectroscopy, photoluminescence spectroscopy, vibrating sample magnetometer measurement and electron spin resonance spectroscopy were employed to characterize the nanostructured tin oxide materials.

Light-dependent microbial metabolisms drive carbon fluxes on glacier surfaces.

PubMed

Franzetti, Andrea; Tagliaferri, Ilario; Gandolfi, Isabella; Bestetti, Giuseppina; Minora, Umberto; Mayer, Christoph; Azzoni, Roberto S; Diolaiuti, Guglielmina; Smiraglia, Claudio; Ambrosini, Roberto

2016-12-01

Biological processes on glacier surfaces affect glacier reflectance, influence surface energy budget and glacier response to climate warming, and determine glacier carbon exchange with the atmosphere. Currently, carbon balance of supraglacial environment is assessed as the balance between the activity of oxygenic phototrophs and the respiration rate of heterotrophic organisms. Here we present a metagenomic analysis of tiny wind-blown supraglacial sediment (cryoconite) from Baltoro (Pakistani Karakoram) and Forni (Italian Alps) glaciers, providing evidence for the occurrence in these environments of different and previously neglected metabolic pathways. Indeed, we observed high abundance of heterotrophic anoxygenic phototrophs, suggesting that light might directly supplement the energy demand of some bacterial strains allowing them to use as carbon source organic molecules, which otherwise would be respired. Furthermore, data suggest that CO 2 could be produced also by microbiologically mediated oxidation of CO, which may be produced by photodegradation of organic matter.

α-Enolase Causes Proinflammatory Activation of Pulmonary Microvascular Endothelial Cells and Primes Neutrophils Through Plasmin Activation of Protease-Activated Receptor 2.

PubMed

Bock, Ashley; Tucker, Nicole; Kelher, Marguerite R; Khan, Samina Y; Gonzalez, Eduardo; Wohlauer, Max; Hansen, Kirk; Dzieciatkowska, Monika; Sauaia, Angels; Banerjee, Anirban; Moore, Ernest E; Silliman, Christopher C

2015-08-01

Proinflammatory activation of vascular endothelium leading to increased surface expression of adhesion molecules and neutrophil (PMN) sequestration and subsequent activation is paramount in the development of acute lung injury and organ injury in injured patients. We hypothesize that α-enolase, which accumulates in injured patients, primes PMNs and causes proinflammatory activation of endothelial cells leading to PMN-mediated cytotoxicity. Proteomic analyses of field plasma samples from injured versus healthy patients were used for protein identification. Human pulmonary microvascular endothelial cells (HMVECs) were incubated with α-enolase or thrombin, and intercellular adhesion molecule-1 surface expression was measured by flow cytometry. A two-event in vitro model of PMN cytotoxicity HMVECs activated with α-enolase, thrombin, or buffer was used as targets for lysophosphatidylcholine-primed or buffer-treated PMNs. The PMN priming activity of α-enolase was completed, and lysates from both PMNs and HMVECs were immunoblotted for protease-activated receptor 1 (PAR-1) and PAR-2 and coprecipitation of α-enolase with PAR-2 and plasminogen/plasmin. α-Enolase increased 10.8-fold in injured patients (P < 0.05). Thrombin and α-enolase significantly increased intercellular adhesion molecule-1 surface expression on HMVECs, which was inhibited by antiproteases, induced PMN adherence, and served as the first event in the two-event model of PMN cytotoxicity. α-Enolase coprecipitated with PAR-2 and plasminogen/plasmin on HMVECs and PMNs and induced PMN priming, which was inhibited by tranexamic acid, and enzymatic activity was not required. α-Enolase increases after injury and may activate pulmonary endothelial cells and prime PMNs through plasmin activity and PAR-2 activation. Such proinflammatory endothelial activation may predispose to PMN-mediated organ injury.

Rapid and enhanced activation of microporous coordination polymers by flowing supercritical CO.sub.2

DOEpatents

Matzger, Adam J.; Liu, Baojian; Wong-Foy, Antek G.

2016-07-19

Flowing supercritical CO.sub.2 is used to activate metal organic framework materials (MOF). MOFs are activated directly from N,N-dimethylformamide (DMF) thus avoiding exchange with a volatile solvent. Most MCPs display increased surface areas directly after treatment although those with coordinatively unsaturated metal centers benefit from additional heating.

The role of beaded activated carbon's surface oxygen groups on irreversible adsorption of organic vapors.

PubMed

Jahandar Lashaki, Masoud; Atkinson, John D; Hashisho, Zaher; Phillips, John H; Anderson, James E; Nichols, Mark

2016-11-05

The objective of this study is to determine the contribution of surface oxygen groups to irreversible adsorption (aka heel formation) during cyclic adsorption/regeneration of organic vapors commonly found in industrial systems, including vehicle-painting operations. For this purpose, three chemically modified activated carbon samples, including two oxygen-deficient (hydrogen-treated and heat-treated) and one oxygen-rich sample (nitric acid-treated) were prepared. The samples were tested for 5 adsorption/regeneration cycles using a mixture of nine organic compounds. For the different samples, mass balance cumulative heel was 14 and 20% higher for oxygen functionalized and hydrogen-treated samples, respectively, relative to heat-treated sample. Thermal analysis results showed heel formation due to physisorption for the oxygen-deficient samples, and weakened physisorption combined with chemisorption for the oxygen-rich sample. Chemisorption was attributed to consumption of surface oxygen groups by adsorbed species, resulting in formation of high boiling point oxidation byproducts or bonding between the adsorbates and the surface groups. Pore size distributions indicated that different pore sizes contributed to heel formation - narrow micropores (<7Å) in the oxygen-deficient samples and midsize micropores (7-12Å) in the oxygen-rich sample. The results from this study help explain the heel formation mechanism and how it relates to chemically tailored adsorbent materials. Copyright © 2016 Elsevier B.V. All rights reserved.

Comparative study on the process behavior and reaction kinetics in sonocatalytic degradation of organic dyes by powder and nanotubes TiO2.

PubMed

Pang, Yean Ling; Abdullah, Ahmad Zuhairi

2012-05-01

Sonocatalytic degradation of various organic dyes (Congo Red, Reactive Blue 4, Methyl Orange, Rhodamine B and Methylene Blue) catalyzed by powder and nanotubes TiO(2) was studied. Both catalysts were characterized using transmission electron microscope (TEM), surface analyzer, Raman spectroscope and thermal gravimetric analyzer (TGA). Sonocatalytic activity of powder and nanotubes TiO(2) was elucidated based on the degradation of various organic dyes. The former catalyst was favorable for treatment of anionic dyes, while the latter was more beneficial for cationic dyes. Sonocatalytic activity of TiO(2) nanotubes could be up to four times as compared to TiO(2) powder under an ultrasonic power of 100 W and a frequency of 42 kHz. This was associated with the higher surface area and the electrostatic attraction between dye molecules and TiO(2) nanotubes. Fourier transform-infrared spectrometer (FT-IR) was used to identify changes that occurred on the functional group in Rhodamine B molecules and TiO(2) nanotubes after the reaction. Sonocatalytic degradation of Rhodamine B by TiO(2) nanotubes apparently followed the Langmuir-Hinshelwood adsorption kinetic model with surface reaction rate of 1.75 mg/L min. TiO(2) nanotubes were proven for their high potential to be applied in sonocatalytic degradation of organic dyes. Copyright © 2011 Elsevier B.V. All rights reserved.

Detection of semi-volatile organic compounds (SVOCs) in surface water, soil, and groundwater in a chemical industrial park in Eastern China.

PubMed

Liu, Benhua; Li, Yuehua; Ma, Jianfeng; Huang, Linxian; Chen, Liang

2016-01-01

China is suffering from serious water and soil pollution, especially in the North China Plain. This work investigated semi-volatile organic compounds (SVOCs) in surface water, groundwater and soil within a chemical industrial park in Eastern China, for which the volatile organic compound (VOC) results have been previously reported. A total of 20 samples were collected from the field, and analyzed in the laboratory. A 100% detection frequency of SVOCs in samples from this chemical industrial park was observed (same as VOCs). Moreover, the detection frequency of 113 SVOCs in each sample reached 15.93, 12.39 and 20.35% for surface water, groundwater and soil, respectively. The most detected SVOCs in the park included N-containing SVOCs, polycyclic aromatic hydrocarbons, phthalates, organic pesticides and polychlorodiphenyls. The elevated detecting frequencies and concentration levels of SVOCs identified in the groundwater were attributed to the intensive chemical production activities in the park. In addition, the agricultural activities in the area might also have contributed to the SVOCs to the groundwater. The results of VOCs and SVOCs from this and previous studies suggest that the groundwater in this industrial park has been severely contaminated, and the contamination likely spreads beyond the park. Imminent hydrogeological assessments and remedial actions are warranted to eliminate the source and mitigate the potential plume expansion beyond the park boundary.

Effects of Enhanced Thaw Depth on the Composition of Arctic Soil Organic Matter Leachate

NASA Astrophysics Data System (ADS)

Hutchings, J.; Zhang, X.; Bianchi, T. S.; Schuur, E.; Arellano, A. R.; Liu, Y.

2016-12-01

Pan-Arctic permafrost is increasingly susceptible to thaw due to the disproportionally high rate of temperature change in high latitudes. These soils contain a globally significant quantity of organic carbon that, when thawed, interacts with the modern carbon cycle. Current research has focused on atmospheric carbon fluxes and transport by rivers and streams to continental shelves, but has overlooked the lateral flux of carbon within watershed soils, which is the primary link between terrestrial and riverine ecosystems. Understanding the effects of water movement through permafrost soils on dissolved organic carbon is critical to better modelling of lateral carbon fluxes and interpreting the resulting observed riverine carbon fluxes with applications to investigations of the past, present, and future of the pan-Arctic. We conducted a laboratory leaching experiment using active layer soils from the Eight Mile Lake region of interior Alaska. Cores were sampled into surface and deep sections. Surface sections were subjected to a three-stage leaching process using artificial rain, with cores stored frozen overnight between stages (which crudely simulated freeze-thaw mechanisms). Surface leachates were sampled for analysis and the remainder percolated through deep soils using the same three-staged approach. Measurements of surface and deep leachates were selected to characterize transport-related changes to dissolved organic matter and included dissolved organic carbon, fluorescent dissolved organic matter via excitation emission matrices, and molecular composition via Fourier transform ion cyclotron resonance mass spectrometry. Primary findings from the experiment include a net retention of 2.4 to 27% of dissolved organic carbon from surface leachates in deep soils, a net release of fluorescent dissolved organic matter from deep soils that was 43 to 106% greater than surface leachates, increased hydrophobicity during stage three of leaching, and the preferential leaching of lignin- and tannin-like formulas from deep soils, consistent with fluorescence measurements.

The astrobiology of Titan

NASA Astrophysics Data System (ADS)

Raulin, F.; Coll, P.; Cabane, M.; Hebrard, E.; Israel, G.; Nguyen, M.-J.; Szopa, C.; Gpcos Team

Largest satellite of Saturn and the only satellite in the solar system having a dense atmosphere, Titan is one of the key planetary bodies for astrobiological studies, due to several aspects: Its analogies with planet Earth, in spite of much lower temperatures, The Cassini-Huygens data have largely confirmed the many analogies between Titan and our own planet. Both have similar vertical temperature profiles, (although much colder, of course, on Titan). Both have condensable and non condensable greenhouse gases in their atmosphere. Both are geologically very active. Furthermore, the data also suggest strongly the presence of a methane cycle on Titan analogous to the water cycle on Earth. The presence of an active organic chemistry, involving several of the key compounds of prebiotic chemistry. The recent data obtained from the Huygens instruments show that the organic matter in Titan low atmosphere (stratosphere and troposphere) is mainly concentrated in the aerosol particles. Because of the vertical temperature profile in this part of the atmosphere, most of the volatile organics are probably mainly condensed on the aerosol particles. The nucleus of these particles seems to be made of complex macromolecular organic matter, well mimicked in the laboratory by the "Titan's tholins". Now, laboratory tholins are known to release many organic compounds of biological interest, such as amino acids and purine and pyrimidine bases, when they are in contact with liquid water. Such hydrolysis may have occurred on the surface of Titan, in the bodies of liquid water which episodically may form on Titan's surface from meteoritic and cometary impacts. The formation of biologically interesting compounds may also occur in the deep water ocean, from the hydrolysis of complex organic material included in the chrondritic matter accreted during the formation of Titan. The possible emergence and persistence of Life on Titan 1 All ingredients which seems necessary for Life are present on Titan : • liquid water : permanently as a deep sub-surface ocean, and even episodically on the surface, • organic matter : in the internal structure, from chondritic materials, and in the atmosphere and on the surface, from the atmospheric organic chemistry • and energy : in the atmosphere (solar UV photons, energetic electrons from Saturn magnetosphere and cosmic rays) and, probably, in the environment of the sub-surface ocean (radioactive nuclei in the deep interior and tidal energy dissipation) as also supported by the likely presence of cryovolcanism on the surface Thus, it cannot be excluded that life may have emerged on or in Titan. In spite of the extreme conditions in this environment life may have been able to adapt and to persist. Many data are still expected from the Cassini-Huygens mission and future astrobiological exploration mission of Titan are now under consideration. Nevertheless, Titan already looks like another word, with an active prebiotic-like chemistry, but in the absence of permanent liquid water, on the surface: a natural laboratory for prebiotic-like chemistry. References. Fortes, A.D. (2000), `Exobiological implications of a possible ammonia-water ocean inside Titan', Icarus 146, 444-452 Raulin, F. (2005), `Exo-Astrobiological Aspects of Europa and Titan: From Observations to Speculations', Space Science Review 116 (1-2), 471-496. Nature, (2005), `The Huygens probe on Titan', 8 News & Views, Articles and Letters 438, 756-802 Schulze-Makuch, D., and Grinspoon D.H. (2005), `Biologically enhanced energy and carbon cycling on Titan?',Astrobiology 5, 560-567. 2

Probing the energetics of organic–nanoparticle interactions of ethanol on calcite

PubMed Central

Wu, Di; Navrotsky, Alexandra

2015-01-01

Knowing the nature of interactions between small organic molecules and surfaces of nanoparticles (NP) is crucial for fundamental understanding of natural phenomena and engineering processes. Herein, we report direct adsorption enthalpy measurement of ethanol on a series of calcite nanocrystals, with the aim of mimicking organic–NP interactions in various environments. The energetics suggests a spectrum of adsorption events as a function of coverage: strongest initial chemisorption on active sites on fresh calcite surfaces, followed by major chemical binding to form an ethanol monolayer and, subsequently, very weak, near-zero energy, physisorption. These thermochemical observations directly support a structure where the ethanol monolayer is bonded to the calcite surface through its polar hydroxyl group, leaving the hydrophobic ends of the ethanol molecules to interact only weakly with the next layer of adsorbing ethanol and resulting in a spatial gap with low ethanol density between the monolayer and subsequent added ethanol molecules, as predicted by molecular dynamics and density functional calculations. Such an ordered assembly of ethanol on calcite NP is analogous to, although less strongly bonded than, a capping layer of organics intentionally introduced during NP synthesis, and suggests a continuous variation of surface structure depending on molecular chemistry, ranging from largely disordered surface layers to ordered layers that nevertheless are mobile and can rearrange or be displaced by other molecules to strongly bonded immobile organic capping layers. These differences in surface structure will affect chemical reactions, including the further nucleation and growth of nanocrystals on organic ligand-capped surfaces. PMID:25870281

Surface dynamics and mechanics in liquid crystal polymer coatings

NASA Astrophysics Data System (ADS)

Liu, Danqing; Broer, Dirk J.

2015-03-01

Based on liquid crystal networks we developed `smart' coatings with responsive surface topographies. Either by prepatterning or by the formation of self-organized structures they can be switched on and off in a pre-designed manner. Here we provide an overview of our methods to generate coatings that form surface structures upon the actuation by light. The coating oscillates between a flat surface and a surface with pre-designed 3D micro-patterns by modulating a light source. With recent developments in solid state lighting, light is an attractive trigger medium as it can be integrated in a device for local control or can be used remotely for flood or localized exposure. The basic principle of formation of surface topographies is based on the change of molecular organization in ordered liquid crystal polymer networks. The change in order leads to anisotropic dimensional changes with contraction along the director and expansion to the two perpendicular directions and an increase in volume by the formation of free volume. These two effects work in concert to provide local expansion and contraction in the coating steered by the local direction of molecular orientation. The surface deformation, expressed as the height difference between the activated regions and the non-activated regions divided by the initial film thickness, is of the order of 20%. Switching occurs immediately when the light is switched `on' and `off' and takes several tens of seconds.

Effects of surface active agents on DNAPL migration and distribution in saturated porous media.

PubMed

Cheng, Zhou; Gao, Bin; Xu, Hongxia; Sun, Yuanyuan; Shi, Xiaoqing; Wu, Jichun

2016-11-15

Dissolved surface active agents such as surfactant and natural organic matter can affect the distribution and fate of dense nonaqueous liquids (DNAPLs) in soil and groundwater systems. This work investigated how two common groundwater surface active agents, humic acid (HA) and Tween 80, affected tetrachloroethylene (PCE) migration and source zone architecture in saturated porous media under environmentally relevant conditions. Batch experiments were first conducted to measure the contact angles and interfacial tensions (IFT) between PCE and quartz surface in water containing different amount of surface active agents. Results showed that the contact angle increased and IFT decreased with concentration of surface active agent increasing, and Tween 80 was much more effective than HA. Five 2-D flow cell experiments were then conducted. Correspondingly, Tween 80 showed strong effects on the migration and distribution of PCE in the porous media due to its ability to change the medium wettability from water-wet into intermediate/NAPL-wet. The downward migration velocities of the PCE in three Tween 80 cells were slower than those in the other two cells. In addition, the final saturation of the PCE in the cells containing surface active agents was higher than that in the water-only cell. Results from this work indicate that the presence of surface active agents in groundwater may strongly affect the fate and distribution of DNAPL through altering porous medium wettability. Copyright © 2016 Elsevier B.V. All rights reserved.

Engineering interfacial properties of organic semiconductors through soft-contact lamination and surface functionalization

NASA Astrophysics Data System (ADS)

Shu, Andrew Leo

Organic electronics is a topic of interest due to its potential for low temperature and solution processing for large area and flexible applications. Examples of organic electronic devices are already available on the market; however these are, in general, still rather expensive. In order to fully realize inexpensive and efficient organic electronics, the properties of organic films need to be understood and strategies developed to take advantage of these properties to improve device performance. This work focuses on two strategies that can be used to control charge transport at interfaces with active organic semiconducting thin films. These strategies are studied and verified with a range of photoemission spectroscopy, surface probe microscopy, and electrical measurements. Vacuum evaporated molecular organic devices have long used layer stacking of different materials as a method of dividing roles in a device and modifying energy level alignment to improve device performance and efficiency. Applying this type of architecture for solution-processed devices, on the other hand, is nontrivial, as an issue of removal of or mixing with underlying layers arises. We present and examine here soft-contact lamination as a viable technique for depositing solution-processed multilayer structures. The energetics at homojunctions of a couple of air-stable polymers is investigated. Charge transport is then compared between a two-layer film and a single-layer film of equivalent thicknesses. The interface formed by soft-contact lamination is found to be transparent with respect to electronic charge carriers. We also propose a technique for modifying electronic level alignment at active organic-organic heterojunctions using dipolar self-assembled monolayers (SAM). An ultra-thin metal oxide is first deposited via a gentle low temperature chemical vapor deposition as an adhesion layer for the SAM. The deposition is shown to be successful for a variety of organic films. A series of phenylphosphonic acid SAM molecules with various molecular dipoles is then used to functionalize the surface of an organic film and found to modify the work function depending on the molecular dipole across the molecule. This in turn is found to modify the energy level alignment between the underlying organic film with an organic film deposited on top.

Biogeochemistry of the coupled manganese-iron-sulfur cycles of intertidal surface sediments

NASA Astrophysics Data System (ADS)

Bosselmann, K.; Boettcher, M. E.; Billerbeck, M.; Walpersdorf, E.; Debeer, D.; Brumsack, H.-J.; Huettel, M.; Joergensen, B. B.

2003-04-01

The biogeochemistry of the coupled iron-manganese-sulfur-carbon cycles was studied in temperate intertidal surface sediments of the German Wadden Sea (North Sea). Coastal sampling sites include sand, mixed and mud flats with different organic matter and metal contents and permeability reflecting different hydrodynamic regimes. The field study focusses on the influence of temperature, organic matter load, and sediment types on the dynamics of biogeochemical reactions on different time scales (season, day-night, tidal cycles). One of the main interests was related to the cycling of metals (Mn, Fe) in relation to the activity of sulfate-reducing bacteria. Pore water profiles were investigated by sediment sectioning and high resolution gel sampling techniques. Microbial sulfate reduction rates were measured using radiolabeled sulfate with the whole core incubation technique and the spatial distribution of bacterial activity was visualised by using "2D-photoemulsion-monitoring technique". The biogeochemical sulfur cycle was additionally characterised by the stable isotope ratios (S,O) of different sulfur species (e.g., SO_4, AVS, pyrite). Element transfers (metals, nutrients) across the sediment-water interface were additionally quantified by the application of benthic flux chambers. Microbial sulfate reduction was generally highest in the suboxic zone of the surface sediments indicating its potential importance for the mobilization of iron and manganese. In organic matter poor permeable sediments tidal effects additionally influence the spatial and temporal distribution of dissolved redox-sensitive metals. In organic matter-rich silty and muddy sediments, temperature controlled the microbial sulfate reduction rates. Depth-integrated sulfate reduction rates in sandy sediments were much lower and controlled by both temperature and organic matter. Formation of anoxic sediment surfaces due to local enhanced organic matter load (so-called "black spots") may create windows of an increase flux of metals, nutrients and hydrogen sulfide. Acknowledgements: The study was supported by German Science Foundation within the DFG-research group "BioGeoChemistry of the Waddensea" and Max Planck Society.

Occurrence and distribution of pesticides and volatile organic compounds in ground water and surface water in Central Arizona Basins, 1996-98, and their relation to land use

USGS Publications Warehouse

Gellenbeck, Dorinda J.; Anning, David W.

2002-01-01

Samples of ground water and surface water from the Sierra Vista subbasin, the Upper Santa Cruz Basin, and the West Salt River Valley were collected and analyzed to determine the occurrence and distribution of pesticides and volatile organic compounds in central Arizona. The study was done during 1996-98 within the Central Arizona Basins study unit of the National Water-Quality Assessment program. This study included 121 wells and 4 surface-water sites in the 3 basins and the analyses of samples from 4 sites along the Santa Cruz River that were part of a separate study. Samples were collected from 121 wells and 3 surface-water sites for pesticide analyses, and samples were collected from 109 wells and 3 surface-water sites for volatile organic compound analyses. Certain pesticides detected in ground water and surface water can be related specifically to agricultural or urban uses; others can be related to multiple land uses. Effects from historical agriculture are made evident by detections of DDE in ground-water and surface-water samples collected in the West Salt River Valley and detections of atrazine and deethylatrazine in the ground water in the Upper Santa Cruz Basin. Effects from present agriculture are evident in the seasonal variability in concentrations of pre-emergent pesticides in surface-water samples from the West Salt River Valley. Several detections of DDE and dieldrin in surface water were higher than established water-quality limits. Effects of urban land use are made evident by detections of volatile organic compounds in ground water and surface water from the West Salt River Valley. Detections of volatile organic compounds in surface water from the Santa Cruz River near Nogales, Arizona, also are indications of the effects of urban land use. One detection of tetrachloroethene in ground water was higher than established water-quality limits. Water reuse is an important conservation technique in the Southwest; however, the reuse of water provides a transport mechanism for pesticides and volatile organic compounds to reach areas that are not normally affected by manmade compounds from specific land-use activities. The most complex mixture of pesticides and volatile organic compounds is in the West Salt River Valley and is the result of water-management practices and the combination of land uses in this basin throughout history.

Synthesis of antibacterial surfaces by plasma grafting of zinc oxide based nanocomposites onto polypropylene.

PubMed

de Rancourt, Yoann; Couturaud, Benoit; Mas, André; Robin, Jean Jacques

2013-07-15

Antibacterial polymer surfaces were designed using ZnO nanoparticles as a bactericide. Mineral encapsulated nanoparticles were grafted onto activated polymer surfaces through their shells. Polypropylene (PP) surfaces were treated using an innovative process coupling core-shell technology and plasma grafting, well-known techniques commonly used to obtain active surfaces for biomedical applications. First, ZnO nanoparticles were encapsulated by (co)polymers: poly(acrylic acid) (PAA) or a poly(methyl methacrylate-co-methacrylic acid) copolymer [P(MMA-MA)]. Second, PP substrates were activated using plasma treatment. Finally, plasma-treated surfaces were immersed in solutions containing the encapsulated nanoparticles dispersed in an organic solvent and allowed to graft onto it. The presence of nanoparticles on the substrates was demonstrated using Fourier-Transform Infrared Spectroscopy (FTIR) analysis, Scanning Electron Microspcopy (SEM)/Energy-Dispersive X-ray (EDX), and Atomic Force Microscopy (AFM) studies. Indeed, the ZnO-functionalized substrates exhibited an antibacterial response in Escherichia coli adhesion tests. Moreover, this study revealed that, surprisingly, native ZnO nanoparticles without any previous functionalization could be directly grafted onto polymeric surfaces through plasma activation. The antibacterial activity of the resulting sample was shown to be comparable to that of the other samples. Copyright © 2013 Elsevier Inc. All rights reserved.

Tritium labeling of organic compounds deposited on porous structures

DOEpatents

Ehrenkaufer, Richard L. E.; Wolf, Alfred P.; Hembree, Wylie C.

1979-01-01

An improved process for labeling organic compounds with tritium is carried out by depositing the selected compound on the extensive surface of a porous structure such as a membrane filter and exposing the membrane containing the compound to tritium gas activated by the microwave discharge technique. The labeled compound is then recovered from the porous structure.

Microbial activities and dissolved organic matter dynamics in oil-contaminated surface seawater from the Deepwater Horizon oil spill site.

PubMed

Ziervogel, Kai; McKay, Luke; Rhodes, Benjamin; Osburn, Christopher L; Dickson-Brown, Jennifer; Arnosti, Carol; Teske, Andreas

2012-01-01

The Deepwater Horizon oil spill triggered a complex cascade of microbial responses that reshaped the dynamics of heterotrophic carbon degradation and the turnover of dissolved organic carbon (DOC) in oil contaminated waters. Our results from 21-day laboratory incubations in rotating glass bottles (roller bottles) demonstrate that microbial dynamics and carbon flux in oil-contaminated surface water sampled near the spill site two weeks after the onset of the blowout were greatly affected by activities of microbes associated with macroscopic oil aggregates. Roller bottles with oil-amended water showed rapid formation of oil aggregates that were similar in size and appearance compared to oil aggregates observed in surface waters near the spill site. Oil aggregates that formed in roller bottles were densely colonized by heterotrophic bacteria, exhibiting high rates of enzymatic activity (lipase hydrolysis) indicative of oil degradation. Ambient waters surrounding aggregates also showed enhanced microbial activities not directly associated with primary oil-degradation (β-glucosidase; peptidase), as well as a twofold increase in DOC. Concurrent changes in fluorescence properties of colored dissolved organic matter (CDOM) suggest an increase in oil-derived, aromatic hydrocarbons in the DOC pool. Thus our data indicate that oil aggregates mediate, by two distinct mechanisms, the transfer of hydrocarbons to the deep sea: a microbially-derived flux of oil-derived DOC from sinking oil aggregates into the ambient water column, and rapid sedimentation of the oil aggregates themselves, serving as vehicles for oily particulate matter as well as oil aggregate-associated microbial communities.

Microbial Activities and Dissolved Organic Matter Dynamics in Oil-Contaminated Surface Seawater from the Deepwater Horizon Oil Spill Site

PubMed Central

Ziervogel, Kai; McKay, Luke; Rhodes, Benjamin; Osburn, Christopher L.; Dickson-Brown, Jennifer; Arnosti, Carol; Teske, Andreas

2012-01-01

The Deepwater Horizon oil spill triggered a complex cascade of microbial responses that reshaped the dynamics of heterotrophic carbon degradation and the turnover of dissolved organic carbon (DOC) in oil contaminated waters. Our results from 21-day laboratory incubations in rotating glass bottles (roller bottles) demonstrate that microbial dynamics and carbon flux in oil-contaminated surface water sampled near the spill site two weeks after the onset of the blowout were greatly affected by activities of microbes associated with macroscopic oil aggregates. Roller bottles with oil-amended water showed rapid formation of oil aggregates that were similar in size and appearance compared to oil aggregates observed in surface waters near the spill site. Oil aggregates that formed in roller bottles were densely colonized by heterotrophic bacteria, exhibiting high rates of enzymatic activity (lipase hydrolysis) indicative of oil degradation. Ambient waters surrounding aggregates also showed enhanced microbial activities not directly associated with primary oil-degradation (β-glucosidase; peptidase), as well as a twofold increase in DOC. Concurrent changes in fluorescence properties of colored dissolved organic matter (CDOM) suggest an increase in oil-derived, aromatic hydrocarbons in the DOC pool. Thus our data indicate that oil aggregates mediate, by two distinct mechanisms, the transfer of hydrocarbons to the deep sea: a microbially-derived flux of oil-derived DOC from sinking oil aggregates into the ambient water column, and rapid sedimentation of the oil aggregates themselves, serving as vehicles for oily particulate matter as well as oil aggregate-associated microbial communities. PMID:22509359

Characterization of organic composition in snow and surface waters in the Athabasca Oil Sands Region, using ultrahigh resolution Fourier transform mass spectrometry.

PubMed

Yi, Y; Birks, S J; Cho, S; Gibson, J J

2015-06-15

This study was conducted to characterize the composition of dissolved organic compounds present in snow and surface waters in the Athabasca Oil Sands Region (AOSR) with the goal of identifying whether atmospherically-derived organic compounds present in snow are a significant contributor to the compounds detected in surface waters (i.e., rivers and lakes). We used electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR MS) to characterize the dissolved organic compound compositions of snow and surface water samples. The organic profiles obtained for the snow samples show compositional differences between samples from near-field sites (<5 km from oil sands activities) and those from more distant locations (i.e., far-field sites). There are also significant compositional differences between samples collected in near-field sites and surface water samples in the AOSR. The composition of dissolved organic compounds at the upstream Athabasca River site (i.e., Athabasca River at Athabasca) is found to be different from samples obtained from downstream sites in the vicinity of oil sands operations (i.e., Athabasca River at Fort McMurray and Athabasca River at Firebag confluence). The upstream Athabasca River sites tended to share some compositional similarities with far-field snow deposition, while the downstream Athabasca River sites are more similar to local lakes and tributaries. This contrast likely indicates the relative role of regional snowmelt contributions to the Athabasca River vs inputs from local catchments in the reach downstream of Fort McMurray. Copyright © 2015 Elsevier B.V. All rights reserved.

Integrity and Biological Activity of DNA after UV Exposure

NASA Astrophysics Data System (ADS)

Lyon, Delina Y.; Monier, Jean-Michel; Dupraz, Sébastien; Freissinet, Caroline; Simonet, Pascal; Vogel, Timothy M.

2010-04-01

The field of astrobiology lacks a universal marker with which to indicate the presence of life. This study supports the proposal to use nucleic acids, specifically DNA, as a signature of life (biosignature). In addition to its specificity to living organisms, DNA is a functional molecule that can confer new activities and characteristics to other organisms, following the molecular biology dogma, that is, DNA is transcribed to RNA, which is translated into proteins. Previous criticisms of the use of DNA as a biosignature have asserted that DNA molecules would be destroyed by UV radiation in space. To address this concern, DNA in plasmid form was deposited onto different surfaces and exposed to UVC radiation. The surviving DNA was quantified via the quantitative polymerase chain reaction (qPCR). Results demonstrate increased survivability of DNA attached to surfaces versus non-adsorbed DNA. The DNA was also tested for biological activity via transformation into the bacterium Acinetobacter sp. and assaying for antibiotic resistance conferred by genes encoded by the plasmid. The success of these methods to detect DNA and its gene products after UV exposure (254 nm, 3.5 J/m2s) not only supports the use of the DNA molecule as a biosignature on mineral surfaces but also demonstrates that the DNA retained biological activity.

Virucidal activity of chemical biocides against mimivirus, a putative pneumonia agent.

PubMed

Campos, Rafael Kroon; Andrade, Ketyllen Reis; Ferreira, Paulo Cesar Peregrino; Bonjardim, Cláudio Antônio; La Scola, Bernard; Kroon, Erna Geessien; Abrahão, Jônatas Santos

2012-12-01

Acanthamoeba polyphaga mimivirus (APMV), the largest known virus, has been studied as a putative pneumonia agent, especially in hospital environments. Despite the repercussions of the discovery of APMV, there has been no study related to the control of APMV and the susceptibility of this virus to disinfectants. This work investigated the virucidal activity against mimivirus of chemical biocides commonly used in clinical practice for the disinfection of hospital equipment and rooms. APMV was dried on sterilized steel coupons, exposed to different concentrations of alcohols (ethanol, 1-propanol and 2-propanol) and commercial disinfectants (active chlorine, glutaraldehyde and benzalkonium chloride) and titrated in amoebas using the TCID50 value. The stability of APMV on an inanimate surface was also tested in the presence and absence of organic matter for 30 days. APMV showed a high level of resistance to chemical biocides, especially alcohols. Only active chlorine and glutaraldehyde were able to decrease the APMV titers to undetectable levels. Dried APMV showed long-lasting stability on an inanimate surface (30 days), even in the absence of organic matter. The data presented herein may help health and laboratory workers plan the best strategy to control this putative pneumonia agent from surfaces and devices. Copyright © 2012 Elsevier B.V. All rights reserved.

Ozonation of 1,2-dihydroxybenzene in the presence of activated carbon.

PubMed

Zaror, C; Soto, G; Valdés, H; Mansilla, H

2001-01-01

This work aims at obtaining experimental data on ozonation of 1,2-dihydroxybenzene (DHB) in the presence of activated carbon, with a view to assessing possible changes in its surface chemical structure and adsorption capacity. Experiments were conducted in a 0.5 L reactor, loaded with 2 g Filtrasorb 400 granular activated carbon, and 1-5 mM DHB aqueous solution at pH 2-8. Ozone gas was generated with an Ozocav generator, and fed into the reactor for a given exposure time, in the range 0.5-240 min, at 25 degrees C and 1 atm. After each run, liquid and activated carbon samples were taken for chemical assays. Soluble organic groups present on the active carbon surface were desorbed and analysed by GC-MS and HPLC. Activated carbon chemical surface properties were analysed using TPD, FT-IR, and XPS techniques. Reactions between ozone and adsorbed DHB were shown to be fast, leading to formation of C-6, C-4 and C-2 by-products. Oxygenated surface groups, particularly, COOH and C = O, increased as a result of ozonation.

Surface Properties and Catalytic Performance of Activated Carbon Fibers Supported TiO2 Photocatalyst

NASA Astrophysics Data System (ADS)

Yang, Huifen; Fu, Pingfeng

Activated carbon fibers supported TiO2 photocatalyst (TiO2/ACF) in felt-form was successfully prepared with a dip-coating process using organic silicon modified acrylate copolymer as a binder followed by calcination at 500°C in a stream of Ar gas. The photocatalyst was characterized by SEM, XRD, XPS, FTIR, and BET surface area. Most of carbon fibers were coated with uniformly distributed TiO2 clusters of nearly 100 nm. The loaded TiO2 layer was particulate for the organic binder in the compact film was carbonized. According to XPS and FTIR analysis, amorphous silica in carbon grains was synthesized after carbonizing organic silicon groups, and the Ti-O-Si bond was formed between the interface of loaded TiO2 and silica. Additionally, the space between adjacent carbon fibers still remained unfilled after TiO2 coating, into which both UV light and polluted solutions could penetrate to form a three-dimensional environment for photocatalytic reactions. While loaded TiO2 amount increased to 456 mg TiO2/1 g ACF, the TiO2/ACF catalyst showed its highest photocatalytic activity, and this activity only dropped about 10% after 12 successive runs, exhibiting its high fixing stability of coated TiO2.

Rapid determination of trace nitrophenolic organics in water by combining solid-phase extraction with surface-assisted laser desorption/ionization time-of-flight mass spectrometry.

PubMed

Chen, Y C; Shiea, J; Sunner, J

2000-01-01

A rapid technique for the screening of trace compounds in water by combining solid-phase extraction (SPE) with activated carbon surface-assisted laser desorption/ionization (SALDI) time-of-flight mass spectrometry is demonstrated. Activated carbon is used both as the sorbent in SPE and as the solid in the SALDI matrix system. This eliminates the need for an SPE elution process. After the analytes have been adsorbed on the surfaces of the activated carbon during SPE extraction, the activated carbon is directly mixed with the SALDI liquid and mass spectrometric analysis is performed. Trace phenolic compounds in water were used to demonstrate the effectiveness of the method. The detection limit for these compounds is in the ppb to ppt range. Copyright 2000 John Wiley & Sons, Ltd.

Organic materials for ceramic molding processes

NASA Technical Reports Server (NTRS)

Saito, K.

1984-01-01

Ceramic molding processes are examined. Binders, wetting agents, lubricants, plasticizers, surface active agents, dispersants, etc., for pressing, rubber pressing, sip casting, injection casting, taping, extrusion, etc., are described, together with forming machines.

Temperature sensitivity differences with depth and season between carbon, nitrogen, and phosphorus cycling enzyme activities in an ombrotrophic peatland system

NASA Astrophysics Data System (ADS)

Steinweg, J. M.; Kostka, J. E.; Hanson, P. J.; Schadt, C. W.

2017-12-01

Northern peatlands have large amounts of soil organic matter due to reduced decomposition. Breakdown of organic matter is initially mediated by extracellular enzymes, the activity of which may be controlled by temperature, moisture, and substrate availability, all of which vary seasonally throughout the year and with depth. In typical soils the majority of the microbial biomass and decomposition occurs within the top 30cm due to reduced organic matter inputs in the subsurface however peatlands by their very nature contain large amounts of organic matter throughout their depth profile. We hypothesized that potential enzyme activity would be greatest at the surface of the peat due to a larger microbial biomass compared to 40cm and 175cm below the surface and that temperature sensitivity would be greatest at the surface during winter but lowest during the summer due to high temperatures and enzyme efficiency. Peat samples were collected in February, July, and August 2012 from the DOE Spruce and Peatland Responses Under Climatic and Environmental Change project at Marcell Experimental Forest S1 bog. We measured potential activity of hydrolytic enzymes involved in three different nutrient cycles: beta-glucosidase (carbon), leucine amino peptidase (nitrogen), and phosphatase (phosphorus) at 15 temperature points ranging from 3°C to 65°C. Enzyme activity decreased with depth as expected but there was no concurrent change in activation energy (Ea). The reduction in enzyme activity with depth indicates a smaller pool which coincided with a decreased microbial biomass. Differences in enzyme activity with depth also mirrored the changes in peat composition from the acrotelm to the catotelm. Season did play a role in temperature sensitivity with Ea of β-glucosidase and phosphatase being the lowest in August as expected but leucine amino peptidase (a nitrogen acquiring enzyme) Ea was not influenced by season. As temperatures rise, especially in winter months, enzymatic carbon and phosphorus acquisition in the Marcell bog may increase whereas nitrogen acquisition would remain unchanged. The lack of temperature response for leucine amino peptidase has been measured in other systems but may be less of a concern in the Marcell bog due to low microbial biomass and enzymatic activity at depth and relatively low peat C:N ratios.

Contamination of ground water, surface water, and soil, and evaluation of selected ground-water pumping alternatives in the Canal Creek area of Aberdeen Proving Ground, Maryland

USGS Publications Warehouse

Lorah, Michelle M.; Clark, Jeffrey S.

1996-01-01

Chemical manufacturing, munitions filling, and other military-support activities have resulted in the contamination of ground water, surface water, and soil in the Canal Creek area of Aberdeen Proving Ground, Maryland. Chlorinated volatile organic compounds, including 1,1,2,2-tetrachloroethane and trichloroethylene, are widespread ground-water contaminants in two aquifers that are composed of unconsolidated sand and gravel. Distribution and fate of chlorinated organic compounds in the ground water has been affected by the movement and dissolution of solvents in their dense immiscible phase and by microbial degradation under anaerobic conditions. Detection of volatile organic contaminants in adjacent surface water indicates that shallow contaminated ground water discharges to surface water. Semivolatile organic compounds, especially polycyclic aromatic hydrocarbons, are the most prevalent organic contaminants in soils. Various trace elements, such as arsenic, cadmium, lead, and zinc, were found in elevated concentrations in ground water, surface water, and soil. Simulations with a ground-water-flow model and particle tracker postprocessor show that, without remedial pumpage, the contaminants will eventually migrate to Canal Creek and Gunpowder River. Simulations indicate that remedial pumpage of 2.0 million gallons per day from existing wells is needed to capture all particles originating in the contaminant plumes. Simulated pumpage from offsite wells screened in a lower confined aquifer does not affect the flow of contaminated ground water in the Canal Creek area.

GPI-anchored protein organization and dynamics at the cell surface

PubMed Central

Saha, Suvrajit; Anilkumar, Anupama Ambika; Mayor, Satyajit

2016-01-01

The surface of eukaryotic cells is a multi-component fluid bilayer in which glycosylphosphatidylinositol (GPI)-anchored proteins are an abundant constituent. In this review, we discuss the complex nature of the organization and dynamics of GPI-anchored proteins at multiple spatial and temporal scales. Different biophysical techniques have been utilized for understanding this organization, including fluorescence correlation spectroscopy, fluorescence recovery after photobleaching, single particle tracking, and a number of super resolution methods. Major insights into the organization and dynamics have also come from exploring the short-range interactions of GPI-anchored proteins by fluorescence (or Förster) resonance energy transfer microscopy. Based on the nanometer to micron scale organization, at the microsecond to the second time scale dynamics, a picture of the membrane bilayer emerges where the lipid bilayer appears inextricably intertwined with the underlying dynamic cytoskeleton. These observations have prompted a revision of the current models of plasma membrane organization, and suggest an active actin-membrane composite. PMID:26394904

GPI-anchored protein organization and dynamics at the cell surface.

PubMed

Saha, Suvrajit; Anilkumar, Anupama Ambika; Mayor, Satyajit

2016-02-01

The surface of eukaryotic cells is a multi-component fluid bilayer in which glycosylphosphatidylinositol (GPI)-anchored proteins are an abundant constituent. In this review, we discuss the complex nature of the organization and dynamics of GPI-anchored proteins at multiple spatial and temporal scales. Different biophysical techniques have been utilized for understanding this organization, including fluorescence correlation spectroscopy, fluorescence recovery after photobleaching, single particle tracking, and a number of super resolution methods. Major insights into the organization and dynamics have also come from exploring the short-range interactions of GPI-anchored proteins by fluorescence (or Förster) resonance energy transfer microscopy. Based on the nanometer to micron scale organization, at the microsecond to the second time scale dynamics, a picture of the membrane bilayer emerges where the lipid bilayer appears inextricably intertwined with the underlying dynamic cytoskeleton. These observations have prompted a revision of the current models of plasma membrane organization, and suggest an active actin-membrane composite. Copyright © 2016 by the American Society for Biochemistry and Molecular Biology, Inc.

Dissolved organic carbon and nitrogen release from boreal Holocene permafrost and seasonally frozen soils of Alaska

NASA Astrophysics Data System (ADS)

Wickland, Kimberly P.; Waldrop, Mark P.; Aiken, George R.; Koch, Joshua C.; Torre Jorgenson, M.; Striegl, Robert G.

2018-06-01

Permafrost (perennially frozen) soils store vast amounts of organic carbon (C) and nitrogen (N) that are vulnerable to mobilization as dissolved organic carbon (DOC) and dissolved organic and inorganic nitrogen (DON, DIN) upon thaw. Such releases will affect the biogeochemistry of permafrost regions, yet little is known about the chemical composition and source variability of active-layer (seasonally frozen) and permafrost soil DOC, DON and DIN. We quantified DOC, total dissolved N (TDN), DON, and DIN leachate yields from deep active-layer and near-surface boreal Holocene permafrost soils in interior Alaska varying in soil C and N content and radiocarbon age to determine potential release upon thaw. Soil cores were collected at three sites distributed across the Alaska boreal region in late winter, cut in 15 cm thick sections, and deep active-layer and shallow permafrost sections were thawed and leached. Leachates were analyzed for DOC, TDN, nitrate (NO3 ‑), and ammonium (NH4 +) concentrations, dissolved organic matter optical properties, and DOC biodegradability. Soils were analyzed for C, N, and radiocarbon (14C) content. Soil DOC, TDN, DON, and DIN yields increased linearly with soil C and N content, and decreased with increasing radiocarbon age. These relationships were significantly different for active-layer and permafrost soils such that for a given soil C or N content, or radiocarbon age, permafrost soils released more DOC and TDN (mostly as DON) per gram soil than active-layer soils. Permafrost soil DOC biodegradability was significantly correlated with soil Δ14C and DOM optical properties. Our results demonstrate that near-surface Holocene permafrost soils preserve greater relative potential DOC and TDN yields than overlying seasonally frozen soils that are exposed to annual leaching and decomposition. While many factors control the fate of DOC and TDN, the greater relative yields from newly thawed Holocene permafrost soils will have the largest potential impact in areas dominated by organic-rich soils.

GaN-based vertical-cavity surface-emitting lasers with tunnel junction contacts grown by metal-organic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Lee, SeungGeun; Forman, Charles A.; Lee, Changmin; Kearns, Jared; Young, Erin C.; Leonard, John T.; Cohen, Daniel A.; Speck, James S.; Nakamura, Shuji; DenBaars, Steven P.

2018-06-01

We report the first demonstration of III–nitride vertical-cavity surface-emitting lasers (VCSELs) with tunnel junction (TJ) intracavity contacts grown completely by metal–organic chemical vapor deposition (MOCVD). For the TJs, n++-GaN was grown on in-situ activated p++-GaN after buffered HF surface treatment. The electrical properties and epitaxial morphologies of the TJs were first investigated on TJ LED test samples. A VCSEL with a TJ intracavity contact showed a lasing wavelength of 408 nm, a threshold current of ∼15 mA (10 kA/cm2), a threshold voltage of 7.8 V, a maximum output power of 319 µW, and a differential efficiency of 0.28%.

Spectral properties of Titan's impact craters imply chemical weathering of its surface

PubMed Central

Barnes, J. W.; Sotin, C.; MacKenzie, S.; Soderblom, J. M.; Le Mouélic, S.; Kirk, R. L.; Stiles, B. W.; Malaska, M. J.; Le Gall, A.; Brown, R. H.; Baines, K. H.; Buratti, B.; Clark, R. N.; Nicholson, P. D.

2015-01-01

Abstract We examined the spectral properties of a selection of Titan's impact craters that represent a range of degradation states. The most degraded craters have rims and ejecta blankets with spectral characteristics that suggest that they are more enriched in water ice than the rims and ejecta blankets of the freshest craters on Titan. The progression is consistent with the chemical weathering of Titan's surface. We propose an evolutionary sequence such that Titan's craters expose an intimate mixture of water ice and organic materials, and chemical weathering by methane rainfall removes the soluble organic materials, leaving the insoluble organics and water ice behind. These observations support the idea that fluvial processes are active in Titan's equatorial regions. PMID:27656006

Gene Expression and Metabolism in Tomato Fruit Surface Tissues1[C][W

PubMed Central

Mintz-Oron, Shira; Mandel, Tali; Rogachev, Ilana; Feldberg, Liron; Lotan, Ofra; Yativ, Merav; Wang, Zhonghua; Jetter, Reinhard; Venger, Ilya; Adato, Avital; Aharoni, Asaph

2008-01-01

The cuticle, covering the surface of all primary plant organs, plays important roles in plant development and protection against the biotic and abiotic environment. In contrast to vegetative organs, very little molecular information has been obtained regarding the surfaces of reproductive organs such as fleshy fruit. To broaden our knowledge related to fruit surface, comparative transcriptome and metabolome analyses were carried out on peel and flesh tissues during tomato (Solanum lycopersicum) fruit development. Out of 574 peel-associated transcripts, 17% were classified as putatively belonging to metabolic pathways generating cuticular components, such as wax, cutin, and phenylpropanoids. Orthologs of the Arabidopsis (Arabidopsis thaliana) SHINE2 and MIXTA-LIKE regulatory factors, activating cutin and wax biosynthesis and fruit epidermal cell differentiation, respectively, were also predominantly expressed in the peel. Ultra-performance liquid chromatography coupled to a quadrupole time-of-flight mass spectrometer and gas chromatography-mass spectrometry using a flame ionization detector identified 100 metabolites that are enriched in the peel tissue during development. These included flavonoids, glycoalkaloids, and amyrin-type pentacyclic triterpenoids as well as polar metabolites associated with cuticle and cell wall metabolism and protection against photooxidative stress. Combined results at both transcript and metabolite levels revealed that the formation of cuticular lipids precedes phenylpropanoid and flavonoid biosynthesis. Expression patterns of reporter genes driven by the upstream region of the wax-associated SlCER6 gene indicated progressive activity of this wax biosynthetic gene in both fruit exocarp and endocarp. Peel-associated genes identified in our study, together with comparative analysis of genes enriched in surface tissues of various other plant species, establish a springboard for future investigations of plant surface biology. PMID:18441227

Filterable redox cycling activity: a comparison between diesel exhaust particles and secondary organic aerosol constituents.

PubMed

McWhinney, Robert D; Badali, Kaitlin; Liggio, John; Li, Shao-Meng; Abbatt, Jonathan P D

2013-04-02

The redox activity of diesel exhaust particles (DEP) collected from a light-duty diesel passenger car engine was examined using the dithiothreitol (DTT) assay. DEP was highly redox-active, causing DTT to decay at a rate of 23-61 pmol min(-1) μg(-1) of particle used in the assay, which was an order of magnitude higher than ambient coarse and fine particulate matter (PM) collected from downtown Toronto. Only 2-11% of the redox activity was in the water-soluble portion, while the remainder occurred at the black carbon surface. This is in contrast to redox-active secondary organic aerosol constituents, in which upward of 90% of the activity occurs in the water-soluble fraction. The redox activity of DEP is not extractable by moderately polar (methanol) and nonpolar (dichloromethane) organic solvents, and is hypothesized to arise from redox-active moieties contiguous with the black carbon portion of the particles. These measurements illustrate that "Filterable Redox Cycling Activity" may therefore be useful to distinguish black carbon-based oxidative capacity from water-soluble organic-based activity. The difference in chemical environment leading to redox activity highlights the need to further examine the relationship between activity in the DTT assay and toxicology measurements across particles of different origins and composition.

Incredible antibacterial activity of noble metal functionalized magnetic core-zeolitic shell nanostructures.

PubMed

Padervand, M; Janatrostami, S; Karanji, A Kiani; Gholami, M R

2014-02-01

Functionalized magnetic core-zeolitic shell nanostructures were prepared by hydrothermal and coprecipitation methods. The products were characterized by Vibrating Sample Magnetometer (VSM), X-ray powder diffraction (XRD), Fourier Transform Infrared (FTIR) spectra, nitrogen adsorption-desorption isotherms, and Transmission Electron Microscopy (TEM). The growth of mordenite nanoparticles on the surface of silica coated nickel ferrite nanoparticles in the presence of organic templates was also confirmed. Antibacterial activity of the prepared nanostructures was investigated by the inactivation of Escherichia coli as a gram negative bacterium. A new mechanism was proposed for inactivation of E. coli over the prepared samples. In addition, the Minimum Inhibitory Concentration (MIC) and reuse ability were studied. TEM images of the destroyed cell wall after the treatment time were performed to illustrate the inactivation mechanism. According to the experimental results, the core-shell nanostructures which were modified by organic agents and then functionalized with noble metal nanoparticles were the most active. The interaction of the noble metals with the organic components on the surface of nanostructures was studied theoretically and the obtained results were used to interpret the experimental results. © 2013. Published by Elsevier B.V. All rights reserved.

Nascent body ego: metapsychological and neurophysiological aspects.

PubMed

Lehtonen, Johannes; Partanen, Juhani; Purhonen, Maija; Valkonen-Korhonen, Minna; Kononen, Mervi; Saarikoski, Seppo; Launiala, Kari

2006-10-01

For Freud, body ego was the organizing basis of the structural theory. He defined it as a psychic projection of the body surface. Isakower's and Lewin's classical findings suggest that the body surface experiences of nursing provide the infant with sensory-affective stimulation that initiates a projection of sensory processes towards the psychic realm. During nursing, somato-sensory, gustatory and olfactory modalities merge with a primitive somatic affect of satiation, whereas auditory modality is involved more indirectly and visual contact more gradually. Repeated regularly, such nascent experiences are likely to play a part in the organization of the primitive protosymbolic mental experience. In support of this hypothesis, the authors review findings from a neurophysiological study of infants before, during and after nursing. Nursing is associated with a significant amplitude change in the newborn electroencephalogram (EEG), which wanes before the age of 3 months, and is transformed at the age of 6 months into rhythmic 3-5 Hz hedonic theta-activity. Sucking requires active physiological work, which is shown in a regular rise in heart rate. The hypothesis of a sensory-affective organization of the nascent body ego, enhanced by nursing and active sucking, seems concordant with neurophysiological phenomena related to nursing.

Atomically Precise Growth of Catalytically Active Cobalt Sulfide on Flat Surfaces and within a Metal–Organic Framework via Atomic Layer Deposition

DOE PAGES

Peters, Aaron W.; Li, Zhanyong; Farha, Omar K.; ...

2015-08-04

Atomic layer deposition (ALD) has been employed as a new synthetic route to thin films of cobalt sulfide on silicon and fluorine-doped tin oxide platforms. The self-limiting nature of the stepwise synthesis is established through growth rate studies at different pulse times and temperatures. Additionally, characterization of the materials by X-ray diffraction and X-ray photoelectron spectroscopy indicates that the crystalline phase of these films has the composition Co 9S 8. The nodes of the metal–organic framework (MOF) NU-1000 were then selectively functionalized with cobalt sulfide via ALD in MOFs (AIM). Spectroscopic techniques confirm uniform deposition of cobalt sulfide throughout themore » crystallites, with no loss in crystallinity or porosity. The resulting material, CoS-AIM, is catalytically active for selective hydrogenation of m-nitrophenol to m-aminophenol, and outperforms the analogous oxide AIM material (CoO-AIM) as well as an amorphous CoS x reference material. Here, these results reveal AIM to be an effective method of incorporating high surface area and catalytically active cobalt sulfide in metal–organic frameworks.« less

Short-term and long-term effects of protein kinase C on the trafficking and stability of human organic anion transporter 3

PubMed Central

Zhang, Qiang; Suh, Wonmo; Pan, Zui; You, Guofeng

2012-01-01

Human organic anion transporter 3 (hOAT3) belongs to a family of organic anion transporters that play critical roles in the body disposition of numerous clinically important drugs. Therefore, understanding the regulation of this transporter has profound clinical significance. In the current study, we investigated the short-term and long-term regulation of hOAT3 by protein kinase C (PKC). We showed that short-term activation of PKC by phobol 12-Myristate 13-Acetate (PMA) inhibited hOAT3 activity through accelerating its internalization from cell surface to intracellular recycling endosomes. The colocalization of hOAT3 with EEA1-positive recycling endosomes was demonstrated by immunolocalization with confocal microscopy. Furthermore, we showed that long-term activation of PKC resulted in the enhanced degradation of cell surface hOAT3. The pathways for hOAT3 degradation were further examined using proteasomal and lysosomal inhibitors. Our results showed that both proteasomal inhibitors and the lysosomal inhibitors significantly blocked hOAT3 degradation. These results demonstrate that PKC plays critical roles in the trafficking and the stability of hOAT3. PMID:22773962

Occurrence of Surface Active Agents in the Environment

PubMed Central

Olkowska, Ewa; Ruman, Marek; Polkowska, Żaneta

2014-01-01

Due to the specific structure of surfactants molecules they are applied in different areas of human activity (industry, household). After using and discharging from wastewater treatment plants as effluent stream, surface active agents (SAAs) are emitted to various elements of the environment (atmosphere, waters, and solid phases), where they can undergo numerous physic-chemical processes (e.g., sorption, degradation) and freely migrate. Additionally, SAAs present in the environment can be accumulated in living organisms (bioaccumulation), what can have a negative effect on biotic elements of ecosystems (e.g., toxicity, disturbance of endocrine equilibrium). They also cause increaseing solubility of organic pollutants in aqueous phase, their migration, and accumulation in different environmental compartments. Moreover, surfactants found in aerosols can affect formation and development of clouds, which is associated with cooling effect in the atmosphere and climate changes. The environmental fate of SAAs is still unknown and recognition of this problem will contribute to protection of living organisms as well as preservation of quality and balance of various ecosystems. This work contains basic information about surfactants and overview of pollution of different ecosystems caused by them (their classification and properties, areas of use, their presence, and behavior in the environment). PMID:24527257

The molecular mechanism of mediation of adsorbed serum proteins to endothelial cells adhesion and growth on biomaterials.

PubMed

Yang, Dayun; Lü, Xiaoying; Hong, Ying; Xi, Tingfei; Zhang, Deyuan

2013-07-01

To explore molecular mechanism of mediation of adsorbed proteins to cell adhesion and growth on biomaterials, this study examined endothelial cell adhesion, morphology and viability on bare and titanium nitride (TiN) coated nickel titanium (NiTi) alloys and chitosan film firstly, and then identified the type and amount of serum proteins adsorbed on the three surfaces by proteomic technology. Subsequently, the mediation role of the identified proteins to cell adhesion and growth was investigated with bioinformatics analyses, and further confirmed by a series of cellular and molecular biological experiments. Results showed that the type and amount of adsorbed serum proteins associated with cell adhesion and growth was obviously higher on the alloys than on the chitosan film, and these proteins mediated endothelial cell adhesion and growth on the alloys via four ways. First, proteins such as adiponectin in the adsorbed protein layer bound with cell surface receptors to generate signal transduction, which activated cell surface integrins through increasing intracellular calcium level. Another way, thrombospondin 1 in the adsorbed protein layer promoted TGF-β signaling pathway activation and enhanced integrins expression. The third, RGD sequence containing proteins such as fibronectin 1, vitronectin and thrombospondin 1 in the adsorbed protein layer bound with activated integrins to activate focal adhesion pathway, increased focal adhesion formation and actin cytoskeleton organization and mediated cell adhesion and spreading. In addition, the activated focal adhesion pathway promoted the expression of cell growth related genes and resulted in cell proliferation. The fourth route, coagulation factor II (F2) and fibronectin 1 in the adsorbed protein layer bound with cell surface F2 receptor and integrin, activated regulation of actin cytoskeleton pathway and regulated actin cytoskeleton organization. Copyright © 2013 Elsevier Ltd. All rights reserved.

Radioactivity decontamination of materials commonly used as surfaces in general-purpose radioisotope laboratories.

PubMed

Leonardi, Natalia M; Tesán, Fiorella C; Zubillaga, Marcela B; Salgueiro, María J

2014-12-01

In accord with as-low-as-reasonably-achievable and good-manufacturing-practice concepts, the present study evaluated the efficiency of radioactivity decontamination of materials commonly used in laboratory surfaces and whether solvent spills on these materials affect the findings. Four materials were evaluated: stainless steel, a surface comprising one-third acrylic resin and two-thirds natural minerals, an epoxy cover, and vinyl-based multipurpose flooring. Radioactive material was eluted from a (99)Mo/(99m)Tc generator, and samples of the surfaces were control-contaminated with 37 MBq (100 μL) of this eluate. The same procedure was repeated with samples of surfaces previously treated with 4 solvents: methanol, methyl ethyl ketone, acetone, and ethanol. The wet radioactive contamination was allowed to dry and then was removed with cotton swabs soaked in soapy water. The effectiveness of decontamination was defined as the percentage of activity removed per cotton swab, and the efficacy of decontamination was defined as the total percentage of activity removed, which was obtained by summing the percentages of activity in all the swabs required to complete the decontamination. Decontamination using our protocol was most effective and most efficacious for stainless steel and multipurpose flooring. Moreover, treatment with common organic solvents seemed not to affect the decontamination of these surfaces. Decontamination of the other two materials was less efficient and was interfered with by the organic solvents; there was also great variability in the overall results obtained for these other two materials. In expanding our laboratory, it is possible for us to select those surface materials on which our decontamination protocol works best. © 2014 by the Society of Nuclear Medicine and Molecular Imaging, Inc.

Pesticide seed dressings can affect the activity of various soil organisms and reduce decomposition of plant material.

PubMed

Zaller, Johann G; König, Nina; Tiefenbacher, Alexandra; Muraoka, Yoko; Querner, Pascal; Ratzenböck, Andreas; Bonkowski, Michael; Koller, Robert

2016-08-17

Seed dressing with pesticides is widely used to protect crop seeds from pest insects and fungal diseases. While there is mounting evidence that especially neonicotinoid seed dressings detrimentally affect insect pollinators, surprisingly little is known on potential side effects on soil biota. We hypothesized that soil organisms would be particularly susceptible to pesticide seed dressings as they get in direct contact with these chemicals. Using microcosms with field soil we investigated, whether seeds treated either with neonicotinoid insecticides or fungicides influence the activity and interaction of earthworms, collembola, protozoa and microorganisms. The full-factorial design consisted of the factor Seed dressing (control vs. insecticide vs. fungicide), Earthworm (no earthworms vs. addition Lumbricus terrestris L.) and collembola (no collembola vs. addition Sinella curviseta Brook). We used commercially available wheat seed material (Triticum aesticum L. cf. Lukullus) at a recommended seeding density of 367 m(-2). Seed dressings (particularly fungicides) increased collembola surface activity, increased the number of protozoa and reduced plant decomposition rate but did not affect earthworm activity. Seed dressings had no influence on wheat growth. Earthworms interactively affected the influence of seed dressings on collembola activity, whereas collembola increased earthworm surface activity but reduced soil basal respiration. Earthworms also decreased wheat growth, reduced soil basal respiration and microbial biomass but increased soil water content and electrical conductivity. The reported non-target effects of seed dressings and their interactions with soil organisms are remarkable because they were observed after a one-time application of only 18 pesticide treated seeds per experimental pot. Because of the increasing use of seed dressing in agriculture and the fundamental role of soil organisms in agroecosystems these ecological interactions should receive more attention.

Comparative study of singlet oxygen production by photosensitiser dyes encapsulated in silicone: towards rational design of anti-microbial surfaces.

PubMed

Noimark, Sacha; Salvadori, Enrico; Gómez-Bombarelli, Rafael; MacRobert, Alexander J; Parkin, Ivan P; Kay, Christopher W M

2016-10-12

Surfaces with built-in antimicrobial activity have the potential to reduce hospital-acquired infections. One promising strategy is to create functionalised surfaces which, following illumination with visible light, are able to generate singlet oxygen under aerobic conditions. In contrast to antibiotics, the mechanism of bacterial kill by species derived from reactions with singlet oxygen is completely unselective, therefore offering little room for evolutionary adaptation. Here we consider five commercially available organic photosensitiser dyes encapsulated in silicone polymer that show varied antimicrobial activity. We correlate density functional theory calculations with UV-Vis spectroscopy, electron paramagnetic resonance spectroscopy and singlet oxygen production measurements in order to define and test the elements required for efficacious antimicrobial activity. Our approach forms the basis for the rational in silico design and spectroscopic screening of simple and efficient self-sterilising surfaces made from cheap, low toxicity photosensitiser dyes encapsulated in silicone.

Mobilization of hydrophobic contaminants from soils by enzymatic depolymerization of soil organic matter.

PubMed

Wicke, Daniel; Reemtsma, Thorsten

2010-02-01

The effect of hydrolytic exoenzymes on the release of hydrophobic organic contaminants (HOC) from two different surface soils was studied in laboratory batch experiments. Incubation of the soils with cellulase with an activity fivefold above the inherent soil activity enhanced the release of hydrophobic contaminants (polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB) and hydroxylated PCB) by 40-200%. Xylanase and invertase did not show measurable effects at comparable relative activity levels. This suggests that cellulose substructures are important for the retention of HOC in soil organic matter (SOM). Hydrolytic exoenzymes, and the microorganisms that release them, contribute to the mobilization of HOC from soil, by shifting the sorption equilibrium in the course of SOM transformation into dissolved organic matter or by facilitating HOC diffusion as a consequence of reduced rigidity of SOM. We conclude that not only biodegradation but also sorption and desorption of HOC in soil can be influenced by (micro-) biology and the factors that determine its activity.

Poly(2-ethyloxazoline) as matrix for highly active electrospun enzymes in organic solvents.

PubMed

Plothe, Ramona; Sittko, Ina; Lanfer, Franziska; Fortmann, Maximilian; Roth, Meike; Kolbach, Vivien; Tiller, Joerg C

2017-01-01

Nanofibers are advantageous carriers for biocatalysts, because they show lower diffusion limitations due to their high surface/volume ratio. Only a few samples are known where enzymes are directly spun into nanofibers, mostly because there are not many suited polymer carriers. In this study, poly(2-ethyloxazoline) (PEtOx) was explored regarding its usefulness to activate various enzymes in organic solvents by directly electrospinning them from aqueous solutions containing the polymer. It was found that the concentration of PEtOx in the spinning solution and also the swellability of the fibers play a great role in the activity of the enzymes in organic solvents. Using electrospun lipase B from Candida antarctica (CaLB) under optimized conditions revealed a higher carrier activity than the commercial Novozyme 435 with 10 times less immobilized protein. The electrospinning of PEtOx/CaLB fibers onto a stirrer is used to realize a biocatalytic stirrer for organic solvents. Biotechnol. Bioeng. 2017;114: 39-45. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Surfactants from the gas phase may promote cloud droplet formation.

PubMed

Sareen, Neha; Schwier, Allison N; Lathem, Terry L; Nenes, Athanasios; McNeill, V Faye

2013-02-19

Clouds, a key component of the climate system, form when water vapor condenses upon atmospheric particulates termed cloud condensation nuclei (CCN). Variations in CCN concentrations can profoundly impact cloud properties, with important effects on local and global climate. Organic matter constitutes a significant fraction of tropospheric aerosol mass, and can influence CCN activity by depressing surface tension, contributing solute, and influencing droplet activation kinetics by forming a barrier to water uptake. We present direct evidence that two ubiquitous atmospheric trace gases, methylglyoxal (MG) and acetaldehyde, known to be surface-active, can enhance aerosol CCN activity upon uptake. This effect is demonstrated by exposing acidified ammonium sulfate particles to 250 parts per billion (ppb) or 8 ppb gas-phase MG and/or acetaldehyde in an aerosol reaction chamber for up to 5 h. For the more atmospherically relevant experiments, i.e., the 8-ppb organic precursor concentrations, significant enhancements in CCN activity, up to 7.5% reduction in critical dry diameter for activation, are observed over a timescale of hours, without any detectable limitation in activation kinetics. This reduction in critical diameter enhances the apparent particle hygroscopicity up to 26%, which for ambient aerosol would lead to cloud droplet number concentration increases of 8-10% on average. The observed enhancements exceed what would be expected based on Köhler theory and bulk properties. Therefore, the effect may be attributed to the adsorption of MG and acetaldehyde to the gas-aerosol interface, leading to surface tension depression of the aerosol. We conclude that gas-phase surfactants may enhance CCN activity in the atmosphere.

Nonleachable Imidazolium-Incorporated Composite for Disruption of Bacterial Clustering, Exopolysaccharide-Matrix Assembly, and Enhanced Biofilm Removal.

PubMed

Hwang, Geelsu; Koltisko, Bernard; Jin, Xiaoming; Koo, Hyun

2017-11-08

Surface-grown bacteria and production of an extracellular polymeric matrix modulate the assembly of highly cohesive and firmly attached biofilms, making them difficult to remove from solid surfaces. Inhibition of cell growth and inactivation of matrix-producing bacteria can impair biofilm formation and facilitate removal. Here, we developed a novel nonleachable antibacterial composite with potent antibiofilm activity by directly incorporating polymerizable imidazolium-containing resin (antibacterial resin with carbonate linkage; ABR-C) into a methacrylate-based scaffold (ABR-modified composite; ABR-MC) using an efficient yet simplified chemistry. Low-dose inclusion of imidazolium moiety (∼2 wt %) resulted in bioactivity with minimal cytotoxicity without compromising mechanical integrity of the restorative material. The antibiofilm properties of ABR-MC were assessed using an exopolysaccharide-matrix-producing (EPS-matrix-producing) oral pathogen (Streptococcus mutans) in an experimental biofilm model. Using high-resolution confocal fluorescence imaging and biophysical methods, we observed remarkable disruption of bacterial accumulation and defective 3D matrix structure on the surface of ABR-MC. Specifically, the antibacterial composite impaired the ability of S. mutans to form organized bacterial clusters on the surface, resulting in altered biofilm architecture with sparse cell accumulation and reduced amounts of EPS matrix (versus control composite). Biofilm topology analyses on the control composite revealed a highly organized and weblike EPS structure that tethers the bacterial clusters to each other and to the surface, forming a highly cohesive unit. In contrast, such a structured matrix was absent on the surface of ABR-MC with mostly sparse and amorphous EPS, indicating disruption in the biofilm physical stability. Consistent with lack of structural organization, the defective biofilm on the surface of ABR-MC was readily detached when subjected to low shear stress, while most of the biofilm biomass remained on the control surface. Altogether, we demonstrate a new nonleachable antibacterial composite with excellent antibiofilm activity without affecting its mechanical properties, which may serve as a platform for development of alternative antifouling biomaterials.

Evolutionary and geologic consequences of organic carbon fixing in the primitive anoxic ocean

NASA Astrophysics Data System (ADS)

Berry, W. B. N.; Wilde, P.

1983-03-01

Steps leading to development of the modern photic-based marine food web are postulated as the result of modifications of the environment, enhanced by the activity of Archean sulfur chemoautotrophs. Such organisms (Anoxium) evolved in an anoxic ocean prior to 3.9 × 109 yr ago at Archean analogs of modern oceanic hydrothermal vents. At this time geothermal energy was more readily available to organisms than photic energy, given atmospheric conditions at the surface similar to Venus, where intensity is low and only middle and red visible wavelengths penetrate the cloudy CO2-rich atmosphere. Competition for the reduced sulfur developed due to oxidation and loss of sulfur to sediments. Consequently, evolutionary advantage shifted to Anoxium isolates that could use alternate energy sources such as light to supplement the diminished supplies of reduced sulfur. Initially, photo-sulfur organisms evolved similar to modern purple bacteria that absorb in the red visible spectra. Subsequent carbon fixing and oxidation improved both the quantity and range of light reaching the ocean surface. This permitted absorption in the blue visible range so that water splitting was now feasible, releasing free oxygen and accelerating oxidation. Eventually, reducing environments became restricted, completing the shift in the principal marine carbon-fixing activity from anoxic chemoautotrophic to aerobic photosynthetic organisms.

Dynamic Bubble Surface Tension Measurements in Northwest Atlantic Seawater

NASA Astrophysics Data System (ADS)

Kieber, D. J.; Long, M. S.; Keene, W. C.; Kinsey, J. D.; Frossard, A. A.; Beaupre, S. R.; Duplessis, P.; Maben, J. R.; Lu, X.; Chang, R.; Zhu, Y.; Bisgrove, J.

2017-12-01

Numerous reports suggest that most organic matter (OM) associated with newly formed primary marine aerosol (PMA) originates from the sea-surface microlayer. However, surface-active OM rapidly adsorbs onto bubble surfaces in the water column and is ejected into the atmosphere when bubbles burst at the air-water interface. Here we present dynamic surface tension measurements of bubbles produced in near surface seawater from biologically productive and oligotrophic sites and in deep seawater collected from 2500 m in the northwest Atlantic. In all cases, the surface tension of bubble surfaces decreased within seconds after the bubbles were exposed to seawater. These observations demonstrate that bubble surfaces are rapidly saturated by surfactant material scavenged from seawater. Spatial and diel variability in bubble surface evolution indicate corresponding variability in surfactant concentrations and/or composition. Our results reveal that surface-active OM is found throughout the water column, and that at least some surfactants are not of recent biological origin. Our results also support the hypothesis that the surface microlayer is a minor to negligible source of OM associated with freshly produced PMA.

Methylmercury Mass Budgets and Distribution Characteristics in the Western Pacific Ocean.

PubMed

Kim, Hyunji; Soerensen, Anne L; Hur, Jin; Heimbürger, Lars-Eric; Hahm, Doshik; Rhee, Tae Siek; Noh, Seam; Han, Seunghee

2017-02-07

Methylmercury (MeHg) accumulation in marine organisms poses serious ecosystem and human health risk, yet the sources of MeHg in the surface and subsurface ocean remain uncertain. Here, we report the first MeHg mass budgets for the Western Pacific Ocean estimated based on cruise observations. We found the major net source of MeHg in surface water to be vertical diffusion from the subsurface layer (1.8-12 nmol m -2  yr -1 ). A higher upward diffusion in the North Pacific (12 nmol m -2  yr -1 ) than in the Equatorial Pacific (1.8-5.7 nmol m -2  yr -1 ) caused elevated surface MeHg concentrations observed in the North Pacific. We furthermore found that the slope of the linear regression line for MeHg versus apparent oxygen utilization in the Equatorial Pacific was about 2-fold higher than that in the North Pacific. We suggest this could be explained by redistribution of surface water in the tropical convergence-divergence zone, supporting active organic carbon decomposition in the Equatorial Pacific Ocean. On the basis of this study, we predict oceanic regions with high organic carbon remineralization to have enhanced MeHg concentrations in both surface and subsurface waters.

Biologically Enhanced Energy and Carbon Cycling on Titan?

NASA Astrophysics Data System (ADS)

Schulze-Makuch, Dirk; Grinspoon, David H.

2005-08-01

With the Cassini-Huygens Mission in orbit around Saturn, the large moon Titan, with its reducing atmosphere, rich organic chemistry, and heterogeneous surface, moves into the astrobiological spotlight. Environmental conditions on Titan and Earth were similar in many respects 4 billion years ago, the approximate time when life originated on Earth. Life may have originated on Titan during its warmer early history and then developed adaptation strategies to cope with the increasingly cold conditions. If organisms originated and persisted, metabolic strategies could exist that would provide sufficient energy for life to persist, even today. Metabolic reactions might include the catalytic hydrogenation of photochemically produced acetylene, or involve the recombination of radicals created in the atmosphere by ultraviolet radiation. Metabolic activity may even contribute to the apparent youth, smoothness, and high activity of Titan's surface via biothermal energy.

Biologically enhanced energy and carbon cycling on Titan?

PubMed

Schulze-Makuch, Dirk; Grinspoon, David H

2005-08-01

With the Cassini-Huygens Mission in orbit around Saturn, the large moon Titan, with its reducing atmosphere, rich organic chemistry, and heterogeneous surface, moves into the astrobiological spotlight. Environmental conditions on Titan and Earth were similar in many respects 4 billion years ago, the approximate time when life originated on Earth. Life may have originated on Titan during its warmer early history and then developed adaptation strategies to cope with the increasingly cold conditions. If organisms originated and persisted, metabolic strategies could exist that would provide sufficient energy for life to persist, even today. Metabolic reactions might include the catalytic hydrogenation of photochemically produced acetylene, or involve the recombination of radicals created in the atmosphere by ultraviolet radiation. Metabolic activity may even contribute to the apparent youth, smoothness, and high activity of Titan's surface via biothermal energy.

Surface Chemistry and Nano-/Microstructure Engineering on Photocatalytic In2S3 Nanocrystals.

PubMed

Berestok, Taisiia; Guardia, Pablo; Portals, Javier Blanco; Estradé, Sònia; Llorca, Jordi; Peiró, Francesca; Cabot, Andreu; Brock, Stephanie L

2018-06-05

Colloidal nanocrystals (NCs) compete with molecular catalysts in the field of homogenous catalysis, offering easier recyclability and a number of potentially advantageous functionalities, such as tunable band gaps, plasmonic properties, or a magnetic moment. Using high-throughput printing technologies, colloidal NCs can also be supported onto substrates to produce cost-effective electronic, optoelectronic, electrocatalytic, and sensing devices. For both catalytic and technological application, NC surface chemistry and supracrystal organization are key parameters determining final performance. Here, we study the influence of the surface ligands and the NC organization on the catalytic properties of In 2 S 3 , both as a colloid and as a supported layer. As a colloid, NCs stabilized by inorganic ligands show the highest photocatalytic activities, which we associate with their large and more accessible surfaces. On the other hand, when NCs are supported on a substrate, their organization becomes an essential parameter determining performance. For instance, NC-based films produced through a gelation process provided five-fold higher photocurrent densities than those obtained from dense films produced by the direct printing of NCs.

Electroless silver plating of the surface of organic semiconductors.

PubMed

Campione, Marcello; Parravicini, Matteo; Moret, Massimo; Papagni, Antonio; Schröter, Bernd; Fritz, Torsten

2011-10-04

The integration of nanoscale processes and devices demands fabrication routes involving rapid, cost-effective steps, preferably carried out under ambient conditions. The realization of the metal/organic semiconductor interface is one of the most demanding steps of device fabrication, since it requires mechanical and/or thermal treatments which increment costs and are often harmful in respect to the active layer. Here, we provide a microscopic analysis of a room temperature, electroless process aimed at the deposition of a nanostructured metallic silver layer with controlled coverage atop the surface of single crystals and thin films of organic semiconductors. This process relies on the reaction of aqueous AgF solutions with the nonwettable crystalline surface of donor-type organic semiconductors. It is observed that the formation of a uniform layer of silver nanoparticles can be accomplished within 20 min contact time. The electrical characterization of two-terminal devices performed before and after the aforementioned treatment shows that the metal deposition process is associated with a redox reaction causing the p-doping of the semiconductor. © 2011 American Chemical Society

Microbiologically Influenced Corrosion: Causative Organisms and Mechanisms

DTIC Science & Technology

2012-01-31

corrosion is both predictable and complex. In aquatic environments and under some atmospheric conditions . microorganisms settle on surfaces and alter the...some atmospheric conditions , microorganisms settle on sin laces and alter the surface chemistry controlling the rates of corrosion or shifting the...pitting corrosion of some allO) S continues under deposits of iron-oxidizing bacteria independent of bacterial activity. Similarly, microbiologicall

Effects of native perennial vegetation buffer strips on dissolved organic carbon in surface runoff from an agricultural landscape

Treesearch

Tomorra E. Smith; Randall K. Kolka; Xiaobo Zhou; Matthew J. Helmers; Richard M. Cruse; Mark D. Tomer

2014-01-01

Dissolved organic carbon (DOC) constitutes a small yet important part of a watershed's carbon budget because it is mobile and biologically active. Agricultural conservation practices such as native perennial vegetation (NPV) strips will influence carbon cycling of an upland agroecosystem, and could affect how much DOC enters streams in runoff, potentially...

A marine biogenic source of atmospheric ice-nucleating particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilson, T. W.; Ladino, L. A.; Alpert, Peter A.

2015-09-09

The formation of ice in clouds is facilitated by the presence of airborne ice nucleating particles1,2. Sea spray is one of the major global sources of atmospheric particles, but it is unclear to what extent these particles are capable of nucleating ice3–11. Here we show that material in the sea surface microlayer, which is enriched in surface active organic material representative of that found in sub-micron sea- spray aerosol12–21, nucleates ice under conditions that occur in mixed-phase clouds and high-altitude ice clouds. The ice active material is likely biogenic and is less than ~0.2 ?m in size. We also showmore » that organic material (exudate) released by a common marine diatom nucleates ice when separated from cells and propose that organic material associated with phytoplankton cell exudates are a candidate for the observed ice nucleating ability of the microlayer samples. By combining our measurements with global model simulations of marine organic aerosol, we show that ice nucleating particles of marine origin are dominant in remote marine environments, such as the Southern Ocean, the North Pacific and the North Atlantic.« less

Surface functionalization of 3D glass-ceramic porous scaffolds for enhanced mineralization in vitro

NASA Astrophysics Data System (ADS)

Ferraris, Sara; Vitale-Brovarone, Chiara; Bretcanu, Oana; Cassinelli, Clara; Vernè, Enrica

2013-04-01

Bone reconstruction after tissue loosening due to traumatic, pathological or surgical causes is in increasing demand. 3D scaffolds are a widely studied solution for supporting new bone growth. Bioactive glass-ceramic porous materials can offer a three-dimensional structure that is able to chemically bond to bone. The ability to surface modify these devices by grafting biologically active molecules represents a challenge, with the aim of stimulating physiological bone regeneration with both inorganic and organic signals. In this research work glass ceramic scaffolds with very high mechanical properties and moderate bioactivity have been functionalized with the enzyme alkaline phosphatase (ALP). The material surface was activated in order to expose hydroxyl groups. The activated surface was further grafted with ALP both via silanization and also via direct grafting to the surface active hydroxyl groups. Enzymatic activity of grafted samples were measured by means of UV-vis spectroscopy before and after ultrasonic washing in TRIS-HCl buffer solution. In vitro inorganic bioactivity was investigated by soaking the scaffolds after the different steps of functionalization in a simulated body fluid (SBF). SEM observations allowed the monitoring of the scaffold morphology and surface chemical composition after soaking in SBF. The presence of ALP enhanced the in vitro inorganic bioactivity of the tested material.

Silver Nanoparticle Impregnated Bio-Based Activated Carbon with Enhanced Antimicrobial Activity

NASA Astrophysics Data System (ADS)

Selvakumar, R.; Suriyaraj, S. P.; Jayavignesh, V.; Swaminathan, K.

2013-08-01

The present study involves the production of silver nanoparticles using a novel yeast strain Saccharomyces cerevisiae BU-MBT CY-1 isolated from coconut cell sap. The biological reduction of silver nitrate by the isolate was deducted at various time intervals. The yeast cells after biological silver reduction were harvested and subjected to carbonization at 400°C for 1 h and its properties were analyzed using Fourier transform infra-red spectroscopy, X-ray diffraction, scanning electron microscope attached with energy dispersive spectroscopy and transmission electron microscopy. The average size of the silver nanoparticles present on the surface of the carbonized silver containing yeast cells (CSY) was 19 ± 9 nm. The carbonized control yeast cells (CCY) did not contain any particles on its surface. The carbonized silver nanoparticles containing yeast cells (CSY) were made into bioactive emulsion and tested for its efficacy against various pathogenic Gram positive and Gram negative bacteria. The antimicrobial activity studies indicated that CSY bioactive nanoemulsion was effective against Gram negative organisms than Gram positive organism.

Development and characterization of activated hydrochars from orange peels as potential adsorbents for emerging organic contaminants.

PubMed

Fernandez, M E; Ledesma, B; Román, S; Bonelli, P R; Cukierman, A L

2015-05-01

Activated hydrochars obtained from the hydrothermal carbonization of orange peels (Citrus sinensis) followed by various thermochemical processing were assessed as adsorbents for emerging contaminants in water. Thermal activation under flows of CO2 or air as well as chemical activation with phosphoric acid were applied to the hydrochars. Their characteristics were analyzed and related to their ability to uptake three pharmaceuticals (diclofenac sodium, salicylic acid and flurbiprofen) considered as emerging contaminants. The hydrothermal carbonization and subsequent activations promoted substantial chemical transformations which affected the surface properties of the activated hydrochars; they exhibited specific surface areas ranging from 300 to ∼620 m(2)/g. Morphological characterization showed the development of coral-like microspheres dominating the surface of most hydrochars. Their ability to adsorb the three pharmaceuticals selected was found largely dependent on whether the molecules were ionized or in their neutral form and on the porosity developed by the new adsorbents. Copyright © 2015 Elsevier Ltd. All rights reserved.

Spent coffee-based activated carbon: specific surface features and their importance for H2S separation process.

PubMed

Kante, Karifala; Nieto-Delgado, Cesar; Rangel-Mendez, J Rene; Bandosz, Teresa J

2012-01-30

Activated carbons were prepared from spent ground coffee. Zinc chloride was used as an activation agent. The obtained materials were used as a media for separation of hydrogen sulfide from air at ambient conditions. The materials were characterized using adsorption of nitrogen, elemental analysis, SEM, FTIR, and thermal analysis. Surface features of the carbons depend on the amount of an activation agent used. Even though the residual inorganic matter takes part in the H(2)S retention via salt formation, the porous surface of carbons governs the separation process. The chemical activation method chosen resulted in formation of large volume of pores with sizes between 10 and 30Å, optimal for water and hydrogen sulfide adsorption. Even though the activation process can be optimized/changed, the presence of nitrogen in the precursor (caffeine) is a significant asset of that specific organic waste. Nitrogen functional groups play a catalytic role in hydrogen sulfide oxidation. Copyright © 2011 Elsevier B.V. All rights reserved.

Probing the energetics of organic–nanoparticle interactions of ethanol on calcite

DOE PAGES

Wu, Di; Navrotsky, Alexandra

2015-04-13

Knowing the nature of interactions between small organic molecules and surfaces of nanoparticles (NP) is crucial for fundamental understanding of natural phenomena and engineering processes. In this paper, we report direct adsorption enthalpy measurement of ethanol on a series of calcite nanocrystals, with the aim of mimicking organic–NP interactions in various environments. The energetics suggests a spectrum of adsorption events as a function of coverage: strongest initial chemisorption on active sites on fresh calcite surfaces, followed by major chemical binding to form an ethanol monolayer and, subsequently, very weak, near-zero energy, physisorption. Furthermore, these thermochemical observations directly support a structuremore » where the ethanol monolayer is bonded to the calcite surface through its polar hydroxyl group, leaving the hydrophobic ends of the ethanol molecules to interact only weakly with the next layer of adsorbing ethanol and resulting in a spatial gap with low ethanol density between the monolayer and subsequent added ethanol molecules, as predicted by molecular dynamics and density functional calculations. Such an ordered assembly of ethanol on calcite NP is analogous to, although less strongly bonded than, a capping layer of organics intentionally introduced during NP synthesis, and suggests a continuous variation of surface structure depending on molecular chemistry, ranging from largely disordered surface layers to ordered layers that nevertheless are mobile and can rearrange or be displaced by other molecules to strongly bonded immobile organic capping layers. Finally, these differences in surface structure will affect chemical reactions, including the further nucleation and growth of nanocrystals on organic ligand-capped surfaces.« less

Enhanced catalyst activity by decorating of Au on Ag@Cu2O nanoshell

NASA Astrophysics Data System (ADS)

Chen, Lei; Liu, Maomao; Zhao, Yue; Kou, Qiangwei; Wang, Yaxin; Liu, Yang; Zhang, Yongjun; Yang, Jinghai; Jung, Young Mee

2018-03-01

We successfully synthesized Au-decorated Ag@Cu2O heterostructures via a simple galvanic replacement method. As the Au precursor concentration increased, the density of the Au nanoparticles (NPs) on the Ag@Cu2O surface increased, which changed the catalytic activity of the Ag@Cu2O-Au structure. The combination of Au, Ag, and Cu2O exhibited excellent catalytic properties, which can further effect on the catalyst activity of the Ag@Cu2O-Au structure. In addition, the proposed Ag@Cu2O-Au nanocomposite was used to transform the organic, toxic pollutant, 4-nitrophenol (4-NP), into its nontoxic and medicinally important amino derivative via a catalytic reduction to optimize the material performance. The proposed Au-decorated Ag@Cu2O exhibited excellent catalytic activity, and the catalytic reduction time greatly decreased (5 min). Thus, three novel properties of Ag@Cu2O-Au, i.e., charge redistribution and transfer, adsorption, and catalytic reduction of organic pollutants, were ascertained for water remediation. The proposed catalytic properties have potential applications for photocatalysis and localized surface plasmon resonance (LSPR)- and peroxidase-like catalysis.

Screening of multiple hormonal activities in surface water and sediment from the Pearl River system, South China, using effect-directed in vitro bioassays.

PubMed

Zhao, Jian-Liang; Ying, Guang-Guo; Yang, Bin; Liu, Shan; Zhou, Li-Jun; Chen, Zhi-Feng; Lai, Hua-Jie

2011-10-01

This paper reports screening of multiple hormonal activities (estrogenic and androgenic activities, antiestrogenic and antiandrogenic activities) for surface water and sediment from the Pearl River system (Liuxi, Zhujiang, and Shijing rivers) in South China, using in vitro recombinant yeast bioassays. The detection frequencies for estrogenic and antiandrogenic activities were both 100% in surface water and 81 and 93% in sediment, respectively. The levels of estrogenic activity were 0.23 to 324 ng 17β-estradiol equivalent concentration (EEQ)/L in surface water and 0 to 101 ng EEQ/g in sediment. Antiandrogenic activities were in the range of 20.4 to 935 × 10(3) ng flutamide equivalent concentration (FEQ)/L in surface water and 0 to 154 × 10(3) ng FEQ/g in sediment. Moreover, estrogenic activity and antiandrogenic activity in sediment showed good correlation (R(2) = 0.7187), suggesting that the agonists of estrogen receptor and the antagonists of androgen receptor co-occurred in sediment. The detection frequencies for androgenic and antiestrogenic activities were 41 and 29% in surface water and 61 and 4% in sediment, respectively. The levels of androgenic activities were 0 to 45.4 ng dihydrotestosterone equivalent concentration (DEQ)/L in surface water, and the potency was very weak in the only detected sediment site. The levels of antiestrogenic activity were 0 to 1,296 × 10(3) ng tamoxifen equivalent concentration (TEQ)/L in surface water and 0 to 89.5 × 10(3) ng TEQ/g in sediment. The Shijing River displayed higher levels of hormonal activities than the Zhujiang and Liuxi rivers, indicating that the Shijing River had been suffering from heavy contamination with endocrine-disrupting chemicals. The equivalent concentrations of hormonal activities in some sites were greater than the lowest-observed-effect concentrations reported in the literature, suggesting potential adverse effects on aquatic organisms. Copyright © 2011 SETAC.

PROCESS OF TREATING OR FORMING AN INSOLUBLE PLUTONIUM PRECIPITATE IN THE PRESENCE OF AN ORGANIC ACTIVE AGENT

DOEpatents

Balthis, J.H.

1961-07-18

Carrier precipitation processes for the separation of plutonium from fission products are described. In a process in which an insoluble precipitate is formed in a solution containing plutonium and fission products under conditions whereby plutonium is carried by the precipitate, and the precipitate is then separated from the remaining solution, an organic surface active agent is added to the mixture of precipitate and solution prior to separation of the precipitate from the supernatant solution, thereby improving the degree of separation of the precipitate from the solution.

Some Surface-Active Agents and Their Virucidal Effect on Foot-and-Mouth Disease Virus

PubMed Central

Fellowes, O. N.

1965-01-01

Selected cationic and anionic surface-active compounds were tested to determine their virucidal effect on the foot-and-mouth disease virus, type O, strain M11, propagated in primary calf kidney cells. The chemical inactivation of the virus was tested with 0.5, 1.0, 2.0, and 5.0% concentrations of the selected compounds. Virus controls with pH adjusted to cover the expected range of the mixtures of the chemicals and virus were also tested. The absence of virus from the mixtures of chemical and virus after reaction at 28 C for 2 hr was assayed by inoculating suckling mice with the mixtures. One cationic compound, alkyl methyl isoquinilinium chloride, showed considerable antiviral activity due largely to pH effect. The use of the surface-active agents investigated in this study, in the presence of organic material, would not be recommended as virucides. PMID:4286396

The Activity of Antimicrobial Surfaces Varies by Testing Protocol Utilized

PubMed Central

Campos, Matias D.; Zucchi, Paola C.; Phung, Ann; Leonard, Steven N.; Hirsch, Elizabeth B.

2016-01-01

Background Contaminated hospital surfaces are an important source of nosocomial infections. A major obstacle in marketing antimicrobial surfaces is a lack of efficacy data based on standardized testing protocols. Aim We compared the efficacy of multiple testing protocols against several “antimicrobial” film surfaces. Methods Four clinical isolates were used: one Escherichia coli, one Klebsiella pneumoniae, and two Staphylococcus aureus strains. Two industry methods (modified ISO 22196 and ASTM E2149), a “dried droplet”, and a “transfer” method were tested against two commercially available antimicrobial films, one film in development, an untreated control, and a positive (silver) control film. At 2 (only ISO) and 24 hours following inoculation, bacteria were collected from film surfaces and enumerated. Results Compared to untreated films in all protocols, there were no significant differences in recovery on either commercial brand at 2 or 24 hours after inoculation. The silver surface demonstrated significant microbicidal activity (mean loss 4.9 Log10 CFU/ml) in all methods and time points with the exception of 2 hours in the ISO protocol and the transfer method. Using our novel droplet method, no differences between placebo and active surfaces were detected. The surface in development demonstrated variable activity depending on method, organism, and time point. The ISO demonstrated minimal activity at 2 hours but significant activity at 24 hours (mean 4.5 Log10 CFU/ml difference versus placebo). The ASTEM protocol exhibited significant differences in recovery of staphylococci (mean 5 Log10 CFU/ml) but not Gram-negative isolates (10 fold decrease). Minimal activity was observed with this film in the transfer method. Conclusions Varying results between protocols suggested that efficacy of antimicrobial surfaces cannot be easily and reproducibly compared. Clinical use should be considered and further development of representative methods is needed. PMID:27494336

Biochemical evolution. I. Polymerization on internal, organophilic silica surfaces of dealuminated zeolites and feldspars

PubMed Central

Smith, Joseph V.

1998-01-01

Catalysis at mineral surfaces might generate replicating biopolymers from simple chemicals supplied by meteorites, volcanic gases, and photochemical gas reactions. Many ideas are implausible in detail because the proposed mineral surfaces strongly prefer water and other ionic species to organic ones. The molecular sieve silicalite (Union Carbide; = Al-free Mobil ZSM-5 zeolite) has a three-dimensional, 10-ring channel system whose electrically neutral Si-O surface strongly adsorbs organic species over water. Three -O-Si tetrahedral bonds lie in the surface, and the fourth Si-O points inwards. In contrast, the outward Si-OH of simple quartz and feldspar crystals generates their ionic organophobicity. The ZSM-5-type zeolite mutinaite occurs in Antarctica with boggsite and tschernichite (Al-analog of Mobil Beta). Archean mutinaite might have become de-aluminated toward silicalite during hot/cold/wet/dry cycles. Catalytic activity of silicalite increases linearly with Al-OH substitution for Si, and Al atoms tend to avoid each other. Adjacent organophilic and catalytic Al-OH regions in nanometer channels might have scavenged organic species for catalytic assembly into specific polymers protected from prompt photochemical destruction. Polymer migration along weathered silicic surfaces of micrometer-wide channels of feldspars might have led to assembly of replicating catalytic biomolecules and perhaps primitive cellular organisms. Silica-rich volcanic glasses should have been abundant on the early Earth, ready for crystallization into zeolites and feldspars, as in present continental basins. Abundant chert from weakly metamorphosed Archaean rocks might retain microscopic clues to the proposed mineral adsorbent/catalysts. Other framework silicas are possible, including ones with laevo/dextro one-dimensional channels. Organic molecules, transition-metal ions, and P occur inside modern feldspars. PMID:9520372

Biochemical evolution. I. Polymerization On internal, organophilic silica surfaces of dealuminated zeolites and feldspars.

PubMed

Smith, J V

1998-03-31

Catalysis at mineral surfaces might generate replicating biopolymers from simple chemicals supplied by meteorites, volcanic gases, and photochemical gas reactions. Many ideas are implausible in detail because the proposed mineral surfaces strongly prefer water and other ionic species to organic ones. The molecular sieve silicalite (Union Carbide; = Al-free Mobil ZSM-5 zeolite) has a three-dimensional, 10-ring channel system whose electrically neutral Si-O surface strongly adsorbs organic species over water. Three -O-Si tetrahedral bonds lie in the surface, and the fourth Si-O points inwards. In contrast, the outward Si-OH of simple quartz and feldspar crystals generates their ionic organophobicity. The ZSM-5-type zeolite mutinaite occurs in Antarctica with boggsite and tschernichite (Al-analog of Mobil Beta). Archean mutinaite might have become de-aluminated toward silicalite during hot/cold/wet/dry cycles. Catalytic activity of silicalite increases linearly with Al-OH substitution for Si, and Al atoms tend to avoid each other. Adjacent organophilic and catalytic Al-OH regions in nanometer channels might have scavenged organic species for catalytic assembly into specific polymers protected from prompt photochemical destruction. Polymer migration along weathered silicic surfaces of micrometer-wide channels of feldspars might have led to assembly of replicating catalytic biomolecules and perhaps primitive cellular organisms. Silica-rich volcanic glasses should have been abundant on the early Earth, ready for crystallization into zeolites and feldspars, as in present continental basins. Abundant chert from weakly metamorphosed Archaean rocks might retain microscopic clues to the proposed mineral adsorbent/catalysts. Other framework silicas are possible, including ones with laevo/dextro one-dimensional channels. Organic molecules, transition-metal ions, and P occur inside modern feldspars.

From organized internal traffic to collective navigation of bacterial swarms

NASA Astrophysics Data System (ADS)

Ariel, Gil; Shklarsh, Adi; Kalisman, Oren; Ingham, Colin; Ben-Jacob, Eshel

2013-12-01

Bacterial swarming resulting in collective navigation over surfaces provides a valuable example of cooperative colonization of new territories. The social bacterium Paenibacillus vortex exhibits successful and diverse swarming strategies. When grown on hard agar surfaces with peptone, P. vortex develops complex colonies of vortices (rotating bacterial aggregates). In contrast, during growth on Mueller-Hinton broth gelled into a soft agar surface, a new strategy of multi-level organization is revealed: the colonies are organized into a special network of swarms (or ‘snakes’ of a fraction of millimeter in width) with intricate internal traffic. More specifically, cell movement is organized in two or three lanes of bacteria traveling between the back and the front of the swarm. This special form of cellular logistics suggests new methods in which bacteria can share resources and risk while searching for food or migrating into new territories. While the vortices-based organization on hard agar surfaces has been modeled before, here, we introduce a new multi-agent bacterial swarming model devised to capture the swarms-based organization on soft surfaces. We test two putative generic mechanisms that may underlie the observed swarming logistics: (i) chemo-activated taxis in response to chemical cues and (ii) special align-and-push interactions between the bacteria and the boundary of the layer of lubricant collectively generated by the swarming bacteria. Using realistic parameters, the model captures the observed phenomena with semi-quantitative agreement in terms of the velocity as well as the dynamics of the swarm and its envelope. This agreement implies that the bacteria interactions with the swarm boundary play a crucial role in mediating the interplay between the collective movement of the swarm and the internal traffic dynamics.

Electrochemical decolorization of dye wastewater by surface-activated boron-doped nanocrystalline diamond electrode.

PubMed

Chen, Chienhung; Nurhayati, Ervin; Juang, Yaju; Huang, Chihpin

2016-07-01

Complex organics contained in dye wastewater are difficult to degrade and often require electrochemical advanced oxidation processes (EAOPs) to treat it. Surface activation of the electrode used in such treatment is an important factor determining the success of the process. The performance of boron-doped nanocrystalline diamond (BD-NCD) film electrode for decolorization of Acid Yellow (AY-36) azo dye with respect to the surface activation by electrochemical polarization was studied. Anodic polarization found to be more suitable as electrode pretreatment compared to cathodic one. After anodic polarization, the originally H-terminated surface of BD-NCD was changed into O-terminated, making it more hydrophilic. Due to the oxidation of surface functional groups and some portion of sp(2) carbon in the BD-NCD film during anodic polarization, the electrode was successfully being activated showing lower background current, wider potential window and considerably less surface activity compared to the non-polarized one. Consequently, electrooxidation (EO) capability of the anodically-polarized BD-NCD to degrade AY-36 dye was significantly enhanced, capable of nearly total decolorization and chemical oxygen demand (COD) removal even after several times of re-using. The BD-NCD film electrode favored acidic condition for the dye degradation; and the presence of chloride ion in the solution was found to be more advantageous than sulfate active species. Copyright © 2016. Published by Elsevier B.V.

Surface Plasmon-Assisted Solar Energy Conversion.

PubMed

Dodekatos, Georgios; Schünemann, Stefan; Tüysüz, Harun

2016-01-01

The utilization of localized surface plasmon resonance (LSPR) from plasmonic noble metals in combination with semiconductors promises great improvements for visible light-driven photocatalysis, in particular for energy conversion. This review summarizes the basic principles of plasmonic photocatalysis, giving a comprehensive overview about the proposed mechanisms for enhancing the performance of photocatalytically active semiconductors with plasmonic devices and their applications for surface plasmon-assisted solar energy conversion. The main focus is on gold and, to a lesser extent, silver nanoparticles in combination with titania as semiconductor and their usage as active plasmonic photocatalysts. Recent advances in water splitting, hydrogen generation with sacrificial organic compounds, and CO2 reduction to hydrocarbons for solar fuel production are highlighted. Finally, further improvements for plasmonic photocatalysts, regarding performance, stability, and economic feasibility, are discussed for surface plasmon-assisted solar energy conversion.

Fabrication and characterization of inverted organic solar cells using shuttle cock-type metal phthalocyanine and PCBM:P3HT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suzuki, Atsushi, E-mail: suzuki@mat.usp.ac.jp; Furukawa, Ryo, E-mail: suzuki@mat.usp.ac.jp; Akiyama, Tsuyoshi, E-mail: suzuki@mat.usp.ac.jp

2015-02-27

Inverted organic solar cells using shuttle cock-type phthalocyanine, semiconducting polymer and fullerenes were fabricated and characterized. Photovoltaic and optical properties of the solar cells with inverted structures were investigated by optical absorption, current density-voltage characteristics. The photovoltaic properties of the tandem organic solar cell using titanyl phthalocyanine, vanadyl phthalocyanine, poly(3-hexylthiophene) (P3HT) and [6, 6]-phenyl C{sub 61}-butyric acid methyl ester (PCBM) were improved. Effect of annealing and solvent treatment on surface morphologies of the active layer was investigated. The photovoltaic mechanisms, energy levels and band gap of active layers were discussed for improvement of the photovoltaic performance.

Active devices based on organic semiconductors for wearable applications.

PubMed

Barbaro, Massimo; Caboni, Alessandra; Cosseddu, Piero; Mattana, Giorgio; Bonfiglio, Annalisa

2010-05-01

Plastic electronics is an enabling technology for obtaining active (transistor based) electronic circuits on flexible and/or nonplanar surfaces. For these reasons, it appears as a perfect candidate to promote future developments of wearable electronics toward the concept of fabrics and garments made by functional (in this case, active electronic) yarns. In this paper, a panoramic view of recent achievements and future perspectives is given.

Organic marker compounds in surface soils of crop fields from the San Joaquin Valley fugitive dust characterization study

NASA Astrophysics Data System (ADS)

Rogge, Wolfgang F.; Medeiros, Patricia M.; Simoneit, Bernd R. T.

Fugitive dust from the erosion of arid and fallow land, after harvest and during agricultural activities, can at times be the dominant source of airborne particulate matter. In order to assess the source contributions to a given site, chemical mass balance (CMB) modeling is typically used together with source-specific profiles for organic and inorganic constituents. Yet, the mass balance closure can be achieved only if emission profiles for all major sources are considered. While a higher degree of mass balance closure has been achieved by adding individual organic marker compounds to elements, ions, EC, and organic carbon (OC), major source profiles for fugitive dust are not available. Consequently, neither the exposure of the population living near fugitive dust sources from farm land, nor its chemical composition is known. Surface soils from crop fields are enriched in plant detritus from both above and below ground plant parts; therefore, surface soil dust contains natural organic compounds from the crops and soil microbiota. Here, surface soils derived from fields growing cotton, safflower, tomato, almonds, and grapes have been analyzed for more than 180 organic compounds, including natural lipids, saccharides, pesticides, herbicides, and polycyclic aromatic hydrocarbon (PAH). The major result of this study is that selective biogenically derived organic compounds are suitable markers of fugitive dust from major agricultural crop fields in the San Joaquin Valley. Aliphatic homologs exhibit the typical biogenic signatures of epicuticular plant waxes and are therefore indicative of fugitive dust emissions and mechanical abrasion of wax protrusions from leaf surfaces. Saccharides, among which α- and β-glucose, sucrose, and mycose show the highest concentrations in surface soils, have been proposed to be generic markers for fugitive dust from cultivated land. Similarly, steroids are strongly indicative of fugitive dust. Yet, triterpenoids reveal the most pronounced distribution differences for all types of cultivated soils examined here and are by themselves powerful markers for fugitive dust that allow differentiation between the types of crops cultivated. PAHs are also found in some surface soils, as well as persistent pesticides, e.g., DDE, Fosfall, and others.

Effect of Organic Cations on Hydrogen Oxidation Reaction of Carbon Supported Platinum

DOE PAGES

Chung, Hoon Taek; Choe, Yong-Kee; Martinez, Ulises; ...

2016-11-02

Effect of organic cations on hydrogen oxidation reaction (HOR) of carbon supported platinum (Pt/C) is investigated using three 0.1 M alkaline electrolytes, tetramethylammonium hydroxide (TMAOH), tetrabutylammonium hydroxide (TBAOH) and tetrabutylphosphonium hydroxide (TBPOH). Rotating disk electrode experiments indicate that the HOR of Pt/C is adversely impacted by time-dependent and potential-driven chemisorption of organic cations. In-situ infrared reflection adsorption spectroscopy experiments indicated that the specific chemisorption of organic cations drives the hydroxide co-adsorption on Pt surface. The co-adsorption of TMA + and hydroxide at 0.1 V vs. reversible hydrogen electrode is the strongest; consequently, complete removal of the co-adsorbed layer from Ptmore » surface is difficult even after exposure the Pt surface to 1.2 V. Conversely, the chemisorption of TBP+ is the weakest, yet notable decrease of HOR current density is still observed. The adsorption energies, ΔE, for TMA +, TBA +, and TBP + on Pt (111) surface from density functional theory are computed to be -2.79, -2.42 and -2.00 eV, respectively. The relatively low adsorption energy of TBP + is explained by the steric hindrance and electronic effect. This study emphasizes the importance of cationic group on HOR activity of alkaline anion exchange membrane fuel cells.« less

Indigenous Carbonaceous Matter in the Nakhla Mars Meteorite

NASA Technical Reports Server (NTRS)

Clemett, S. J.; Thomas-Keprta, K. L.; Rahman, Z.; Le, L.; Wentworth, S. J.; Gibson, E. K.; McKay, D. S.

2016-01-01

Detailed microanalysis of the Martian meteorite Nakhla has shown there are morphologically distinct carbonaceous features spatially associated with low-T aqueous alteration phases including salts and id-dingsite. A comprehensive suite of analytical instrumentation including optical microscopy, field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) spectroscopy, focused ion beam (FIB) microscopy, transmission electron microscopy (TEM), two-step laser mass spectrometry (mu-L(sup 2)MS), laser mu-Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), and nanoscale secondary ion mass spectrometry (NanoSIMS) are being used to characterize the carbonaceous matter and host mineralogy. The search for carbonaceous matter on Mars has proved challenging. Viking Landers failed to unambiguously detect simple organics at either of the two landing sites although the Martian surface is estimated to have acquired at least 10(exp15) kg of C as a consequence of meteoritic accretion over the last several Ga. The dearth of organics at the Martian surface has been attributed to various oxidative processes including UV photolysis and peroxide activity. Consequently, investigations of Martian organics need to be focused on the sub-surface regolith where such surface processes are either severely attenuated or absent. Fortuitously since Martian meteorites are derived from buried regolith materials they provide a unique opportunity to study Martian organic geochemistry.

Evidence for a Biological Control on Emissions of Marine Ice Nucleating Particles: Laboratory, Field and Modeling Results

NASA Astrophysics Data System (ADS)

McCluskey, Christina Song

Laboratory, field, and modeling studies were used to (1) confirm the hypothesized source of marine ice nucleating particle (INP) emissions associated with marine organic aerosol that arises from elevated oceanic biological productivity; (2) identify marine INP compositions and their activation temperatures; (3) determine the natural abundances and variability of the number concentrations of marine INPs (nINPs); and (4) evaluate the current best model estimates of marine INPs against new observations. Observations of seawater biology, aerosol composition and ice nucleation ability of bulk seawater, the sea surface microlayer (upper 50 mum of the ocean surface), and laboratory-generated sea spray aerosol (SSA) during simulated phytoplankton blooms revealed that emissions of INPs active at temperatures warmer than -22°C increased during the decay of two phytoplankton blooms. Enrichment of organic matter in the sea surface microlayer and its subsequent control on transferring organic material into the aerosol phase was found to be an important factor in the release of INPs from the ocean surface. Integration of all size and compositional analyses led to two proposed classes of marine INPs: (A) ice nucleation active molecules and (B) ice nucleation active intact or fragmented microbes (e.g., diatoms or bacteria). To investigate marine INPs present in nature, several field campaigns were carried out over oceans and at two remote coastal sites. Regarding their abundance and variability, the number concentrations of ice nucleating particles, nINPs, active at temperatures warmer than -30 °C, ranged over three or more orders of magnitude at any particular temperature for samples collected in the marine boundary layer during six research voyages over the Pacific Ocean, spanning 70°S to 60°N over various seasons. nINPs were greater and more variable in the Northern Hemisphere compared to the Southern Hemisphere. Factors that contributed to this variability were investigated in detail at a North Atlantic Ocean coastal site (Mace Head Research Station, MHD) and over the Southern Ocean (SO). At MHD, normalizing observations by aerosol surface area and limiting measurements to pristine marine air masses narrowed the variability in nINPs. That subset of data was used to develop a parameterization for INPs in pristine sea spray organic aerosol over the North Atlantic Ocean. Higher n INPs active at temperatures warmer than -22°C were observed in pristine SSA during a period that was influenced by organic aerosol arising from offshore biological activity. The INPs observed during this event comprised ice nucleation active microbes (marine INP class B), which were distinct from other marine organic INPs at MHD. These observations indicate that further research is required to incorporate the microbe INP type into parameterizations. Measurements of INPs in the SO marine boundary layer aerosol and in seawater samples were the first in this region in over four decades. Observed nINPs were a factor of 100 lower than those historical measurements. nINPs observed over the SO were less variable than MHD and INP composition included refractory, heat-stable organic (marine INP class A), and heat-labile materials (marine INP class B). These data serve as new observational constraints on nINPs and their sources and compositions that can be applied to evaluate numerical modeling studies. The database from this work was used in an exploratory study to evaluate current modeling approaches for predicting marine INPs. Simulations with the atmospheric component (CAM5) of the Department of Energy Community Earth System Model with implementation of a physically-based parameterization for sea spray organic aerosol were conducted for the MHD and SO study periods. Modeled aerosol mass, number and composition were used as input for two marine INP parameterizations that have been developed since the beginning of this work (circa 2014). Findings indicated that, for INPs active at -15°C during the MHD study period, observed nINPs were bounded by estimates derived from the two marine INP parameterizations. Periods with discrepancies between modeled estimates and observed nINPs were explained by observational evidence that different classes of marine INPs were present at MHD, further supporting the need for additional studies regarding the emissions of different marine INP classes. Different INP types (e.g., marine organic, mineral dust) are active at different temperatures and the observations from this work clearly indicate that organic aerosol is an important factor for determining marine nINPs. Thus, further evaluation of these parameterizations for INPs active at a range of temperatures (0 to -27°C) and against measurements over the Southern Ocean, where sea spray organic aerosol production may be quite different from other regions, will be conducted in the future with these simulations. This deeper analysis may reveal underlying limitations of the parameterizations and provide insights on how to further refine numerical representations of INPs. (Abstract shortened by ProQuest.).

[The effect of hydrophobic surface properties of protein on its resistance to denaturation by organic solvents (using modified alpha-chymotrypsin as an example].

PubMed

Kudriashova, E V; Belova, A B; Vinogradov, A A; Mozhaev, V V

1994-03-01

Catalytic activity of covalently modified alpha-chymotrypsin in water/cosolvent solutions was investigated. The stability of chymotrypsin increases upon modification with hydrophilic reagents, such as glyceraldehyde, pyrometallic and succinic anhydrides, and glucosamine. Correlation was observed between the protein's stability in organic solvents and the degree of hydrophilization of the protein's surface. The protein is the more stable, the higher are the modification degree and the hydrophilicity of the modifying residue. At a certain critical hydrophilization degree of chymotrypsin a limit of stability is achieved. The stabilization effect can be accounted for by the fact that the interaction between water molecules on the surface and protein's functional groups become stronger in the hydrophilized protein.

Orientation-Dependent Exciton-Plasmon Coupling in Embedded Organic/Metal Nanowire Heterostructures.

PubMed

Li, Yong Jun; Hong, Yan; Peng, Qian; Yao, Jiannian; Zhao, Yong Sheng

2017-10-24

The excitation of surface plasmons by optical emitters based on exciton-plasmon coupling is important for plasmonic devices with active optical properties. It has been theoretically demonstrated that the orientation of exciton dipole can significantly influence the coupling strength, yet systematic study of the coupling process in nanostructures is still hindered by the lack of proper material systems. In this work, we have experimentally investigated the orientation-dependent exciton-plasmon coupling in a rationally designed organic/metal nanowire heterostructure system. The heterostructures were prepared by inserting silver nanowires into crystalline organic waveguides during the self-assembly of dye molecules. Structures with different exciton orientations exhibited varying coupling efficiencies. The near-field exciton-plasmon coupling facilitates the design of nanophotonic devices based on the directional surface plasmon polariton propagations.

Synthesis of novel cellulose- based antibacterial composites of Ag nanoparticles@ metal-organic frameworks@ carboxymethylated fibers.

PubMed

Duan, Chao; Meng, Jingru; Wang, Xinqi; Meng, Xin; Sun, Xiaole; Xu, Yongjian; Zhao, Wei; Ni, Yonghao

2018-08-01

A novel cellulose-based antibacterial material, namely silver nanoparticles@ metal-organic frameworks@ carboxymethylated fibers composites (Ag NPs@ HKUST-1@ CFs), was synthesized. The results showed that the metal-organic frameworks (HKUST-1) were uniformly anchored on the fiber's surfaces by virtue of complexation between copper ions in HKUST-1 and carboxyl groups on the carboxymethylated fibers (CFs). The silver nanoparticles (Ag NPs) were immobilized and well-dispersed into the pores and/or onto the surfaces of HKUST-1 via in situ microwave reduction, resulting in the formation of novel Ag NPs@ HKUST-1@ CFs composites. The antibacterial assays showed that the as-prepared composites exhibited a much higher antibacterial activity than Ag NPs@ CFs or HKUST-1@ CFs samples. Copyright © 2018 Elsevier Ltd. All rights reserved.

Evaluation of dose dependent antimicrobial activity of self-assembled chitosan, nano silver and chitosan-nano silver composite against several pathogens.

PubMed

Tareq, Foysal Kabir; Fayzunnesa, Mst; Kabir, Md Shahariar; Nuzat, Musrat

2018-01-01

The aim of this investigation to preparation of silver nanoparticles organized chitosan nano polymer, which effective against microbial and pathogens, when apply to liquid medium and edible food products surface, will rescue the growth of microbes. Self-assembly approach used to synthesis of silver nanoparticles and silver nanoparticles organized chitosan nano polymer. Silver nanoparticles and silver nanoparticles organized chitosan nano polymer and film characterized using Ultra-violate visible spectrometer (UV-vis), X-ray diffraction (X-ray), and Scanning electronic microscope (SEM). The crystalline structured protein capped nano silver successfully synthesized at range of 12 nm-29 nm and organized into chitosan nano polymer. Antimicrobial ingredient in liquid medium and food product surface provide to rescue oxidative change and growth of microorganism to provide higher safety. The silver nanoparticles organized chitosan nano polymer caused the death of microorganism. The materials in nano scale synthesized successfully using self-assembly method, which showed good antimicrobial properties. Copyright © 2017 Elsevier Ltd. All rights reserved.

Waterflooding employing surfactants derived from metallic soaps

DOE Office of Scientific and Technical Information (OSTI.GOV)

Williams, S.A.

1975-12-16

A waterflooding process is described in which a petroleum oil containing divalent metal soaps is contacted with an inorganic acid in order to convert the soaps to the corresponding organic acids. The organic acids thus obtained may be injected into the reservoir followed by an aqueous alkaline solution. Alternatively, the organic acids may be contacted with an aqueous solution in order to convert the acids to the corresponding surface-active monovalent salts, which may be then injected into the reservoir. (4 claims)

Within-storm and Seasonal Differences in Particulate Organic Material Composition and Sources in White Clay Creek, USA

NASA Astrophysics Data System (ADS)

Karwan, D. L.; Aufdenkampe, A. K.; Aalto, R. E.; Newbold, J. D.; Pizzuto, J. E.

2011-12-01

The material exported from a watershed reflects its origin and the processes it undergoes during downhill and downstream transport. Due to its nature as a complex mixture of material, the composition of POM integrates the physical, biological, and chemical processes effecting watershed material. In this study, we integrate sediment fingerprint analyses common in geomorphological studies of mineral suspended particulate material (SPM) with biological and ecological characterizations of particulate organic carbon (POC). Through this combination, we produce quantifiable budgets of particulate organic carbon and mineral material, as well as integrate our calculations of carbon and mineral cycling in a complex, human-influenced watershed. More specifically, we quantify the composition and sources of POM in the third-order White Clay Creek Watershed, and examine the differences in composition and source with hydrologic variations produced by storms and seasonality. POM and watershed sources have been analyzed for particle size, mineral surface area, total mineral elemental composition, fallout radioisotope activity for common erosion tracers (7Be, 210Pb, 137Cs), and organic carbon and nitrogen content with stable isotope (13C, 15N) abundance. Results indicate a difference in POM source with season as well as within individual storms. Beryllium-7 activity, an indicator of landscape surface erosion, nearly triples within a single spring storm, from 389 mBq/g on the rising limb and 1190 mBq/g at the storm hydrograph peak. Fall storms have even lower 7Be concentrations, below 100 mBq/g. Furthermore, weight-percent of organic carbon nearly doubles from 4 - 5% during spring storms to over 8% during fall storms, with smaller variation occurring within individual storms. Despite changes in percent organic carbon, organic carbon to mineral surface area ratios and carbon to nitrogen molar ratios remain similar within storms and across seasons.

Anthropogenic activities have contributed moderately to increased inputs of organic materials in marginal seas off China.

PubMed

Liu, Liang-Ying; Wei, Gao-Ling; Wang, Ji-Zhong; Guan, Yu-Feng; Wong, Charles S; Wu, Feng-Chang; Zeng, Eddy Y

2013-10-15

Sediment has been recognized as a gigantic sink of organic materials and therefore can record temporal input trends. To examine the impact of anthropogenic activities on the marginal seas off China, sediment cores were collected from the Yellow Sea, the inner shelf of the East China Sea (ECS), and the South China Sea (SCS) to investigate the sources and spatial and temporal variations of organic materials, i.e., total organic carbon (TOC) and aliphatic hydrocarbons. The concentration ranges of TOC were 0.5-1.29, 0.63-0.83, and 0.33-0.85%, while those of Σn-C14-35 (sum of n-alkanes with carbon numbers of 14-35) were 0.08-1.5, 0.13-1.97, and 0.35-0.96 μg/g dry weight in sediment cores from the Yellow Sea, ECS inner shelf, and the SCS, respectively. Terrestrial higher plants were an important source of aliphatic hydrocarbons in marine sediments off China. The spatial distribution of Σn-C14-35 concentrations and source diagnostic ratios suggested a greater load of terrestrial organic materials in the Yellow Sea than in the ECS and SCS. Temporally, TOC and Σn-C14-35 concentrations increased with time and peaked at either the surface or immediate subsurface layers. This increase was probably reflective of elevated inputs of organic materials to marginal seas off China in recent years, and attributed partly to the impacts of intensified anthropogenic activities in mainland China. Source diagnostics also suggested that aliphatic hydrocarbons were mainly derived from biogenic sources, with a minority in surface sediment layers from petroleum sources, consistent with the above-mentioned postulation.

Biomimicry enhances sequential reactions of tethered glycolytic enzymes, TPI and GAPDHS.

PubMed

Mukai, Chinatsu; Gao, Lizeng; Bergkvist, Magnus; Nelson, Jacquelyn L; Hinchman, Meleana M; Travis, Alexander J

2013-01-01

Maintaining activity of enzymes tethered to solid interfaces remains a major challenge in developing hybrid organic-inorganic devices. In nature, mammalian spermatozoa have overcome this design challenge by having glycolytic enzymes with specialized targeting domains that enable them to function while tethered to a cytoskeletal element. As a step toward designing a hybrid organic-inorganic ATP-generating system, we implemented a biomimetic site-specific immobilization strategy to tether two glycolytic enzymes representing different functional enzyme families: triose phosphoisomerase (TPI; an isomerase) and glyceraldehyde 3-phosphate dehydrogenase (GAPDHS; an oxidoreductase). We then evaluated the activities of these enzymes in comparison to when they were tethered via classical carboxyl-amine crosslinking. Both enzymes show similar surface binding regardless of immobilization method. Remarkably, specific activities for both enzymes were significantly higher when tethered using the biomimetic, site-specific immobilization approach. Using this biomimetic approach, we tethered both enzymes to a single surface and demonstrated their function in series in both forward and reverse directions. Again, the activities in series were significantly higher in both directions when the enzymes were coupled using this biomimetic approach versus carboxyl-amine binding. Our results suggest that biomimetic, site-specific immobilization can provide important functional advantages over chemically specific, but non-oriented attachment, an important strategic insight given the growing interest in recapitulating entire biological pathways on hybrid organic-inorganic devices.

Biomimicry Enhances Sequential Reactions of Tethered Glycolytic Enzymes, TPI and GAPDHS

PubMed Central

Mukai, Chinatsu; Gao, Lizeng; Bergkvist, Magnus; Nelson, Jacquelyn L.; Hinchman, Meleana M.; Travis, Alexander J.

2013-01-01

Maintaining activity of enzymes tethered to solid interfaces remains a major challenge in developing hybrid organic-inorganic devices. In nature, mammalian spermatozoa have overcome this design challenge by having glycolytic enzymes with specialized targeting domains that enable them to function while tethered to a cytoskeletal element. As a step toward designing a hybrid organic-inorganic ATP-generating system, we implemented a biomimetic site-specific immobilization strategy to tether two glycolytic enzymes representing different functional enzyme families: triose phosphoisomerase (TPI; an isomerase) and glyceraldehyde 3-phosphate dehydrogenase (GAPDHS; an oxidoreductase). We then evaluated the activities of these enzymes in comparison to when they were tethered via classical carboxyl-amine crosslinking. Both enzymes show similar surface binding regardless of immobilization method. Remarkably, specific activities for both enzymes were significantly higher when tethered using the biomimetic, site-specific immobilization approach. Using this biomimetic approach, we tethered both enzymes to a single surface and demonstrated their function in series in both forward and reverse directions. Again, the activities in series were significantly higher in both directions when the enzymes were coupled using this biomimetic approach versus carboxyl-amine binding. Our results suggest that biomimetic, site-specific immobilization can provide important functional advantages over chemically specific, but non-oriented attachment, an important strategic insight given the growing interest in recapitulating entire biological pathways on hybrid organic-inorganic devices. PMID:23626684

Nano Engineered Energetic Materials (NEEM)

DTIC Science & Technology

2011-01-12

Al nanoparticles, owing to the surface oxidation of the unpassivated particles. The major drawback with utilizing organic capping groups is the...increases seen with nano-sized aluminum are promising, there are certain drawbacks . A thin layer of alumina (Al2O3) usually forms on the exterior...rocket motor by lowering the active aluminum content of the particles. Because of these drawbacks , surface protection in the form of coatings is

Active Camouflage for Infantry Headwear Applications

DTIC Science & Technology

2007-02-01

incorporates a rewriteable display medium. Military, academic, and commercial groups are aiming at developing OLEDs for full- color flexible displays...as shown in Figure 7. Figure 7: Organic LED Prototype shown on a Flexible surface (Kincade, 2004). OLEDs are self-luminous and do not require...brighter, more stable color displays. The OLED manufacturing process is much more amenable to retaining optimum performance on a flexible surface

Fluorescent Nanocrystals Reveal Regulated Portals of Entry into and Between the Cells of Hydra

PubMed Central

Tortiglione, Claudia; Quarta, Alessandra; Malvindi, Maria Ada; Tino, Angela; Pellegrino, Teresa

2009-01-01

Initially viewed as innovative carriers for biomedical applications, with unique photophysical properties and great versatility to be decorated at their surface with suitable molecules, nanoparticles can also play active roles in mediating biological effects, suggesting the need to deeply investigate the mechanisms underlying cell-nanoparticle interaction and to identify the molecular players. Here we show that the cell uptake of fluorescent CdSe/CdS quantum rods (QRs) by Hydra vulgaris, a simple model organism at the base of metazoan evolution, can be tuned by modifying nanoparticle surface charge. At acidic pH, amino-PEG coated QRs, showing positive surface charge, are actively internalized by tentacle and body ectodermal cells, while negatively charged nanoparticles are not uptaken. In order to identify the molecular factors underlying QR uptake at acidic pH, we provide functional evidence of annexins involvement and explain the QR uptake as the combined result of QR positive charge and annexin membrane insertion. Moreover, tracking QR labelled cells during development and regeneration allowed us to uncover novel intercellular trafficking and cell dynamics underlying the remarkable plasticity of this ancient organism. PMID:19888325

Post Modification of Metal-Organic Framework and Their Application In Cancer Theranostics

NASA Astrophysics Data System (ADS)

Lakkakula, Hima bindu

The research proposal aims to demonstrate that Metal-Organic Frameworks (MOFs) are mainly used for cancer theranostics which is the combination of both diagnostic and therapeutic functions. The research will emphasis on synthesis of Fe- MOFs by solvothermal nucleation, crystallization, characterization by microscopy and spectroscopy and evaluation with different lattice parameters and its morphology. Nowadays MOFs are used for the novel drug delivery purposes. The current published Fe- MOFs research focus is on the cancer theranostics by Indian medicines which will be impregnated into the MOFs and which will evaluate bioavailability and the chemotherapeutic activity of the drug. Nanotechnology provides the target specificity without affecting the healthy tissues. Other research problems to be addressed are the relationship between metal connectivity and ligand-based luminescence, MOF stability in an aqueous environment and activating it at increased temperature serves as a crucial role. The merits of this research are to increase the surface area and pore size of the drug so that the therapeutic efficacy can be improved. Moreover, the stabilization of metal-organic frameworks can also be enhanced with high surface area.

Mercury adsorption properties of sulfur-impregnated adsorbents

USGS Publications Warehouse

Hsi, N.-C.; Rood, M.J.; Rostam-Abadi, M.; Chen, S.; Chang, R.

2002-01-01

Carbonaceous and noncarbonaceous adsorbents were impregnated with elemental sulfur to evaluate the chemical and physical properties of the adsorbents and their equilibrium mercury adsorption capacities. Simulated coal combustion flue gas conditions were used to determine the equilibrium adsorption capacities for Hg0 and HgCl2 gases to better understand how to remove mercury from gas streams generated by coal-fired utility power plants. Sulfur was deposited onto the adsorbents by monolayer surface deposition or volume pore filling. Sulfur impregnation increased the total sulfur content and decreased the total and micropore surface areas and pore volumes for all of the adsorbents tested. Adsorbents with sufficient amounts of active adsorption sites and sufficient microporous structure had mercury adsorption capacities up to 4,509 ??g Hg/g adsorbent. Elemental sulfur, organic sulfur, and sulfate were formed on the adsorbents during sulfur impregnation. Correlations were established with R2>0.92 between the equilibrium Hg0/HgCl2 adsorption capacities and the mass concentrations of elemental and organic sulfur. This result indicates that elemental and organic sulfur are important active adsorption sites for Hg0 and HgCl2.

Occurrence and sources of natural and anthropogenic lipid tracers in surface soils from arid urban areas of Saudi Arabia.

PubMed

Rushdi, Ahmed I; Al-Mutlaq, Khalid F; El-Mubarak, Aarif H; Al-Saleh, Mohammed A; El-Otaibi, Mubarak T; Ibrahim, Sami M M; Simoneit, Bernd R T

2016-01-01

Soil particles contain a variety of natural and anthropogenic organic components, and in urban areas can be considered as local collectors of pollutants. Surface soil samples were taken from ten urban areas in Riyadh during early winter of 2007. They were extracted with dichloromethane-methanol mixture and the extracts were analyzed by gas chromatography-mass spectrometry. The major compounds were unresolved complex mixture (UCM), plasticizers, n-alkanes, carbohydrates, n-alkanoic acids, hopanes, n-alkanols, and sterols. Vegetation detritus was the major natural source of organic compounds (24.0 ± 15.7%) in samples from areas with less human activities and included n-alkanes, n-alkanoic acids, n-alkanols, sterols and carbohydrates. Vehicular emission products and discarded plastics were the major anthropogenic sources in the soil particles (53.3 ± 21.3% and 22.7 ± 10.7%, respectively). The anthropogenic tracers were UCM, plasticizers, n-alkanes, hopanes and traces of steranes. Vegetation and human activities control the occurrence and distribution of natural and anthropogenic extractable organic matter in this arid urban area. Copyright © 2015 Elsevier Ltd. All rights reserved.

Enzyme Sorption onto Soil and Biocarbon Amendments Alters Catalytic Capacity and Depends on the Specific Protein and pH

NASA Astrophysics Data System (ADS)

Foster, E.; Fogle, E. J.; Cotrufo, M. F.

2017-12-01

Enzymes catalyze biogeochemical reactions in soils and play a key role in nutrient cycling in agricultural systems. Often, to increase soil nutrients, agricultural managers add organic amendments and have recently experimented with charcoal-like biocarbon products. These amendments can enhance soil water and nutrient holding capacity through increasing porosity. However, the large surface area of the biocarbon has the potential to sorb nutrients and other organic molecules. Does the biocarbon decrease nutrient cycling through sorption of enzymes? In a laboratory setting, we compared the interaction of two purified enzymes β-glucosidase and acid phosphatase with a sandy clay loam and two biocarbons. We quantified the sorbed enzymes at three different pHs using a Bradford protein assay and then measured the activity of the sorbed enzyme via high-throughput fluorometric analysis. Both sorption and activity depended upon the solid phase, pH, and specific enzyme. Overall the high surface area biocarbon impacted the catalytic capacity of the enzymes more than the loam soil, which may have implications for soil nutrient management with these organic amendments.

Rational Design of Bi Nanoparticles for Efficient Electrochemical CO 2 Reduction: The Elucidation of Size and Surface Condition Effects

DOE PAGES

Zhang, Zhiyong; Chi, Miaofang; Veith, Gabriel M.; ...

2016-08-08

Here we report an efficient electrochemical conversion of CO 2 to CO on surface-activated bismuth nanoparticles (NPs) in acetonitrile (MeCN) under ambient conditions, with the assistance of 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([bmim][OTf]). Through the comparison between electrodeposited Bi films (Bi-ED) and different types of Bi NPs, we, for the first time, demonstrate the effects of catalyst’s size and surface condition on organic phase electrochemical CO 2 reduction. Our study reveals that the surface inhibiting layer (hydrophobic surfactants and Bi 3+ species) formed during the synthesis and purification process hinders the CO 2 reduction, leading to a 20% drop in Faradaic efficiency formore » CO evolution (FE CO). Bi particle size showed a significant effect on FE CO when the surface of Bi was air-oxidized, but this effect of size on FE CO became negligible on surface-activated Bi NPs. After the surface activation (hydrazine treatment) that effectively removed the native inhibiting layer, activated 36-nm Bi NPs exhibited an almost-quantitative conversion of CO 2 to CO (96.1% FE CO), and a mass activity for CO evolution (MA CO) of 15.6 mA mg –1, which is three-fold higher than the conventional Bi-ED, at ₋2.0 V (vs Ag/AgCl). Ultimately, this work elucidates the importance of the surface activation for an efficient electrochemical CO 2 conversion on metal NPs and paves the way for understanding the CO 2 electrochemical reduction mechanism in nonaqueous media.« less

Surface oxidation of GaN(0001): Nitrogen plasma-assisted cleaning for ultrahigh vacuum applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gangopadhyay, Subhashis; Schmidt, Thomas, E-mail: tschmidt@ifp.uni-bremen.de; Kruse, Carsten

The cleaning of metal-organic vapor-phase epitaxial GaN(0001) template layers grown on sapphire has been investigated. Different procedures, performed under ultrahigh vacuum conditions, including degassing and exposure to active nitrogen from a radio frequency nitrogen plasma source have been compared. For this purpose, x-ray photoelectron spectroscopy, reflection high-energy electron diffraction, and scanning tunneling microscopy have been employed in order to assess chemical as well as structural and morphological surface properties. Initial degassing at 600 °C under ultrahigh vacuum conditions only partially eliminates the surface contaminants. In contrast to plasma assisted nitrogen cleaning at temperatures as low as 300 °C, active-nitrogen exposure at temperaturesmore » as high as 700 °C removes the majority of oxide species from the surface. However, extended high-temperature active-nitrogen cleaning leads to severe surface roughening. Optimum results regarding both the removal of surface oxides as well as the surface structural and morphological quality have been achieved for a combination of initial low-temperature plasma-assisted cleaning, followed by a rapid nitrogen plasma-assisted cleaning at high temperature.« less

Fabrication of Annealed Gold Nanostructures on Pre-Treated Glow-Discharge Cleaned Glasses and Their Used for Localized Surface Plasmon Resonance (LSPR) and Surface Enhanced Raman Spectroscopy (SERS) Detection of Adsorbed (Bio)molecules.

PubMed

Ionescu, Rodica Elena; Aybeke, Ece Neslihan; Bourillot, Eric; Lacroute, Yvon; Lesniewska, Eric; Adam, Pierre-Michel; Bijeon, Jean-Louis

2017-01-26

Metallic nanoparticles are considered as active supports in the development of specific chemical or biological biosensors. Well-organized nanoparticles can be prepared either through expensive (e.g., electron beam lithography) or inexpensive (e.g., thermal synthesis) approaches where different shapes of nanoparticles are easily obtained over large solid surfaces. Herein, the authors propose a low-cost thermal synthesis of active plasmonic nanostructures on thin gold layers modified glass supports after 1 h holding on a hot plate (~350 °C). The resulted annealed nanoparticles proved a good reproducibility of localized surface plasmon resonance (LSPR) and surface enhanced Raman spectroscopy (SERS) optical responses and where used for the detection of low concentrations of two model (bio)chemical molecules, namely the human cytochrome b5 (Cyt-b5) and trans -1,2-bis(4-pyridyl)ethylene (BPE).

Surface grafting of Corchorus olitorius fibre: a green approach for the development of activated bioadsorbent.

PubMed

Roy, Aparna; Chakraborty, Sumit; Kundu, Sarada Prasad; Majumder, Subhasish Basu; Adhikari, Basudam

2013-02-15

The present work is an endeavor to prepare lignocellulosic biomass based adsorbent, suitable for removal of organic and inorganic pollutants from industrial effluents. Lignocellulosic Corchorus olitorius fibre (jute fibre) surface was grafted with naturally available polyphenol, tannin, preceded by the epoxy-activation of fibre surface with epichlorohydrin under mild condition in an aqueous suspension. The reaction parameters for the modification, viz., concentration of epichlorohydrin and tannin, time, and temperature were optimized. The successful occurrence of surface modification of jute fibre (JF) was characterized and estimated from weight gain percent, elemental analysis, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction, scanning electron and atomic force microscopy, and thermogravimetric analysis. An extensive analysis of deconvoluted FTIR spectra using the Voigt model was utilized to ensure the surface grafting. The microbiological susceptibility study revealed high persistency of JF towards biodegradation after efficient grafting with tannin. Copyright © 2012 Elsevier Ltd. All rights reserved.

Application of the IAS theory combining to a three compartments description of natural organic matter to the adsorption of atrazine or diuron on activated carbon.

PubMed

Baudu, M; Raveau, D; Guibaud, G

2004-07-01

The study of natural organic matter (NOM) adsorption on an activated carbon showed that equilibrium cannot be described according to a simple model such as a Freundlich isotherm and confirms the need for a closer description of the organic matter to simulate the competitive adsorption with micropollutants. A representation of the organic matter in three fractions is chosen: non-adsorbable, weak and strong adsorbable. The Ideal Adsorbed Solution Theory (IAST) can, under restrictive conditions, be used to effectively predict the competition between the pesticides and the organic matter. Therefore, it was noted that the model simulated with good precision the competition between atrazine or diuron and natural organic matter in aqueous solution for two activated carbons (A and B). The same parameters for the modeling of organic matter adsorption (Freudlich constants for two absorbable fractions) are used with the two pesticides. However, IAST does not allow correct modeling of pesticide adsorption onto two other (C and D) activated carbons in solution in natural water to be described. IAS theory does not reveal competition between diuron and NOM and pore blockage mechanism by the NOM is proposed as the major effect for the adsorption capacity reduction. However, the difference observed between the two pesticides could be due to in addition to the pore blockage effect, a particular phenomenon with the diuron, especially with D activated carbon. We can suppose specific interactions between the diuron and the adsorbed organic matter and a competition between adsorption sites of NOM and activated carbon surface.

Spatial variation in water loss predicts terrestrial salamander distribution and population dynamics.

PubMed

Peterman, W E; Semlitsch, R D

2014-10-01

Many patterns observed in ecology, such as species richness, life history variation, habitat use, and distribution, have physiological underpinnings. For many ectothermic organisms, temperature relationships shape these patterns, but for terrestrial amphibians, water balance may supersede temperature as the most critical physiologically limiting factor. Many amphibian species have little resistance to water loss, which restricts them to moist microhabitats, and may significantly affect foraging, dispersal, and courtship. Using plaster models as surrogates for terrestrial plethodontid salamanders (Plethodon albagula), we measured water loss under ecologically relevant field conditions to estimate the duration of surface activity time across the landscape. Surface activity time was significantly affected by topography, solar exposure, canopy cover, maximum air temperature, and time since rain. Spatially, surface activity times were highest in ravine habitats and lowest on ridges. Surface activity time was a significant predictor of salamander abundance, as well as a predictor of successful recruitment; the probability of a juvenile salamander occupying an area with high surface activity time was two times greater than an area with limited predicted surface activity. Our results suggest that survival, recruitment, or both are demographic processes that are affected by water loss and the ability of salamanders to be surface-active. Results from our study extend our understanding of plethodontid salamander ecology, emphasize the limitations imposed by their unique physiology, and highlight the importance of water loss to spatial population dynamics. These findings are timely for understanding the effects that fluctuating temperature and moisture conditions predicted for future climates will have on plethodontid salamanders.

p47phox Molecular Activation for Assembly of the Neutrophil NADPH Oxidase Complex*

PubMed Central

Marcoux, Julien; Man, Petr; Petit-Haertlein, Isabelle; Vivès, Corinne; Forest, Eric; Fieschi, Franck

2010-01-01

The p47phox cytosolic factor from neutrophilic NADPH oxidase has always been resistant to crystallogenesis trials due to its modular organization leading to relative flexibility. Hydrogen/deuterium exchange coupled to mass spectrometry was used to obtain structural information on the conformational mechanism that underlies p47phox activation. We confirmed a relative opening of the protein with exposure of the SH3 Src loops that are known to bind p22phox upon activation. A new surface was shown to be unmasked after activation, representing a potential autoinhibitory surface that may block the interaction of the PX domain with the membrane in the resting state. Within this surface, we identified 2 residues involved in the interaction with the PX domain. The double mutant R162A/D166A showed a higher affinity for specific phospholipids but none for the C-terminal part of p22phox, reflecting an intermediate conformation between the autoinhibited and activated forms. PMID:20592030

Coatings with a Mole-hill Structure of Nanoparticle-Raspberry Containers for Surfaces with Abrasion-Refreshable Reservoir Functionality.

PubMed

Ballweg, Thomas; Gellermann, Carsten; Mandel, Karl

2015-11-11

Active silica nanoparticle-based raspberry-like container depots for agents such as antimicrobial substances are presented. The nano raspberry-containers are integrated into coatings in a way that they form a mole-hill structure; i.e., they are partly standing out of the coating. As an application example, it is demonstrated that the containers can be filled with antimicrobially active agents such as nano ZnO or Ag or organic molecules such as thymol. It is demonstrated that the containers can be partly chopped-off via abrasion by rubbing over the surface. This mechanism proves to be an attractive approach to render surfaces refreshable. A first proof of principle for antimicrobial activity of the intact containers in the coatings and the abrasion treated, chopped-off (and thereby reactivated) containers is demonstrated.

Nascent Marine Aerosol Acting as Ultra-Efficient Cloud Nuclei

NASA Astrophysics Data System (ADS)

Ovadnevaite, J.; Zuend, A.; Laaksonen, A.; Sanchez, K.; Roberts, G.; Ceburnis, D.; Decesari, S.; Rinaldi, M.; Hodas, N.; Facchini, C.; Seinfeld, J.; O'Dowd, C. D. D.

2017-12-01

Marine aerosol is an important part of the natural aerosol and often dominates the total burden in remote locations. Moreover, it contributes significantly to the global radiative budget through the formation of haze and cloud layers. Even if these layers are optically-thin at times, they can have a profound impact on the radiative budget as they overly a dark and extensive ocean surface. Since the postulation of marine aerosol global importance several decades ago1, understanding has progressed from evaluation of the nss-sulphate and sea salt effects to the acknowledgement of a significant role of organic aerosol2. Dependence of organic matter (OM) fraction enrichment in sea spray on phytoplankton biomass has been shown3 as well as an apparent dichotomous OM behaviour in terms of water uptake4. Hygroscopicity of organic aerosol in sub-saturated humidity fields is typically less than most common salts found in the atmospheric aerosol; however, the ability of organic aerosol to activate cloud droplets is predicted to be greatly increased in supersaturated air due a lowering of the droplets surface tension5. While this phenomenon has been acknowledged for some time, it has yet to be demonstrated in the real atmosphere. Here, we present evidence that recently-formed secondary organic aerosol particles, in marine air, lead to enhanced cloud droplet activation resulting from surface tension reduction. Whilst the surface tension lowering is expected to be negated by a concomitant reduction in the Raoult effect, driven by the displacement of solute ions by surfactant molecules at the droplet-vapour interface, we present new observational and theoretical evidence illustrating that, in ambient air, the former can prevail over the latter. Consideration of liquid-liquid phase-separation, leading to complete or partial engulfing of a hygroscopic particle core by a hydrophobic organic-rich phase, explains the lack of suppression of the Raoult effect, while maintaining substantial surface tension lowering and resulting in a tenfold increase in predicted CCN number concentration. 1Charlson R. J. et al. Nature 326, 655-661, 1987; 2O'Dowd C. D. et al. Nature 431, 676-680, 2004; 3O'Dowd C. et al. Scientific Reports 5, 2015; 4Ovadnevaite J. et al. Geophys Res Lett 38, 2011; 5Facchini M. C. et al. Atmos Environ 34, 4853-4857, 2000.

Marine natural flavonoids: chemistry and biological activities.

PubMed

Martins, Beatriz T; Correia da Silva, Marta; Pinto, Madalena; Cidade, Honorina; Kijjoa, Anake

2018-05-04

As more than 70% of the world's surface is covered by oceans, marine organisms offer a rich and unlimited resource of structurally diverse bioactive compounds. These organisms have developed unique properties and bioactive compounds that are, in majority of them, unparalleled by their terrestrial counterparts due to the different surrounding ecological systems. Marine flavonoids have been extensively studied in the last decades due to a growing interest concerning their promising biological/pharmacological activities. The most common classes of marine flavonoids are flavones and flavonols, which are mostly isolated from marine plants. Although most of flavonoids are hydroxylated and methoxylated, some marine flavonoids possess an unusual substitution pattern, not commonly found in terrestrial organisms, namely the presence of sulphate, chlorine, and amino groups. This review presents, for the first time in a systematic way, the structure, natural occurrence, and biological activities of marine flavonoids.

VERUCLAY – a new type of photo-adsorbent active in the visible light range: modification of montmorillonite surface with organic surfactant

EPA Science Inventory

Montmorillonite K10 was treated with VeruSOL-3, a biodegradable and food-grade surfactant mixture of coconut oil, castor oil and citrus extracts, to manufacture a benign catalytic adsorbent that is active in the visible light. Veruclay was characterized by SEM, XRD, TGA, UVDRS, a...

Stabilized sulfur binding using activated fillers

DOEpatents

Kalb, Paul D.; Vagin, Vyacheslav P.; Vagin, Sergey P.

2015-07-21

A method of making a stable, sulfur binding composite comprising impregnating a solid aggregate with an organic modifier comprising unsaturated hydrocarbons with at least one double or triple covalent bond between adjacent carbon atoms to create a modifier-impregnated aggregate; heating and drying the modifier-impregnated aggregate to activate the surface of the modifier-impregnated aggregate for reaction with sulfur.

[When textiles help your recovery].

PubMed

Martel, Bernard; Campagne, Christine; Behary Massika, Nemeshwaree

2017-01-01

Textiles are widely used in the biomedical domain, particularly in wound dressings or as implantable devices for strengthening or even replacing some damaged organs. Nowadays they present more and more sophisticated functionalities contributing to the healing process, to the organs regeneration, and fight against infection or thrombosis. Advanced spinning technologies of biostable or bioresorbable polymers and surface treatment technologies are often used, as well as nanotechnologies, to implement two main strategies for development of bio-active textiles. A long or medium term technology is obtained by grafting the bio-active molecule through stable chemical bonds while a short term activity is produced by using "reservoir" systems such as hydrogels and cyclodextrins that release the active agents in situ. ‡. © 2017 médecine/sciences – Inserm.

Influence of the Amino Acid Sequence on Protein-Mineral Interactions in Soil

NASA Astrophysics Data System (ADS)

Chacon, S. S.; Reardon, P. N.; Purvine, S.; Lipton, M. S.; Washton, N.; Kleber, M.

2017-12-01

The intimate associations between protein and mineral surfaces have profound impacts on nutrient cycling in soil. Proteins are an important source of organic C and N, and a subset of proteins, extracellular enzymes (EE), can catalyze the depolymerization of soil organic matter (SOM). Our goal was to determine how variation in the amino acid sequence could influence a protein's susceptibility to become chemically altered by mineral surfaces to infer the fate of adsorbed EE function in soil. We hypothesized that (1) addition of charged amino acids would enhance the adsorption onto oppositely charged mineral surfaces (2) addition of aromatic amino acids would increase adsorption onto zero charged surfaces (3) Increase adsorption of modified proteins would enhance their susceptibility to alterations by redox active minerals. To test these hypotheses, we generated three engineered proxies of a model protein Gb1 (IEP 4.0, 6.2 kDA) by inserting either negatively charged, positively charged or aromatic amino acids in the second loop. These modified proteins were allowed to interact with functionally different mineral surfaces (goethite, montmorillonite, kaolinite and birnessite) at pH 5 and 7. We used LC-MS/MS and solution-state Heteronuclear Single Quantum Coherence Spectroscopy NMR to observe modifications on engineered proteins as a consequence to mineral interactions. Preliminary results indicate that addition of any amino acids to a protein increase its susceptibility to fragmentation and oxidation by redox active mineral surfaces, and alter adsorption to the other mineral surfaces. This suggest that not all mineral surfaces in soil may act as sorbents for EEs and chemical modification of their structure should also be considered as an explanation for decrease in EE activity. Fragmentation of proteins by minerals can bypass the need to produce proteases, but microbial acquisition of other nutrients that require enzymes such as cellulases, ligninases or phosphatases may be hampered by mineral association.

Interference with the Mannose Binding and Epithelial Cell Adherence of Escherichia coli by Sublethal Concentrations of Streptomycin

PubMed Central

Eisenstein, Barry I.; Ofek, Itzhak; Beachey, Edwin H.

1979-01-01

When Escherichia coli was grown in sublethal concentrations of streptomycin, mannose binding activity and epithelial cell adherence of the E. coli cultures at stationary phase were significantly reduced in the drug-grown organisms. In a strain whose minimal inhibitory concentrations was 30 μg/ml, the percentage of reduction in mannose binding activity was dose related over a range of concentrations between 0.5 and 10 μg/ml streptomycin. Concomitant with the drug-induced suppression of mannose binding activity, antigenic and ultrastructural alterations on the surface of the drug-grown organisms were observed by agglutination tests and electron microscopy, respectively. The streptomycin effect was reversible, required actively growing organisms, and was most apparent in the early log-phase of growth. High doses of antibiotic were ineffective when added to cultures which had acquired mannose binding activity. An isogenic derivative with high-level resistance to streptomycin was obtained as a single-step mutation from the test E. coli strain. Whereas the isogenic mutant possessed mannose binding activity and adhering ability similar to the parent strain, it was resistant to the streptomycin-induced suppression of the two activities at enormous concentrations (up to 10,000 μg/ml) of streptomycin. Taken together the results suggest that the suppression of epithelial cell adherence and mannose binding activity of E. coli grown in sublethal concentrations of streptomycin is a result of classic mechanisms of drug action upon the bacterial ribosome. The results support the possibility that antibiotics may act through mechanisms other than inhibition of growth and bacterial killing to eradicate bacteria from mucosal surfaces. Images PMID:376556

Sum-Frequency Generation Spectroscopy for Studying Organic Layers at Water-Air Interfaces: Microlayer Monitoring and Surface Reactivity

NASA Astrophysics Data System (ADS)

Laß, Kristian; Kleber, Joscha; Bange, Hermann; Friedrichs, Gernot

2015-04-01

The sea surface microlayer, according to commonly accepted terminology, comprises the topmost millimetre of the oceanic water column. It is often enriched with organic matter and is directly influenced by sunlight exposure and gas exchange with the atmosphere, hence making it a place for active biochemistry and photochemistry as well as for heterogeneous reactions. In addition, surface active material either is formed or accumulates directly at the air-water interface and gives rise to very thin layers, sometimes down to monomolecular thickness. This "sea surface nanolayer" determines the viscoelastic properties of the seawater surface and thus may impact the turbulent air-sea gas exchange rates. To this effect, this small scale layer presumably plays an important role for large scale changes of atmospheric trace gas concentrations (e.g., by modulating the ocean carbon sink characteristics) with possible implications for coupled climate models. To date, detailed knowledge about the composition, structure, and reactivity of the sea surface nanolayer is still scarce. Due to its small vertical dimension and the small amount of material, this surfactant layer is very difficult to separate and analyse. A way out is the application of second-order nonlinear optical methods, which make a direct surface-specific and background-free detection of this interfacial layer possible. In recent years, we have introduced the use of vibrational sum frequency generation (VSFG) spectroscopy to gain insight into natural and artificial organic monolayers at the air-water interface. In this contribution, the application of VSFG spectroscopy for the analysis of the sea surface nanolayer will be illustrated. Resulting spectra are interpreted in terms of layer composition and surfactant classes, in particular with respect to carbohydrate-containing molecules such as glycolipids. The partitioning of the detected surfactants into soluble and non-soluble ("wet" and "dry") surfactants will be discussed. Furthermore, the application of a combined VSFG/Langmuir trough experiment to investigate the reaction kinetics of heterogeneous oxidation processes will be highlighted. The ozonolysis of monolayers of unsaturated fatty acids serves as model system for natural aging processes of surfactant layers at the sea surface. Finally, a VSFG time series study of the sea surface nanolayer at a western Baltic Sea near-shore sampling station will be presented. The observed seasonality reveals a significant temporal shift with respect to the spring algal bloom showing that high organic material content in the microlayer does not necessarily correlate with high nanolayer abundance. This interesting finding and implications for the formation of surfactant material by degradation of biological material will be discussed briefly.

Removal of organic dyes using Cr-containing activated carbon prepared from leather waste.

PubMed

Oliveira, Luiz C A; Coura, Camila Van Zanten; Guimarães, Iara R; Gonçalves, Maraisa

2011-09-15

In this work, hydrogen peroxide decomposition and oxidation of organics in aqueous medium were studied in the presence of activated carbon prepared from wet blue leather waste. The wet blue leather waste, after controlled pyrolysis under CO(2) flow, was transformed into chromium-containing activated carbons. The carbon with Cr showed high microporous surface area (up to 889 m(2)g(-1)). Moreover, the obtained carbon was impregnated with nanoparticles of chromium oxide from the wet blue leather. The chromium oxide was nanodispersed on the activated carbon, and the particle size increased with the activation time. It is proposed that these chromium species on the carbon can activate H(2)O(2) to generate HO radicals, which can lead to two competitive reactions, i.e. the hydrogen peroxide decomposition or the oxidation of organics in water. In fact, in this work we observed that activated carbon obtained from leather waste presented high removal of methylene blue dye combining the adsorption and oxidation processes. Copyright © 2011 Elsevier B.V. All rights reserved.

Effect of organic ligands on Mg partitioning and Mg isotope fractionation during low-temperature precipitation of calcite

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; Immenhauser, Adrian; Buhl, Dieter; Purgstaller, Bettina; Baldermann, Andre; Dietzel, Martin

2016-04-01

Calcite growth experiments have been performed at 25 oC and 1 bar pCO2 in the presence of aqueous Mg and six organic ligands in the concentration range from 10-5 to 10-3 M. These experiments were performed in order to quantify the effect of distinct organic ligands on the Mg partitioning and Mg stable isotope fractionation during its incorporation in calcite at similar growth rates normalized to total surface area. The organic ligands used in this study comprise of (i) acetate acid, (ii) citrate, (iii) glutamate, (iv) salicylate, (v) glycine and (vi) ethylenediaminetetraacetic acid (EDTA), containing carboxyl- and amino-groups. These fuctional groups are required for bacterial activity and growth as well as related to biotic and abiotic mineralization processes occurring in sedimentary and earliest diagenetic aquatic environments (e.g. soil, cave, lacustrine, marine). The results obtained in this study indicate that the presence of organic ligands promotes an increase in the partition coefficient of Mg in calcite (DMg = (Mg/Ca)calcite (Mg/Ca)fluid). This behaviour can be explained by the temporal formation of aqueous Mg-ligand complexes that are subsequently adsorbed on the calcite surfaces and thereby reducing the active growth sites of calcite. The increase of DMg values as a function of the supersaturation degree of calcite in the fluid phase can be described by the linear equation LogDMg =0.3694 (±0.0329)×SIcalcite - 1.9066 (±0.0147); R2=0.92 In contrast, the presence of organic ligands, with exception of citrate, does not significantly affect the Mg isotope fractionation factor between calcite and reactive fluid (Δ26Mgcalcite-fluid = -2.5 ±0.1). Citrate likely exhibits larger fractionation between the Mg-ligand complexes and free aqueous Mg2+, compared to the other organic ligands studied in this work, as evidenced by the smaller Δ26Mgcalcite-fluid values. These results indicate that in Earth's surface calcite precipitating environments that are characterized by low dissolved organic carbon levels, the presence of organic ligands is rather unlikely to significantly affect the Mg isotope composition of precipitated calcite.

Digging a Little Deeper: Microbial Communities, Molecular Composition and Soil Organic Matter Turnover along Tropical Forest Soil Depth Profiles

NASA Astrophysics Data System (ADS)

Pett-Ridge, J.; McFarlane, K. J.; Heckman, K. A.; Reed, S.; Green, E. A.; Nico, P. S.; Tfaily, M. M.; Wood, T. E.; Plante, A. F.

2016-12-01

Tropical forest soils store more carbon (C) than any other terrestrial ecosystem and exchange vast amounts of CO2, water, and energy with the atmosphere. Much of this C is leached and stored in deep soil layers where we know little about its fate or the microbial communities that drive deep soil biogeochemistry. Organic matter (OM) in tropical soils appears to be associated with mineral particles, suggesting deep soils may provide greater C stabilization. However, few studies have evaluated sub-surface soils in tropical ecosystems, including estimates of the turnover times of deep soil C, the sensitivity of this C to global environmental change, and the microorganisms involved. We quantified bulk C pools, microbial communities, molecular composition of soil organic matter, and soil radiocarbon turnover times from surface soils to 1.5m depths in multiple soil pits across the Luquillo Experimental Forest, Puerto Rico. Soil C, nitrogen, and root and microbial biomass all declined exponentially with depth; total C concentrations dropped from 5.5% at the surface to <0.5% at 140cm depth. High-throughput sequencing highlighted distinct microbial communities in surface soils (Acidobacteria and Proteobacteria) versus those below the active rooting zone (Verrucomicrobia and Thaumarchaea). High resolution mass spectrometry (FTICR-MS) analyses suggest a shift in the composition of OM with depth (especially in the water soluble fraction), an increase in oxidation, and decreasing H/C with depth (indicating higher aromaticity). Additionally, surface samples were rich in lignin-like compounds of plant origin that were absent with depth. Soil OM 14C and mean turnover times were variable across replicate horizons, ranging from 3-1500 years at the surface, to 5000-40,000 years at depth. In comparison to temperate deciduous forests, these 14C values reflect far older soil C. Particulate organic matter (free light fraction), with a relatively modern 14C was found in low but measureable concentration in even the deepest soil horizons. Our results indicate these tropical subsoils contain small but metabolically active microbial communities that are highly OM limited and may persist via degradation of recent inputs.

Biologically Inspired Model for Inference of 3D Shape from Texture

PubMed Central

Gomez, Olman; Neumann, Heiko

2016-01-01

A biologically inspired model architecture for inferring 3D shape from texture is proposed. The model is hierarchically organized into modules roughly corresponding to visual cortical areas in the ventral stream. Initial orientation selective filtering decomposes the input into low-level orientation and spatial frequency representations. Grouping of spatially anisotropic orientation responses builds sketch-like representations of surface shape. Gradients in orientation fields and subsequent integration infers local surface geometry and globally consistent 3D depth. From the distributions in orientation responses summed in frequency, an estimate of the tilt and slant of the local surface can be obtained. The model suggests how 3D shape can be inferred from texture patterns and their image appearance in a hierarchically organized processing cascade along the cortical ventral stream. The proposed model integrates oriented texture gradient information that is encoded in distributed maps of orientation-frequency representations. The texture energy gradient information is defined by changes in the grouped summed normalized orientation-frequency response activity extracted from the textured object image. This activity is integrated by directed fields to generate a 3D shape representation of a complex object with depth ordering proportional to the fields output, with higher activity denoting larger distance in relative depth away from the viewer. PMID:27649387

Evaluating the performance of water purification in a vegetated groundwater recharge basin maintained by short-term pulsed infiltration events.

PubMed

Mindl, Birgit; Hofer, Julia; Kellermann, Claudia; Stichler, Willibald; Teichmann, Günter; Psenner, Roland; Danielopol, Dan L; Neudorfer, Wolfgang; Griebler, Christian

2015-01-01

Infiltration of surface water constitutes an important pillar in artificial groundwater recharge. However, insufficient transformation of organic carbon and nutrients, as well as clogging of sediments often cause major problems. The attenuation efficiency of dissolved organic carbon (DOC), nutrients and pathogens versus the risk of bioclogging for intermittent recharge were studied in an infiltration basin covered with different kinds of macrovegetation. The quality and concentration of organic carbon, major nutrients, as well as bacterial biomass, activity and diversity in the surface water, the porewater, and the sediment matrix were monitored over one recharge period. Additionally, the numbers of viral particles and Escherichia coli were assessed. Our study showed a fast establishment of high microbial activity. DOC and nutrients have sustainably been reduced within 1.2 m of sediment passage. Numbers of E. coli, which were high in the topmost centimetres of sediment porewater, dropped below the detection limit. Reed cover was found to be advantageous over bushes and trees, since it supported higher microbial activities along with a good infiltration and purification performance. Short-term infiltration periods of several days followed by a break of similar time were found suitable for providing high recharge rates, and good water purification without the risk of bioclogging.

A Campaign Study of Sea Spray Aerosol Properties in the Bay of Aarhus

NASA Astrophysics Data System (ADS)

Nguyen, Quynh; Rasmussen, Berit; Kristensen, Kasper; Sloth Nielsen, Lærke; Bilde, Merete

2016-04-01

The oceans of the world are a dominant source of atmospheric aerosol. Together with mineral dust, sea spray aerosols (SSA) constitute the largest mass flux of particulate matter in the atmosphere (Andreae and Rosenfeld, 2008). Due to their effects on the global radiative budget - both directly as scatterers and absorbers of solar and terrestrial radiation, and indirectly as cloud condensation nuclei (CCN), SSA are considered an important component of the climate system. The sea-surface microlayer (SML) is an ultra-thin boundary layer between the ocean and the atmosphere. The high concentration of surface-active organic compounds in the SML, compared to that of the underlying water column, creates rigid film-like layer over the surface of the ocean. The SML is believed to play an important role in the formation and composition of SSA. However, current knowledge on the SML and its impacts on SSA remain limited. To characterize the SML of natural seawater and examine its impacts on aerosol properties, a field campaign was conducted in the bay of Aarhus, Denmark, during spring 2015. Bulk seawater was collected 1-2 times every week along with selective sampling of the SML. Characterization of the sea water and SML included a wide range of measurements, including surface tension, water activity, dissolved organic matter, and chemical composition analysis by liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS). SSA was generated from sampled sea water by diffusion of air bubbles through a 10L seawater sample situated in a sea spray tank. Particle number concentration and CCN measurements were conducted along with measurements of the organic share in the aerosol phase as indicated by volatility measurements. To investigate the effect of the SML, spiking of the seawater samples with additional SML was performed and measurements repeated for comparison. Preliminary results show that the SML samples only displayed slightly lower surface tension compared to subsurface seawater. A number of overlapping masses were observed in dissolved organic matter extracted from SML and slick samples, which requires further identification. Spiking bulk seawater with SML seems to lead to a small increase in organic share in the aerosol phase as indicated by volatility measurements, while the trend is unclear in CCN measurements. Andreae, M. O., and Rosenfeld, D.: Aerosol-cloud-precipitation interactions. Part 1. The nature and sources of cloud-active aerosols, Earth-Sci Rev, 89, 13-41, 2008.

Facile preparation of robust microcapsules by manipulating metal-coordination interaction between biomineral layer and bioadhesive layer.

PubMed

Zhang, Lei; Shi, Jiafu; Jiang, Zhongyi; Jiang, Yanjun; Meng, Ruijie; Zhu, Yuanyuan; Liang, Yanpeng; Zheng, Yang

2011-02-01

A novel approach combining biomimetic mineralization and bioadhesion is proposed to prepare robust and versatile organic-inorganic hybrid microcapsules. More specifically, these microcapsules are fabricated by sequential deposition of inorganic layer and organic layer on the surface of CaCO(3) microparticles, followed by the dissolution of CaCO(3) microparticles using EDTA. During the preparation process, protamine induces the hydrolysis and condensation of titania or silica precursor to form the inorganic layer or the biomineral layer. The organic layer or bioadhesive layer was formed through the rapid, spontaneous oxidative polymerization of dopamine into polydopamine (PDA) on the surface of the biomineral layer. There exist multiple interactions between the inorganic layer and the organic layer. Thus, the as-prepared organic-inorganic hybrid microcapsules acquire much higher mechanical stability and surface reactivity than pure titania or pure silica microcapsules. Furthermore, protamine/titania/polydopamine hybrid microcapsules display superior mechanical stability to protamine/silica/polydopamine hybrid microcapsules because of the formation of Ti(IV)-catechol coordination complex between the biomineral layer and the bioadhesive layer. As an example of application, three enzymes are respectively immobilized through physical encapsulation in the lumen, in situ entrapment within the wall and chemical attachment on the out surface of the hybrid microcapsules. The as-constructed multienzyme system displays higher catalytic activity and operational stability. Hopefully, the approach developed in this study will evolve as a generic platform for facile and controllable preparation of organic-inorganic hybrid materials with different compositions and shapes for a variety of applications in catalysis, sensor, drug/gene delivery.

UVolution, a photochemistry experiment in low earth orbit: investigation of the photostability of carboxylic acids exposed to mars surface UV radiation conditions.

PubMed

Stalport, Fabien; Guan, Yuan Yong; Coll, Patrice; Szopa, Cyril; Macari, Frédérique; Raulin, François; Chaput, Didier; Cottin, Hervé

2010-05-01

The detection and identification of organic molecules on Mars are of prime importance to establish the existence of a possible ancient prebiotic chemistry or even a biological activity. To date, however, no complex organic compounds have been detected on Mars. The harsh environmental conditions at the surface of Mars are commonly advocated to explain this nondetection, but few studies have been implemented to test this hypothesis. To investigate the nature, abundance, and stability of organic molecules that could survive under such environmental conditions, we exposed, in low Earth orbit, organic molecules of martian astrobiological relevance to solar UV radiation (>200 nm). The experiment, called UVolution, was flown on board the Biopan ESA module, which was situated outside a Russian Foton automated capsule and exposed to space conditions for 12 days in September 2007. The targeted organic molecules [alpha-aminoisobutyric acid (AIB), mellitic acid, phthalic acid, and trimesic acid] were exposed with, and without, an analogous martian soil. Here, we present experimental results of the impact of solar UV radiation on the targeted molecules. Our results show that none of the organic molecules studied seemed to be radiotolerant to the solar UV radiation when directly exposed to it. Moreover, the presence of a mineral matrix seemed to increase the photodestruction rate. AIB, mellitic acid, phthalic acid, and trimesic acid should not be considered as primary targets for in situ molecular analyses during future surface missions if samples are only collected from the first centimeters of the top surface layer.

Changes in optical characteristics of surface microlayers in the Peruvian upwelling region hint to photochemically and microbially-mediated DOM turnover

NASA Astrophysics Data System (ADS)

Engel, A.; Galgani, L.

2016-02-01

The coastal upwelling system off Peru is characterized by high biological activity and associated subsurface oxygen minimum zone, leading to an enhanced emission of atmospheric trace gases. High biological productivity in the water column may promote the establishment of enriched organic surface films, key environments for processes regulating gas fluxes across the water-air interface. During M91 cruise to the Peruvian upwelling, we focused our attention on the composition of the sea-surface microlayer (SML), the oceanic uppermost boundary directly subject to high solar radiation, often enriched in specific organic compounds of biological origin like Chromophoric Dissolved Organic Matter (CDOM) and marine gels. In the SML, the continuous photochemical and microbial recycling of organic matter may strongly influence gas exchange between marine systems and the atmosphere. In order to understand organic matter cycling in surface films, we analyzed SML and underlying water samples in 38 stations determining DOC concentrations, amino acids composition, marine gels, CDOM and bacterial abundance as indicators of photochemical and microbial alteration processes. CDOM composition was characterized by spectral slopes (S) values and Excitation-Emission Matrix fluorescence (EEMs), which allow to track changes in molecular weight (MW) of DOM, and to determine potential DOM sources. Profound changes in spectral slope properties were observed suggesting smaller MW CDOM in the SML compared to underlying water. Microbial and photochemical degradation are likely the main drivers for organic matter cycling in the top layer of the ocean. Consequences on the formation of inorganic and organic species highly relevant for air-sea gas exchange and for climate dynamics will be discussed.

Rapid removal of Chernobyl fallout from Mediterranean surface waters by biological activity

NASA Astrophysics Data System (ADS)

Fowler, Scott W.; Buat-Menard, Patrick; Yokoyama, Yuji; Ballestra, Serge; Holm, Elis; Nguyen, Huu Van

1987-09-01

The sinking of participate organic matter from the euphotic zone is an important pathway for the vertical transport of many elements and organic compounds in the sea1-3. Many natural4-5 and artificial5-7 radionuclides in surface waters are readily adsorbed onto suspended particles and are presumably scavenged and removed to depth on time scales commensurate with both particle sinking rate and retention time of the radionuclide on the particle. Previously, abyssal benthic organisms from the northeast Pacific were found to contain short-lived fission products which entered the sea surface as fallout from nuclear testing8. The presence of these radionuclides at great depth could not be explained by Stokesian settling of small fallout particles and it was hypothesized8 that zooplankton grazing in the surface layers packaged these particle-reactive radionuclides into large, relatively dense faecal pellets which rapidly sank to depth. We report here data from a time-series sediment trap experiment and concomitant zooplankton collections which show conclusively that Chernobyl radioactivity, in particular the rare earth nuclides 141Ce and 144Ce, entering the Mediterranean as a single pulse, was rapidly removed from surface waters and transported to 200m in a few days primarily by zooplankton grazing.

Plasmonics and SERS activity of post-transition metal nanoparticles

NASA Astrophysics Data System (ADS)

Bezerra, A. G.; Machado, T. N.; Woiski, T. D.; Turchetti, D. A.; Lenz, J. A.; Akcelrud, L.; Schreiner, W. H.

2018-05-01

Nanoparticles of the post-transition metals, In, Sn, Pb, and Bi, and of the metalloid Sb were produced by laser ablation synthesis in solution (LASiS) and tested for localized surface plasmon resonances (LSPR) and surface-enhanced Raman scattering (SERS). The nanoparticles were characterized by UV-Vis optical absorption, dynamic light scattering (DLS), and transmission electron microscopy (TEM). Several organic and biological molecules were tested, and SERS activity was demonstrated for all tested nanoparticles and molecules. The Raman enhancement factor for each nanoparticle class and molecule was experimentally determined. The search for new plasmonic nanostructures is important mainly for life sciences-related applications and this study expands the range of SERS active systems.

Effects of morphological control on the characteristics of vertical-type OTFTs using Alq3.

PubMed

Kim, Young Do; Park, Jong Wook; Kang, In Nam; Oh, Se Young

2008-09-01

We have fabricated vertical-type organic thin-film transistors (OTFTs) using tris-(8-hydroxyquinoline) aluminum (Alq(3)) as an n-type active material. Vertical-type OTFT using Alq(3) has a layered structure of Al(source electrode)/Alq(3)(active layer)/Al(gate electrode)/Alq(3)(active layer)/ITO glass(drain electrode). Alq(3) thin films containing various surface morphologies could be obtained by the control of evaporation rate and substrate temperature. The effects of the morphological control of Alq(3) thin layer on the grain size and the flatness of film surface were investigated. The characteristics of vertical-type OTFT significantly influenced the growth condition of Alq(3) layer.

Effect of bentonite modification on hardness and mechanical properties of natural rubber nanocomposites

NASA Astrophysics Data System (ADS)

Santiago, Denise Ester O.; Pajarito, Bryan B.; Mangaccat, Winna Faye F.; Tigue, Maelyn Rose M.; Tipton, Monica T.

2016-05-01

The effect of sodium activation, ion-exchange with tertiary amine salt, surface treatment with non-ionic surfactant, and wet grinding of bentonite on hardness and mechanical properties of natural rubber nanocomposites (NRN) was studied using full factorial design of experiment. Results of X-ray diffraction (XRD) show increase in basal spacing d of bentonite due to modification, while attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) confirm the organic modification of bentonite. Analysis of variance (ANOVA) shows that the main effect of surface treatment increases the hardness and decreases the tensile modulus of the NRN. The surface treatment and wet grinding of bentonite decrease the tensile stresses at 100, 200 and 300% strain of NRN. Sodium activation and ion-exchange negatively affect the compressive properties, while surface treatment significantly improves the compressive properties of NRN.

The signaling phospholipid PIP 3 creates a new interaction surface on the nuclear receptor SF-1

DOE PAGES

Blind, Raymond D.; Sablin, Elena P.; Kuchenbecker, Kristopher M.; ...

2014-10-06

We previously reported that lipids PI(4,5)P 2 (PIP 2) and PI(3,4,5)P 3 (PIP 3) bind NR5A nuclear receptors to regulate their activity. Here, the crystal structures of PIP 2 and PIP 3 bound to NR5A1 (SF-1) define a new interaction surface that is organized by the solvent-exposed PIPn headgroups. We find that stabilization by the PIP 3 ligand propagates a signal that increases coactivator recruitment to SF-1, consistent with our earlier work showing that PIP 3 increases SF-1 activity. This newly created surface harbors a cluster of human mutations that lead to endocrine disorders, thus explaining how these puzzling mutationsmore » cripple SF-1 activity. Finally, we propose that this new surface acts as a PIP 3-regulated interface between SF-1 and coregulatory proteins, analogous to the function of membrane-bound phosphoinositides.« less

Molluscicidal properties and selective toxicity of surface-active agents

PubMed Central

Visser, S. A.

1965-01-01

Of over 100 commercially produced surface-active agents tested against the bilharziasis vector snail Biomphalaria sudanica, 13 were found to possess considerable and highly selective molluscicidal properties at concentrations of less than 1 ppm for exposures of 48 hours. Against crustacea, fish, water plants, mosquito larvae, mice, and the eggs of B. sudanica, the toxicities of the 13 surfactants were slight. The chemicals did not appear to be absorbed by organic matter to any appreciable extent. It is thought that the toxicity to B. sudanica is of both a chemical and a physical nature. PMID:5294185

Self-organized TiO2 nanotube arrays in the photocatalytic degradation of methylene blue under UV light irradiation

NASA Astrophysics Data System (ADS)

Chung, Eun Hyuk; Baek, Seong Rim; Yu, Seong Mi; Kim, Jong Pil; Hong, Tae Eun; Kim, Hyun Gyu; Bae, Jong-Seong; Jeong, Euh Duck; Khan, F. Nawaz; Jung, Ok-sang

2015-04-01

Nanostructured titanium dioxide (NTiO2) is known to possess efficient photocatalytic activity and to have diverse applications in many fields due to its chemical stability, high surface area/volume ratio, high transmittance, and high refractive index in the visible and the near-ultraviolet regions. These facts prompted us to develop TiO2 nanotube (TiO2 NT) arrays through electrochemical anodic oxidation involving different electrolytes comprised of phosphoric acid — hydrofluoric acid aqueous systems by varying the voltage and the time. The annealing temperature of the nanotubes, TiO2 NTs, were varied to modify the surface morphology and were characterized by using X-ray diffraction and scanning electron microscopy. Scanning electron microscopy and X-ray diffraction results showed that the samples had uniform morphologies and good crystalline structures of the anatase phase at lower annealing temperatures and of the rutile phase at higher annealing temperatures. A secondary-ion mass-spectrometry analysis was used to investigate the surface atoms and to conduct a depth profile analysis of the TiO2 NTs. The efficiency of the photocatalytic activity of the TiO2 NT arrays in degrading methylene blue (MB) was investigated under UV-Vis light irradiation. The maximum photocatalytic activity was achieved for the samples with lower annealing temperatures due to their being in the anatase phase and having a higher surface area and a smaller crystal size, which play important roles in the degradation of organic pollutants.

Observing the formation of ice and organic crystals in active sites

PubMed Central

Campbell, James M.; Meldrum, Fiona C.; Christenson, Hugo K.

2017-01-01

Heterogeneous nucleation is vital to a wide range of areas as diverse as ice nucleation on atmospheric aerosols and the fabrication of high-performance thin films. There is excellent evidence that surface topography is a key factor in directing crystallization in real systems; however, the mechanisms by which nanoscale pits and pores promote nucleation remain unclear. Here, we use natural cleavage defects on Muscovite mica to investigate the activity of topographical features in the nucleation from vapor of ice and various organic crystals. Direct observation of crystallization within surface pockets using optical microscopy and also interferometry demonstrates that these sharply acute features provide extremely effective nucleation sites and allows us to determine the mechanism by which this occurs. A confined phase is first seen to form along the apex of the wedge and then grows out of the pocket opening to generate a bulk crystal after a threshold saturation has been achieved. Ice nucleation proceeds in a comparable manner, although our resolution is insufficient to directly observe a condensate before the growth of a bulk crystal. These results provide insight into the mechanism of crystal deposition from vapor on real surfaces, where this will ultimately enable us to use topography to control crystal deposition on surfaces. They are also particularly relevant to our understanding of processes such as cirrus cloud formation, where such topographical features are likely candidates for the “active sites” that make clay particles effective nucleants for ice in the atmosphere. PMID:27994140

Removal of Biologically Active Organic Contaminants using Atomic Oxygen

NASA Technical Reports Server (NTRS)

Banks, Bruce A. (Inventor); Banks, Michael A. (Inventor); Banks, Eric B. (Inventor)

2003-01-01

Biomedical devices that are to come into contact with living tissue, such as prosthetic and other implants for the human body and the containers used to store and transport them, are together cleaned of non-living, but biologically active organic materials, including endotoxins such as lipopolysaccharides, and assembled into a hermetically sealed package without recontamination. This is achieved by cleaning both the device and package components together in an apparatus, which includes a hermetically sealed chamber, in which they are contacted with atomic oxygen which biocleans them, by oxidizing the biologically active organic materials. The apparatus also includes means for manipulating the device and container and hermetically sealing the cleaned device into the cleaned container to form the package. A calibrated witness coupon visually indicates whether or not the device and container have received enough exposure to the atomic oxygen to have removed the organic materials from their surfaces. Gamma radiation is then used to sterilize the device in the sealed container.

Photosystem I assembly on chemically tailored SAM/ Au substrates for bio-hybrid device fabrication

NASA Astrophysics Data System (ADS)

Mukherjee, Dibyendu; Khomami, Bamin

2011-03-01

Photosystem I (PS I), a supra-molecular protein complex and a biological photodiode responsible for driving natural photosynthesis mechanism, charge separates upon exposure to light. Effective use of the photo-electrochemical activities of PS I for future bio-hybrid electronic devices requires controlled attachment of these proteins onto organic/ inorganic substrates. Our results indicate that various experimental parameters alter the surface topography of PS I deposited from colloidal aqueous buffer suspensions onto OH-terminated alkanethiolate SAM /Au substrates, thereby resulting in complex columnar structures that affect the electron capture pathway of PS I. Specifically, solution phase characterizations indicate that specific detergents used for PS I stabilization in buffer solutions drive the unique colloidal chemistry to tune protein-protein interactions and prevent aggregation, thereby allowing us to tailor the morphology of surface immobilized PS I. We present surface topographical, adsorption, and electrochemical characterizations of PSI /SAM/Au substrates to elucidate protein-surface attachment dynamics and its effect on the photo-activated electronic activities of surface immobilized PS I. Sustainable Energy Education and Research Center (SEERC).

Surface grafting of zwitterionic polymers onto dye doped AIE-active luminescent silica nanoparticles through surface-initiated ATRP for biological imaging applications

NASA Astrophysics Data System (ADS)

Mao, Liucheng; Liu, Xinhua; Liu, Meiying; Huang, Long; Xu, Dazhuang; Jiang, Ruming; Huang, Qiang; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen

2017-10-01

Aggregation-induced emission (AIE) dyes have recently been intensively explored for biological imaging applications owing to their outstanding optical feature as compared with conventional organic dyes. The AIE-active luminescent silica nanoparticles (LSNPs) are expected to combine the advantages both of silica nanoparticles and AIE-active dyes. Although the AIE-active LSNPs have been prepared previously, surface modification of these AIE-active LSNPs with functional polymers has not been reported thus far. In this work, we reported a rather facile and general strategy for preparation of polymers functionalized AIE-active LSNPs through the surface-initiated atom transfer radical polymerization (ATRP). The AIE-active LSNPs were fabricated via direct encapsulation of AIE-active dye into silica nanoparticles through a non-covalent modified Stöber method. The ATRP initiator was subsequently immobilized onto these AIE-active LSNPs through amidation reaction between 3-aminopropyl-triethoxy-silane and 2-bromoisobutyryl bromide. Finally, the zwitterionic 2-(methacryloyloxy)ethyl phosphorylcholine (MPC) was selected as model monomer and grafted onto MSNs through ATRP. The characterization results suggested that LSNPs can be successfully modified with poly(MPC) through surface-initiated ATRP. The biological evaluation results demonstrated that the final SNPs-AIE-pMPC composites possess low cytotoxicity, desirable optical properties and great potential for biological imaging. Taken together, we demonstrated that AIE-active LSNPs can be fabricated and surface modified with functional polymers to endow novel functions and better performance for biomedical applications. More importantly, this strategy developed in this work could also be extended for fabrication of many other LSNPs polymer composites owing to the good monomer adoptability of ATRP.

The Preservation of Organic Matter and its Signatures at Experimental Lava Flow Interfaces: Implications for Mars

NASA Astrophysics Data System (ADS)

Junium, C. K.; Karson, J. A.; Kahan, T.

2015-12-01

The oxidizing nature of Martian soils suggests that the preservation of organic molecules or any direct evidence for life at the surface may not be possible. Future rover missions will need to focus on a variety localitions including those that provide the best possibility for the preservation of organic matter. Volcanic glass and basalt flow surfaces are favored environments for microbial colonization on Earth and this may have been similar on an early Mars. Trace metals and nutrients from easily weathered surface would have provided nutrients as well as substrates for chemolithoautotrophs. In regions of igneous activity, successive flows could overrun microbial communities, trapping potential organic signatures between flows. Here we present experimental evidence for the preservation of organic matter between lava flows and that flow interfaces may be excellent sites for exploratory efforts in the search for Martian biosignatures. We performed a series of experiments using the infrastructure of the Syracuse Lava Project that allows for natural-scale lava flows of up to several hundred kilograms. We subjected cyanobacterial organic matter to overrun by lava under a variety of conditions. In all cases organic matter was preserved between lava flows as chars on the overrun 'colonized" lava and as thin shiny carbon coatings on the overriding flow. The carbon coatings are likely the result of rapid heating and pyrolysis of organic matter that sears to the underside of the overriding lava. Controls yielded no positive signatures for organic matter. We also tested the degree to which the organic matter could be detected remotely using technologies that are found on the Mars Science Laboratory or planned for future missions. We employed elemental and stable isotopes analysis, and Raman spectroscopy. Elemental analysis demonstrated that organic carbon and nitrogen remain in the charred material and that the carbon and nitrogen isotopes of the chars do not deviate significantly from the precursor organic matter (-24.3‰ cyanobacterial biomass; -24.2‰ black carbon). Raman spectroscopy revealed spectra for black carbon, even from the thinnest carbon coatings on overriding lava surfaces. These findings demonstrate that if organic matter is preserved beneath lava flows it may be readily detectable.

Automated life-detection experiments for the Viking mission to Mars

NASA Technical Reports Server (NTRS)

Klein, H. P.

1974-01-01

As part of the Viking mission to Mars in 1975, an automated set of instruments is being built to test for the presence of metabolizing organisms on that planet. Three separate modules are combined in this instrument so that samples of the Martian surface can be subjected to a broad array of experimental conditions so as to measure biological activity. The first, the Pyrolytic Release Module, will expose surface samples to a mixture of C-14O and C-14O2 in the presence of Martian atmosphere and a light source that simulates the Martian visible spectrum. The assay system is designed to determine the extent of assimilation of CO or CO2 into organic compounds. The Gas Exchange Module will incubate surface samples in a humidified CO2 atmosphere. At specified times, portions of the incubation atmosphere will be analyzed by gas chromatography to detect the release or uptake of CO2 and several additional gases. The Label Release Module will incubate surface samples with a dilute aqueous solution of simple radioactive organic substrates in Martian atmosphere, and the gas phase will be monitored continuously for the release of labeled CO2.

Effect of UV/ozone treatment on polystyrene dielectric and its application on organic field-effect transistors

PubMed Central

2014-01-01

The influence of UV/ozone treatment on the property of polystyrene (PS) dielectric surface was investigated, and pentacene organic field-effect transistors (OFETs) based on the treated dielectric was fabricated. The dielectric and pentacene active layers were characterized by atomic force microscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. The results showed that, at short UVO exposure time (<10 s), the chemical composition of PS dielectric surface remained the same. While at long UVO exposure time (>60 s), new chemical groups, including alcohol/ether, carbonyl, and carboxyl/ester groups, were formed. By adjusting the UVO exposure time to 5 s, the hole mobility of the OFETs increased to 0.52 cm2/Vs, and the threshold voltage was positively shifted to -12 V. While the time of UVO treatment exceeded 30 s, the mobility started to shrink, and the off-current was enlarged. These results indicate that, as a simple surface treatment method, UVO treatment could quantitatively modulate the property of PS dielectric surface by controlling the exposure time, and thus, pioneered a new way to modulate the characteristics of organic electronic devices. PMID:25258603

Role of molecular size in cloud droplet activation

NASA Astrophysics Data System (ADS)

Petters, M. D.; Kreidenweis, S. M.; Prenni, A. J.; Sullivan, R. C.; Carrico, C. M.; Koehler, K. A.; Ziemann, P. J.

2009-11-01

We examine the observed relationships between molar volume (the ratio of molar mass and density) and cloud condensation nuclei (CCN) activity for sufficiently soluble organic compounds found in atmospheric particulate matter. Our data compilation includes new CCN data for certain carbohydrates and oligoethylene glycols, as well as published data for organic compounds. We compare predictions of CCN activity using water activities based on Raoult's law and Flory-Huggins theory to observations. The Flory-Huggins water activity expression, with an assumed surface tension of pure water, generally predicts CCN activity within a factor of two over the full range of molar volumes considered. CCN activity is only weakly dependent on molar volume for values exceeding 600 cm3 mol-1, and the diminishing sensitivity to molar volume, combined with the significant scatter in the data, limits the accuracy with which molar volume can be inferred from CCN measurements.

Deterministic influences exceed dispersal effects on hydrologically-connected microbiomes.

PubMed

Graham, Emily B; Crump, Alex R; Resch, Charles T; Fansler, Sarah; Arntzen, Evan; Kennedy, David W; Fredrickson, Jim K; Stegen, James C

2017-04-01

Subsurface groundwater-surface water mixing zones (hyporheic zones) have enhanced biogeochemical activity, but assembly processes governing subsurface microbiomes remain a critical uncertainty in understanding hyporheic biogeochemistry. To address this obstacle, we investigated (a) biogeographical patterns in attached and waterborne microbiomes across three hydrologically-connected, physicochemically-distinct zones (inland hyporheic, nearshore hyporheic and river); (b) assembly processes that generated these patterns; (c) groups of organisms that corresponded to deterministic changes in the environment; and (d) correlations between these groups and hyporheic metabolism. All microbiomes remained dissimilar through time, but consistent presence of similar taxa suggested dispersal and/or common selective pressures among zones. Further, we demonstrated a pronounced impact of deterministic assembly in all microbiomes as well as seasonal shifts from heterotrophic to autotrophic microorganisms associated with increases in groundwater discharge. The abundance of one statistical cluster of organisms increased with active biomass and respiration, revealing organisms that may strongly influence hyporheic biogeochemistry. Based on our results, we propose a conceptualization of hyporheic zone metabolism in which increased organic carbon concentrations during surface water intrusion support heterotrophy, which succumbs to autotrophy under groundwater discharge. These results provide new opportunities to enhance microbially-explicit ecosystem models describing hyporheic zone biogeochemistry and its influence over riverine ecosystem function. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

Liquid eutectic GaIn as an alternative electrode for PTB7:PCBM organic solar cells

NASA Astrophysics Data System (ADS)

Thanh Hau Pham, Viet; Kieu Trinh, Thanh; Tam Nguyen Truong, Nguyen; Park, Chinho

2017-04-01

Conventional vacuum deposition process of aluminum (Al) is costly, time-consuming and difficult to apply to the large-scale production of organic photovoltaic devices (OPV). This paper reports a vacuum-free fabrication process of poly[[4,8-bis(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b‧]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thienophenediyl]:[6,6]-phenyl C71 butyric acid methyl ester (PTB7:PCBM) bulk heterojunction organic solar cell with liquid eutectic gallium-indium (EGaIn) electrode as an alternative to the common Al electrode. The insertion of a thin poly(ethylene oxide) (PEO) layer after depositing organic photoactive layer could help prevent the diffusion of liquid EGaIn into the active layer and allow the deposition of the EGaIn electrode. The PEO interfacial layer was formed by spin-coating from a mixed solvent of alcohol and water. Among different alcohol+water (methanol, ethanol, ethylene glycol, n-propanol, isopropanol, and isobutanol) mixed solvent tested, the n-propanol+water mixed solvent showed the greatest enhancement to the performance of OPVs. The improved device performance was attributed to the reactivity of mixed solvent n-propanol+water toward the surface of PTB7:PCBM active layer, which could help optimize surface morphology.

Chromium(II) Metal–Organic Polyhedra as Highly Porous Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Jinhee; Perry, Zachary; Chen, Ying-Pin

2017-08-10

Herein we report for the first time the synthesis of Cr(II)-based metal–organic polyhedra (MOPs) and the characterization of their porosities. Unlike the isostructural Cu(II)- or Mo(II)-based MOPs, Cr(II)-based MOPs show unusually high gas uptakes and surface areas. The combination of comparatively robust dichromium paddlewheel units (Cr 2 units), cage symmetries, and packing motifs enable these materials to achieve Brunauer–Emmett–Teller surface areas of up to 1000 m 2/g. Reducing the aggregation of the Cr(II)-based MOPs upon activation makes their pores more accessible than their Cu(II) or Mo(II) counterparts. Further comparisons of surface areas on a molar (m2/mol cage) rather than gravimetricmore » (m 2/g) basis is proposed as a rational method of comparing members of a family of related molecular materials.« less

Surface-Enhanced Raman Scattering Using Silica Whispering-Gallery Mode Resonators

NASA Technical Reports Server (NTRS)

Anderson, Mark S.

2013-01-01

The motivation of this work was to have robust spectroscopic sensors for sensitive detection and chemical analysis of organic and molecular compounds. The solution is to use silica sphere optical resonators to provide surface-enhanced spectroscopic signal. Whispering-gallery mode (WGM) resonators made from silica microspheres were used for surface-enhanced Raman scattering (SERS) without coupling to a plasmonic mechanism. Large Raman signal enhancement is observed by exclusively using 5.08-micron silica spheres with 785-nm laser excitation. The advantage of this non-plasmonic approach is that the active substrate is chemically inert silica, thermally stable, and relatively simple to fabricate. The Raman signal enhancement is broadly applicable to a wide range of molecular functional groups including aliphatic hydrocarbons, siloxanes, and esters. Applications include trace organic analysis, particularly for in situ planetary instruments that require robust sensors with consistent response.

Chirality-dependent cellular uptake of chiral nanocarriers and intracellular delivery of different amounts of guest molecules

NASA Astrophysics Data System (ADS)

Kehr, Nermin Seda; Jose, Joachim

2017-12-01

We demonstrate the organic molecules loaded and chiral polymers coated periodic mesoporous organosilica (PMO) to generate chiral nanocarriers that we used to study chirality-dependent cellular uptake in serum and serum-free media and the subsequent delivery of different amounts of organic molecules into cells. Our results show that the amount of internalized PMO and thus the transported amount of organic molecules by nanocarrier PMO into cells was chirality dependent and controlled by hard/soft protein corona formation on the PMO surfaces. Therefore, this study demonstrate that chiral porous nanocarriers could potentially be used as advanced drug delivery systems which are able to use the specific chiral surface-protein interactions to influence/control the amount of (bio)active molecules delivered to cells in drug delivery and/or imaging applications.

A mathematical framework for modelling cambial surface evolution using a level set method

PubMed Central

Sellier, Damien; Plank, Michael J.; Harrington, Jonathan J.

2011-01-01

Background and Aims During their lifetime, tree stems take a series of successive nested shapes. Individual tree growth models traditionally focus on apical growth and architecture. However, cambial growth, which is distributed over a surface layer wrapping the whole organism, equally contributes to plant form and function. This study aims at providing a framework to simulate how organism shape evolves as a result of a secondary growth process that occurs at the cellular scale. Methods The development of the vascular cambium is modelled as an expanding surface using the level set method. The surface consists of multiple compartments following distinct expansion rules. Growth behaviour can be formulated as a mathematical function of surface state variables and independent variables to describe biological processes. Key Results The model was coupled to an architectural model and to a forest stand model to simulate cambium dynamics and wood formation at the scale of the organism. The model is able to simulate competition between cambia, surface irregularities and local features. Predicting the shapes associated with arbitrarily complex growth functions does not add complexity to the numerical method itself. Conclusions Despite their slenderness, it is sometimes useful to conceive of trees as expanding surfaces. The proposed mathematical framework provides a way to integrate through time and space the biological and physical mechanisms underlying cambium activity. It can be used either to test growth hypotheses or to generate detailed maps of wood internal structure. PMID:21470972

Low temperature surface chemistry and nanostructures

NASA Astrophysics Data System (ADS)

Sergeev, G. B.; Shabatina, T. I.

2002-03-01

The new scientific field of low temperature surface chemistry, which combines the low temperature chemistry (cryochemistry) and surface chemistry approaches, is reviewed in this paper. One of the most exciting achievements in this field of science is the development of methods to create highly ordered hybrid nanosized structures on different organic and inorganic surfaces and to encapsulate nanosized metal particles in organic and polymer matrices. We consider physical and chemical behaviour for the systems obtained by co-condensation of the components vapours on the surfaces cooled down to 4-10 and 70-100 K. In particular the size effect of both types, the number of atoms in the reactive species structure and the thickness of growing co-condensate film, on the chemical activity of the system is analysed in detail. The effect of the internal mechanical stresses on the growing interfacial co-condensate film formation and on the generation of fast (explosive) spontaneous reactions at low temperatures is discussed. The examples of unusual chemical interactions of metal atoms, clusters and nanosized particles, obtained in co-condensate films on the cooled surfaces under different conditions, are presented. The examples of highly ordered surface and volume hybrid nanostructures formation are analysed.

Surface characterization studies of walnut-shell biochar catalysts for simultaneously removing of organic sulfur from yellow phosphorus tail gas

NASA Astrophysics Data System (ADS)

Song, Xin; Li, Kai; Ning, Ping; Wang, Chi; Sun, Xin; Tang, Lihong; Ruan, Haotian; Han, Shuang

2017-12-01

The influences of different preparation conditions for surface characteristics on removing organic sulfur were studied. From BET, XRD, FTIR, DRIFTS, TG/DTA, CO2-TPD results, it can be seen that these preparation conditions had great influences on the pore structure, specific surface area, crystal structure and surface functional groups. The micropore volume, amorphous structure and alkalinity site strength played major roles in desulfurization process. H2S was oxidized by oxygen containing functional groups, such as sbnd COO, sbnd Cdbnd O. H2O molecule could be converted into some groups, such as sbnd CH and Csbnd OH groups, and promoted the hydrolysis reaction. The strong alkalinity site was the key factor for chemical adsorption and hydrolysis. H2O molecule, sbnd CH, Csbnd OH groups promoted the hydrolysis reaction and sbnd COO, sbnd Cdbnd O groups promoted the oxidation of H2S on the surface of WSB. Meanwhile, the main desulfurization process over WSB after carbonization was adsorption and it changed to hydrolysis reaction after activation on the surface of WSB. Furthermore, the reaction mechanism was investigated by DRIFTS measurement according to the change of surface functional groups.

Photosynthetic Activity and Adaptation Capacities of Lichens and Cyanobacteria to Martian Surface Conditions

NASA Astrophysics Data System (ADS)

De Vera, Jean-Pierre; Schulze-Makuch, D.; Khan, A.; Lorek, A.; Koncz, A.; Stivaletta, N.; Möhlmann, D.; Spohn, T.

2012-05-01

We observed an increase in photosynthetic activity in the lichen Pleopsidium chlorophanum but a strong negative effect on the photosynthetic activity of endolithic cyanobacteria when subjected for 34 days to environmental stresses likely to be encountered in semi-protected habitats on the Martian surface. Stresses were simulated in a Mars Simulation Chamber (MSC) and included high UV fluxes, low temperatures, low water activity, high atmospheric CO2 concentrations, and an atmospheric pressure of about 6 mbar. P. chlorophanum is an extremophile: it lives in very cold, dry, high-altitude habitats which are Earth's best approximation of the Martian surface. Our lichen samples came from North Victoria Land in Antarctica whereas the investigated samples of cyanobacteria came from tropic regions in the Sahara. Three samples of each group of organisms were exposed uninterruptedly to simulated conditions (as above) of the naked, unprotected Martian surface for 34 days, receiving the full Martian solar spectrum (200 - 2500 nm) for a cumulative UV dose of 6343.6 kJm-2. For a second sample set - containing also three lichen thalli and three endolithic cyanobacteria communities - the cumulative (34-day) UV dose was reduced to 268.8 kJm-2, to reasonably simulate the amount the microorganisms might receive in (semi-) protected surface sites (e.g., fissures, cracks and micro-caves within rocks or permafrost soil). In the 'unprotected' experiment it was unclear if the lichen was still actively photosynthesizing but still clear that the cyanobacteria were affected. However, under 'protected site' conditions, the cyanobacteria had no clear photosynthetic response under and after simulated Martian conditions but the lichen not only survived and remained photosynthetically active, it even adapted physiologically by increasing its photosynthetic activity over 34 days. Comparison with other Mars simulation experiments on exposure platforms in space and in the laboratory with other investigated species show results of remarkable survival rates and maintained photosynthesizing activity which strongly supports the interconnected notions (1) that terrestrial life most likely can adapt physiologically to live on Mars (hence justifying stringent measures to prevent human activities from contaminating/infecting Mars with terrestrial organisms); (2) that in searching for extant life on Mars we should focus on "protected" habitats; and (3) that early-originating (Noachian Period) indigenous Martian life might still survive in such habitats despite Mars' cooling and drying during the last 4 billion years.

Soil hydrological and soil property changes resulting from termite activity on agricultural fields in Burkina Faso

NASA Astrophysics Data System (ADS)

Mettrop, I.; Cammeraat, L. H.; Verbeeten, E.

2009-04-01

Termites are important ecosystem-engineers in subtropical and tropical regions. The effect of termite activity affecting soil infiltration is well documented in the Sahelian region. Most studies find increased infiltration rates on surfaces that are affected by termite activity in comparison to crusted areas showing non-termite presence. Crusted agricultural fields in the Sanmatenga region in Burkina Faso with clear termite activity were compared to control fields without visual ground dwelling termite activity. Fine scale rainfall simulations were carried out on crusted termite affected and control sites. Furthermore soil moisture change, bulk density, soil organic matter as well as general soil characteristics were studied. The top soils in the study area were strongly crusted (structural crust) after the summer rainfall and harvest of millet. They have a loamy sand texture underlain by a shallow sandy loam Bt horizon. The initial soil moisture conditions were significantly higher on the termite plots when compared to control sites. It was found that the amount of runoff produced on the termite plots was significantly higher, and also the volumetric soil moisture content after the experiments was significantly lower if compared to the control plots. Bulk density showed no difference whereas soil organic matter was significantly higher under termite affected areas, in comparison to the control plots. Lab tests showed no significant difference in hydrophobic behavior of the topsoil and crust material. Micro and macro-structural properties of the topsoil did not differ significantly between the termite sites and the control sites. The texture of the top 5 cm of the soil was also found to be not significantly different. The infiltration results are contradictory to the general literature, which reports increased infiltration rates after prolonged termite activity although mostly under different initial conditions. The number of nest entrances was clearly higher in the termite areas, but apparently did not significantly affect infiltration. The increased soil organic matter contents in the termite affected areas however, are as expected from literature, but did not improve soil aggregation which would be expected given the importance of organic matter in soil aggregation in this type of soils. One of the explanations for the reduced infiltration rates might be that termites bring clay from the finer textured subsoil to the surface to build casts over the organic material on the surface (mainly millet stems). It is speculated that the excavated clay material could be involved in crust formation, only present is in the upper 0.5 cm of the soil crust, which is enough to block pores in the crust surface, hampering infiltration. The topsoil aggregates are slaking under the summer rainfall and the increase in fine textured material, excavated by the termites, could be incorporated into the crust and reduce infiltration. Furthermore this specific effect might also be related to the type of termite involved, as impacts from ecosystem engineers on their environment is highly dependent on the specific species involved.

The Institutionalization of Private Sector Strategic Planning Methods in a Public Sector Research & Development Organization: The Naval Surface Warfare Center Case 1982-1989

DTIC Science & Technology

1990-02-01

infancy during Cycle I, at the novice level during Cycle II, and at the advanced beginner level during Cycle III. The next two sections and Chapters 6...5 Table 1 - 1983 NSWC Planning Activities . . . . . . . 14 Table 1A - Planning Activity Flowchart . . . . . . . 14.1 Table 2 - Sector/SBU

Metal-organic frameworks derived platinum-cobalt bimetallic nanoparticles in nitrogen-doped hollow porous carbon capsules as a highly active and durable catalyst for oxygen reduction reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ying, Jie; Li, Jing; Jiang, Gaopeng

Pt-based nanomaterials are regarded as the most efficient electrocatalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). However, widespread adoption of PEMFCs requires solutions to major challenges encountered with ORR catalysts, namely high cost, sluggish kinetics, and low durability. In this paper, a new efficient method utilizing Co-based metal-organic frameworks is developed to produce PtCo bimetallic nanoparticles embedded in unique nitrogen-doped hollow porous carbon capsules. The obtained catalyst demonstrates an outstanding ORR performance, with a mass activity that is 5.5 and 13.5 times greater than that of commercial Pt/C and Pt black, respectively. Most importantly,more » the product exhibits dramatically improved durability in terms of both electrochemically active surface area (ECAS) and mass activity compared to commercial Pt/C and Pt black catalysts. Finally, the remarkable ORR performance demonstrated here can be attributed to the structural features of the catalyst (its alloy structure, high dispersion and fine particle size) and the carbon support (its nitrogen dopant, large surface area and hollow porous structure).« less

Metal-organic frameworks derived platinum-cobalt bimetallic nanoparticles in nitrogen-doped hollow porous carbon capsules as a highly active and durable catalyst for oxygen reduction reaction

DOE PAGES

Ying, Jie; Li, Jing; Jiang, Gaopeng; ...

2017-11-29

Pt-based nanomaterials are regarded as the most efficient electrocatalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). However, widespread adoption of PEMFCs requires solutions to major challenges encountered with ORR catalysts, namely high cost, sluggish kinetics, and low durability. In this paper, a new efficient method utilizing Co-based metal-organic frameworks is developed to produce PtCo bimetallic nanoparticles embedded in unique nitrogen-doped hollow porous carbon capsules. The obtained catalyst demonstrates an outstanding ORR performance, with a mass activity that is 5.5 and 13.5 times greater than that of commercial Pt/C and Pt black, respectively. Most importantly,more » the product exhibits dramatically improved durability in terms of both electrochemically active surface area (ECAS) and mass activity compared to commercial Pt/C and Pt black catalysts. Finally, the remarkable ORR performance demonstrated here can be attributed to the structural features of the catalyst (its alloy structure, high dispersion and fine particle size) and the carbon support (its nitrogen dopant, large surface area and hollow porous structure).« less

Influence of temperature and organic load on chemical disinfection of Geobacillus steareothermophilus spores, a surrogate for Bacillus anthracis

PubMed Central

Guan, Jiewen; Chan, Maria; Brooks, Brian W.; Rohonczy, Liz

2013-01-01

This study evaluated the influence of temperature and organic load on the effectiveness of domestic bleach (DB), Surface Decontamination Foam (SDF), and Virkon in inactivating Geobacillus stearothermophilus spores, which are a surrogate for Bacillus anthracis spores. The spores were suspended in light or heavy organic preparations and the suspension was applied to stainless steel carrier disks. The dried spore inoculum was covered with the disinfectants and the disks were then incubated at various temperatures. At −20°C, the 3 disinfectants caused less than a 2.0 log10 reduction of spores in both organic preparations during a 24-h test period. At 4°C, the DB caused a 4.4 log10 reduction of spores in light organic preparations within 2 h, which was about 3 log10 higher than what was achieved with SDF or Virkon. In heavy organic preparations, after 24 h at 4°C the SDF had reduced the spore count by 4.5 log10, which was about 2 log10 higher than for DB or Virkon. In general, the disinfectants were most effective at 23°C but a 24-h contact time was required for SDF and Virkon to reduce spore counts in both organic preparations by at least 5.5 log10. Comparable disinfecting activity with DB only occurred with the light organic load. In summary, at temperatures as low as 4°C, DB was the most effective disinfectant, inactivating spores within 2 h on surfaces with a light organic load, whereas SDF produced the greatest reduction of spores within 24 h on surfaces with a heavy organic load. PMID:24082400

Ureaplasma diversum Genome Provides New Insights about the Interaction of the Surface Molecules of This Bacterium with the Host

PubMed Central

Marques, Lucas M.; Rezende, Izadora S.; Barbosa, Maysa S.; Guimarães, Ana M. S.; Martins, Hellen B.; Campos, Guilherme B.; do Nascimento, Naíla C.; dos Santos, Andrea P.; Amorim, Aline T.; Santos, Verena M.; Farias, Sávio T.; Barrence, Fernanda Â. C.; de Souza, Lauro M.; Buzinhani, Melissa; Arana-Chavez, Victor E.; Zenteno, Maria E.; Amarante-Mendes, Gustavo P.; Messick, Joanne B.; Timenetsky, Jorge

2016-01-01

Whole genome sequencing and analyses of Ureaplasma diversum ATCC 49782 was undertaken as a step towards understanding U. diversum biology and pathogenicity. The complete genome showed 973,501 bp in a single circular chromosome, with 28.2% of G+C content. A total of 782 coding DNA sequences (CDSs), and 6 rRNA and 32 tRNA genes were predicted and annotated. The metabolic pathways are identical to other human ureaplasmas, including the production of ATP via hydrolysis of the urea. Genes related to pathogenicity, such as urease, phospholipase, hemolysin, and a Mycoplasma Ig binding protein (MIB)—Mycoplasma Ig protease (MIP) system were identified. More interestingly, a large number of genes (n = 40) encoding surface molecules were annotated in the genome (lipoproteins, multiple-banded antigen like protein, membrane nuclease lipoprotein and variable surface antigens lipoprotein). In addition, a gene encoding glycosyltransferase was also found. This enzyme has been associated with the production of capsule in mycoplasmas and ureaplasma. We then sought to detect the presence of a capsule in this organism. A polysaccharide capsule from 11 to 17 nm of U. diversum was observed trough electron microscopy and using specific dyes. This structure contained arabinose, xylose, mannose, galactose and glucose. In order to understand the inflammatory response against these surface molecules, we evaluated the response of murine macrophages J774 against viable and non-viable U. diversum. As with viable bacteria, non-viable bacteria were capable of promoting a significant inflammatory response by activation of Toll like receptor 2 (TLR2), indicating that surface molecules are important for the activation of inflammatory response. Furthermore, a cascade of genes related to the inflammasome pathway of macrophages was also up-regulated during infection with viable organisms when compared to non-infected cells. In conclusion, U. diversum has a typical ureaplasma genome and metabolism, and its surface molecules, including the identified capsular material, represent major components of the organism immunopathogenesis. PMID:27603136

Ureaplasma diversum Genome Provides New Insights about the Interaction of the Surface Molecules of This Bacterium with the Host.

PubMed

Marques, Lucas M; Rezende, Izadora S; Barbosa, Maysa S; Guimarães, Ana M S; Martins, Hellen B; Campos, Guilherme B; do Nascimento, Naíla C; Dos Santos, Andrea P; Amorim, Aline T; Santos, Verena M; Farias, Sávio T; Barrence, Fernanda  C; de Souza, Lauro M; Buzinhani, Melissa; Arana-Chavez, Victor E; Zenteno, Maria E; Amarante-Mendes, Gustavo P; Messick, Joanne B; Timenetsky, Jorge

2016-01-01

Whole genome sequencing and analyses of Ureaplasma diversum ATCC 49782 was undertaken as a step towards understanding U. diversum biology and pathogenicity. The complete genome showed 973,501 bp in a single circular chromosome, with 28.2% of G+C content. A total of 782 coding DNA sequences (CDSs), and 6 rRNA and 32 tRNA genes were predicted and annotated. The metabolic pathways are identical to other human ureaplasmas, including the production of ATP via hydrolysis of the urea. Genes related to pathogenicity, such as urease, phospholipase, hemolysin, and a Mycoplasma Ig binding protein (MIB)-Mycoplasma Ig protease (MIP) system were identified. More interestingly, a large number of genes (n = 40) encoding surface molecules were annotated in the genome (lipoproteins, multiple-banded antigen like protein, membrane nuclease lipoprotein and variable surface antigens lipoprotein). In addition, a gene encoding glycosyltransferase was also found. This enzyme has been associated with the production of capsule in mycoplasmas and ureaplasma. We then sought to detect the presence of a capsule in this organism. A polysaccharide capsule from 11 to 17 nm of U. diversum was observed trough electron microscopy and using specific dyes. This structure contained arabinose, xylose, mannose, galactose and glucose. In order to understand the inflammatory response against these surface molecules, we evaluated the response of murine macrophages J774 against viable and non-viable U. diversum. As with viable bacteria, non-viable bacteria were capable of promoting a significant inflammatory response by activation of Toll like receptor 2 (TLR2), indicating that surface molecules are important for the activation of inflammatory response. Furthermore, a cascade of genes related to the inflammasome pathway of macrophages was also up-regulated during infection with viable organisms when compared to non-infected cells. In conclusion, U. diversum has a typical ureaplasma genome and metabolism, and its surface molecules, including the identified capsular material, represent major components of the organism immunopathogenesis.

[Dynamics of quickly absorption of the carbon source in wastewater by activated sludge].

PubMed

Liu, Hong-Bo; Wen, Xiang-Hua; Zhao, Fang

2011-09-01

In this paper, absorption characteristics of organic matter in municipal wastewater by three kinds of activated sludge (carbon-enriching, nitrification and denitrification sludge) were studied, and the absorption kinetic data was checked using three kinds of absorption kinetic equations based on Ritchie rate equation. The objectives of this study were to investigate the absorption mechanism of activated sludge to organic matter in municipal wastewater, and to identify the possibility of reclaiming organic matter by activated sludge. Results indicated that in the early 30 min, absorption process of organic matter by activated sludge was found to be mainly physical adsorption, which could be expressed by the Lagergren single-layer adsorption model. The carbon-enriching sludge had the highest adsorption capacity (COD/SS) which was 60 mg/g but the adsorption rate was lower than that of denitrification sludge. While nitrification sludge had the lowest adsorption rate and higher adsorption capacity compared with denitrification sludge, which was about 35 mg/g. The rates of the fitting index theta(0) of carbon-enriching, nitrification and denitrification sludge were 0.284, 0.777 and 0.923, respectively, which indicated that the sorbed organic matter on the surface of carbon-enriching sludge was the easiest fraction to be washed away. That is, the combination intensity of carbon-enriching sludge and organic matter was the feeblest, which was convenient for carbon-enriching sludge to release sorbed carbon. Furthermore, by fitting with Langmuir model, concentration of organic matter was found to be the key parameter influencing the adsorption capacity of activated sludge, while the influence of temperature was not obvious. The kinetic law of organic matter absorption by activated sludge was developed, which introduces a way to kinetically analyze the removing mechanism of pollutant by activated sludge and provides theoretical base for the reclaiming of nutriments in wastewater by the absorption of activated sludge.

Synthesis and characterization of a novel organic corrosion inhibitor for mild steel in 1 M hydrochloric acid

NASA Astrophysics Data System (ADS)

Ahmed, Mohammed H. Othman; Al-Amiery, Ahmed A.; Al-Majedy, Yasmin K.; Kadhum, Abdul Amir H.; Mohamad, Abu Bakar; Gaaz, Tayser Sumer

2018-03-01

The synthesis and characterization of a novel organic corrosion inhibitor (4-(3-mercapto-5,6,7,8-tetrahydro-[1,2,4]triazolo[4,3-b][1,2,4,5]tetrazin-6-yl)phenol), for mild steel in 1 M hydrochloric acid (HCl) has been successfully reported for the first time. The inhibitor evaluated as corrosion inhibitor for mild steel in 1 M of Hydrochloric acid solution using electrochemical impedance spectroscopy (EIS), and electrochemical frequency modulation (EFM) measurement techniques. Changes in the impedance parameters suggested an adsorption of the inhibitor onto the mild steel surface, leading to the formation of protective films. The results show that the inhibition efficiencies increased with increasing the concentrations of the inhibitors and decreased with increasing temperature. The maximum inhibition efficiency up to 67% at the maximum concentration 0.5 mM. This shows that those inhibitors are effective in helping to reduce and slowing down the corrosion process that occurs to mild steel with a hydrochloric acid solution by providing an organic inhibitor for the mild steel that can be weakened by increasing the temperature. The adsorption process of the synthesized organic inhibitor depends on its electronic characteristics in addition to steric effects and the nature of metal surface, temperature degree and the varying degrees of surface-site activity. The synthesized inhibitor molecules were absorbed by metal surface and follow Langmuir isotherms.

Surface-enhanced Raman spectroscopy on litographically constructed microelectrodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhelyaskov, V.R.; Milne, E.T.; Weldon, M.K.

1995-12-31

A novel silicon substrate microelectrode array has been demonstrated to function as a surface-enhanced Raman Spectroscopy (SERS) microelectrode. SERS from adenosine and pyridine down to 10 mM concentration on silver coated iridium and gold microelectrode arrays have been observed with excitation at 532 nm and 633 nm correspondingly. Ag/AgCl reference electrode and platinum or integrated on the microelectrode iridium counter electrodes were used. Owing to the small area of the activated sites on the microelectrode (10 mm x 15 mm) the SERS signal exhibited a strong laser power dependence. The optimal laser power on the activated site was shown tomore » be in the order of x 100 mW. Good quality SERS spectra were recorded with exposure times of 10s and less. The small size of the electrodes makes them promising for studies in confined spaces. This includes potential applications as capillary electrophoreses detectors and probes of chemistry of biological organisms. A work on detection of lipids adhered to self-organized monolayers (SAM)s of alkanethiols on the activated microelectrodes is in progress.« less

Metal-Organic Frameworks as Highly Active Electrocatalysts for High-Energy Density, Aqueous Zinc-Polyiodide Redox Flow Batteries.

PubMed

Li, Bin; Liu, Jian; Nie, Zimin; Wang, Wei; Reed, David; Liu, Jun; McGrail, Pete; Sprenkle, Vincent

2016-07-13

The new aqueous zinc-polyiodide redox flow battery (RFB) system with highly soluble active materials as well as ambipolar and bifunctional designs demonstrated significantly enhanced energy density, which shows great potential to reduce RFB cost. However, the poor kinetic reversibility and electrochemical activity of the redox reaction of I3(-)/I(-) couples on graphite felts (GFs) electrode can result in low energy efficiency. Two nanoporous metal-organic frameworks (MOFs), MIL-125-NH2 and UiO-66-CH3, that have high surface areas when introduced to GF surfaces accelerated the I3(-)/I(-) redox reaction. The flow cell with MOF-modified GFs serving as a positive electrode showed higher energy efficiency than the pristine GFs; increases of about 6.4% and 2.7% occurred at the current density of 30 mA/cm(2) for MIL-125-NH2 and UiO-66-CH3, respectively. Moreover, UiO-66-CH3 is more promising due to its excellent chemical stability in the weakly acidic electrolyte. This letter highlights a way for MOFs to be used in the field of RFBs.

Oxidant activity in hyperarid soils from Atacama Desert in southern Peru, under conditions of the labeled release and thermal evolved gas analysis experiments: Implications for the search of organic matter on Mars

NASA Astrophysics Data System (ADS)

Valdivia-Silva, Julio E.; Navarro-Gonzalez, Rafael; McKay, Chris

Thermal evolved gas analysis (TEGA), one of several instruments on board of the Phoenix Lander, is a combination of a high temperature furnace and a mass spectrometer that was used to analyze Mars soil samples heated at a programmed ramp rate up to 1000 ° C. The evolved gases generated during the process were analyzed with the evolved gas analyzer (a mass spectrometer) in order to determine the composition of gases released as a function of temperature. In other hand, labeled release experiment (LR), one of the Viking biology anal-ysis used on Mars, monitored the radioactive gas evolution after the addition of a 14C-labeled aqueous organic substrate into a sealed test cell that contained a Martian surface sample. This experiment was designed to test Martian surface samples for the presence of life by measuring metabolic activity and distinguishing it from physical or chemical activity. The interpretation of the Viking LR experiment was that the tested soils were chemically reactive and not biolog-ically active, and that at least two oxidative processes with different kinetics were required to explain the observed decomposition of organics, while TEGA experiment of the Phoenix mis-sion apparently didn't detect organic matter on the surface of Mars. Both of these experiments showed little possibility of the presence of organics, and therefore the presence of life. Here we examine the evolved gas properties of hyperarid soils from the Pampas de La Joya, which is considered as a new analogue to Mars, in order to investigate the effect of the soil matrix on the TEGA response, and additionally, we conducted experiments under Viking LR protocol to test the decomposition kinetics of organic compounds in aqueous solution added to these soils. Our TEGA results indicate that native or added organics present in these samples were oxidized to CO2 during thermal process, suggesting the existence in these soils of a thermolabile oxidant which is highly oxidative and other thermostable oxidant which has a minor oxidative activity and that survives the heat-treatment. Interestingly, LR experiment shows that the 13C-labeled formate and DL-alanine were oxidized to 13CO2 when added in aqueous solution to soils collected from the Pampas de La Joya region. The observation of similar 13CO2 initial releasing by soils treated with L-alanine, compared to soils treated D-alanine, indicates the presence of one or more nonbiological chemical decomposition mechanisms similar to Yungay soils and the Viking LR experiment. Thus, the soils from Pampas of La Joya, are potentially excellent analogues of the oxidative processes that occur on Mars, and can be used to study mechanisms of destruction of organics on this planet. The nature of oxidant(s) present in the soils from Pampas de La Joya is still unknown.

Biosurfactant Production by Bacillus salmalaya for Lubricating Oil Solubilization and Biodegradation.

PubMed

Dadrasnia, Arezoo; Ismail, Salmah

2015-08-19

This study investigated the capability of a biosurfactant produced by a novel strain of Bacillus salmalaya to enhance the biodegradation rates and bioavailability of organic contaminants. The biosurfactant produced by cultured strain 139SI showed high physicochemical properties and surface activity in the selected medium. The biosurfactant exhibited a high emulsification index and a positive result in the drop collapse test, with the results demonstrating the wetting activity of the biosurfactant and its potential to produce surface-active molecules. Strain 139SI can significantly reduce the surface tension (ST) from 70.5 to 27 mN/m, with a critical micelle concentration of 0.4%. Moreover, lubricating oil at 2% (v/v) was degraded on Day 20 (71.5). Furthermore, the biosurfactant demonstrated high stability at different ranges of salinity, pH, and temperature. Overall, the results indicated the potential use of B. salmalaya 139SI in environmental remediation processes.

Promoted Iron Nanocrystals Obtained via Ligand Exchange as Active and Selective Catalysts for Synthesis Gas Conversion

PubMed Central

2017-01-01

Colloidal synthesis routes have been recently used to fabricate heterogeneous catalysts with more controllable and homogeneous properties. Herein a method was developed to modify the surface composition of colloidal nanocrystal catalysts and to purposely introduce specific atoms via ligands and change the catalyst reactivity. Organic ligands adsorbed on the surface of iron oxide catalysts were exchanged with inorganic species such as Na2S, not only to provide an active surface but also to introduce controlled amounts of Na and S acting as promoters for the catalytic process. The catalyst composition was optimized for the Fischer–Tropsch direct conversion of synthesis gas into lower olefins. At industrially relevant conditions, these nanocrystal-based catalysts with controlled composition were more active, selective, and stable than catalysts with similar composition but synthesized using conventional methods, possibly due to their homogeneity of properties and synergic interaction of iron and promoters. PMID:28824820

Endothelial cell regulation of leukocyte infiltration in inflammatory tissues

PubMed Central

Mantovani, A.; Introna, M.; Dejana, E.

1995-01-01

Endothelial cells play an important, active role in the onset and regulation of inflammatory and immune reactions. Through the production of chemokines they attract leukocytes and activate their adhesive receptors. This leads to the anchorage of leukocytes to the adhesive molecules expressed on the endothelial surface. Leukocyte adhesion to endothelial cells is frequently followed by their extravasation. The mechanisms which regulate the passage of leukocytes through endothelial clefts remain to be clarified. Many indirect data suggest that leukocytes might transfer signals to endothelial cells both through the release of active agents and adhesion to the endothelial cell surface. Adhesive molecules (such as PECAM) on the endothelial cell surface might also ‘direct’ leukocytes through the intercellular junction by haptotaxis. The information available on the molecular structure and functional properties of endothelial chemokines, adhesive molecules or junction organization is still fragmentary. Further work is needed to clarify how they interplay in regulating leukocyte infiltration into tissues. PMID:18475659

Preface: special topic on supramolecular self-assembly at surfaces.

PubMed

Bartels, Ludwig; Ernst, Karl-Heinz; Gao, Hong-Jun; Thiel, Patricia A

2015-03-14

Supramolecular self-assembly at surfaces is one of the most exciting and active fields in Surface Science today. Applications can take advantage of two key properties: (i) versatile pattern formation over a broad length scale and (ii) tunability of electronic structure and transport properties, as well as frontier orbital alignment. It provides a new frontier for Chemical Physics as it uniquely combines the versatility of Organic Synthesis and the Physics of Interfaces. The Journal of Chemical Physics is pleased to publish this Special Topic Issue, showcasing recent advances and new directions.

Improvement of the Earth's gravity field from terrestrial and satellite data

NASA Technical Reports Server (NTRS)

Rapp, Richard H.

1992-01-01

The determination of the Earth's gravitational potential can be done through the analysis of satellite perturbations, the analysis of surface gravity data, or both. The combination of the two data types yields a solution that combines the strength of each method: the longer wavelength strength in the satellite analysis with the better high frequency information from surface gravity data. Since 1972, Ohio State has carried out activities that have provided surface gravity data to a number of organizations who have developed combination potential coefficient models that describe the Earth's gravitational potential.

Characterization of Missouri surface waters near point sources of pollution reveals potential novel atmospheric route of exposure for bisphenol A and wastewater hormonal activity pattern.

PubMed

Kassotis, Christopher D; Alvarez, David A; Taylor, Julia A; vom Saal, Frederick S; Nagel, Susan C; Tillitt, Donald E

2015-08-15

Surface water contamination by chemical pollutants increasingly threatens water quality around the world. Among the many contaminants found in surface water, there is growing concern regarding endocrine disrupting chemicals, based on their ability to interfere with some aspect of hormone action in exposed organisms, including humans. This study assessed water quality at several sites across Missouri (near wastewater treatment plants and airborne release sites of bisphenol A) based on hormone receptor activation potencies and chemical concentrations present in the surface water. We hypothesized that bisphenol A and ethinylestradiol would be greater in water near permitted airborne release sites and wastewater treatment plant inputs, respectively, and that these two compounds would be responsible for the majority of activities in receptor-based assays conducted with water collected near these sites. Concentrations of bisphenol A and ethinylestradiol were compared to observed receptor activities using authentic standards to assess contribution to total activities, and quantitation of a comprehensive set of wastewater compounds was performed to better characterize each site. Bisphenol A concentrations were found to be elevated in surface water near permitted airborne release sites, raising questions that airborne releases of BPA may influence nearby surface water contamination and may represent a previously underestimated source to the environment and potential for human exposure. Estrogen and androgen receptor activities of surface water samples were predictive of wastewater input, although the lower sensitivity of the ethinylestradiol ELISA relative to the very high sensitivity of the bioassay approaches did not allow a direct comparison. Wastewater-influenced sites also had elevated anti-estrogenic and anti-androgenic equivalence, while sites without wastewater discharges exhibited no antagonist activities. Published by Elsevier B.V.

Characterization of Missouri surface waters near point sources of pollution reveals potential novel atmospheric route of exposure for bisphenol A and wastewater hormonal activity pattern

USGS Publications Warehouse

Kassotis, Christopher D.; Alvarez, David A.; Taylor, Julia A.; vom Saal, Frederick S.; Nagel, Susan C.; Tillitt, Donald E.

2015-01-01

Surface water contamination by chemical pollutants increasingly threatens water quality around the world. Among the many contaminants found in surface water, there is growing concern regarding endocrine disrupting chemicals, based on their ability to interfere with some aspect of hormone action in exposed organisms, including humans. This study assessed water quality at several sites across Missouri (near wastewater treatment plants and airborne release sites of bisphenol A) based on hormone receptor activation potencies and chemical concentrationspresent in the surface water. We hypothesized that bisphenol A and ethinylestradiol would be greater in water near permitted airborne release sites and wastewater treatment plant inputs, respectively, and that these two compounds would be responsible for the majority of activities in receptor-based assays conducted with water collected near these sites. Concentrations of bisphenol A and ethinylestradiol were compared to observed receptor activities using authentic standards to assess contribution to total activities, and quantitation of a comprehensive set of wastewater compounds was performed to better characterize each site. Bisphenol A concentrations were found to be elevated in surface water near permitted airborne release sites, raising questions that airborne releases of BPA may influence nearby surface water contamination and may represent a previously underestimated source to the environment and potential for human exposure. Estrogen and androgen receptor activities of surface water samples were predictive of wastewater input, although the lower sensitivity of the ethinylestradiol ELISA relative to the very high sensitivity of the bioassay approaches did not allow a direct comparison. Wastewater-influenced sites also had elevated anti-estrogenic and anti-androgenic equivalence, while sites without wastewater discharges exhibited no antagonist activities.

Achieving Weak Light Response with Plasmonic Nanogold-Decorated Organic Phototransistors.

PubMed

Luo, Xiao; Du, Lili; Liang, Yuanlong; Zhao, Feiyu; Lv, Wenli; Xu, Kun; Wang, Ying; Peng, Yingquan

2018-05-09

Weak light response of organic photodetectors has fascinating potentials in fields of modern science and technology. However, their photoresponsivity is hindered by poor photocarrier excitation and transport. Decorating active-layer surface with plasmonic nanometals is considered a viable strategy to address this issue. Here, we demonstrate a plasmonic nanogold decorated organic phototransistor achieving remarkable enhancement of photoresponsivity. Meanwhile, the photoresponsive range is broadened by 4 orders of magnitude. The proposed design is substantiated by a schematic energy level model combined with theoretical simulation analysis, enabling the development of the advanced optoelectronics.

Chemical activation of bituminous coal for hampering oligomerization of organic contaminants.

PubMed

Yan, Liang; Sorial, George A

2011-12-15

Activated carbons prepared by KOH activation of bituminous coal were studied for hampering oligomerization of phenolic compounds on its surface. A total of 24 activated carbons with different microporosity and BET surface area were created. The effect of the different variables of the activation process (KOH/bituminous coal ratio, heating temperature, activation time, and flow rate of nitrogen gas) on critical carbon parameters was analyzed. The impact of activated carbon on oligomerization was examined by conducting isotherm experiments at a neutral pH on Carbon(exp) produced with optimal characteristics and granular activated carbon (GAC) F400 for phenol, 2-methylphenol and 2-ethylphenol. These isotherms were collected under anoxic (absence of molecular oxygen) and oxic (presence of molecular oxygen) conditions. The single solute adsorption of phenol, 2-methylphenol and 2-ethylphenol on Carbon(exp) showed no obvious differences between oxic and anoxic environment, which indicated that the Carbon(exp) sample is very effective in hampering the oligomerization of phenolic compounds under oxic conditions. On the other hand, F400, which have lower micropore percentage and BET surface area, significant increases in the adsorptive capacity had been observed when molecular oxygen was present. Copyright © 2011 Elsevier B.V. All rights reserved.

Polarity control at interfaces: Quantifying pseudo-solvent effects in nano-confined systems

DOE PAGES

Singappuli-Arachchige, Dilini; Manzano, J. Sebastian; Sherman, Lindy M.; ...

2016-08-02

Surface functionalization controls local environments and induces solvent-like effects at liquid–solid interfaces. We explored structure–property relationships between organic groups bound to pore surfaces of mesoporous silica nanoparticles and Stokes shifts of the adsorbed solvatochromic dye Prodan. Correlating shifts of the dye on the surfaces with its shifts in solvents resulted in a local polarity scale for functionalized pores. The scale was validated by studying the effects of pore polarity on quenching of Nile Red fluorescence and on the vibronic band structure of pyrene. Measurements were done in aqueous suspensions of porous particles, proving that the dielectric properties in the poresmore » are different from the bulk solvent. The precise control of pore polarity was used to enhance the catalytic activity of TEMPO in the aerobic oxidation of furfuryl alcohol in water. Furthermore, an inverse relationship was found between pore polarity and activity of TEMPO in the pores, demonstrating that controlling the local polarity around an active site allows modulating the activity of nanoconfined catalysts.« less

Soil Minerals Affect Extracellular Enzyme Activities in Cold and Warm Environments

NASA Astrophysics Data System (ADS)

Yang, Z.; Morin, M. M.; Graham, D. E.; Wullschleger, S. D.; Gu, B.

2017-12-01

Extracellular enzymes are mainly responsible for degrading and cycling soil organic matter (SOM) in both cold and warm terrestrial ecosystems. Minerals can play important roles in affecting soil enzyme activities, however, the interactions between enzyme and soil minerals remain poorly understood. In this study, we developed a model soil-enzyme system to examine the mineral effects on a hydrolytic enzyme (i.e., β-glucosidase) under both cold (4°C) and relatively warm (20 and 30°C) conditions. Minerals including iron oxides and clays (e.g., kaolinite and montmorillonite) were used to mimic different types of soils, and enzyme adsorption experiments were conducted to determine the enzyme interactions with different mineral surfaces. Time-series experiments were also carried out to measure enzymatic degradation of the organic substrates, such as cellobiose and indican. We observed that fractions of adsorbed enzyme and the hydrolytic activity were higher on iron oxides (e.g., hematite) compared to kaolinite and montmorillonite at given experimental conditions. The degradation of cellobiose was significantly faster than that of indican in the presence of minerals. We also found that the adsorption of enzyme was not dependent on the mineral surface areas, but was controlled by the mineral surface charge. In addition, temperature increase from 4 to 30°C enhanced mineral-assisted glucosidase hydrolysis by 2 to 4 fold, suggesting greater degradation under warmer environments. The present work demonstrates that the enzyme activity is influenced not only by the soil temperature but also by the surface chemistry of soil minerals. Our results highlight the need to consider the physical and chemical properties of minerals in biogeochemical models, which could provide a better prediction for enzyme-facilitated SOM transformations in terrestrial ecosystems.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maughan, Bret; Zahl, Percy; Sutter, Peter

Switching the magnetic properties of organic semiconductors on a metal surface has thus far largely been limited to molecule-by-molecule tip-induced transformations in scanned probe experiments. Here we demonstrate with molecular resolution that collective control of activated Kondo screening can be achieved in thin-films of the organic semiconductor titanyl phthalocyanine on Cu(110) to obtain tunable concentrations of Kondo impurities. Using low-temperature scanning tunneling microscopy and spectroscopy, we show that a thermally activated molecular distortion dramatically shifts surface–molecule coupling and enables ensemble-level control of Kondo screening in the interfacial spin system. This is accompanied by the formation of a temperature-dependent Abrikosov–Suhl–Kondo resonancemore » in the local density of states of the activated molecules. This enables coverage-dependent control over activation to the Kondo screening state. Finally, our study thus advances the versatility of molecular switching for Kondo physics and opens new avenues for scalable bottom-up tailoring of the electronic structure and magnetic texture of organic semiconductor interfaces at the nanoscale.« less

Ensemble control of Kondo screening in molecular adsorbates

DOE PAGES

Maughan, Bret; Zahl, Percy; Sutter, Peter; ...

2017-04-06

Switching the magnetic properties of organic semiconductors on a metal surface has thus far largely been limited to molecule-by-molecule tip-induced transformations in scanned probe experiments. Here we demonstrate with molecular resolution that collective control of activated Kondo screening can be achieved in thin-films of the organic semiconductor titanyl phthalocyanine on Cu(110) to obtain tunable concentrations of Kondo impurities. Using low-temperature scanning tunneling microscopy and spectroscopy, we show that a thermally activated molecular distortion dramatically shifts surface–molecule coupling and enables ensemble-level control of Kondo screening in the interfacial spin system. This is accompanied by the formation of a temperature-dependent Abrikosov–Suhl–Kondo resonancemore » in the local density of states of the activated molecules. This enables coverage-dependent control over activation to the Kondo screening state. Finally, our study thus advances the versatility of molecular switching for Kondo physics and opens new avenues for scalable bottom-up tailoring of the electronic structure and magnetic texture of organic semiconductor interfaces at the nanoscale.« less

Photodegradation of organic contamination in wastewaters by bonding TiO2/single-walled carbon nanotube composites with enhanced photocatalytic activity.

PubMed

Zhou, Wei; Pan, Kai; Qu, Yang; Sun, Fanfei; Tian, Chungui; Ren, Zhiyu; Tian, Guohui; Fu, Honggang

2010-10-01

Bonding TiO(2)/single-walled carbon nanotube (SWCNT) composites have been successfully synthesized through a facile sol-solvothermal technique. The obtained materials were characterized in detail by XRD, FT-IR, Raman and TEM. The results revealed that TiO(2) and SWNCT linked compactly through ester bonds and thus improved their interfaces. Therefore, the recombination of photogenerated electron-hole pairs was inhibited efficiently, which improved the photocatalytic activity. A reasonable mechanism was proposed to explain its formation. The photocatalytic activity was investigated utilizing rhodamine B and nitrobenzene (NB) as models for organic contamination in wastewaters. Experimental results indicated that this bonding composite exhibited higher photocatalytic activity than that of Degussa P25. The excellent photocatalytic activity could be attributed to larger surface area, smaller crystalline size, and especially the ester bonds, which was further confirmed by surface photovoltage spectroscopy. Furthermore, by adding ()OH scavenger tert-butanol, the obvious decrease of NB photodegradation indicated that NB was oxidized primarily by ()OH. The photodegradation products were identified by GC/MS, further indicating that the degradation proceeded via ()OH oxidation. A possible reaction pathway for the degradation of NB was suggested by the evidence presented in this study. Copyright © 2010. Published by Elsevier Ltd.

Surface biology of collagen scaffold explains blocking of wound contraction and regeneration of skin and peripheral nerves

PubMed Central

Yannas, IV; Tzeranis, D; So, PT

2018-01-01

We review the details of preparation and of the recently elucidated mechanism of biological (regenerative) activity of a collagen scaffold (dermis regeneration template, DRT) that has induced regeneration of skin and peripheral nerves (PN) in a variety of animal models and in the clinic. DRT is a 3D protein network with optimized pore size in the range 20–125 μm, degradation half-life 14 ± 7 d and ligand densities that exceed 200 μ α1β1 or α2β1 ligands. The pore has been optimized to allow migration of contractile cells (myofibroblasts, MFB) into the scaffold and to provide sufficient specific surface for cell–scaffold interaction; the degradation half-life provides the required time window for satisfactory binding interaction of MFB with the scaffold surface; and the ligand density supplies the appropriate ligands for specific binding of MFB on the scaffold surface. A dramatic change in MFB phenotype takes place following MFB-scaffold binding which has been shown to result in blocking of wound contraction. In both skin wounds and PN wounds the evidence has shown clearly that contraction blocking by DRT is followed by induction of regeneration of nearly perfect organs. The biologically active structure of DRT is required for contraction blocking; well-matched collagen scaffold controls of DRT, with structures that varied from that of DRT, have failed to induce regeneration. Careful processing of collagen scaffolds is required for adequate biological activity of the scaffold surface. The newly understood mechanism provides a relatively complete paradigm of regenerative medicine that can be used to prepare scaffolds that may induce regeneration of other organs in future studies. PMID:26694657

Broad spectrum antimicrobial activity of melimine covalently bound to contact lenses.

PubMed

Dutta, Debarun; Cole, Nerida; Kumar, Naresh; Willcox, Mark D P

2013-01-07

To develop a stable antimicrobial contact lens, which is effective against the International Organization for Standardization (ISO) panel microorganisms, Acanthamoeba castellanii and drug resistant strains of Pseudomonas aeruginosa and Staphylococcus aureus. Melimine was covalently incorporated into etafilcon A lenses. The amount of peptide present on the lens surface was quantified using amino acid analysis. After coating, the heat stability (121°C), lens surface hydrophobicity (by captive bubble), and in vitro cytotoxicity to mouse L929 cells of the lenses were investigated. Antimicrobial activity against the micro-organisms was evaluated by viable plate count and fluorescence microscopy, measuring the proportion of cell death compared with control lenses with no melimine. The most effective concentration was determined to be 152 ± 44 μg lens(-1) melimine on the lens surface. After coating, lenses were relatively hydrophilic and were nontoxic to mammalian cells. The activity remained high after autoclaving (e.g., 3.1, 3.9, 1.2, and 1.0 log inhibition against P. aeruginosa, S. aureus, A. castellanii, and Fusarium solani, respectively). Fluorescence microscopy confirmed significantly reduced (P < 0.001) adhesion of viable bacteria to melimine contact lenses. Viable count confirmed that lenses were active against all the bacteria and fungi from the ISO panel, Acanthamoeba and gave at least 2 log inhibition against all the multidrug resistant S. aureus and P. aeruginosa strains. Melimine may offer excellent potential for development as a broad spectrum antimicrobial coating for contact lenses, showing activity against all the bacterial and fungal ISO panel microorganisms, Acanthamoeba, and antibiotic resistant strains of P. aeruginosa and S. aureus.

New insights into modeling an organic mass fraction of sea spray aerosol

NASA Astrophysics Data System (ADS)

Meskhidze, N.; Gantt, B.

2010-12-01

As the study of climate change progresses, a need to separate the effects of natural and anthropogenic processes becomes essential in order to correctly forecast the future climate. Due to their massive source regions underlying an atmosphere with low aerosol concentration, marine aerosols derived from sea spray and ocean emitted biogenic volatile organic compounds (BVOCs) are extremely important for the Earth’s radiative budget, regional air quality and biogeochemical cycling of elements. Measurements of freshly-emitted sea spray have revealed that bubble bursting processes, largely responsible for the production of sea salt aerosol, also control sea-to-air transfer of marine organic matter. It has been established that the organic mass fraction of sea spray can be a function of sea-water composition (e.g., concentrations of Chlorophyll-a, [Chl-a], dissolved organic carbon, [DOC], particulate organic carbon, [POC], types of organic carbon, and the amount of surfactants). Current paramaterizations of marine primary organic aerosol emissions use remotely sensed [Chl-a] data as a proxy for oceanic biological activity. However, it has also been shown that the path length, size, and lifetime of bubbles in seawater as well as spatial coverage of seawater surface by streaks or slicks (visible film of a roughly 50 μm thick layer, highly enriched in organics) can have dramatic effect on organic mass fraction of sea spray (OCss). Dynamics of bubble entrainment and the level of microlayer enrichment by organics relative to the underlying bulk water can be controlled by surface wind speed. For bubble entrainment, high winds can increase rising bubble path length and therefore the amount of organics scavenged by the bubble. However, when the surface wind speeds exceed 8 m s-1 breaking of ocean waves can entirely destroy surface organic films and diminish the amount of organics leaving the sea. Despite the probable impact of wind speed, existing parameterizations do not consider the wind speed dependence of OCss. In this study we use remotely sensed data for ocean slick coverage and surface wind speed in conjunction with an upwind averaged concentrations of [Chl-a], [DOC] and [POC] to derive marine primary organic aerosol emission function. Derived empirical relationships between the aerosol and ocean/meteorological data are then compared to observed OCss at Mace Head and Point Reyes National Seashore. MATLAB curve fitting tool revealed that multi-variable regression analysis (with both wind speed and [Chl-a]) yields a significant improvement between model predicted and observed submicron fraction of OCss. The coefficient of determination increased from R2=0.1 for previous parameterizations to R2=0.6. Based on the results of this study we propose that in addition to sea-water composition, future parameterizations of marine primary organic aerosol emissions should include sea spray organic mass fraction dependence on surface wind speed.

Organic coating on biochar explains its nutrient retention and stimulation of soil fertility.

PubMed

Hagemann, Nikolas; Joseph, Stephen; Schmidt, Hans-Peter; Kammann, Claudia I; Harter, Johannes; Borch, Thomas; Young, Robert B; Varga, Krisztina; Taherymoosavi, Sarasadat; Elliott, K Wade; McKenna, Amy; Albu, Mihaela; Mayrhofer, Claudia; Obst, Martin; Conte, Pellegrino; Dieguez-Alonso, Alba; Orsetti, Silvia; Subdiaga, Edisson; Behrens, Sebastian; Kappler, Andreas

2017-10-20

Amending soil with biochar (pyrolized biomass) is suggested as a globally applicable approach to address climate change and soil degradation by carbon sequestration, reducing soil-borne greenhouse-gas emissions and increasing soil nutrient retention. Biochar was shown to promote plant growth, especially when combined with nutrient-rich organic matter, e.g., co-composted biochar. Plant growth promotion was explained by slow release of nutrients, although a mechanistic understanding of nutrient storage in biochar is missing. Here we identify a complex, nutrient-rich organic coating on co-composted biochar that covers the outer and inner (pore) surfaces of biochar particles using high-resolution spectro(micro)scopy and mass spectrometry. Fast field cycling nuclear magnetic resonance, electrochemical analysis and gas adsorption demonstrated that this coating adds hydrophilicity, redox-active moieties, and additional mesoporosity, which strengthens biochar-water interactions and thus enhances nutrient retention. This implies that the functioning of biochar in soil is determined by the formation of an organic coating, rather than biochar surface oxidation, as previously suggested.

Large-Scale Distribution and Activity of Prokaryotes in Deep-Sea Surface Sediments of the Mediterranean Sea and the Adjacent Atlantic Ocean

PubMed Central

Giovannelli, Donato; Molari, Massimiliano; d’Errico, Giuseppe; Baldrighi, Elisa; Pala, Claudia; Manini, Elena

2013-01-01

The deep-sea represents a substantial portion of the biosphere and has a major influence on carbon cycling and global biogeochemistry. Benthic deep-sea prokaryotes have crucial roles in this ecosystem, with their recycling of organic matter from the photic zone. Despite this, little is known about the large-scale distribution of prokaryotes in the surface deep-sea sediments. To assess the influence of environmental and trophic variables on the large-scale distribution of prokaryotes, we investigated the prokaryotic assemblage composition (Bacteria to Archaea and Euryarchaeota to Crenarchaeota ratio) and activity in the surface deep-sea sediments of the Mediterranean Sea and the adjacent North Atlantic Ocean. Prokaryotic abundance and biomass did not vary significantly across the Mediterranean Sea; however, there were depth-related trends in all areas. The abundance of prokaryotes was positively correlated with the sedimentary concentration of protein, an indicator of the quality and bioavailability of organic matter. Moving eastwards, the Bacteria contribution to the total prokaryotes decreased, which appears to be linked to the more oligotrophic conditions of the Eastern Mediterranean basins. Despite the increased importance of Archaea, the contributions of Crenarchaeota Marine Group I to the total pool was relatively constant across the investigated stations, with the exception of Matapan-Vavilov Deep, in which Euryarchaeota Marine Group II dominated. Overall, our data suggest that deeper areas of the Mediterranean Sea share more similar communities with each other than with shallower sites. Freshness and quality of sedimentary organic matter were identified through Generalized Additive Model analysis as the major factors for describing the variation in the prokaryotic community structure and activity in the surface deep-sea sediments. Longitude was also important in explaining the observed variability, which suggests that the overlying water masses might have a critical role in shaping the benthic communities. PMID:24039667

Enhanced photocatalytic properties of the 3D flower-like Mg-Al layered double hydroxides decorated with Ag{sub 2}CO{sub 3} under visible light illumination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ao, Yanhui, E-mail: andyao@hhu.edu.cn; Wang, Dandan; Wang, Peifang

Highlights: • 3D flower-like Ag{sub 2}CO{sub 3}/Mg-Al layered double hydroxide composite was prepared. • The nanocomposites exhibited high photocatalytic activities on different organic pollutants. • The mechanism of the enhanced activity were investigated. - Abstract: A facile anion-exchange precipitation method was employed to synthesize 3D flower-like Ag{sub 2}CO{sub 3}/Mg-Al layered double hydroxide composite photocatalyst. Results showed that Ag{sub 2}CO{sub 3} nanoparticles dispersed uniformly on the petals of the flower-like Mg-Al LDH. The obtained nanocomposites exhibited high photocatalytic activities on different organic pollutants (cationic and anionic dyes, phenol) under visible light illumination. The high photocatalytic activity can be ascribed to themore » special structure which accomplishes the wide-distribution of Ag{sub 2}CO{sub 3} nanoparticles on the surfaces of the 3D flower-like nanocomposites. Therefore, it can provide much more active sites for the degradation of organic pollutant. Then the photocatalytic mechanism was also verified by reactive species trapping experiments in detail. The work would pave a facile way to prepare LDHs based hierarchical photocatalysts with high activity for the degradation of wide range organic pollutants under visible light irradiation.« less

Protection of Nonself Surfaces from Complement Attack by Factor H-Binding Peptides: Implications for Therapeutic Medicine

PubMed Central

Wu, You-Qiang; Qu, Hongchang; Sfyroera, Georgia; Tzekou, Apostolia; Kay, Brian K.; Nilsson, Bo; Ekdahl, Kristina Nilsson; Ricklin, Daniel; Lambris, John D.

2011-01-01

Exposure of nonself surfaces such as those of biomaterials or transplanted cells and organs to host blood frequently triggers innate immune responses, thereby affecting both their functionality and tolerability. Activation of the alternative pathway of complement plays a decisive role in this unfavorable reaction. Whereas previous studies demonstrated that immobilization of physiological regulators of complement activation (RCA) can attenuate this foreign body-induced activation, simple and efficient approaches for coating artificial surfaces with intact RCA are still missing. The conjugation of small molecular entities that capture RCA with high affinity is an intriguing alternative, as this creates a surface with autoregulatory activity upon exposure to blood. We therefore screened two variable cysteine-constrained phage-displayed peptide libraries for factor H-binding peptides. We discovered three peptide classes that differed with respect to their main target binding areas. Peptides binding to the broad middle region of factor H (domains 5–18) were of particular interest, as they do not interfere with either regulatory or binding activities. One peptide in this group (5C6) was further characterized and showed high factor H-capturing activity while retaining its functional integrity. Most importantly, when 5C6 was coated to a model polystyrene surface and exposed to human lepirudin-anticoagulated plasma, the bound peptide captured factor H and substantially inhibited complement activation by the alternative pathway. Our study therefore provides a promising and novel approach to produce therapeutic materials with enhanced biocompatibility. PMID:21339361

Low proliferation and high apoptosis of osteoblastic cells on hydrophobic surface are associated with defective Ras signaling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chang, Eun-Ju; Kim, Hong-Hee; Huh, Jung-Eun

2005-02-01

The hydrophobic (HPB) nature of most polymeric biomaterials has been a major obstacle in using those materials in vivo due to low compatibility with cells. However, there is little knowledge of the molecular detail to explain how surface hydrophobicity affects cell responses. In this study, we compared the proliferation and apoptosis of human osteoblastic MG63 cells adhered to hydrophilic (HPL) and hydrophobic surfaces. On the hydrophobic surface, less formation of focal contacts and actin stress fibers, a delay in cell cycle progression, and an increase in apoptosis were observed. By using fibroblast growth factor 1 (FGF1) as a model growthmore » factor, we also investigated intracellular signaling pathways on hydrophilic and hydrophobic surfaces. The activation of Ras, Akt, and ERK by FGF1 was impaired in MG63 cells on the hydrophobic surface. The overexpression of constitutively active form of Ras and Akt rescued those cells from apoptosis and recovered cell cycle progression. Furthermore, their overexpression also restored the actin cytoskeletal organization on the hydrophobic surface. Finally, the proliferative, antiapoptotic, and cytoskeletal effects of constitutively active Ras in MG63 cells on the hydrophobic surface were blocked by wortmannin and PD98059 that inhibit Akt and ERK activation, respectively. Therefore, our results suggest that the activation of Ras and its downstream molecules Akt and ERK to an appropriate level is one of crucial elements in the determination of osteoblast cell responses. The Ras pathway may represent a cell biological target that should be considered for successful surface modification of biomaterials to induce adequate cell responses in the bone tissue.« less

Prefunctionalized Porous Organic Polymers: Effective Supports of Surface Palladium Nanoparticles for the Enhancement of Catalytic Performances in Dehalogenation.

PubMed

Zhong, Hong; Liu, Caiping; Zhou, Hanghui; Wang, Yangxin; Wang, Ruihu

2016-08-22

Three porous organic polymers (POPs) containing H, COOMe, and COO(-) groups at 2,6-bis(1,2,3-triazol-4-yl)pyridyl (BTP) units (i.e., POP-1, POP-2, and POP-3, respectively) were prepared for the immobilization of metal nanoparticles (NPs). The ultrafine palladium NPs are uniformly encapsulated in the interior pores of POP-1, whereas uniform- and dual-distributed palladium NPs are located on the external surface of POP-2 and POP-3, respectively. The presence of carboxylate groups not only endows POP-3 an outstanding dispersibility in H2 O/EtOH, but also enables the palladium NPs at the surface to show the highest catalytic activity, stability, and recyclability in dehalogenation reactions of chlorobenzene at 25 °C. The palladium NPs on the external surface are effectively stabilized by the functionalized POPs containing BTP units and carboxylate groups, which provides a new insight for highly efficient catalytic systems based on surface metal NPs of porous materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Second Skin: Ecological Role of Epibiotic Biofilms on Marine Organisms

PubMed Central

Wahl, Martin; Goecke, Franz; Labes, Antje; Dobretsov, Sergey; Weinberger, Florian

2012-01-01

In the aquatic environment, biofilms on solid surfaces are omnipresent. The outer body surface of marine organisms often represents a highly active interface between host and biofilm. Since biofilms on living surfaces have the capacity to affect the fluxes of information, energy, and matter across the host’s body surface, they have an important ecological potential to modulate the abiotic and biotic interactions of the host. Here we review existing evidence how marine epibiotic biofilms affect their hosts’ ecology by altering the properties of and processes across its outer surfaces. Biofilms have a huge potential to reduce its host’s access to light, gases, and/or nutrients and modulate the host’s interaction with further foulers, consumers, or pathogens. These effects of epibiotic biofilms may intensely interact with environmental conditions. The quality of a biofilm’s impact on the host may vary from detrimental to beneficial according to the identity of the epibiotic partners, the type of interaction considered, and prevailing environmental conditions. The review concludes with some unresolved but important questions and future perspectives. PMID:22936927

Effect of bentonite modification on hardness and mechanical properties of natural rubber nanocomposites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Santiago, Denise Ester O.; Department of Chemical Engineering, University of the Philippines, Los Baños, College, Laguna 4031 Philippines; Pajarito, Bryan B.

The effect of sodium activation, ion-exchange with tertiary amine salt, surface treatment with non-ionic surfactant, and wet grinding of bentonite on hardness and mechanical properties of natural rubber nanocomposites (NRN) was studied using full factorial design of experiment. Results of X-ray diffraction (XRD) show increase in basal spacing d of bentonite due to modification, while attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) confirm the organic modification of bentonite. Analysis of variance (ANOVA) shows that the main effect of surface treatment increases the hardness and decreases the tensile modulus of the NRN. The surface treatment and wet grinding of bentonitemore » decrease the tensile stresses at 100, 200 and 300% strain of NRN. Sodium activation and ion-exchange negatively affect the compressive properties, while surface treatment significantly improves the compressive properties of NRN.« less

FOCUS AREA 4 BACKGROUND PAPER: AQUATIC ECOTOXICITY ASSESSMENT

EPA Science Inventory

In parallel with a growing literature on the presence of Active Pharmaceutical Ingredients (APIs) in effluents and surface waters, recent years have witnessed a steady increase in published studies on the ecotoxicity of APIs to aquatic organisms. Against this background, key issu...

Cellulose Microfibril Formation by Surface-Tethered Cellulose Synthase Enzymes.

PubMed

Basu, Snehasish; Omadjela, Okako; Gaddes, David; Tadigadapa, Srinivas; Zimmer, Jochen; Catchmark, Jeffrey M

2016-02-23

Cellulose microfibrils are pseudocrystalline arrays of cellulose chains that are synthesized by cellulose synthases. The enzymes are organized into large membrane-embedded complexes in which each enzyme likely synthesizes and secretes a β-(1→4) glucan. The relationship between the organization of the enzymes in these complexes and cellulose crystallization has not been explored. To better understand this relationship, we used atomic force microscopy to visualize cellulose microfibril formation from nickel-film-immobilized bacterial cellulose synthase enzymes (BcsA-Bs), which in standard solution only form amorphous cellulose from monomeric BcsA-B complexes. Fourier transform infrared spectroscopy and X-ray diffraction techniques show that surface-tethered BcsA-Bs synthesize highly crystalline cellulose II in the presence of UDP-Glc, the allosteric activator cyclic-di-GMP, as well as magnesium. The cellulose II cross section/diameter and the crystal size and crystallinity depend on the surface density of tethered enzymes as well as the overall concentration of substrates. Our results provide the correlation between cellulose microfibril formation and the spatial organization of cellulose synthases.

Defluoridation of water using activated alumina in presence of natural organic matter via response surface methodology.

PubMed

Samarghandi, Mohammad Reza; Khiadani, Mehdi; Foroughi, Maryam; Zolghadr Nasab, Hasan

2016-01-01

Adsorption by activated alumina is considered to be one of the most practiced methods for defluoridation of freshwater. This study was conducted, therefore, to investigate the effect of natural organic matters (NOMs) on the removal of fluoride by activated alumina using response surface methodology. To the authors' knowledge, this has not been previously investigated. Physico-chemical characterization of the alumina was determined by scanning electron microscope (SEM), Brunauer-Emmett-Teller (BET), Fourier transform infrared spectroscopy (FTIR), X-ray fluorescence (XRF), and X-ray diffractometer (XRD). Response surface methodology (RSM) was applied to evaluate the effect of single and combined parameters on the independent variables such as the initial concentration of fluoride, NOMs, and pH on the process. The results revealed that while presence of NOM and increase of pH enhance fluoride adsorption on the activated alumina, initial concentration of fluoride has an adverse effect on the efficiency. The experimental data were analyzed and found to be accurately and reliably fitted to a second-order polynomial model. Under optimum removal condition (fluoride concentration 20 mg/L, NOM concentration 20 mg/L, and pH 7) with a desirability value of 0.93 and fluoride removal efficiency of 80.6%, no significant difference was noticed with the previously reported sequence of the co-exiting ion affinity to activated alumina for fluoride removal. Moreover, aluminum residual was found to be below the recommended value by the guideline for drinking water. Also, the increase of fluoride adsorption on the activated alumina, as NOM concentrations increase, could be due to the complexation between fluoride and adsorbed NOM. Graphical abstract ᅟ.

Do Contaminants Originating from State-of-the-Art Treated Wastewater Impact the Ecological Quality of Surface Waters?

PubMed Central

Stalter, Daniel; Magdeburg, Axel; Quednow, Kristin; Botzat, Alexandra; Oehlmann, Jörg

2013-01-01

Since the 1980s, advances in wastewater treatment technology have led to considerably improved surface water quality in the urban areas of many high income countries. However, trace concentrations of organic wastewater-associated contaminants may still pose a key environmental hazard impairing the ecological quality of surface waters. To identify key impact factors, we analyzed the effects of a wide range of anthropogenic and environmental variables on the aquatic macroinvertebrate community. We assessed ecological water quality at 26 sampling sites in four urban German lowland river systems with a 0–100% load of state-of-the-art biological activated sludge treated wastewater. The chemical analysis suite comprised 12 organic contaminants (five phosphor organic flame retardants, two musk fragrances, bisphenol A, nonylphenol, octylphenol, diethyltoluamide, terbutryn), 16 polycyclic aromatic hydrocarbons, and 12 heavy metals. Non-metric multidimensional scaling identified organic contaminants that are mainly wastewater-associated (i.e., phosphor organic flame retardants, musk fragrances, and diethyltoluamide) as a major impact variable on macroinvertebrate species composition. The structural degradation of streams was also identified as a significant factor. Multiple linear regression models revealed a significant impact of organic contaminants on invertebrate populations, in particular on Ephemeroptera, Plecoptera, and Trichoptera species. Spearman rank correlation analyses confirmed wastewater-associated organic contaminants as the most significant variable negatively impacting the biodiversity of sensitive macroinvertebrate species. In addition to increased aquatic pollution with organic contaminants, a greater wastewater fraction was accompanied by a slight decrease in oxygen concentration and an increase in salinity. This study highlights the importance of reducing the wastewater-associated impact on surface waters. For aquatic ecosystems in urban areas this would lead to: (i) improvement of the ecological integrity, (ii) reduction of biodiversity loss, and (iii) faster achievement of objectives of legislative requirements, e.g., the European Water Framework Directive. PMID:23593263

Do contaminants originating from state-of-the-art treated wastewater impact the ecological quality of surface waters?

PubMed

Stalter, Daniel; Magdeburg, Axel; Quednow, Kristin; Botzat, Alexandra; Oehlmann, Jörg

2013-01-01

Since the 1980s, advances in wastewater treatment technology have led to considerably improved surface water quality in the urban areas of many high income countries. However, trace concentrations of organic wastewater-associated contaminants may still pose a key environmental hazard impairing the ecological quality of surface waters. To identify key impact factors, we analyzed the effects of a wide range of anthropogenic and environmental variables on the aquatic macroinvertebrate community. We assessed ecological water quality at 26 sampling sites in four urban German lowland river systems with a 0-100% load of state-of-the-art biological activated sludge treated wastewater. The chemical analysis suite comprised 12 organic contaminants (five phosphor organic flame retardants, two musk fragrances, bisphenol A, nonylphenol, octylphenol, diethyltoluamide, terbutryn), 16 polycyclic aromatic hydrocarbons, and 12 heavy metals. Non-metric multidimensional scaling identified organic contaminants that are mainly wastewater-associated (i.e., phosphor organic flame retardants, musk fragrances, and diethyltoluamide) as a major impact variable on macroinvertebrate species composition. The structural degradation of streams was also identified as a significant factor. Multiple linear regression models revealed a significant impact of organic contaminants on invertebrate populations, in particular on Ephemeroptera, Plecoptera, and Trichoptera species. Spearman rank correlation analyses confirmed wastewater-associated organic contaminants as the most significant variable negatively impacting the biodiversity of sensitive macroinvertebrate species. In addition to increased aquatic pollution with organic contaminants, a greater wastewater fraction was accompanied by a slight decrease in oxygen concentration and an increase in salinity. This study highlights the importance of reducing the wastewater-associated impact on surface waters. For aquatic ecosystems in urban areas this would lead to: (i) improvement of the ecological integrity, (ii) reduction of biodiversity loss, and (iii) faster achievement of objectives of legislative requirements, e.g., the European Water Framework Directive.

Habitability from the Surface to the Deep

NASA Astrophysics Data System (ADS)

Cox, A. D.; Schmidt, R.; Dahlquist, G. R.; Foster, J.; Dillard, M.

2016-12-01

Merging aqueous geochemical parameters of habitability with microbial identity and activity will help determine microbial contributions to observed water-rock reactions in surface to deep environments. To determine habitability for microbial life and decipher mechanisms by which microbes survive and perform chemical reactions, over one hundred sites in diverse geological and geochemical environs have been sampled for aqueous geochemistry, mineralogy, and microbial identity and activity. Sites ranged from surficial creeks and rivers to the flooded mine shafts beneath to hydrothermal features in the caldera of a supervolcano 250 km distant; these environments contain metal scarcity, extreme anoxia, and wide variations in metal, organic carbon, and oxygen scarcity, respectively. Aqueous geochemistry included in situ measurement of temperature, pH, conductivity, and dissolved oxygen by meters; field spectrophotometry for redox active species; and synchronous sample collection and preservation for water isotopes, major cations and anions, trace elements, and dissolved inorganic and organic carbon, and more. Concurrent collection and preservation of planktonic and sediment biomass at each site will allow for microbial community identification and assessment of microbial activity. DNA extraction and PCR amplification using universal, eukaryotic, bacterial, and archaeal small subunit ribosomal RNA gene primers yielded products for sequencing. For many of the aqueous geochemical parameters analyzed, including Li and B, concentrations in flooded mine shafts fell on a continuum directly between local surface waters and those resulting from hydrothermal alteration suggesting an intermediate level of water-rock interaction in flooded mine shaft habitats. Concentrations of Li and B ranged from low micromolal in surface waters to millimolal in thermal waters. Other elements - Fe, Mn, Zn, and As included - were enriched in anoxic mine shafts by three to four orders of magnitude, due to exposure to and reaction with minerals. Concentrations of Fe and Zn ranged up to tens of millimolal whereas millimolal Mn and submillimolal As concentrations were reached. The transition from mostly unreacted surface water to waters nearly in equilibrium with rock provides vast geochemical habitat for microbes to exploit.

Regeneration of granular activated carbon saturated with acetone and isopropyl alcohol via a recirculation process under H2O2/UV oxidation.

PubMed

Horng, Richard S; Tseng, I-Chin

2008-06-15

This study examines a water-based system, coupling an adsorber and a photoreactor, for regeneration of granular activated carbon (GAC) saturated with acetone and isopropyl alcohol (IPA). Through water recirculation the regeneration reaction was operated in both intermittent and continuous ultraviolet illumination modes. With a periodic dosage of hydrogen peroxide not only was regeneration efficient but it was also catalyzed by GAC in the adsorber. The concentrations of acetone, solution chemical oxygen demand (COD), pH and organic residues on GAC surfaces were measured during regenerations. Both pH and solution COD were found to correlate with regeneration completion as measured by organic residue on GAC surfaces in four regeneration cycles with acetone. Solution pH decreased to the acidic values and then returned to near its original value when organic residues were 0.085-0.255 mg/g GAC, that is, destruction efficiency of adsorbed acetone on the GAC surface was more than 99%. Likewise, solution COD became low (<100 mg/l) at regeneration completion. The pH variation pattern was then applied to another four cycles of regeneration with IPA, and successfully reflected the timing of complete regeneration. The final levels of organic residue on GAC surfaces were between 0.135 and 0.310 mg/g GAC in each of four regeneration cycles, each of which had been stopped based on the measurements of pH and solution COD. Furthermore, nearly the same batch of GAC could be repeatedly used with little changes in physicochemical properties in each of eight cycles: adsorptive capacities were 95+/-7 mg acetone/g GAC and 87+/-3 mg IPA/g GAC, and breakthrough time was 0.86+/-0.05 for acetone and 0.78+/-0.03 h for IPA. An economic assessment of the system showed that the operating cost was about 0.04 USD for treating every gram of acetone in the air.

The geomicrobiology of the Greenland Ice Sheet: impact on DOC export (Invited)

NASA Astrophysics Data System (ADS)

Wadham, J. L.; Stibal, M.; Lawson, E. C.; Barnett, M. J.; Hasan, F.; Telling, J.; Anesio, A.; Lis, G.; Cullen, D.; Butler, C.; Tranter, M.; Nienow, P. W.

2010-12-01

The Greenland Ice Sheet (GrIS) is the largest mass of ice in the northern hemisphere, and contributes ~370 km3 in runoff annually to the Arctic Ocean. While recent work has highlighted runoff increases of up to 100% from the GrIS over the next century, very little is known about the associated impacts upon rates of sediment-bound and dissolved organic carbon export from the ice sheet to the coastal ocean. This is relevant given recent work that has suggested that the high proportion of labile dissolved organic carbon (DOC) present in glacial runoff may be important in sustaining the productivity of ecosystems downstream. Here we report the phylogenetic and functional diversity of micro-organisms inhabiting the surface and basal regions of the Greenland Ice Sheet (at Leverett Glacier, SW Greenland), and whose activity influences the biogeochemical composition of runoff. Real time PCR data on runoff, together with 16S-rRNA bacterial clone libraries on sediments, demonstrate a subglacial microbial community that contrasts phylogenetically and functionally with the ice sheet surface ecosystem. We envisage that large sectors of the subglacial environment are microbially active, with overridden paleosols and in-washed surface organic matter providing a carbon substrate for a range of metabolic pathways. This includes methanogenesis which proceeds at rates similar to deep ocean sediments and via a CO2/H2 pathway. These subglacial microbial communities serve to chemically modify the DOC composition of meltwater inputs from the ice sheet surface and modulate the reactivity of bulk DOC exported in runoff. Evidence for subglacial microbial influences on DOC in runoff includes elevated concentrations of dissolved carbohydrates (e.g. glucose and fructose of up to 1 μmol/L), which are preferentially exported during subglacial outburst events. We examine the temporal changes in DOC export in runoff from the ice sheet over a full melt season, and consider how changes in total runoff over the coming century may perturb this contribution.

Regulating Surface Facets of Metallic Aerogel Electrocatalysts by Size-dependent Localized Ostwald Ripening.

PubMed

Wenchao, Duan; Zhang, Peina; Xiahou, Yujiao; Song, Yahui; Bi, Cuixia; Zhan, Jie; Du, Wei; Huang, Lihui; Möhwald, Helmuth; Xia, Haibing

2018-06-21

It is well known that the activity and stability of electrocatalysts are largely dependent on their surface facets. In this work, we have successfully regulated surface facets of three-dimensional (3D) metallic Au m-n aerogels by salt-induced assembly of citrate-stabilized gold nanoparticles (Au NPs) of two different sizes and further size-dependent localized Ostwald ripening at controlled particle-number ratios, where m and n represent the size of Au NPs, respectively. In addition, 3D Au m-n @Pd aerogels were further synthesized on the basis of Au m-n aerogels and also bear controlled surface facets due to the formation of ultrathin Pd layers on Au m-n aerogels. Taking the electrooxidation of small organic molecules (such as methanol and ethanol) by the resulting Au m-n and Au m-n @Pd aerogels as examples, it is found that surface facets of metallic aerogels with excellent performance can be regulated to realize preferential surface facets for methanol oxidation and ethanol oxidation, respectively. Moreover, they also indeed simultaneously bear high activity and excellent stability. Furthermore, their activities and stability are also highly dependent on the area ratio of active facets and inactive facets on their surfaces, respectively, and these ratios are varied via the mismatch of sizes of adjacent nanoparticles. Thus, this work not only demonstrates the realization of the regulation of the surface facets of metallic aerogels by size-dependent localized Ostwald ripening, but also will open up a new way to improve electrocatalytic performance of three-dimensional metallic aerogels by surface regulation.

Band-engineering of TiO2 as a wide-band gap semiconductor using organic chromophore dyes

NASA Astrophysics Data System (ADS)

Wahyuningsih, S.; Kartini, I.; Ramelan, A. H.; Saputri, L. N. M. Z.; Munawaroh, H.

2017-07-01

Bond-engineering as applied to semiconductor materials refers to the manipulation of the energy bands in order to control charge transfer processes in a device. When the device in question is a photoelectrochemical cell, the charges affected by drift become the focus of the study. The ideal band gap of semiconductors for enhancement of photocatalyst activity can be lowered to match with visible light absorption and the location of conduction Band (CB) should be raised to meet the reducing capacity. Otherwise, by the addition of the chromofor organic dyes, the wide-band gab can be influences by interacation resulting between TiO2 surface and the dyes. We have done the impruvisation wide-band gap of TiO2 by the addition of organic chromophore dye, and the addition of transition metal dopand. The TiO2 morphology influence the light absorption as well as the surface modification. The organic chromophore dye was syntesized by formation complexes compound of Co(PAR)(SiPA)(PAR)= 4-(2-piridylazoresorcinol), SiPA = Silyl propil amine). The result showed that the chromophore groups adsorbed onto TiO2 surface can increase the visible light absorption of wide-band gab semiconductor. Initial absorption of a chromophore will affect light penetration into the material surfaces. The use of photonic material as a solar cell shows this phenomenon clearly from the IPCE (incident photon to current conversion efficiency) measurement data. Organic chromophore dyes of Co(PAR)(SiPA) exhibited the long wavelength absorption character compared to the N719 dye (from Dyesol).

Microfluidic Investigation Reveals Distinct Roles for Actin Cytoskeleton and Myosin II Activity in Capillary Leukocyte Trafficking

PubMed Central

Gabriele, Sylvain; Benoliel, Anne-Marie; Bongrand, Pierre; Théodoly, Olivier

2009-01-01

Circulating leukocyte sequestration in pulmonary capillaries is arguably the initiating event of lung injury in acute respiratory distress syndrome. We present a microfluidic investigation of the roles of actin organization and myosin II activity during the different stages of leukocyte trafficking through narrow capillaries (entry, transit and shape relaxation) using specific drugs (latrunculin A, jasplakinolide, and blebbistatin). The deformation rate during entry reveals that cell stiffness depends strongly on F-actin organization and hardly on myosin II activity, supporting a microfilament role in leukocyte sequestration. In the transit stage, cell friction is influenced by stiffness, demonstrating that the actin network is not completely broken after a forced entry into a capillary. Conversely, membrane unfolding was independent of leukocyte stiffness. The surface area of sequestered leukocytes increased by up to 160% in the absence of myosin II activity, showing the major role of molecular motors in microvilli wrinkling and zipping. Finally, cell shape relaxation was largely independent of both actin organization and myosin II activity, whereas a deformed state was required for normal trafficking through capillary segments. PMID:19450501

Decomposition of energetic molecules by interfacing with a catalytic oxide: opportunities and challenges

NASA Astrophysics Data System (ADS)

Wang, Fenggong; Tsyshevsky, Roman; Zverev, Anton; Mitrofanov, Anatoly; Kuklja, Maija

Organic-inorganic interfaces provide both intrigues and opportunities for designing systems that possess properties and functionalities inaccessible by each individual component. In particular, mixing with a photocatalyst may significantly affect the adsorption, decomposition, and photoresponse of organic molecules. Here, we choose the formulation of TiO2 and trinitrotoluene (TNT), a highly catalytic oxide and a prominent explosive, as a prototypical example to explore the interaction at the interface on the photosensitivity of energetic materials. We show that, whether or not a catalytic oxide additive can help molecular decompositions under light illumination depends largely on the band alignment between the oxide surface and the energetic molecule. Furthermore, an oxygen vacancy can lead to the electron density transfer from the surface to the energetic molecules, causing an enhancement of the bonding between molecules and surface and a reduction of the molecular decomposition activation barriers.

Cloud condensation nuclei activity and hygroscopicity of fresh and aged cooking organic aerosol

NASA Astrophysics Data System (ADS)

Li, Yanwei; Tasoglou, Antonios; Liangou, Aikaterini; Cain, Kerrigan P.; Jahn, Leif; Gu, Peishi; Kostenidou, Evangelia; Pandis, Spyros N.

2018-03-01

Cooking organic aerosol (COA) is potentially a significant fraction of organic particulate matter in urban areas. COA chemical aging experiments, using aerosol produced by grilling hamburgers, took place in a smog chamber in the presence of UV light or excess ozone. The water solubility distributions, cloud condensation nuclei (CCN) activity, and corresponding hygroscopicity of fresh and aged COA were measured. The average mobility equivalent activation diameter of the fresh particles at 0.4% supersaturation ranged from 87 to 126 nm and decreased for aged particles, ranging from 65 to 88 nm. Most of the fresh COA had water solubility less than 0.1 g L-1, even though the corresponding particles were quite CCN active. After aging, the COA fraction with water solubility greater than 0.1 g L-1 increased more than 2 times. Using the extended Köhler theory for multiple partially soluble components in order to predict the measured activation diameters, the COA solubility distribution alone could not explain the CCN activity. Surface tensions less than 30 dyn cm-1 were required to explain the measured activation diameters. In addition, COA particles appear to not be spherical, which can introduce uncertainties into the corresponding calculations.

Fabrication of Annealed Gold Nanostructures on Pre-Treated Glow-Discharge Cleaned Glasses and Their Used for Localized Surface Plasmon Resonance (LSPR) and Surface Enhanced Raman Spectroscopy (SERS) Detection of Adsorbed (Bio)molecules

PubMed Central

Ionescu, Rodica Elena; Aybeke, Ece Neslihan; Bourillot, Eric; Lacroute, Yvon; Lesniewska, Eric; Adam, Pierre-Michel; Bijeon, Jean-Louis

2017-01-01

Metallic nanoparticles are considered as active supports in the development of specific chemical or biological biosensors. Well-organized nanoparticles can be prepared either through expensive (e.g., electron beam lithography) or inexpensive (e.g., thermal synthesis) approaches where different shapes of nanoparticles are easily obtained over large solid surfaces. Herein, the authors propose a low-cost thermal synthesis of active plasmonic nanostructures on thin gold layers modified glass supports after 1 h holding on a hot plate (~350 °C). The resulted annealed nanoparticles proved a good reproducibility of localized surface plasmon resonance (LSPR) and surface enhanced Raman spectroscopy (SERS) optical responses and where used for the detection of low concentrations of two model (bio)chemical molecules, namely the human cytochrome b5 (Cyt-b5) and trans-1,2-bis(4-pyridyl)ethylene (BPE). PMID:28134754

Surface studies of heterogeneous catalysts by time-of-flight secondary ion mass spectrometry.

PubMed

Grams, Jacek

2010-01-01

The aim of this paper was to present potentialities of time-of-flight secondary ion mass spectrometry (ToF- SIMS) in the studies of heterogeneous catalysts. The results of ToF-SIMS investigations of Co/Al2O3, Mo/Al2O3, Co-Mo/Al2O3, Au/Al2O3, Pt/TiO2 and Pd/TiO2 systems were described. It was demonstrated that, in this case, an application of ToF-SIMS makes possible the determination of surface composition of investigated catalysts (including an identification of surface contaminants), characterization of interactions between an active phase and support, estimation of active phase dispersion on the analyzed surface, comparison of the degree of metal oxidation after treatment of the catalyst in different conditions, investigation of catalyst deactivation processes (formation of new chemical compounds, adsorption of various impurities and poisons on the catalyst surface) and determination of organic precursors of catalysts.

Adhesion and proliferation of fibroblasts on RF plasma-deposited nanostructured fluorocarbon coatings: evidence of FAK activation.

PubMed

Rosso, Francesco; Marino, Gerardo; Muscariello, Livio; Cafiero, Gennaro; Favia, Pietro; D'Aloia, Erica; d'Agostino, Riccardo; Barbarisi, Alfonso

2006-06-01

We used combined plasma-deposition process to deposit smooth and nanostructured fluorocarbon coatings on polyethylenethereftalate (PET) substrates, to obtain surfaces with identical chemical composition and different roughness, and investigate the effect of surface nanostructures on adhesion and proliferation of 3T3 Swiss Albino Mouse fibroblasts. Untreated PET and polystyrene (PS) were used as controls for cell culture. We have found that the statistically significant increase of cell proliferation rate and FAK (a nonreceptor tyrosine kinase) activation detected on ROUGH fluorocarbon surfaces is due to the presence of nanostructures. Changes in cytoskeletal organization and phospho FAK (tyr 397) localization were evident after 60 min on cells adhering to ROUGH surfaces. This change was characterized by the formation of actin stress fibers along lamellar membrane protrusion instead of usual focal contacts. Also the morphology of the adhering fibroblasts (60 min) adhering on ROUGH surfaces was found quite different compared to cells adhering on smooth ones. Copyright 2006 Wiley-Liss, Inc.

Packing, Scheduling and Covering Problems in a Game-Theoretic Perspective

NASA Astrophysics Data System (ADS)

Karlstrom, Leif

Magma transport pathways through Earth's crust span 12--15 orders of magnitude in time and space, with unsteadiness at all scales. However emergent organization of this system is widespread, recorded by spatial loci of volcanism at the surface and large-scale, rapid outpourings of magma throughout the geologic record. This thesis explores several mechanisms for the organization and time evolution of magma transport, from the deep crust to the surface. A primary focus (Chapters 2--5) is the filling, stability and drainage of magma chambers, structures which function both as reservoirs feeding individual volcanic eruptions and as stalling points in the crust where magma accumulates and differentiation occurs. We show that magma chambers may dictate the spatio-temporal organization of magma rising through crust (Chapters 2--3), control the surface eruptive progression of extreme mantle melting events (Chapter 4), and actively set the size of calderas that form during shallow, crystal rich eruptions (Chapter 5). Each of these chapters explores variations on a hypothesis: interactions between magma chamber stresses and the rheology of surrounding crustal materials evolve during magma transport and this unsteady process helps determine the magnitude, location, and timing of surface eruptions. The last part of this thesis (Chapters 6--7) focuses on surface transport processes, the meandering of melt channels on the surface of glaciers and lava flows. We show that the meandering instability is a generic feature of flow over an erodable substrate, despite significantly different fluid characteristics and erosion mechanics.

Survey for Life-related Species During a Planetary Surface Exploration; System Type I - UV Stimulated Fluorescent Sensor

NASA Technical Reports Server (NTRS)

Wang, Alian; Haskin, L. A.; Gillis, J. J.

2003-01-01

The widely accepted minimum requirements for life on Earth include the presence of water and accessible sources of carbon. We assume that the same criteria must hold for putative life on past or present Mars. The evidence for CO2 and H2O at or near the Martian surface, carbon in Martian meteorites, aqueous alteration, and probable hydrothermal activity suggest that conditions conducive to the origin and evolution of life on Mars may have existed for long periods of time and may still obtain at present. Surface exploration on Mars that enables the direct detection of water in minerals and of organic carbon (including not just organic and biogenic materials but their degradation products such as kerogen-like hydrocarbons and graphitized carbon) that might be products or residues of biologic activity, is crucial. The search for evidence of life, past or present, will nevertheless be difficult. The lack of direct evidence for organic carbon and the low amounts of water found in the soils at the Viking sites demonstrated the difficulties. Recent results of GRS experiment of Odyssey mission indicated the existence of abundant water ice beneath the Mars surface. Mineralogical evidence for the presence of carbonate, sulfates, or clay minerals, products of weathering and aqueous deposition, have not been identified unambiguously on Mars. Rocks such as shales and, more particularly, limestones, which we associate with moist and benign environments on Earth, are evidently not abundant. Presumably, then, neither were the photosynthetic organisms that might have produced them. In addition, the harsh present environment on Mars (e.g., dryness, low temperatures, large temperature cycles, high level of UV light on the surface, frequent dust storms, etc.) can both destroy carbon- and water-bearing materials and hide them. Therefore, directly detecting life-related materials on Mars was likened to seeking and examining proverbial needles in haystacks. We argue that survey type instruments, that can frequently and quickly check a relatively large amount of material at many locations during a mission, are essential.

Surface and Active Layer Pore Water Chemistry from Ice Wedge Polygons, Barrow, Alaska, 2013-2014

DOE Data Explorer

David E. Graham; Baohua Gu; Elizabeth M. Herndon; Stan D. Wullschleger; Ziming Yang; Liyuan Liang

2016-11-10

This data set reports the results of spatial surveys of aqueous geochemistry conducted at Intensive Site 1 of the Barrow Environmental Observatory in 2013 and 2014 (Herndon et al., 2015). Surface water and soil pore water samples were collected from multiple depths within the tundra active layer of different microtopographic features (troughs, ridges, center) of a low-centered polygon (area A), high-centered polygon (area B), flat-centered polygon (area C), and transitional polygon (area D). Reported analytes include dissolved organic and inorganic carbon, dissolved carbon dioxide and methane, major inorganic anions, and major and minor cations.

A preliminary view on adsorption of organics on ice at temperatures close to melting point

NASA Astrophysics Data System (ADS)

Kong, Xiangrui; Waldner, Astrid; Orlando, Fabrizio; Artiglia, Luca; Ammann, Markus; Bartels-Rausch, Thorsten

2016-04-01

Ice and snow play active roles in the water cycle, the energy budget of the Earth, and environmental chemistry in the atmosphere and cryosphere. The uptake of trace gases from the atmosphere may induce changes in the structure of the surface layer of ice crystals and has important consequences for atmospheric chemistry and the climate system. However, a molecular-level understanding of trace gas adsorption on ice is still missing, and also little is known about the impurity-induced ice-surface disorder in the context of environmental relevance. It is a general challenge to apply highly sensitive experimental approaches to ambient air conditions, e.g. studies of volatile surfaces, because of the strict requirements of vacuum experimental conditions. In this study, we employed synchrotron-based X-ray Photoelectron Spectroscopy (XPS) and partial electron yield Near Edge X-ray Absorption Fine Structure (NEXAFS) in a state-of-the-art Near-Ambient Pressure Photoelectron (NAPP) spectroscopy end station. The NAPP enables to utilize the surface sensitive experimental methods, XPS and NEXAFS with electron detection, on volatile surfaces, i.e. ice at temperatures approaching zero degree Celsius. XPS and NEXAFS provide unique information of hydrogen bonding network, surface concentration of organic adsorbates, depth profile of dopants in the ice, and acid-base dissociation on the surfaces. For instance, a few carboxylic acids, e.g. acetic acid and formic acid, have been recently studied by XPS and NEXAFS in NAPP. Amines are a group of nitrogen-containing basic organics with atmospheric relevance. Only few studies have been focused on amines, and atmospheric models rarely take account of them due to the limitation of knowledge. Several amines have been found to play active roles in the processes of aerosol formation, e.g. dimethylamine (DMA), trimethylamine (TMA) and 1-propanamine. In this study, we will focus on one of these three amines after pre-tests, and perform core-level spectroscopies to reveal the behaviour of adsorption and dissociation on ice. Additionally, pure ice and amine doped ice will be compared for their surface structure change at different temperatures, which will indicate the differences of surface disordering caused by different factors. For instance, we will have a chance to know better if impurities will cause local disordering, i.e. forming hydration shell, which challenges the traditional picture of a homogenous disordered doped ice surface. The findings of this study could not only improve our understanding of how acidic organics adsorb to ice, and of their chemical properties on ice, but also have potentials to know better the behaviour of pure ice at temperatures approaching to the melting point.

Adsorption uptake of synthetic organic chemicals by carbon nanotubes and activated carbons.

PubMed

Brooks, A J; Lim, Hyung-nam; Kilduff, James E

2012-07-27

Carbon nanotubes (CNTs) have shown great promise as high performance materials for adsorbing priority pollutants from water and wastewater. This study compared uptake of two contaminants of interest in drinking water treatment (atrazine and trichloroethylene) by nine different types of carbonaceous adsorbents: three different types of single walled carbon nanotubes (SWNTs), three different sized multi-walled nanotubes (MWNTs), two granular activated carbons (GACs) and a powdered activated carbon (PAC). On a mass basis, the activated carbons exhibited the highest uptake, followed by SWNTs and MWNTs. However, metallic impurities in SWNTs and multiple walls in MWNTs contribute to adsorbent mass but do not contribute commensurate adsorption sites. Therefore, when uptake was normalized by purity (carbon content) and surface area (instead of mass), the isotherms collapsed and much of the CNT data was comparable to the activated carbons, indicating that these two characteristics drive much of the observed differences between activated carbons and CNT materials. For the limited data set here, the Raman D:G ratio as a measure of disordered non-nanotube graphitic components was not a good predictor of adsorption from solution. Uptake of atrazine by MWNTs having a range of lengths and diameters was comparable and their Freundlich isotherms were statistically similar, and we found no impact of solution pH on the adsorption of either atrazine or trichloroethylene in the range of naturally occurring surface water (pH = 5.7-8.3). Experiments were performed using a suite of model aromatic compounds having a range of π-electron energy to investigate the role of π-π electron donor-acceptor interactions on organic compound uptake by SWNTs. For the compounds studied, hydrophobic interactions were the dominant mechanism in the uptake by both SWNTs and activated carbon. However, comparing the uptake of naphthalene and phenanthrene by activated carbon and SWNTs, size exclusion effects appear to be more pronounced with activated carbon materials, perhaps due to smaller pore sizes or larger adsorption surface areas in small pores.

Adsorption uptake of synthetic organic chemicals by carbon nanotubes and activated carbons

NASA Astrophysics Data System (ADS)

Brooks, A. J.; Lim, Hyung-nam; Kilduff, James E.

2012-07-01

Carbon nanotubes (CNTs) have shown great promise as high performance materials for adsorbing priority pollutants from water and wastewater. This study compared uptake of two contaminants of interest in drinking water treatment (atrazine and trichloroethylene) by nine different types of carbonaceous adsorbents: three different types of single walled carbon nanotubes (SWNTs), three different sized multi-walled nanotubes (MWNTs), two granular activated carbons (GACs) and a powdered activated carbon (PAC). On a mass basis, the activated carbons exhibited the highest uptake, followed by SWNTs and MWNTs. However, metallic impurities in SWNTs and multiple walls in MWNTs contribute to adsorbent mass but do not contribute commensurate adsorption sites. Therefore, when uptake was normalized by purity (carbon content) and surface area (instead of mass), the isotherms collapsed and much of the CNT data was comparable to the activated carbons, indicating that these two characteristics drive much of the observed differences between activated carbons and CNT materials. For the limited data set here, the Raman D:G ratio as a measure of disordered non-nanotube graphitic components was not a good predictor of adsorption from solution. Uptake of atrazine by MWNTs having a range of lengths and diameters was comparable and their Freundlich isotherms were statistically similar, and we found no impact of solution pH on the adsorption of either atrazine or trichloroethylene in the range of naturally occurring surface water (pH = 5.7-8.3). Experiments were performed using a suite of model aromatic compounds having a range of π-electron energy to investigate the role of π-π electron donor-acceptor interactions on organic compound uptake by SWNTs. For the compounds studied, hydrophobic interactions were the dominant mechanism in the uptake by both SWNTs and activated carbon. However, comparing the uptake of naphthalene and phenanthrene by activated carbon and SWNTs, size exclusion effects appear to be more pronounced with activated carbon materials, perhaps due to smaller pore sizes or larger adsorption surface areas in small pores.

Comparison on pore development of activated carbon produced by chemical and physical activation from palm empty fruit bunch

NASA Astrophysics Data System (ADS)

Hidayat, A.; Sutrisno, B.

2016-11-01

It is well-known that activated carbon is considered to be the general adsorbent due to the large range of applications. Numerous works are being continuously published concerning its use as adsorbent for: treatment of potable water; purification of air; retention of toxins by respirators; removal of organic and inorganic pollutants from flue gases and industrial waste gases and water; recuperation of solvents and hydrocarbons volatilized from petroleum derivatives; catalysis; separation of gas mixtures (molecularsieve activated carbons); storage of natural gas and hydrogen; energy storage in supercapacitors; recovery of gold, silver and othernoble metals; etc. This work presents producing activated carbons from palm empty fruit bunch using both physical activation with CO2 and chemical activation with KOH. The resultant activated carbons were characterized by measuring their porosities and pore size distributions. A comparison of the textural characteristics and surface chemistry of the activated carbon from palm empty fruit bunch by the CO2 and the KOH activation leads to the following findings: An activated carbon by the CO2 activation under the optimum conditions has a BET surface area of 717 m2/g, while that by the KOH activation has a BET surface area of 613 m2/g. The CO2 activation generated a highly microporous carbon (92%) with a Type-I isotherm, while the KOH activation generated a mesoporous one (70%) with a type-IV isotherm, the pore volumes are 0.2135 and 0.7426 cm3.g-1 respectively. The average pore size of the activated carbons is 2.72 and 2.56 nm for KOH activation and CO2 activation, respectively. The FT-IR spectra indicated significant variation in the surface functional groups are quite different for the KOH activated and CO2 activated carbons.

Single Silver Adatoms on Nanostructured Manganese Oxide Surfaces: Boosting Oxygen Activation for Benzene Abatement.

PubMed

Chen, Yaxin; Huang, Zhiwei; Zhou, Meijuan; Ma, Zhen; Chen, Jianmin; Tang, Xingfu

2017-02-21

The involvement of a great amount of active oxygen species is a crucial requirement for catalytic oxidation of benzene, because complete mineralization of one benzene molecule needs 15 oxygen atoms. Here, we disperse single silver adatoms on nanostructured hollandite manganese oxide (HMO) surfaces by using a thermal diffusion method. The single-atom silver catalyst (Ag 1 /HMO) shows high catalytic activity in benzene oxidation, and 100% conversion is achieved at 220 °C at a high space velocity of 23 000 h -1 . The Mars-van Krevelen mechanism is valid in our case as the reaction orders for both benzene and O 2 approach one, according to reaction kinetics data. Data from H 2 temperature-programmed reduction and O core-level X-ray photoelectron spectra (XPS) reveal that Ag 1 /HMO possesses a great amount of active surface lattice oxygen available for benzene oxidation. Valence-band XPS and density functional theoretical calculations demonstrate that the single Ag adatoms have the upshifted 4d orbitals, thus facilitating the activation of gaseous oxygen. Therefore, the excellent activation abilities of Ag 1 /HMO toward both surface lattice oxygen and gaseous oxygen account for its high catalytic activity in benzene oxidation. This work may assist with the rational design of efficient metal-oxide catalysts for the abatement of volatile organic compounds such as benzene.

Biohazard potential of putative Martian organisms during missions to Mars.

PubMed

Warmflash, David; Larios-Sanz, Maia; Jones, Jeffrey; Fox, George E; McKay, David S

2007-04-01

Exploration Class missions to Mars will require precautions against potential contamination by any native microorganisms that may be incidentally pathogenic to humans. While the results of NASA's Viking biology experiments of the 1970s have been generally interpreted as inconclusive for surface organisms, and attributed to active but nonbiological chemistries, the possibility of native surface life has never been ruled out completely. It is possible that, prior to the first human landing on Mars, robotic craft and sample return missions will provide enough data to know with certainty whether future human landing sites harbor extant life forms. If native life were found to exist, it would be problematic to determine whether any of its species might present a medical danger to astronauts. Therefore, it will become necessary to assess empirically the risk that the planet contains pathogens based on terrestrial examples of pathogenicity and to take a reasonably cautious approach to biohazard protection. A survey of terrestrial pathogens was conducted with special emphasis on those whose evolution has not depended on the presence of animal hosts. The history of the development and implementation of Apollo anti-contamination protocol and recommendations of the National Research Council's Space Studies Board regarding Mars were reviewed. Organisms can emerge in Nature in the absence of indigenous animal hosts and both infectious and non-infectious human pathogens are therefore theoretically possible on Mars. Although remote, the prospect of Martian surface life, together with the existence of a diversity of routes by which pathogenicity has emerged on Earth, suggests that the probability of human pathogens on Mars, while low, is not zero. Still, since the discovery and study of Martian life can have long-term benefits for humanity, the risk that Martian life might include pathogens should not be an obstacle to human exploration. As a precaution, it is recommended that EVA (extravehicular activity) suits be decontaminated when astronauts enter surface habitats upon returning from field activity and that biosafety protocols approximating laboratory BSL 2 be developed for astronauts working in laboratories on the Martian surface. Quarantine of astronauts and Martian materials arriving on Earth should also be part of a human mission to Mars, and this and the surface biosafety program should be integral to human expeditions from the earliest stages of the mission planning.

Bidirectional reflectance and VIS-NIR spectroscopy of cometary analogues under simulated space conditions

NASA Astrophysics Data System (ADS)

Jost, Bernhard; Pommerol, Antoine; Poch, Olivier; Yoldi, Zuriñe; Fornasier, Sonia; Hasselmann, Pedro Henrique; Feller, Clément; Carrasco, Nathalie; Szopa, Cyril; Thomas, Nicolas

2017-10-01

This work is intended to be the second publication in a series of papers reporting on the spectro-photometric properties of cometary analogues measured in the laboratory. Herein, we provide in-situ hyperspectral imaging data in the 0.40-2.35 μm range from three sublimation experiments under simulated space conditions in thermal vacuum from samples made of water ice, carbonaceous compounds and complex organic molecules. The dataset is complemented by measurements of the bidirectional reflectance in the visible (750 nm) spectral range before and after sublimation. A qualitative characterization of surface evolution processes is provided as well as a description of morphological changes during the simulation experiment. The aim of these experiments is to mimic the spectrum of comet 67P/Churyumov-Gerasimenko (67P) as acquired by the Rosetta mission by applying sublimation experiments on the mixtures of water ice with a complex organic material (tholins) and carbonaceous compounds (carbon black; activated charcoal) studied in our companion publication (Jost et al., submitted). Sublimation experiments are needed to develop the particular texture (high porosity), expected on the nucleus' surface, which might have a strong influence on spectro-photometric properties. The spectrally best matching mixtures of non volatile organic molecules from Jost et al. (submitted) are mixed with fine grained water ice particles and evolved in a thermal vacuum chamber, in order to monitor the influence of the sublimation process on their spectro-photometric properties. We demonstrate that the way the water ice and the non-volatile constituents are mixed, plays a major role in the formation and evolution of a surface residue mantle as well as having influence on the consolidation processes of the underlying ice. Additionally it results in different activity patterns under simulated insolation cycles. Further we show that the phase curves of samples having a porous surface mantle layer display higher coincidence with data of 67P than the phase curves of the samples having a more compact surface layer with smooth texture. The analysis of spectral absorption bands of water ice in the near-infrared (NIR) range, similar to those acquired by the VIRTIS instrument onboard Rosetta, allows to link compositional considerations with surface activity and texture.

EFFECT OF MOLECULAR OXYGEN ON THE SCALEUP OF GAC ADSORBERS

EPA Science Inventory

A rapid small-scale column test (RSSCT), designed according to the assumption of no dependency of the intraparticle surface diffusion coefficient on the activated carbon particle size, was able to accurately predict breakthrough of three volatile organic chemicals as well as back...

EFFECT OF GAC CHARACTERISTICS ON ADSORPTION OF ORGANIC POLLUTANTS

EPA Science Inventory

The impact of the characteristics of granular activated carbon (GAC) on adsorption capacity and on the potential for polymerization of phenolic compounds on the surface of GAC in the presence of molecular oxygen is evaluated in this study. Adsorption isotherm data were collected...

49 CFR 1014.110 - Self-evaluation.

Code of Federal Regulations, 2014 CFR

2014-10-01

... or organizations representing handicapped persons, to participate in the self-evaluation process by... 49 Transportation 8 2014-10-01 2014-10-01 false Self-evaluation. 1014.110 Section 1014.110... HANDICAP IN PROGRAMS OR ACTIVITIES CONDUCTED BY THE SURFACE TRANSPORTATION BOARD § 1014.110 Self-evaluation...

49 CFR 1014.110 - Self-evaluation.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 49 Transportation 8 2010-10-01 2010-10-01 false Self-evaluation. 1014.110 Section 1014.110... HANDICAP IN PROGRAMS OR ACTIVITIES CONDUCTED BY THE SURFACE TRANSPORTATION BOARD § 1014.110 Self-evaluation... or organizations representing handicapped persons, to participate in the self-evaluation process by...

Structural Characterization of Sputtered Silicon Thin Films after Rapid Thermal Annealing for Active-Matrix Organic Light Emitting Diode

NASA Astrophysics Data System (ADS)

de Dieu Mugiraneza, Jean; Miyahira, Tomoyuki; Sakamoto, Akinori; Chen, Yi; Okada, Tatsuya; Noguchi, Takashi; Itoh, Taketsugu

2010-12-01

The microcrystalline phase obtained by adopting a two-step rapid thermal annealing (RTA) process for rf-sputtered silicon films deposited on thermally durable glass was characterized. The optical properties, surface morphology, and internal stress of the annealed Si films are investigated. As the thermally durable glass substrate allows heating of the deposited films at high temperatures, micro-polycrystalline silicon (micro-poly-Si) films of uniform grain size with a smooth surface and a low internal stress could be obtained after annealing at 750 °C. The thermal stress in the Si films was 100 times lower than that found in the films deposited on conventional glass. Uniform grains with an average grain size of 30 nm were observed by transmission electron microscopy (TEM) in the films annealed at 800 °C. These micro-poly-Si films have potential application for fabrication of uniform and reliable thin film transistors (TFTs) for large scale active-matrix organic light emitting diode (AMOLED) displays.

Ectoenzymatic ratios in relation to particulate organic matter distribution (Ross Sea, Antarctica).

PubMed

Misic, C; Povero, P; Fabiano, M

2002-10-01

The results of a study on ectoenzymatic activity (the enzyme activity bound to particles larger than 0.2 micro m) and its relation to organic particle concentration are reported here. The sampling was carried out during the 1994 Antarctic spring, at a fixed station (Station 11) in the polynya of the Ross Sea, an area characterized by quick changes in sea ice cover. The sampling was repeated 4 times over a 20-day time period. The particulate organic matter distribution followed the physical structure of the water column, which depends on ice dynamics and is mainly determined by salinity. In the mixed-water surface layer (0-50 m) the concentrations were higher (on average 65.6 micro gC/L) than in the deeper water layer (50 m-bottom) (on average 19.1 micro gC/L). This distribution and quality, expressed by the protein:carbohydrate ratio, linked the particulate organic matter to the phytoplanktonic bloom which was in progress in the area. We determined the kinetic parameters of the glycolytic and proteolytic ectoenzymes and also the total activity for the proteolytic enzyme, in order to evaluate the contribution of the particle-bound activity. We observed higher values in the surface layer than in the deeper layer. b-Glucosidase activity ranged between 0.03 and 0.92 nmol L(-1) h(-1); b-N-acetylglucosaminidase activity was in the range of 0.04-0.58 nmol (L-1) (h-1). The total proteolytic activity (leucine aminopeptidase) ranged between 0.85 and 33.71 nmol L(-1) (h-1). The ectoproteolytic activity was about 35-60% of the total. The Km values were slightly higher for the proteolytic activity (on average 0.43 micro M for ectoproteolytic activity and 0.58 micro M for total proteolytic activity) than for the b-glucosidase (on average 0.36 micro M) and b-N-acetylglucosaminidase (on average 0.17 micro M), showing no remarkable variations in the water column. The ectoenzymatic ratios and their relationship with particulate organic substrates confirm the close link between organic substrate availability and degradation system response. The significant and positive correlations are not specific and suggest a prompt and efficient systemic response to the input of trophic resources. Nevertheless, changes in ectoenzyme activity and synthesis may act as adaptive responses to changing features of the ecosystem. In particular, variations in the proteolysis:glycolysis ratio depend on the functional features of the ecological system. In our study area this ratio is higher (about 10 or more) during production (particularly autotrophic) and lower (about 5 or less) during degradation/consumption events. The analysis of previous data, collected over a larger area characterized by different environmental conditions due to the changes of the pack ice cover, during the same cruise, confirms the existence of a significant relationship. Furthermore, the analysis of enzyme-uptake systems, expressed as Vmax:Km ratio, suggests that glycolytic ectoenzymes, although poorly expressed, may encourage microconsumers to grow rapidly on a wide range of organic substrates, including the refractory ones such as cellulose and chitin. However, low ectoenzyme potential exploitation rates of available organic substrates (on average about 5% for glycolytic and 12% for proteolytic ectoenzymes) would suggest that, during spring, zooplankton grazing or vertical and lateral transport are likely to play an important role in the removal of organic materials from the system.

Modeling Secondary Organic Aerosols over Europe: Impact of Activity Coefficients and Viscosity

NASA Astrophysics Data System (ADS)

Kim, Y.; Sartelet, K.; Couvidat, F.

2014-12-01

Semi-volatile organic species (SVOC) can condense on suspended particulate materials (PM) in the atmosphere. The modeling of condensation/evaporation of SVOC often assumes that gas-phase and particle-phase concentrations are at equilibrium. However, recent studies show that secondary organic aerosols (SOA) may not be accurately represented by an equilibrium approach between the gas and particle phases, because organic aerosols in the particle phase may be very viscous. The condensation in the viscous liquid phase is limited by the diffusion from the surface of PM to its core. Using a surrogate approach to represent SVOC, depending on the user's choice, the secondary organic aerosol processor (SOAP) may assume equilibrium or model dynamically the condensation/evaporation between the gas and particle phases to take into account the viscosity of organic aerosols. The model is implemented in the three-dimensional chemistry-transport model of POLYPHEMUS. In SOAP, activity coefficients for organic mixtures can be computed using UNIFAC for short-range interactions between molecules and AIOMFAC to also take into account the effect of inorganic species on activity coefficients. Simulations over Europe are performed and POLYPHEMUS/SOAP is compared to POLYPHEMUS/H2O, which was previously used to model SOA using the equilibrium approach with activity coefficients from UNIFAC. Impacts of the dynamic approach on modeling SOA over Europe are evaluated. The concentrations of SOA using the dynamic approach are compared with those using the equilibrium approach. The increase of computational cost is also evaluated.

Changes in optical characteristics of surface microlayers hint to photochemically and microbially-mediated DOM turnover in the upwelling region off Peru

NASA Astrophysics Data System (ADS)

Galgani, L.; Engel, A.

2015-12-01

The coastal upwelling system off Peru is characterized by high biological activity and a pronounced subsurface oxygen minimum zone, as well as associated emissions of atmospheric trace gases such as N2O, CH4 and CO2. During the Meteor (M91) cruise to the Peruvian upwelling system in 2012, we investigated the composition of the sea-surface microlayer (SML), the oceanic uppermost boundary directly subject to high solar radiation, often enriched in specific organic compounds of biological origin like Chromophoric Dissolved Organic Matter (CDOM) and marine gels. In the SML, the continuous photochemical and microbial recycling of organic matter may strongly influence gas exchange between marine systems and the atmosphere. In order to understand organic matter cycling in surface films, we analyzed SML and underlying water samples at 38 stations determining DOC concentration, amino acid composition, marine gels, CDOM and bacterial and phytoplankton abundance as indicators of photochemical and microbial alteration processes. CDOM composition was characterized by spectral slope (S) values and Excitation-Emission Matrix fluorescence (EEMs), which allow to track changes in molecular weight (MW) of DOM, and to determine potential DOM sources and sinks. We identified five fluorescent components of the CDOM pool, of which two had excitation/emission characteristics of protein-like fluorophores and were highly enriched in the SML. CDOM composition and changes in spectral slope properties suggested a local microbial release of HMW DOM directly in the SML as a response to light exposure in this extreme environment. Our results suggest that microbial and photochemical processes play an important role for the production, alteration and loss of optically active substances in the SML.

Carbon stable isotope composition of DNA isolated from an incipient paleosol

NASA Astrophysics Data System (ADS)

Jahren, A. Hope; Kelm, Kellie; Wendland, Beverly; Petersen, Gitte; Seberg, Ole

2006-05-01

We determined the carbon isotope (δ13C) value of double-stranded DNA (dsDNA) isolated from the organic horizons of a Delaware soil that is actively being covered by an encroaching sand dune. The soil belongs to a Nymphaea odorata Ait. (water lily) wetland, and we regard its active acquisition of a thick (˜24 cm) surface mantle to embody the process of paleopedogenesis; therefore, we have termed it an “incipient paleosol.” In this study, we compared the δ13C value of paleosol dsDNA to the bulk δ13C value of N. odorata, as well as to the δ13C value of plants that had colonized the surface mantle. The isotopic offset between paleosol δ13CdsDNA and N. odorata δ13Ctissue was identical to the relationship between δ13CdsDNA and δ13Ctissue for tracheophytes, which we had previously determined. In contrast, the isotopic offset between paleosol δ13CdsDNA and the δ13Ctissue of plants colonizing the surface mantle differed from this relationship by as much as 4‰. Similarly, the δ13C value of bulk paleosol organic matter was extremely heterogeneous and varied across 6‰. All paleosol DNA polymerase chain reaction (PCR) products produced clear, sharp, 350 base-pair (bp) fragments of rbcL, a gene shared by all photosynthetic organisms. These results open the exciting possibility that stable isotope analysis of dsDNA isolated from paleosol organic matter can be used to infer the δ13C value of the plant that dominated the nucleic acid contribution.

Identification of Acetylene on Titan's Surface

NASA Astrophysics Data System (ADS)

Singh, S.; McCord, T. B.; Rodriguez, S.; Combe, J. P.; Cornet, T.; Le Mouelic, S.; Maltagliati, L.; Chevrier, V.; Clark, R. N.

2015-12-01

Titan's atmosphere is opaque in the near infrared due to gaseous absorptions, mainly by methane, and scattering by aerosols, except in a few "transparency windows" (e.g., Sotin et al., 2005). Thus, the composition of Titan surface remains difficult to access from space and is still poorly constrained, limited to ethane in the polar lakes (Brown et al., 2008) and a few possible organic molecules on the surface (Clark et al., 2010). Photochemical models suggest that most of the organic compounds formed in the atmosphere are heavy enough to condense and build up at the surface in liquid and solid states over geological timescale (Cordier et al., 2009, 2011). Acetylene (C2H2) is one of the most abundant organic molecules in the atmosphere and thus thought to present on the surface as well. Here we report direct evidence of solid C2H2 on Titan's surface using Cassini Visual and Infrared Mapping Spectrometer (VIMS) data. By comparing VIMS observations and laboratory measurements of solid and liquid C2H2, we identify a specific absorption at 1.55 µm that is widespread over Titan but is particularly strong in the brightest terrains. This surface variability suggests that C2H2 is mobilized by surface processes, such as surface weathering, topography, and dissolution/evaporation. The detection of C2H2 on the surface of Titan opens new paths to understand and constrain Titan's surface activity. Since C2H2 is highly soluble in Titan liquids (Singh et al. 2015), it can easily dissolve in methane/ethane and may play an important role in carving of fluvial channels and existence of karstic lakes at higher latitudes on Titan. These processes imply the existence of a dynamic surface with a continued history of erosion and deposition of C2H2 on Titan.

A Physically Based Framework for Modelling the Organic Fractionation of Sea Spray Aerosol from Bubble Film Langmuir Equilibria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burrows, Susannah M.; Ogunro, O.; Frossard, Amanda

2014-12-19

The presence of a large fraction of organic matter in primary sea spray aerosol (SSA) can strongly affect its cloud condensation nuclei activity and interactions with marine clouds. Global climate models require new parameterizations of the SSA composition in order to improve the representation of these processes. Existing proposals for such a parameterization use remotely-sensed chlorophyll-a concentrations as a proxy for the biogenic contribution to the aerosol. However, both observations and theoretical considerations suggest that existing relationships with chlorophyll-a, derived from observations at only a few locations, may not be representative for all ocean regions. We introduce a novel frameworkmore » for parameterizing the fractionation of marine organic matter into SSA based on a competitive Langmuir adsorption equilibrium at bubble surfaces. Marine organic matter is partitioned into classes with differing molecular weights, surface excesses, and Langmuir adsorption parameters. The classes include a lipid-like mixture associated with labile dissolved organic carbon (DOC), a polysaccharide-like mixture associated primarily with semi-labile DOC, a protein-like mixture with concentrations intermediate between lipids and polysaccharides, a processed mixture associated with recalcitrant surface DOC, and a deep abyssal humic-like mixture. Box model calculations have been performed for several cases of organic adsorption to illustrate the underlying concepts. We then apply the framework to output from a global marine biogeochemistry model, by partitioning total dissolved organic carbon into several classes of macromolecule. Each class is represented by model compounds with physical and chemical properties based on existing laboratory data. This allows us to globally map the predicted organic mass fraction of the nascent submicron sea spray aerosol. Predicted relationships between chlorophyll-\\textit{a} and organic fraction are similar to existing empirical parameterizations, but can vary between biologically productive and non-productive regions, and seasonally within a given region. Major uncertainties include the bubble film thickness at bursting and the variability of organic surfactant activity in the ocean, which is poorly constrained. In addition, marine colloids and cooperative adsorption of polysaccharides may make important contributions to the aerosol, but are not included here. This organic fractionation framework is an initial step towards a closer linking of ocean biogeochemistry and aerosol chemical composition in Earth system models. Future work should focus on improving constraints on model parameters through new laboratory experiments or through empirical fitting to observed relationships in the real ocean and atmosphere, as well as on atmospheric implications of the variable composition of organic matter in sea spray.« less

Effects of food supplementation on the physiological ecology of female Western diamond-backed rattlesnakes (Crotalus atrox).

PubMed

Taylor, Emily N; Malawy, Michael A; Browning, Dawn M; Lemar, Shea V; DeNardo, Dale F

2005-06-01

Food availability is an important factor in the life histories of organisms because it is often limiting and thus can affect growth, mass change, reproduction, and behaviors such as thermoregulation, locomotion, and mating. Experimental studies in natural settings allow researchers to examine the effects of food on these parameters while animals are free to behave naturally. The wide variation among organisms in energy demands and among environmental food resources suggest that responses to changes in food availability may vary among organisms. Since most supplemental feeding field experiments have been conducted on species with high energy demands, we conducted a supplemental feeding study on free-ranging, female Western diamond-backed rattlesnakes (Crotalus atrox), a species with low energy demands and infrequent reproductive investment. Snakes were offered thawed rodents 1-4 times per week. Over two active seasons, we collected data on surface activity, home range size, growth, mass change, and reproduction of supplementally fed and control snakes. Fed and control snakes did not differ in surface activity levels (proportion of time encountered above versus below ground) or home range size. Fed snakes grew and gained mass faster, and had a dramatically higher occurrence of reproduction than control snakes. Also, fed snakes were in better body condition following reproduction than snakes that were not fed. However, litter characteristics such as offspring number and size were not increased by feeding, suggesting that these characteristics may be fixed. These data experimentally demonstrate that food availability can directly impact some life history traits (i.e., growth and reproduction for C. atrox), but not others (i.e., surface activity and home range size for C. atrox). The relationship between food availability and life history traits is affected in a complex way by ecological traits and physiological constraints, and thus interspecific variation in this relationship is likely to be high.

Wrinkles and Folds of Activated Graphene Nanosheets as Fast and Efficient Adsorptive Sites for Hydrophobic Organic Contaminants.

PubMed

Wang, Jun; Chen, Baoliang; Xing, Baoshan

2016-04-05

To create more wrinkles and folds as available adsorption sites, graphene nanosheets (GNS) were thermally treated with KOH for morphological alteration. The surface structures and properties of the activated graphene nanosheets (AGN) were characterized by BET-N2, SEM, TEM, Raman, XRD, XPS, and FTIR. After KOH etching, the highly crystal structure was altered, self-aggregation of graphene layers were evidently relieved, and more single to few layer graphene nanosheets were created with wrinkles and folds. Also both specific surface area and micropore volume of AGN increased relative to GNS. The adsorption of AGN toward p-nitrotoluene, naphthalene and phenanthrene were greatly enhanced in comparison with GNS, and gradually promoted with increasing degree of KOH etching. Adsorption rate of organic contaminants on AGN was very fast and efficient, whereas small molecules showed higher adsorption rates due to the more porous surface of graphene. In addition to π-π interaction, the high affinities of p-nitrotoluene to AGN are suggested from strong electron charge transfer interactions between nitro groups on p-nitrotoluene and defect sites of AGN. A positively linear correlation between organic molecule uptake and the micropore volume of AGN indicated that pore-filling mechanism may play an important role in adsorption. Morphological wrinkles and folds of graphene nanosheets can be regulated to enhance the adsorption capability and kinetics for efficient pollutant removal and to selectively preconcentrate adsorbates with different sizes for detection.

Hydrogeology and chemical quality of water and soil at Carroll Island, Aberdeen Proving Ground, Maryland

USGS Publications Warehouse

Tenbus, F.J.; Phillips, S.W.

1996-01-01

Carroll Island was used for open-air testing of chemical warfare agents from the late 1940's until 1971. Testing and disposal activities weresuspected of causing environmental contamination at 16 sites on the island. The hydrogeology and chemical quality of ground water, surface water, and soil at these sites were investigated with borehole logs, environmental samples, water-level measurements, and hydrologic tests. A surficial aquifer, upper confining unit, and upper confined aquifer were defined. Ground water in the surficial aquifer generally flows from the east-central part of the island toward the surface-water bodies, butgradient reversals caused by evapotranspiration can occur during dry seasons. In the confined aquifer, hydraulic gradients are low, and hydraulic head is affected by tidal loading and by seasonal pumpage from the west. Inorganic chemistry in the aquifers is affected by brackish-water intrusion from gradient reversals and by dissolution ofcarboniferous shell material in the confining unit.The concentrations of most inorganic constituents probably resulted from natural processes, but some concentrations exceeded Federal water-quality regulations and criteria. Organic compounds were detected in water and soil samples at maximum concentrations of 138 micrograms per liter (thiodiglycol in surface water) and 12 micrograms per gram (octadecanoic acid in soil).Concentrations of organic compounds in ground water exceeded Federal drinking-water regulations at two sites. The organic compounds that weredetected in environmental samples were variously attributed to natural processes, laboratory or field- sampling contamination, fallout from industrial air pollution, and historical military activities.

Copper effects on bacterial activity of estuarine silty sediments

NASA Astrophysics Data System (ADS)

Almeida, Adelaide; Cunha, Ângela; Fernandes, Sandra; Sobral, Paula; Alcântara, Fernanda

2007-07-01

Bacteria of silty estuarine sediments were spiked with copper to 200 μg Cu g -1 dry weight sediment in order to assess the impact of copper on bacterial degradation of organic matter and on bacterial biomass production. Bacterial density was determined by direct counting under epifluorescence microscopy and bacterial production by the incorporation of 3H-Leucine. Leucine turnover rate was evaluated by 14C-leucine incorporation and ectoenzymatic activities were estimated as the hydrolysis rate of model substrates for β-glucosidase and leucine-aminopeptidase. The presence of added copper in the microcosms elicited, after 21 days of incubation, generalised anoxia and a decrease in organic matter content. The non-eroded surface of the copper-spiked sediment showed, when compared to the control, a decrease in bacterial abundance and significant lower levels of bacterial production and of leucine turnover rate. Bacterial production and leucine turnover rate decreased to 1.4% and 13% of the control values, respectively. Ectoenzymatic activities were also negatively affected but by smaller factors. After erosion by the water current in laboratory flume conditions, the eroded surface of the control sediment showed a generalised decline in all bacterial activities. The erosion of the copper-spiked sediment showed, however, two types of responses with respect to bacterial activities at the exposed surface: positive responses of bacterial production and leucine turnover rate contrasting with slight negative responses of ectoenzymatic activities. The effects of experimental erosion in the suspended cells were also different in the control and in the copper-spiked sediment. Bacterial cells in the control microcosm exhibited, when compared to the non-eroded sediment cells, decreases in all activities after the 6-h suspension. The response of the average suspended copper-spiked sediment cell differed from the control by a less sharp decrease in ectoenzymatic activities and, mainly, by the great intensification of bacterial biomass production and leucine turnover rate. We conclude that the bacterial community of silty estuarine sediments seems to withstand considerable concentrations of copper at the cost of reduced bacterial organic matter degradation and of the almost halting of bacterial production. The toxic effects elicited by copper on protein and carbohydrate degradation were not rapidly repaired by erosion and oxygenation of the sediment cells but, in contrast, bacterial biomass production and leucine turnover were rapidly and efficiently reactivated.

Fructose-1,6-bisphosphate aldolase of Neisseria meningitidis binds human plasminogen via its C-terminal lysine residue.

PubMed

Shams, Fariza; Oldfield, Neil J; Lai, Si Kei; Tunio, Sarfraz A; Wooldridge, Karl G; Turner, David P J

2016-04-01

Neisseria meningitidis is a leading cause of fatal sepsis and meningitis worldwide. As for commensal species of human neisseriae, N. meningitidis inhabits the human nasopharynx and asymptomatic colonization is ubiquitous. Only rarely does the organism invade and survive in the bloodstream leading to disease. Moonlighting proteins perform two or more autonomous, often dissimilar, functions using a single polypeptide chain. They have been increasingly reported on the surface of both prokaryotic and eukaryotic organisms and shown to interact with a variety of host ligands. In some organisms moonlighting proteins perform virulence-related functions, and they may play a role in the pathogenesis of N. meningitidis. Fructose-1,6-bisphosphate aldolase (FBA) was previously shown to be surface-exposed in meningococci and involved in adhesion to host cells. In this study, FBA was shown to be present on the surface of both pathogenic and commensal neisseriae, and surface localization and anchoring was demonstrated to be independent of aldolase activity. Importantly, meningococcal FBA was found to bind to human glu-plasminogen in a dose-dependent manner. Site-directed mutagenesis demonstrated that the C-terminal lysine residue of FBA was required for this interaction, whereas subterminal lysine residues were not involved. © 2016 The Authors. MicrobiologyOpen published by John Wiley & Sons Ltd.

GPI-anchored proteins are confined in subdiffraction clusters at the apical surface of polarized epithelial cells

PubMed Central

Paladino, Simona; Lebreton, Stéphanie; Lelek, Mickaël; Riccio, Patrizia; De Nicola, Sergio; Zimmer, Christophe

2017-01-01

Spatio-temporal compartmentalization of membrane proteins is critical for the regulation of diverse vital functions in eukaryotic cells. It was previously shown that, at the apical surface of polarized MDCK cells, glycosylphosphatidylinositol (GPI)-anchored proteins (GPI-APs) are organized in small cholesterol-independent clusters of single GPI-AP species (homoclusters), which are required for the formation of larger cholesterol-dependent clusters formed by multiple GPI-AP species (heteroclusters). This clustered organization is crucial for the biological activities of GPI-APs; hence, understanding the spatio-temporal properties of their membrane organization is of fundamental importance. Here, by using direct stochastic optical reconstruction microscopy coupled to pair correlation analysis (pc-STORM), we were able to visualize and measure the size of these clusters. Specifically, we show that they are non-randomly distributed and have an average size of 67 nm. We also demonstrated that polarized MDCK and non-polarized CHO cells have similar cluster distribution and size, but different sensitivity to cholesterol depletion. Finally, we derived a model that allowed a quantitative characterization of the cluster organization of GPI-APs at the apical surface of polarized MDCK cells for the first time. Experimental FRET (fluorescence resonance energy transfer)/FLIM (fluorescence-lifetime imaging microscopy) data were correlated to the theoretical predictions of the model. PMID:29046391

Near-surface Heating of Young Rift Sediment Causes Mass Production and Discharge of Reactive Dissolved Organic Matter

PubMed Central

Lin, Yu-Shih; Koch, Boris P.; Feseker, Tomas; Ziervogel, Kai; Goldhammer, Tobias; Schmidt, Frauke; Witt, Matthias; Kellermann, Matthias Y.; Zabel, Matthias; Teske, Andreas; Hinrichs, Kai-Uwe

2017-01-01

Ocean margin sediments have been considered as important sources of dissolved organic carbon (DOC) to the deep ocean, yet the contribution from advective settings has just started to be acknowledged. Here we present evidence showing that near-surface heating of sediment in the Guaymas Basin, a young extensional depression, causes mass production and discharge of reactive dissolved organic matter (DOM). In the sediment heated up to ~100 °C, we found unexpectedly low DOC concentrations in the pore waters, reflecting the combined effect of thermal desorption and advective fluid flow. Heating experiments suggested DOC production to be a rapid, abiotic process with the DOC concentration increasing exponentially with temperature. The high proportions of total hydrolyzable amino acids and presence of chemical species affiliated with activated hydrocarbons, carbohydrates and peptides indicate high reactivity of the DOM. Model simulation suggests that at the local scale, near-surface heating of sediment creates short and massive DOC discharge events that elevate the bottom-water DOC concentration. Because of the heterogeneous distribution of high heat flow areas, the expulsion of reactive DOM is spotty at any given time. We conclude that hydrothermal heating of young rift sediments alter deep-ocean budgets of bioavailable DOM, creating organic-rich habitats for benthic life. PMID:28327661

Soft lithographic functionalization and patterning oxide-free silicon and germanium.

PubMed

Bowers, Carleen M; Toone, Eric J; Clark, Robert L; Shestopalov, Alexander A

2011-12-16

The development of hybrid electronic devices relies in large part on the integration of (bio)organic materials and inorganic semiconductors through a stable interface that permits efficient electron transport and protects underlying substrates from oxidative degradation. Group IV semiconductors can be effectively protected with highly-ordered self-assembled monolayers (SAMs) composed of simple alkyl chains that act as impervious barriers to both organic and aqueous solutions. Simple alkyl SAMs, however, are inert and not amenable to traditional patterning techniques. The motivation for immobilizing organic molecular systems on semiconductors is to impart new functionality to the surface that can provide optical, electronic, and mechanical function, as well as chemical and biological activity. Microcontact printing (μCP) is a soft-lithographic technique for patterning SAMs on myriad surfaces. Despite its simplicity and versatility, the approach has been largely limited to noble metal surfaces and has not been well developed for pattern transfer to technologically important substrates such as oxide-free silicon and germanium. Furthermore, because this technique relies on the ink diffusion to transfer pattern from the elastomer to substrate, the resolution of such traditional printing is essentially limited to near 1 μm. In contrast to traditional printing, inkless μCP patterning relies on a specific reaction between a surface-immobilized substrate and a stamp-bound catalyst. Because the technique does not rely on diffusive SAM formation, it significantly expands the diversity of patternable surfaces. In addition, the inkless technique obviates the feature size limitations imposed by molecular diffusion, facilitating replication of very small (<200 nm) features. However, up till now, inkless μCP has been mainly used for patterning relatively disordered molecular systems, which do not protect underlying surfaces from degradation. Here, we report a simple, reliable high-throughput method for patterning passivated silicon and germanium with reactive organic monolayers and demonstrate selective functionalization of the patterned substrates with both small molecules and proteins. The technique utilizes a preformed NHS-reactive bilayered system on oxide-free silicon and germanium. The NHS moiety is hydrolyzed in a pattern-specific manner with a sulfonic acid-modified acrylate stamp to produce chemically distinct patterns of NHS-activated and free carboxylic acids. A significant limitation to the resolution of many μCP techniques is the use of PDMS material which lacks the mechanical rigidity necessary for high fidelity transfer. To alleviate this limitation we utilized a polyurethane acrylate polymer, a relatively rigid material that can be easily functionalized with different organic moieties. Our patterning approach completely protects both silicon and germanium from chemical oxidation, provides precise control over the shape and size of the patterned features, and gives ready access to chemically discriminated patterns that can be further functionalized with both organic and biological molecules. The approach is general and applicable to other technologically-relevant surfaces.

Porosity control in nanoporous carbide-derived carbon by oxidation in air and carbon dioxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Osswald, S.; Portet, C.; Gogotsi, Y., E-mail: gogotsi@drexel.ed

2009-07-15

Carbide-derived carbons (CDC) allow a precise control over the pore size through the selection of the carbide precursor and varying of the synthesis conditions. However, their pore volume is limited by the carbide stoichiometry. While activation of carbons derived from various organic precursors has been widely studied, this process may similarly be able to increase the pore volume and specific surface area of CDC. Oxidation of carbide-derived carbon in air and CO{sub 2} at different temperatures and times allows for significant increase in pore volume and specific surface area as well as control over average pore size with subnanometer accuracy.more » The effect of activation and associated changes in the pore volume and surface area on the hydrogen uptake are also discussed. - Graphical abstract: Carbide-derived carbons (CDC) provide great potential for sorption of toxicants and gas storage applications. Activation of CDC in air and CO{sub 2} at different temperatures and times is applied in order to maximize pore volume and specific surface area, and control the average pore size with subnanometer accuracy.« less

Enhancing antimicrobial activity of TiO2/Ti by torularhodin bioinspired surface modification.

PubMed

Ungureanu, Camelia; Dumitriu, Cristina; Popescu, Simona; Enculescu, Monica; Tofan, Vlad; Popescu, Marian; Pirvu, Cristian

2016-02-01

Implant-associated infections are a major cause of morbidity and mortality. This study was performed using titanium samples coated by anodization with a titanium dioxide (TiO2) shielded nanotube layer. TiO2/Ti surface was modified by simple immersion in torularhodin solution and by using a mussel-inspired method based on polydopamine as bio adhesive for torularhodin immobilization. SEM analysis revealed tubular microstructures of torularhodin and the PDA ability to function as a catchy anchor between torularhodin and TiO2 surface. Corrosion resistance was associated with TiO2 barrier oxide layer and nano-organized oxide layer and the torularhodin surface modification does not bring significant changes in resistance of the oxide layer. Our results demonstrated that the torularhodin modified TiO2/Ti surface could effectively prevent adhesion and proliferation of Escherichia coli, Staphylococcus aureus, Enterococcus faecalis, Bacillus subtilis, and Pseudomonas aeruginosa. The new modified titanium surface showed good biocompatibility and well-behaved haemocompatibility. This biomaterial with enhanced antimicrobial activity holds great potential for future biomedical applications. Copyright © 2015 Elsevier B.V. All rights reserved.

Microlayer source of oxygenated volatile organic compounds in the summertime marine Arctic boundary layer

NASA Astrophysics Data System (ADS)

Mungall, Emma L.; Abbatt, Jonathan P. D.; Wentzell, Jeremy J. B.; Lee, Alex K. Y.; Thomas, Jennie L.; Blais, Marjolaine; Gosselin, Michel; Miller, Lisa A.; Papakyriakou, Tim; Willis, Megan D.; Liggio, John

2017-06-01

Summertime Arctic shipboard observations of oxygenated volatile organic compounds (OVOCs) such as organic acids, key precursors of climatically active secondary organic aerosol (SOA), are consistent with a novel source of OVOCs to the marine boundary layer via chemistry at the sea surface microlayer. Although this source has been studied in a laboratory setting, organic acid emissions from the sea surface microlayer have not previously been observed in ambient marine environments. Correlations between measurements of OVOCs, including high levels of formic acid, in the atmosphere (measured by an online high-resolution time-of-flight mass spectrometer) and dissolved organic matter in the ocean point to a marine source for the measured OVOCs. That this source is photomediated is indicated by correlations between the diurnal cycles of the OVOC measurements and solar radiation. In contrast, the OVOCs do not correlate with levels of isoprene, monoterpenes, or dimethyl sulfide. Results from box model calculations are consistent with heterogeneous chemistry as the source of the measured OVOCs. As sea ice retreats and dissolved organic carbon inputs to the Arctic increase, the impact of this source on the summer Arctic atmosphere is likely to increase. Globally, this source should be assessed in other marine environments to quantify its impact on OVOC and SOA burdens in the atmosphere, and ultimately on climate.

Microlayer source of oxygenated volatile organic compounds in the summertime marine Arctic boundary layer.

PubMed

Mungall, Emma L; Abbatt, Jonathan P D; Wentzell, Jeremy J B; Lee, Alex K Y; Thomas, Jennie L; Blais, Marjolaine; Gosselin, Michel; Miller, Lisa A; Papakyriakou, Tim; Willis, Megan D; Liggio, John

2017-06-13

Summertime Arctic shipboard observations of oxygenated volatile organic compounds (OVOCs) such as organic acids, key precursors of climatically active secondary organic aerosol (SOA), are consistent with a novel source of OVOCs to the marine boundary layer via chemistry at the sea surface microlayer. Although this source has been studied in a laboratory setting, organic acid emissions from the sea surface microlayer have not previously been observed in ambient marine environments. Correlations between measurements of OVOCs, including high levels of formic acid, in the atmosphere (measured by an online high-resolution time-of-flight mass spectrometer) and dissolved organic matter in the ocean point to a marine source for the measured OVOCs. That this source is photomediated is indicated by correlations between the diurnal cycles of the OVOC measurements and solar radiation. In contrast, the OVOCs do not correlate with levels of isoprene, monoterpenes, or dimethyl sulfide. Results from box model calculations are consistent with heterogeneous chemistry as the source of the measured OVOCs. As sea ice retreats and dissolved organic carbon inputs to the Arctic increase, the impact of this source on the summer Arctic atmosphere is likely to increase. Globally, this source should be assessed in other marine environments to quantify its impact on OVOC and SOA burdens in the atmosphere, and ultimately on climate.

Interactions on External MOF Surfaces: Desorption of Water and Ethanol from CuBDC Nanosheets.

PubMed

Elder, Alexander C; Aleksandrov, Alexandr B; Nair, Sankar; Orlando, Thomas M

2017-10-03

The external surfaces of metal-organic framework (MOF) materials are difficult to experimentally isolate due to the high porosities of these materials. MOF surface surrogates in the form of copper benzenedicarboxylate (CuBDC) nanosheets were synthesized using a bottom-up approach, and the surface interactions of water and ethanol were investigated by temperature-programmed desorption (TPD). A method of analysis of diffusion-influenced TPD was developed to measure the desorption properties of these porous materials. This approach also allows the extraction of diffusion coefficients from TPD data. The transmission Fourier transform infrared spectra, powder X-ray diffraction patterns, and TPD data indicate that water desorbs from CuBDC nanosheets with activation energies of 44 ± 2 kJ/mol at edge sites and 58 ± 1 kJ/mol at external surface and internal and pore sites. Ethanol desorbs with activation energies of 58 ± 1 kJ/mol at internal pore sites and 66 ± 0.4 kJ/mol at external surface sites. Co-adsorption of water and ethanol was also investigated. The presence of ethanol was found to inhibit the desorption of water, resulting in a water desorption process with an activation energy of 68 ± 0.7 kJ/mol.

The role of surface implant treatments on the biological behavior of SaOS-2 osteoblast-like cells. An in vitro comparative study.

PubMed

Conserva, Enrico; Menini, Maria; Ravera, Giambattista; Pera, Paolo

2013-08-01

The aim of this study was an in vitro comparison of osteoblast adhesion, proliferation and differentiation related to six dental implants with different surface characteristics, and to determine if the interaction between cells and implant is influenced by surface structure and chemical composition. Six types of implants were tested, presenting four different surface treatments: turned, sandblasted, acid-etched, anodized. The implant macro- and microstructure were analyzed using SEM, and the surface chemical composition was investigated using energy-dispersive X-ray analysis. SaOS-2 osteoblasts were used for the evaluation of cell adhesion and proliferation by SEM, and cell viability in contact with the various surfaces was determined using cytotoxicity MTT assays. Alkaline phosphatase (ALP) enzymatic activity in contact with the six surfaces was evaluated. Data relative to MTT assay and ALP activity were statistically analyzed using Kruskal-Wallis not parametric test and Nemenyi-Damico-Wolfe-Dunn post hoc test. All the implants tested supported cell adhesion, proliferation and differentiation, revealing neither organic contaminants nor cytotoxicity effects. The industrial treatments investigated changed the implant surface microscopic aspect and SaOS-2 cell morphology appeared to be influenced by the type of surface treatment at 6, 24, and 72 h of growth. SaOS-2 cells spread more rapidly on sandblasted surfaces. Turned surfaces showed the lowest cell proliferation at SEM observation. Sandblasted surfaces showed the greatest ALP activity values per cell, followed by turned surfaces (P < 0.05). On the base of this in vitro investigation, differently surfaced implants affected osteoblast morphology, adhesion, proliferation, and differentiation. Sandblasted surfaces promoted the most suitable osteoblast behavior. © 2012 John Wiley & Sons A/S.

Terrestrial and marine biomarker estimates of organic matter sources and distributions in surface sediments from the East China Sea shelf

NASA Astrophysics Data System (ADS)

Xing, Lei; Zhang, Hailong; Yuan, Zineng; Sun, Yao; Zhao, Meixun

2011-07-01

Revealing of the sources and distributions of sedimentary organic matter in the East China Sea (ECS) is important for understanding its carbon cycle, which has significant temporal and spatial variability due to the influences of recent climate changes and anthropogenic activities. In this study, we report the contents of both terrestrial and marine biomarkers including ∑C 27+C 29+C 31n-alkanes (38.6-580 ng/g), C 37 alkenones (5.6-124.6 ng/g), brassicasterol (98-913 ng/g) and dinosterol (125-1521 ng/g) from the surface sediments in the Changjiang River Estuary (CRE) and shelf areas of the ECS. Several indices based on biomarker contents and ratios are calculated to assess the spatial distributions of both terrestrial and marine organic matter in the ECS surface sediments, and these results are compared with organic matter distribution patterns revealed by the δ13C (-20.1‰ to -22.7‰) and C/N ratio (5-7.5) of total organic matter. The contents of terrestrial biomarkers in the ECS surface sediments decrease seaward, controlled mostly by Changjiang River (CR) inputs and surface currents; while higher contents of the two marine biomarkers (brassicasterol and dinosterol) occur in upwelling areas outside the CRE and in the Zhejiang-Fujian coastal zone, controlled mostly by marine productivity. Four proxies, fTerr( δ13C) (the fraction of terrestrial organic matter in TOC estimated by TOC δ13C), odd-alkanes (∑C 27+C 29+C 31n-alkanes), 1/ Pmar-aq ((C 23+C 25+C 29+C 31)/(C 23+C 25) n-alkanes) and TMBR (terrestrial and marine biomarker ratio) (C 27+C 29+C 31n-alkanes)/((C 27+C 29+C 31) n-alkanes+(brassicasterol+dinosterol+alkenones)), reveal a consistent pattern showing the relative contribution of terrestrial organic matter (TOM) is higher in the CRE and along the Zhejiang-Fujian coastline, controlled mostly by CR inputs and currents, but the TOM contribution decreases seaward, as the influences of the CR discharge decrease.

Discontinuous hygroscopic growth of an aqueous surfactant/salt aerosol particle levitated in an electrodynamic balance

NASA Astrophysics Data System (ADS)

Soonsin, V.; Krieger, U. K.; Peter, T.

2010-12-01

Organic compounds are a major fraction of tropospheric aerosol. The organic fraction is usually internally mixed with inorganic salts. Surface-active organic matter or surfactants, enriched in the oceanic surface layer and transferred to the atmosphere by bubble-bursting processes, are the most likely candidates to contribute the observed organic fraction in sea salt aerosol [1, 2]. If the organic substance is a surfactant, it will lower the surface tension. In addition aggregates of the organic monomers, called micelles, will form if the concentration of the organic exceeds a certain limit (critical micelle concentration). These aggregates do have different morphology (spheres or globular or rod like micelles, or spherical bilayer vesicles etc.) and size, depending on the nature of the organic molecule, its concentration and the concentration of inorganic salts [3]. These aggregate may promote solubilisation of organic compounds in aqueous atmospheric aerosol. We performed measurements of ternary aqueous solution particles consisting of tetraethylene glycol monooctyl ether (C8E4) as organic surfactant and sodium chloride (NaCl) as inorganic salt and water (H2O) using single levitated aerosol particles in an electrodynamic balance. The particles can be stored contact-free in a temperature and humidity controlled chamber and optical resonance spectroscopy is used to monitor radius change [4]. Mie resonance spectra of ternary droplets show discontinuous growth with increasing relative humidity (RH) and also discontinuous shrinkage with decreasing relative humidity. We observe this behavior at temperatures and RHs at which the salt is completely deliquesced and the concentration of the organic surfactant is larger than the critical micelle concentration. Independent measurements of particle mass show also discontinuous water uptake. We speculate that this discontinuous, step-like, growth is caused by disaggregation of a micelle needed to conserve the monolayer of surfactant molecules on the aqueous aerosol particle surface upon growing. The number of molecules of the disaggregating micelle can be deduced from the known polar surface area of the C8E4 molecule and the surface area increase of the aerosol particle calculated from the step increase in radius. Our measurements yield a broad distribution of aggregation numbers with a peak aggregation number of 105 molecules. This number agrees reasonably well with aggregate sizes directly observed with Cryo-TEM in a related system [5]. References: [1] Oppo, C., Bellandi, S., Degli Innocenti, N., Stortini, A.M., Loglio, G., Schiavuta, E., & Cini, R., Marine Chemistry, 63, 235-253, 1999. [2] O'Dowd, C.D., Facchini, M.C., Cavalli, F., Ceburnis, D., Mircea, M., Decesari, S., Fuzzi, S., Yoon, Y.J., & Putaud, J.P., Nature, 431, 676-680, 2004. [3] Israelachvili, J.N., Intermolecular and surface forces, Academic press London, 1991. [4] Zardini, A.A., Krieger, U.K., & Marcolli, C., Optics Express, 14, 6951-6962, 2006. [5] Bernheim-Groswasser, A., Wachtel E., & Talmon, Y., Langmuir, 16, 4131-4140, 2000.

40 CFR 63.5752 - How do I calculate the organic HAP content of aluminum recreational boat surface coatings?

Code of Federal Regulations, 2010 CFR

2010-07-01

... clear coat i used in the past 12 months, liters. Di= density of coating i, kilograms per liter. Wi= mass... of thinner, activator, or additive k used in the past 12 months, liters. Dk= density of thinner...

IMPACT OF OIL PRODUCTION RELEASES ON SOME SOIL CHEMICAL PROPERTIES AT THE OSPER SITES

EPA Science Inventory

Surface and soil core samples were collected at two field sites in an old oil production area near Skiatook Lake in Oklahoma. The soil samples were analyzed for nitrates, organic matter, total petroleum hydrocarbons, conductivity, chlorides and dehydrogenase activity. Low level...

Comparison of algorithms and parameterisations for infiltration into organic-covered permafrost soils

USDA-ARS?s Scientific Manuscript database

Infiltration into frozen and unfrozen soils is critical in hydrology, controlling active layer soil water dynamics and influencing runoff. Few Land Surface Models (LSMs) and Hydrological Models (HMs) have been developed, adapted or tested for frozen conditions and permafrost soils. Considering the v...

Spatially selective modification of PLLA surface: From hydrophobic to hydrophilic or to repellent

NASA Astrophysics Data System (ADS)

Bastekova, Kristina; Guselnikova, Olga; Postnikov, Pavel; Elashnikov, Roman; Kunes, Martin; Kolska, Zdenka; Švorčík, Vaclav; Lyutakov, Oleksiy

2017-03-01

A universal approach to controlled surface modification of polylactic acid (PLLA) films using diazonium chemistry was proposed. The multistep procedure includes surface activation of PLLA by argon plasma treatment and chemical activation of arenediazonium tosylates by NaBH4. The surface of PLLA film was grafted with different functional organic groups (OFGs), changing the PLLA surface properties (wettability, morphology, zeta potential, chemical composition, and mechanical response). Three approaches of OFG grafting were examined: (i) plasma treatment following by PLLA immersion into diazonium salt aqueous solution; (ii) grafting of PLLA surface through the reaction with chemically created aryl radicals; (iii) mutual combination of both methods The best results were achieved in the last case, where the previous plasma treatment was combined with further reaction of PLLA surface with generated aryl radicals. Using this method PLLA surface was successfully grafted with amino, carboxyl, aliphatic and fluorinated OFGs. Further investigation of surface properties from potential biological and medical points of view was performed using zeta potential, biodegradation and biofouling tests. It was shown that proposed technique allows preparation of biorepellent or bioabsorptive surfaces, tuning of PLLA biodegradation rate and nanomechanical properties, as well as the introduction of inverse properties (such as hydrophilic and hydrophobic) on both sides of PLLA films.

Comparison of self-cleaning properties of three titania coatings on float glass

NASA Astrophysics Data System (ADS)

Piispanen, Minna; Hupa, Leena

2011-11-01

This work compares the self-cleaning properties of experimental TiO2 and TiO2-Ag coatings on float glass with a commercial self-cleaning glass. In the experimental surfaces, TiO2 coating was applied to float glass via the sol-gel route, while TiO2-Ag coating was applied by the liquid flame spray method, which deposits TiO2-Ag composite nanoparticles on the surface. The effect of the coatings on the surface wettability and the activation time for achieving hydrophilicity was studied through water contact angle as a function of exposure time to UV light. The surface morphology was investigated by using scanning electron microscopy (SEM) and confocal optical microscopy. The photocatalytic activity of the coatings was examined with methylene blue and stearic acid degradation tests. Finally, the soil attachment to the surfaces was tested with a sebum-based model soil. The sol-gel TiO2 coating became superhydrophilic within a few hours, while the activation time needed for the commercial titania coated glass was several days. The surface with the TiO2-Ag nanoparticles did not show any marked changes in the water contact angle. The commercial titania coated and the sol-gel TiO2 surfaces showed self-cleaning properties and clearly lower attachment of soil than the uncoated and TiO2-Ag coated surfaces. The difference in the interaction of the surfaces with the organic contaminants was assumed to depend mainly on differences in the thickness of the coatings.

Electro-optic properties of organic nanotubes.

PubMed

Stoylov, Stoyl P; Stoilova-McPhie, Svetla

2011-08-10

In this review article the theoretical and experimental possibilities of applying EO-methods for estimation of the physico-chemical properties of the organic nanotubes (ONTs) are studied. The ONTs are highly organized nanostructures of strongly elongated, anysometric, and hollow cylinders with a size range of 1 nm to 10,000 nm, e.g. in aqueous solutions they could behave as colloid (disperse) particles. They have high interaction ability due to their extremely large curved, rolled-up external surfaces (bilayers of membrane walls) and unique properties because of their specific electric charge distribution and dynamics that make possible the functionalization of their surfaces. Thus they could template guestsubstances such as membrane proteins and protein complexes on the exterior surfaces and in the membrane. We performed our investigations for the case of ONT aqueous colloid suspension. Following our earlier proposition of the general expression for the electro-optic (EO) effect we derived equations for the evaluation of the electric properties of ONT particles such as mechanism of electric polarization and identification of their most important electric Dipole Moments (DM), permanent (pDM) and induced (iDMs). Further we recommend ways for the calculation of their magnitude and direction. Also we evaluated some geometrical properties such as length of the ONT particles and their polydispersity. The knowledge that we provided about the ONT properties may enable us to elucidate and predict their biological activity. Templating biological active ligands (such as membrane proteins and protein complexes) on the inner and outer surfaces as well as in the surface membrane creates their potential usefulness as carrier and deliverer of biopharmaceuticals in bio-nanodevices. The theoretical equations were compared with the experimental data for ONTs such as (lipid) LNT, Tobacco Mosaic Virus (TMV) and microtubules (MT). Comparison of EO methods with other methods used till now shows that the EO methods are faster, not invasive and do not alter the studied particles. Copyright © 2011 Elsevier B.V. All rights reserved.

The geochemistry of water near a surficial organic-rich uranium deposit, northeastern Washington State, U.S.A.

USGS Publications Warehouse

Zielinski, R.A.; Otton, J.K.; Wanty, R.B.; Pierson, C.T.

1987-01-01

The chemistry of three stream, three spring and six near-surface waters in the vicinity of a Holocene organic-rich uranium deposit is described, with particular emphasis on the chemistry of U. Results characterize the solution behavior of uranium as U-bearing water interacts with relatively undecomposed, surficial organic matter. Of the measured major and trace chemical species, only U is consistently highly enriched (17-318 ppb) relative to reported values for regional waters, or to literature values for waters in largely granitic terrains. R-mode factor analysis of the chemical data suggests that most U is present in a soluble form, but that some U is also associated with fine suspended particulates of clay, organic matter, or hydrous oxides. Calculations that apply thermodynamic data to predict U speciation in solution indicate the relative importance of uranyl carbonate and uranyl phosphate complexes. Analysis of more finely filtered samples (0.05 ??m vs. 0.45 ??m), and direct radiographic observations using fission-track detectors suspended in the waters indicate the presence of some uraniferous particulate matter. Application of existing thermodynamic data for uranous- and uranyl-bearing minerals indicates that all waters are undersaturated with U minerals as long as ambient Eh ??? +0.1 v. If coexisting surface and near-surface waters are sufficiently oxidizing, initial fixation of U in the deposit should be by a mechanism of adsorption. Alternatively, more reducing conditions may prevail in deeper pore waters of the organic-rich host sediments, perhaps leading to direct precipitation or diagenetic formation of U4+ minerals. A 234U 238U alpha activity ratio of 1.08 ?? 0.02 in a spring issuing from a hillslope above the deposit suggests a relatively soluble source of U. In contrast, higher activity ratios of 234U 238U (??? 1.3) in waters in contact with the uraniferous valley-fill sediments suggest differences in the nature of interaction between groundwater and the local, U-rich source rocks. ?? 1987.

CD56 Is a Pathogen Recognition Receptor on Human Natural Killer Cells.

PubMed

Ziegler, Sabrina; Weiss, Esther; Schmitt, Anna-Lena; Schlegel, Jan; Burgert, Anne; Terpitz, Ulrich; Sauer, Markus; Moretta, Lorenzo; Sivori, Simona; Leonhardt, Ines; Kurzai, Oliver; Einsele, Hermann; Loeffler, Juergen

2017-07-21

Aspergillus (A.) fumigatus is an opportunistic fungal mold inducing invasive aspergillosis (IA) in immunocompromised patients. Although antifungal activity of human natural killer (NK) cells was shown in previous studies, the underlying cellular mechanisms and pathogen recognition receptors (PRRs) are still unknown. Using flow cytometry we were able to show that the fluorescence positivity of the surface receptor CD56 significantly decreased upon fungal contact. To visualize the interaction site of NK cells and A. fumigatus we used SEM, CLSM and dSTORM techniques, which clearly demonstrated that NK cells directly interact with A. fumigatus via CD56 and that CD56 is re-organized and accumulated at this interaction site time-dependently. The inhibition of the cytoskeleton showed that the receptor re-organization was an active process dependent on actin re-arrangements. Furthermore, we could show that CD56 plays a role in the fungus mediated NK cell activation, since blocking of CD56 surface receptor reduced fungal mediated NK cell activation and reduced cytokine secretion. These results confirmed the direct interaction of NK cells and A. fumigatus, leading to the conclusion that CD56 is a pathogen recognition receptor. These findings give new insights into the functional role of CD56 in the pathogen recognition during the innate immune response.

Engineering stem cells into organs: Topobiological transformations demonstrated by beak, feather and other ectodermal organ morphogenesis

PubMed Central

Chuong, Cheng-Ming; Wu, Ping; Plikus, Maksim; Jiang, Ting-Xin; Widelitz, Randall Bruce

2015-01-01

To accomplish regenerative medicine, several critical issues in stem cell biology have to be solved, including the identification of sources, expanding populations, building them into organs, and assimilating them to the host. While many stem cells can now differentiate along certain lineages, knowledge on how to use them to build organs lags behind. Here we focus on topobiological events that bridge this gap, i.e., the regulation of number, size, axis, shape, arrangement, and architecture during organogenesis. Rather than reviewing detailed molecular pathways known to disrupt organogenesis when perturbed, we highlight conceptual questions at the topobiological level, and ask how cellular and molecular mechanisms can work to explain these phenomena. The avian integument is used as the Rosetta stone because the molecular activities are linked to organ forms which are visually apparent and have functional consequences during evolution as shown by the fossil record and extant diversity. For example, we show that feather pattern formation is the equilibrium of stochastic interactions among multiple activators and inhibitors. While morphogens and receptors are coded by the genome, the result is based on the summed physical-chemical properties on the whole cell surface and is self-organizing. For another example, we show developing chicken and duck beaks contain differently configured localized growth zones (LoGZ) and can modulate chicken beaks to phenocopy diverse avian beaks in Nature by altering the position, number, size, and duration of LoGZs. Different organs have their unique topology and we also discuss shaping mechanisms of the liver and different ways of branching morphogenesis. Multi-primordia organs (e.g., feathers, hairs, teeth) have additional topographic specificities across the body surface, an appendage field, or within an appendage. Promises and problems in reconstituted feather / hair follicles and other organs are discussed. Finally, simple modifications at the topobiological level may lead to novel morphologies for natural selection at the evolution level. PMID:16564337

The nanoscale spatial organization of B-cell receptors on immunoglobulin M- and G-expressing human B-cells.

PubMed

Lee, Jinmin; Sengupta, Prabuddha; Brzostowski, Joseph; Lippincott-Schwartz, Jennifer; Pierce, Susan K

2017-02-15

B-cell activation is initiated by the binding of antigen to the B-cell receptor (BCR). Here we used dSTORM superresolution imaging to characterize the nanoscale spatial organization of immunoglobulin M (IgM) and IgG BCRs on the surfaces of resting and antigen--activated human peripheral blood B-cells. We provide insights into both the fundamental process of antigen-driven BCR clustering and differences in the spatial organization of IgM and IgG BCRs that may contribute to the characteristic differences in the responses of naive and memory B-cells to antigen. We provide evidence that although both IgM and IgG BCRs reside in highly heterogeneous protein islands that vary in size and number of BCR single-molecule localizations, both resting and activated B-cells intrinsically maintain a high -frequency of single isolated BCR localizations, which likely represent BCR monomers. IgG BCRs are more clustered than IgM BCRs on resting cells and form larger protein islands after antigen activation. Small, dense BCR clusters likely formed via protein-protein interactions are present on the surface of resting cells, and antigen activation induces these to come together to form less dense, larger islands, a process likely governed, at least in part, by protein-lipid interactions. © 2017 Lee, Sengupta, et al. This article is distributed by The American Society for Cell Biology under license from the author(s). Two months after publication it is available to the public under an Attribution–Noncommercial–Share Alike 3.0 Unported Creative Commons License (http://creativecommons.org/licenses/by-nc-sa/3.0).

Surface engineering of nanoparticles in suspension for particle based bio-sensing

PubMed Central

Sen, Tapas; Bruce, Ian J.

2012-01-01

Surface activation of nanoparticles in suspension using amino organosilane has been carried out via strict control of a particle surface ad-layer of water using a simple but efficient protocol ‘Tri-phasic Reverse Emulsion’ (TPRE). This approach produced thin and ordered layers of particle surface functional groups which allowed the efficient conjugation of biomolecules. When used in bio-sensing applications, the resultant conjugates were highly efficient in the hybrid capture of complementary oligonucleotides and the detection of food borne microorganism. TPRE overcomes a number of fundamental problems associated with the surface modification of particles in aqueous suspension viz. particle aggregation, density and organization of resultant surface functional groups by controlling surface condensation of the aminosilane. The approach has potential for application in areas as diverse as nanomedicine, to food technology and industrial catalysis. PMID:22872809

Electrocatalytic oxidation of small organic molecules in acid medium: enhancement of activity of noble metal nanoparticles and their alloys by supporting or modifying them with metal oxides.

PubMed

Kulesza, Pawel J; Pieta, Izabela S; Rutkowska, Iwona A; Wadas, Anna; Marks, Diana; Klak, Karolina; Stobinski, Leszek; Cox, James A

2013-11-01

Different approaches to enhancement of electrocatalytic activity of noble metal nanoparticles during oxidation of small organic molecules (namely potential fuels for low-temperature fuel cells such as methanol, ethanol and formic acid) are described. A physical approach to the increase of activity of catalytic nanoparticles (e.g. platinum or palladium) involves nanostructuring to obtain highly dispersed systems of high surface area. Recently, the feasibility of enhancing activity of noble metal systems through the formation of bimetallic (e.g. PtRu, PtSn, and PdAu) or even more complex (e.g. PtRuW, PtRuSn) alloys has been demonstrated. In addition to possible changes in the electronic properties of alloys, specific interactions between metals as well as chemical reactivity of the added components have been postulated. We address and emphasize here the possibility of utilization of noble metal and alloyed nanoparticles supported on robust but reactive high surface area metal oxides (e.g. WO 3 , MoO 3 , TiO 2 , ZrO 2 , V 2 O 5 , and CeO 2 ) in oxidative electrocatalysis. This paper concerns the way in which certain inorganic oxides and oxo species can act effectively as supports for noble metal nanoparticles or their alloys during electrocatalytic oxidation of hydrogen and representative organic fuels. Among important issues are possible changes in the morphology and dispersion, as well as specific interactions leading to the improved chemisorptive and catalytic properties in addition to the feasibility of long time operation of the discussed systems.

Highly Stable Hierarchical Flower-like β-In2S3 Assembled from 2D Nanosheets with high Adsorption-Photodecolorization Activities for the Treatment of Wastewater

NASA Astrophysics Data System (ADS)

Cheng, Yang; Niu, Helin; Chen, Jingshuai; Song, Jiming; Mao, Changjie; Zhang, Shengyi; Chen, Changle; Gao, Yuanhao

2017-05-01

The hierarchical flower-like β-In2S3 catalyst assembled from 2D nanosheets was prepared using an organic-component depletion method utilizing inorganic-organic hybrids indium diethyldithiocarbamate (In-DDTC) as a single-source precursor. The crystallization, morphology and composition of the as-synthesized β-In2S3 were characterized by XRD, SEM, TEM, EDS and XPS, respectively. The β-In2S3 possessed high specific surface area of 134.1 m2 g-1, adsorption capacity of 195.5 mg g-1 for methylene blue, and extreme photodecolorization speed under visible light irradiation for the complete removal of methyl orange (MO) dye within 15 min and tetracycline within 60 min. Although methyl orange concentration decreased quickly, the total organic carbon (TOC) decreased slowly. UV-vis and mass spectrometry (MS) were applied to analyze the intermediates coming from the photodecolorization of MO. In order to estimate the roles of active species during the decolorization of MO, trapping experiments were conducted to determine the main active species during the decolorization process. The results indicated that . O2 - radicals and e-1 were the key intermediates. This enhanced activity was attributed to its unique structures assembled from 2D nanosheets with thickness of ca. 5-7 nm, leading to high specific surface area, wide range of pore size distribution and great efficiency in absorbing light and electron/hole separation. The hierarchical flower-like β-In2S3 demonstrated great advantages in the treatment of various wastewater pollutants including textile dyes and antibiotics.

Electrocatalytic oxidation of small organic molecules in acid medium: enhancement of activity of noble metal nanoparticles and their alloys by supporting or modifying them with metal oxides

PubMed Central

Kulesza, Pawel J.; Pieta, Izabela S.; Rutkowska, Iwona A.; Wadas, Anna; Marks, Diana; Klak, Karolina; Stobinski, Leszek; Cox, James A.

2013-01-01

Different approaches to enhancement of electrocatalytic activity of noble metal nanoparticles during oxidation of small organic molecules (namely potential fuels for low-temperature fuel cells such as methanol, ethanol and formic acid) are described. A physical approach to the increase of activity of catalytic nanoparticles (e.g. platinum or palladium) involves nanostructuring to obtain highly dispersed systems of high surface area. Recently, the feasibility of enhancing activity of noble metal systems through the formation of bimetallic (e.g. PtRu, PtSn, and PdAu) or even more complex (e.g. PtRuW, PtRuSn) alloys has been demonstrated. In addition to possible changes in the electronic properties of alloys, specific interactions between metals as well as chemical reactivity of the added components have been postulated. We address and emphasize here the possibility of utilization of noble metal and alloyed nanoparticles supported on robust but reactive high surface area metal oxides (e.g. WO3, MoO3, TiO2, ZrO2, V2O5, and CeO2) in oxidative electrocatalysis. This paper concerns the way in which certain inorganic oxides and oxo species can act effectively as supports for noble metal nanoparticles or their alloys during electrocatalytic oxidation of hydrogen and representative organic fuels. Among important issues are possible changes in the morphology and dispersion, as well as specific interactions leading to the improved chemisorptive and catalytic properties in addition to the feasibility of long time operation of the discussed systems. PMID:24443590

Microbicidal effects of weakly acidified chlorous acid water against feline calicivirus and Clostridium difficile spores under protein-rich conditions

PubMed Central

Goda, Hisataka; Yamaoka, Hitoshi; Nakayama-Imaohji, Haruyuki; Kawata, Hiroyuki; Horiuchi, Isanori; Fujita, Yatsuka; Nagao, Tamiko; Tada, Ayano; Terada, Atsushi; Kuwahara, Tomomi

2017-01-01

Sanitation of environmental surfaces with chlorine based-disinfectants is a principal measure to control outbreaks of norovirus or Clostridium difficile. The microbicidal activity of chlorine-based disinfectants depends on the free available chlorine (FAC), but their oxidative potential is rapidly eliminated by organic matter. In this study, the microbicidal activities of weakly acidified chlorous acid water (WACAW) and sodium hypochlorite solution (NaClO) against feline calcivirus (FCV) and C. difficile spores were compared in protein-rich conditions. WACAW inactivated FCV and C. difficile spores better than NaClO under all experimental conditions used in this study. WACAW above 100 ppm FAC decreased FCV >4 log10 within 30 sec in the presence of 0.5% each of bovine serum albumin (BSA), polypeptone or meat extract. Even in the presence of 5% BSA, WACAW at 600 ppm FAC reduced FCV >4 log10 within 30 sec. Polypeptone inhibited the virucidal activity of WACAW against FCV more so than BSA or meat extract. WACAW at 200 ppm FAC decreased C. difficile spores >3 log10 within 1 min in the presence of 0.5% polypeptone. The microbicidal activity of NaClO was extensively diminished in the presence of organic matter. WACAW recovered its FAC to the initial level after partial neutralization by sodium thiosulfate, while no restoration of the FAC was observed in NaClO. These results indicate that WACAW is relatively stable under organic matter-rich conditions and therefore may be useful for treating environmental surfaces contaminated by human excretions. PMID:28472060

Effect of lipid/polysaccharide ratio on surface activity of model root mucilage in its solid and liquid states

NASA Astrophysics Data System (ADS)

Chen, Fengxian; Arye, Gilboa

2016-04-01

The rhizosphere can be defined as the volume of soil around living roots, which is influenced by root activity. The biological, chemical and physical conditions that prevail in the rhizosphere are significantly different from those of the bulk soil. Plant roots can release diverse organic materials in the rhizosphere which may have different effects on its bio-chemo-physical activity. Among these exudates is the root mucilage which can play a role on the maintenance of root-soil contact, lubrication of the root tip, protection of roots from desiccation and disease, stabilization of soil micro-aggregates and the selective absorption and storage of ions. The surface activity of the root mucilage at the liquid-air interface deduced from its surface tension depression relative to water, implying on its amphiphilic nature. Consequently as the rhizosphere dry out, hydrophobic functional groups may exhibit orientation at the solid-air interface and thus, the wettability of the rhizosphere may temporarily decrease. The major fraction of the root mucilage comprise of polysaccharides and to a much lesser extent, amino acids, organic acids, and phospholipids. The most frequent polysaccharide and phospholipids detected in root mucilage are polygalacturonic acid (PGA) and Phosphatidylcholine (PC), respectively. The latter, is thought to be main cause for the surface active nature of root mucilage. Nevertheless, the role and function of root mucilage in the rhizosphere is commonly studied based on model root mucilage that comprise of only one component, where the most frequent ones are PGA or PC (or lecithin). The main objective of this study was to quantify the effect of concentration and PGA/PC ratios on the wettability of a model rhizosphere soil and the surface tension of the model root mucilage at the liquid-air interface. The PGA/PC mixtures were measured for their equilibrium and dynamic surface tension using the Wilhelmy-Plate method. Quartz sand or glass slides were coated with PGA and/or PC using the above solutions and measured for their initial advancing contact angle and dynamic one, using the capillary rise and sessile drop methods, respectively. The results of this study will be presented and their implications for the wettability of the rhizosphere will be discussed.

On a non-thermal atmospheric pressure plasma jet used for the deposition of silicon-organic films

NASA Astrophysics Data System (ADS)

Schäfer, Jan; Sigeneger, Florian; Foest, Rüdiger; Loffhagen, Detlef; Weltmann, Klaus-Dieter

2018-05-01

This work represents a concise overview on the results achieved by the authors over the last years on the plasma of a non-thermal reactive plasma jet at atmospheric pressure and of related thin film formation by plasma enhanced chemical vapour deposition (PECVD). The source was developed considering the application of the plasma self-organization for PECVD. The experimental methods comprise spectroscopic measurements of plasma parameters in the active zone, temperature measurements in the active zone and the effluent as well as the analysis of deposited films at the substrate surface. The theoretical investigations are devoted to a single filament in the active zone using a phase-resolved model and to an overall description of the jet including the substrate using a period-averaged model.

Metal-Organic Framework-Templated Porous Carbon for Highly Efficient Catalysis: The Critical Role of Pyrrolic Nitrogen Species.

PubMed

Huang, Gang; Yang, Li; Ma, Xiao; Jiang, Jun; Yu, Shu-Hong; Jiang, Hai-Long

2016-03-01

Metal-free catalysts are of great importance and alternative candidates to conventional metal-based catalysts for many reactions. Herein, several types of metal-organic frameworks have been exploited as templates/precursors to afford porous carbon materials with various nitrogen dopant forms and contents, degrees of graphitization, porosities, and surface areas. Amongst these materials, the PCN-224-templated porous carbon material optimized by pyrolysis at 700 °C (denoted as PCN-224-700) is composed of amorphous carbon coated with well-defined graphene layers, offering a high surface area, hierarchical pores, and high nitrogen content (mainly, pyrrolic nitrogen species). Remarkably, as a metal-free catalyst, PCN-224-700 exhibits a low activation energy and superior activity to most metallic catalysts in the catalytic reduction of 4-nitrophenol to 4-aminophenol. Theoretical investigations suggest that the content and type of the nitrogen dopant play crucial roles in determining the catalytic performance and that the pyrrolic nitrogen species makes the dominant contribution to this activity, which explains the excellent efficiency of the PCN-224-700 catalyst well. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

CO2 leakage from carbon dioxide capture and storage (CCS) systems affects organic matter cycling in surface marine sediments.

PubMed

Rastelli, Eugenio; Corinaldesi, Cinzia; Dell'Anno, Antonio; Amaro, Teresa; Greco, Silvestro; Lo Martire, Marco; Carugati, Laura; Queirós, Ana M; Widdicombe, Stephen; Danovaro, Roberto

2016-12-01

Carbon dioxide capture and storage (CCS), involving the injection of CO 2 into the sub-seabed, is being promoted worldwide as a feasible option for reducing the anthropogenic CO 2 emissions into the atmosphere. However, the effects on the marine ecosystems of potential CO 2 leakages originating from these storage sites have only recently received scientific attention, and little information is available on the possible impacts of the resulting CO 2 -enriched seawater plumes on the surrounding benthic ecosystem. In the present study, we conducted a 20-weeks mesocosm experiment exposing coastal sediments to CO 2 -enriched seawater (at 5000 or 20,000 ppm), to test the effects on the microbial enzymatic activities responsible for the decomposition and turnover of the sedimentary organic matter in surface sediments down to 15 cm depth. Our results indicate that the exposure to high-CO 2 concentrations reduced significantly the enzymatic activities in the top 5 cm of sediments, but had no effects on subsurface sediment horizons (from 5 to 15 cm depth). In the surface sediments, both 5000 and 20,000 ppm CO 2 treatments determined a progressive decrease over time in the protein degradation (up to 80%). Conversely, the degradation rates of carbohydrates and organic phosphorous remained unaltered in the first 2 weeks, but decreased significantly (up to 50%) in the longer term when exposed at 20,000 ppm of CO 2 . Such effects were associated with a significant change in the composition of the biopolymeric carbon (due to the accumulation of proteins over time in sediments exposed to high-pCO 2 treatments), and a significant decrease (∼20-50% at 5000 and 20,000 ppm respectively) in nitrogen regeneration. We conclude that in areas immediately surrounding an active and long-lasting leak of CO 2 from CCS reservoirs, organic matter cycling would be significantly impacted in the surface sediment layers. The evidence of negligible impacts on the deeper sediments should be considered with caution and further investigated simulating the intrusion of CO 2 from a subsurface source, as occurring during real CO 2 leakages from CCS sites. Copyright © 2016 Elsevier Ltd. All rights reserved.

Concentration Effects of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Activity for Three Platinum Catalysts

DOE PAGES

Christ, J. M.; Neyerlin, K. C.; Richards, R.; ...

2014-10-04

A rotating disk electrode (RDE) along with cyclic voltammetry (CV) and linear sweep voltammetry (LSV), were used to investigate the impact of two model compounds representing degradation products of Nafion and 3M perfluorinated sulfonic acid membranes on the electrochemical surface area (ECA) and oxygen reduction reaction (ORR) activity of polycrystalline Pt, nano-structured thin film (NSTF) Pt (3M), and Pt/Vulcan carbon (Pt/Vu) (TKK) electrodes. ORR kinetic currents (measured at 0.9 V and transport corrected) were found to decrease linearly with the log of concentration for both model compounds on all Pt surfaces studied. Ultimately, model compound adsorption effects on ECA weremore » more abstruse due to competitive organic anion adsorption on Pt surfaces superimposing with the hydrogen underpotential deposition (HUPD) region.« less

Ecosystem productivity is associated with bacterial phylogenetic distance in surface marine waters.

PubMed

Galand, Pierre E; Salter, Ian; Kalenitchenko, Dimitri

2015-12-01

Understanding the link between community diversity and ecosystem function is a fundamental aspect of ecology. Systematic losses in biodiversity are widely acknowledged but the impact this may exert on ecosystem functioning remains ambiguous. There is growing evidence of a positive relationship between species richness and ecosystem productivity for terrestrial macro-organisms, but similar links for marine micro-organisms, which help drive global climate, are unclear. Community manipulation experiments show both positive and negative relationships for microbes. These previous studies rely, however, on artificial communities and any links between the full diversity of active bacterial communities in the environment, their phylogenetic relatedness and ecosystem function remain hitherto unexplored. Here, we test the hypothesis that productivity is associated with diversity in the metabolically active fraction of microbial communities. We show in natural assemblages of active bacteria that communities containing more distantly related members were associated with higher bacterial production. The positive phylogenetic diversity-productivity relationship was independent of community diversity calculated as the Shannon index. From our long-term (7-year) survey of surface marine bacterial communities, we also found that similarly, productive communities had greater phylogenetic similarity to each other, further suggesting that the traits of active bacteria are an important predictor of ecosystem productivity. Our findings demonstrate that the evolutionary history of the active fraction of a microbial community is critical for understanding their role in ecosystem functioning. © 2015 John Wiley & Sons Ltd.

The earthworm gastrointestinal effect on the release of organic bound residues in soils

NASA Astrophysics Data System (ADS)

Du, J. H.

2018-03-01

Earthworm activities promote the release of bound residues and the digestive activities of earthworms contribute to the process. Earthworm digestive effects on bound residues can be divided into physical and chemical effects. Physical effects include gastrointestinal abrasion and mixing. The abrasion of soil and litter residues in earthworm gizzards and intestine can grind the food into fine particles, which increase the contact surface with microbial and promote the desorption of bound residues. Chemical effects are attributed to the secreted surfactant substances and digestive enzymes. The surfactants, especially at levels that lead to micellization, can enhance the desorption process of the organic contaminants that sored in the soil. The enzymes in earthworm digestive tracts can decompose the humus in soil, which may promote the release of organic residues that bind with humus.

Biochar modification to enhance sorption of inorganics from water.

PubMed

Sizmur, Tom; Fresno, Teresa; Akgül, Gökçen; Frost, Harrison; Moreno-Jiménez, Eduardo

2017-12-01

Biochar can be used as a sorbent to remove inorganic pollutants from water but the efficiency of sorption can be improved by activation or modification. This review evaluates various methods to increase the sorption efficiency of biochar including activation with steam, acids and bases and the production of biochar-based composites with metal oxides, carbonaceous materials, clays, organic compounds, and biofilms. We describe the approaches, and explain how each modification alters the sorption capacity. Physical and chemical activation enhances the surface area or functionality of biochar, whereas modification to produce biochar-based composites uses the biochar as a scaffold to embed new materials to create surfaces with novel surface properties upon which inorganic pollutants can sorb. Many of these approaches enhance the retention of a wide range of inorganic pollutants in waters, but here we provide a comparative assessment for Cd 2+ , Cu 2+ , Hg 2+ , Pb 2+ , Zn 2+ , NH 4 + , NO 3 - , PO 4 3- , CrO 4 2- and AsO 4 3- . Copyright © 2017 Elsevier Ltd. All rights reserved.

Organ Dose Assessment and Evaluation of Cancer Risk on Mars Surface

NASA Technical Reports Server (NTRS)

Kim, Myung-Hee; Cucinotta, Francis A.

2011-01-01

Organ specific fluence spectra and doses for large solar particle events (SPE) and galactic cosmic rays (GCR) at various levels of solar activity are simulated on the surface of Mars using the HZETRN/QMSFRG computer code and the 2010 version of the Badhwar and O Neill GCR model. The NASA JSC propensity model of SPE fluence and occurrence is used to consider upper bounds on SPE fluence for increasing mission lengths. To account for the radiation transmission through the Mars atmosphere, a vertical distribution of Mars atmospheric thickness is calculated from the temperature and pressure data of Mars Global Surveyor. To describe the spherically distributed atmospheric distance on the Mars surface at each elevation, the directional cosine distribution is implemented. The resultant directional shielding by Mars atmosphere at each elevation is then coupled with vehicle and body shielding for organ dose estimates. Finally, cancer risks for astronauts exploring Mars can be assessed by applying the NASA Space Radiation Cancer Risk 2010 model with the resultant organ dose estimates. Variations of organ doses and cancer risk quantities on the surface of Mars, which are due to a 16-km elevation range between the Tharsis Montes and the Hellas impact basin, are visualized on the global topography of Mars measured by the Mars Orbiter Laser Altimeter. It is found that cancer incidence risks are about 2-fold higher than mortality risks with a disproportionate increase in skin and thyroid cancers for male and female astronauts and in breast cancer for female astronauts. The number of safe days, defined by the upper 95% percent confidence level to be below cancer limits, on Mars is analyzed for several Mars mission design scenarios.

Transport and transportation pathways of hazardous chemicals from solid waste disposal.

PubMed Central

Van Hook, R I

1978-01-01

To evaluate the impact of hazardous chemicals in solid wastes on man and other organisms, it is necessary to have information about amounts of chemical present, extent of exposure, and chemical toxicity. This paper addresses the question of organism exposure by considering the major physical and biological transport pathways and the physicochemical and biochemical transformations that may occur in sediments, soils, and water. Disposal of solid wastes in both terrestrial and oceanic environments is considered. Atmospheric transport is considered for emissions from incineration of solid wastes and for wind resuspension of particulates from surface waste deposits. Solid wastes deposited in terrestrial environments are subject to leaching by surface and ground waters. Leachates may then be transported to other surface waters and drinking water aquifers through hydrologic transport. Leachates also interact with natural organic matter, clays, and microorganisms in soils and sediments. These interactions may render chemical constituents in leachates more or less mobile, possibly change chemical and physical forms, and alter their biological activity. Oceanic waste disposal practices result in migration through diffusion and ocean currents. Surface area-to-volume ratios play a major role in the initial distributions of chemicals in the aquatic environment. Sediments serve as major sources and sinks of chemical contaminants. Food chain transport in both aquatic and terrestrial environments results in the movement of hazardous chemicals from lower to higher positions in the food web. Bioconcentration is observed in both terrestrial and aquatic food chains with certain elements and synthetic organics. Bioconcentration factors tend to be higher for synthetic organics, and higher in aquatic than in terrestrial systems. Biodilution is not atypical in terrestrial environments. Synergistic and antagonistic actions are common occurrences among chemical contaminants and can be particularly important toxicity considerations in aquatic environments receiving runoff from several terrestrial sources. PMID:367772

Antifouling activity in some benthic Antarctic invertebrates by "in situ" experiments at Deception Island, Antarctica.

PubMed

Angulo-Preckler, Carlos; Cid, Cristina; Oliva, Francesc; Avila, Conxita

2015-04-01

Competition for space is a remarkable ecological force, comparable to predation, producing a strong selective pressure on benthic invertebrates. Some invertebrates, thus, possess antimicrobial compounds to reduce surface bacterial growth. Antimicrobial inhibition is the first step in avoiding being overgrown by other organisms, which may have a negative impact in feeding, respiration, reproduction … The in situ inhibition of bacterial biofilm was used here as an indicator of antifouling activity by testing hydrophilic extracts of twelve Antarctic invertebrates. Using two different approaches (genetics and confocal techniques) different levels of activity were found in the tested organisms. In fact, differences within body parts of the studied organisms were determined, in agreement with the Optimal Defense Theory. Eight out of 15 extracts tested had negative effects on fouling after 28 days submerged in Antarctic waters. Thus, although chemical defenses may be quite species-specific in their ecological roles, these results suggest that different chemical strategies exist to deal with space competition. Copyright © 2015 Elsevier Ltd. All rights reserved.

A Structural and Molecular Approach for the Study Biomarkers

NASA Technical Reports Server (NTRS)

Thomas-Keprta, Kathie; Vali, Hojatollah; Sears, S. Kelly; Roh, Yul

2001-01-01

Investigation of the nucleation and growth of crystals in both abiotic and biotic systems is critical to seemingly diverse disciplines of geology, biology, environmental science, and astrobiology. While there are abundant studies devoted to the determination of the structure and composition of inorganic crystals, as well as to the development of thermodynamic and kinetic models, it is only recently that research efforts have been directed towards understanding mineralization in biological systems (i.e., biomineralization). Biomineralization refers to the processes by which living organisms form inorganic solids. Studies of the processes of biomineralization under low temperature aqueous conditions have focused primarily on magnetite forming bacteria and shell forming marine organisms. Many of the biological building materials consist of inorganic minerals (calcium carbonate, calcium phosphate, silica or iron oxide) intricately combined with organic polymers (like proteins). More recently, efforts have been undertaken to explore the nature of biological activities in ancient rocks. In the absence of well-preserved microorganisms or genetic material required for the polmerase chain reaction (PCR) method in molecular phylogenetic studies, using biominerals as biomarkers offers an alternative approach for the recognition of biogenic activity in both terrestrial and extraterrestrial environments. The primary driving force in biomineralization is the interaction between organic and inorganic phases. Thus, the investigation of the ultrastructure and the nature of reactions at the molecular level occurring at the interface between inorganic and organic phases is essential to understanding the processes leading to the nucleation and growth of crystals. It is recognized that crystal surfaces can serve as the substrate for the organization of organic molecules that lead to the formation of polymers and other complex organic molecules, and in discussions of the origins of life, is referred to as organic synthesis on mineral surfaces. Furthermore, it is suggested that the interaction between mineral surfaces and simple organic molecules resulted in the formation of amino acids, RNA, and perhaps other more complex molecules such as proteins. On the other hand, in natural systems, it is recognized that functional groups on cell walls or membranes of microorganisms serve as sites of nucleation and crystallization. The precise replication of biominerals with controlled structure, morphology, size and texture is not confined to higher organisms as it also occurs in primitive prokaryotic cells such as magnetotactic bacteria and cyanobacteria. This suggests that the principal strategies of biomineralization were established early on in the evolutionary history of organisms. It is critical, therefore, to search for common mechanisms within diverse biological systems. One such common factor is the capability for organization and self-assembly. Organic macromolecules such as proteins and lipids can aggregate and polymerize forming membranes or extracellular matrix. At the organic-inorganic interface, several factors such as lattice geometry, polarity, stereochemistry and topography may act in concert to control nucleation and growth of crystals. Although several models have been proposed that discuss the significance of these factors for biomineralization, no comprehensive experimental data are available. In contrast to crystallization in exclusively inorganic systems, the kinetics of reaction and structural relationships between organic and inorganic phases in biominerals or biomimetic material is poorly understood. For example, it is not clear if the concept of epitactic growth (geometrical matching of unit cells at the interface of a secondary crystal growing on a primary crystal) applies to organic-inorganic systems. In contrast to inorganic templates that often have a smooth and rigid surface that promotes epitactic growth, biological substrates are usually rough and result in a large degree of mismatch. It is apparent that factors controlling the reaction at the crystal-matrix interface are strongly dependent upon the nature of the substrate. Therefore, characterization of the assembled organic surface and surface structure of the inorganic phase is crucial to understanding the processes of biomineralization. The focus of our research is the investigation of the processes leading to the nucleation and growth of crystals on both natural and synthetic systems through an interdisciplinary approach that integrates molecular biology, morphology and mineralogy using advanced preparation and analytical techniques. We have studied run-products, particularly magnetite, siderite and other carbonates, that resulted from extracellular biomineralization by extremophiles isolated from a variety of extreme environments ranging from permafrost to hydrothermal vent systems. The results of this study are critical to recognizing biomarkers in terrestrial and extraterrestrial environments.

High Sensitivity Stress Sensor Based on Hybrid Materials

NASA Technical Reports Server (NTRS)

Cao, Xian-An (Inventor)

2014-01-01

A sensing device is used to detect the spatial distributions of stresses applied by physical contact with the surface of the sensor or induced by pressure, temperature gradients, and surface absorption. The sensor comprises a hybrid active layer that includes luminophores doped in a polymeric or organic host, altogether embedded in a matrix. Under an electrical bias, the sensor simultaneously converts stresses into electrical and optical signals. Among many applications, the device may be used for tactile sensing and biometric imaging.

Mineral induced phosphorylation of glycolate ion--a metaphor in chemical evolution

NASA Technical Reports Server (NTRS)

Kolb, V.; Zhang, S.; Xu, Y.; Arrhenius, G.

1997-01-01

Bilateral surface-active minerals with excess positive charge concentrate glycolate and trimetaphosphate ion from l0(-3) m aqueous solution to half-saturation of the internal surface sites, and induce phosphorylation of glycolate ion in the mineral with trimetaphosphate, sorbed from l0(-2) m solution. By utilizing reactants from dilute solution at near-neutral pH, and eliminating the need for participating organic nitrogen compounds, the reaction comprises several elements considered necessary for geochemical realism in models for molecular evolution.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bartels, Ludwig; Ernst, Karl-Heinz; Gao, Hong-Jun

Supramolecular self-assembly at surfaces is one of the most exciting and active fields in Surface Science today. Applications can take advantage of two key properties: (i) versatile pattern formation over a broad length scale and (ii) tunability of electronic structure and transport properties, as well as frontier orbital alignment. It provides a new frontier for Chemical Physics as it uniquely combines the versatility of Organic Synthesis and the Physics of Interfaces. The Journal of Chemical Physics is pleased to publish this Special Topic Issue, showcasing recent advances and new directions.

The MarsOrganiX experiment: Understanding the influence of the secondary X-Rays on the organic matter at Mars' near-surface.

NASA Astrophysics Data System (ADS)

Buch, A.; Szopa, C.; Freissinet, C.; Stalport, F.; Coscia, D.; Pavlov, A.; Gilbert, P.; Bonnet, J. Y.; Guerrini, V.; Navarro-Gonzalez, R.

2017-12-01

Mars may have harbored a prebiotic chemistry that could have led to the emergence of life. If such, traces of these could be preserved in the oldest (3.5 billion years and more) rocks at the surface of the planet. Because of the thin atmosphere of Mars and the absence of an active magnetic field, the harsh radiative environment at the near-surface consists of UV and X-ray radiation, galactic and solar cosmic rays (GCRs and SCRs), as well as secondary particles produced by the interaction of GCRs and SCRs with the atmosphere and soil (secondary X-rays). The majority of the X-rays at the martian surface are generated in the rocks by the penetrating GCR and SCR particles. The GCRs' secondary X-rays' absorbed dose, at the top centimeters of the surface of Mars, has been estimated at about 0.05 Gy per year. All these radiation (direct and indirect) are prone to induce extended degradation or transformation of organic matter that would be present at Mars' near-surface, down to the 3 m depth of the GCRs/SCRs penetration. The SAM experiment onboard Curiosity rover led to the first in situ detection of organic molecules in martian rocks and soils. Chlorobenzene was detected in Cumberland at a concentration of up to 300 parts per billion in weight. However, chlorobenzene was thought to be formed in the SAM oven, during the pyrolysis of the sample. Nevertheless, Cumberland sample has been exposed to GCRs and SCRs for about 80 million years, and thus, the undergone X-rays radiation may have processed the organic matter and chlorinated the organic molecules in presence of perchlorate. Therefore, this study aims at evaluating the possible precursor(s), that would lead to the formation of chlorobenzene (detected with SAM) when irradiated in presence of perchlorate. Using the PSICHE beam line at SOLEIL, a synchrotron facility in France, we studied the extend of degradation and transformation of two organic molecules of interest, a carboxylic acid (benzoic acid) and an amino acid (L-alanine) in absence and presence of perchlorate, under the simulated X-rays radiative environments present at Mars' near-surface. The solid and gaseous phases of the samples were analyzed to evaluate the potential degradation of the molecules during irradiation (MS) and to characterize the residual organic content after irradiation in the retrieved samples (FTIR and GCMS).

NREL: Renewable Resource Data Center - Solar Resource Related Links

Science.gov Websites

the world. Baseline Surface Radiation Network (BSRN) Measures solar and atmospheric radiation at change. EnergyPlus Weather Data Offers weather data, arranged by World Meteorological Organization region and country, for more than 1,300 locations throughout the world. NASA Langley Distributed Active

Ground Water in a Fish Tank.

ERIC Educational Resources Information Center

Mayshark, Robin K.

1992-01-01

Describes creating a Model Aquatic/Terrestrial Ecosystem for use in helping students understand how water moves beneath the ground's surface. The model is constructed from a fish tank using rocks, soil, gravel, clay, and organic materials. Author describes possible cooperative-learning and problem-solving activities that can be done with this…

Monolayer-Mediated Growth of Organic Semiconductor Films with Improved Device Performance.

PubMed

Huang, Lizhen; Hu, Xiaorong; Chi, Lifeng

2015-09-15

Increased interest in wearable and smart electronics is driving numerous research works on organic electronics. The control of film growth and patterning is of great importance when targeting high-performance organic semiconductor devices. In this Feature Article, we summarize our recent work focusing on the growth, crystallization, and device operation of organic semiconductors intermediated by ultrathin organic films (in most cases, only a monolayer). The site-selective growth, modified crystallization and morphology, and improved device performance of organic semiconductor films are demonstrated with the help of the inducing layers, including patterned and uniform Langmuir-Blodgett monolayers, crystalline ultrathin organic films, and self-assembled polymer brush films. The introduction of the inducing layers could dramatically change the diffusion of the organic semiconductors on the surface and the interactions between the active layer with the inducing layer, leading to improved aggregation/crystallization behavior and device performance.

Macrophyte disturbance alters aquatic surface microlayer structure, metabolism, and fate.

PubMed

Seliskar, Denise M; Gallagher, John L

2014-03-01

Macrophytes drive the functioning of many salt marsh ecosystem components. We questioned how temporary clearing of the macrophyte community, during restoration, would impact processes at the scale of the aquatic surface microlayer. Development, deposition, and breakup of the tidal creek surface microlayer were followed over tidal cycles seasonally in a cleared "former" Phragmites marsh and an adjacent restored Spartina marsh. Metabolic and physical processes of the mobile surface microlayers and underlying water were compared, along with distribution of organic and inorganic components onto simulated plant stems. In July and October, chlorophyll-a quantities were less on simulated stems in the cleared site than in the restored site. The aquatic microlayer in the cleared site creek exhibited lower photosynthesis and respiration rates, fewer diatoms and green algae, and less chlorophyll-a. There was a lower concentration (250 times) and reduced diversity of fatty acids in the surface microlayer of the cleared site, reflecting a smaller and less diverse microbial community and reduced food resources. Fiddler crab activity was an order of magnitude higher where macrophytes had been cleared. Their consumption of edaphic algae on the mud surface may account for the reduced algae and other organics in the creek surface microlayer, thus representing a redirection of this food resource from creek consumers. Overall, there were less total particulates in the creek surface microlayer at the cleared site, and they dropped out of the surface microlayer sooner in the tidal cycle, resulting in a lower sediment load available for deposit onto marsh surfaces.

Organic extract of diesel exhaust particles stimulates expression of Ia and costimulatory molecules associated with antigen presentation in rat peripheral blood monocytes but not in alveolar macrophages

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koike, Eiko; Kobayashi, Takahiro

2005-12-15

We hypothesized that diesel exhaust particles (DEP) induce the activation of antigen-presenting cells (APC) in lung. The present study was designed to clarify the following about DEP: (1) whether it affects the expression of Ia and B7 molecules in alveolar macrophages (AM) as a mature cell or in peripheral blood monocytes (PBM) as an immature cell (2) if it affects the antigen-presenting (AP) activity of PBM (3) what component of DEP is responsible for the effects, and (4) whether the effect of DEP is related to oxidative stress. DEP was extracted with methylene chloride. Cells were exposed to whole DEP,more » organic extract, or residual particles for 24 h. Cell-surface molecules were measured by flow cytometry. AP activity was assessed by antigen-specific T cell proliferation. Whole DEP or organic extract significantly increased the expression of Ia and B7 molecules on PBM but not on AM. No significant effect of residual particles was observed. A low concentration of organic extract also increased the AP activity of PBM. When the induction of an antioxidative enzyme was assessed, heme oxygenase-1 protein was found to be significantly increased by exposure to whole DEP, and the organic extract was more effective than the residual particles. Furthermore, the organic extract-induced expression of Ia antigen on PBM was reduced by the addition of an antioxidative agent. These results suggest that DEP may act on immature APC and enhance their AP activity and that the action contributing to oxidative stress may be mediated by organic compounds of DEP.« less

Organic photodetectors and their applications for hemispherical imaging focal plane arrays

NASA Astrophysics Data System (ADS)

Xu, Xin

Softness of organic semiconducting materials holds promise for fabricating optoelectronic devices and circuits on nonplanar surfaces. The low growth temperature of organic small molecules also allows for the deposition onto a plastic substrate, which has the potential for significantly lowering the fabrication cost. However, the softness of organic small molecules can become problematic. Most of the well-established patterning techniques in the semiconductor industry are not suitable for patterning organic-based devices. High temperatures, high pressures, exposure to wet chemicals or high-energy particles that may exist in the conventional patterning approaches can damage the organic active layers. Although methods for large area patterning of organic electronics onto planar substrates have been demonstrated, in this thesis we extend the patterning capability to curved surfaces by using a novel three dimensional (3D) cold welding method. We use 3D cold welding to fabricate a hemispherical focal plane array (FPA) for compact imaging systems that mimic the architecture and function of the human eye. A 10 kilopixel organic photodetector FPA is thus demonstrated on a 1 cm radius hemisphere. By patterning brittle yet transparent indium tin oxide anodes instead of semitransparent metal anodes on the hemispheres, the detectivity of the FPA is improved. We introduce a sensitive hybrid photodetector employing a carbon nanotube/small molecular organic junction with a broad spectral response extending into the near infrared. Since the photodetector array shows an increased noise level with the array size, integrated arrays of organic photodetectors and thin film transistors as switches are demonstrated.

Cloud Activation Potentials for Atmospheric α-Pinene and β-Caryophyllene Ozonolysis Products.

PubMed

Gray Bé, Ariana; Upshur, Mary Alice; Liu, Pengfei; Martin, Scot T; Geiger, Franz M; Thomson, Regan J

2017-07-26

The formation of atmospheric cloud droplets due to secondary organic aerosol (SOA) particles is important for quantifying the Earth's radiative balance under future, possibly warmer, climates, yet is only poorly understood. While cloud activation may be parametrized using the surface tension depression that coincides with surfactant partitioning to the gas-droplet interface, the extent to which cloud activation is influenced by both the chemical structure and reactivity of the individual molecules comprising this surfactant pool is largely unknown. We report herein considerable differences in the surface tension depression of aqueous pendant droplets that contain synthetically prepared ozonolysis products derived from α-pinene and β-caryophyllene, the most abundant of the monoterpenes and sesquiterpenes, respectively, that are emitted over the planet's vast forest ecosystems. Oxidation products derived from β-caryophyllene were found to exhibit significantly higher surface activity than those prepared from α-pinene, with the critical supersaturation required for cloud droplet activation reduced by 50% for β-caryophyllene aldehyde at 1 mM. These considerable reductions in the critical supersaturation were found to coincide with free energies of adsorption that exceed ∼25 kJ/mol, or just one hydrogen bond equivalent, depending on the ammonium sulfate and oxidation product concentration in the solution. Additional experiments showed that aldehyde-containing oxidation products exist in equilibrium with hydrated forms in aqueous solution, which may modulate their bulk solubility and surface activity. Equilibration time scales on the order of 10 -5 to 10 -4 s calculated for micrometer-sized aerosol particles indicate instantaneous surface tension depression in the activation processes leading to cloud formation in the atmosphere. Our findings highlight the underlying importance of molecular structure and reactivity when considering cloud condensation activity in the presence of SOA particles.

Structural hierarchy in molecular films of two class II hydrophobins.

PubMed

Paananen, Arja; Vuorimaa, Elina; Torkkeli, Mika; Penttilä, Merja; Kauranen, Martti; Ikkala, Olli; Lemmetyinen, Helge; Serimaa, Ritva; Linder, Markus B

2003-05-13

Hydrophobins are highly surface-active proteins that are specific to filamentous fungi. They function as coatings on various fungal structures, enable aerial growth of hyphae, and facilitate attachment to surfaces. Little is known about their structures and structure-function relationships. In this work we show highly organized surface layers of hydrophobins, representing the most detailed structural study of hydrophobin films so far. Langmuir-Blodgett films of class II hydrophobins HFBI and HFBII from Trichoderma reesei were prepared and analyzed by atomic force microscopy. The films showed highly ordered two-dimensional crystalline structures. By combining our recent results on small-angle X-ray scattering of hydrophobin solutions, we found that the unit cells in the films have dimensions similar to those of tetrameric aggregates found in solutions. Further analysis leads to a model in which the building blocks of the two-dimensional crystals are shape-persistent supramolecules consisting of four hydrophobin molecules. The results also indicate functional and structural differences between HFBI and HFBII that help to explain differences in their properties. The possibility that the highly organized surface assemblies of hydrophobins could allow a route for manufacturing functional surfaces is suggested.

Molecular Photovoltaics in Nanoscale Dimension

PubMed Central

Burtman, Vladimir; Zelichonok, Alexander; Pakoulev, Andrei V.

2011-01-01

This review focuses on the intrinsic charge transport in organic photovoltaic (PVC) devices and field-effect transistors (SAM-OFETs) fabricated by vapor phase molecular self-assembly (VP-SAM) method. The dynamics of charge transport are determined and used to clarify a transport mechanism. The 1,4,5,8-naphthalene-tetracarboxylic diphenylimide (NTCDI) SAM devices provide a useful tool to study the fundamentals of polaronic transport at organic surfaces and to discuss the performance of organic photovoltaic devices in nanoscale. Time-resolved photovoltaic studies allow us to separate the charge annihilation kinetics in the conductive NTCDI channel from the overall charge kinetic in a SAM-OFET device. It has been demonstrated that tuning of the type of conductivity in NTCDI SAM-OFET devices is possible by changing Si substrate doping. Our study of the polaron charge transfer in organic materials proposes that a cation-radical exchange (redox) mechanism is the major transport mechanism in the studied SAM-PVC devices. The role and contribution of the transport through delocalized states of redox active surface molecular aggregates of NTCDI are exposed and investigated. This example of technological development is used to highlight the significance of future technological development of nanotechnologies and to appreciate a structure-property paradigm in organic nanostructures. PMID:21339983

Effect of organic matter on cyanide removal by illuminated titanium dioxide or zinc oxide nanoparticles

PubMed Central

2013-01-01

Effect of different type of organic compounds (humic acid, oxalate, ethylenediaminetetraacetic acid, nitrilotriacetic acid, phenol) on the photocatalytic removal of cyanide with TiO2 or ZnO was studied in this work with variation of the solution pH, contact time, initial cyanide concentration and type of organic compounds. Photocatalytic oxidation efficiency of cyanide with TiO2 was greatly affected by the solution pH. It increased as the solution pH decreased. Also maximum removal of cyanide by ZnO was observed near at neutral pH because of the reduced photocatalytic activity of ZnO at exceedingly low and high pH values originated from either acidic/photochemical corrosion of the catalyst and/or surface passivation with Zn(OH)2. Removal efficiency of cyanide greatly decreased in the presence of humic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid compared to that without presence of organic compound because of the competitive oxidation as well as surface blocking by relatively large organic compounds. The oxidation pattern of cyanide was better described by first-order kinetic model. Finally photocatalytic reaction with TiO2 or ZnO can be effectively applied to treat synthetic wastewater contaminated with cyanide. PMID:24499704

Salt-induced square prism Pd microtubes and their ethanol electrocatalysis properties

NASA Astrophysics Data System (ADS)

Jiang, Kunpeng; Ma, Shenghua; Wang, Yinan; Zhang, Ying; Han, Xiaojun

2017-05-01

The synthesis of square prism tubes are always challenging due to their thermo and dynamical instability. We demonstrated a simple method using Pd2+ doped PoPD oligomers as building blocks to assemble into 1D square prism metal-organic microtubes, which consists of cataphracted nanosheets on the surfaces. After high temperature treatment, the microtubes became square prism Pd tubes with a cross section size of 3 μm. The pure Pd microtubes showed excellent catalyzing activity towards the electro oxidation of ethanol. Their electrochemically active surface area is 48.2 m2 g-1, which indicates the square prism Pd tubes have great potential in the field of fuel cell.

Real-time x-ray studies of crystal growth modes during metal-organic vapor phase epitaxy of GaN on c- and m-plane single crystals

DOE PAGES

Perret, Edith; Highland, M. J.; Stephenson, G. B.; ...

2014-08-04

Non-polar orientations of III-nitride semiconductors have attracted significant interest due to their potential application in optoelectronic devices with enhanced efficiency. Using in-situ surface x-ray scattering during metal-organic vapor phase epitaxy (MOVPE) of GaN on non-polar (m-plane) and polar (c-plane) orientations of single crystal substrates, we have observed the homoepitaxial growth modes as a function of temperature and growth rate. On the m-plane surface we observe all three growth modes (step-flow, layer-by-layer, and three-dimensional) as conditions are varied. In contrast, the +c-plane surface exhibits a direct cross over between step-flow and 3-D growth, with no layer-by-layer regime. The apparent activation energymore » of 2.8 ± 0.2 eV observed for the growth rate at the layer-by-layer to step-flow boundary on the m-plane surface is consistent with those observed for MOVPE growth of other III-V compounds, indicating a large critical nucleus size for islands.« less

To Covary or Not to Covary, That is the Question

NASA Astrophysics Data System (ADS)

Oehlert, A. M.; Swart, P. K.

2016-12-01

The meaning of covariation between the δ13C values of carbonate carbon and that of organic material is classically interpreted as reflecting original variations in the δ13C values of the dissolved inorganic carbon in the depositional environment. However, recently it has been shown by the examination of a core from Great Bahama Bank (Clino) that during exposure not only do the rocks become altered acquiring a negative δ13C value, but at the same time terrestrial vegetation adds organic carbon to the system masking the original marine values. These processes yield a strong positive covariation between δ13Corg and δ13Ccar values even though the signals are clearly not original and unrelated to the marine δ13C values. Examining the correlation between the organic and inorganic system in a stratigraphic sense at Clino and in a second more proximally located core (Unda) using a windowed correlation coefficient technique reveals that the correlation is even more complex. Changes in slope and the magnitude of the correlation are associated with exposure surfaces, facies changes, dolomitized bodies, and non-depositional surfaces. Finally other isotopic systems such as the δ13C value of specific organic compounds as well as δ15N values of bulk and individual compounds can provide additional information. In the case of δ15N values, decreases reflect a changes in the influence of terrestrial organic material and an increase contribution of organic material from the platform surface where the main source of nitrogen is derived from the activities of cyanobacteria.

Effect of PAC dosage in a pilot-scale PAC-MBR treating micro-polluted surface water.

PubMed

Hu, Jingyi; Shang, Ran; Deng, Huiping; Heijman, Sebastiaan G J; Rietveld, Luuk C

2014-02-01

To address the water scarcity issue and advance the traditional drinking water treatment technique, a powdered activated carbon-amended membrane bioreactor (PAC-MBR) is proposed for micro-polluted surface water treatment. A pilot-scale study was carried out by initially dosing different amounts of PAC into the MBR. Comparative results showed that 2g/L performed the best among 0, 1, 2 and 3g/L PAC-MBR regarding organic matter and ammonia removal as well as membrane flux sustainability. 1g/L PAC-MBR exhibited a marginal improvement in pollutant removal compared to the non-PAC system. The accumulation of organic matter in the bulk mixture of 3g/L PAC-MBR led to poorer organic removal and severer membrane fouling. Molecular weight distribution of the bulk liquid in 2g/L PAC-MBR revealed the synergistic effects of PAC adsorption/biodegradation and membrane rejection on organic matter removal. Additionally, a lower amount of soluble extracellular polymer substances in the bulk can be secured in 21 days operation. Copyright © 2013 Elsevier Ltd. All rights reserved.

Application of a mixed metal oxide catalyst to a metallic substrate

NASA Technical Reports Server (NTRS)

Sevener, Kathleen M. (Inventor); Lohner, Kevin A. (Inventor); Mays, Jeffrey A. (Inventor); Wisner, Daniel L. (Inventor)

2009-01-01

A method for applying a mixed metal oxide catalyst to a metallic substrate for the creation of a robust, high temperature catalyst system for use in decomposing propellants, particularly hydrogen peroxide propellants, for use in propulsion systems. The method begins by forming a prepared substrate material consisting of a metallic inner substrate and a bound layer of a noble metal intermediate. Alternatively, a bound ceramic coating, or frit, may be introduced between the metallic inner substrate and noble metal intermediate when the metallic substrate is oxidation resistant. A high-activity catalyst slurry is applied to the surface of the prepared substrate and dried to remove the organic solvent. The catalyst layer is then heat treated to bind the catalyst layer to the surface. The bound catalyst layer is then activated using an activation treatment and calcinations to form the high-activity catalyst system.

Organic matter in sediment layers of an acidic mining lake as assessed by lipid analysis. Part II: Neutral lipids.

PubMed

Poerschmann, Juergen; Koschorreck, Matthias; Górecki, Tadeusz

2017-02-01

Natural neutralization of acidic mining lakes is often limited by organic matter. The knowledge of the sources and degradability of organic matter is crucial for understanding alkalinity generation in these lakes. Sediments collected at different depths (surface sediment layer from 0 to 1 cm and deep sediment layer from 4 to 5cm) from an acidic mining lake were studied in order to characterize sedimentary organic matter based on neutral signature markers. Samples were exhaustively extracted, subjected to pre-chromatographic derivatizations and analyzed by GC/MS. Herein, molecular distributions of diagnostic alkanes/alkenes, terpenes/terpenoids, polycyclic aromatic hydrocarbons, aliphatic alcohols and ketones, sterols, and hopanes/hopanoids were addressed. Characterization of the contribution of natural vs. anthropogenic sources to the sedimentary organic matter in these extreme environments was then possible based on these distributions. With the exception of polycyclic aromatic hydrocarbons, combined concentrations across all marker classes proved higher in the surface sediment layer as compared to those in the deep sediment layer. Alkane and aliphatic alcohol distributions pointed to predominantly allochthonous over autochthonous contribution to sedimentary organic matter. Sterol patterns were dominated by phytosterols of terrestrial plants including stigmasterol and β-sitosterol. Hopanoid markers with the ββ-biohopanoid "biological" configuration were more abundant in the surface sediment layer, which pointed to higher bacterial activity. The pattern of polycyclic aromatic hydrocarbons pointed to prevailing anthropogenic input. Pyrolytic makers were likely to due to atmospheric deposition from a nearby former coal combustion facility. The combined analysis of the array of biomarkers provided new insights into the sources and transformations of organic matter in lake sediments. Copyright © 2016 Elsevier B.V. All rights reserved.

Gas-phase formaldehyde adsorption isotherm studies on activated carbon: correlations of adsorption capacity to surface functional group density.

PubMed

Carter, Ellison M; Katz, Lynn E; Speitel, Gerald E; Ramirez, David

2011-08-01

Formaldehyde (HCHO) adsorption isotherms were developed for the first time on three activated carbons representing one activated carbon fiber (ACF) cloth, one all-purpose granular activated carbon (GAC), and one GAC commercially promoted for gas-phase HCHO removal. The three activated carbons were evaluated for HCHO removal in the low-ppm(v) range and for water vapor adsorption from relative pressures of 0.1-0.9 at 26 °C where, according to the IUPAC isotherm classification system, the adsorption isotherms observed exhibited Type V behavior. A Type V adsorption isotherm model recently proposed by Qi and LeVan (Q-L) was selected to model the observed adsorption behavior because it reduces to a finite, nonzero limit at low partial pressures and it describes the entire range of adsorption considered in this study. The Q-L model was applied to a polar organic adsorbate to fit HCHO adsorption isotherms for the three activated carbons. The physical and chemical characteristics of the activated carbon surfaces were characterized using nitrogen adsorption isotherms, X-ray photoelectron spectroscopy (XPS), and Boehm titrations. At low concentrations, HCHO adsorption capacity was most strongly related to the density of basic surface functional groups (SFGs), while water vapor adsorption was most strongly influenced by the density of acidic SFGs.

[Priming effect of biochar on the minerialization of native soil organic carbon and the mechanisms: A review.

PubMed

Chen, Ying; Liu, Yu Xue; Chen, Chong Jun; Lyu, Hao Hao; Wa, Yu Ying; He, Li Li; Yang, Sheng Mao

2018-01-01

In recent years, studies on carbon sequestration of biochar in soil has been in spotlight owing to the specific characteristics of biochar such as strong carbon stability and well developed pore structure. However, whether biochar will ultimately increase soil carbon storage or promote soil carbon emissions when applied into the soil? This question remains controversial in current academic circles. Further research is required on priming effect of biochar on mineralization of native soil organic carbon and its mechanisms. Based on the analysis of biochar characteristics, such as its carbon composition and stability, pore structure and surface morphology, research progress on the priming effect of biochar on the decomposition of native soil organic carbon was reviewed in this paper. Furthermore, possible mechanisms of both positive and negative priming effect, that is promoting and suppressing the mineralization, were put forward. Positive priming effect is mainly due to the promotion of soil microbial activity caused by biochar, the preferential mineralization of easily decomposed components in biochar, and the co-metabolism of soil microbes. While negative priming effect is mainly based on the encapsulation and adsorption protection of soil organic matter due to the internal pore structure and the external surface of biochar. Other potential reasons for negative priming effect can be the stabilization resulted from the formation of organic-inorganic complex promoted by biochar in the soil, and the inhibition of activity of soil microbes and its enzymes by biochar. Finally, future research directions were proposed in order to provide theoretical basis for the application of biochar in soil carbon sequestration.

Protein Surface Softness Is the Origin of Enzyme Cold-Adaptation of Trypsin

PubMed Central

Isaksen, Geir Villy; Åqvist, Johan; Brandsdal, Bjørn Olav

2014-01-01

Life has effectively colonized most of our planet and extremophilic organisms require specialized enzymes to survive under harsh conditions. Cold-loving organisms (psychrophiles) express heat-labile enzymes that possess a high specific activity and catalytic efficiency at low temperatures. A remarkable universal characteristic of cold-active enzymes is that they show a reduction both in activation enthalpy and entropy, compared to mesophilic orthologs, which makes their reaction rates less sensitive to falling temperature. Despite significant efforts since the early 1970s, the important question of the origin of this effect still largely remains unanswered. Here we use cold- and warm-active trypsins as model systems to investigate the temperature dependence of the reaction rates with extensive molecular dynamics free energy simulations. The calculations quantitatively reproduce the catalytic rates of the two enzymes and further yield high-precision Arrhenius plots, which show the characteristic trends in activation enthalpy and entropy. Detailed structural analysis indicates that the relationship between these parameters and the 3D structure is reflected by significantly different internal protein energy changes during the reaction. The origin of this effect is not localized to the active site, but is found in the outer regions of the protein, where the cold-active enzyme has a higher degree of softness. Several structural mechanisms for softening the protein surface are identified, together with key mutations responsible for this effect. Our simulations further show that single point-mutations can significantly affect the thermodynamic activation parameters, indicating how these can be optimized by evolution. PMID:25165981

Impact of Polymer Colonization on the Fate of Organic Contaminants in Sediment.

PubMed

Wu, Chen-Chou; Bao, Lian-Jun; Liu, Liang-Ying; Shi, Lei; Tao, Shu; Zeng, Eddy Y

2017-09-19

Plastic pellets and microbes are important constitutes in sediment, but the significance of microbes colonizing on plastic pellets to the environmental fate and transport of organic contaminants has not been adequately recognized and assessed. To address this issue, low-density polyethylene (LDPE), polyoxymethylene (POM) and polypropylene (PP) slices were preloaded with dichlorodiphenyltrichloroethanes (DDTs), polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) and incubated in abiotic and biotic sediment microcosms. Images from scanning electron microscope, Lysogeny Broth agar plates and confocal laser scanning microscope indicated that all polymer slices incubated in biotic sediments were colonized by microorganisms, particularly the LDPE slices. The occurrence of biofilms induced higher dissipation rates of DDTs and PAHs from the LDPE slice surfaces incubated in the biotic sediments than in the abiotic sediments. Plastic colonization on LDPE slice surfaces enhanced the biotransformation of DDT and some PAHs in both marine and river sediments, but had little impact on PCBs. By comparison, PP and POM with unique properties were shown to exert different impacts on the physical and microbial activities as compared to LDPE. These results clearly demonstrated that the significance of polymer surface affiliated microbes to the environmental fate and behavior of organic contaminants should be recognized.

Excitation of surface plasmon polaritons by fluorescent light from organic nanofibers

NASA Astrophysics Data System (ADS)

Sobolewska, Elżbieta Karolina; Józefowski, Leszek; Kawalec, Tomasz; Leißner, Till; Rubahn, Horst-Günter; Adam, Jost; Fiutowski, Jacek

2017-11-01

Micro- and nano-scale systems with defined active elements acting as local surface plasmons polariton (SPP) sources are crucial for the development of future plasmonic circuits. We demonstrate SPP excitation by fluorescent light from crystalline organic para-hexaphenylene nanofibers deposited on a dielectric/metal surface. We characterize the SPPs using angle-resolved leakage radiation spectroscopy, in the excitation wavelength range 420 - 675 nm, corresponding to the nanofiber photoluminescence band. The nanofiber arrangement's capability to act as an SPP coupler for coherent as well as non-coherent excitation indicates its prospect for future integrated systems. To support our experimental results, we investigate the proposed geometries by analytical calculations and finite-difference-time-domain (FDTD) modelling. The experimentally obtained angular leakage radiation peak positions can readily be predicted by our analytical calculations. Nevertheless, the experimental results exhibit a distinct asymmetry in the peak intensities. In agreement with our FDTD calculations, we address this asymmetrical SPP excitation to the nanofiber molecular orientation. The proposed structure's high flexibility, the ease of selective positioning of organic nanofibers, together with the gained insight into its photon-SPP coupling mechanism show great promise towards future local SPP excitation-based integrated devices.

An efficient hybrid, nanostructured, epoxidation catalyst: titanium silsesquioxane-polystyrene copolymer supported on SBA-15.

PubMed

Zhang, Lei; Abbenhuis, Hendrikus C L; Gerritsen, Gijsbert; Bhriain, Nollaig Ní; Magusin, Pieter C M M; Mezari, Brahim; Han, Wei; van Santen, Rutger A; Yang, Qihua; Li, Can

2007-01-01

A novel interfacial hybrid epoxidation catalyst was designed with a new immobilization method for homogeneous catalysts by coating an inorganic support with an organic polymer film containing active sites. The titanium silsesquioxane (TiPOSS) complex, which contains a single-site titanium active center, was immobilized successfully by in-situ copolymerization on a mesoporous SBA-15-supported polystyrene polymer. The resulting hybrid materials exhibit attractive textural properties (highly ordered mesostructure, large specific surface area (>380 m2 g-1) and pore volume (>or==0.46 cm3 g-1)), and high activity in the epoxidation of alkenes. In the epoxidation of cyclooctene with tert-butyl hydrogen peroxide (TBHP), the hybrid catalysts have rate constants comparable with that of their homogeneous counterpart, and can be recycled at least seven times. They can also catalyze the epoxidation of cyclooctene with aqueous H2O2 as the oxidant. In two-phase reaction media, the catalysts show much higher activity than their homogeneous counterpart due to the hydrophobic environment around the active centers. They behave as interfacial catalysts due to their multifunctionality, that is, the hydrophobicity of polystyrene and the polyhedral oligomeric silsesquioxanes (POSS), and the hydrophilicity of the silica and the mesoporous structure. Combination of the immobilization of homogeneous catalysts on two conventional supports, inorganic solid and organic polymer, is demonstrated to achieve novel heterogeneous catalytic ensembles with the merits of attractive textural properties, tunable surface properties, and optimized environments around the active sites.

Efforts of a Kansas foundation to increase physical activity and improve health by funding community trails, 2012.

PubMed

Heinrich, Katie M; Lightner, Joseph; Oestman, Katherine B; Hughey, S Morgan; Kaczynski, Andrew T

2014-11-26

Trails are associated with increased physical activity; however, little is known about the process of building trails by various types of organizations. From 2005 through 2012 the Sunflower Foundation: Health Care for Kansans (Sunflower) funded multiple organizations to construct 70 trails of varying lengths and surfaces in municipalities, schools, and communities across Kansas. The purpose of this study was to assess the process of developing and implementing community trail projects across Kansas with funding from a public foundation. In 2012, we stratified funded organizations by type and conducted proportional random sampling to select 20 key informants from those organizations to participate in structured telephone interviews. Interviews were recorded and transcribed verbatim. Two researchers coded interview transcripts according to issues identified by participants. Issues associated with trail-building identified as important were collaboration among groups, unexpected construction costs, champions for the project, and level of difficulty of construction. Participants indicated that trails facilitated physical activity. Trails were integrated into communities through events such as walking events and other promotional efforts; these efforts were thought to increase trail use. The perceived outcomes of building the trails included providing the community with a physical activity resource, inspiring the community to start additional trail projects, and increasing the physical activity of local residents. Sunflower's funding was instrumental in developing trail projects to provide new physical activity resources across Kansas. Public health practitioners seeking to increase physical activity should seek funding from foundations that focus on health.

A study on the interactions of Aurein 2.5 with bacterial membranes.

PubMed

Dennison, Sarah R; Morton, Leslie H G; Shorrocks, Andrea J; Harris, Frederick; Phoenix, David A

2009-02-01

Aurein 2.5 (GLFDIVKKVVGAFGSL-NH(2)) is an uncharacterised antimicrobial peptide. At an air/water interface, it exhibited strong surface activity (maximal surface pressure 25mNm(-1)) and molecular areas consistent with the adoption of alpha-helical structure orientated either perpendicular (1.72nm(2)molecule(-1)) or parallel (3.6nm(2)molecule(-1)) to the interface. Aurein 2.5 was strongly antibacterial, exhibiting a minimum inhibitory concentration (MIC) of 30microM against Bacillus subtilis and Escherichia coli. The peptide induced maximal surface pressure changes of 9mNm(-1) and 5mNm(-1), respectively, in monolayers mimicking membranes of these organisms whilst compression isotherm analysis of these monolayers showed DeltaG(Mix)>0, indicating destabilisation by Aurein 2.5. These combined data suggested that toxicity of the peptide to these organisms may involve membrane invasion via the use of oblique orientated alpha-helical structure. The peptide induced strong, comparable maximal surface changes in monolayers of DOPG (7.5mNm(-1)) and DOPE monolayers (6mNm(-1)) suggesting that the membrane interactions of Aurein 2.5 were driven by amphiphilicity rather than electrostatic interaction. Based on these data, it was suggested that the differing ability of Aurein 2.5 to insert into membranes of B. subtilis and E. coli was probably related to membrane-based factors such as differences in lipid packing characteristics. The peptide was active against both sessile E. coli and Staphylococcus aureus with an MIC of 125microM. The broad-spectrum antibacterial activity and non-specific modes of membrane action used by Aurein 2.5 suggested use as an anti-biofilm agent such as in the decontamination of medical devices.

Photoelectrochemical Degradation of Organic Compounds Coupled with Molecular Hydrogen Generation Using Electrochromic TiO2 Nanotube Arrays.

PubMed

Koo, Min Seok; Cho, Kangwoo; Yoon, Jeyong; Choi, Wonyong

2017-06-06

Vertically aligned TiO 2 nanotube arrays (TNTs) were prepared by electrochemical anodization, and then cathodically polarized with dark blue coloration for the dual-functional photoelectrochemical water treatment of organic substrates degradation and accompanying H 2 generation. The resulting Blue-TNTs (inner diameter: ∼40 nm; length: ∼9 μm) showed negligible shift in X-ray diffraction pattern compared with the intact TNTs, but the X-ray photoelectron spectra indicated a partial reduction of Ti 4+ to Ti 3+ on the surface. The electrochemical analyses of Blue-TNTs revealed a marked enhancement in donor density and electrical conductivity by orders of magnitude. Degradations of test organic substrates on Blue-TNTs were compared with the intact TNTs in electrochemical (EC), photocatalytic (PC), and photoelectrochemical (PEC) conditions (potential bias: 1.64 V NHE ; λ > 320 nm). The degradation of 4-chlorophenol was greatly enhanced on Blue-TNTs particularly in PEC condition, whereas the PC activities of the Blue- and intact TNTs were similar. The potential bias of 1.64 V NHE did not induce any noticeable activity in EC condition. Similar trends were observed for the degradation of humic acid and fulvic acid, where main working oxidants were found to be the surface hydroxyl radical as confirmed by hydroxyl radical probe and scavenger tests. H 2 generation coupled with the organic degradation was observed only in PEC condition, where the H 2 generation rate with Blue-TNTs was more than doubled from that of intact TNTs. Such superior PEC activity was not observed when a common TiO 2 nanoparticle film was used as a photoanode. The enhanced electric conductivity of Blue-TNTs coupled with a proper band bending in PEC configuration seemed to induce a highly synergic enhancement.

Effects of the low Earth orbital environment on spacecraft materials

NASA Technical Reports Server (NTRS)

Leger, L. J.

1986-01-01

It is evident from space flights during the last three years that the low Earth orbital (LEO) environment interacts with spacecraft surfaces in significant ways. One manifestation of these interactions is recession of, in particular, organic-polymer-based surfaces presumably due to oxidation by atomic oxygen, the major component of the LEO environment. Three experiments have been conducted on Space Shuttle flights 5, 8 and 41-G to measure reaction rates and the effects of various parameters on reaction rates. Surface recession on these flights indicates reaction efficiencies approximately 3 x 10(-24) cu cm/atoms for unfilled organic polymers. Of the metals, silver and osmium are very reactive. Effects on spacecraft or experiment surfaces can be evaluated using the derived reaction efficiencies and a definition of the total exposure to atomic oxygen. This exposure is obtained using an ambient density model, solar activity data and spacecraft parameters of altitude, attitude and operational date. Oxygen flux on a given surface is obtained from the ambient density and spacecraft velocity and can then be integrated to provide the total exposure or fluence. Such information can be generated using simple computational programs and can be converted to various formats. Overall, the extent of damage is strongly dependent on the type of surface and total exposure time.

Osteogenic activity and antibacterial effect of porous titanium modified with metal-organic framework films.

PubMed

Chen, Junyu; Zhang, Xin; Huang, Chao; Cai, He; Hu, Shanshan; Wan, Qianbing; Pei, Xibo; Wang, Jian

2017-03-01

As a new class of crystalline nanoporous materials, metal-organic frameworks (MOFs) have recently been used for biomedical applications due to their large surface area, high porosity, and theoretically infinite structures. To improve the biological performance of titanium, MOF films were applied to surface modification of titanium. Zn-based MOF films composed of zeolitic imidazolate framework-8 (ZIF-8) crystals with nanoscale and microscale sizes (nanoZIF-8 and microZIF-8) were prepared on porous titanium surfaces by hydrothermal and solvothermal methods, respectively. The ZIF-8 films were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The nanoZIF-8 film exhibited good biocompatibility, whereas the microZIF-8 film showed obvious cytotoxicity to MG63 cells. Compared to pure titanium and alkali- and heat-treated porous titanium, the nanoZIF-8 film not only enhanced alkaline phosphatase (ALP) activity, extracellular matrix mineralization, and expression of osteogenic genes (ALP, Runx2) in MG63 cells but also inhibited the growth of Streptococcus mutans. These results indicate that MOF films or coatings may be promising candidates for bone tissue engineering. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 834-846, 2017. © 2016 Wiley Periodicals, Inc.

Enhanced antibacterial activity and biocompatibility of zinc-incorporated organic-inorganic nanocomposite coatings via electrophoretic deposition.

PubMed

Huang, Pin; Ma, Kena; Cai, Xinjie; Huang, Dan; Yang, Xu; Ran, Jiabing; Wang, Fushi; Jiang, Tao

2017-12-01

Increased use of reconstruction procedures in orthopedics has improved the life of patients undergoing surgery. However, surgical site infection remains a major challenge. Efforts were made to fabricate antibacterial surfaces with good biocompatibility. This present study aimed to fabricate zinc-incorporated chitosan/gelatin (CS/G) nanocomposite coatings on the titanium substrates via electrophoretic deposition (EPD). Physicochemical characterization confirmed that zinc was successfully deposited in a metallic oxide/salt complex status. Transmission electron microscopic (TEM) results observed formation of core-shell nanosized particles released from the coatings. The selected-area electron diffraction (SAED) pattern of the particles presented faces of ZnO with organic background. Mechanical tests showed improved tensile and shear bond strength between substrates and zinc-incorporated coating surfaces. Zinc-incorporated CS/G coatings presented antibacterial abilities against both Gram-negative E. coli and Gram-positive S. aureus in a concentration-dependent manner. The generation of ZnO/Zn 2+ complex in the coatings may contribute to bacteria inhibition. In vitro study demonstrated that appropriate concentration of zinc could promote proliferative and osteogenic activities of rat bone marrow stromal cells. The present study suggested that zinc-incorporated CS/G coating was a promising candidate for surface modification of biomedical materials. Copyright © 2017 Elsevier B.V. All rights reserved.

Anthropogenic tritium in the Loire River estuary, France

NASA Astrophysics Data System (ADS)

Péron, O.; Gégout, C.; Reeves, B.; Rousseau, G.; Montavon, G.; Landesman, C.

2016-12-01

This work is carried out in the frame of a radioecological monitoring of anthropogenic tritium from upstream and downstream of several nuclear power plants along the Loire River to its estuary. This paper studies the variation of anthropogenic tritium species in the Loire River system from upstream to the mouth of the estuary. Tritiated water (HTO and HTO in sediment pore water) and organically bound tritium (OBT) forms were analysed after dedicated pre-treatments. The collected environmental samples consist in (i) surface-sediment and core samples from the river floor, (ii) surface and water column samples. A maximum 3H activity concentration of 26 ± 3 Bq·L- 1 in the Loire River estuary is obtained whereas an environmental background level around 1 Bq·L- 1 is determined for a non influenced continental area by anthropogenic activities. The European follow-up indicator used as a screening value is 100 Bq·L- 1. The conservative tritium behaviour was used in order to characterize the tidal regime and river flow influences in the mixing zone of the Loire River estuary. Furthermore, OBT levels and total organically carbon (TOC) content are explored. Finally, ratios of OBT relative to HTO in sediment pore water in surface-sediment and core samples are also discussed.

Influence of natural organic matter on equilibrium adsorption of neutral and charged pharmaceuticals onto activated carbon.

PubMed

de Ridder, D J; Verliefde, A R D; Heijman, S G J; Verberk, J Q J C; Rietveld, L C; van der Aa, L T J; Amy, G L; van Dijk, J C

2011-01-01

Natural organic matter (NOM) can influence pharmaceutical adsorption onto granular activated carbon (GAC) by direct adsorption competition and pore blocking. However, in the literature there is limited information on which of these mechanisms is more important and how this is related to NOM and pharmaceutical properties. Adsorption batch experiments were carried out in ultrapure, waste- and surface water and fresh and NOM preloaded GAC was used. Twenty-one pharmaceuticals were selected with varying hydrophobicity and with neutral, negative or positive charge. The influence of NOM competition and pore blocking could not be separated. However, while reduction in surface area was similar for both preloaded GACs, up to 50% lower pharmaceutical removal was observed on wastewater preloaded GAC. This was attributed to higher hydrophobicity of wastewater NOM, indicating that NOM competition may influence pharmaceutical removal more than pore blocking. Preloaded GAC was negatively charged, which influenced removal of charged pharmaceuticals significantly. At a GAC dose of 6.7 mg/L, negatively charged pharmaceuticals were removed for 0-58%, while removal of positively charged pharmaceuticals was between 32-98%. Charge effects were more pronounced in ultrapure water, as it contained no ions to shield the surface charge. Solutes with higher log D could compete better with NOM, resulting in higher removal.

Holographic patterning of organic-inorganic photopolymerizable nanocomposites

NASA Astrophysics Data System (ADS)

Sakhno, Oksana V.; Goldenberg, Leonid M.; Smirnova, Tatiana N.; Stumpe, J.

2009-09-01

We present here novel easily processible organic-inorganic nanocomposites suitable for holographic fabrication of diffraction optical elements (DOE). The nanocomposites are based on photocurable acrylate monomers and inorganic nanoparticles (NP). The compatibility of inorganic NP with monomers was achieved by capping the NP surface with proper organic shells. Surface modification allows to introduce up to 50wt.% of inorganic NP in organic media. Depending on the NP nature (metal oxides, phosphates, semiconductors, noble metals) and their properties, the materials for both efficient DOE and multifunctional elements can be designed. Organic-inorganic composites prepared have been successfully used for the effective inscription of periodic volume refractive index structures using the holographic photopolymerization method. The nanocomposite preparation procedure, their properties and optical performance of holographic gratings are reported. The use of functional NP makes it possible to obtain effective holographic gratings having additional physical properties such as light-emission or NLO. Some examples of such functional polymer-NP structures and their possible application fields are presented. The combination of easy photo-patterning of soft organic compounds with physical properties of inorganic materials in new nanocomposites and the flexibility of the holographic patterning method allow the fabrication of mono- and multifunctional one- and multi-dimensional passive or active optical and photonic elements.

Combined effects of physiologically relevant disturbed wall shear stress and glycated albumin on endothelial cell functions associated with inflammation, thrombosis and cytoskeletal dynamics.

PubMed

Maria, Zahra; Yin, Wei; Rubenstein, David Alan

2014-07-01

Diabetes mellitus is a major risk factor in the development of cardiovascular diseases (CVDs). The presence of advanced glycation end-products (AGEs) promotes CVDs by upregulating endothelial cell (EC) inflammatory and thrombotic responses, in a similar manner as disturbed shear stress. However, the combined effect of disturbed shear stress and AGEs on EC function has yet to be determined. Our goal was to evaluate these effects on EC responses. ECs were incubated with AGEs for 5 days. ECs were then subjected to physiological or pathological shear stress. Cell metabolic activity, surface expression of intercellular adhesion molecule-1, thrombomodulin, connexin-43 and caveolin-1, and cytoskeleton organization were quantified. The results show that irreversibly glycated albumin and pathological shear stress increased EC metabolic activity, and upregulated and downregulated the EC surface expression of intercellular adhesion molecule-1 and thrombomodulin, respectively. Expression of connexin-43, caveolin-1 and cytoskeletal organization was independent of shear stress; however, the presence of irreversibly glycated AGEs markedly increased connexin-43, and decreased caveolin-1 expression and actin cytoskeletal connectivity. Our data suggest that irreversibly glycated albumin and disturbed shear stress could promote CVD pathogenesis by enhancing EC inflammatory and thrombotic responses, and through the deterioration of the cytoskeletal organization.

Controllable Spatial Configuration on Cathode Interface for Enhanced Photovoltaic Performance and Device Stability.

PubMed

Li, Jiangsheng; Duan, Chenghao; Wang, Ning; Zhao, Chengjie; Han, Wei; Jiang, Li; Wang, Jizheng; Zhao, Yingjie; Huang, Changshui; Jiu, Tonggang

2018-05-08

The molecular structure of cathode interface modification materials can affect the surface morphology of the active layer and key electron transfer processes occurring at the interface of polymer solar cells in inverted structures mostly due to the change of molecular configuration. To investigate the effects of spatial configuration of the cathode interfacial modification layer on polymer solar cells device performances, we introduced two novel organic ionic salts (linear NS2 and three-dimensional (3D) NS4) combined with the ZnO film to fabricate highly efficient inverted solar cells. Both organic ionic salts successfully decreased the surface traps of the ZnO film and made its work function more compatible. Especially NS4 in three-dimensional configuration increased the electron mobility and extraction efficiency of the interfacial film, leading to a significant improvement of device performance. Power conversion efficiency (PCE) of 10.09% based on NS4 was achieved. Moreover, 3D interfacial modification could retain about 92% of its initial PCE over 160 days. It is proposed that 3D interfacial modification retards the element penetration-induced degradation without impeding the electron transfer from the active layer to the ZnO film, which significantly improves device stability. This indicates that inserting three-dimensional organic ionic salt is an efficient strategy to enhance device performance.

Scaling trace organic contaminant adsorption capacity by granular activated carbon.

PubMed

Corwin, Christopher J; Summers, R Scott

2010-07-15

The role of particle size on the reduction of granular activated carbon (GAC) adsorption capacity for trace organic contaminants by dissolved organic matter (DOM) is examined and applied to performance scale-up. The adsorption capacity reduction, termed fouling, must be scalable in order to use bench scale tests, such as the rapid small-scale column test (RSSCT) to predict full-scale breakthrough. Equilibrium adsorption capacity tests with GAC preloaded with DOM and RSSCT breakthrough curves at three different GAC particle sizes indicate that GAC adsorption capacity is dependent on GAC particle size when DOM is present. Thus, the RSSCT cannot be expected to match full-scale results regardless of which RSSCT design approach is used (constant or proportional diffusivity), unless a scaling factor is applied to the results. Proportional diffusivity RSSCT breakthrough curves demonstrate that surface concentration of DOM is not a good measure of fouling. It is hypothesized that pore blockage is the mechanism responsible for the dependence on particle size. As GAC particle size increases, the microporous surface area behind a constricted pore also increases. The result is lower adsorption capacity per mass of adsorbent in the larger GAC particles. A scaling methodology for equilibrium and breakthrough data is presented that accounts for the dependence of NOM preloading effects on GAC particle diameter.

Compounds from silicones alter enzyme activity in curing barnacle glue and model enzymes.

PubMed

Rittschof, Daniel; Orihuela, Beatriz; Harder, Tilmann; Stafslien, Shane; Chisholm, Bret; Dickinson, Gary H

2011-02-17

Attachment strength of fouling organisms on silicone coatings is low. We hypothesized that low attachment strength on silicones is, in part, due to the interaction of surface available components with natural glues. Components could alter curing of glues through bulk changes or specifically through altered enzyme activity. GC-MS analysis of silicone coatings showed surface-available siloxanes when the coatings were gently rubbed with a cotton swab for 15 seconds or given a 30 second rinse with methanol. Mixtures of compounds were found on 2 commercial and 8 model silicone coatings. The hypothesis that silicone components alter glue curing enzymes was tested with curing barnacle glue and with commercial enzymes. In our model, barnacle glue curing involves trypsin-like serine protease(s), which activate enzymes and structural proteins, and a transglutaminase which cross-links glue proteins. Transglutaminase activity was significantly altered upon exposure of curing glue from individual barnacles to silicone eluates. Activity of purified trypsin and, to a greater extent, transglutaminase was significantly altered by relevant concentrations of silicone polymer constituents. Surface-associated silicone compounds can disrupt glue curing and alter enzyme properties. Altered curing of natural glues has potential in fouling management.

Compounds from Silicones Alter Enzyme Activity in Curing Barnacle Glue and Model Enzymes

PubMed Central

Rittschof, Daniel; Orihuela, Beatriz; Harder, Tilmann; Stafslien, Shane; Chisholm, Bret; Dickinson, Gary H.

2011-01-01

Background Attachment strength of fouling organisms on silicone coatings is low. We hypothesized that low attachment strength on silicones is, in part, due to the interaction of surface available components with natural glues. Components could alter curing of glues through bulk changes or specifically through altered enzyme activity. Methodology/Principal Findings GC-MS analysis of silicone coatings showed surface-available siloxanes when the coatings were gently rubbed with a cotton swab for 15 seconds or given a 30 second rinse with methanol. Mixtures of compounds were found on 2 commercial and 8 model silicone coatings. The hypothesis that silicone components alter glue curing enzymes was tested with curing barnacle glue and with commercial enzymes. In our model, barnacle glue curing involves trypsin-like serine protease(s), which activate enzymes and structural proteins, and a transglutaminase which cross-links glue proteins. Transglutaminase activity was significantly altered upon exposure of curing glue from individual barnacles to silicone eluates. Activity of purified trypsin and, to a greater extent, transglutaminase was significantly altered by relevant concentrations of silicone polymer constituents. Conclusions/Significance Surface-associated silicone compounds can disrupt glue curing and alter enzyme properties. Altered curing of natural glues has potential in fouling management. PMID:21379573

The Effectiveness of the Removal of DNA from the Surfaces of EVA-Based Mouthguards using Standard Cleaning Protocols

DTIC Science & Technology

2016-06-16

Dental Association has recognized the value of mouthguards for all those who participate in contact sports and recreational activities in the...sustaining dental injuries in sporting activities , including organized and unorganized sports at both recreational and competitive levels.3 Since mouthguards...Overall p-value=0.008 based on logged analysis. Air dry and Commercial mouthguard cleaning tablet performed better than the antibacterial hand soap (p

Organic Nitrogen Utilization by Phytoplankton: The Role of Cell-Surface Deaminases

DTIC Science & Technology

1989-06-01

Pleurochrysis carterae (Coccoll-N) is a coccolithless clone isolated by the authors from Coccoll. Emiliania huxleyi (12-1) was isolated from the Sargasso Sea...another coccolithophorid, Emiliania huxleyi from the Sargasso Sea (now 12-1, CCMP) for L-amino acid oxidase activity. No activity was found under log...acid oxidase regulation. Saturated oxidase rate constants (Vmax) are shown for Pleurochrysis isolates and one Emiliania huxleyi isolate (12-1). Nlim

830-nm Polarization Controlled Lasing of InGaAs Quantum Wire Vertical-Cavity Surface-Emitting Lasers Grown on (775)B GaAs Substrates by Molecular Beam Epitaxy

NASA Astrophysics Data System (ADS)

Higuchi, Yu; Osaki, Shinji; Sasahata, Yoshifumi; Kitada, Takahiro; Shimomura, Satoshi; Ogura, Mutsuo; Hiyamizu, Satoshi

2007-02-01

We report the first demonstration of room temperature (RT) current injection lasing of vertical-cavity surface-emitting lasers (VCSELs), with self-organized InGaAs/(GaAs)6(AlAs)1 quantum wires (QWRs) in their active region, grown on (775)B-oriented GaAs substrates by molecular beam epitaxy. A (775)B InGaAs QWR-VCSEL with an aperture diameter of 4 μm lased at a wavelength of 829.7 nm and a threshold current of 0.7 mA at RT. The light output was linearly polarized in the direction parallel to the QWRs due to optical anisotropy of the self-organized (775)B InGaAs QWRs.

Fabrication of superhydrophobic Pt3Fe/Fe surface for its application

NASA Astrophysics Data System (ADS)

Cui, Shuo; Lu, Shixiang; Xu, Wenguo; Wu, Bei

2017-10-01

Well-defined Pt3Fe/Fe superhydrophobic materials on iron sheet with special properties, such as corrosion resistance, superhydrophobicity and superoleophilicity, was fabricated. The fabrication process involved etching in hydrochloric acid aqueous solution and simple replacement deposition process without using any seed and organic solvent, and then annealing. The electrochemical measurements show that the resultant surface in 3.5% sodium chloride solution displays good corrosion resistance. Also, it is proved that the obtained surface has better mechanical abrasion resistance via scratch test. The superoleophilicity and low water adhesion force of the obtained surface endow it high oil/water separation capacity. The as-prepared nanocomposites display enhanced catalytic activity and kinetics toward degradation of methyl orange. In particular, it possesses the most efficient degradation capacity (95%) towards methyl orange at a high concentration (17.5 mg/L) in 80 min. The improved stability and excellent catalytic activity of the Pt3Fe/Fe nanocomposites promise new opportunities for the development of waste water treatment.

Non-Equilibrium Plasma Processing for the Preparation of Antibacterial Surfaces

PubMed Central

Sardella, Eloisa; Palumbo, Fabio; Camporeale, Giuseppe; Favia, Pietro

2016-01-01

Non-equilibrium plasmas offer several strategies for developing antibacterial surfaces that are able to repel and/or to kill bacteria. Due to the variety of devices, implants, and materials in general, as well as of bacteria and applications, plasma assisted antibacterial strategies need to be tailored to each specific surface. Nano-composite coatings containing inorganic (metals and metal oxides) or organic (drugs and biomolecules) compounds can be deposited in one step, and used as drug delivery systems. On the other hand, functional coatings can be plasma-deposited and used to bind antibacterial molecules, for synthesizing surfaces with long lasting antibacterial activity. In addition, non-fouling coatings can be produced to inhibit the adhesion of bacteria and reduce the formation of biofilm. This paper reviews plasma-based strategies aimed to reduce bacterial attachment and proliferation on biomedical materials and devices, but also onto materials used in other fields. Most of the activities described have been developed in the lab of the authors. PMID:28773637

In Vitro Assessment of Early Bacterial Activity on Micro/Nanostructured Ti6Al4V Surfaces.

PubMed

Valdez-Salas, Benjamin; Beltrán-Partida, Ernesto; Castillo-Uribe, Sandra; Curiel-Álvarez, Mario; Zlatev, Roumen; Stoytcheva, Margarita; Montero-Alpírez, Gisela; Vargas-Osuna, Lidia

2017-05-18

It is imperative to understand and systematically compare the initial interactions between bacteria genre and surface properties. Thus, we fabricated a flat, anodized with 80 nm TiO₂ nanotubes (NTs), and a rough Ti6Al4V surface. The materials were characterized using field-emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDX) and atomic force microscopy (AFM). We cultured in vitro Staphylococcus epidermidis ( S. epidermidis ) and Pseudomonas aeruginosa ( P. aeruginosa ) to evaluate the bacterial-surface behavior by FE-SEM and viability calculation. In addition, the initial effects of human osteoblasts were tested on the materials. Gram-negative bacteria showed promoted adherence and viability over the flat and rough surface, while NTs displayed opposite activity with altered morphology. Gram-positive bacteria illustrated similar cellular architecture over the surfaces but with promoted surface adhesion bonds on the flat alloy. Rough surfaces supported S. epidermidis viability, whilst NTs exhibited lower vitality. NTs advocated promoted better osteoblast organization with enhanced vitality. Gram-positive bacteria suggested preferred adhesion capability over flat and carbon-rich surfaces. Gram-negative bacteria were strongly disturbed by NTs but largely stimulated by flat and rough materials. Our work proposed that the chemical profile of the material surface and the bacterial cell wall characteristics might play an important role in the bacteria-surface interactions.

Biofilm architecture in a novel pressurized biofilm reactor.

PubMed

Jiang, Wei; Xia, Siqing; Duan, Liang; Hermanowicz, Slawomir W

2015-01-01

A novel pure-oxygen pressurized biofilm reactor was operated at different organic loading, mechanical shear and hydrodynamic conditions to understand the relationships between biofilm architecture and its operation. The ultimate goal was to improve the performance of the biofilm reactor. The biofilm was labeled with seven stains and observed with confocal laser scanning microscopy. Unusual biofilm architecture of a ribbon embedded between two surfaces with very few points of attachment was observed. As organic loading increased, the biofilm morphology changed from a moderately rough layer into a locally smoother biomass with significant bulging protuberances, although the chemical oxygen demand (COD) removal efficiency remained unchanged at about 75%. At higher organic loadings, biofilms contained a larger fraction of active cells distributed uniformly within a proteinaceous matrix with decreasing polysaccharide content. Higher hydrodynamic shear in combination with high organic loading resulted in the collapse of biofilm structure and a substantial decrease in reactor performance (a COD removal of 16%). Moreover, the important role of proteins for the spatial distribution of active cells was demonstrated quantitatively.

Enzymatic Regulation of Organic Matter Metabolism in Siberia's Kolyma River Watershed

NASA Astrophysics Data System (ADS)

Mann, P. J.; Sobczak, W. V.; Vonk, J. E.; Davydova, A.; Schade, J. D.; Bulygina, E. B.; Davydov, S.; Zimov, N.; Holmes, R. M.

2011-12-01

Arctic soils contain vast amounts of ancient organic carbon locked up in permafrost. This organic matter can be unlocked via permafrost thaw and bacterial processing. Microbial communities release enzymes into the environment (ectoenzymes) as a means of degrading organic matter and to acquire carbon, nitrogen and phosphorus for assimilation. Limited ectoenzyme production, or unfavourable in-situ conditions (e.g. temperature, oxygen) can limit degradation of permafrost on land. Environmental conditions may become more favourable for bacterial degradation as carbon compounds are released from permafrost into Arctic streams and rivers. We measured the potential activities of a suite of ectoenzymes within surface waters collected from a range of streams and rivers throughout the Kolyma River basin, Siberia. Ectoenzyme activities were additionally measured in Kolyma river waters collected at three distinct periods of the hydrograph (under-ice, freshet and summer conditions). In total, seven enzymes were studied allowing bacterial requirements for a wide range of compounds including lignin, carbohydrates, proteins and cellulose to be assessed. To investigate the lability of the carbon pool within these waters, we measured the biological oxygen demand over 5 days (BOD). Significant correlations were observed between phenol oxidase activity and BOD across all of the study sites, suggesting the rate of phenolic degradation may be a controlling factor in organic carbon metabolism. The activity rate in ectoenzymes that catalyze phosphate, lignin and carbon substrates varied significantly within the Kolyma river over the hydrograph, indicating that seasonal changes in organic matter composition may also shift the limiting resource for bacterial degradation. High activity rates in ectoenzymes that catalyze lignin, chitin, cellulose and proteins were measured in waters draining permafrost ice complexes. These results suggest that organic carbon is continually processed throughout the stream network, and that its ultimate fate is linked to organic matter composition. We demonstrate that organic carbon derived from ancient permafrost thaw may be highly labile to bacterial communities within Arctic aquatic ecosystems.

Oxygen Plasma Modification of Poss-Coated Kapton(Registered TradeMark) HN Films

NASA Technical Reports Server (NTRS)

Wohl, C. J.; Belcher, M. A.; Ghose, S.; Connell, J. W.

2008-01-01

The surface energy of a material depends on both surface composition and topographic features. In an effort to modify the surface topography of Kapton(Registered TradeMark) HN film, organic solutions of a polyhedral oligomeric silsesquioxane, octakis(dimethylsilyloxy)silsesquioxane (POSS), were spray-coated onto the Kapton(Registered TradeMark) HN surface. Prior to POSS application, the Kapton(Registered TradeMark) HN film was activated by exposure to radio frequency (RF)-generated oxygen plasma. After POSS deposition and solvent evaporation, the films were exposed to various durations of RF-generated oxygen plasma to create a topographically rich surface. The modified films were characterized using optical microscopy, attenuated total reflection infrared (ATR-IR) spectroscopy, and high-resolution scanning electron microscopy (HRSEM). The physical properties of the modified films will be presented.

Enhanced biomimic bactericidal surfaces by coating with positively-charged ZIF nano-dagger arrays.

PubMed

Yuan, Yuan; Zhang, Yugen

2017-10-01

Cicada wing surfaces are covered with dense patterns of nano-pillar structure that prevent bacterial growth by rupturing adhered microbial cells. To mimic the natural nano-pillar structure, we developed a general and simple method to grow metal organic framework (MOF) nano-dagger arrays on a wide range of surfaces. These nano-daggers possess high bactericidal activity, with log reduction >7 for Escherichia coli and Staphylococcus aureus. It was hypothesized that the positively-charged ZIF-L nano-dagger surfaces enhance bacterial cell adhesion, facilitating selective and efficient bacteria killing by the rigid and sharp nano-dagger tips. This research provides a safe and clean antimicrobial surface technology which does not require external chemicals and will not cause drug resistance. Copyright © 2017 Elsevier Inc. All rights reserved.

Optimized conditions for selective gold flotation by ToF-SIMS and ToF-LIMS

NASA Astrophysics Data System (ADS)

Chryssoulis, S. L.; Dimov, S. S.

2004-06-01

This work describes a comprehensive characterization of the factors controlling the floatability of free gold from flotation test using reagents (collectors) at plant concentration levels. A relationship between the collectors loadings on gold particles and their surface composition has been established. The findings of this study show that silver activates gold flotation and there is a strong correlation between the surface concentration of silver and the loading of certain collectors. The organic surface analysis was done by ToF-SIMS while the inorganic surface analysis was carried out by time-of-flight laser ionization mass spectrometry (ToF-LIMS). The developed testing protocol based on ToF-LIMS and ToF-SIMS complementary surface analysis allows for optimization of the flotation scheme and hence improved gold recovery.

A depocenter of organic matter at 7800 m depth in the SE Pacific Ocean

NASA Astrophysics Data System (ADS)

Danovaro, R.; Della Croce, N.; Dell'Anno, A.; Pusceddu, A.

2003-12-01

The Atacama trench, the deepest ecosystem of the southern Pacific Ocean (ca. 8000 m depth) was investigated during the Atacama Trench International Expedition. Sediments, collected at three bathyal stations (1040-1355 m depth) and at a hadal site (7800 m) were analyzed for organic matter quantity and biochemical composition (in terms of phytopigments, proteins, carbohydrates and lipids), bacterial abundance, biomass and carbon production and extracellular enzymatic activities. Functional chlorophyll- a (18.0±0.10 mg m -2), phytodetritus (322.2 mg m -2) and labile organic carbon (16.9±4.3 g C m -2) deposited on surface sediments at hadal depth (7800 m) reached concentrations similar to those encountered in highly productive shallow coastal areas. High values of bacterial C production and aminopeptidase activity were also measured (at in situ temperature and 1 atm). The chemical analyses of the Atacama hadal sediments indicate that this trench behaves as a deep oceanic trap for organic material. We hypothesize that, despite the extreme physical conditions, benthic microbial processes might be accelerated as a result of the organic enrichment.