Central auditory processing effects induced by solvent exposure.

PubMed

Fuente, Adrian; McPherson, Bradley

2007-01-01

Various studies have demonstrated that organic solvent exposure may induce auditory damage. Studies conducted in workers occupationally exposed to solvents suggest, on the one hand, poorer hearing thresholds than in matched non-exposed workers, and on the other hand, central auditory damage due to solvent exposure. Taking into account the potential auditory damage induced by solvent exposure due to the neurotoxic properties of such substances, the present research aimed at studying the possible auditory processing disorder (APD), and possible hearing difficulties in daily life listening situations that solvent-exposed workers may acquire. Fifty workers exposed to a mixture of organic solvents (xylene, toluene, methyl ethyl ketone) and 50 non-exposed workers matched by age, gender and education were assessed. Only subjects with no history of ear infections, high blood pressure, kidney failure, metabolic and neurological diseases, or alcoholism were selected. The subjects had either normal hearing or sensorineural hearing loss, and normal tympanometric results. Hearing-in-noise (HINT), dichotic digit (DD), filtered speech (FS), pitch pattern sequence (PPS), and random gap detection (RGD) tests were carried out in the exposed and non-exposed groups. A self-report inventory of each subject's performance in daily life listening situations, the Amsterdam Inventory for Auditory Disability and Handicap, was also administered. Significant threshold differences between exposed and non-exposed workers were found at some of the hearing test frequencies, for both ears. However, exposed workers still presented normal hearing thresholds as a group (equal or better than 20 dB HL). Also, for the HINT, DD, PPS, FS and RGD tests, non-exposed workers obtained better results than exposed workers. Finally, solvent-exposed workers reported significantly more hearing complaints in daily life listening situations than non-exposed workers. It is concluded that subjects exposed to solvents may acquire an APD and thus the sole use of pure-tone audiometry is insufficient to assess hearing in solvent-exposed populations.

A template-free solvent-mediated synthesis of high surface area boron nitride nanosheets for aerobic oxidative desulfurization.

PubMed

Wu, Peiwen; Zhu, Wenshuai; Chao, Yanhong; Zhang, Jinshui; Zhang, Pengfei; Zhu, Huiyuan; Li, Changfeng; Chen, Zhigang; Li, Huaming; Dai, Sheng

2016-01-04

Hexagonal boron nitride nanosheets (h-BNNs) with rather high specific surface area (SSA) are important two-dimensional layer-structured materials. Here, a solvent-mediated synthesis of h-BNNs revealed a template-free lattice plane control strategy that induced high SSA nanoporous structured h-BNNs with outstanding aerobic oxidative desulfurization performance.

29 CFR 1915.51 - Ventilation and protection in welding, cutting and heating.

Code of Federal Regulations, 2010 CFR

2010-07-01

... from the exposed arc, and surfaces prepared with chlorinated solvents shall be thoroughly dry before... heating shall be protected by suitable eye protective equipment in accordance with the requirements of...

A template-free solvent-mediated synthesis of high surface area boron nitride nanosheets for aerobic oxidative desulfurization

DOE PAGES

Wu, Peiwen; Zhu, Wenshuai; Chao, Yanhong; ...

2015-10-16

Hexagonal boron nitride nanosheets (h-BNNs) with rather high specific surface area (SSA) are important two-dimensional layer-structured materials. Here in this study, a solvent-mediated synthesis of h-BNNs revealed a template-free lattice plane control strategy that induced high SSA nanoporous structured h-BNNs with outstanding aerobic oxidative desulfurization performance.

Single Layer Surface-Grafted PMMA as a Negative-Tone e-Beam Resist.

PubMed

Yamada, Hirotaka; Aydinoglu, Ferhat; Liu, Yaoze; Dey, Ripon K; Cui, Bo

2017-12-05

One of the important challenges in electron beam lithography is nanofabrication on nonflat or irregular surfaces. Although spin coating is the most popular technique for resist coating, it is not suitable for nonflat, irregular substrates because a uniform film cannot be achieved on those surfaces. Here, it is demonstrated that single layer surface-grafted PMMA can be used as a negative-tone e-beam resist, and it can be applied to nonflat, irregular surfaces as well as flat, conventional surfaces. Although it is well known that heavily exposed PMMA undergoes cross-linking and works as a negative-tone e-beam resist when developed by solvent, solvent does not work as a developer for negative-tone single-layer surface-grafted PMMA. Instead, thermal treatment at 360 °C for 1 min is used to develop PMMA.

Surface area generation and droplet size control in solvent extraction systems utilizing high intensity electric fields

DOEpatents

Scott, Timothy C.; Wham, Robert M.

1988-01-01

A method and system for solvent extraction where droplets are shattered by a high intensity electric field. These shattered droplets form a plurality of smaller droplets which have a greater combined surface area than the original droplet. Dispersion, coalescence and phase separation are accomplished in one vessel through the use of the single pulsing high intensity electric field. Electric field conditions are chosen so that simultaneous dispersion and coalescence are taking place in the emulsion formed in the electric field. The electric field creates a large amount of interfacial surface area for solvent extraction when the droplet is disintegrated and is capable of controlling droplet size and thus droplet stability. These operations take place in the presence of a counter current flow of the continuous phase.

Nanostructure and surface activation of mayenite (12CaO·7Al2O3) ceramics via femtosecond laser irradiation in solvents

NASA Astrophysics Data System (ADS)

Visbal, Heidy; Hirano, Minami; Omura, Takuya; Shimizu, Masahiro; Takaishi, Taigo; Hirao, Kazuyuki

2017-07-01

Mayenite (12CaO·7Al2O3) is a highly interesting functional material due to the wide variety of its possible future applications. In this study, we used femtosecond laser irradiation in several solvents with varying polarities to increase the specific surface area of 12CaO·7Al2O3 ceramics and reduce their particle size without any structural degradation or loss of crystallinity. We observed that when femtosecond laser irradiation was applied to solvents bearing hydroxyl groups, a smaller particle size was obtained with the particle size decreasing as the polarity of the solvent increased. Using infrared spectroscopy, we confirmed the presence of hydroxyl and carbonyl surface functional groups at the surface of 12CaO·7Al2O3 ceramics after femtosecond laser irradiation. This is attributed to the direct chemical bonds breaking of the solvent via multiphoton ionization and/or tunneling ionization, followed by the Coulomb explosion and the subsequent production of ions that are adsorbed on the surfaces of 12CaO·7Al2O3 ceramics. Femtosecond laser irradiation in polar solvents with hydroxyl groups can reduce the particle size and increase the specific surface area without degradation or loss of crystallinity of 12CaO·7Al2O3 ceramics. Additionally, this method can be used for the surface modification and introduction of functional groups on the 12CaO·7Al2O3 ceramics surface.

Comparison of volume and surface area nonpolar solvation free energy terms for implicit solvent simulations.

PubMed

Lee, Michael S; Olson, Mark A

2013-07-28

Implicit solvent models for molecular dynamics simulations are often composed of polar and nonpolar terms. Typically, the nonpolar solvation free energy is approximated by the solvent-accessible-surface area times a constant factor. More sophisticated approaches incorporate an estimate of the attractive dispersion forces of the solvent and∕or a solvent-accessible volume cavitation term. In this work, we confirm that a single volume-based nonpolar term most closely fits the dispersion and cavitation forces obtained from benchmark explicit solvent simulations of fixed protein conformations. Next, we incorporated the volume term into molecular dynamics simulations and find the term is not universally suitable for folding up small proteins. We surmise that while mean-field cavitation terms such as volume and SASA often tilt the energy landscape towards native-like folds, they also may sporadically introduce bottlenecks into the folding pathway that hinder the progression towards the native state.

Comparison of volume and surface area nonpolar solvation free energy terms for implicit solvent simulations

NASA Astrophysics Data System (ADS)

Lee, Michael S.; Olson, Mark A.

2013-07-01

Implicit solvent models for molecular dynamics simulations are often composed of polar and nonpolar terms. Typically, the nonpolar solvation free energy is approximated by the solvent-accessible-surface area times a constant factor. More sophisticated approaches incorporate an estimate of the attractive dispersion forces of the solvent and/or a solvent-accessible volume cavitation term. In this work, we confirm that a single volume-based nonpolar term most closely fits the dispersion and cavitation forces obtained from benchmark explicit solvent simulations of fixed protein conformations. Next, we incorporated the volume term into molecular dynamics simulations and find the term is not universally suitable for folding up small proteins. We surmise that while mean-field cavitation terms such as volume and SASA often tilt the energy landscape towards native-like folds, they also may sporadically introduce bottlenecks into the folding pathway that hinder the progression towards the native state.

Synthesis of porous Cu-BTC with ultrasonic treatment: Effects of ultrasonic power and solvent condition.

PubMed

Israr, Farrukh; Kim, Duk Kyung; Kim, Yeongmin; Oh, Seung Jin; Ng, Kim Choon; Chun, Wongee

2016-03-01

Cu-BTC (BTC=1,3,5-benzenetricarboxylate) metal organic framework (MOF) was synthesized using different solvent conditions with ultrasonic treatment. Solvent mixtures of water/N,N-dimethylformamide (DMF), water/ethanol were used for the reactions with or without a variety of bases under 20 kHz ultrasonically treated conditions. Prepared crystals were purified through 30 min of sonication to remove unreacted chemicals. Treatment time and ultrasonic power effects were compared to get optimum synthetic condition. The characterization of MOF powders was performed by scanning electron microscopy, X-ray powder diffraction, infrared-spectroscopy, thermo-gravimetric analysis and specific surface determination using the BET method. Isolated crystal yields varied with different solvent and applied ultrasonic power conditions. A high isolated crystal yield of 86% was obtained from water/ethanol/DMF solvent system after 120 min of ultrasonic treatment at 40% power of 750 W. Different solvent conditions led to the formation of Cu-BTC with different surface area, and an extremely high surface area of 1430 m(2)/g was obtained from the crystals taken with the solvent condition of water:DMF=70:30. Copyright © 2015 Elsevier B.V. All rights reserved.

Assessing implicit models for nonpolar mean solvation forces: The importance of dispersion and volume terms

PubMed Central

Wagoner, Jason A.; Baker, Nathan A.

2006-01-01

Continuum solvation models provide appealing alternatives to explicit solvent methods because of their ability to reproduce solvation effects while alleviating the need for expensive sampling. Our previous work has demonstrated that Poisson-Boltzmann methods are capable of faithfully reproducing polar explicit solvent forces for dilute protein systems; however, the popular solvent-accessible surface area model was shown to be incapable of accurately describing nonpolar solvation forces at atomic-length scales. Therefore, alternate continuum methods are needed to reproduce nonpolar interactions at the atomic scale. In the present work, we address this issue by supplementing the solvent-accessible surface area model with additional volume and dispersion integral terms suggested by scaled particle models and Weeks–Chandler–Andersen theory, respectively. This more complete nonpolar implicit solvent model shows very good agreement with explicit solvent results and suggests that, although often overlooked, the inclusion of appropriate dispersion and volume terms are essential for an accurate implicit solvent description of atomic-scale nonpolar forces. PMID:16709675

Assessment of central auditory processing in a group of workers exposed to solvents.

PubMed

Fuente, Adrian; McPherson, Bradley; Muñoz, Verónica; Pablo Espina, Juan

2006-12-01

Despite having normal hearing thresholds and speech recognition thresholds, results for central auditory tests were abnormal in a group of workers exposed to solvents. Workers exposed to solvents may have difficulties in everyday listening situations that are not related to a decrement in hearing thresholds. A central auditory processing disorder may underlie these difficulties. To study central auditory processing abilities in a group of workers occupationally exposed to a mix of organic solvents. Ten workers exposed to a mix of organic solvents and 10 matched non-exposed workers were studied. The test battery comprised pure-tone audiometry, tympanometry, acoustic reflex measurement, acoustic reflex decay, dichotic digit, pitch pattern sequence, masking level difference, filtered speech, random gap detection and hearing-in-noise tests. All the workers presented normal hearing thresholds and no signs of middle ear abnormalities. Workers exposed to solvents had lower results in comparison with the control group and previously reported normative data, in the majority of the tests.

Innovative eco-friendly bio- solvent for combating sea surface and sedimented oil pollution

NASA Astrophysics Data System (ADS)

Theodorou, Paraskevas

2017-04-01

The combating of oil spill at sea surface by chemical dispersants accelerates the evaporation and disperse the oil into the water column, where it is broken down by natural processes and/or is sedimented at the sea bottom, especially at near coastal shallow areas, ports and marinas. The usual methodology for cleaning the sedimented oil from the sea bottom is mainly carried out via excavation and dumping of the polluted sediment into deeper sea areas, where the contamination is transferred from one area to another. The eco-friendly bio-solvent MSL Aqua 250 is an innovative new solution based mainly on natural constituents. The action mechanism and the effectiveness of this eco-friendly solvent is based on the high surface tension process. Organic compounds, including hydrocarbons upon coming in contact with MSL Aqua 250 solvent generate a significant surface tension reaction, which is able to alter the organic compounds to liquid form and then to drastically evaporate it. The use of MSL Aqua 250 solvent, both at sea surface and at the bottom, has the following advantages compared to the dispersants: • Efficient solution without transferring the pollution from sea surface to the water column and to the bottom or disturbing the Aquatic Eco System. • Non-Toxic. • Environmentally friendly with a restoration of marine life in the Eco System. • Cost effective. The MSL Aqua 250 solvent has been tested in cooperation with the Cyprus Department of Fisheries and Marine Research and the Technological University of Cyprus and used during the years 2015 and 2016 in marinas and fishing shelters in Cyprus faced oil pollution, with high concentration in the sea water and at the sea bottom of chemical parameters (BOD5, COD, FOG, TKN, TP, TPH), with excellent results.

Denaturation of RNA secondary and tertiary structure by urea: simple unfolded state models and free energy parameters account for measured m-values

PubMed Central

Lambert, Dominic; Draper, David E.

2012-01-01

To investigate the mechanism by which urea destabilizes RNA structure, urea-induced unfolding of four different RNA secondary and tertiary structures was quantified in terms of an m-value, the rate at which the free energy of unfolding changes with urea molality. From literature data and our osmometric study of a backbone analog, we derived average interaction potentials (per Å2 of solvent accessible surface) between urea and three kinds of RNA surfaces: phosphate, ribose, and base. Estimates of the increases in solvent accessible surface areas upon RNA denaturation were based on a simple model of unfolded RNA as a combination of helical and single strand segments. These estimates, combined with the three interaction potentials and a term to account for urea interactions with released ions, yield calculated m-values in good agreement with experimental values (200 mm monovalent salt). Agreement was obtained only if single-stranded RNAs were modeled in a highly stacked, A form conformation. The primary driving force for urea induced denaturation is the strong interaction of urea with the large surface areas of bases that become exposed upon denaturation of either RNA secondary or tertiary structure, though urea interactions with backbone and released ions may account for up to a third of the m-value. Urea m-values for all four RNA are salt-dependent, which we attribute to an increased extension (or decreased charge density) of unfolded RNAs with increased urea concentration. The sensitivity of the urea m-value to base surface exposure makes it a potentially useful probe of the conformations of RNA unfolded states. PMID:23088364

Large-area fabrication of patterned ZnO-nanowire arrays using light stamping lithography.

PubMed

Hwang, Jae K; Cho, Sangho; Seo, Eun K; Myoung, Jae M; Sung, Myung M

2009-12-01

We demonstrate selective adsorption and alignment of ZnO nanowires on patterned poly(dimethylsiloxane) (PDMS) thin layers with (aminopropyl)siloxane self-assembled monolayers (SAMs). Light stamping lithography (LSL) was used to prepare patterned PDMS thin layers as neutral passivation regions on Si substrates. (3-Aminopropyl)triethoxysilane-based SAMs were selectively formed only on regions exposing the silanol groups of the Si substrates. The patterned positively charged amino groups define and direct the selective adsorption of ZnO nanowires with negative surface charges in the protic solvent. This procedure can be adopted in automated printing machines that generate patterned ZnO-nanowire arrays on large-area substrates. To demonstrate its usefulness, the LSL method was applied to prepare ZnO-nanowire transistor arrays on 4-in. Si wafers.

Method for the preparation of high surface area high permeability carbons

DOEpatents

Lagasse, Robert R.; Schroeder, John L.

1999-05-11

A method for preparing carbon materials having high surface area and high macropore volume to provide high permeability. These carbon materials are prepared by dissolving a carbonizable polymer precursor, in a solvent. The solution is cooled to form a gel. The solvent is extracted from the gel by employing a non-solvent for the polymer. The non-solvent is removed by critical point drying in CO.sub.2 at an elevated pressure and temperature or evaporation in a vacuum oven. The dried product is heated in an inert atmosphere in a first heating step to a first temperature and maintained there for a time sufficient to substantially cross-link the polymer material. The cross-linked polymer material is then carbonized in an inert atmosphere.

Microfluidic process monitor for industrial solvent extraction system

DOEpatents

Gelis, Artem; Pereira, Candido; Nichols, Kevin Paul Flood

2016-01-12

The present invention provides a system for solvent extraction utilizing a first electrode with a raised area formed on its surface, which defines a portion of a microfluidic channel; a second electrode with a flat surface, defining another portion of the microfluidic channel that opposes the raised area of the first electrode; a reversibly deformable substrate disposed between the first electrode and second electrode, adapted to accommodate the raised area of the first electrode and having a portion that extends beyond the raised area of the first electrode, that portion defining the remaining portions of the microfluidic channel; and an electrolyte of at least two immiscible liquids that flows through the microfluidic channel. Also provided is a system for performing multiple solvent extractions utilizing several microfluidic chips or unit operations connected in series.

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

Ivanov, Ilia N.; Simpson, John T.

A method of preparing a network comprises disposing a solution comprising particulate materials in a solvent onto a superhydrophobic surface comprising a plurality of superhydrophobic features and interfacial areas between the superhydrophobic features. The plurality of superhydrophobic features has a water contact angle of at least about 150.degree.. The method of preparing the network also comprises removing the solvent from the solution of the particulate materials, and forming a network of the particulate materials in the interfacial areas, the particulate materials receding to the interfacial areas as the solvent is removed.

Identification of Surface-Exposed Protein Radicals and A Substrate Oxidation Site in A-Class Dye-Decolorizing Peroxidase from Thermomonospora curvata

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

Shrestha, Ruben; Chen, Xuejie; Ramyar, Kasra X.

Dye-decolorizing peroxidases (DyPs) are a family of heme peroxidases in which a catalytic distal aspartate is involved in H 2O 2 activation to catalyze oxidations under acidic conditions. They have received much attention due to their potential applications in lignin compound degradation and biofuel production from biomass. However, the mode of oxidation in bacterial DyPs remains unknown. We have recently reported that the bacterial TcDyP from Thermomonospora curvata is among the most active DyPs and shows activity toward phenolic lignin model compounds. On the basis of the X-ray crystal structure solved at 1.75 Å, sigmoidal steady-state kinetics with Reactive Bluemore » 19 (RB19), and formation of compound II like product in the absence of reducing substrates observed with stopped-flow spectroscopy and electron paramagnetic resonance (EPR), we hypothesized that the TcDyP catalyzes oxidation of large-size substrates via multiple surface-exposed protein radicals. Among 7 tryptophans and 3 tyrosines in TcDyP consisting of 376 residues for the matured protein, W263, W376, and Y332 were identified as surface-exposed protein radicals. Only the W263 was also characterized as one of the surface-exposed oxidation sites. SDS-PAGE and size-exclusion chromatography demonstrated that W376 represents an off-pathway destination for electron transfer, resulting in the cross-linking of proteins in the absence of substrates. Mutation of W376 improved compound I stability and overall catalytic efficiency toward RB19. While Y332 is highly conserved across all four classes of DyPs, its catalytic function in A-class TcDyP is minimal, possibly due to its extremely small solvent-accessible areas. Identification of surface-exposed protein radicals and substrate oxidation sites is important for understanding the DyP mechanism and modulating its catalytic functions for improved activity on phenolic lignin.« less

Method for the preparation of high surface area high permeability carbons

DOEpatents

Lagasse, R.R.; Schroeder, J.L.

1999-05-11

A method for preparing carbon materials having high surface area and high macropore volume to provide high permeability. These carbon materials are prepared by dissolving a carbonizable polymer precursor, in a solvent. The solution is cooled to form a gel. The solvent is extracted from the gel by employing a non-solvent for the polymer. The non-solvent is removed by critical point drying in CO{sub 2} at an elevated pressure and temperature or evaporation in a vacuum oven. The dried product is heated in an inert atmosphere in a first heating step to a first temperature and maintained there for a time sufficient to substantially cross-link the polymer material. The cross-linked polymer material is then carbonized in an inert atmosphere. 3 figs.

Behavior of Solvent-Exposed Hydrophobic Groove in the Anti-Apoptotic Bcl-XL Protein: Clues for Its Ability to Bind Diverse BH3 Ligands from MD Simulations

PubMed Central

Sankararamakrishnan, Ramasubbu

2013-01-01

Bcl-XL is a member of Bcl-2 family of proteins involved in the regulation of intrinsic pathway of apoptosis. Its overexpression in many human cancers makes it an important target for anti-cancer drugs. Bcl-XL interacts with the BH3 domain of several pro-apoptotic Bcl-2 partners. This helical bundle protein has a pronounced hydrophobic groove which acts as a binding region for the BH3 domains. Eight independent molecular dynamics simulations of the apo/holo forms of Bcl-XL were carried out to investigate the behavior of solvent-exposed hydrophobic groove. The simulations used either a twin-range cut-off or particle mesh Ewald (PME) scheme to treat long-range interactions. Destabilization of the BH3 domain-containing helix H2 was observed in all four twin-range cut-off simulations. Most of the other major helices remained stable. The unwinding of H2 can be related to the ability of Bcl-XL to bind diverse BH3 ligands. The loss of helical character can also be linked to the formation of homo- or hetero-dimers in Bcl-2 proteins. Several experimental studies have suggested that exposure of BH3 domain is a crucial event before they form dimers. Thus unwinding of H2 seems to be functionally very important. The four PME simulations, however, revealed a stable helix H2. It is possible that the H2 unfolding might occur in PME simulations at longer time scales. Hydrophobic residues in the hydrophobic groove are involved in stable interactions among themselves. The solvent accessible surface areas of bulky hydrophobic residues in the groove are significantly buried by the loop LB connecting the helix H2 and subsequent helix. These observations help to understand how the hydrophobic patch in Bcl-XL remains stable in the solvent-exposed state. We suggest that both the destabilization of helix H2 and the conformational heterogeneity of loop LB are important factors for binding of diverse ligands in the hydrophobic groove of Bcl-XL. PMID:23468841

The solvation structures of cellulose microfibrils in ionic liquids.

PubMed

Mostofian, Barmak; Smith, Jeremy C; Cheng, Xiaolin

2011-12-01

The use of ionic liquids for non-derivatized cellulose dissolution promises an alternative method for the thermochemical pretreatment of biomass that may be more efficient and environmentally acceptable than more conventional techniques in aqueous solution. Here, we performed equilibrium MD simulations of a cellulose microfibril in the ionic liquid 1-butyl-3-methylimidazolium chloride (BmimCl) and compared the solute structure and the solute-solvent interactions at the interface with those from corresponding simulations in water. The results indicate a higher occurrence of solvent-exposed orientations of cellulose surface hydroxymethyl groups in BmimCl than in water. Moreover, spatial and radial distribution functions indicate that hydrophilic surfaces are a preferred site of interaction between cellulose and the ionic liquid. In particular, hydroxymethyl groups on the hydrophilic fiber surface adopt a different conformation from their counterparts oriented towards the fiber's core. Furthermore, the glucose units with these solvent-oriented hydroxymethyls are surrounded by the heterocyclic organic cation in a preferred parallel orientation, suggesting a direct and distinct interaction scheme between cellulose and BmimCl.

The role of ultra-fast solvent evaporation on the directed self-assembly of block polymer thin films

NASA Astrophysics Data System (ADS)

Drapes, Chloe; Nelson, G.; Grant, M.; Wong, J.; Baruth, A.

The directed self-assembly of nano-structures in block polymer thin films viasolvent vapor annealing is complicated by several factors, including evaporation rate. Solvent vapor annealing exposes a disordered film to solvent(s) in the vapor phase, increasing mobility and tuning surface energy, with the intention of producing an ordered structure. Recent theoretical predictions reveal the solvent evaporation affects the resultant nano-structuring. In a competition between phase separation and kinetic trapping during drying, faster solvent removal can enhance the propagation of a given morphology into the bulk of the thin film down to the substrate. Recent construction of a purpose-built, computer controlled solvent vapor annealing chamber provides control over forced solvent evaporation down to 15 ms. This is accomplished using pneumatically actuated nitrogen flow into and out of the chamber. Furthermore, in situ spectral reflectance, with 10 ms temporal resolution, monitors the swelling and evaporation. Presently, cylinder-forming polystyrene-block-polylactide thin films were swollen with 40% (by volume) tetrahydrofuran, followed by immediate evaporation under a variety of designed conditions. This includes various evaporation times, ranging from 15 ms to several seconds, and four unique rate trajectories, including linear, exponential, and combinations. Atomic force microscopy reveals specific surface, free and substrate, morphologies of the resultant films, dependent on specific evaporation conditions. Funded by the Clare Boothe Luce Foundation and Nebraska EPSCoR.

Equilibrium disorders in workers exposed to mixed solvents.

PubMed

Giorgianni, Concetto; Tanzariello, Mariagiuseppina; De Pasquale, Domenico; Brecciaroli, Renato; Spatari, Giovanna

2018-02-06

Organic solvents cause diseases of the vestibular system. However, little is known regarding the correlation between vestibular damage and exposure to organic solvents below threshold limit values. The best measure by which to evaluate vestibular disorders is static and dynamic posturography. The aim of this study was to evaluate equilibrium disorders via static and dynamic posturography in workers without clear symptoms and exposed to low doses of mixed solvents. 200 subjects were selected. Using an Otometrics device (Madsen, Denmark), all subjects endured static and dynamic posturography testing with both eyes-open and eyes-closed conditions. Results were compared with a control group of unexposed individuals. Based on the obtained data, the following results can be drawn: (a) subjects exposed to mixtures of solvents show highly significant differences regarding all static and dynamic posturography parameters in comparison to the control group; (b) posturography testing has proven to be a valid means by which to detect subliminal equilibrium disorders in subjects exposed to solvents. We can confirm that refinery workers exposed to mixtures of solvents can present subliminal equilibrium disorders. Early diagnosis of the latter is made possible by static and dynamic posturography.

Allotropic control: How certain fluorinated carbonate electrolytes protect aluminum current collectors by promoting the formation of insoluble coordination polymers

DOE PAGES

Shkrob, Ilya A.; Pupek, Krzysztof Z.; Abraham, Daniel P.

2016-07-28

Here, there is a strong incentive for increasing the operation voltage of Li-ion cells above 4.5 V in order to increase the density of stored energy. Aluminum is an inexpensive, lightweight metal that is commonly used as a positive electrode current collector in these cells. Imide LiX salts, such as lithium bis(trifluoromethylsulfonyl)imide (X = TFSI), and lithium bis(fluorosulfonyl)imide (X = FSI), are chemically stable on the energized lithiated transition metal oxide electrodes, but their presence in the electrolyte causes rapid anodic dissolution and pitting of Al current collectors at potentials exceeding 4.0 V versus Li/Li +. For LiBF 4 andmore » LiPF 6, the release of HF near the energized surfaces passivates the exposed Al metal, inhibiting this pitting corrosion, but it also causes the gradual degradation of the cathode active material, negating this important advantage. Here we report that in certain electrolytes containing fluorinated carbonate solvents and LiX salts, the threshold voltage for safe operation of Al current collectors can be increased to 5.5 V versus Li/Li +. Interestingly, the most efficient solvent also facilitates the formation of an insoluble gel when AlX 3 is introduced into this solvent. We suggest that this solvent promotes the aggregation of coordination polymers of AlX 3 at the exposed Al surface that isolate this surface from the electrolyte, thereby preventing further Al dissolution and corrosion. Other examples of Al collector protection may also involve this mechanism. Our study suggests that such “allotropic control” could be a way of widening the operation window of Li-ion cells without electrode deterioration, Al current collector corrosion, and electrolyte breakdown.« less

Allotropic control: How certain fluorinated carbonate electrolytes protect aluminum current collectors by promoting the formation of insoluble coordination polymers

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

Shkrob, Ilya A.; Pupek, Krzysztof Z.; Abraham, Daniel P.

Here, there is a strong incentive for increasing the operation voltage of Li-ion cells above 4.5 V in order to increase the density of stored energy. Aluminum is an inexpensive, lightweight metal that is commonly used as a positive electrode current collector in these cells. Imide LiX salts, such as lithium bis(trifluoromethylsulfonyl)imide (X = TFSI), and lithium bis(fluorosulfonyl)imide (X = FSI), are chemically stable on the energized lithiated transition metal oxide electrodes, but their presence in the electrolyte causes rapid anodic dissolution and pitting of Al current collectors at potentials exceeding 4.0 V versus Li/Li +. For LiBF 4 andmore » LiPF 6, the release of HF near the energized surfaces passivates the exposed Al metal, inhibiting this pitting corrosion, but it also causes the gradual degradation of the cathode active material, negating this important advantage. Here we report that in certain electrolytes containing fluorinated carbonate solvents and LiX salts, the threshold voltage for safe operation of Al current collectors can be increased to 5.5 V versus Li/Li +. Interestingly, the most efficient solvent also facilitates the formation of an insoluble gel when AlX 3 is introduced into this solvent. We suggest that this solvent promotes the aggregation of coordination polymers of AlX 3 at the exposed Al surface that isolate this surface from the electrolyte, thereby preventing further Al dissolution and corrosion. Other examples of Al collector protection may also involve this mechanism. Our study suggests that such “allotropic control” could be a way of widening the operation window of Li-ion cells without electrode deterioration, Al current collector corrosion, and electrolyte breakdown.« less

Apparatus and method for removing solvent from carbon dioxide in resin recycling system

DOEpatents

Bohnert, George W [Harrisonville, MO; Hand, Thomas E [Lee's Summit, MO; DeLaurentiis, Gary M [Jamestown, CA

2009-01-06

A two-step resin recycling system and method solvent that produces essentially contaminant-free synthetic resin material. The system and method includes one or more solvent wash vessels to expose resin particles to a solvent, the solvent contacting the resin particles in the one or more solvent wash vessels to substantially remove contaminants on the resin particles. A separator is provided to separate the solvent from the resin particles after removal from the one or more solvent wash vessels. The resin particles are next exposed to carbon dioxide in a closed loop carbon dioxide system. The closed loop system includes a carbon dioxide vessel where the carbon dioxide is exposed to the resin, substantially removing any residual solvent remaining on the resin particles after separation. A separation vessel is also provided to separate the solvent from the solvent laden carbon dioxide. Both the carbon dioxide and the solvent are reused after separation in the separation vessel.

On-the-fly Numerical Surface Integration for Finite-Difference Poisson-Boltzmann Methods.

PubMed

Cai, Qin; Ye, Xiang; Wang, Jun; Luo, Ray

2011-11-01

Most implicit solvation models require the definition of a molecular surface as the interface that separates the solute in atomic detail from the solvent approximated as a continuous medium. Commonly used surface definitions include the solvent accessible surface (SAS), the solvent excluded surface (SES), and the van der Waals surface. In this study, we present an efficient numerical algorithm to compute the SES and SAS areas to facilitate the applications of finite-difference Poisson-Boltzmann methods in biomolecular simulations. Different from previous numerical approaches, our algorithm is physics-inspired and intimately coupled to the finite-difference Poisson-Boltzmann methods to fully take advantage of its existing data structures. Our analysis shows that the algorithm can achieve very good agreement with the analytical method in the calculation of the SES and SAS areas. Specifically, in our comprehensive test of 1,555 molecules, the average unsigned relative error is 0.27% in the SES area calculations and 1.05% in the SAS area calculations at the grid spacing of 1/2Å. In addition, a systematic correction analysis can be used to improve the accuracy for the coarse-grid SES area calculations, with the average unsigned relative error in the SES areas reduced to 0.13%. These validation studies indicate that the proposed algorithm can be applied to biomolecules over a broad range of sizes and structures. Finally, the numerical algorithm can also be adapted to evaluate the surface integral of either a vector field or a scalar field defined on the molecular surface for additional solvation energetics and force calculations.

Revealing Surface Waters on an Antifreeze Protein by Fusion Protein Crystallography Combined with Molecular Dynamic Simulations.

PubMed

Sun, Tianjun; Gauthier, Sherry Y; Campbell, Robert L; Davies, Peter L

2015-10-08

Antifreeze proteins (AFPs) adsorb to ice through an extensive, flat, relatively hydrophobic surface. It has been suggested that this ice-binding site (IBS) organizes surface waters into an ice-like clathrate arrangement that matches and fuses to the quasi-liquid layer on the ice surface. On cooling, these waters join the ice lattice and freeze the AFP to its ligand. Evidence for the generality of this binding mechanism is limited because AFPs tend to crystallize with their IBS as a preferred protein-protein contact surface, which displaces some bound waters. Type III AFP is a 7 kDa globular protein with an IBS made up two adjacent surfaces. In the crystal structure of the most active isoform (QAE1), the part of the IBS that docks to the primary prism plane of ice is partially exposed to solvent and has clathrate waters present that match this plane of ice. The adjacent IBS, which matches the pyramidal plane of ice, is involved in protein-protein crystal contacts with few surface waters. Here we have changed the protein-protein contacts in the ice-binding region by crystallizing a fusion of QAE1 to maltose-binding protein. In this 1.9 Å structure, the IBS that fits the pyramidal plane of ice is exposed to solvent. By combining crystallography data with MD simulations, the surface waters on both sides of the IBS were revealed and match well with the target ice planes. The waters on the pyramidal plane IBS were loosely constrained, which might explain why other isoforms of type III AFP that lack the prism plane IBS are less active than QAE1. The AFP fusion crystallization method can potentially be used to force the exposure to solvent of the IBS on other AFPs to reveal the locations of key surface waters.

Group extraction of organic compounds present in liquid samples

NASA Technical Reports Server (NTRS)

Jahnsen, Vilhelm J. (Inventor)

1976-01-01

An extraction device is disclosed comprising a tube containing a substantially inert, chemically non-reactive packing material with a large surface area to volume ratio. A sample which consists of organic compounds dissolved in a liquid, is introduced into the tube. As the sample passes through the packing material it spreads over the material's large surface area to form a thin liquid film which is held on the packing material in a stationary state. A particular group or family of compounds is extractable from the sample by passing a particular solvent system consisting of a solvent and selected reagents through the packing material. The reagents cause optimum conditions to exist for the compounds of the particular family to pass through the phase boundary between the sample liquid and the solvent of the solvent system. Thus, the compounds of the particular family are separated from the sample liquid and become dissolved in the solvent of the solvent system. The particular family of compounds dissolved in the solvent, representing an extract, exits the tube together with the solvent through the tube's nozzle, while the rest of the sample remains on the packing material in a stationary state. Subsequently, a different solvent system may be passed through the packing material to extract another family of compounds from the remaining sample on the packing material.

A robust and efficient method for the extraction of plant extracellular surface lipids as applied to the analysis of silks and seedling leaves of maize

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

Loneman, Derek M.; Peddicord, Layton; Al-Rashid, Amani

Aerial plant organs possess a diverse array of extracellular surface lipids, including both non-polar and amphipathic constituents that collectively provide a primary line of defense against environmental stressors. Extracellular surface lipids on the stigmatic silks of maize are composed primarily of saturated and unsaturated linear hydrocarbons, as well as fatty acids, and aldehydes. To efficiently extract lipids of differing polarities from maize silks, five solvent systems (hexanes; hexanes:diethyl ether (95:5); hexanes:diethyl ether (90:10); chloroform:hexanes (1:1) and chloroform) were tested by immersing fresh silks in solvent for different extraction times. Surface lipid recovery and the relative composition of individual constituents weremore » impacted to varying degrees depending on solvent choice and duration of extraction. Analyses were performed using both silks and leaves to demonstrate the utility of the solvent- and time-optimized protocol in comparison to extraction with the commonly used chloroform solvent. Overall, the preferred solvent system was identified as hexanes:diethyl ether (90:10), based on its effectiveness in extracting surface hydrocarbons and fatty acids as well as its reduced propensity to extract presumed internal fatty acids. Metabolite profiling of wildtype and glossy1 seedlings, which are impaired in surface lipid biosynthesis, demonstrated the ability of the preferred solvent to extract extracellular surface lipids rich in amphipathic compounds (aldehydes and alcohols). In addition to the expected deficiencies in dotriacontanal and dotriacontan-1-ol for gl1 seedlings, an unexpected increase in fatty acid recovery was observed in gl1 seedlings extracted in chloroform, suggesting that chloro-form extracts lipids from internal tissues of gl1 seedlings. This highlights the importance of extraction method when evaluating mutants that have altered cuticular lipid compositions. Lastly, metabolite profiling of silks from maize inbreds B73 and Mo17, exposed to different environments and harvested at different ages, revealed differences in hydrocarbon and fatty acid composition, demonstrating the dynamic nature of surface lipid accumulation on silks.« less

A robust and efficient method for the extraction of plant extracellular surface lipids as applied to the analysis of silks and seedling leaves of maize

DOE PAGES

Loneman, Derek M.; Peddicord, Layton; Al-Rashid, Amani; ...

2017-07-11

Aerial plant organs possess a diverse array of extracellular surface lipids, including both non-polar and amphipathic constituents that collectively provide a primary line of defense against environmental stressors. Extracellular surface lipids on the stigmatic silks of maize are composed primarily of saturated and unsaturated linear hydrocarbons, as well as fatty acids, and aldehydes. To efficiently extract lipids of differing polarities from maize silks, five solvent systems (hexanes; hexanes:diethyl ether (95:5); hexanes:diethyl ether (90:10); chloroform:hexanes (1:1) and chloroform) were tested by immersing fresh silks in solvent for different extraction times. Surface lipid recovery and the relative composition of individual constituents weremore » impacted to varying degrees depending on solvent choice and duration of extraction. Analyses were performed using both silks and leaves to demonstrate the utility of the solvent- and time-optimized protocol in comparison to extraction with the commonly used chloroform solvent. Overall, the preferred solvent system was identified as hexanes:diethyl ether (90:10), based on its effectiveness in extracting surface hydrocarbons and fatty acids as well as its reduced propensity to extract presumed internal fatty acids. Metabolite profiling of wildtype and glossy1 seedlings, which are impaired in surface lipid biosynthesis, demonstrated the ability of the preferred solvent to extract extracellular surface lipids rich in amphipathic compounds (aldehydes and alcohols). In addition to the expected deficiencies in dotriacontanal and dotriacontan-1-ol for gl1 seedlings, an unexpected increase in fatty acid recovery was observed in gl1 seedlings extracted in chloroform, suggesting that chloro-form extracts lipids from internal tissues of gl1 seedlings. This highlights the importance of extraction method when evaluating mutants that have altered cuticular lipid compositions. Lastly, metabolite profiling of silks from maize inbreds B73 and Mo17, exposed to different environments and harvested at different ages, revealed differences in hydrocarbon and fatty acid composition, demonstrating the dynamic nature of surface lipid accumulation on silks.« less

A neurological evaluation of workers exposed to mixtures of organic solvents.

PubMed Central

Maizlish, N A; Fine, L J; Albers, J W; Whitehead, L; Langolf, G D

1987-01-01

Workers with long term exposure to mixtures of organic solvents below regulatory limits have been reported to experience mild, but clinically detectable, sensory or sensorimotor polyneuropathies. In conjuction with a cross sectional study of behavioural performance a clinical neurological evaluation was conducted among printers and spray painters to examine dose response relations. All 240 subjects completed an occupational history and symptom questionnaire and underwent a clinical neurological examination. On average, subjects had been employed on their current job for six years. Classification of solvent exposure for each subject was based on exposed versus non-exposed job titles and observations during an industrial hygiene walk-through or on the measured concentration of solvents in full shift personal air samples. The average full shift solvent concentration was 302 ppm for printing plant workers and 6-13 ppm for workers at other plants. Isopropanol and hexane were the major constituents. Neurological abnormalities consistent with mild polyneuropathy were found in 16% of subjects; none was clinically significant. Exposed/non-exposed comparisons showed slightly higher frequency of symptoms in the exposed subjects which was not related to solvent level. Subjects categorised as exposed during the walk- through survey also had poorer vibratory sensation measured at the foot and diminished ankle reflexes. In multiple linear regression models, however, controlling for age, sex, alcohol intake, and examiner, no significant (p less than 0.05) relation was found between solvent concentration and poor neurological function except for two point discrimination measured at the foot. This investigation has not provided evidence for dose related adverse neurological effects from exposure to moderately low levels of solvent mixtures for a relatively short duration, although this may be due to the shortness of exposure duration, the type of solvent exposure, or to selection factors. PMID:3814530

Electrode holder useful in a corrosion testing device

DOEpatents

Murphy, R.J. Jr.; Jamison, D.E.

1986-08-19

The present invention is directed to an apparatus and method for holding one or more test electrodes of precisely known exposed surface area. The present invention is particularly useful in a device for determining the corrosion properties of the materials from which the test electrodes have been formed. The present invention relates to a device and method for holding the described electrodes wherein the exposed surface area of the electrodes is only infinitesimally decreased. Further, in the present invention the exposed, electrically conductive surface area of the contact devices is small relative to the test electrode surface area. The holder of the present invention conveniently comprises a device for contacting and engaging each test electrode at two point contacts infinitesimally small in relation to the exposed surface area of the electrodes. 4 figs.

Electrode holder useful in a corrosion testing device

DOEpatents

Murphy, Jr., Robert J.; Jamison, Dale E.

1986-01-01

The present invention is directed to an apparatus and method for holding one or more test electrodes of precisely known exposed surface area. The present invention is particularly useful in a device for determining the corrosion properties of the materials from which the test electrodes have been formed. The present invention relates to a device and method for holding the described electrodes wherein the exposed surface area of the electrodes is only infinitesimally decreased. Further, in the present invention the exposed, electrically conductive surface area of the contact devices is small relative to the test electrode surface area. The holder of the present invention conveniently comprises a device for contacting and engaging each test electrode at two point contacts infinitesimally small in relation to the exposed surface area of the electrodes.

Solid-Supported Lipid Membranes: Formation, Stability and Applications

NASA Astrophysics Data System (ADS)

Goh, Haw Zan

This thesis presents a comprehensive investigation of the formation of supported lipid membranes with vesicle hemifusion, their stability under detergents and organic solvents and their applications in molecular biology. In Chapter 3, we describe how isolated patches of DOPC bilayers supported on glass surfaces are dissolved by various detergents (decyl maltoside, dodecyl maltoside, CHAPS, CTAB, SDS, TritonX-100 and Tween20) at their CMC, as investigated by fluorescence video microscopy. In general, detergents partition into distal leaflets of bilayers and lead to the expansion of the bilayers through a rolling motion of the distal over the proximal leaflets, in agreement with the first stage of the established 3-stage model of lipid vesicle solubilization by detergents. Subsequently, we study the partitioning of organic solvents (methanol, ethanol, isopropanol, propanol, acetone and chloroform) into isolated bilayer patches on glass in Chapter 4 with fluorescence microscopy. The area expansion of bilayers due to the partitioning of organic solvents is measured. From the titration of organic solvents, we measured the rate of area expansion as a function of the volume fraction of organic solvents, which is proposed to be a measure of strength of interactions between solvents and membranes. From the same experiments, we also measure the maximum expansion of bilayers (or the maximum binding stoichiometry between organic solvents and lipids) before structural breakdown, which depends on the depth of penetration of solvents to the membranes. In Chapter 5, we investigate the formation of sparsely-tethered bilayer lipid membranes (stBLMs) with vesicle hemifusion. In vesicle hemifusion, lipid vesicles in contact with a hydrophobic alkyl-terminated self-assembled monolayer (SAM) deposit a lipid monolayer to the SAM surface, thus completing the bilayer. Electrical Impedance Spectroscopy and Neutron Reflectivity are used to probe the integrity of stBLMs in terms of their insulating and structural properties. Preparation conditions are screened for those that are optimal for stBLM formation. Concentrations of lipid vesicles, hydrophobicity of SAMs, the presence of calcium and high concentrations of salt are identified as the key parameters. We show that stBLMs can be formed with vesicles of different compositions. Vesicle hemifusion opens up a new route in preserving the chemical compositions of stBLMs and facilitating membrane proteins incorporation. In Chapter 6, we visualize the hemifusion pathway of giant unilamellar vesicles (GUVs) with planar hydrophobic surfaces at the single vesicle level with fluorescence video microscopy. When a GUV hemifuses to a surface, its outer leaflet breaks apart and remains connected to the surface presumably through a hemifusion diaphragm. Lipids from the outer leaflet are transferred to the surface as a lipid monolayer that expands radially outward from the hemifusion diaphragm, thereby forming the loosely packed outer hemifusion zone. In Chapter 7, we develop an in vitro assay employing stBLMs and lipid vesicles to examine the functionality of GRASP in membrane tethering. Membrane-bound GRASP on opposing membranes dimerizes and tethers fluorescently-labeled vesicles to stBLMs. The fluorescence intensity of images taken at stBLM surfaces is used to quantify the tethering activity. Both wild type and mutant proteins were studied to shed light on the molecular mechanism of tethering. We show that the GRASP domain is sufficient and necessary for membrane tethering. In addition, the tethering capability of GRASP is impaired when the internal ligands and the binding pockets participating in dimerization are deleted and mutated. Membrane anchors, sizes of vesicles and membrane compositions are explored for their influence on the outcomes of the assay. Furthermore, preliminary analysis from neutron reflectivity measurements shows that both the internal ligands and binding pockets are exposed instead of buried toward the membrane surface. In summary, we establish a functional assay for studying GRASP activity in vitro. (Abstract shortened by UMI.)

Interfacial Interaction in Anodic Aluminum Oxide Templates Modifies Morphology, Surface Area, and Crystallization of Polyamide-6 Nanofibers.

PubMed

Xue, Junhui; Xu, Yizhuang; Jin, Zhaoxia

2016-03-08

Here, we demonstrated that, when the precipitation process of polyamide-6 (PA6) solution happens in cylindrical channels of an anodized aluminum oxide membrane (AAO), interface interactions between a solid surface, solvent, non-solvent, and PA6 will influence the obtained polymer nanostructures, resulting in complex morphologies, increased surface area, and crystallization changes. With the enhancing interaction of PA6 and the AAO surface, the morphology of PA6 nanostructures changes from solid nanofibers, mesoporous, to bamboo-like, while at the same time, metastable γ-phase domains increase in these PA6 nanostructures. Brunauer-Emmett-Teller (BET) surface areas of solid, bamboo-like, and mesoporous PA6 nanofibers rise from 16, 20.9, to 25 m(2)/g. This study shows that interfacial interaction in AAO template fabrication can be used in manipulating the morphology and crystallization of one-dimensional polymer nanostructures. It also provides us a simple and novel method to create porous PA6 nanofibers with a large surface area.

Material for surface-enhanced Raman spectroscopy, and SER sensors and method for preparing same

NASA Technical Reports Server (NTRS)

Farquharson, Stuart (Inventor); Nelson, Chad (Inventor); Lee, Yuan-Hsiang (Inventor)

2003-01-01

Metal-doped sol-gel materials, suitable for use as sensors for surface-enhanced Raman spectroscopic analysis for trace chemical detection, are produced by effecting gelation and solvent removal of a doped sol-gel under mild temperature conditions. At least in certain instances reaction and drying will desirably be effected in an oxygen-starved environment. The metal of the sol-gel material functions, when irradiated, to produce a plasmon field for interaction with molecules of an analyte in contact therewith, increasing by orders of magnitude Raman photons that are generate by excitation radiation, and the method allows matching of the metal and metal particle size to a wavelength of light (or incident radiation, e.g., laser radiation) to generate surface plasmons. The porosity of the sol-gel material dramatically increases the surface area, and thereby the amount of metal exposed for analyte interaction. The sensors provided may be in the form of glass vials, fiber optics, multi-well micro-sample plates, etc., having surface coatings of the doped sol-gel material, to provide sampling systems for use in a Raman instrument.

Continuous shear rheometry of o/w emulsions; control of evaporation in cone/plate geometry.

PubMed

Orafidiya, L O

1989-05-01

Volatile solvents may evaporate during cone/plate viscometry so that false rheograms develop. This surface evaporation was prevented in a cod-liver oil-in-water emulsion stabilized with zanthoxylum gum by layering a film of cod-liver oil on the exposed surface of the emulsion test sample. The oil layer effectively prevented evaporation and did not alter significantly the rheological behaviour of the test material.

Exacerbation of noise-induced hearing loss by co-exposure to workplace chemicals.

PubMed

Sliwinska-Kowalska, Mariola; Zamyslowska-Szmytke, Ewa; Szymczak, Wieslaw; Kotylo, Piotr; Fiszer, Marta; Wesolowski, Wiktor; Pawlaczyk-Luszczynska, Malgorzata

2005-05-01

: Numerous organic solvents applied in industry, like toluene, styrene, xylene and n-hexane have been demonstrated to impair hearing in animals. However, the effects of exposure to a given organic solvent and the interaction of noise and solvents on hearing in humans are still not fully recognized. : The study was aimed to assess the effects of occupational exposure to solvents alone or in combination with noise on hearing in 1117 employees of yacht, ship, plastic, shoe, and paint and lacquer industry. These persons were exposed either to the mixture of organic solvents with xylene as the main component, or predominantly to styrene, or to the mixture of n-hexane and toluene. Detailed questionnaire data and pure-tone audiometry were compared with data of the reference group that included white collar workers, exposed neither to solvents nor noise and metal factory workers exposed to noise only. In all statistics, the confounding factors were recognized as gender, age, exposure to noise, and other variables occurring at a different rate in study and reference group. : Odds ratio (OR) of hearing loss related with the particular exposure to chemicals was 2.4 (95%CI 1.59-3.74) in case of solvent mixture, 3.9 (95%CI 2.4-6.2) in case of styrene and 5.3 (95%CI 2.6-10.9) in case of n-hexane and toluene exposure. The odds of developing hearing loss substantially increased in the case of combined exposure to organic solvents and noise as compared to isolated exposure to each of these hazards. The highest OR (over 20-fold) was demonstrated in subgroups of subjects exposed simultaneously to noise and two ototoxic solvents (i.e. styrene and toluene or n-hexane and toluene). The mean hearing thresholds were significantly higher in the solvent-exposed groups than in the reference group. The differences in thresholds were observed at high frequencies in the solvent mixture- and n-hexane + toluene-exposed groups and at all frequencies in the styrene-exposed group. A positive linear relationship existed between exposure to solvents and hearing thresholds at high frequencies. : The results of the study provide the epidemiological evidence that exposure to organic solvents in humans is associated with an increased risk of hearing loss. The simultaneous exposure to organic solvents and noise seems to enhance the hearing deficit if compared with isolated exposures.

[Evaluation of exposure of auto painters to organic solvents in the city of Bogota].

PubMed

Palma, Marien; Briceño, Leonardo; Idrovo, Álvaro J; Varona, Marcela

2015-08-01

Painters of automobiles are exposed to pure and mixed solvents that have been associated with neurological effects and carcinogenic mutations. To characterize the health and work conditions of individuals who are occupationally exposed to organic solvents used in sheet metal and auto body shops in Bogota. Descriptive, cross-sectional study that characterizes the health and work conditions of individuals exposed to organic solvents in sheet metal and auto body shops in Bogota. A group exposed to the solvents was compared to an unexposed group. Air concentrations of benzene, toluene and xylene (BTX) were determined, individual questionnaires were administered and phenylmercapturic, hippuric and ortho- and para-methylhippuric acids were measured in urine. The results of the measurements and the questionnaires were correlated to determine the exposure panorama. For the three BTX metabolites, statistically significant differences (p<0.001) were found between the population exposed to the solvents and the unexposed population. For the exposed population, positive correlations were found between toluene in air and hippuric acid in urine (rho=0.82) and between xylene in air and o-methylhippuric acid in urine (rho=0.76). Hippuric acid values exceeded permissible levels in 11 workers and p-methylhippuric acid exceeded permissible levels in 8 workers. None of the phenylmercapturic values exceeded the limit. Auto painters are exposed to high levels of organic solvents at the workplace and do not have adequate industrial health and safety conditions to perform their jobs.

First-principles calculation of electronic energy level alignment at electrochemical interfaces

NASA Astrophysics Data System (ADS)

Azar, Yavar T.; Payami, Mahmoud

2017-08-01

Energy level alignment at solid-solvent interfaces is an important step in determining the properties of electrochemical systems. The positions of conduction and valence band edges of a semiconductor are affected by its environment. In this study, using first-principles DFT calculation, we have determined the level shifts of the semiconductors TiO2 and ZnO at the interfaces with MeCN and DMF solvent molecules. The level shifts of semiconductor are obtained using the potential difference between the clean and exposed surfaces of asymmetric slabs. In this work, neglecting the effects of present ions in the electrolyte solution, we have shown that the solvent molecules give rise to an up-shift for the levels, and the amount of this shift varies with coverage. It is also shown that the shapes of density of states do not change sensibly near the gap. Molecular dynamics simulations of the interface have shown that at room temperatures the semiconductor surface is not fully covered by the solvent molecules, and one must use intermediate values in an static calculations.

Work ability score of solvent-exposed workers.

PubMed

Furu, Heidi; Sainio, Markku; Hyvärinen, Hanna-Kaisa; Kaukiainen, Ari

2018-03-28

Occupational chronic solvent encephalopathy (CSE), characterized by neurocognitive dysfunction, often leads to early retirement. However, only the more severe cases are diagnosed with CSE, and little is known about the work ability of solvent-exposed workers in general. The aim was to study memory and concentration symptoms, work ability and the effect of both solvent-related and non-occupational factors on work ability, in an actively working solvent-exposed population. A questionnaire on exposure and health was sent to 3640 workers in four solvent-exposed fields, i.e. painters and floor-layers, boat builders, printers, and metal workers. The total number of responses was 1730. We determined the work ability score (WAS), a single question item of the Work Ability Index, and studied solvent exposure, demographic factors, Euroquest memory and concentration symptoms, chronic diseases, and employment status using univariate and multivariate analyses. The findings were compared to those of a corresponding national blue-collar reference population (n = 221), and a small cohort of workers with CSE (n = 18). The proportion of workers with memory and concentration symptoms was significantly associated with solvent exposure. The WAS of solvent-exposed workers was lower than that of the national blue-collar reference group, and the difference was significant in the oldest age group (those aged over 60). Solvent-exposed worker's WAS were higher than those of workers diagnosed with CSE. The WAS were lowest among painters and floor-layers, followed by metal workers and printers, and highest among boat builders. The strongest explanatory factors for poor work ability were the number of chronic diseases, age and employment status. Solvent exposure was a weak independent risk factor for reduced WAS, comparable to a level of high alcohol consumption. Even if memory and concentration symptoms were associated with higher solvent exposure, the effect of solvents on self-experienced work ability was relatively weak. This in line with the improved occupational hygiene and reduced solvent exposure levels in industrialized countries, thus the effect may be stronger in high-level exposure environments. As a single question, WAS is easily included, applicable, and recommendable in occupational screening questionnaires.

Solvent friction effects propagate over the entire protein molecule through low-frequency collective modes.

PubMed

Moritsugu, Kei; Kidera, Akinori; Smith, Jeremy C

2014-07-24

Protein solvation dynamics has been investigated using atom-dependent Langevin friction coefficients derived directly from molecular dynamics (MD) simulations. To determine the effect of solvation on the atomic friction coefficients, solution and vacuum MD simulations were performed for lysozyme and staphylococcal nuclease and analyzed by Langevin mode analysis. The coefficients thus derived are roughly correlated with the atomic solvent-accessible surface area (ASA), as expected from the fact that friction occurs as the result of collisions with solvent molecules. However, a considerable number of atoms with higher friction coefficients are found inside the core region. Hence, the influence of solvent friction propagates into the protein core. The internal coefficients have large contributions from the low-frequency modes, yielding a simple picture of the surface-to-core long-range damping via solvation governed by collective low-frequency modes. To make use of these findings in implicit-solvent modeling, we compare the all-atom friction results with those obtained using Langevin dynamics (LD) with two empirical representations: the constant-friction and the ASA-dependent (Pastor-Karplus) friction models. The constant-friction model overestimates the core and underestimates the surface damping whereas the ASA-dependent friction model, which damps protein atoms only on the solvent-accessible surface, reproduces well the friction coefficients for both the surface and core regions observed in the explicit-solvent MD simulations. Therefore, in LD simulation, the solvent friction coefficients should be imposed only on the protein surface.

Solvent friction effects propagate over the entire protein molecule through low-frequency collective modes

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

Moritsugu, Kei; Kidera, Akinori; Smith, Jeremy C.

2014-06-25

Protein solvation dynamics has been investigated using atom-dependent Langevin friction coefficients derived directly from molecular dynamics (MD) simulations. To determine the effect of solvation on the atomic friction coefficients, solution and vacuum MD simulations were performed for lysozyme and staphylococcal nuclease and analyzed by Langevin mode analysis. The coefficients thus derived are roughly correlated with the atomic solvent-accessible surface area (ASA), as expected from the fact that friction occurs as the result of collisions with solvent molecules. However, a considerable number of atoms with higher friction coefficients are found inside the core region. Hence, the influence of solvent friction propagatesmore » into the protein core. The internal coefficients have large contributions from the low-frequency modes, yielding a simple picture of the surface-to-core long-range damping via solvation governed by collective low-frequency modes. To make use of these findings in implicit-solvent modeling, we compare the all-atom friction results with those obtained using Langevin dynamics (LD) with two empirical representations: the constant-friction and the ASA-dependent (Pastor Karplus) friction models. The constant-friction model overestimates the core and underestimates the surface damping whereas the ASA-dependent friction model, which damps protein atoms only on the solvent-accessible surface, reproduces well the friction coefficients for both the surface and core regions observed in the explicit-solvent MD simulations. Furthermore, in LD simulation, the solvent friction coefficients should be imposed only on the protein surface.« less

Sleep disturbances and exposure to organic solvents

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

Lindelof, B.; Almkvist, O.; Goethe, C.

An inquiry about sleep habits and sleep disturbances revealed a significantly higher prevalence of insomnia in a solvent-exposed group than in a comparable group that had no occupational exposure to organic solvents. The solvent-exposed group has also registered an increased consumption of hypnotics, and a significant increase occurred in the number of individuals who had consulted physicians because of sleep disorders. The results indicate that solvent exposure could induce sleep disturbances.

Self-Organization of Polymer Brush Layers in a Poor Solvent

NASA Astrophysics Data System (ADS)

Karim, A.; Tsukruk, V. V.; Douglas, J. F.; Satija, S. K.; Fetters, L. J.; Reneker, D. H.; Foster, M. D.

1995-10-01

Synthesis of densely grafted polymer brushes from good solvent polymer solutions is difficult when the surface interaction is only weakly attractive because of the strong steric repulsion between the polymer chains. To circumvent this difficulty we graft polymer layers in a poor solvent to exploit attractive polymer-polymer interactions which largely nullify the repulsive steric interactions. This simple strategy gives rise to densely grafted and homogeneous polymer brush layers. Model end-grafted polystyrene chains (M_w = 105,000) are prepared in the poor solvent cyclohexane (9.5 °C) where the chains are chemically attached to the surface utilizing a trichlorosilane end-group. Polished silicon wafers were then exposed to the reactive polymer solutions for a series of “induction times” tau_I and the evolving layer was characterized by X-ray reflectivity and atomic force microscopy. Distinct morphologies were found depending on tau_I. For short tau_I, corresponding to a grafting density less than 5 mg/m^2, the grafted layer forms an inhomogeneous island-like structure. At intermediate tau_I, where the coverage becomes percolating, a surface pattern develops which appears similar to spinodal decomposition in bulk solution. Finally, after sufficiently long tau_I, a dense and nearly homogeneous layer with a sharp interface is formed which does not exhibit surface pattern formation. The stages of brush growth are discussed qualitatively in terms of a random deposition model.

Combined effects of exposure to occupational noise and mixed organic solvents on blood pressure in car manufacturing company workers.

PubMed

Attarchi, Mirsaeed; Golabadi, Majid; Labbafinejad, Yasser; Mohammadi, Saber

2013-02-01

Recent studies suggest that occupational exposures such as noise and organic solvents may affect blood pressure. The aim of this study was to investigate interaction of noise and mixed organic solvents on blood pressure. Four hundred seventy-one workers of a car manufacturing plant were divided into four groups: group one or G1 workers exposed to noise and mixed organic solvents in the permitted limit or control group, G3 exposed to noise only, G2 exposed to solvents only, and G4 workers exposed to noise and mixed organic solvents at higher than the permitted limit or co-exposure group. Biological interaction of two variables on hypertension was calculated using the synergistic index. The workers of co-exposure group (G4), noise only group (G3), and solvents only group (G2) had significantly higher mean values of SBP and DBP than workers of control group (G1) or office workers (P < 0.05). Also logistic regression analysis showed a significant association between hypertension and exposure to noise and mixture of organic solvents. Odds ratio for hypertension in the co-exposure group and the noise only and solvents only exposed groups was 14.22, 9.43, and 4.38, respectively, compared to control group. In this study, the estimated synergism index was 1.11. Our results indicate that exposure to noise or a mixture of organic solvents may be associated with the prevalence of hypertension in car manufacturing company workers and co-exposure to noise and a mixture of solvents has an additive effect in this regard. Therefore appropriate preventive programs in these workers recommended. Copyright © 2012 Wiley Periodicals, Inc.

Auditory dysfunction associated with solvent exposure

PubMed Central

2013-01-01

Background A number of studies have demonstrated that solvents may induce auditory dysfunction. However, there is still little knowledge regarding the main signs and symptoms of solvent-induced hearing loss (SIHL). The aim of this research was to investigate the association between solvent exposure and adverse effects on peripheral and central auditory functioning with a comprehensive audiological test battery. Methods Seventy-two solvent-exposed workers and 72 non-exposed workers were selected to participate in the study. The test battery comprised pure-tone audiometry (PTA), transient evoked otoacoustic emissions (TEOAE), Random Gap Detection (RGD) and Hearing-in-Noise test (HINT). Results Solvent-exposed subjects presented with poorer mean test results than non-exposed subjects. A bivariate and multivariate linear regression model analysis was performed. One model for each auditory outcome (PTA, TEOAE, RGD and HINT) was independently constructed. For all of the models solvent exposure was significantly associated with the auditory outcome. Age also appeared significantly associated with some auditory outcomes. Conclusions This study provides further evidence of the possible adverse effect of solvents on the peripheral and central auditory functioning. A discussion of these effects and the utility of selected hearing tests to assess SIHL is addressed. PMID:23324255

A rapid solvent accessible surface area estimator for coarse grained molecular simulations.

PubMed

Wei, Shuai; Brooks, Charles L; Frank, Aaron T

2017-06-05

The rapid and accurate calculation of solvent accessible surface area (SASA) is extremely useful in the energetic analysis of biomolecules. For example, SASA models can be used to estimate the transfer free energy associated with biophysical processes, and when combined with coarse-grained simulations, can be particularly useful for accounting for solvation effects within the framework of implicit solvent models. In such cases, a fast and accurate, residue-wise SASA predictor is highly desirable. Here, we develop a predictive model that estimates SASAs based on Cα-only protein structures. Through an extensive comparison between this method and a comparable method, POPS-R, we demonstrate that our new method, Protein-C α Solvent Accessibilities or PCASA, shows better performance, especially for unfolded conformations of proteins. We anticipate that this model will be quite useful in the efficient inclusion of SASA-based solvent free energy estimations in coarse-grained protein folding simulations. PCASA is made freely available to the academic community at https://github.com/atfrank/PCASA. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Crystal structures of native and xylosaccharide-bound alkali thermostable xylanase from an alkalophilic Bacillus sp. NG-27: Structural insights into alkalophilicity and implications for adaptation to polyextreme conditions

PubMed Central

Manikandan, Karuppasamy; Bhardwaj, Amit; Gupta, Naveen; Lokanath, Neratur K.; Ghosh, Amit; Reddy, Vanga Siva; Ramakumar, Suryanarayanarao

2006-01-01

Crystal structures are known for several glycosyl hydrolase family 10 (GH10) xylanases. However, none of them is from an alkalophilic organism that can grow in alkaline conditions. We have determined the crystal structures at 2.2 Å of a GH10 extracellular endoxylanase (BSX) from an alkalophilic Bacillus sp. NG-27, for the native and the complex enzyme with xylosaccharides. The industrially important enzyme is optimally active and stable at 343 K and at a pH of 8.4. Comparison of the structure of BSX with those of other thermostable GH10 xylanases optimally active at acidic or close to neutral pH showed that the solvent-exposed acidic amino acids, Asp and Glu, are markedly enhanced in BSX, while solvent-exposed Asn was noticeably depleted. The BSX crystal structure when compared with putative three-dimensional homology models of other extracellular alkalophilic GH10 xylanases from alkalophilic organisms suggests that a protein surface rich in acidic residues may be an important feature common to these alkali thermostable enzymes. A comparison of the surface features of BSX and of halophilic proteins allowed us to predict the activity of BSX at high salt concentrations, which we verified through experiments. This offered us important lessons in the polyextremophilicity of proteins, where understanding the structural features of a protein stable in one set of extreme conditions provided clues about the activity of the protein in other extreme conditions. The work brings to the fore the role of the nature and composition of solvent-exposed residues in the adaptation of enzymes to polyextreme conditions, as in BSX. PMID:16823036

Functionalization of Cadmium Selenide Quantum Dots with Poly(ethylene glycol): Ligand Exchange, Surface Coverage, and Dispersion Stability.

PubMed

Wenger, Whitney Nowak; Bates, Frank S; Aydil, Eray S

2017-08-22

Semiconductor quantum dots synthesized using rapid mixing of precursors by injection into a hot solution of solvents and surfactants have surface ligands that sterically stabilize the dispersions in nonpolar solvents. Often, these ligands are exchanged to disperse the quantum dots in polar solvents, but quantitative studies of quantum dot surfaces before and after ligand exchange are scarce. We studied exchanging trioctylphosphine (TOP) and trioctylphosphine oxide (TOPO) ligands on as-synthesized CdSe quantum dots dispersed in hexane with a 2000 g/mol thiolated poly(ethylene glycol) (PEG) polymer. Using infrared spectroscopy we quantify the absolute surface concentration of TOP/TOPO and PEG ligands per unit area before and after ligand exchange. While 50-85% of the TOP/TOPO ligands are removed upon ligand exchange, only a few are replaced with PEG. Surprisingly, the remaining TOP/TOPO ligands outnumber the PEG ligands, but these few PEG ligands are sufficient to disperse the quantum dots in polar solvents such as chloroform, tetrahydrofuran, and water. Moreover, as-synthesized quantum dots once easily dispersed in hexane are no longer dispersible in nonpolar solvents after ligand exchange. A subtle coverage-dependent balance between attractive PEG-solvent interactions and repulsive TOP/TOPO-solvent interactions determines the dispersion stability.

Determining eyeball surface area directly exposed to the effects of external factors.

PubMed

Juliszewski, Tadeusz; Kadłuczka, Filip; Kiełbasa, Paweł

2016-01-01

This article discusses determining the surface area of eyeballs of men and women exposed to the direct effects of external factors in the working environment. For one eye, the mean surface is 172-182 mm(2). The determined surface area can be used in formulas for calculating the exposure of eyeballs to harmful chemical substances in workplace air.

Activation of porous MOF materials

DOEpatents

Hupp, Joseph T; Farha, Omar K

2013-04-23

A method for the treatment of solvent-containing MOF material to increase its internal surface area involves introducing a liquid into the MOF in which liquid the solvent is miscible, subjecting the MOF to supercritical conditions for a time to form supercritical fluid, and releasing the supercritical conditions to remove the supercritical fluid from the MOF. Prior to introducing the liquid into the MOF, occluded reaction solvent, such as DEF or DMF, in the MOF can be exchanged for the miscible solvent.

Activation of porous MOF materials

DOEpatents

Hupp, Joseph T; Farha, Omar K

2014-04-01

A method for the treatment of solvent-containing MOF material to increase its internal surface area involves introducing a liquid into the MOF in which liquid the solvent is miscible, subjecting the MOF to supercritical conditions for a time to form supercritical fluid, and releasing the supercritical conditions to remove the supercritcal fluid from the MOF. Prior to introducing the liquid into the MOF, occluded reaction solvent, such as DEF or DMF, in the MOF can be exchanged for the miscible solvent.

Enhanced ion signals in desorption electrospray ionization using surfactant spray solutions.

PubMed

Badu-Tawiah, Abraham; Cooks, R Graham

2010-08-01

Solvent optimization is an important procedure in desorption electrospray ionization (DESI) and in this study the effects of solvent surface tension are explored. Data are presented for methanol/water/surfactant solvent systems, which show increases in ion signals of more than an order of magnitude when low concentrations of surfactants are added to the standard methanol/water (1:1) spray solvent. Examples of analytes tested include food chemicals, peptides, pharmaceuticals, and drugs of abuse. The improvement in ion intensity is mainly attributed to the effect of surface tension in producing smaller spray droplets, which are shown to cover a larger surface area. Surfactant-containing spray solutions allowed extension of DESI-MS analysis to previously intractable analytes like melamine and highly hydrophobic compounds like the sudan dyes. Copyright 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.

System for removing contaminants from plastic resin

DOEpatents

Bohnert, George W.; Hand, Thomas E.; DeLaurentiis, Gary M.

2010-11-23

A resin recycling system that produces essentially contaminant-free synthetic resin material in an environmentally safe and economical manner. The system includes receiving the resin in container form. A grinder grinds the containers into resin particles. The particles are exposed to a solvent in one or more solvent wash vessels, the solvent contacting the resin particles and substantially removing contaminants on the resin particles. A separator is used to separate the resin particles and the solvent. The resin particles are then placed in solvent removing element where they are exposed to a solvent removing agent which removes any residual solvent remaining on the resin particles after separation.

Method of performing sugar dehydration and catalyst treatment

DOEpatents

Hu, Jianli [Kennewick, WA; Holladay, Johnathan E [Kennewick, WA; Zhang, Xinjie [Burlington, MA; Wang, Yong [Richland, WA

2010-06-01

The invention includes a method of treating a solid acid catalyst. After exposing the catalyst to a mixture containing a sugar alcohol, the catalyst is washed with an organic solvent and is then exposed to a second reaction mixture. The invention includes a process for production of anhydrosugar alcohol. A solid acid catalyst is provided to convert sugar alcohol in a first sample to an anhydrosugar alcohol. The catalyst is then washed with an organic solvent and is subsequently utilized to expose a second sample. The invention includes a method for selective production of an anhydrosugar. A solid acid catalyst is provided within a reactor and anhydrosugar alcohol is formed by flowing a starting sugar alcohol into the reactor. The acid catalyst is then exposed to an organic solvent which allows a greater amount of additional anhydrosugar to be produced than would occur without exposing the acid catalyst to the organic solvent.

Auditory Effects of Exposure to Noise and Solvents: A Comparative Study

PubMed Central

Lobato, Diolen Conceição Barros; Lacerda, Adriana Bender Moreira De; Gonçalves, Cláudia Giglio De Oliveira; Coifman, Herton

2013-01-01

Introduction Industry workers are exposed to different environmental risk agents that, when combined, may potentiate risks to hearing. Objective To evaluate the effects of the combined exposure to noise and solvents on hearing in workers. Methods A transversal retrospective cohort study was performed through documentary analysis of an industry. The sample (n = 198) was divided into four groups: the noise group (NG), exposed only to noise; the noise and solvents group (NSG), exposed to noise and solvents; the noise control group and noise and solvents control group (CNS), no exposure. Results The NG showed 16.66% of cases suggestive of bilateral noise-induced hearing loss and NSG showed 5.26%. The NG and NSG had worse thresholds than their respective control groups. Females were less susceptible to noise than males; however, when simultaneously exposed to solvents, hearing was affected in a similar way, resulting in significant differences (p < 0.05). The 40- to 49-year-old age group was significantly worse (p < 0.05) in the auditory thresholds in the NSG compared with the CNS. Conclusion The results observed in this study indicate that simultaneous exposure to noise and solvents can damage the peripheral auditory system. PMID:25992079

Evaluation of Chemical Warfare Agent Wipe Sampling ...

EPA Pesticide Factsheets

Report This investigation tested specific (CWAs), including sarin (GB), soman (GD), cyclosarin (GF), sulfur mustard (HD), and O-ethyl-S-(2-diisopropylaminoethyl) methylphosphonothioate (VX) on the non-ideal (e.g., porous and permeable) surfaces of drywall, vinyl tile, wood, laminate, and coated glass. Pesticides (diazinon and malathion) were used so that a comparison is possible with existing literature data (1). Experiments included testing with coupons having surface areas of 10 cm2 and 100 cm2. The 10-cm2 coupons were of a size that could easily be extracted in a 2 oz jar (to provide comparative data for CWA recoveries generated by direct extraction) and the 100-cm2 coupons better represented the area of a surface that might typically be sampled by wipe extraction. In addition, CWA, at a normalized surface concentration of 0.1 µg per cm2 surface area, were spiked on coupons of the tested surfaces. Wipes were wetted with either dichloromethane (DCM) or isopropanol (IPA) before sampling for CWA. Experimental parameters include multiple wipe types, porous/permeable surfaces, coupon surface area, solvent used to wet the wipe (i.e., wetting solvent), and the utility of VX-d14 as an extracted internal standard.

A survey of airborne and skin exposures to chemicals in footwear and equipment factories in Thailand.

PubMed

Todd, Lori A; Mottus, Kathleen; Mihlan, Gary J

2008-03-01

This research reports on a pilot industrial hygiene study that was performed at four footwear factories and two equipment factories in Thailand. Workers in these factories were exposed through inhalation and dermal contact to a large number of organic vapors from solvents and cements that were hand applied. In addition, these workers were exposed to highly toxic isocyanates primarily through the dermal route. A total of 286 personal air samples were obtained at the four footwear factories using organic vapor monitors; individual job tasks were monitored using a real-time MIRAN Spectrometer. A total of 64 surface, tool, or hand samples were monitored for isocyanates using surface contamination detectors. Real-time measurements were also obtained for organic vapors in two equipment factories. From 8% to 21% of the workers sampled in each footwear factory were overexposed to mixtures of chemicals from solvents and cements. Up to 100% of the workers performing specific job tasks were overexposed to mixtures of chemicals. From 39% to 69% of the surface samples were positive for unreacted isocyanates. Many of the real-time measurements obtained in the equipment factories exceeded occupational exposure limits. Personal protective equipment and engineering controls were inadequate in all of the factories.

Air formaldehyde and solvent concentrations during surface coating with acid-curing lacquers and paints in the woodworking and furniture industry.

PubMed

Thorud, Syvert; Gjolstad, Merete; Ellingsen, Dag G; Molander, Paal

2005-06-01

An investigation of contemporary exposure to formaldehyde and organic solvents has been carried out during surface coating with acid-curing lacquers and paints in the Norwegian woodworking and furniture industry over a period of 3 years. The investigation covered 27 factories of different sizes and with different types of production, and totally 557 parallel formaldehyde and solvent samples were collected. The formaldehyde concentration (geometric mean) was 0.15 ppm (range 0.01-1.48 ppm) with about 10% of the samples exceeding the Norwegian occupational exposure limit of 0.5 ppm. The solvent concentration as additive effect (geometric mean) was 0.13 (range 0.0004-5.08) and about 5% of the samples exceeded the Norwegian occupational exposure limit. The most frequently occurring solvents from acid-curing lacquers were n-butyl acetate, ethanol, ethyl acetate and 1-butanol, which were found in 88-98% of the samples. Toluene, n-butyl acetate and 1-butanol were the only solvents with maximum concentrations exceeding their respective occupational exposure limits. Curtain painting machine operators were exposed to the highest concentrations of both formaldehyde (geometric mean 0.51 ppm, range 0.08-1.48 ppm) and organic solvents (additive effect, geometric mean 1.18, range 0.02-5.08). Other painting application work tasks such as automatic and manual spray-painting, manual painting and dip painting, showed on average considerably lower concentrations of both formaldehyde (geometric means 0.07-0.16 ppm) and organic solvents (additive effect, geometric mean 0.02-0.18). Non-painting work tasks also displayed moderate concentrations of formaldehyde (geometric means 0.11-0.17 ppm) and organic solvents (additive effect, geometric mean 0.04-0.07).

Clean Transfer of Wafer-Scale Graphene via Liquid Phase Removal of Polycyclic Aromatic Hydrocarbons.

PubMed

Kim, Hyun Ho; Kang, Boseok; Suk, Ji Won; Li, Nannan; Kim, Kwang S; Ruoff, Rodney S; Lee, Wi Hyoung; Cho, Kilwon

2015-05-26

Pentacene (C22H14), a polycyclic aromatic hydrocarbon, was used as both supporting and sacrificing layers for the clean and doping-free graphene transfer. After successful transfer of graphene to a target substrate, the pentacene layer was physically removed from the graphene surface by using intercalating organic solvent. This solvent-mediated removal of pentacene from graphene surface was investigated by both theoretical calculation and experimental studies with various solvents. The uses of pentacene and appropriate intercalation solvent enabled graphene transfer without forming a residue from the supporting layer. Such residues tend to cause charged impurity scattering and unintentional graphene doping effects. As a result, this clean graphene exhibited extremely homogeneous surface potential profiles over a large area. A field-effect transistor fabricated using this graphene displayed a high hole (electron) mobility of 8050 cm(2)/V·s (9940 cm(2)/V·s) with a nearly zero Dirac point voltage.

Color vision impairments among shipyard workers exposed to mixed organic solvents, especially xylene.

PubMed

Lee, Eun-Hee; Paek, Domyung; Kho, Young Lim; Choi, Kyungho; Chae, Hong Jae

2013-01-01

We evaluated color vision impairment in workers exposed to organic solvents, especially xylene. Three groups of subjects, comprising 63 workers occupationally exposed to organic solvents, 122 non-exposed workers in the same industry, and 185 subjects from the general population as controls, were evaluated for color vision. Exposure to solvents was indirectly evaluated by measuring the concentration of a urinary metabolite. Color vision was assessed using the Lanthony Desaturated 15-hue (Lanthony D-15) panel. Color confusion index (CCI) values in the exposed group were significantly higher than in the non-exposed workers or the general population, after adjustment for age and education, and significantly correlated with the concentration of methylhippuric acid. Color vision impairments were detected more frequently among the exposed group, and the most common types were type III and complex impairments. The rate of type III impairments was 9.52% in the exposed group, 1.64% in the non-exposed group, and 1.62% in the general population. Our results support the hypothesis that acquired color vision impairments could be induced by exposure to xylene. Testing for color vision impairment is a relatively simple, non-invasive and sensitive diagnostic method for relatively low-level exposures to xylene. Copyright © 2013 Elsevier Inc. All rights reserved.

High surface area nanocrystalline hausmannite synthesized by a solvent-free route

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

Herrera-Miranda, Daniel; Ponrouch, Alexandre; Pons, Josefina

Highlights: ► High surface area Mn{sub 3}O{sub 4} nanoparticles obtained by a solvent-free low temperature route. ► 3,6,9-Trioxadecanoic acid allows to obtain nanocrystalline hausmannite. ► Tape casted electrodes show up to 300 mAh g{sup −1} capacity after more than 40 cycles at a C/3 rate. ► Upper cut off voltage strongly influences capacity retention upon cycling at high C rates. -- Abstract: Nanocrystalline high surface area Mn{sub 3}O{sub 4} powder was obtained at low temperature by a solvent-free route. The precursor was a mixture of manganese (II) acetate, 3,6,9-trioxadecanoic acid (TODA) and ammonium acetate that were intimately mixed by groundingmore » in an agate mortar. Nanocrystalline Mn{sub 3}O{sub 4} was obtained by thermal treatment at 120 °C. Powder X-ray diffraction, selected area electron diffraction, high resolution transmission electron microscopy, and Fourier transformed infrared characterization confirmed the formation of the hausmannite phase. The as-prepared mesoporous material has high specific surface area (120 m{sup 2} g{sup −1}). The performances of tape casted Mn{sub 3}O{sub 4} nanopowder electrodes were investigated as anode material for lithium ion batteries. High capacity values were achieved at diverse C rates. Capacity fading was found to be dependent on the upper cut off voltage, the presence of a plateau at 2.25 V vs. Li{sup +}/Li being detrimental for long term cyclability.« less

Chronic Organic Solvent Exposure Changes Visual Tracking in Men and Women.

PubMed

de Oliveira, Ana R; Campos Neto, Armindo de Arruda; Bezerra de Medeiros, Paloma C; de Andrade, Michael J O; Dos Santos, Natanael A

2017-01-01

Organic solvents can change CNS sensory and motor function. Eye-movement analyses can be important tools when investigating the neurotoxic changes that result from chronic organic solvent exposure. The current research measured the eye-movement patterns of men and women with and without histories of chronic organic solvent exposure. A total of 44 volunteers between 18 and 41 years old participated in this study; 22 were men (11 exposed and 11 controls), and 22 were women (11 exposed and 11 controls). Eye movement was evaluated using a 250-Hz High-Speed Video Eye Tracker Toolbox (Cambridge Research Systems) via an image of a maze. Specific body indices of exposed and non-exposed men and women were measured with an Inbody 720 to determine whether the differences in eye-movement patterns were associated with body composition. The data were analyzed using IBM SPSS Statistics version 20.0.0. The results indicated that exposed adults showed significantly more fixations ( t = 3.82; p = 0.001; r = 0.51) and longer fixations ( t = 4.27; p = 0.001, r = 0.54) than their non-exposed counterparts. Comparisons within men (e.g., exposed and non-exposed) showed significant differences in the number of fixations ( t = 2.21; p = 0.04; r = 0.20) and duration of fixations ( t = 3.29; p = 0.001; r = 0.35). The same was true for exposed vs. non-exposed women, who showed significant differences in the number of fixations ( t = 3.10; p = 0.001; r = 0.32) and fixation durations ( t = 2.76; p = 0.01; r = 0.28). However, the results did not show significant differences between exposed women and men in the number and duration of fixations. No correlations were found between eye-movement pattern and body composition measures ( p > 0.05). These results suggest that chronic organic solvent exposure affects eye movements, regardless of sex and body composition, and that eye tracking contributes to the investigation of the visual information processing disorders acquired by workers exposed to organic solvents.

Superinsulating Polyisocyanate Based Aerogels: A Targeted Search for the Optimum Solvent System.

PubMed

Zhu, Zhiyuan; Snellings, Geert M B F; Koebel, Matthias M; Malfait, Wim J

2017-05-31

Polyisocyanate based aerogels combine ultralow thermal conductivities with better mechanical properties than silica aerogel, but these properties critically depend on the nature of the gelation solvent, perhaps more so than on any other parameter. Here, we present a systematic study of the relationship between the polyurethane-polyisocyanurate (PUR-PIR) aerogel microstructure, surface area, thermal conductivity, and density and the gelation solvent's Hansen solubility parameters for an industrially relevant PUR-PIR rigid foam formulation. We first investigated aerogels prepared in acetone-dimethyl sulfoxide (DMSO) blends and observed a minimum in thermal conductivity (λ) and maximum in specific surface area for an acetone:DMSO ratio of 85:15 v/v. We then prepared PUR-PIR aerogels in 32 different solvent blends, divided into three series with δ Dispersion , δ Polarity , and δ H-bonding fixed at 15.94, 11.30, and 7.48 MPa 1/2 , respectively, corresponding to the optimum parameters for the acetone:DMSO series. The aerogel properties display distinct dependencies on the various solubility parameters: aerogels with low thermal conductivity can be synthesized in solvents with a high δ H-bonding parameter (above 7.2) and δ Dispersion around 16.3 MPa 1/2 . In contrast, the δ Polarity parameter is of lesser importance. Our study highlights the importance of the gelation solvent, clarifies the influence of the different solvent properties, and provides a methodology for a targeted search across the solvent chemical space based on the Hansen solubility parameters.

Determination of protein secondary structure and solvent accessibility using site-directed fluorescence labeling. Studies of T4 lysozyme using the fluorescent probe monobromobimane.

PubMed

Mansoor, S E; McHaourab, H S; Farrens, D L

1999-12-07

We report an investigation of how much protein structural information could be obtained using a site-directed fluorescence labeling (SDFL) strategy. In our experiments, we used 21 consecutive single-cysteine substitution mutants in T4 lysozyme (residues T115-K135), located in a helix-turn-helix motif. The mutants were labeled with the fluorescent probe monobromobimane and subjected to an array of fluorescence measurements. Thermal stability measurements show that introduction of the label is substantially perturbing only when it is located at buried residue sites. At buried sites (solvent surface accessibility of <40 A(2)), the destabilizations are between 3 and 5.5 kcal/mol, whereas at more exposed sites, DeltaDeltaG values of < or = 1.5 kcal/mol are obtained. Of all the fluorescence parameters that were explored (excitation lambda(max), emission lambda(max), fluorescence lifetime, quantum yield, and steady-state anisotropy), the emission lambda(max) and the steady-state anisotropy values most accurately reflect the solvent surface accessibility at each site as calculated from the crystal structure of cysteine-less T4 lysozyme. The parameters we identify allow the classification of each site as buried, partially buried, or exposed. We find that the variations in these parameters as a function of residue number reflect the sequence-specific secondary structure, the determination of which is a key step for modeling a protein of unknown structure.

SPINE: SParse eIgengene NEtwork linking gene expression clusters in Dehalococcoides mccartyi to perturbations in experimental conditions

DOE PAGES

Mansfeldt, Cresten B.; Logsdon, Benjamin A.; Debs, Garrett E.; ...

2015-02-25

We present a statistical model designed to identify the effect of experimental perturbations on the aggregate behavior of the transcriptome expressed by the bacterium Dehalococcoides mccartyi strain 195. Strains of Dehalococcoides are used in sub-surface bioremediation applications because they organohalorespire tetrachloroethene and trichloroethene (common chlorinated solvents that contaminate the environment) to non-toxic ethene. However, the biochemical mechanism of this process remains incompletely described. Additionally, the response of Dehalococcoides to stress-inducing conditions that may be encountered at field-sites is not well understood. The constructed statistical model captured the aggregate behavior of gene expression phenotypes by modeling the distinct eigengenes of 100more » transcript clusters, determining stable relationships among these clusters of gene transcripts with a sparse network-inference algorithm, and directly modeling the effect of changes in experimental conditions by constructing networks conditioned on the experimental state. Based on the model predictions, we discovered new response mechanisms for DMC, notably when the bacterium is exposed to solvent toxicity. The network identified a cluster containing thirteen gene transcripts directly connected to the solvent toxicity condition. Transcripts in this cluster include an iron-dependent regulator (DET0096-97) and a methylglyoxal synthase (DET0137). To validate these predictions, additional experiments were performed. Continuously fed cultures were exposed to saturating levels of tetrachloethene, thereby causing solvent toxicity, and transcripts that were predicted to be linked to solvent toxicity were monitored by quantitative reverse-transcription polymerase chain reaction. Twelve hours after being shocked with saturating levels of tetrachloroethene, the control transcripts (encoding for a key hydrogenase and the 16S rRNA) did not significantly change. By contrast, transcripts for DET0137 and DET0097 displayed a 46.8±11.5 and 14.6±9.3 fold up-regulation, respectively, supporting the model. This is the first study to identify transcripts in Dehalococcoides that potentially respond to tetrachloroethene solvent-toxicity conditions that may be encountered near contamination source zones in sub-surface environments.« less

Towards ultra-fast solvent evaporation, the development of a computer controlled solvent vapor annealing chamber

NASA Astrophysics Data System (ADS)

Nelson, Gunnar; Wong, J.; Drapes, C.; Grant, M.; Baruth, A.

Despite the promise of cheap and fast nanoscale ordering of block polymer thin films via solvent vapor annealing, a standardized, scalable production scheme remains elusive. Solvent vapor annealing exposes a nano-thin film to the vapors of one or more solvents with the goal of forming a swollen and mobile state to direct the self-assembly process by tuning surface energies and mediating unfavorable chain interactions. We have shown that optimized annealing conditions, where kinetic and thermal properties for crystal growth are extremely fast (<1s), exist at solvent concentrations just below the order-disorder transition of the film. However, when investigating the propagation of a given morphology into the bulk of a film during drying, the role of solvent evaporation comes under great scrutiny. During this process, the film undergoes a competition between two fronts; phase separation and kinetic trapping. Recent results in both theory and experiment point toward this critical element in controlling the resultant morphologies; however, no current method includes a controllable solvent evaporation rate at ultra-fast time scales. We report on a computer-controlled, pneumatically actuated chamber that provides control over solvent evaporation down to 15 ms. Furthermore, in situ spectral reflectance monitors solvent concentration with 10 ms temporal resolution and reveals several possible evaporation trajectories, ranging from linear to exponential to logarithmic. Funded by Dr. Randolph Ferlic Summer Research Scholarship and NASA Nebraska Space Grant.

Health effects of long-term solvent exposure among women in blue-collar occupations.

PubMed

Parkinson, D K; Bromet, E J; Cohen, S; Dunn, L O; Dew, M A; Ryan, C; Schwartz, J E

1990-01-01

The relationship of solvent exposure to self-reported neurologic and somatic symptoms as well as neuropsychological performance was examined in a sample of 567 female blue collar workers who were members of the International Brotherhood of Electrical Workers (IBEW). Structured interviews were conducted at IBEW offices. Five solvent exposure categories were derived--never exposed, exposed prior to but not during the past year, exposed during the past year but not currently, currently exposed less than 50% of the time, and currently exposed more than 50% of the time. No differences among the groups on neuropsychological performance were found. On the other hand, heightened exposure was significantly related to depression, severe headaches, light-headedness, room spinning, appetite difficulties, funny taste in mouth, weakness/fatigue, rashes, and abdominal pain after controlling for the effects of seven risk factors (age, smoking, moderate-heavy alcohol consumption, severe obesity, history of physician-diagnosed chronic illness, working in a clean room, and exposure to other chemicals). These findings are consistent with Scandinavian studies of solvent-exposed male workers and point to the need for careful prospective research.

Improved Detection Technique for Solvent Rinse Cleanliness Verification

NASA Technical Reports Server (NTRS)

Hornung, S. D.; Beeson, H. D.

2001-01-01

The NASA White Sands Test Facility (WSTF) has an ongoing effort to reduce or eliminate usage of cleaning solvents such as CFC-113 and its replacements. These solvents are used in the final clean and cleanliness verification processes for flight and ground support hardware, especially for oxygen systems where organic contaminants can pose an ignition hazard. For the final cleanliness verification in the standard process, the equivalent of one square foot of surface area of parts is rinsed with the solvent, and the final 100 mL of the rinse is captured. The amount of nonvolatile residue (NVR) in the solvent is determined by weight after the evaporation of the solvent. An improved process of sampling this rinse, developed at WSTF, requires evaporation of less than 2 mL of the solvent to make the cleanliness verification. Small amounts of the solvent are evaporated in a clean stainless steel cup, and the cleanliness of the stainless steel cup is measured using a commercially available surface quality monitor. The effectiveness of this new cleanliness verification technique was compared to the accepted NVR sampling procedures. Testing with known contaminants in solution, such as hydraulic fluid, fluorinated lubricants, and cutting and lubricating oils, was performed to establish a correlation between amount in solution and the process response. This report presents the approach and results and discusses the issues in establishing the surface quality monitor-based cleanliness verification.

Polymer Film Dewetting by Water/Surfactant/Good-Solvent Mixtures: A Mechanistic Insight and Its Implications for the Conservation of Cultural Heritage.

PubMed

Baglioni, Michele; Montis, Costanza; Chelazzi, David; Giorgi, Rodorico; Berti, Debora; Baglioni, Piero

2018-06-18

Aqueous nanostructured fluids (NSFs) have been proposed to remove polymer coatings from the surface of works of art; this process usually involves film dewetting. The NSF cleaning mechanism was studied using several techniques that were employed to obtain mechanistic insight on the interaction of a methacrylic/acrylic copolymer (Paraloid B72) film laid on glass surfaces and several NSFs, based on two solvents and two surfactants. The experimental results provide a detailed picture of the dewetting process. The gyration radius and the reduction of the T g of Paraloid B72 fully swollen in the two solvents is larger for propylene carbonate than for methyl ethyl ketone, suggesting higher mobility of polymer chains for the former, while a nonionic alcohol ethoxylate surfactant was more effective than sodium dodecylsulfate in favoring the dewetting process. FTIR 2D imaging showed that the dewetting patterns observed on model samples are also present on polymer-coated mortar tiles when exposed to NSFs. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of nanoparticles from malleable and ductile metals using powder-free, reactant-assisted mechanical attrition.

PubMed

McMahon, Brandon W; Perez, Jesus Paulo L; Yu, Jiang; Boatz, Jerry A; Anderson, Scott L

2014-11-26

A reactant-assisted mechanochemical method was used to produce copious nanoparticles from malleable/ductile metals, demonstrated here for aluminum, iron, and copper. The milling media is intentionally degraded via a reactant-accelerated wear process, where the reactant aids particle production by binding to the metal surfaces, enhancing particle production, and reducing the tendency toward mechanochemical (cold) welding. The mechanism is explored by comparing the effects of different types of solvents and solvent mixtures on the amount and type of particles produced. Particles were functionalized with oleic acid to aid in particle size separation, enhance dispersion in hydrocarbon solvents, and protect the particles from oxidation. For aluminum and iron, the result is air-stable particles, but for copper, the suspended particles are found to dissolve when exposed to air. Characterization was performed using electron microscopy, dynamic light scattering, Fourier transform infrared spectroscopy, solid state nuclear magnetic resonance, and X-ray photoelectron spectroscopy. Density functional theory was used to examine the nature of carboxylic acid binding to the aluminum surface, confirming the dominance of bridging bidentate binding.

Three-dimensional simulation of rivulet and film flows over an inclined plate: Effects of solvent properties and contact angle

DOE PAGES

Singh, Rajesh K.; Galvin, Janine E.; Sun, Xin

2015-12-10

We numerically investigated the film flow down an inclined plate using the volume of fluid (VOF) method. The flow simulations have been systematically carried out for a wide range of parameters, such as inlet size, inclination angle, contact angle, flow rates and solvent properties (viscosity and surface tension). Based on the simulation results, scaling theory is proposed for both interfacial area and for film thickness in terms of the Kapitza number (Ka).The Kapitza number is advantageous because it depends only on solvent properties. The Kapitza number decreases with increased solvent viscosity and is fixed for a given fluid. Here, tomore » investigate the effects of solvent properties on interfacial area a small inlet cross-section was used. The interfacial area decreases with increased value of Ka. The time to reach pseudo-steady state of rivulet is also observed to increase with decreasing Ka. For a fixed flow rate, the inlet cross-section has marginal effect on the interfacial area; however, the developed width of the rivulet remains unchanged. In addition to inlet size, flow rate and solvent properties, the impact of contact angle on film thickness and interfacial area was also investigated. The contact angle has negligible effect for a fully wetted plate, but it significantly affects the interfacial area of the rivulet. Finally, a scaling theory for interfacial area in terms of the contact angle and Ka is presented.« less

Occupational exposure to organic solvents as a cause of sleep apnoea.

PubMed Central

Edling, C; Lindberg, A; Ulfberg, J

1993-01-01

A high prevalence of sleep apnoea was found in a group of men occupationally exposed to organic solvents. Workers with long term exposure to organic solvents often report symptoms such as fatigue, forgetfulness, and concentration difficulties. These symptoms are strikingly similar to those reported by patients with obstructive sleep apnoea syndrome (OSAS). This is a frequently diagnosed disorder characterised by disturbed sleep causing psychic or somatic complications and daytime sleepiness. A study was undertaken to evaluate whether people with long term occupational exposure to organic solvents have a higher prevalence of sleep apnoea than the general population. Patients exposed to solvents (66 men) were invited to participate in a screening for sleep apnoea. A static charge sensitive bed was used for the monitoring of respiration movements and pulse oximetry during one night. A classical sleep apnoea was diagnosed if periodic respiration movement exceeded 45% of estimated sleep time and the oxygen desaturation index exceeded 6. The prevalence of sleep apnoea among the men exposed to solvents was compared with the prevalence in the general population (1.4%). The prevalence among the participating exposed men was 19.7% which gave a conservative relative risk estimate of 14.1 (95% confidence interval (95% CI) 7.5-24.2). The results indicate that exposure to organic solvents causes sleep apnoea. An alternative possibility is that people with sleep apnoea are misdiagnosed as cases of solvent induced toxic encephalopathy. The interpretation has importance for the caring of the patient. PMID:8457496

Competitive interactions and controlled release of a natural antioxidant from halloysite nanotubes.

PubMed

Hári, József; Gyürki, Ádám; Sárközi, Márk; Földes, Enikő; Pukánszky, Béla

2016-01-15

Halloysite nanotubes used as potential carrier material for a controlled release stabilizer in polyethylene were thoroughly characterized with several techniques including the measurement of specific surface area, pore volume and surface energy. The high surface energy of the halloysite results in the strong bonding of the additive to the surface. Dissolution experiments carried out with eight different solvents for the determination of the effect of solvent characteristics on the amount of irreversibly bonded quercetin proved that adsorption and dissolution depend on competitive interactions prevailing in the system. Solvents with low polarity dissolve only surplus quercetin adsorbed in multilayers. Polyethylene is a very apolar polymer forming weak interactions with every substance; quercetin dissolves into it from the halloysite surface only above a critical surface coverage. Stabilization experiments confirmed that strong adhesion prevents dissolution and results in limited stabilization efficiency. At larger adsorbed amounts better stability and extended effect were measured indicating dissolution and controlled release. Copyright © 2015 Elsevier Inc. All rights reserved.

Method for removing organic liquids from aqueous solutions and mixtures

DOEpatents

Hrubesh, Lawrence W.; Coronado, Paul R.; Dow, Jerome P.

2004-03-23

A method for removing organic liquids from aqueous solutions and mixtures. The method employs any porous material preferably in granular form and having small pores and a large specific surface area, that is hydrophobic so that liquid water does not readily wet its surface. In this method, organics, especially organic solvents that mix with and are more volatile than water, are separated from aqueous solution by preferentially evaporating across the liquid/solid boundary formed at the surfaces of the hydrophobic porous materials. Also, organic solvents that are immiscible with water, preferentially wet the surfaces of the hydrophobic material and are drawn within the porous materials by capillary action.

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

Tande, Brian; Seames, Wayne; Benson, Steve

The objective of this project was to evaluate the use of composite polymer membranes and porous membrane contactors to regenerate physical and chemical solvents for capture of carbon dioxide (CO 2) from synthesis gas or flue gas, with the goal of improving the energy efficiency of carbon capture. Both a chemical solvent (typical for a post-combustion capture of CO 2 from flue gas) and a physical solvent (typical for pre- combustion capture of CO 2 from syngas) were evaluated using two bench-scale test systems constructed for this project. For chemical solvents, polytetrafluoroethylene and polypropylene membranes were found to be ablemore » to strip CO 2 from a monoethanolamine (MEA) solution with high selectivity without significant degradation of the material. As expected, the regeneration temperature was the most significant parameter affecting the CO 2 flux through the membrane. Pore size was also found to be important, as pores larger than 5 microns lead to excessive pore wetting. For physical solvents, polydimethyl-siloxane (PDMS)-based membranes were found to have a higher CO 2 permeability than polyvinylalcohol (PVOH) based membranes, while also minimizing solvent loss. Overall, however, the recovery of CO 2 in these systems is low – less than 2% for both chemical and physical solvents – primarily due to the small surface area of the membrane test apparatus. To obtain the higher regeneration rates needed for this application, a much larger surface area would be needed. Further experiments using, for example, a hollow fiber membrane module could determine if this process could be commercially viable.« less

Conformation and hydration of surface grafted and free polyethylene oxide chains in solutions

NASA Astrophysics Data System (ADS)

Dahal, Udaya; Wang, Zilu; Dormidontova, Elena

Due to the wide application of polyethylene oxide (PEO), ranging from biomedicine to fuel cells, it is one of the most studied polymers in the scientific world. In order to elucidate detailed molecular-level insights on the impact of surface grafting on PEO conformation, we performed atomistic molecular dynamics simulations of PEO chains in solution and grafted to a flat gold surface in different solvents. We examined the hydration as well as conformation of the free chain compared to the grafted polymer in pure water and mixed solvents. We find that grafted chains are stiffer and have a stronger tendency to form helical structures in isobutyric acid or mixture of isobutyric acid and water solution than the free chains in corresponding solutions. For grafted chains exposed to pure water the random coil conformation is retained at low grafting density, but becomes stretched and more dehydrated as the grafting density or temperature increases. This research is supported by NSF (DMR-1410928).

qHNMR Analysis of Purity of Common Organic Solvents--An Undergraduate Quantitative Analysis Laboratory Experiment

ERIC Educational Resources Information Center

Bell, Peter T.; Whaley, W. Lance; Tochterman, Alyssa D.; Mueller, Karl S.; Schultz, Linda D.

2017-01-01

NMR spectroscopy is currently a premier technique for structural elucidation of organic molecules. Quantitative NMR (qNMR) methodology has developed more slowly but is now widely accepted, especially in the areas of natural product and medicinal chemistry. However, many undergraduate students are not routinely exposed to this important concept.…

Effects of solvent evaporation conditions on solvent vapor annealed cylinder-forming block polymer thin films

NASA Astrophysics Data System (ADS)

Grant, Meagan; Jakubowski, William; Nelson, Gunnar; Drapes, Chloe; Baruth, A.

Solvent vapor annealing is a less time and energy intensive method compared to thermal annealing, to direct the self-assembly of block polymer thin films. Periodic nanostructures have applications in ultrafiltration, magnetic arrays, or other structures with nanometer dimensions, driving its continued interest. Our goal is to create thin films with hexagonally packed, perpendicular aligned cylinders of poly(lactide) in a poly(styrene) matrix that span the thickness of the film with low anneal times and low defect densities, all with high reproducibility, where the latter is paramount. Through the use of our computer-controlled, pneumatically-actuated, purpose-built solvent vapor annealing chamber, we have the ability to monitor and control vapor pressure, solvent concentration within the film, and solvent evaporation rate with unprecedented precision and reliability. Focusing on evaporation, we report on two previously unexplored areas, chamber pressure during solvent evaporation and the flow rate of purging gas aiding the evaporation. We will report our exhaustive results following atomic force microscopy analysis of films exposed to a wide range of pressures and flow rates. Reliably achieving well-ordered films, while occurring within a large section of this parameter space, was correlated with high-flow evaporation rates and low chamber pressures. These results have significant implications on other methods of solvent annealing, including ``jar'' techniques.

Compressed air-assisted solvent extraction (CASX) for metal removal.

PubMed

Li, Chi-Wang; Chen, Yi-Ming; Hsiao, Shin-Tien

2008-03-01

A novel process, compressed air-assisted solvent extraction (CASX), was developed to generate micro-sized solvent-coated air bubbles (MSAB) for metal extraction. Through pressurization of solvent with compressed air followed by releasing air-oversaturated solvent into metal-containing wastewater, MSAB were generated instantaneously. The enormous surface area of MSAB makes extraction process extremely fast and achieves very high aqueous/solvent weight ratio (A/S ratio). CASX process completely removed Cr(VI) from acidic electroplating wastewater under A/S ratio of 115 and extraction time of less than 10s. When synthetic wastewater containing Cd(II) of 50mgl(-1) was treated, A/S ratios of higher than 714 and 1190 could be achieved using solvent with extractant/diluent weight ratio of 1:1 and 5:1, respectively. Also, MSAB have very different physical properties, such as size and density, compared to the emulsified solvent droplets, making separation and recovery of solvent from treated effluent very easy.

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

Schaeffer, Daniel A.; Polizos, Georgios; Smith, D. Barton

Optical surfaces such as mirrors and windows that are exposed to outdoor environmental conditions are susceptible to dust buildup and water condensation. The application of transparent superhydrophobic coatings on optical surfaces can improve outdoor performance via a self-cleaning effect similar to the Lotus effect. The contact angle (CA) of water droplets on a typical hydrophobic flat surface varies from 100° to 120°. Adding roughness or microtexture to a hydrophobic surface leads to an enhancement of hydrophobicity and the CA can be increased to a value in the range of 16≥0° to 175°. This result is remarkable because such behavior cannotmore » be explained using surface chemistry alone. When surface features are on the order of 100 nm or smaller, surfaces exhibit superhydrophobic behavior and maintain their optical transparency. In this work we discuss our results on transparent superhydrophobic coatings that can be applied across large surface areas. We have used functionalized silica nanoparticles to coat various optical elements and have measured the contact angle and optical transmission between 190 to 1100 nm on these elements. The functionalized silica nanoparticles were dissolved in a solution of the solvents isopropyl alcohol and 4-chlorobenzotrifluoride (PCBTF) and a proprietary ceramic binder (Cerakote ). Finally, this solution was spin-coated onto a variety of test glass substrates, and following a curing period of about 30 minutes, these coatings exhibited superhydrophobic behavior with a static CA ≥160°.« less

Structural Insights into Membrane Targeting by the Flagellar Calcium-binding Protein (FCaBP) a Myristoylated and Palmitoylated Calcium Sensor in Trypanosoma cruzi

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

J Wingard; J Ladner; M Vanarotti

2011-12-31

The flagellar calcium-binding protein (FCaBP) of the protozoan Trypanosoma cruzi is targeted to the flagellar membrane where it regulates flagellar function and assembly. As a first step toward understanding the Ca{sup 2+}-induced conformational changes important for membrane-targeting, we report here the x-ray crystal structure of FCaBP in the Ca{sup 2+}-free state determined at 2.2{angstrom} resolution. The first 17 residues from the N terminus appear unstructured and solvent-exposed. Residues implicated in membrane targeting (Lys-19, Lys-22, and Lys-25) are flanked by an exposed N-terminal helix (residues 26-37), forming a patch of positive charge on the protein surface that may interact electrostatically withmore » flagellar membrane targets. The four EF-hands in FCaBP each adopt a 'closed conformation' similar to that seen in Ca{sup 2+}-free calmodulin. The overall fold of FCaBP is closest to that of grancalcin and other members of the penta EF-hand superfamily. Unlike the dimeric penta EF-hand proteins, FCaBP lacks a fifth EF-hand and is monomeric. The unstructured N-terminal region of FCaBP suggests that its covalently attached myristoyl group at the N terminus may be solvent-exposed, in contrast to the highly sequestered myristoyl group seen in recoverin and GCAP1. NMR analysis demonstrates that the myristoyl group attached to FCaBP is indeed solvent-exposed in both the Ca{sup 2+}-free and Ca{sup 2+}-bound states, and myristoylation has no effect on protein structure and folding stability. We propose that exposed acyl groups at the N terminus may anchor FCaBP to the flagellar membrane and that Ca{sup 2+}-induced conformational changes may control its binding to membrane-bound protein targets..« less

Vibrational energy transfer between carbon nanotubes and liquid water: a molecular dynamics study.

PubMed

Nelson, Tammie R; Chaban, Vitaly V; Kalugin, Oleg N; Prezhdo, Oleg V

2010-04-08

The rates and magnitudes of vibrational energy transfer between single-wall carbon nanotubes (CNTs) and water are investigated by classical molecular dynamics. The interactions between the CNT and solvent confined inside of the tube, the CNT and solvent surrounding the tube, as well as the solvent inside and outside of the tube are considered for the (11,11), (15,15), and (19,19) armchair CNTs. The vibrational energy transfer exhibits two time scales, subpicosecond and picosecond, of roughly equal importance. Solvent molecules confined within CNTs are more strongly coupled to the tubes than the outside molecules. The energy exchange is facilitated by slow collective motions, including CNT radial breathing modes (RBM). The transfer rate between CNTs and the inside solvent shows strong dependence on the CNT diameter. In smaller tubes, the transfer is faster and the solvent coupling to RBMs is stronger. The magnitude of the CNT-outside solvent interaction scales with the CNT surface area, while that of the CNT-inside solvent exhibits scaling that is intermediate between the CNT volume and surface. The Coulomb interaction between the solvent molecules inside and outside of the CNTs is much weaker than the CNT-solvent interactions. The results indicate that the excitation energy supplied to CNTs in chemical and biological applications is rapidly deposited to the active molecular agents and should remain localized sufficiently long in order to perform the desired function.

Organic-inorganic nano-composite films for photonic applications made by multi-beam multi-target pulsed laser deposition with remote control of the plume directions

NASA Astrophysics Data System (ADS)

Darwish, Abdalla M.; Moore, Shaelynn; Mohammed, Aziz; Alexander, Deonte'; Bastian, Tyler; Dorlus, Wydglif; Sarkisov, Sergey S.; Patel, Darayas N.; Mele, Paolo; Koplitz, Brent

2016-09-01

There has been an explosive interest in the technique of laser assisted deposition of polymer nano-composite films exploiting the matrix assisted pulsed laser evaporation (MAPLE) with regard to the polymer host as can be judged form recent publications.1-4 In MAPLE, a frozen solution of a polymer in a relatively volatile solvent is used as a laser target. The solvent and concentration are selected so that first, the polymer of interest can dissolve to form a dilute, particulate free solution, second, the majority of the laser energy is initially absorbed by the solvent molecules and not by the solute molecules, and third, there is no photochemical reaction between the solvent and the solute. The light-material interaction in MAPLE can be described as a photothermal process. The photon energy absorbed by the solvent is converted to thermal energy that causes the polymer to be heated but the solvent to vaporize. As the surface solvent molecules are evaporated into the gas phase, polymer molecules are exposed at the gas-target matrix interface. The polymer molecules attain sufficient kinetic energy through collective collisions with the evaporating solvent molecules, to be transferred into the gas phase. By careful optimization of the MAPLE deposition conditions (laser wavelength, repetition rate, solvent type, concentration, temperature, and background gas and gas pressure), this process can occur without any significant polymer decomposition. The MAPLE process proceeds layer-by-layer, depleting the target of solvent and polymer in the same concentration as the starting matrix. When a substrate is positioned directly in the path of the plume, a coating starts to form from the evaporated polymer molecules, while the volatile solvent molecules are evacuated by the pump from the deposition chamber. In case of fabrication of polymer nanocomposites, MAPLE targets are usually prepared as nano-colloids of the additives of interest in the initial polymer solutions. Mixing the components of different nature, organic polymers and inorganic dopants, in the same target at a certain proportion and exposing them to the same laser beam not necessarily brings good quality nano-composite films. The laser pulse energy and wavelength cannot be optimized for each component individually. Also, the mixing proportion in the composite film is dictated by the initial proportion of the target and thus cannot be changed in the process. These limitations were removed in the recently proposed method of multi-beam and multi-target deposition (in its doublebeam/ dual-target variation) using a MAPLE polymer target and one inorganic target, each being concurrently exposed to laser beams of different wavelengths.5-14 Using the method, nano-composite films of polymer poly(methyl methacrylate) known as PMMA doped with a rare earth (RE) inorganic upconversion phosphor compounds were prepared. Also, a nano-composite film of thermoelectric film of inorganic aluminum-doped ZnO known as AZO was impregnated with PMMA nano-fillers with the purpose of improving electrical conductivity and thermoelectric performance.10, 14 The polymer target was a frozen (to a temperature of liquid nitrogen) PMMA solution in chlorobenzene exposed to a 1064- nm laser beam from a Q-switched Nd:YAG pulsed laser. The inorganic targets were the pellets made of the compressed micro-powders of highly efficient RE-doped NaYF4 or the sintered powder of AZO concurrently ablated with the

Synthesis and characterization of binary titania-silica mixed oxides

NASA Astrophysics Data System (ADS)

Budhi, Sridhar

A series of binary titania-silica mixed oxides were synthesized by the sol-gel method at room temperature. The mixed oxides were prepared that involved the hydrolysis of titanium isopropoxide and tetraethylorthosilicate (TEOS) by co-solvent induced gelation usually in acidic media. The resulting gels were dried, calcined and then characterized by powder X-ray diffractometric studies, nitrogen sorption studies (at 77K), diffuse reflectance spectroscopy, Raman microscopy and transmission electron microscopic studies. The nitrogen sorption studies indicate that the specific surface areas, pore volume, pore diameter and pore size distribution of the mixed oxides were substantially enhanced when non-polar solvents such as toluene, p-xylene or mesitylene were added as co-solvents to the synthesis gel. Transmission electron microscopic (TEM) studies confirm the results obtained from the nitrogen sorption studies. Our results indicate that we can obtain binary metal oxides possessing high surface area and large pore volumes with tunable pore size distribution at room temperature. Photocatalytic evaluation of the mixed oxides is currently in progress.

Anti-solvent derived non-stacked reduced graphene oxide for high performance supercapacitors.

PubMed

Yoon, Yeoheung; Lee, Keunsik; Baik, Chul; Yoo, Heejoun; Min, Misook; Park, Younghun; Lee, Sae Mi; Lee, Hyoyoung

2013-08-27

An anti-solvent for graphene oxide (GO), hexane, is introduced to increase the surface area and the pore volume of the non-stacked GO/reduced GO 3D structure and allows the formation of a highly crumpled non-stacked GO powder, which clearly shows ideal supercapacitor behavior. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hazardous particle binder, coagulant and re-aerosolization inhibitor

DOEpatents

Krauter, Paula [Livermore, CA; Zalk, David [San Jose, CA; Hoffman, D Mark [Livermore, CA

2011-04-12

A copolymer and water/ethanol solvent solution capable of binding with airborne contaminants or potential airborne contaminants, such as biological weapon agents or toxic particulates, coagulating as the solvent evaporates, and adhering the contaminants to a surface so as to inhibit the re-suspension of such contaminants. The solution uses a water or ethanol/water mixture for the solvent, and a copolymer having one of several functional group sets so as to have physical and chemical characteristics of high adhesion, low viscosity, low surface tension, negative electrostatic charge, substantially neutral pH, and a low pKa. Use of the copolymer solution prevents re-aerosolization and transport of unwanted, reactive species thus increasing health and safety for personnel charged with decontamination of contaminated buildings and areas.

Hazardous particle binder, coagulant and re-aerosolization inhibitor

DOEpatents

Krauter, Paula; Zalk, David; Hoffman, D. Mark

2012-07-10

A copolymer and water/ethanol solvent solution capable of binding with airborne contaminants or potential airborne contaminants, such as biological weapon agents or toxic particulates, coagulating as the solvent evaporates, and adhering the contaminants to a surface so as to inhibit the re-suspension of such contaminants. The solution uses a water or ethanol/water mixture for the solvent, and a copolymer having one of several functional group sets so as to have physical and chemical characteristics of high adhesion, low viscosity, low surface tension, negative electrostatic charge, substantially neutral pH, and a low pKa. Use of the copolymer solution prevents re-aerosolization and transport of unwanted, reactive species thus increasing health and safety for personnel charged with decontamination of contaminated buildings and areas.

Surveying implicit solvent models for estimating small molecule absolute hydration free energies

PubMed Central

Knight, Jennifer L.

2011-01-01

Implicit solvent models are powerful tools in accounting for the aqueous environment at a fraction of the computational expense of explicit solvent representations. Here, we compare the ability of common implicit solvent models (TC, OBC, OBC2, GBMV, GBMV2, GBSW, GBSW/MS, GBSW/MS2 and FACTS) to reproduce experimental absolute hydration free energies for a series of 499 small neutral molecules that are modeled using AMBER/GAFF parameters and AM1-BCC charges. Given optimized surface tension coefficients for scaling the surface area term in the nonpolar contribution, most implicit solvent models demonstrate reasonable agreement with extensive explicit solvent simulations (average difference 1.0-1.7 kcal/mol and R2=0.81-0.91) and with experimental hydration free energies (average unsigned errors=1.1-1.4 kcal/mol and R2=0.66-0.81). Chemical classes of compounds are identified that need further optimization of their ligand force field parameters and others that require improvement in the physical parameters of the implicit solvent models themselves. More sophisticated nonpolar models are also likely necessary to more effectively represent the underlying physics of solvation and take the quality of hydration free energies estimated from implicit solvent models to the next level. PMID:21735452

Materials Compatibility Testing in RSRM ODC: Free Cleaner Selection

NASA Technical Reports Server (NTRS)

Keen, Jill M.; Sagers, Neil W.; McCool, Alex (Technical Monitor)

2001-01-01

Government regulations have mandated production phase-outs of a number of solvents, including 1,1,1-trichloroethane, an ozone-depleting chemical (ODC). This solvent was used extensively in the production of the Reusable Solid Rocket Motors (RSRMs) for the Space Shuttle. Many tests have been performed to identify replacement cleaners. One major area of concern in the selection of a new cleaner has been compatibility. Some specific areas considered included cleaner compatibility with non-metallic surfaces, painted surfaces, support materials such as gloves and wipers as well as corrosive properties of the cleaners on the alloys used on these motors. The intent of this paper is to summarize the test logic, methodology, and results acquired from testing the many cleaner and material combinations.

Spine-like Nanostructured Carbon Interconnected by Graphene for High-performance Supercapacitors

NASA Astrophysics Data System (ADS)

Park, Sang-Hoon; Yoon, Seung-Beom; Kim, Hyun-Kyung; Han, Joong Tark; Park, Hae-Woong; Han, Joah; Yun, Seok-Min; Jeong, Han Gi; Roh, Kwang Chul; Kim, Kwang-Bum

2014-08-01

Recent studies on supercapacitors have focused on the development of hierarchical nanostructured carbons by combining two-dimensional graphene and other conductive sp2 carbons, which differ in dimensionality, to improve their electrochemical performance. Herein, we report a strategy for synthesizing a hierarchical graphene-based carbon material, which we shall refer to as spine-like nanostructured carbon, from a one-dimensional graphitic carbon nanofiber by controlling the local graphene/graphitic structure via an expanding process and a co-solvent exfoliation method. Spine-like nanostructured carbon has a unique hierarchical structure of partially exfoliated graphitic blocks interconnected by thin graphene sheets in the same manner as in the case of ligaments. Owing to the exposed graphene layers and interconnected sp2 carbon structure, this hierarchical nanostructured carbon possesses a large, electrochemically accessible surface area with high electrical conductivity and exhibits high electrochemical performance.

Spine-like nanostructured carbon interconnected by graphene for high-performance supercapacitors.

PubMed

Park, Sang-Hoon; Yoon, Seung-Beom; Kim, Hyun-Kyung; Han, Joong Tark; Park, Hae-Woong; Han, Joah; Yun, Seok-Min; Jeong, Han Gi; Roh, Kwang Chul; Kim, Kwang-Bum

2014-08-19

Recent studies on supercapacitors have focused on the development of hierarchical nanostructured carbons by combining two-dimensional graphene and other conductive sp(2) carbons, which differ in dimensionality, to improve their electrochemical performance. Herein, we report a strategy for synthesizing a hierarchical graphene-based carbon material, which we shall refer to as spine-like nanostructured carbon, from a one-dimensional graphitic carbon nanofiber by controlling the local graphene/graphitic structure via an expanding process and a co-solvent exfoliation method. Spine-like nanostructured carbon has a unique hierarchical structure of partially exfoliated graphitic blocks interconnected by thin graphene sheets in the same manner as in the case of ligaments. Owing to the exposed graphene layers and interconnected sp(2) carbon structure, this hierarchical nanostructured carbon possesses a large, electrochemically accessible surface area with high electrical conductivity and exhibits high electrochemical performance.

Spine-like Nanostructured Carbon Interconnected by Graphene for High-performance Supercapacitors

PubMed Central

Park, Sang-Hoon; Yoon, Seung-Beom; Kim, Hyun-Kyung; Han, Joong Tark; Park, Hae-Woong; Han, Joah; Yun, Seok-Min; Jeong, Han Gi; Roh, Kwang Chul; Kim, Kwang-Bum

2014-01-01

Recent studies on supercapacitors have focused on the development of hierarchical nanostructured carbons by combining two-dimensional graphene and other conductive sp2 carbons, which differ in dimensionality, to improve their electrochemical performance. Herein, we report a strategy for synthesizing a hierarchical graphene-based carbon material, which we shall refer to as spine-like nanostructured carbon, from a one-dimensional graphitic carbon nanofiber by controlling the local graphene/graphitic structure via an expanding process and a co-solvent exfoliation method. Spine-like nanostructured carbon has a unique hierarchical structure of partially exfoliated graphitic blocks interconnected by thin graphene sheets in the same manner as in the case of ligaments. Owing to the exposed graphene layers and interconnected sp2 carbon structure, this hierarchical nanostructured carbon possesses a large, electrochemically accessible surface area with high electrical conductivity and exhibits high electrochemical performance. PMID:25134517

Solvent Effects of Model Polymeric Corrosion Control Coatings on Water Transport and Corrosion Rate

NASA Astrophysics Data System (ADS)

Konecki, Christina

Industrial coating formulations are often made for volatile organic content compliance and ease of application, with little regard for the solvent impact on resultant performance characteristics. Our research objective was to understand the effect of both solvent retention and chemical structure on water transport through polymer films and resultant corrosion area growth of coated steel substrates. A clear, unpigmented Phenoxy(TM) thermoplastic polymer (PKHH) was formulated into resin solutions with three separate solvent blends selected by Hansen solubility parameter (HSP), boiling point, and ability to solubilize PKHH. Polymer films cast from MEK/PGME (methyl ethyl ketone/ propylene glycol methyl ether), dried under ambient conditions (AMB, > 6wt.% residual solvent) produced a porous morphology, which resulted in a corrosion area greater than 50%. We attributed this to the water-soluble solvent used in film preparation, which enabled residual PGME to be extracted by water. The resin solution prepared with CYCOH/DXL (Cyclohexanol/ 1,3 dioxolane) was selected because CYCOH is a solid at room temperature which acts as a pigment in the final film. Therefore, increasing the tortuosity of water transport, as well as a high hydrogen bonding character, which caused more interactions with water, slowing diffusion, producing a nodular morphology, and 37% less corrosion area than MEK/PGME AMB. The HSP of PKHH and EEP (ethyl 3-ethoxypropionate) are within 5% of each other, which produced a homogeneous morphology and resulted in comparable corrosion rates regardless of residual solvent content. We utilized electrochemical techniques and attenuated total reflectance- Fourier transform infrared spectroscopy to elucidate dynamic water absorption and solvent extraction in the exposed model formulations. We found that water absorption resulted in a loss of barrier properties, and increased corrosion due to the voids formed by solvent extraction. The polymer films were rejuvenated (removal of water) as an attempt to decrease the number of water transport pathways during exposure. Results found that samples rejuvenated at temperatures above the glass transition temperature of the samples achieved lower moisture content and consequently, lower corrosion growth rates. In commercial systems, rejuvenation lowered the corrosion rate up to 60% indicating better coating formulations and maintenance cycles would control the corrosion rate.

Olfactory function in painters exposed to organic solvents.

PubMed

Sandmark, B; Broms, I; Löfgren, L; Ohlson, C G

1989-02-01

The olfactory receptor cells are in direct contact with the exterior environment, and some chemical agents can impair olfactory function. The olfactory function of 54 painters exposed to organic solvents was compared with that of 42 unexposed referents. A new clinical test validated for the sense of smell was used, the University of Pennsylvania Smell Identification Test. Age, smoking habits, exposure to organic solvents, and medical disorders of importance for the sense of smell were recorded. The painters had a somewhat lower test score than the referents. However, the influence of the exposure variable was not statistically significant in a multiple regression analysis including age and smoking habits. The exposure to organic solvents was low, and therefore an effect of high exposure on olfactory function cannot be ruled out. Since some of the painters had earlier been highly exposed, the effects of high exposure are likely to be reversible.

Controlling the Electrochemically Active Area of Carbon Fiber Microelectrodes by the Electrodeposition and Selective Removal of an Insulating Photoresist

PubMed Central

Lambie, Bradley A.; Orwar, Owe; Weber, Stephen G.

2008-01-01

A new and simple method permits control of the electrochemically active area of a carbon fiber microelectrode. An electrophoretic photoresist insulates the 10 μm diameter carbon fiber microelectrodes. Photolysis of the photoresist followed by immersion of the exposed area into a developing solution reveals electroactive carbon fiber surface. The electroactive surface area exposed can be controlled with a good degree of reproducibility. PMID:16841943

A QSPR study on the solvent-induced frequency shifts of acetone and dimethyl sulfoxide in organic solvents.

PubMed

Ou, Yu Heng; Chang, Chia Ming; Chen, Ying Shao

2016-06-05

In this study, solvent-induced frequency shifts (SIFS) in the infrared spectrum of acetone and dimethyl sulfoxide in organic solvents were investigated by using four types of quantum-chemical reactivity descriptors. The results showed that the SIFS of acetone is mainly affected by the electron-acceptance chemical potential and the maximum nucleophilic condensed local softness of organic solvents, which represent the electron flow and the polarization between acetone and solvent molecules. On the other hand, the SIFS of dimethyl sulfoxide changes with the maximum positive charge of hydrogen atom and the inverse of apolar surface area of solvent molecules, showing that the electrostatic and hydrophilic interactions are main mechanisms between dimethyl sulfoxide and solvent molecules. The introduction of the four-element theory model-based quantitative structure-property relationship approach improved the assessing quality and provided a basis for interpreting the solute-solvent interactions. Copyright © 2016 Elsevier B.V. All rights reserved.

Comparison of binding energies of SrcSH2-phosphotyrosyl peptides with structure-based prediction using surface area based empirical parameterization.

PubMed Central

Henriques, D. A.; Ladbury, J. E.; Jackson, R. M.

2000-01-01

The prediction of binding energies from the three-dimensional (3D) structure of a protein-ligand complex is an important goal of biophysics and structural biology. Here, we critically assess the use of empirical, solvent-accessible surface area-based calculations for the prediction of the binding of Src-SH2 domain with a series of tyrosyl phosphopeptides based on the high-affinity ligand from the hamster middle T antigen (hmT), where the residue in the pY+ 3 position has been changed. Two other peptides based on the C-terminal regulatory site of the Src protein and the platelet-derived growth factor receptor (PDGFR) are also investigated. Here, we take into account the effects of proton linkage on binding, and test five different surface area-based models that include different treatments for the contributions to conformational change and protein solvation. These differences relate to the treatment of conformational flexibility in the peptide ligand and the inclusion of proximal ordered solvent molecules in the surface area calculations. This allowed the calculation of a range of thermodynamic state functions (deltaCp, deltaS, deltaH, and deltaG) directly from structure. Comparison with the experimentally derived data shows little agreement for the interaction of SrcSH2 domain and the range of tyrosyl phosphopeptides. Furthermore, the adoption of the different models to treat conformational change and solvation has a dramatic effect on the calculated thermodynamic functions, making the predicted binding energies highly model dependent. While empirical, solvent-accessible surface area based calculations are becoming widely adopted to interpret thermodynamic data, this study highlights potential problems with application and interpretation of this type of approach. There is undoubtedly some agreement between predicted and experimentally determined thermodynamic parameters: however, the tolerance of this approach is not sufficient to make it ubiquitously applicable. PMID:11106171

Structure and energetics of model amphiphilic molecules at the water liquid-vapor interface - A molecular dynamics study

NASA Technical Reports Server (NTRS)

Pohorille, Andrew; Benjamin, Ilan

1993-01-01

A molecular dynamics study of adsorption of p-n-pentylphenol at infinite dilution at the water liquid-vapor interface is reported. The calculated free energy of adsorption is -8.8 +/- 0.7 kcal/mol, in good agreement with the experimental value of -7.3 kcal/mol. The transition between the interfacial region and the bulk solution is sharp and well-defined by energetic, conformational, and orientational criteria. At the water surface, the phenol head group is mostly immersed in aqueous solvent. The most frequent orientation of the hydrocarbon tail is parallel to the interface, due to dispersion interactions with the water surface. This arrangement of the phenol ring and the alkyl chain requires that the chain exhibits a kink. As the polar head group is being moved into the solvent, the chain length increases and the tail becomes increasingly aligned toward the surface normal, such that the nonpolar part of the molecule exposed to water is minimized. The same effect was achieved when phenol was replaced by a more polar head group, phenolate.

Solvent selection for explaining the morphology of nitroguanidine crystal by molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Song, Liang; Chen, Lizhen; Cao, Duanlin; Wang, Jianlong

2018-02-01

In this article, a method was performed to predict the morphology of needle-shaped crystals by analyzing the growth mechanisms for the various crystal faces. As an example, the crystal morphology of a nitroguanidine (NQ) was investigated via molecular dynamics simulations. The modified attachment energy (MEA) model was constructed by introducing surface chemistry terms and the relevant morphology of the habit crystal faces. The results indicate that the growth morphology of NQ in vacuum is dominated by {2 2 0}, {0 4 0}, {1 1 1}, {1 3 1} and {3 1 1} faces. The {2 2 0} and {0 4 0} faces are parallel to the elongation direction of the crystal, while the other faces are at the needle tips direction. The atoms or atomic groups exposed in crystal surface were used to analyze the relationship between structure and morphology. Compared to the surrounding faces, the needle tip faces have a large number of polar atoms or atomic groups. The needle tip faces have a high electronegativity on N, O atoms via molecular electrostatic potential (ESP) analysis. Furthermore, the protic solvent was used to reduce the attachment energy of the tip surfaces for achieving the purpose of inhibiting the growth of needle tips. Gamma-butyrolactone as the selected solvent inhibited effectively the growth of the needle tip faces. The predicted result is serviceable for the formation design.

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

Tachi, N.; Shimotori, S.; Naruse, N.

Synthetic adhesives are widely used in various industries as well as at home. Adhesives usually contain several organic solvents which easily vaporize. Exposure can cause aplastic anemia and polyneuropathy in adults. Chronic glue sniffing results in aplastic anemia, polyneuropathy, and muscular atrophy. Inhalation of the solvent contained in adhesives, such as n-hexane, toluene, xylene, and benzene by pregnant animals can decrease the number of live fetuses and retard fetal growth. In humans, the risk of spontaneous abortion is increased in workers exposed to organic solvents. However, information is still limited about the effects of exposure to organic solvents vaporized frommore » adhesives on fetuses. In the present study, female mice were exposed throughout pregnancy to organic solvents vaporized from an adhesive to clarify the effects of the inhalation on progeny. 19 refs., 1 fig., 4 tabs.« less

Residual contamination and corrosion on electrochemically marked uranium

NASA Astrophysics Data System (ADS)

Seals, R. D.; Bullock, J. S.; Cristy, S. S.; Bennett, R. K.

Residual contamination and potential corrosion problems on uranium parts electrochemically marked with PHB-1 and PHB-1E electroetchants have been investigated using ion microprobe mass analysis (IMMA), scanning electron microscopy (SEM), and light microscopy (LM). The effectiveness of various solvent-cleaning sequences and the influence of the use of an abrasive cleaner were evaluated. The corrosion depths and chlorine distributions resulting from the electroetching process were determined. To meet the objective, the surfaces of uranium coupons, which had been processed according to production procedures for parts, i.e., machining, cleaning, marking, inspecting and coating with Shell Vitrea-29® oil, were studied. The greater surface wetting capability of the PHB-1E electroetchant solution relative to PHB-1 resulted in less localized corrosion at the point of attack which provided a more legible mark. Components of the electroetchants (aluminum, potassium and chromium) were found in the marked areas of both types of electroetched samples. Chromium, resulting from the corrosion inhibitor in the electroetchants, was found in the etched areas as well as on the coupon away from the electroetched areas. Depth profile data indicated that the major etching action (marking thickness) of the electroetchants penetrated to a depth of approximately 200 nm. Trace amounts of chlorine were present primarily within the first 65 nm of the marked surface. Comparison of the solvent rinsing sequences revealed that the most effective cleaning process included a degreaser, such as perchloroethylene, followed by a polar solvent, such as alcohol. Evaluation of the use of an abrasive cleaner on the electroetched areas indicates that this process removed residual contaminants, increased mark legibility and did not introduce significant residuals from the abrading material or cause significant surface damage.

Indolylarylsulfones carrying a heterocyclic tail as very potent and broad spectrum HIV-1 non-nucleoside reverse transcriptase inhibitors.

PubMed

Famiglini, Valeria; La Regina, Giuseppe; Coluccia, Antonio; Pelliccia, Sveva; Brancale, Andrea; Maga, Giovanni; Crespan, Emmanuele; Badia, Roger; Riveira-Muñoz, Eva; Esté, José A; Ferretti, Rosella; Cirilli, Roberto; Zamperini, Claudio; Botta, Maurizio; Schols, Dominique; Limongelli, Vittorio; Agostino, Bruno; Novellino, Ettore; Silvestri, Romano

2014-12-11

We synthesized new indolylarylsulfone (IAS) derivatives carrying a heterocyclic tail at the indole-2-carboxamide nitrogen as potential anti-HIV/AIDS agents. Several new IASs yielded EC50 values <1.0 nM against HIV-1 WT and mutant strains in MT-4 cells. The (R)-11 enantiomer proved to be exceptionally potent against the whole viral panel; in the reverse transcriptase (RT) screening assay, it was remarkably superior to NVP and EFV and comparable to ETV. The binding poses were consistent with the one previously described for the IAS non-nucleoside reverse transcriptase inhibitors. Docking studies showed that the methyl group of (R)-11 points toward the cleft created by the K103N mutation, different from the corresponding group of (S)-11. By calculating the solvent-accessible surface, we observed that the exposed area of RT in complex with (S)-11 was larger than the area of the (R)-11 complex. Compounds 6 and 16 and enantiomer (R)-11 represent novel robust lead compounds of the IAS class.

Method for producing high surface area chromia materials for catalysis

DOEpatents

Gash, Alexander E [Brentwood, CA; Satcher, Joe [Patterson, CA; Tillotson, Thomas [Tracy, CA; Hrubesh, Lawrence [Pleasanton, CA; Simpson, Randall [Livermore, CA

2007-05-01

Nanostructured chromium(III)-oxide-based materials using sol-gel processing and a synthetic route for producing such materials are disclosed herein. Monolithic aerogels and xerogels having surface areas between 150 m.sup.2/g and 520 m.sup.2/g have been produced. The synthetic method employs the use of stable and inexpensive hydrated-chromium(III) inorganic salts and common solvents such as water, ethanol, methanol, 1-propanol, t-butanol, 2-ethoxy ethanol, and ethylene glycol, DMSO, and dimethyl formamide. The synthesis involves the dissolution of the metal salt in a solvent followed by an addition of a proton scavenger, such as an epoxide, which induces gel formation in a timely manner. Both critical point (supercritical extraction) and atmospheric (low temperature evaporation) drying may be employed to produce monolithic aerogels and xerogels, respectively.

Behavioral effects of environmental chemicals in rats exposed in an inhalational behavioral chamber

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

Ghosh, T.K.; Copeland, R.L. Jr.; Pradhan, S.N.

1986-03-01

In order to study the behavioral toxicity of environmental chemicals at low concentrations (conc.), effects of inhalation of xylene or toluene were investigated in rats on fixed-ratio (FR24) liquid (5% sucrose) reinforcement (RIF) and intracranial self-stimulation (SS, with electrodes in A10 area) while being exposed to the solvent vapor in an inhalational behavioral chamber designed in the laboratory. While exposed to 3 graded conc. of xylene vapor for 2 hr each during 6 hr sessions, decreases in RIF was observed during 1,3 and 5 hr. Levels of behavioral performance were improved during 2,4 and 6 hr indicating development of tolerance.more » Similar effects were also observed in experiments (expt.) with toluene, which appeared to be somewhat less potent. Exposed to graded conc. of xylene for 2 hr each on separate days, rats also showed similar RIF decreases which appeared to be conc.-dependent. Prolonged (5hr) exposure to the lowest effective conc. of xylene used (139 ppm) which showed slight or no effect in these expt. decreased RIF only at hr 1 and hr 2 following which RIF improved further showing development of tolerance. Similar decreases in RIF was also observed at middle and high xylene conc. in ss expt. Thus, behavioral depression and subsequent development of tolerance were observed in these expt. with the industrial solvents.« less

Semiconductor surface protection material

NASA Technical Reports Server (NTRS)

Packard, R. D. (Inventor)

1973-01-01

A method and a product for protecting semiconductor surfaces is disclosed. The protective coating material is prepared by heating a suitable protective resin with an organic solvent which is solid at room temperature and converting the resulting solution into sheets by a conventional casting operation. Pieces of such sheets of suitable shape and thickness are placed on the semiconductor areas to be coated and heat and vacuum are then applied to melt the sheet and to drive off the solvent and cure the resin. A uniform adherent coating, free of bubbles and other defects, is thus obtained exactly where it is desired.

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.

Optically transparent and environmentally durable superhydrophobic coating based on functionalized SiO 2 nanoparticles

DOE PAGES

Schaeffer, Daniel A.; Polizos, Georgios; Smith, D. Barton; ...

2015-01-09

Optical surfaces such as mirrors and windows that are exposed to outdoor environmental conditions are susceptible to dust buildup and water condensation. The application of transparent superhydrophobic coatings on optical surfaces can improve outdoor performance via a self-cleaning effect similar to the Lotus effect. The contact angle (CA) of water droplets on a typical hydrophobic flat surface varies from 100° to 120°. Adding roughness or microtexture to a hydrophobic surface leads to an enhancement of hydrophobicity and the CA can be increased to a value in the range of 16≥0° to 175°. This result is remarkable because such behavior cannotmore » be explained using surface chemistry alone. When surface features are on the order of 100 nm or smaller, surfaces exhibit superhydrophobic behavior and maintain their optical transparency. In this work we discuss our results on transparent superhydrophobic coatings that can be applied across large surface areas. We have used functionalized silica nanoparticles to coat various optical elements and have measured the contact angle and optical transmission between 190 to 1100 nm on these elements. The functionalized silica nanoparticles were dissolved in a solution of the solvents isopropyl alcohol and 4-chlorobenzotrifluoride (PCBTF) and a proprietary ceramic binder (Cerakote ). Finally, this solution was spin-coated onto a variety of test glass substrates, and following a curing period of about 30 minutes, these coatings exhibited superhydrophobic behavior with a static CA ≥160°.« less

Personality and long term exposure to organic solvents

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

Lindstroem, K.; Martelin, T.

1980-01-01

Personality, especially emotional reactions of two solvent exposed groups and a nonexposed reference group were described by means of 20 formal, content and check-list type of Rorschach variables. Another objective of the study was to explore the suitability and psychological meaning of other types of Rorschach variables than those applied earlier in the field of behavioral toxicology. The factor analyses grouped the applied variables into factors of Productivity, Ego Strength, Control of Emotionality, Defensive Introversion and Aggressiveness. One solvent group, a patient groups (N.53), was characterized by a high number of Organic signs and a low Genetic Level, indicating possiblemore » psychoorganic deterioration. The other solvent group, styrene exposed but subjectively healthy (N.98), was characterized by few emotional reactions, low Anxiety and a low number of Neurotic Signs. the long duration of exposure of the solvent patient group (mean 10.2 +/- 8.7 years) was related to variables of the Productivity factor, a finding that indicates a possible better adjustment of those exposed for a longer time. The duration of exposure of the styrene exposed group (mean 4.9 +/- 3.2 years) revealed a very slight relation to personality variables, but the mean urinary mandelic acid concentration, indicating the level of styrene exposure, correlated with increased emotional reactions. For the most part definite causal conclusions could not be drawn because of the cross-sectional design of the study.« less

Solvent inhalation (toluene and n-hexane) during the brain growth spurt impairs the maturation of frontal, parietal and occipital cerebrocortical neurons in rats.

PubMed

Pascual, Rodrigo; Aedo, Luz; Meneses, Juan Carlos; Vergara, Daniela; Reyes, Alvaro; Bustamante, Carlos

2010-10-01

Solvent abuse during pregnancy may cause "fetal solvent syndrome", which is characterized by mild brain atrophy and associated with behavioral, cognitive, and emotional abnormalities. The present study investigated whether solvent inhalation during the preweaning period (P2-P21) alters the morphological maturation of frontal, parietal, and occipital cortical neurons. Twelve hours after delivery (postnatal day 0, P0), litters were cross-fostered, culled to 8 pups/dam and housed together with a dam in standard laboratory cages. Litters were randomly assigned to the "air-only" group (n=64, 8 litters) and to the "solvent-sniffer" group (n=72, 9 litters). During P2-P21, each animal was exposed daily to either organic solvent vapors (75% toluene and 18% n-hexane, a solvent mixture commonly found in glues and adhesives) or clean air. To determine the impact of early solvent inhalation on cortical neuronal differentiation, brains were stained using the Golgi-Cox-Sholl procedure to quantitatively assess neocortical pyramidal cell dendrogenesis. Preweaning, solvent-exposed animals displayed dramatic impairments in dendritic growth as well as significant reductions in brain weight and size. Copyright 2010 ISDN. Published by Elsevier Ltd. All rights reserved.

Deep eutectic-solvothermal synthesis of nanostructured ceria

PubMed Central

Hammond, Oliver S.; Edler, Karen J.; Bowron, Daniel T.; Torrente-Murciano, Laura

2017-01-01

Ceria is a technologically important material with applications in catalysis, emissions control and solid-oxide fuel cells. Nanostructured ceria becomes profoundly more active due to its enhanced surface area to volume ratio, reactive surface oxygen vacancy concentration and superior oxygen storage capacity. Here we report the synthesis of nanostructured ceria using the green Deep Eutectic Solvent reline, which allows morphology and porosity control in one of the less energy-intensive routes reported to date. Using wide Q-range liquid-phase neutron diffraction, we elucidate the mechanism of reaction at a molecular scale at considerably milder conditions than the conventional hydrothermal synthetic routes. The reline solvent plays the role of a latent supramolecular catalyst where the increase in reaction rate from solvent-driven pre-organization of the reactants is most significant. This fundamental understanding of deep eutectic-solvothermal methodology will enable future developments in low-temperature synthesis of nanostructured ceria, facilitating its large-scale manufacturing using green, economic, non-toxic solvents. PMID:28120829

Cleavable ester linked magnetic nanoparticles for labeling of solvent exposed primary amine groups of peptides/proteins

USDA-ARS?s Scientific Manuscript database

In order to study the solvent exposed lysine residues of peptides/proteins, we previously reported disulfide linked N-hydrosuccinimide ester modified silica coated iron oxide magnetic nanoparticles (NHS-SS-SiO2@Fe3O4 MNPs). The presence of a disulfide bond in the linker limits the use of disulfide r...

Long-range single domain array of a 5 nm pattern of supramolecules via solvent annealing in a double-sandwich cell.

PubMed

Kwon, Kiok; Park, Kangho; Jung, Hee-Tae

2018-05-10

In nanotechnology and microelectronics research, the generation of an ultradense, single-grain nanostructure with a long-range lateral order is challenging. In this paper, we report upon a new solvent-annealing method using a double-sandwich confinement to promote the formation of a large-area, single-domain array (>0.3 × 0.3 mm2) of supramolecular cylinders with a small feature size (4.7 nm). The in situ GISAXS experiment result shows the ordering process during solvent evaporation. The diffusion of the solvent molecules led to the disassembly of the supramolecules confined between the top and bottom surfaces and their subsequent mobilization, thereby producing a highly ordered hexagonal array of supramolecular materials under the double-sandwich confinement upon solvent evaporation. In addition, two key factors were found to be crucial in this process for generating highly-ordered supramolecular building blocks: (i) the presence of a top coat during solvent evaporation to provide a geometric confinement template, and (ii) the control of the solvent evaporation rate during the solvent evaporation step to provide the dendrimer sufficient time to self-assemble into the highly ordered state over a large area. Our developed approach, which can be extended to be used for a large family of supramolecules, is of critical importance in providing a new bottom-up lithographic method based on supramolecular self-assembly.

Evaluation of the utility of a standard history questionnaire in assessing the neurological effects of solvents.

PubMed

Bukowski, J A; Sargent, E V; Pena, B M

1992-01-01

Using a standard battery of medical surveillance questions, a study was undertaken to determine if an increase in reported neurologic symptoms was resulting from solvent exposure at a pharmaceutical research, development, and manufacturing site. The prevalence of positive responses to 13 interval history questions pertaining to neurological symptoms was compared between those enrolled in exposed surveillance programs (n = 840) and those enrolled in other, non-solvent exposed surveillance programs (n = 1,042). The ratio of positive responders between the exposed and unexposed groups was used to generate a relative prevalence ratio (RPR). No significantly elevated RPRs were seen when the analysis was adjusted for the confounding factors of age, sex, smoking, alcohol use, noise exposure, and number of interval histories. These results suggest that workplace solvent exposures in the employees studied did not appear to result in obvious neurologic symptoms. However, low-level neurotoxic exposures can cause asymptomatic or sub-clinical disorders. Therefore, more sensitive neurotoxic surveillance systems need to be developed.

Extent and Depth to Top of Basalt and Interbed Hydrogeologic Units, Yakima River Basin Aquifer System, Washington

USGS Publications Warehouse

Jones, M.A.; Vaccaro, J.J.

2008-01-01

The hydrogeologic framework was delineated for the ground-water flow system of the three basalt formations and two interbeds in the Yakima River Basin, Washington. The basalt units are nearly equivalent to the Saddle Mountains, Wanapum, and Grande Ronde. The two major interbed units between the basalt formations generally are referred to as the Mabton and Vantage. The basalt formations are a productive source of ground-water for the Yakima River Basin. The Grande Ronde unit comprises the largest area in the Yakima River Basin aquifer system. This unit encompasses an area of about 5,390 mi2 and ranges in altitude from 6,900 ft, where it is exposed at land surface, to a depth of 2,800 ft below land surface. The Wanapum unit encompasses an area of 3,450 mi2 and ranges in altitude from 5,680 ft, where exposed at land surface, to a depth of 2,050 ft below land surface. The Saddle Mountains unit, the least extensive, encompasses an area of 2,290 mi2 and ranges from 4,290 ft, where exposed at the surface, to a depth of 1,840 ft below land surface.

Linear regression models for solvent accessibility prediction in proteins.

PubMed

Wagner, Michael; Adamczak, Rafał; Porollo, Aleksey; Meller, Jarosław

2005-04-01

The relative solvent accessibility (RSA) of an amino acid residue in a protein structure is a real number that represents the solvent exposed surface area of this residue in relative terms. The problem of predicting the RSA from the primary amino acid sequence can therefore be cast as a regression problem. Nevertheless, RSA prediction has so far typically been cast as a classification problem. Consequently, various machine learning techniques have been used within the classification framework to predict whether a given amino acid exceeds some (arbitrary) RSA threshold and would thus be predicted to be "exposed," as opposed to "buried." We have recently developed novel methods for RSA prediction using nonlinear regression techniques which provide accurate estimates of the real-valued RSA and outperform classification-based approaches with respect to commonly used two-class projections. However, while their performance seems to provide a significant improvement over previously published approaches, these Neural Network (NN) based methods are computationally expensive to train and involve several thousand parameters. In this work, we develop alternative regression models for RSA prediction which are computationally much less expensive, involve orders-of-magnitude fewer parameters, and are still competitive in terms of prediction quality. In particular, we investigate several regression models for RSA prediction using linear L1-support vector regression (SVR) approaches as well as standard linear least squares (LS) regression. Using rigorously derived validation sets of protein structures and extensive cross-validation analysis, we compare the performance of the SVR with that of LS regression and NN-based methods. In particular, we show that the flexibility of the SVR (as encoded by metaparameters such as the error insensitivity and the error penalization terms) can be very beneficial to optimize the prediction accuracy for buried residues. We conclude that the simple and computationally much more efficient linear SVR performs comparably to nonlinear models and thus can be used in order to facilitate further attempts to design more accurate RSA prediction methods, with applications to fold recognition and de novo protein structure prediction methods.

Penetration of carbon-fabric-reinforced composites by edge cracks during thermal aging

NASA Technical Reports Server (NTRS)

Bowles, Kenneth J.; Kamvouris, John E.

1994-01-01

Thermo-oxidative stability (TOS) test results are significantly influenced by the formation and growth or presence of interlaminar and interlaminar cracks in the cut edges of all carbon-fiber-crosslinked high-temperature polymer matrix composites(exp 1-5) (i.e., unidirectional, crossplied, angle-plied, and fabric composites). The thermo-oxidative degradation of these composites is heavily dependent on the surface area that is exposed to the harmful environment and on the surface-to-volume ratio of the structure under study. Since the growth of cracks and voids on the composite surfaces significantly increases the exposed surface areas, it is imperative that the interaction between the aging process and the formation of new surface area as the aging time progresses be understood.

[Exposure to solvents and tardy epilepsy: 2 clinical cases].

PubMed

Bernardini, P; Scoppetta, C

1992-01-01

Organic solvents (OS) are widely used in industry and craft work. The neurotoxic effects of OS are well known in occupational exposure occurring in poor industrial hygiene conditions. There has been interest recently in a possible epileptogenic effect of OS exposure. Two cases are reported of late onset epilepsy observed in workers heavily exposed to OS. Case 1 was a 27-year-old male painter employed in a car body repair workshop. Solvent exposure was high for a few months because after his regular work, the man continued working as a car body painter in his own private concern. After a period of weakness and headache, probably indicating an excessive solvent absorption, he suffered two generalized paroxysmal seizures during sleep which necessitated hospitalization and continuous treatment with barbiturates. Case 2 was a 44-year-old male painter in a road advertising billboard factory who was continuously exposed to OS. Ten years previously he had been exposed to accidental massive inhalation of solvent vapours while opening a drum of solvents for coloured paint. Acute solvent poisoning followed and seven weeks later he suffered several epileptic episodes associated with typical EEG alterations; for many years, however, treatment was ineffective. In both cases there was neither a history of neurologic disease nor any other neurologic dysfunctions and the results of comprehensive neuroradiological studies were normal. Evidence exists of a chronological connection between high exposure to paint solvents and clinical evidence of late onset epilepsy, but it is not possible to identify a definite causal relationship.(ABSTRACT TRUNCATED AT 250 WORDS)

Preparation and Characterization of Single Ion Conductors from High Surface Area Fumed Silica

NASA Technical Reports Server (NTRS)

Zhang, H.; Maitra, P.; Liu, B.; Wunder, S. L.; Lin, H.-P.; Salomon, M.; Hagedorn, Norman H. (Technical Monitor)

2002-01-01

Anions that can form dissociative salts with Li(+) have been prepared and covalently attached to high surface area fumed silica. When blended with polyethylene oxide (PEO), the functionalized fumed silica suppresses the crystallization of the PEO, provides dimensional stability, and serves as a single ion conductor. Since functionalized fumed silica is easily dispersed in common polar solvents, it can be incorporated in both the polymer electrolyte and the electrodes.

Role of solvent in metal-on-metal surface diffusion: A case for rational solvent selection for materials synthesis

NASA Astrophysics Data System (ADS)

Imandi, Venkataramana; Jagannath, Mantha Sai Pavan; Chatterjee, Abhijit

2018-09-01

The effect of solvent on diffusion at metal surfaces is poorly understood despite its importance to morphological evolution during materials processing, corrosion and catalysis. In this article, we probe the metal-solvent interfacial structure, effective nature of interactions and dynamics when a solvent is in contact with a metal using a novel accelerated molecular dynamics simulation technique called temperature programmed molecular dynamics (TPMD). TPMD simulations reveal that surface diffusion of metal-on-metal can be made to vary over orders-of-magnitude by tuning the metal-solvent interaction. Ultimately, the solvent can have an indirect effect on diffusion. As the solvent tugs at the metal surface the separation between the adsorbed metal atom (adatom) and the surface layer can be modulated via metal-solvent interactions. The resulting adatom-surface separation can cause stronger/weaker binding of the adatom to the metal surface, which in turn results in the observed slower/enhanced diffusion in the presence of solvent. We believe this effect is ubiquitous in pure metal and metal alloys and in principle one could rationally select solvent to control the material structural evolution. Implications on materials synthesis are discussed in the context of formation of nanoporous materials.

Method of bonding functional surface materials to substrates and applications in microtechnology and anti-fouling

DOEpatents

Feng, Xiangdong; Liu, Jun; Liang, Liang

2001-01-01

A simple and effective method to bond a thin coating of poly(N-isopropylacylamide) (NIPAAm) on a glass surface by UV photopolymerization, and the use of such a coated surface in nano and micro technology applications. A silane coupling agent with a dithiocarbamate group is provided as a photosensitizer preferably, (N,N'-diethylamine) dithiocarbamoylpropyl-(trimethoxy) silane (DATMS). The thiocarbamate group of the sensitizer is then bonded to the glass surface by coupling the silane agent with the hydroxyl groups on the glass surface. The modified surface is then exposed to a solution of NIPAAm and a crosslinking agent which may be any organic molecule having an acrylamide group and at least two double bonds in its structure, such as N, N'-methylenebisacrylamide, and a polar solvent which may be any polar liquid which will dissolve the monomer and the crosslinking agent such as acetone, water, ethanol, or combinations thereof. By exposing the glass surface to a UV light, free radicals are generated in the thiocarbamate group which then bonds to the crosslinking agent and the NIPAAm. Upon bonding, the crosslinking agent and the NIPAAm polymerize to form a thin coating of PNIPAAm bonded to the glass. Depending upon the particular configuration of the glass, the properties of the PNIPAAm allow applications in micro and nano technology.

Method of bonding functional surface materials to substrates and applications in microtechnology and antifouling

DOEpatents

Feng, Xiangdong; Liu, Jun; Liang, Liang

1999-01-01

A simple and effective method to bond a thin coating of poly(N-isopropylacylamide) (NIPAAm) on a glass surface by UV photopolymerization, and the use of such a coated surface in nano and micro technology applications. A silane coupling agent with a dithiocarbamate group is provided as a photosensitizer, preferably, (N,N'-diethylamine)dithiocarbamoylpropyl-(trimethoxy)silane (DATMS). The thiocarbamate group of the sensitizer is then bonded to the glass surface by coupling the silane agent with the hydroxyl groups on the glass surface. The modified surface is then exposed to a solution of NIPAAm and a crosslinking agent which may be any organic molecule having an acrylamide group and at least two double bonds in its structure, such as N,N'-methylenebisacrylamide, and a polar solvent which may be any polar liquid which will dissolve the monomer and the crosslinking agent such as acetone, water, ethanol, or combinations thereof. By exposing the glass surface to a UV light, free radicals are generated in the thiocarbamate group which then bonds to the crosslinking agent and the NIPAAm. Upon bonding, the crosslinking agent and the NIPAAm polymerize to form a thin coating of PNIPAAm bonded to the glass. Depending upon the particular configuration of the glass, the properties of the PNIPAAm allow applications in micro and nano technology.

Method And Apparatus For Production Of Bi-213 From The Activity Ac-225 Source

DOEpatents

Egorov, Oleg B.; O'Hara, Matthew J.

2005-12-06

A method and apparatus for isolating and purifying a .sup.213 Bi radioactive isotope from an .sup.225 Ac source using a primary column and a primary sorbent which preferentially retains .sup.225 Ac over .sup.213 Bi when exposed to a compatible solvent in combination with a secondary column having a secondary sorbent which retains .sup.213 Bi when exposed to a mixture of the compatible solvent and .sup.213 Bi. A "compatible solvent" is a solvent which will preferentially remove .sup.213 Bi radioactive isotopes from a primary sorbent without removing .sup.225 Ac radioactive isotopes, and then allow .sup.213 Bi radioactive isotopes removed from the primary sorbent to be retained on a secondary sorbent, without having to dilute or otherwise chemically or physically modify the compatible solvent in between exposure to the primary and secondary sorbents.

Contribution of Charged Groups to the Enthalpic Stabilization of the Folded States of Globular Proteins

PubMed Central

Dadarlat, Voichita M.; Post, Carol Beth

2016-01-01

In this paper we use the results from all atom MD simulations of proteins and peptides to assess individual contribution of charged atomic groups to the enthalpic stability of the native state of globular proteins and investigate how the distribution of charged atomic groups in terms of solvent accessibility relates to protein enthalpic stability. The contributions of charged groups is calculated using a comparison of nonbonded interaction energy terms from equilibrium simulations of charged amino acid dipeptides in water (the “unfolded state”) and charged amino acids in globular proteins (the “folded state”). Contrary to expectation, the analysis shows that many buried, charged atomic groups contribute favorably to protein enthalpic stability. The strongest enthalpic contributions favoring the folded state come from the carboxylate (COO−) groups of either Glu or Asp. The contributions from Arg guanidinium groups are generally somewhat stabilizing, while NH3+ groups from Lys contribute little toward stabilizing the folded state. The average enthalpic gain due to the transfer of a methyl group in an apolar amino acid from solution to the protein interior is described for comparison. Notably, charged groups that are less exposed to solvent contribute more favorably to protein native-state enthalpic stability than charged groups that are solvent exposed. While solvent reorganization/release has favorable contributions to folding for all charged atomic groups, the variation in folded state stability among proteins comes mainly from the change in the nonbonded interaction energy of charged groups between the unfolded and folded states. A key outcome is that the calculated enthalpic stabilization is found to be inversely proportional to the excess charge density on the surface, in support of an hypothesis proposed previously. PMID:18303881

Dried calcium alginate/magnetite spheres: a new support for chromatographic separations and enzyme immobilization

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

Burns, M.A.; Kvesitadze, G.I.; Graves, D.J.

1985-02-01

Dried spheres made from an alginate solution containing magnetite particles have excellent potential as a support for enzyme immobilization and chromatographic applications. The beads were found to be much stronger than gels such as polyacrylamide and dextran, indicating that high flow rates and pressures could be used in column separations. The support withstood not only temperatures of up to 120/sup 0/C, but also most pH values and common solvents. While some solutions, such as phosphate buffers, dissolved the spheres, stabilization with Tyzor TE eliminated this problem. The physical properties of the beads include a glasslike density of 2.2 g/mL, excellentmore » sphericity, low porosity, and a narrow size distribution. The magnetite present in the support allows the beads to be used for magnetic separations such as high gradient magnetic filtration. Their high degree of microroughness provides a large exposed surface area for enzyme and ligand binding. Mixed Actinomyces fradiae proteases and Aspergillus niger ..cap alpha..-amylase, two enzymes representative of classes which attack large substrates, were immobilized on the bead's surface with high activity and stability. A cyanuric dye which can be used in chromatographic applications (Cibacron Blue F3GA) was also readily coupled to the surface of this support with good yield.« less

Mesoporous-silica films, fibers, and powders by evaporation

DOEpatents

Bruinsma, Paul J.; Baskaran, Suresh; Bontha, Jagannadha R.; Liu, Jun

2008-05-06

This invention pertains to surfactant-templated nanometer-scale porosity of a silica precursor solution and forming a mesoporous material by first forming the silica precursor solution into a preform having a high surface area to volume ratio, then rapid drying or evaporating a solvent from the silica precursor solution. The mesoporous material may be in any geometric form, but is preferably in the form of a film, fiber, powder or combinations thereof. The rapid drying or evaporation of solvent from the solution is accomplished by layer thinning, for example spin casting, liquid drawing, and liquid spraying respectively. Production of a film is by layer thinning, wherein a layer of the silica precursor solution is formed on a surface followed by removal of an amount of the silica precursor solution and leaving a geometrically thinner layer of the silica precursor solution from which the solvent quickly escapes via evaporation. Layer thinning may be by any method including but not limited to squeegeeing and/or spin casting. In powder formation by spray drying, the same conditions of fast drying exists as in spin-casting (as well as in fiber spinning) because of the high surface-area to volume ratio of the product. When a powder is produced by liquid spraying, the particles or micro-bubbles within the powder are hollow spheres with walls composed of mesoporous silica. Mesoporous fiber formation starts with a similar silica precursor solution but with an added pre-polymer making a pituitous mixture that is drawn into a thin strand from which solvent is evaporated leaving the mesoporous fiber(s).

Mesoporous-silica films, fibers, and powders by evaporation

DOEpatents

Bruinsma, Paul J.; Baskaran, Suresh; Bontha, Jagannadha R.; Liu, Jun

1999-01-01

This invention pertains to surfactant-templated nanometer-scale porosity of a silica precursor solution and forming a mesoporous material by first forming the silica precursor solution into a preform having a high surface area to volume ratio, then rapid drying or evaporating a solvent from the silica precursor solution. The mesoporous material may be in any geometric form, but is preferably in the form of a film, fiber, powder or combinations thereof. The rapid drying or evaporation of solvent from the solution is accomplished by layer thinning, for example spin casting, liquid drawing, and liquid spraying respectively. Production of a film is by layer thinning, wherein a layer of the silica precursor solution is formed on a surface followed by removal of an amount of the silica precursor solution and leaving a geometrically thinner layer of the silica precursor solution from which the solvent quickly escapes via evaporation. Layer thinning may be by any method including but not limited to squeegeeing and/or spin casting. In powder formation by spray drying, the same conditions of fast drying exists as in spin-casting (as well as in fiber spinning) because of the high surface-area to volume ratio of the product. When a powder is produced by liquid spraying, the particles or micro-bubbles within the powder are hollow spheres with walls composed of mesoporous silica. Mesoporous fiber formation starts with a similar silica precursor solution but with an added pre-polymer making a pituitous mixture that is drawn into a thin strand from which solvent is evaporated leaving the mesoporous fiber(s).

Mesoporous-silica films, fibers, and powders by evaporation

DOEpatents

Bruinsma, P.J.; Baskaran, S.; Bontha, J.R.; Liu, J.

1999-07-13

This invention pertains to surfactant-templated nanometer-scale porosity of a silica precursor solution and forming a mesoporous material by first forming the silica precursor solution into a preform having a high surface area to volume ratio, then rapid drying or evaporating a solvent from the silica precursor solution. The mesoporous material may be in any geometric form, but is preferably in the form of a film, fiber, powder or combinations thereof. The rapid drying or evaporation of solvent from the solution is accomplished by layer thinning, for example spin casting, liquid drawing, and liquid spraying respectively. Production of a film is by layer thinning, wherein a layer of the silica precursor solution is formed on a surface followed by removal of an amount of the silica precursor solution and leaving a geometrically thinner layer of the silica precursor solution from which the solvent quickly escapes via evaporation. Layer thinning may be by any method including but not limited to squeegeeing and/or spin casting. In powder formation by spray drying, the same conditions of fast drying exists as in spin-casting (as well as in fiber spinning) because of the high surface-area to volume ratio of the product. When a powder is produced by liquid spraying, the particles or micro-bubbles within the powder are hollow spheres with walls composed of mesoporous silica. Mesoporous fiber formation starts with a similar silica precursor solution but with an added pre-polymer making a pituitous mixture that is drawn into a thin strand from which solvent is evaporated leaving the mesoporous fiber(s). 24 figs.

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

Mo, Alan K; Brown, Victoria L.; Rugg, Brandon K.

The adhesion of 100 nm thick electron-beam deposited Au and Pt and magnetron sputtered Au thin films onto poly(methyl methacrylate) (PMMA) substrates can be significantly enhanced to over 90% adhesion by either spin-casting or vapor-exposure to hydrohalocarbon solvents prior to metal deposition compared to samples that are either cleaned in isopropyl alcohol or pre-treated with a remote O2 plasma. X-ray photoelectron spectroscopy (XPS) and evolved gas Fourier transform infrared spectroscopy (EGA-FTIR) reveal the presence of residual halogenated solvent molecules at the PMMA surface which chemically activates the surface to produce a stable chemical interaction between the noble metal film andmore » the PMMA. Density functional theory (DFT) calculations show that the halogenated solvent molecules preferentially form a Lewis acid-base adduct with the oxygen atoms in the ester group in PMMA which is consistent with the measured enthalpy of desorption of chloroform (CHCl3) on PMMA determined by EGA-FTIR to be 36 kJ mol-1. The DFT model also supports the experimentally observed change in the high resolution XPS O 1s peak at 533.77 eV after metallization attributed to a change in the local bonding environment of the bridging O in the PMMA ester group. DFT also predicts that the deposited metal atom (M) inserts into the C-X bond where X is the halogen atom on either CHCl3 or bromoform (CHBr3) to form a O M X interaction that is observed by a M-X bond in the high resolution XPS Cl 2p3/2 peak at 198.03 eV and Br 3p3/2 peak at 182.06 eV. A range of solvents with differing polarities for PMMA pre-treatment have been used and it is proposed that non-complexing solvents result in significant metal adhesion improvement. The Gutmann acceptor number can be used to predict the effectiveness of solvent treatment for noble metal adhesion. A model is proposed in which the bond energy of the C-X bond of the solvent must be sufficiently low so that the C-X bond can be cleaved to form the M-X bond. Supporting this model, a negative control of vapor phase exposure to fluoroform (CHF3) is shown to have no effect on noble metal adhesion due to the higher bond dissociation energy of the C-F bond compared to the C-Cl and C-Br bond energy. The surface activation of vapor-phase exposed PMMA surfaces is technologically significant for the fabrication of polymer microdevices requiring Au or Pt metallization.« less

Grafted Polystyrene Monolayer Brush as Both Negative and Positive Tone Electron Beam Resist.

PubMed

Aydinoglu, Ferhat; Yamada, Hirotaka; Dey, Ripon K; Cui, Bo

2017-05-23

Although spin coating is the most widely used electron-beam resist coating technique in nanolithography, it cannot typically be applied for nonflat or irregular surfaces. Here, we demonstrate that monolayer polystyrene brush can be grafted on substrates and used as both positive and negative electron-beam resist, which can be applied for such unconventional surfaces. Polystyrene is a popular negative resist when using solvent developer but solvent cannot be used for grafted polystyrene brush that is firmly bonded to the substrate. Instead, we employed two unconventional development methods to lead polystyrene brush to positive or negative tone behavior. Negative tone was achieved by thermal development at 300 °C because exposed thus cross-linked polystyrene brush is more thermally stable against vaporization than unexposed linear one. Surprisingly, positive tone behavior occurred when the brush was grafted onto an aluminum (Al) layer and the film stack was developed using diluted hydrofluoric acid (HF) that etched the underlying Al layer. By transferring the patterns into the silicon (Si) substrates using the thin Al layer as a sacrificial hard mask for dry etch, well-defined structures in Si were obtained in two different electron-beam resist tones as well as in nonflat surfaces.

Synthesis and Properties of Cross-Linked Polyamide Aerogels

NASA Technical Reports Server (NTRS)

Williams, Jarrod; Meador, Mary Ann; McCorkle, Linda

2014-01-01

We report our ongoing research on polyamide aerogels made by step growth polymerization using a combination of terephthaloyl chloride, isophthaloyl chloride and m-phenylenediamine. Crosslinking of the amine capped polymer chains with 1,3,5-benzenetricarbonyl trichloride causes gelation in as little as two to five minutes. Removing the reaction solvent is accomplished through solvent exchange, followed by drying using supercritical CO2 extraction to give colorless aerogels with densities ranging from 0.07 to 0.33 grams per cubic centimeter and surface areas as high as 440 square meters per gram. Statistical experimental design methodology has been utilized to investigate dependence of properties of these aerogels, such as density, compressive modulus, and surface area, on changes in fabrication parameters including formulated number of amide oligomer repeat units (n-value), acid chloride (meta, para or combination), and solids concentration of solution used for gelation. For example, the density of these materials was found to be dependent on the acid chloride type and the solids concentration, but n was not a significant variable. However, surface area was significantly influenced by all three parameters. The polyamide aerogels represent a potential cost savings over previously reported polyimide aerogels, since monomers are all inexpensive and commercially available. Surface area and density were both highest when 100 terephthaloyl chloride was used but a combination of 5 solid concentration, 100 terephthaloyl chloride and n of 20 gave the best combination of properties.

Exploration of crystal simulation potential by fluconazole isomorphism and its application in improvement of pharmaceutical properties

NASA Astrophysics Data System (ADS)

Thakur, Amitha; Kumar, Dinesh; Thipparaboina, Rajesh; Shastri, Nalini R.

2014-11-01

Control of crystal morphology during crystallization is a paramount challenge in pharmaceutical processing. Hence, there is need to introduce computational methods for morphology prediction to manage production cost of drugs and improve related pharmaceutical and biopharmaceutical properties. Layer docking approach with molecular dynamics opens a new avenue for crystal habit prediction in presence of solvent. In the present study, attempts were made to correlate predicted and experimental crystal habits of fluconazole considering solvent interactions using layer docking approach. Simulated results from layer docking approach with methanol as solvent gave two dominant facets (0 1 1) and (1 0 1) with a surface area 22.43% and 19.82% respectively, which were in agreement with the experimental results. Experimentally grown modified crystal habit of fluconazole in methanol showed enhanced dissolution rate (p<0.05) when compared to plain drug. This was attributed to the increased surface area on the specified facets caused by interactions with the solvent. Furthermore, Differential Scanning Calorimetry, Fourier Transform Infrared (FTIR) Spectroscopy and powder X-ray Diffraction of recrystallized samples confirmed only a habit change and absence of any polymorphs, hydrates or solvates. Flow and compressibility of fluconazole recrystallized in methanol was significantly improved when compared to plain drug. This study demonstrates a methodical approach using computational tools for prediction and modification of crystal habit, to enhance dissolution of poorly soluble drugs, for future pharmaceutical applications.

Hydrophobic potential of mean force as a solvation function for protein structure prediction.

PubMed

Lin, Matthew S; Fawzi, Nicolas Lux; Head-Gordon, Teresa

2007-06-01

We have developed a solvation function that combines a Generalized Born model for polarization of protein charge by the high dielectric solvent, with a hydrophobic potential of mean force (HPMF) as a model for hydrophobic interaction, to aid in the discrimination of native structures from other misfolded states in protein structure prediction. We find that our energy function outperforms other reported scoring functions in terms of correct native ranking for 91% of proteins and low Z scores for a variety of decoy sets, including the challenging Rosetta decoys. This work shows that the stabilizing effect of hydrophobic exposure to aqueous solvent that defines the HPMF hydration physics is an apparent improvement over solvent-accessible surface area models that penalize hydrophobic exposure. Decoys generated by thermal sampling around the native-state basin reveal a potentially important role for side-chain entropy in the future development of even more accurate free energy surfaces.

Hydration property of globular proteins: An analysis of solvation free energy by energy representation method

NASA Astrophysics Data System (ADS)

Saito, Hiroaki; Matubayasi, Nobuyuki; Nishikawa, Kiyoshi; Nagao, Hidemi

2010-09-01

Molecular dynamics simulations and solvation free energy calculations of five globular proteins (BPTI, RNase A, Lysozyme, β-lactoglobulin A, and α-chymotrypsinogen A) have been carried out to elucidate the hydration properties. Solvation free energies of the proteins with explicit solvent were estimated by energy representation (ER) method. The calculated solvation free energies were correlated with the solvent accessible surface area of hydrophilic portion, being consistent with the hydrophilic property of the proteins. These results showed that the ER method should be a powerful tool for estimating the hydration property of proteins, showing a progress of the free energy calculation with explicit solvent.

BIM (BCL-2 interacting mediator of cell death) SAHB (stabilized α helix of BCL2) not always convinces BAX (BCL-2-associated X protein) for apoptosis.

PubMed

Verma, Sharad; Goyal, Sukriti; Tyagi, Chetna; Jamal, Salma; Singh, Aditi; Grover, Abhinav

2016-06-01

The interaction of BAX (BCL-2-associated X protein) with BIM (BCL-2 interacting mediator of cell death) SAHB (stabilized α helix of BCL2) directly initiates BAX-mediated mitochondrial apoptosis. This molecular dynamics study reveals that BIM SAHB forms a stable complex with BAX but it remains in a non-functional conformation. N terminal of BAX folds towards the core which has been reported exposed in the functional monomer. The α1-α2 loop, which has been reported in open conformation in functional BAX, acquires a closed conformation during the simulation. BH3/α2 remains less exposed as compared to initial structure. The hydrophobic residues of BIM accommodates in the rear pocket of BAX during the simulation. A steep decrease in radius of gyration and solvent accessible surface area (SASA) indicates the complex folding to acquire a more stable but inactive conformation. Further the covariance matrix reveals that the backbone atoms' motions favour the inactive conformation of the complex. This is the first report on the non-functional BAX-BIM SAHB complex by molecular dynamics simulation in the best of our knowledge. Copyright © 2016 Elsevier Inc. All rights reserved.

FreeSASA: An open source C library for solvent accessible surface area calculations.

PubMed

Mitternacht, Simon

2016-01-01

Calculating solvent accessible surface areas (SASA) is a run-of-the-mill calculation in structural biology. Although there are many programs available for this calculation, there are no free-standing, open-source tools designed for easy tool-chain integration. FreeSASA is an open source C library for SASA calculations that provides both command-line and Python interfaces in addition to its C API. The library implements both Lee and Richards' and Shrake and Rupley's approximations, and is highly configurable to allow the user to control molecular parameters, accuracy and output granularity. It only depends on standard C libraries and should therefore be easy to compile and install on any platform. The library is well-documented, stable and efficient. The command-line interface can easily replace closed source legacy programs, with comparable or better accuracy and speed, and with some added functionality.

Deformation processes within wheel-rail adhesion in contact area

NASA Astrophysics Data System (ADS)

Albagachiev, A. Yu; Keropyan, A. M.

2018-03-01

The study of working surface deformation during interaction of open-pit locomotive tires allowed defining outstanding features of phenomena occurring in the contact area of interacting surfaces. It was found that processes typical for plastic saturated contact occur in the area of wheel-rail interaction of industrial railway transport. In case of plastic deformation exposed to heavy loads typical for open-pit locomotives, upon all rough surfaces of the contour contact area being fully deformed, the frame on which they are found is exposed to plastic deformation. Plastic deformation of roughness within the contact area of interacting surfaces leads to the increase in the actual area of their contact and, therefore, increases the towing capacity of mining machines. Finally, the available data on deformation characteristics with regard to processes occurring in the contact area of wheel-rail interaction will allow making theoretical forecasts on the expected design value of friction coefficient and, therefore, the towing capacity of open-pit locomotives.

Solvent exposure and cognitive function in automotive technicians.

PubMed

Bates, Michael N; Reed, Bruce R; Liu, Sa; Eisen, Ellen A; Hammond, S Katharine

2016-12-01

Automotive technicians are commonly exposed to organic and chlorinated solvents, particularly through use of cleaning products. Occupational solvent exposures have been associated with deficits in cognitive function but, to our knowledge, no previous studies have investigated automotive technicians. The purpose of the present study was to investigate whether previous exposures to n-hexane, in particular, or general solvents posed a persistent neurotoxic hazard to automotive workers. Enrolled in the study were 830 San Francisco Bay Area automotive repair workers. Each participant underwent a battery of cognitive function tests to investigate central nervous system impairment, with a primary focus on the domains of psychomotor speed, fine motor function, memory and mood. Cognitive test results regressed against estimated hexane and total solvent exposures showed little evidence of associations. Exposures to both solvents and hexane were well below the occupational exposure limits. Our results provide some reassurance about persistent neuropsychological effects in automotive workers who use solvent-based products and those who previously used hexane-containing automotive cleaning products, since this solvent is believed no longer to be used in automotive cleaning products. The lack of observed effect in this study may be attributable to low exposures, or it may reflect improved cognitive function since hexane use in automotive cleaning products was discontinued. However, impacts on results of exposure misclassification and/or the healthy worker survivor effect cannot be discounted. Irrespective of the outcome of this study, the main known neurologic effect of n-hexane is peripheral neuropathy, and such an association in automotive technicians is not excluded by these results. Copyright © 2016 Elsevier B.V. All rights reserved.

Insecticide solvents: interference with insecticidal action.

PubMed

Brattsten, L B; Wilkinson, C F

1977-06-10

Several commercial solvent mixtures commonly used as insecticide carriers in spray formulations increase by more than threefold the microsomal N-demethylation of p-chloro N-methylaniline in midgut preparations of southern army-worm (Spodoptera eridania) larvae exposed orally to the test solvents. Under laboratory conditions, the same solvent mixtures exhibit a protective action against the in vivo toxicity of the insecticide carbaryl to the larvae. The data are discussed with respect to possible solvent-insecticide interactions occurring under field conditions and, more broadly, to potential toxicological hazards of these solvents to humans.

Optical and Scanning Electron Microscopy of the Materials International Space Station Experiment (MISSE) Spacecraft Silicone Experiment

NASA Technical Reports Server (NTRS)

Hung, Ching-cheh; de Groh, Kim K.; Banks, Bruce A.

2012-01-01

Under a microscope, atomic oxygen (AO) exposed silicone surfaces are crazed and seen as "islands" separated by numerous crack lines, much analogous to mud-tile cracks. This research characterized and compared the degree of AO degradation of silicones by analyzing optical microscope images of samples exposed to low Earth orbit (LEO) AO as part of the Spacecraft Silicone Experiment. The Spacecraft Silicone Experiment consisted of eight DC 93-500 silicone samples exposed to eight different AO fluence levels (ranged from 1.46 to 8.43 10(exp 21) atoms/sq cm) during two different Materials International Space Station Experiment (MISSE) missions. Image analysis software was used to analyze images taken using a digital camera. To describe the morphological degradation of each AO exposed flight sample, three different parameters were selected and estimated: (1) average area of islands was determined and found to be in the 1000 to 3100 sq mm range; (2) total length of crack lines per unit area of the sample surface were determined and found to be in the range of 27 to 59 mm of crack length per sq mm of sample surface; and (3) the fraction of sample surface area that is occupied by crack lines was determined and found to be in the 25 to 56 percent range. In addition, average crack width can be estimated from crack length and crack area measurements and was calculated to be about 10 mm. Among the parameters studied, the fraction of sample surface area that is occupied by crack lines is believed to be most useful in characterizing the degree of silicone conversion to silicates by AO because its value steadily increases with increasing fluence over the entire fluence range. A series of SEM images from the eight samples exposed to different AO fluences suggest a complex sequence of surface stress due to surface shrinkage and crack formation, followed by re-distribution of stress and shrinking rate on the sample surface. Energy dispersive spectra (EDS) indicated that upon AO exposure, carbon content on the surface decreased relatively quickly at the beginning, to 32 percent of the pristine value for the least exposed sample in this set of experiments (1.46 10(exp 21) atoms/sq cm), but then decreased slowly, to 22 percent of the pristine value for the most exposed sample in this set of experiment (8.43 10(exp 21) atoms/sq cm). The oxygen content appears to increase at a slower rate. The least and most AO exposed samples were, respectively, 52 and 150 percent above the pristine values. The silicone samples with the greater AO exposure (7.75 10(exp 21) atoms/sq cm and higher) appear to have a surface layer which contains SiO2 with perhaps small amounts of unreacted silicone, CO and CO2 sealed inside.

Ultrafast Thermal Plasma Preparation of Solid Si Films with Potential Application in Photovoltaic Cells: A Parametric Study

NASA Astrophysics Data System (ADS)

Mostajeran Goortani, Behnam; Gitzhofer, François; Bouyer, Etienne; Mousavi, Mehdi

2009-03-01

An innovative method, namely ultrafast plasma surface melting, is developed to fabricate solid films of silicon with very high rates (150 cm2/min). The method is composed of preparing a suspension of solid particles in a volatile solvent and spreading it on a refractory substrate such as Mo. After solvent evaporation, the resulting porous layer is exposed to the flame tale of inductively coupled RF plasma to sinter and melt the surface particles and to prepare a solid film of silicon. It is shown that by controlling the flow dynamics and heat transfer around the substrate, and managing the kinetic parameters (i.e., exposure time, substrate transport speed, and reaction kinetics) in the reactor, we can produce solid crystalline Si films with the potential applications in photovoltaic cells industry. The results indicate that the optimum formation conditions with a film thickness of 250-700 μm is when the exposure time in the plasma is in the range of 5-12.5 s for a 100 × 50 mm large layer. By combining the Fourier’s law of conduction with the experimental measurements, we obtained an effective heat diffusivity and developed a model to obtain heat diffusion in the porous layer exposed to the plasma. The model further predicts the minimum and maximum exposure time for the substrate in the plasma flame as a function of material properties, the porous layer thickness and of the imposed heat flux.

Molecular receptors in metal oxide sol-gel materials prepared via molecular imprinting

DOEpatents

Sasaki, Darryl Y.; Brinker, C. Jeffrey; Ashley, Carol S.; Daitch, Charles E.; Shea, Kenneth J.; Rush, Daniel J.

2000-01-01

A method is provided for molecularly imprinting the surface of a sol-gel material, by forming a solution comprised of a sol-gel material, a solvent, an imprinting molecule, and a functionalizing siloxane monomer of the form Si(OR).sub.3-n X.sub.n, wherein n is an integer between zero and three and X is a functional group capable of reacting with the imprinting molecule, evaporating the solvent, and removing the imprinting molecule to form the molecularly imprinted metal oxide sol-gel material. The use of metal oxide sol-gels allows the material porosity, pore size, density, surface area, hardness, electrostatic charge, polarity, optical density, and surface hydrophobicity to be tailored and be employed as sensors and in catalytic and separations operations.

Large-Area Atomic Oxygen Facility Used to Clean Fire-Damaged Artwork

NASA Technical Reports Server (NTRS)

Rutledge, Sharon K.; Banks, Bruce A.; Steuber, Thomas J.; Sechkar, Edward A.

2000-01-01

In addition to completely destroying artwork, fires in museums and public buildings can soil a displayed artwork with so much accumulated soot that it can no longer be used for study or be enjoyed by the public. In situations where the surface has not undergone extensive charring or melting, restoration can be attempted. However, soot deposits can be very difficult to remove from some types of painted surfaces, particularly when the paint is fragile or flaking or when the top surface of the paint binder has been damaged. Restoration typically involves the use of organic solvents to clean the surface, but these solvents may cause the paint layers to swell or leach out. Also, immersion of the surface or swabbing during solvent cleaning may move or remove pigment through mechanical contact, especially if the fire damage extends into the paint binder. A noncontact technique of removing organic deposits from surfaces was developed out of NASA research on the effects of oxygen atoms on various materials. Atomic oxygen is present in the atmosphere surrounding the Earth at the altitudes where satellites typically orbit. It can react chemically with surface coatings or deposits that contain carbon. In the reaction, the carbon is converted to carbon monoxide and some carbon dioxide. Water vapor is also a byproduct of the reaction if the surface contains carbon-hydrogen bonds. To study this reaction, NASA developed Earth-based facilities to produce atomic oxygen for material exposure and testing. A vacuum facility designed and built by the Electro-Physics Branch of the NASA Glenn Research Center at Lewis Field to provide atomic oxygen over a large area for studying reactions in low Earth orbit has been used to successfully clean several full-size paintings. (This facility can accommodate paintings up to 1.5 by 2.1 m. The atomic oxygen plasma is produced between two large parallel aluminum plates using a radiofrequency power source operating at roughly 400 W. Atomic oxygen is generated uniformly over this area at an operating pressure of 1 to 5 mtorr.

Nonhazardous solvent composition and method for cleaning metal surfaces

DOEpatents

Googin, John M.; Simandl, Ronald F.; Thompson, Lisa M.

1993-01-01

A solvent composition for displacing greasy and oily contaminants as well as water and/or aqueous residue from metallic surfaces, especially surfaces of radioactive materials so that such surfaces can be wiped clean of the displaced contaminants, water and/or aqueous residue. The solvent composition consists essentially of a blend of nonpolar aliphatic hydrocarbon solvent having a minimum flash point of about 140.degree. F. and 2 to 25 volume percent of a polar solvent having a flash point sufficiently high so as to provide the solvent composition with a minimum flash point of at least 140.degree. F. The solvent composition is nonhazardous so that when it is used to clean the surfaces of radioactive materials the waste in the form of paper or cloth wipes, lab coats and the like used in the cleaning operation is not considered to be mixed waste composed of a hazardous solvent and a radioactive material.

Nonhazardous solvent composition and method for cleaning metal surfaces

DOEpatents

Googin, J.M.; Simandl, R.F.; Thompson, L.M.

1993-05-04

A solvent composition for displacing greasy and oily contaminants as well as water and/or aqueous residue from metallic surfaces, especially surfaces of radioactive materials so that such surfaces can be wiped clean of the displaced contaminants, water and/or aqueous residue. The solvent composition consists essentially of a blend of nonpolar aliphatic hydrocarbon solvent having a minimum flash point of about 140 F and 2 to 25 volume percent of a polar solvent having a flash point sufficiently high so as to provide the solvent composition with a minimum flash point of at least 140 F. The solvent composition is nonhazardous so that when it is used to clean the surfaces of radioactive materials the waste in the form of paper or cloth wipes, lab coats and the like used in the cleaning operation is not considered to be mixed waste composed of a hazardous solvent and a radioactive material.

Differently ordered TiO2 nanoarrays regulated by solvent polarity, and their photocatalytic performances

NASA Astrophysics Data System (ADS)

Hu, Wenyuan; Dong, Faqin; Zhang, Jing; Liu, Mingxue; He, Huichao; Wu, Yadong; Yang, Dingming; Deng, Hongquan

2018-06-01

Special TiO2 arrays with exposed facets were prepared in different solvents by low- temperature solvothermal synthesis. The morphology, phase and photocatalytic performance influenced by the various solvent polarities were characterized using field emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Raman spectra and electrochemical testing. The results show that differences of solvent polarity are the main force driving differences in array growth; therefore, anatase TiO2 arrays with different crystal facets can be synthesized by tuning solvent polarity. TiO2 arrays prepared in cyclohexane are the best at oxidizing methyl orange through photocatalysis, followed by arrays prepared in toluene and ethanol. Arrays prepared in toluene are the best at reducing Cr(VI) photocatalytically, followed by those prepared in cyclohexane and ethanol. These differences in photocatalytic power are due to the ratio among the different crystal facets that are exposed, which affects the migration behavior of the photogenerated electrons and holes. In addition, the probable growth mechanisms of self-assembled ordered TiO2 arrays in different solvents are described.

Self-assembly of short amyloidogenic peptides at the air-water interface.

PubMed

Chaudhary, Nitin; Nagaraj, Ramakrishnan

2011-08-01

Short peptide stretches in amyloidogenic proteins can form amyloid fibrils in vitro and have served as good models for studying amyloid fibril formation. Recently, these amyloidogenic peptides have gained considerable attention, as non-amyloid ordered structures can be obtained from these peptides by carefully tuning the conditions of self-assembly, especially pH, temperature and presence of organic solvents. We have examined the effect of surface pressure on the self-assembled structures of two amyloidogenic peptides, Pβ(2)m (Ac-DWSFYLLYYTEFT-am) and AcPHF6 (Ac-VQIVYK-am) at the air-water interface when deposited from different solvents. Both the peptides are surface-active and form Thioflavin T (ThT) positive structures at the air-water interface. There is considerable hysteresis in the compression and expansion isotherms, suggesting the occurrence of structural rearrangements during compression. Preformed Pβ(2)m fibrillar structures at the air-water interface are disrupted as peptide is compressed to lower molecular areas but restored if the film is expanded, suggesting that the process is reversible. AcPHF6, on the other hand, shows largely sheet-like structures at lower molecular areas. The solvents used for dissolution of the peptides appear to influence the nature of the aggregates formed. Our results show that like hydrostatic pressure, surface pressure can also be utilized for modulating the self-assembly of the amyloidogenic and self-assembling peptides. Copyright © 2011 Elsevier Inc. All rights reserved.

Conserved Cysteine Residues Provide a Protein-Protein Interaction Surface in Dual Oxidase (DUOX) Proteins*

PubMed Central

Meitzler, Jennifer L.; Hinde, Sara; Bánfi, Botond; Nauseef, William M.; Ortiz de Montellano, Paul R.

2013-01-01

Intramolecular disulfide bond formation is promoted in oxidizing extracellular and endoplasmic reticulum compartments and often contributes to protein stability and function. DUOX1 and DUOX2 are distinguished from other members of the NOX protein family by the presence of a unique extracellular N-terminal region. These peroxidase-like domains lack the conserved cysteines that confer structural stability to mammalian peroxidases. Sequence-based structure predictions suggest that the thiol groups present are solvent-exposed on a single protein surface and are too distant to support intramolecular disulfide bond formation. To investigate the role of these thiol residues, we introduced four individual cysteine to glycine mutations in the peroxidase-like domains of both human DUOXs and purified the recombinant proteins. The mutations caused little change in the stabilities of the monomeric proteins, supporting the hypothesis that the thiol residues are solvent-exposed and not involved in disulfide bonds that are critical for structural integrity. However, the ability of the isolated hDUOX1 peroxidase-like domain to dimerize was altered, suggesting a role for these cysteines in protein-protein interactions that could facilitate homodimerization of the peroxidase-like domain or, in the full-length protein, heterodimeric interactions with a maturation protein. When full-length hDUOX1 was expressed in HEK293 cells, the mutations resulted in decreased H2O2 production that correlated with a decreased amount of the enzyme localized to the membrane surface rather than with a loss of activity or with a failure to synthesize the mutant proteins. These results support a role for the cysteine residues in intermolecular disulfide bond formation with the DUOX maturation factor DUOXA1. PMID:23362256

Quality of Chemical Safety Information in Printing Industry.

PubMed

Tsai, Chung-Jung; Mao, I-Fang; Ting, Jo-Yu; Young, Chi-Hsien; Lin, Jhih-Sian; Li, Wei-Lun

2016-04-01

Employees in printing industries can be exposed to multiple solvents in their work environment. The objectives of this study were to investigate the critical components of chemical solvents by analyzing the components of the solvents and collecting the Safety data sheets (SDSs), and to evaluate the hazard communication implementation status in printing industries. About 152 printing-related industries were recruited by area-stratified random sampling and included 23 plate-making, 102 printing and 27 printing-assistance companies in Taiwan. We analyzed company questionnaires (n = 152), SDSs (n = 180), and solvents (n = 20) collected from this sample of printing-related companies. Analytical results indicated that benzene and ethylbenzene, which were carcinogen and possibly carcinogen, were detectable in the cleaning solvents, and the detection rate were 54.5% (concentrations: <0.011-0.035 wt%) and 63.6% (concentrations: <0.011-6.22 wt%), respectively; however, neither compound was disclosed in the SDS for the solvents. Several other undisclosed components, including methanol, isopropanol and n-butanol, were also identified in the printing inks, fountain solutions and dilution solvents. We noted that, of the companies we surveyed, only 57.2% had a hazard communication program, 61.8% had SDSs on file and 59.9% provided employee safety and health training. We note that hazard communication programs were missing or ineffective in almost half of the 152 printing industries surveyed. Current safety information of solvents components in printing industries was inadequate, and many hazardous compounds were undisclosed in the SDSs of the solvents or the labels of the containers. The implementation of hazard communications in printing industries was still not enough for protecting the employees' safety and health. © The Author 2015. Published by Oxford University Press on behalf of the British Occupational Hygiene Society.

Quality of Chemical Safety Information in Printing Industry

PubMed Central

Tsai, Chung-Jung; Mao, I-Fang; Ting, Jo-Yu; Young, Chi-Hsien; Lin, Jhih-Sian; Li, Wei-Lun

2016-01-01

Objectives: Employees in printing industries can be exposed to multiple solvents in their work environment. The objectives of this study were to investigate the critical components of chemical solvents by analyzing the components of the solvents and collecting the Safety data sheets (SDSs), and to evaluate the hazard communication implementation status in printing industries. Method: About 152 printing-related industries were recruited by area-stratified random sampling and included 23 plate-making, 102 printing and 27 printing-assistance companies in Taiwan. We analyzed company questionnaires (n = 152), SDSs (n = 180), and solvents (n = 20) collected from this sample of printing-related companies. Results: Analytical results indicated that benzene and ethylbenzene, which were carcinogen and possibly carcinogen, were detectable in the cleaning solvents, and the detection rate were 54.5% (concentrations: <0.011–0.035 wt%) and 63.6% (concentrations: <0.011–6.22 wt%), respectively; however, neither compound was disclosed in the SDS for the solvents. Several other undisclosed components, including methanol, isopropanol and n-butanol, were also identified in the printing inks, fountain solutions and dilution solvents. We noted that, of the companies we surveyed, only 57.2% had a hazard communication program, 61.8% had SDSs on file and 59.9% provided employee safety and health training. We note that hazard communication programs were missing or ineffective in almost half of the 152 printing industries surveyed. Conclusions: Current safety information of solvents components in printing industries was inadequate, and many hazardous compounds were undisclosed in the SDSs of the solvents or the labels of the containers. The implementation of hazard communications in printing industries was still not enough for protecting the employees’ safety and health. PMID:26568584

Survey of Extreme Solvent Tolerance in Gram-Positive Cocci: Membrane Fatty Acid Changes in Staphylococcus haemolyticus Grown in Toluene

PubMed Central

Nielsen, Lindsey E.; Kadavy, Dana R.; Rajagopal, Soumitra; Drijber, Rhae; Nickerson, Kenneth W.

2005-01-01

We exploited the unique ecological niche of oil fly larval guts to isolate a strain of Staphylococcus haemolyticus which may be the most solvent-tolerant gram-positive bacterium yet described. This organism is able to tolerate 100% toluene, benzene, and p-xylene on plate overlays and saturating levels of these solvents in monophasic liquid cultures. A comparison of membrane fatty acids by gas chromatography after growth in liquid media with and without toluene showed that in cells continuously exposed to solvent the proportion of anteiso fatty acids increased from 25.8 to 33.7% while the proportion of 20:0 straight-chain fatty acids decreased from 19.3 to 10.1%. No changes in the membrane phospholipid composition were noted. Thus, S. haemolyticus alters its membrane fluidity via fatty acid composition to become more fluid when it is exposed to solvent. This response is opposite that commonly found in gram-negative bacteria, which change their fatty acids so that the cytoplasmic membrane is less fluid. Extreme solvent tolerance in S. haemolyticus is not accompanied by abnormal resistance to anionic or cationic detergents. Finally, six strains of Staphylococcus aureus and five strains of Staphylococcus epidermidis, which were not obtained by solvent selection, also exhibited exceptional solvent tolerance. PMID:16151101

Survey of extreme solvent tolerance in gram-positive cocci: membrane fatty acid changes in Staphylococcus haemolyticus grown in toluene.

PubMed

Nielsen, Lindsey E; Kadavy, Dana R; Rajagopal, Soumitra; Drijber, Rhae; Nickerson, Kenneth W

2005-09-01

We exploited the unique ecological niche of oil fly larval guts to isolate a strain of Staphylococcus haemolyticus which may be the most solvent-tolerant gram-positive bacterium yet described. This organism is able to tolerate 100% toluene, benzene, and p-xylene on plate overlays and saturating levels of these solvents in monophasic liquid cultures. A comparison of membrane fatty acids by gas chromatography after growth in liquid media with and without toluene showed that in cells continuously exposed to solvent the proportion of anteiso fatty acids increased from 25.8 to 33.7% while the proportion of 20:0 straight-chain fatty acids decreased from 19.3 to 10.1%. No changes in the membrane phospholipid composition were noted. Thus, S. haemolyticus alters its membrane fluidity via fatty acid composition to become more fluid when it is exposed to solvent. This response is opposite that commonly found in gram-negative bacteria, which change their fatty acids so that the cytoplasmic membrane is less fluid. Extreme solvent tolerance in S. haemolyticus is not accompanied by abnormal resistance to anionic or cationic detergents. Finally, six strains of Staphylococcus aureus and five strains of Staphylococcus epidermidis, which were not obtained by solvent selection, also exhibited exceptional solvent tolerance.

Weathering pits as indicators of the relative age of granite surfaces in the Cairngorm mountains, Scotland

USGS Publications Warehouse

Hall, A.M.; Phillips, W.M.

2006-01-01

Weathering pits 1-140 cm deep occur on granite surfaces in the Cairngorms associated with a range of landforms, including tors, glacially exposed slabs, large erratics and blockfields. Pit depth is positively correlated with cosmogenic exposure age, and both measures show consistent relationships on individual rock landforms. Rates of pit deepening are non-linear and a best fit is provided by the sigmoidal function D = b1+ exp(b2+b3/t). The deepest pits occur on unmodified tor summits, where 10 Be exposure ages indicate that surfaces have been exposed to weathering for a minimum of 52-297 ka. Glacially exposed surfaces with pits 10-46 cm deep have given 10 Be exposure durations of 21-79 ka, indicating exposure by glacial erosion before the last glacial cycle. The combination of cosmogenic exposure ages with weathering pit depths greatly extends the area over which inferences can be made regarding the ages of granite surfaces in the Cairngorms. Well-developed weathering pits on glacially exposed surfaces in other granite areas are potential indicators of glacial erosion before the Last Glacial Maximum. ?? Swedish Society for Anthropology and Geography.

Issues Related to Cleaning Complex Geometry Surfaces with ODC-Free Solvents

NASA Technical Reports Server (NTRS)

Bradford, Blake F.; Wurth, Laura A.; Nayate, Pramod D.; McCool, Alex (Technical Monitor)

2001-01-01

Implementing ozone depleting chemicals (ODC)-free solvents into full-scale reusable solid rocket motor cleaning operations has presented problems due to the low vapor pressures of the solvents. Because of slow evaporation, solvent retention is a problem on porous substrates or on surfaces with irregular geometry, such as threaded boltholes, leak check ports, and nozzle backfill joints. The new solvents are being evaluated to replace 1,1,1-trichloroethane, which readily evaporates from these surfaces. Selection of the solvents to be evaluated on full-scale hardware was made based on results of subscale tests performed with flat surface coupons, which did not manifest the problem. Test efforts have been undertaken to address concerns with the slow-evaporating solvents. These concerns include effects on materials due to long-term exposure to solvent, potential migration from bolthole threads to seal surfaces, and effects on bolt loading due to solvent retention in threads. Tests performed to date have verified that retained solvent does not affect materials or hardware performance. Process modifications have also been developed to assist drying, and these can be implemented if additional drying becomes necessary.

29 CFR 1910.106 - Flammable and combustible liquids.

Code of Federal Regulations, 2010 CFR

2010-07-01

... venting devices shall be not less than that derived from Table H-10 except as provided in subdivision (e... 30 feet above grade of the exposed shell area of a vertical tank. Table H-10—Wetted Area Versus Cubic... determined in accordance with Table H-10, except that when the exposed wetted area of the surface is greater...

Laser-driven fusion etching process

DOEpatents

Ashby, C.I.H.; Brannon, P.J.; Gerardo, J.B.

1987-08-25

The surfaces of solids are etched by a radiation-driven chemical reaction. The process involves exposing a substrate coated with a layer of a reactant material on its surface to radiation, e.g., a laser, to induce localized melting of the substrate which results in the occurrence of a fusion reaction between the substrate and coating material. The resultant reaction product and excess reactant salt are then removed from the surface of the substrate with a solvent which is relatively inert towards the substrate. The laser-driven chemical etching process is especially suitable for etching ionic substrates, e.g., LiNbO/sub 3/, such as used in electro-optical/acousto-optic devices. It is also suitable for applications wherein the etching process is required to produce an etched ionic substrate having a smooth surface morphology or when a very rapid etching rate is desired.

Dry efficient cleaning of poly-methyl-methacrylate residues from graphene with high-density H{sub 2} and H{sub 2}-N{sub 2} plasmas

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

Cunge, G., E-mail: gilles.cunge@cea.fr; Petit-Etienne, C.; Davydova, A.

Graphene is the first engineering electronic material, which is purely two-dimensional: it consists of two exposed sp{sup 2}-hybridized carbon surfaces and has no bulk. Therefore, surface effects such as contamination by adsorbed polymer residues have a critical influence on its electrical properties and can drastically hamper its widespread use in devices fabrication. These contaminants, originating from mandatory technological processes of graphene synthesis and transfer, also impact fundamental studies of the electronic and structural properties at the atomic scale. Therefore, graphene-based technology and research requires “soft” and selective surface cleaning techniques dedicated to limit or to suppress this surface contamination. Here,more » we show that a high-density H{sub 2} and H{sub 2}-N{sub 2} plasmas can be used to selectively remove polymeric residues from monolayer graphene without any damage on the graphene surface. The efficiency of this dry-cleaning process is evidenced unambiguously by a set of spectroscopic and microscopic methods, providing unprecedented insights on the cleaning mechanisms and highlighting the role of specific poly-methyl-methacrylate residues at the graphene interface. The plasma is shown to perform much better cleaning than solvents and has the advantage to be an industrially mature technology adapted to large area substrates. The process is transferable to other kinds of two-dimensional material and heterostructures.« less

Effect of dynamic surface polarization on the oxidative stability of solvents in nonaqueous Li-O 2 batteries

NASA Astrophysics Data System (ADS)

Khetan, Abhishek; Pitsch, Heinz; Viswanathan, Venkatasubramanian

2017-09-01

Polarization-induced renormalization of the frontier energy levels of interacting molecules and surfaces can cause significant shifts in the excitation and transport behavior of electrons. This phenomenon is crucial in determining the oxidative stability of nonaqueous electrolytes in high-energy density electrochemical systems such as the Li-O2 battery. On the basis of partially self-consistent first-principles Sc G W0 calculations, we systematically study how the electronic energy levels of four commonly used solvent molecules, namely, dimethylsulfoxide (DMSO), dimethoxyethane (DME), tetrahydrofuran (THF), and acetonitrile (ACN), renormalize when physisorbed on the different stable surfaces of Li2O2 , the main discharge product. Using band level alignment arguments, we propose that the difference between the solvent's highest occupied molecular orbital (HOMO) level and the surface's valence-band maximum (VBM) is a refined metric of oxidative stability. This metric and a previously used descriptor, solvent's gas phase HOMO level, agree quite well for physisorbed cases on pristine surfaces where ACN is oxidatively most stable followed by DME, THF, and DMSO. However, this effect is intrinsically linked to the surface chemistry of the solvent's interaction with the surface states and defects, and depends strongly on their nature. We conclusively show that the propensity of solvent molecules to oxidize will be significantly higher on Li2O2 surfaces with defects as compared to pristine surfaces. This suggests that the oxidative stability of a solvent is dynamic and is a strong function of surface electronic properties. Thus, while gas phase HOMO levels could be used for preliminary solvent candidate screening, a more refined picture of solvent stability requires mapping out the solvent stability as a function of the state of the surface under operating conditions.

Iodination of insulin in aqueous and organic solvents

PubMed Central

Massaglia, A.; Rosa, U.; Rialdi, G.; Rossi, C. A.

1969-01-01

1. The iodination of insulin was studied under various experimental conditions in aqueous media and in some organic solvents, by measuring separately the uptake of iodine by the four tyrosyl groups and the relative amounts of monoiodotyrosine and di-iodotyrosine that are formed. In aqueous media from pH1 to pH9 the iodination occurs predominantly on the tyrosyl groups of the A chain. Some organic solvents increase the iodine uptake of the B-chain tyrosyl groups. Their efficacy in promoting iodination of Tyr-B-16 and Tyr-B-26 is in the order: ethylene glycol and propylene glycol≃methanol and ethanol>dioxan>8m-urea. 2. It is suggested that each of the four tyrosyl groups in insulin has a different environment: Tyr-A-14 is fully exposed to the solvent; Tyr-A-19 is sterically influenced by the environmental structure, possibly by the vicinity of a disulphide interchain bond; Tyr-B-16 is embedded into a non-polar area whose stability is virtually independent of the molecular conformation; Tyr-B-26 is probably in a situation similar to Tyr-B-16 with the difference that its non-polar environment depends on the preservation of the native structure. PMID:5346365

Optimization of instantaneous solvent exchange/surface modification process for ambient synthesis of monolithic silica aerogels.

PubMed

Hwang, Sung-Woo; Kim, Tae-Youn; Hyun, Sang-Hoon

2008-06-01

The instantaneous solvent exchange/surface modification (ISE/SM) process for the ambient synthesis of crack-free silica aerogel monoliths with a high production yield was optimized. Monolithic forms of silica wet gels were obtained from aqueous colloidal silica sols prepared via the ion exchange of sodium silicate solutions. Crack-free silica aerogel monoliths were synthesized via an ISE/SM process using isopropyl alcohol/trimethylchlorosilane as a modification agent and n-hexane as a main solvent, followed by ambient drying. The optimum process conditions of the ISE/SM process were investigated by clarifying the reaction mechanism and phenomena. Most effective ranges of process variables on the ISE/SM stage were determined as 0.2500-0.3567 of TMCS/H2O (pore water) in molar ratio and 15-30 of n-hexane/TMCS in volumetric ratio, with a reaction temperature below 283 K. Crack-free silica aerogel monoliths synthesized via these conditions had a well-developed mesoporous structure and excellent properties (bulk density of 0.12-0.14 g/cm3, specific surface area of 724 m2/g), and a high yield (nearly 80%).

Probing the Self-Assembly and the Accompanying Structural Changes of Hydrophobin SC3 on a Hydrophobic Surface by Mass Spectrometry

PubMed Central

Wang, X.; Permentier, H. P.; Rink, R.; Kruijtzer, J. A. W.; Liskamp, R. M. J.; Wösten, H. A. B.; Poolman, B.; Robillard, G. T.

2004-01-01

The fungal class I hydrophobin SC3 self-assembles into an amphipathic membrane at hydrophilic-hydrophobic interfaces such as the water-air and water-Teflon interface. During self-assembly, the water-soluble state of SC3 proceeds via the intermediate α-helical state to the stable end form called the β-sheet state. Self-assembly of the hydrophobin at the Teflon surface is arrested in the α-helical state. The β-sheet state can be induced at elevated temperature in the presence of detergent. The structural changes of SC3 were monitored by various mass spectrometry techniques. We show that the so-called second loop of SC3 (C39–S72) has a high affinity for Teflon. Binding of this part of SC3 to Teflon was accompanied by the formation of α-helical structure and resulted in low solvent accessibility. The solvent-protected region of the second loop extended upon conversion to the β-sheet state. In contrast, the C-terminal part of SC3 became more exposed to the solvent. The results indicate that the second loop of class I hydrophobins plays a pivotal role in self-assembly at the hydrophilic-hydrophobic interface. Of interest, this loop is much smaller in case of class II hydrophobins, which may explain the differences in their assembly. PMID:15345568

Impact of organic solvents and environmental pollutants on the physiological function in petrol filling workers.

PubMed

Uzma, Nazia; Salar, B M Khaja Mohinuddin; Kumar, B Santhosh; Aziz, Nusrat; David, M Anthony; Reddy, V Devender

2008-09-01

Long term exposure to solvents and air pollutants can lead to deleterious effects on respiratory, haematological and thyroid functioning. The aim of this study was to investigate whether chronic exposure to solvents like benzene and pollutants like carbon monoxide in petrol filling workers had adverse effect on blood parameters, thyroid and respiratory functions. The study group consisted of 42 healthy, non-smoker petrol filling workers, aged 20-50 years with work (exposure) duration from 2-15 years while 36 healthy subjects of the same age group served as controls. Physical examination and measurement of pulmonary functions by portable electronic spirometer were performed. Complete blood pictures (CBP) were determined by normal haematology lab procedure and hormones by Chemiluminescence immunoassay (CLIA) light absorption techniques. There was a significant decrease in the lung volumes and capacities; the restrictive pattern was more prevalent in the workers when compared with the control groups. But in the workers exposed for long period (more than 10 years) the restrictive pattern was changed to mixed pattern. A significant increase in haemoglobin (Hb) (>16 mg %) and red blood cells (RBC) (5.4 million cells/mm3) were observed in workers with longer period of exposure when compared with the control subjects (14.483 mg% and 4.83 million cells/mm3 for Hb and RBC respectively). White blood cell count except eosinophils and platelets were significantly lower in workers compared to controls. Marked increase in the tetra iodothyroinine (T4), free thyroxine (T4F) level and significant decrease in thyroid stimulating hormones (TSH), and tri-iodothyronine (T3) were observed between long term exposed and non-exposed groups. Till now researchers focused only on the effect of solvents in workers professionally exposed to solvents without considering the effect of concomittant air pollution. The result obtained from present study indicates that there is a significant toxic effect of solvents and air pollutants on workers exposed for longer duration. Improved detection and prevention technologies are needed to answer environmentally related health questions for petrol filling workers.

Bioadhesion of mussels and geckos: Molecular mechanics, surface chemistry, and nanoadhesives

NASA Astrophysics Data System (ADS)

Lee, Haeshin

The adhesive strategies of living creatures are diverse, ranging from temporary to permanent adhesions with various functions such as locomotion, self-defense, communication, colony formation, and so on. The classic example of temporary adhesion is the gecko, which is known for its ability to walk along vertical and even inverted surfaces; this remarkable adhesion arises from the interfacial weak interactions of van der Waals and capillary forces. In contrast, a celerbrated example of permanent adhesion is found in marine mussels which secrete protein adhesives that function in aqueous environments without mechanical failure against turbulent conditions on the seashore. In addition, mussel adhesives stick to virtually all inorganic and organic surfaces. However, most commonly used man-made adhesives lack such unique adhesion properties compared to their natural counterparts. For example, many commercial adhesives quickly lose their adhesive strength when exposed to solvents, particularly water. The first part of this thesis focused on adhesion mechanics of mussels at a single-molecule level, in which the adhesive molecule showed surprisingly strong yet reversible adhesion on inorganic surfaces but exhibited irreversible covalent bond formation on organic surfaces. Strong and reversible adhesion on mucin surfaces was found, indicating potential application for drug delivery via mucus layers. Next, inspired by the mussel's versatile adhesion on a wide variety of material surfaces, a material-independent surface modification chemistry called 'polydopamine coating' is described. This concept was subsequently adapted to develop a surface-independent polymeric primer for layer-by-layer assembly of multifunctional coatings. Finally, a new bio-hybrid adhesive 'geckel' was developed by the functional combination of adhesion strategies of geckos and mussels. The new bio-inspired adhesive and material-independent surface chemistry can revolutionize the research areas such as medical devices, adhesives, and diagnostics, nanotechnology, biointerface, and catalysis.

Surface and Bulk Phase Separations in Block Copolymers and Their Blends.

DTIC Science & Technology

1984-03-01

research effort in _. the biomedical area to study polymeric surfaces which may be applied where biocompatibility (particularly, blood compatibilty) is...elasticity(thermoplastic) and good biocompatibility . Two such commercially available polyurethanes-, Avcothane and Biomer, have been used in this...the biocompatible properties depended considerably on the rate of evaporation of solvent during the film preparation. ATR-IR spectroscopy showed that

Effect of cocrystallization techniques on compressional properties of caffeine/oxalic acid 2:1 cocrystal.

PubMed

Aher, Suyog; Dhumal, Ravindra; Mahadik, Kakasaheb; Ketolainen, Jarkko; Paradkar, Anant

2013-02-01

Caffeine/oxalic acid 2:1 cocrystal exhibited superior stability to humidity over caffeine, but compressional behavior is not studied yet. To compare compressional properties of caffeine/oxalic acid 2:1 cocrystal obtained by different cocrystallization techniques. Cocrystal was obtained by solvent precipitation and ultrasound assisted solution cocrystallization (USSC) and characterized by X-ray powder diffraction and scanning electron microscopy. Compaction study was carried out at different compaction forces. Compact crushing strength, thickness and elastic recovery were determined. Compaction was in order, caffeine > solvent precipitation cocrystal > USSC cocrystal. Caffeine exhibited sticking and lamination, where solvent precipitation compacts showed advantage. Caffeine and solvent precipitation compacts showed sudden drop in compactability, higher elastic recovery with severe lamination at 20,000 N. This was due to overcompaction. Crystal habit of two cocrystal products was same, but USSC cocrystals were difficult to compact. Uniform needle shaped USSC cocrystals must be difficult to orient in different direction and fracture during compression. Elastic recovery of USSC cocrystals was also more compared to other powders indicating less fracture and poor bonding between particles resulting in poor compaction. Cocrystal formation did not improve compressional property of caffeine. Cocrystals exposed to different crystallization environments in two techniques may have resulted in generation of different surface properties presenting different compressional properties.

Gold nanorod linking to control plasmonic properties in solution and polymer nanocomposites.

PubMed

Ferrier, Robert C; Lee, Hyun-Su; Hore, Michael J A; Caporizzo, Matthew; Eckmann, David M; Composto, Russell J

2014-02-25

A novel, solution-based method is presented to prepare bifunctional gold nanorods (B-NRs), assemble B-NRs end-to-end in various solvents, and disperse linked B-NRs in a polymer matrix. The B-NRs have poly(ethylene glycol) grafted along its long axis and cysteine adsorbed to its ends. By controlling cysteine coverage, bifunctional ligands or polymer can be end-grafted to the AuNRs. Here, two dithiol ligands (C6DT and C9DT) are used to link the B-NRs in organic solvents. With increasing incubation time, the nanorod chain length increases linearly as the longitudinal surface plasmon resonance shifts toward lower adsorption wavelengths (i.e., red shift). Analogous to step-growth polymerization, the polydispersity in chain length also increases. Upon adding poly(ethylene glycol) or poly(methyl methacrylate) to chloroform solution with linked B-NR, the nanorod chains are shown to retain end-to-end linking upon spin-casting into PEO or PMMA films. Using quartz crystal microbalance with dissipation (QCM-D), the mechanism of nanorod linking is investigated on planar gold surfaces. At submonolayer coverage of cysteine, C6DT molecules can insert between cysteines and reach an areal density of 3.4 molecules per nm(2). To mimic the linking of Au NRs, this planar surface is exposed to cysteine-coated Au nanoparticles, which graft at 7 NPs per μm(2). This solution-based method to prepare, assemble, and disperse Au nanorods is applicable to other nanorod systems (e.g., CdSe) and presents a new strategy to assemble anisotropic particles in organic solvents and polymer coatings.

Gold Nanorod Linking to Control Plasmonic Properties in Solution and Polymer Nanocomposites

PubMed Central

2015-01-01

A novel, solution-based method is presented to prepare bifunctional gold nanorods (B-NRs), assemble B-NRs end-to-end in various solvents, and disperse linked B-NRs in a polymer matrix. The B-NRs have poly(ethylene glycol) grafted along its long axis and cysteine adsorbed to its ends. By controlling cysteine coverage, bifunctional ligands or polymer can be end-grafted to the AuNRs. Here, two dithiol ligands (C6DT and C9DT) are used to link the B-NRs in organic solvents. With increasing incubation time, the nanorod chain length increases linearly as the longitudinal surface plasmon resonance shifts toward lower adsorption wavelengths (i.e., red shift). Analogous to step-growth polymerization, the polydispersity in chain length also increases. Upon adding poly(ethylene glycol) or poly(methyl methacrylate) to chloroform solution with linked B-NR, the nanorod chains are shown to retain end-to-end linking upon spin-casting into PEO or PMMA films. Using quartz crystal microbalance with dissipation (QCM-D), the mechanism of nanorod linking is investigated on planar gold surfaces. At submonolayer coverage of cysteine, C6DT molecules can insert between cysteines and reach an areal density of 3.4 molecules per nm2. To mimic the linking of Au NRs, this planar surface is exposed to cysteine-coated Au nanoparticles, which graft at 7 NPs per μm2. This solution-based method to prepare, assemble, and disperse Au nanorods is applicable to other nanorod systems (e.g., CdSe) and presents a new strategy to assemble anisotropic particles in organic solvents and polymer coatings. PMID:24483622

The preparation of large surface area lanthanum based perovskite supports for AuPt nanoparticles: tuning the glycerol oxidation reaction pathway by switching the perovskite B site

PubMed Central

Evans, Christopher D.; Smith, Paul J.; Manning, Troy D.; Miedziak, Peter J.; Brett, Gemma L.; Armstrong, Robert D.; Bartley, Jonathan K.; Taylor, Stuart H.; Rosseinsky, Matthew J.; Hutchings, Graham J.

2016-01-01

Gold and gold alloys, in the form of supported nanoparticles, have been shown over the last three decades to be highly effective oxidation catalysts. Mixed metal oxide perovskites, with their high structural tolerance, are ideal for investigating how changes in the chemical composition of supports affect the catalysts' properties, while retaining similar surface areas, morphologies and metal co-ordinations. However, a significant disadvantage of using perovskites as supports is their high crystallinity and small surface area. We report the use of a supercritical carbon dioxide anti-solvent precipitation methodology to prepare large surface area lanthanum based perovskites, making the deposition of 1 wt% AuPt nanoparticles feasible. These catalysts were used for the selective oxidation of glycerol. By changing the elemental composition of the perovskite B site, we dramatically altered the reaction pathway between a sequential oxidation route to glyceric or tartronic acid and a dehydration reaction pathway to lactic acid. Selectivity profiles were correlated to reported oxygen adsorption capacities of the perovskite supports and also to changes in the AuPt nanoparticle morphologies. Extended time on line analysis using the best oxidation catalyst (AuPt/LaMnO3) produced an exceptionally high tartronic acid yield. LaMnO3 produced from alternative preparation methods was found to have lower activities, but gave comparable selectivity profiles to that produced using the supercritical carbon dioxide anti-solvent precipitation methodology. PMID:27074316

The preparation of large surface area lanthanum based perovskite supports for AuPt nanoparticles: tuning the glycerol oxidation reaction pathway by switching the perovskite B site.

PubMed

Evans, Christopher D; Kondrat, Simon A; Smith, Paul J; Manning, Troy D; Miedziak, Peter J; Brett, Gemma L; Armstrong, Robert D; Bartley, Jonathan K; Taylor, Stuart H; Rosseinsky, Matthew J; Hutchings, Graham J

2016-07-04

Gold and gold alloys, in the form of supported nanoparticles, have been shown over the last three decades to be highly effective oxidation catalysts. Mixed metal oxide perovskites, with their high structural tolerance, are ideal for investigating how changes in the chemical composition of supports affect the catalysts' properties, while retaining similar surface areas, morphologies and metal co-ordinations. However, a significant disadvantage of using perovskites as supports is their high crystallinity and small surface area. We report the use of a supercritical carbon dioxide anti-solvent precipitation methodology to prepare large surface area lanthanum based perovskites, making the deposition of 1 wt% AuPt nanoparticles feasible. These catalysts were used for the selective oxidation of glycerol. By changing the elemental composition of the perovskite B site, we dramatically altered the reaction pathway between a sequential oxidation route to glyceric or tartronic acid and a dehydration reaction pathway to lactic acid. Selectivity profiles were correlated to reported oxygen adsorption capacities of the perovskite supports and also to changes in the AuPt nanoparticle morphologies. Extended time on line analysis using the best oxidation catalyst (AuPt/LaMnO3) produced an exceptionally high tartronic acid yield. LaMnO3 produced from alternative preparation methods was found to have lower activities, but gave comparable selectivity profiles to that produced using the supercritical carbon dioxide anti-solvent precipitation methodology.

Solvent polarity effect on quality of n-octadecanethiol self-assembled monolayers on copper and oxidized copper

NASA Astrophysics Data System (ADS)

Zhang, Yaozhong; Zhou, Jun; Zhang, Xiaoli; Hu, Jun; Gao, Han

2014-11-01

This article reports the effect of solvent polarity on the formation of n-octadecanethiol self-assembled monolayers (C18SH-SAMs) on pure copper surface and oxidized copper surface. The quality of SAMs prepared in different solvents (n-hexane, toluene, trichloroethylene, chloroform, acetone, acetonitrile, ethanol) was monitored by EIS, RAIRS and XPS. The results indicated that C18SH-SAMs formed in these solvents were in good barrier properties on pure copper surface and the structures of monolayers formed in high polarity solvents were more compact and orderly than that formed in low polarity solvents. For comparison, C18SH adsorbed on the surface of oxidized copper in these solvents were studied and the results indicated that C18SH could be adsorbed on oxidized copper surface after the reduction of copper oxide layer by thiols. Compared with high polarity solvents, a limited reduction process of oxidized copper by thiols led to the incompletely formation of monolayers in low polarity solvents. This can be interpreted that the generated water on solid-liquid interface and a smaller reaction force restrict the continuous reduction reaction in low polarity solvents

Method for forming a nano-textured substrate

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

Jeong, Sangmoo; Hu, Liangbing; Cui, Yi

A method for forming a nano-textured surface on a substrate is disclosed. An illustrative embodiment of the present invention comprises dispensing of a nanoparticle ink of nanoparticles and solvent onto the surface of a substrate, distributing the ink to form substantially uniform, liquid nascent layer of the ink, and enabling the solvent to evaporate from the nanoparticle ink thereby inducing the nanoparticles to assemble into an texture layer. Methods in accordance with the present invention enable rapid formation of large-area substrates having a nano-textured surface. Embodiments of the present invention are well suited for texturing substrates using high-speed, large scale,more » roll-to-roll coating equipment, such as that used in office product, film coating, and flexible packaging applications. Further, embodiments of the present invention are well suited for use with rigid or flexible substrates.« less

30 CFR 57.22218 - Seals and stoppings (III, V-A, and V-B mines).

Code of Federal Regulations, 2013 CFR

2013-07-01

... materials may be used in face areas. (b) Exposed surfaces on the intake side of stoppings constructed of... construction shall be solid. (c) Exposed surfaces on the fresh air side of seals constructed of combustible... other coatings with equivalent fire resistance. Stoppings constructed to phenolic foam blocks at least...

30 CFR 57.22218 - Seals and stoppings (III, V-A, and V-B mines).

Code of Federal Regulations, 2014 CFR

2014-07-01

... materials may be used in face areas. (b) Exposed surfaces on the intake side of stoppings constructed of... construction shall be solid. (c) Exposed surfaces on the fresh air side of seals constructed of combustible... other coatings with equivalent fire resistance. Stoppings constructed to phenolic foam blocks at least...

30 CFR 57.22218 - Seals and stoppings (III, V-A, and V-B mines).

Code of Federal Regulations, 2012 CFR

2012-07-01

... materials may be used in face areas. (b) Exposed surfaces on the intake side of stoppings constructed of... construction shall be solid. (c) Exposed surfaces on the fresh air side of seals constructed of combustible... other coatings with equivalent fire resistance. Stoppings constructed to phenolic foam blocks at least...

Apparatus to measure adsorption of condensable solvents on technical surfaces by photothermal deflection

NASA Astrophysics Data System (ADS)

Plimmer, M. D.; du Colombier, D.; Iraqi Houssaini, N.; Silvestri, Z.; Pinot, P.; Hannachi, R.

2012-11-01

This article describes an instrument for the measurement of the mirage effect as a tool to determine the molar adsorption per unit surface area Y1 of condensable solvents in the presence of a non-condensable carrier gas. The present apparatus is a much improved version of previous prototypes developed in our laboratory and elsewhere with a higher surface bake-out temperature (150 °C rather than 40 °C), lower residual vacuum (3 Pa versus 100 Pa), greater sample surface (40 mm diameter instead of 10 mm), more powerful optical pump beam (150 W cf. 50 W), and larger saturated vapour preparation volume (4 L instead of 1 L). The new set-up also includes the in situ monitoring of the surface via a reflected HeNe laser beam for the real-time detection of the onset of condensation. Here, we give a detailed description of the various components, outline the experimental procedure, show typical results, and suggest some straightforward improvements.

Apparatus to measure adsorption of condensable solvents on technical surfaces by photothermal deflection.

PubMed

Plimmer, M D; du Colombier, D; Iraqi Houssaini, N; Silvestri, Z; Pinot, P; Hannachi, R

2012-11-01

This article describes an instrument for the measurement of the mirage effect as a tool to determine the molar adsorption per unit surface area Y(1) of condensable solvents in the presence of a non-condensable carrier gas. The present apparatus is a much improved version of previous prototypes developed in our laboratory and elsewhere with a higher surface bake-out temperature (150 °C rather than 40 °C), lower residual vacuum (3 Pa versus 100 Pa), greater sample surface (40 mm diameter instead of 10 mm), more powerful optical pump beam (150 W cf. 50 W), and larger saturated vapour preparation volume (4 L instead of 1 L). The new set-up also includes the in situ monitoring of the surface via a reflected HeNe laser beam for the real-time detection of the onset of condensation. Here, we give a detailed description of the various components, outline the experimental procedure, show typical results, and suggest some straightforward improvements.

Organic solvent exposure and hearing loss in a cohort of aluminium workers.

PubMed

Rabinowitz, P M; Galusha, D; Slade, M D; Dixon-Ernst, C; O'Neill, A; Fiellin, M; Cullen, M R

2008-04-01

Organic solvent exposure has been shown to cause hearing loss in animals and humans. Less is known about the risk of hearing loss due to solvent exposures typically found in US industry. The authors performed a retrospective cohort study to examine the relationship between solvent exposure and hearing loss in US aluminium industry workers. A cohort of 1319 workers aged 35 years or less at inception was followed for 5 years. Linkage of employment, industrial hygiene and audiometric surveillance records allowed for estimation of noise and solvent exposures and hearing loss rates over the study period. Study subjects were classified as "solvent exposed" or not, on the basis of industrial hygiene records linked with individual job histories. High frequency hearing loss was modelled as both a continuous and a dichotomous outcome. Typical solvent exposures involved mixtures of xylene, toluene and/or methyl ethyl ketone (MEK). Recorded solvent exposure levels varied widely both within and between jobs. In a multivariate logistic model, risk factors for high frequency hearing loss included age (OR = 1.06, p = 0.004), hunting or shooting (OR = 1.35, p = 0.049), noisy hobbies (OR = 1.74, p = 0.01), baseline hearing level (OR = 1.04, p<0.001) and solvent exposure (OR = 1.87, p = 0.004). A multivariate linear regression analysis similarly found significant associations between high frequency hearing loss and age (p<0.001), hunting or shooting (p<0.001), noisy hobbies (p = 0.03), solvent exposure (p<0.001) and baseline hearing (p = 0.03). These results suggest that occupational exposure to organic solvent mixtures is a risk factor for high frequency hearing loss, although the data do not allow conclusions about dose-response relationships. Industries with solvent-exposed workers should include such workers in hearing conservation programs.

Space Weathering of Lunar Rocks

NASA Technical Reports Server (NTRS)

Noble, S. K.; Keller, L. P.; Christoffersen, R.; Rahman, Z.

2012-01-01

All materials exposed at the lunar surface undergo space weathering processes. On the Moon, boulders make up only a small percentage of the exposed surface, and areas where such rocks are exposed, like central peaks, are often among the least space weathered regions identified from remote sensing data. Yet space weathered surfaces (patina) are relatively common on returned rock samples, some of which directly sample the surface of larger boulders. Because, as witness plates to lunar space weathering, rocks and boulders experience longer exposure times compared to lunar soil grains, they allow us to develop a deeper perspective on the relative importance of various weathering processes as a function of time.

Phytoremediation of Trichloroethylene and Perchloroethylene at the Savannah River Site

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

Brigmon, R.L.

Bioremediation of chlorinated solvents, both natural and accelerated, is exemplified by phytoremediation and biodegradation by rhizosphere microorganisms. Phytoremediation is the use of vegetation for the treatment of contaminated soils, sediments, and water. The potential for phytoremediation of chlorinated solvents has been demonstrated at the Savannah River Site (SRS) Miscellaneous Chemical Basin, Southern Sector of A/M Area and TNX/D-Area. Recent characterization work at the SRS has delineated widespread plumes (1-2 miles) of low concentration (40 ppb -10-ppm range) trichloroethylene (TCE) and perchloroethylene (PCE) contaminated groundwater. Phytoremediation deployments are underway for TCE and PCE phytoremediation in select SRS areas. Phytoremediation appears tomore » be an excellent technology to intercept and control plume migration. The ongoing Southern Sector treatability study is part of a multi-year field study of SRS seepline-soil systems maintained under saturated conditions. The primary focus is on determining how trees, seepline groundcover, soil microbial communities, and geochemical and surface-volatilization processes affect TCE and PCE in contaminated groundwater that flows through surface seepline areas. Therefore, FY00 represented an initial acclimation phase for soil and plant systems and will facilitate examination of seepline phyto- and bioactivity in subsequent growth season in FY01.« less

Evaluation of cleaners for photovoltaic modules exposed in an outdoor environment

NASA Technical Reports Server (NTRS)

Knapp, W. D.

1979-01-01

Power recovery of silicone encapsulated and glass covered photovoltaic modules, exposed for two years to a suburban environment, was measured after washing with a variety of cleaners including detergents, abrasive soap, and hydrocarbon solvents. Silicone encapsulated modules in operating environments may experience significant power losses or require extensive periodic cleaning. Glass front-faced modules in similar situations are much less affected. Organic hydrocarbon solvents or abrasives were found to be about five times more effective than mild detergents in cleaning encapsulated modules.

Mapping bedrock surface contours using the horizontal-to-vertical spectral ratio (HVSR) method near the middle quarter srea, Woodbury, Connecticut

USGS Publications Warehouse

Brown, Craig J.; Voytek, Emily B.; Lane, John W.; Stone, Janet R.

2013-01-01

The bedrock surface contours in Woodbury, Connecticut, were determined downgradient of a commercial zone known as the Middle Quarter area (MQA) using the novel, noninvasive horizontal-to-vertical (H/V) spectral ratio (HVSR) passive seismic geophysical method. Boreholes and monitoring wells had been drilled in this area to characterize the shallow subsurface to within 20 feet (ft) of the land surface, but little was known about the deep subsurface, including sediment thicknesses and depths to bedrock (Starn and Brown, 2007; Brown and others, 2009). Improved information on the altitude of the bedrock surface and its spatial variation was needed for assessment and remediation of chlorinated solvents that have contaminated the overlying glacial aquifer that supplies water to wells in the area.

Combining H/D exchange mass spectroscopy and computational docking reveals extended DNA-binding surface on uracil-DNA glycosylase

PubMed Central

Roberts, Victoria A.; Pique, Michael E.; Hsu, Simon; Li, Sheng; Slupphaug, Geir; Rambo, Robert P.; Jamison, Jonathan W.; Liu, Tong; Lee, Jun H.; Tainer, John A.; Ten Eyck, Lynn F.; Woods, Virgil L.

2012-01-01

X-ray crystallography provides excellent structural data on protein–DNA interfaces, but crystallographic complexes typically contain only small fragments of large DNA molecules. We present a new approach that can use longer DNA substrates and reveal new protein–DNA interactions even in extensively studied systems. Our approach combines rigid-body computational docking with hydrogen/deuterium exchange mass spectrometry (DXMS). DXMS identifies solvent-exposed protein surfaces; docking is used to create a 3-dimensional model of the protein–DNA interaction. We investigated the enzyme uracil-DNA glycosylase (UNG), which detects and cleaves uracil from DNA. UNG was incubated with a 30 bp DNA fragment containing a single uracil, giving the complex with the abasic DNA product. Compared with free UNG, the UNG–DNA complex showed increased solvent protection at the UNG active site and at two regions outside the active site: residues 210–220 and 251–264. Computational docking also identified these two DNA-binding surfaces, but neither shows DNA contact in UNG–DNA crystallographic structures. Our results can be explained by separation of the two DNA strands on one side of the active site. These non-sequence-specific DNA-binding surfaces may aid local uracil search, contribute to binding the abasic DNA product and help present the DNA product to APE-1, the next enzyme on the DNA-repair pathway. PMID:22492624

Solvent-vapor-assisted dewetting of prepatterned thin polymer films: control of morphology, order, and pattern miniaturization.

PubMed

Bhandaru, Nandini; Goohpattader, Partho Sarathi; Faruqui, Danish; Mukherjee, Rabibrata; Sharma, Ashutosh

2015-03-17

Ultrathin (<100 nm) unstable polymer films exposed to a solvent vapor dewet by the growth of surface instability, the wavelength (λ) of which depends on the film thickness (h(f)). While the dewetting of a flat polymer thin film results in random structures, we show that the dewetting of a prepatterned film results in myriad ordered mesoscale morphologies under specific conditions. Such a film undergoes rupture over the thinnest parts when the initial local thickness of these zones (h(rm)) is lower than a limiting thickness h(lim) ≈ 10 nm. Additionally, the width of the pattern grooves (l(s)) must be wider than λ(s) corresponding to a flat film having a thickness of h(rm) for pattern-directed dewetting to take place over surface-tension-induced flattening. We first present an experimentally obtained morphology phase diagram that captures the conditions where a transition from surface-tension-induced flattening to pattern-directed-rupture takes place. Subsequently, we show the versatility of this technique in achieving a variety of aligned mesopatterns starting from a prepatterned film with simple grating geometry. The morphology of the evolving patterns depends on several parameters such as the initial film thickness (h(f)), prepattern amplitude (h(st)), duration of solvent vapor exposure (SVE), and wettability of the stamp used for patterning. Periodic rupture of the film at regular intervals imposes directionality on the evolving patterns, resulting in isolated long threads/cylindrical ridges of polymers, which subsequently disintegrate into an aligned array of droplets due to Rayleigh-Plateau instability under specific conditions. Other patterns such as a double periodic array of droplets and an array of holes are also possible to obtain. The evolution can be interrupted at any intermediate stage by terminating the solvent vapor annealing, allowing the creation of pattern morphology on demand. The created patterns are significantly miniaturized in size as compared to features obtained from dewetting a flat film with the same hf.

Reproductive failure of the red shiner (Cyprinella lutrensis) after exposure to an exogenous estrogen

USGS Publications Warehouse

McGree, M.M.; Winkelman, D.L.; Vieira, N.K.M.; Vajda, A.M.

2010-01-01

Endocrine disrupting chemicals (EDCs) have been detected in surface waters worldwide and can lead to developmental and reproductive disruption in exposed fishes. In the US Great Plains, EDCs are impacting streams and rivers and may be causing adverse reproductive effects. To examine how estrogenic EDCs might affect reproductive success of plains fishes, we experimentally exposed male red shiners (Cyprinella lutrensis) to exogenous 17b-estradiol. We characterized the effects of estradiol on male gonadal histology and secondary sexual characteristics, determined whether exposure reduced reproductive success, and examined the effects of depuration. Adults were exposed to a mean concentration of 70 ng L-1 estradiol, a solvent control, or a water control for at least 83 days. Male exposure to estradiol resulted in elevated plasma vitellogenin concentrations, changes in spermatogenesis, reduced mating coloration and tubercles, altered mating behaviors, and reduced reproductive success with no viable progeny produced. Reproductive endpoints improved upon depuration (28 days). Exposure to estradiol had significant adverse effects on red shiners, indicating that wild populations may face developmental and reproductive difficulties if they are chronically exposed to estradiol.

Predicting the Activity Coefficients of Free-Solvent for Concentrated Globular Protein Solutions Using Independently Determined Physical Parameters

PubMed Central

McBride, Devin W.; Rodgers, Victor G. J.

2013-01-01

The activity coefficient is largely considered an empirical parameter that was traditionally introduced to correct the non-ideality observed in thermodynamic systems such as osmotic pressure. Here, the activity coefficient of free-solvent is related to physically realistic parameters and a mathematical expression is developed to directly predict the activity coefficients of free-solvent, for aqueous protein solutions up to near-saturation concentrations. The model is based on the free-solvent model, which has previously been shown to provide excellent prediction of the osmotic pressure of concentrated and crowded globular proteins in aqueous solutions up to near-saturation concentrations. Thus, this model uses only the independently determined, physically realizable quantities: mole fraction, solvent accessible surface area, and ion binding, in its prediction. Predictions are presented for the activity coefficients of free-solvent for near-saturated protein solutions containing either bovine serum albumin or hemoglobin. As a verification step, the predictability of the model for the activity coefficient of sucrose solutions was evaluated. The predicted activity coefficients of free-solvent are compared to the calculated activity coefficients of free-solvent based on osmotic pressure data. It is observed that the predicted activity coefficients are increasingly dependent on the solute-solvent parameters as the protein concentration increases to near-saturation concentrations. PMID:24324733

Enhanced bulk heterojunction devices prepared by thermal and solvent vapor annealing processes

DOEpatents

Forrest, Stephen R.; Thompson, Mark E.; Wei, Guodan; Wang, Siyi

2017-09-19

A method of preparing a bulk heterojunction organic photovoltaic cell through combinations of thermal and solvent vapor annealing are described. Bulk heterojunction films may prepared by known methods such as spin coating, and then exposed to one or more vaporized solvents and thermally annealed in an effort to enhance the crystalline nature of the photoactive materials.

Organic solvent exposure and contrast sensitivity: comparing men and women

PubMed Central

Oliveira, A.R.; Campos, A.A.; de Andrade, M.J.O.; de Medeiros, P.C.B.; dos Santos, N.A.

2018-01-01

The goal of this study was to compare the visual contrast sensitivity (CS) of men and women exposed and not exposed to organic solvents. Forty-six volunteers of both genders aged between 18 and 41 years (mean±SD=27.72±6.28) participated. Gas station attendants were exposed to gas containing 46.30 ppm of solvents at a temperature of 304±274.39 K, humidity of 62.25±7.59% and ventilation of 0.69±0.46 m/s (a passive gas chromatography-based sampling method was used considering the microclimate variables). Visual CS was measured via the psychophysical method of two-alternative forced choice using vertical sinusoidal gratings with spatial frequencies of 0.2, 0.5, 1.0, 2.0, 5.0, 10.0, and 16.0 cpd (cycles per degree) and an average luminance of 34.4 cd/m2. The results showed that visual CS was significantly lower (P<0.05) in the following groups: i) exposed men compared to unexposed men at frequencies of 0.2, 0.5, 1.0, and 2.0 cpd; ii) exposed women compared to unexposed women at a frequency of 5.0 cpd; and iii) exposed women compared to exposed men at a frequency of 0.5 cpd, even at exposures below the tolerance limit (300 ppm). These results suggest that the visual CS of exposed men was impaired over a wider range of spatial frequencies than that of exposed women. This difference may have been due to the higher body fat content of women compared to that of men, suggesting that body fat in women can serve as a protective factor against neurotoxic effects. PMID:29340521

Quantification of peroxide ion passage in dentin, enamel, and cementum after internal bleaching with hydrogen peroxide.

PubMed

Palo, R M; Bonetti-Filho, I; Valera, M C; Camargo, C H R; Camargo, Sea; Moura-Netto, C; Pameijer, C

2012-01-01

The aim of this study was to evaluate the amount of peroxide passage from the pulp chamber to the external enamel surface during the internal bleaching technique. Fifty bovine teeth were sectioned transversally 5 mm below the cemento-enamel junction (CEJ), and the remaining part of the root was sealed with a 2-mm layer of glass ionomer cement. The external surface of the samples was coated with nail varnish, with the exception of standardized circular areas (6-mm diameter) located on the enamel, exposed dentin, or cementum surface of the tooth. The teeth were divided into three experimental groups according to exposed areas close to the CEJ and into two control groups (n=10/group), as follows: GE, enamel exposure area; GC, cementum exposed area; GD, dentin exposed area; Negative control, no presence of internal bleaching agent and uncoated surface; and Positive control, pulp chamber filled with bleaching agent and external surface totally coated with nail varnish. The pulp chamber was filled with 35% hydrogen peroxide (Opalescence Endo, Ultradent). Each sample was placed inside of individual flasks with 1000 μL of acetate buffer solution, 2 M (pH 4.5). After seven days, the buffer solution was transferred to a glass tube, in which 100 μL of leuco-crystal violet and 50 μL of horseradish peroxidase were added, producing a blue solution. The optical density of the blue solution was determined by spectrophotometer and converted into microgram equivalents of hydrogen peroxide. Data were submitted to Kruskal-Wallis and Dunn-Bonferroni tests (α=0.05). All experimental groups presented passage of peroxide to the external surface that was statistically different from that observed in the control groups. It was verified that the passage of peroxide was higher in GD than in GE (p<0.01). The GC group presented a significantly lower peroxide passage than did GD and GE (p<0.01). It can be concluded that the hydrogen peroxide placed into the pulp chamber passed through the dental hard tissues, reaching the external surface and the periodontal tissue. The cementum surface was less permeable than were the dentin and enamel surfaces.

Membrane-Based Emitter for Coupling Microfluidics with Ultrasensitive Nanoelectrospray Ionization-Mass Spectrometry

PubMed Central

Sun, Xuefei; Kelly, Ryan T.; Tang, Keqi; Smith, Richard D.

2011-01-01

An integrated poly(dimethylsiloxane) (PDMS) membrane-based microfluidic emitter for high performance nanoelectrospray ionization-mass spectrometry (nanoESI-MS) has been fabricated and evaluated. The ~100-μm-thick emitter was created by cutting a PDMS membrane that protrudes beyond the bulk substrate. The reduced surface area at the emitter enhances the electric field and reduces wetting of the surface by the electrospray solvent. As such, the emitter enables highly stable electrosprays at flow rates as low as 10 nL/min, and is compatible with electrospray solvents containing a large organic component (e.g., 90% methanol). This approach enables facile emitter construction, and provides excellent stability, reproducibility and sensitivity, as well as compatibility with multilayer soft lithography. PMID:21657269

Laser-driven fusion etching process

DOEpatents

Ashby, Carol I. H.; Brannon, Paul J.; Gerardo, James B.

1989-01-01

The surfaces of solid ionic substrates are etched by a radiation-driven chemical reaction. The process involves exposing an ionic substrate coated with a layer of a reactant material on its surface to radiation, e.g. a laser, to induce localized melting of the substrate which results in the occurrance of a fusion reaction between the substrate and coating material. The resultant reaction product and excess reactant salt are then removed from the surface of the substrate with a solvent which is relatively inert towards the substrate. The laser-driven chemical etching process is especially suitable for etching ionic salt substrates, e.g., a solid inorganic salt such as LiNbO.sub.3, such as used in electro-optical/acousto-optic devices. It is also suitable for applications wherein the etching process is required to produce an etched ionic substrate having a smooth surface morphology or when a very rapid etching rate is desired.

Synthesis of metal oxide nanoparticles via a robust ``solvent-deficient'' method

NASA Astrophysics Data System (ADS)

Smith, Stacey J.; Huang, Baiyu; Liu, Shengfeng; Liu, Qingyuan; Olsen, Rebecca E.; Boerio-Goates, Juliana; Woodfield, Brian F.

2014-11-01

We report an efficient, general methodology for producing high-surface area metal oxide nanomaterials for a vast range of metal oxides, including at least one metal oxide nanomaterial from nearly every transition metal and semi-metal group in the periodic table (groups 3-4 and 6-15) as well as several from the lanthanide group (see Table 1). The method requires only 2-3 simple steps; a hydrated metal salt (usually a nitrate or chloride salt) is ground with bicarbonate (usually NH4HCO3) for 10-30 minutes to form a precursor that is then either untreated or rinsed before being calcined at relatively low temperatures (220-550 °C) for 1-3 hours. The method is thus similar to surfactant-free aqueous methods such as co-precipitation but is unique in that no solvents are added. The resulting ``solvent-deficient'' environment has interesting and unique consequences, including increased crystallinity of the products over other aqueous methods and a mesoporous nature in the inevitable agglomerates. The products are chemically pure and phase pure with crystallites generally 3-30 nm in average size that aggregate into high surface area, mesoporous agglomerates 50-300 nm in size that would be useful for catalyst and gas sensing applications. The versatility of products and efficiency of the method lend its unique potential for improving the industrial viability of a broad family of useful metal oxide nanomaterials. In this paper, we outline the methodology of the solvent-deficient method using our understanding of its mechanism, and we describe the range and quality of nanomaterials it has produced thus far.We report an efficient, general methodology for producing high-surface area metal oxide nanomaterials for a vast range of metal oxides, including at least one metal oxide nanomaterial from nearly every transition metal and semi-metal group in the periodic table (groups 3-4 and 6-15) as well as several from the lanthanide group (see Table 1). The method requires only 2-3 simple steps; a hydrated metal salt (usually a nitrate or chloride salt) is ground with bicarbonate (usually NH4HCO3) for 10-30 minutes to form a precursor that is then either untreated or rinsed before being calcined at relatively low temperatures (220-550 °C) for 1-3 hours. The method is thus similar to surfactant-free aqueous methods such as co-precipitation but is unique in that no solvents are added. The resulting ``solvent-deficient'' environment has interesting and unique consequences, including increased crystallinity of the products over other aqueous methods and a mesoporous nature in the inevitable agglomerates. The products are chemically pure and phase pure with crystallites generally 3-30 nm in average size that aggregate into high surface area, mesoporous agglomerates 50-300 nm in size that would be useful for catalyst and gas sensing applications. The versatility of products and efficiency of the method lend its unique potential for improving the industrial viability of a broad family of useful metal oxide nanomaterials. In this paper, we outline the methodology of the solvent-deficient method using our understanding of its mechanism, and we describe the range and quality of nanomaterials it has produced thus far. Electronic supplementary information (ESI) available: (1) Preliminary Netzsch milling results for Al2O3 and CeO2, (2) XRD patterns/analyses of the dried and rinsed precursors plotted with the ICDD standard patterns of the materials they contain, (3) all TG/DTA-MS data. See DOI: 10.1039/c4nr04964k

Buried and accessible surface area control intrinsic protein flexibility.

PubMed

Marsh, Joseph A

2013-09-09

Proteins experience a wide variety of conformational dynamics that can be crucial for facilitating their diverse functions. How is the intrinsic flexibility required for these motions encoded in their three-dimensional structures? Here, the overall flexibility of a protein is demonstrated to be tightly coupled to the total amount of surface area buried within its fold. A simple proxy for this, the relative solvent-accessible surface area (Arel), therefore shows excellent agreement with independent measures of global protein flexibility derived from various experimental and computational methods. Application of Arel on a large scale demonstrates its utility by revealing unique sequence and structural properties associated with intrinsic flexibility. In particular, flexibility as measured by Arel shows little correspondence with intrinsic disorder, but instead tends to be associated with multiple domains and increased α-helical structure. Furthermore, the apparent flexibility of monomeric proteins is found to be useful for identifying quaternary-structure errors in published crystal structures. There is also a strong tendency for the crystal structures of more flexible proteins to be solved to lower resolutions. Finally, local solvent accessibility is shown to be a primary determinant of local residue flexibility. Overall, this work provides both fundamental mechanistic insight into the origin of protein flexibility and a simple, practical method for predicting flexibility from protein structures. © 2013 Elsevier Ltd. All rights reserved.

Modification of the crystal habit of celecoxib for improved processability.

PubMed

Banga, Sheere; Chawla, Garima; Varandani, Deepak; Mehta, B R; Bansal, Arvind K

2007-01-01

Crystallization is often used in the pharmaceutical industry for purification and isolation of drugs, and also as a means of generating polymorphs or isomorphs. The aim of this study was to investigate the role of extrinsic crystallization parameters on the crystallized product, with special emphasis on improving the mechanical properties of acicular celecoxib. Celecoxib isomorphs were prepared using different techniques (solvent crystallization and vapour diffusion) and crystallization conditions (solvents, stirring, degree of supersaturation, crystallization temperature and seeding). Powder X-ray diffractometry, spectroscopic and thermal methods were used to investigate physical characteristics of crystals. Growth kinetics and aggregation dynamics of crystallization in polar and non-polar solvents were simulated using a dynamic light scattering method. The quick appearance of broad peaks over the range of 10-8000 nm in chloroform during crystallization simulation studies indicated faster aggregation in non-polar solvents. Aspect ratio, flow, compressibility and surface area of recrystallized products were also determined. Surface topography was determined by atomic force microscopy and the lath-shaped crystals (aspect ratio of 2-4) exhibited a roughness index of 1.79 in comparison with 2.92 for needles. Overall, the lath-shaped isomorphs exhibited improved flow and better compressibility.

How wood adhesives work and where are the areas for improvement

Treesearch

Charles R. Frihart

2013-01-01

Invoking normal adhesion theory, bonding of wood would seem to be easy in that the surface has plenty of roughness for mechanical interlocking with high enough surface energy, there is an abundance of hydroxyl groups on the wood for hydrogen bonding to the adhesives, and the aqueous solvent in the adhesive can readily soak into the wood. In fact most adhesives will...

Single crystal growth in spin-coated films of polymorphic phthalocyanine derivative under solvent vapor

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

Higashi, T.; Ohmori, M.; Ramananarivo, M. F.

2015-12-01

The effects of solvent vapor on spin-coated films of a polymorphic phthalocyanine derivative were investigated. Growth of single crystal films via redissolving organic films under solvent vapor was revealed by in situ microscopic observations of the films. X-ray diffraction measurement of the films after exposing to solvent vapor revealed the phase transition of polymorphs under solvent vapor. The direction of crystal growth was clarified by measuring the crystal orientation in a grown monodomain film. The mechanism of crystal growth based on redissolving organic films under solvent vapor was discussed in terms of the different solubilities of the polymorphs.

Carborane-Based Metal-Organic Framework with High Methane and Hydrogen Storage Capacities

DTIC Science & Technology

2013-01-01

guest solvent molecules were removed via supercritical CO2 (see the Supporting Information for activation details),30,31 the samples were further...unique geometry of the carborane unit, NU-135 has a very high volumetric BET surface area of ca. 1900 m2/cm3. CH4, CO2 , and H2 adsorption isotherms...NU-135 has a very high volumetric BET surface area of ca. 1900 m2/cm3. CH4, CO2 , and H2 adsorption isotherms were measured over a broad range of

NMR shielding and a thermodynamic study of the effect of environmental exposure to petrochemical solvent on DPPC, an important component of lung surfactant

NASA Astrophysics Data System (ADS)

Monajjemi, M.; Afsharnezhad, S.; Jaafari, M. R.; Abdolahi, T.; Nikosade, A.; Monajemi, H.

2007-12-01

The chemical and petrochemical industries are the major air polluters. Millions of workers are exposed to toxic chemicals on the job, and it is becoming more toxic, causing much damage to respiratory system, today. One of the main components of lung alveoli is a surfactant. DPPC (Dipalmitolphosphatidylcholine) is the predominant lipid component in the lung surfactant, which is responsible for lowering surface tension in alveoli. In this article, we used an approximate model and ab initio computations to describe interactions between DPPC and some chemical solvents, such as benzene, toluene, heptane, acetone, chloroform, ether, and ethanol, which cause lung injuries and lead to respiratory distress such as ARDS. The effect of these solvents on the conformation and disordering of the DPPC head group was investigated by calculations at the Hatree-Fock level using the 6-31G basis set with the Onsager continuum solvation, GAIO, and frequency models. The simulation model was confirmed by accurate NMR measurements as concerns conformational energy. Water can be the most suitable solvent for DPPC. Furthermore, this study shows that ethanol has the most destructive effect on the conformation and lipid disorder of the DPPC head group of the lung surfactant in our model. Our finding will be useful for detecting the dysfunction of DPPC in the lung surfactant caused by acute or chronic exposures to air toxics from petrochemical organic solvent emission source and chronic alcohol consumption, which may lead to ARDS.

Water isotope effect on the thermostability of a polio viral RNA hairpin: A metadynamics study.

PubMed

Pathak, Arup K; Bandyopadhyay, Tusar

2017-04-28

Oral polio vaccine is considered to be the most thermolabile of all the common childhood vaccines. Despite heavy water (D 2 O) having been known for a long time to stabilise attenuated viral RNA against thermodegradation, the molecular underpinnings of its mechanism of action are still lacking. Whereas, understanding the basis of D 2 O action is an important step that might reform the way other thermolabile drugs are stored and could possibly minimize the cold chain problem. Here using a combination of parallel tempering and well-tempered metadynamics simulation in light water (H 2 O) and in D 2 O, we have fully described the free energy surface associated with the folding/unfolding of a RNA hairpin containing a non-canonical basepair motif, which is conserved within the 3'-untranslated region of poliovirus-like enteroviruses. Simulations reveal that in heavy water (D 2 O) there is a considerable increase of the stability of the folded basin as monitored through an intramolecular hydrogen bond (HB), size, shape, and flexibility of RNA structures. This translates into a higher melting temperature in D 2 O by 41 K when compared with light water (H 2 O). We have explored the hydration dynamics of the RNA, hydration shell around the RNA surface, and spatial dependence of RNA-solvent collective HB dynamics in the two water systems. Simulation in heavy water clearly showed that D 2 O strengthens the HB network in the solvent, lengthens inter-residue water-bridge lifetime, and weakens dynamical coupling of the hairpin to its solvation environment, which enhances the rigidity of solvent exposed sites of the native configurations. The results might suggest that like other added osmoprotectants, D 2 O can act as a thermostabilizer when used as a solvent.

Water isotope effect on the thermostability of a polio viral RNA hairpin: A metadynamics study

NASA Astrophysics Data System (ADS)

Pathak, Arup K.; Bandyopadhyay, Tusar

2017-04-01

Oral polio vaccine is considered to be the most thermolabile of all the common childhood vaccines. Despite heavy water (D2O) having been known for a long time to stabilise attenuated viral RNA against thermodegradation, the molecular underpinnings of its mechanism of action are still lacking. Whereas, understanding the basis of D2O action is an important step that might reform the way other thermolabile drugs are stored and could possibly minimize the cold chain problem. Here using a combination of parallel tempering and well-tempered metadynamics simulation in light water (H2O) and in D2O, we have fully described the free energy surface associated with the folding/unfolding of a RNA hairpin containing a non-canonical basepair motif, which is conserved within the 3'-untranslated region of poliovirus-like enteroviruses. Simulations reveal that in heavy water (D2O) there is a considerable increase of the stability of the folded basin as monitored through an intramolecular hydrogen bond (HB), size, shape, and flexibility of RNA structures. This translates into a higher melting temperature in D2O by 41 K when compared with light water (H2O). We have explored the hydration dynamics of the RNA, hydration shell around the RNA surface, and spatial dependence of RNA-solvent collective HB dynamics in the two water systems. Simulation in heavy water clearly showed that D2O strengthens the HB network in the solvent, lengthens inter-residue water-bridge lifetime, and weakens dynamical coupling of the hairpin to its solvation environment, which enhances the rigidity of solvent exposed sites of the native configurations. The results might suggest that like other added osmoprotectants, D2O can act as a thermostabilizer when used as a solvent.

Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions.

PubMed

Marenich, Aleksandr V; Cramer, Christopher J; Truhlar, Donald G

2009-05-07

We present a new continuum solvation model based on the quantum mechanical charge density of a solute molecule interacting with a continuum description of the solvent. The model is called SMD, where the "D" stands for "density" to denote that the full solute electron density is used without defining partial atomic charges. "Continuum" denotes that the solvent is not represented explicitly but rather as a dielectric medium with surface tension at the solute-solvent boundary. SMD is a universal solvation model, where "universal" denotes its applicability to any charged or uncharged solute in any solvent or liquid medium for which a few key descriptors are known (in particular, dielectric constant, refractive index, bulk surface tension, and acidity and basicity parameters). The model separates the observable solvation free energy into two main components. The first component is the bulk electrostatic contribution arising from a self-consistent reaction field treatment that involves the solution of the nonhomogeneous Poisson equation for electrostatics in terms of the integral-equation-formalism polarizable continuum model (IEF-PCM). The cavities for the bulk electrostatic calculation are defined by superpositions of nuclear-centered spheres. The second component is called the cavity-dispersion-solvent-structure term and is the contribution arising from short-range interactions between the solute and solvent molecules in the first solvation shell. This contribution is a sum of terms that are proportional (with geometry-dependent proportionality constants called atomic surface tensions) to the solvent-accessible surface areas of the individual atoms of the solute. The SMD model has been parametrized with a training set of 2821 solvation data including 112 aqueous ionic solvation free energies, 220 solvation free energies for 166 ions in acetonitrile, methanol, and dimethyl sulfoxide, 2346 solvation free energies for 318 neutral solutes in 91 solvents (90 nonaqueous organic solvents and water), and 143 transfer free energies for 93 neutral solutes between water and 15 organic solvents. The elements present in the solutes are H, C, N, O, F, Si, P, S, Cl, and Br. The SMD model employs a single set of parameters (intrinsic atomic Coulomb radii and atomic surface tension coefficients) optimized over six electronic structure methods: M05-2X/MIDI!6D, M05-2X/6-31G, M05-2X/6-31+G, M05-2X/cc-pVTZ, B3LYP/6-31G, and HF/6-31G. Although the SMD model has been parametrized using the IEF-PCM protocol for bulk electrostatics, it may also be employed with other algorithms for solving the nonhomogeneous Poisson equation for continuum solvation calculations in which the solute is represented by its electron density in real space. This includes, for example, the conductor-like screening algorithm. With the 6-31G basis set, the SMD model achieves mean unsigned errors of 0.6-1.0 kcal/mol in the solvation free energies of tested neutrals and mean unsigned errors of 4 kcal/mol on average for ions with either Gaussian03 or GAMESS.

Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions

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

Marenich, Aleksandr; Cramer, Christopher J; Truhlar, Donald G

2009-04-30

We present a new continuum solvation model based on the quantum mechanical charge density of a solute molecule interacting with a continuum description of the solvent. The model is called SMD, where the “D” stands for “density” to denote that the full solute electron density is used without defining partial atomic charges. “Continuum” denotes that the solvent is not represented explicitly but rather as a dielectric medium with surface tension at the solute-solvent boundary. SMD is a universal solvation model, where “universal” denotes its applicability to any charged or uncharged solute in any solvent or liquid medium for which amore » few key descriptors are known (in particular, dielectric constant, refractive index, bulk surface tension, and acidity and basicity parameters). The model separates the observable solvation free energy into two main components. The first component is the bulk electrostatic contribution arising from a self-consistent reaction field treatment that involves the solution of the nonhomogeneous Poisson equation for electrostatics in terms of the integral-equation-formalism polarizable continuum model (IEF-PCM). The cavities for the bulk electrostatic calculation are defined by superpositions of nuclear-centered spheres. The second component is called the cavity-dispersion-solvent-structure term and is the contribution arising from short-range interactions between the solute and solvent molecules in the first solvation shell. This contribution is a sum of terms that are proportional (with geometry-dependent proportionality constants called atomic surface tensions) to the solvent-accessible surface areas of the individual atoms of the solute. The SMD model has been parametrized with a training set of 2821 solvation data including 112 aqueous ionic solvation free energies, 220 solvation free energies for 166 ions in acetonitrile, methanol, and dimethyl sulfoxide, 2346 solvation free energies for 318 neutral solutes in 91 solvents (90 nonaqueous organic solvents and water), and 143 transfer free energies for 93 neutral solutes between water and 15 organic solvents. The elements present in the solutes are H, C, N, O, F, Si, P, S, Cl, and Br. The SMD model employs a single set of parameters (intrinsic atomic Coulomb radii and atomic surface tension coefficients) optimized over six electronic structure methods: M05-2X/MIDI!6D, M05-2X/6-31G*, M05-2X/6-31+G**, M05-2X/cc-pVTZ, B3LYP/6-31G*, and HF/6-31G*. Although the SMD model has been parametrized using the IEF-PCM protocol for bulk electrostatics, it may also be employed with other algorithms for solving the nonhomogeneous Poisson equation for continuum solvation calculations in which the solute is represented by its electron density in real space. This includes, for example, the conductor-like screening algorithm. With the 6-31G* basis set, the SMD model achieves mean unsigned errors of 0.6-1.0 kcal/mol in the solvation free energies of tested neutrals and mean unsigned errors of 4 kcal/mol on average for ions with either Gaussian03 or GAMESS.« less

Handbook for Repairing Nonconventional Roofing Systems

DTIC Science & Technology

1988-12-01

membrane. 61 PIMB (solvent) Figure 71. Apply welding solvent to the PIB patch. Figure 72. Work the solvent Into the P113 patch. Pila 62 (solvent) Figure 73...when exposed to flame but will not burn nor support combustion . PVC repair techniques are basically the same as for a new application of a PVC fully...granules (if desired) before the final coat dries. 83 PUF F4gue 102. Remove the damaged material and bevel the s! des of the hole. 4󈧵, Figure 103. Trim th

Method for removing contaminants from plastic resin

DOEpatents

Bohnert, George W [Harrisonville, MO; Hand, Thomas E [Lee's Summit, MO; DeLaurentiis, Gary M [Jamestown, CA

2008-12-09

A resin recycling method that produces essentially contaminant-free synthetic resin material in an environmentally safe and economical manner. The method includes receiving the resin in container form. The containers are then ground into resin particles. The particles are exposed to a solvent, the solvent contacting the resin particles and substantially removing contaminants on the resin particles. After separating the particles and the resin, a solvent removing agent is used to remove any residual solvent remaining on the resin particles after separation.

Selectively-etched nanochannel electrophoretic and electrochemical devices

DOEpatents

Surh, Michael P.; Wilson, William D.; Barbee, Jr., Troy W.; Lane, Stephen M.

2004-11-16

Nanochannel electrophoretic and electrochemical devices having selectively-etched nanolaminates located in the fluid transport channel. The normally flat surfaces of the nanolaminate having exposed conductive (metal) stripes are selectively-etched to form trenches and baffles. The modifications of the prior utilized flat exposed surfaces increase the amount of exposed metal to facilitate electrochemical redox reaction or control the exposure of the metal surfaces to analytes of large size. These etched areas variously increase the sensitivity of electrochemical detection devices to low concentrations of analyte, improve the plug flow characteristic of the channel, and allow additional discrimination of the colloidal particles during cyclic voltammetry.

Selectively-etched nanochannel electrophoretic and electrochemical devices

DOEpatents

Surh, Michael P [Livermore, CA; Wilson, William D [Pleasanton, CA; Barbee, Jr., Troy W.; Lane, Stephen M [Oakland, CA

2006-06-27

Nanochannel electrophoretic and electrochemical devices having selectively-etched nanolaminates located in the fluid transport channel. The normally flat surfaces of the nanolaminate having exposed conductive (metal) stripes are selectively-etched to form trenches and baffles. The modifications of the prior utilized flat exposed surfaces increase the amount of exposed metal to facilitate electrochemical redox reaction or control the exposure of the metal surfaces to analytes of large size. These etched areas variously increase the sensitivity of electrochemical detection devices to low concentrations of analyte, improve the plug flow characteristic of the channel, and allow additional discrimination of the colloidal particles during cyclic voltammetry.

Are Water-lean Solvent Systems Viable for Post-Combustion CO 2 Capture?

DOE PAGES

Heldebrant, David J.; Koech, Phillip K.; Rousseau, Roger; ...

2017-08-18

Here, we present here an overview of water-lean solvents that compares their projected costs and performance to aqueous amine systems, emphasizing critical areas of study needed to evaluate their performance against their water-based brethren. The work presented her focuses on bridging these knowledge gaps. Because the majority of water-lean solvents are still at the lab scale, substantial studies are still needed to model their performance at scale. This presents a significant challenge as eachformulation has different physical and thermodynamic properties and behavior, and quantifying how these different properties manifest themselves in conventional absorber-stripper configurations, or identifying new configurations that aremore » specific for a solvent’s signature behavior. We identify critical areas of study that are needed, and our efforts (e.g. custom infrastructure, molecular models) to predict, measure, and model these behaviors. Such findings are critical for determining the rheology required for heat exchanger design; absorber designs and packing to accommodate solvents with gradient changes (e.g. viscosity, contact angle, surface tension), and stripper configurations without direct steam utilization or water reflux. Another critical area of research need is to understand the molecular structure of the liquid interface and bulk as a function of CO 2 loading, and to assess whether conventional film theories accurately quantify solvent behavior, or if thermodynamic models adequately quantify activity coefficients of ions in solution. We conclude with an assessment of our efforts to aid in bridging the knowledge gaps in understanding water-lean solvents, and suggestions of what is needed to enable large-scale demonstrations to meet the United States Department of Energy’s year 2030 goal.« less

Are Water-lean Solvent Systems Viable for Post-Combustion CO 2 Capture?

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

Heldebrant, David J.; Koech, Phillip K.; Rousseau, Roger

Here, we present here an overview of water-lean solvents that compares their projected costs and performance to aqueous amine systems, emphasizing critical areas of study needed to evaluate their performance against their water-based brethren. The work presented her focuses on bridging these knowledge gaps. Because the majority of water-lean solvents are still at the lab scale, substantial studies are still needed to model their performance at scale. This presents a significant challenge as eachformulation has different physical and thermodynamic properties and behavior, and quantifying how these different properties manifest themselves in conventional absorber-stripper configurations, or identifying new configurations that aremore » specific for a solvent’s signature behavior. We identify critical areas of study that are needed, and our efforts (e.g. custom infrastructure, molecular models) to predict, measure, and model these behaviors. Such findings are critical for determining the rheology required for heat exchanger design; absorber designs and packing to accommodate solvents with gradient changes (e.g. viscosity, contact angle, surface tension), and stripper configurations without direct steam utilization or water reflux. Another critical area of research need is to understand the molecular structure of the liquid interface and bulk as a function of CO 2 loading, and to assess whether conventional film theories accurately quantify solvent behavior, or if thermodynamic models adequately quantify activity coefficients of ions in solution. We conclude with an assessment of our efforts to aid in bridging the knowledge gaps in understanding water-lean solvents, and suggestions of what is needed to enable large-scale demonstrations to meet the United States Department of Energy’s year 2030 goal.« less

New poly(ester urea) derived from L-leucine: electrospun scaffolds loaded with antibacterial drugs and enzymes.

PubMed

Díaz, Angélica; del Valle, Luis J; Tugushi, David; Katsarava, Ramaz; Puiggalí, Jordi

2015-01-01

Electrospun scaffolds from an amino acid containing poly(ester urea) (PEU) were developed as promising materials in the biomedical field and specifically in tissue engineering applications. The selected poly(ester urea) was obtained with a high yield and molecular weight by reaction of phosgene with a bis(α-aminoacyl)-α,ω-diol-diester monomer. The polymer having L-leucine, 1,6-hexanediol and carbonic acid units had a semicrystalline character and relatively high glass transition and melting temperatures. Furthermore it was highly soluble in most organic solvents, an interesting feature that facilitated the electrospinning process and the effective incorporation of drugs with bactericidal activity (e.g. biguanide derivatives such as clorhexidine and polyhexamethylenebiguanide) and enzymes (e.g. α-chymotrypsin) that accelerated the degradation process. Continuous micro/nanofibers were obtained under a wide range of processing conditions, being diameters of electrospun fibers dependent on the drug and solvent used. Poly(ester urea) samples were degradable in media containing lipases and proteinases but the degradation rate was highly dependent on the surface area, being specifically greater for scaffolds with respect to films. The high hydrophobicity of new scaffolds had repercussions on enzymatic degradability since different weight loss rates were found depending on how samples were exposed to the medium (e.g. forced or non-forced immersion). New scaffolds were biocompatible, as demonstrated by adhesion and proliferation assays performed with fibroblast and epithelial cells. Copyright © 2014 Elsevier B.V. All rights reserved.

A Distinct Proof on Interplay between Trehalose and Guanidinium Chloride for the Stability of Stem Bromelain.

PubMed

Rani, Anjeeta; Venkatesu, Pannuru

2016-09-01

Guanidinium chloride (GdnHCl), a potential denaturant, is well-known to denature a number of proteins in vitro as well as in vivo studies. Its deleterious action on stem bromelain (BM) is quite prominent resulting decrease in protein structure and stability. The counteraction of this adverse effect of GdnHCl by the use of osmolytes is scarcely studied and the mechanism is still illusive and not exclusive. For the first time, to test elegant and simple counteraction hypothesis as a general mechanism we utilized fluorescence, circular dichroism, Fourier transform infrared spectroscopy, and dynamic light scattering to study the counteraction of GdnHCl-induced denaturation of BM by the trehalose. It is revealed from the investigation of the results that trehalose is efficiently counteracting GdnHCl undesirable impacts on BM stability at molar ratio 1:1 of trehalose and GdnHCl. On the contrary, proteolytic activity of BM is increased only for the counteraction study of BM at very high concentrations of GdnHCl although still less than BM in buffer. The mutual exclusion of both trehalose and GdnHCl may stand for the counteraction of denaturation of BM resulting in a compact conformation with less solvent exposed surface area and increased secondary and tertiary structures. In addition, a decrease in BM-solvent interactions may also be contributing to some extent as there is little binding of trehalose replacing some water molecules and reducing binding of GdnHCl.

Meletin sustained-release gliadin nanoparticles prepared via solvent surface modification on blending electrospraying

NASA Astrophysics Data System (ADS)

Yang, Yao-Yao; Zhang, Man; Liu, Zhe-Peng; Wang, Ke; Yu, Deng-Guang

2018-03-01

Almost all electrospraying processes are carried out under an air-solution interface, thereby overlooking the potential influence of an additional solvent surface modification between air and the working solution. A pure solvent was explored to temporarily and dynamically surround the solutions utilized for blending electrospraying, which contained a guest drug meletin and a protein drug carrier gliadin. The new modified processes created protein-based medicated nanoparticles (P2) with higher quality than their counterparts (P1) from blending processes, as demonstrated by the SEM and TEM images. Although the particles from the two processes were similar (nanocomposites), and the particles P1 were larger than P2, the later provided a better meletin sustained-release profile than the former. This finding was verified by the smaller initial burst release, longer sustained-release time period, and shorter late leveling-off stage. These unanticipated results were attributed to the rounder surface, the more uniform size distribution, and the smaller total surface area of particles P2 than P1. The microformation mechanism of the modified coaxial process was suggested. The protocols reported here paved a new way for the development of new kinds of functional nanoparticles by modifying the interfaces of working fluids during electrospraying.

Regular Nanoscale Protein Patterns via Directed Adsorption through Self-Assembled DNA Origami Masks.

PubMed

Ramakrishnan, Saminathan; Subramaniam, Sivaraman; Stewart, A Francis; Grundmeier, Guido; Keller, Adrian

2016-11-16

DNA origami has become a widely used method for synthesizing well-defined nanostructures with promising applications in various areas of nanotechnology, biophysics, and medicine. Recently, the possibility to transfer the shape of single DNA origami nanostructures into different materials via molecular lithography approaches has received growing interest due to the great structural control provided by the DNA origami technique. Here, we use ordered monolayers of DNA origami nanostructures with internal cavities on mica surfaces as molecular lithography masks for the fabrication of regular protein patterns over large surface areas. Exposure of the masked sample surface to negatively charged proteins results in the directed adsorption of the proteins onto the exposed surface areas in the holes of the mask. By controlling the buffer and adsorption conditions, the protein coverage of the exposed areas can be varied from single proteins to densely packed monolayers. To demonstrate the versatility of this approach, regular nanopatterns of four different proteins are fabricated: the single-strand annealing proteins Redβ and Sak, the iron-storage protein ferritin, and the blood protein bovine serum albumin (BSA). We furthermore demonstrate the desorption of the DNA origami mask after directed protein adsorption, which may enable the fabrication of hierarchical patterns composed of different protein species. Because selectivity in adsorption is achieved by electrostatic interactions between the proteins and the exposed surface areas, this approach may enable also the large-scale patterning of other charged molecular species or even nanoparticles.

Oligomerization as a strategy for cold adaptation: Structure and dynamics of the GH1 β-glucosidase from Exiguobacterium antarcticum B7

NASA Astrophysics Data System (ADS)

Zanphorlin, Leticia Maria; de Giuseppe, Priscila Oliveira; Honorato, Rodrigo Vargas; Tonoli, Celisa Caldana Costa; Fattori, Juliana; Crespim, Elaine; de Oliveira, Paulo Sergio Lopes; Ruller, Roberto; Murakami, Mario Tyago

2016-03-01

Psychrophilic enzymes evolved from a plethora of structural scaffolds via multiple molecular pathways. Elucidating their adaptive strategies is instrumental to understand how life can thrive in cold ecosystems and to tailor enzymes for biotechnological applications at low temperatures. In this work, we used X-ray crystallography, in solution studies and molecular dynamics simulations to reveal the structural basis for cold adaptation of the GH1 β-glucosidase from Exiguobacterium antarcticum B7. We discovered that the selective pressure of low temperatures favored mutations that redesigned the protein surface, reduced the number of salt bridges, exposed more hydrophobic regions to the solvent and gave rise to a tetrameric arrangement not found in mesophilic and thermophilic homologues. As a result, some solvent-exposed regions became more flexible in the cold-adapted tetramer, likely contributing to enhance enzymatic activity at cold environments. The tetramer stabilizes the native conformation of the enzyme, leading to a 10-fold higher activity compared to the disassembled monomers. According to phylogenetic analysis, diverse adaptive strategies to cold environments emerged in the GH1 family, being tetramerization an alternative, not a rule. These findings reveal a novel strategy for enzyme cold adaptation and provide a framework for the semi-rational engineering of β-glucosidases aiming at cold industrial processes.

POLLUTION PREVENTION RESEARCH FOR ORGANIC AIR EMISSIONS

EPA Science Inventory

The paper gives an overview of the U.S. EPA's pollution prevention (P2) research in three areas: (1) Surface Coating, such as wood furniture finishing, printing, and the use of adhesives and radiation-cured coatings; (2) Solvent Cleaning, such as vapor degreasing, process equipme...

SIMPLE METHOD FOR THE REPRESENTATION, QUANTIFICATION, AND COMPARISON OF THE VOLUMES AND SHAPES OF CHEMICAL COMPOUNDS

EPA Science Inventory

A conceptually and computationally simple method for the definition, display, quantification, and comparison of the shapes of three-dimensional mathematical molecular models is presented. Molecular or solvent-accessible volume and surface area can also be calculated. Algorithms, ...

Effect of structural changes of lignocelluloses material upon pre-treatment using green solvents

NASA Astrophysics Data System (ADS)

Gunny, Ahmad Anas Nagoor; Arbain, Dachyar; Jamal, Parveen

2017-04-01

The Malaysia Biomass strategy 2020 stated that the key step of biofuel production from biomass lies on the pretreatment process. Conventional `pre-treatment' methods are `non-green" and costly. The recent green and cost-effective biomass pretreatment is using new generation of Ionic Liquids also known as Deep Eutectic Solvents (DESs). DESs are made of renewable components are cheaper, greener and the process synthesis are easier. Thus, the present paper concerns with the preparation of various combination of DES and to study the effect of DESs pretreatment process on microcrystalline cellulose (MCC), a model substrate. The crystalline structural changes were studied using using X-ray Diffraction Methods, Fourier Transformed Infrared Spectroscopy (FTIR) and surface area and pore size analysis. Results showed reduction of crystalline structure of MCC treated with the DESs and increment of surface area and pore size of MCC after pre-treatment process. These results indicated the DES has successfully converted the lignocelluloses material in the form suitable for hydrolysis and conversion to simple sugar.

Shape-Dependent Photocatalytic Activity of Hydrothermally Synthesized Cadmium Sulfide Nanostructures.

PubMed

Kundu, Joyjit; Khilari, Santimoy; Pradhan, Debabrata

2017-03-22

The effective surface area of the nanostructured materials is known to play a prime role in catalysis. Here we demonstrate that the shape of the nanostructured materials plays an equally important role in their catalytic activity. Hierarchical CdS microstructures with different morphologies such as microspheres assembled of nanoplates, nanorods, nanoparticles, and nanobelts are synthesized using a simple hydrothermal method by tuning the volume ratio of solvents, i.e., water or ethylenediamine (en). With an optimum solvent ratio of 3:1 water:en, the roles of other synthesis parameters such as precursor's ratio, temperature, and precursor combinations are also explored and reported here. Four selected CdS microstructures are used as photocatalysts for the degradation of methylene blue and photoelectrochemical water splitting for hydrogen generation. In spite of smaller effective surface area of CdS nanoneedles/nanorods than that of CdS nanowires network, the former exhibits higher catalytic activity under visible light irradiation which is ascribed to the reduced charge recombination as confirmed from the photoluminescence study.

Solvation effects on alanine dipeptide: A MP2/cc-pVTZ//MP2/6-31G** study of (Phi, Psi) energy maps and conformers in the gas phase, ether, and water.

PubMed

Wang, Zhi-Xiang; Duan, Yong

2004-11-15

The effects of solvation on the conformations and energies of alanine dipeptide (AD) have been studied by ab initio calculations up to MP2/cc-pVTZ//MP2/6-31G**, utilizing the polarizable continuum model (PCM) to mimic solvation effects. The energy surfaces in the gas phase, ether, and water bear similar topological features carved by the steric hindrance, but the details differ significantly due to the solvent effects. The gas-phase energy map is qualitatively consistent with the Ramachandran plot showing seven energy minima. With respect to the gas-phase map, the significant changes of the aqueous map include (1) the expanded low-energy regions, (2) the emergence of an energy barrier between C5-beta and alpha(R)-beta(2) regions, (3) a clearly pronounced alpha(R) minimum, a new beta-conformer, and the disappearance of the gas-phase global minimum, and (4) the shift of the dominant region in LEII from the gas-phase C7(ax) region to the alpha(L) region. These changes bring the map in water to be much closer to the Ramachandran plot than the gas-phase map. The solvent effects on the geometries include the elongation of the exposed N-H and C=O bonds, the shortening of the buried HN--CO peptide bonds, and the enhanced planarity of the peptide bonds. The energy surface in ether has features similar to those both in the gas phase and in water. The free energy order computed in the gas phase and in ether is in good agreement with experimental studies that concluded that C5 and C7(eq) are the dominant species in both the gas phase and nonpolar solvents. The free energy order in water is consistent with the experimental observation that the dominant C7(eq) in the nonpolar solvent was largely replaced by P(II)-like (i.e., beta) and alpha(R) in the strong polar solvents. Based on calculations on AD + 4H(2)O and other AD-water clusters, we suggest that explicit water-AD interactions may distort C5 and beta (or alpha(R) and beta) to an intermediate conformation. Our analysis also shows that the PCM calculations at the MP2/cc-pVTZ//MP2/6-31G** level give good descriptions to the bulk solvent polarization effect. The results presented in this article should be of sufficient quality to characterize the peptide bonds in the gas phase and solvents. The energy surfaces may serve as the basis for developing of strategies enabling the inclusion of solvent polarization in the force field.

Effects of Solvent Diols on the Synthesis of ZnFe2O4 Particles and Their Use as Heterogeneous Photo-Fenton Catalysts

PubMed Central

Anchieta, Chayene Gonçalves; Cancelier, Adriano; Mazutti, Marcio Antonio; Jahn, Sérgio Luiz; Kuhn, Raquel Cristine; Gündel, Andre; Chiavone-Filho, Osvaldo; Foletto, Edson Luiz

2014-01-01

A solvothermal method was used to prepare zinc ferrite spinel oxide (ZnFe2O4) using ethylene glycol and 1,4 butanediol as solvent diols, and the influence of diols on the physical properties of ZnFe2O4 particles was investigated. The produced particles were characterized by X-ray powder diffraction (XRD), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR) and nitrogen adsorption isotherms, and the catalytic activity for the organic pollutant decomposition by heterogeneous photo-Fenton reaction was investigated. Both solvents produced particles with cubic spinel structure. Microporous and mesoporous structures were obtained when ethylene glycol and 1,4 butanediol were used as diols, respectively. A higher pore volume and surface area, as well as a higher catalytic activity for the pollutant degradation were found when 1,4 butanediol was used as solvent. PMID:28788191

The Use of Solar Heating and Heat Cured Polymers for Lunar Surface Stabilization

NASA Technical Reports Server (NTRS)

Hintze, Paul; Curran, Jerry; Back, Reddy

2008-01-01

Dust ejecta can affect visibility during a lunar landing, erode nearby coated surfaces and get into mechanical assemblies of in-place infrastructure. Regolith erosion was observed at many of the Apollo landing sites. This problem needs to be addressed at the beginning of the lunar base missions, as the amount of infrastructure susceptible to problems will increase with each landing. Protecting infrastructure from dust and debris is a crucial step in its long term functionality. A proposed way to mitigate these hazards is to build a lunar launch pad. Other areas of a lunar habitat will also need surface stabilization methods to help mitigate dust hazards. Roads would prevent dust from being lifted during movement and dust free zones might be required for certain areas critical to crew safety or to critical science missions. Work at NASA Kennedy Space Center (KSC) is investigating methods of stabilizing the lunar regolith including: sintering the regolith into a solid and using heat or UV cured polymers to stabilize the surface. Sintering, a method in which powders are heated until fusing into solids, has been proposed as one way of building a Lunar launch/landing pad. A solar concentrator has been built and used in the field to sinter JSC-1 Lunar stimulant. Polymer palliatives are used by the military to build helicopter landing pads and roads in dusty and sandy areas. Those polymers are dispersed in a solvent (water), making them unsuitable for lunar use. Commercially available, solvent free, polymer powders are being investigated to determine their viability to work in the same way as the solvent borne terrestrial analog. This presentation will describe the ongoing work at KSC in this field. Results from field testing will be presented. Physical testing results, including compression and abrasion, of field and laboratory prepared samples will be presented.

Cardio-pulmonary effects of inhaled solvents: computer-assisted measurement and analysis

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

Engwall, M.J.

The physiological effects of the inhalation of three solvent vapors were measured on anesthetized dogs. The tested solvents were: acetone, ethanol, and toluene. Measurements of respiratory mechanics, pulmonary and systemic hemodynamics, cardiac output, and gas-exchange were taken while exposing the animals to the vaporized solvents. After the exposures, the animals were terminated and lung tissue and alveolar lining material (ALM) were collected. The ALM was analyzed by high performance liquid chromatography for the amounts of component phospholipids. The tissues were inspected under light microscopy for evidence of acute damage associated with the solvent exposures.

Bioremediation of a Large Chlorinated Solvent Plume, Dover AFB, DE

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

Bloom, Aleisa C

2015-01-01

Bioremediation of a Large Chlorinated Solvent Plume, Dover AFB, DE Aleisa Bloom, (Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA) Robert Lyon (bob.lyon@aecom.com), Laurie Stenberg, and Holly Brown (AECOM, Germantown, Maryland, USA) ABSTRACT: Past disposal practices at Dover Air Force Base (AFB), Delaware, created a large solvent plume called Area 6 (about 1 mile long, 2,000 feet wide, and 345 acres). The main contaminants are PCE, TCE, and their degradation products. The remedy is in-situ accelerated anaerobic bioremediation (AAB). AAB started in 2006 and is focusing on source areas and downgradient plume cores. Direct-push injections occurred in source areas wheremore » contamination is typically between 5 and 20 feet below ground surface. Lower concentration dissolved-phased contamination is present downgradient at 35 and 50 feet below ground surface. Here, permanent injection/extraction wells installed in transects perpendicular to the flow of groundwater are used to apply AAB. The AAB substrate is a mix of sodium lactate, emulsified vegetable oil, and nutrients. After eight years, dissolved contaminant mass within the main 80-acre treatment area has been reduced by over 98 percent. This successful application of AAB has stopped the flux of contaminants to the more distal portions of the plume. While more time is needed for effects to be seen in the distal plume, AAB injections will soon cease, and the remedy will transition to natural attenuation. INTRODUCTION Oak Ridge National Laboratory Environmental Science Division (ORNL) and AECOM (formerly URS Corporation) have successfully implemented in situ accelerated anaerobic bioremediation (AAB) to remediate chlorinated solvent contamination in a large, multi-sourced groundwater plume at Dover Air Force Base (AFB). AAB has resulted in significant reductions of dissolved phase chlorinated solvent concentrations. This plume, called Area 6, was originally over 1 mile in length and over 2,000 feet wide (Figure 1). It originated from at least four separate source areas that comingled in the subsurface to form the large plume. The major contaminants of concern (COCs) are tetrachloroethene (PCE), trichloroethene (TCE), and 1,1,1-trichloroethane (1,1,1-TCA), which were historically used for degreasing operations in the maintenance of aircraft and support vehicles. Relatively small areas of elevated PCE, TCE, and 1,1,1-TCA were delineated in the shallow portion of the water table aquifer by direct-push groundwater sampling. Focused direct-push AAB treatment occurred in March 2006 at these source areas (Figure 1). Downgradient of the these areas and deeper in the aquifer, AAB treatment was implemented using rows of extraction/injection wells oriented perpendicular to groundwater flow to create multiple reductive zones across the plume cores, defined as areas where more than 1,000 micrograms per liter (ug/L) total solvent concentrations were present. Initial indications of successful degradation were observed within 6 months of starting injections. FIGURE 1. Dover AFB Area 6 plume. This paper describes the AAB implementation and progress of remediation after 8 years of treatment and periodic groundwater monitoring. SITE LITHOLOGY Contamination at the site is limited to the surficial aquifer, which consists of 35 to 50 feet (ft) (11 to 15 meters [m]) of unconsolidated Pleistocene deposits of the Columbia Formation. The Columbia Formation consists of fine to coarse sand with silt and clay lenses and less common gravel lenses. Silts and silty sands are generally encountered to a depth of 10 to 12 ft (3.05 to 3.65 m) below ground surface (bgs) and grade to medium- and coarse-grained sands to a depth of 35 to 50 ft (11 to 15 m) bgs. There is a clay and silt unit (part of the Calvert Formation) below the surficial aquifer that acts as an aquitard to the downward migration of contaminants. The depth to the water table varies across the site but usually ranges from 8 to 15 ft (2.4 to 4.5 m) bgs in the treatment area. REMEDIAL APPROACH AND OPERATIONS Because the Columbia Aquifer is used as a source of potable water off base, the remedial goal is to restore the aquifer to usable condition, i.e., reduce all chemicals of concern to below drinking water maximum contaminant levels (MCLs). To achieve this goal, AAB was selected as the best remedial alternative to reduce the solvent contamination. Source areas with high solvent concentrations were present in the shallow portion of the aquifer. From the source areas, dissolved solvents migrated downgradient and deeper in the aquifer with the flow of groundwater. In the deeper portion of the aquifer, the individual plumes comingle to form the larger Area 6 Plume, which covers approximately 345 acres. Types of Substrate. Previous AAB pilot tests at Dover AFB used either sodium lactate or emulsified vegetable oil (EVO) as substrates to stimulate microbial growth. The best results were obtained with...« less

Synthesis, fractionation, and thin film processing of nanoparticles using the tunable solvent properties of carbon dioxide gas expanded liquids

NASA Astrophysics Data System (ADS)

Anand, Madhu

Nanoparticles have received significant attention because of their unusual characteristics including high surface area to volume ratios. Materials built from nanoparticles possess unique chemical, physical, mechanical and optical properties. Due to these properties, they hold potential in application areas such as catalysts, sensors, semiconductors and optics. At the same time, CO 2 in the form of supercritical fluid or CO2 gas-expanded liquid mixtures has gained significant attention in the area of processing nanostructures. This dissertation focuses on the synthesis and processing of nanoparticles using CO2 tunable solvent systems. Nanoparticle properties depend heavily on their size and, as such, the ability to finely control the size and uniformity of nanoparticles is of utmost importance. Solution based nanoparticle formation techniques are attractive due to their simplicity, but they often result in the synthesis of particles with a wide size range. To address this limitation, a post-synthesis technique has been developed in this dissertation to fractionate polydisperse nanoparticles ( s . = 30%) into monodisperse fractions ( s . = 8%) using tunable physicochemical properties of CO 2 expanded liquids, where CO2 is employed as an antisolvent. This work demonstrates that by controlling the addition of CO2 (pressurization) to an organic dispersion of nanoparticles, the ligand stabilized nanoparticles can be size selectively precipitated within a novel high pressure apparatus that confines the particle precipitation to a specified location on a surface. Unlike current techniques, this CO2 expanded liquid approach provides faster and more efficient particle size separation, reduction in organic solvent usage, and pressure tunable size selection in a single process. To improve our fundamental understanding and to further refine the size separation process, a detailed study has been performed to identify the key parameters enabling size separation of various nanoparticle populations. This study details the influence of various factors on the size separation process, such as the types of nanoparticles, ligand type and solvent type as well as the use of recursive fractionation and the time allowed for settling during each fractionation step. This size selective precipitation technique was also applied to fractionate and separate polydisperse dispersions of CdSe/ZnS semiconductor nanocrystals into very distinct size and color fractions based solely on the pressure tunable solvent properties of CO2 expanded liquids. This size selective precipitation of nanoparticles is achieved by finely tuning the solvent strength of the CO2/organic solvent medium by simply adjusting the applied CO2 pressure. These subtle changes affect the balance between osmotic repulsive and van der Waals attractive forces thereby allowing fractionation of the nanocrystals into multiple narrow size populations. Thermodynamic analysis of nanoparticle size selective fractionation was performed to develop a theoretical model based on the thermodynamic properties of gas expanded liquids. We have used the general phenomenon of nanoparticle precipitation with CO2 expanded liquids to create dodecanethiol stabilized gold nanoparticle thin films. This method utilizes CO2 as an anti-solvent for low defect, wide area gold nanoparticle film formation employing monodisperse gold nanoparticles. Dodecanethiol stabilized gold particles are precipitated from hexane by controllably expanding the solution with carbon dioxide. Subsequent addition of carbon dioxide as a dense supercritical fluid then provides for removal of the organic solvent while avoiding the dewetting effects common to evaporating solvents. Unfortunately, the use of carbon dioxide as a neat solvent in nanoparticles synthesis and processing is limited by the very poor solvent strength of dense phase CO2. As a result, most current techniques employed to synthesize and disperse nanoparticles in neat carbon dioxide require the use of environmentally persistent fluorinated compounds as metal precursors and/or stabilizing ligands. This dissertation presents the first report of the simultaneous synthesis and stabilization of metallic nanoparticles in carbon dioxide solvent without the use of any fluorinated compounds thereby further enabling the use of CO 2 as a green solvent medium in nanomaterials synthesis and processing.

Occupational exposure to organic solvents and sleep-disordered breathing.

PubMed

Ulfberg, J; Carter, N; Talbäck, M; Edling, C

1997-01-01

To investigate whether people with occupational exposure to organic solvents have a higher prevalence of obstructive sleep apnea syndrome (OSAS) than the general population and to examine the relationship between snoring and exposure to organic solvents. Consecutive patients, aged 30-64 years, referred during a 3-year period to the sleep laboratory at Avesta Hospital, Sweden, because of suspected OSAS made up the patient groups. Following admission, patients underwent a simplified sleep apnea investigation and were divided into two groups, OSAS (n = 320) and snorers (n = 443). A random sample of 296 men and 289 women aged 30-64 years obtained from a register of all country residents maintained by the county tax authority served as referents (controls). Both patients and referents responded to two questionnaires, including questions about occupation, exposure to organic solvents, and other chemical and physical agents. Men with OSAS or snoring and women with snoring had more often been occupationally exposed to organic solvents than the referents, showing an almost twofold increase in risk for those exposed during whole workdays. For men, the risk of OSAS or snoring increased with increasing exposure. The result indicates that occupational exposure to organic solvents might cause sleep apnea. A new observation is that even snoring could be caused by exposure to organic solvents. It is important to elucidate whether exposure to organic solvents is a cause of OSAS, because such a finding may have important implications for prevention and treatment of sleep disturbances.

Insights into the effects of solvent properties in graphene based electric double-layer capacitors with organic electrolytes

NASA Astrophysics Data System (ADS)

Zhang, Shuo; Bo, Zheng; Yang, Huachao; Yang, Jinyuan; Duan, Liangping; Yan, Jianhua; Cen, Kefa

2016-12-01

Organic electrolytes are widely used in electric double-layer capacitors (EDLCs). In this work, the microstructure of planar graphene-based EDLCs with different organic solvents are investigated with molecular dynamics simulations. Results show that an increase of solvent polarity could weaken the accumulation of counter-ions nearby the electrode surface, due to the screen of electrode charges and relatively lower ionic desolvation. It thus suggests that solvents with low polarity could be preferable to yield high EDL capacitance. Meanwhile, the significant effects of the size and structure of solvent molecules are reflected by non-electrostatic molecule-electrode interactions, further influencing the adsorption of solvent molecules on electrode surface. Compared with dimethyl carbonate, γ-butyrolactone, and propylene carbonate, acetonitrile with relatively small-size and linear structure owns weak non-electrostatic interactions, which favors the easy re-orientation of solvent molecules. Moreover, the shift of solvent orientation in surface layer, from parallel orientation to perpendicular orientation relative to the electrode surface, deciphers the solvent twin-peak behavior near negative electrode. The as-obtained insights into the roles of solvent properties on the interplays among particles and electrodes elucidate the solvent influences on the microstructure and capacitive behavior of EDLCs using organic electrolytes.

40 CFR 761.389 - Testing parameter requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... variable testing parameters described in this section which may be used in the validation study. The conditions demonstrated in the validation study for these variables shall become the required conditions for.... During the validation study, use the same ratio of contaminated surface area to soak solvent volume as...

40 CFR 761.389 - Testing parameter requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... variable testing parameters described in this section which may be used in the validation study. The conditions demonstrated in the validation study for these variables shall become the required conditions for.... During the validation study, use the same ratio of contaminated surface area to soak solvent volume as...

40 CFR 761.389 - Testing parameter requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... variable testing parameters described in this section which may be used in the validation study. The conditions demonstrated in the validation study for these variables shall become the required conditions for.... During the validation study, use the same ratio of contaminated surface area to soak solvent volume as...

Solvent-Induced Cadmium(II) Metal-Organic Frameworks with Adjustable Guest-Evacuated Porosity: Application in the Controllable Assembly of MOF-Derived Porous Carbon Materials for Supercapacitors.

PubMed

Yue, Man-Li; Jiang, Yi-Fan; Zhang, Lin; Yu, Cheng-Yan; Zou, Kang-Yu; Li, Zuo-Xi

2017-11-07

In this work, five new cadmium metal-organic frameworks (Cd-MOFs 1-5) have been synthesized from solvothermal reactions of Cd(NO 3 ) 2 ⋅4 H 2 O with isophthalic acid and 1,4-bis(imidazol-1-yl)-benzene under different solvent systems of CH 3 OH, C 2 H 5 OH, (CH 3 ) 2 CHOH, DMF, and N-methyl-2-pyrrolidone (NMP), respectively. Cd-MOF 1 shows a 3D diamondoid framework with 1D rhombic and hexagonal channels, and the porosity is 12.9 %. Cd-MOF 2 exhibits a 2D (4,4) layer with a 1D parallelogram channel and porosity of 23.6 %. Cd-MOF 3 has an 8-connected dense network with the Schäfli symbol of [4 24 ⋅6 4 ] based on the Cd 6 cluster. Cd-MOFs 4-5 are isomorphous, and display an absolutely double-bridging 2D (4,4) layer with 1D tetragonal channels and porosities of 29.2 and 28.2 %, which are occupied by DMF and NMP molecules, respectively. Followed by the calcination-thermolysis procedure, Cd-MOFs 1-5 are employed as precursors to prepare MOF-derived porous carbon materials (labeled as PC-me, PC-eth, PC-ipr, PC-dmf and PC-nmp), which have the BET specific surface area of 23, 51, 10, 122, and 96 m 2  g -1 , respectively. The results demonstrate that the specific surface area of PCs is tuned by the porosity of Cd-MOFs, where the later is highly dependent on the solvent. Thereby, the specific surface area of PCs could be adjusted by the solvent used in the synthese of MOF precusors. Significantly, PCs have been further activated by KOH to obtain activated carbon materials (APCs), which possess even higher specific surface area and larger porosity. After a series of characterization and electrochemical investigations, the APC-dmf electrode exhibits the best porous properties and largest specific capacitances (153 F g -1 at 5 mV s -1 and 156 F g -1 at 0.5 Ag -1 ). Meanwhile, the APC-dmf electrode shows excellent cycling stability (ca. 84.2 % after 5000 cycles at 1 Ag -1 ), which can be applied as a suitable electrode material for supercapacitors. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Occupational exposure to solvents and risk of head and neck cancer in women: a population-based case-control study in France.

PubMed

Carton, Matthieu; Barul, Christine; Menvielle, Gwenn; Cyr, Diane; Sanchez, Marie; Pilorget, Corinne; Trétarre, Brigitte; Stücker, Isabelle; Luce, Danièle

2017-01-09

Our objective was to investigate the association between head and neck cancer and occupational exposure to chlorinated, oxygenated and petroleum solvents in women. Investigation of occupational and environmental CAuses of REspiratory cancers (ICARE), a French population-based case-control study, included 296 squamous cell carcinomas of the head and neck (HNSCC) in women and 775 female controls. Lifelong occupational history was collected. Job-exposure matrices allowed to assess exposure to 5 chlorinated solvents (carbon tetrachloride; chloroform; methylene chloride; perchloroethylene; trichloroethylene), 5 petroleum solvents (benzene; special petroleum product; gasoline; white spirits and other light aromatic mixtures; diesel, fuels and kerosene) and 5 oxygenated solvents (alcohols; ketones and esters; ethylene glycol; diethyl ether; tetrahydrofuran). OR and 95% CIs, adjusted for smoking, alcohol drinking, age and geographical area, were estimated with logistic models. Elevated ORs were observed among women ever exposed to perchloroethylene (OR=2.97, 95% CI 1.05 to 8.45) and trichloroethylene (OR=2.15, 95% CI 1.21 to 3.81). These ORs increased with exposure duration (OR=3.75, 95% CI 0.64 to 21.9 and OR=4.44, 95% CI 1.56 to 12.6 for 10 years or more, respectively). No significantly increased risk of HNSCC was found for occupational exposure to the other chlorinated, petroleum or oxygenated solvents. These findings suggest that exposure to perchloroethylene or trichloroethylene may increase the risk of HNSCC in women. In our study, there is no clear evidence that the other studied solvents are risk factors for HNSCC. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/.

Evaluating and modeling the effects of surface sampling factors on the recovery of organic chemical attribution signatures using the accelerated diffusion sampler and solvent extraction

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

Mo, Kai-For; Heredia-Langner, Alejandro; Fraga, Carlos G.

In this study, an experimental design matrix was created and executed in order to test the effects of various real-world factors on the ability of the (1) accelerated diffusion sampler with solid phase micro-extraction (ADS-SPME) and (2) solvent extraction to capture organic chemical attribution signatures (CAS) from dimethyl methylphosphonate (DMMP) spiked onto painted wall board (PWB) surfaces. The DMMP CAS organic impurities sampled by ADS-SPME and solvent extraction were analyzed by gas chromatography/mass spectrometry (GC/MS). The number of detected DMMP CAS impurities and their respective GC/MS peak areas were determined as a function of DMMP stock, DMMP spiked volume, exposuremore » time, SPME sampling time, and ADS headspace pressure. Based on the statistical analysis of experimental results, several general conclusions are made: (1) ADS-SPME with vacuum (i.e., reduced pressure) increased the amount of detected CAS impurity, as measured by GC/MS peak area, by a factor of 1.7 to 1.9 for PWB under certain experimental conditions, (2) the amount of detected CAS impurity was most influenced by spiked volume, stock, and ADS headspace pressure, (3) the ADS had no measurable effect on the number of detected DMMP impurities, that is, the ADS (with and without reduced pressure) had no practical effect on the DMMP impurity profile collected from spiked PWB, and (4) solvent extraction out performed ADS-SPME in terms of consistently capturing all or most of the targeted DMMP impurities from spiked PWB.« less

Evaluating and modeling the effects of surface sampling factors on the recovery of organic chemical attribution signatures using the accelerated diffusion sampler and solvent extraction.

PubMed

Mo, Kai-For; Heredia-Langner, Alejandro; Fraga, Carlos G

2017-03-01

In this study, an experimental design matrix was created and executed to test the effects of various real-world factors on the ability of (1) the accelerated diffusion sampler with solid phase micro-extraction (ADS-SPME) and (2) solvent extraction to capture organic chemical attribution signatures (CAS) from dimethyl methylphosphonate (DMMP) spiked onto painted wall board (PWB) surfaces. The DMMP CAS organic impurities sampled by ADS-SPME and solvent extraction were analyzed by gas chromatography/mass spectrometry (GC/MS). The number of detected DMMP CAS impurities and their respective GC/MS peak areas were determined as a function of DMMP stock, DMMP spiked volume, exposure time, SPME sampling time, and ADS headspace pressure. Based on the statistical analysis of experimental results, several general conclusions are made: (1) the amount of CAS impurity detected using ADS-SPME and GC/MS was most influenced by spiked volume, stock, and ADS headspace pressure, (2) reduced ADS headspace pressure increased the amount of detected CAS impurity, as measured by GC/MS peak area, by up to a factor of 1.7-1.9 compared to ADS at ambient headspace pressure, (3) the ADS had no measurable effect on the number of detected DMMP impurities, that is, ADS (with and without reduced pressure) had no practical effect on the DMMP impurity profile collected from spiked PWB, and (4) solvent extraction out performed ADS-SPME in terms of consistently capturing all or most of the targeted DMMP impurities from spiked PWB. Copyright © 2016 Elsevier B.V. All rights reserved.

Machine learning of single molecule free energy surfaces and the impact of chemistry and environment upon structure and dynamics

NASA Astrophysics Data System (ADS)

Mansbach, Rachael A.; Ferguson, Andrew L.

2015-03-01

The conformational states explored by polymers and proteins can be controlled by environmental conditions (e.g., temperature, pressure, and solvent) and molecular chemistry (e.g., molecular weight and side chain identity). We introduce an approach employing the diffusion map nonlinear machine learning technique to recover single molecule free energy landscapes from molecular simulations, quantify changes to the landscape as a function of external conditions and molecular chemistry, and relate these changes to modifications of molecular structure and dynamics. In an application to an n-eicosane chain, we quantify the thermally accessible chain configurations as a function of temperature and solvent conditions. In an application to a family of polyglutamate-derivative homopeptides, we quantify helical stability as a function of side chain length, resolve the critical side chain length for the helix-coil transition, and expose the molecular mechanisms underpinning side chain-mediated helix stability. By quantifying single molecule responses through perturbations to the underlying free energy surface, our approach provides a quantitative bridge between experimentally controllable variables and microscopic molecular behavior, guiding and informing rational engineering of desirable molecular structure and function.

Machine learning of single molecule free energy surfaces and the impact of chemistry and environment upon structure and dynamics.

PubMed

Mansbach, Rachael A; Ferguson, Andrew L

2015-03-14

The conformational states explored by polymers and proteins can be controlled by environmental conditions (e.g., temperature, pressure, and solvent) and molecular chemistry (e.g., molecular weight and side chain identity). We introduce an approach employing the diffusion map nonlinear machine learning technique to recover single molecule free energy landscapes from molecular simulations, quantify changes to the landscape as a function of external conditions and molecular chemistry, and relate these changes to modifications of molecular structure and dynamics. In an application to an n-eicosane chain, we quantify the thermally accessible chain configurations as a function of temperature and solvent conditions. In an application to a family of polyglutamate-derivative homopeptides, we quantify helical stability as a function of side chain length, resolve the critical side chain length for the helix-coil transition, and expose the molecular mechanisms underpinning side chain-mediated helix stability. By quantifying single molecule responses through perturbations to the underlying free energy surface, our approach provides a quantitative bridge between experimentally controllable variables and microscopic molecular behavior, guiding and informing rational engineering of desirable molecular structure and function.

Hydrophobic Collapse of Ubiquitin Generates Rapid Protein-Water Motions.

PubMed

Wirtz, Hanna; Schäfer, Sarah; Hoberg, Claudius; Reid, Korey M; Leitner, David M; Havenith, Martina

2018-06-04

We report time-resolved measurements of the coupled protein-water modes of solvated ubiquitin during protein folding. Kinetic terahertz absorption (KITA) spectroscopy serves as a label-free technique for monitoring large scale conformational changes and folding of proteins subsequent to a sudden T-jump. We report here KITA measurements at an unprecedented time resolution of 500 ns, a resolution 2 orders of magnitude better than those of any previous KITA measurements, which reveal the coupled ubiquitin-solvent dynamics even in the initial phase of hydrophobic collapse. Complementary equilibrium experiments and molecular simulations of ubiquitin solutions are performed to clarify non-equilibrium contributions and reveal the molecular picture upon a change in structure, respectively. On the basis of our results, we propose that in the case of ubiquitin a rapid (<500 ns) initial phase of the hydrophobic collapse from the elongated protein to a molten globule structure precedes secondary structure formation. We find that these very first steps, including large-amplitude changes within the unfolded manifold, are accompanied by a rapid (<500 ns) pronounced change of the coupled protein-solvent response. The KITA response upon secondary structure formation exhibits an opposite sign, which indicates a distinct effect on the solvent-exposed surface.

Preparation of hydrophobic coatings

DOEpatents

Branson, Eric D [Albuquerque, NM; Shah, Pratik B [Albuquerque, NM; Singh, Seema [Rio Rancho, NM; Brinker, C Jeffrey [Albuquerque, NM

2009-02-03

A method for preparing a hydrophobic coating by preparing a precursor sol comprising a metal alkoxide, a solvent, a basic catalyst, a fluoroalkyl compound and water, depositing the precursor sol as a film onto a surface, such as a substrate or a pipe, heating, the film and exposing the film to a hydrophobic silane compound to form a hydrophobic coating with a contact angle greater than approximately 150.degree.. The contact angle of the film can be controlled by exposure to ultraviolet radiation to reduce the contact angle and subsequent exposure to a hydrophobic silane compound to increase the contact angle.

Mechanistic principles of colloidal crystal growth by evaporation-induced convective steering.

PubMed

Brewer, Damien D; Allen, Joshua; Miller, Michael R; de Santos, Juan M; Kumar, Satish; Norris, David J; Tsapatsis, Michael; Scriven, L E

2008-12-02

We simulate evaporation-driven self-assembly of colloidal crystals using an equivalent network model. Relationships between a regular hexagonally close-packed array of hard, monodisperse spheres, the associated pore space, and selectivity mechanisms for face-centered cubic microstructure propagation are described. By accounting for contact line rearrangement and evaporation at a series of exposed menisci, the equivalent network model describes creeping flow of solvent into and through a rigid colloidal crystal. Observations concerning colloidal crystal growth are interpreted in terms of the convective steering hypothesis, which posits that solvent flow into and through the pore space of the crystal may play a major role in colloidal self-assembly. Aspects of the convective steering and deposition of high-Peclet-number rigid spherical particles at a crystal boundary are inferred from spatially resolved solvent flow into the crystal. Gradients in local flow through boundary channels were predicted due to the channels' spatial distribution relative to a pinned free surface contact line. On the basis of a uniform solvent and particle flux as the criterion for stability of a particular growth plane, these network simulations suggest the stability of a declining {311} crystal interface, a symmetry plane which exclusively propagates fcc microstructure. Network simulations of alternate crystal planes suggest preferential growth front evolution to the declining {311} interface, in consistent agreement with the proposed stability mechanism for preferential fcc microstructure propagation in convective assembly.

WORK SITE CLINICAL AND NEUROBEHAVIORAL ASSESSMENT OF SOLVENT EXPOSED MICROELECTRONICS WORKERS

EPA Science Inventory

A group of 25 workers currently (5), or formerly (20), involved in the manufacture of hybrid microcircuits underwent clinical evaluations at the request of a management-union committee concerned about chronic solvent exposures in a research and development laboratory. attery of n...

Neurologic effects of solvents in older adults. (UW retired worker study). Final performance report

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

Daniell, W.E.

The possibility that previous occupational exposure to solvents might be associated with clinically significant neurological dysfunction in older adults was investigated in a cross-sectional study. Subjects included 67 painters, 22 aerospace painters and fuel cell sealers, and a comparison group of 126 carpenters. All subjects had retired from regular employment at least 1 year prior to the study. As measured by semiquantitative exposure index, the cumulative histories of lifetime occupational solvent exposure were on the average comparable in the two exposed study groups, painters and aerospace workers. The carpenters differed from the other groups in solvent exposure by several ordersmore » of magnitude. The painters had a significantly higher history of consuming alcoholic beverages than did the other two study groups. The painters had a significantly higher score on the Beck Depression Inventory, a measure of current depressive symptoms. The painters reported significantly more general neurologic symptoms than did the other two groups. The aerospace workers showed much greater evidence of possible adverse effects from former solvent exposure on current neuropsychological function than did the painters when determined by reasoning and memory tests, memory visual motor speed and motor tests. No evidence of persistent effects on liver or renal excretory function was seen in solvent exposed subjects.« less

Ultrathin Hydrophobic Coatings Obtained on Polyethylene Terephthalate Materials in Supercritical Carbon Dioxide with Co-Solvents

NASA Astrophysics Data System (ADS)

Kumeeva, T. Yu.; Prorokova, N. P.

2018-02-01

The surface properties of ultradisperse polytetrafluoroethylene coatings on polyethylene terephthalate materials modified in a supercritical carbon dioxide medium with co-solvent additions (aliphatic alcohols) were analyzed. An atomic force microscopy study revealed the peculiarities of the morphology of the hydrophobic coatings formed in the presence of co-solvents. The contribution of the co-solvents to the formation of the surface layer with a low surface energy was evaluated from the surface energy components of the modified polyester material. The stability of the coatings against dry friction was analyzed.

Method for cleaning and passivating a metal surface

NASA Technical Reports Server (NTRS)

Alexander, George B. (Inventor); Carpenter, Norman F. (Inventor)

1976-01-01

A cleaning solvent useful in the cleaning of metal surfaces, e.g. nickle-iron alloys, contains sulfamic acid, citric acid, a solvent for hydrocarbon residues, and a surfactant. Metal surfaces are cleaned by contacting the surface with the cleaning solvent and then passivated by contact with aqueous solutions of citric acid or sodium nitrite or a combination of the two.

InterProSurf: a web server for predicting interacting sites on protein surfaces

PubMed Central

Negi, Surendra S.; Schein, Catherine H.; Oezguen, Numan; Power, Trevor D.; Braun, Werner

2009-01-01

Summary A new web server, InterProSurf, predicts interacting amino acid residues in proteins that are most likely to interact with other proteins, given the 3D structures of subunits of a protein complex. The prediction method is based on solvent accessible surface area of residues in the isolated subunits, a propensity scale for interface residues and a clustering algorithm to identify surface regions with residues of high interface propensities. Here we illustrate the application of InterProSurf to determine which areas of Bacillus anthracis toxins and measles virus hemagglutinin protein interact with their respective cell surface receptors. The computationally predicted regions overlap with those regions previously identified as interface regions by sequence analysis and mutagenesis experiments. PMID:17933856

Large heat capacity change in a protein-monovalent cation interaction.

PubMed

Guinto, E R; Di Cera, E

1996-07-09

Current views about protein-ligand interactions state that electrostatic forces drive the binding of charged species and that burial of hydrophobic and polar surfaces controls the heat capacity change associated with the reaction. For the interaction of a protein with a monovalent cation the electrostatic components are expected to be significant due to the ionic nature of the ligand, whereas the heat capacity change is expected to be small due to the size of the surface area involved in the recognition event. The physiologically important interaction of Na+ with thrombin was studied over the temperature range from 5 to 45 degrees C and the ionic strength range from 50 to 800 mM. These measurements reveal an unanticipated result that bears quite generally on studies of molecular recognition and protein folding. Binding of Na+ to thrombin is characterized by a modest dependence on ionic strength but a large and negative heat capacity change of -1.1 +/- 0.1 kcal mol-1 K-1. The small electrostatic coupling can be explained in terms of a minimal perturbation of the ionic atmosphere of the protein upon Na+ binding. The large heat capacity change, however, is difficult to reconcile with current views on the origin of this effect from surface area changes or large folding transitions coupled to binding. It is proposed that this change is linked to burial of a large cluster of water molecules in the Na+ binding pocket upon Na+ binding. Due to their reduced mobility and highly ordered structure, water molecules sequestered in the interior of a protein must have a lower heat capacity compared to those on the surface of a protein or in the bulk solvent. Hence, a binding or folding event where water molecules are buried may result in significant heat capacity changes independent of changes in exposed hydrophobic surface or coupled conformational transitions.

Edge profiles and limiter tests in Extrap T2

NASA Astrophysics Data System (ADS)

Bergsåker, H.; Hedin, G.; Ilyinsky, L.; Larsson, D.; Möller, A.

New edge profile measurements, including calorimetric measurements of the parallel heat flux, were made in Extrap T2. Test limiters of pure molybdenum and the TZM molybdenum alloy have been exposed in the edge plasma. The surface damage was studied, mainly by microscopy. Tungsten coated graphite probes were also exposed, and the surfaces were studied by microscopy, ion beam analysis and XPS. In this case cracking and mixing of carbon and tungsten at the interface was observed in the most heated areas, whereas carbide formation at the surface was seen in less heated areas. In these tests pure Mo generally fared better than TZM, and thin and cleaner coatings fared better than thicker and less clean.

Efficient continuous dryer for flexible polyurethane foam and cleaning apparatus

DOEpatents

Jody, Bassam; Daniels, Edward; Libera, Joseph A.

1999-01-01

A method of cleaning polyurethane foams where the material is transported through a wash station while alternately soaking the polyurethane foam in an organic solvent and squeezing solvent from the polyurethane foam a number of times. Then the polyurethane foam is sent through a rinse or solvent transfer station for reducing the concentration of solvent in the foam. The rinsed polyurethane foam is sent to a drying station wherein the foam is repeatedly squeezed while being exposed to hot air to remove wet air from the foam.

Efficient continuous dryer for flexible polyurethane foam and cleaning apparatus

DOEpatents

Jody, B.; Daniels, E.; Libera, J.A.

1999-03-16

A method of cleaning polyurethane foams where the material is transported through a wash station while alternately soaking the polyurethane foam in an organic solvent and squeezing solvent from the polyurethane foam a number of times. Then the polyurethane foam is sent through a rinse or solvent transfer station for reducing the concentration of solvent in the foam. The rinsed polyurethane foam is sent to a drying station wherein the foam is repeatedly squeezed while being exposed to hot air to remove wet air from the foam. 4 figs.

Synthesis and characterization of gold nanodogbones by the seeded mediated growth method

NASA Astrophysics Data System (ADS)

Huang, Chien-Jung; Chiu, Pin-Hsiang; Wang, Yeong-Her; Meen, Teen-Hang; Yang, Cheng-Fu

2007-10-01

Novel gold nanodogbones (GDBs) are successfully fabricated using a simple seeded mediated growth (SMG) method. The shapes of GDBs depend on the amount of added vitamin C solvent. The amount of vitamin C solvent was varied from 10 to 40 µl to investigate the influence of vitamin C solvent on the GDBs. It is found that the aspect ratios (R) of GDBs were in the range from 2.34 to 1.46, and the UV-vis absorption measurement revealed a pronounced blueshift on the longitudinal surface plasmon resonance (SPR) band from 713 to 676 nm. The GDBs were determined by x-ray diffraction (XRD) to be single-crystalline with a face-centered cubic (fcc) structure. The lattice constant calculated from this selected-area electron diffraction (SAED) pattern is 4.068 Å.

Solvophobic and solvophilic contributions in the water-to-aqueous guanidinium chloride transfer free energy of model peptides

NASA Astrophysics Data System (ADS)

Tomar, Dheeraj S.; Ramesh, Niral; Asthagiri, D.

2018-06-01

We study the solvation free energy of two different conformations (helix and extended) of two different peptides (deca-alanine and deca-glycine) in two different solvents (water and aqueous guanidinium chloride, GdmCl). The free energies are obtained using the quasichemical organization of the potential distribution theorem, an approach that naturally provides the repulsive (solvophobic or cavity) and attractive (solvophilic) contributions to solvation. The solvophilic contribution is further parsed into a chemistry contribution arising from solute interaction with the solvent in the first solvation shell and a long-range contribution arising from non-specific interactions between the solute and the solvent beyond the first solvation shell. The cavity contribution is obtained for two different envelopes, ΣS E, which theory helps identify as the solvent excluded volume, and ΣG, a larger envelope beyond which solute-solvent interactions are Gaussian. The ΣS E envelope is independent of the solvent, as expected on the basis of the insensitivity to the solvent type of the distance of closest approach between protein heavy atoms and solvent heavy atoms, but contrary to the intuition based on treating solvent constituents as spheres of some effective radii. For both envelopes, the cavity contribution in water is proportional to the surface area of the envelope. The same does not hold for GdmCl(aq), revealing the limitation of using molecular area to assess solvation energetics. The ΣG-cavity contribution predicts that GdmCl(aq) should favor the more compact state, contrary to the role of GdmCl in unfolding proteins. The chemistry contribution attenuates this effect, but still the net local (chemistry plus ΣG-packing) contribution is inadequate in capturing the role of GdmCl. With the inclusion of the long-range contribution, which is dominated by van der Waals interaction, aqueous GdmCl favors the extended conformation over the compact conformation. Our finding emphasizes the importance of weak, but attractive, long-range dispersion interactions in protein solution thermodynamics.

Solvophobic and solvophilic contributions in the water-to-aqueous guanidinium chloride transfer free energy of model peptides.

PubMed

Tomar, Dheeraj S; Ramesh, Niral; Asthagiri, D

2018-06-14

We study the solvation free energy of two different conformations (helix and extended) of two different peptides (deca-alanine and deca-glycine) in two different solvents (water and aqueous guanidinium chloride, GdmCl). The free energies are obtained using the quasichemical organization of the potential distribution theorem, an approach that naturally provides the repulsive (solvophobic or cavity) and attractive (solvophilic) contributions to solvation. The solvophilic contribution is further parsed into a chemistry contribution arising from solute interaction with the solvent in the first solvation shell and a long-range contribution arising from non-specific interactions between the solute and the solvent beyond the first solvation shell. The cavity contribution is obtained for two different envelopes, Σ SE , which theory helps identify as the solvent excluded volume, and Σ G , a larger envelope beyond which solute-solvent interactions are Gaussian. The Σ SE envelope is independent of the solvent, as expected on the basis of the insensitivity to the solvent type of the distance of closest approach between protein heavy atoms and solvent heavy atoms, but contrary to the intuition based on treating solvent constituents as spheres of some effective radii. For both envelopes, the cavity contribution in water is proportional to the surface area of the envelope. The same does not hold for GdmCl(aq), revealing the limitation of using molecular area to assess solvation energetics. The Σ G -cavity contribution predicts that GdmCl(aq) should favor the more compact state, contrary to the role of GdmCl in unfolding proteins. The chemistry contribution attenuates this effect, but still the net local (chemistry plus Σ G -packing) contribution is inadequate in capturing the role of GdmCl. With the inclusion of the long-range contribution, which is dominated by van der Waals interaction, aqueous GdmCl favors the extended conformation over the compact conformation. Our finding emphasizes the importance of weak, but attractive, long-range dispersion interactions in protein solution thermodynamics.

Lipophilicity of a series of 1,2-benzisothiazol-3(2H)-ones determined by reversed-phase thin-layer chromatography.

PubMed

Sławik, Tomasz; Kowalski, Cezary

2002-04-05

The lipophilicity (R(Mo)) and specific hydrophobic surface area of seven 1,2-benzisothiazol-3(2H)-ones have been determined by reversed-phase TLC and the effect of different mobile-phase modifiers (acetone, acetonitrile, methanol) on the retention has been studied. The linear correlations between the volume fraction of the organic solvent and the R(M) values over a limited range were established for each solute with high values of correlation coefficients (>0.99). The influence of solvent pH on R(M) values was investigated.

Response Mechanisms in Serratia marcescens IBBPo15 During Organic Solvents Exposure.

PubMed

Stancu, Mihaela Marilena

2016-12-01

Serratia marcescens strain IBB Po15 (KT315653) which possesses serratiopeptidase (ser) gene (KT894207) exhibited good solvent tolerance. During the exposure of S. marcescens IBB Po15 cells to 5 % organic solvents, n-decane was less toxic for this bacterium, compared with n-hexane, cyclohexane, ethylbenzene, toluene, and styrene. The exposure of the S. marcescens IBB Po15 cells to n-hexane, cyclohexane, ethylbenzene, toluene, and styrene induced the formation of large clusters, while in control and n-decane-exposed cells, only organization into small clusters was observed. The data obtained suggested that S. marcescens IBB Po15 cells produced some secondary metabolites (i.e., surfactant serrawettin, red pigment prodigiosin) which are well known as valuable molecules due to their large applications. The exposure of the bacterial cells to organic solvents induced secondary metabolites profile modifications. However, S. marcescens IBB Po15 possesses only alkB1, todM, rhlAB, pswP, mpr, and ser genes, the unspecific amplification of other fragments being acquired also when the primers for alkM1, xylM, ndoM, and C23DO genes were used. Modifications of DNA patterns were not depicted in S. marcescens IBB Po15 cells exposed to organic solvents.

Binary Polymer Brushes of Strongly Immiscible Polymers.

PubMed

Chu, Elza; Babar, Tashnia; Bruist, Michael F; Sidorenko, Alexander

2015-06-17

The phenomenon of microphase separation is an example of self-assembly in soft matter and has been observed in block copolymers (BCPs) and similar materials (i.e., supramolecular assemblies (SMAs) and homo/block copolymer blends (HBCs)). In this study, we use microphase separation to construct responsive polymer brushes that collapse to generate periodic surfaces. This is achieved by a chemical reaction between the minor block (10%, poly(4-vinylpyridine)) of the block copolymer and a substrate. The major block of polystyrene (PS) forms mosaic-like arrays of grafted patches that are 10-20 nm in size. Depending on the nature of the assembly (SMA, HBC, or neat BCP) and annealing method (exposure to vapors of different solvents or heating above the glass transition temperature), a range of "mosaic" brushes with different parameters can be obtained. Successive grafting of a secondary polymer (polyacrylamide, PAAm) results in the fabrication of binary polymer brushes (BPBs). Upon being exposed to specific selective solvents, BPBs may adopt different conformations. The surface tension and adhesion of the binary brush are governed by the polymer occupying the top stratum. The "mosaic" brush approach allows for a combination of strongly immiscible polymers in one brush. This facilitates substantial contrast in the surface properties upon switching, previously only possible for substrates composed of predetermined nanostructures. We also demonstrate a possible application of such PS/PAAm brushes in a tunable bioadhesion-bioadhesive (PS on top) or nonbioadhesive (PAAm on top) surface as revealed by Escherichia coli bacterial seeding.

Non-invasive biomonitoring for PFRs and PBDEs: new insights in analysis of human hair externally exposed to selected flame retardants.

PubMed

Kucharska, Agnieszka; Covaci, Adrian; Vanermen, Guido; Voorspoels, Stefan

2015-02-01

In this study, we investigated the hypothesis whether externally adsorbed and internally deposited flame retardants (FRs) in hair could be distinguished. To this extent, hair samples collected from one volunteer were exposed under controlled conditions to phosphate FR (PFR) and polybrominated diphenyl ether (PBDE) standards to mimic external contamination. Afterwards, suitable washing procedures to selectively remove contaminants from the hair surface were investigated. The samples were measured by GC-(ECNI)-MS for PBDEs and LC-(ESI+)-MS/MS for PFRs. All investigated compounds were transferred onto the hair surface. One of the most important finding was that dust particles are not mandatory to transfer compounds on the hair surface and to be able to measure high levels of compounds in human hair. To assess different protocols to selectively remove external contamination, the exposed hair samples were washed in different media before analysis: water, methanol, hexane:dichloromethane (1:1, v/v), acetone and shampoo. Results indicated that there is no washing medium able to entirely and exclusively remove external contamination. Among investigated media, methanol removed a meaningful part of the external contamination (42-105%), but the removal efficiencies differed among compounds. We therefore concluded that hair should not be washed prior to analysis and in case of visible contamination (e.g. with cosmetic products), water would be the recommended agent. Organic solvents should not be used for the washing step. Although it is impossible to distinguish external from internal exposure, hair samples may be used as valuable biomarker of human exposure, providing a measure of integral exposure. To the best of our knowledge, this is the first study which has used externally exposed hair samples to PBDEs and PFRs. Copyright © 2014 Elsevier B.V. All rights reserved.

The bias of a 2D view: Comparing 2D and 3D mesophyll surface area estimates using non-invasive imaging

USDA-ARS?s Scientific Manuscript database

The surface area of the leaf mesophyll exposed to intercellular airspace per leaf area (Sm) is closely associated with CO2 diffusion and photosynthetic rates. Sm is typically estimated from two-dimensional (2D) leaf sections and corrected for the three-dimensional (3D) geometry of mesophyll cells, l...

High Surface Area, Thermally Stable, Hydrophobic, Microporous, Rigid Gels Generated at Ambient from MeSi(OEt)3 /(EtO)3 SiCH2 CH2 Si(OEt)3 Mixtures by F- -Catalyzed Hydrolysis.

PubMed

Furgal, Joseph C; Yamane, Honami; Odykirk, Timothy R; Yi, Eongyu; Chujo, Yoshiki; Laine, Richard M

2018-01-02

High surface area materials are of considerable interest for gas storage/capture, molecular sieving, catalyst supports, as well as for slow-release drug-delivery systems. We report here a very simple and fast route to very high surface area, mechanically robust, hydrophobic polymer gels prepared by fluoride-catalyzed hydrolysis of mixtures of MeSi(OEt) 3 and bis-triethoxysilylethane (BTSE) at room temperature. These materials offer specific surface areas up to 1300 m 2  g -1 , peak pore sizes of 0.8 nm and thermal stabilities above 200 °C. The gelation times and surface areas can be controlled by adjusting the solvent volume (dichloromethane), percent fluoride (as nBu 4 NF or TBAF) and the BTSE contents. Polymers with other corners and linkers were also explored. These materials will further expand the materials databank for use in vacuum insulation panels and as thermally stable release and capture media. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Studies on the industrial styrene poisoning (Part X). Determination of styrene in biological materials by gas chromatography (author's transl)].

PubMed

Teramoto, K; Horiguchi, S

1980-09-01

For monitoring solvents exposure, it is useful to determine not only metabolites of the solvents in urine but also the solvents themselves in blood and tissues. In a series of studies on the industrial styrene poisoning, we have been determining styrene in blood and other tissues as occasion calls. Our examination of the method is presented in this report. The outline on the method is as follows: Aliquots of 0.5g of tissues being added 5 ml of n-hexane are homogenized by a high-speed homogenizer (Polytoron) for 10 to 30 seconds and the filtrates containing extracts are analyzed for styrene by gas chromatography. The linearity was ascertained from the calibration curve obtained by adding the known quantities of styrene (4, 10, 20, 40, 100 ppm) to the blood, liver and adipose tissues of rats. Rates of recoveries of styrene from the above tissues were 92 to 101 per cent. Reproducibility of this method was examined by repeating determinations of styrene in the blood, liver and adipose tissues of rats exposed to 500 ppm styrene for 4 hours, the coefficients of variation being 2.8 to 14.0 per cent. There was an approximately linear relationship between the styrene concentration (0 to 1,000 ppm) of the exposed air and those in the blood of exposed rats. We conclude that our simple and rapid method is applicable to determination of solvents other than styrene in organs and tissues by combining suitable solvents for extraction and packings of gas chromatography.

Surface functionalization of carbon nanotubes by direct encapsulation with varying dosages of amphiphilic block copolymers

NASA Astrophysics Data System (ADS)

Yao, Xueping; Li, Jie; Kong, Liang; Wang, Yong

2015-08-01

Encapsulation of carbon nanotubes (CNTs) by amphiphilic block copolymers is an efficient way to stabilize CNTs in solvents. However, the appropriate dosages of copolymers and the assembled structures are difficult to predict and control because of the insufficient understanding on the encapsulation process. We encapsulate multiwalled CNTs with polystyrene-block-poly (4-vinyl pyridine) (PS-b-P4VP) by directly mixing them in acetic acid under sonication. The copolymer forms a lamellar structure along the surface of CNTs with the PS blocks anchoring on the tube wall and the P4VP blocks exposed to the outside. The encapsulated CNTs achieve good dispersibility in polar solvents over long periods. To increase our understanding of the encapsulation process we investigate the assembled structures and stability of copolymer/CNTs mixtures with changing mass ratios. Stable dispersions are obtained at high mass ratios between the copolymer and CNTs, i.e. 2 or 3, with the presence of free spherical micelles. Transmission electron microscopy and thermal gravimetric analysis determine that the threshold for the complete coverage of CNTs by the copolymer occurs at the mass ratio of 1.5. The coated copolymer layer activates the surface of CNTs, enabling further functionalization of CNTs. For instance, atomic layer deposition of TiO2 produces conformal thin layers on the encapsulated CNTs while isolated TiO2 bumps are produced on the pristine, inert CNTs.

Thermal Motion and Forced Migration of Colloidal Particles Generate Hydrostatic Pressure in Solvent

PubMed Central

Hammel, H. T.; Scholander, P. F.

1973-01-01

A colloidal solution of ferrite particles in an osmometer has been used to demonstrate that the property that propels water across the semipermeable membrane is the decrease in hydrostatic pressure in the water of the solution. A magnetic field gradient directed so as to force the ferrite particles away from the semipermeable membrane of the osmometer and toward the free surface of the solution enhanced the colloidal osmotic pressure. The enhancement of this pressure was always exactly equal to the augmentation of the pressure as measured by the outward force of the particles, against the area of the free surface. Contrariwise, directing the magnetic field gradient so as to force the ferrite particles away from the free surface and toward the semipermeable membrane diminished the colloidal osmotic pressure of the solution. For a sufficiently forceful field gradient, the initial colloidal osmotic pressure could be negative, followed by an equilibrium pressure approaching zero regardless of the force of the particles against the membrane. Thus, the osmotic pressure of a solution is to be attributed to the pressure in the solvent generated in opposition to the pressure of the solute particles caused by their interaction with the free surface (Brownian motion and/or an external field force), or by their viscous shear when they migrate through the solvent, or both. PMID:16592046

Measured and Predicted Burial of Cylinders During the Indian Rocks Beach Experiment

DTIC Science & Technology

2007-01-01

in shallow water (15-16 m) with fine-sand (133-/xm) and coarse-sand (566-/xm) sediments off Indian Rocks Beach (IRB), FL. Scour pits developed...eter) relative to the sediment- water interface, but only 20%-50% relative to surface area covered. The difference was caused by the lack of...sensors intended to indicate the surface area of the cylinder covered by sediment or water (i.e., percent surface area exposed during burial) and

Solvent mimicry with methylene carbene to probe protein topography.

PubMed

Gómez, Gabriela Elena; Monti, José Luis E; Mundo, Mariana Rocío; Delfino, José María

2015-10-06

The solvent accessible surface area (SASA) of the polypeptide chain plays a key role in protein folding, conformational change, and interaction. This fundamental biophysical parameter is elusive in experimental measurement. Our approach to this problem relies on the reaction of the minimal photochemical reagent diazirine (DZN) with polypeptides. This reagent (i) exerts solvent mimicry because its size is comparable to water and (ii) shows scant chemical selectivity because it generates extremely reactive methylene carbene. Methylation gives rise to the EM (extent of modification) signal, which is useful for scrutinizing the conformational change triggered by Ca(2+) binding to calmodulin (CaM). The increased EM observed for the full protein is dominated by the enhanced exposure of hydrophobic area in Ca(2+)-CaM. Fragmentation allowed us to quantify the methylene incorporation at specific sites. Peptide 91-106 reveals a major reorganization around the calcium 151 binding site, resulting in local ordering and a greater exposure of the hydrophobic surface. Additionally, this technique shows a high sensitivity to probe recognition between CaM and melittin (Mel). The large decrease in EM indicates the occlusion of a significant hydrophobic area upon complexation. Protection from labeling reveals a larger involvement of the N-terminal and central regions of CaM in this interaction. Despite its smaller size, Mel's differential exposure can also be quantified. Moreover, MS/MS fragmentation realizes the goal of extending the resolution of labeled sites at the amino acid level. Overall, DZN labeling emerges as a useful footprinting method capable of shedding light on physiological conformational changes and interactions.

Super-hydrophobic coatings based on non-solvent induced phase separation during electro-spraying.

PubMed

Gao, Jiefeng; Huang, Xuewu; Wang, Ling; Zheng, Nan; Li, Wan; Xue, Huaiguo; Li, Robert K Y; Mai, Yiu-Wing

2017-11-15

The polymer solution concentration determines whether electrospinning or electro-spraying occurs, while the addition of the non-solvent into the polymer solution strongly influences the surface morphology of the obtained products. Both smooth and porous surfaces of the electro-sprayed microspheres can be harvested by choosing different non-solvent and its amount as well as incorporating polymeric additives. The influences of the solution concentration, weight ratio between the non-solvent and the copolymer, and the polymeric additives on the surface morphology and the wettability of the electro-sprayed products were systematically studied. Surface pores and/or asperities on the microsphere surface were mainly caused by the non-solvent induced phase separation (NIPS) and subsequent evaporation of the non-solvent during electro-spraying. With increasing polymer solution concentration, the microsphere was gradually changed to the bead-on-string geometry and finally to a nanofiber form, leading to a sustained decrease of the contact angle (CA). It was found that the substrate coatings derived from the microspheres possessing hierarchical surface pores or dense asperities had high surface roughness and super-hydrophobicity with CAs larger than 150° while sliding angles smaller than 10°; but coatings composed of microspheres with smooth surfaces gave relatively low CAs. Copyright © 2017 Elsevier Inc. All rights reserved.

Determination of the surface area of smectite in water by ethylene oxide chain adsorption.

PubMed

Yuang, Paul-Cheng; Shen, Yun-Hwei

2005-05-15

This study investigates the feasibility of using ethylene oxide (EO) chain adsorption to determine the surface area of smectite in water. Experimental results indicate that high-molecular-weight poly(ethylene oxide) (PEO) should be used to provide reasonable estimations for monolayer capacity of PEO on smectite. The surface areas of smectites in water are calculated from the monolayer capacity of PEO adsorbed on smectite by taking the area per EO unit as 8.05 A(2). The method measures the actual surface area of smectite exposed when dispersed in water, which is important to applications of smectite under aqueous conditions.

PMR polyimide prepreg with improved tack characteristics

NASA Technical Reports Server (NTRS)

Serafini, T. T.; Delvigs, P.

1976-01-01

Current PMR Polyimide prepreg technology utilizes methanol or ethanol solvents for preparation of the PMR prepreg solutions. The volatility of these solvents limits the tack and drape retention characteristics of unprotected prepreg exposed to ambient conditions. Studies conducted to achieve PMR 15 Polyimide prepreg with improved tack and drape characteristics were described. Improved tack and drape retention were obtained by incorporation of an additional monomer. The effects of various levels of the added monomer on the thermo-oxidative stability and mechanical properties of graphite fiber reinforced PMR 15 composites exposed and tested at 316 C (600 F) were discussed.

Experimental and theoretical aspects of studying themodynamics and mass transport in polymer-solvent systems

NASA Astrophysics Data System (ADS)

Davis, Peter Kennedy

Mass transport and thermodynamics in polymer-solvent systems are two key areas of importance to the polymer industry. Numerous processes including polymerization reactors, membrane separations, foam production, devolatilization processes, film and coating drying, supercritical extractions, drug delivery, and even nano-technology require fundamental phase equilibria and diffusion information. Although such information is vital in equipment design and optimization, acquisition and modeling of these data are still in the research and development stages. This thesis is rather diverse as it addresses many realms of this broad research area. From high pressure to low pressure, experimental to theoretical, and infinite dilution to finite concentration, the thesis covers a wide range of topics that are of current importance to the industrial and academic polymer community. Chapter 1 discusses advances in the development of a new volumetric sorption pressure decay technique to make phase equilibrium and diffusion measurements in severe temperature-pressure environments. Chapter 2 provides the derivations and results of a new completely predictive Group Contribution Lattice Fluid Equation of State for multi-component polymer-solvent systems. The remaining four chapters demonstrate advances in the modeling of inverse gas chromatography (IGC) experiments. IGC has been used extensively of the last 50 years to make low pressure sorption and diffusion measurements at infinitely dilute and finite solvent concentrations. Chapter 3 proposes a new IGC experiment capable of obtaining ternary vapor-liquid equilibria in polymer-solvent-solvent systems. Also in that chapter, an extensive derivation is provided for a continuum model capable of describing the results of such an experiment. Chapter 4 presents new data collected on a packed column IGC experiment and a new model that can be used with those experimental data to obtain diffusion and partition coefficients. Chapter 5 addresses a rather controversial topic about IGC experiments near the polymer glass transition temperature. Using a new IGC model capable of describing both bulk absorption and surface adsorption, IGC behavior around the glass transition was able to be better understood. Finally, Chapter 6 presents an IGC model that can be used to separate bulk effects from surface effects in capillary column IGC experiments.

Effect of gel formation on the dissolution behavior of clarithromycin tablets.

PubMed

Inukai, Koki; Takiyama, Kei; Noguchi, Shuji; Iwao, Yasunori; Itai, Shigeru

2017-04-15

Clarithromycin (CAM) is a macrolide antibiotic that is widely used at clinical sites. We found that release of CAM is suppressed when tablets of CAM were exposed to an external solvent containing carboxylate buffers such as citrate. The suppressed release of CAM can be attributed to the formation of gels on the tablet surfaces, which inhibits penetration of the solvent into the tablet and thus disintegration of the tablets. Delayed disintegration of the tablets was also observed for commercial tablets. This suggests that taking CAM and carboxylates at the same time might be avoided. The crystal structure of CAM citrate reveals that molecular chains of CAM are cross-linked by hydrogen bond between citrate groups in the crystal. The crystal structure indicates that cross-linked CAM chains of the three-dimensional mesh structure might also be formed in high concentration CAM solutions in the presence of carboxylates, resulting in gel formation. Copyright © 2017 Elsevier B.V. All rights reserved.

21 CFR 177.1040 - Acrylonitrile/styrene copoly-mer.

Code of Federal Regulations, 2010 CFR

2010-04-01

... article Nitrogen content of copolymer Maximum extractable fractions at specified temperatures and times... Total nonvolatile extractives not to exceed 0.01 mg/in 2 surface area of the food contact article when... not exceed 0.001 mg/in 2 surface area of the food contact article when exposed to distilled water and...

Wetting and phase separation in soft adhesion

PubMed Central

Jensen, Katharine E.; Sarfati, Raphael; Style, Robert W.; Boltyanskiy, Rostislav; Chakrabarti, Aditi; Chaudhury, Manoj K.; Dufresne, Eric R.

2015-01-01

In the classic theory of solid adhesion, surface energy drives deformation to increase contact area whereas bulk elasticity opposes it. Recently, solid surface stress has been shown also to play an important role in opposing deformation of soft materials. This suggests that the contact line in soft adhesion should mimic that of a liquid droplet, with a contact angle determined by surface tensions. Consistent with this hypothesis, we observe a contact angle of a soft silicone substrate on rigid silica spheres that depends on the surface functionalization but not the sphere size. However, to satisfy this wetting condition without a divergent elastic stress, the gel phase separates from its solvent near the contact line. This creates a four-phase contact zone with two additional contact lines hidden below the surface of the substrate. Whereas the geometries of these contact lines are independent of the size of the sphere, the volume of the phase-separated region is not, but rather depends on the indentation volume. These results indicate that theories of adhesion of soft gels need to account for both the compressibility of the gel network and a nonzero surface stress between the gel and its solvent. PMID:26553989

ODC-Free Solvent Implementation for Phenolics Cleaning

NASA Technical Reports Server (NTRS)

Wurth, Laura; Biegert, Lydia; Lamont, DT; McCool, Alex (Technical Monitor)

2001-01-01

During phenolic liner manufacture, resin-impregnated (pre-preg) bias tape of silica, glass, or carbon cloth is tape-wrapped, cured, machined, and then wiped with 1,1,1 tri-chloroethane (TCA) to remove contaminants that may have been introduced during machining and handling. Following the TCA wipe, the machined surface is given a resin wet-coat and over-wrapped with more prepreg and cured. A TCA replacement solvent for these wiping operations must effectively remove both surface contaminants, and sub-surface oils and greases while not compromising the integrity of this interface. Selection of a TCA replacement solvent for phenolic over-wrap interface cleaning began with sub-scale compatibility tests with cured phenolics. Additional compatibility tests included assessment of solvent retention in machined phenolic surfaces. Results from these tests showed that, while the candidate solvent did not degrade the cured phenolics, it was retained in higher concentrations than TCA in phenolic surfaces. This effect was most pronounced with glass and silica cloth phenolics with steep ply angles relative to the wiped surfaces.

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

Aines, Roger D; Spadaccini, Christopher M; Stolaroff, Joshuah K

Method and apparatus for separating a target substance from a fluid or mixture. Capsules having a coating and stripping solvents encapsulated in the capsules are provided. The coating is permeable to the target substance. The capsules having a coating and stripping solvents encapsulated in the capsules are exposed to the fluid or mixture. The target substance migrates through the coating and is taken up by the stripping solvents. The target substance is separated from the fluid or mixture by driving off the target substance from the capsules.

Impact of processing parameters on the haemocompatibility of Bombyx mori silk films.

PubMed

Seib, F Philipp; Maitz, Manfred F; Hu, Xiao; Werner, Carsten; Kaplan, David L

2012-02-01

Silk has traditionally been used for surgical sutures due to its lasting strength and durability; however, the use of purified silk proteins as a scaffold material for vascular tissue engineering goes beyond traditional use and requires application-orientated biocompatibility testing. For this study, a library of Bombyx mori silk films was generated and exposed to various solvents and treatment conditions to reflect current silk processing techniques. The films, along with clinically relevant reference materials, were exposed to human whole blood to determine silk blood compatibility. All substrates showed an initial inflammatory response comparable to polylactide-co-glycolide (PLGA), and a low to moderate haemostasis response similar to polytetrafluoroethylene (PTFE) substrates. In particular, samples that were water annealed at 25 °C for 6 h demonstrated the best blood compatibility based on haemostasis parameters (e.g. platelet decay, thrombin-antithrombin complex, platelet factor 4, granulocytes-platelet conjugates) and inflammatory parameters (e.g. C3b, C5a, CD11b, surface-associated leukocytes). Multiple factors such as treatment temperature and solvent influenced the biological response, though no single physical parameter such as β-sheet content, isoelectric point or contact angle accurately predicted blood compatibility. These findings, when combined with prior in vivo data on silk, support a viable future for silk-based vascular grafts. Copyright © 2011 Elsevier Ltd. All rights reserved.

Free energy landscape of protein folding in water: explicit vs. implicit solvent.

PubMed

Zhou, Ruhong

2003-11-01

The Generalized Born (GB) continuum solvent model is arguably the most widely used implicit solvent model in protein folding and protein structure prediction simulations; however, it still remains an open question on how well the model behaves in these large-scale simulations. The current study uses the beta-hairpin from C-terminus of protein G as an example to explore the folding free energy landscape with various GB models, and the results are compared to the explicit solvent simulations and experiments. All free energy landscapes are obtained from extensive conformation space sampling with a highly parallel replica exchange method. Because solvation model parameters are strongly coupled with force fields, five different force field/solvation model combinations are examined and compared in this study, namely the explicit solvent model: OPLSAA/SPC model, and the implicit solvent models: OPLSAA/SGB (Surface GB), AMBER94/GBSA (GB with Solvent Accessible Surface Area), AMBER96/GBSA, and AMBER99/GBSA. Surprisingly, we find that the free energy landscapes from implicit solvent models are quite different from that of the explicit solvent model. Except for AMBER96/GBSA, all other implicit solvent models find the lowest free energy state not the native state. All implicit solvent models show erroneous salt-bridge effects between charged residues, particularly in OPLSAA/SGB model, where the overly strong salt-bridge effect results in an overweighting of a non-native structure with one hydrophobic residue F52 expelled from the hydrophobic core in order to make better salt bridges. On the other hand, both AMBER94/GBSA and AMBER99/GBSA models turn the beta-hairpin in to an alpha-helix, and the alpha-helical content is much higher than the previously reported alpha-helices in an explicit solvent simulation with AMBER94 (AMBER94/TIP3P). Only AMBER96/GBSA shows a reasonable free energy landscape with the lowest free energy structure the native one despite an erroneous salt-bridge between D47 and K50. Detailed results on free energy contour maps, lowest free energy structures, distribution of native contacts, alpha-helical content during the folding process, NOE comparison with NMR, and temperature dependences are reported and discussed for all five models. Copyright 2003 Wiley-Liss, Inc.

Deployment of Phytotechnology in the 317/319 Area at Argonne National Laboratory-East, Innovative Technology Evaluation Report

EPA Science Inventory

Hybrid poplar and hybrid willow trees were planted for several environmental objectives at the Argonne National Laboratory - East, near Chicago, IL. Some trees were planted to clean TCE and other solvents from soil, some were planted to control surface water flow on a landfill, a...

Process for electrospinning chitin fibers from chitinous biomass solution

DOEpatents

Swatloski, Richard P.; Barber, Patrick S.; Opichka, Terrance; Bonner, Jonathan R.; Gurau, Gabriela; Griggs, Christopher Scott; Rogers, Robin D.

2017-06-20

Disclosed are methods for electrospinning chitinous biomass solution to form chitin fibers, using ionic liquids or other ion-containing liquids as solvent. Chitin fibers produced thereby and articles containing such chitin fibers are also disclosed. The chitin fiber thus obtained has very high surface area and improved strength over currently commercially available chitin materials.

Water Quality Criteria for Colored Smokes: Solvent Yellow 33

DTIC Science & Technology

1987-11-01

Y . ’~ ~% d .’ 4’ . TABLE 4. DISTRIBUTION OF [1 4 C]-SOLVENT YELLOW 33 IN RATS 1 hr AFTER- EXPOSURE TO SOLVENT YELLOW 33 (SY) OR SOLVENT YELLOW 33...have shown that some individuals react strongly Lo this dye. The repeat insult patch test is used most often. The subjects receive five to ten exposures...70 Neutrophils Control 5 ± 2 0 ± 0 7 ± 3 3( lO cells/g) Exposed 1300 ± 130 d 470 ± i 0 0d 290 ± 50 d a. Adapted from Henderson et al. 1985b. b. Values

Application of two dimensional periodic molecular dynamics to interfaces.

NASA Astrophysics Data System (ADS)

Gay, David H.; Slater, Ben; Catlow, C. Richard A.

1997-08-01

We have applied two-dimensional molecular dynamics to the surface of a crystalline aspartame and the interface between the crystal face and a solvent (water). This has allowed us to look at the dynamic processes at the surface. Understanding the surface structure and properties are important to controlling the crystal morphology. The thermodynamic ensemble was constant Number, surface Area and Temperature (NAT). The calculations have been carried out using a 2D Ewald summation and 2D periodic boundary conditions for the short range potentials. The equations of motion integration has been carried out using the standard velocity Verlet algorithm.

Preparation and characterization of uniform nanosized cephradine by combination of reactive precipitation and liquid anti-solvent precipitation under high gravity environment.

PubMed

Zhong, Jie; Shen, Zhigang; Yang, Yan; Chen, Jianfeng

2005-09-14

In this work, a novel direct method, which was combined with reactive precipitation and liquid anti-solvent precipitation under high gravity environment, had been developed to prepare nanosized cephradine with narrow particle size distribution. Compared with commercial crude cephradine, the prepared cephradine showed a significant decrease in particle size, a significant increase in the specific surface area and shorter dissolving time when used for injection. The characteristic particle size was between 200-400 nm. The specific surface area increased from 2.95 to 10.87 m2/g after micronization. When the amount of L-arginin decreased from 0.25 to 0.18 g, the mixture of nanosized cephradine and L-arginine could still dissolve in 1 min. The X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR) analysis indicated that the physical characteristics and molecular states remained unchanged after the recrystallization process. This method had potential application in industrial fields because of its low cost, efficient processing and the ease of scaling-up.

Solvent-accessible surface area: How well can be applied to hot-spot detection?

PubMed

Martins, João M; Ramos, Rui M; Pimenta, António C; Moreira, Irina S

2014-03-01

A detailed comprehension of protein-based interfaces is essential for the rational drug development. One of the key features of these interfaces is their solvent accessible surface area profile. With that in mind, we tested a group of 12 SASA-based features for their ability to correlate and differentiate hot- and null-spots. These were tested in three different data sets, explicit water MD, implicit water MD, and static PDB structure. We found no discernible improvement with the use of more comprehensive data sets obtained from molecular dynamics. The features tested were shown to be capable of discerning between hot- and null-spots, while presenting low correlations. Residue standardization such as rel SASAi or rel/res SASAi , improved the features as a tool to predict ΔΔGbinding values. A new method using support machine learning algorithms was developed: SBHD (Sasa-Based Hot-spot Detection). This method presents a precision, recall, and F1 score of 0.72, 0.81, and 0.76 for the training set and 0.91, 0.73, and 0.81 for an independent test set. Copyright © 2013 Wiley Periodicals, Inc.

Polyacrylonitrile nanofiber as polar solvent N,N-dimethyl formamide sensor based on quartz crystal microbalance technique

NASA Astrophysics Data System (ADS)

Rianjanu, A.; Julian, T.; Hidayat, S. N.; Suyono, E. A.; Kusumaatmaja, A.; Triyana, K.

2018-04-01

Here, we describe an N,N-dimethyl formamide (DMF) vapour sensor fabricated by coating polyacrylonitrile (PAN) nanofiber structured on quartz crystal microbalance (QCM). The PAN nanofiber sensors with an average diameter of 225 nm to 310 nm were fabricated via electrospinning process with different mass deposition on QCM substrate. The nanostructured of PAN nanofiber offers a high specific surface area that improved the sensing performance of nanofiber sensors. Benefiting from that fine structure, and high polymer-solvent affinity between PAN and DMF, the development of DMF sensors presented good response at ambient temperature. Since there is no chemical reaction between PAN nanofiber and DMF vapour, weak physical interaction such absorption and swelling were responsible for the sensing behavior. The results are indicating that the response of PAN nanofiber sensors has more dependency on the nanofiber structure (specific surface area) rather than its mass deposition. The sensor also showed good stability after a few days sensing. These findings have significant implications for developing DMF vapour sensor based on QCM coated polymer nanofibers.

Ultra-lightweight and highly porous carbon aerogels from bamboo pulp fibers as an effective sorbent for water treatment

NASA Astrophysics Data System (ADS)

Yuan, Wei; Zhang, Xiaofang; Zhao, Jiangqi; Li, Qingye; Ao, Chenghong; Xia, Tian; Zhang, Wei; Lu, Canhui

Sorbents derived from biomass provide a novel approach to settle issues of organic solvent and/or oil leakage. In this work, a novel carbon aerogel (CA) was prepared as sorbents using the cheap and abundant bamboo pulp fibers as precursors through the pyrolysis method. The CA displayed an ultra-low density (5.65 mg cm-3), high hydrophobicity (water contact angle of 135.9°) and a large specific surface area (379.39 m2 g-1) as well as great mechanical properties. The absorption capacities of CA for organic solvents/oils were extraordinary (50-150 g/g). Particularly, its absorption on organic solvents was superior to many other bio-based CAs. The reusability of CA was also found impressive. For over five absorption-desorption cycles, the CA still showed excellent absorption behaviors on organic solvents and oils. Importantly, the fabrication process of CA is quite simple and environmentally friendly, demonstrating high potentials for future water treatment applications.

Role of excited state solvent fluctuations on time-dependent fluorescence Stokes shift

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

Li, Tanping, E-mail: tanping@lsu.edu, E-mail: revatik@lsu.edu; Kumar, Revati, E-mail: tanping@lsu.edu, E-mail: revatik@lsu.edu

2015-11-07

We explore the connection between the solvation dynamics of a chromophore upon photon excitation and equilibrium fluctuations of the solvent. Using molecular dynamics simulations, fluorescence Stokes shift for the tryptophan in Staphylococcus nuclease was examined using both nonequilibrium calculations and linear response theory. When the perturbed and unperturbed surfaces exhibit different solvent equilibrium fluctuations, the linear response approach on the former surface shows agreement with the nonequilibrium process. This agreement is excellent when the perturbed surface exhibits Gaussian statistics and qualitative in the case of an isomerization induced non-Gaussian statistics. However, the linear response theory on the unperturbed surface breaksmore » down even in the presence of Gaussian fluctuations. Experiments also provide evidence of the connection between the excited state solvent fluctuations and the total fluorescence shift. These observations indicate that the equilibrium statistics on the excited state surface characterize the relaxation dynamics of the fluorescence Stokes shift. Our studies specifically analyze the Gaussian fluctuations of the solvent in the complex protein environment and further confirm the role of solvent fluctuations on the excited state surface. The results are consistent with previous investigations, found in the literature, of solutes dissolved in liquids.« less

Chemically exfoliating large sheets of phosphorene via choline chloride urea viscosity-tuning

NASA Astrophysics Data System (ADS)

Ng, A.; Sutto, T. E.; Matis, B. R.; Deng, Y.; Ye, P. D.; Stroud, R. M.; Brintlinger, T. H.; Bassim, N. D.

2017-04-01

Exfoliation of two-dimensional phosphorene from bulk black phosphorous through chemical means is demonstrated where the solvent system of choice (choline chloride urea diluted with ethanol) has the ability to successfully exfoliate large-area multi-layer phosphorene sheets and further protect the flakes from ambient degradation. The intercalant solvent molecules, aided by low-powered sonication, diffuse between the layers of the bulk black phosphorus, allowing for the exfoliation of the multi-layer phosphorene through breaking of the interlayer van der Waals bonds. Through viscosity tuning, the optimal parameters (1:1 ratio between the intercalant and the diluting solvent) at which the exfoliation takes place is determined. Our exfoliation technique is shown to produce multi-layer phosphorene flakes with surface areas greater than 3 μm2 (a factor of three larger than what has previously been reported for a similar exfoliation method) while limiting exposure to the ambient environment, thereby protecting the flakes from degradation. Characterization techniques such as optical microscopy, Raman spectroscopy, ultraviolet-visible spectroscopy, and (scanning) transmission electron microscopy are used to investigate the quality, quantity, and thickness of the exfoliated flakes.

Hydration structure of the α-chymotrypsin substrate binding pocket: the impact of constrained geometry

NASA Astrophysics Data System (ADS)

Carey, Christina; Cheng, Yuen-Kit; Rossky, Peter J.

2000-08-01

The concave substrate binding pocket of α-chymotrypsin binds specifically hydrophobic side chains. In order to understand the hydration structure present in the absence of substrate, and elucidate the character of the solvent displaced on binding, molecular dynamics computer simulation of the solvent in a fully hydrated protein has been carried out and analyzed. The pocket is found to be characterized in terms of a mixed polar and apolar macromolecular surface. It is shown that the simulated solvent structure within it is spatially consistent with that seen via crystallography. The solvent structure is energetically characterized by large losses in hydrogen bonding among solvent molecules except at the mouth of the pocket where exposure to bulk-like solvent is possible. The loss in hydrogen bonding is attributed to the highly constrained geometry available to the solvent, preventing formation of a hydrogen bonding network, with only partial compensation by interactions with the macromolecular surface. The solvent displacement concomitant with substrate binding will therefore be associated with a large enthalpic driving force. This result is at the extreme of a continuum of variable cases of "hydrophobic" hydration, which differ most basically in surface curvature. These range from convex solute surfaces, inducing clathrate-like structures, with negligible hydrogen bond loss, to flat surfaces with significant interfacial loss, to the present concave case with hydrogen bonding losses exceeding 50%.

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

Effects of copolymer composition, film thickness, and solvent vapor annealing time on dewetting of ultrathin block copolymer films.

PubMed

Huang, Changchun; Wen, Gangyao; Li, Jingdan; Wu, Tao; Wang, Lina; Xue, Feifei; Li, Hongfei; Shi, Tongfei

2016-09-15

Effects of copolymer composition, film thickness, and solvent vapor annealing time on dewetting of spin-coated polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) films (<20nm thick) were mainly investigated by atomic force microscopy. Surface chemical analysis of the ultrathin films annealed for different times were performed using X-ray photoelectron spectroscopy and contact angle measurement. With the annealing of acetone vapor, dewetting of the films with different thicknesses occur via the spinodal dewetting and the nucleation and growth mechanisms, respectively. The PS-b-PMMA films rupture into droplets which first coalesce into large ones to reduce the surface free energy. Then the large droplets rupture into small ones to increase the contact area between PMMA blocks and acetone molecules resulting from ultimate migration of PMMA blocks to droplet surface, which is a novel dewetting process observed in spin-coated films for the first time. Copyright © 2016 Elsevier Inc. All rights reserved.

Surface tension driven aggregation of organic nanowires via lab in a droplet.

PubMed

Gu, Jianmin; Yin, Baipeng; Fu, Shaoyan; Feng, Man; Zhang, Ziming; Dong, Haiyun; Gao, Faming; Zhao, Yong Sheng

2018-06-05

Directing the architecture of complex organic nanostructures is desirable and still remains a challenge in areas of materials science due to their structure-dependent collective optoelectronic properties. Herein, we demonstrate a simple and versatile solution strategy that allows surface tension to drive low-dimensional nanostructures to aggregate into complex structures via a lab in a droplet technique. By selecting a suitable combination of a solvent and an anti-solvent with controllable surface tension difference, the droplets can be automatically cracked into micro-droplets, which provides an aggregation force directed toward the centre of the droplet to drive the low-dimensional building blocks to form the special aggregations during the self-assembly process. This synthetic strategy has been shown to be universal for organic materials, which is beneficial for further optimizing the optoelectronic properties. These results contribute to gaining an insightful understanding on the detailed growth mechanism of complex organic nanostructures and greatly promoting the development of organic nanophotonics.

Supercritical Carbon Dioxide and Its Potential as a Life-Sustaining Solvent in a Planetary Environment

PubMed Central

Budisa, Nediljko; Schulze-Makuch, Dirk

2014-01-01

Supercritical fluids have different properties compared to regular fluids and could play a role as life-sustaining solvents on other worlds. Even on Earth, some bacterial species have been shown to be tolerant to supercritical fluids. The special properties of supercritical fluids, which include various types of selectivities (e.g., stereo-, regio-, and chemo-selectivity) have recently been recognized in biotechnology and used to catalyze reactions that do not occur in water. One suitable example is enzymes when they are exposed to supercritical fluids such as supercritical carbon dioxide: enzymes become even more stable, because they are conformationally rigid in the dehydrated state. Furthermore, enzymes in anhydrous organic solvents exhibit a “molecular memory”, i.e., the capacity to “remember” a conformational or pH state from being exposed to a previous solvent. Planetary environments with supercritical fluids, particularly supercritical carbon dioxide, exist, even on Earth (below the ocean floor), on Venus, and likely on Super-Earth type exoplanets. These planetary environments may present a possible habitat for exotic life. PMID:25370376

Supercritical carbon dioxide and its potential as a life-sustaining solvent in a planetary environment.

PubMed

Budisa, Nediljko; Schulze-Makuch, Dirk

2014-08-08

Supercritical fluids have different properties compared to regular fluids and could play a role as life-sustaining solvents on other worlds. Even on Earth, some bacterial species have been shown to be tolerant to supercritical fluids. The special properties of supercritical fluids, which include various types of selectivities (e.g., stereo-, regio-, and chemo-selectivity) have recently been recognized in biotechnology and used to catalyze reactions that do not occur in water. One suitable example is enzymes when they are exposed to supercritical fluids such as supercritical carbon dioxide: enzymes become even more stable, because they are conformationally rigid in the dehydrated state. Furthermore, enzymes in anhydrous organic solvents exhibit a "molecular memory", i.e., the capacity to "remember" a conformational or pH state from being exposed to a previous solvent. Planetary environments with supercritical fluids, particularly supercritical carbon dioxide, exist, even on Earth (below the ocean floor), on Venus, and likely on Super-Earth type exoplanets. These planetary environments may present a possible habitat for exotic life.

Non-encapsulation approach for high-performance Li-S batteries through controlled nucleation and growth

NASA Astrophysics Data System (ADS)

Pan, Huilin; Chen, Junzheng; Cao, Ruiguo; Murugesan, Vijay; Rajput, Nav Nidhi; Han, Kee Sung; Persson, Kristin; Estevez, Luis; Engelhard, Mark H.; Zhang, Ji-Guang; Mueller, Karl T.; Cui, Yi; Shao, Yuyan; Liu, Jun

2017-10-01

High-surface-area, nanostructured carbon is widely used for encapsulating sulfur and improving the cyclic stability of Li-S batteries, but the high carbon content and low packing density limit the specific energy that can be achieved. Here we report an approach that does not rely on sulfur encapsulation. We used a low-surface-area, open carbon fibre architecture to control the nucleation and growth of the sulfur species by manipulating the carbon surface chemistry and the solvent properties, such as donor number and Li+ diffusivity. Our approach facilitates the formation of large open spheres and prevents the production of an undesired insulating sulfur-containing film on the carbon surface. This mechanism leads to 100% sulfur utilization, almost no capacity fading, over 99% coulombic efficiency and high energy density (1,835 Wh kg-1 and 2,317 Wh l-1). This finding offers an alternative approach for designing high-energy and low-cost Li-S batteries through controlling sulfur reaction on low-surface-area carbon.

Synthesis of porous inorganic hollow fibers without harmful solvents.

PubMed

Shukla, Sushumna; de Wit, Patrick; Luiten-Olieman, Mieke W J; Kappert, Emiel J; Nijmeijer, Arian; Benes, Nieck E

2015-01-01

A route for the fabrication of porous inorganic hollow fibers with high surface-area-to-volume ratio that avoids harmful solvents is presented. The approach is based on bio-ionic gelation of an aqueous mixture of inorganic particles and sodium alginate during wet spinning. In a subsequent thermal treatment, the bio-organic material is removed and the inorganic particles are sintered. The method is applicable to the fabrication of various inorganic fibers, including metals and ceramics. The route completely avoids the use of organic solvents, such as N-methyl-2-pyrrolidone, and additives associated with the currently used fiber fabrication methods. In addition, it inherently avoids the manifestation of so-called macro voids and allows the facile incorporation of additional metal oxides in the inorganic hollow fibers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multibody correlations in the hydrophobic solvation of glycine peptides

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

Harris, Robert C.; Drake, Justin A.; Pettitt, B. Montgomery, E-mail: mpettitt@utmb.edu

2014-12-14

Protein collapse during folding is often assumed to be driven by a hydrophobic solvation energy (ΔG{sub vdw}) that scales linearly with solvent-accessible surface area (A). In a previous study, we argued that ΔG{sub vdw}, as well as its attractive (ΔG{sub att}) and repulsive (ΔG{sub rep}) components, was not simply a linear function of A. We found that the surface tensions, γ{sub rep}, γ{sub att}, and γ{sub vdw}, gotten from ΔG{sub rep}, ΔG{sub att}, and ΔG{sub vdw} against A for four configurations of deca-alanine differed from those obtained for a set of alkanes. In the present study, we extend our analysismore » to fifty decaglycine structures and atomic decompositions. We find that different configurations of decaglycine generate different estimates of γ{sub rep}. Additionally, we considered the reconstruction of the solvation free energy from scaling the free energy of solvation of each atom type, free in solution. The free energy of the isolated atoms, scaled by the inverse surface area the atom would expose in the molecule does not reproduce the γ{sub rep} for the intact decaglycines. Finally, γ{sub att} for the decaglycine conformations is much larger in magnitude than those for deca-alanine or the alkanes, leading to large negative values of γ{sub vdw} (−74 and −56 cal/mol/Å{sup 2} for CHARMM27 and AMBER ff12sb force fields, respectively). These findings imply that ΔG{sub vdw} favors extended rather than compact structures for decaglycine. We find that ΔG{sub rep} and ΔG{sub vdw} have complicated dependencies on multibody correlations between solute atoms, on the geometry of the molecular surface, and on the chemical identities of the atoms.« less

Method for forming polymerized microfluidic devices

DOEpatents

Sommer, Gregory J [Livermore, CA; Hatch, Anson V [Tracy, CA; Wang, Ying-Chih [Pleasanton, CA; Singh, Anup K [Danville, CA; Renzi, Ronald F [Tracy, CA; Claudnic, Mark R [Livermore, CA

2011-11-01

Methods for making a micofluidic device according to embodiments of the present invention include defining a cavity. Polymer precursor solution is positioned in the cavity, and exposed to light to begin the polymerization process and define a microchannel. In some embodiments, after the polymerization process is partially complete, a solvent rinse is performed, or fresh polymer precursor introduced into the microchannel. This may promote removal of unpolymerized material from the microchannel and enable smaller feature sizes. The polymer precursor solution may contain an iniferter. Polymerized features therefore may be capped with the iniferter, which is photoactive. The iniferter may aid later binding of a polyacrylamide gel to the microchannel surface.

Method for forming polymerized microfluidic devices

DOEpatents

Sommer, Gregory J.; Hatch, Anson V.; Wang, Ying-Chih; Singh, Anup K.; Renzi, Ronald F.; Claudnic, Mark R.

2013-03-12

Methods for making a microfluidic device according to embodiments of the present invention include defining.about.cavity. Polymer precursor solution is positioned in the cavity, and exposed to light to begin the polymerization process and define a microchannel. In some embodiments, after the polymerization process is partially complete, a solvent rinse is performed, or fresh polymer precursor introduced into the microchannel. This may promote removal of unpolymerized material from the microchannel and enable smaller feature sizes. The polymer precursor solution may contain an iniferter. Polymerized features therefore may be capped with the iniferter, which is photoactive. The iniferter may aid later binding of a polyacrylamide gel to the microchannel surface.

Protective effects of a freeze-dried extract of vegetables and fruits on the hydroxyl radical-mediated oxidative damage of DNA and decrease of erythrocytes deformability.

PubMed

Wang, Hsiao-Ning; Liu, Tsan-Zon; Chen, Ya-Lei; Shiuan, David

2007-01-01

The protective effects of a freeze-dried extracts of vegetables and fruits (BauYuan; BY) on the hydroxyl radical-mediated DNA strand breakages and the structural integrity of human red blood cells (RBCs) were investigated. First, the supercoiled plasmid (pEGFP-C1) DNA was subjected to oxidation damage by an ascorbate-fortified Fenton reaction and the protective effects were analyzed by agarose gel electrophoresis. In the absence of BY extracts, exposure of the high-throughput .OH-generating system (Fe2+ concentration >1.0 microM) caused a complete fragmentation of DNA. Supplementation of BY extract (1 mg/mL) to the plasmid DNA prior to the exposure could prevent it significantly. In contrast, as the plasmid exposed to a low-grade .OH-generating system (Fe2+<0.1 microM), the BY extract (1 mg/mL) provided an almost complete protection. Next, the cell deformabilities were measured to assess the protection effects of various BY extracts on human erythrocytes exposed to the oxidative insults. We found that both the aqueous extract and the organic solvent-derived extracts could strongly protect human RBCs from the reactive oxygen species (ROS)-mediated decrease in the deformability indices. The results implicated that the BY extracts could effectively protect the cell membrane integrity via scavenging ROS which enabling RBCs to maintain a balance of water content and surface area to prevent the drop of cell deformability.

To Evaluate the Effect of Solvents and Different Relative Humidity Conditions on Thermal and Rheological Properties of Microcrystalline Cellulose 101 Using METHOCEL™ E15LV as a Binder.

PubMed

Jagia, Moksh; Trivedi, Maitri; Dave, Rutesh H

2016-08-01

The solvent used for preparing the binder solution in wet granulation can affect the granulation end point and also impact the thermal, rheological, and flow properties of the granules. The present study investigates the effect of solvents and percentage relative humidity (RH) on the granules of microcrystalline cellulose (MCC) with hydroxypropyl methyl cellulose (HPMC) as the binder. MCC was granulated using 2.5% w/w binder solution in water and ethanol/water mixture (80:20 v/v). Prepared granules were dried until constant percentage loss on drying, sieved, and further analyzed. Dried granules were exposed to different percentage RH for 48 h at room temperature. Powder rheometer was used for the rheological and flow characterization, while thermal effusivity and differential scanning calorimeter were used for thermal analysis. The thermal effusivity values for the wet granules showed a sharp increase beginning 50% w/w binder solution in both cases, which reflected the over-wetting of granules. Ethanol/water solvent batches showed greater resistance to flow as compared to the water solvent batches in the wet granule stage, while the reverse was true for the dried granule stage, as evident from the basic flowability energy values. Although the solvents used affected the equilibration kinetics of moisture content, the RH-exposed granules remained unaffected in their flow properties in both cases. This study indicates that the solvents play a vital role on the rheology and flow properties of MCC granules, while the different RH conditions have little or no effect on them for the above combination of solvent and binder.

Present-day Exposures of Water Ice in the Northern Mid-latitudes of Mars

NASA Technical Reports Server (NTRS)

Allen, Carlton C.; Kanner, Lisa C.

2007-01-01

Water ice is exposed in the martian north polar cap, but is rarely exposed beyond the cap boundary. Orbital gamma ray spectrometry data strongly imply the presence of water ice within meters of the surface at latitudes north of approximately 60deg. We have examined mid-latitude areas of the northern plains displaying residual ice-rich layers, and report evidence of present-day surface exposures of water ice. These exposures, if confirmed, could con-strain the latitudinal and temporal stability of surface ice on Mars.

Solvent free tin oxide nanoparticle for gas sensing application

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

Ranjan, Pranay, E-mail: pranjan@iitp.ac.in; Thakur, Ajay D.; Centre for Energy and Environment, Indian Institute of Technology Patna, Patliputra, Patna 800013 India

2016-05-06

A new modified technique of synthesizing tin oxide nanoparticles with crystallite size of 2 nm to 6 nm has been developed. Surface area of the nanoparticle has been increased as we approached towards the Debye length. Such a techniques for approaching the Debye length is expected to bring remarkable changes in the properties of resistive based gas sensors. The technique used here is less toxic, economical and has high yield. Phase purity, size, shape and composition has been investigated using x-ray diffraction, micro Raman, scanning electron microscopy and energy dispersive x ray spectroscopy. While surface area has been calculated through Brunaur-Emmett-Teller (BET).

Differential geometry-based solvation and electrolyte transport models for biomolecular modeling: a review

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

Wei, Guowei; Baker, Nathan A.

2016-11-11

This chapter reviews the differential geometry-based solvation and electrolyte transport for biomolecular solvation that have been developed over the past decade. A key component of these methods is the differential geometry of surfaces theory, as applied to the solvent-solute boundary. In these approaches, the solvent-solute boundary is determined by a variational principle that determines the major physical observables of interest, for example, biomolecular surface area, enclosed volume, electrostatic potential, ion density, electron density, etc. Recently, differential geometry theory has been used to define the surfaces that separate the microscopic (solute) domains for biomolecules from the macroscopic (solvent) domains. In thesemore » approaches, the microscopic domains are modeled with atomistic or quantum mechanical descriptions, while continuum mechanics models (including fluid mechanics, elastic mechanics, and continuum electrostatics) are applied to the macroscopic domains. This multiphysics description is integrated through an energy functional formalism and the resulting Euler-Lagrange equation is employed to derive a variety of governing partial differential equations for different solvation and transport processes; e.g., the Laplace-Beltrami equation for the solvent-solute interface, Poisson or Poisson-Boltzmann equations for electrostatic potentials, the Nernst-Planck equation for ion densities, and the Kohn-Sham equation for solute electron density. Extensive validation of these models has been carried out over hundreds of molecules, including proteins and ion channels, and the experimental data have been compared in terms of solvation energies, voltage-current curves, and density distributions. We also propose a new quantum model for electrolyte transport.« less

Probing protein surface with a solvent mimetic carbene coupled to detection by mass spectrometry.

PubMed

Gómez, Gabriela E; Mundo, Mariana R; Craig, Patricio O; Delfino, José M

2012-01-01

Much knowledge into protein folding, ligand binding, and complex formation can be derived from the examination of the nature and size of the accessible surface area (SASA) of the polypeptide chain, a key parameter in protein science not directly measurable in an experimental fashion. To this end, an ideal chemical approach should aim at exerting solvent mimicry and achieving minimal selectivity to probe the protein surface regardless of its chemical nature. The choice of the photoreagent diazirine to fulfill these goals arises from its size comparable to water and from being a convenient source of the extremely reactive methylene carbene (:CH(2)). The ensuing methylation depends primarily on the solvent accessibility of the polypeptide chain, turning it into a valuable signal to address experimentally the measurement of SASA in proteins. The superb sensitivity and high resolution of modern mass spectrometry techniques allows us to derive a quantitative signal proportional to the extent of modification (EM) of the sample. Thus, diazirine labeling coupled to electrospray mass spectrometry (ESI-MS) detection can shed light on conformational features of the native as well as non-native states, not easily addressable by other methods. Enzymatic fragmentation of the polypeptide chain at the level of small peptides allows us to locate the covalent tag along the amino acid sequence, therefore enabling the construction of a map of solvent accessibility. Moreover, by subsequent MS/MS analysis of peptides, we demonstrate here the feasibility of attaining amino acid resolution in defining the target sites. © American Society for Mass Spectrometry, 2011

Solvent effects on adsorption of CO over CuCl(1 1 1) surface: A density functional theory study

NASA Astrophysics Data System (ADS)

Zhang, Riguang; Ling, Lixia; Wang, Baojun; Huang, Wei

2010-09-01

DFT calculations have been performed to investigate the effect of dielectric responses of the solvent environment on the CO adsorption over CuCl(1 1 1) surface by using COSMO (conductor-like solvent model) model in Dmol 3. Different dielectric constants, including vacuum, liquid paraffin, methylene chloride, methanol and water solution, are considered. The effects of solvent model on the structural parameters, adsorption energies and vibrational frequency of CO adsorption over CuCl(1 1 1) surface have been investigated. The calculation results suggest that solvent effects can improve the stability of CO adsorption and reduce the intensity of C-O bond, which might mean that solvent is in favor of C-O bond activation and improve the reaction activity of oxidative carbonylation in a slurry reactor.

Comparison of the exposure-excretion relationship between men and women exposed to organic solvents.

PubMed

Kawai, Toshio; Takeuchi, Akito; Ikeda, Masayuki

2015-01-01

The present study was initiated to examine if application of the same biological occupational exposure limits (BOELs) for organic solvents is applicable across the sexes. A survey was conducted in 69 micro-scale enterprises in a furniture-producing industrial park. In practice, 211 men and 52 women participated in the survey. They worked in a series of production process, and were exposed to solvent vapor mixtures. The exposure intensities were monitored with two types of diffusive samplers, one with carbon cloth (for solvents in general) and the other with water (for methyl alcohol) as adsorbents. Solvents in the adsorbents and head-space air from urine samples were analyzed with capillary FID-GC. The measured values were subjected to linear regression analysis followed by statistical evaluation for possible sex-related differences in slopes. Essentially no significant difference was detected between men and women in regression line parameters including slopes. Possible differences in the cases of acetone and toluene were discussed and excluded. With the exceptions for acetone and toluene, the present study did not detect any clear differences between men and women. In examinations of past reports, no support for the observed differences was found. The present findings deserve further study so that a solid conclusion can be formed.

Fluorescence Determination of Tryptophan Side-Chain Accessibility and Dynamics in Triple-Helical Collagen-Like Peptides

PubMed Central

Simon-Lukasik, Kristine V.; Persikov, Anton V.; Brodsky, Barbara; Ramshaw, John A. M.; Laws, William R.; Alexander Ross, J. B.; Ludescher, Richard D.

2003-01-01

We report tryptophan fluorescence measurements of emission intensity, iodide quenching, and anisotropy that describe the environment and dynamics at X and Y sites in stable collagen-like peptides of sequence (Gly-X-Y)n. About 90% of tryptophans at both sites have similar solvent exposed fluorescence properties and a lifetime of 8.5–9 ns. Analysis of anisotropy decays using an associative model indicates that these long lifetime populations undergo rapid depolarizing motion with a 0.5 ns correlation time; however, the extent of fast motion at the Y site is considerably less than the essentially unrestricted motion at the X site. About 10% of tryptophans at both sites have a shorter (∼3 ns) lifetime indicating proximity to a protein quenching group; these minor populations are immobile on the peptide surface, depolarizing only by overall trimer rotation. Iodide quenching indicates that tryptophans at the X site are more accessible to solvent. Side chains at X sites are more solvent accessible and considerably more mobile than residues at Y sites and can more readily fluctuate among alternate intermolecular interactions in collagen fibrils. This fluorescence analysis of collagen-like peptides lays a foundation for studies on the structure, dynamics, and function of collagen and of triple-helical junctions in gelatin gels. PMID:12524302

Free energy landscape of a minimalist salt bridge model.

PubMed

Li, Xubin; Lv, Chao; Corbett, Karen M; Zheng, Lianqing; Wu, Dongsheng; Yang, Wei

2016-01-01

Salt bridges are essential to protein stability and dynamics. Despite the importance, there has been scarce of detailed discussion on how salt bridge partners interact with each other in distinct solvent exposed environments. In this study, employing a recent generalized orthogonal space tempering (gOST) method, we enabled efficient molecular dynamics simulation of repetitive breaking and reforming of salt bridge structures within a minimalist salt-bridge model, the Asp-Arg dipeptide and thereby were able to map its detailed free energy landscape in aqueous solution. Free energy surface analysis shows that although individually-solvated states are more favorable, salt-bridge states still occupy a noticeable portion of the overall population. Notably, the competing forces, e.g. intercharge attractions that drive the formation of salt bridges and solvation forces that pull the charged groups away from each other, are energetically comparable. As the result, the salt bridge stability is highly tunable by local environments; for instance when local water molecules are perturbed to interact more strongly with each other, the population of the salt-bridge states is likely to increase. Our results reveal the critical role of local solvent structures in modulating salt-bridge partner interactions and imply the importance of water fluctuations on conformational dynamics that involves solvent accessible salt bridge formations. © 2015 The Protein Society.

Rectification of nanopores in aprotic solvents - transport properties of nanopores with surface dipoles

NASA Astrophysics Data System (ADS)

Plett, Timothy; Shi, Wenqing; Zeng, Yuhan; Mann, William; Vlassiouk, Ivan; Baker, Lane A.; Siwy, Zuzanna S.

2015-11-01

Nanopores have become a model system to understand transport properties at the nanoscale. We report experiments and modeling of ionic current in aprotic solvents with different dipole moments through conically shaped nanopores in a polycarbonate film and through glass nanopipettes. We focus on solutions of the salt LiClO4, which is of great importance in modeling lithium based batteries. Results presented suggest ion current rectification observed results from two effects: (i) adsorption of Li+ ions to the pore walls, and (ii) a finite dipole moment rendered by adsorbed solvent molecules. Properties of surfaces in various solvents were probed by means of scanning ion conductance microscopy, which confirmed existence of an effectively positive surface potential in aprotic solvents with high dipole moments.Nanopores have become a model system to understand transport properties at the nanoscale. We report experiments and modeling of ionic current in aprotic solvents with different dipole moments through conically shaped nanopores in a polycarbonate film and through glass nanopipettes. We focus on solutions of the salt LiClO4, which is of great importance in modeling lithium based batteries. Results presented suggest ion current rectification observed results from two effects: (i) adsorption of Li+ ions to the pore walls, and (ii) a finite dipole moment rendered by adsorbed solvent molecules. Properties of surfaces in various solvents were probed by means of scanning ion conductance microscopy, which confirmed existence of an effectively positive surface potential in aprotic solvents with high dipole moments. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06340j

Assessing color vision loss among solvent-exposed workers.

PubMed

Mergler, D; Blain, L

1987-01-01

Acquired color vision loss has been associated with exposure to organic solvents in the workplace. However, not all tests of chromatic discrimination loss are designed to detect acquired, as opposed to congenital, loss. The Lanthony D-15 desaturated panel (D-15-d), a simple 15 cap color arrangement test, designed to identify mild acquired dyschromatopsia, can be administered rapidly in the field, under standard conditions. The objective of the present study was to evaluate the D-15-d among 23 solvent-exposed workers of a paint manufacturing plant, by comparing the results obtained with the D-15-d to those obtained with the Farnsworth-Munsell 100 Hue (FM-100), a highly sensitive measure of color vision loss. The D-15-d revealed a significantly higher prevalence of dyschromatopsia among the ten highly exposed workers (80%) as compared to the 13 moderately exposed workers (30.8%); FM-100 results revealed one false positive. All dyschromatopic workers presented blue-yellow loss; the FM-100 detected eight complex patterns, while the D-15-d identified 5. Comparison of D-15-d and FM-100 scores were highly correlated (corr. coeff. 0.87; p less than 0.001). Multiple regression analyses showed both scores to be significantly related to age and exposure level. The findings of this study indicate that the D-15-d is an adequate instrument for field study batteries. However, the FM-100 should be used for more detailed assessment.

Protein-style dynamical transition in a non-biological polymer and a non-aqueous solvent

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

Mamontov, E.; Sharma, V. K.; Borreguero, J. M.

Using neutron scattering and molecular dynamics simulation, techniques most often associated with protein dynamical transition studies, we have investigated the microscopic dynamics of one of the most common polymers, polystyrene, which was exposed to toluene vapor, mimicking the process of protein hydration from water vapor. Polystyrene with adsorbed toluene is an example of a solvent-solute system, which, unlike biopolymers, is anhydrous and lacks hydrogen bonding. Nevertheless, it exhibits the essential traits of the dynamical transition in biomolecules, such as a specific dependence of the microscopic dynamics of both solvent and host on the temperature and the amount of solvent adsorbed.more » Ultimately, we conclude that the protein dynamical transition is a manifestation of a universal solvent-solute dynamical relationship, which is not specific to either biomolecules as solute, or aqueous media as solvent, or even a particular type of interactions between solvent and solute.« less

Protein-style dynamical transition in a non-biological polymer and a non-aqueous solvent

DOE PAGES

Mamontov, E.; Sharma, V. K.; Borreguero, J. M.; ...

2016-03-15

Using neutron scattering and molecular dynamics simulation, techniques most often associated with protein dynamical transition studies, we have investigated the microscopic dynamics of one of the most common polymers, polystyrene, which was exposed to toluene vapor, mimicking the process of protein hydration from water vapor. Polystyrene with adsorbed toluene is an example of a solvent-solute system, which, unlike biopolymers, is anhydrous and lacks hydrogen bonding. Nevertheless, it exhibits the essential traits of the dynamical transition in biomolecules, such as a specific dependence of the microscopic dynamics of both solvent and host on the temperature and the amount of solvent adsorbed.more » Ultimately, we conclude that the protein dynamical transition is a manifestation of a universal solvent-solute dynamical relationship, which is not specific to either biomolecules as solute, or aqueous media as solvent, or even a particular type of interactions between solvent and solute.« less

Non-encapsulation approach for high-performance Li–S batteries through controlled nucleation and growth

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

Pan, Huilin; Chen, Junzheng; Cao, Ruiguo

Sulfur encapsulation in high surface area, nanoporous carbon is currently the most widely studied approach to improve the cycling stability of Li-S batteries. However, the relatively large amount of high surface area carbon decreases the overall volumetric energy density in the system and makes it difficult to compete with other battery chemistries. In this paper, we report a new approach that does not depend on sulfur encapsulation and high surface area carbon. We investigate the nucleation and deposition of sulfur using low surface area carbon in the cathode (surface area 17 m2 g-1). Optimization of the solvent properties and themore » deposition condition produce large spherical porous agglomerated particles rather than thin films. A solution mediated nucleation and growth mechanism is identified to form the large porous polysulfide particles. This new mechanism leads to close to 100% sulfur utilization, almost no capacity fading, over 99% coulombic efficacy, and high energy density (2350 Wh kg-1 and 2600 Wh L-1 based on overall mass/volume of cathode). This study may open a fundamentally new approach of using a low surface area carbon host for designing high energy Li-S battery by controlling the nucleation/growth pathway and morphology of sulfur species.« less

Computational design of cyclic peptides for the customized oriented immobilization of globular proteins.

PubMed

Soler, Miguel A; Rodriguez, Alex; Russo, Anna; Adedeji, Abimbola Feyisara; Dongmo Foumthuim, Cedrix J; Cantarutti, Cristina; Ambrosetti, Elena; Casalis, Loredana; Corazza, Alessandra; Scoles, Giacinto; Marasco, Daniela; Laio, Alessandro; Fortuna, Sara

2017-01-25

The oriented immobilization of proteins, key for the development of novel responsive biomaterials, relies on the availability of effective probes. These are generally provided by standard approaches based on in vivo maturation and in vitro selection of antibodies and/or aptamers. These techniques can suffer technical problems when a non-immunogenic epitope needs to be targeted. Here we propose a strategy to circumvent this issue by in silico design. In our method molecular binders, in the form of cyclic peptides, are computationally evolved by stochastically exploring their sequence and structure space to identify high-affinity peptides for a chosen epitope of a target globular protein: here a solvent-exposed site of β2-microglobulin (β2m). Designed sequences were screened by explicit solvent molecular dynamics simulations (MD) followed by experimental validation. Five candidates gave dose-response surface plasmon resonance signals with dissociation constants in the micromolar range. One of them was further analyzed by means of isothermal titration calorimetry, nuclear magnetic resonance, and 250 ns of MD. Atomic-force microscopy imaging showed that this peptide is able to immobilize β2m on a gold surface. In short, we have shown by a variety of experimental techniques that it is possible to capture a protein through an epitope of choice by computational design.

Pregnancy outcome after risk assessment of occupational exposure to organic solvents: a prospective cohort study.

PubMed

Testud, François; D'Amico, Andrea; Lambert-Chhum, Rachel; Garayt, Christelle; Descotes, Jacques

2010-11-01

A rational medical, occupational and toxicological approach is instrumental to select objectively among pregnant women exposed to chemicals at the workplace those who should be withdrawn or benefit from improvements of working conditions. Risk assessment is based on a comprehensive review of compounds' hazards and a thorough evaluation of the actual exposure including biomonitoring whenever as possible. Since 1996, the Lyon Poison Center has been conducting a prospective follow-up of pregnant women exposed to chemicals at the workplace. Of these, 206 exposed to organic solvents since conception were selected and matched with 206 exposed to a non-embryotoxic agent. Total withdrawal from the workplace was recommended in 22% of cases, but exposure was not considered to be hazardous to pregnancy in 51%. Overall, no increase in adverse outcomes was found. Maintaining pregnant women at their workplace, particularly most of the laboratory technicians, is reasonably possible after careful toxicological risk assessment. Copyright © 2010 Elsevier Inc. All rights reserved.

PMR Polyimide prepreg with improved tack characteristics. [Polymerization of Monomer Reactants applications to fiber reinforced plastics

NASA Technical Reports Server (NTRS)

Serafini, T. T.; Delvigs, P.

1978-01-01

Current PMR Polyimide prepreg technology utilizes methanol or ethanol solvents for preparation of the PMR prepreg solutions. The volatility of these solvents limits the tack and drape retention characteristics of unprotected prepreg exposed to ambient conditions. Studies conducted to achieve PMR 15 Polyimide prepreg with improved tack and drape characteristics are described. Improved tack and drape retention were obtained by incorporation of an additional monomer. The effects of various levels of the added monomer on the thermo-oxidative stability and mechanical properties of graphite fiber reinforced PMR 15 composites exposed and tested at 316 C (600 F) are discussed.

Apparatus for diffusion-gap thermal desalination

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

Lowenstein, Andrew

A thermal distillation apparatus including evaporation surfaces that are wetted with a solution, and from which at least some of the volatile solvent contained in the solution evaporates, condensers having an external surface in close proximity to, but not touching, a corresponding one of the one or more evaporation surfaces, and on which vapors of the solvent condense, releasing thermal energy that heats a flow of the solution moving upward within the condensers, spacers that prevent contact between the evaporating surfaces and the condensers, wherein spaces between the evaporating surfaces and the condensers are filled with a gaseous mixture composedmore » of solvent vapor and one or more non-condensable gases, and except for diffusion of the solvent vapor relative to the non-condensable gases, the gaseous mixture is stationary.« less

Variational Implicit Solvation with Solute Molecular Mechanics: From Diffuse-Interface to Sharp-Interface Models.

PubMed

Li, Bo; Zhao, Yanxiang

2013-01-01

Central in a variational implicit-solvent description of biomolecular solvation is an effective free-energy functional of the solute atomic positions and the solute-solvent interface (i.e., the dielectric boundary). The free-energy functional couples together the solute molecular mechanical interaction energy, the solute-solvent interfacial energy, the solute-solvent van der Waals interaction energy, and the electrostatic energy. In recent years, the sharp-interface version of the variational implicit-solvent model has been developed and used for numerical computations of molecular solvation. In this work, we propose a diffuse-interface version of the variational implicit-solvent model with solute molecular mechanics. We also analyze both the sharp-interface and diffuse-interface models. We prove the existence of free-energy minimizers and obtain their bounds. We also prove the convergence of the diffuse-interface model to the sharp-interface model in the sense of Γ-convergence. We further discuss properties of sharp-interface free-energy minimizers, the boundary conditions and the coupling of the Poisson-Boltzmann equation in the diffuse-interface model, and the convergence of forces from diffuse-interface to sharp-interface descriptions. Our analysis relies on the previous works on the problem of minimizing surface areas and on our observations on the coupling between solute molecular mechanical interactions with the continuum solvent. Our studies justify rigorously the self consistency of the proposed diffuse-interface variational models of implicit solvation.

Lid opening and conformational stability of T1 Lipase is mediated by increasing chain length polar solvents

PubMed Central

Mohamad Ali, Mohd Shukuri; Salleh, Abu Bakar; Rahman, Raja Noor Zaliha Raja Abd; Normi, Yahaya M.; Mohd Shariff, Fairolniza

2017-01-01

The dynamics and conformational landscape of proteins in organic solvents are events of potential interest in nonaqueous process catalysis. Conformational changes, folding transitions, and stability often correspond to structural rearrangements that alter contacts between solvent molecules and amino acid residues. However, in nonaqueous enzymology, organic solvents limit stability and further application of proteins. In the present study, molecular dynamics (MD) of a thermostable Geobacillus zalihae T1 lipase was performed in different chain length polar organic solvents (methanol, ethanol, propanol, butanol, and pentanol) and water mixture systems to a concentration of 50%. On the basis of the MD results, the structural deviations of the backbone atoms elucidated the dynamic effects of water/organic solvent mixtures on the equilibrium state of the protein simulations in decreasing solvent polarity. The results show that the solvent mixture gives rise to deviations in enzyme structure from the native one simulated in water. The drop in the flexibility in H2O, MtOH, EtOH and PrOH simulation mixtures shows that greater motions of residues were influenced in BtOH and PtOH simulation mixtures. Comparing the root mean square fluctuations value with the accessible solvent area (SASA) for every residue showed an almost correspondingly high SASA value of residues to high flexibility and low SASA value to low flexibility. The study further revealed that the organic solvents influenced the formation of more hydrogen bonds in MtOH, EtOH and PrOH and thus, it is assumed that increased intraprotein hydrogen bonding is ultimately correlated to the stability of the protein. However, the solvent accessibility analysis showed that in all solvent systems, hydrophobic residues were exposed and polar residues tended to be buried away from the solvent. Distance variation of the tetrahedral intermediate packing of the active pocket was not conserved in organic solvent systems, which could lead to weaknesses in the catalytic H-bond network and most likely a drop in catalytic activity. The conformational variation of the lid domain caused by the solvent molecules influenced its gradual opening. Formation of additional hydrogen bonds and hydrophobic interactions indicates that the contribution of the cooperative network of interactions could retain the stability of the protein in some solvent systems. Time-correlated atomic motions were used to characterize the correlations between the motions of the atoms from atomic coordinates. The resulting cross-correlation map revealed that the organic solvent mixtures performed functional, concerted, correlated motions in regions of residues of the lid domain to other residues. These observations suggest that varying lengths of polar organic solvents play a significant role in introducing dynamic conformational diversity in proteins in a decreasing order of polarity. PMID:28533982

40 CFR 52.253 - Metal surface coating thinner and reducer.

Code of Federal Regulations, 2010 CFR

2010-07-01

... PROGRAMS (CONTINUED) APPROVAL AND PROMULGATION OF IMPLEMENTATION PLANS California § 52.253 Metal surface... conform to paragraph (k) of § 52.254 so as to be defined as a nonphotochemically reactive solvent. (d...-photochemically reactive solvent. (e) If there is an inadequate supply of necessary solvent ingredients needed in...

Implicit Solvation Parameters Derived from Explicit Water Forces in Large-Scale Molecular Dynamics Simulations

PubMed Central

2012-01-01

Implicit solvation is a mean force approach to model solvent forces acting on a solute molecule. It is frequently used in molecular simulations to reduce the computational cost of solvent treatment. In the first instance, the free energy of solvation and the associated solvent–solute forces can be approximated by a function of the solvent-accessible surface area (SASA) of the solute and differentiated by an atom–specific solvation parameter σiSASA. A procedure for the determination of values for the σiSASA parameters through matching of explicit and implicit solvation forces is proposed. Using the results of Molecular Dynamics simulations of 188 topologically diverse protein structures in water and in implicit solvent, values for the σiSASA parameters for atom types i of the standard amino acids in the GROMOS force field have been determined. A simplified representation based on groups of atom types σgSASA was obtained via partitioning of the atom–type σiSASA distributions by dynamic programming. Three groups of atom types with well separated parameter ranges were obtained, and their performance in implicit versus explicit simulations was assessed. The solvent forces are available at http://mathbio.nimr.mrc.ac.uk/wiki/Solvent_Forces. PMID:23180979

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.

Influence of solvent polarity and supersaturation on template-induced nucleation of carbamazepine crystal polymorphs

NASA Astrophysics Data System (ADS)

Parambil, Jose V.; Poornachary, Sendhil K.; Tan, Reginald B. H.; Heng, Jerry Y. Y.

2017-07-01

Studies on the use of template surfaces to induce heterogeneous crystal nucleation have gained momentum in recent years-with potential applications in selective crystallisation of polymorphs and in the generation of seed crystals in a continuous crystallisation process. In developing a template-assisted solution crystallisation process, the kinetics of homogeneous versus heterogeneous crystal nucleation could be influenced by solute-solvent, solute-template, and solvent-template interactions. In this study, we report the effect of solvents of varying polarity on the nucleation of carbamazepine (CBZ) crystal polymorphs, a model active pharmaceutical ingredient. The experimental results demonstrate that functionalised template surfaces are effective in promoting crystallisation of either the metastable (form II) or stable (form III) polymorphs of CBZ only in moderately (methanol, ethanol, isopropanol) and low polar (toluene) solvents. A solvent with high polarity (acetonitrile) is thought to mask the template effect on heterogeneous nucleation due to strong solute-solvent and solvent-template interactions. The current study highlights that a quality-by-design (QbD) approach-considering the synergistic effects of solute concentration, solvent type, solution temperature, and template surface chemistry on crystal nucleation-is critical to the development of a template-induced crystallisation process.

On the theory of electric double layer with explicit account of a polarizable co-solvent.

PubMed

Budkov, Yu A; Kolesnikov, A L; Kiselev, M G

2016-05-14

We present a continuation of our theoretical research into the influence of co-solvent polarizability on a differential capacitance of the electric double layer. We formulate a modified Poisson-Boltzmann theory, using the formalism of density functional approach on the level of local density approximation taking into account the electrostatic interactions of ions and co-solvent molecules as well as their excluded volume. We derive the modified Poisson-Boltzmann equation, considering the three-component symmetric lattice gas model as a reference system and minimizing the grand thermodynamic potential with respect to the electrostatic potential. We apply present modified Poisson-Boltzmann equation to the electric double layer theory, showing that accounting for the excluded volume of co-solvent molecules and ions slightly changes the main result of our previous simplified theory. Namely, in the case of small co-solvent polarizability with its increase under the enough small surface potentials of electrode, the differential capacitance undergoes the significant growth. Oppositely, when the surface potential exceeds some threshold value (which is slightly smaller than the saturation potential), the increase in the co-solvent polarizability results in a differential capacitance decrease. However, when the co-solvent polarizability exceeds some threshold value, its increase generates a considerable enhancement of the differential capacitance in a wide range of surface potentials. We demonstrate that two qualitatively different behaviors of the differential capacitance are related to the depletion and adsorption of co-solvent molecules at the charged electrode. We show that an additive of the strongly polarizable co-solvent to an electrolyte solution can shift significantly the saturation potential in two qualitatively different manners. Namely, a small additive of strongly polarizable co-solvent results in a shift of saturation potential to higher surface potentials. On the contrary, a sufficiently large additive of co-solvent shifts the saturation potential to lower surface potentials. We obtain that an increase in the co-solvent polarizability makes the electrostatic potential profile longer-ranged. However, increase in the co-solvent concentration in the bulk leads to non-monotonic behavior of the electrostatic potential profile. An increase in the co-solvent concentration in the bulk at its sufficiently small values makes the electrostatic potential profile longer-ranged. Oppositely, when the co-solvent concentration in the bulk exceeds some threshold value, its further increase leads to decrease in electrostatic potential at all distances from the electrode.

The influence of sterilization on nitrogen-included ultrananocrystalline diamond for biomedical applications.

PubMed

Tong, Wei; Tran, Phong A; Turnley, Ann M; Aramesh, Morteza; Prawer, Steven; Brandt, Milan; Fox, Kate

2016-04-01

Diamond has shown great potential in different biomedical applications, but the effects of sterilization on its properties have not been investigated. Here, we studied the influence of five sterilization techniques (solvent cleaning, oxygen plasma, UV irradiation, autoclave and hydrogen peroxide) on nitrogen-included ultrananocrystalline diamond. The chemical modification of the diamond surface was evaluated using X-ray photoelectron spectroscopy and water contact angle measurements. Different degrees of surface oxidation and selective sp(2) bonded carbon etching were found following all sterilization techniques, resulting in an increase of hydrophilicity. Higher viabilities of in vitro mouse 3T3 fibroblasts and rat cortical neuron cells were observed on oxygen plasma, autoclave and hydrogen peroxide sterilized diamond, which correlated with their higher hydrophilicity. By examination of apatite formation in simulated body fluid, in vivo bioactivity was predicted to be best on those surfaces which have been oxygen plasma treated and lowest on those which have been exposed to UV irradiation. The charge injection properties were also altered by the sterilization process and there appears to be a correlation between these changes and the degree of oxygen termination of the surface. We find that the modification brought by autoclave, oxygen plasma and hydrogen peroxide were most consistent with the use of N-UNCD in biological applications as compared to samples sterilized by solvent cleaning or UV exposure or indeed non-sterilized. A two-step process of sterilization by hydrogen peroxide following oxygen plasma treatment was then suggested. However, the final choice of sterilization technique will depend on the intended end application. Copyright © 2015 Elsevier B.V. All rights reserved.

Mechanisms of Enhanced Hemoglobin Electroactivity on Carbon Electrodes upon Exposure to a Water-Miscible Primary Alcohol.

PubMed

Tom, Justin; Jakubec, Philip J; Andreas, Heather A

2018-05-01

Exposing a carbon electrode to hemoglobin (Hb) and alcoholic solvents, such as methanol, ethanol or 1-propanol, drastically changes Hb electroactivity, but until this work, the important underlying mechanisms were unclear. For the first time, we show that these alcohols impact Hb electroactivity via three mechanisms: modification of the carbon surface oxides on the glassy carbon (GC) electrode, Hb film formation, and structural changes to Hb. C 1s X-ray photoelectron spectroscopy provided evidence for significant alcohol-induced modification of the carbon surface oxides, and differential pulse voltammetry showed links between these modifications and Hb electroactivity. Spectroscopic ellipsometry showed that Hb films formed during exposure to Hb- and alcohol-containing electrolytes increased in thickness with increasing alcohol content, although film thickness played only a minor role in Hb electroactivity. Alcohol-induced structural changes in Hb are confirmed with UV-visible absorption and fluorescence data, showing that Hb denaturation also was a significant factor in increasing Hb electroactivity. Carbon-surface-oxide modification and Hb denaturation worked in tandem to maximally increase the Hb electroactivity in 60% methanol. While in ethanol and 1-propanol, the significant increases in Hb electroactivity caused by Hb denaturation were offset by an increase in Hb-inhibiting carbon surface oxides. Knowledge of these mechanisms shows the impact of alcohols on both Hb and carbon electrodes, allows for thoughtful design of the Hb-sensing system, is vital for proper analysis of Hb electroactivity in the presence of these alcohols (e.g., when used as binder solvents for immobilizing Hb into films), and provides fundamental understanding of the Hb-carbon interactions.

The Hinge Region as a Key Regulatory Element of Androgen Receptor Dimerization, DNA Binding and Transactivation

DTIC Science & Technology

2006-05-01

Mutations in the human androgen receptor gene as a learning tool for molecular endocrinology’ III. Poster presentations at international meetings...nonconsensus half-site, the cognate half-complex buries slightly more surface area from solvent (1,230 Å2) than the noncognate one (960 Å2). AR Mutations ...energetic penalty in- Fig. 4. (A) The AR DBD dimer interface. The molecular surfaces of the AR subunits are shown in red and blue. Dashed black lines

Functionalization of CNTs surface with phosphonuim based deep eutectic solvents for arsenic removal from water

NASA Astrophysics Data System (ADS)

AlOmar, Mohamed Khalid; Alsaadi, Mohammed Abdulhakim; Hayyan, Maan; Akib, Shatirah; Hashim, Mohd Ali

2016-12-01

Herein, we present the use of deep eutectic solvent (DES) as functionalization agents for carbon nanotubes (CNTs) to form novel adsorbents for removal of arsenic ions (As3+) from water. Two DESs systems were prepared using methyltriphenylphosphonium bromide (MTPB) and benzyltriphenylphosphonium chloride (BTPC) as salts, in conjugation with glycerol (Gly) as a hydrogen bond donor. The resulting novel adsorbents were characterized using thermogravimetric analysis (TGA), Zeta potential, Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, XRD, EDX, FESEM, and BET surface area. Optimization studies were carried out utilizing RSM-CCD experimental design to estimate the optimum removal conditions for each adsorbent. The adsorption experimental data of both adsorbents were found to fit well with pseudo-second-order kinetics model, as well as with Langmuir and Freundlich adsorption isotherm models. The maximum adsorption capacity of a MTPB-DES-functionalized CNTs adsorbent was 23.4 mg/g.

Computational screening of biomolecular adsorption and self-assembly on nanoscale surfaces.

PubMed

Heinz, Hendrik

2010-05-01

The quantification of binding properties of ions, surfactants, biopolymers, and other macromolecules to nanometer-scale surfaces is often difficult experimentally and a recurring challenge in molecular simulation. A simple and computationally efficient method is introduced to compute quantitatively the energy of adsorption of solute molecules on a given surface. Highly accurate summation of Coulomb energies as well as precise control of temperature and pressure is required to extract the small energy differences in complex environments characterized by a large total energy. The method involves the simulation of four systems, the surface-solute-solvent system, the solute-solvent system, the solvent system, and the surface-solvent system under consideration of equal molecular volumes of each component under NVT conditions using standard molecular dynamics or Monte Carlo algorithms. Particularly in chemically detailed systems including thousands of explicit solvent molecules and specific concentrations of ions and organic solutes, the method takes into account the effect of complex nonbond interactions and rotational isomeric states on the adsorption behavior on surfaces. As a numerical example, the adsorption of a dodecapeptide on the Au {111} and mica {001} surfaces is described in aqueous solution. Copyright 2009 Wiley Periodicals, Inc.

Adsorption behavior of acetone solvent at the HMX crystal faces: A molecular dynamics study.

PubMed

Liu, Yingzhe; Yu, Tao; Lai, Weipeng; Ma, Yiding; Kang, Ying; Ge, Zhongxue

2017-06-01

Molecular dynamics simulations have been performed to understand the adsorption behavior of acetone (AC) solvent at the three surfaces of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctan (HMX) crystal, i.e. (011), (110), and (020) faces. The simulation results show that the structural features and electrostatic potentials of crystal faces are determined by the HMX molecular packing, inducing distinct mass density distribution, dipole orientation, and diffusion of solvent molecules in the interfacial regions. The solvent adsorption is mainly governed by the van der Waals forces, and the crystal-solvent interaction energies among three systems are ranked as (020)≈(110)>(011). The adsorption sites for solvent incorporation at the crystal surface were found and visualized with the aid of occupancy analysis. A uniform arrangement of adsorption sites is observed at the rough (020) surface as a result of ordered adsorption motif. Copyright © 2017 Elsevier Inc. All rights reserved.

Developmental toxicity of prenatal exposure to toluene.

PubMed

Bowen, Scott E; Hannigan, John H

2006-01-01

Organic solvents have become ubiquitous in our environment and are essential for industry. Many women of reproductive age are increasingly exposed to solvents such as toluene in occupational settings (ie, long-term, low-concentration exposures) or through inhalant abuse (eg, episodic, binge exposures to high concentrations). The risk for teratogenic outcome is much less with low to moderate occupational solvent exposure compared with the greater potential for adverse pregnancy outcomes, developmental delays, and neurobehavioral problems in children born to women exposed to high concentrations of abused organic solvents such as toluene, 1,1,1-trichloroethane, xylenes, and nitrous oxide. Yet the teratogenic effects of abuse patterns of exposure to toluene and other inhalants remain understudied. We briefly review how animal models can aid substantially in clarifying the developmental risk of exposure to solvents for adverse biobehavioral outcomes following abuse patterns of use and in the absence of associated health problems and co-drug abuse (eg, alcohol). Our studies also begin to establish the importance of dose (concentration) and critical perinatal periods of exposure to specific outcomes. The present results with our clinically relevant animal model of repeated, brief, high-concentration binge prenatal toluene exposure demonstrate the dose-dependent effect of toluene on prenatal development, early postnatal maturation, spontaneous exploration, and amphetamine-induced locomotor activity. The results imply that abuse patterns of toluene exposure may be more deleterious than typical occupational exposure on fetal development and suggest that animal models are effective in studying the mechanisms and risk factors of organic solvent teratogenicity.

43 CFR 11.63 - Injury determination phase-pathway determination.

Code of Federal Regulations, 2011 CFR

2011-10-01

...; and (C) Depth of exposed bed, bank, or shoreline sediments. (ii) As appropriate to the exposed... adhered to, bound to, or otherwise covered surface tissue, or was ingested, or inhaled but not assimilated, the area of dispersion may be determined based upon chemical analysis of the appropriate tissues or...

43 CFR 11.63 - Injury determination phase-pathway determination.

Code of Federal Regulations, 2013 CFR

2013-10-01

...; and (C) Depth of exposed bed, bank, or shoreline sediments. (ii) As appropriate to the exposed... adhered to, bound to, or otherwise covered surface tissue, or was ingested, or inhaled but not assimilated, the area of dispersion may be determined based upon chemical analysis of the appropriate tissues or...

43 CFR 11.63 - Injury determination phase-pathway determination.

Code of Federal Regulations, 2014 CFR

2014-10-01

...; and (C) Depth of exposed bed, bank, or shoreline sediments. (ii) As appropriate to the exposed... adhered to, bound to, or otherwise covered surface tissue, or was ingested, or inhaled but not assimilated, the area of dispersion may be determined based upon chemical analysis of the appropriate tissues or...

30 CFR 77.508 - Lightning arresters, ungrounded and exposed power conductors and telephone wires.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Lightning arresters, ungrounded and exposed... AND SURFACE WORK AREAS OF UNDERGROUND COAL MINES Electrical Equipment-General § 77.508 Lightning... conductors and telephone wires shall be equipped with suitable lightning arresters which are adequately...

30 CFR 77.508 - Lightning arresters, ungrounded and exposed power conductors and telephone wires.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Lightning arresters, ungrounded and exposed... AND SURFACE WORK AREAS OF UNDERGROUND COAL MINES Electrical Equipment-General § 77.508 Lightning... conductors and telephone wires shall be equipped with suitable lightning arresters which are adequately...

30 CFR 77.508 - Lightning arresters, ungrounded and exposed power conductors and telephone wires.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Lightning arresters, ungrounded and exposed... AND SURFACE WORK AREAS OF UNDERGROUND COAL MINES Electrical Equipment-General § 77.508 Lightning... conductors and telephone wires shall be equipped with suitable lightning arresters which are adequately...

Evaluation of neuropsychological symptoms and exposure to benzene, toluene and xylene among two different furniture worker groups in Izmir.

PubMed

Mandiracioglu, Aliye; Akgur, Serap; Kocabiyik, Nesrin; Sener, Ufuk

2011-10-01

This study was conducted to determine whether there was any exposure to toluene, xylene and benzene and to assess the health impact of these solvents on workers in furniture enterprises in Karabaglar, Izmir. This cross-sectional study covered furniture enterprises in Karabaglar, Izmir. This study was comprised of an exposed group consisting of workers engaged in painting and varnishing and therefore exposed either directly or indirectly toluene, xylene and benzene in the workplace and the non-exposed group engaged in other aspects of production. While a total of 261 individuals completed questionnaires, 210 workers agreed to provide blood samples. Blood solvents levels were determined using gas chromatograph at Ege University, Intoxication Research and Application Centre. The modified EUROQUEST questionnaire was used to assess neuropsychological symptoms and neurological and general examination were performed. Occupational and exposure history, demographic and work-related information was collected. In this study of workers, blood toluene and benzene levels were found to be significantly higher among those engaged in painting and varnishing compared to those who perform other tasks. The average blood toluene and benzene concentrations among exposed workers were 6.95 times and 1.64 times respectively higher than those in the nonexposed groups. Smokers and participants who worked in excess of 8 hours/day had higher blood toluene and benzene levels. The most frequently work-related health complaints were back pain, allergies and asthma. No differences were found in the average scores in the neuropsychological symptoms questionnaire between exposed and non-exposed groups. Neurological examination of two individuals with these complaints revealed a loss of reflexes. The workers were unaware that they were being exposed to solvents at work. Tobacco smoke is a major source of internal exposure to benzene. Improving working conditions in furniture work places is a priority.

40 CFR 63.5753 - How do I calculate the combined organic HAP content of aluminum wipedown solvents and aluminum...

Code of Federal Regulations, 2010 CFR

2010-07-01

... HAP content of aluminum wipedown solvents and aluminum recreational boat surface coatings? 63.5753... Standards for Hazardous Air Pollutants for Boat Manufacturing Standards for Aluminum Recreational Boat... wipedown solvents and aluminum recreational boat surface coatings? (a) Use equation 1 of this section to...

40 CFR 63.5753 - How do I calculate the combined organic HAP content of aluminum wipedown solvents and aluminum...

Code of Federal Regulations, 2011 CFR

2011-07-01

... HAP content of aluminum wipedown solvents and aluminum recreational boat surface coatings? 63.5753... Standards for Hazardous Air Pollutants for Boat Manufacturing Standards for Aluminum Recreational Boat... wipedown solvents and aluminum recreational boat surface coatings? (a) Use equation 1 of this section to...

High yield synthesis of Ni-BTC metal-organic framework with ultrasonic irradiation: Role of polar aprotic DMF solvent.

PubMed

Israr, Farrukh; Chun, Daye; Kim, Yeongmin; Kim, Duk Kyung

2016-07-01

Nickel based porous solid was synthesized with 20 kHz ultrasonic irradiation. The reaction of Ni(II) nitrate hexahydrate with 1,3,5-benzene tricarboxylic acid in N,N-Dimethylformamide (DMF) as the sole solvent under ultrasonic radiation produced porous Ni-BTC MOF. Choice of correct solvent for the ultrasonic treatment was proven important. The effect of varying ultrasonic powers (40%, 60% and 80% of 750 W) along with different temperature conditions (50 °C, 60 °C, 70 °C and 80 °C) influenced the respective yield. A very high yield of 88% Ni-BTC MOF was obtained from 80% ultrasonic power at 60 °C. BET surface areas of the MOF crystals measured by N2 gas adsorption isotherms were in the range of 960-1000 m(2)/g. Copyright © 2015 Elsevier B.V. All rights reserved.

Bubbles in solvent microextraction: the influence of intentionally introduced bubbles on extraction efficiency.

PubMed

Williams, D Bradley G; George, Mosotho J; Meyer, Riaan; Marjanovic, Ljiljana

2011-09-01

Significant improvements to microdrop extractions of triazine pesticides are realized by the intentional incorporation of an air bubble into the solvent microdroplet used in this microextraction technique. The increase is attributed partly to greater droplet surface area resulting from the air bubble being incorporated into the solvent droplet as opposed to it sitting thereon and partly to thin film phenomena. The method is useful at nanogram/liter levels (LOD 0.002-0.012 μg/L, LOQ 0.007-0.039 μg/L), is precise (7-12% at 10 μg/L concentration level), and is validated against certified reference materials containing 0.5 and 5.0 μg/L analyte. It tolerates water and fruit juice as matrixes without serious matrix effects. This new development brings a simple, inexpensive, and efficient preconcentration technique to bear which rivals solid phase microextraction methods.

Rectification of nanopores in aprotic solvents--transport properties of nanopores with surface dipoles.

PubMed

Plett, Timothy; Shi, Wenqing; Zeng, Yuhan; Mann, William; Vlassiouk, Ivan; Baker, Lane A; Siwy, Zuzanna S

2015-12-07

Nanopores have become a model system to understand transport properties at the nanoscale. We report experiments and modeling of ionic current in aprotic solvents with different dipole moments through conically shaped nanopores in a polycarbonate film and through glass nanopipettes. We focus on solutions of the salt LiClO4, which is of great importance in modeling lithium based batteries. Results presented suggest ion current rectification observed results from two effects: (i) adsorption of Li(+) ions to the pore walls, and (ii) a finite dipole moment rendered by adsorbed solvent molecules. Properties of surfaces in various solvents were probed by means of scanning ion conductance microscopy, which confirmed existence of an effectively positive surface potential in aprotic solvents with high dipole moments.

ELECTRORETINOGRAMS ARE ALTERED BY SUBCHRONIC TOLUENE EXPOSURE TO LONG EVANS RATS: EXPERIMENTAL EVIDENCE SUPPORTING OBSERVATIONS FROM STUDIES OF EXPOSED HUMANS

EPA Science Inventory

Impaired visual functions, including low contrast sensitivity and reduced color discrimination, have been reported in studies of humans chronically exposed to several volatile organic solvents. These reports remain controversial, however, in part due to a lack of confirmation fro...

Subchronic Toluene Exposure alters Retinal Function in Long Evans Rats: Experimental Evidence Supporting Observations from Studies of Exposed Humans.

EPA Science Inventory

Studies of humans chronically exposed to volatile organic solvents commonly report impaired visual functions, including low contrast sensitivity and reduced color discrimination. These reports have been controversial, however, in part due to a lack of confirmation from controlled...

The National Shipbuilding Research Program. Update Handbook for Surface Preparation and Coatings in Tanks and Confined Areas

DTIC Science & Technology

2000-10-31

cleaning method are described in Naval Ships’ Technical Manual Chapter 631. 4.6.4 Citric Acid Cleaning The citric acid cleaning system is intended to...acquisition of necessary chemicals and tools, degreasing/cleaning, paint/stripping/removal, citric acid rust removal, passivation of bare steel, and drying...Figure 9-7 Hanging Explosion -Proof Light Box • Figure 9-8 Lighting in Tank • Figure 10-1 Hazardous Waste Storage Area • Figure 10-2 Solvent

Defined drug release from 3D-printed composite tablets consisting of drug-loaded polyvinylalcohol and a water-soluble or water-insoluble polymer filler.

PubMed

Tagami, Tatsuaki; Nagata, Noriko; Hayashi, Naomi; Ogawa, Emi; Fukushige, Kaori; Sakai, Norihito; Ozeki, Tetsuya

2018-05-30

3D-printed tablets are a promising new approach for personalized medicine. In this study, we fabricated composite tablets consisting of two components, a drug and a filler, by using a fused deposition modeling-type 3D printer. Polyvinylalcohol (PVA) polymer containing calcein (a model drug) was used as the drug component and PVA or polylactic acid (PLA) polymer without drug was used as the water-soluble or water-insoluble filler, respectively. Various kinds of drug-PVA/PVA and drug-PVA/PLA composite tablets were designed, and the 3D-printed tablets exhibited good formability. The surface area of the exposed drug component is highly correlated with the initial drug release rate. Composite tablets with an exposed top and a bottom covered with a PLA layer were fabricated. These tablets showed zero-order drug release by maintaining the surface area of the exposed drug component during drug dissolution. In contrast, the drug release profile varied for tablets whose exposed surface area changed. Composite tablets with different drug release lag times were prepared by changing the thickness of the PVA filler coating the drug component. These results which used PVA and PLA filler will provide useful information for preparing the tablets with multi-components and tailor-made tablets with defined drug release profiles using 3D printers. Copyright © 2018 Elsevier B.V. All rights reserved.

Unified interpretation of exciplex formation and marcus electron transfer on the basis of two-dimensional free energy surfaces.

PubMed

Murata, Shigeo; Tachiya, M

2007-09-27

The mechanism of exciplex formation proposed in a previous paper has been refined to show how exciplex formation and Marcus electron transfer (ET) in fluorescence quenching are related to each other. This was done by making simple calculations of the free energies of the initial (DA*) and final (D+A-) states of ET. First it was shown that the decrease in D-A distance can induce intermolecular ET even in nonpolar solvents where solvent orientational polarization is absent, and that it leads to exciplex formation. This is consistent with experimental results that exciplex is most often observed in nonpolar solvents. The calculation was then extended to ET in polar solvents where the free energies are functions of both D-A distance and solvent orientational polarization. This enabled us to discuss both exciplex formation and Marcus ET in the same D-A pair and solvent on the basis of 2-dimensional free energy surfaces. The surfaces contain more information about the rates of these reactions, the mechanism of fluorescence quenching by ET, etc., than simple reaction schemes. By changing the parameters such as the free energy change of reaction, solvent dielectric constants, etc., one can construct the free energy surfaces for various systems. The effects of free energy change of reaction and of solvent polarity on the mechanism and relative importance of exciplex formation and Marcus ET in fluorescence quenching can be well explained. The free energy surface will also be useful for discussion of other phenomena related to ET reactions.

Alcohols Reduce Lateral Membrane Pressures: Predictions from Molecular Theory

PubMed Central

Frischknecht, Amalie L.; Frink, Laura J. Douglas

2006-01-01

We explore the effects of alcohols on fluid lipid bilayers using a molecular theory with a coarse-grained model. We show that the trends predicted from the theory in the changes in area per lipid, alcohol concentration in the bilayer, and area compressibility modulus, as a function of alcohol chain length and of the alcohol concentration in the solvent far from the bilayer, follow those found experimentally. We then use the theory to study the effect of added alcohol on the lateral pressure profile across the membrane, and find that added alcohol reduces the surface tensions at both the headgroup/solvent and headgroup/tailgroup interfaces, as well as the lateral pressures in the headgroup and tailgroup regions. These changes in lateral pressures could affect the conformations of membrane proteins, providing a nonspecific mechanism for the biological effects of alcohols on cells. PMID:16980354

The Effects of Secondary Oxides on Copper-Based Catalysts for Green Methanol Synthesis.

PubMed

Hayward, James S; Smith, Paul J; Kondrat, Simon A; Bowker, Michael; Hutchings, Graham J

2017-05-10

Catalysts for methanol synthesis from CO 2 and H 2 have been produced by two main methods: co-precipitation and supercritical anti-solvent (SAS) precipitation. These two methods are compared, along with the behaviour of copper supported on Zn, Mg, Mn, and Ce oxides. Although the SAS method produces initially active material with high Cu specific surface area, they appear to be unstable during reaction losing significant amounts of surface area and hence activity. The CuZn catalysts prepared by co-precipitation, however, showed much greater thermal and reactive stability than the other materials. There appeared to be the usual near-linear dependence of activity upon Cu specific area, though the initial performance relationship was different from that post-reaction, after some loss of surface area. The formation of the malachite precursor, as reported before, is important for good activity and stability, whereas if copper oxides are formed during the synthesis and ageing process, then a detrimental effect on these properties is seen.

The Effects of Secondary Oxides on Copper‐Based Catalysts for Green Methanol Synthesis

PubMed Central

Hayward, James S.; Smith, Paul J.; Kondrat, Simon A.; Bowker, Michael

2017-01-01

Abstract Catalysts for methanol synthesis from CO2 and H2 have been produced by two main methods: co‐precipitation and supercritical anti‐solvent (SAS) precipitation. These two methods are compared, along with the behaviour of copper supported on Zn, Mg, Mn, and Ce oxides. Although the SAS method produces initially active material with high Cu specific surface area, they appear to be unstable during reaction losing significant amounts of surface area and hence activity. The CuZn catalysts prepared by co‐precipitation, however, showed much greater thermal and reactive stability than the other materials. There appeared to be the usual near‐linear dependence of activity upon Cu specific area, though the initial performance relationship was different from that post‐reaction, after some loss of surface area. The formation of the malachite precursor, as reported before, is important for good activity and stability, whereas if copper oxides are formed during the synthesis and ageing process, then a detrimental effect on these properties is seen. PMID:28706570

Low-Temperature, Solution-Processed, Transparent Zinc Oxide-Based Thin-Film Transistors for Sensing Various Solvents.

PubMed

You, Hsin-Chiang; Wang, Cheng-Jyun

2017-02-26

A low temperature solution-processed thin-film transistor (TFT) using zinc oxide (ZnO) film as an exposed sensing semiconductor channel was fabricated to detect and identify various solution solvents. The TFT devices would offer applications for low-cost, rapid and highly compatible water-soluble detection and could replace conventional silicon field effect transistors (FETs) as bio-sensors. In this work, we demonstrate the utility of the TFT ZnO channel to sense various liquids, such as polar solvents (ethanol), non-polar solvents (toluene) and deionized (DI) water, which were dropped and adsorbed onto the channel. It is discussed how different dielectric constants of polar/non-polar solvents and DI water were associated with various charge transport properties, demonstrating the main detection mechanisms of the thin-film transistor.

Brain damage in a large cohort of solvent abusers.

PubMed

Al-Hajri, Zahra; Del Bigio, Marc R

2010-04-01

The neuropathology of solvent inhalation consists of patchy myelin loss with white matter macrophages that contain granular inclusions. It has been described only in a small number of cases. We sought to characterize the abnormalities in greater detail. In a retrospective study from 1995 to 2009, we encountered 88 autopsy cases with documented history of solvent abuse by inhalation and 1 with industrial exposure. Among these are 6 fetuses and infants with maternal exposure, 23 children (12-17 years), and 60 adults (18-66 years). Available brain samples from 75 cases were stained with solochrome cyanein (to demonstrate myelin) and periodic acid-Schiff (PAS) (to highlight the inclusions). Forty brains of ethanol and/or illicit drug exposed individuals and ten cases of multiple sclerosis were examined as controls. We found that 16 cases (age 23-49, median 37 years) had well-established leukoencephalopathy with multifocal myelin loss and abundant macrophages that stain with PAS and which contain birefringent inclusions. Six cases (age 15-55, median 27 years) had early leukoencephalopathy with scattered macrophages but no obvious myelin changes. Clusters of PAS-staining but non-birefringent macrophages were seen in 2/10 cases of (active) multiple sclerosis and in none of the ethanol/drug exposed brains. Ultrastructurally, inclusions from solvent cases differed from multiple sclerosis cases. Although exposure to solvents is impossible to quantify, there appears to be a duration-dependent effect. Brain damage related to solvent abuse can begin within only a few years of the onset. In the context of substance abuse, the changes are relatively specific for solvent inhalation and do not appear to result from demyelination alone. Interaction with ethanol cannot be excluded as a compounding risk factor.

Potential contribution of exposed resin to ecosystem emissions of monoterpenes

NASA Astrophysics Data System (ADS)

Eller, Allyson S. D.; Harley, Peter; Monson, Russell K.

2013-10-01

Conifers, especially pines, produce and store under pressure monoterpene-laden resin in canals located throughout the plant. When the plants are damaged and resin canals punctured, the resin is exuded and the monoterpenes are released into the atmosphere, a process that has been shown to influence ecosystem-level monoterpene emissions. Less attention has been paid to the small amounts of resin that are exuded from branches, expanding needles, developing pollen cones, and terminal buds in the absence of any damage. The goal of this study was to provide the first estimate of the potential of this naturally-exposed resin to influence emissions of monoterpenes from ponderosa pine (Pinus ponderosa) ecosystems. When resin is first exuded as small spherical beads from undamaged tissues it emits monoterpenes to the atmosphere at a rate that is four orders of magnitude greater than needle tissue with an equivalent exposed surface area and the emissions from exuded beads decline exponentially as the resin dries. We made measurements of resin beads on the branches of ponderosa pine trees in the middle of the growing season and found, on average, 0.15 cm2 of exposed resin bead surface area and 1250 cm2 of total needle surface area per branch tip. If the resin emerged over the course of 10 days, resin emissions would make up 10% of the ecosystem emissions each day. Since we only accounted for exposed resin at a single point in time, this is probably an underestimate of how much total resin is exuded from undamaged pine tissues over the course of a growing season. Our observations, however, reveal the importance of this previously unrecognized source of monoterpenes emitted from pine forests and its potential to influence regional atmospheric chemistry dynamics.

Exposure of Water Ice in the Northern Mid-lattitudes of Mars

NASA Technical Reports Server (NTRS)

Allen, Carlton C.; Kanner, Lisa C.

2007-01-01

Water ice is exposed in the martian north polar cap, and is occasionally exposed beyond the cap boundary. Orbital gamma ray spectrometry data strongly imply the presence of water ice within meters of the surface at latitudes north of approximately 60 deg. We have examined midlatitude areas of the northern plains displaying evidence of residual ice-rich layers, and report possible present-day exposures of ice. These exposures, if confirmed, could constrain the latitudinal and temporal stability of surface ice on Mars.

Solvent Vapor Annealing of Amorphous Carbamazepine Films for Fast Polymorph Screening and Dissolution Alteration.

PubMed

Schrode, Benedikt; Bodak, Brigitta; Riegler, Hans; Zimmer, Andreas; Christian, Paul; Werzer, Oliver

2017-09-30

Solubility enhancement and thus higher bioavailability are of great importance and a constant challenge in pharmaceutical research whereby polymorph screening and selection is one of the most important tasks. A very promising approach for polymorph screening is solvent vapor annealing where a sample is exposed to an atmosphere saturated with molecules of a specific chemical/solvent. In this work, amorphous carbamazepine thin films were prepared by spin coating, and the transformation into crystalline forms under exposure to solvent vapors was investigated. Employing grazing incidence X-ray diffraction, four distinct carbamazepine polymorphs, a solvate, and hydrates could be identified, while optical microscopy showed mainly spherulitic morphologies. In vitro dissolution experiments revealed different carbamazepine release from the various thin-film samples containing distinct polymorphic compositions: heat treatment of amorphous samples at 80 °C results in an immediate release; samples exposed to EtOH vapors show a drug release about 5 times slower than this immediate one; and all the others had intermediate release profiles. Noteworthy, even the sample of slowest release has a manifold faster release compared to a standard powder sample demonstrating the capabilities of thin-film preparation for faster drug release in general. Despite the small number of samples in this screening experiment, the results clearly show how solvent vapor annealing can assist in identifying potential polymorphs and allows for estimating their impact on properties like bioavailability.

Crystal Structure of the Bovine lactadherin C2 Domain, a Membrane Binding Motif, Shows Similarity to the C2 Domains of Factor V and Factor VIII

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

Lin,L.

2007-01-01

Lactadherin, a glycoprotein secreted by a variety of cell types, contains two EGF domains and two C domains with sequence homology to the C domains of blood coagulation proteins factor V and factor VIII. Like these proteins, lactadherin binds to phosphatidylserine (PS)-containing membranes with high affinity. We determined the crystal structure of the bovine lactadherin C2 domain (residues 1 to 158) at 2.4 {angstrom}. The lactadherin C2 structure is similar to the C2 domains of factors V and VIII (rmsd of C{sub {alpha}} atoms of 0.9 {angstrom} and 1.2 {angstrom}, and sequence identities of 43% and 38%, respectively). The lactadherinmore » C2 domain has a discoidin-like fold containing two {beta}-sheets of five and three antiparallel {beta}-strands packed against one another. The N and C termini are linked by a disulfide bridge between Cys1 and Cys158. One {beta}-turn and two loops containing solvent-exposed hydrophobic residues extend from the C2 domain {beta}-sandwich core. In analogy with the C2 domains of factors V and VIII, some or all of these solvent-exposed hydrophobic residues, Trp26, Leu28, Phe31, and Phe81, likely participate in membrane binding. The C2 domain of lactadherin may serve as a marker of cell surface phosphatidylserine exposure and may have potential as a unique anti-thrombotic agent.« less

Crystal Structure of the Bovine lactadherin C2 Domain, a Membrane Binding Motif, Shows Similarity of the C2 Domains of Factor V and Factor VIII

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

Lin,L.; Huai, Q.; Huang, M.

2007-01-01

Lactadherin, a glycoprotein secreted by a variety of cell types, contains two EGF domains and two C domains with sequence homology to the C domains of blood coagulation proteins factor V and factor VIII. Like these proteins, lactadherin binds to phosphatidylserine (PS)-containing membranes with high affinity. We determined the crystal structure of the bovine lactadherin C2 domain (residues 1 to 158) at 2.4 Angstroms. The lactadherin C2 structure is similar to the C2 domains of factors V and VIII (rmsd of C? atoms of 0.9 Angstroms and 1.2 Angstroms, and sequence identities of 43% and 38%, respectively). The lactadherin C2more » domain has a discoidin-like fold containing two ?-sheets of five and three antiparallel ?-strands packed against one another. The N and C termini are linked by a disulfide bridge between Cys1 and Cys158. One ?-turn and two loops containing solvent-exposed hydrophobic residues extend from the C2 domain ?-sandwich core. In analogy with the C2 domains of factors V and VIII, some or all of these solvent-exposed hydrophobic residues, Trp26, Leu28, Phe31, and Phe81, likely participate in membrane binding. The C2 domain of lactadherin may serve as a marker of cell surface phosphatidylserine exposure and may have potential as a unique anti-thrombotic agent.« less

The extraction of bitumen from western oil sands. Final report, July 1989--September 1993

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

Oblad, A.G.; Bunger, J.W.; Dahlstrom, D.A.

1994-03-01

Research and development of surface extraction and upgrading processes of western tar sands are described. Research areas included modified hot water, fluidized bed, and rotary kiln pyrolysis of tar sands for extraction of bitumen. Bitumen upgrading included solvent extraction of bitumen, and catalytic hydrotreating of bitumen. Characterization of Utah tar sand deposits is also included.

Rapid assessment of oxidation via middle-down LCMS correlates with methionine side-chain solvent-accessible surface area for 121 clinical stage monoclonal antibodies.

PubMed

Yang, Rong; Jain, Tushar; Lynaugh, Heather; Nobrega, R Paul; Lu, Xiaojun; Boland, Todd; Burnina, Irina; Sun, Tingwan; Caffry, Isabelle; Brown, Michael; Zhi, Xiaoyong; Lilov, Asparouh; Xu, Yingda

Susceptibility of methionine to oxidation is an important concern for chemical stability during the development of a monoclonal antibody (mAb) therapeutic. To minimize downstream risks, leading candidates are usually screened under forced oxidation conditions to identify oxidation-labile molecules. Here we report results of forced oxidation on a large set of in-house expressed and purified mAbs with variable region sequences corresponding to 121 clinical stage mAbs. These mAb samples were treated with 0.1% H 2 O 2 for 24 hours before enzymatic cleavage below the hinge, followed by reduction of inter-chain disulfide bonds for the detection of the light chain, Fab portion of heavy chain (Fd) and Fc by liquid chromatography-mass spectrometry. This high-throughput, middle-down approach allows detection of oxidation site(s) at the resolution of 3 distinct segments. The experimental oxidation data correlates well with theoretical predictions based on the solvent-accessible surface area of the methionine side-chains within these segments. These results validate the use of upstream computational modeling to predict mAb oxidation susceptibility at the sequence level.

Profiling charge complementarity and selectivity for binding at the protein surface.

PubMed

Sulea, Traian; Purisima, Enrico O

2003-05-01

A novel analysis and representation of the protein surface in terms of electrostatic binding complementarity and selectivity is presented. The charge optimization methodology is applied in a probe-based approach that simulates the binding process to the target protein. The molecular surface is color coded according to calculated optimal charge or according to charge selectivity, i.e., the binding cost of deviating from the optimal charge. The optimal charge profile depends on both the protein shape and charge distribution whereas the charge selectivity profile depends only on protein shape. High selectivity is concentrated in well-shaped concave pockets, whereas solvent-exposed convex regions are not charge selective. This suggests the synergy of charge and shape selectivity hot spots toward molecular selection and recognition, as well as the asymmetry of charge selectivity at the binding interface of biomolecular systems. The charge complementarity and selectivity profiles map relevant electrostatic properties in a readily interpretable way and encode information that is quite different from that visualized in the standard electrostatic potential map of unbound proteins.

Gas flow-field induced director alignment in polymer dispersed liquid crystal microdroplets deposited on a glass substrate

NASA Technical Reports Server (NTRS)

Parmar, D. S.; Singh, J. J.

1993-01-01

Polymer dispersed liquid crystal thin films have been deposited on glass substrates by the processes of polymerization and solvent evaporation induced phase separation. The electron and the optical polarization microscopies of the films reveal that PDLC microdroplets formed during the process of phase separation near the top surface of the film remain exposed and respond to shear stress due to air or gas flow on the surface. Optical response of the film to an air flow-induced shear stress input on the free surface has been measured. Director orientation in the droplets changes with the applied shear stress leading to time varying transmitted light intensity. Director dynamics of the droplet for an applied step shear stress has been discussed from free energy considerations. Results on the measurement of light transmission as a function of the gas flow parameter unambiguously demonstrate the potential of these systems for use as boundary layer and gas flow sensors.

Structure and Dynamics of Solvated Polymers near a Silica Surface: On the Different Roles Played by Solvent.

PubMed

Perrin, Elsa; Schoen, Martin; Coudert, François-Xavier; Boutin, Anne

2018-04-26

Whereas it is experimentally known that the inclusion of nanoparticles in hydrogels can lead to a mechanical reinforcement, a detailed molecular understanding of the adhesion mechanism is still lacking. Here we use coarse-grained molecular dynamics simulations to investigate the nature of the interface between silica surfaces and solvated polymers. We show how differences in the nature of the polymer and the polymer-solvent interactions can lead to drastically different behavior of the polymer-surface adhesion. Comparing explicit and implicit solvent models, we conclude that this effect cannot be fully described in an implicit solvent. We highlight the crucial role of polymer solvation for the adsorption of the polymer chain on the silica surface, the significant dynamics of polymer chains on the surface, and details of the modifications in the structure solvated polymer close to the interface.

Final Stages of the 1:24,000-Scale Geologic Mapping of Basin Deposits Exposed in Hadriacus Cavi, Mars

NASA Astrophysics Data System (ADS)

Skinner, J. A.; Fortezzo, C. M.

2018-06-01

This abstract presents a brief summary of the surface and section characteristics of a type area for stratified deposits exposed in Hadriacus Cavi (78.0°E, –27.3°N), Mars based on 1:24,000 scale geologic mapping and stratigraphic analyses.

Central nervous system diseases of organic solvents exposed workers based on nationwide medical surveillance-data in Korea.

PubMed

Min, Young-Sun; Ahn, Yeon-Soon

2016-05-01

New light is being shed on the relationship between chronic neurotoxicity of the central nervous system (CNS) and exposure to low-level organic solvents (OS). However, there are few longitudinal studies with a large sample size. A cohort of OS-exposed male workers was selected who had undergone an OS-associated specialized medical check-up at least once between 2000 and 2004 in Korea. The standardized admission ratios (SAR) for CNS diseases were calculated with reference to the Korean adult male population. Adjusted relative risks (ARR) were also estimated in comparison to noise-exposed male workers. There were 238,574 OS-exposed workers, yielding 954,772 person-years of exposure. OS-exposed workers were at elevated risk of "other extrapyramidal and movement disorders" (G25) with a SAR = 2.95 (95% CI: 1.41-5.42) and "systemic atrophies primarily affecting the CNS" (G10-G13) SAR = 2.08 (95% CI: 1.03-3.74). There were no significant differences between the OS-exposed workers and noise-exposed workers. A limited number of CNS diseases identified through hospital admissions data and short observation periods reduced statistical power to determine effect size. OS exposure was positively associated with "other extrapyramidal and movement disorder and systemic atrophies primarily affecting the CNS. © 2016 Wiley Periodicals, Inc.

Probing Contaminant Transport to and from Clay Surfaces in Organic Solvents and Water Using Solution Calorimetry.

PubMed

Pourmohammadbagher, Amin; Shaw, John M

2015-09-15

Clays, in tailings, are a significant ongoing environmental concern in the mining and oilsands production industries, and clay rehabilitation following contamination poses challenges episodically. Understanding the fundamentals of clay behavior can lead to better environmental impact mitigation strategies. Systematic calorimetric measurements are shown to provide a framework for parsing the synergistic and antagonistic impacts of trace (i.e., parts per million level) components on the surface compositions of clays. The enthalpy of solution of as-received and "contaminated" clays, in as-received and "contaminated" organic solvents and water, at 60 °C and atmospheric pressure, provides important illustrative examples. Clay contamination included pre-saturation of clays with water and organic liquids. Solvent contamination included the addition of trace water to organic solvents and trace organic liquids to water. Enthalpy of solution outcomes are interpreted using a quantitative mass and energy balance modeling framework that isolates terms for solvent and trace contaminant sorption/desorption and surface energy effects. Underlying surface energies are shown to dominate the energetics of the solvent-clay interaction, and organic liquids as solvents or as trace contaminants are shown to displace water from as-received clay surfaces. This approach can be readily extended to include pH, salts, or other effects and is expected to provide mechanistic and quantitative insights underlying the stability of clays in tailings ponds and the behaviors of clays in diverse industrial and natural environments.

Effect of surface hydroxyl groups on heat capacity of mesoporous silica

NASA Astrophysics Data System (ADS)

Marszewski, Michal; Butts, Danielle; Lan, Esther; Yan, Yan; King, Sophia C.; McNeil, Patricia E.; Galy, Tiphaine; Dunn, Bruce; Tolbert, Sarah H.; Hu, Yongjie; Pilon, Laurent

2018-05-01

This paper quantifies the effect of surface hydroxyl groups on the effective specific and volumetric heat capacities of mesoporous silica. To achieve a wide range of structural diversity, mesoporous silica samples were synthesized by various methods, including (i) polymer-templated nanoparticle-based powders, (ii) polymer-templated sol-gel powders, and (iii) ambigel silica samples dried by solvent exchange at room temperature. Their effective specific heat capacity, specific surface area, and porosity were measured using differential scanning calorimetry and low-temperature nitrogen adsorption-desorption measurements. The experimentally measured specific heat capacity was larger than the conventional weight-fraction-weighted specific heat capacity of the air and silica constituents. The difference was attributed to the presence of OH groups in the large internal surface area. A thermodynamic model was developed based on surface energy considerations to account for the effect of surface OH groups on the specific and volumetric heat capacity. The model predictions fell within the experimental uncertainty.

Mortality and cancer incidence of aircraft maintenance workers exposed to trichloroethylene and other organic solvents and chemicals: extended follow up

PubMed Central

Blair, A.; Hartge, P.; Stewart, P. A.; McAdams, M.; Lubin, J.

1998-01-01

OBJECTIVES: To extend the follow up of a cohort of 14,457 aircraft maintenance workers to the end of 1990 to evaluate cancer risks from potential exposure to trichloroethylene and other chemicals. METHODS: The cohort comprised civilians employed for at least one year between 1952 and 1956, of whom 5727 had died by 31 December 1990. Analyses compared the mortality of the cohort with the general population of Utah and the mortality and cancer incidence of exposed workers with those unexposed to chemicals, while adjusting for age, sex and calendar time. RESULTS: In the combined follow up period (1952-90), mortality from all causes and all cancer was close to expected (standardised mortality ratios (SMRs) 97 and 96, respectively). Significant excesses occurred for ischaemic heart disease (SMR 108), asthma (SMR 160), and cancer of the bone (SMR 227), whereas significant deficits occurred for cerebrovascular disease (SMR 88), accidents (SMR 70), and cancer of the central nervous system (SMR 64). Workers exposed to trichloroethylene showed non-significant excesses for non-Hodgkin's lymphoma (relative risk (RR) 2.0), and cancers of the oesophagus (RR 5.6), colon (RR 1.4), primary liver (RR 1.7), breast (RR 1.8), cervix (RR 1.8), kidney (RR 1.6), and bone (RR 2.1). None of these cancers showed an exposure- response gradient and RRs among workers exposed to other chemicals but not trichloroethylene often had RRs as large as workers exposed to trichloroethylene. Workers exposed to solvents other than trichloroethylene had slightly increased mortality from asthma, non- Hodgkin's lymphoma, multiple myeloma, and breast cancer. CONCLUSION: These findings do not strongly support a causal link with trichloroethylene because the associations were not significant, not clearly dose-related, and inconsistent between men and women. Because findings from experimental investigations and other epidemiological studies on solvents other than trichloroethylene provide some biological plausibility, the suggested links between these chemicals and non-Hodgkin's lymphoma, multiple myeloma, and breast cancer found here deserve further attention. Although this extended follow up cannot rule out a connection between exposures to solvents and some diseases, it seems clear that these workers have not experienced a major increase in cancer mortality or cancer incidence.   PMID:9624267

Ototoxic effects of occupational exposure to styrene and co-exposure to styrene and noise.

PubMed

Sliwińska-Kowalska, Mariola; Zamyslowska-Szmytke, Ewa; Szymczak, Wieslaw; Kotylo, Piotr; Fiszer, Marta; Wesolowski, Wiktor; Pawlaczyk-Luszczynska, Malgorzata

2003-01-01

Ototoxicity of styrene and the synergistic action of styrene and noise have been shown in rats. The respective data in humans are scarce and equivocal. This study evaluated the effects of occupational exposure to styrene and combined exposures to styrene and noise on hearing. The study group, comprised of 290-yacht yard and plastic factory workers, was exposed to a mixture of organic solvents, having styrene as its main compound. The reference group, totaling 223 subjects, included (1) white-collar workers, exposed neither to solvents nor noise and (2) metal factory workers, exposed exclusively to noise. All subjects were assessed by means of a detailed questionnaire and underwent otorhinolaryngological and audiometric examinations. Multiple logistic regression analysis revealed almost a 4-fold (or 3.9; 95% CI = 2.4-6.2) increase in the odds of developing hearing loss related to styrene exposure. The factors adjusted for were: age, gender, current occupational exposure to noise, and exposure to noise in the past. In cases of the combined exposures to styrene and noise, the odds ratios were two to three times higher than the respective values for styrene-only and noise-only exposed subjects. The mean hearing thresholds--adjusted for age, gender, and exposure to noise--were significantly higher in the solvent-exposed group than in the unexposed reference group at all frequencies tested. A positive linear relationship existed between an averaged working life exposure to styrene concentration and a hearing threshold at the frequencies of 6 and 8 kHz. This study provides the epidemiological evidence that occupational exposure to styrene is related to an increased risk of hearing loss. Combined exposures to noise and styrene seem to be more ototoxic than exposure to noise alone.

Synthesis and characterization of nanoporous silica aerogel beads using cheap industrial grade sodium silacte precursor

NASA Astrophysics Data System (ADS)

Khan, Tasneem M. A.; Khan, Asiya; Sarawade, Pradip B.

2018-05-01

We report a method to synthesize low-density transparent mesoporous silica aerogel beads by ambient pressure drying (APD). The beads were prepared by acid-base sol-gel polymerization of sodium silicate in via the ball dropping method (BDM). To minimize shrinkage during drying, wet silica beads were initially prepared; their surfaces were then modified using trimethylchlorosilane (TMCS) via simultaneous solvent exchange and surface modification. The specific surface area and cumulative pore volume of the silica aerogel beads increased with an increase in the %V of TMCS. Silica aerogel beads with low packing bed density, high surface area, and large cumulative pore volume was obtained when TMCS was used. Properties of the final product were examined by BET, and TG-DT analyses. The hydrophobic silica aerogel beads were thermally stable up to 350°C. We discuss our results and compare our findings for modified versus unmodified silica beads.

Improving the Efficiency of Non-equilibrium Sampling in the Aqueous Environment via Implicit-Solvent Simulations.

PubMed

Liu, Hui; Chen, Fu; Sun, Huiyong; Li, Dan; Hou, Tingjun

2017-04-11

By means of estimators based on non-equilibrium work, equilibrium free energy differences or potentials of mean force (PMFs) of a system of interest can be computed from biased molecular dynamics (MD) simulations. The approach, however, is often plagued by slow conformational sampling and poor convergence, especially when the solvent effects are taken into account. Here, as a possible way to alleviate the problem, several widely used implicit-solvent models, which are derived from the analytic generalized Born (GB) equation and implemented in the AMBER suite of programs, were employed in free energy calculations based on non-equilibrium work and evaluated for their abilities to emulate explicit water. As a test case, pulling MD simulations were carried out on an alanine polypeptide with different solvent models and protocols, followed by comparisons of the reconstructed PMF profiles along the unfolding coordinate. The results show that when employing the non-equilibrium work method, sampling with an implicit-solvent model is several times faster and, more importantly, converges more rapidly than that with explicit water due to reduction of dissipation. Among the assessed GB models, the Neck variants outperform the OBC and HCT variants in terms of accuracy, whereas their computational costs are comparable. In addition, for the best-performing models, the impact of the solvent-accessible surface area (SASA) dependent nonpolar solvation term was also examined. The present study highlights the advantages of implicit-solvent models for non-equilibrium sampling.

Comparison of MM/GBSA calculations based on explicit and implicit solvent simulations.

PubMed

Godschalk, Frithjof; Genheden, Samuel; Söderhjelm, Pär; Ryde, Ulf

2013-05-28

Molecular mechanics with generalised Born and surface area solvation (MM/GBSA) is a popular method to calculate the free energy of the binding of ligands to proteins. It involves molecular dynamics (MD) simulations with an explicit solvent of the protein-ligand complex to give a set of snapshots for which energies are calculated with an implicit solvent. This change in the solvation method (explicit → implicit) would strictly require that the energies are reweighted with the implicit-solvent energies, which is normally not done. In this paper we calculate MM/GBSA energies with two generalised Born models for snapshots generated by the same methods or by explicit-solvent simulations for five synthetic N-acetyllactosamine derivatives binding to galectin-3. We show that the resulting energies are very different both in absolute and relative terms, showing that the change in the solvent model is far from innocent and that standard MM/GBSA is not a consistent method. The ensembles generated with the various solvent models are quite different with root-mean-square deviations of 1.2-1.4 Å. The ensembles can be converted to each other by performing short MD simulations with the new method, but the convergence is slow, showing mean absolute differences in the calculated energies of 6-7 kJ mol(-1) after 2 ps simulations. Minimisations show even slower convergence and there are strong indications that the energies obtained from minimised structures are different from those obtained by MD.

A novel carbon electrode material for highly improved EDLC performance.

PubMed

Fang, Baizeng; Binder, Leo

2006-04-20

Porous materials, developed by grafting functional groups through chemical surface modification with a surfactant, represent an innovative concept in energy storage. This work reports, in detail, the first practical realization of a novel carbon electrode based on grafting of vinyltrimethoxysilane (vtmos) functional group for energy storage in electric double layer capacitor (EDLC). Surface modification with surfactant vtmos enhances the hydrophobisation of activated carbon and the affinity toward propylene carbonate (PC) solvent, which improves the wettability of activated carbon in the electrolyte solution based on PC solvent, resulting in not only a lower resistance to the transport of electrolyte ions within micropores of activated carbon but also more usable surface area for the formation of electric double layer, and accordingly, higher specific capacitance, energy density, and power capability available from the capacitor based on modified carbon. Especially, the effects from surface modification become superior at higher discharge rate, at which much better EDLC performance (i.e., much higher energy density and power capability) has been achieved by the modified carbon, suggesting that the modified carbon is a novel and very promising electrode material of EDLC for large current applications where both high energy density and power capability are required.

Aqueous or solvent based surface modification: The influence of the combination solvent - organic functional group on the surface characteristics of titanium dioxide grafted with organophosphonic acids

NASA Astrophysics Data System (ADS)

Roevens, Annelore; Van Dijck, Jeroen G.; Geldof, Davy; Blockhuys, Frank; Prelot, Benedicte; Zajac, Jerzy; Meynen, Vera

2017-09-01

To alter the versatility of interactions at its surface, TiO2 is modified with organophosphonic acids (PA). A thorough understanding of the role of all synthesis conditions is necessary to achieve controlled functionalization. This study reports on the effect of using water, toluene and their mixtures when performing the modification of TiO2 with PA. Sorption and calorimetry measurements of surface interactions with various probing species clearly indicate that, by grafting PA in water, clear differences appear in the distribution of organic groups on the surface. Also the functional group of the PA determines the impact of using water as solvent. Modification in toluene results in a higher modification degree for propylphosphonic acid (3PA), as the solvent-solute interaction may hinder the grafting with phenylphosphonic acid (PhPA) in toluene. Water is preferred as solvent for PhPA modification as stabilizing π-OH interactions enhance surface grafting overcoming the competitive interaction of water at the surface as observed with 3PA. By using water in toluene mixtures for the functionalization of TiO2 with 3PA, the degree of functionalization is higher than when only water or toluene is used. Furthermore, adding small amounts of water leads to the formation of titanium propylphosphonates, next to surface grafting.

The impact of surface area, volume, curvature, and Lennard-Jones potential to solvation modeling.

PubMed

Nguyen, Duc D; Wei, Guo-Wei

2017-01-05

This article explores the impact of surface area, volume, curvature, and Lennard-Jones (LJ) potential on solvation free energy predictions. Rigidity surfaces are utilized to generate robust analytical expressions for maximum, minimum, mean, and Gaussian curvatures of solvent-solute interfaces, and define a generalized Poisson-Boltzmann (GPB) equation with a smooth dielectric profile. Extensive correlation analysis is performed to examine the linear dependence of surface area, surface enclosed volume, maximum curvature, minimum curvature, mean curvature, and Gaussian curvature for solvation modeling. It is found that surface area and surfaces enclosed volumes are highly correlated to each other's, and poorly correlated to various curvatures for six test sets of molecules. Different curvatures are weakly correlated to each other for six test sets of molecules, but are strongly correlated to each other within each test set of molecules. Based on correlation analysis, we construct twenty six nontrivial nonpolar solvation models. Our numerical results reveal that the LJ potential plays a vital role in nonpolar solvation modeling, especially for molecules involving strong van der Waals interactions. It is found that curvatures are at least as important as surface area or surface enclosed volume in nonpolar solvation modeling. In conjugation with the GPB model, various curvature-based nonpolar solvation models are shown to offer some of the best solvation free energy predictions for a wide range of test sets. For example, root mean square errors from a model constituting surface area, volume, mean curvature, and LJ potential are less than 0.42 kcal/mol for all test sets. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Water adsorption on TiO2 surfaces probed by soft X-ray spectroscopies: bulk materials vs. isolated nanoparticles

PubMed Central

Benkoula, Safia; Sublemontier, Olivier; Patanen, Minna; Nicolas, Christophe; Sirotti, Fausto; Naitabdi, Ahmed; Gaie-Levrel, François; Antonsson, Egill; Aureau, Damien; Ouf, François-Xavier; Wada, Shin-Ichi; Etcheberry, Arnaud; Ueda, Kiyoshi; Miron, Catalin

2015-01-01

We describe an experimental method to probe the adsorption of water at the surface of isolated, substrate-free TiO2 nanoparticles (NPs) based on soft X-ray spectroscopy in the gas phase using synchrotron radiation. To understand the interfacial properties between water and TiO2 surface, a water shell was adsorbed at the surface of TiO2 NPs. We used two different ways to control the hydration level of the NPs: in the first scheme, initially solvated NPs were dried and in the second one, dry NPs generated thanks to a commercial aerosol generator were exposed to water vapor. XPS was used to identify the signature of the water layer shell on the surface of the free TiO2 NPs and made it possible to follow the evolution of their hydration state. The results obtained allow the establishment of a qualitative determination of isolated NPs’ surface states, as well as to unravel water adsorption mechanisms. This method appears to be a unique approach to investigate the interface between an isolated nano-object and a solvent over-layer, paving the way towards new investigation methods in heterogeneous catalysis on nanomaterials. PMID:26462615

Partially nanofibrous architecture of 3D tissue engineering scaffolds.

PubMed

Wei, Guobao; Ma, Peter X

2009-11-01

An ideal tissue-engineering scaffold should provide suitable pores and appropriate pore surface to induce desired cellular activities and to guide 3D tissue regeneration. In the present work, we have developed macroporous polymer scaffolds with varying pore wall architectures from smooth (solid), microporous, partially nanofibrous, to entirely nanofibrous ones. All scaffolds are designed to have well-controlled interconnected macropores, resulting from leaching sugar sphere template. We examine the effects of material composition, solvent, and phase separation temperature on the pore surface architecture of 3D scaffolds. In particular, phase separation of PLLA/PDLLA or PLLA/PLGA blends leads to partially nanofibrous scaffolds, in which PLLA forms nanofibers and PDLLA or PLGA forms the smooth (solid) surfaces on macropore walls, respectively. Specific surface areas are measured for scaffolds with similar macroporosity but different macropore wall architectures. It is found that the pore wall architecture predominates the total surface area of the scaffolds. The surface area of a partially nanofibrous scaffold increases linearly with the PLLA content in the polymer blend. The amounts of adsorbed proteins from serum increase with the surface area of the scaffolds. These macroporous scaffolds with adjustable pore wall surface architectures may provide a platform for investigating the cellular responses to pore surface architecture, and provide us with a powerful tool to develop superior scaffolds for various tissue-engineering applications.

Acute effects of an organic solvent mixture on the human central nervous system.

PubMed

Muttray, Axel; Martus, P; Schachtrup, S; Müller, E; Mayer-Popken, O; Konietzko, J

2005-09-12

At workplaces, organic solvents are often used as mixtures. Nevertheless, there is limited knowledge of their acute effects on human central nervous system. Here we report the effects of a toluene-acetone mixture. In a parallel design, subgroups of 12 healthy men each were exposed to a mixture containing 25 ppm acetone and 250 ppm toluene or to air (control) in an exposure chamber for 4.5 hours. Concentrations corresponded to the German TLV (TRGS 403). Concentrations of toluene and acetone in venous blood were measured by headspace gas chromatography. Subjects were sedentary. The following tests were performed before and at the end of exposure: Questionnaires, simple reaction time, vigilance, quantitative analysis of EEG with open and closed eyes and during the Color Word Stress test, and visual evoked potentials (VEP). Blood levels were 0.14 (+/- 0.04 SD) mg toluene/l and 5.43 (+/- 1.37 SD) mg acetone/l at the end of solvent exposure. Scores of neurotoxic and irritating symptoms were not elevated during solvent exposure. Exposed subjects performed as well as control subjects on the simple reaction time test and on the vigilance test, neither reaction time nor number of hits differed significantly. A general linear model on log transformed spectral power values showed insignificant changes in EEG. In the alpha subset2-band an average reduction to 86 % was observed in exposed as compared to non exposed subjects with closed eyes, a reduction to 88 % in the theta-band with open eyes, and a reduction to 92 % in the theta-band during the Color Word Stress test. VEP P 100 latencies and amplitudes did not change. The mixture consisting of toluene and acetone did not cause any adverse acute effect. With respect to EEG data, possible subclinical effects on central nervous system cannot be excluded.

The inconsistency in adsorption properties and powder XRD data of MOF-5 is rationalized by framework interpenetration and the presence of organic and inorganic species in the nanocavities.

PubMed

Hafizovic, Jasmina; Bjørgen, Morten; Olsbye, Unni; Dietzel, Pascal D C; Bordiga, Silvia; Prestipino, Carmelo; Lamberti, Carlo; Lillerud, Karl Petter

2007-03-28

MOF-5 is the archetype metal-organic framework and has been subjected to numerous studies the past few years. The focal point of this report is the pitfalls related to the MOF-5 phase identification based on powder XRD data. A broad set of conditions and procedures have been reported for MOF-5 synthesis. These variations have led to materials with substantially different adsorption properties (specific surface areas in the range 700 to 3400 m(2)/g). The relatively low weight loss observed for some as synthesized samples upon solvent removal is also indicative of a low pore volume. Regrettably, these materials have all been described as MOF-5 without any further comments. Furthermore, the reported powder XRD patterns hint at structural differences: The variations in surface area are accompanied by peak splitting phenomena and rather pronounced changes in the relative peak intensities in the powder XRD patterns. In this work, we use single-crystal XRD to investigate structural differences between low and high surface area MOF-5. The low surface area MOF-5 sample had two different classes of crystals. For the dominant phase, Zn(OH)2 species partly occupied the cavities. The presence of Zn species makes the hosting cavity and possibly also adjacent cavities inaccessible and thus efficiently reduces the pore volume of the material. Furthermore, the minor phase consisted of doubly interpenetrated MOF-5 networks, which lowers the adsorption capacity. The presence of Zn species and lattice interpenetration changes the symmetry from cubic to trigonal and explains the peak splitting observed in the powder XRD patterns. Pore-filling effects from the Zn species (and partly the solvent molecules) are also responsible for the pronounced variations in powder XRD peak intensities. This latter conclusion is particularly useful for predicting the adsorption properties of a MOF-5-type material from powder XRD.

Versatile fabrication of paper-based microfluidic devices with high chemical resistance using scholar glue and magnetic masks.

PubMed

Cardoso, Thiago M G; de Souza, Fabrício R; Garcia, Paulo T; Rabelo, Denilson; Henry, Charles S; Coltro, Wendell K T

2017-06-29

Simple methods have been developed for fabricating microfluidic paper-based analytical devices (μPADs) but few of these devices can be used with organic solvents and/or aqueous solutions containing surfactants. This study describes a simple fabrication strategy for μPADs that uses readily available scholar glue to create the hydrophobic flow barriers that are resistant to surfactants and organic solvents. Microfluidic structures were defined by magnetic masks designed with either neodymium magnets or magnetic sheets to define the patter, and structures were created by spraying an aqueous solution of glue on the paper surface. The glue-coated paper was then exposed to UV/Vis light for cross-linking to maximize chemical resistance. Examples of microzone arrays and microfluidic devices are demonstrated. μPADs fabricated with scholar glue retained their barriers when used with surfactants, organic solvents, and strong/weak acids and bases unlike common wax-printed barriers. Paper microzones and microfluidic devices were successfully used for colorimetric assays of clinically relevant analytes commonly detected in urinalysis to demonstrate the low background of the barrier material and generally applicability to sensing. The proposed fabrication method is attractive for both its ability to be used with diverse chemistries and the low cost and simplicity of the materials and process. Copyright © 2017 Elsevier B.V. All rights reserved.

Photopatternable sorbent and functionalized films

DOEpatents

Grate, Jay W [West Richland, WA; Nelson, David A [Richland, WA

2006-01-31

A composition containing a polymer, a crosslinker and a photo-activatable catalyst is placed on a substrate. The composition is exposed to a predetermined pattern of light, leaving an unexposed region. The light causes the polymer to become crosslinked by hydrosilylation. A solvent is used to remove the unexposed composition from the substrate, leaving the exposed pattern to become a sorbent polymer film that will absorb a predetermined chemical species when exposed to such chemical species.

Communication: Contrasting effects of glycerol and DMSO on lipid membrane surface hydration dynamics and forces

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

Schrader, Alex M.; Cheng, Chi-Yuan; Israelachvili, Jacob N.

2016-07-28

Glycerol and dimethyl sulfoxide (DMSO) are commonly used cryoprotectants in cellular systems, but due to the challenges of measuring the properties of surface-bound solvent, fundamental questions remain regarding the concentration, interactions, and conformation of these solutes at lipid membrane surfaces. We measured the surface water diffusivity at gel-phase dipalmitoylphosphatidylcholine (DPPC) bilayer surfaces in aqueous solutions containing ≤7.5 mol. % of DMSO or glycerol using Overhauser dynamic nuclear polarization. We found that glycerol similarly affects the diffusivity of water near the bilayer surface and that in the bulk solution (within 20%), while DMSO substantially increases the diffusivity of surface water relativemore » to bulk water. We compare these measurements of water dynamics with those of equilibrium forces between DPPC bilayers in the same solvent mixtures. DMSO greatly decreases the range and magnitude of the repulsive forces between the bilayers, whereas glycerol increases it. We propose that the differences in hydrogen bonding capability of the two solutes leads DMSO to dehydrate the lipid head groups, while glycerol affects surface hydration only as much as it affects the bulk water properties. The results suggest that the mechanism of the two most common cryoprotectants must be fundamentally different: in the case of DMSO by decoupling the solvent from the lipid surface, and in the case of glycerol by altering the hydrogen bond structure and intermolecular cohesion of the global solvent, as manifested by increased solvent viscosity.« less

Observation of chain stretching in Langmuir diblock copolymer monolayers

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

Factor, B.J.; Lee, L.; Kent, M.S.

1993-10-01

We report observations of chain stretching in diblock copolymer monolayers on the surface of a selective solvent. Using neutron reflectivity, we have studied the concentration profile of the submerged block over a large range of surface density [sigma] (chains per area) for two different molecular weights. The observed increase in the layer thickness is weaker than the [sigma][sup 1/3] prediction of mean-field and scaling theories for the limiting behavior, but is in agreement with recent numerical self-consistent-field calculations by Whitmore and Noolandi [Macromolecules 23, 3321 (1990)].

Empirical correlation between hydrophobic free energy and aqueous cavity surface area

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

Reynolds, J.A.; Gilbert, D.B.; Tanford, C.

1974-08-01

The unitary free energy of transfer of a hydrocarbon molecule from a hydrocarbon solvent to an aqueous medium is a measure of the hydrophobic interaction in the aqueous medium. We have reexamined available data on this phenomenon and have confirmed that the free energy for saturated hydrocarbons is proportional to the surface area of the cavity created by the solute in the aqueous solution, with the same proportionality constant for linear, branched, and cyclic hydrocarbon molecules. The numerical value of the proportionality constant is uncertain because absolute and self-consistent area measurements are not available. We estimate that it falls betweenmore » 20 and 25 cal/mole per Angstrom/sup 2/ at 25/sup 0/ (for areas measured at the distance of closest approach of water molecules), which is significantly less than the figure of 33 cal/mole per Angstrom/sup 2/ that has been assigned to the same parameter by Hermann.« less

Low-Temperature, Solution-Processed, Transparent Zinc Oxide-Based Thin-Film Transistors for Sensing Various Solvents

PubMed Central

You, Hsin-Chiang; Wang, Cheng-Jyun

2017-01-01

A low temperature solution-processed thin-film transistor (TFT) using zinc oxide (ZnO) film as an exposed sensing semiconductor channel was fabricated to detect and identify various solution solvents. The TFT devices would offer applications for low-cost, rapid and highly compatible water-soluble detection and could replace conventional silicon field effect transistors (FETs) as bio-sensors. In this work, we demonstrate the utility of the TFT ZnO channel to sense various liquids, such as polar solvents (ethanol), non-polar solvents (toluene) and deionized (DI) water, which were dropped and adsorbed onto the channel. It is discussed how different dielectric constants of polar/non-polar solvents and DI water were associated with various charge transport properties, demonstrating the main detection mechanisms of the thin-film transistor. PMID:28772592

AFM fluid delivery/liquid extraction surface sampling/electrostatic spray cantilever probe

DOEpatents

Van Berkel, Gary J.

2015-06-23

An electrospray system comprises a liquid extraction surface sampling probe. The probe comprises a probe body having a liquid inlet and a liquid outlet, and having a liquid extraction tip. A solvent delivery conduit is provided for receiving solvent liquid from the liquid inlet and delivering the solvent liquid to the liquid extraction tip. An open liquid extraction channel extends across an exterior surface of the probe body from the liquid extraction tip to the liquid outlet. An electrospray emitter tip is in liquid communication with the liquid outlet of the liquid extraction surface sampling probe. A system for analyzing samples, a liquid junction surface sampling system, and a method of analyzing samples are also disclosed.

Solvent dependence of the activation energy of attachment determined by single molecule observations of surfactant adsorption.

PubMed

Honciuc, Andrei; Baptiste, Denver Jn; Campbell, Ian P; Schwartz, Daniel K

2009-07-07

Single-molecule total internal reflection fluorescence microscopy was used to obtain real-time images of fluorescently labeled hexadecanoic (palmitic) acid molecules as they adsorbed at the interface between fused silica and three different solvents: hexadecane (HD), tetrahydrofuran (THF), and water. These solvents were chosen to explore the effect of solvent polarity on the activation energy associated with the attachment rate, i.e., the rate at which molecules were transferred to the surface from the near-surface layer. Direct counting of single-molecule events, made under steady-state conditions at extremely low coverage, provided direct, model-independent measurements of this attachment rate, in contrast with conventional ensemble-averaged methods, which are influenced by bulk transport and competing detachment processes. We found that the attachment rate increased with increasing temperature for all solvents. Arrhenius analyses gave activation energies of 5+/-2 kJ/mol for adsorption from HD, 10+/-2 kJ/mol for adsorption from THF, and 19+/-2 kJ/mol for adsorption from water. These energies increased systematically with the solvent polarity and, therefore, with the expected strength of the solvent-substrate interaction. We hypothesize that the adsorption of amphiphilic solute molecules from solution can be regarded as a competitive exchange between solute molecules and surface-bound solvent. In this scenario, adsorption is an activated process, and the activation energy for attachment is associated with the solvent-substrate interaction energy.

Organic solvent desorption from two tegafur polymorphs.

PubMed

Bobrovs, Raitis; Actiņš, Andris

2013-11-30

Desorption behavior of 8 different solvents from α and β tegafur (5-fluoro-1-(tetrahydro-2-furyl)uracil) has been studied in this work. Solvent desorption from samples stored at 95% and 50% relative solvent vapor pressure was studied in isothermal conditions at 30 °C. The results of this study demonstrated that: solvent desorption rate did not differ significantly for both phases; solvent desorption in all cases occurred faster from samples with the largest particle size; and solvent desorption in most cases occurred in two steps. Structure differences and their surface properties were not of great importance on the solvent desorption rates because the main factor affecting desorption rate was sample particle size and sample morphology. Inspection of the structure packing showed that solvent desorption rate and amount of solvent adsorbed were mainly affected by surface molecule arrangement and ability to form short contacts between solvent molecule electron donor groups and freely accessible tegafur tetrahydrofuran group hydrogens, as well as between solvents molecule proton donor groups and fluorouracil ring carbonyl and fluoro groups. Solvent desorption rates of acetone, acetonitrile, ethyl acetate and tetrahydrofuran multilayers from α and β tegafur were approximately 30 times higher than those of solvent monolayers. Scanning electron micrographs showed that sample storage in solvent vapor atmosphere promotes small tegafur particles recrystallization to larger particles. Copyright © 2013 Elsevier B.V. All rights reserved.

Anisotropic solvent model of the lipid bilayer. 1. Parameterization of long-range electrostatics and first solvation shell effects.

PubMed

Lomize, Andrei L; Pogozheva, Irina D; Mosberg, Henry I

2011-04-25

A new implicit solvation model was developed for calculating free energies of transfer of molecules from water to any solvent with defined bulk properties. The transfer energy was calculated as a sum of the first solvation shell energy and the long-range electrostatic contribution. The first term was proportional to solvent accessible surface area and solvation parameters (σ(i)) for different atom types. The electrostatic term was computed as a product of group dipole moments and dipolar solvation parameter (η) for neutral molecules or using a modified Born equation for ions. The regression coefficients in linear dependencies of solvation parameters σ(i) and η on dielectric constant, solvatochromic polarizability parameter π*, and hydrogen-bonding donor and acceptor capacities of solvents were optimized using 1269 experimental transfer energies from 19 organic solvents to water. The root-mean-square errors for neutral compounds and ions were 0.82 and 1.61 kcal/mol, respectively. Quantification of energy components demonstrates the dominant roles of hydrophobic effect for nonpolar atoms and of hydrogen-bonding for polar atoms. The estimated first solvation shell energy outweighs the long-range electrostatics for most compounds including ions. The simplicity and computational efficiency of the model allows its application for modeling of macromolecules in anisotropic environments, such as biological membranes.

Acidification of lake water due to drought

NASA Astrophysics Data System (ADS)

Mosley, L. M.; Zammit, B.; Jolley, A. M.; Barnett, L.

2014-04-01

Droughts are predicted to increase in many river systems due to increased demand on water resources and climate variability. A severe drought in the Murray-Darling Basin of Australia from 2007 to 2009 resulted in unprecedented declines in water levels in the Lower Lakes (Ramsar-listed ecosystem of international importance) at the end of the river system. The receding water exposed large areas (>200 km2) of sediments on the lake margins. The pyrite (FeS2) in these sediments oxidised and generated high concentrations of acidity. Upon rewetting of the exposed sediments, by rainfall or lake refill, surface water acidification (pH 2-3) occurred in several locations (total area of 21.7 km2). High concentrations of dissolved metals (Al, As, Co, Cr, Cu, Fe, Mn, Ni, Zn), which greatly exceeded aquatic ecosystem protection guidelines, were mobilised in the acidic conditions. In many areas neutralisation of the surface water acidity occurred naturally during lake refill, but aerial limestone dosing was required in two areas to assist in restoring alkalinity. However acidity persists in the submerged lake sediment and groundwater several years after surface water neutralisation. The surface water acidification proved costly to manage and improved water management in the Murray-Darling Basin is required to prevent similar events occurring in the future.

Discrimination between native and intentionally misfolded conformations of proteins: ES/IS, a new method for calculating conformational free energy that uses both dynamics simulations with an explicit solvent and an implicit solvent continuum model.

PubMed

Vorobjev, Y N; Almagro, J C; Hermans, J

1998-09-01

A new method for calculating the total conformational free energy of proteins in water solvent is presented. The method consists of a relatively brief simulation by molecular dynamics with explicit solvent (ES) molecules to produce a set of microstates of the macroscopic conformation. Conformational energy and entropy are obtained from the simulation, the latter in the quasi-harmonic approximation by analysis of the covariance matrix. The implicit solvent (IS) dielectric continuum model is used to calculate the average solvation free energy as the sum of the free energies of creating the solute-size hydrophobic cavity, of the van der Waals solute-solvent interactions, and of the polarization of water solvent by the solute's charges. The reliability of the solvation free energy depends on a number of factors: the details of arrangement of the protein's charges, especially those near the surface; the definition of the molecular surface; and the method chosen for solving the Poisson equation. Molecular dynamics simulation in explicit solvent relaxes the protein's conformation and allows polar surface groups to assume conformations compatible with interaction with solvent, while averaging of internal energy and solvation free energy tend to enhance the precision. Two recently developed methods--SIMS, for calculation of a smooth invariant molecular surface, and FAMBE, for solution of the Poisson equation via a fast adaptive multigrid boundary element--have been employed. The SIMS and FAMBE programs scale linearly with the number of atoms. SIMS is superior to Connolly's MS (molecular surface) program: it is faster, more accurate, and more stable, and it smooths singularities of the molecular surface. Solvation free energies calculated with these two programs do not depend on molecular position or orientation and are stable along a molecular dynamics trajectory. We have applied this method to calculate the conformational free energy of native and intentionally misfolded globular conformations of proteins (the EMBL set of deliberately misfolded proteins) and have obtained good discrimination in favor of the native conformations in all instances.

Dispersing surface-modified imogolite nanotubes in polar and non-polar solvents

NASA Astrophysics Data System (ADS)

Li, Ming; Brant, Jonathan A.

2018-02-01

Furthering the development of nanocomposite structures, namely membranes for water treatment applications, requires that methods be developed to ensure nanoparticle dispersion in polar and non-polar solvents, as both are widely used in associated synthesis techniques. Here, we report on a two-step method to graft polyvinylpyrrolidone (PVP), and a one-step method for octadecylphosphonic acid (OPA), onto the outer surfaces of imogolite nanotubes. The goal of these approaches was to improve and maintain nanotube dispersion in polymer compatible polar and non-polar solvents. The PVP coating modified the imogolite surface charge from positive to weakly negative at pH ≤ 9; the OPA made it weakly positive at acidic pH values to negative at pH ≥ 7. The PVP surface coating stabilized the nanotubes through steric hindrance in polar protic, dipolar aprotic, and chloroform. In difference to the PVP, the OPA surface coating allowed the nanotubes to be dispersed in n-hexane and chloroform, but not in the polar solvents. The lack of miscibility in the polar solvents, as well as the better dispersion in n-hexane, was attributed to the stronger hydrophobicity of the OPA polymer relative to the PVP. [Figure not available: see fulltext.

Effect of stearic acid modified HAp nanoparticles in different solvents on the properties of Pickering emulsions and HAp/PLLA composites.

PubMed

Zhang, Ming; Wang, Ai-Juan; Li, Jun-Ming; Song, Na

2017-10-01

Stearic acid (Sa) was used to modify the surface properties of hydroxyapatite (HAp) in different solvents (water, ethanol or dichloromethane(CH 2 Cl 2 )). Effect of different solvents on the properties of HAp particles (activation ratio, grafting ratio, chemical properties), emulsion properties (emulsion stability, emulsion type, droplet morphology) as well as the cured materials (morphology, average pore size) were studied. FT-IR and XPS results confirmed the interaction occurred between stearic acid and HAp particles. Stable O/W and W/O type Pickering emulsions were prepared using unmodified and Sa modified HAp nanoparticles respectively, which indicated a catastrophic inversion of the Pickering emulsion happened possibly because of the enhanced hydrophobicity of HAp particles after surface modification. Porous materials with different structures and pore sizes were obtained using Pickering emulsion as the template via in situ evaporation solvent method. The results indicated the microstructures of cured samples are different form each other when HAp was surface modified in different solvents. HAp particles fabricated using ethanol as solvent has higher activation ratio and grafting ratio. Pickering emulsion with higher stability and cured porous materials with uniform morphology were obtained compared with samples prepared using water and CH 2 Cl 2 as solvents. In conclusion, surface modification of HAp in different solvents played a very important role for its stabilized Pickering emulsion as well as the microstructure of cured samples. It is better to use ethanol as the solvent for Sa modified HAp particles, which could increase the stability of Pickering emulsion and obtain cured samples with uniform pore size. Copyright © 2017 Elsevier B.V. All rights reserved.

Atlantis TPS Processing

NASA Image and Video Library

2003-10-01

In the Orbiter Processing Facility, Harrell Watts (left), with United Space Alliance, removes a tile from the thermal barrier around the umbilical areas, the external tank attach points, on the underside of Atlantis. The umbilical areas are closed off after ET separation by a door, seen here. The exposed area of each closed door is covered with reusable surface insulation.

Facile room-temperature solution-phase synthesis of a spherical covalent organic framework for high-resolution chromatographic separation.

PubMed

Yang, Cheng-Xiong; Liu, Chang; Cao, Yi-Meng; Yan, Xiu-Ping

2015-08-07

A simple and facile room-temperature solution-phase synthesis was developed to fabricate a spherical covalent organic framework with large surface area, good solvent stability and high thermostability for high-resolution chromatographic separation of diverse important industrial analytes including alkanes, cyclohexane and benzene, α-pinene and β-pinene, and alcohols with high column efficiency and good precision.

Seismic Technology Adapted to Analyzing and Developing Geothermal Systems Below Surface-Exposed High-Velocity Rocks Final Report

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

Hardage, Bob A.; DeAngelo, Michael V.; Ermolaeva, Elena

The objective of our research was to develop and demonstrate seismic data-acquisition and data-processing technologies that allow geothermal prospects below high-velocity rock outcrops to be evaluated. To do this, we acquired a 3-component seismic test line across an area of exposed high-velocity rocks in Brewster County, Texas, where there is high heat flow and surface conditions mimic those found at numerous geothermal prospects. Seismic contractors have not succeeded in creating good-quality seismic data in this area for companies who have acquired data for oil and gas exploitation purposes. Our test profile traversed an area where high-velocity rocks and low-velocity sedimentmore » were exposed on the surface in alternating patterns that repeated along the test line. We verified that these surface conditions cause non-ending reverberations of Love waves, Rayleigh waves, and shallow critical refractions to travel across the earth surface between the boundaries of the fast-velocity and slow-velocity material exposed on the surface. These reverberating surface waves form the high level of noise in this area that does not allow reflections from deep interfaces to be seen and utilized. Our data-acquisition method of deploying a box array of closely spaced geophones allowed us to recognize and evaluate these surface-wave noise modes regardless of the azimuth direction to the surface anomaly that backscattered the waves and caused them to return to the test-line profile. With this knowledge of the surface-wave noise, we were able to process these test-line data to create P-P and SH-SH images that were superior to those produced by a skilled seismic data-processing contractor. Compared to the P-P data acquired along the test line, the SH-SH data provided a better detection of faults and could be used to trace these faults upward to the boundaries of exposed surface rocks. We expanded our comparison of the relative value of S-wave and P-wave seismic data for geothermal applications by inserting into this report a small part of the interpretation we have done with 3C3D data across Wister geothermal field in the Imperial Valley of California. This interpretation shows that P-SV data reveal faults (and by inference, also fractures) that cannot be easily, or confidently, seen with P-P data, and that the combination of P-P and P-SV data allows VP/VS velocity ratios to be estimated across a targeted reservoir interval to show where an interval has more sandstone (the preferred reservoir facies). The conclusion reached from this investigation is that S-wave seismic technology can be invaluable to geothermal operators. Thus we developed a strong interest in understanding the direct-S modes produced by vertical-force sources, particularly vertical vibrators, because if it can be demonstrated that direct-S modes produced by vertical-force sources can be used as effectively as the direct-S modes produced by horizontal-force sources, geothermal operators can acquire direct-S data across many more prospect areas than can be done with horizontal-force sources, which presently are limited to horizontal vibrators. We include some of our preliminary work in evaluating direct-S modes produced by vertical-force sources.« less

Improved strategies for DNP-enhanced 2D 1 H-X heteronuclear correlation spectroscopy of surfaces

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

Kobayashi, Takeshi; Perras, Frederic A.; Chaudhary, Umesh

We demonstrate that dynamic nuclear polarization (DNP)-enhanced 1H-X heteronuclear correlation (HETCOR) measurements of hydrogen-rich surface species are better accomplished by using proton-free solvents. This approach notably prevents HETCOR spectra from being obfuscated by the solvent-derived signals otherwise present in DNP measurements. Additionally, in the hydrogen-rich materials studied here, which included functionalized mesoporous silica nanoparticles and metal organic frameworks, the use of proton-free solvents afforded higher sensitivity gains than the commonly used solvents containing protons. Here, we also explored the possibility of using a solvent-free sample formulation and the feasibility of indirect detection in DNP-enhanced HETCOR experiments.

Improved strategies for DNP-enhanced 2D 1 H-X heteronuclear correlation spectroscopy of surfaces

DOE PAGES

Kobayashi, Takeshi; Perras, Frederic A.; Chaudhary, Umesh; ...

2017-08-12

We demonstrate that dynamic nuclear polarization (DNP)-enhanced 1H-X heteronuclear correlation (HETCOR) measurements of hydrogen-rich surface species are better accomplished by using proton-free solvents. This approach notably prevents HETCOR spectra from being obfuscated by the solvent-derived signals otherwise present in DNP measurements. Additionally, in the hydrogen-rich materials studied here, which included functionalized mesoporous silica nanoparticles and metal organic frameworks, the use of proton-free solvents afforded higher sensitivity gains than the commonly used solvents containing protons. Here, we also explored the possibility of using a solvent-free sample formulation and the feasibility of indirect detection in DNP-enhanced HETCOR experiments.

40 CFR 761.372 - Specific requirements for relatively clean surfaces.

Code of Federal Regulations, 2012 CFR

2012-07-01

... that each 900 cm2 (1 square foot) of the surface is always very wet for 1 minute. Wipe smooth surfaces with a solvent-soaked, disposable absorbent pad such that each 900 cm2 (1 square foot) is wiped for 1 minute. Any surface square foot shall also be wiped for 1 minute. Wipe, mop, and/or sorb the solvent...

40 CFR 761.372 - Specific requirements for relatively clean surfaces.

Code of Federal Regulations, 2014 CFR

2014-07-01

... that each 900 cm2 (1 square foot) of the surface is always very wet for 1 minute. Wipe smooth surfaces with a solvent-soaked, disposable absorbent pad such that each 900 cm2 (1 square foot) is wiped for 1 minute. Any surface square foot shall also be wiped for 1 minute. Wipe, mop, and/or sorb the solvent...

Green synthesis of mesoporous molecular sieve incorporated monoliths using room temperature ionic liquid and deep eutectic solvents.

PubMed

Zhang, Li-Shun; Zhao, Qing-Li; Li, Xin-Xin; Li, Xi-Xi; Huang, Yan-Ping; Liu, Zhao-Sheng

2016-12-01

A hybrid monolith incorporated with mesoporous molecular sieve MCM-41 of uniform pore structure and high surface area was prepared with binary green porogens in the first time. With a mixture of room temperature ionic liquids and deep eutectic solvents as porogens, MCM-41 was modified with 3-(trimethoxysilyl) propyl methacrylate (γ-MPS) and the resulting MCM-41-MPS was incorporated into poly (BMA-co-EDMA) monoliths covalently. Because of good dispersibility of MCM-41-MPS in the green solvent-based polymerization system, high permeability and homogeneity for the resultant hybrid monolithic columns was achieved. The MCM-41-MPS grafted monolith was characterized by scanning electron microscopy, energy dispersive spectrometer area scanning, transmission electron microscopy, FT-IR spectra and nitrogen adsorption tests. Chromatographic performance of MCM-41-MPS grafted monolith was characterized by separating small molecules in capillary electrochromatography, including phenol series, naphthyl substitutes, aniline series and alkyl benzenes. The maximum column efficiency of MCM-41-MPS grafted monolith reached 209,000 plates/m, which was twice higher than the corresponding MCM-41-MPS free monolith. Moreover, successful separation of non-steroidal anti-inflammatory drugs and polycyclic aromatic hydrocarbons demonstrated the capacity in broad-spectrum application of the MCM-41-MPS incorporated monolith. The results indicated that green synthesis using room temperature ionic liquid and deep eutectic solvents is an effective method to prepare molecular sieve-incorporated monolithic column. Copyright © 2016 Elsevier B.V. All rights reserved.

Supercapacitor Electrolyte Solvents with Liquid Range Below -80 C

NASA Technical Reports Server (NTRS)

Brandon, Erik; Smart, Marshall; West, William

2010-01-01

A previous NASA Tech Brief ["Low-Temperature Supercapacitors" (NPO-44386) NASA Tech Briefs, Vol. 32, No 7 (July 2008), page 32] detailed ongoing efforts to develop non-aqueous supercapacitor electrolytes capable of supporting operation at temperatures below commercially available cells (which are typically limited to charging and discharging at > or equal to -40 C). These electrolyte systems may enable energy storage and power delivery for systems operating in extreme environments, such as those encountered in the Polar regions on Earth or in the exploration of space. Supercapacitors using these electrolytes may also offer improved power delivery performance at moderately low temperatures (e.g. -40 to 0 C) relative to currently available cells, offering improved cold-cranking and cold-weather acceleration capabilities for electrical or hybrid vehicles. Supercapacitors store charge at the electrochemical double-layer, formed at the interface between a high surface area electrode material and a liquid electrolyte. The current approach to extending the low-temperature limit of the electrolyte focuses on using binary solvent systems comprising a high-dielectric-constant component (such as acetonitrile) in conjunction with a low-melting-point co-solvent (such as organic formates, esters, and ethers) to depress the freezing point of the system, while maintaining sufficient solubility of the salt. Recent efforts in this area have led to the identification of an electrolyte solvent formulation with a freezing point of -85.7 C, which is achieved by using a 1:1 by volume ratio of acetonitrile to 1,3-dioxolane

Proximity charge sensing for semiconductor detectors

DOEpatents

Luke, Paul N; Tindall, Craig S; Amman, Mark

2013-10-08

A non-contact charge sensor includes a semiconductor detector having a first surface and an opposing second surface. The detector includes a high resistivity electrode layer on the first surface and a low resistivity electrode on the high resistivity electrode layer. A portion of the low resistivity first surface electrode is deleted to expose the high resistivity electrode layer in a portion of the area. A low resistivity electrode layer is disposed on the second surface of the semiconductor detector. A voltage applied between the first surface low resistivity electrode and the second surface low resistivity electrode causes a free charge to drift toward the first or second surface according to a polarity of the free charge and the voltage. A charge sensitive preamplifier coupled to a non-contact electrode disposed at a distance from the exposed high resistivity electrode layer outputs a signal in response to movement of free charge within the detector.

Facile preparation of polymer microspheres and fibers with a hollow core and porous shell for oil adsorption and oil/water separation

NASA Astrophysics Data System (ADS)

Gao, Jiefeng; Song, Xin; Huang, Xuewu; Wang, Ling; Li, Bei; Xue, Huaiguo

2018-05-01

Non-solvent assisted electrospinning was proposed for fabricating Polymethylmethacrylate (PMMA) microspheres and fibers with a hollow core and porous shell, which could be used for oil adsorption and oil/water separation. Propanediol was chosen as the non-solvent because of its high surface tension and viscosity as well as large phase separation tendency with polymer, which was beneficial to the formation of both the hollow core and porous shell during the electrospinning. With the increase of the polymer solution concentration, the microsphere gradually evolved to the bead-on-string geometry and finally to a continuous fiber form, indicating the transition from electro-spraying to electrospinning. The hollow core and dense surface pores enhanced the hydrophobicity, oleophilicity, permeability, and specific surface area of the fibers, and hence imparted the fibrous mat a high oil adsorption capacity. When the porous hollow microspheres were electro-sprayed onto the stainless steel mesh followed by the PDMS modification, the modified mesh became super-hydrophobic and super-oleophilic with the contact angle of 153° and sliding angle of 4°. The as-prepared mesh showed rapid oil/water separation with high efficiency and excellent recycling performance. The flux for separation of oil/water mixture could reach as high as 11,000 L m-2 h-1. This facile non-solvent assisted electrospinning method provides a new avenue for preparation of multifunctional porous materials which possess potential applications in large-scale oil/water separation.

Alcohols react with MCM-41 at room temperature and chemically modify mesoporous silica.

PubMed

Björklund, Sebastian; Kocherbitov, Vitaly

2017-08-30

Mesoporous silica has received much attention due to its well-defined structural order, high surface area, and tunable pore diameter. To successfully employ mesoporous silica for nanotechnology applications it is important to consider how it is influenced by solvent molecules due to the fact that most preparation procedures involve treatment in various solvents. In the present work we contribute to this important topic with new results on how MCM-41 is affected by a simple treatment in alcohol at room temperature. The effects of alcohol treatment are characterized by TGA, FTIR, and sorption calorimetry. The results are clear and show that treatment of MCM-41 in methanol, ethanol, propanol, butanol, pentanol, or octanol at room temperature introduces alkoxy groups that are covalently bound to the silica surface. It is shown that alcohol treated MCM-41 becomes more hydrophobic and that this effect is sequentially more prominent going from methanol to octanol. Chemical formation of alkoxy groups onto MCM-41 occurs both for calcined and hydroxylated MCM-41 and the alkoxy groups are hydrolytically unstable and can be replaced by silanol groups after exposure to water. The results are highly relevant for mesoporous silica applications that involve contact or treatment in protic solvents, which is very common.

The Effects of Anchor Groups on (1) TiO2-Catalyzed Photooxidation and (2) Linker-Assisted Assembly on TiO2

NASA Astrophysics Data System (ADS)

Anderson, Ian Mark

Quantum dot-sensitized solar cells (QDSSCs) are a popular target for research due to their potential for highly efficient, easily tuned absorption. Typically, light is absorbed by quantum dots attached to a semiconductor substrate, such as TiO2, via bifunctional linker molecules. This research aims to create a patterned monolayer of linker molecules on a TiO2 film, which would in turn allow the attachment of a patterned layer of quantum dots. One method for the creation of a patterned monolayer is the functionalization of a TiO2 film with a linker molecule, followed by illumination with a laser at 355 nm. This initiates a TiO 2-catalyzed oxidation reaction, causing loss of surface coverage. A second linker molecule can then be adsorbed onto the TiO2 surface in the illuminated area. Towards that end, the behaviors of carboxylic and phosphonic acids adsorbed on TiO2 have been studied. TiO2 films were functionalized by immersion in solutions a single adsorbate and surface coverage was determined by IR spectroscopy. It is shown that phosphonic acids attain higher surface coverage than carboxylic acids, and will displace them from TiO2 when in a polar solvent. Alkyl chain lengths, which can influence stabilities of monolayers, are shown not to have an effect on this relationship. Equilibrium binding data for the adsorption of n-hexadecanoic acid to TiO2 from a THF solution are presented. It is shown that solvent polarity can affect monolayer stability; carboxylates and phosphonates undergo more desorption into polar solvents than nonpolar. Through illumination, it was possible to remove nearly all adsorbed linkers from TiO2. However, the illuminated areas were found not to be receptive to attachment by a second adsorbate. A possible reason for this behavior is presented. I also report on the synthesis and characterization of a straight-chain, thiol-terminated phosphonic acid. Initial experiments involving monolayer formation and quantum dot attachment are presented. Finally, it was found that quantum dots attach in high amounts to linker-functionalized TiO2 when suspended in pyridine. This increased surface attachment was present even when the linker molecule used lacked a functional group which would bind to the CdSe surface.

Solvent Reaction Field Potential inside an Uncharged Globular Protein: A Bridge between Implicit and Explicit Solvent Models?

PubMed Central

Baker, Nathan A.; McCammon, J. Andrew

2008-01-01

The solvent reaction field potential of an uncharged protein immersed in Simple Point Charge/Extended (SPC/E) explicit solvent was computed over a series of molecular dynamics trajectories, intotal 1560 ns of simulation time. A finite, positive potential of 13 to 24 kbTec−1 (where T = 300K), dependent on the geometry of the solvent-accessible surface, was observed inside the biomolecule. The primary contribution to this potential arose from a layer of positive charge density 1.0 Å from the solute surface, on average 0.008 ec/Å3, which we found to be the product of a highly ordered first solvation shell. Significant second solvation shell effects, including additional layers of charge density and a slight decrease in the short-range solvent-solvent interaction strength, were also observed. The impact of these findings on implicit solvent models was assessed by running similar explicit-solvent simulations on the fully charged protein system. When the energy due to the solvent reaction field in the uncharged system is accounted for, correlation between per-atom electrostatic energies for the explicit solvent model and a simple implicit (Poisson) calculation is 0.97, and correlation between per-atom energies for the explicit solvent model and a previously published, optimized Poisson model is 0.99. PMID:17949217

Solvent reaction field potential inside an uncharged globular protein: A bridge between implicit and explicit solvent models?

NASA Astrophysics Data System (ADS)

Cerutti, David S.; Baker, Nathan A.; McCammon, J. Andrew

2007-10-01

The solvent reaction field potential of an uncharged protein immersed in simple point charge/extended explicit solvent was computed over a series of molecular dynamics trajectories, in total 1560ns of simulation time. A finite, positive potential of 13-24 kbTec-1 (where T =300K), dependent on the geometry of the solvent-accessible surface, was observed inside the biomolecule. The primary contribution to this potential arose from a layer of positive charge density 1.0Å from the solute surface, on average 0.008ec/Å3, which we found to be the product of a highly ordered first solvation shell. Significant second solvation shell effects, including additional layers of charge density and a slight decrease in the short-range solvent-solvent interaction strength, were also observed. The impact of these findings on implicit solvent models was assessed by running similar explicit solvent simulations on the fully charged protein system. When the energy due to the solvent reaction field in the uncharged system is accounted for, correlation between per-atom electrostatic energies for the explicit solvent model and a simple implicit (Poisson) calculation is 0.97, and correlation between per-atom energies for the explicit solvent model and a previously published, optimized Poisson model is 0.99.

An easy-to-use approach for determining the disintegration ability of disintegrants by analysis of available surface area.

PubMed

Iwao, Yasunori; Tanaka, Shoko; Uchimoto, Takeaki; Noguchi, Shuji; Itai, Shigeru

2013-05-01

With the aim of directly predicting the functionality and mechanism of disintegrants during the disintegration and dissolution of tablets, we investigated an analysis method based on available surface area, which is the surface area of a drug in a formulation in direct contact with the external solvent during dissolution. We evaluated the following disintegrants in this study: sodium starch glycolate (Glycolys), crospovidone (Kollidon CL), carboxymethylcellulose calcium (CMC-Ca), low-substituted hydroxypropylcellulose (L-HPC), and croscarmellose sodium (Ac-Di-Sol). When disintegrant was added to a 50% ethenzamide tablet formulation, an increase in the dissolution rate dependent on disintegrant concentration was observed, according to the type of disintegrant. In addition, the available surface area also differed between disintegrants. For Glycolys, CMC-Ca, and Ac-Di-Sol, a rapid increase in available surface area and a large increase in maximum available surface area (Smax) were observed due to high swellability and wicking, even when the disintegrant concentration was only 1.0%. In contrast, for Kollidon CL and LH-21, a gradual increase in available surface area was observed, depending on the disintegrant concentration. To evaluate the disintegrant ability, Δtmax and ΔSmax were calculated by subtracting peak time (tmax) at 5.0% from that at 1.0% and subtracting Smax at 1.0% from that at 5.0%, respectively, and it was found that the water absorption ratio had strong negative correlations with Δtmax and ΔSmax. Therefore, this study demonstrates that analysis of only available surface area and parameters thereby obtained can directly provide useful information, especially about the disintegration ability of disintegrants. Copyright © 2013 Elsevier B.V. All rights reserved.

Electric field-driven, magnetically-stabilized ferro-emulsion phase contactor

DOEpatents

Scott, T.C.

1990-07-17

Methods and systems are disclosed for interfacial surface area contact between a dispersed phase liquid and a continuous phase liquid in counter-current flow for purposes such as solvent extraction. Initial droplets of a dispersed phase liquid material containing ferromagnetic particles functioning as a packing'' are introduced to a counter-current flow of the continuous phase. A high intensity pulsed electric field is applied so as to shatter the initial droplets into a ferromagnetic emulsion comprising many smaller daughter droplets having a greater combined total surface area than that of the initial droplets in contact with the continuous phase material. A magnetic field is applied to control the position of the ferromagnetic emulsion for enhanced coalescence of the daughter droplets into larger reformed droplets. 2 figs.

Electric field-driven, magnetically-stabilized ferro-emulsion phase contactor

DOEpatents

Scott, Timothy C.

1990-01-01

Methods and systems for interfacial surface area contact between a dispersed phase liquid and a continuous phase liquid in counter-current flow for purposes such as solvent extraction. Initial droplets of a dispersed phase liquid material containing ferromagnetic particles functioning as a "packing" are introduced to a counter-current flow of the continuous phase. A high intensity pulsed electric field is applied so as to shatter the initial droplets into a ferromagnetic emulsion comprising many smaller daughter droplets having a greater combined total surface area than that of the initial droplets in contact with the continuous phase material. A magnetic field is applied to control the position of the ferromagnetic emulsion for enhanced coalescence of the daughter droplets into larger reformed droplets.

Catalyst for hydrotreating carbonaceous liquids

DOEpatents

Berg, Lloyd; McCandless, Frank P.; Ramer, Ronald J.

1982-01-01

A catalyst for denitrogenating and desulfurating carbonaceous liquid such as solvent refined coal includes catalytic metal oxides impregnated within a porous base of mostly alumina with relatively large pore diameters, surface area and pore volume. The base material includes pore volumes of 0.7-0.85 ml/g, surface areas of 200-350 m.sup.2 /g and pore diameters of 85-200 Angstroms. The catalytic metals impregnated into these base materials include the oxides of Group VI metals, molybdenum and tungsten, and the oxides of Group VIII metals, nickel and cobalt, in various combinations. These catalysts and bases in combination have effectively promoted the removal of chemically combined sulfur and nitrogen within a continuous flowing mixture of carbonaceous liquid and hydrogen gas.

Solvent coarsening around colloids driven by temperature gradients

NASA Astrophysics Data System (ADS)

Roy, Sutapa; Dietrich, Siegfried; Maciolek, Anna

2018-04-01

Using mesoscopic numerical simulations and analytical theory, we investigate the coarsening of the solvent structure around a colloidal particle emerging after a temperature quench of the colloid surface. Qualitative differences in the coarsening mechanisms are found, depending on the composition of the binary liquid mixture forming the solvent and on the adsorption preferences of the colloid. For an adsorptionwise neutral colloid, the phase next to its surface alternates as a function of time. This behavior sets in on the scale of the relaxation time of the solvent and is absent for colloids with strong adsorption preferences. A Janus colloid, with a small temperature difference between its two hemispheres, reveals an asymmetric structure formation and surface enrichment around it, even if the solvent is within its one-phase region and if the temperature of the colloid is above the critical demixing temperature Tc of the solvent. Our phenomenological model turns out to capture recent experimental findings according to which, upon laser illumination of a Janus colloid and due to the ensuing temperature gradient between its two hemispheres, the surrounding binary liquid mixture develops a concentration gradient.

Conversion of glycerol to polyglycerol over waste duck-bones as a catalyst in solvent free etherification process

NASA Astrophysics Data System (ADS)

Ayoub, Muhammad; Sufian, Suriati; Mekuria Hailegiorgis, Sintayehu; Ullah, Sami; Uemura, Yoshimitsu

2017-08-01

The alkaline catalyst derived from the duck-bones was used for conversion of glycerol to polyglycerol via solvent free etherification process. The physicochemical properties of prepared materials were duck-bones were systematically investigated as a catalyst by latest techniques of Thermo gravimetric analysis (TGA), X-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) surface properties. TGA showed different trends of duck-bones decomposition from room temperature to 1000C. XRD pattern showed a clear and sharp peaks of a crystalline phase of CaO. The activity of the catalysts was in line with the basic amount of the strong base sites, surface area, and crystalline phase in the catalysts. The prepared catalyst derived from duck-bones provided high activity (99 %) for glycerol conversion and around 68 % yield for polyglycerol production. These ample wastes of duck-bones have good potential to be used as polyglycerol production catalysts due to have high quantity of Ca compare to other types of bones like cow, chicken and fish bones.

Superhydrophobic Blood-Repellent Surfaces.

PubMed

Jokinen, Ville; Kankuri, Esko; Hoshian, Sasha; Franssila, Sami; Ras, Robin H A

2018-06-01

Superhydrophobic surfaces repel water and, in some cases, other liquids as well. The repellency is caused by topographical features at the nano-/microscale and low surface energy. Blood is a challenging liquid to repel due to its high propensity for activation of intrinsic hemostatic mechanisms, induction of coagulation, and platelet activation upon contact with foreign surfaces. Imbalanced activation of coagulation drives thrombogenesis or formation of blood clots that can occlude the blood flow either on-site or further downstream as emboli, exposing tissues to ischemia and infarction. Blood-repellent superhydrophobic surfaces aim toward reducing the thrombogenicity of surfaces of blood-contacting devices and implants. Several mechanisms that lead to blood repellency are proposed, focusing mainly on platelet antiadhesion. Structured surfaces can: (i) reduce the effective area exposed to platelets, (ii) reduce the adhesion area available to individual platelets, (iii) cause hydrodynamic effects that reduce platelet adhesion, and (iv) reduce or alter protein adsorption in a way that is not conducive to thrombus formation. These mechanisms benefit from the superhydrophobic Cassie state, in which a thin layer of air is trapped between the solid surface and the liquid. The connections between water- and blood repellency are discussed and several recent examples of blood-repellent superhydrophobic surfaces are highlighted. © 2018 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

40 CFR 63.5746 - How do I demonstrate compliance with the emission limits for aluminum wipedown solvents and...

Code of Federal Regulations, 2011 CFR

2011-07-01

...) to determine the density of each aluminum surface coating and wipedown solvent. (d) Compliance is... Hazardous Air Pollutants for Boat Manufacturing Standards for Aluminum Recreational Boat Surface Coating... of solids per liter of coating, or volume fraction) of each aluminum surface coating, including...

Low-Temperature Soft-Cover Deposition of Uniform Large-Scale Perovskite Films for High-Performance Solar Cells.

PubMed

Ye, Fei; Tang, Wentao; Xie, Fengxian; Yin, Maoshu; He, Jinjin; Wang, Yanbo; Chen, Han; Qiang, Yinghuai; Yang, Xudong; Han, Liyuan

2017-09-01

Large-scale high-quality perovskite thin films are crucial to produce high-performance perovskite solar cells. However, for perovskite films fabricated by solvent-rich processes, film uniformity can be prevented by convection during thermal evaporation of the solvent. Here, a scalable low-temperature soft-cover deposition (LT-SCD) method is presented, where the thermal convection-induced defects in perovskite films are eliminated through a strategy of surface tension relaxation. Compact, homogeneous, and convection-induced-defects-free perovskite films are obtained on an area of 12 cm 2 , which enables a power conversion efficiency (PCE) of 15.5% on a solar cell with an area of 5 cm 2 . This is the highest efficiency at this large cell area. A PCE of 15.3% is also obtained on a flexible perovskite solar cell deposited on the polyethylene terephthalate substrate owing to the advantage of presented low-temperature processing. Hence, the present LT-SCD technology provides a new non-spin-coating route to the deposition of large-area uniform perovskite films for both rigid and flexible perovskite devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Covalent Surface Modification of Silicon Oxides with Alcohols in Polar Aprotic Solvents.

PubMed

Lee, Austin W H; Gates, Byron D

2017-09-05

Alcohol-based monolayers were successfully formed on the surfaces of silicon oxides through reactions performed in polar aprotic solvents. Monolayers prepared from alcohol-based reagents have been previously introduced as an alternative approach to covalently modify the surfaces of silicon oxides. These reagents are readily available, widely distributed, and are minimally susceptible to side reactions with ambient moisture. A limitation of using alcohol-based compounds is that previous reactions required relatively high temperatures in neat solutions, which can degrade some alcohol compounds or could lead to other unwanted side reactions during the formation of the monolayers. To overcome these challenges, we investigate the condensation reaction of alcohols on silicon oxides carried out in polar aprotic solvents. In particular, propylene carbonate has been identified as a polar aprotic solvent that is relatively nontoxic, readily accessible, and can facilitate the formation of alcohol-based monolayers. We have successfully demonstrated this approach for tuning the surface chemistry of silicon oxide surfaces with a variety of alcohol containing compounds. The strategy introduced in this research can be utilized to create silicon oxide surfaces with hydrophobic, oleophobic, or charged functionalities.

From microporous regular frameworks to mesoporous materials with ultrahigh surface area: dynamic reorganization of porous polymer networks.

PubMed

Kuhn, Pierre; Forget, Aurélien; Su, Dangsheng; Thomas, Arne; Antonietti, Markus

2008-10-08

High surface area organic materials featuring both micro- and mesopores were synthesized under ionothermal conditions via the formation of polyaryltriazine networks. While the polytrimerization of nitriles in zinc chloride at 400 degrees C produces microporous polymers, higher reaction temperatures induce the formation of additional spherical mesopores with a narrow dispersity. The nitrogen-rich carbonaceous polymer materials thus obtained present surface areas and porosities up to 3300 m(2) g(-1) and 2.4 cm(3) g(-1), respectively. The key point of this synthesis relies on the occurrence of several high temperature polymerization reactions, where irreversible carbonization reactions coupled with the reversible trimerization of nitriles allow the reorganization of the dynamic triazine network. The ZnCl2 molten salt fulfills the requirement of a high temperature solvent, but is also required as catalyst. Thus, this dynamic polymerization system provides not only highly micro- and mesoporous materials, but also allows controlling the pore structure in amorphous organic materials.

Synthesis by extrusion: continuous, large-scale preparation of MOFs using little or no solvent† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4sc03217a Click here for additional data file.

PubMed Central

Crawford, Deborah; Casaban, José; Haydon, Robert; Giri, Nicola; McNally, Tony

2015-01-01

Grinding solid reagents under solvent-free or low-solvent conditions (mechanochemistry) is emerging as a general synthetic technique which is an alternative to conventional solvent-intensive methods. However, it is essential to find ways to scale-up this type of synthesis if its promise of cleaner manufacturing is to be realised. Here, we demonstrate the use of twin screw and single screw extruders for the continuous synthesis of various metal complexes, including Ni(salen), Ni(NCS)2(PPh3)2 as well as the commercially important metal organic frameworks (MOFs) Cu3(BTC)2 (HKUST-1), Zn(2-methylimidazolate)2 (ZIF-8, MAF-4) and Al(fumarate)(OH). Notably, Al(fumarate)(OH) has not previously been synthesised mechanochemically. Quantitative conversions occur to give products at kg h–1 rates which, after activation, exhibit surface areas and pore volumes equivalent to those of materials produced by conventional solvent-based methods. Some reactions can be performed either under completely solvent-free conditions whereas others require the addition of small amounts of solvent (typically 3–4 mol equivalents). Continuous neat melt phase synthesis is also successfully demonstrated by both twin screw and single screw extrusion for ZIF-8. The latter technique provided ZIF-8 at 4 kg h–1. The space time yields (STYs) for these methods of up to 144 × 103 kg per m3 per day are orders of magnitude greater than STYs for other methods of making MOFs. Extrusion methods clearly enable scaling of mechanochemical and melt phase synthesis under solvent-free or low-solvent conditions, and may also be applied in synthesis more generally. PMID:29308131

Debinding and Sintering of an Injection-Moulded Hypereutectic Al⁻Si Alloy.

PubMed

Ni, Jiaqi; Yu, Muhuo; Han, Keqing

2018-05-16

Hypereutectic Al⁻Si (20 wt.%) alloy parts were fabricated by employing a powder injection moulding (PIM) technique with a developed multi-component binder system composed of high-density polyethylene (35 wt.%), carnauba wax (62 wt.%) and stearic acid (3 wt.%). The feedstocks contained 83 wt.% metal powders. The debinding process was carried out by a combination of solvent extraction and thermal decomposition. The effects of solvent debinding variables such as kind of solvents, debinding temperatures and time, and the bulk surface area to volume ratios on the debinding process were investigated. Thermal debinding and the subsequent sintering process were carried out in a heating sequence under a nitrogen atmosphere. The influences of sintering temperature and sintering time on the mechanical properties and structure were considered. Under the optimal sintering condition, sintering at 550 °C for 3 h, the final sintering parts were free of distortion and exhibited good mechanical properties. Relative sintered density, Brinell hardness, and tensile strength were ~95.5%, 58 HBW and ~154, respectively.

Protein-Style Dynamical Transition in a Non-Biological Polymer and a Non-Aqueous Solvent.

PubMed

Mamontov, E; Sharma, V K; Borreguero, J M; Tyagi, M

2016-03-31

Temperature-dependent onset of apparent anharmonicity in the microscopic dynamics of hydrated proteins and other biomolecules has been known as protein dynamical transition for the last quarter of a century. Using neutron scattering and molecular dynamics simulation, techniques most often associated with protein dynamical transition studies, we have investigated the microscopic dynamics of one of the most common polymers, polystyrene, which was exposed to toluene vapor, mimicking the process of protein hydration from water vapor. Polystyrene with adsorbed toluene is an example of a solvent-solute system, which, unlike biopolymers, is anhydrous and lacks hydrogen bonding. Nevertheless, it exhibits the essential traits of the dynamical transition in biomolecules, such as a specific dependence of the microscopic dynamics of both solvent and host on the temperature and the amount of solvent adsorbed. We conclude that the protein dynamical transition is a manifestation of a universal solvent-solute dynamical relationship, which is not specific to either biomolecules as solute, or aqueous media as solvent, or even a particular type of interactions between solvent and solute.

Neuropsychological Symptoms among Workers Exposed to Toluene and Xylene in Two Paint Manufacturing Factories in Eastern Thailand

PubMed Central

Thetkathuek, Anamai; Jaidee, Wanlop; Saowakhontha, Sastri; Ekburanawat, Wiwat

2015-01-01

The study analyzed the exposure factors that may lead to neuropsychological symptoms among 92 workers who were exposed to xylene and toluene and 100 workers who were not exposed to the solvents. The airborne concentration of xylene and toluene was evaluated with personal passive badges. The levels of methyl hippuric acid and hippuric acid in urine were assessed, and interviews were performed to observe the neuropsychological symptoms that may result from exposure to the solvents. The result showed that the average concentration for the exposed group of xylene in the paint company working environment was 2.7 (SD = 2.4) ppm and the average concentration of toluene was 9.5 (SD = 10.4) ppm. The average level of methyl hippuric acid in urine was 78 (SD = 74.7) mg/g creatinine. Factors that affected the neuropsychological symptoms included the following. (1) The impact of age: the risk (adjusted odds ratio) for getting psychosomatic symptoms in persons over 40 and exposed to xylene was 9.5 and the aOR of those exposed to toluene was 8.3. (2) The impact of not providing personal protective equipment was found to be sleep disturbance; it was found that the aOR of those exposed to xylene was 3.9, and the aOR of those exposed to toluene was 4.4. In summary, periodic examination of workers by occupational physician is needed for detection of early neuropsychological effects, especially psychosomatic symptoms, and sleep disturbances. PMID:26290757

An analysis of historical exposures of pressmen to airborne benzene (1938-2006).

PubMed

Novick, Rachel M; Keenan, James J; Gross, Sherilyn A; Paustenbach, Dennis J

2013-07-01

Benzene is an aromatic hydrocarbon that, with sufficient cumulative lifetime doses, can cause acute myelogenous leukemia. Because of its volatility and solvent properties, it was used in the printing industry in inks, ink solvents, and cleaning agents from the 1930s to the 1970s. This analysis represents the first known attempt to gather and synthesize the available data on historical airborne benzene concentrations in printing facilities and exposures to pressmen. The sources of fugitive benzene vapors from printing operations have been identified as evaporation from ink fountains, exposed sections of the printing cylinder, the paper web, the paper post exit, and spilled ink. In addition, specific activities that could lead to benzene exposure, such as filling the fountains, using solvents to clean the press, and using solvents as personal cleaning agents, potentially occurred multiple times per work period. Eighteen studies were identified that reported workplace airborne concentrations in printing facilities between 1938 and 2006. Typical benzene air concentrations, considering both personal and area samples of various durations, were as high as 200 p.p.m. in the 1930s through the 1950s, 3-35 p.p.m. in the 1960s, 1.3-16 p.p.m. in the 1970s, 0.013-1 in the 1980s, and far less than 1 p.p.m. in the 1990s and 2000s. The decrease in benzene air concentrations by the late 1970s was likely to be linked to the decreased benzene content of printing materials, increased engineering controls, and to more stringent occupational exposure limits.

Prevention of corrosion with polyaniline

NASA Technical Reports Server (NTRS)

Ahmad, Naseer (Inventor); MacDiarmid, Alan G. (Inventor)

1997-01-01

Methods for improving the corrosion inhibition of a metal or metal alloy substrate surface are provided wherein the substrate surface is coated with a polyaniline film. The polyaniline film coating is applied by contacting the substrate surface with a solution of polyaniline. The polyaniline is dissolved in an appropriate organic solvent and the solvent is allowed to evaporate from the substrate surface yielding the polyaniline film coating.

2D SnO2 Nanosheets: Synthesis, Characterization, Structures, and Excellent Sensing Performance to Ethylene Glycol

PubMed Central

Wan, Wenjin; Li, Yuehua; Ren, Xingping; Zhao, Yinping; Gao, Fan; Zhao, Heyun

2018-01-01

Two dimensional (2D)SnO2 nanosheets were synthesized by a substrate-free hydrothermal route using sodium stannate and sodium hydroxide in a mixed solvent of absolute ethanol and deionized water at a lower temperature of 130 °C. The characterization results of the morphology, microstructure, and surface properties of the as-prepared products demonstrated that SnO2 nanosheets with a tetragonal rutile structure, were composed of oriented SnO2 nanoparticles with a diameter of 6–12 nm. The X-ray diffraction (XRD) and high-resolution transmission electron microscope (FETEM) results demonstrated that the dominant exposed surface of the SnO2 nanoparticles was (101), but not (110). The growth and formation was supposed to follow the oriented attachment mechanism. The SnO2 nanosheets exhibited an excellent sensing response toward ethylene glycol at a lower optimal operating voltage of 3.4 V. The response to 400 ppm ethylene glycol reaches 395 at 3.4 V. Even under the low concentration of 5, 10, and 20 ppm, the sensor exhibited a high response of 6.9, 7.8, and 12.0 to ethylene glycol, respectively. The response of the SnO2 nanosheets exhibited a linear dependence on the ethylene glycol concentration from 5 to 1000 ppm. The excellent sensing performance was attributed to the present SnO2 nanoparticles with small size close to the Debye length, the larger specific surface, the high-energy exposed facets of the (101) surface, and the synergistic effects of the SnO2 nanoparticles of the nanosheets. PMID:29462938

Nanobubbles do not sit alone at the solid-liquid interface.

PubMed

Peng, Hong; Hampton, Marc A; Nguyen, Anh V

2013-05-21

The unexpected stability and anomalous contact angle of gaseous nanobubbles at the hydrophobic solid-liquid interface has been an issue of debate for almost two decades. In this work silicon-nitride tipped AFM cantilevers are used to probe the highly ordered pyrolytic graphite (HOPG)-water interface with and without solvent-exchange (a common nanobubble production method). Without solvent-exchange the force obtained by the single force and force mapping techniques is consistent over the HOPG atomic layers and described by DLVO theory (strong EDL repulsion). With solvent-exchange the force is non-DLVO (no EDL repulsion) and the range of the attractive jump-in (>10 nm) over the surface is grouped into circular areas of longer range, consistent with nanobubbles, and the area of shorter range. The non-DLVO nature of the area between nanobubbles suggests that the interaction is no longer between a silicon-nitride tip and HOPG. Interfacial gas enrichment (IGE) covering the entire area between nanobubbles is suggested to be responsible for the non-DLVO forces. The absence of EDL repulsion suggests that both IGE and nanobubbles are not charged. The coexistence of nanobubbles and IGE provides further evidence of nanobubble stability by dynamic equilibrium. The IGE cannot be removed by contact mode scanning of a cantilever tip in pure water, but in a surfactant (SDS) solution the mechanical action of the tip and the chemical action of the surfactant molecules can successfully remove the enrichment. Strong EDL repulsion between the tip and nanobubbles/IGE in surfactant solutions is due to the polar heads of the adsorbed surfactant molecules.

Risk assessment for adult butterflies exposed to the mosquito control pesticide naled

USGS Publications Warehouse

Bargar, Timothy A.

2012-01-01

A prospective risk assessment was conducted for adult butterflies potentially exposed to the mosquito control insecticide naled. Published acute mortality data, exposure data collected during field studies, and morphometric data (total surface area and fresh body weight) for adult butterflies were combined in a probabilistic estimate of the likelihood that adult butterfly exposure to naled following aerial applications would exceed levels associated with acute mortality. Adult butterfly exposure was estimated based on the product of (1) naled residues on samplers and (2) an exposure metric that normalized total surface area for adult butterflies to their fresh weight. The likelihood that the 10th percentile refined effect estimate for adult butterflies exposed to naled would be exceeded following aerial naled applications was 67 to 80%. The greatest risk would be for butterflies in the family Lycaenidae, and the lowest risk would be for those in the family Hesperidae, assuming equivalent sensitivity to naled. A range of potential guideline naled deposition levels is presented that, if not exceeded, would reduce the risk of adult butterfly mortality. The results for this risk assessment were compared with other risk estimates for butterflies, and the implications for adult butterflies in areas targeted by aerial naled applications are discussed.

Fabrication and Modification of Nanoporous Silicon Particles

NASA Technical Reports Server (NTRS)

Ferrari, Mauro; Liu, Xuewu

2010-01-01

Silicon-based nanoporous particles as biodegradable drug carriers are advantageous in permeation, controlled release, and targeting. The use of biodegradable nanoporous silicon and silicon dioxide, with proper surface treatments, allows sustained drug release within the target site over a period of days, or even weeks, due to selective surface coating. A variety of surface treatment protocols are available for silicon-based particles to be stabilized, functionalized, or modified as required. Coated polyethylene glycol (PEG) chains showed the effective depression of both plasma protein adsorption and cell attachment to the modified surfaces, as well as the advantage of long circulating. Porous silicon particles are micromachined by lithography. Compared to the synthesis route of the nanomaterials, the advantages include: (1) the capability to make different shapes, not only spherical particles but also square, rectangular, or ellipse cross sections, etc.; (2) the capability for very precise dimension control; (3) the capacity for porosity and pore profile control; and (4) allowance of complex surface modification. The particle patterns as small as 60 nm can be fabricated using the state-of-the-art photolithography. The pores in silicon can be fabricated by exposing the silicon in an HF/ethanol solution and then subjecting the pores to an electrical current. The size and shape of the pores inside silicon can be adjusted by the doping of the silicon, electrical current application, the composition of the electrolyte solution, and etching time. The surface of the silicon particles can be modified by many means to provide targeted delivery and on-site permanence for extended release. Multiple active agents can be co-loaded into the particles. Because the surface modification of particles can be done on wafers before the mechanical release, asymmetrical surface modification is feasible. Starting from silicon wafers, a treatment, such as KOH dipping or reactive ion etching (RIE), may be applied to make the surface rough. This helps remove the nucleation layer. A protective layer is then deposited on the wafer. The protective layer, such as silicon nitride film or photoresist film, protects the wafer from electrochemical etching in an HF-based solution. A lithography technique is applied to pattern the particles onto the protective film. The undesired area of the protective film is removed, and the protective film on the back side of the wafer is also removed. Then the pattern is exposed to HF/surfactant solution, and a larger DC electrical current is applied to the wafers for a selected time. This step removes the nucleation layer. Then a DC current is applied to generate the nanopores. Next, a large electrical current is applied to generate a release layer. The particles are mechanically suspended in the solvent and collected by filtration or centrifuge.

Surface Nanobubbles in Nonaqueous Media: Looking for Nanobubbles in DMSO, Formamide, Propylene Carbonate, Ethylammonium Nitrate, and Propylammonium Nitrate.

PubMed

An, Hongjie; Liu, Guangming; Atkin, Rob; Craig, Vincent S J

2015-07-28

Surface nanobubbles produced by supersaturation during the exchange of ethanol for water are routinely observed on hydrophobic surfaces, are stable for days, and have contact angles that are very much greater than observed macroscopically. Here, we test the hypothesis that nanobubbles can also be observed in nonaqueous solvents in order to ascertain if their anomalous lifetimes and contact angles are related to properties of the solvent. Nanobubbles were seen in the protic solvents formamide, ethylammonium nitrate, and propylammonium nitrate, but not in propylene carbonate or dimethyl sulfoxide. Solvents in which nanobubbles were observed exhibit a three-dimensional hydrogen-bonding network. Like in aqueous systems, the nanobubbles were stable for days and exhibited high contact angles (∼165°).

Prediction of the solvent affecting site and the computational design of stable Candida antarctica lipase B in a hydrophilic organic solvent.

PubMed

Park, Hyun June; Joo, Jeong Chan; Park, Kyungmoon; Kim, Yong Hwan; Yoo, Young Je

2013-02-10

Enzyme reactions in organic solvent such as for organic synthesis have great industrial potential. However, enzymes lose their stability in hydrophilic organic solvents due to the deformation of the enzyme by the solvent. It is thus important to enhance the stability of enzymes in hydrophilic organic solvents. Previous approaches have not considered on the interaction between enzymes and solvents due to the lack of information. In this study, the structural motions of the enzyme in methanol cosolvent and the interaction between the enzyme surface and the solvent molecule were investigated using molecular dynamics simulation (MD). By analyzing the MD simulation results, the surface residues of Candida antarctica lipase B (CalB) with higher root mean square deviation (RMSD) in a methanol solvent were considered as methanol affecting site and selected for site-directed mutagenesis. The methanol affecting site was computationally redesigned by lowering the RMSD. Among the candidate mutants, the A8T, A92E, N97Q and T245S mutants showed higher organic solvent stability at various methanol concentrations. The rational approach developed in this study could be applied to the stabilization of other industrial enzymes used in organic solvents. Copyright © 2012 Elsevier B.V. All rights reserved.

Formation of silk fibroin nanoparticles in water-miscible organic solvent and their characterization

NASA Astrophysics Data System (ADS)

Zhang, Yu-Qing; Shen, Wei-De; Xiang, Ru-Li; Zhuge, Lan-Jian; Gao, Wei-Jian; Wang, Wen-Bao

2007-10-01

When Silk fibre derived from Bombyx mori, a native biopolymer, was dissolved in highly concentrated neutral salts such as CaCl2, the regenerated liquid silk, a gradually degraded peptide mixture of silk fibroin, could be obtained. The silk fibroin nanoparticles were prepared rapidly from the liquid silk by using water-miscible protonic and polar aprotonic organic solvents. The nanoparticles are insoluble but well dispersed and stable in aqueous solution and are globular particles with a range of 35-125 nm in diameter by means of TEM, SEM, AFM and laser sizer. Over one half of the ɛ-amino groups exist around the protein nanoparticles by using a trinitrobenzenesulfonic acid (TNBS) method. Raman spectra shows the tyrosine residues on the surface of the globules are more exposed than those on native silk fibers. The crystalline polymorph and conformation transition of the silk nanoparticles from random-coil and α-helix form (Silk I) into anti-parallel β-sheet form (Silk II) are investigated in detail by using infrared, fluorescence and Raman spectroscopy, DSC, 13C CP-MAS NMR and electron diffraction. X-ray diffraction of the silk nanoparticles shows that the nanoparticles crystallinity is about four fifths of the native fiber. Our results indicate that the degraded peptide chains of the regenerated silk is gathered homogeneously or heterogeneously to form a looser globular structure in aqueous solution. When introduced into excessive organic solvent, the looser globules of the liquid silk are rapidly dispersed and simultaneously dehydrated internally and externally, resulting in the further chain-chain contact, arrangement of those hydrophobic domains inside the globules and final formation of crystalline silk nanoparticles with β-sheet configuration. The morphology and size of the nanoparticles are relative to the kinds, properties and even molecular structures of organic solvents, and more significantly to the looser globular substructure of the degraded silk fibroin in aqueous solution. It is possible that the silk protein nanoparticles are potentially useful in biomaterials such as cosmetics, anti-UV skincare products, industrial materials and surface improving materials, especially in enzyme/drug delivery system as vehicle.

Systems and methods for laser assisted sample transfer to solution for chemical analysis

DOEpatents

Van Berkel, Gary J.; Kertesz, Vilmos; Ovchinnikova, Olga S.

2014-06-03

Systems and methods are described for laser ablation of an analyte from a specimen and capturing of the analyte in a dispensed solvent to form a testing solution. A solvent dispensing and extraction system can form a liquid microjunction with the specimen. The solvent dispensing and extraction system can include a surface sampling probe. The laser beam can be directed through the surface sampling probe. The surface sampling probe can also serve as an atomic force microscopy probe. The surface sampling probe can form a seal with the specimen. The testing solution including the analyte can then be analyzed using an analytical instrument or undergo further processing.

Systems and methods for laser assisted sample transfer to solution for chemical analysis

DOEpatents

Van Berkel, Gary J.; Kertesz, Vilmos; Ovchinnikova, Olga S.

2015-09-29

Systems and methods are described for laser ablation of an analyte from a specimen and capturing of the analyte in a dispensed solvent to form a testing solution. A solvent dispensing and extraction system can form a liquid microjunction with the specimen. The solvent dispensing and extraction system can include a surface sampling probe. The laser beam can be directed through the surface sampling probe. The surface sampling probe can also serve as an atomic force microscopy probe. The surface sampling probe can form a seal with the specimen. The testing solution including the analyte can then be analyzed using an analytical instrument or undergo further processing.

Systems and methods for laser assisted sample transfer to solution for chemical analysis

DOEpatents

Van Berkel, Gary J; Kertesz, Vilmos; Ovchinnikova, Olga S

2013-08-27

Systems and methods are described for laser ablation of an analyte from a specimen and capturing of the analyte in a dispensed solvent to form a testing solution. A solvent dispensing and extraction system can form a liquid microjunction with the specimen. The solvent dispensing and extraction system can include a surface sampling probe. The laser beam can be directed through the surface sampling probe. The surface sampling probe can also serve as an atomic force microscopy probe. The surface sampling probe can form a seal with the specimen. The testing solution including the analyte can then be analyzed using an analytical instrument or undergo further processing.

Influence of the type of solvent on the development of superhydrophobicity from silane-based solution containing nanoparticles

NASA Astrophysics Data System (ADS)

Pantoja, M.; Abenojar, J.; Martinez, M. A.

2017-03-01

Superhydrophobic surfaces are very appealing for numerous industrial applications due to their self-cleaning capacity. Although there are different methods to manufacture superhydrophobic surfaces, some of them do not keep the aesthetic appearance of the neat surface. Sol-gel processes are a valid alternative when transparent coatings are desired. The main goal of this research is to study the viability of this method by making superhydrophobic coatings from silane-based solution containing SiO2 nanoparticles. The effect of using different solvents is investigated, as well as the role played by the different components of the solution (silane, nanoparticles and solvent). Solutions of methyltrimethoxisilane (MTS) and tetraethoxysilane (TEOS) and 1% of SiO2 (%wt) were prepared with different solvents (ethanol, ethanol/water and white spirit). The hydrophobicity of the developed coatings is studied using contact angle measurements, while the aesthetic appearance is evaluated with gloss and color measurements. Also, infrared spectroscopy, dynamic light scattering (DSL), and surface tension measurements are used to study the silane solutions. The results show that the capacity of solvents to promote the dispersion of the nanoparticles is crucial to ensuring superhydrophobicity, since these agglomerates provide the micro- and nano- surface roughness required to get a hierarchical structure. However, the combined use of silanes and nanoparticles is key to make a superhydrophobic surface because physical (the surface roughness provided by nanoparticles) and chemical characteristics (hydrophobicity provided by silanes) are coupled.

Protein Stability in Mixed Solvents: A Balance of Contact Interaction and Excluded Volume

PubMed Central

Schellman, John A.

2003-01-01

Changes in excluded volume and contact interaction with the surface of a protein have been suggested as mechanisms for the changes in stability induced by cosolvents. The aim of the present paper is to present an analysis that combines both effects in a quantitative manner. The result is that both processes are present in both stabilizing and destabilizing interactions and neither can be ignored. Excluded volume was estimated using accessible surface area calculations of the kind introduced by Lee and Richards. The change in excluded volume on unfolding, ΔX, is quite large. For example, ΔX for ribonuclease is 6.7 L in urea and ∼16 L in sucrose. The latter number is greater than the molar volume of the protein. Direct interaction with the protein is represented as the solvent exchange mechanism, which differs from ordinary association theory because of the weakness of the interaction and the high concentrations of cosolvents. The balance between the two effects and their contribution to overall stability are most simply presented as bar diagrams as in Fig. 3. Our finding for five proteins is that excluded volume contributes to the stabilization of the native structure and that contact interaction contributes to destabilization. This is true for five proteins and four cosolvents including both denaturants and osmolytes. Whether a substance stabilizes a protein or destabilizes it depends on the relative size of these two contributions. The constant for the cosolvent contact with the protein is remarkably uniform for four of the proteins, indicating a similarity of groups exposed during unfolding. One protein, staphylococcus nuclease, is anomalous in almost all respects. In general, the strength of the interaction with guanidinium is about twice that of urea, which is about twice that of trimethylamine-N-oxide and sucrose. Arguments are presented for the use of volume fractions in equilibrium equations and the ignoring of activity coefficients of the cosolvent. It is shown in the Appendix that both the excluded volume and the direct interaction can be extracted in a unified way from the McMillan-Mayer formula for the second virial coefficient. PMID:12829469

40 CFR 63.5746 - How do I demonstrate compliance with the emission limits for aluminum wipedown solvents and...

Code of Federal Regulations, 2014 CFR

2014-07-01

...) to determine the density of each aluminum surface coating and wipedown solvent. (d) Compliance is... Surface Coating Operations § 63.5746 How do I demonstrate compliance with the emission limits for aluminum... (liters of solids per liter of coating, or volume fraction) of each aluminum surface coating, including...

40 CFR 63.5746 - How do I demonstrate compliance with the emission limits for aluminum wipedown solvents and...

Code of Federal Regulations, 2013 CFR

2013-07-01

...) to determine the density of each aluminum surface coating and wipedown solvent. (d) Compliance is... Surface Coating Operations § 63.5746 How do I demonstrate compliance with the emission limits for aluminum... (liters of solids per liter of coating, or volume fraction) of each aluminum surface coating, including...

Solvent jet desorption capillary photoionization-mass spectrometry.

PubMed

Haapala, Markus; Teppo, Jaakko; Ollikainen, Elisa; Kiiski, Iiro; Vaikkinen, Anu; Kauppila, Tiina J; Kostiainen, Risto

2015-03-17

A new ambient mass spectrometry method, solvent jet desorption capillary photoionization (DCPI), is described. The method uses a solvent jet generated by a coaxial nebulizer operated at ambient conditions with nitrogen as nebulizer gas. The solvent jet is directed onto a sample surface, from which analytes are extracted into the solvent and ejected from the surface in secondary droplets formed in collisions between the jet and the sample surface. The secondary droplets are directed into the heated capillary photoionization (CPI) device, where the droplets are vaporized and the gaseous analytes are ionized by 10 eV photons generated by a vacuum ultraviolet (VUV) krypton discharge lamp. As the CPI device is directly connected to the extended capillary inlet of the MS, high ion transfer efficiency to the vacuum of MS is achieved. The solvent jet DCPI provides several advantages: high sensitivity for nonpolar and polar compounds with limit of detection down to low fmol levels, capability of analyzing small and large molecules, and good spatial resolution (250 μm). Two ionization mechanisms are involved in DCPI: atmospheric pressure photoionization, capable of ionizing polar and nonpolar compounds, and solvent assisted inlet ionization capable of ionizing larger molecules like peptides. The feasibility of DCPI was successfully tested in the analysis of polar and nonpolar compounds in sage leaves and chili pepper.

The Parkinsons Registry Investigation of Diagnosis and Etiology (PRIDE) Study

DTIC Science & Technology

2016-04-01

Committee for the Protection of Human Subjects (CPHS) through the State of California Health and Human Services Agency on 20-June-2011 as a minimal... pesticides , solvents or traumatic brain injury increase PD risk. This study takes advantage of the population-based PD registry in Santa Clara County...related morbidity and mortality are greater in persons exposed to pesticides , solvents, PCBs, and air pollutants. In addition, we will conduct a case

Solvent-induced synthesis of nitrogen-doped hollow carbon spheres with tunable surface morphology for supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Feng; Yuan, Ren-Lu; Zhang, Ning; Ke, Chang-Ce; Ma, Shao-Xia; Zhang, Ru-Liang; Liu, Lei

2018-04-01

Nitrogen doped hollow carbon spheres (NHCSs) with tunable surface morphology have been prepared through one-pot carbonization method by using melamine-formaldehyde spheres as template and resorcinol-based resin as carbon precursor in ethanol-water solution. Well-dispersed NHCSs with particle size of 800 nm were obtained and the surface of NHCSs turn from smooth to tough, wrinkled, and finally concave by increasing the ethanol concentration. The fabricated NHCSs possessed high nitrogen content (3.99-4.83%) and hierarchical micro-dual mesoporous structure with surface area range of 265-405 m2 g-1 and total pore volume of 0.18-0.29 cm3 g-1, which contributed to high specific capacitance, excellent rate capability and long cycle life.

Surface charge modification increases firefly luciferase rigidity without alteration in bioluminescence spectra.

PubMed

Mortazavi, Mojtaba; Hosseinkhani, Saman

2017-01-01

Protein engineering can provide useful approaches for loop anchoring and mutation of surface-exposed loop residues to Arg for the design of thermostable proteins. In this context and due to the high proportion of surface loops, some of the solvent-exposed residues in the Lampyris turkestanicus luciferase were mutated to Arg. Using the red-emitter mutant luciferase (E354R/Arg356), the single (-Q35R, -I182R, -I232R and -L300R), double (-Q35R/I232R) and triple (-Q35R/I232R/I182R) mutant luciferases were introduced. The relative remaining activity of -I232R, double and triple mutants increased significantly compared to the wild-type at 40°C. The optimal temperature of these mutants increased up to 40°C which were 15°C more than wild-type luciferase. It is anticipated that these mutations increased the local interactions that finally improved the thermostability and optimum temperature of luciferase. It should be noted that Arg substitution at amino acid positions 35, 182 and 232 had no effect on the bioluminescence emission spectra. Furthermore, these mutations have not significantly changed the specific activities of firefly luciferases. Finally, with the use of the homology modeling and molecular docking, the effects of these substitutions were evaluated. In conclusion, this study provides beneficial insights on how the thermal stability of luciferase can be improved by protein engineering for biological applications. Copyright © 2016 Elsevier Inc. All rights reserved.

Assessment of DNA damage in car spray painters exposed to organic solvents by the high-throughput comet assay.

PubMed

Londoño-Velasco, Elizabeth; Martínez-Perafán, Fabián; Carvajal-Varona, Silvio; García-Vallejo, Felipe; Hoyos-Giraldo, Luz Stella

2016-05-01

Occupational exposure as a painter is associated with DNA damage and development of cancer. Comet assay has been widely adopted as a sensitive and quantitative tool for DNA damage assessment at the individual cell level in populations exposed to genotoxics. The aim of this study was to assess the application of the high-throughput comet assay, to determine the DNA damage in car spray painters. The study population included 52 car spray painters and 52 unexposed subjects. A significant increase in the %TDNA median (p <  0.001) was observed in the exposed group in comparison to the unexposed group. Neither age (%TDNA: p =  0.913) nor time of exposure (%TDNA: p = 0.398) were significantly correlated with DNA damage. The car spray painters who consumed alcohol did not show a significant increase in DNA damage compared to nonalcohol consumers (p  > 0.05). The results showed an increase in DNA breaks in car spray painters exposed to organic solvents and paints; furthermore, they demonstrated the application of high-throughput comet assay in an occupational exposure study to genotoxic agents.

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

Deane, M.; Swan, S.H.; Harris, J.A.

Residents of a census tract that received drinking water from a well contaminated with solvents were previously shown to experience a spontaneous abortion rate over twice that occurring in an unexposed census tract. In addition, the rate of birth defects in the exposed tract was three times that in the unexposed tract. Surprisingly, increased tapwater consumption was associated with higher rates of spontaneous abortions in both the exposed and the unexposed tracts. Subsequent studies in this area have investigated the relation between spontaneous abortions and consumption of tapwater in more detail. In this report, data from the original study havemore » been re-analyzed using methods comparable with those used in more recent studies. These results confirm the association between spontaneous abortions and reported cold tapwater consumption that was seen in the original study. The observed effect was not due to maternal risk factors, nor was it a function of consumption of bottled water. After controlling for bottled water, the odds ratio for consumption of tapwater was 3.4 (95% confidence interval = 0.6-19.4).« less

Scanning tunneling microscopy studies of pulse deposition of dinuclear organometallic molecules on Au(111)

NASA Astrophysics Data System (ADS)

Guo, Song; Alex Kandel, S.

2008-01-01

Ultrahigh-vacuum scanning tunneling microscopy (STM) was used to study trans-[Cl(dppe)2Ru(CC)6Ru(dppe)2Cl] [abbreviated as Ru2, diphenylphosphinoethane (dppe)] on Au(111). This large organometallic molecule was pulse deposited onto the Au(111) surface under ultrahigh-vacuum (UHV) conditions. UHV STM studies on the prepared sample were carried out at room temperature and 77K in order to probe molecular adsorption and to characterize the surface produced by the pulse deposition process. Isolated Ru2 molecules were successfully imaged by STM at room temperature; however, STM images were degraded by mobile toluene solvent molecules that remain on the surface after the deposition. Cooling the sample to 77K allows the solvent molecules to be observed directly using STM, and under these conditions, toluene forms organized striped domains with regular domain boundaries and a lattice characterized by 5.3 and 2.7Å intermolecular distances. When methylene chloride is used as the solvent, it forms analogous domains on the surface at 77K. Mild annealing under vacuum causes most toluene molecules to desorb from the surface; however, this annealing process may lead to thermal degradation of Ru2 molecules. Although pulse deposition is an effective way to deposit molecules on surfaces, the presence of solvent on the surface after pulse deposition is unavoidable without thermal annealing, and this annealing may cause undesired chemical changes in the adsorbates under study. Preparation of samples using pulse deposition must take into account the characteristics of sample molecules, solvent, and surfaces.

Supercritical fluid extraction

DOEpatents

Wai, Chien M.; Laintz, Kenneth

1994-01-01

A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a supercritical fluid solvent containing a chelating agent. The chelating agent forms chelates that are soluble in the supercritical fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is a fluorinated or lipophilic crown ether or fluorinated dithiocarbamate. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process.

Measuring and predicting the emission rate of phthalate plasticizer from vinyl flooring in a specially-designed chamber.

PubMed

Xu, Ying; Liu, Zhe; Park, Jinsoo; Clausen, Per A; Benning, Jennifer L; Little, John C

2012-11-20

The emission of di-2-ethylhexyl phthalate (DEHP) from vinyl flooring (VF) was measured in specially designed stainless steel chambers. In duplicate chamber studies, the gas-phase concentration in the chamber increased slowly and reached a steady state level of 0.8-0.9 μg/m(3) after about 20 days. By increasing the area of vinyl flooring and decreasing that of the stainless steel surface within the chamber, the time to reach steady state was significantly reduced, compared to a previous study (1 month versus 5 months). The adsorption isotherm of DEHP on the stainless steel chamber surfaces was explicitly measured using solvent extraction and thermal desorption. The strong partitioning of DEHP onto the stainless steel surface was found to follow a simple linear relationship. Thermal desorption resulted in higher recovery than solvent extraction. Investigation of sorption kinetics showed that it takes several weeks for the sorption of DEHP onto the stainless steel surface to reach equilibrium. The content of DEHP in VF was measured at about 15% (w/w) using pressurized liquid extraction. The independently measured or calculated parameters were used to validate an SVOC emission model, with excellent agreement between model prediction and the observed gas-phase DEHP chamber concentrations.

Exposures of tungsten nanostructures to divertor plasmas in DIII-D

DOE PAGES

Rudakov, D. L.; Wong, C. P. C.; Doerner, R. P.; ...

2016-01-22

Tungsten nanostructures (W-fuzz) prepared in the PISCES-A linear device have been found to survive direct exposure to divertor plasmas in DIII-D. W-fuzz was exposed in the lower divertor of DIII-D using the divertor material evaluation system. Two samples were exposed in lower single null (LSN) deuterium H-mode plasmas. The first sample was exposed in three discharges terminated by vertical displacement event disruptions, and the second in two discharges near the lowered X-point. More recently, three samples were exposed near the lower outer strike point in predominantly helium H-mode LSN plasmas. In all cases, the W-fuzz survived plasma exposure with littlemore » obvious damage except in the areas where unipolar arcing occurred. In conclusion, arcing is effective in W-fuzz removal, and it appears that surfaces covered with W-fuzz can be more prone to arcing than smooth W surfaces.« less

The addition of nanostructured hydroxyapatite to an experimental adhesive resin.

PubMed

Leitune, Vicente Castelo Branco; Collares, Fabrício Mezzomo; Trommer, Rafael Mello; Andrioli, Daniela Guerra; Bergmann, Carlos Pérez; Samuel, Susana Maria Werner

2013-04-01

Was produced nanostructured hydroxyapatite (HAnano) and evaluated the influence of its incorporation in an adhesive resin. HAnano was produced by a flame-based process and was characterized by scanning electron microscopy. The surface area, particle size, micro-Raman and cytotoxicity were evaluated. The organic phase was formulated by mixing 50 wt.% Bis-GMA, 25 wt.% TEGDMA, and 25 wt.% HEMA. HAnano was added at seven different concentrations: 0; 0.5; 1; 2; 5; 10 and 20 wt.%. Adhesive resins with hydroxyapatite incorporation were evaluated for their radiopacity, degree of conversion, flexural strength, softening in solvent and microshear bond strength. The data were analyzed by one-way ANOVA and Tukey's post hoc test (α=0.05), except for softening in solvent (paired t-test) and cytotoxicity (two-way ANOVA and Bonferroni). HAnano presented 15.096 m(2)/g of specific surface area and a mean size of 26.7 nm. The radiopacity values were not different from those of 1-mm aluminium. The degree of conversion ranged from 52.2 to 63.8%. The incorporation of HAnano did not influence the flexural strength, which ranged from 123.3 to 143.4MPa. The percentage of reduction of the microhardness after immersion in the solvent became lower as the HAnano concentration increased. The addition of 2% nanostructured hydroxyapatite resulted in a higher value of microshear bond strength than the control group (p<0.05). The incorporation of 2% of nanostructured hydroxyapatite into an adhesive resin presented the best results. The incorporation of nanostructured hydroxyapatite increases the adhesive properties and may be a promising filler for adhesive resin. Copyright © 2013 Elsevier Ltd. All rights reserved.

Analysis of the Early Stages and Evolution of Dental Enamel Erosion.

PubMed

Derceli, Juliana Dos Reis; Faraoni, Juliana Jendiroba; Pereira-da-Silva, Marcelo Assumpção; Palma-Dibb, Regina Guenka

2016-01-01

The aim of this study was to evaluate by atomic force microscopy (AFM) the early phases and evolution of dental enamel erosion caused by hydrochloric acid exposure, simulating gastroesophageal reflux episodes. Polished bovine enamel slabs (4x4x2 mm) were selected and exposed to 0.1 mL of 0.01 M hydrochloric acid (pH=2) at 37 ?#61472;?#61616;C using five different exposure intervals (n=1): no acid exposure (control), 10 s, 20 s, 30 s and 40 s. The exposed area was analyzed by AFM in 3 regions to measure the roughness, surface area and morphological surface. The data were analyzed qualitatively. Roughness started as low as that of the control sample, Rrms=3.5 nm, and gradually increased at a rate of 0.3 nm/s, until reaching Rrms=12.5 nm at 30 s. After 40 s, the roughness presented increment of 0.40 nm only. Surface area (SA) increased until 20 s, and for longer exposures, the surface area was constant (at 30 s, SA=4.40 μm2 and at 40 s, SA=4.43 μm2). As regards surface morphology, the control sample presented smaller hydroxyapatite crystals (22 nm) and after 40 s the crystal size was approximately 60 nm. Short periods of exposure were sufficient to produce enamel demineralization in different patterns and the morphological structure was less affected by exposure to hydrochloric acid over 30 s.

Double-grooved nanofibre surfaces with enhanced anisotropic hydrophobicity.

PubMed

Liang, Meimei; Chen, Xin; Xu, Yang; Zhu, Lei; Jin, Xiangyu; Huang, Chen

2017-11-02

This study reports a facile method for fabricating double-grooved fibrous surfaces. The primary grooves of the surface are formed by aligned fibres, while the secondary grooves are achieved by oriented nanogrooves on the fibre surface. Investigation into the formation mechanism reveals that the nanogrooves can be readily tailored through adjusting the solvent ratio and relative humidity. With this understanding, a variety of polymers have been successfully electrospun into fibres having the same nanogrooved feature. These fibres show high resemblance to natural hierarchical structures, and thereby endowing the corresponding double-grooved surface with enhanced anisotropic hydrophobicity. A water droplet at a parallel direction to the grooves exhibits a much higher contact angle and a lower roll-off angle than the droplet at a perpendicular direction. The application potential of such anisotropic hydrophobicity has been demonstrated via a fog collection experiment, in which the double-grooved surface can harvest the largest amount of water. Moreover, the fabrication method requires neither post-treatment nor sophisticated equipment, making us anticipate that the double-grooved surface would be competitive in areas where a highly ordered surface, a large surface area and an anisotropic hydrophobicity are preferred.

'GREENER' SOLVENT-FREE CHEMICAL SYNTHESIS USING MICROWAVE IRRADIATION

EPA Science Inventory

Solvent-free approach that involves microwave (MW) irradiation of neat reactants (undiluted) catalyzed by the surfaces of less-expensive and recyclable mineral supports such as alumina, silica, clay, or 'doped' surfaces is presented which is applicable to a wide range of cleavage...

Clean Air Act Guidelines and Standards for Solvent Use and Surface Coating Industry

EPA Pesticide Factsheets

This page contains the stationary sources of air pollution for the solvent use and surface coating industries, and their corresponding air pollution regulations. To learn more about the regulations for each industry, just click on the links below.

Simultaneously 'pushing' and 'pulling' graphene oxide into low-polar solvents through a designed interface.

PubMed

Liu, Zhen; Liu, Jingquan; Wang, Yichao; Razal, Joselito M; Francis, Paul S; Biggs, Mark J; Barrow, Colin J; Yang, Wenrong

2018-08-03

Dispersing graphene oxide (GO) in low-polar solvents can realize a perfect self-assembly with functional molecules and application in removal of organic impurities that only dissolve in low-polar solvents. The surface chemistry of GO plays an important role in its dispersity in these solvents. The direct transfer of hydrophilic GO into low-polar solvents, however, has remained an experimental challenge. In this study, we design an interface to transfer GO by simultaneously 'pushing and pulling' the nanosheets into low-polar solvents. Our approach is outstanding due to the ability to obtain monolayers of chemically reduced GO (CRGO) with designed surface properties in the organic phase. Using the transferred GO or CRGO dispersions, we have fabricated GO/fullerene nanocomposites and assessed the ability of CRGOs for dye adsorption. We hope our work can provide a universal approach for the phase transfer of other nanomaterials.

Micro- and nano-porous surface patterns prepared by surface-confined directional melt crystallization of solvent

NASA Astrophysics Data System (ADS)

Kim, Byoung Soo; Kim, Hyun Jin; An, Suyeong; Chi, Sangwon; Kim, Junseok; Lee, Jonghwi

2017-07-01

Recently, numerous attempts have been made to engineer micro- and nano-porous surface patterns or to develop convenient preparation methods for the practical applications of self-cleaning surfaces, water-repellent surfaces, novel textures, etc. Herein, we introduce a simple, cheap, and repeatable crystallization-based method to produce porous surface structures, on any surface of already fabricated polymeric materials. Contact of the solvent phase with cooled polymer surfaces enabled the limited dissolution of the surfaces and the subsequent extremely fast melt crystallization of the solvent. After removing the crystals, various micro- and nano-porous patterns were obtained, whose pore sizes ranged over three orders of magnitude. Pore depth was linearly dependent on the dissolution time. Crystal growth was mainly directed normal to the surfaces, but it was also controlled in-plane, resulting in cylindrical or lamellar structures. Superhydrophobic surfaces were successfully prepared on both polystyrene and polycarbonate. This process offers a novel surface engineering tool for a variety of polymer surfaces, whose topology can be conveniently controlled over a wide range by crystal engineering.

STABILITY OF A CYLINDRICAL SOLUTE-SOLVENT INTERFACE: EFFECT OF GEOMETRY, ELECTROSTATICS, AND HYDRODYNAMICS.

PubMed

Li, B O; Sun, Hui; Zhou, Shenggao

The solute-solvent interface that separates biological molecules from their surrounding aqueous solvent characterizes the conformation and dynamics of such molecules. In this work, we construct a solvent fluid dielectric boundary model for the solvation of charged molecules and apply it to study the stability of a model cylindrical solute-solvent interface. The motion of the solute-solvent interface is defined to be the same as that of solvent fluid at the interface. The solvent fluid is assumed to be incompressible and is described by the Stokes equation. The solute is modeled simply by the ideal-gas law. All the viscous force, hydrostatic pressure, solute-solvent van der Waals interaction, surface tension, and electrostatic force are balanced at the solute-solvent interface. We model the electrostatics by Poisson's equation in which the solute-solvent interface is treated as a dielectric boundary that separates the low-dielectric solute from the high-dielectric solvent. For a cylindrical geometry, we find multiple cylindrically shaped equilibrium interfaces that describe polymodal (e.g., dry and wet) states of hydration of an underlying molecular system. These steady-state solutions exhibit bifurcation behavior with respect to the charge density. For their linearized systems, we use the projection method to solve the fluid equation and find the dispersion relation. Our asymptotic analysis shows that, for large wavenumbers, the decay rate is proportional to wavenumber with the proportionality half of the ratio of surface tension to solvent viscosity, indicating that the solvent viscosity does affect the stability of a solute-solvent interface. Consequences of our analysis in the context of biomolecular interactions are discussed.

Physical characterization of MxiH and PrgI, the needle component of the type III secretion apparatus from Shigella and Salmonella

PubMed Central

Darboe, Numukunda; Kenjale, Roma; Picking, Wendy L.; Picking, William D.; Middaugh, C. Russell

2006-01-01

Shigella and Salmonella use similar type III secretion systems for delivering effector proteins into host cells. This secretion system consists of a base anchored in both bacterial membranes and an extracellular “needle” that forms a rod-like structure exposed on the pathogen surface. The needle is composed of multiple subunits of a single protein and makes direct contact with host cells to facilitate protein delivery. The proteins that make up the needle of Shigella and Salmonella are MxiH and PrgI, respectively. These proteins are attractive vaccine candidates because of their essential role in virulence and surface exposure. We therefore isolated, purified, and characterized the monomeric forms of MxiH and PrgI. Their far-UV circular dichroism spectra show structural similarities with hints of subtle differences in their secondary structure. Both proteins are highly helical and thermally unstable, with PrgI having a midpoint of thermal unfolding (Tm) near 37°C and MxiH having a value near 42°C. The two proteins also have comparable intrinsic stabilities as measured by chemically induced (urea) unfolding. MxiH, however, with a free energy of unfolding (ΔG°0,un) of 1.6 kcal/mol, is slightly more stable than PrgI (1.2 kcal/mol). The relatively low m-values obtained for the urea-induced unfolding of the proteins suggest that they undergo only a small change in solvent-accessible surface area. This argues that when MxiH and PrgI are incorporated into the needle complex, they obtain a more stable structural state through the introduction of protein–protein interactions. PMID:16501225

Physical characterization of MxiH and PrgI, the needle component of the type III secretion apparatus from Shigella and Salmonella.

PubMed

Darboe, Numukunda; Kenjale, Roma; Picking, Wendy L; Picking, William D; Middaugh, C Russell

2006-03-01

Shigella and Salmonella use similar type III secretion systems for delivering effector proteins into host cells. This secretion system consists of a base anchored in both bacterial membranes and an extracellular "needle" that forms a rod-like structure exposed on the pathogen surface. The needle is composed of multiple subunits of a single protein and makes direct contact with host cells to facilitate protein delivery. The proteins that make up the needle of Shigella and Salmonella are MxiH and PrgI, respectively. These proteins are attractive vaccine candidates because of their essential role in virulence and surface exposure. We therefore isolated, purified, and characterized the monomeric forms of MxiH and PrgI. Their far-UV circular dichroism spectra show structural similarities with hints of subtle differences in their secondary structure. Both proteins are highly helical and thermally unstable, with PrgI having a midpoint of thermal unfolding (Tm) near 37 degrees C and MxiH having a value near 42 degrees C. The two proteins also have comparable intrinsic stabilities as measured by chemically induced (urea) unfolding. MxiH, however, with a free energy of unfolding (DeltaG degrees 0,un) of 1.6 kcal/mol, is slightly more stable than PrgI (1.2 kcal/mol). The relatively low m-values obtained for the urea-induced unfolding of the proteins suggest that they undergo only a small change in solvent-accessible surface area. This argues that when MxiH and PrgI are incorporated into the needle complex, they obtain a more stable structural state through the introduction of protein-protein interactions.

Study on the disparate transition behaviors of the electrical/physical properties in PEDOT:PSS film depending on solvent species under a follow-up solution-treatment process

NASA Astrophysics Data System (ADS)

Yun, Dong-Jin; Kim, Jung-Hwa; Kim, Seong Heon; Seol, Minsu; Yu, DaEun; Kwon, Hyukju; Ham, Yongnam; Chung, JaeGwan; Kim, Yongsu; Heo, Sung

2016-04-01

In most solution-processed organic devices, a poly(3,4-ethylenedioxythiophene) (PEDOT) polymerized with poly(4-styrenesulfonate) (PSS) film is inevitably affected by various conditions during the subsequent solution-coating processes. To investigate the effects of direct solvent exposure on the properties of PEDOT polymerized with PSS (PEDOT:PSS) films, photoemission spectroscopy-based analytical methods were used before and after solvent-coating processes. Our results clearly indicate that PEDOT:PSS films undergo a different transition mechanism depending on the solubility of the solvent in water. The water-miscible solvents induce the solvation of hydrophilic PSS chains. As a result, this process allows the solvent to diffuse into the PEDOT:PSS film, and a conformational change between PEDOT and PSS occurs. On the other hand, the water-immiscible organic solvents cause the partial adsorption of solvent molecules at the PE surface, which leads to changes in the surface properties, including work function. Based on our finding, we demonstrate that the energy-level alignments at the organic semiconductor/electrode interface for the PEDOT:PSS films can be controlled by simple solvent treatments.

1H NMR-based metabolomics reveals interactive effects between the carrier solvent methanol and a pharmaceutical mixture in an amphibian developmental bioassay with Limnodynastes peronii.

PubMed

Melvin, Steven D; Jones, Oliver A H; Carroll, Anthony R; Leusch, Frederic D L

2018-05-01

Organic carrier solvents are used in aquatic toxicity testing to improve chemical solubility and facilitate the exploration of dose-response relationships. Both water- and solvent-control groups are normally included in these scenarios to ensure that the solvent itself has no effect on the test organism, but this fails to consider possible interactive effects between carrier solvents and contaminants of interest. We explored this topic by exposing Limnodynastes peronii tadpoles to a mixture of common water-soluble pharmaceuticals (diclofenac, metformin and valproic acid) in the presence and absence of the carrier solvent methanol, according to standard developmental bioassay methodology. Nuclear Magnetic Resonance (NMR) spectroscopy was applied as a platform for untargeted metabolomics, to compare broad sub-lethal hepatotoxicity in solvent- and solvent-free exposure scenarios. Considerable interactive effects were identified between the pharmaceutical mixture and a typical dose of methanol (0.003%). Specifically, pronounced differences were observed between the solvent- and solvent-free exposure groups for leucine, acetate, glutamine, citrate, glycogen, tyrosine, arginine, purine nucleotides and an unidentified metabolite at 6.53 ppm. Various other metabolites exhibited similar disparity related to the use of carrier solvent, but the interactions were non-significant. These results raise important questions about the use of carrier solvents for chemical exposures in aquatic ecotoxicology, and particularly for studies interested in sub-lethal mechanistic information and/or biomarker discovery. Copyright © 2018 Elsevier Ltd. All rights reserved.

D-Area Drip Irrigation-Phytoremediation Project: SRTC Final Report

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

Wilde, E.W.

2003-01-14

Groundwater in D-Area at the Savannah River Site (SRS) is contaminated with trichloroethylene (TCE) and by-products resulting from discharges of this organic solvent during past operations. Several potential clean-up strategies are being or have been investigated, including a novel drip irrigation-phytoremediation process that is the focus of the treatability study described in this report. The contaminated groundwater in D-Area occurs primarily at depths of 30 to 50 feet below ground surface, well below the depths that are typically penetrated by plant roots. The system investigated in this study involved pumping water from the contaminated aquifer and discharging the water intomore » overlying test plots below the surface using drip irrigation. The test plots contained pines, cottonwoods, or no vegetation (controls). The primary objective was to determine the overall effectiveness of the process for TCE removal and to elucidate the biotic and abiotic pathways for its removal.« less

Method for preparing ultraflat, atomically perfect areas on large regions of a crystal surface by heteroepitaxy deposition

DOEpatents

El Gabaly, Farid; Schmid, Andreas K.

2013-03-19

A novel method of forming large atomically flat areas is described in which a crystalline substrate having a stepped surface is exposed to a vapor of another material to deposit a material onto the substrate, which material under appropriate conditions self arranges to form 3D islands across the substrate surface. These islands are atomically flat at their top surface, and conform to the stepped surface of the substrate below at the island-substrate interface. Thereafter, the deposited materials are etched away, in the etch process the atomically flat surface areas of the islands transferred to the underlying substrate. Thereafter the substrate may be cleaned and annealed to remove any remaining unwanted contaminants, and eliminate any residual defects that may have remained in the substrate surface as a result of pre-existing imperfections of the substrate.

Superhydrophobic perfluoropolymer/polystyrene blend films induced by nonsolvent

NASA Astrophysics Data System (ADS)

Gengec, Nevin Atalay; Cengiz, Ugur; Erbil, H. Yildirim

2016-10-01

Statistical copolymers of perfluoroalkyl ethyl acrylate (Zonyl-TAN) and methyl methacrylate (MMA) were synthesized in a CO2 polymerization system where a CO2-expanded monomer mixture was formed at 13 MPa, and 80 °C by using AIBN as initiator. Flat and superhydrophobic surfaces were subsequently prepared on glass slides by applying a phase separation process where the synthesized p(TAN-co-MMA) copolymer and polystyrene (PS) were dissolved in THF solvent. Ethanol was added as the non-solvent to introduce superhydrophobicity during film formation. Water contact angle on the flat p(TAN-co-MMA) copolymer was 118° and increased up to 170° with the formation of surface roughness. The ratio of the ethanol non-solvent in the blend solution has an important effect on the magnitude of surface roughness during the phase separation process. Both pits and protrusions of 1-10 μm in size were formed on the surface when non-solvent was used. Surface roughness increased with the increase in the ethanol ratio and the PS content of the blend solution.

Field induced decrystallization of silicon: Evidence of a microwave non-thermal effect

NASA Astrophysics Data System (ADS)

Nozariasbmarz, Amin; Dsouza, Kelvin; Vashaee, Daryoosh

2018-02-01

It is rather strange and not fully understood that some materials decrystallize when exposed to microwave radiation, and it is still debatable if such a transformation is a thermal or non-thermal effect. We hereby report experimental evidences that weight the latter effect. First, a single crystal silicon wafer exposed to microwaves showed strong decrystallization at high temperature. Second, when some areas of the wafer were masked with metal coating, only the exposed areas underwent decrystallization. Transmission electron microscopy analysis, x-ray diffraction data, and thermal conductivity measurements all indicated strong decrystallization, which occurred in the bulk of the material and was not a surface effect. These observations favor the existence of a non-thermal microwave effect.

Academic Difficulties in Children with Prenatal Alcohol Exposure: Presence, Profile, and Neural Correlates.

PubMed

Glass, Leila; Moore, Eileen M; Akshoomoff, Natacha; Jones, Kenneth Lyons; Riley, Edward P; Mattson, Sarah N

2017-05-01

Academic achievement was evaluated in children with heavy prenatal alcohol exposure to determine potential strengths and weaknesses, evaluate the utility of different definitions for identifying low academic performance, and explore the neural correlates that may underlie academic performance. Children (8 to 16 years) were assessed using the WIAT-II. Patterns of performance were examined in 2 subject groups: children with heavy prenatal alcohol exposure (n = 67) and controls (n = 61). A repeated-measures MANCOVA examining group differences on academic domain (reading, spelling, math) scores was conducted. Post hoc comparisons examined within-group profiles. Numbers and percentage of children with low achievement were calculated using several criteria. In a subsample (n = 42), neural correlates were analyzed using FreeSurfer v5.3 to examine relations between cortical structure (thickness and surface area) and performance. The alcohol-exposed group performed worse than controls on all domains and had a unique academic profile, supported by a significant group × academic domain interaction (p < 0.001). For the alcohol-exposed group, math reasoning was significantly lower than numerical operations, which was significantly lower than spelling and word reading. Over half of the alcohol-exposed group (58.2%) demonstrated low achievement on 1 or more academic domains. The number and percentage of children meeting criteria for low achievement varied based on the domain and definition used. The imaging analysis identified several surface area clusters that were differentially related to math (L superior parietal and R lateral/middle occipital) and spelling (bilateral inferior and medial temporal) performance by group, with no relations for the other academic domains. Generally, scores improved as surface area decreased in controls, whereas no relation or a positive relation was observed in the alcohol-exposed group. Alcohol-exposed children demonstrated deficits in academic performance across domains and definitions, with a relative weakness in math functioning. Atypical brain development may contribute to these impairments in academic achievement. Understanding academic difficulties can assist in advocating effectively for alcohol-exposed children. Copyright © 2017 by the Research Society on Alcoholism.

CHEMISTRY UNDER 'GREENER' CONDITIONS: SOLVENT-FREE SYNTHESIS USING MICROWAVE IRRADIATION

EPA Science Inventory

Solvent-free approach is emphasized that involves microwave (MW) irradiation of neat reactants (undiluted) catalyzed by the surfaces of less-expensive and recyclable mineral supports such as alumina, silica, clay, or 'doped' surfaces which is applicable to a wide range of cleavag...

ORGANIC SYNTHESES IN SOLVENT-FREE AND AQUEOUS MEDIA USING MICROWAVES

EPA Science Inventory

A solvent-free approach that involves microwave (MW) exposure of neat reactants (undiluted) catalyzed by the surfaces of recyclable mineral supports such as alumina, silica, clay, or 'doped' surfaces is presented which is applicable to a wide range of cleavage, condensation, cycl...

Cellulose Surface Degradation by a Lytic Polysaccharide Monooxygenase and Its Effect on Cellulase Hydrolytic Efficiency*

PubMed Central

Eibinger, Manuel; Ganner, Thomas; Bubner, Patricia; Rošker, Stephanie; Kracher, Daniel; Haltrich, Dietmar; Ludwig, Roland; Plank, Harald; Nidetzky, Bernd

2014-01-01

Lytic polysaccharide monooxygenase (LPMO) represents a unique principle of oxidative degradation of recalcitrant insoluble polysaccharides. Used in combination with hydrolytic enzymes, LPMO appears to constitute a significant factor of the efficiency of enzymatic biomass depolymerization. LPMO activity on different cellulose substrates has been shown from the slow release of oxidized oligosaccharides into solution, but an immediate and direct demonstration of the enzyme action on the cellulose surface is lacking. Specificity of LPMO for degrading ordered crystalline and unordered amorphous cellulose material of the substrate surface is also unknown. We show by fluorescence dye adsorption analyzed with confocal laser scanning microscopy that a LPMO (from Neurospora crassa) introduces carboxyl groups primarily in surface-exposed crystalline areas of the cellulosic substrate. Using time-resolved in situ atomic force microscopy we further demonstrate that cellulose nano-fibrils exposed on the surface are degraded into shorter and thinner insoluble fragments. Also using atomic force microscopy, we show that prior action of LPMO enables cellulases to attack otherwise highly resistant crystalline substrate areas and that it promotes an overall faster and more complete surface degradation. Overall, this study reveals key characteristics of LPMO action on the cellulose surface and suggests the effects of substrate morphology on the synergy between LPMO and hydrolytic enzymes in cellulose depolymerization. PMID:25361767

Characterization of the binding of 8-anilinonaphthalene sulphonate to rat class Mu GST M1-1

PubMed Central

Kinsley, Nichole; Sayed, Yasien; Armstrong, Richard N.; Dirr, Heini W.

2008-01-01

Molecular docking and ANS-displacement experiments indicated that 8-anilinonaphthalene sulphonate (ANS) binds the hydrophobic site (H-site) in the active site of dimeric class Mu rGST M1-1. The naphthalene moiety provides most of the van der Waals contacts at the ANS-binding interface while the anilino group is able to sample different rotamers. The energetics of ANS binding were studied by isothermal titration calorimetry (ITC) over the temperature range of 5–30 °C. Binding is both enthalpically and entropically driven and displays a stoichiometry of one ANS molecule per subunit (or H-site). ANS binding is linked to the uptake of 0.5 protons at pH 6.5. Enthalpy of binding depends linearly upon temperature yielding a ΔCp of −80 ± 4 cal K−1 mol−1 indicating the burial of solvent-exposed nonpolar surface area upon ANS-protein complex formation. While ion-pair interactions between the sulfonate moiety of ANS and protein cationic groups may be significant for other ANS-binding proteins, the binding of ANS to rGST M1-1 is primarily hydrophobic in origin. The binding properties are compared with those of other GSTs and ANS-binding proteins. PMID:18703268

Albumin Hydrogels Formed by Electrostatically Triggered Self-Assembly and Their Drug Delivery Capability

PubMed Central

2015-01-01

Biological hydrogels are fundamentally biocompatible and have intrinsic similarities to extracellular matrices in medical applications and drug delivery systems. Herein we demonstrate the ability to form drug-eluting protein hydrogels using a novel mechanism that involves the electrostatically triggered partial denaturation and self-assembly of the protein via changes in pH. Partial denaturation increases the protein’s solvent exposed hydrophobic surface area, which then drives self-assembly of the protein into a hydrogel within 10 min at 37 °C. We describe the properties of an albumin hydrogel formed by this mechanism. Intrinsic drug binding properties of albumin to all-trans retinoic acid (atRA) are conserved through the partial denaturation process, as confirmed by fluorescence quenching. atRA released from the hydrogel inhibited smooth muscle cell migration as per an in vitro scratch wound assay. Atomistic molecular dynamics and potential of mean force calculations show the preservation and potential creation of new atRA binding sites with a binding energy of −41 kJ/mol. The resulting hydrogel is also biocompatible and exhibits rapid postgelation degradation after its implantation in vivo. This interdisciplinary work provides a new tool for the development of biocompatible protein hydrogel drug delivery systems. PMID:25148603

Profiling Charge Complementarity and Selectivity for Binding at the Protein Surface

PubMed Central

Sulea, Traian; Purisima, Enrico O.

2003-01-01

A novel analysis and representation of the protein surface in terms of electrostatic binding complementarity and selectivity is presented. The charge optimization methodology is applied in a probe-based approach that simulates the binding process to the target protein. The molecular surface is color coded according to calculated optimal charge or according to charge selectivity, i.e., the binding cost of deviating from the optimal charge. The optimal charge profile depends on both the protein shape and charge distribution whereas the charge selectivity profile depends only on protein shape. High selectivity is concentrated in well-shaped concave pockets, whereas solvent-exposed convex regions are not charge selective. This suggests the synergy of charge and shape selectivity hot spots toward molecular selection and recognition, as well as the asymmetry of charge selectivity at the binding interface of biomolecular systems. The charge complementarity and selectivity profiles map relevant electrostatic properties in a readily interpretable way and encode information that is quite different from that visualized in the standard electrostatic potential map of unbound proteins. PMID:12719221

Solvent/co-solvent effects on the electronic properties and adsorption mechanism of anticancer drug Thioguanine on Graphene oxide surface as a nanocarrier: Density functional theory investigation and a molecular dynamics

NASA Astrophysics Data System (ADS)

Hasanzade, Zohre; Raissi, Heidar

2017-11-01

In this work, the adsorption of Thioguanine (TG) anticancer drug on the surface of Graphene oxide (GO) nanosheet has investigated using density functional theory (DFT) and molecular dynamics simulation (MDs). Quantum mechanics calculations by two methods including M06-2X/6-31G**and ωB97X-D/6-31G** have been employed to calculate the details of energetic, geometric, and electronic properties of the TG molecule interacting with Graphene oxide nanosheet (GONS). DFT calculations confirmed that the strongest adsorption is observed when hydrogen bond interactions between TG molecule and the functional groups of Graphene oxide nanosheet are predominate. In all calculations, solvent effects have been considered in water using the PCM method. It is found that TG molecule can be adsorbed on Graphene oxide with negative solvation energy, indicating the TG adsorption on Graphene oxide surfaces is thermodynamically favored. Moreover, MD simulations are examined to understand the solvent/co-solvent effect (water, ethanol, nicotine) on the Thioguanine drug delivery through Graphene oxide. The results of RDF patterns and the van der Waals energy calculations show that interaction between TG drugs and the Graphene oxide surface is stronger in water solvent compared to the other co-solvent. The obtained MD results illustrate that when nicotine and ethanol exist in the system, the drug takes longer time to bind with GO nanosheet and the system becomes unstable. It can be concluded that Graphene oxide can be a promising candidate in water media for delivery the TG molecule.

KSC-03pd2762

NASA Image and Video Library

2003-10-01

KENNEDY SPACE CENTER, FLA. - In the Orbiter Processing Facility, Ryan Levann, with United Space Alliance, checks data on the tile removed from the thermal barrier around the umbilical areas, the external tank attach points, on the underside of Atlantis. The umbilical areas are closed off after ET separation by a door, seen here. The exposed area of each closed door is covered with reusable surface insulation.

Self assembled molecular monolayers on high surface area materials as molecular getters

DOEpatents

King, David E.; Herdt, Gregory C.; Czanderna, Alvin W.

1997-01-01

The present invention relates to a gettering material that may be used as a filtration medium to remove pollutants from the environment. The gettering material comprises a high surface area material having a metal surface that chemically bonds n-alkanethiols in an organized manner thereby forming a molecular monolayer over the metal surface. The n-alkanethiols have a free functional group that interacts with the environment thereby binding specific pollutants that may be present. The gettering material may be exposed to streams of air in heating, ventilation, and air conditioning systems or streams of water to remove specific pollutants from either medium.

Self assembled molecular monolayers on high surface area materials as molecular getters

DOEpatents

King, D.E.; Herdt, G.C.; Czanderna, A.W.

1997-01-07

The present invention relates to a gettering material that may be used as a filtration medium to remove pollutants from the environment. The gettering material comprises a high surface area material having a metal surface that chemically bonds n-alkanethiols in an organized manner thereby forming a molecular monolayer over the metal surface. The n-alkanethiols have a free functional group that interacts with the environment thereby binding specific pollutants that may be present. The gettering material may be exposed to streams of air in heating, ventilation, and air conditioning systems or streams of water to remove specific pollutants from either medium. 9 figs.

Chemical tapering of polymer optical fiber

NASA Astrophysics Data System (ADS)

Rashid, Affa Rozana Abdul; Afiqah Nasution, Amna; Hanim Suranin, Aisyah; Athirah Taib, Nur; Maisarah Mukhtar, Wan; Dasuki, Karsono Ahmad; Annuar Ehsan, Abang

2017-11-01

Polymer optical fibers (POFs) have significant advantages over numerous sensing applications. The key element in developing sensor is by removing the cladding of the fiber. The use of organic solvent is one of the methods to create tapered POF in order to expose the core region. In this study, the etching chemicals involved is acetone, methyl isobutyl ketone (MIBK), and acetone-methanol mixture. The POF is immersed in 100%, 80%, and 50% of acetone and MIBK dilution. In addition, the mixture of acetone and methanol is also used for POF etching by the ratio 2:1 of the volume. Acetone has shown to be the most reactive solvent towards POF due to its fastest etching rate compared to MIBK and acetone-methanol mixture. The POF is immersed and lifted from the solution for a specific time, depending on the power loss properties for the purpose of producing unclad POF. In comparison to silica fiber optic, the advantages of POF in terms of its simple technique and easy handling enable it to produce unclad POF without damaging the core region. The surface roughness of the POF is investigated under the microscope after being immersed into different solvent. This method of chemical tapering of POF can be used as the fundamental technique for sensor development. Next, the unclad fiber is immersed into ethanol solutions in order to determine the reaction of unclad POF towards its surrounding. The findings show that this particular sensor is sensitive towards concentration changes ranging between 10 wt% to 50 wt%.

Increased rate of solvent diffusion in a prototypical supramolecular gel measured on the picosecond timescale.

PubMed

Seydel, Tilo; Edkins, Robert M; Jones, Christopher D; Foster, Jonathan A; Bewley, Robert; Aguilar, Juan A; Edkins, Katharina

2018-06-14

Solvent diffusion in a prototypical supramolecular gel probed by quasi-elastic neutron scattering on the picosecond timescale is faster than that in the respective bulk solvent. This phenomenon is hypothesized to be due to disruption of the hydrogen bonding of the solvent by the large hydrophobic surface of the gel network.

Oxidative stress-mediated hemolytic activity of solvent exchange-prepared fullerene (C60) nanoparticles

NASA Astrophysics Data System (ADS)

Trpkovic, Andreja; Todorovic-Markovic, Biljana; Kleut, Duska; Misirkic, Maja; Janjetovic, Kristina; Vucicevic, Ljubica; Pantovic, Aleksandar; Jovanovic, Svetlana; Dramicanin, Miroslav; Markovic, Zoran; Trajkovic, Vladimir

2010-09-01

The present study investigated the hemolytic properties of fullerene (C60) nanoparticles prepared by solvent exchange using tetrahydrofuran (nC60THF), or by mechanochemically assisted complexation with macrocyclic oligosaccharide gamma-cyclodextrin (nC60CDX) or the copolymer ethylene vinyl acetate-ethylene vinyl versatate (nC60EVA-EVV). The spectrophotometrical analysis of hemoglobin release revealed that only nC60THF, but not nC60CDX or nC60EVA-EVV, was able to cause lysis of human erythrocytes in a dose- and time-dependent manner. Atomic force microscopy revealed that nC60THF-mediated hemolysis was preceded by erythrocyte shrinkage and increase in cell surface roughness. A flow cytometric analysis confirmed a decrease in erythrocyte size and demonstrated a significant increase in reactive oxygen species production in red blood cells exposed to nC60THF. The nC60THF-triggered hemolytic activity was efficiently reduced by the antioxidants N-acetylcysteine and butylated hydroxyanisole, as well as by serum albumin, the most abundant protein in human blood plasma. These data indicate that nC60THF can cause serum albumin-preventable hemolysis through oxidative stress-mediated damage of the erythrocyte membrane.

Low-cost and fast synthesis of nanoporous silica cryogels for thermal insulation applications.

PubMed

Su, Li Fen; Miao, Lei; Tanemura, Sakae; Xu, Gang

2012-06-01

Nanoporous silica cryogels with a high specific surface area of 1095 m 2 g -1 were fabricated using tert-butyl alcohol as a reaction solvent, via a cost-effective sol-gel process followed by vacuum freeze drying. The total time of cryogel production was reduced markedly to one day. The molar ratio of solvent/precursor, which was varied from 5 to 13, significantly affected the porous structure and thermal insulating properties of the cryogels. The silica cryogels with low densities in the range of 0.08-0.18 g cm -3 and thermal conductivities as low as 6.7 mW (m·K) -1 at 100 Pa and 28.3 mW (m·K) -1 at 10 5 Pa were obtained using this new technique.

Freeze drying for gas chromatography stationary phase deposition

DOEpatents

Sylwester, Alan P [Livermore, CA

2007-01-02

The present disclosure relates to methods for deposition of gas chromatography (GC) stationary phases into chromatography columns, for example gas chromatography columns. A chromatographic medium is dissolved or suspended in a solvent to form a composition. The composition may be inserted into a chromatographic column. Alternatively, portions of the chromatographic column may be exposed or filled with the composition. The composition is permitted to solidify, and at least a portion of the solvent is removed by vacuum sublimation.

HCl, KCl and KOH solvation resolved solute-solvent interactions and solution surface stress

NASA Astrophysics Data System (ADS)

Zhang, Xi; Xu, Yan; Zhou, Yong; Gong, Yinyan; Huang, Yongli; Sun, Chang Q.

2017-11-01

An incorporation of the hydrogen bond (O:Hsbnd O or HB) cooperativity notion, contact angle detection, and the differential phonon spectrometrics (DPS) has enabled us to gain refined information on the HCl, KCl and KOH solvation resolved solute-solvent molecular interactions and the solution surface stresses. Results show that ionic polarization stiffens the solvent Hsbnd O bond phonon from 3200 to 3480 cm-1 in the hydration shells. The HO- in alkaline solution, however, shares not only the same Hsbnd O phonon redshift of compressed water from 3200 to < 3100 cm-1 but also the dangling bonds of H2O surface featured at 3610 cm-1. Salt and alkaline solvation enhances the solution surface stress by K+ and Cl- ionic polarization. The excessive H+ proton in acid solution forms a H↔H anti-HB that depresses the solution surface stress, instead. The solute capability of transforming the fraction of the O:Hsbnd O bonds of the solvent matrix is featured by: fH = 0 and fx ∝ 1-exp(-C/C0) (x = HO-, K+ and Cl-) towards saturation. Exercises not only confirm the presence of the H↔H anti-HB point fragilization, the O:⇔:O super-HB point compression, and ionic polarization dominating the performance of the respective HCl, KOH, and KCl solutions, but also demonstrate the power of the DPS that enables high resolution of solute-solute-solvent interactions and correlation between HB relaxation and solution surface stress.

Occupational solvent exposure and cognition

PubMed Central

Sabbath, E.L.; Glymour, M.M.; Berr, C.; Singh-Manoux, A.; Zins, M.; Goldberg, M.

2012-01-01

Objective: Chronic occupational solvent exposure is associated with long-term cognitive deficits. Cognitive reserve may protect solvent-exposed workers from cognitive impairment. We tested whether the association between chronic solvent exposure and cognition varied by educational attainment, a proxy for cognitive reserve. Methods: Data were drawn from a prospective cohort of French national gas and electricity (GAZEL) employees (n = 4,134). Lifetime exposure to 4 solvent types (chlorinated solvents, petroleum solvents, benzene, and nonbenzene aromatic solvents) was assessed using a validated job-exposure matrix. Education was dichotomized at less than secondary school or below. Cognitive impairment was defined as scoring below the 25th percentile on the Digit Symbol Substitution Test at mean age 59 (SD 2.8; 88% of participants were retired at testing). Log-binomial regression was used to model risk ratios (RRs) for poor cognition as predicted by solvent exposure, stratified by education and adjusted for sociodemographic and behavioral factors. Results: Solvent exposure rates were higher among less-educated patients. Within this group, there was a dose-response relationship between lifetime exposure to each solvent type and RR for poor cognition (e.g., for high exposure to benzene, RR = 1.24, 95% confidence interval 1.09–1.41), with significant linear trends (p < 0.05) in 3 out of 4 solvent types. Recency of solvent exposure also predicted worse cognition among less-educated patients. Among those with secondary education or higher, there was no significant or near-significant relationship between any quantification of solvent exposure and cognition. Conclusions: Solvent exposure is associated with poor cognition only among less-educated individuals. Higher cognitive reserve in the more-educated group may explain this finding. PMID:22641403

Effects of geometry and chemistry on hydrophobic solvation

PubMed Central

Harris, Robert C.; Pettitt, B. Montgomery

2014-01-01

Inserting an uncharged van der Waals (vdw) cavity into water disrupts the distribution of water and creates attractive dispersion interactions between the solvent and solute. This free-energy change is the hydrophobic solvation energy (ΔGvdw). Frequently, it is assumed to be linear in the solvent-accessible surface area, with a positive surface tension (γ) that is independent of the properties of the molecule. However, we found that γ for a set of alkanes differed from that for four configurations of decaalanine, and γ = −5 was negative for the decaalanines. These findings conflict with the notion that ΔGvdw favors smaller A. We broke ΔGvdw into the free energy required to exclude water from the vdw cavity (ΔGrep) and the free energy of forming the attractive interactions between the solute and solvent (ΔGatt) and found that γ < 0 for the decaalanines because −γatt > γrep and γatt < 0. Additionally, γatt and γrep for the alkanes differed from those for the decaalanines, implying that none of ΔGatt, ΔGrep, and ΔGvdw can be computed with a constant surface tension. We also showed that ΔGatt could not be computed from either the initial or final water distributions, implying that this quantity is more difficult to compute than is sometimes assumed. Finally, we showed that each atom’s contribution to γrep depended on multibody interactions with its surrounding atoms, implying that these contributions are not additive. These findings call into question some hydrophobic models. PMID:25258413