Use of aluminum phosphate as the dehydration catalyst in single step dimethyl ether process

DOEpatents

Peng, Xiang-Dong; Parris, Gene E.; Toseland, Bernard A.; Battavio, Paula J.

1998-01-01

The present invention pertains to a process for the coproduction of methanol and dimethyl ether (DME) directly from a synthesis gas in a single step (hereafter, the "single step DME process"). In this process, the synthesis gas comprising hydrogen and carbon oxides is contacted with a dual catalyst system comprising a physical mixture of a methanol synthesis catalyst and a methanol dehydration catalyst. The present invention is an improvement to this process for providing an active and stable catalyst system. The improvement comprises the use of an aluminum phosphate based catalyst as the methanol dehydration catalyst. Due to its moderate acidity, such a catalyst avoids the coke formation and catalyst interaction problems associated with the conventional dual catalyst systems taught for the single step DME process.

Foamed-metal-based catalytic afterburners in automotive exhaust systems

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

Pestryakov, A.N.; Ametov, V.A.

1994-08-10

Properties of exhaust afterburning catalysts based on porous cellular materials (foamed metals) have been investigated. Catalysts containing oxides of base metals provide a two-to-threefold reduction of CO emission. Platinum-containing foamed catalysts lower the toxicity of exhaust by 85-90%. A favorable effect is demonstrated by the combined use of afterburners and a motor oil additive based on ultradispersed copper.

Synthesis of biodiesel using local natural zeolite as heterogeneous anion exchange catalyst

NASA Astrophysics Data System (ADS)

Hartono, R.; Wijanarko, A.; Hermansyah, H.

2018-04-01

Production of biodiesel using homogen catalyst: alkaline catalysts, acid catalysts, biocatalysts, and supercritical methanol are very inefficient, because these catalysts have a very high cost production of biodiesel and non-ecofriendly. The heterogeneous catalyst is then used to avoid adverse reaction of biodiesel production. The heterogeneous catalysts used is ion exchanger using natural zeolit catalists bayah banten (ZABBrht) and macroporous lewatit that can be used to produce biodiesel in the solid phase so that the separation is easier and can be used repeatedly. The results of biodiesel reach its optimum in engineering ion exchange catalyst natural zeolit bayah and macroporous lewatit which has been impregnated and calcinated at temperature 60 °C at reaction time 2 hours, are 94.8% and 95.24%, using 100 gr.KOH/100 mL Aquadest.

A systems evaluation on the effectiveness of a catalyst retrofit program in China.

PubMed

Jones, M; Wilson, R; Norbeck, J M; Han, W; Hurley, R; Schuetzle, D

2001-09-01

A low-cost, rare-earth oxide (REO) catalyst has been recommended as part of China's retrofit program for Chinese carbureted vehicles. This study evaluated: (1) the emission reduction efficiency of the REO catalyst during chassis dynamometer testing on the FTP cycle; (2) the effect that fuel properties had on tailpipe emissions and catalyst efficiency; (3) the importance of vehicle premaintenance as part of a retrofit protocol; and (4) the emission reductions obtained following implementation of the program. Results also show that current in-use Chinese noncatalyst, carbureted vehicles operate excessively rich, resulting in extremely high emissions of CO, gaseous toxic compounds, and other non-methane hydrocarbon species (NMHC). Preretrofit maintenance alone has the potential to reduce these emissions by approximately 50%. Dynamometer emission tests showed emissions reductions of >95% for hydrocarbons, CO, and gaseous toxics after retrofit of the REO catalyst. In particular, the relative unit health risk associated with the decrease in emissions of airborne toxic compounds using unleaded Chinese fuel was reduced from 6.33 to 0.30. (Use of low-sulfur California Phase II gasoline rather than current in-use Chinese fuel reduced emissions further.) Following implementation of the program, a follow-up study showed that in-use emissions benefits were considerably less than anticipated, primarily because of poor quality control at the retrofit service centers, a less aggressive preretrofit maintenance procedure, and unauthorized modification to the recommended retrofit control system. Overall results indicate that a carefully controlled retrofit program using REO catalyst technology can reduce emissions significantly. However, well-defined implementation guidelines, and strict adherence to these guidelines are needed to achieve maximum benefits.

H₃PW₁₂O₄₀/TiO₂ catalyst-induced photodegradation of bisphenol A (BPA): kinetics, toxicity and degradation pathways.

PubMed

Lu, Nan; Lu, Ying; Liu, Fangyuan; Zhao, Kun; Yuan, Xing; Zhao, Yahui; Li, Yuan; Qin, Hongwei; Zhu, Jia

2013-05-01

A series of experiments were conducted to investigate the kinetics of bisphenol A (2,2-bis(4-hydroxyphenyl)propane, BPA) degradation using H₃PW₁₂O₄₀/TiO₂ (PW₁₂/TiO₂) composite catalyst, toxicity of BPA intermediate products and degradation pathways. The results showed that the BPA photodegradation using PW₁₂/TiO₂ catalyst followed the first-order kinetics, and under the optimal experimental conditions at H₃PW₁₂O₄₀ loading amount of 6.3%, BPA initial concentration of 5 mg L(-1), and the solution pH of 8.2, the kinetic constant was 3.7-fold larger than that of pristine TiO₂. The hydroxyl radicals derived from the electroreduction of dissolved oxygen with electrons via chain reactions was the main reactive oxygen species. According to the identified intermediates, 4-isopropanolphenol, hydroquinone, 4-hydroxybenzoic acid, and phenol, the possible BPA photodegradation pathways were proposed. Upon 12h irradiation, 77% BPA (20 mg L(-1)) was mineralized and the toxicity to Daphnia magna (D. magna) was almost disappeared, implying the strong oxidation ability of PW₁₂/TiO₂ catalyst. The studies provide important information about the BPA degradation and promote the technical development for BPA removal. Copyright © 2013 Elsevier Ltd. All rights reserved.

Synthesis of 2‐Alkynoates by Palladium(II)‐Catalyzed Oxidative Carbonylation of Terminal Alkynes and Alcohols

PubMed Central

Cao, Qun; Hughes, N. Louise

2016-01-01

Abstract A homogeneous PdII catalyst, utilizing a simple and inexpensive amine ligand (TMEDA), allows 2‐alkynoates to be prepared in high yields by an oxidative carbonylation of terminal alkynes and alcohols. The catalyst system overcomes many of the limitations of previous palladium carbonylation catalysts. It has an increased substrate scope, avoids large excesses of alcohol substrate and uses a desirable solvent. The catalyst employs oxygen as the terminal oxidant and can be operated under safer gas mixtures. PMID:27305489

Heterogeneous catalytic ozonation of biologically pretreated Lurgi coal gasification wastewater using sewage sludge based activated carbon supported manganese and ferric oxides as catalysts.

PubMed

Zhuang, Haifeng; Han, Hongjun; Hou, Baolin; Jia, Shengyong; Zhao, Qian

2014-08-01

Sewage sludge of biological wastewater treatment plant was converted into sewage sludge based activated carbon (SBAC) with ZnCl₂ as activation agent, which supported manganese and ferric oxides as catalysts (including SBAC) to improve the performance of ozonation of real biologically pretreated Lurgi coal gasification wastewater. The results indicated catalytic ozonation with the prepared catalysts significantly enhanced performance of pollutants removal and the treated wastewater was more biodegradable and less toxic than that in ozonation alone. On the basis of positive effect of higher pH and significant inhibition of radical scavengers in catalytic ozonation, it was deduced that the enhancement of catalytic activity was responsible for generating hydroxyl radicals and the possible reaction pathway was proposed. Moreover, the prepared catalysts showed superior stability and most of toxic and refractory compounds were eliminated at successive catalytic ozonation runs. Thus, the process with economical, efficient and sustainable advantages was beneficial to engineering application. Copyright © 2014 Elsevier Ltd. All rights reserved.

Tailor-made Molecular Cobalt Catalyst System for the Selective Transformation of Carbon Dioxide to Dialkoxymethane Ethers.

PubMed

Schieweck, Benjamin G; Klankermayer, Jürgen

2017-08-28

Herein a non-precious transition-metal catalyst system for the selective synthesis of dialkoxymethane ethers from carbon dioxide and molecular hydrogen is presented. The development of a tailored catalyst system based on cobalt salts in combination with selected Triphos ligands and acidic co-catalysts enabled a synthetic pathway, avoiding the oxidation of methanol to attain the formaldehyde level of the central CH 2 unit. This unprecedented productivity based on the molecular cobalt catalyst is the first example of a non-precious transition-metal system for this transformation utilizing renewable carbon dioxide sources. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Construction of new biopolymer (chitosan)-based pincer-type Pd(II) complex and its catalytic application in Suzuki cross coupling reactions

NASA Astrophysics Data System (ADS)

Baran, Talat; Menteş, Ayfer

2017-04-01

In this paper we described the fabrication, characterization and application of a new biopolymer (chitosan)-based pincer-type Pd(II) catalyst in Suzuki cross coupling reactions using a non-toxic, cheap, eco-friendly and practical method. The catalytic activity tests showed remarkable product yields as well as TON (19800) and TOF (330000) values with a small catalyst loading. In addition, the catalyst indicated good recyclability in the Suzuki C-C reaction. This biopolymer supported catalyst can be used with various catalyst systems due to its unique properties, such as being inert, green in nature, low cost and chemically durable.

Oxidation-reduction catalyst and its process of use

NASA Technical Reports Server (NTRS)

Schryer, Jacqueline L. (Inventor); Oglesby, Donald M. (Inventor); Jordan, Jeffrey D. (Inventor); Watkins, Anthony Neal (Inventor)

2008-01-01

This invention relates generally to a ruthenium stabilized oxidation-reduction catalyst useful for oxidizing carbon monoxide, and volatile organic compounds, and reducing nitrogen oxide species in oxidizing environments, substantially without the formation of toxic and volatile ruthenium oxide species upon said oxidizing environment being at high temperatures.

Benign by design: catalyst-free in-water, on-water green chemical methodologies in organic synthesis

EPA Science Inventory

The development of organic synthesis under sustainable conditions is a primary goal of practicing green chemists who want to prevent pollution and design safer pathways. Although, it is challenging to avoid the use of catalysts, or solvents in all the organic reactions but progre...

Catalytic Destruction Of Toxic Organic Compounds

NASA Technical Reports Server (NTRS)

Voecks, Gerald E.

1990-01-01

Proposed process disposes of toxic organic compounds in contaminated soil or carbon beds safely and efficiently. Oxidizes toxic materials without producing such other contaminants as nitrogen oxides. Using air, fuel, catalysts, and steam, system consumes less fuel and energy than decontamination processes currently in use. Similar process regenerates carbon beds used in water-treatment plants.

Challenges in Catalytic Manufacture of Renewable Pyrrolidinones from Fermentation Derived Succinate

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

White, James F.; Holladay, Johnathan E.; Zacher, Alan H.

2014-09-05

Fermentation derived succinic acid ammonium salt is an ideal precursor for manufacture of renewable N-methyl pyrrolidinone (NMP) or 2-pyrrolidinone (2P) via heterogeneous catalysis. However, there are many challenges to making this a practical reality. Chief among the challenges is avoiding catalyst poisoning by fermentation by- and co-products. Battelle / Pacific Northwest National Laboratory (PNNL) have developed an economically effective technology strategy for this purpose. The technology is a combination of purely thermal processing, followed by simple catalytic hydrogenation that together avoids catalyst poisoning from fermentation impurities and provides high selectivity and yields of NMP or 2P.

Vertical Alignment of Single-Walled Carbon Nanotubes on Nanostructure Fabricated by Atomic Force Microscope

DTIC Science & Technology

2009-12-16

decreased by iron sintering into the Si substrate and forming metal silicide [26, 27]. To avoid the iron sintering into the Si substrate, we deposited... metal catalysts onto the Si substrate selectively by lithographic lift-off, soft lithography, offset printing, or micro-contact printing (µCP). The...Experiment 1. Preparation of Fe-Mo catalyst solution An Fe-Mo bimetallic catalyst solution was prepared by ultrasonication for 30 min using an

Catalysts for the decomposition of hydrazine and its derivatives and a method for its production

NASA Technical Reports Server (NTRS)

Sasse, R.

1986-01-01

Catalysts of various types are used to decompose hydrazine and its derivatives. One type of catalyst is made as follows: the aluminum is dissolved out of an alloy of cobalt or nickel/aluminum so that a structure is produced that is chemically active for the monergol and that has a large active surface. The objective was to avoid difficulties and to create a catalyst that not only has a short start time but that can also be manufactured easily and relatively inexpensively. The solution to this task is to coat the base structure of the catalyst with oxides of copper, cobalt and cerium or oxides of copper, cobalt and cerite earth.

Fischer-Tropsch process

DOEpatents

Dyer, Paul N.; Pierantozzi, Ronald; Withers, Howard P.

1987-01-01

A Fischer-Tropsch process utilizing a product selective and stable catalyst by which synthesis gas, particularly carbon-monoxide rich synthesis gas is selectively converted to higher hydrocarbons of relatively narrow carbon number range is disclosed. In general, the selective and notably stable catalyst, consist of an inert carrier first treated with a Group IV B metal compound (such as zirconium or titanium), preferably an alkoxide compound, and subsequently treated with an organic compound of a Fischer-Tropsch metal catalyst, such as cobalt, iron or ruthenium carbonyl. Reactions with air and water and calcination are specifically avoided in the catalyst preparation procedure.

Supported molten-metal catalysts

DOEpatents

Datta, Ravindra; Singh, Ajeet; Halasz, Istvan; Serban, Manuela

2001-01-01

An entirely new class of catalysts called supported molten-metal catalysts, SMMC, which can replace some of the existing precious metal catalysts used in the production of fuels, commodity chemicals, and fine chemicals, as well as in combating pollution. SMMC are based on supporting ultra-thin films or micro-droplets of the relatively low-melting (<600.degree. C.), inexpensive, and abundant metals and semimetals from groups 1, 12, 13, 14, 15 and 16, of the periodic table, or their alloys and intermetallic compounds, on porous refractory supports, much like supported microcrystallites of the traditional solid metal catalysts. It thus provides orders of magnitude higher surface area than is obtainable in conventional reactors containing molten metals in pool form and also avoids corrosion. These have so far been the chief stumbling blocks in the application of molten metal catalysts.

Ruthenium-catalysed alkoxycarbonylation of alkenes with carbon dioxide.

PubMed

Wu, Lipeng; Liu, Qiang; Fleischer, Ivana; Jackstell, Ralf; Beller, Matthias

2014-01-01

Alkene carbonylations represent a major technology for the production of value-added bulk and fine chemicals. Nowadays, all industrial carbonylation processes make use of highly toxic and flammable carbon monoxide. Here we show the application of abundantly available carbon dioxide as C1 building block for the alkoxycarbonylations of industrially important olefins in the presence of a convenient and inexpensive ruthenium catalyst system. In our system, carbon dioxide works much better than the traditional combination of carbon monoxide and alcohols. The unprecedented in situ formation of carbon monoxide from carbon dioxide and alcohols permits an efficient synthesis of carboxylic acid esters, which can be used as detergents and polymer-building blocks. Notably, this transformation allows the catalytic formation of C-C bonds with carbon dioxide as C1 source and avoids the use of sensitive and/or expensive reducing agents (for example, Grignard reagents, diethylzinc or triethylaluminum).

Separation of catalyst from Fischer-Tropsch slurry

DOEpatents

White, Curt M.; Quiring, Michael S.; Jensen, Karen L.; Hickey, Richard F.; Gillham, Larry D.

1998-10-27

In a catalytic process for converting synthesis gas including hydrogen and carbon monoxide to hydrocarbons and oxygenates by a slurry Fischer-Tropsch synthesis, the wax product along with dispersed catalyst is removed from the slurry and purified by removing substantially all of the catalyst prior to upgrading the wax and returning a portion to the Fischer-Tropsch reaction. Separation of the catalyst particles from the wax product is accomplished by dense gas and/or liquid extraction in which the organic compounds in the wax are dissolved and carried away from the insoluble inorganic catalyst particles that are primarily inorganic in nature. The purified catalyst free wax product can be subsequently upgraded by various methods such as hydrogenation, isomerization, hydrocracking, conversion to gasoline and other products over ZSM-5 aluminosilicate zeolite, etc. The catalyst particles are returned to the Fischer-Tropsch Reactor by slurring them with a wax fraction of appropriate molecular weight, boiling point and viscosity to avoid reactor gelation.

A modified preparation procedure for carbon nanotube-confined Nd/Na heterobimetallic catalyst for anti-selective catalytic asymmetric nitroaldol reactions.

PubMed

Sureshkumar, Devarajulu; Hashimoto, Kazuki; Kumagai, Naoya; Shibasaki, Masakatsu

2013-11-15

A recyclable asymmetric metal-based catalyst is a rare entity among the vast collection of asymmetric catalysts developed so far. Recently we found that the combination of a self-assembling metal-based asymmetric catalyst and multiwalled carbon nanotubes (MWNTs) produced a highly active and recyclable catalyst in which the catalytically active metal complex was dispersed in the MWNT network. Herein we describe an improved preparation procedure and full details of a Nd/Na heterobimetallic complex confined in MWNTs. Facilitated self-assembly of the catalyst with MWNTs avoided the sacrificial use of excess chiral ligand for the formation of the heterobimetallic complex, improving the loading ratio of the catalyst components. Eighty-five percent of the catalyst components were incorporated onto MWNTs to produce the confined catalyst, which was a highly efficient and recyclable catalyst for the anti-selective asymmetric nitroaldol reaction. The requisite precautions for the catalyst preparation to elicit reproducible catalytic performance are summarized. Superior catalytic profiles over the prototype catalyst without MWNTs were revealed in the synthesis of optically active 1,2-nitroalkanols, which are key intermediates for the synthesis of therapeutics.

Perovskites in catalysis and electrocatalysis

NASA Astrophysics Data System (ADS)

Hwang, Jonathan; Rao, Reshma R.; Giordano, Livia; Katayama, Yu; Yu, Yang; Shao-Horn, Yang

2017-11-01

Catalysts for chemical and electrochemical reactions underpin many aspects of modern technology and industry, from energy storage and conversion to toxic emissions abatement to chemical and materials synthesis. This role necessitates the design of highly active, stable, yet earth-abundant heterogeneous catalysts. In this Review, we present the perovskite oxide family as a basis for developing such catalysts for (electro)chemical conversions spanning carbon, nitrogen, and oxygen chemistries. A framework for rationalizing activity trends and guiding perovskite oxide catalyst design is described, followed by illustrations of how a robust understanding of perovskite electronic structure provides fundamental insights into activity, stability, and mechanism in oxygen electrocatalysis. We conclude by outlining how these insights open experimental and computational opportunities to expand the compositional and chemical reaction space for next-generation perovskite catalysts.

External Catalyst Breakup Phenomena

DTIC Science & Technology

1976-06-01

catalyst particle can cause high internal pressures which result in particle destruction. Analytical results suggest rhat erosion effects from solid...mechanisms. * Pressure Forces. High G loadings and bed pressure drops should be avoided. Bed pre-loads should be kept at a minimum value. Thruster...5.2.7.1 Failure Theories ............................ 243 5.2.7.2 Maximum Tension Stress Criterion ............ 244 5.2.7.3 Distortion Energy Approach

Nitrogen doped nanocrystalline semiconductor metal oxide: An efficient UV active photocatalyst for the oxidation of an organic dye using slurry Photoreactor.

PubMed

Ramachandran, Saranya; Sivasamy, A; Kumar, B Dinesh

2016-12-01

Water pollution is a cause for serious concern in today's world. A major contributor to water pollution is industrial effluents containing dyes and other organic molecules. Waste water treatment has become a priority area in today's applied scientific research as it seeks to minimize the toxicity of the effluents being discharged and increase the possibility of water recycling. An efficient and eco-friendly way of degrading toxic molecules is to use nano metal-oxide photocatalysts. The present study aims at enhancing the photocatalytic activity of a semiconductor metal oxide by doping it with nitrogen. A sol-gel cum combustion method was employed to synthesize the catalyst. The prepared catalyst was characterized by FT-IR, XRD, UV-DRS, FESEM and AFM techniques. UV-DRS result showed the catalyst to possess band gap energy of 2.97eV, thus making it active in the UV region of the spectrum. Its photocatalytic activity was evaluated by the degradation of a model pollutant-Orange G dye, under UV light irradiation. Preliminary experiments were carried out to study the effects of pH, catalyst dosage and initial dye concentration on the extent of dye degradation. Kinetic studies revealed that the reaction followed pseudo first order kinetics. The effect of electrolytes on catalyst efficiency was also studied. The progress of the reaction was monitored by absorption studies and measuring the reduction in COD. The catalyst thus prepared was seen to have a high photocatalytic efficiency. The use of this catalyst is a promising means of waste water treatment. Copyright © 2016 Elsevier Inc. All rights reserved.

Options and processes for spent catalyst handling and utilization.

PubMed

Marafi, M; Stanislaus, A

2003-07-18

The quantity of spent hydroprocessing catalysts discarded as solid wastes in the petroleum refining industries has increased remarkably in recent years due to a rapid growth in the hydroprocessing capacity to meet the rising demand for low-sulfur fuels. Due to their toxic nature, spent hydroprocessing catalysts have been branded as hazardous wastes, and the refiners are experiencing pressure from environmental authorities to handle them safely. Several alternative methods such as reclamation of metals, rejuvenation and reuse, disposal in landfills and preparation of useful materials using spent catalysts as raw materials are available to deal with the spent catalyst problem. The technical feasibility as well as the environmental and economic aspects of these options are reviewed. In addition, details of two bench-scale processes, one for rejuvenation of spent hydroprocessing catalysts, and the other for producing non-leachable synthetic aggregate materials that were developed in this laboratory, are presented in this paper.

Separation of catalyst from Fischer-Tropsch slurry

DOEpatents

White, C.M.; Quiring, M.S.; Jensen, K.L.; Hickey, R.F.; Gillham, L.D.

1998-10-27

In a catalytic process for converting synthesis gas including hydrogen and carbon monoxide to hydrocarbons and oxygenates by a slurry Fischer-Tropsch synthesis, the wax product along with dispersed catalyst is removed from the slurry and purified by removing substantially all of the catalyst prior to upgrading the wax and returning a portion to the Fischer-Tropsch reaction. Separation of the catalyst particles from the wax product is accomplished by dense gas and/or liquid extraction in which the organic compounds in the wax are dissolved and carried away from the insoluble inorganic catalyst particles that are primarily inorganic in nature. The purified catalyst-free wax product can be subsequently upgraded by various methods such as hydrogenation, isomerization, hydrocracking, conversion to gasoline and other products over ZSM-5 aluminosilicate zeolite, etc. The catalyst particles are returned to the Fischer-Tropsch Reactor by mixing them with a wax fraction of appropriate molecular weight, boiling point and viscosity to avoid reactor gelation. 2 figs.

Heterogeneous photo-Fenton decolorization of Orange II over Al-pillared Fe-smectite: response surface approach, degradation pathway, and toxicity evaluation.

PubMed

Li, Huiyuan; Li, Yanli; Xiang, Luojing; Huang, Qianqian; Qiu, Juanjuan; Zhang, Hui; Sivaiah, Matte Venkata; Baron, Fabien; Barrault, Joel; Petit, Sabine; Valange, Sabine

2015-04-28

A ferric smectite clay material was synthesized and further intercalated with Al2O3 pillars for the first time with the aim of evaluating its ability to be used as heterogeneous catalyst for the photo-Fenton decolorization of azo dye Orange II. UV irradiation was found to enhance the activity of the catalyst in the heterogeneous photo-Fenton process. Catalyst loading of 0.5g/L and hydrogen peroxide concentration of 13.5mM yielded a remarkable color removal, accompanied by excellent catalyst stability. The decolorization of Orange II followed the pseudo-first-order kinetics for initial dye concentrations from 20 to 160mg/L. The central composite design (CCD) based on the response surface methodology (RSM) was applied to evaluate the effects of several operating parameters, namely initial pH, catalyst loading and hydrogen peroxide concentration, on the decolorization efficiency. The RSM model was derived and the response surface plots were developed based on the results. Moreover, the main intermediate products were separated and identified using gas chromatography-mass spectrometry (GC-MS) and a possible degradation pathway was proposed accordingly. The acute toxicity experiments illustrated that the Daphniamagna immobilization rate continuously decreased during 150min reaction, indicating that the effluent was suitable for sequential biological treatment. Copyright © 2015 Elsevier B.V. All rights reserved.

Nontoxic Hydroxylammonium Nitrate (HAN) Monopropellant Propulsion

NASA Technical Reports Server (NTRS)

McKechnie, Timothy N.

2015-01-01

Nontoxic monopropellants have been developed that provide better performance than toxic hydrazine. Formulations based on HAN have superior performance as compared to hydrazine with enhanced specific impulse (Isp), higher density and volumetric impulse, lower melting point, and much lower toxicity. However, HAN-based monopropellants require higher chamber temperatures (2,083 K vs. 883 K) to combust. Current hydrazine-based combustion chamber technology (Inconel® or niobium C103 and silicide coating) and catalyst (Shell 405) are inadequate. In Phase I, state-of-the-art iridium-lined rhenium chambers and innovative new foam catalysts were demonstrated in pulse and 10-second firings. Phase II developed and tested a flight-weight thruster for an environmentally green monopropellant.

Permanganate with a double-edge role in photodegradation of sulfamethoxazole: Kinetic, reaction mechanism and toxicity.

PubMed

Gong, Han; Chu, Wei

2018-01-01

In this study, the double-edge role of permanganate in sulfamethoxazole (SMX) photodegradation with a recyclable catalyst was revealed for the first time. The role of the catalyst under different UV wavelength, the role of permanganate in the treatment process, the effects of permanganate dosage and solution pH on the removal efficiency were investigated. Moreover, the transformation products, TOC reduction and the toxicity of the treated final product to Chlorella vulgaris and Artemia salina were determined. Sole permanganate showed no effect in SMX degradation, while its introduction to the photocatalytic process doubled the reaction rate at the optimal dosage. It is interesting to find that the reaction rate showed a fluctuation trend in terms of permanganate dosage due to the summation of positive effect of permanganate oxidation and the negative effect of the formed MnO 2 at the surface of the catalyst, as well as the light attenuation due to overdosed permanganate. The determined intermediates, the higher inorganic ions release and TOC reduction provided a clue on a higher mineralization compared to SMX degradation in the same process without permanganate. Permanganate above 1 μM may pose a threat to the algae growth, therefore a good monitoring and control of residual permanganate dosage should be incorporated into the process design. A good toxicity reduction to A. salina was observed in the treated effluent; a longer detention is suggested for the complete removal of toxicity. Copyright © 2017 Elsevier Ltd. All rights reserved.

Non-conventional Pt-Cu alloy/carbon paper electrochemical catalyst formed by electrodeposition using hydrogen bubble as template

NASA Astrophysics Data System (ADS)

Kim, Youngkwang; Lee, Hyunjoon; Lim, Taeho; Kim, Hyun-Jong; Kwon, Oh Joong

2017-10-01

With emerging stability issues in fuel cell technology, a non-conventional catalyst not supported on carbon materials has been highlighted because it can avoid negative influences of carbon support materials on the stability, such as carbon corrosion. The nanostructured thin film catalyst is representative of non-conventional catalysts, which shows improved stability, enhanced mass specific activity, and fast mass transfer at high current densities. However, the nanostructured thin film catalyst usually requires multi-step processes for fabrication, making its mass production complex and irreproducible. We introduce a Pt-Cu alloy nanostructured thin film catalyst, which can be simply prepared by electrodeposition. By using hydrogen bubbles as a template, a three-dimensional free-standing foam of Cu was electrodeposited directly on the micro-porous layer/carbon paper and it was then displaced with Pt by simple immersion. The structure characterization revealed that a porous thin Pt-Cu alloy catalyst layer was successfully formed on the micro-porous layer/carbon paper. The synthesized Pt-Cu alloy catalyst exhibited superior durability compared to a conventional Pt/C in single cell test.

Supercritical/Solid Catalyst (SSC)

ScienceCinema

Ginosar, Daniel; Fox, Robert; Bright, Patricia

2018-05-23

INL's patented, continuous-flow Supercritical/Solid Catalyst (SSC) produces the highest ASTM-quality B-100 biodiesel from waste fats, oils, and greases at the site of waste generation. SSC delivers low-cost transportation fuel, avoids significant landfill costs for municipalities, and reduces potent methane and other emissions produced in landfills from these wastes. You can learn more about INL's energy research programs at http://www.facebook.com/idahonationallaboratory.

Supercritical/Solid Catalyst (SSC)

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

Ginosar, Daniel; Fox, Robert; Bright, Patricia

2010-05-28

INL's patented, continuous-flow Supercritical/Solid Catalyst (SSC) produces the highest ASTM-quality B-100 biodiesel from waste fats, oils, and greases at the site of waste generation. SSC delivers low-cost transportation fuel, avoids significant landfill costs for municipalities, and reduces potent methane and other emissions produced in landfills from these wastes. You can learn more about INL's energy research programs at http://www.facebook.com/idahonationallaboratory.

Synthesis of multi-walled carbon nanotubes using CoMnMgO catalysts through catalytic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Yang, Wen; Feng, Yan-Yan; Jiang, Cheng-Fa; Chu, Wei

2014-12-01

The CoMgO and CoMnMgO catalysts are prepared by a co-precipitation method and used as the catalysts for the synthesis of carbon nanotubes (CNTs) through the catalytic chemical vapor deposition (CCVD). The effects of Mn addition on the carbon yield and structure are investigated. The catalysts are characterized by temperature programmed reduction (TPR) and X-ray diffraction (XRD) techniques, and the synthesized carbon materials are characterized by transmission electron microscopy (TEM) and thermo gravimetric analysis (TG). TEM measurement indicates that the catalyst CoMgO enclosed completely in the produced graphite layer results in the deactivation of the catalyst. TG results suggest that the CoMnMgO catalyst has a higher selectivity for CNTs than CoMgO. Meanwhile, different diameters of CNTs are synthesized by CoMnMgO catalysts with various amounts of Co content, and the results show that the addition of Mn avoids forming the enclosed catalyst, prevents the formation of amorphous carbon, subsequently promotes the growth of CNTs, and the catalyst with decreased Co content is favorable for the synthesis of CNTs with a narrow diameter distribution. The CoMnMgO catalyst with 40% Co content has superior catalytic activity for the growth of carbon nanotubes.

Catalytic decomposition of toxic chemicals over metal-promoted carbon nanotubes.

PubMed

Li, Lili; Han, Changxiu; Han, Xinyu; Zhou, Yixiao; Yang, Li; Zhang, Baogui; Hu, Jianli

2011-01-15

Effective decomposition of toxic gaseous compounds is important for pollution control at many chemical manufacturing plants. This study explores catalytic decomposition of phosphine (PH(3)) using novel metal-promoted carbon nanotubes (CNTs). The cerium-promoted Co/CNTs catalysts (CoCe/CNTs) are synthesized by means of coimpregnation method and reduced by three different methods (H(2), KBH(4), NaH(2)PO(2)·H(2)O/KBH(4)). The morphology, structure, and composition of the catalysts are characterized using a number of analytical instrumentations including high-resolution transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, BET surface area measurement, and inductively coupled plasma. The activity of the catalysts in PH(3) decomposition reaction is measured and correlated with their surface and structural properties. The characterization results show that the CoCe/CNTs catalyst reduced by H(2) possesses small particles and is shown thermally stable in PH(3) decomposition reaction. The activities of these catalysts are compared and are shown in the following sequence: CoCe/CNTs > Co/CNTs > CoCeBP/CNTs> CoCeB/CNTs. The difference in reduction method results in the formation of different active phases during the PH(3) decomposition reaction. After a catalytic activity test, only the CoP phase is formed on CoCe/CNTs and Co/CNTs catalysts, whereas multiphases CoP, Co(2)P, and Co phases are formed on CoCeBP/CNTs and CoCeB/CNTs. Results show that the CoP phase is formed predominantly on the CoCe/CNTs and Co/CNTs catalysts and is found to likely be the most active phase for this reaction. Furthermore, the CoCe/CNTs catalyst exhibits not only highest activity but also long-term stability in PH(3) decomposition reaction. When operated in a fixed-bed reactor at 360 °C, single-pass PH(3) conversion of about 99.8% can be achieved.

Inhibition of Microbial Growth by Fatty Amine Catalysts from Polyurethane Foam Test Tube Plugs

PubMed Central

Bach, John A.; Wnuk, Richard J.; Martin, Delano G.

1975-01-01

When polyurethane foam test tube plugs are autoclaved, they release volatile fatty amines that inhibit the growth of some microorganisms. The chemical structures of these amines were determined by the use of a gas chromatographmass spectrometer. They are catalysts used to produce the foam. The problem of contaminating growth media with toxic substances released from polymeric materials is discussed. PMID:1096816

Perovskites in catalysis and electrocatalysis.

PubMed

Hwang, Jonathan; Rao, Reshma R; Giordano, Livia; Katayama, Yu; Yu, Yang; Shao-Horn, Yang

2017-11-10

Catalysts for chemical and electrochemical reactions underpin many aspects of modern technology and industry, from energy storage and conversion to toxic emissions abatement to chemical and materials synthesis. This role necessitates the design of highly active, stable, yet earth-abundant heterogeneous catalysts. In this Review, we present the perovskite oxide family as a basis for developing such catalysts for (electro)chemical conversions spanning carbon, nitrogen, and oxygen chemistries. A framework for rationalizing activity trends and guiding perovskite oxide catalyst design is described, followed by illustrations of how a robust understanding of perovskite electronic structure provides fundamental insights into activity, stability, and mechanism in oxygen electrocatalysis. We conclude by outlining how these insights open experimental and computational opportunities to expand the compositional and chemical reaction space for next-generation perovskite catalysts. Copyright © 2017, American Association for the Advancement of Science.

Catalyst- and Reagent-free Electrochemical Azole C-H Amination.

PubMed

Qiu, Youai; Struwe, Julia; Meyer, Tjark H; Oliveira, Joao Carlos Agostinho Carlos Agostinho; Ackermann, Lutz

2018-06-14

Catalyst-, and chemical oxidant-free electrochemical azole C-H aminations were accomplished via cross-dehydrogenative C-H/N-H functionalization. The catalyst-free electrochemical C-H amination proved feasible on azoles with high levels of efficacy and selectivity, avoiding the use of stoichiometric oxidants under ambient conditions. Likewise, the C(sp3)-H nitrogenation proved viable under otherwise identical conditions. The dehydrogenative C-H amination featured ample scope, including cyclic and acyclic aliphatic amines as well as anilines, and employed sustainable electricity as the sole oxidant. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A prolific catalyst for dehydrogenation of neat formic acid

PubMed Central

Celaje, Jeff Joseph A.; Lu, Zhiyao; Kedzie, Elyse A.; Terrile, Nicholas J.; Lo, Jonathan N.; Williams, Travis J.

2016-01-01

Formic acid is a promising energy carrier for on-demand hydrogen generation. Because the reverse reaction is also feasible, formic acid is a form of stored hydrogen. Here we present a robust, reusable iridium catalyst that enables hydrogen gas release from neat formic acid. This catalysis works under mild conditions in the presence of air, is highly selective and affords millions of turnovers. While many catalysts exist for both formic acid dehydrogenation and carbon dioxide reduction, solutions to date on hydrogen gas release rely on volatile components that reduce the weight content of stored hydrogen and/or introduce fuel cell poisons. These are avoided here. The catalyst utilizes an interesting chemical mechanism, which is described on the basis of kinetic and synthetic experiments. PMID:27076111

External Catalyst Breakup Phenomena

DTIC Science & Technology

1975-09-01

thruster exposure. a Erosion .by a pulsed liquid stream at high velocity. * Thermal shock from liquid quench cooldovn. 9 Erosion resulting from solid...the liquid velocity. During a cold start contact with hydrazine leading to liquid wetting can lead to very high internal pressures as a result ot the...compression and final dilation, suggest benefits from reducing this variable. A . Isolating the catalyst particles from one another so as to avoid high

Catalytic wet air oxidation of aniline with nanocasted Mn-Ce-oxide catalyst.

PubMed

Levi, R; Milman, M; Landau, M V; Brenner, A; Herskowitz, M

2008-07-15

The catalytic wet air oxidation of aqueous solution containing 1000 ppm aniline was conducted in a trickle-bed reactor packed with a novel nanocasted Mn-Ce-oxide catalyst (surface area of 300 m2/g) prepared using SBA-15 silica as a hard template. A range of liquid hourly space velocities (5-20 h(-1)) and temperatures (110-140 degrees C) at 10 bar of oxygen were tested. The experiments were conducted to provide the intrinsic performance of the catalysts. Complete aniline conversion, 90% TOC conversion, and 80% nitrogen mineralization were achieved at 140 degrees C and 5 h(-1). Blank experiments yielded relatively low homogeneous aniline (<35%) and negligible TOC conversions. Fast deactivation of the catalysts was experienced due to leaching caused by complexation with aniline. Acidification of the solution with HCI (molar HCI to aniline ratio of 1.2) was necessary to avoid colloidization and leaching of the nanoparticulate catalyst components. The catalyst displayed stable performance for over 200 h on stream.

Synthesis of 5'-O-DMT-2'-O-TBS Mononucleosides Using an Organic Catalyst.

PubMed

Lee, Sunggi; Blaisdell, Thomas P; Kasaplar, Pinar; Sun, Xixi; Tan, Kian L

2014-06-24

This unit describes a highly effective method to produce 5'-O-DMT-2'-O-TBS mononucleosides selectively using a small organic catalyst. This methodology avoids the tedious protection/deprotection strategy necessary to differentiate the 2'- and 3'-hydroxyl groups in a ribonucleoside. The catalyst was synthesized in two steps, starting from the condensation of valinol and cyclopentyl aldehyde, followed by anionic addition of N-methylimidazole. Ring closure of the amino alcohol with N,N-dimethylformamide dimethyl acetal in methanol furnishes the catalyst. All four 2'-O-TBS protected mono-nucleosides, U, A(Bz), G(Ib), and C(Ac), were produced in a single step using 10 to 20 mol% of the catalyst at room temperature with excellent yields and selectivity. Further transformation to phosphoramidite demonstrates the utility of this protocol in the preparation of monomers useful for automated synthesis of RNA. Copyright © 2014 John Wiley & Sons, Inc.

[Sugar Chain Construction of Functional Natural Products Using Plant Glucosyltransferases].

PubMed

Mizukami, Hajime

2015-01-01

Plant secondary product glycosyltransferases belong to family 1 of the glycosyltransferase superfamily and mediate the transfer of a glycosyl residue from activated nucleotide sugars to lipophilic small molecules, thus affecting the solubility, stability and pharmacological activities of the sugar-accepting compounds. The biotechnological application of plant glycosyltransferases in glycoside synthesis has attracted attention because enzymatic glycosylation offers several advantages over chemical methods, including (1) avoiding the use of harsh conditions and toxic catalysts, (2) providing strict control of regio-and stereo-selectivity and (3) high efficiency. This review describes the in vivo and in vitro glycosylation of natural organic compounds using glycosyltransferases, focusing on our investigation of enzymatic synthesis of curcumin glycosides. Our current efforts toward functional characterization of some glycosyltransferases involved in the biosynthesis of iridoids and crocin, as well as in the sugar chain elongation of quercetin glucosides, are described. Finally, I describe the relationship of the structure of sugar chains and the intestinal absorption which was investigated using chemoenzymatically synthesized quercetin glycosides.

Effect of advanced aftertreatment for PM and NOx reduction on heavy-duty diesel engine ultrafine particle emissions.

PubMed

Herner, Jorn Dinh; Hu, Shaohua; Robertson, William H; Huai, Tao; Chang, M-C Oliver; Rieger, Paul; Ayala, Alberto

2011-03-15

Four heavy-duty and medium-duty diesel vehicles were tested in six different aftertreament configurations using a chassis dynamometer to characterize the occurrence of nucleation (the conversion of exhaust gases to particles upon dilution). The aftertreatment included four different diesel particulate filters and two selective catalytic reduction (SCR) devices. All DPFs reduced the emissions of solid particles by several orders of magnitude, but in certain cases the occurrence of a volatile nucleation mode could increase total particle number emissions. The occurrence of a nucleation mode could be predicted based on the level of catalyst in the aftertreatment, the prevailing temperature in the aftertreatment, and the age of the aftertreatment. The particles measured during nucleation had a high fraction of sulfate, up to 62% of reconstructed mass. Additionally the catalyst reduced the toxicity measured in chemical and cellular assays suggesting a pathway for an inverse correlation between particle number and toxicity. The results have implications for exposure to and toxicity of diesel PM.

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

PubMed

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

2013-12-01

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

Iron-based catalysts for photocatalytic ozonation of some emerging pollutants of wastewater.

PubMed

Espejo, Azahara; Beltrán, Fernando J; Rivas, Francisco J; García-Araya, Juan F; Gimeno, Olga

2015-01-01

A synthetic secondary effluent containing an aqueous mixture of emerging contaminants (ECs) has been treated by photocatalytic ozonation using Fe(3+) or Fe3O4 as catalysts and black light lamps as the radiation source. For comparative purposes, ECs have also been treated by ultraviolet radiation (UVA radiation, black light) and ozonation (pH 3 and 7). With the exception of UVA radiation, O3-based processes lead to the total removal of ECs in the mixture. The time taken to achieve complete degradation depends on the oxidation process applied. Ozonation at pH 3 is the most effective technique. The addition of iron based catalysts results in a slight inhibition of the parent compounds degradation rate. However, a positive effect is experienced when measuring the total organic carbon (TOC) and the chemical oxygen demand (COD) removals. Photocatalytic oxidation in the presence of Fe(3+) leads to 81% and 88% of TOC and COD elimination, respectively, compared to only 23% and 29% of TOC and COD removals achieved by single ozonation. The RCT concept has been used to predict the theoretical ECs profiles in the homogeneous photocatalytic oxidation process studied. Treated wastewater effluent was toxic to Daphnia magna when Fe(3+) was used in photocatalytic ozonation. In this case, toxicity was likely due to the ferryoxalate formed in the process. Single ozonation significantly reduced the toxicity of the treated wastewater.

Preparation, structural characterization, and catalytic performance of Pd(II) and Pt(II) complexes derived from cellulose Schiff base

NASA Astrophysics Data System (ADS)

Baran, Talat; Yılmaz Baran, Nuray; Menteş, Ayfer

2018-05-01

In this study, we reported production, characterization, and catalytic behavior of two novel heterogeneous palladium(II) and platinum(II) catalysts derived from cellulose biopolymer. In order to eliminate the use of toxic organic or inorganic solvents and to reduce the use of excess energy in the coupling reactions, we have developed a very simple, rapid, and eco-friendly microwave irradiation protocol. The developed microwave-assisted method of Suzuki cross coupling reactions produced excellent reaction yields in the presence of cellulose supported palladium and platinum (II) catalysts. Moreover, the catalysts easily regenerated after simple filtration, and they gave good reusability. This study revealed that the designed catalysts and method provide clean, simple, rapid, and impressive catalytic performance for Suzuki coupling reactions.

ZnO/La 2O 2CO 3 layered composite: A new heterogeneous catalyst for the efficient ultra-fast microwave biofuel production

DOE PAGES

Jin, Lei; Zhang, Yashan; Dombrowski, James; ...

2011-01-21

The search for solid state materials with high catalytic activities and with no leaching into the reaction medium is one of the key steps toward reducing the cost of producing biodiesel. We report a high biodiesel yield (>95%) in less than 5 min under mild reaction conditions (<100°C) on a ZnO/La₂O₂CO₃ heterogeneous catalyst, showing no catalyst leaching into the reaction medium. The ZnO/La₂O₂CO₃ catalyst is prepared by a co-precipitation method and characterized by X-ray diffraction (XRD), thermogravimetric analyses (TGA), transmission electron microscopy (SEM), and transmission electron microscopy (TEM). The fatty acid methyl ester (FAME) yields as function of different amountsmore » of catalyst was also investigated. Less than 1.0 wt.% catalyst can be used in the reaction to get higher than a 95% FAME yield under mild reaction conditions. The catalytic performance is maintained after storing the catalyst in Ar for a month and no catalyst leaching into the products was found based on XRF analysis. The catalyst has a higher reaction rate than the homogeneous KOH catalyst with the assistance of microwave irradiation. All of these results promote the industrial application of the synthesized ZnO/La₂O₂CO₃ as an ideal catalyst for fast biodiesel production, avoiding many of the issues found in both commercial and independently published catalysts.« less

Developments in the use of rare earth metal complexes as efficient catalysts for ring-opening polymerization of cyclic esters used in biomedical applications

NASA Astrophysics Data System (ADS)

Cota, Iuliana

2017-04-01

Biodegradable polymers represent a class of particularly useful materials for many biomedical and pharmaceutical applications. Among these types of polyesters, poly(ɛ-caprolactone) and polylactides are considered very promising for controlled drug delivery devices. These polymers are mainly produced by ring-opening polymerization of their respective cyclic esters, since this method allows a strict control of the molecular parameters (molecular weight and distribution) of the obtained polymers. The most widely used catalysts for ring-opening polymerization of cyclic esters are tin- and aluminium-based organometallic complexes; however since the contamination of the aliphatic polyesters by potentially toxic metallic residues is particularly of concern for biomedical applications, the possibility of replacing organometallic initiators by novel less toxic or more efficient organometallic complexes has been intensively studied. Thus, in the recent years, the use of highly reactive rare earth initiators/catalysts leading to lower polymer contamination has been developed. The use of rare earth complexes is considered a valuable strategy to decrease the polyester contamination by metallic residues and represents an attractive alternative to traditional organometallic complexes.

Highly efficient water-mediated approach to access benzazoles: metal catalyst and base-free synthesis of 2-substituted benzimidazoles, benzoxazoles, and benzothiazoles.

PubMed

Bala, Manju; Verma, Praveen Kumar; Sharma, Deepika; Kumar, Neeraj; Singh, Bikram

2015-05-01

An efficient water-catalyzed method has been developed for the synthesis of 2-substituted benzimidazoles, benzoxazoles, and benzothiazoles in one step. The present method excludes the usage of toxic metal catalysts and bases to produce benzazoles in good to excellent yields. An efficient and versatile water-mediated method has been established for the synthesis of various 2-arylbenzazoles. The present protocol excludes the usage of any catalyst and additive provided excellent selectivities and yields with high functional group tolerance for the synthesis of 2-arylated benzimidazoles, benzoxazoles, and benzothiazoles. Benzazolones were also synthesized using similar reaction protocol.

Applications of polymeric smart materials to environmental problems.

PubMed Central

Gray, H N; Bergbreiter, D E

1997-01-01

New methods for the reduction and remediation of hazardous wastes like carcinogenic organic solvents, toxic materials, and nuclear contamination are vital to environmental health. Procedures for effective waste reduction, detection, and removal are important components of any such methods. Toward this end, polymeric smart materials are finding useful applications. Polymer-bound smart catalysts are useful in waste minimization, catalyst recovery, and catalyst reuse. Polymeric smart coatings have been developed that are capable of both detecting and removing hazardous nuclear contaminants. Such applications of smart materials involving catalysis chemistry, sensor chemistry, and chemistry relevant to decontamination methodology are especially applicable to environmental problems. PMID:9114277

Mechanistic Understanding of Toxicity from Nanocatalysts

PubMed Central

Jiang, Cuijuan; Jia, Jianbo; Zhai, Shumei

2014-01-01

Nanoparticle-based catalysts, or nanocatalysts, have been applied in various industrial sectors, including refineries, petrochemical plants, the pharmaceutical industry, the chemical industry, food processing, and environmental remediation. As a result, there is an increasing risk of human exposure to nanocatalysts. This review evaluates the toxicity of popular nanocatalysts applied in industrial processes in cell and animal models. The molecular mechanisms associated with such nanotoxicity are emphasized to reveal common toxicity-inducing pathways from various nanocatalysts and the uniqueness of each specific nanocatalyst. PMID:25119861

Batch Processing with the Radioiodine Laser Induced-Fluorescence Detector.

DTIC Science & Technology

1980-08-27

out by ourselves and by Burger. (2) Can the poisoning of the Au catalyst be avoided by eliminating the silica tube in which the reaction is run? (3) Can...of alkyl Iodides and HI to 12 have been quantitatively evaluated for use in batch processing. Scrubbing properties of silver zeolites in terms of their...to an apparent poisoning of the gold catalyst after a short period of time. Subsequently, studies by ourselves and conversations with Lee Burger of

An Eco-Friendly Improved Protocol for the Synthesis of Bis(3-indolyl)methanes Using Poly(4-vinylpyridinium)hydrogen Sulfate as Efficient, Heterogeneous, and Recyclable Solid Acid Catalyst

PubMed Central

Banothu, Janardhan; Gali, Rajitha; Velpula, Ravibabu; Bavantula, Rajitha; Crooks, Peter A.

2013-01-01

Highly efficient and eco-friendly protocol for the synthesis of bis(3-indolyl)methanes by the electrophilic substitution reaction of indole with aldehydes catalyzed by poly(4-vinylpyridinium)hydrogen sulfate was described. Excellent yields, shorter reaction times, simple work-up procedure, avoiding hazardous organic solvents, and reusability of the catalyst are the most obvious advantages of this method. PMID:24052864

Copper catalyzed oxidative homocoupling of terminal alkynes to 1,3-diynes: a Cu3(BTC)2 MOF as an efficient and ligand free catalyst for Glaser-Hay coupling.

PubMed

Devarajan, Nainamalai; Karthik, Murugan; Suresh, Palaniswamy

2017-11-07

A straightforward and efficient method has been demonstrated for the oxidative coupling of terminal alkynes using a simple Cu 3 (BTC) 2 -metal organic framework as a sustainable heterogeneous copper catalyst. A series of symmetrical 1,3-diynes bearing diverse functional groups have been synthesized in moderate to excellent yields via a Cu 3 (BTC) 2 catalyzed Glaser-Hay reaction. The presence of the coordinatively unsaturated open Cu II sites in Cu 3 (BTC) 2 catalyzes the homocoupling in the presence of air, as an environment friendly oxidant without the use of external oxidants, ligands or any additives. The present methodology avoids stoichiometric reagents and harsher or special reaction conditions, and shows good functional group tolerance. The as-prepared catalyst could be separated easily by simple filtration and reused several times without any notable loss in activity. The hot filtration test has investigated the true heterogeneity of the catalyst. Additionally, the powder X-ray diffraction pattern of the reused catalyst revealed the high stability of the catalyst.

Process and catalyst for carbonylating olefins

DOEpatents

Zoeller, Joseph Robert

1998-06-02

Disclosed is an improved catalyst system and process for preparing aliphatic carbonyl compounds such as aliphatic carboxylic acids, alkyl esters of aliphatic carboxylic acids and anhydrides of aliphatic carboxylic acids by carbonylating olefins in the presence of a catalyst system comprising (1) a first component selected from at least one Group 6 metal, i.e., chromium, molybdenum, and/or tungsten and (2) a second component selected from at least one of certain halides and tertiary and quaternary compounds of a Group 15 element, i.e., nitrogen, phosphorus and/or arsenic, and (3) as a third component, a polar, aprotic solvent. The process employing the improved catalyst system is carried out under carbonylating conditions of pressure and temperature discussed herein. The process constitutes and improvement over known processes since it can be carried out at moderate carbonylation conditions without the necessity of using an expensive noble metal catalyst, volatile, toxic materials such as nickel tetracarbonyl, formic acid or a formate ester. Further, the addition of a polar, aprotic solvent to the catalyst system significantly increases, or accelerates, the rate at which the carbonylation takes place.

Hybrid Mo-CT nanowires as highly efficient catalysts for direct dehydrogenation of isobutane.

PubMed

Mu, Jiali; Shi, Junjun; France, Liam John; Wu, Yongshan; Zeng, Qiang; Liu, Baoan; Jiang, Lilong; Long, Jinxing; Li, Xuehui

2018-06-20

Direct dehydrogenation of isobutane to isobutene has drawn extensive attention for synthesizing various chemicals. The Mo-based catalysts hold promise as an alternative to the toxic CrOx- and scarce Pt-based catalysts. However, the low activity and rapid deactivation of the Mo-based catalysts greatly hinder their practical applications. Herein, we demonstrate a feasible approach towards the development of efficient and non-noble metal dehydrogenation catalysts basing on Mo-CT hybrid nanowires calcined at different temperatures. In particular, the optimal Mo-C700 catalyst exhibits isobutane consumption rate of 3.9 mmol g-1 h-1, and isobutene selectivity of 73% with production rate of 2.8 mmol g-1 h-1. The catalyst maintained 90% of its initial activity after 50 h of reaction. Extensive characterizations reveal that such prominent performance is well-correlated with the adsorption abilities of isobutane and isobutene, and the formation of η-MoC species. By contrast, the generation of β-Mo2C crystalline phase during long-term reaction causes minor decline in activity. Compared to MoO2 and β-Mo2C, η-MoC plays a role more likely in suppressing the cracking reaction. This work demonstrates a feasible approach towards the development of efficient and non-noble metal dehydrogenation catalysts.

Catalyst Development for Hydrogen Peroxide Rocket Engines

NASA Technical Reports Server (NTRS)

Morlan, P. W.; Wu, P.-K.; Ruttle, D. W.; Fuller, R. P.; Nejad, A. S.; Anderson, W. E.

1999-01-01

The development of various catalysts of hydrogen peroxide was conducted for the applications of liquid rocket engines. The catalyst development includes silver screen technology, solid catalyst technology, and homogeneous catalyst technology. The silver screen technology development was performed with 85% (by weight) hydrogen peroxide. The results of this investigation were used as the basis for the catalyst design of a pressure-fed liquid-fueled upper stage engine. Both silver-plated nickel 200 screens and pure silver screens were used as the active metal catalyst during the investigation, The data indicate that a high decomposition efficiency (greater than 90%) of 85% hydrogen peroxide can be achieved at a bed loading of 0.5 lbm/sq in/sec with both pure silver and silver plated screens. Samarium oxide coating, however, was found to retard the decomposition process and the catalyst bed was flooded at lower bed loading. A throughput of 200 lbm of hydrogen peroxide (1000 second run time) was tested to evaluate the catalyst aging issue and performance degradation was observed starting at approximately 400 seconds. Catalyst beds of 3.5 inch in diameter was fabricated using the same configuration for a 1,000-lbf rocket engine. High decomposition efficiency was obtained with a low pressure drop across the bed. Solid catalyst using precious metal was also developed for the decomposition of hydrogen peroxide from 85% to 98% by weight. Preliminary results show that the catalyst has a strong reactivity even after 15 minutes of peroxide decomposition. The development effort also includes the homogeneous catalyst technology. Various non-toxic catalysts were evaluated with 98% peroxide and hydrocarbon fuels. The results of open cup drop tests indicate an ignition delay around 11 ms.

Synthesis of carbon nanotubes using green plant extract as catalyst: unconventional concept and its realization

NASA Astrophysics Data System (ADS)

Tripathi, Nishant; Pavelyev, Vladimir; Islam, S. S.

2017-11-01

Green catalyst derived from plants, a cheap and abundant natural source, is used for the synthesis of multi-walled carbon nanotubes (MWNTs). The concept is unconventional and practically realized into existence by simple CVD growth while keeping away the potential hazards caused by metal catalyst on environment and living organisms. The notable points to mention of such growth are: (1) grown CNTs are free from toxic metal catalyst, (2) low growth temperature (575 °C) required and produced high yield vis-à-vis any other catalyst used so far reported, and (3) no need of expensive and complex systems for its synthesis. Besides, growth of SWNT as well as carbon nano-belts with hollow rectangular cross-section is observed when growth temperature increased to 800 °C, specifically, for the wall-nut extract. The samples were characterized by microscopic and spectroscopic analysis and the results verified our study. The present work provides innovative technique and may open up new avenues for CNTs synthesis and its applications.

Interstitial modification of palladium nanoparticles with boron atoms as a green catalyst for selective hydrogenation

NASA Astrophysics Data System (ADS)

Chan, Chun Wong Aaron; Mahadi, Abdul Hanif; Li, Molly Meng-Jung; Corbos, Elena Cristina; Tang, Chiu; Jones, Glenn; Kuo, Winson Chun Hsin; Cookson, James; Brown, Christopher Michael; Bishop, Peter Trenton; Tsang, Shik Chi Edman

2014-12-01

Lindlar catalysts comprising of palladium/calcium carbonate modified with lead acetate and quinoline are widely employed industrially for the partial hydrogenation of alkynes. However, their use is restricted, particularly for food, cosmetic and drug manufacture, due to the extremely toxic nature of lead, and the risk of its leaching from catalyst surface. In addition, the catalysts also exhibit poor selectivities in a number of cases. Here we report that a non-surface modification of palladium gives rise to the formation of an ultra-selective nanocatalyst. Boron atoms are found to take residence in palladium interstitial lattice sites with good chemical and thermal stability. This is favoured due to a strong host-guest electronic interaction when supported palladium nanoparticles are treated with a borane tetrahydrofuran solution. The adsorptive properties of palladium are modified by the subsurface boron atoms and display ultra-selectivity in a number of challenging alkyne hydrogenation reactions, which outclass the performance of Lindlar catalysts.

Undergraduate research studies program at participating institutions of the HBCU Fossil Energy Consortium

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

Bhatia, S.C.; Cardelino, B.H.; Hall, J.H. Jr.

1990-01-31

This report consists of five quarterly progress reports from four participating universities. The titles of the projects are: Competition of NO and SO{sub 2} for OH generated within electrical aerosol analyzers; Dispersed iron catalysts for coal gasification; Catalytic gasification of coal chars by potassium sulfate and ferrous sulfate mixtures; Removal of certain toxic heavy metal ions in coal conversion process wastewaters; and Study of coal liquefaction catalysts. All reports have been indexed separately for inclusion on the data base. (CK)

Furfural production using ionic liquids: A review.

PubMed

Peleteiro, Susana; Rivas, Sandra; Alonso, José Luis; Santos, Valentín; Parajó, Juan Carlos

2016-02-01

Furfural, a platform chemical with a bright future, is commercially obtained by acidic processing of xylan-containing biomass in aqueous media. Ionic liquids (ILs) can be employed in processed for furfural manufacture as additives, as catalysts and/or as reaction media. Depending on the IL utilized, externally added catalysts (usually, Lewis acids, Brönsted acids and/or solid acid catalysts) can be necessary to achieve high reaction yields. Oppositely, acidic ionic liquids (AILs) can perform as both solvents and catalysts, enabling the direct conversion of suitable substrates (pentoses, pentosans or xylan-containing biomass) into furfural. Operating in IL-containing media, the furfural yields can be improved when the product is continuously removed along the reaction (for example, by stripping or extraction), to avoid unwanted side-reactions leading to furfural consumption. These topics are reviewed, as well as the major challenges involved in the large scale utilization of ILs for furfural production. Copyright © 2015 Elsevier Ltd. All rights reserved.

Method of producing pyrolysis gases from carbon-containing materials

DOEpatents

Mudge, Lyle K.; Brown, Michael D.; Wilcox, Wayne A.; Baker, Eddie G.

1989-01-01

A gasification process of improved efficiency is disclosed. A dual bed reactor system is used in which carbon-containing feedstock materials are first treated in a gasification reactor to form pyrolysis gases. The pyrolysis gases are then directed into a catalytic reactor for the destruction of residual tars/oils in the gases. Temperatures are maintained within the catalytic reactor at a level sufficient to crack the tars/oils in the gases, while avoiding thermal breakdown of the catalysts. In order to minimize problems associated with the deposition of carbon-containing materials on the catalysts during cracking, a gaseous oxidizing agent preferably consisting of air, oxygen, steam, and/or mixtures thereof is introduced into the catalytic reactor at a high flow rate in a direction perpendicular to the longitudinal axis of the reactor. This oxidizes any carbon deposits on the catalysts, which would normally cause catalyst deactivation.

Rapid Catalyst Capture Enables Metal-Free para-Hydrogen-Based Hyperpolarized Contrast Agents.

PubMed

Barskiy, Danila A; Ke, Lucia A; Li, Xingyang; Stevenson, Vincent; Widarman, Nevin; Zhang, Hao; Truxal, Ashley; Pines, Alexander

2018-05-10

Hyperpolarization techniques based on the use of para-hydrogen provide orders of magnitude signal enhancement for magnetic resonance spectroscopy and imaging. The main drawback limiting widespread applicability of para-hydrogen-based techniques in biomedicine is the presence of organometallic compounds (the polarization transfer catalysts) in solution with hyperpolarized contrast agents. These catalysts are typically complexes of platinum-group metals, and their administration in vivo should be avoided. Herein, we show how extraction of a hyperpolarized compound from an organic phase to an aqueous phase combined with a rapid (less than 10 s) Ir-based catalyst capture by metal scavenging agents can produce pure para-hydrogen-based hyperpolarized contrast agents, as demonstrated by high-resolution nuclear magnetic resonance (NMR) spectroscopy and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The presented methodology enables fast and efficient means of producing pure hyperpolarized aqueous solutions for biomedical and other uses.

Surface Immobilization of Molecular Electrocatalysts for Energy Conversion

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

Bullock, R. Morris; Das, Atanu K.; Appel, Aaron M.

2017-03-22

Electrocatalysts are critically important for a secure energy future, as they facilitate the conversion between electrical energy and chemical energy. Molecular catalysts offer precise control of their structure, and the ability to modify the substituents to understand structure-reactivity relationships that are more difficult to achieve with heterogeneous catalysts. Molecular electrocatalysts can be immobilized on surfaces by covalent bonds or through non-covalent interactions. Advantages of surface immobilization include the need for less catalyst, avoidance of bimolecular decomposition pathways, and easier determination of catalyst lifetime. Copper-catalyzed click reactions are often used to form covalent bonds to surfaces, and pi-pi stacking of pyrenemore » substituents appended to the ligand of a molecular complex is a frequently used method to achieve non-covalent surface immobilization. This mini-review highlights surface confinement of molecular electrocatalysts for reduction of O2, oxidation of H2O, production of H2, and reduction of CO2.« less

Alkali-catalyzed low temperature wet crosslinking of plant proteins using carboxylic acids.

PubMed

Reddy, Narendra; Li, Ying; Yang, Yiqi

2009-01-01

We report the development of a new method of alkali-catalyzed low temperature wet crosslinking of plant proteins to improve their breaking tenacity without using high temperatures or phosphorus-containing catalysts used in conventional poly(carboxylic acid) crosslinking of cellulose and proteins. Carboxylic acids are preferred over aldehyde-containing crosslinkers for crosslinking proteins and cellulose because of their low toxicity and cost and ability to improve the desired properties of the materials. However, current knowledge in carboxylic acid crosslinking of proteins and cellulose requires the use of carboxylic acids with at least three carboxylic groups, toxic phosphorous-containing catalysts and curing at high temperatures (150-185 degrees C). The use of high temperatures and low pH in conventional carboxylic acid crosslinking has been reported to cause substantial strength loss and/or undesired changes in the properties of the crosslinked materials. In this research, gliadin, soy protein, and zein fibers have been crosslinked with malic acid, citric acid, and butanetetracarboxylic acid to improve the tenacity of the fibers without using high temperatures and phosphorus-containing catalysts. The new method of wet crosslinking using carboxylic acids containing two or more carboxylic groups will be useful to crosslink proteins for various industrial applications.

Facile and gram-scale synthesis of metal-free catalysts: toward realistic applications for fuel cells.

PubMed

Kim, Ok-Hee; Cho, Yong-Hun; Chung, Dong Young; Kim, Min Jeong; Yoo, Ji Mun; Park, Ji Eun; Choe, Heeman; Sung, Yung-Eun

2015-03-02

Although numerous reports on nonprecious metal catalysts for replacing expensive Pt-based catalysts have been published, few of these studies have demonstrated their practical application in fuel cells. In this work, we report graphitic carbon nitride and carbon nanofiber hybrid materials synthesized by a facile and gram-scale method via liquid-based reactions, without the use of toxic materials or a high pressure-high temperature reactor, for use as fuel cell cathodes. The resulting materials exhibited remarkable methanol tolerance, selectivity, and stability even without a metal dopant. Furthermore, these completely metal-free catalysts exhibited outstanding performance as cathode materials in an actual fuel cell device: a membrane electrode assembly with both acidic and alkaline polymer electrolytes. The fabrication method and remarkable performance of the single cell produced in this study represent progressive steps toward the realistic application of metal-free cathode electrocatalysts in fuel cells.

Facile and Gram-scale Synthesis of Metal-free Catalysts: Toward Realistic Applications for Fuel Cells

PubMed Central

Kim, Ok-Hee; Cho, Yong-Hun; Chung, Dong Young; Kim, Min Jeong; Yoo, Ji Mun; Park, Ji Eun; Choe, Heeman; Sung, Yung-Eun

2015-01-01

Although numerous reports on nonprecious metal catalysts for replacing expensive Pt-based catalysts have been published, few of these studies have demonstrated their practical application in fuel cells. In this work, we report graphitic carbon nitride and carbon nanofiber hybrid materials synthesized by a facile and gram-scale method via liquid-based reactions, without the use of toxic materials or a high pressure-high temperature reactor, for use as fuel cell cathodes. The resulting materials exhibited remarkable methanol tolerance, selectivity, and stability even without a metal dopant. Furthermore, these completely metal-free catalysts exhibited outstanding performance as cathode materials in an actual fuel cell device: a membrane electrode assembly with both acidic and alkaline polymer electrolytes. The fabrication method and remarkable performance of the single cell produced in this study represent progressive steps toward the realistic application of metal-free cathode electrocatalysts in fuel cells. PMID:25728910

Electrochemical enhanced heterogeneous activation of peroxydisulfate by Fe-Co/SBA-15 catalyst for the degradation of Orange II in water.

PubMed

Cai, Chun; Zhang, Hui; Zhong, Xin; Hou, Liwei

2014-12-01

Mesoporous silica SBA-15 supported iron and cobalt catalysts (Fe-Co/SBA-15) were prepared and used in the electrochemical (EC) enhanced heterogeneous activation of peroxydisulfate (PDS, S2O8(2-)) process for the removal of Orange II. The effects of some important reaction parameters such as initial pH, current density, PDS concentration and dosage of Fe-Co/SBA-15 catalysts were investigated. The results showed that the decolorization efficiency was not significantly affected by the initial pH value, and it did increase with the higher PDS concentration, current density and Fe-Co/SBA-15 dosage. Both the sulfate radical (SO4(·-)) and the hydroxyl radical (OH) are considered as the primary reactive oxidants for the Orange II decolorization. The Fe-Co/SBA-15 catalyst maintained its high activity during repeated batch experiments. The intermediate products were identified by GC-MS analysis and a plausible degradation pathway is proposed accordingly. The removal efficiencies of chemical oxygen demand (COD) and total organic carbon (TOC) were 52.1% and 31.9%, respectively after 60 min of reaction time but reached 82.9% and 51.5%, respectively when the reaction time was extended to 24 h. Toxicity tests with activated sludge indicated that the toxicity of the solution increased during the first 30 min and then decreased as the oxidation proceeded. Copyright © 2014 Elsevier Ltd. All rights reserved.

Influences of synthesis methods and modifier addition on the properties of Ni-based catalysts supported on reticulated ceramic foams

NASA Astrophysics Data System (ADS)

Nikolić, Vesna; Kamberović, Željko; Anđić, Zoran; Korać, Marija; Sokić, Miroslav; Maksimović, Vesna

2014-08-01

A method of synthesizing Ni-based catalysts supported on α-Al2O3-based foams was developed. The foams were impregnated with aqueous solutions of metal chlorides under an air atmosphere using an aerosol route. Separate procedures involved calcination to form oxides and drying to obtain chlorides on the foam surface. The synthesized samples were subsequently reduced with hydrogen. With respect to the Ni/Al2O3 catalysts, the chloride reduction route enabled the formation of a Ni coating without agglomerates or cracks. Further research included catalyst modification by the addition of Pd, Cu, and Fe. The influences of the additives on the degree of reduction and on the low-temperature reduction effectiveness (533 and 633 K) were examined and compared for the catalysts obtained from oxides and chlorides. Greater degrees of reduction were achieved with chlorides, whereas Pd was the most effective modifier among those investigated. The reduction process was nearly complete at 533 K in the sample that contained 0.1wt% Pd. A lower reduction temperature was utilized, and the calcination step was avoided, which may enhance the economical and technological aspects of the developed catalyst production method.

Distribution of free radicals and intermediates during the photodegradation of polychlorinated biphenyls strongly affected by cosolvents and TiO₂ catalyst.

PubMed

Zhu, Xiangdong; Wang, Yujun; Qin, Wenxiu; Zhang, Shicheng; Zhou, Dongmei

2016-02-01

Polychlorinated biphenyls (PCBs) pose potential ecological risk because of their high toxicity and carcinogenicity. Photodegradation, which is an important process for the removal of PCBs, is greatly influenced by the cosolvent and catalyst. Hence, it is important to explore their effects on the photodegradation behavior of PCBs. In this study, 2,4,4'-trichlorobiphenyl (PCB28) was selected as a model compound, and the effects of two typical cosolvents, namely acetone and ethanol, and TiO2 catalyst on the distributions of free radicals and intermediates were investigated. Interestingly, the TiO2 catalyst did not promote PCB28 photodegradation. Moreover, the free radical distribution was greatly influenced in the presence of the TiO2 catalyst, while was only slightly affected in its absence by the cosolvent kinds. The main photodegradation pathways are proposed on the basis of the distribution of detected intermediates, which were significantly regulated by both the cosolvent and TiO2 catalyst. The results provide novel insights into the photodegradation of PCBs and may have important implications for choosing cosolvent in desorbing soil PCBs and consequently enhancing PCBs degradation. Copyright © 2015 Elsevier Ltd. All rights reserved.

A new generation of zirconia supported metal oxide catalysts for converting low grade renewable feedstocks to biodiesel.

PubMed

Kim, Manhoe; DiMaggio, Craig; Salley, Steven O; Simon Ng, K Y

2012-08-01

A new class of zirconia supported mixed metal oxides (ZnO-TiO(2)-Nd(2)O(3)/ZrO(2) and ZnO-SiO(2)-Yb(2)O(3)/ZrO(2)) has demonstrated the ability to convert low quality, high free fatty acid (FFA) bio-oils into biodiesel. Pelletized catalysts of ZrO(2) supported metal oxides were prepared via a sol-gel process and tested in continuous flow packed bed reactors for up to 6 months. In a single pass, while operating at mild to moderate reaction conditions, 195 °C and 300 psi, these catalysts can perform simultaneous esterification and transesterification reactions on feedstock of 33% FFA and 67% soybean oil to achieve FAME yields higher than 90%. Catalytic activity of the ZrO(2) supported metal oxide catalysts was highly dependent on the metal oxide composition. These heterogeneous catalysts will enable biodiesel manufacturers to avoid problems inherent in homogeneous processes, such as separation and washing, corrosive conditions, and excessive methanol usage. Copyright © 2012 Elsevier Ltd. All rights reserved.

Two Catalysts for Selective Oxidation of Contaminant Gases

NASA Technical Reports Server (NTRS)

Wright, John D.

2011-01-01

Two catalysts for the selective oxidation of trace amounts of contaminant gases in air have been developed for use aboard the International Space Station. These catalysts might also be useful for reducing concentrations of fumes in terrestrial industrial facilities especially facilities that use halocarbons as solvents, refrigerant liquids, and foaming agents, as well as facilities that generate or utilize ammonia. The first catalyst is of the supported-precious-metal type. This catalyst is highly active for the oxidation of halocarbons, hydrocarbons, and oxygenates at low concentrations in air. This catalyst is more active for the oxidation of hydrocarbons and halocarbons than are competing catalysts developed in recent years. This catalyst completely converts these airborne contaminant gases to carbon dioxide, water, and mineral acids that can be easily removed from the air, and does not make any chlorine gas in the process. The catalyst is thermally stable and is not poisoned by chlorine or fluorine atoms produced on its surface during the destruction of a halocarbon. In addition, the catalyst can selectively oxidize ammonia to nitrogen at a temperature between 200 and 260 C, without making nitrogen oxides, which are toxic. The temperature of 260 C is higher than the operational temperature of any other precious-metal catalyst that can selectively oxidize ammonia. The purpose of the platinum in this catalyst is to oxidize hydrocarbons and to ensure that the oxidation of halocarbons goes to completion. However, the platinum exhibits little or no activity for initiating the destruction of halocarbons. Instead, the attack on the halocarbons is initiated by the support. The support also provides a high surface area for exposure of the platinum. Moreover, the support resists deactivation or destruction by halogens released during the destruction of halocarbons. The second catalyst is of the supported- metal-oxide type. This catalyst can selectively oxidize ammonia to nitrogen at temperatures up to 400 C, without producing nitrogen oxides. This catalyst converts ammonia completely to nitrogen, even when the concentration of ammonia is very low. No other catalyst is known to oxidize ammonia selectively at such a high temperature and low concentration. Both the metal oxide and the support contribute to the activity and selectivity of this catalyst.

Lagrangian Approach to Study Catalytic Fluidized Bed Reactors

NASA Astrophysics Data System (ADS)

Madi, Hossein; Hossein Madi Team; Marcelo Kaufman Rechulski Collaboration; Christian Ludwig Collaboration; Tilman Schildhauer Collaboration

2013-03-01

Lagrangian approach of fluidized bed reactors is a method, which simulates the movement of catalyst particles (caused by the fluidization) by changing the gas composition around them. Application of such an investigation is in the analysis of the state of catalysts and surface reactions under quasi-operando conditions. The hydrodynamics of catalyst particles within a fluidized bed reactor was studied to improve a Lagrangian approach. A fluidized bed methanation employed in the production of Synthetic Natural Gas from wood was chosen as the case study. The Lagrangian perspective was modified and improved to include different particle circulation patterns, which were investigated through this study. Experiments were designed to evaluate the concepts of the model. The results indicate that the setup is able to perform the designed experiments and a good agreement between the simulation and the experimental results were observed. It has been shown that fluidized bed reactors, as opposed to fixed beds, can be used to avoid the deactivation of the methanation catalyst due to carbon deposits. Carbon deposition on the catalysts tested with the Lagrangian approach was investigated by temperature programmed oxidation (TPO) analysis of ex-situ catalyst samples. This investigation was done to identify the effects of particles velocity and their circulation patterns on the amount and type of deposited carbon on the catalyst surface. Ecole Polytechnique Federale de Lausanne(EPFL), Paul Scherrer Institute (PSI)

Identification of intermediates and assessment of ecotoxicity in the oxidation products generated during the ozonation of clofibric acid.

PubMed

Rosal, Roberto; Gonzalo, María S; Boltes, Karina; Letón, Pedro; Vaquero, Juan J; García-Calvo, E

2009-12-30

The degradation of an aqueous solution of clofibric acid was investigated during catalytic and non-catalytic ozonation. The catalyst, TiO(2), enhanced the production of hydroxyl radicals from ozone and raised the fraction or clofibric acid degraded by hydroxyl radicals. The rate constant for the reaction of clofibric acid and hydroxyl radicals was not affected by the presence of the catalyst. The toxicity of the oxidation products obtained during the reaction was assessed by means of Vibrio fischeri and Daphnia magna tests in order to evaluate the potential formation of toxic by-products. The results showed that the ozonation was enhanced by the presence of TiO(2,) the clofibric acid being removed completely after 15 min at pH 5. The evolution of dissolved organic carbon, specific ultraviolet absorption at 254 nm and the concentration of carboxylic acids monitored the degradation process. The formation of 4-chlorophenol, hydroquinone, 4-chlorocatechol, 2-hydroxyisobutyric acid and three non-aromatic compounds identified as a product of the ring-opening reaction was assessed by exact mass measurements performed by liquid chromatography coupled to time-of-flight mass spectrometry (LC-TOF-MS). The bioassays showed a significant increase in toxicity during the initial stages of ozonation following a toxicity pattern closely related to the formation of ring-opening by-products.

Environmental implications on the oxygenation of gasoline with ethanol in the metropolitan area of Mexico City.

PubMed

Schifter, I; Vera, M; Díaz, L; Guzmán, E; Ramos, F; López-Salinas, E

2001-05-15

Motor vehicle emission tests were performed on 12 in-use light duty vehicles, made up of the most representative emission control technologies in Mexico City: no catalyst, oxidative catalyst, and three way catalyst. Exhaust regulated (CO, NOx, and hydrocarbons) and toxic (benzene, formaldehyde, acetaldehyde, and 1,3-butadiene) emissions were evaluated for MTBE (5 vol %)- and ethanol (3, 6, and 10 vol %)-gasoline blends. The most significant overall emissions variations derived from the use of 6 vol % ethanol (relative to a 5% MTBE base gasoline) were 16% decrease in CO, 28% reduction in formaldehyde, and 80% increase in acetaldehyde emissions. A 26% reduction in CO emissions from the oldest fleet (< MY 1991, without catalytic converter), which represents about 44% of the in-use light duty vehicles in Mexico city, can be attained when using 6 vol% ethanol-gasoline, without significant variation in hydrocarbons and NOx emissions, when compared with a 5% vol MTBE-gasoline. On the basis of the emissions results, an estimation of the change in the motor vehicle emissions of the metropolitan area of Mexico city was calculated for the year 2010 if ethanol were to be used instead of MTBE, and the outcome was a considerable decrease in all regulated and toxic emissions, despite the growing motor vehicle population.

Esterification free fatty acid in sludge palm oil using ZrO2/SO42- - rice husk ash catalyst

NASA Astrophysics Data System (ADS)

Hidayat, Arif; Sutrisno, Bachrun

2017-05-01

Indonesia, as one of the biggest palm oil producers and exporters in the world, is producing large amounts of low-grade oil such as sludge palm oil (SPO) from palm oil industries. The use of SPO can lower the cost of biodiesel production significantly, which makes SPO a highly potential alternative feedstock for biodiesel production. In this paper, the esterification of free fatty acid on sludge palm oil was studied using rice husk ash as heterogeneous solid catalysts. Heterogeneous solid catalysts offer significant advantages of eliminating separation, corrosion, toxicity and environmental problems. In this paper the esterification of SPO, a by-product from palm oil industry, in the presence of modified rice husk ash catalysts was studied. The rice husk ash catalysts were synthesized by impregnating of Zirconia (Zr) on rice husk ash followed by sulfonation. The rice husk ash catalysts were characterized by using different techniques, such as FT-IR, XRD, and porous analysis. The effects of the mass ratio of catalyst to oil (1 - 10%), the molar ratio of methanol to oil (4:1 - 10:1), and the reaction temperature (40 - 60°C) were studied for the conversion of free fatty acids (FFAs) to optimize the reaction conditions. The results showed that the optimal conditions were an methanol to oil molar ratio of 10:1, the amount of catalyst of 10%w, and reaction temperature of 60°C.

Low temperature destruction of PCDD/Fs over V2O5-CeO2/TiO2 catalyst with ozone.

PubMed

Yu, Ming-Feng; Lin, Xiao-Qing; Yan, Mi; Li, Xiao-Dong; Chen, Tong; Yan, Jian-Hua

2016-09-01

Catalytic destruction of PCDD/Fs (polychlorinated dibenzo-p-dioxins and furans) over V2O5-CeO2/TiO2 catalyst was investigated at a low temperature range of 140-180 °C, in the absence and presence of ozone (200 ppm). Nano-TiO2 support was used to prepare the catalyst by step impregnation method. A stable PCDD/Fs-generating system was established to support the catalytic destruction tests. In the presence of ozone alone, destruction efficiencies of PCDD/Fs are between 32.2 and 43.1 % with temperature increasing from 140 to 180 °C. The activity of V2O5-CeO2/TiO2 catalyst alone on PCDD/Fs destruction is also studied. The increase of temperature from 140 to 180 °C enhances the activity of catalyst with destruction efficiencies increasing from 54.7 to 73.4 %. However, ozone addition greatly enhances the catalytic activity of V2O5-CeO2/TiO2 catalyst on PCDD/Fs decomposition. At 180 °C, the destruction efficiency of PCDD/Fs achieved with V2O5-CeO2/TiO2 catalyst and ozone is above 86.0 %. It indicates that the combined use of ozone and catalyst reduces the reaction temperature of PCDD/Fs oxidation and offers a new method to destroy PCDD/Fs with high destruction efficiency at a low temperature. Furthermore, the destruction efficiencies of 17 toxic PCDD/F congeners, achieved with ozone alone, catalyst alone, and catalyst/ozone are analyzed.

Facile and Green Synthesis of Palladium Nanoparticles-Graphene-Carbon Nanotube Material with High Catalytic Activity

NASA Astrophysics Data System (ADS)

Sun, Tai; Zhang, Zheye; Xiao, Junwu; Chen, Chen; Xiao, Fei; Wang, Shuai; Liu, Yunqi

2013-08-01

We report a facile and green method to synthesize a new type of catalyst by coating Pd nanoparticles (NPs) on reduced graphene oxide (rGO)-carbon nanotube (CNT) nanocomposite. An rGO-CNT nanocomposite with three-dimensional microstructures was obtained by hydrothermal treatment of an aqueous dispersion of graphene oxide (GO) and CNTs. After the rGO-CNT composites have been dipped in K2PdCl4 solution, the spontaneous redox reaction between the GO-CNT and PdCl42- led to the formation of nanohybrid materials consisting rGO-CNT decorated with 4 nm Pd NPs, which exhibited excellent and stable catalytic activity: the reduction of 4-nitrophenol to 4-aminophenol using NaBH4 as a catalyst was completed in only 20 s at room temperature, even when the Pd content of the catalyst was 1.12 wt%. This method does not require rigorous conditions or toxic agents and thus is a rapid, efficient, and green approach to the fabrication of highly active catalysts.

Chloroform Hydrodechlorination over Palladium–Gold Catalysts: A First-Principles DFT Study

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

Xu, Lang; Yao, Xiaoqian; Khan, Ahmad

2016-04-20

Hydrodechlorination is a promising method for treating toxic chlorocarbon compounds. Pd is among the most effective catalysts for chloroform hydrodechlorination, and experiments have shown that the Pd–Au alloy catalyst yields superior catalytic performance over pure Pd. In this paper, we examine the chloroform hydrodechlorination mechanism over Pd(1 1 1) and Pd ML/Au(1 1 1) surfaces using periodic, self-consistent density functional theory calculations (DFT, GGA–PW91) and maximum rate analysis. We suggest that the reaction occurs on both surfaces through complete dechlorination of chloroform followed by hydrogenation of CH* to methane, and that the initial dechlorination step is likely the rate-limiting step.more » Finally, on Pd(1 1 1), the chloroform dechlorination barrier is 0.24 eV higher than the desorption barrier, whereas on Pd ML/Au(1 1 1), the chloroform dechlorination barrier is 0.07 eV lower than the desorption barrier, which can explain the higher hydrodechlorination activity of the Pd–Au alloy catalyst.« less

Protective effects of chlorogenic acid in 3-nitropropionic acid induced toxicity and genotoxicity.

PubMed

Alarcón-Herrera, Norberto; Flores-Maya, Saúl; Bellido, Belén; García-Bores, Ana M; Mendoza, Ernesto; Ávila-Acevedo, Guillermo; Hernández-Echeagaray, Elizabeth

2017-11-01

Mitochondrial inhibition with the toxin 3-Nitropropionic acid (3-NP) has been used to study the underlying mechanisms in striatal neurodegeneration, but few experiments have evaluated its toxicity and genotoxicity of in vivo administration. Furthermore, different antioxidant molecules may prevent degeneration induced by the toxic effects of 3-NP. Therefore, the purpose of this study was to evaluate the toxicity and genotoxicity induced by 3-NP (15 mg/kg) in the micronuclei assay method; also, we assessed chlorogenic acid (CGA, 100 mg/kg) for its anti-toxic and anti-genotoxic effect in damage produced by in vivo treatment with 3-NP. 3-NP induced toxicity and genotoxicity. CGA administered as a co-treatment with 3-NP (3-NP + CA) reduced toxicity by 32.76%, as a pre-treatment for 5 days only, followed by 3-NP treatment (P/CA, 3-NP) inhibiting toxicity by 24.04%, or as a pre-treatment, plus a co-treatment with 3-NP (P/CA, 3-NP + CA) avoided any toxic effect. CGA alone did not exhibit any toxic effect. Only P/CGA, 3-NP + CGA group, avoided toxicity and genotoxicity, suggesting that CGA could be suitable to prevent, reduce or delay toxicity and cell death. Copyright © 2017 Elsevier Ltd. All rights reserved.

Homogeneous And Heterogeneous Activation Of Peroxymonosulfate With Iron-Based Catalysts

EPA Science Inventory

Polychlorinated biphenyls (PCBs) in the environment pose long-term risk to public health because of their persistent and toxic nature. This study investigates the degradation of PCBs using sulfate radical-based advanced oxidation technologies (SR-AOTs). SR-AOTs are attracting c...

Ultraviolet and solar photocatalytic ozonation of municipal wastewater: Catalyst reuse, energy requirements and toxicity assessment.

PubMed

Mecha, Achisa C; Onyango, Maurice S; Ochieng, Aoyi; Momba, Maggy N B

2017-11-01

The present study evaluated the treatment of municipal wastewater containing phenol using solar and ultraviolet (UV) light photocatalytic ozonation processes to explore comparative performance. Important aspects such as catalyst reuse, mineralization of pollutants, energy requirements, and toxicity of treated wastewater which are crucial for practical implementation of the processes were explored. The activity of the photocatalysts did not change significantly even after three consecutive uses despite approximately 2% of the initial quantity of catalyst being lost in each run. Analysis of the change in average oxidation state (AOS) demonstrated the formation of more oxidized degradation products (ΔAOS values of 1.0-1.7) due to mineralization. The energy requirements were determined in terms of electrical energy per order (E EO ) and the collector area per order (A CO ). The E EO (kWh m -3  Order -1 ) values were 26.2 for ozonation, 38-47 for UV photocatalysis and 7-22 for UV photocatalytic ozonation processes. On the other hand, A CO (m 2  m -3  order -1 ) values were 31-69 for solar photocatalysis and 8-13 for solar photocatalytic ozonation. Thus photocatalytic ozonation processes required less energy input compared to the individual processes. The cytotoxicity of the wastewater was analysed using the 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide (MTT) assay with Vero cells. The cell viability increased from 28.7% in untreated wastewater to 80% in treated wastewater; thus showing that the treated wastewater was less toxic. The effectiveness of photocatalytic ozonation, recovery and reusability of the photocatalysts, as well as detoxification of the wastewater make this low energy consumption process attractive for wastewater remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Preparation of a Bimetal Using Mechanical Alloying for Environmental or Industrial Use

NASA Technical Reports Server (NTRS)

Quinn, Jacqueline; Geiger, Cherie; Clausen, Christian

2013-01-01

Following the 1976 Toxic Substances Control Act ban on their manufacture, PCBs remain an environmental threat. PCBs are known to bio-accumulate and concentrate in fatty tissues. Further complications arise from the potential for contamination of commercial mixtures with other more toxic chlorinated compounds such as polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Until recently, only one option was available for the treatment of PCB-contaminated materials: incineration. This may prove to be more detrimental to the environment than the PCBs themselves due to the potential for formation of PCDDs. Metals have been used for the past ten years for the remediation of halogenated solvents and other contaminants in the environment; however, zero-valent metals alone do not possess the activity required to dehalogenate PCBs. Palladium has been shown to act as an excellent catalyst for the dechlorination of PCBs with active metals. This invention is a method for the production of a palladium/magnesium bimetal capable of dechlorinating PCBs using mechanical milling/mechanical alloying. Other base metals and catalysts may also be alloyed together (e.g., nickel or zinc) to create a similarly functioning catalyst system. Several bimetal catalyst systems currently can be used for processes such as hydrogen peroxide synthesis, oxidation of ethane, selective oxidation, hydrogenation, and production of syngas for further conversion to clean fuels. The processes for making these bimetal catalysts often involve vapor deposition. This technology provides an alternative to vapor deposition that may provide equally active catalysts. A hydrogenation catalyst including a base material coated with a catalytic metal is made using mechanical milling techniques. The hydrogenation catalysts are used as an excellent catalyst for the dehalogenation of contaminated compounds and the remediation of other industrial compounds. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts. Preferably, the hydrogenation catalyst is a bimetallic particle formed from a zero-valent iron or zero-valent magnesium particle coated with palladium that is impregnated onto a high-surface-area graphite support. The zero-valent metal particles should be microscale or nanoscale zero-valent magnesium or zero-valent iron particles. Other zero-valent metal particles and combinations may be used. Additionally, the base material may be selected from a variety of minerals including, but not limited to, alumina and zeolites. The catalytic metal is preferably selected from the group consisting of noble metals and transition metals, preferably palladium. The mechanical milling process includes milling the base material with a catalytic metal impregnated into a high-surface-area support to form the hydrogenation catalyst. In a preferred mechanical milling process, a zero-valent metal particle is provided as the base material, preferably having a particle size of less than about 10 microns, preferably 0.1 to 10 microns or smaller, prior to milling. The catalytic metal is supported on a conductive carbon support structure prior to milling. For example, palladium may be impregnated on a graphite support. Other support structures such as semiconductive metal oxides may also be used.

Application of microscopy technology in thermo-catalytic methane decomposition to hydrogen

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

Mei, Irene Lock Sow, E-mail: irene.sowmei@gmail.com; Lock, S. S. M., E-mail: serenelock168@gmail.com; Abdullah, Bawadi, E-mail: bawadi-abdullah@petronas.com.my

2015-07-22

Hydrogen production from the direct thermo-catalytic decomposition of methane is a promising alternative for clean fuel production because it produces pure hydrogen without any CO{sub x} emissions. However, thermal decomposition of methane can hardly be of any practical and empirical interest in the industry unless highly efficient and effective catalysts, in terms of both specific activity and operational lifetime have been developed. In this work, bimetallic Ni-Pd on gamma alumina support have been developed for methane cracking process by using co-precipitation and incipient wetness impregnation method. The calcined catalysts were characterized to determine their morphologies and physico-chemical properties by usingmore » Brunauer-Emmett-Teller method, Field Emission Scanning Electron Microscopy, Energy-dispersive X-ray spectroscopy and Thermogravimetric Analysis. The results suggested that that the catalyst which is prepared by the co-precipitation method exhibits homogeneous morphology, higher surface area, have uniform nickel and palladium dispersion and higher thermal stability as compared to the catalyst which is prepared by wet impregnation method. This characteristics are significant to avoid deactivation of the catalysts due to sintering and carbon deposition during methane cracking process.« less

Worms taste bitter: ASH neurons, QUI-1, GPA-3 and ODR-3 mediate quinine avoidance in Caenorhabditis elegans

PubMed Central

Hilliard, Massimo A; Bergamasco, Carmela; Arbucci, Salvatore; Plasterk, Ronald HA; Bazzicalupo, Paolo

2004-01-01

An animal's ability to detect and avoid toxic compounds in the environment is crucial for survival. We show that the nematode Caenorhabditis elegans avoids many water-soluble substances that are toxic and that taste bitter to humans. We have used laser ablation and a genetic cell rescue strategy to identify sensory neurons involved in the avoidance of the bitter substance quinine, and found that ASH, a polymodal nociceptive neuron that senses many aversive stimuli, is the principal player in this response. Two G protein α subunits GPA-3 and ODR-3, expressed in ASH and in different, nonoverlapping sets of sensory neurons, are necessary for the response to quinine, although the effect of odr-3 can only be appreciated in the absence of gpa-3. We identified and cloned a new gene, qui-1, necessary for quinine and SDS avoidance. qui-1 codes for a novel protein with WD-40 domains and which is expressed in the avoidance sensory neurons ASH and ADL. PMID:14988722

A jellium model of a catalyst particle in carbon nanotube growth

NASA Astrophysics Data System (ADS)

Artyukhov, Vasilii I.; Liu, Mingjie; Penev, Evgeni S.; Yakobson, Boris I.

2017-06-01

We show how a jellium model can represent a catalyst particle within the density-functional theory based approaches to the growth mechanism of carbon nanotubes (CNTs). The advantage of jellium is an abridged, less computationally taxing description of the multi-atom metal particle, while at the same time in avoiding the uncertainty of selecting a particular atomic geometry of either a solid or ever-changing liquid catalyst particle. A careful choice of jellium sphere size and its electron density as a descriptive parameter allows one to calculate the CNT-metal interface energies close to explicit full atomistic models. Further, we show that using jellium permits computing and comparing the formation of topological defects (sole pentagons or heptagons, the culprits of growth termination) as well as pentagon-heptagon pairs 5|7 (known as chirality-switching dislocation).

Considerations for Incorporating Bioavailability in Effect-Directed Analysis and Toxicity Identification Evaluation.

EPA Science Inventory

In order to avoid a bias toward highly toxic but poorly bioavailable compounds in the effect-directed analysis (EDA) of soils and sediments, approaches are discussed to consider bioavailability in EDA procedures. In parallel, complimentary approaches for making toxicity identific...

HYDROCARBON OXIDATION OVER VANADIUM PHOSPHORUS OXIDE CATALYST USING HYDROGEN PEROXIDE

EPA Science Inventory

Selective oxidation of hydrocarbons is one of the very important and challenging areas in industrial chemistry due to the wide ranging utility of the resulting oxygenates in fine chemical synthesis. Most of the existing processes for their oxidations employ toxic and often stoich...

Direct Conversion of Cellulose into Ethyl Lactate in Supercritical Ethanol-Water Solutions.

PubMed

Yang, Lisha; Yang, Xiaokun; Tian, Elli; Lin, Hongfei

2016-01-08

Biomass-derived ethyl lactate is a green solvent with a growing market as the replacement for petroleum-derived toxic organic solvents. Here we report, for the first time, the production of ethyl lactate directly from cellulose with the mesoporous Zr-SBA-15 silicate catalyst in a supercritical mixture of ethanol and water. The relatively strong Lewis and weak Brønsted acid sites on the catalyst, as well as the surface hydrophobicity, were beneficial to the reaction and led to synergy during consecutive reactions, such as depolymerization, retro-aldol condensation, and esterification. Under the optimum reaction conditions, ∼33 % yield of ethyl lactate was produced from cellulose with the Zr-SBA-15 catalyst at 260 °C in supercritical 95:5 (w/w) ethanol/water. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanistic insights into heterogeneous methane activation

DOE PAGES

Latimer, Allegra A.; Aljama, Hassan; Kakekhani, Arvin; ...

2017-01-11

While natural gas is an abundant chemical fuel, its low volumetric energy density has prompted a search for catalysts able to transform methane into more useful chemicals. This search has often been aided through the use of transition state (TS) scaling relationships, which estimate methane activation TS energies as a linear function of a more easily calculated descriptor, such as final state energy, thus avoiding tedious TS energy calculations. It has been shown that methane can be activated via a radical or surface-stabilized pathway, both of which possess a unique TS scaling relationship. Herein, we present a simple model tomore » aid in the prediction of methane activation barriers on heterogeneous catalysts. Analogous to the universal radical TS scaling relationship introduced in a previous publication, we show that a universal TS scaling relationship that transcends catalysts classes also seems to exist for surface-stabilized methane activation if the relevant final state energy is used. We demonstrate that this scaling relationship holds for several reducible and irreducible oxides, promoted metals, and sulfides. By combining the universal scaling relationships for both radical and surface-stabilized methane activation pathways, we show that catalyst reactivity must be considered in addition to catalyst geometry to obtain an accurate estimation for the TS energy. Here, this model can yield fast and accurate predictions of methane activation barriers on a wide range of catalysts, thus accelerating the discovery of more active catalysts for methane conversion.« less

Mechanistic insights into heterogeneous methane activation

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

Latimer, Allegra A.; Aljama, Hassan; Kakekhani, Arvin

While natural gas is an abundant chemical fuel, its low volumetric energy density has prompted a search for catalysts able to transform methane into more useful chemicals. This search has often been aided through the use of transition state (TS) scaling relationships, which estimate methane activation TS energies as a linear function of a more easily calculated descriptor, such as final state energy, thus avoiding tedious TS energy calculations. It has been shown that methane can be activated via a radical or surface-stabilized pathway, both of which possess a unique TS scaling relationship. Herein, we present a simple model tomore » aid in the prediction of methane activation barriers on heterogeneous catalysts. Analogous to the universal radical TS scaling relationship introduced in a previous publication, we show that a universal TS scaling relationship that transcends catalysts classes also seems to exist for surface-stabilized methane activation if the relevant final state energy is used. We demonstrate that this scaling relationship holds for several reducible and irreducible oxides, promoted metals, and sulfides. By combining the universal scaling relationships for both radical and surface-stabilized methane activation pathways, we show that catalyst reactivity must be considered in addition to catalyst geometry to obtain an accurate estimation for the TS energy. Here, this model can yield fast and accurate predictions of methane activation barriers on a wide range of catalysts, thus accelerating the discovery of more active catalysts for methane conversion.« less

Metaloxide--ZrO2 catalysts for the esterification and transesterification of free fatty acids and triglycerides to obtain bio-diesel

DOEpatents

Kim, Manhoe; Salley, Steven O.; Ng, K. Y. Simon

2016-09-06

Mixed metal oxide catalysts (ZnO, CeO, La2O3, NiO, Al203, SiO2, TiO2, Nd2O3, Yb2O3, or any combination of these) supported on zirconia (ZrO2) or hydrous zirconia are provided. These mixed metal oxide catalysts can be prepared via coprecipitation, impregnation, or sol-gel methods from metal salt precursors with/without a Zirconium salt precursor. Metal oxides/ZrO2 catalyzes both esterification and transesterification of oil containing free fatty acids in one batch or in single stage. In particular, these mixed metal oxides supported or added on zirconium oxide exhibit good activity and selectivity for esterification and transesterification. The low acid strength of this catalyst can avoid undesirable side reaction such as alcohol dehydration or cracking of fatty acids. Metal oxides/ZrO2 catalysts are not sensitive to any water generated from esterification. Thus, esterification does not require a water free condition or the presence of excess methanol to occur when using the mixed metal oxide catalyst. The FAME yield obtained with metal oxides/ZrO2 is higher than that obtained with homogeneous sulfuric acid catalyst. Metal oxides/ZrO2 catalasts can be prepared as strong pellets and in various shapes for use directly in a flow reactor. Furthermore, the pellet has a strong resistance toward dissolution to aqueous or oil phases.

Pyrolysis and dehalogenation of plastics from waste electrical and electronic equipment (WEEE): a review.

PubMed

Yang, Xiaoning; Sun, Lushi; Xiang, Jun; Hu, Song; Su, Sheng

2013-02-01

Plastics from waste electrical and electronic equipment (WEEE) have been an important environmental problem because these plastics commonly contain toxic halogenated flame retardants which may cause serious environmental pollution, especially the formation of carcinogenic substances polybrominated dibenzo dioxins/furans (PBDD/Fs), during treat process of these plastics. Pyrolysis has been proposed as a viable processing route for recycling the organic compounds in WEEE plastics into fuels and chemical feedstock. However, dehalogenation procedures are also necessary during treat process, because the oils collected in single pyrolysis process may contain numerous halogenated organic compounds, which would detrimentally impact the reuse of these pyrolysis oils. Currently, dehalogenation has become a significant topic in recycling of WEEE plastics by pyrolysis. In order to fulfill the better resource utilization of the WEEE plastics, the compositions, characteristics and dehalogenation methods during the pyrolysis recycling process of WEEE plastics were reviewed in this paper. Dehalogenation and the decomposition or pyrolysis of WEEE plastics can be carried out simultaneously or successively. It could be 'dehalogenating prior to pyrolysing plastics', 'performing dehalogenation and pyrolysis at the same time' or 'pyrolysing plastics first then upgrading pyrolysis oils'. The first strategy essentially is the two-stage pyrolysis with the release of halogen hydrides at low pyrolysis temperature region which is separate from the decomposition of polymer matrixes, thus obtaining halogenated free oil products. The second strategy is the most common method. Zeolite or other type of catalyst can be used in the pyrolysis process for removing organohalogens. The third strategy separate pyrolysis and dehalogenation of WEEE plastics, which can, to some degree, avoid the problem of oil value decline due to the use of catalyst, but obviously, this strategy may increase the cost of whole recycling process. Copyright © 2012 Elsevier Ltd. All rights reserved.

Toxin constraint explains diet choice, survival and population dynamics in a molluscivore shorebird

PubMed Central

van Gils, Jan A.; van der Geest, Matthijs; Leyrer, Jutta; Oudman, Thomas; Lok, Tamar; Onrust, Jeroen; de Fouw, Jimmy; van der Heide, Tjisse; van den Hout, Piet J.; Spaans, Bernard; Dekinga, Anne; Brugge, Maarten; Piersma, Theunis

2013-01-01

Recent insights suggest that predators should include (mildly) toxic prey when non-toxic food is scarce. However, the assumption that toxic prey is energetically as profitable as non-toxic prey misses the possibility that non-toxic prey have other ways to avoid being eaten, such as the formation of an indigestible armature. In that case, predators face a trade-off between avoiding toxins and minimizing indigestible ballast intake. Here, we report on the trophic interactions between a shorebird (red knot, Calidris canutus canutus) and its two main bivalve prey, one being mildly toxic but easily digestible, and the other being non-toxic but harder to digest. A novel toxin-based optimal diet model is developed and tested against an existing one that ignores toxin constraints on the basis of data on prey abundance, diet choice, local survival and numbers of red knots at Banc d'Arguin (Mauritania) over 8 years. Observed diet and annual survival rates closely fit the predictions of the toxin-based model, with survival and population size being highest in years when the non-toxic prey is abundant. In the 6 of 8 years when the non-toxic prey is not abundant enough to satisfy the energy requirements, red knots must rely on the toxic alternative. PMID:23740782

Toxin constraint explains diet choice, survival and population dynamics in a molluscivore shorebird.

PubMed

van Gils, Jan A; van der Geest, Matthijs; Leyrer, Jutta; Oudman, Thomas; Lok, Tamar; Onrust, Jeroen; de Fouw, Jimmy; van der Heide, Tjisse; van den Hout, Piet J; Spaans, Bernard; Dekinga, Anne; Brugge, Maarten; Piersma, Theunis

2013-07-22

Recent insights suggest that predators should include (mildly) toxic prey when non-toxic food is scarce. However, the assumption that toxic prey is energetically as profitable as non-toxic prey misses the possibility that non-toxic prey have other ways to avoid being eaten, such as the formation of an indigestible armature. In that case, predators face a trade-off between avoiding toxins and minimizing indigestible ballast intake. Here, we report on the trophic interactions between a shorebird (red knot, Calidris canutus canutus) and its two main bivalve prey, one being mildly toxic but easily digestible, and the other being non-toxic but harder to digest. A novel toxin-based optimal diet model is developed and tested against an existing one that ignores toxin constraints on the basis of data on prey abundance, diet choice, local survival and numbers of red knots at Banc d'Arguin (Mauritania) over 8 years. Observed diet and annual survival rates closely fit the predictions of the toxin-based model, with survival and population size being highest in years when the non-toxic prey is abundant. In the 6 of 8 years when the non-toxic prey is not abundant enough to satisfy the energy requirements, red knots must rely on the toxic alternative.

Conditioned flavor aversion and location avoidance in hamsters from toxic extract of tall larkspur (Delphinium barbeyi)

USDA-ARS?s Scientific Manuscript database

Studies were conducted to address conditioned flavour aversion (CFA) and place avoidance learning in hamsters given injections of alkaloid extracts from tall larkspur (Delphinium barbeyi), to determine if larkspur had reinforcing or negative properties sufficient to cause place avoidance or preferen...

EVALUATING THE GREENNESS OF GREEN CHEMISTRY VIA TRADITIONAL AND THERMODYNAMIC LIFE CYCLE ASSESSMENT

EPA Science Inventory

Developments in Green Chemistry are expected to result in novel approaches that are more environmentally benign than traditional methods. Much of the research in green chemistry focuses on replacing toxic and hazardous substances such as solvents, catalysts and reaction media by...

Development of a novel wet oxidation process for hazardous and mixed wastes

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

Dhooge, P.M.

1994-12-31

Many DOE waste streams and remediates contain complex and variable mixtures of organic compounds, toxic metals, and radionuclides. These materials are often dispersed in organic or inorganic matrices, such as personal protective equipment, various sludges, soils, and water. The over all objective of the effort described here is to develop a novel catalytic wet oxidation process for the treatment of these multi-component wastes, with the aim of providing a versatile, non-thermal method which will destroy hazardous organic compounds while simultaneously containing and concentrating toxic and radioactive metals for recovery or disposal in a readily stabilized matrix. The DETOX process usesmore » a unique combination of metal catalysts to increase the rate of oxidation of organic materials. The metal catalysts are in the form of salts dissolved in a dilute acid solution. A typical catalyst composition is 60% ferric chloride, 3--4% hydrochloric acid, 0.13% platinum ions, and 0.13% ruthenium ions in a water solution. The catalyst solution is maintained at 423--473 K. Wastes are introduced into contact with the solution, where their organic portion is oxidized to carbon dioxide and water. If the organic portion is chlorinated, hydrogen chloride will be produced as a product. The process is a viable alternative to incineration for the treatment of organic mixed wastes. Estimated costs for waste treatment using the process are from $2.50/kg to $25.00/kg, depending on the size of the unit and the amount of waste processed. Process units can be mobile for on-site treatment of wastes. Results from phase 1 and 2, design and engineering studies, are described.« less

Attractiveness of food and avoidance from contamination as conflicting stimuli to habitat selection by fish.

PubMed

Araújo, Cristiano V M; Rodríguez, Elizabeth N V; Salvatierra, David; Cedeño-Macias, Luis A; Vera-Vera, Victoria C; Moreira-Santos, Matilde; Ribeiro, Rui

2016-11-01

Habitat selection by fish is the outcome of a choice between different stimuli. Typically, the presence of food tends to attract organisms, while contamination triggers an avoidance response to prevent toxic effects. Given that both food and contaminants are not homogeneously distributed in the environment and that food can be available in contaminated zones, a key question has been put forward in the present study: does a higher availability of food in contaminated areas interfere in the avoidance response to contaminants regardless of the contamination level? Tilapia fry (Oreochromis sp.; 2.5-3.0 cm and 0.5-0.8 g) were exposed to two different effluent samples, diluted along a free-choice, non-forced exposure system simulating a contamination gradient. Initially, avoidance to the effluents was checked during a one hour exposure. Afterwards, food was added to the system so that the availability of food increased with the increase in the level of contamination, and the avoidance response to contamination was checked during another hour. Results clearly showed a concentration-dependent avoidance response for both effluents during the first hour (i.e., with no food). However, in presence of the food, the avoidance pattern was altered: organisms were propelled to intermittently move towards contaminated areas where food availability was higher. The incursions were taken regardless of the potential risk linked to the toxic effects. In conclusion, even when the risk of toxicity was imminent, tilapia fry were more intensively stimulated by the attractiveness of the food than by repulsion to the contamination. Copyright © 2016 Elsevier Ltd. All rights reserved.

Diet composition modifies the toxicity of repeated soman exposure in rats.

PubMed

Langston, Jeffrey L; Myers, Todd M

2011-12-01

It was previously demonstrated that diet potently modulates the toxic effects of an acute lethal dose of the nerve agent soman. The current investigation was undertaken to examine the influence of diet on the cumulative toxicity of repeated soman administration. Rats were fed one of four distinct diets (standard, choline-enriched, glucose-enriched, or ketogenic) for four weeks prior to and throughout a repeated soman dosing and recovery regimen. Each diet group included animals exposed to an equivalent volume of saline that served as negative controls. In exposure Week 1, animals received three consecutive daily doses of 0.4 LD(50) soman. In exposure Week 2, animals received four consecutive daily doses of 0.5 LD(50) soman. In exposure Week 3, animals received five consecutive daily doses of 0.5 LD(50) soman. Week 4 constituted a post-exposure recovery evaluation. Throughout the experiment, behavioral function was assessed by a discriminated avoidance test that required intact sensory and motor function. Survival and body weight changes were recorded daily. Differences in toxicity as a function of diet composition became apparent during the first week. Specifically, rats fed the glucose-enriched diet showed pronounced intoxication during Week 1, resulting in imperfect survival, weight loss, and deteriorated avoidance performance relative to all other groups. All rats fed the glucose-enriched diet died by the end of exposure Week 2. In contrast, only 10% of animals fed the standard diet died by the end of Week 2. Also in Week 2, weight loss and disrupted avoidance performance were apparent for all groups except for those fed the ketogenic diet. This differential effect of diet composition became even more striking in Week 3 when survival in the standard and choline diet groups approximated 50%, whereas survival equaled 90% in the ketogenic diet group. Avoidance performance and weight loss measures corroborated the differential toxicity observed across diet groups. Upon cessation of soman exposure during the final week, recovery of weight and avoidance performance in survivors was comparable across diet groups. These results systematically replicate previous findings demonstrating that diet composition exacerbates or attenuates toxicity in rodents exposed acutely to organophosphorus compounds. Published by Elsevier B.V.

I.C. Engine emission reduction by copper oxide catalytic converter

NASA Astrophysics Data System (ADS)

Venkatesan, S. P.; Shubham Uday, Desai; Karan Hemant, Borana; Rajarshi Kushwanth Goud, Kagita; Lakshmana Kumar, G.; Pavan Kumar, K.

2017-05-01

The toxic gases emitted from diesel engines are more than petrol engines. Predicting the use of diesel engines, even more in future, this system is developed and can be used to minimize the harmful gases. Toxic gases include NOX, CO, HC and Smoke which are harmful to the atmosphere as well as to the human beings. The main aim of this work is to fabricate system, where the level of intensity of toxic gases is controlled through chemical reaction to more agreeable level. This system acts itself as an exhaust system; hence there is no needs to fit separate the silencer. The whole assembly is fitted in the exhaust pipe from engine. In this work, catalytic converter with copper oxide as a catalyst, by replacing noble catalysts such as platinum, palladium and rhodium is fabricated and fitted in the engine exhaust. With and without catalytic converter, the experimentations are carried out at different loads such as 0%, 25%, 50%, 75%, and 100% of maximum rated load. From the experimental results it is found that the maximum reduction is 32%, 61% and 21% for HC, NOx and CO respectively at 100% of maximum rated load when compared to that of without catalytic converter. This catalytic converter system is cash effective and more economical than the existing catalytic converter.

Responsive Management: Practical Strategies for Avoiding Overreaction to Minor Misbehavior

ERIC Educational Resources Information Center

Allday, R. Allan

2011-01-01

Minor misbehavior causes frustration for many teachers and can serve as the catalyst for escalating into a public confrontation between student and teacher. This confrontation can be caused by teacher overreaction to minor misbehavior. When teachers take the initiative and predetermine their response to misbehavior, they reduce and possibly…

Conflict: A Catalyst for Institutional Change

ERIC Educational Resources Information Center

Schaller-Demers, Debra

2008-01-01

This article focuses on perceptions and behaviors surrounding potential conflicts of interest and/or commitment on both personal and institutional levels. It references past cases, public reaction and subsequent policy decisions. Most people believe conflict to be negative, something to be avoided. While conflict might make one feel stressed,…

Catalyst displacement assay: a supramolecular approach for the design of smart latent catalysts for pollutant monitoring and removal† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc05584b Click here for additional data file.

PubMed Central

Ho, Pui-Yu; Lu, Yu-Jing; Tang, Qian

2017-01-01

Latent catalysts can be tuned to function smartly by assigning a sensing threshold using the displacement approach for targeted analytes. Three cyano-bridged bimetallic complexes were synthesized as “smart” latent catalysts through the supramolecular assembly of different metallic donors [FeII(CN)6]4–, [FeII(tBubpy)(CN)4]2–, and FeII(tBubpy)2(CN)2 with a metallic acceptor [CuII(dien)]2+. The investigation of both their thermodynamic and kinetic properties on binding with toxic pollutants provided insight into their smart off–on catalytic capabilities, enabling us to establish a threshold-controlled catalytic system for the degradation of pollutants such as cyanide and oxalate. With these smart latent catalysts, a new catalyst displacement assay (CDA) was demonstrated and applied in a real wastewater treatment process to degrade cyanide pollutants in both domestic (level I, untreated) and industrial wastewater samples collected in Hong Kong, China. The smart system was adjusted to be able to initiate the catalytic oxidation of cyanide at a threshold concentration of 20 μM (the World Health Organization’s suggested maximum allowable level for cyanide in wastewater) to the less harmful cyanate under ambient conditions. PMID:28580114

Methanation process utilizing split cold gas recycle

DOEpatents

Tajbl, Daniel G.; Lee, Bernard S.; Schora, Jr., Frank C.; Lam, Henry W.

1976-07-06

In the methanation of feed gas comprising carbon monoxide and hydrogen in multiple stages, the feed gas, cold recycle gas and hot product gas is mixed in such proportions that the mixture is at a temperature sufficiently high to avoid carbonyl formation and to initiate the reaction and, so that upon complete reaction of the carbon monoxide and hydrogen, an excessive adiabatic temperature will not be reached. Catalyst damage by high or low temperatures is thereby avoided with a process that utilizes extraordinarily low recycle ratios and a minimum of investment in operating costs.

Effect of qualitative and quantitative variation in allelochemicals on a generalist insect: Iridoid glycosides and the southern armyworm.

PubMed

Puttick, G M; Bowers, M D

1988-01-01

The behavioral and physiological effects of plant allelochemicals have been difficult to demonstrate; it is not often clear whether the compounds are deterrent, toxic, or both. In this study, we compared the qualitative and quantitative effects of several iridoid glycosides on a generalist lepidopteran herbivore,Spodoptera eridania (Noctuidae). Larval growth and survivorship and larval preference or avoidance were measured on artificial diets containing different iridoid glycosides at different concentrations. We also tested the toxicity/deterrence of these compounds. We found that iridoid glycosides retarded larval growth significantly at relatively low concentrations and that they were usually avoided in preference tests. The toxicity/ deterrence test did not always reflect the results of these other tests. The merits of using a variety of methods for determining deterrence and/or toxicity of plant allelochemicals are discussed.

Bulk scale production of carbon nanofibers in an economical way

NASA Astrophysics Data System (ADS)

Rajarao, Ravindra; Bhat, Badekai Ramachandra

2012-12-01

An economical route for the scalable production of carbon nanofibers (CNFs) on a sodium chloride support has been developed. CNFs have been synthesized by chemical vapor deposition (CVD) method by using metal formate as catalyst precursors at 680°C. Products were characterized by SEM, TEM, Raman spectroscopy and XRD method. By thermal analysis, the purity of the as grown products and purified products were determined. This method avoids calcination and reduction process which was employed in commercial catalysts such as metal oxide or nitrate. The problems such as detrimental effect, environmental and even cost have been overcome by using sodium chloride as support. The yield of CNFs up to 7800 wt.% relative to the nickel catalyst has been achieved in the growth time of 15 min. The advantage of this synthesis technique is the simplicity and use of easily available low cost precursors.

Uniform, dense arrays of vertically aligned, large-diameter single-walled carbon nanotubes.

PubMed

Han, Zhao Jun; Ostrikov, Kostya

2012-04-04

Precisely controlled reactive chemical vapor synthesis of highly uniform, dense arrays of vertically aligned single-walled carbon nanotubes (SWCNTs) using tailored trilayered Fe/Al(2)O(3)/SiO(2) catalyst is demonstrated. More than 90% population of thick nanotubes (>3 nm in diameter) can be produced by tailoring the thickness and microstructure of the secondary catalyst supporting SiO(2) layer, which is commonly overlooked. The proposed model based on the atomic force microanalysis suggests that this tailoring leads to uniform and dense arrays of relatively large Fe catalyst nanoparticles on which the thick SWCNTs nucleate, while small nanotubes and amorphous carbon are effectively etched away. Our results resolve a persistent issue of selective (while avoiding multiwalled nanotubes and other carbon nanostructures) synthesis of thick vertically aligned SWCNTs whose easily switchable thickness-dependent electronic properties enable advanced applications in nanoelectronic, energy, drug delivery, and membrane technologies.

Moon Express Media Event

NASA Image and Video Library

2014-11-03

Bob Richards, co-founder and chief executive officer of Moon Express Inc., of Moffett Field, California, speaks to the media during an event to announce the company's selection to use Kennedy Space Center's facilities as part of NASA's Lunar Cargo Transportation and Landing by Soft Touchdown, or Lunar CATALYST, initiative. The event took place at Kennedy's automated landing and hazard avoidance technology, or ALHAT, hazard field at the north end of the Shuttle Landing Facility. Moon Express is developing a lander with capabilities that will enable delivery of payloads to the surface of the moon, as well as new science and exploration missions of interest to NASA and scientific and academic communities. Moon Express will base its activities at Kennedy and utilize the Morpheus ALHAT field and a hangar nearby for CATALYST testing. The Advanced Exploration Systems Division of NASA's Human Exploration and Operations Mission Directorate manages Lunar CATALYST.

KSC-2014-4371

NASA Image and Video Library

2014-11-03

CAPE CANAVERAL, Fla. - Tom Engler, deputy director of Center Planning and Development at NASA's Kennedy Space Center in Florida, speaks to members of the media during an event to announce the agency's Lunar Cargo Transportation and Landing by Soft Touchdown, or Lunar CATALYST, initiative and introduced one of the partners, Moon Express Inc. of Moffett Field, California. The event took place at Kennedy's automated landing and hazard avoidance technology, or ALHAT, hazard field at the north end of the Shuttle Landing Facility. Moon Express is developing a lander with capabilities that will enable delivery of payloads to the surface of the moon, as well as new science and exploration missions of interest to NASA and scientific and academic communities. Moon Express will base its activities at Kennedy and utilize the Morpheus ALHAT field and a hangar nearby for CATALYST testing. The Advanced Exploration Systems Division of NASA's Human Exploration and Operations Mission Directorate manages Lunar CATALYST. Photo credit: NASA/Ben Smegelsky

KSC-2014-4372

NASA Image and Video Library

2014-11-03

CAPE CANAVERAL, Fla. - Greg C. Shavers, Lander Technology director at Marshall Space Flight Center in Alabama, speaks to members of the media during an event to announce the agency's Lunar Cargo Transportation and Landing by Soft Touchdown, or Lunar CATALYST, initiative and introduced one of the partners, Moon Express Inc. of Moffett Field, California. The event took place at Kennedy's automated landing and hazard avoidance technology, or ALHAT, hazard field at the north end of the Shuttle Landing Facility. Moon Express is developing a lander with capabilities that will enable delivery of payloads to the surface of the moon, as well as new science and exploration missions of interest to NASA and scientific and academic communities. Moon Express will base its activities at Kennedy and utilize the Morpheus ALHAT field and a hangar nearby for CATALYST testing. The Advanced Exploration Systems Division of NASA's Human Exploration and Operations Mission Directorate manages Lunar CATALYST. Photo credit: NASA/Ben Smegelsky

KSC-2014-4373

NASA Image and Video Library

2014-11-03

CAPE CANAVERAL, Fla. - Bob Richards, co-founder and chief executive officer of Moon Express Inc., of Moffett Field, California, speaks to the media during an event to announce the company's selection to use Kennedy Space Center's facilities as part of NASA's Lunar Cargo Transportation and Landing by Soft Touchdown, or Lunar CATALYST, initiative. The event took place at Kennedy's automated landing and hazard avoidance technology, or ALHAT, hazard field at the north end of the Shuttle Landing Facility. Moon Express is developing a lander with capabilities that will enable delivery of payloads to the surface of the moon, as well as new science and exploration missions of interest to NASA and scientific and academic communities. Moon Express will base its activities at Kennedy and utilize the Morpheus ALHAT field and a hangar nearby for CATALYST testing. The Advanced Exploration Systems Division of NASA's Human Exploration and Operations Mission Directorate manages Lunar CATALYST. Photo credit: NASA/Ben Smegelsky

Moon Express Media Event

NASA Image and Video Library

2014-11-03

Greg C. Shavers, Lander Technology director at Marshall Space Flight Center in Alabama, speaks to members of the media during an event to announce the agency's Lunar Cargo Transportation and Landing by Soft Touchdown, or Lunar CATALYST, initiative and introduced one of the partners, Moon Express Inc. of Moffett Field, California. The event took place at Kennedy's automated landing and hazard avoidance technology, or ALHAT, hazard field at the north end of the Shuttle Landing Facility. Moon Express is developing a lander with capabilities that will enable delivery of payloads to the surface of the moon, as well as new science and exploration missions of interest to NASA and scientific and academic communities. Moon Express will base its activities at Kennedy and utilize the Morpheus ALHAT field and a hangar nearby for CATALYST testing. The Advanced Exploration Systems Division of NASA's Human Exploration and Operations Mission Directorate manages Lunar CATALYST.

Moon Express Media Event

NASA Image and Video Library

2014-11-03

Rob Mueller, NASA senior technologist in the Surface Systems Office in Kennedy Space Center's Engineering and Technology Directorate, demonstrates the Regolith Advanced Surface System Operations Robot, or RASSOR, during a media event at Kennedy's automated landing and hazard avoidance technology, or ALHAT, hazard field at the north end of the Shuttle Landing Facility. The event was held to announce Moon Express Inc., of Moffett Field, California is selected to utilize Kennedy facilities for NASA's Lunar Cargo Transportation and Landing by Soft Touchdown, or Lunar CATALYST, initiative. Moon Express is developing a lander with capabilities that will enable delivery of payloads to the surface of the moon, as well as new science and exploration missions of interest to NASA and scientific and academic communities. Moon Express will base its activities at Kennedy and utilize the Morpheus ALHAT field and a hangar nearby for CATALYST testing. The Advanced Exploration Systems Division of NASA's Human Exploration and Operations Mission Directorate manages Lunar CATALYST.

Moon Express Media Event

NASA Image and Video Library

2014-11-03

Tom Engler, deputy director of Center Planning and Development at NASA's Kennedy Space Center in Florida, speaks to members of the media during an event to announce the agency's Lunar Cargo Transportation and Landing by Soft Touchdown, or Lunar CATALYST, initiative and introduced one of the partners, Moon Express Inc. of Moffett Field, California. The event took place at Kennedy's automated landing and hazard avoidance technology, or ALHAT, hazard field at the north end of the Shuttle Landing Facility. Moon Express is developing a lander with capabilities that will enable delivery of payloads to the surface of the moon, as well as new science and exploration missions of interest to NASA and scientific and academic communities. Moon Express will base its activities at Kennedy and utilize the Morpheus ALHAT field and a hangar nearby for CATALYST testing. The Advanced Exploration Systems Division of NASA's Human Exploration and Operations Mission Directorate manages Lunar CATALYST.

Molecular Monolayers for Electrical Passivation and Functionalization of Silicon-Based Solar Energy Devices.

PubMed

Veerbeek, Janneke; Firet, Nienke J; Vijselaar, Wouter; Elbersen, Rick; Gardeniers, Han; Huskens, Jurriaan

2017-01-11

Silicon-based solar fuel devices require passivation for optimal performance yet at the same time need functionalization with (photo)catalysts for efficient solar fuel production. Here, we use molecular monolayers to enable electrical passivation and simultaneous functionalization of silicon-based solar cells. Organic monolayers were coupled to silicon surfaces by hydrosilylation in order to avoid an insulating silicon oxide layer at the surface. Monolayers of 1-tetradecyne were shown to passivate silicon micropillar-based solar cells with radial junctions, by which the efficiency increased from 8.7% to 9.9% for n + /p junctions and from 7.8% to 8.8% for p + /n junctions. This electrical passivation of the surface, most likely by removal of dangling bonds, is reflected in a higher shunt resistance in the J-V measurements. Monolayers of 1,8-nonadiyne were still reactive for click chemistry with a model catalyst, thus enabling simultaneous passivation and future catalyst coupling.

Insights into semiconductor nanowire conductivity using electrodeposition

NASA Astrophysics Data System (ADS)

Liu, C.; Salehzadeh, O.; Poole, P. J.; Watkins, S. P.; Kavanagh, K. L.

2012-10-01

Copper (Cu) and iron (Fe) electrical contacts to gallium arsenide (GaAs) and indium arsenide (InAs) nanowires (NWs) have been fabricated via electrodeposition. For undoped or low carbon-doped (1017/cm-3), p-type GaAs NWs, Cu or Fe nucleate and grow only on the gold catalyst at the NW tip, avoiding the sidewalls. Metal growth is limited by the Au contact resistance due to thick sidewall depletion layers. For InAs NWs and heavier-doped, core-shell (undoped core-C-doped shell) GaAs NWs, metal nucleation and growth occurs on the sidewalls as well as on the gold catalyst limited now by the ion electrolyte diffusivity.

Novel low-cost Fenton-like layered Fe-titanate catalyst: preparation, characterization and application for degradation of organic colorants.

PubMed

Chen, Yongzhou; Li, Nian; Zhang, Ye; Zhang, Lide

2014-05-15

Novel low-cost layered Fe-titanate catalyst for photo-Fenton degradation of organic contaminants was successfully developed by ion exchange of Fe(3+) with Na(+) layered nano Na-titanates which was prepared by alkali hydrothermal method. The as prepared materials were characterized by powder X-ray diffraction analysis (XRD), field emission scanning electron microscopy (FESEM) and energy-dispersive X-ray spectrometer (EDX). The catalytic activity of the Fe-titanate catalyst was evaluated by the decolorization of three different dyes (rhodamine 6G (R6G), methyl blue (MB), and methyl orange (MO)) under UV irradiation at room temperature. Effect of several important factors such as Fe loading in the catalyst, initial solution pH, catalyst dosage, H2O2 amount, and reaction time was systematically studied. It was found that the decolorization was very efficient for all three dyes. The efficiency reached 98% for R6G, 98.5% for MB, and 97% for MO, respectively, under optimal conditions. The oxidation process was quick, and only 15 min is needed for all three dyes. Moreover, the Fe-titanate catalyst could be used in a wider and near neutral pH range compared with classic Fenton systems which need to be operated at around pH 3.0. Kinetic analysis results showed that the oxidation kinetics was accurately represented by pseudo-first-order model. More importantly, the catalyst was very stable and could be reused for at least four cycles when operated under near neutral pH. The Fe leaching from the catalyst measured was almost negligible, which not only demonstrated the stability of the catalyst, but also avoided the formation of secondary Fe pollution. Therefore, the reported Fe-titanates are promising nanomaterials which can be used as Fenton like catalyst for the degradation of organic contaminant in wastewater. Crown Copyright © 2014. Published by Elsevier Inc. All rights reserved.

Partial oxidation (“aging”) and surface modification decrease the toxicity of nano-sized zero valent iron.

EPA Science Inventory

Nanosize zero-valent iron (nZVI) is used as a redox-active catalyst for in situ remediation of contaminated ground waters. In aqueous environments, nZVI oxidizes over time (i.e., “ages”) to magnetite and other oxides. For remediation, hi...

Coupled Metal/Oxide Catalysts with Tunable Product Selectivity for Electrocatalytic CO2 Reduction.

PubMed

Huo, Shengjuan; Weng, Zhe; Wu, Zishan; Zhong, Yiren; Wu, Yueshen; Fang, Jianhui; Wang, Hailiang

2017-08-30

One major challenge to the electrochemical conversion of CO 2 to useful fuels and chemical products is the lack of efficient catalysts that can selectively direct the reaction to one desirable product and avoid the other possible side products. Making use of strong metal/oxide interactions has recently been demonstrated to be effective in enhancing electrocatalysis in the liquid phase. Here, we report one of the first systematic studies on composition-dependent influences of metal/oxide interactions on electrocatalytic CO 2 reduction, utilizing Cu/SnO x heterostructured nanoparticles supported on carbon nanotubes (CNTs) as a model catalyst system. By adjusting the Cu/Sn ratio in the catalyst material structure, we can tune the products of the CO 2 electrocatalytic reduction reaction from hydrocarbon-favorable to CO-selective to formic acid-dominant. In the Cu-rich regime, SnO x dramatically alters the catalytic behavior of Cu. The Cu/SnO x -CNT catalyst containing 6.2% of SnO x converts CO 2 to CO with a high faradaic efficiency (FE) of 89% and a j CO of 11.3 mA·cm -2 at -0.99 V versus reversible hydrogen electrode, in stark contrast to the Cu-CNT catalyst on which ethylene and methane are the main products for CO 2 reduction. In the Sn-rich regime, Cu modifies the catalytic properties of SnO x . The Cu/SnO x -CNT catalyst containing 30.2% of SnO x reduces CO 2 to formic acid with an FE of 77% and a j HCOOH of 4.0 mA·cm -2 at -0.99 V, outperforming the SnO x -CNT catalyst which only converts CO 2 to formic acid in an FE of 48%.

Achieving Biocompatible SABRE: An in vitro Cytotoxicity Study

PubMed Central

Manoharan, Anand; Rayner, Peter J.; Iali, Wissam; Burns, Michael J.; Perry, V. Hugh

2018-01-01

Abstract Production of a biocompatible hyperpolarized bolus for signal amplification by reversible exchange (SABRE) could open the door to simple clinical diagnosis via magnetic resonance imaging. Essential to successful progression to preclinical/clinical applications is the determination of the toxicology profile of the SABRE reaction mixture. Herein, we exemplify the cytotoxicity of the SABRE approach using in vitro cell assays. We conclude that the main cause of the observed toxicity is due to the SABRE catalyst. We therefore illustrate two catalyst removal methods: one involving deactivation and ion‐exchange chromatography, and the second using biphasic catalysis. These routes produce a bolus suitable for future in vivo study. PMID:29232489

New Element Organic Frameworks Based on Sn, Sb, and Bi, with Permanent Porosity and High Catalytic Activity

PubMed Central

Fritsch, Julia; Rose, Marcus; Wollmann, Philipp; Böhlmann, Winfried; Kaskel, Stefan

2010-01-01

We present new element organic frameworks based on Sn, Sb and Bi atoms connected via organic linkers by element-carbon bonds. The open frameworks are characterized by specific surface areas (BET) of up to 445 m2 g-1 and a good stability under ambient conditions resulting from a highly hydrophobic inner surface. They show good performance as heterogeneous catalysts in the cyanosylilation of benzaldehyde as a test reaction. Due to their catalytic activity, this class of materials might be able to replace common homogeneous element-organic and often highly toxic catalysts especially in the food industry.

Environmental Determinants of Chronic Disease and Medical Approaches: Recognition, Avoidance, Supportive Therapy, and Detoxification

PubMed Central

Sears, Margaret E.; Genuis, Stephen J.

2012-01-01

The World Health Organization warns that chronic, noncommunicable diseases are rapidly becoming epidemic worldwide. Escalating rates of neurocognitive, metabolic, autoimmune and cardiovascular diseases cannot be ascribed only to genetics, lifestyle, and nutrition; early life and ongoing exposures, and bioaccumulated toxicants may also cause chronic disease. Contributors to ill health are summarized from multiple perspectives—biological effects of classes of toxicants, mechanisms of toxicity, and a synthesis of toxic contributors to major diseases. Healthcare practitioners have wide-ranging roles in addressing environmental factors in policy and public health and clinical practice. Public health initiatives include risk recognition and chemical assessment then exposure reduction, remediation, monitoring, and avoidance. The complex web of disease and environmental contributors is amenable to some straightforward clinical approaches addressing multiple toxicants. Widely applicable strategies include nutrition and supplements to counter toxic effects and to support metabolism; as well as exercise and sweating, and possibly medication to enhance excretion. Addressing environmental health and contributors to chronic disease has broad implications for society, with large potential benefits from improved health and productivity. PMID:22315626

Advanced oxidation treatment of pulp mill effluent for TOC and toxicity removals.

PubMed

Catalkaya, Ebru Cokay; Kargi, Fikret

2008-05-01

Pulp mill effluent was treated by different advanced oxidation processes (AOPs) consisting of UV, UV/H2O2, TiO2-assisted photo-catalysis (UV/TiO2) and UV/H2O2/TiO2 in lab-scale reactors for total organic carbon (TOC) and toxicity removals. Effects of some operating parameters such as the initial pH, oxidant and catalyst concentrations on TOC and toxicity removals were investigated. Almost every method resulted in some degree of TOC and toxicity removal from the pulp mill effluent. However, the TiO2-assisted photo-catalysis (UV/TiO2) resulted in the highest TOC and toxicity removals under alkaline conditions when compared with the other AOPs tested. Approximately, 79.6% TOC and 94% toxicity removals were obtained by the TiO2-assisted photo-catalysis (UV/TiO2) with a titanium dioxide concentration of 0.75gl(-1) at pH 11 within 60min.

Catalytic Oxidation of Chlorobenzene over MnxCe1-xO2/HZSM-5 Catalysts: A Study with Practical Implications.

PubMed

Weng, Xiaole; Sun, Pengfei; Long, Yu; Meng, Qingjie; Wu, Zhongbiao

2017-07-18

Industrial-use catalysts usually encounter severe deactivation after long-term operation for catalytic oxidation of chlorinate volatile organic compounds (CVOCs), which becomes a "bottleneck" for large-scale application of catalytic combustion technology. In this work, typical acidic solid-supported catalysts of Mn x Ce 1-x O 2 /HZSM-5 were investigated for the catalytic oxidation of chlorobenzene (CB). The activation energy (E a ), Brønsted and Lewis acidities, CB adsorption and activation behaviors, long-term stabilities, and surficial accumulation compounds (after aging) were studied using a range of analytical techniques, including XPS, H 2 -TPR, pyridine-IR, DRIFT, and O 2 -TP-Ms. Experimental results revealed that the Brønsted/Lewis (B/L) ratio of Mn x Ce 1-x O 2 /HZSM-5 catalysts could be adjusted by ion exchange of H• (in HZSM-5) with Mn n+ (where the exchange with Ce 4+ did not distinctly affect the acidity); the long-term aged catalysts could accumulate ca. 14 organic compounds at surface, including highly toxic tetrachloromethane, trichloroethylene, tetrachloroethylene, o-dichlorobenzene, etc.; high humid operational environment could ensure a stable performance for Mn x Ce 1-x O 2 /HZSM-5 catalysts; this was due to the effective removal of Cl• and coke accumulations by H 2 O washing, and the distinct increase of Lewis acidity by the interaction of H 2 O with HZSM-5. This work gives an in-depth view into the CB oxidation over acidic solid-supported catalysts and could provide practical guidelines for the rational design of reliable catalysts for industrial applications.

Silica nanosphere-supported palladium(II) furfural complex as a highly efficient and recyclable catalyst for oxidative amination of aldehydes.

PubMed

Sharma, R K; Sharma, Shivani

2014-01-21

The present work reports the fabrication of a novel and highly efficient silica nanospheres-based palladium catalyst (SiO2@APTES@Pd-FFR) via immobilization of a palladium complex onto silica nanospheres functionalized with 3-aminopropyltriethoxysilane (APTES), and its catalytic application for the oxidative amination of aldehydes to yield commercially important amides. The structure of the nano-catalyst was confirmed by Solid-state (13)C CPMAS and (29)Si CPMAS NMR spectroscopy, Brunauer-Emmett-Teller (BET) surface area analysis, Fourier transform infrared spectroscopy (FT-IR), Energy dispersive X-ray fluorescence spectroscopy (ED-XRF), Atomic absorption spectroscopy (AAS), Transmission electron microscopy (TEM) and elemental analysis. The nano-catalyst was found to be highly effective for the oxidative amination of aldehydes using hydrogen peroxide as an environmentally benign oxidant to give amides. The effect of various reaction parameters such as temperature, amount of catalyst, reaction time, type of solvent, oxidant used, substrate to oxidant ratio etc. have been demonstrated to achieve high catalytic efficacy. Moreover, this nanostructured catalyst could be recovered with simplicity and reused for several cycles without any significant loss in its catalytic activity. In addition, the stability of the reused nano-catalyst was proved by FT-IR and HRTEM techniques. It is worth noting that the features of mild reaction conditions, simple work-up procedure, high product yield, no use of toxic organic solvents, high turn-over frequency (TOF), and easy recovery and reusability of the present quasi-homogeneous nano-catalyst make this protocol an attractive alternative to the existing catalytic methods for the oxidative amination of aldehydes to furnish industrially important amides.

2D-COS of in situ μ-Raman and in situ IR spectra for structure evolution characterisation of NEP-deposited cobalt oxide catalyst during n-nonane combustion

NASA Astrophysics Data System (ADS)

Chlebda, Damian K.; Jodłowski, Przemysław J.; Jędrzejczyk, Roman J.; Łojewska, Joanna

2017-11-01

New catalytic systems are still in development to meet the challenge of regulations concerning the emission of volatile organic compounds (VOCs). This is because such compounds have a significant impact on air quality and some of them are toxic to the environment and human beings. The catalytic combustion process of VOCs over non-noble metal catalysts is of great interest to researchers. The high conversion parameters and cost effective preparation makes them a valuable alternative to monoliths and noble metal catalysts. In this study, the cobalt catalyst was prepared by non-equilibrium plasma deposition of organic precursor on calcined kanthal steel. Thus prepared, cobalt oxide based microstructural short-channel reactors were tested for n-nonane combustion and the catalyst surfaces were examined by in situ μ-Raman spectroscopy and in situ infrared spectroscopy. The spectra collected at various temperatures were used in generalised two-dimensional correlation analysis to establish the sequential order of spectral intensity changes and correlate the simultaneous changes in bands selectively coupled by different interaction mechanisms. The 2D synchronous and asynchronous contour maps were proved to be a valuable extension to the standard analysis of the temperature dependent 1D spectra.

Bimetallic Nanoparticles as Efficient Catalysts: Facile and Green Microwave Synthesis

PubMed Central

Blosi, Magda; Ortelli, Simona; Costa, Anna Luisa; Dondi, Michele; Lolli, Alice; Andreoli, Sara; Benito, Patricia; Albonetti, Stefania

2016-01-01

This work deals with the development of a green and versatile synthesis of stable mono- and bi-metallic colloids by means of microwave heating and exploiting ecofriendly reagents: water as the solvent, glucose as a mild and non-toxic reducer and polyvinylpirrolidone (PVP) as the chelating agent. Particle size-control, total reaction yield and long-term stability of colloids were achieved with this method of preparation. All of the materials were tested as effective catalysts in the reduction of p-nitrophenol in the presence of NaBH4 as the probe reaction. A synergistic positive effect of the bimetallic phase was assessed for Au/Cu and Pd/Au alloy nanoparticles, the latter showing the highest catalytic performance. Moreover, monoand bi-metallic colloids were used to prepare TiO2- and CeO2-supported catalysts for the liquid phase oxidation of 5-hydroxymethylfufural (HMF) to 2,5-furandicarboxylic acid (FDCA). The use of Au/Cu and Au/Pd bimetallic catalysts led to an increase in FDCA selectivity. Finally, preformed Pd/Cu nanoparticles were incorporated into the structure of MCM-41-silica. The resulting Pd/Cu MCM-41 catalysts were tested in the hydrodechlorination of CF3OCFClCF2Cl to CF3OCF=CF2. The effect of Cu on the hydrogenating properties of Pd was demonstrated. PMID:28773672

Denitration of 2,4,6-trinitrotoluene in aqueous solutions using small-molecular-weight catalyst(s) secreted by Pseudomonas aeruginosa ESA-5.

PubMed

Stenuit, Ben; Eyers, Laurent; Rozenberg, Raoul; Habib-Jiwan, Jean-Louis; Matthijs, Sandra; Cornelis, Pierre; Agathos, Spiros N

2009-03-15

The denitration of 2,4,6-trinitrotoluene (TNT) can produce mono- or dinitro aromatic compounds susceptible to microbial mineralization. In the present study, denitration of TNT and other nitro aromatic compounds was investigated with a solid-phase extract obtained from the culture supernatant of Pseudomonas aeruginosa ESA-5 grown on a chemically defined aerobic medium. When the C18 solid-phase extract containing extracellular catalysts (EC) was incubated with TNT and NAD(P)H, we observed a significant release of nitrite. The concentration of nitrite released in the reaction medium was strongly dependent on the concentration of NAD(P)H and EC. Denitration also occurred with two TNT-related molecules, 2,4,6-trinitrobenzaldehyde, and 2,4,6-trinitrobenzyl alcohol. The release of nitrite was coupled with the formation of two polar metabolites, and mass spectrometry analyses indicated that each of these compounds had lost two nitro groups from the trinitro aromatic parent molecule. During this process, the production of toxic reduced TNT metabolites was minimal. The incubation of EC with TNT, NAD(P)H, and specific scavengers of reactive oxygen species suggested the involvement of superoxide radicals (O2*-) and hydrogen peroxide in the denitration process. Results obtained in this study reveal for the first time that extracellular small-molecular-weight substance(s) of bacterial origin can serve as green catalyst(s) to initiate TNT denitration. In addition, this study gives clear evidence for the production of a TNT metabolite bearing a single nitro groupfollowing a denitration reaction with catalyst(s) of biotic origin.

Flexible nitrogen-doped graphene/carbon nanotube/Co3O4 paper and its oxygen reduction activity

NASA Astrophysics Data System (ADS)

Li, Shan-Shan; Cong, Huai-Ping; Wang, Ping; Yu, Shu-Hong

2014-06-01

Due to the demand of an efficient, inexpensive and scalable synthesis of oxygen reduction reaction (ORR) catalyst for practical application in fuel cell, we demonstrate a facile strategy to fabricate the flexible nitrogen-doped graphene/carbon nanotube/Co3O4 (NG/CNT/Co3O4) paper catalyst. In the hydrothermal process, the in situ formation of Co3O4 nanoparticles, reduction of GO and doping of nitrogen species occur simultaneously in the assembled paper in ammonia solution. Because of the synergistic effects of three active components and the spacing effect of CNTs and Co3O4 nanoparticles on avoiding the re-aggregation of assembled graphene nanosheets, the free-standing NG/CNT/Co3O4 paper exhibits an enhanced ORR catalytic performance with stable durability and strong methanol-tolerant capability, indicating promising potential as ORR electrocatalyst in practical applications.Due to the demand of an efficient, inexpensive and scalable synthesis of oxygen reduction reaction (ORR) catalyst for practical application in fuel cell, we demonstrate a facile strategy to fabricate the flexible nitrogen-doped graphene/carbon nanotube/Co3O4 (NG/CNT/Co3O4) paper catalyst. In the hydrothermal process, the in situ formation of Co3O4 nanoparticles, reduction of GO and doping of nitrogen species occur simultaneously in the assembled paper in ammonia solution. Because of the synergistic effects of three active components and the spacing effect of CNTs and Co3O4 nanoparticles on avoiding the re-aggregation of assembled graphene nanosheets, the free-standing NG/CNT/Co3O4 paper exhibits an enhanced ORR catalytic performance with stable durability and strong methanol-tolerant capability, indicating promising potential as ORR electrocatalyst in practical applications. Electronic supplementary information (ESI) available: XRD patterns, elemental mapping images, DSC-TGA curves and XPS spectrum of NG/CNT/Co3O4 paper; SEM images and XPS spectra of NG/Co3O4 paper; RDE curves and corresponding K-L plots of different catalysts. See DOI: 10.1039/c4nr02101k

A Green Alternative to Aluminum Chloride Alkylation of Xylene

ERIC Educational Resources Information Center

Sereda, Grigoriy A.; Rajpara, Vikul B.

2007-01-01

An acutely less toxic 2-bromobutane is used to develop a simple graphite-promoted procedure of alkylation of p-xylene. It is further demonstrated that aluminum chloride is not required, the need for aqueous workup is eliminated, waste solutions are not produced and the multiple use of the catalyst is allowed.

Wet air oxidation and catalytic wet air oxidation for dyes degradation.

PubMed

Ovejero, Gabriel; Sotelo, José Luis; Rodríguez, Araceli; Vallet, Ana; García, Juan

2011-11-01

Textile industry produces wastewater which contributes to water pollution since it utilizes a lot of chemicals. Preliminary studies show that the wastewater from textile industries contains grease, wax, surfactant, and dyes. The objective of this study was to determine the treatment efficiency of the nickel catalysts supported on hydrotalcites in three-dye model compounds and two types of wastewater. Hydrotalcites were employed to prepare supported nickel catalysts by wetness impregnation technique. Metal loadings from 1 to 10 wt% were tested. Catalysts were characterized by several techniques. They were tested in a catalytic wet air oxidation of three dyes and two wastewaters with different origins. It could be observed that the higher the metal content, the lower the BET area, possibly due to sintering of Ni and the consequent blocking of the pores by the metal. In addition, metallic dispersion was also higher when the metal content was lower. Dye conversion was more than 95% for every catalyst showing no differences with the nickel content. A high degree of dye conversion was achieved. Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) processes have been proved to be extremely efficient in TOC removal for wastewaters. The CWAO process can be used to remove dyes from wastewater. Three different dyes were tested showing satisfactory results in all of them. TOC degradation and dye removal in the presence of the catalyst were effective. Also, the HTNi catalyst is very active for organic matter and toxicity removal in wastewaters.

Pesticide poisoning.

PubMed

Goel, Ashish; Aggarwal, Praveen

2007-01-01

Acute poisoning with pesticides is a global public health problem and accounts for as many as 300,000 deaths worldwide every year. The majority of deaths occur due to exposure to organophosphates, organochlorines and aluminium phosphide. Organophosphate compounds inhibit acetylcholinesterase resulting in acute toxicity. Intermediate syndrome can develop in a number of patients and may lead to respiratory paralysis and death. Management consists of proper oxygenation, atropine in escalating doses and pralidoxime in high doses. It is Important to decontaminate the skin while taking precautions to avoid secondary contamination of health personnel. Organochlorine pesticides are toxic to the central nervous system and sensitize the myocardium to catecholamines. Treatment involves supportive care and avoiding exogenous sympathomimetic agents. Ingestion of paraquat causes severe inflammation of the throat, corrosive injury to the gastrointestinal tract, renal tubular necrosis, hepatic necrosis and pulmonary fibrosis. Administration of oxygen should be avoided as it produces more fibrosis. Use of immunosuppressive agents have improved outcome in patients with paraquat poisoning. Rodenticides include thallium, superwarfarins, barium carbonate and phosphides (aluminium and zinc phosphide). Alopecia is an atypical feature of thallium toxicity. Most exposures to superwarfarins are harmless but prolonged bleeding may occur. Barium carbonate Ingestion can cause severe hypokalaemia and respiratory muscle paralysis. Aluminium phosphide is a highly toxic agent with mortality ranging from 37% to 100%. It inhibits mitochondrial cytochrome c oxidase and leads to pulmonary and cardiac toxicity. Treatment is supportive with some studies suggesting a beneficial effect of magnesium sulphate. Pyrethroids and insect repellants (e.g. diethyltoluamide) are relatively harmless but can cause toxic effects to pulmonary and central nervous systems. Ethylene dibromide-a highly toxic, fumigant pesticide-produces oral ulcerations, followed by liver and renal toxicity, and is almost uniformly fatal. Physicians working in remote and rural areas need to be educated about early diagnosis and proper management using supportive care and antidotes, wherever available.

Ultrafine cobalt nanoparticles supported on reduced graphene oxide: Efficient catalyst for fast reduction of hexavalent chromium at room temperature

NASA Astrophysics Data System (ADS)

Xu, Tingting; Xue, Jinjuan; Zhang, Xiaolei; He, Guangyu; Chen, Haiqun

2017-04-01

A novel composite ultrafine cobalt nanoparticles-reduced graphene oxide (Co-RGO) was firstly synthesized through a modified one-step solvothermal method with Co(OH)2 as the precursor. The prepared low-cost Co-RGO composite exhibited excellent catalytic activity for the reduction of highly toxic Cr(VI) to nontoxic Cr(III) at room temperature when formic acid (HCOOH) was employed as the reductant, and its catalytic performance was even comparable with that of noble metal-based catalysts in the same reduction reaction. Moreover, Co-RGO composite could be readily recovered under an external magnetic field and efficiently participated in recycled reaction for Cr(VI) reduction.

Biomass-derived chemicals: synthesis of biodegradable surfactant ether molecules from hydroxymethylfurfural.

PubMed

Arias, Karen S; Climent, Maria J; Corma, Avelino; Iborra, Sara

2014-01-01

A new class of biodegradable anionic surfactants with structures based on 5-alkoxymethylfuroate was prepared starting from 5-hydroxymethylfurfural (HMF), through a one-pot-two-steps process which involves the selective etherification of HMF with fatty alcohols using heterogeneous solid acid, followed by a highly selective oxidation of the formyl group with a gold catalyst. The etherification step was optimized using aluminosilicates as acid catalysts with different pore topologies (H-Beta, HY, Mordenite, ZSM-5, ITQ-2, and MCM-41), different active sites (Bronsted or Lewis) and different adsorption properties. It was shown that highly hydrophobic defect-free H-Beta zeolites with Si/Al ratios higher than 25 are excellent acid catalysts to perform the selective etherification of HMF with fatty alcohols, avoiding the competitive self-etherification of HMF. Moreover, the 5-alkoxymethylfurfural derivatives obtained can be selectively oxidized to the corresponding furoic salts in excellent yield using Au/CeO2 as catalyst and air as oxidant, at moderated temperatures. Both H-Beta zeolite and Au/CeO2 could be reused several times without loss of activity. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sol-gel (template) synthesis of macroporous Mo-based catalysts for hydrothermal oxidation of radionuclide-organic complexes

NASA Astrophysics Data System (ADS)

Papynov, E. K.; Palamarchuk, M. S.; Mayorov, V. Yu; Modin, E. B.; Portnyagin, A. S.; Sokol'nitskaya, T. A.; Belov, A. A.; Tananaev, I. G.; Avramenko, V. A.

2017-07-01

Molybdenum compounds are industrially demanding as heterogeneous catalysts for oxidation of various organic substances. Highly porous structure of molybdenum-containing catalysts avoids surface's colmatation and prevents blocking catalytic sites that makes these materials play a key role in processes of hydrothermal oxidation of radionuclide organic complexes. The study presents an original way of sol-gel synthesis of new macroporous molybdenum compounds using ;core-shell; colloid template (polymer latex) as poreforming agent. We have described three individual routs of template removal via thermal decomposition to obtain porous materials based on molybdenum compounds. Thermal treatment conditions (temperature, gaseous atmosphere) have been studied with respect to their influence on composition, structure and catalytic properties of synthesized molybdenum systems. The optimal way to synthesis of crystal molybdenum (VI) oxide with ordered porous structure (mean pore size 100-160 nm) has been suggested. Catalytic properties of macroporous molybdenum materials have been investigated in the process of liquid phase and hydrothermal oxidation of such organic substances thiazine and stable Co-EDTA complex. It was shown that macroporous molybdenum oxides could be applied as prospective catalysts for hydrothermal oxidation of organic radionuclide complexes during the processing of radioactive waste.

Modularized and water-cooled photo-catalyst cleaning devices for aquaponics based on ultraviolet light-emitting diodes

NASA Astrophysics Data System (ADS)

Yang, Henglong; Lung, Louis; Wei, Yu-Chien; Huang, Yi-Bo; Chen, Zi-Yu; Chou, Yu-Yang; Lin, Anne-Chin

2017-08-01

The feasibility of applying ultraviolet light-emitting diodes (UV-LED's) as triggering sources of photo-catalyst based on titanium dioxide (TiO2) nano-coating specifically for water-cleaning process in an aquaponics system was designed and proposed. The aquaponics system is a modern farming system to integrate aquaculture and hydroponics into a single system to establish an environmental-friendly and lower-cost method for farming fish and vegetable all together in urban area. Water treatment in an aquaponics system is crucial to avoid mutual contamination. we proposed a modularized watercleaning device composed of all commercially available components and parts to eliminate organic contaminants by using UV-LED's for TiO2 photo-catalyst reaction. This water-cleaning module consisted of two coaxial hollowed cylindrical pipes can be submerged completely in water for water treatment and cooling UV-LED's. The temperature of the UV-LED after proper thermal management can be reduced about 16% to maintain the optimal operation condition. Our preliminary experimental result by using Methylene Blue solution to simulate organic contaminants indicated that TiO2 photo-catalyst triggered by UV-LED's can effectively decompose organic compound and decolor Methylene Blue solution.

Polymer nanocomposite membranes with hierarchically structured catalysts for high throughput dehalogenation

NASA Astrophysics Data System (ADS)

Crock, Christopher A.

Halogenated organics are categorized as primary pollutants by the Environmental Protection Agency. Trichloroethylene (TCE), which had broad industrial use in the past, shows persistence in the environment because of its chemical stability. The large scale use and poor control of TCE resulted in its prolonged release into the environment before the carcinogenic risk associated with TCE was fully understood. TCE pollution stemmed from industrial effluents and improper disposal of solvent waste. Membrane reactors are promising technology for treating TCE polluted groundwater because of the high throughput, relatively low cost of membrane fabrication and facile retrofitting of existing membrane based water treatment facilities with catalytic membrane reactors. Compared to catalytic fluidized or fixed bed reactors, catalytic membrane reactors feature minimal diffusional limitation. Additionally, embedding catalyst within the membrane avoids the need for catalyst recovery and can prevent aggregation of catalytic nanoparticles. In this work, Pd/xGnP, Pd-Au/xGnP, and commercial Pd/Al2O3 nanoparticles were employed in batch and flow-through membrane reactors to catalyze the dehalogenation of TCE in the presence of dissolved H2. Bimetallic Pd-Au/xGnP catalysts were shown to be more active than monometallic Pd/xGnP or commercial Pd/Al 2O3 catalysts. In addition to synthesizing nanocomposite membranes for high-throughput TCE dehalogenation, the membrane based dehalogenation process was designed to minimize the detrimental impact of common catalyst poisons (S2-, HS-, and H2S -) by concurrent oxidation of sulfide species to gypsum in the presence of Ca2+ and removal of gypsum through membrane filtration. The engineered membrane dehalogenation process demonstrated that bimetallic Pd-Au/xGnP catalysts resisted deactivation by residual sulfide species after oxidation, and showed complete removal of gypsum during membrane filtration.

Electrochemical treatment of aqueous solutions of organic pollutants by electro-Fenton with natural heterogeneous catalysts under pressure using Ti/IrO2-Ta2O5 or BDD anodes.

PubMed

Ltaïef, Aziza Hadj; Sabatino, Simona; Proietto, Federica; Ammar, Salah; Gadri, Abdellatif; Galia, Alessandro; Scialdone, Onofrio

2018-07-01

The treatment of toxic organic pollutants by electro-Fenton (EF) presents some drawbacks such as the necessity to work at low pH and the low solubility of oxygen in water contacted with air or oxygen at room pressure that results often in slow and relatively low abatements. Here, the coupled adoption of natural heterogeneous catalysts and of relatively high pressure was proposed in order to improve the performances of EF for the treatment of organic pollutants. Caffeic acid (CA) and 3-chlorophenol were used as model resistant organic pollutants. EF process was performed using both conventional homogeneous FeSO 4 and natural heterogeneous catalysts (pyrite, chalcopyrite, Fe 2 O 3 and Fe 3 O 4 ) as iron catalysts and oxygen at various pressures in the absence or in the presence of BDD anode. The effect of the nature of the catalyst, the oxygen pressure, the current density and the catalyst load was widely investigated in order to optimize the process. It was shown that the coupled utilization of a natural heterogeneous catalyst such as chalcopyrite and a relatively high pressure allows to obtain the total removal of CA and a high removal of the TOC (about 75%) in short times (2 h) with relatively high current efficiencies using an Iridium based anode. In the case of 3-chlorophenol, the utilization of a BDD anode was necessary to achieve a high removal of the pollutant and the TOC. It was shown that the removal of 3-chlorophenol can be effectively performed in different water bodies and with different initial concentrations of 3-chlorophenol. Copyright © 2018 Elsevier Ltd. All rights reserved.

An empirical study on the preparation of the modified coke and its catalytic oxidation properties

NASA Astrophysics Data System (ADS)

Liu, Hao; Jiang, Wenqiang

2017-05-01

T As a methyl acrylic ester fungicide, pyraclostrobin has the advantages of high activity, wide sterilization spectrum and high safety level comparing with the traditional fungicide. Due to less toxicity and side effects on human and environment, the use of pyraclostrobin and its mixture in agriculture is increasing. The heavy use of pyraclostrobin will inevitably cause pollution to the biological and abiotic environment. Therefore, it is of great significance to do the research on the degradation of pyraclostrobin. In this study, coke, as matrix, was modified by chemical modification. The modified coke was used as the catalyst and the pyraclostrobin was used as the degradation object. The degradation experiment of pyraclostrobin was carried out by using catalytic oxidation. The catalytic oxidation performance of modified coke was studied. The result showed that in the catalytic oxidation system of using modified coke as catalyst and H2O2 as oxidant, the best reaction condition is as following: The modified coke which is modified by using 70% concentration nitric acid is used as catalyst; The dosage of the catalyst is10g; The dosage of H2O2 is 0.6ml; The reaction time is 6 hours.

Comparative evaluation of effects of ozonated and chlorinated thermal discharges on estuarine and fresh water organisms. First quarterly progress report, April 1979

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

Guerra, C.R.; DelMonaco, J.L.; Singletary, J.H.

1979-01-01

The biological evaluation program incorporates three types of experimental tests: acute (96 hour) toxicity studies; behavioral (avoidance) response studies; and physiological (cough) response studies. In addition, specimens used in testing are examined for physical damage resulting from exposure to chlorine or ozoen. The objective of the acute (96 hour) toxicity study is to determine the respective lethal levels (LC/sub 50/) of chlorinated and ozonated waters. The objective of the behavioral (avoidance) response study is to determine what (if any) concentrations of ozone and of chlorine will be avoided. The objective of physiological (cough) response study is to determine what concentrationsmore » of ozone and of chlorine are physiologically detected. Ozonated and chlorinated waters were evaluated in all studies for both the addition of increased temperature and without it. Results indicate that ozone is less toxic than chlorine under the test conditions used. The lethal levels vary according to species of water quality measurements at Bergen Generating Station, New York are tabulated. (JBG)« less

How Much is Too Much? Toxic Chemicals in High School Labs.

ERIC Educational Resources Information Center

Nagel, Miriam C.

1982-01-01

Lists 37 chemicals classified as suspected carcinogens and suspected teratogens (chemicals capable of producing malformations in an embryo). Offers suggestions to high school chemistry teachers for conducting safe laboratory investigations by avoiding use of these potentially toxic materials. (Author/JN)

Removal of ammonia solutions used in catalytic wet oxidation processes.

PubMed

Hung, Chang Mao; Lou, Jie Chung; Lin, Chia Hua

2003-08-01

Ammonia (NH(3)) is an important product used in the chemical industry, and is common place in industrial wastewater. Industrial wastewater containing ammonia is generally either toxic or has concentrations or temperatures such that direct biological treatment is unfeasible. This investigation used aqueous solutions containing more of ammonia for catalytic liquid-phase oxidation in a trickle-bed reactor (TBR) based on Cu/La/Ce composite catalysts, prepared by co-precipitation of Cu(NO(3))(2), La(NO(3))(2), and Ce(NO(3))(3) at 7:2:1 molar concentrations. The experimental results indicated that the ammonia conversion of the wet oxidation in the presence of the Cu/La/Ce composite catalysts was determined by the Cu/La/Ce catalyst. Minimal ammonia was removed from the solution by the wet oxidation in the absence of any catalyst, while approximately 91% ammonia removal was achieved by wet oxidation over the Cu/La/Ce catalyst at 230 degrees C with oxygen partial pressure of 2.0 MPa. Furthermore, the effluent streams were conducted at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes, and a reaction pathway was found linking the oxidizing ammonia to nitric oxide, nitrogen and water. The solution contained by-products, including nitrates and nitrites. Nitrite selectivity was minimized and ammonia removal maximized when the feed ammonia solution had a pH of around 12.0.

Multifaceted toxicity assessment of catalyst composites in transgenic zebrafish embryos.

PubMed

Jang, Gun Hyuk; Lee, Keon Yong; Choi, Jaewon; Kim, Sang Hoon; Lee, Kwan Hyi

2016-09-01

Recent development in the field of nanomaterials has given rise into the inquiries regarding the toxicological characteristics of the nanomaterials. While many individual nanomaterials have been screened for their toxicological effects, composites that accompany nanomaterials are not common subjects to such screening through toxicological assessment. One of the widely used composites that accompany nanomaterials is catalyst composite used to reduce air pollution, which was selected as a target composite with nanomaterials for the multifaceted toxicological assessment. As existing studies did not possess any significant data regarding such catalyst composites, this study focuses on investigating toxicological characteristics of catalyst composites from various angles in both in-vitro and in-vivo settings. Initial toxicological assessment on catalyst composites was conducted using HUVECs for cell viability assays, and subsequent in-vivo assay regarding their direct influence on living organisms was done. The zebrafish embryo and its transgenic lines were used in the in-vivo assays to obtain multifaceted analytic results. Data obtained from the in-vivo assays include blood vessel formation, mutated heart morphology, and heart functionality change. Our multifaceted toxicological assessment pointed out that chemical composites augmented with nanomaterials can too have toxicological threat as much as individual nanomaterials do and alarms us with their danger. This manuscript provides a multifaceted assessment for composites augmented with nanomaterials, of which their toxicological threats have been overlooked. Copyright © 2016 Elsevier Ltd. All rights reserved.

Moon Express Media Event

NASA Image and Video Library

2014-11-03

Members of the media watch a demonstration of the Regolith Advanced Surface System Operations Robot, or RASSOR, during a media event at the automated landing and hazard avoidance technology, or ALHAT, hazard field at the north end of the Shuttle Landing Facility at NASA's Kennedy Space Center in Florida. Tom Engler, center, in the suit, deputy director of Kennedy's Center Planning and Development, announced Moon Express Inc., of Moffett Field, California is selected to utilize Kennedy facilities for NASA's Lunar Cargo Transportation and Landing by Soft Touchdown, or Lunar CATALYST, initiative. Moon Express is developing a lander with capabilities that will enable delivery of payloads to the surface of the moon, as well as new science and exploration missions of interest to NASA and scientific and academic communities. Moon Express will base its activities at Kennedy and utilize the Morpheus ALHAT field and a hangar nearby for CATALYST testing. The Advanced Exploration Systems Division of NASA's Human Exploration and Operations Mission Directorate manages Lunar CATALYST.

KSC-2014-4375

NASA Image and Video Library

2014-11-03

CAPE CANAVERAL, Fla. - Rob Mueller, NASA senior technologist in the Surface Systems Office in Kennedy Space Center's Engineering and Technology Directorate, demonstrates the Regolith Advanced Surface System Operations Robot, or RASSOR, during a media event at Kennedy's automated landing and hazard avoidance technology, or ALHAT, hazard field at the north end of the Shuttle Landing Facility. The event was held to announce Moon Express Inc., of Moffett Field, California is selected to utilize Kennedy facilities for NASA's Lunar Cargo Transportation and Landing by Soft Touchdown, or Lunar CATALYST, initiative. Moon Express is developing a lander with capabilities that will enable delivery of payloads to the surface of the moon, as well as new science and exploration missions of interest to NASA and scientific and academic communities. Moon Express will base its activities at Kennedy and utilize the Morpheus ALHAT field and a hangar nearby for CATALYST testing. The Advanced Exploration Systems Division of NASA's Human Exploration and Operations Mission Directorate manages Lunar CATALYST. Photo credit: NASA/Ben Smegelsky

Moon Express Media Event

NASA Image and Video Library

2014-11-03

Rob Mueller, left, NASA senior technologist in the Surface Systems Office in Kennedy Space Center's Engineering and Technology Directorate, talks with former NASA Apollo astronaut Buzz Aldrin during a demonstration of the Regolith Advanced Surface Systems Operations Robot, or RASSOR, at the automated landing and hazard avoidance technology, or ALHAT, hazard field at the north end of the Shuttle Landing Facility at NASA's Kennedy Space Center in Florida. The event was held to announce Moon Express Inc., of Moffett Field, California is selected to utilize Kennedy facilities for NASA's Lunar Cargo Transportation and Landing by Soft Touchdown, or Lunar CATALYST, initiative. Moon Express is developing a lander with capabilities that will enable delivery of payloads to the surface of the moon, as well as new science and exploration missions of interest to NASA and scientific and academic communities. Moon Express will base its activities at Kennedy and utilize the Morpheus ALHAT field and a hangar nearby for CATALYST testing. The Advanced Exploration Systems Division of NASA's Human Exploration and Operations Mission Directorate manages Lunar CATALYST.

KSC-2014-4376

NASA Image and Video Library

2014-11-03

CAPE CANAVERAL, Fla. - Members of the media watch a demonstration of the Regolith Advanced Surface System Operations Robot, or RASSOR, during a media event at the automated landing and hazard avoidance technology, or ALHAT, hazard field at the north end of the Shuttle Landing Facility at NASA's Kennedy Space Center in Florida. Tom Engler, center, in the suit, deputy director of Kennedy's Center Planning and Development, announced Moon Express Inc., of Moffett Field, California is selected to utilize Kennedy facilities for NASA's Lunar Cargo Transportation and Landing by Soft Touchdown, or Lunar CATALYST, initiative. Moon Express is developing a lander with capabilities that will enable delivery of payloads to the surface of the moon, as well as new science and exploration missions of interest to NASA and scientific and academic communities. Moon Express will base its activities at Kennedy and utilize the Morpheus ALHAT field and a hangar nearby for CATALYST testing. The Advanced Exploration Systems Division of NASA's Human Exploration and Operations Mission Directorate manages Lunar CATALYST. Photo credit: NASA/Ben Smegelsky

Moon Express Media Event

NASA Image and Video Library

2014-11-03

Rob Mueller, left, NASA senior technologist in the Surface Systems Office in Kennedy Space Center's Engineering and Technology Directorate, talks with former NASA Apollo astronaut Buzz Aldrin during a demonstration of the Regolith Advanced Surface System Operations Robot, or RASSOR, at the automated landing and hazard avoidance technology, or ALHAT, hazard field at the north end of the Shuttle Landing Facility at NASA's Kennedy Space Center in Florida. The event was held to announce Moon Express Inc., of Moffett Field, California is selected to utilize Kennedy facilities for NASA's Lunar Cargo Transportation and Landing by Soft Touchdown, or Lunar CATALYST, initiative. Moon Express is developing a lander with capabilities that will enable delivery of payloads to the surface of the moon, as well as new science and exploration missions of interest to NASA and scientific and academic communities. Moon Express will base its activities at Kennedy and utilize the Morpheus ALHAT field and a hangar nearby for CATALYST testing. The Advanced Exploration Systems Division of NASA's Human Exploration and Operations Mission Directorate manages Lunar CATALYST.

Templated Growth of Pd Nanoparticles Using Sputtering Deposition Process and Its Catalytic Activities.

PubMed

Eberhardt, Dario; Migowski, Pedro; Teixeira, Sérgio R; Feil, Adriano F

2018-03-01

A simple method based on sputtering deposition of Pd onto mesoporous SiO2 (SBA-15) was employed to produce supported Pd nanoparticles (NPs) that can be used as hydrogenation catalysts. The use of sputtering deposition eliminates contaminants and avoids additional drawbacks of traditional chemical methods applied to prepare heterogeneous supported metal catalysts. A mechanical resonant stirrer was used to revolve the SBA-15 powder and ensure homogeneous distribution of the Pd NPs over the support. The SBA-15 pores act as templates for Pd NPs and drive nanostructure growth. Consequently, the NPs obtained have the same diameter as that of the SBA-15 channels (~5 nm) and elongated particles are formed as sputtering deposition increases. The SBA-15 supported Pd NPs (Pd NPs/SBA-15) were tested in a probe hydrogenation of cyclohexene reaction to evaluate the catalytic activity of the Pd NPs. Turnover frequency (TOF) of 2000 min-1 were achieved with the lower Pd NPs concentration (0.15 wt%) catalyst.

Organocatalytic removal of formaldehyde adducts from RNA and DNA bases.

PubMed

Karmakar, Saswata; Harcourt, Emily M; Hewings, David S; Scherer, Florian; Lovejoy, Alexander F; Kurtz, David M; Ehrenschwender, Thomas; Barandun, Luzi J; Roost, Caroline; Alizadeh, Ash A; Kool, Eric T

2015-09-01

Formaldehyde is universally used to fix tissue specimens, where it forms hemiaminal and aminal adducts with biomolecules, hindering the ability to retrieve molecular information. Common methods for removing these adducts involve extended heating, which can cause extensive degradation of nucleic acids, particularly RNA. Here, we show that water-soluble bifunctional catalysts (anthranilates and phosphanilates) speed the reversal of formaldehyde adducts of mononucleotides over standard buffers. Studies with formaldehyde-treated RNA oligonucleotides show that the catalysts enhance adduct removal, restoring unmodified RNA at 37 °C even when extensively modified, while avoiding the high temperatures that promote RNA degradation. Experiments with formalin-fixed, paraffin-embedded cell samples show that the catalysis is compatible with common RNA extraction protocols, with detectable RNA yields increased by 1.5-2.4-fold using a catalyst under optimized conditions and by 7-25-fold compared with a commercial kit. Such catalytic strategies show promise for general use in reversing formaldehyde adducts in clinical specimens.

A new charge-tagged proline-based organocatalyst for mechanistic studies using electrospray mass spectrometry

PubMed Central

Willms, J Alexander; Beel, Rita; Schmidt, Martin L; Mundt, Christian

2014-01-01

Summary A new 4-hydroxy-L-proline derivative with a charged 1-ethylpyridinium-4-phenoxy substituent has been synthesized with the aim of facilitating mechanistic studies of proline-catalyzed reactions by ESI mass spectrometry. The charged residue ensures a strongly enhanced ESI response compared to neutral unmodified proline. The connection by a rigid linker fixes the position of the charge tag far away from the catalytic center in order to avoid unwanted interactions. The use of a charged catalyst leads to significantly enhanced ESI signal abundances for every catalyst-derived species which are the ones of highest interest present in a reacting solution. The new charged proline catalyst has been tested in the direct asymmetric inverse aldol reaction between aldehydes and diethyl ketomalonate. Two intermediates in accordance with the List–Houk mechanism for enamine catalysis have been detected and characterized by gas-phase fragmentation. In addition, their temporal evolution has been followed using a microreactor continuous-flow technique. PMID:25246962

Organocatalytic Removal of Formaldehyde Adducts from RNA and DNA Bases

PubMed Central

Karmakar, Saswata; Harcourt, Emily M.; Hewings, David S.; Lovejoy, Alexander F.; Kurtz, David M.; Ehrenschwender, Thomas; Barandun, Luzi J.; Roost, Caroline; Alizadeh, Ash A.; Kool, Eric T.

2015-01-01

Formaldehyde is universally employed to fix tissue specimens, where it forms hemiaminal and aminal adducts with biomolecules, hindering the ability to retrieve molecular information. Common methods for removing these adducts involve extended heating, which can cause extensive degradation of nucleic acids, particularly RNA. Here we show that water-soluble bifunctional catalysts (anthranilates and phosphanilates) speed the reversal of formaldehyde adducts of mononucleotides over standard buffers. Studies with formaldehyde-treated RNA oligonucleotides show that the catalysts enhance adduct removal, restoring unmodified RNA at 37 °C even when extensively modified, and avoiding high temperatures that promote RNA degradation. Experiments with formalin-fixed, paraffin-embedded cell samples show that the catalysis is compatible with common RNA extraction protocols, with detectable RNA yields increased by 1.5–2.4 fold using a catalyst under optimized conditions, and by 7–25 fold compared to a commercial kit. Such catalytic strategies show promise for general use in reversing formaldehyde adducts in clinical specimens. PMID:26291948

Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C-H activation

NASA Astrophysics Data System (ADS)

Marcinkowski, Matthew D.; Darby, Matthew T.; Liu, Jilei; Wimble, Joshua M.; Lucci, Felicia R.; Lee, Sungsik; Michaelides, Angelos; Flytzani-Stephanopoulos, Maria; Stamatakis, Michail; Sykes, E. Charles H.

2018-03-01

The recent availability of shale gas has led to a renewed interest in C-H bond activation as the first step towards the synthesis of fuels and fine chemicals. Heterogeneous catalysts based on Ni and Pt can perform this chemistry, but deactivate easily due to coke formation. Cu-based catalysts are not practical due to high C-H activation barriers, but their weaker binding to adsorbates offers resilience to coking. Using Pt/Cu single-atom alloys (SAAs), we examine C-H activation in a number of systems including methyl groups, methane and butane using a combination of simulations, surface science and catalysis studies. We find that Pt/Cu SAAs activate C-H bonds more efficiently than Cu, are stable for days under realistic operating conditions, and avoid the problem of coking typically encountered with Pt. Pt/Cu SAAs therefore offer a new approach to coke-resistant C-H activation chemistry, with the added economic benefit that the precious metal is diluted at the atomic limit.

Undergraduate research studies program at participating institutions of the HBCU Fossil Energy Consortium

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

Bota, K.B.

1991-01-01

The primary objective of this research program is to expose students in the Historically Black Colleges and Universities (HBCU) Fossil Energy Consortium Institutions to energy and fossil fuels research, to stimulate their interest in the sciences and engineering and to encourage them to pursue graduate studies. This report provides the research accomplishment of the various students who participated in the program. Research results are presented on the following topics: Energy Enhancement and Pollutant Reduction in Coal by Cryogenic Diminution; Competition of NO and SO[sub 2] for OH Generated witin Electrical Aerosol Analyzers; Dispersed Iron Catalysts for Coal Gasification; NQR/NMR Studiesmore » of Copper-Cobalt Catalysts for Syngas Concersion; Catalytic gasification of Coal Chars by Potassium Sulfate and Ferrous Sulfate Mixtures; A New Method for Cleaning and Beneficiation of Ultrafine Coal; Characterization Studies of Coal-Derived Liquids; Study of Coal Liquefaction Catalysts and Removal of Certain Toxic Heavy Metal Ions from Coal Conversion Process Wastewaters.« less

Undergraduate research studies program at participating institutions of the HBCU Fossil Energy Consortium. Final report

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

Bota, K.B.

1991-12-31

The primary objective of this research program is to expose students in the Historically Black Colleges and Universities (HBCU) Fossil Energy Consortium Institutions to energy and fossil fuels research, to stimulate their interest in the sciences and engineering and to encourage them to pursue graduate studies. This report provides the research accomplishment of the various students who participated in the program. Research results are presented on the following topics: Energy Enhancement and Pollutant Reduction in Coal by Cryogenic Diminution; Competition of NO and SO{sub 2} for OH Generated witin Electrical Aerosol Analyzers; Dispersed Iron Catalysts for Coal Gasification; NQR/NMR Studiesmore » of Copper-Cobalt Catalysts for Syngas Concersion; Catalytic gasification of Coal Chars by Potassium Sulfate and Ferrous Sulfate Mixtures; A New Method for Cleaning and Beneficiation of Ultrafine Coal; Characterization Studies of Coal-Derived Liquids; Study of Coal Liquefaction Catalysts and Removal of Certain Toxic Heavy Metal Ions from Coal Conversion Process Wastewaters.« less

Ozone decomposition

PubMed Central

Batakliev, Todor; Georgiev, Vladimir; Anachkov, Metody; Rakovsky, Slavcho

2014-01-01

Catalytic ozone decomposition is of great significance because ozone is a toxic substance commonly found or generated in human environments (aircraft cabins, offices with photocopiers, laser printers, sterilizers). Considerable work has been done on ozone decomposition reported in the literature. This review provides a comprehensive summary of the literature, concentrating on analysis of the physico-chemical properties, synthesis and catalytic decomposition of ozone. This is supplemented by a review on kinetics and catalyst characterization which ties together the previously reported results. Noble metals and oxides of transition metals have been found to be the most active substances for ozone decomposition. The high price of precious metals stimulated the use of metal oxide catalysts and particularly the catalysts based on manganese oxide. It has been determined that the kinetics of ozone decomposition is of first order importance. A mechanism of the reaction of catalytic ozone decomposition is discussed, based on detailed spectroscopic investigations of the catalytic surface, showing the existence of peroxide and superoxide surface intermediates. PMID:26109880

Synthesis, characterization and catalytic performance of ZnO-CeO2 nanoparticles in wet oxidation of wastewater containing chlorinated compounds

NASA Astrophysics Data System (ADS)

Anushree; Kumar, S.; Sharma, C.

2017-11-01

Here we report the catalytic property of ZnO-CeO2 nanoparticles towards oxidative degradation of organic pollutants present in industrial wastewater. The catalysts were prepared by co-precipitation method without using any surfactant. The physicochemical properties of catalysts were studied by XRD, Raman, XPS, N2-sorption, FE-SEM, TEM and EDX techniques. The characterization results confirmed the formation of porous ZnO-CeO2 nanocatalysts with high surface area, pore volume and oxygen vacancies. ZnO-CeO2 nanocatalysts exhibited appreciable efficiency in CWAO of industrial wastewater under mild conditions. The Ce40Zn60 catalyst was found to be most efficient with 72% color, 64% chemical oxygen demand (COD) and 63% total organic carbon (TOC) removal. Efficient removal of chlorophenolics (CHPs, 59%) and adsorbable organic halides (AOX, 54%) indicated the feasibility of using ZnO-CeO2 nanocatalysts in degradation of non-biodegradable and toxic chlorinated compounds.

Catalytic and atmospheric effects on microwave pyrolysis of corn stover.

PubMed

Huang, Yu-Fong; Kuan, Wen-Hui; Chang, Chi-Cheng; Tzou, Yu-Min

2013-03-01

Corn stover, which is one of the most abundant agricultural residues around the world, could be converted into valuable biofuels and bio based products by means of microwave pyrolysis. After the reaction at the microwave power level of 500W for the processing time of 30min, the reaction performance under N2 atmosphere was generally better than under CO2 atmosphere. This may be due to the better heat absorbability of CO2 molecules to reduce the heat for stover pyrolysis. Most of the metal-oxide catalysts effectively increased the maximum temperature and mass reduction ratio but lowered the calorific values of solid residues. The gas most produced was CO under N2 atmosphere but CO2 under CO2 atmosphere. Catalyst addition lowered the formation of PAHs and thus made liquid products less toxic. More liquid products and less gas products were generated when using the catalysts possibly due to the existence of the Fischer-Tropsch synthesis. Copyright © 2013 Elsevier Ltd. All rights reserved.

Zwitterionic-surfactant-stabilized palladium nanoparticles as catalysts in the hydrogen transfer reductive amination of benzaldehydes.

PubMed

Drinkel, Emma E; Campedelli, Roberta R; Manfredi, Alex M; Fiedler, Haidi D; Nome, Faruk

2014-03-21

Palladium nanoparticles (NPs) stabilized by a zwitterionic surfactant are revealed here to be good catalysts for the reductive amination of benzaldehydes using formate salts as hydrogen donors in aqueous isopropanol. In terms of environmental impact and economy, metallic NPs offer several advantages over homogeneous and traditional heterogeneous catalysts. NPs usually display greater activity due to the increased metal surface area and sometimes exhibit enhanced selectivity. Thus, it is possible to use very low loadings of expensive metal. The methodology eliminates the use of a hydrogen gas atmosphere or toxic or expensive reagents. A range of aromatic aldehydes were converted to benzylamines when reacted with primary and secondary amines in the presence of the Pd NPs, which also displayed good activity when supported on alumina. In every case, the Pd NPs could be easily recovered and reused up to three more times, and at the end of the process, the product was metal-free.

Homogenous Electrocatalytic Oxygen Reduction Rates Correlate with Reaction Overpotential in Acidic Organic Solutions

PubMed Central

2016-01-01

Improved electrocatalysts for the oxygen reduction reaction (ORR) are critical for the advancement of fuel cell technologies. Herein, we report a series of 11 soluble iron porphyrin ORR electrocatalysts that possess turnover frequencies (TOFs) from 3 s–1 to an unprecedented value of 2.2 × 106 s–1. These TOFs correlate with the ORR overpotential, which can be modulated by changing the E1/2 of the catalyst using different ancillary ligands, by changing the solvent and solution acidity, and by changing the catalyst’s protonation state. The overpotential is well-defined for these homogeneous electrocatalysts by the E1/2 of the catalyst and the proton activity of the solution. This is the first such correlation for homogeneous ORR electrocatalysis, and it demonstrates that the remarkably fast TOFs are a consequence of high overpotential. The correlation with overpotential is surprising since the turnover limiting steps involve oxygen binding and protonation, as opposed to turnover limiting electron transfer commonly found in Tafel analysis of heterogeneous ORR materials. Computational studies show that the free energies for oxygen binding to the catalyst and for protonation of the superoxide complex are in general linearly related to the catalyst E1/2, and that this is the origin of the overpotential correlations. This analysis thus provides detailed understanding of the ORR barriers. The best catalysts involve partial decoupling of the influence of the second coordination sphere from the properties of the metal center, which is suggested as new molecular design strategy to avoid the limitations of the traditional scaling relationships for these catalysts. PMID:27924314

Applications of Neutron Scattering in the Chemical Industry: Proton Dynamics of Highly Dispersed Materials, Characterization of Fuel Cell Catalysts, and Catalysts from Large-Scale Chemical Processes

NASA Astrophysics Data System (ADS)

Albers, Peter W.; Parker, Stewart F.

The attractiveness of neutron scattering techniques for the detailed characterization of materials of high degrees of dispersity and structural complexity as encountered in the chemical industry is discussed. Neutron scattering picks up where other analytical methods leave off because of the physico-chemical properties of finely divided products and materials whose absorption behavior toward electromagnetic radiation and electrical conductivity causes serious problems. This is demonstrated by presenting typical applications from large-scale production technology and industrial catalysis. These include the determination of the proton-related surface chemistry of advanced materials that are used as reinforcing fillers in the manufacture of tires, where interrelations between surface chemistry, rheological properties, improved safety, and significant reduction of fuel consumption are the focus of recent developments. Neutron scattering allows surface science studies of the dissociative adsorption of hydrogen on nanodispersed, supported precious metal particles of fuel cell catalysts under in situ loading at realistic gas pressures of about 1 bar. Insight into the occupation of catalytically relevant surface sites provides valuable information about the catalyst in the working state and supplies essential scientific input for tailoring better catalysts by technologists. The impact of deactivation phenomena on industrial catalysts by coke deposition, chemical transformation of carbonaceous deposits, and other processes in catalytic hydrogenation processes that result in significant shortening of the time of useful operation in large-scale plants can often be traced back in detail to surface or bulk properties of catalysts or materials of catalytic relevance. A better understanding of avoidable or unavoidable aspects of catalyst deactivation phenomena under certain in-process conditions and the development of effective means for reducing deactivation leads to more energy-efficient and, therefore, environmentally friendly processes and helps to save valuable resources. Even small or gradual improvements in all these fields are of considerable economic impact.

Hydrogenation and dehydrogenation iron pincer catalysts capable of metal-ligand cooperation by aromatization/dearomatization.

PubMed

Zell, Thomas; Milstein, David

2015-07-21

The substitution of expensive and potentially toxic noble-metal catalysts by cheap, abundant, environmentally benign, and less toxic metals is highly desirable and in line with green chemistry guidelines. We have recently discovered a new type of metal-ligand cooperation, which is based on the reversible dearomatization/aromatization of different heteroaromatic ligand cores caused by deprotonation/protonation of the ligand. More specifically, we have studied complexes of various transition metals (Ru, Fe, Co, Rh, Ir, Ni, Pd, Pt, and Re) bearing pyridine- and bipyridine-based PNP and PNN pincer ligands, which have slightly acidic methylene protons. In addition, we have discovered long-range metal-ligand cooperation in acridine-based pincer ligands, where the cooperation takes place at the electrophilic C-9 position of the acridine moiety leading to dearomatization of its middle ring. This type of metal-ligand cooperation was used for the activation of chemical bonds, including H-H, C-H (sp(2) and sp(3)), O-H, N-H, and B-H bonds. This unusual reactivity likely takes place in various catalytic hydrogenation, dehydrogenation, and related reactions. In this Account, we summarize our studies on novel bifunctional iron PNP and PNN pincer complexes, which were designed on the basis of their ruthenium congeners. Iron PNP pincer complexes serve as efficient (pre)catalysts for hydrogenation and dehydrogenation reactions under remarkably mild conditions. Their catalytic applications include atom-efficient and industrially important hydrogenation reactions of ketones, aldehydes, and esters to the corresponding alcohols. Moreover, they catalyze the hydrogenation of carbon dioxide to sodium formate in the presence of sodium hydroxide, the selective decomposition of formic acid to carbon dioxide and hydrogen, and the E-selective semihydrogenation of alkynes to give E-alkenes. These catalysts feature, compared to other iron-based catalysts, very high catalytic activities which in some cases can even exceed those of state-of-the-art noble-metal catalysts. For the iron PNP systems, we describe the synthesis of the pyridine- and acridine-based PNP iron complexes and their performances and limitations in catalytic reactions, and we present studies on their reactivity with relevance to their catalytic mechanisms. In the case of the bipyridine-based PNN system, we summarize the synthesis of new complexes and describe studies on the noninnocence of the methylene position, which can be reversibly deprotonated, as well as on the noninnocence of the bipyridine unit. Overall, this Account underlines that the combination of cheap and abundant iron with ligands that are capable of metal-ligand cooperation can result in the development of novel, versatile, and efficient catalysts for atom-efficient catalytic reactions.

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

Dayton, David C; Kataria, Atish; Gupta, Rabhubir

The objective of the project is to develop and demonstrate a novel fluidized-bed process module called a Therminator to simultaneously destroy and/or remove tar, NH3 and H2S from raw syngas produced by a fluidized-bed biomass gasifier. The raw syngas contains as much as 10 g/m3 of tar, 4,000 ppmv of NH3 and 100 ppmv of H2S. The goal of the Therminator module would be to use promising regenerable catalysts developed for removing tar, ammonia, and H2S down to low levels (around 10 ppm). Tars are cracked to a non-condensable gas and coke that would deposit on the acid catalyst. Wemore » will deposit coke, much like a fluid catalytic cracker (FCC) in a petroleum refinery. The deposited coke fouls the catalyst, much like FCC, but the coke would be burned off in the regenerator and the regenerated catalyst would be returned to the cracker. The rapid circulation between the cracker and regenerator would ensure the availability of the required amount of regenerated catalyst to accomplish our goal. Also, by removing sulfur down to less than 10 ppmv, NH3 decomposition would also be possible in the cracker at 600-700°C. In the cracker, tar decomposes and lays down coke on the acid sites of the catalyst, NH3 is decomposed using a small amount of metal (e.g., nickel or iron) catalyst incorporated into the catalyst matrix, and H2S is removed by a small amount of a metal oxide (e.g. zinc oxide or zinc titanate) by the H2S-metal oxide reaction to form metal sulfide. After a tolerable decline in activity for these reactions, the catalyst particles (and additives) are transported to the regenerator where they are exposed to air to remove the coke and to regenerate the metal sulfide back to metal oxide. Sulfate formation is avoided by running the regeneration with slightly sub-stoichiometric quantity of oxygen. Following regeneration, the catalyst is transported back to the cracker and the cycling continues. Analogous to an FCC reactor system, rapid cycling will allow the use of very active cracking catalysts that lose activity due to coking within the order of several seconds.« less

Aerobic Alcohol Oxidation Using a Copper(I)/TEMPO Catalyst System: A Green, Catalytic Oxidation Reaction for the Undergraduate Organic Chemistry Laboratory

ERIC Educational Resources Information Center

Hill, Nicholas J.; Hoover, Jessica M.; Stahl, Shannon S.

2013-01-01

Modern undergraduate organic chemistry textbooks provide detailed discussion of stoichiometric Cr- and Mn-based reagents for the oxidation of alcohols, yet the use of such oxidants in instructional and research laboratories, as well as industrial chemistry, is increasingly avoided. This work describes a laboratory exercise that uses ambient air as…

Experimental investigation of the catalytic decomposition and combustion characteristics of a non-toxic ammonium dinitramide (ADN)-based monopropellant thruster

NASA Astrophysics Data System (ADS)

Chen, Jun; Li, Guoxiu; Zhang, Tao; Wang, Meng; Yu, Yusong

2016-12-01

Low toxicity ammonium dinitramide (ADN)-based aerospace propulsion systems currently show promise with regard to applications such as controlling satellite attitude. In the present work, the decomposition and combustion processes of an ADN-based monopropellant thruster were systematically studied, using a thermally stable catalyst to promote the decomposition reaction. The performance of the ADN propulsion system was investigated using a ground test system under vacuum, and the physical properties of the ADN-based propellant were also examined. Using this system, the effects of the preheating temperature and feed pressure on the combustion characteristics and thruster performance during steady state operation were observed. The results indicate that the propellant and catalyst employed during this work, as well as the design and manufacture of the thruster, met performance requirements. Moreover, the 1 N ADN thruster generated a specific impulse of 223 s, demonstrating the efficacy of the new catalyst. The thruster operational parameters (specifically, the preheating temperature and feed pressure) were found to have a significant effect on the decomposition and combustion processes within the thruster, and the performance of the thruster was demonstrated to improve at higher feed pressures and elevated preheating temperatures. A lower temperature of 140 °C was determined to activate the catalytic decomposition and combustion processes more effectively compared with the results obtained using other conditions. The data obtained in this study should be beneficial to future systematic and in-depth investigations of the combustion mechanism and characteristics within an ADN thruster.

Adsorption and dissociation of sulfur-based toxic gas molecules on silicene nanoribbons: a quest for high-performance gas sensors and catalysts.

PubMed

Walia, Gurleen Kaur; Randhawa, Deep Kamal Kaur

2018-03-16

The adsorption behavior of sulfur-based toxic gases (H 2 S and SO 2 ) on armchair silicene nanoribbons (ASiNRs) was investigated using first-principles density functional theory (DFT). Being a zero band gap material, application of bulk silicene is limited in nanoelectronics, despite its high carrier mobility. By restricting its dimensions into one dimension, construction of nanoribbons, and by introduction of a defect, its band gap can be tuned. Pristine armchair silicene nanoribbons (P-ASiNRs) have a very low sensitivity to gas molecules. Therefore, a defect was introduced by removal of one Si atom, leading to increased sensitivity. To deeply understand the impact of the aforementioned gases on silicene nanoribbons, electronic band structures, density of states, charge transfers, adsorption energies, electron densities, current-voltage characteristics and most stable adsorption configurations were calculated. H 2 S is dissociated completely into HS and H species when adsorbed onto defective armchair silicene nanoribbons (D-ASiNRs). Thus, D-ASiNR is a likely catalyst for dissociation of the H 2 S gas molecule. Conversely, upon SO 2 adsorption, P-ASiNR acts as a suitable sensor, whereas D-ASiNR provides enhanced sensitivity compared with P-ASiNR. On the basis of these results, D-ASiNR can be expected to be a disposable sensor for SO 2 detection as well as a catalyst for H 2 S reduction. Graphical abstract Comparison of I-V characteristics of pristine and defective armchair silicene nanoribbons with H 2 S and SO 2 adsorbed on them.

Treatment of real industrial wastewaters through nano-TiO2 and nano-Fe2O3 photocatalysis: case study of mining and kraft pulp mill effluents.

PubMed

Nogueira, V; Lopes, I; Rocha-Santos, T A P; Gonçalves, F; Pereira, R

2018-06-01

High quantities of industrial wastewaters containing a wide range of organic and inorganic pollutants are being directly discharged into the environment, sometimes without proper treatment. Nanotechnology has a tremendous potential improving the existing treatments or even develop new treatment solutions. In this study, nano-TiO 2 or nano-Fe 2 O 3 was used for the photocatalytic treatment of kraft pulp mill effluent and mining effluent. The experiments with the organic effluent lead to reduction percentages of 93.3%, 68.4% and 89.8%, for colour, aromatic compounds and chemical oxygen demand, respectively, when treated with nano-TiO 2 /H 2 O 2 /UV and nano-Fe 2 O 3 /H 2 O 2 /UV, at pH 3.0. Significant removal of metals from the mining effluent was recorded but only for Zn, Al and Cd, the highest removal attained with 1.0 g L -1 of nano-TiO 2 /UV and nano-Fe 2 O 3 /UV. Regarding the toxicity of the organic effluent to Vibrio fischeri, it was reduced with the treatments combining the oxidant and the catalyst. However, for the inorganic effluent, the best reduction was achieved using 1.0 g L -1 of catalyst. In fact, the increase in dose of the catalyst, especially for nano-TiO 2 , enhanced toxicity reduction. Our results have shown that the use of these NMs seemed to be more effective in the organic effluent than in metal-rich effluent.

Achieving Biocompatible SABRE: An in vitro Cytotoxicity Study.

PubMed

Manoharan, Anand; Rayner, Peter J; Iali, Wissam; Burns, Michael J; Perry, V Hugh; Duckett, Simon B

2018-02-20

Production of a biocompatible hyperpolarized bolus for signal amplification by reversible exchange (SABRE) could open the door to simple clinical diagnosis via magnetic resonance imaging. Essential to successful progression to preclinical/clinical applications is the determination of the toxicology profile of the SABRE reaction mixture. Herein, we exemplify the cytotoxicity of the SABRE approach using in vitro cell assays. We conclude that the main cause of the observed toxicity is due to the SABRE catalyst. We therefore illustrate two catalyst removal methods: one involving deactivation and ion-exchange chromatography, and the second using biphasic catalysis. These routes produce a bolus suitable for future in vivo study. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Female Representation in Gikuyu Popular Music: A Catalyst for Domestic Violence.

ERIC Educational Resources Information Center

Maina, Faith

The females portrayed in the Gikuyu popular music of Kenya are almost always evil. Women are often viewed as prostitutes who see their sexuality as a commodity to be exchanged for material goods. After the unsuspecting males have delivered the goods, the women are more often than not betrayed. These portraits create a hostile and toxic environment…

Highly Active Iridium/Iridium Tin/Tin Oxide Heterogeneous Nanoparticles as Alternative Electrocatalysts for the Ethanol Oxidation Reaction

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

Du W.; Su D.; Wang Q.

2011-08-03

Ethanol is a promising fuel for low-temperature direct fuel cell reactions due to its low toxicity, ease of storage and transportation, high-energy density, and availability from biomass. However, the implementation of ethanol fuel cell technology has been hindered by the lack of low-cost, highly active anode catalysts. In this paper, we have studied Iridium (Ir)-based binary catalysts as low-cost alternative electrocatalysts replacing platinum (Pt)-based catalysts for the direct ethanol fuel cell (DEFC) reaction. We report the synthesis of carbon supported Ir{sub 71}Sn{sub 29} catalysts with an average diameter of 2.7 {+-} 0.6 nm through a 'surfactant-free' wet chemistry approach. Themore » complementary characterization techniques, including aberration-corrected scanning transmission electron microscopy equipped with electron energy loss spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy, are used to identify the 'real' heterogeneous structure of Ir{sub 71}Sn{sub 29}/C particles as Ir/Ir-Sn/SnO{sub 2}, which consists of an Ir-rich core and an Ir-Sn alloy shell with SnO{sub 2} present on the surface. The Ir{sub 71}Sn{sub 29}/C heterogeneous catalyst exhibited high electrochemical activity toward the ethanol oxidation reaction compared to the commercial Pt/C (ETEK), PtRu/C (Johnson Matthey) as well as PtSn/C catalysts. Electrochemical measurements and density functional theory calculations demonstrate that the superior electro-activity is directly related to the high degree of Ir-Sn alloy formation as well as the existence of nonalloyed SnO{sub 2} on surface. Our cross-disciplinary work, from novel 'surfactant-free' synthesis of Ir-Sn catalysts, theoretical simulations, and catalytic measurements to the characterizations of 'real' heterogeneous nanostructures, will not only highlight the intriguing structure-property correlations in nanosized catalysts but also have a transformative impact on the commercialization of DEFC technology by replacing Pt with low-cost, highly active Ir-based catalysts.« less

The promoting effect of CeO2@Ce-O-P multi-core@shell structure on SO2 tolerance for selective catalytic reduction of NO with NH3 at low temperature

NASA Astrophysics Data System (ADS)

Yao, Weiyuan; Liu, Yue; Wu, Zhongbiao

2018-06-01

A series of CeO2@Ce-O-P "multi-core@shell" catalysts were synthesized in this paper for selective catalytic reduction (SCR) of NO with NH3. The experimental results had showed that CeO2@Ce-O-P-30:3 yielded best SO2 tolerance of an over 70% deNOx efficiency at 250 °C in the presence of 100 ppm SO2 for 20 h, which was much higher compared to pure Ce-O-P and CeO2 samples. Further characterization results indicated that Ce-O-P coating layer could somewhat inhibit sulfur depositing on the catalysts during SCR reaction in the presence of SO2, thereby protecting the active sites from SO2 poisoning. Especially, O2-TPD results illustrated that a great amount of active oxygen species were retained on used CeO2@Ce-O-P catalyst after a long term reaction. The synergetic effect of "multi-core@shell" structure could be attributed to such enhanced performances. The "core" CeO2 devoted abundant active oxygen sites to fulfill the SCR reaction. And the "shell" Ce-O-P could not only provide acid sites, but also protect the active oxygen species by avoiding the over-adsorption of SO2 on the catalyst. This work could provide a new way to increase the sulfur resistance for low temperature SCR catalysts.

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

Raugei, Simone; DuBois, Daniel L.; Rousseau, Roger J.

Rational design of molecular catalysts requires a systematic approach to designing ligands with specific functionality and precisely tailored electronic and steric properties. It then becomes possible to devise computer protocols to predict accurately the required properties and ultimately to design catalysts by computer. In this account we first review how thermodynamic properties such as oxidation-reduction potentials (E0), acidities (pKa), and hydride donor abilities (ΔGH-) form the basis for a systematic design of molecular catalysts for reactions that are critical for a secure energy future (hydrogen evolution and oxidation, oxygen and nitrogen reduction, and carbon dioxide reduction). We highlight how densitymore » functional theory allows us to determine and predict these properties within “chemical” accuracy (~ 0.06 eV for redox potentials, ~ 1 pKa unit for pKa values, and ~ 1.5 kcal/mol for hydricities). These quantities determine free energy maps and profiles associated with catalytic cycles, i.e. the relative energies of intermediates, and help us distinguish between desirable and high-energy pathways and mechanisms. Good catalysts have flat profiles that avoid high activation barriers due to low and high energy intermediates. We illustrate how the criterion of a flat energy profile lends itself to the prediction of design points by computer for optimum catalysts. This research was carried out in the Center for Molecular Electro-catalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory (PNNL) is operated for the DOE by Battelle.« less

Selective and eco-friendly procedures for the synthesis of benzimidazole derivatives. The role of the Er(OTf)3 catalyst in the reaction selectivity

PubMed Central

Herrera Cano, Natividad; Uranga, Jorge G; Nardi, Mónica; Procopio, Antonio; Wunderlin, Daniel A

2016-01-01

An improved and greener protocol for the synthesis of benzimidazole derivatives, starting from o-phenylenediamine, with different aldehydes is reported. Double-condensation products were selectively obtained when Er(OTf)3 was used as the catalyst in the presence of electron-rich aldehydes. Conversely, the formation of mono-condensation products was the preferred path in absence of this catalyst. One of the major advantages of these reactions was the formation of a single product, avoiding extensive isolation and purification of products, which is frequently associated with these reactions. Theoretical calculations helped to understand the different reactivity established for these reactions. Thus, we found that the charge density on the oxygen of the carbonyl group has a significant impact on the reaction pathway. For instance, electron-rich aldehydes better coordinate to the catalyst, which favours the addition of the amine group to the carbonyl group, therefore facilitating the formation of double-condensation products. Reactions with aliphatic or aromatic aldehydes were possible, without using organic solvents and in a one-pot procedure with short reaction time (2–5 min), affording single products in excellent yields (75–99%). This convenient and eco-friendly methodology offers numerous benefits with respect to other protocols reported for similar compounds. PMID:28144309

Selective and eco-friendly procedures for the synthesis of benzimidazole derivatives. The role of the Er(OTf)3 catalyst in the reaction selectivity.

PubMed

Herrera Cano, Natividad; Uranga, Jorge G; Nardi, Mónica; Procopio, Antonio; Wunderlin, Daniel A; Santiago, Ana N

2016-01-01

An improved and greener protocol for the synthesis of benzimidazole derivatives, starting from o -phenylenediamine, with different aldehydes is reported. Double-condensation products were selectively obtained when Er(OTf) 3 was used as the catalyst in the presence of electron-rich aldehydes. Conversely, the formation of mono-condensation products was the preferred path in absence of this catalyst. One of the major advantages of these reactions was the formation of a single product, avoiding extensive isolation and purification of products, which is frequently associated with these reactions. Theoretical calculations helped to understand the different reactivity established for these reactions. Thus, we found that the charge density on the oxygen of the carbonyl group has a significant impact on the reaction pathway. For instance, electron-rich aldehydes better coordinate to the catalyst, which favours the addition of the amine group to the carbonyl group, therefore facilitating the formation of double-condensation products. Reactions with aliphatic or aromatic aldehydes were possible, without using organic solvents and in a one-pot procedure with short reaction time (2-5 min), affording single products in excellent yields (75-99%). This convenient and eco-friendly methodology offers numerous benefits with respect to other protocols reported for similar compounds.

Chemical oxidation of a malodorous compound, indole, using iron entrapped in calcium alginate beads.

PubMed

Ben Hammouda, Samia; Adhoum, Nafaâ; Monser, Lotfi

2016-01-15

Iron-alginate beads (Fe-ABs) were successfully prepared by the ion-gelation method, and applied as heterogeneous Fenton catalysts for the removal of a malodorous compound 'indole'. Similarly, copper-enriched alginate beads (Cu-ABs) were synthesized and tested as like-Fenton catalyst, however, their application proved not to be effective for this purpose. Fe-ABs catalysts were characterized by FTIR, SEM, EDS and AAS spectroscopy. Results pointed out that the parameters affecting Fenton catalysis must be carefully chosen to avoid excessive iron release. Under optimal conditions, complete indole removal and considerably high reduction of TOC, without significant leaching was achieved. Indole decay followed a pseudo-first-order kinetics. The absolute rate constant for indole hydroxylation was 3.59×10(9) M(-1) s(-1), as determined by the competition kinetics method. Four reaction intermediates (Isatin, Dioxindole, Oxindole and Anthralinic acid) were identified by ULC/MS/MS analysis. Short-chain aliphatic carboxylic acids like formic, acetic, oxalic, maleic, oxamic and pyruvic acids were identified by ion exclusion chromatography and as end-products. Based on the identified by-products, a plausible mineralization pathway was proposed. Moreover, the catalyst was recovered quantitatively by simple filtration and reused for several times without significant loss of activity. Copyright © 2015 Elsevier B.V. All rights reserved.

Ternary PtRuPd/C catalyst for high-performance, low-temperature direct dimethyl ether fuel cells

DOE PAGES

Dumont, Joseph Henry; Martinez, Ulises; Chung, Hoon T.; ...

2016-08-19

Here, dimethyl ether (DME) is a promising alternative fuel option for direct-feed low-temperature fuel cells. Until recently, DME had not received the same attention as alcohol fuels, such as methanol or ethanol, despite its notable advantages. These advantages include a high theoretical open-cell voltage (1.18 V at 25 °C) that is similar to that of methanol (1.21 V), much lower toxicity than methanol, and no need for the carbon–carbon bond scission that is needed in ethanol oxidation. DME is biodegradable, has a higher energy content than methanol (8.2 vs. 6.1 kWh kg –1), and, like methanol, can be synthesized frommore » recycled carbon dioxide. Although the performance of direct DME fuel cells (DDMEFCs) has progressed over the past few years, DDMEFCs have not been viewed as fully viable. In this work, we report much improved performance from the ternary Pt 55Ru 35Pd 10/C anode catalyst, allowing DDMEFCs to compete directly with direct methanol fuel cells (DMFCs). We also report results involving binary Pt alloys as reference catalysts and an in situ infrared electrochemical study to better understand the mechanism of DME electro-oxidation on ternary PtRuPd/C catalysts.« less

Selective Transformation of Various Nitrogen-Containing Exhaust Gases toward N2 over Zeolite Catalysts.

PubMed

Zhang, Runduo; Liu, Ning; Lei, Zhigang; Chen, Biaohua

2016-03-23

In this review we focus on the catalytic removal of a series of N-containing exhaust gases with various valences, including nitriles (HCN, CH3CN, and C2H3CN), ammonia (NH3), nitrous oxide (N2O), and nitric oxides (NO(x)), which can cause some serious environmental problems, such as acid rain, haze weather, global warming, and even death. The zeolite catalysts with high internal surface areas, uniform pore systems, considerable ion-exchange capabilities, and satisfactory thermal stabilities are herein addressed for the corresponding depollution processes. The sources and toxicities of these pollutants are introduced. The important physicochemical properties of zeolite catalysts, including shape selectivity, surface area, acidity, and redox ability, are described in detail. The catalytic combustion of nitriles and ammonia, the direct catalytic decomposition of N2O, and the selective catalytic reduction and direct catalytic decomposition of NO are systematically discussed, involving the catalytic behaviors as well as mechanism studies based on spectroscopic and kinetic approaches and molecular simulations. Finally, concluding remarks and perspectives are given. In the present work, emphasis is placed on the structure-performance relationship with an aim to design an ideal zeolite-based catalyst for the effective elimination of harmful N-containing compounds.

Low Temperature Catalyst for NH3 Removal

NASA Technical Reports Server (NTRS)

Monje, Oscar; Melendez, Orlando

2013-01-01

Air revitalization technologies maintain a safe atmosphere inside spacecraft by the removal of C02, ammonia (NH3), and trace contaminants. NH3 onboard the International Space Station (ISS) is produced by crew metabolism, payloads, or during an accidental release of thermal control refrigerant. Currently, the ISS relies on removing NH3 via humidity condensate and the crew wears hooded respirators during emergencies. A different approach to cabin NH3 removal is to use selective catalytic oxidation (SCO), which builds on thermal catalytic oxidation concepts that could be incorporated into the existing TCCS process equipment architecture on ISS. A low temperature platinum-based catalyst (LTP-Catalyst) developed at KSC was used for converting NH3 to H20 and N2 gas by SCO. The challenge of implementing SCO is to reduce formation of undesirable byproducts like NOx (N20 and NO). Gas mixture analysis was conducted using FTIR spectrometry in the Regenerable VOC Control System (RVCS) Testbed. The RVCS was modified by adding a 66 L semi-sealed chamber, and a custom NH3 generator. The effect of temperature on NH3 removal using the LTP-Catalyst was examined. A suitable temperature was found where NH3 removal did not produce toxic NO, (NO, N02) and N20 formation was reduced.

Chemicals from ethanol: the acetone synthesis from ethanol employing Ce0.75Zr0.25O2, ZrO2 and Cu/ZnO/Al2O3.

PubMed

Rodrigues, Clarissa Perdomo; Zonetti, Priscila da Costa; Appel, Lucia Gorenstin

2017-04-04

Acetone is an important solvent and widely used in the synthesis of drugs and polymers. Currently, acetone is mainly generated by the Cumene Process, which employs benzene and propylene as fossil raw materials. Phenol is a co-product of this synthesis. However, this ketone can be generated from ethanol (a renewable feedstock) in one-step. The aim of this work is to describe the influence of physical-chemical properties of three different catalysts on each step of this reaction. Furthermore, contribute to improve the description of the mechanism of this synthesis. The acetone synthesis from ethanol was studied employing Cu/ZnO/Al 2 O 3 , Ce 0.75 Zr 0.25 O 2 and ZrO 2 . It was verified that the acidity of the catalysts needs fine-tuning in order to promote the oxygenate species adsorption and avoid the dehydration of ethanol. The higher the reducibility and the H 2 O dissociation activity of the catalysts are, the higher the selectivity to acetone is. In relation to the oxides, these properties are associated with the presence of O vacancies. The H 2 generation, which occurs during the TPSR, indicates the redox character of this synthesis. The main steps of the acetone synthesis from ethanol are the generation of acetaldehyde, the oxidation of this aldehyde to acetate species (which reduces the catalyst), the H 2 O dissociation, the oxidation of the catalyst producing H 2 , and, finally, the ketonization reaction. These pieces of information will support the development of active catalysts for not only the acetone synthesis from ethanol, but also the isobutene and propylene syntheses in which this ketone is an intermediate. Graphical abstract Acetone from ethanol.

Enhancing Cooperativity in Bifunctional Acid–Pd Catalysts with Carboxylic Acid-Functionalized Organic Monolayers

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

Coan, Patrick D.; Ellis, Lucas D.; Griffin, Michael B.

Here, cooperative catalysts containing a combination of noble metal hydrogenation sites and Bronsted acid sites are critical for many reactions, including the deoxygenation (DO) of biomass-derived oxygenates in the upgrading of pyrolysis oil. One route toward the design of cooperative catalysts is to tether two different catalytically active functions so that they are in close proximity while avoiding undesirable interactions that can block active sites. Here, we deposited carboxylic acid (CA)-functionalized organophosphonate monolayers onto Al 2O 3-supported Pd nanoparticle catalysts to prepare bifunctional catalysts containing both Bronsted acid and metal sites. Modification with phosphonic acids (PAs) improved activity and selectivitymore » for gas-phase DO reactions, but the degree of improvement was highly sensitive to both the presence and positioning of the CA group, suggesting a significant contribution from both the PA and CA sites. Short spacer lengths of 1-2 methylene groups between the phosphonate head and CA tail were found to yield the best DO rates and selectivities, whereas longer chains performed similarly to self-assembled monolayers having alkyl tails. Results from a combination of density functional theory and Fourier transform infrared spectroscopy suggested that the enhanced catalyst performance on the optimally positioned CAs was due to the generation of strong acid sites on the Al 2O 3 support adjacent to the metal. Furthermore, the high activity of these sites was found to result from a hydrogen-bonded cyclic structure involving cooperativity between the phosphonate head group and CA tail function. More broadly, these results indicate that functional groups tethered to supports via organic ligands can influence catalytic chemistry on metal nanoparticles.« less

Enhancing Cooperativity in Bifunctional Acid–Pd Catalysts with Carboxylic Acid-Functionalized Organic Monolayers

DOE PAGES

Coan, Patrick D.; Ellis, Lucas D.; Griffin, Michael B.; ...

2018-03-05

Here, cooperative catalysts containing a combination of noble metal hydrogenation sites and Bronsted acid sites are critical for many reactions, including the deoxygenation (DO) of biomass-derived oxygenates in the upgrading of pyrolysis oil. One route toward the design of cooperative catalysts is to tether two different catalytically active functions so that they are in close proximity while avoiding undesirable interactions that can block active sites. Here, we deposited carboxylic acid (CA)-functionalized organophosphonate monolayers onto Al 2O 3-supported Pd nanoparticle catalysts to prepare bifunctional catalysts containing both Bronsted acid and metal sites. Modification with phosphonic acids (PAs) improved activity and selectivitymore » for gas-phase DO reactions, but the degree of improvement was highly sensitive to both the presence and positioning of the CA group, suggesting a significant contribution from both the PA and CA sites. Short spacer lengths of 1-2 methylene groups between the phosphonate head and CA tail were found to yield the best DO rates and selectivities, whereas longer chains performed similarly to self-assembled monolayers having alkyl tails. Results from a combination of density functional theory and Fourier transform infrared spectroscopy suggested that the enhanced catalyst performance on the optimally positioned CAs was due to the generation of strong acid sites on the Al 2O 3 support adjacent to the metal. Furthermore, the high activity of these sites was found to result from a hydrogen-bonded cyclic structure involving cooperativity between the phosphonate head group and CA tail function. More broadly, these results indicate that functional groups tethered to supports via organic ligands can influence catalytic chemistry on metal nanoparticles.« less

Electrocatalytic Water Oxidation by a Homogeneous Copper Catalyst Disfavors Single-Site Mechanisms.

PubMed

Koepke, Sara J; Light, Kenneth M; VanNatta, Peter E; Wiley, Keaton M; Kieber-Emmons, Matthew T

2017-06-28

Deployment of solar fuels derived from water requires robust oxygen-evolving catalysts made from earth abundant materials. Copper has recently received much attention in this regard. Mechanistic parallels between Cu and single-site Ru/Ir/Mn water oxidation catalysts, including intermediacy of terminal Cu oxo/oxyl species, are prevalent in the literature; however, intermediacy of late transition metal oxo species would be remarkable given the high d-electron count would fill antibonding orbitals, making these species high in energy. This may suggest alternate pathways are at work in copper-based water oxidation. This report characterizes a dinuclear copper water oxidation catalyst, {[(L)Cu(II)] 2 -(μ-OH) 2 }(OTf) 2 (L = Me 2 TMPA = bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)amine) in which water oxidation proceeds with high Faradaic efficiency (>90%) and moderate rates (33 s -1 at ∼1 V overpotential, pH 12.5). A large kinetic isotope effect (k H /k D = 20) suggests proton coupled electron transfer in the initial oxidation as the rate-determining step. This species partially dissociates in aqueous solution at pH 12.5 to generate a mononuclear {[(L)Cu(II)(OH)]} + adduct (K eq = 0.0041). Calculations that reproduce the experimental findings reveal that oxidation of either the mononuclear or dinuclear species results in a common dinuclear intermediate, {[LCu(III)] 2 -(μ-O) 2 } 2+ , which avoids formation of terminal Cu(IV)═O/Cu(III)-O • intermediates. Calculations further reveal that both intermolecular water nucleophilic attack and redox isomerization of {[LCu(III)] 2 -(μ-O) 2 } 2+ are energetically accessible pathways for O-O bond formation. The consequences of these findings are discussed in relation to differences in water oxidation pathways between Cu catalysts and catalysts based on Ru, Ir, and Mn.

[Detection of toxic substances in microbial fuel cells].

PubMed

Wang, Jiefu; Niu, Hao; Wu, Wenguo

2017-05-25

Microbial fuel cells (MFCs) is a highly promising bioelectrochemical technology and uses microorganisms as catalyst to convert chemical energy directly to electrical energy. Microorganisms in the anodic chamber of MFC oxidize the substrate and generate electrons. The electrons are absorbed by the anode and transported through an external circuit to the cathode for corresponding reduction. The flow of electrons is measured as current. This current is a linear measure of the activity of microorganisms. If a toxic event occurs, microbial activity will change, most likely decrease. Hence, fewer electrons are transported and current decreases as well. In this way, a microbial fuel cell-based biosensor provides a direct measure to detect toxicity for samples. This paper introduces the detection of antibiotics, heavy metals, organic pollutants and acid in MFCs. The existing problems and future application of MFCs are also analyzed.

Toxicity following laundry detergent pod ingestion.

PubMed

Schneir, Aaron B; Rentmeester, Landen; Clark, Richard F; Cantrell, F Lee

2013-06-01

Laundry detergent pods (LDPs) have only recently become available in the United States, and there has been increasing concern regarding pediatric ingestions of them. We describe a 15-month-old female infant who ingested an LDP and had a depressed level of consciousness, metabolic acidosis, pulmonary toxicity, and swallowing difficulties. It is currently unclear what the exact etiologic agent(s) is responsible for the toxicity associated with LDPs. The case demonstrates the potential for significant toxicity following the ingestion of an LDP. Clearly, measures should be taken to avoid ingestions of these products.

Locus-specific microemulsion catalysts for sulfur mustard (HD) chemical warfare agent decontamination.

PubMed

Fallis, Ian A; Griffiths, Peter C; Cosgrove, Terence; Dreiss, Cecile A; Govan, Norman; Heenan, Richard K; Holden, Ian; Jenkins, Robert L; Mitchell, Stephen J; Notman, Stuart; Platts, Jamie A; Riches, James; Tatchell, Thomas

2009-07-22

The rates of catalytic oxidative decontamination of the chemical warfare agent (CWA) sulfur mustard (HD, bis(2-chlororethyl) sulfide) and a range (chloroethyl) sulfide simulants of variable lipophilicity have been examined using a hydrogen peroxide-based microemulsion system. SANS (small-angle neutron scattering), SAXS (small-angle X-ray scattering), PGSE-NMR (pulsed-gradient spin-echo NMR), fluorescence quenching, and electrospray mass spectroscopy (ESI-MS) were implemented to examine the distribution of HD, its simulants, and their oxidation/hydrolysis products in a model oil-in-water microemulsion. These measurements not only present a means of interpreting decontamination rates but also a rationale for the design of oxidation catalysts for these toxic materials. Here we show that by localizing manganese-Schiff base catalysts at the oil droplet-water interface or within the droplet core, a range of (chloroethyl) sulfides, including HD, spanning some 7 orders of octanol-water partition coefficient (K(ow)), may be oxidized with equal efficacy using dilute (5 wt. % of aqueous phase) hydrogen peroxide as a noncorrosive, environmentally benign oxidant (e.g., t(1/2) (HD) approximately 18 s, (2-chloroethyl phenyl sulfide, C(6)H(5)SCH(2)CH(2)Cl) approximately 15 s, (thiodiglycol, S(CH(2)CH(2)OH)(2)) approximately 19 s {20 degrees C}). Our observations demonstrate that by programming catalyst lipophilicity to colocalize catalyst and substrate, the inherent compartmentalization of the microemulsion can be exploited to achieve enhanced rates of reaction or to exert control over product selectivity. A combination of SANS, ESI-MS and fluorescence quenching measurements indicate that the enhanced catalytic activity is due to the locus of the catalyst and not a result of partial hydrolysis of the substrate.

Vanadium and tungsten release from V-based selective catalytic reduction diesel aftertreatment

NASA Astrophysics Data System (ADS)

Liu, Z. Gerald; Ottinger, Nathan A.; Cremeens, Christopher M.

2015-03-01

Vanadium-based selective catalytic reduction (V-SCR) catalysts are currently used for the reduction of nitrogen oxides (NOx) in worldwide diesel applications including Euro IV, V, and VI as well as U.S. nonroad Tier 4 Final. Although V-SCR catalysts are attractive because of their high NOx conversion, low cost, resistance to sulfur poisoning, and ability to reduce hydrocarbon emissions, there is concern that V-SCR washcoat material (e.g., vanadium and tungsten) and its derivatives may be released into the atmosphere, potentially harming human health and the environment. In this study, vanadium and tungsten release measurements are made with both a reactor- and engine-based approach in order to determine the potential release of these metals from diesel exhaust aftertreatment systems that contain a V-SCR catalyst. Results for a commercially available V-SCR reveal that both V and W release begin at 500 °C, and both reactor- and engine-based methods are capable of measuring qualitatively similar release. Emissions with the engine-based method are higher at all temperatures evaluated, likely due to this method's ability to capture particle-phase and vapor-phase emissions which become particle-bound after their evolution from the catalyst surface. Certification relevant data (NRTC and NRSC) from a nonroad engine is used to understand probable emissions from V-SCR aftertreatment architectures. Finally, results from a V-SCR catalyst formulated for improved thermal durability illustrate that it is possible to increase the maximum temperature for V-SCR catalysts. This comprehensive understanding of the temperature dependence of vanadium and tungsten volatility can be used to further analyze the full impact of diesel aftertreatment on exhaust emissions and their impact on human health and environmental toxicity.

Heterolytic Activation of Hydrogen Promoted by Ruthenium Nanoparticles immobilized on Basic Supports and Hydrogenation of Aromatic Compounds

NASA Astrophysics Data System (ADS)

Fang, Minfeng

Despite the aggressive development and deployment of new renewable and nuclear technologies, petroleum-derived transportation fuels---gasoline, diesel and jet fuels---will continue to dominate the markets for decades. Environmental legislation imposes severe limits on the tolerable proportion of aromatics, sulfur and nitrogen contents in transportation fuels, which is difficult to achieve with current refining technologies. Catalytic hydrogenation plays an important role in the production of cleaner fuels, both as a direct means to reduce the aromatics and as a key step in the hydrodenitrogenation (HDN) and hydrodesulfurization (HDS) processes. However, conventional catalysts require drastic conditions and/or are easily poisoned by S or N aromatics. Therefore, there is still a need for new efficient catalysts for hydrogenation reactions relevant to the production of cleaner fossil fuels. Our catalyst design involves metallic nanoparticles intimately associated with a basic support, with the aim of creating a nanostructure capable of promoting the heterolytic activation of hydrogen and ionic hydrogenation mechanisms, as a strategy to avoid catalyst poisoning and enhance catalytic activity. We have designed and prepared a new nanostructured catalytic material composed of RuNPs immobilized on the basic polymer P4VPy. We have demonstrated that the Ru/P4VPy catalyst can promote heterolytic hydrogen activation and a unique surface ionic hydrogenation mechanism for the efficient hydrogenation of N-aromatics. This is the first time these ionic hydrogenation pathways have been demonstrated on solid surfaces. For the RuNPs surfaces without basic sites in close proximity, the conventional homolytic H2 splitting is otherwise involved. Using the mechanistic concepts from Ru/P4VPy, we have designed and prepared the Ru/MgO catalyst, with the aim to improve the catalytic efficiency for the hydrogenation of heteroatom aromatics operating by the ionic hydrogenation mechanism. The Ru/MgO catalyst significantly improves the catalytic efficiency for hydrogenation of a variety of N-/S-heteroaromatics and mono-/polycyclic aromatic hydrocarbons representative of components of petroleum-derived fuels. The catalyst is superior to the few other known supported noble metal catalysts for these reactions. Mechanistic studies also point to the ionic hydrogenation mechanism on the Ru/MgO surfaces. In addition, the Ru/MgO catalyst is highly recyclable and long-lived.

Engineering a more sustainable world through catalysis and green chemistry.

PubMed

Sheldon, Roger A

2016-03-01

The grand challenge facing the chemical and allied industries in the twenty-first century is the transition to greener, more sustainable manufacturing processes that efficiently use raw materials, eliminate waste and avoid the use of toxic and hazardous materials. It requires a paradigm shift from traditional concepts of process efficiency, focusing on chemical yield, to one that assigns economic value to replacing fossil resources with renewable raw materials, eliminating waste and avoiding the use of toxic and/or hazardous substances. The need for a greening of chemicals manufacture is readily apparent from a consideration of the amounts of waste generated per kilogram of product (the E factors) in various segments of the chemical industry. A primary source of this waste is the use of antiquated 'stoichiometric' technologies and a major challenge is to develop green, catalytic alternatives. Another grand challenge for the twenty-first century, driven by the pressing need for climate change mitigation, is the transition from an unsustainable economy based on fossil resources--oil, coal and natural gas--to a sustainable one based on renewable biomass. In this context, the valorization of waste biomass, which is currently incinerated or goes to landfill, is particularly attractive. The bio-based economy involves cross-disciplinary research at the interface of biotechnology and chemical engineering, focusing on the development of green, chemo- and biocatalytic technologies for waste biomass conversion to biofuels, chemicals and bio-based materials. Biocatalysis has many benefits to offer in this respect. The catalyst is derived from renewable biomass and is biodegradable. Processes are performed under mild conditions and generally produce less waste and are more energy efficient than conventional ones. Thanks to modern advances in biotechnology 'tailor-made' enzymes can be economically produced on a large scale. However, for economic viability it is generally necessary to recover and re-use the enzyme and this can be achieved by immobilization, e.g. as solid cross-linked enzyme aggregates (CLEAs), enabling separation by filtration or centrifugation. A recent advance is the use of 'smart', magnetic CLEAs, which can be separated magnetically from reaction mixtures containing suspensions of solids; truly an example of cross-disciplinary research at the interface of physical and life sciences, which is particularly relevant to biomass conversion processes. © 2016 The Author(s).

Engineering a more sustainable world through catalysis and green chemistry

PubMed Central

2016-01-01

The grand challenge facing the chemical and allied industries in the twenty-first century is the transition to greener, more sustainable manufacturing processes that efficiently use raw materials, eliminate waste and avoid the use of toxic and hazardous materials. It requires a paradigm shift from traditional concepts of process efficiency, focusing on chemical yield, to one that assigns economic value to replacing fossil resources with renewable raw materials, eliminating waste and avoiding the use of toxic and/or hazardous substances. The need for a greening of chemicals manufacture is readily apparent from a consideration of the amounts of waste generated per kilogram of product (the E factors) in various segments of the chemical industry. A primary source of this waste is the use of antiquated ‘stoichiometric’ technologies and a major challenge is to develop green, catalytic alternatives. Another grand challenge for the twenty-first century, driven by the pressing need for climate change mitigation, is the transition from an unsustainable economy based on fossil resources—oil, coal and natural gas—to a sustainable one based on renewable biomass. In this context, the valorization of waste biomass, which is currently incinerated or goes to landfill, is particularly attractive. The bio-based economy involves cross-disciplinary research at the interface of biotechnology and chemical engineering, focusing on the development of green, chemo- and biocatalytic technologies for waste biomass conversion to biofuels, chemicals and bio-based materials. Biocatalysis has many benefits to offer in this respect. The catalyst is derived from renewable biomass and is biodegradable. Processes are performed under mild conditions and generally produce less waste and are more energy efficient than conventional ones. Thanks to modern advances in biotechnology ‘tailor-made’ enzymes can be economically produced on a large scale. However, for economic viability it is generally necessary to recover and re-use the enzyme and this can be achieved by immobilization, e.g. as solid cross-linked enzyme aggregates (CLEAs), enabling separation by filtration or centrifugation. A recent advance is the use of ‘smart’, magnetic CLEAs, which can be separated magnetically from reaction mixtures containing suspensions of solids; truly an example of cross-disciplinary research at the interface of physical and life sciences, which is particularly relevant to biomass conversion processes. PMID:27009181

The relationship of work avoidance and learning goals to perceived competence, externality and meaning.

PubMed

Seifert, T L; O'Keefe, B A

2001-03-01

Motivational researchers have suggested that work avoidance may be an academic goal in which students seek to minimise the amount of work they do in school. Additionally, research has also suggested that emotions may be catalysts for goals. This study examined the relationship between emotions and learning or work avoidance goals. Do emotions explain goals? The participants were 512 senior high school students in Eastern Canada. Students completed a survey assessing motivation related constructs. A structural equation model was postulated in which students' affect predicted learning goals and work avoidant goals. A cluster analysis of affect scores was performed followed by between-group and within-group contrasts of goal scores. The structural equation model suggested that a sense of competence and control were predictive of a learning goal while lack of meaning was related to work avoidance. The cluster analysis showed that confidence and control were associated with a learning goal but that a sense of inadequacy, lack of control or lack of meaning could give rise to work avoidance. Emotions seem to be directly linked to goals. Teachers who foster feelings of self-assuredness will be helping students develop learning goals. Students who feel less competent, bored or have little control will adopt work avoidant goals.

[Wet oxidation of toxic industrial waste with oxygenated water].

PubMed

Alfieri, M; Colombo, G; Velotti, R

1991-01-01

The industrial toxic waste streams hot treatment technology with hydrogen peroxide and catalysts, developed by the research laboratories of Montefluos in Bollate, allows the abatement of many organic and bio-toxic pollutants. Some treatment examples are here reported. The examples, performed on a laboratory scale, relate to industrial waste streams with a high COD (100000-200000 mg/l) in which it was possible to obtain an abatement over the 90% of pollutants like phenols, formaldehyde, dimethylformamide and phenyl acetate. The application range of this technology is similar to that of oxygen or air wet oxidation, but it has remarkable advantages due to the lower plant, maintenance and energy costs, because the treatment is performed using much more bland conditions (atmospheric pressure and 90-100 degrees C of temperature). The aim of the bio-toxic pollutants abatement and COD reduction (70-80%) is to allow the final bio-digestion waste streams with high organic content, but too diluted to be directly incenerated at a suitable cost.

In vitro investigation of oxide nanoparticle and carbon nanotube toxicity and intracellular accumulation in A549 human pneumocytes.

PubMed

Simon-Deckers, A; Gouget, B; Mayne-L'hermite, M; Herlin-Boime, N; Reynaud, C; Carrière, M

2008-11-20

If released in the environment, nanomaterials might be inhaled by populations and cause damage to the deepest regions of the respiratory tract, i.e., the alveolar compartment. To model this situation, we studied the response of A549 human pneumocytes after exposure to aluminium oxide or titanium oxide nanoparticles, and to multi-walled carbon nanotubes. The influence of size, crystalline structure and chemical composition was investigated. After a detailed identification of nanomaterial physico-chemical characteristics, cells were exposed in vitro and viability and intracellular accumulation were assessed. In our conditions, carbon nanotubes were more toxic than metal oxide nanoparticles. Our results confirmed that both nanotubes and nanoparticles are able to rapidly enter into cells, and distribute in the cytoplasm and intracellular vesicles. Among nanoparticles, we demonstrate significant difference in biological response as a function of size, crystalline phase and chemical composition. Their toxicity was globally lower than nanotubes toxicity. Among nanotubes, the length did not influence cytotoxicity, neither the presence of metal catalyst impurities.

Responses of Earthworm to Aluminum Toxicity in Latosol

Treesearch

Jia-En Zhang; Jiayu Yu; Ying Ouyang; Huaqin Xu

2012-01-01

Excess aluminum (Al) in soils due to acid rain leaching is toxic to water resources and harmful to soil organisms and plants. This study investigated adverse impacts of Al levels upon earthworms (Eisenia fetida) from the latosol (acidic red soil). Laboratory experiments were performed to examine the survival and avoidance of earthworms from high Al...

Process for detoxifying coal tars

DOEpatents

Longwell, John P.; Peters, William A.

1983-01-01

A process for treating liquid hydrocarbons to remove toxic, mutagenic and/or carcinogenic aromatic hydrocarbons comprises feeding the hydrocarbons into a reactor where vapors are thermally treated in contact with a catalyst consisting essentially of calcium oxide or a calcium oxide containing mineral. Thermally treating liquid hydrocarbons in contact with calcium oxide preferentially increases the cracking of aromatics thus producing a product having a reduced amount of aromatic compounds.

Synthesis of an Imidazolidinone Organocatalyst and Its Application in a Diels-Alder Cycloaddition: A Multistep Experiment for the Organic Teaching Laboratory

ERIC Educational Resources Information Center

Murphy, John J.; Driver, Ross B.; Walsh, Ria; Stephens, John C.

2016-01-01

The development of novel, high-yielding, and selective methodologies for the asymmetric synthesis of stereocenters is at the forefront of modern synthetic chemistry research. Organocatalysis can now be viewed as a viable alternative to the use of the sometimes toxic transition-metal catalysts. In this experiment, the simple synthesis of an achiral…

Avoidance behaviour of Enchytraeus albidus: effects of benomyl, carbendazim, phenmedipham and different soil types.

PubMed

Amorim, Mónica J B; Römbke, Jörg; Soares, Amadeu M V M

2005-04-01

Enchytraeids are typical inhabitants of many soils, contributing to vital processes of this environmental compartment. Indirectly they are involved in regulating the degradation of organic matter, as well as improving the pore structure of the soil. Due to their behaviour, they are able to avoid unfavourable environmental conditions. Avoidance tests with enchytraeids, initially developed with earthworms by several authors, are quick and easy to perform. With these tests a first assessment of the toxicity of a (contaminated or spiked) soil is possible in just 48 h by using the reaction of the enchytraeids as measurement endpoint. In this period of time the organisms can choose between the control soil and the other soil (a contaminated or spiked or another soil with different physico-chemical properties). In the tests reported here, the enchytraeids were exposed to control soils spiked with the fungicides Benomyl and Carbendazim and the herbicide Phenmedipham. Several chemical concentrations were tested in order to evaluate the avoidance behaviour to toxic substances. In fact, often these short-term screening tests gave results showing avoidance at concentrations in a range similar to the acute test results but, higher than in chronic tests. Further tests are needed to decide whether the results gained in this study can be extrapolated to other chemicals. It is proposed to standardize the Enchytraeid Avoidance Test as it is currently done for the Earthworm Avoidance Test by the International Standard Organization (ISO).

Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation

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

Marcinkowski, Matthew D.; Darby, Matthew T.; Liu, Jilei

The recent availability of shale gas has led to a renewed interest in C-H bond activation as the first step towards synthesis of fuels and fine chemicals. Heterogeneous catalysts based on Ni and Pt can perform this chemistry, but deactivate easily due to coke formation. Cu- based catalysts are not practical for this chemistry due to high C-H activation barriers, but their weaker binding to adsorbates offers resilience to coking. Utilizing Pt/Cu single atom alloys (SAAs) we examine C-H activation in a number of systems including methyl groups, methane, and butane using a combination of simulations, surface science, and catalysismore » studies. We find that Pt/Cu SAAs activate C-H bonds more efficiently than Cu, are stable for days under realistic operating conditions, and avoid the problem of coking typically encountered with Pt. Pt/Cu SAAs therefore offer a new approach to coke resistant C-H activation chemistry with the added economic benefit that the precious metal is diluted at the atomic limit.« less

KSC-2014-4377

NASA Image and Video Library

2014-11-03

CAPE CANAVERAL, Fla. - Rob Mueller, left, NASA senior technologist in the Surface Systems Office in Kennedy Space Center's Engineering and Technology Directorate, talks with former NASA Apollo astronaut Buzz Aldrin during a demonstration of the Regolith Advanced Surface System Operations Robot, or RASSOR, at the automated landing and hazard avoidance technology, or ALHAT, hazard field at the north end of the Shuttle Landing Facility at NASA's Kennedy Space Center in Florida. The event was held to announce Moon Express Inc., of Moffett Field, California is selected to utilize Kennedy facilities for NASA's Lunar Cargo Transportation and Landing by Soft Touchdown, or Lunar CATALYST, initiative. Moon Express is developing a lander with capabilities that will enable delivery of payloads to the surface of the moon, as well as new science and exploration missions of interest to NASA and scientific and academic communities. Moon Express will base its activities at Kennedy and utilize the Morpheus ALHAT field and a hangar nearby for CATALYST testing. The Advanced Exploration Systems Division of NASA's Human Exploration and Operations Mission Directorate manages Lunar CATALYST. Photo credit: NASA/Ben Smegelsky

KSC-2014-4378

NASA Image and Video Library

2014-11-03

CAPE CANAVERAL, Fla. - Rob Mueller, left, NASA senior technologist in the Surface Systems Office in Kennedy Space Center's Engineering and Technology Directorate, talks with former NASA Apollo astronaut Buzz Aldrin during a demonstration of the Regolith Advanced Surface Systems Operations Robot, or RASSOR, at the automated landing and hazard avoidance technology, or ALHAT, hazard field at the north end of the Shuttle Landing Facility at NASA's Kennedy Space Center in Florida. The event was held to announce Moon Express Inc., of Moffett Field, California is selected to utilize Kennedy facilities for NASA's Lunar Cargo Transportation and Landing by Soft Touchdown, or Lunar CATALYST, initiative. Moon Express is developing a lander with capabilities that will enable delivery of payloads to the surface of the moon, as well as new science and exploration missions of interest to NASA and scientific and academic communities. Moon Express will base its activities at Kennedy and utilize the Morpheus ALHAT field and a hangar nearby for CATALYST testing. The Advanced Exploration Systems Division of NASA's Human Exploration and Operations Mission Directorate manages Lunar CATALYST. Photo credit: NASA/Ben Smegelsky

Etherification of biodiesel-derived glycerol with ethanol for fuel formulation over sulfonic modified catalysts.

PubMed

Melero, Juan A; Vicente, Gemma; Paniagua, Marta; Morales, Gabriel; Muñoz, Patricia

2012-01-01

The present study is focused on the etherification of biodiesel-derived glycerol with anhydrous ethanol over arenesulfonic acid-functionalized mesostructured silicas to produce ethyl ethers of glycerol that can be used as gasoline or diesel fuel biocomponents. Within the studied range, the best conditions to maximize glycerol conversion and yield towards ethyl-glycerols are: T=200 °C, ethanol/glycerol molar ratio=15/1, and catalyst loading=19 wt%. Under these reaction conditions, 74% glycerol conversion and 42% yield to ethyl ethers have been achieved after 4 h of reaction but with a significant presence of glycerol by-products. In contrast, lower reaction temperatures (T=160 °C) and moderate catalyst loading (14 wt%) in presence of a high ethanol concentration (ethanol/glycerol molar ratio=15/1) are necessary to avoid the formation of glycerol by-products and maximize ethyl-glycerols selectivity. Interestingly, a close catalytic performance to that achieved using high purity glycerol has been obtained with low-grade water-containing glycerol. Copyright © 2011 Elsevier Ltd. All rights reserved.

Application of surface modified nano ferrite nickel in catalytic reaction (epoxidation of alkenes) and investigation on its antibacterial and antifungal activities.

PubMed

Golkhatmi, Faezeh Mahdinejad; Bahramian, Bahram; Mamarabadi, Mojtaba

2017-09-01

Newly, magnetic nanoparticles have extensively been used as alternative catalyst supports, in the view of their high surface area which results in high catalyst loading capacity, high dispersion, low toxicity, environmental preservation, distinguished stability, and suitable catalyst reusing. In the present study, the magnetite nanoparticles, NiFe 2 O 4 @Ag and NiFe 2 O 4 @Mo, were synthesized and characterized. The antimicrobial activities and catalytic properties of synthesized nanoparticles were tested afterwards. For synthetizing the nanoparticle NiFe 2 O 4 @Ag, silver ions were loaded onto the surface of the modified NiFe 2 O 4 and reduced to silver crystal by adding NaBH 4 . The antibacterial effects of NiFe 2 O 4 @Ag were examined against two species of soil and plant related bacteria named Bacillus subtilis (gram positive) and Pseudomonas syringae (gram negative), respectively. The antifungal activity of this nanoparticle was evaluated against two species of plant pathogenic fungi called Alternaria solani and Fusarium oxysporum. Biological results indicated that the synthesized material has shown an excellent antibacterial and antifungal activity against all examined bacteria and fungi so that, their growth were completely inhibited 24h after treatment with NiFe 2 O 4 @Ag. For the synthesis of a heterogeneous catalyst NiFe 2 O 4 @Mo, complex Mo(CO) 6 was loaded onto the surface of the modified NiFe 2 O 4 nanoparticle. This catalyst was found as an efficient catalyst for epoxidation of cis-cyclooctene and a wide variety of alkenes, including aromatic and aliphatic terminal ones using tert-butyl hydroperoxide as oxidant. This new heterogenized catalyst could easily be recovered by using a magnetic separator and reused four consecutive and loss only 13% of its catalytic activity. Copyright © 2017 Elsevier B.V. All rights reserved.

Acute and subchronic toxicity of naturally weathered Exxon Valdez crude oil in mallards and ferrets

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

Stubblefield, W.A.; Hancock, G.A.; Ford, W.H.

1995-11-01

The toxic properties of naturally weathered Exxon Valdez crude oil (WEVC) were assessed in a battery of acute and subchronic toxicity tests using mallards, Anas platyrhynchos, and European ferrets, Mustela putorius. Adult mallard acute oral toxicity study results indicated no mortalities or signs o toxicity, i.e., no-observed-adverse-effect level (NOAEL) and median lethal dose (LD50) > 5,000 mg/kg. Acute oral feeding and food avoidance tests with ducklings also indicated no toxicity (NOAEL and LC50 > 50,000 mg/kg diet) with no evidence of food avoidance (FAC50 > 20,000 mg/kg diet). No mortalities or toxic signs were noted in a 14-d feeding studymore » with adult birds at dietary concentrations up to 100,000 mg WEVC/kg diet. Among clinical and physiological end points evaluated, the only significant difference noted was an increase in liver: body weight ratios in the 100,000-mg WEVC/kg diet dose group. No differences in clinical chemistry or hematological parameters were noted, and there were no consistent differences in histological evaluations of organ tissues. Daily oral doses of up to 5,000 mg/kg of WEVC over 5 d resulted in minimal effects on ferrets. Increased serum albumin concentrations were observed in the 5,000-mg/kg dose group females and decreased spleen weights were noted in females of all WEVC treatment groups. No other significant observations were noted.« less

Proposed modification to avoidance test with Eisenia fetida to assess metal toxicity in agricultural soils affected by mining activities.

PubMed

Delgadillo, Víctor; Verdejo, José; Mondaca, Pedro; Verdugo, Gabriela; Gaete, Hernán; Hodson, Mark E; Neaman, Alexander

2017-06-01

Use of avoidance tests is a quick and cost-effective method of assessing contaminants in soils. One option for assessing earthworm avoidance behavior is a two-section test, which consists of earthworms being given the choice to move between a test soil and a control substrate. For ecological relevance, tested soils should be field-contaminated soils. For practical reasons, artificial soils are commonly used as the control substrate. Interpretation of the test results compromised when the test soil and the artificial substrate differ in their physico-chemical properties other than just contaminants. In this study we identified the physico-chemical properties that influence avoidance response and evaluated the usefulness of adjusting these in the control substrate in order to isolate metal-driven avoidance of field soils by earthworms. A standardized two-section avoidance test with Eisenia fetida was performed on 52 uncontaminated and contaminated (Cu >155mgkg -1 , As >19mgkg -1 ) agricultural soils from the Aconcagua River basin and the Puchuncaví Valley in Chile. Regression analysis indicated that the avoidance response was determined by soil organic matter (OM), electrical conductivity (EC) and total soil Cu. Organic matter content of the artificial substrate was altered by peat additions and EC by NaCl so that these properties matched those of the field soils. The resultant EC 80 for avoidance (indicative of soils of "limited habitat") was 433mg Cu kg -1 (339 - 528mgkg -1 95% confidence intervals). The earthworm avoidance test can be used to assess metal toxicity in field-contaminated soils by adjusting physico-chemical properties (OM and EC) of the artificial control substrate in order to mimic those of the field-collected soil. Copyright © 2017 Elsevier Inc. All rights reserved.

Optimization of biodiesel production process using recycled vegetable oil

NASA Astrophysics Data System (ADS)

Lugo, Yarely

Petro diesel toxic emissions and its limited resources have created an interest for the development of new energy resources, such as biodiesel. Biodiesel is traditionally produced by a transesterification reaction between vegetable oil and an alcohol in the presence of a catalyst. However, this process is slow and expensive due to the high cost of raw materials. Low costs feedstock oils such as recycled and animal fats are available but they cannot be transesterified with alkaline catalysts due to high content of free fatty acids, which can lead to undesirable reactions such as saponification. In this study, we reduce free fatty acids content by using an acid pre-treatment. We compare sulfuric acid, hydrochloric acid and ptoluenesulfonic acid (PTSA) to pre-treat recycled vegetable oil. PTSA removes water after 60 minutes of treatment at room temperature or within 15 minutes at 50°C. The pretreatment was followed by a transesterification reaction using alkaline catalyst. To minimize costs and accelerate reaction, the pretreatment and transesterification reaction of recycle vegetable oil was conducted at atmospheric pressure in a microwave oven. Biodiesel was characterized using a GC-MS method.

Catalytic efficiency of macrocyclic-capped gold nanoparticles: cucurbit[n]urils versus cyclodextrins

NASA Astrophysics Data System (ADS)

del Pozo, María; Blanco, Elías; Hernández, Pedro; Casas, José A.; Quintana, Carmen

2018-05-01

In this work, different macrocyclic systems, belonging to cucurbit[n]urils and cyclodextrins families, were employed as stabilizers of gold nanoparticles and their performance as catalysts in the reduction reaction of the toxic 4-nitrophenol to produce the valuable 4-aminophenol, was evaluated. To this goal, six nanosystems were prepared and compared under identical experimental conditions. The influence that (i) differences in shape, (ii) nature of chemical groups constituting the receptor entrances and (iii) differences in the portal sizes of those stabilizing agents have in the activity of these nanoparticles as catalysts in a nitro compound reduction reaction is evaluated and discussed. The TEM characterization of the nanocatalysts prepared is included. From these data, nanoparticles ranging from 3.7-10.7 nm in diameter, depending on the stabilizer employed, were obtained. The evaluation of kinetic rate constants normalized respect to gold concentration and catalyst surface for each system is included and discussed. In addition, the stability of the different nanocatalyst depending on the capping agent employed is also evaluated. [Figure not available: see fulltext.

Impact of Contaminants Present in Coal-Biomass Derived Synthesis Gas on Water-gas Shift and Fischer-Tropsch Synthesis Catalysts

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

Alptekin, Gokhan

2013-02-15

Co-gasification of biomass and coal in large-scale, Integrated Gasification Combined Cycle (IGCC) plants increases the efficiency and reduces the environmental impact of making synthesis gas ("syngas") that can be used in Coal-Biomass-to-Liquids (CBTL) processes for producing transportation fuels. However, the water-gas shift (WGS) and Fischer-Tropsch synthesis (FTS) catalysts used in these processes may be poisoned by multiple contaminants found in coal-biomass derived syngas; sulfur species, trace toxic metals, halides, nitrogen species, the vapors of alkali metals and their salts (e.g., KCl and NaCl), ammonia, and phosphorous. Thus, it is essential to develop a fundamental understanding of poisoning/inhibition mechanisms before investingmore » in the development of any costly mitigation technologies. We therefore investigated the impact of potential contaminants (H 2S, NH 3, HCN, AsH 3, PH 3, HCl, NaCl, KCl, AS 3, NH 4NO 3, NH 4OH, KNO 3, HBr, HF, and HNO 3) on the performance and lifetime of commercially available and generic (prepared in-house) WGS and FT catalysts.« less

Activated carbon as catalyst for microwave-assisted wet peroxide oxidation of aromatic hydrocarbons.

PubMed

Garcia-Costa, Alicia L; Lopez-Perela, Lucia; Xu, Xiyan; Zazo, Juan A; Rodriguez, Juan J; Casas, Jose A

2018-05-21

This paper addresses the removal of four aromatic hydrocarbons typically found in petrochemical wastewater: benzene (B), toluene (T), o-xylene (X), and naphthalene (N), by microwave-assisted catalytic wet peroxide oxidation (MW-CWPO) using activated carbon (AC) as catalyst. Under the studied conditions, complete pollutant elimination (B, 1.28 mM; T, 1.09 mM; X, 0.94 mM; and N, 0.78 mM) was achieved, with more than 90% TOC removal after only 15-min reaction time, working at 120 °C, pH 0  = 3, AC at 1 g L -1 , and H 2 O 2 at the stoichiometric dose. Furthermore, in the case of toluene, naphthalene, and xylene, the hydroxylation and breakdown of the ring is very rapid and toxic intermediates were not detected. The process follows two steps: (i) pollutant adsorption onto AC followed by (ii) adsorbed compounds oxidation. Thus, MW-CWPO with AC as catalyst appears a promising way for a fast and effective process for B, T, X, and N removal in aqueous phase.

The Production of Biodiesel and Bio-kerosene from Coconut Oil Using Microwave Assisted Reaction

NASA Astrophysics Data System (ADS)

SAIFUDDIN, N.; SITI FAZLILI, A.; KUMARAN, P.; PEI-JUA, N.; PRIATHASHINI, P.

2016-03-01

Biofuels including biodiesel, an alternative fuel, is renewable, environmentally friendly, non-toxic and low emissions. The raw material used in this work was coconut oil, which contained saturated fatty acids about 90% with high percentage of medium chain (C8-C12), especially lauric acid and myristic acid. The purpose of this research was to study the effect of power and NaOH catalyst in transesterification assisted by microwave for production of biofuels (biodiesel and bio-kerosene) derived from coconut oil. The reaction was performed with oil and methanol using mole ratio of 1:6, catalyst concentration of 0.6% with microwave power at 100W, 180W, 300W, 450W, 600W, and 850W. The reaction time was set at of 3, 5, 7, 10 and 15 min. The results showed that microwave could accelerate the transesterification process to produce biodiesel and bio-kerosene using NaOH catalyst. The highest yield of biodiesel was 97.17 %, or 99.05 % conversion at 5 min and 100W microwave power. Meanwhile, the bio-kerosene obtained was 65% after distillation.

Toxicity of thermal degradation products of spacecraft materials

NASA Technical Reports Server (NTRS)

Lawrence, W. H.; Turner, J. E.; Sanford, C.; Foster, S.; Baldwin, E.; Oconnor, J.

1982-01-01

Three polymeric materials were evaluated for relative toxicity of their pyrolysis products to rats by inhalation: Y-7683 (LS 200), Y-7684 (Vonar 3 on Fiberglass), and Y-7685 (Vonar 3 on N W Polyester). Criteria employed for assessing relative toxicity were (1) lethality from in-chamber pyrolysis, (2) lethality from an outside-of-chamber pyrolysis MSTL Procedure, and (3) disruption of trained rats' shock-avoidance performance during sub-lethal exposures to in-chamber pyrolysis of the materials.

Direct Assessment of the Toxicity of Molybdenum Disulfide Atomically Thin Film and Microparticles via Cytotoxicity and Patch Testing.

PubMed

Chen, Weibing; Qi, Wenjin; Lu, Wei; Chaudhury, Nikhil Roy; Yuan, Jiangtan; Qin, Lidong; Lou, Jun

2018-03-01

The low toxicity of molybdenum disulfide (MoS 2 ) atomically thin film and microparticles is confirmed via cytotoxicity and patch testing in this report. The toxicity of MoS 2 thin film and microparticles is extensively studied but is still inconclusive due to potential organic contamination in the preparations of samples. Such contamination is avoided here through preparing MoS 2 atomically thin film via direct sulfurization of molybdenum thin film on quartz plate, which permits a direct assessment of its toxicity without any contamination. Six different types of cells, including normal, cancer, and immortal cells, are cultured in the media containing MoS 2 thin film on quartz plates or dispersed MoS 2 microparticles and their viability is evaluated with respect to the concentrations of samples. Detached thin films from the quartz plates are also investigated to estimate the toxicity of dispersed MoS 2 in biological media. Allergy testing on skin of guinea pigs is also conducted to understand their effect on animal skins. By avoiding possible organic contamination, the low toxicity of MoS 2 atomically thin film and microparticles to cells and animal skins paves the way for its applications in flexible biosensing/bioimaging devices and biocompatible coatings. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

WE-AB-202-01: Evaluating the Toxicity Reduction with CT-Ventilation Functional Avoidance Radiation Therapy

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

Vinogradskiy, Y; Miyasaka, Y; Kadoya, N

Purpose: CT-ventilation is an exciting new imaging modality that uses 4DCTs to calculate lung ventilation. Studies have proposed to use 4DCT-ventilation imaging for functional avoidance radiotherapy which implies designing treatment plans to spare functional portions of the lung. Although retrospective studies have been performed to evaluate the dosimetric gains to functional lung; no work has been done to translate the dosimetric gains to an improvement in pulmonary toxicity. The purpose of our work was to evaluate the potential reduction in toxicity for 4DCT-ventilation based functional avoidance. Methods: 70 lung cancer patients with 4DCT imaging were used for the study. CT-ventilationmore » maps were calculated using the patient’s 4DCT, deformable image registrations, and a density-change-based algorithm. Radiation pneumonitis was graded using imaging and clinical information. Log-likelihood methods were used to fit a normal-tissue-complication-probability (NTCP) model predicting grade 2+ radiation pneumonitis as a function of doses (mean and V20) to functional lung (>15% ventilation). For 20 patients a functional plan was generated that reduced dose to functional lung while meeting RTOG 0617-based constraints. The NTCP model was applied to the functional plan to determine the reduction in toxicity with functional planning Results: The mean dose to functional lung was 16.8 and 17.7 Gy with the functional and clinical plans respectively. The corresponding grade 2+ pneumonitis probability was 26.9% with the clinically-used plan and 24.6% with the functional plan (8.5% reduction). The V20-based grade 2+ pneumonitis probability was 23.7% with the clinically-used plan and reduced to 19.6% with the functional plan (20.9% reduction). Conclusion: Our results revealed a reduction of 9–20% in complication probability with functional planning. To our knowledge this is the first study to apply complication probability to convert dosimetric results to toxicity improvement. The results presented in the current work provide seminal data for prospective clinical trials in functional avoidance. YV discloses funding from State of Colorado. TY discloses National Lung Cancer Partnership; Young Investigator Research grant.« less

Evolutionary Responses to Invasion: Cane Toad Sympatric Fish Show Enhanced Avoidance Learning

PubMed Central

Caller, Georgina; Brown, Culum

2013-01-01

The introduced cane toad (Bufo marinus) poses a major threat to biodiversity due to its lifelong toxicity. Several terrestrial native Australian vertebrates are adapting to the cane toad’s presence and lab trials have demonstrated that repeated exposure to B. marinus can result in learnt avoidance behaviour. Here we investigated whether aversion learning is occurring in aquatic ecosystems by comparing cane toad naïve and sympatric populations of crimson spotted rainbow fish (Melanotaenia duboulayi). The first experiment indicated that fish from the sympatric population had pre-existing aversion to attacking cane toad tadpoles but also showed reduced attacks on native tadpoles. The second experiment revealed that fish from both naïve and sympatric populations learned to avoid cane toad tadpoles following repeated, direct exposure. Allopatric fish also developed a general aversion to tadpoles. The aversion learning abilities of both groups was examined using an experiment involving novel distasteful prey items. While both populations developed a general avoidance of edible pellets in the presence of distasteful pellets, only the sympatric population significantly reduced the number of attacks on the novel distasteful prey item. These results indicate that experience with toxic prey items over multiple generations can enhance avoidance leaning capabilities via natural selection. PMID:23372788

[Safety evaluation and risk control measures of Cassiae Semen].

PubMed

Zhao, Yi-Meng; Wu, Li; Zhang, Shuo; Zhang, Li; Gao, Xue-Min; Sun, Xiao-Bo; Wang, Chun

2017-11-01

In this study, the authors reviewed domestic and foreign literatures, conducted the textual research on origin and development of Cassia Semen, studied records in ancient books and ancient and modern literatures, clinical adverse reactions and relevant experimental studies in recent years, and summarized the clinical features and influencing factors related to the safety of Cassiae Semen. According to the findings,Cassia Semen's safety risks are mainly liver and kidney system damages, with the main clinical features of fatigue, anorexia, disgusting of oil, yellow urine and gray stool; digestive system injury, with the main clinical features of diarrhea, abdominal distension, nausea and loose stool; reproductive system damage, with the main clinical features of vaginal bleeding. Allergic reactions and clinical adverse events, with the main clinical features for numb mouth, itching skin, nausea and vomiting, diarrhea, wheezing and lip cyanosis were also reported. The toxicological studies on toxic components of Cassiae Semen obtusifolia were carried out through acute toxicity test, subacute toxicity test, subchronic toxicity test and chronic toxicity test. Risk factors might include patients, compatibility and physicians. Physicians should strictly abide by the medication requirements in the Pharmacopoeia, pay attention to rational compatibility, appropriate dosage,correct usage and appropriate processing, control the dosage below 15 g to avoid excessive intake, strictly control the course of treatment to avoid accumulated poisoning caused by long-term administration. At the same time, clinicians should pay attention to the latest research progress, update the knowledge structure, quickly find the latest and useful materials from clinical practice, scientific research and drug information and other literatures, make evaluation and judgment for the materials, establish a traditional Chinese medicine intelligence information library, and strengthen the control over adverse effects with a pre-warning consciousness. The authors suggested standardizing clinical medication of Cassiae Semen, and avoiding misuse or excessive use; clinicians should prescribe it in strict accordance with there commended usage and dosage in the Pharmacopoeia, and focus on the safety signal accumulation in clinic, while strengthening studies for toxic substance basis and toxicity mechanism, in order to give full play to Cassiae Semen's clinical efficacy and reduce its adverse reactions. Copyright© by the Chinese Pharmaceutical Association.

Patient- and therapy-related factors associated with the incidence of xerostomia in nasopharyngeal carcinoma patients receiving parotid-sparing helical tomotherapy.

PubMed

Lee, Tsair-Fwu; Liou, Ming-Hsiang; Ting, Hui-Min; Chang, Liyun; Lee, Hsiao-Yi; Wan Leung, Stephen; Huang, Chih-Jen; Chao, Pei-Ju

2015-08-20

We investigated the incidence of moderate to severe patient-reported xerostomia among nasopharyngeal carcinoma (NPC) patients treated with helical tomotherapy (HT) and identified patient- and therapy-related factors associated with acute and chronic xerostomia toxicity. The least absolute shrinkage and selection operator (LASSO) normal tissue complication probability (NTCP) models were developed using quality-of-life questionnaire datasets from 67 patients with NPC. For acute toxicity, the dosimetric factors of the mean doses to the ipsilateral submandibular gland (Dis) and the contralateral submandibular gland (Dcs) were selected as the first two significant predictors. For chronic toxicity, four predictive factors were selected: age, mean dose to the oral cavity (Doc), education, and T stage. The substantial sparing data can be used to avoid xerostomia toxicity. We suggest that the tolerance values corresponded to a 20% incidence of complications (TD20) for Dis = 39.0 Gy, Dcs = 38.4 Gy, and Doc = 32.5 Gy, respectively, when mean doses to the parotid glands met the QUANTEC 25 Gy sparing guidelines. To avoid patient-reported xerostomia toxicity, the mean doses to the parotid gland, submandibular gland, and oral cavity have to meet the sparing tolerance, although there is also a need to take inherent patient characteristics into consideration.

Ozone Contamination in Aircraft Cabins. Appendix B: Overview papers. Flight 8 planning to avoid high ozone

NASA Technical Reports Server (NTRS)

Belmont, A. D.

1979-01-01

The problem of preventing cabin ozone from exceeding a given standard was investigated. Statistical analysis of vertical distribution of ozone is summarized. The cost, logistics, maintenance, ability to forecast ozone, and avoiding high ozone concentrations are presented. Filtering approaches and the requirements to remove ozone toxicity are discussed.

A Hard X-ray Study of a Manganese-Terpyridine Dimer Catalyst in a Chromium-based Metal Organic Framework - Oral Presentation

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

Ramsey, Alexandra

2015-08-25

Cleaner forms of energy are needed, and H 2 produced from water spliFng is a possible source. However, a robust catalyst is necessary to carry out the water oxidaKon reacKon. Plants uKlize Photosystem II to catalyze water oxidaKon as a part of photosynthesis, and many syntheKc water oxidaKon catalysts use Photosystem II as a model. In this study, the catalyst of interest was [(terpy)Mn(μ-O)2Mn(terpy)]3+ (MnTD), which was synthesized in a chromium-based Metal Organic Framework (MOF) to avoid degradaKon of MnTD molecules. Hard X-ray powder diffracKon was the primary method of analysis. The diffracKon data was used to detect the presencemore » of MOF in samples at different catalyKc stages, and laFce parameters were assigned to the samples containing MOF. Fourier maps were constructed to determine the contents of the MOF as preliminary studies suggested that MnTD may not be present. Results showed that MOF is present before catalysis occurs, but disappears in the iniKal stages of catalysis. Changes in the MOF’s laFce parameters suggest aWracKve interacKons between the MOF and catalyst; these interacKons may lead to the observed MOF degradaKon. Fourier maps also reveal limited, if any, amounts of MnTD in the system. Molecular manganese oxide may be the source of the high rate of water oxidaKon catalysis in the studied system.« less

Coupling molecular catalysts with nanostructured surfaces for efficient solar fuel production

NASA Astrophysics Data System (ADS)

Jin, Tong

Solar fuel generation via carbon dioxide (CO2) reduction is a promising approach to meet the increasing global demand for energy and to minimize the impact of energy consumption on climate change. However, CO2 is thermodynamically stable; its activation often requires the use of appropriate catalysts. In particular, molecular catalysts with well-defined structures and tunability have shown excellent activity in photochemical CO2 reduction. These homogenous catalysts, however, suffer from poor stability under photochemical conditions and difficulty in recycling from the reaction media. Heterogenized molecular catalysts, particularly those prepared by coupling molecular catalysts with solid-state surfaces, have attracted more attention in recent years as potential solutions to address the issues associated with molecular catalysts. In this work, solar CO2 reduction is investigated using systems coupling molecular catalysts with robust nanostructured surfaces. In Chapter 2, heterogenization of macrocyclic cobalt(III) and nickel (II) complexes on mesoporous silica surface was achieved by different methods. Direct ligand derivatization significantly lowered the catalytic activity of Co(III) complex, while grafting the Co(III) complex onto silica surface through Si-O-Co linkage resulted in hybrid catalysts with excellent activity in CO2 reduction in the presence of p-terphenyl as a molecular photosensitizer. An interesting loading effect was observed, in which the optimal activity was achieved at a medium Co(III) surface density. Heterogenization of the Ni(II) complex on silica surface has also been implemented, the poor photocatalytic activity of the hybrid catalyst can be attributed to the intrinsic nature of the homogeneous analogue. This study highlighted the importance of appropriate linking strategies in preparing functional heterogenized molecular catalysts. Coupling molecular complexes with light-harvesting surfaces could avoid the use of expensive molecular photosensitizers. In Chapter 3, effective coupling of the macrocyclic Co(III) complex with titanium dioxide (TiO¬2) nanoparticles was achieved by two deposition methods. The synthesized hybrid photocatalysts were thoroughly characterized with a variety of techniques. Upon UV light irradiation, photoexcited electrons in TiO2 nanoparticles were transferred to the surface Co(III) catalyst for CO2 reduction. Production of carbon monoxide (CO) from CO2 was confirmed by isotope labeling combined with infrared spectroscopy. Deposition of the Co(III) catalyst through Ti-O-Co linkages was essential for the photo-induced electron transfer and CO2-reduction activity using the hybrid photocatalysts. In Chapter 4, molecular Re(I) and Co(II) catalysts were coupled with silicon-based photoelectrodes, including a silicon nanowire (SiNW) photoelectrode, to achieve photoelectrochemical CO2 reduction. Photovoltages between 300-600 mV were obtained using the molecular catalysts on the silicon photoelectrodes. SiNWs exhibited enhanced properties, including significantly higher photovoltages than a planar silicon photoelectrode, the ability to protect one of the molecular catalysts from photo-induced decomposition, and excellent selectivity towards CO production in CO2 reduction. Recent theoretical and experimental work have demonstrated low-energy, binuclear pathways for CO2-to-CO conversion using several molecular catalysts. In such binuclear pathways, two metal centers work cooperatively to achieve two-electron CO2 reduction. Chapter 5 describes our effort to promote the binuclear pathway by grafting the molecular Co(III) catalyst onto silica surfaces. Different linking strategies were attempted to achieve this goal by planting the surface Co(III) sites in close proximity.

Rapid degradation of azo dye Direct Black BN by magnetic MgFe2O4-SiC under microwave radiation

NASA Astrophysics Data System (ADS)

Gao, Jia; Yang, Shaogui; Li, Na; Meng, Lingjun; Wang, Fei; He, Huan; Sun, Cheng

2016-08-01

A novel microwave (MW) catalyst, MgFe2O4 loaded on SiC (MgFe2O4-SiC), was successfully synthesized by sol-gel method, and pure MgFe2O4 was used as reference. The MgFe2O4 and MgFe2O4-SiC catalysts were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), N2 adsorption analyzer (BET specific surface area), X-ray photoelectron spectroscopy (XPS). The electromagnetic parameters of the prepared catalysts were measured by vector network analyzer. The reflection loss (RL) based on the electromagnetic parameters calculated in Matlab showed MgFe2O4-SiC attained the maximum absorbing value of 13.32 dB at 2.57 GHz, which reached extremely high RL value at low frequency range, revealing the excellent MW absorption property of MgFe2O4-SiC. MW-induced degradation of Direct Black BN (DB BN) over as-synthesized MgFe2O4-SiC indicated that degradation efficiency of DB BN (20 mg L-1) in 5 min reached 96.5%, the corresponding TOC removal was 65%, and the toxicity of DB BN after degradation by MgFe2O4-SiC obviously decreased. The good stability and applicability of MgFe2O4-SiC on the degradation process were also discovered. Moreover, the ionic chromatogram during degradation of DB BN demonstrated that the C-S, C-N and azo bonds in the DB BN molecule were destroyed gradually. MW-induced rad OH and holes could be responsible for the efficient removal involved in the system. These findings make MgFe2O4-SiC become an excellent MW absorbent as well as an effective MW catalyst with rapid degradation of DB BN. Therefore, it may be promising for MgFe2O4-SiC under MW radiation to deal with various dyestuffs and other toxic organic pollutants.

Desulfurization from thiophene by SO(4)(2-)/ZrO(2) catalytic oxidation at room temperature and atmospheric pressure.

PubMed

Wang, Bo; Zhu, Jianpeng; Ma, Hongzhu

2009-05-15

Thiophene, due to its poison, together with its combustion products which causes air pollution and highly toxic characteristic itself, attracted more and more attention to remove from gasoline and some high concentration systems. As the purpose of achieving the novel method of de-thiophene assisted by SO(4)(2-)/ZrO(2) (SZ), three reactions about thiophene in different atmosphere at room temperature and atmospheric pressure were investigated. SO(4)(2-)/ZrO(2) catalyst were synthesized and characterized by X-ray photoelectron spectroscopy (XPS), Fourier transformation infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscope (SEM). The products were detected by gas chromatography-mass spectrometry (GC-MS). XP spectra show that ozone-catalyst system (SZO) have two forms of sulfur element (S(6+) and S(2-)) on the catalyst surface, which distinguished from that of air-catalyst system (SZA) and blank-catalyst system (SZB) (S(6+)). And the results of GC-MS exhibited that some new compounds has been produced under this extremely mild condition. Especially, many kinds of sulfur compounds containing oxygen, that is easier to be extracted by oxidative desulfurization (ODS), have been detected in the SZA-1.5h and SZB-3h system. In addition, some long chain hydrocarbons have also been detected. While in SZO-0.5h system, only long chain hydrocarbons were found. The results show that total efficiency of desulfurization from thiophene with ozone near to 100% can be obtained with the SO(4)(2-)/ZrO(2) catalytic oxidation reaction.

Catalytic decomposition of toxic chemicals over iron group metals supported on carbon nanotubes.

PubMed

Li, Lili; Chen, Can; Chen, Long; Zhu, Zixue; Hu, Jianli

2014-03-18

This study explores catalytic decomposition of phosphine (PH3) using iron group metals (Co, Ni) and metal oxides (Fe2O3, Co(3)O4, NiO) supported on carbon nanotubes (CNTs). The catalysts are synthesized by means of a deposition-precipitation method. The morphology, structure, and composition of the catalysts are characterized using a number of analytical instrumentations, including high-resolution transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, BET surface area measurement, and inductively coupled plasma. The activity of the catalysts in the PH3 decomposition reaction is measured and correlated with their surface and structural properties. The characterization results show that phosphidation occurs on the catalyst surface, and the resulting metal phosphides act as an active phase in the PH3 decomposition reaction. Cobalt phosphide, CoP, is formed on Co/CNTs and Co(3)O4/CNTs, whereas iron phosphide, FeP, is formed on Fe2O3/CNTs. In contrast, phosphorus-rich phosphide NiP2 is formed on Ni/CNTs and NiO/CNTs. The initial activities of the catalysts are shown in the following sequence: Ni/CNTs > Co/CNTs > Co(3)O4/CNTs >NiO/CNTs > Fe2O3/CNTs, whereas activities of metal phosphides are shown in the following order: CoP > NiP2 > FeP. The catalytic activity of metal phosphides is attributed to their electronic properties. Cobalt phosphide formed on Co/CNTs and Co(3)O4/CNTs exhibits not only the highest activity, but also long-term stability in the PH3 decomposition reaction.

Process for photosynthetically splitting water

DOEpatents

Greenbaum, Elias

1984-01-01

The invention is an improved process for producing gaseous hydrogen and oxygen from water. The process is conducted in a photolytic reactor which contains a water-suspension of a photoactive material containing a hydrogen-liberating catalyst. The reactor also includes a volume for receiving gaseous hydrogen and oxygen evolved from the liquid phase. To avoid oxygen-inactivation of the catalyst, the reactor is evacuated continuously by an external pump which circulates the evolved gases through means for selectively recovering hydrogen therefrom. The pump also cools the reactor by evaporating water from the liquid phase. Preferably, product recovery is effected by selectively diffusing the hydrogen through a heated semipermeable membrane, while maintaining across the membrane a magnetic field gradient which biases the oxygen away from the heated membrane. This promotes separation, minimizes the back-reaction of hydrogen and oxygen, and protects the membrane.

The Impact of Detoxification Costs and Predation Risk on Foraging: Implications for Mimicry Dynamics

PubMed Central

Skelhorn, John; Rowe, Candy; Ruxton, Graeme D.; Higginson, Andrew D.

2017-01-01

Prey often evolve defences to deter predators, such as noxious chemicals including toxins. Toxic species often advertise their defence to potential predators by distinctive sensory signals. Predators learn to associate toxicity with the signals of these so-called aposematic prey, and may avoid them in future. In turn, this selects for mildly toxic prey to mimic the appearance of more toxic prey. Empirical evidence shows that mimicry could be either beneficial (‘Mullerian’) or detrimental (‘quasi-Batesian’) to the highly toxic prey, but the factors determining which are unknown. Here, we use state-dependent models to explore how tri-trophic interactions could influence the evolution of prey defences. We consider how predation risk affects predators’ optimal foraging strategies on aposematic prey, and explore the resultant impact this has on mimicry dynamics between unequally defended species. In addition, we also investigate how the potential energetic cost of metabolising a toxin can alter the benefits to eating toxic prey and thus impact on predators’ foraging decisions. Our model predicts that both how predators perceive their own predation risk, and the cost of detoxification, can have significant, sometimes counterintuitive, effects on the foraging decisions of predators. For example, in some conditions predators should: (i) avoid prey they know to be undefended, (ii) eat more mildly toxic prey as detoxification costs increase, (iii) increase their intake of highly toxic prey as the abundance of undefended prey increases. These effects mean that the relationship between a mimic and its model can qualitatively depend on the density of alternative prey and the cost of metabolising toxins. In addition, these effects are mediated by the predators’ own predation risk, which demonstrates that, higher trophic levels than previously considered can have fundamental impacts on interactions among aposematic prey species. PMID:28045959

Avoiding Toxic Levels of Essential Minerals: A Forgotten Factor in Deer Diet Preferences

PubMed Central

Ceacero, Francisco; Landete-Castillejos, Tomás; Olguín, Augusto; Miranda, María; García, Andrés; Martínez, Alberto; Cassinello, Jorge; Miguel, Valentín; Gallego, Laureano

2015-01-01

Ungulates select diets with high energy, protein, and sodium contents. However, it is scarcely known the influence of essential minerals other than Na in diet preferences. Moreover, almost no information is available about the possible influence of toxic levels of essential minerals on avoidance of certain plant species. The aim of this research was to test the relative importance of mineral content of plants in diet selection by red deer (Cervus elaphus) in an annual basis. We determined mineral, protein and ash content in 35 common Mediterranean plant species (the most common ones in the study area). These plant species were previously classified as preferred and non-preferred. We found that deer preferred plants with low contents of Ca, Mg, K, P, S, Cu, Sr and Zn. The model obtained was greatly accurate identifying the preferred plant species (91.3% of correct assignments). After a detailed analysis of these minerals (considering deficiencies and toxicity levels both in preferred and non-preferred plants) we suggest that the avoidance of excessive sulphur in diet (i.e., selection for plants with low sulphur content) seems to override the maximization for other nutrients. Low sulphur content seems to be a forgotten factor with certain relevance for explaining diet selection in deer. Recent studies in livestock support this conclusion, which is highlighted here for the first time in diet selection by a wild large herbivore. Our results suggest that future studies should also take into account the toxicity levels of minerals as potential drivers of preferences. PMID:25615596

Avoiding toxic levels of essential minerals: a forgotten factor in deer diet preferences.

PubMed

Ceacero, Francisco; Landete-Castillejos, Tomás; Olguín, Augusto; Miranda, María; García, Andrés; Martínez, Alberto; Cassinello, Jorge; Miguel, Valentín; Gallego, Laureano

2015-01-01

Ungulates select diets with high energy, protein, and sodium contents. However, it is scarcely known the influence of essential minerals other than Na in diet preferences. Moreover, almost no information is available about the possible influence of toxic levels of essential minerals on avoidance of certain plant species. The aim of this research was to test the relative importance of mineral content of plants in diet selection by red deer (Cervus elaphus) in an annual basis. We determined mineral, protein and ash content in 35 common Mediterranean plant species (the most common ones in the study area). These plant species were previously classified as preferred and non-preferred. We found that deer preferred plants with low contents of Ca, Mg, K, P, S, Cu, Sr and Zn. The model obtained was greatly accurate identifying the preferred plant species (91.3% of correct assignments). After a detailed analysis of these minerals (considering deficiencies and toxicity levels both in preferred and non-preferred plants) we suggest that the avoidance of excessive sulphur in diet (i.e., selection for plants with low sulphur content) seems to override the maximization for other nutrients. Low sulphur content seems to be a forgotten factor with certain relevance for explaining diet selection in deer. Recent studies in livestock support this conclusion, which is highlighted here for the first time in diet selection by a wild large herbivore. Our results suggest that future studies should also take into account the toxicity levels of minerals as potential drivers of preferences.

Advanced oxidation-based treatment of furniture industry wastewater.

PubMed

Tichonovas, Martynas; Krugly, Edvinas; Grybauskas, Arturas; Jankūnaitė, Dalia; Račys, Viktoras; Martuzevičius, Dainius

2017-07-16

The paper presents a study on the treatment of the furniture industry wastewater in a bench scale advanced oxidation reactor. The researched technology utilized a simultaneous application of ozone, ultraviolet radiation and surface-immobilized TiO 2 nanoparticle catalyst. Various combinations of processes were tested, including photolysis, photocatalysis, ozonation, catalytic ozonation, photolytic ozonation and photocatalytic ozonation were tested against the efficiency of degradation. The efficiency of the processes was primarily characterized by the total organic carbon (TOC) analysis, indicating the remaining organic material in the wastewater after the treatment, while the toxicity changes in wastewater were researched by Daphnia magna toxicity tests. Photocatalytic ozonation was confirmed as the most effective combination of processes (99.3% of TOC reduction during 180 min of treatment), also being the most energy efficient (4.49-7.83 MJ/g). Photocatalytic ozonation and photolytic ozonation remained efficient across a wide range of pH (3-9), but the pH was an important factor in photocatalysis. The toxicity of wastewater depended on the duration of the treatment: half treated water was highly toxic, while fully treated water did not possess any toxicity. Our results indicate that photocatalytic ozonation has a high potential for the upscaling and application in industrial settings.

Do migratory or demographic disruptions rule the population impact of pollution in spatial networks?

PubMed

Chaumot, A; Charles, S; Flammarion, P; Auger, P

2003-12-01

Ecotoxicology supplies environmental quality criteria mainly based on the potential effects of contaminants on demographic rates of natural populations. Possible impacts through pollutant-induced disruptions of spatial behaviors are totally neglected. Should it be significant to take into account this "second way"? We developed the example of a hypothetical brown trout population living in a river network. We analyzed how behaviors of toxic avoidance or attraction during the spawning migration alter the impact of pollution. Attraction behaviors basically enhanced the bad effect of pollution. More interesting, avoidance behaviors can weakly lift the asymptotic population growth rate, while if there is density-dependent effects on recruitment, pollutant avoidance can actually lead to a substantial drop in equilibrium size. Our model allowed comparing the relative significance of migratory and demographic disruptions for explaining the population impacts of pollution; we thus stress on the need of increasing efforts to develop knowledge relative to toxicant-induced spatial behaviors and to integrate such effects in the definition of environmental quality criteria.

Diet composition exacerbates or attenuates soman toxicity in rats: implied metabolic control of nerve agent toxicity.

PubMed

Myers, Todd M; Langston, Jeffrey L

2011-06-01

To evaluate the role of diet composition on nerve agent toxicity, rats were fed four distinct diets ad libitum for 28 d prior to challenge with 110 μg/kg (1.0 LD(50), sc) soman. The four diets used were a standard rodent diet, a choline-enriched diet, a glucose-enriched diet, and a ketogenic diet. Body weight was recorded throughout the study. Toxic signs and survival were evaluated at key times for up to 72 h following soman exposure. Additionally, acquisition of discriminated shuttlebox avoidance performance was characterized beginning 24h after soman challenge and across the next 8 d (six behavioral sessions). Prior to exposure, body weight was highest in the standard diet group and lowest in the ketogenic diet group. Upon exposure, differences in soman toxicity as a function of diet became apparent within the first hour, with mortality in the glucose-enriched diet group reaching 80% and exceeding all other groups (in which mortality ranged from 0 to 6%). At 72 h after exposure, mortality was 100% in the glucose-enriched diet group, and survival approximated 50% in the standard and choline-enriched diet groups, but equaled 87% in the ketogenic diet group. Body weight loss was significantly reduced in the ketogenic and choline-enriched diet groups, relative to the standard diet group. At 1 and 4h after exposure, rats in the ketogenic diet group had significantly lower toxic sign scores than all other groups. The ketogenic diet group performed significantly better than the standard diet group on two measures of active avoidance performance. The exacerbated soman toxicity observed in the glucose-enriched diet group coupled with the attenuated soman toxicity observed in the ketogenic diet group implicates glucose availability in the toxic effects of soman. This increased glucose availability may enhance acetylcholine synthesis and/or utilization, thereby exacerbating peripheral and central soman toxicity. Published by Elsevier B.V.

Behavioral technology and its application to fire toxicology research

NASA Technical Reports Server (NTRS)

Russo, D. M.

1978-01-01

The application of behavioral technology to the toxicity testing of pyrolysis/combustion (P/C) products is discussed and two categories of behavioral tests commonly employed in fire toxicology programs are reviewed. Data are presented from a comparison of carbon monoxide (CO) induced incapacitation in rats performing in a rotating wheel or under a Sidmon free-operant schedule of shock avoidance. Rats performing in the rotating wheel were behaviorally incapacitated at CO concentrations and carboxyhemoglobin levels significantly lower than those which incapacitated operant avoidance animals. It is concluded that different measures of behavioral incapacitation may vary since incapacitation is a function of the particular toxic mechanism at work and the behavioral requirements of the specific task employed in the test procedure.

Visible Light Organic Photoredox-Catalyzed C-H Alkoxylation of Imidazopyridine with Alcohol.

PubMed

Kibriya, Golam; Samanta, Sadhanendu; Jana, Sourav; Mondal, Susmita; Hajra, Alakananda

2017-12-15

The visible light-mediated C-3 alkoxylation of imidazopyridines with alcohols has been achieved using rose bengal as an organic photoredox catalyst at room temperature. Widely abundant air acts as the terminal oxidant that avoids the use of a stoichiometric amount of peroxo compounds. A wide range of functional groups could be tolerated under the reaction conditions to produce C(sp 2 )-H alkoxylated products in high yields.

Correlation between degradation pathway and toxicity of acetaminophen and its by-products by using the electro-Fenton process in aqueous media.

PubMed

Le, Thi Xuan Huong; Nguyen, Thi Van; Amadou Yacouba, Zoulkifli; Zoungrana, Laetitia; Avril, Florent; Nguyen, Duy Linh; Petit, Eddy; Mendret, Julie; Bonniol, Valerie; Bechelany, Mikhael; Lacour, Stella; Lesage, Geoffroy; Cretin, Marc

2017-04-01

The evolution of the degradation by-products of an acetaminophen (ACE) solution was monitored by HPLC-UV/MS and IC in parallel with its ecotoxicity (Vibrio fischeri 81.9%, Microtox ® screening tests) during electro-Fenton (EF) oxidation performed on carbon felt. The aromatic compounds 2-hydroxy-4-(N-acetyl) aminophenol, 1,4-benzoquinone, benzaldehyde and benzoic acid were identified as toxic sub-products during the first stage of the electrochemical treatment, whereas aliphatic short-chain carboxylic acids (oxalic, maleic, oxamic, formic, acetic and fumaric acids) and inorganic ions (ammonium and nitrate) were well identified as non-toxic terminal sub-products. Electrogenerated hydroxyl radicals then converted the eco-toxic and bio-refractory property of initial ACE molecule (500 mL, 1 mM) and subsequent aromatic sub-products into non-toxic compounds after 2 h of EF treatment. The toxicity of every intermediate produced during the mineralization of ACE was quantified, and a relationship was established between the degradation pathway of ACE and the global toxicity evolution of the solution. After 8 h of treatment, a total organic carbon removal of 86.9% could be reached for 0.1 mM ACE at applied current of 500 mA with 0.2 mM of Fe 2+ used as catalyst. Copyright © 2016 Elsevier Ltd. All rights reserved.

Physiochemical Control of Composition and Location for Fundamental Studies of Biofouling Resistant, High Fouling Release Surfaces

DTIC Science & Technology

2016-06-22

with increased legislation on toxicity requirements, the research community has been actively exploring and developing new, robust, and...with a brominated end functionality. The presence of active radical species only at locations where light interacts with the catalyst affords...i.e., the burying of the reactive bromo chain ends due to the high surface activity of the fluorinated repeat units, which imposes additional steric

Water oxidation by a nickel-glycine catalyst.

PubMed

Wang, Dong; Ghirlanda, Giovanna; Allen, James P

2014-07-23

The utilization of solar energy requires an efficient means for its storage as chemical energy. In bioinspired artificial photosynthesis, light energy can be used to drive water oxidation, but catalysts that produce molecular oxygen from water are needed to avoid excessive driving potentials. In this paper, we demonstrate the utility of a novel complex utilizing earth-abundant Ni in combination with glycine as an efficient catalyst with a modest overpotential of 0.475 ± 0.005 V at a current density of 1 mA/cm(2) at pH 11. Catalysis requires the presence of the amine moiety with the glycine most likely coordinating the Ni in a 4:1 molar ratio. The production of molecular oxygen at a high potential is verified by measurement of the change in oxygen concentration, yielding a Faradaic efficiency of 60 ± 5%. The catalytic species is most likely a heterogeneous Ni-hydroxide formed by electrochemical oxidation. This Ni species can achieve a current density of 4 mA/cm(2) that persists for at least 10 h. Based upon the observed pH dependence of the current amplitude and oxidation/reduction peaks, the catalytic mechanism is an electron-proton coupled process.

Mobil/Badger to market zeolite-based cumene technology

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

Rotman, D.

1993-02-24

Badger (Cambridge, MA) and Mobil (Fairfax, VA) are ready to jointly license a new cumene technology that they say achieves higher yields and product purity than existing processes. The zeolite-based technology is scheduled to be introduced at next month's DeWitt Petrochemical Review in Houston. The Mobil/Badger technology aims to challenge the dominant position of UOP's (Des Plaines, IL) solid phosphoric acid (SPA) catalyst process - which accounts for 80%-90% of the world's cumene production. In addition, Monsanto/Kellogg's aluminum chloride-based technology has gained significant momentum since its introduction in the 1980s. And late last year, ABB Lummus Crest (Bloomfield, NJ) alsomore » began marketing a zeolite-based cumene technology. While all the technologies make cumene via the alkylation of benzene with propylene, the Mobil/Badger process uses a zeolite-containing catalyst designed by Mobil to selectively catalyze the benzene/propylene reaction, avoiding unwanted propylene oligomerization. Because the olefin reactions are so fast, says Frank A. Demers, Badger's v.p./technology development and marketing, other zeolite technologies are forced to use complex reactor arrangements to stop the propylene-propylene reactions. However, he says, Mobil has designed a catalyst that wants to react benzene with propylene to make cumene.'« less

Nitrogen-Doped Carbon Nanoparticles for Oxygen Reduction Prepared via a Crushing Method Involving a High Shear Mixer.

PubMed

Shi, Lei; Wu, Tao; Wang, Yiqing; Zhang, Jie; Wang, Gang; Zhang, Jinli; Dai, Bin; Yu, Feng

2017-09-04

The disposal of agricultural wastes such as fresh banana peels (BPs) is an environmental issue. In this work, fresh BPs were successfully transformed into nitrogen-doped carbon nanoparticles (N-CNPs) by using a high shear mixer facilitated crushing method (HSM-FCM) followed by carbonization under Ar atmosphere. Ammonia-activated N-CNPs (N-CNPs-NH₃) were prepared via subsequent ammonia activation treatments at a high temperature. The as-prepared N-CNPs and N-CNPs-NH₃ materials both exhibited high surface areas (above 700 m²/g) and mean particle size of 50 nm. N-CNPs-NH 3 showed a relatively higher content of pyridinic and graphitic N compared to N-CNPs. In alkaline media, N-CNPs-NH₃ showed superior performances as an oxygen reduction reaction (ORR) catalyst (E₀ = -0.033 V, J = 2.4 mA/cm²) compared to N-CNPs (E₀ = 0.07 V, J = 1.8 mA/cm²). In addition, N-CNPs-NH₃ showed greater oxygen reduction stability and superior methanol crossover avoidance than a conventional Pt/C catalyst. This study provides a novel, simple, and scalable approach to valorize biomass wastes by synthesizing highly efficient electrochemical ORR catalysts.

Electrocatalysis for oxygen electrodes in fuel cells and water electrolyzers for space applications

NASA Technical Reports Server (NTRS)

Prakash, Jai; Tryk, Donald; Yeager, Ernest

1989-01-01

In most instances separate electrocatalysts are needed to promote the reduction of O2 in the fuel cell mode and to generate O2 in the energy storage-water electrolysis mode in aqueous electrochemical systems operating at low and moderate temperatures (T greater than or equal to 200 C). Interesting exceptions are the lead and bismuth ruthenate pyrochlores in alkaline electrolytes. These catalysts on high area carbon supports have high catalytic activity for both O2 reduction and generation. Rotating ring-disk electrode measurements provide evidence that the O2 reduction proceeds by a parallel four-electron pathway. The ruthenates can also be used as self-supported catalysts to avoid the problems associated with carbon oxidation, but the electrode performance so far achieved in the research at Case Western Reserve University (CWRU) is considerably less. At the potentials involved in the anodic mode the ruthenate pyrochlores have substantial equilibrium solubility in concentrated alkaline electrolyte. This results in the loss of catalyst into the bulk solution and a decline in catalytic activity. Furthermore, the hydrogen generation counter electrode may become contaminated with reduction products from the pyrochlores (lead, ruthenium).

Systematic Structure–Property Relationship Studies in Palladium-Catalyzed Methane Complete Combustion

DOE PAGES

Willis, Joshua J.; Gallo, Alessandro; Sokaras, Dimosthenis; ...

2017-10-09

To limit further rising levels in methane emissions from stationary and mobile sources and to enable promising technologies based on methane, the development of efficient combustion catalysts that completely oxidize CH 4 to CO 2 and H 2O at low temperatures in the presence of high steam concentrations is required. Palladium is widely considered as one of the most promising materials for this reaction, and a better understanding of the factors affecting its activity and stability is crucial to design even more improved catalysts that efficiently utilize this precious metal. Here we report a study of the effect of threemore » important variables (particle size, support, and reaction conditions including water) on the activity of supported Pd catalysts. We use uniform palladium nanocrystals as catalyst precursors to prepare a library of well-defined catalysts to systematically describe structure–property relationships with help from theory and in situ X-ray absorption spectroscopy. With this approach, we confirm that PdO is the most active phase and that small differences in reaction rates as a function of size are likely due to variations in the surface crystal structure. We further demonstrate that the support exerts a limited influence on the PdO activity, with inert (SiO 2), acidic (Al 2O 3), and redox-active (Ce 0.8Zr 0.2O 2) supports providing similar rates, while basic (MgO) supports show remarkably lower activity. Finally, we show that the introduction of steam leads to a considerable decrease in rates that is due to coverage effects, rather than structural and/or phase changes. Altogether, the data suggest that to further increase the activity and stability of Pd-based catalysts for methane combustion, increasing the surface area of supported PdO phases while avoiding strong adsorption of water on the catalytic surfaces is required. Furthermore, this study clarifies contrasting reports in the literature about the active phase and stability of Pd-based materials for methane combustion.« less

Systematic Structure–Property Relationship Studies in Palladium-Catalyzed Methane Complete Combustion

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

Willis, Joshua J.; Gallo, Alessandro; Sokaras, Dimosthenis

To limit further rising levels in methane emissions from stationary and mobile sources and to enable promising technologies based on methane, the development of efficient combustion catalysts that completely oxidize CH 4 to CO 2 and H 2O at low temperatures in the presence of high steam concentrations is required. Palladium is widely considered as one of the most promising materials for this reaction, and a better understanding of the factors affecting its activity and stability is crucial to design even more improved catalysts that efficiently utilize this precious metal. Here we report a study of the effect of threemore » important variables (particle size, support, and reaction conditions including water) on the activity of supported Pd catalysts. We use uniform palladium nanocrystals as catalyst precursors to prepare a library of well-defined catalysts to systematically describe structure–property relationships with help from theory and in situ X-ray absorption spectroscopy. With this approach, we confirm that PdO is the most active phase and that small differences in reaction rates as a function of size are likely due to variations in the surface crystal structure. We further demonstrate that the support exerts a limited influence on the PdO activity, with inert (SiO 2), acidic (Al 2O 3), and redox-active (Ce 0.8Zr 0.2O 2) supports providing similar rates, while basic (MgO) supports show remarkably lower activity. Finally, we show that the introduction of steam leads to a considerable decrease in rates that is due to coverage effects, rather than structural and/or phase changes. Altogether, the data suggest that to further increase the activity and stability of Pd-based catalysts for methane combustion, increasing the surface area of supported PdO phases while avoiding strong adsorption of water on the catalytic surfaces is required. Furthermore, this study clarifies contrasting reports in the literature about the active phase and stability of Pd-based materials for methane combustion.« less

Patient- and therapy-related factors associated with the incidence of xerostomia in nasopharyngeal carcinoma patients receiving parotid-sparing helical tomotherapy

PubMed Central

Lee, Tsair-Fwu; Liou, Ming-Hsiang; Ting, Hui-Min; Chang, Liyun; Lee, Hsiao-Yi; Wan Leung, Stephen; Huang, Chih-Jen; Chao, Pei-Ju

2015-01-01

We investigated the incidence of moderate to severe patient-reported xerostomia among nasopharyngeal carcinoma (NPC) patients treated with helical tomotherapy (HT) and identified patient- and therapy-related factors associated with acute and chronic xerostomia toxicity. The least absolute shrinkage and selection operator (LASSO) normal tissue complication probability (NTCP) models were developed using quality-of-life questionnaire datasets from 67 patients with NPC. For acute toxicity, the dosimetric factors of the mean doses to the ipsilateral submandibular gland (Dis) and the contralateral submandibular gland (Dcs) were selected as the first two significant predictors. For chronic toxicity, four predictive factors were selected: age, mean dose to the oral cavity (Doc), education, and T stage. The substantial sparing data can be used to avoid xerostomia toxicity. We suggest that the tolerance values corresponded to a 20% incidence of complications (TD20) for Dis = 39.0 Gy, Dcs = 38.4 Gy, and Doc = 32.5 Gy, respectively, when mean doses to the parotid glands met the QUANTEC 25 Gy sparing guidelines. To avoid patient-reported xerostomia toxicity, the mean doses to the parotid gland, submandibular gland, and oral cavity have to meet the sparing tolerance, although there is also a need to take inherent patient characteristics into consideration. PMID:26289304

Nanomaterials: biological effects and some aspects of applications in ecology and agriculture

NASA Astrophysics Data System (ADS)

Starodub, Nickolaj F.; Shavanova, Kateryna E.; Taran, Marina V.; Katsev, Andrey M.; Safronyuk, Sergey L.; Son'ko, Roman V.; Bisio, Chiara; Guidotti, Matteo

2014-10-01

Nanosized materials have shown a relevant potential for practical application in a broad number of research fields, in industrial production and in everyday life. However, these substances acquire new properties and therefore may be biologically very active. This raise questions their potential toxic effects on living organisms. In some cases the nanosized materials or nano-composites possess distinct positive properties in enhancing the adaptation of plants in unfavorable conditions and in decreasing the negative effect of some chemical substances. The information about the positive and negative effects of nano-materials as well as the data concerned to the innovative approaches used by authors for the rapid assessment of the total toxicity with the exploitation of bacteria, Daphnia and plants are given. In last case a special attention is paid to the control of natural bioluminescence and chemoluminescence of living medium of organisms, the energy of the seed germination and the efficiency of the photosynthetic apparatus in growing plants by the estimation of chlorophyll fluorescence by the special "Floratest" biosensor. Three specific clases of nano-materials are analysed: a) nano-particles ZnO, Ag2O, FeOx, TiO2 and others, b) colloidal suspension of the same compounds, and c) nanostructured layered clay materials (acid saponites and Nb-containing saponite clays). The next features are analyzed: the biocidal activity (for nanoparticles), the improvement of the nutrition of plants on calcareous soils (for colloidal structures), the activity and performances as heterogeneous catalysts (for Nb-containing saponites, as selective oxidation catalysts for toxic organosulfur compounds into non-noxious products). The chemical and physical characterization of the nanosized materials described here was studied by different spectrophotometric and microscopic techniques, including AFM and SEM.

Applications of density functional theory calculations to selected problems in hydrocarbon processing

NASA Astrophysics Data System (ADS)

Nabar, Rahul

Recent advances in theoretical techniques and computational hardware have made it possible to apply Density Functional Theory (DFT) methods to realistic problems in heterogeneous catalysis. Hydrocarbon processing is economically, and strategically, a very important industrial sector in today's world. In this thesis, we employ DFT methods to examine several important problems in hydrocarbon processing. Fischer Tropsch Synthesis (FTS) is a mature technology to convert synthesis gas derived from coal, natural-gas or biomass into liquid fuels, specifically diesel. Iron is an active FTS catalyst, but the absence of detailed reaction mechanisms make it difficult to maximize activity and optimize product distribution. We evaluate thermochemistry, kinetics and Rate Determining Steps (RDS) for Fischer Tropsch Synthesis on several models of Fe catalysts: Fe(110), Fe(211) and Pt promoted Fe(110). Our studies indicated that CO-dissociation is likely to be the RDS under most reaction conditions, but the DFT-calculated activation energy ( Ea) for direct CO dissociation was too large to explain the observed catalyst activity. Consequently we demonstrate that H-assisted CO-dissociation pathways are competitive with direct CO dissociation on both Co and Fe catalysts and could be responsible for a major fraction of the reaction flux (especially at high CO coverages). We then extend this alternative mechanistic model to closed-packed facets of nine transition metal catalysts (Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt). H-assisted CO dissociation offers a kinetically easier route on each of the metals studied. DFT methods are also applied to another problem from the petroleum industry: discovery of poison-resistant, bimetallic, alloy catalysts (poisons: C, S, CI, P). Our systematic screening studies identify several Near Surface Alloys (NSAs) that are expected to be highly poison-resistant yet stable and avoiding adsorbate induced reconstruction. Adsorption trends are also correlated with electronic structure. Eventually we extend this work to compile a database of Binding Energies for 17 adsorbates of catalytic interest on a set of 17 transition metals and their NSAs. Practical examples of how such a database, in conjunction with screening criteria, can be fruitfully utilized for rational catalyst design, are also provided.

Catalytic Dehydrogenative Coupling of Hydrosilanes with Alcohols for the Production of Hydrogen On-demand: Application of a Silane/Alcohol Pair as a Liquid Organic Hydrogen Carrier.

PubMed

Ventura-Espinosa, David; Carretero-Cerdán, Alba; Baya, Miguel; García, Hermenegildo; Mata, Jose A

2017-08-10

The compound [Ru(p-cym)(Cl) 2 (NHC)] is an effective catalyst for the room-temperature coupling of silanes and alcohols with the concomitant formation of molecular hydrogen. High catalyst activity is observed for a variety of substrates affording quantitative yields in minutes at room temperature and with a catalyst loading as low as 0.1 mol %. The coupling reaction is thermodynamically and, in the presence of a Ru complex, kinetically favourable and allows rapid molecular hydrogen generation on-demand at room temperature, under air, and without any additive. The pair silane/alcohol is a potential liquid organic hydrogen carrier (LOHC) for energy storage over long periods in a safe and secure way. Silanes and alcohols are non-toxic compounds and do not require special handling precautions such as high pressure or an inert atmosphere. These properties enhance the practical applications of the pair silane/alcohol as a good LOHC in the automotive industry. The variety and availability of silanes and alcohols permits a pair combination that fulfils the requirements for developing an efficient LOHC. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of poly(lactic acid)/ montmorillonite nanocomposites by in situ polycondensation catalyzed by non-metal-based compound.

PubMed

Kaewprapan, Kulwadee; Phattanarudee, Siriwan

2012-01-01

Poly(lactic acid)/montmorillonite nanocomposites were prepared by using non-toxic catalysts, i.e., phthalic acid and succinimide, via in situ polycondensation in presence of silicate. Concentrations of catalysts and clay were varied in a range of 0-3% wt and 0-0.5% wt, respectively. The reaction condition was controlled at 180 degrees C for 24 hr under a reduced pressure. Viscosity average molecular weight of the synthesized polymers and nanocomposites were characterized and compared using an Ubbelohde viscometer. Pattern of silicate distribution in the composites was investigated by X-ray diffraction to correlate with thermal properties evaluated by differential scanning calorimetry and thermogravimetric analysis. The results showed that the addition of catalysts at 2% wt gave the highest product yield (55-60%). The presence of silicate affected on molecular weight reduction, and the diffracted patterns suggested an intercalated structure. With a small amount of added filler, a significant improvement in thermal property and crystallinity of the resultant composites was obtained compared to those of the catalyzed polymers, in which the composites with succinimide exhibited overall better thermal stability and higher crystallinity than the ones prepared with phthalic acid.

Nanostructured catalysts applied to degrade atrazine in aqueous phase by heterogeneous photo-Fenton process.

PubMed

Benzaquén, Tamara B; Barrera, Deicy A; Carraro, Paola M; Sapag, Karim; Alfano, Orlando M; Eimer, Griselda A

2018-06-02

SBA-15 and KIT-6 materials have been synthesized and modified with iron salts by the wet impregnation method with different metal loadings. The different mesostructures obtained were characterized by N 2 adsorption-desorption at 77 K, X-ray diffraction, temperature-programmed reduction, and ultraviolet-visible spectroscopy. These iron-containing mesostructured materials have been successfully tested for the heterogeneous photo-Fenton degradation of aqueous solutions of dangerous herbicides, such as atrazine, using UV-visible light irradiation, at room temperature and close to neutral pH. The results showed that the Fe/SBA-15 (10%) and Fe/KIT-6 (5%) catalysts exhibited the highest activities. However, the Fe/KIT-6 (5%) catalyst with minor Fe loading than Fe/SBA-15 (10%) presented a higher degradation of atrazine (above 98% in a reaction time of 240 min). Therefore, the interconnectivity of the cage-like mesopores had an important influence on the catalytic activity, favoring probably mass-transfer effects. Thus, the high performance of these materials indicates that the heterogeneous via of photo-Fenton process can also be efficiently employed to treat wastewaters containing pollutants such as herbicides, in order to reduce them to simplest and less toxic molecules.

Advanced oxidation processes for treatment of effluents from a detergent industry.

PubMed

Martins, Rui C; Silva, Adrián M T; Castro-Silva, Sérgio; Garção-Nunes, Paulo; Quinta-Ferreira, Rosa M

2011-07-01

Ozonation, catalytic ozonation, Fenton's and heterogeneous Fenton-like processes were investigated as possible pretreatments of a low biodegradable and highly toxic wastewater produced by a detergent industry. The presence of a Mn-Ce-O catalyst in ozonation enhances the biodegradability and improves the degradation at low pH values. However, a high content of carbonyl compounds adsorbed on the recovered solid indicates some limitations for real-scale application. A commercial Fe2O3-MnOx catalyst shows higher activity as well as higher stability concerning carbon adsorption, but the leaching of metals is larger than for Mn-Ce-O. Regarding the heterogeneous Fenton-like route with an Fe-Ce-O catalyst, even though a high activity and stability are attained, the intermediates are less biodegradable than the original compounds, indicating that the resulting effluent cannot be conducted to an activated sludge post-treatment. The highest enhancement of effluent biodegradability is obtained with the classic homogeneous Fenton's process, with the BOD5/COD ratio increasing from 0.32 to 0.80. This process was scaled up and the treated effluent is now safely directed to a municipal wastewater treatment plant.

Novel yolk-shell-structured Fe3O4@γ-AlOOH nanocomposite modified with Pd nanoparticles as a recyclable catalyst with excellent catalytic activity

NASA Astrophysics Data System (ADS)

Cui, Xueliang; Zheng, Yunfeng; Tian, Meng; Dong, Zhengping

2017-09-01

A novel yolk-shell-structured material (Fe3O4@γ-AlOOH-YSMs) with hierarchical γ-AlOOH flakes as the mesoporous shell and Fe3O4 nanoparticles (NPs) in the hollow core was prepared by using Fe3O4@SiO2 NPs as the seeds as well as NaAlO2 and urea as the precursor. The prepared Fe3O4@γ-AlOOH-YSMs were used as a catalyst support for fabricating a Pd/Fe3O4@γ-AlOOH-YSMs nanocatalyst with no obvious aggregation of the Pd NPs. The Pd/Fe3O4@γ-AlOOH-YSMs nanocatalyst was utilized for the catalytic reduction of the widely used and highly toxic 4-nitrophenol, rhodamine B, methylene blue, and methyl orange; and showed excellent catalytic activity as compared with other noble-metal-based catalysts. Furthermore, the Pd/Fe3O4@γ-AlOOH-YSMs nanocatalyst also can be easily separated from the reaction mixture and reused for at least ten times without any obvious decrease in the catalytic activity, indicating its reusability and stability.

HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin.

PubMed

Yépez, Rebeca; Illescas, Juan F; Gijón, Paulina; Sánchez-Sánchez, Manuel; González-Zamora, Eduardo; Santillan, Rosa; Álvarez, J Raziel; Ibarra, Ilich A; Aguilar-Pliego, Julia

2016-07-23

Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately 200 different odorant compounds in addition to vanillin. The natural extraction of vanillin (from the orchid Vanilla planifolia, Vanilla tahitiensis and Vanilla pompon) represents only 1% of the worldwide production and since this process is expensive and very long, the rest of the production of vanillin is synthesized. Many biotechnological approaches can be used for the synthesis of vanillin from lignin, phenolic stilbenes, isoeugenol, eugenol, guaicol, etc., with the disadvantage of harming the environment since these processes use strong oxidizing agents and toxic solvents. Thus, eco-friendly alternatives on the production of vanillin are very desirable and thus, under current investigation. Porous coordination polymers (PCPs) are a new class of highly crystalline materials that recently have been used for catalysis. HKUST-1 (Cu3(BTC)2(H2O)3, BTC = 1,3,5-benzene-tricarboxylate) is a very well known PCP which has been extensively studied as a heterogeneous catalyst. Here, we report a synthetic strategy for the production of vanillin by the oxidation of trans-ferulic acid using HKUST-1 as a catalyst.

An empirical study of the toxic capsule crisis in China: risk perceptions and behavioral responses.

PubMed

Feng, Tianjun; Keller, L Robin; Wu, Ping; Xu, Yifan

2014-04-01

The outbreak of the toxic capsule crisis during April 2012 aroused widespread public concern about the risk of chromium-contaminated capsules and drug safety in China. In this article, we develop a conceptual model to investigate risk perceptions of the pharmaceutical drug capsules and behavioral responses to the toxic capsule crisis and the relationship between associated factors and these two variables. An online survey was conducted to test the model, including questions on the measures of perceived efficacy of the countermeasures, trust in the State FDA (Food and Drug Administration), trust in the pharmaceutical companies, trust in the pharmaceutical capsule producers, risk perception, concern, need for information, information seeking, and risk avoidance. In general, participants reported higher levels of risk perception, concern, and risk avoidance, and lower levels of trust in the three different stakeholders. The results from the structural equation modeling procedure suggest that perceived efficacy of the countermeasures is a predictor of each of the three trust variables; however, only trust in the State FDA has a dampening impact on risk perception. Both risk perception and information seeking are significant determinants of risk avoidance. Risk perception is also positively related to concern. Information seeking is positively related to both concern and need for information. The theoretical and policy implications are also discussed. © 2013 Society for Risk Analysis.

Technical trends in industrial lead/acid batteries in Japan

NASA Astrophysics Data System (ADS)

Iwata, Masashi; Tagawa, Yahachiro

1994-02-01

Although there have been only a few major technological changes in stationary lead/acid batteries in the past, some rapid and remarkable developments have occurred recently. The latter have included the introduction of catalyst plugs and valve-regulated lead/acid batteries (VRBs). Catalyst plugs have been used to avoid water addition with stationary lead/acid batteries. By virtue of their advantages (i.e., the elements retain electrolyte and equalizing charging and water addition are unnecessary), VRBs are being developed up to a maximum capacity of 3000 Ah. These designs have now captured about 50% of the stationary lead/acid battery market. The VRB technology has excellent characteristics, such as plate construction that can accommodate grid growth, explosion-resistant plugs, good discharge characteristics, and minimal electrolyte stratification. In addition, by utilizing the benefits of VRBs, horizontal and multistoried systems can be assembled, though in early stages of development the construction was only for interchangeability with flooded-electrolyte type batteries.

Durability of De-Alloyed Platinum-Nickel Cathode Catalyst in Low Platinum Loading Membrane-Electrode Assemblies Subjected to Accelerated Stress Tests

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

Ahluwalia, R. K.; Wang, X.; Peng, J. -K.

Here, the durability of de-alloyed platinum-nickel catalysts supported on high-surface area carbon (d-PtNi/C) in optimized electrodes and membrane electrode assemblies (MEAs) under an accelerated stress test (AST) protocol is investigated with the objective of developing a quantitative understanding of the degradation mechanisms and their relationship to the electrode structure, pre-conditioning, and operating conditions. It is found that the cell degradation can be mitigated by controlling the voltage cycle, acid washing the MEA to remove Ni contaminants that enter the electrode and membrane during fabrication, and monitoring the operating conditions. For example, the electrochemical surface area (ECSA) loss is <25% aftermore » 30,000 triangle cycles with 0.925 V upper potential limit if the MEA is acid washed and extensive diagnostics are avoided. The parameters that exacerbate the cell degradation also accelerate the rate at which Ni leaches out from the catalyst. A mechanistic model is presented for the degradation in performance of d-PtNi/C electrodes. The model correlates a) the degradation in ORR mass and specific activities with ECSA and Ni losses, b) the decrease in limiting current density ( iL), which is inversely proportional to the O 2 mass transport resistance, with the degradation in catalyst roughness factor, and c) the increase in mass transfer overpotentials with the reduced current density, i/iL .« less

Durability of De-Alloyed Platinum-Nickel Cathode Catalyst in Low Platinum Loading Membrane-Electrode Assemblies Subjected to Accelerated Stress Tests

DOE PAGES

Ahluwalia, R. K.; Wang, X.; Peng, J. -K.; ...

2018-04-25

Here, the durability of de-alloyed platinum-nickel catalysts supported on high-surface area carbon (d-PtNi/C) in optimized electrodes and membrane electrode assemblies (MEAs) under an accelerated stress test (AST) protocol is investigated with the objective of developing a quantitative understanding of the degradation mechanisms and their relationship to the electrode structure, pre-conditioning, and operating conditions. It is found that the cell degradation can be mitigated by controlling the voltage cycle, acid washing the MEA to remove Ni contaminants that enter the electrode and membrane during fabrication, and monitoring the operating conditions. For example, the electrochemical surface area (ECSA) loss is <25% aftermore » 30,000 triangle cycles with 0.925 V upper potential limit if the MEA is acid washed and extensive diagnostics are avoided. The parameters that exacerbate the cell degradation also accelerate the rate at which Ni leaches out from the catalyst. A mechanistic model is presented for the degradation in performance of d-PtNi/C electrodes. The model correlates a) the degradation in ORR mass and specific activities with ECSA and Ni losses, b) the decrease in limiting current density ( iL), which is inversely proportional to the O 2 mass transport resistance, with the degradation in catalyst roughness factor, and c) the increase in mass transfer overpotentials with the reduced current density, i/iL .« less

Hierarchical porous silver metal using Pluronic F-127 and graphene oxide as reinforcing agents for the reduction of o-nitroaniline to 1, 2-benzenediamine

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

Bano, Mustri; Ahirwar, Devendra; Thomas, Molly

An elegant method is used to prepare silver monoliths with Pluronic F-127(F-127) as sacrificial template by modified sol-gel method. Si nanoparticles (SiNPs) and graphene oxide (GO) are added in situ to Ag/F-127 hydrogel for the reduction of ο-nitroaniline (ο-NA) to 1, 2-benzenediamine. Fourier Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Thermogravimetric analysis (TGA), Raman Spectroscopy, Powder X-Ray Diffraction (PXRD) analysis and Brunauer-Emmett-Teller (BET) Nitrogen adsorption techniques were used for characterization of monoliths. An epoch-making catalytic activity of Ag/F-127/GO monoliths is observed in the reduction of ο-NA to 1, 2-benzenediamine in presence of NaBH{sub 4} inmore » aqueous media. The catalyst Ag/F-127/GO took only 2 min which is the minimum time reported so far with significant rate constant claimed itself a leading catalyst for the reduction of ο-NA to 1,2-benzenediamine. Pseudo first order rate constant (k) and Turn over frequency (TOF) values are 0.231 min{sup −1} and 30.053×10{sup 19} molecules min{sup −1} respectively suggest that the catalyst has industrial importance. Recyclability and stability of Ag/F-127/GO catalyst are studied successfully up to 10 cycles. Energy of activation (E{sub a}), and thermodynamic parameters viz. activation enthalpy (ΔH{sup ≠}), activation Gibbs free energy (ΔG{sup ≠}), and entropy of activation (ΔS{sup ≠}) were also ascertained. Catalytic activities of Ag/F-127, Ag/F-127/Dextran, Ag/F-127/Trimethylbenzene (TMB), Ag/F-127/SiNPs, and Ag/F-127/Si/GO monoliths were also studied. - Graphical abstract: Significant catalytic activities of silver monoliths against the reduction of ο-NA to 1,2 benzenediamine. - Highlights: • A new catalyst synthesized Ag/F-127/GO for the reduction of ο- NA to 1, 2- benzenediamine took only 2 min. • Turn over frequency of as synthesized catalyst was 30.053×10{sup 19} molecules min{sup −1} claimed itself a leading catalyst. • Recyclability of the catalyst was up to 10 cycles. • The synthesis is non toxic, economically viable and environmentally benign.« less

Efficient degradation of H2S over transition metal modified TiO2 under VUV irradiation: Performance and mechanism

NASA Astrophysics Data System (ADS)

Liu, Gaoyuan; Ji, Jian; Hu, Peng; Lin, Sixin; Huang, Haibao

2018-03-01

Odor pollution causes great harm to the atmospheric environment and human health. H2S, as an odor gas, is highly toxic and corrosive and thus requires removal efficiently. In this study, TiO2 catalysts modified by transition metals including Mn, Cu, Ni and Co, were prepared using a modified sol-gelatin method and tested under UV-PCO or VUV-PCO process. H2S degradation was great enhanced in VUV-PCO compared with conventional UV-PCO. Among the catalysts, 1 wt% Mn-TiO2 showed the highest removal efficiency of 89.9%, which is 30 times higher than that under 254 nm UV irradiation. Residual ozone in the outlet can be completely eliminated by Mn-TiO2. Photocatalytic oxidation, photolysis and ozone-assisted catalytic oxidation all involved in the VUV-PCO process and their contribution were determined by H2S removal efficiency.

Transfer hydrogenation catalysis in cells as a new approach to anticancer drug design

PubMed Central

Soldevila-Barreda, Joan J.; Romero-Canelón, Isolda; Habtemariam, Abraha; Sadler, Peter J.

2015-01-01

Organometallic complexes are effective hydrogenation catalysts for organic reactions. For example, Noyori-type ruthenium complexes catalyse reduction of ketones by transfer of hydride from formate. Here we show that such catalytic reactions can be achieved in cancer cells, offering a new strategy for the design of safe metal-based anticancer drugs. The activity of ruthenium(II) sulfonamido ethyleneamine complexes towards human ovarian cancer cells is enhanced by up to 50 × in the presence of low non-toxic doses of formate. The extent of conversion of coenzyme NAD+ to NADH in cells is dependent on formate concentration. This novel reductive stress mechanism of cell death does not involve apoptosis or perturbation of mitochondrial membrane potentials. In contrast, iridium cyclopentadienyl catalysts cause cancer cell death by oxidative stress. Organometallic complexes therefore have an extraordinary ability to modulate the redox status of cancer cells. PMID:25791197

Nano-palladium is a cellular catalyst for in vivo chemistry

NASA Astrophysics Data System (ADS)

Miller, Miles A.; Askevold, Bjorn; Mikula, Hannes; Kohler, Rainer H.; Pirovich, David; Weissleder, Ralph

2017-07-01

Palladium catalysts have been widely adopted for organic synthesis and diverse industrial applications given their efficacy and safety, yet their biological in vivo use has been limited to date. Here we show that nanoencapsulated palladium is an effective means to target and treat disease through in vivo catalysis. Palladium nanoparticles (Pd-NPs) were created by screening different Pd compounds and then encapsulating bis[tri(2-furyl)phosphine]palladium(II) dichloride in a biocompatible poly(lactic-co-glycolic acid)-b-polyethyleneglycol platform. Using mouse models of cancer, the NPs efficiently accumulated in tumours, where the Pd-NP activated different model prodrugs. Longitudinal studies confirmed that prodrug activation by Pd-NP inhibits tumour growth, extends survival in tumour-bearing mice and mitigates toxicity compared to standard doxorubicin formulations. Thus, here we demonstrate safe and efficacious in vivo catalytic activity of a Pd compound in mammals.

Application of Modified Nanonaturally Montmorillonite in Monochlorobenzene Remediation in River Water

NASA Astrophysics Data System (ADS)

Liu, Chen; Chen, Jun-Feng; Li, Yun; Chen, Rong-Chang; Asaoka, Sachio; Yuan, Guo-Li

2012-12-01

As the inland waterway transportation developed rapidly in China, the frequency of hazardous chemical leakage accidents is increasing every year. Such pollution to inland river environment has become a world-wide issue. Montmorillonite (Mont) is typical 2:1 layer type silicate clay and due to their special structure, it has been used in organic pollution removal process. In order to improve their ability in pollution adsorption, the pillared Mont was made in this work. Since the common toxic structure in most chemical pollutants is the halogen atom-benzene ring part, we select a typical compound Monochlorobenzene (MCB) as the aim contaminant. In this research, the original Mont, Na-Mont, TiO2 and TiO2-Mont were prepared and used in MCB degradation experiment as catalysts. The influence of catalyst amount, promoter (H2O2) amount, MCB concentration and reaction time to MCB removal rate were studied, respectively in detail.

Theophylline-assisted, eco-friendly synthesis of PtAu nanospheres at reduced graphene oxide with enhanced catalytic activity towards Cr(VI) reduction.

PubMed

Hu, Ling-Ya; Chen, Li-Xian; Liu, Meng-Ting; Wang, Ai-Jun; Wu, Lan-Ju; Feng, Jiu-Ju

2017-05-01

Theophylline as a naturally alkaloid is commonly employed to treat asthma and chronic obstructive pulmonary disorder. Herein, a facile theophylline-assisted green approach was firstly developed for synthesis of PtAu nanospheres/reduced graphene oxide (PtAu NSs/rGO), without any surfactant, polymer, or seed involved. The obtained nanocomposites were applied for the catalytic reduction and removal of highly toxic chromium (VI) using formic acid as a model reductant at 50°C, showing the significantly enhanced catalytic activity and improved recyclability when compared with commercial Pt/C (50%) and home-made Au nanocrystals supported rGO (Au NCs/rGO). It demonstrates great potential applications of the catalyst in wastewater treatment and environmental protection. The eco-friendly route provides a new platform to fabricate other catalysts with enhanced catalytic activity. Copyright © 2016 Elsevier Inc. All rights reserved.

Cardiac Amyloidosis

MedlinePlus

... adding salt to food, and avoiding eating in restaurants. Daily weighing can be helpful: a weight gain ... effective but toxic therapy, and very careful patient selection is needed. View this table: View inline View ...

Speciation analysis and leaching behaviors of selected trace elements in spent SCR catalyst.

PubMed

Dai, Zejun; Wang, Lele; Tang, Hao; Sun, Zhijun; Liu, Wei; Sun, Yi; Su, Sheng; Hu, Song; Wang, Yi; Xu, Kai; Liu, Liang; Ling, Peng; Xiang, Jun

2018-09-01

This study investigated heavy metal chemical speciation and leaching behavior from a board-type spent selective catalytic reduction (SCR) catalyst containing high concentrations of vanadium, chromium, nickel, copper, zinc, and lead. A three-step sequential extraction method, standard toxicity characteristic leaching procedure (TCLP), and leaching characteristic tests have been performed. It was found that the mobility of six heavy metals in the spent SCR catalyst was significantly different. The mobility of the six heavy metals exhibited the following order: Ni > Zn > V > Cr > As > Cu. Meanwhile, TCLP test results revealed relatively high Zn and Cr leaching rate of 83.20% and 10.35%, respectively. It was found that leaching rate was positively correlated with available contents (sum of acid soluble, reducible and oxidizable fractions). Leaching characteristics tests indicated that pH substantially affected the leaching of these heavy metals. In particular, the leaching of Cr, Ni, Cu, and Zn was positively influenced by strong acid, while V and As were easily released in the presence of strong acid and strong alkali (pH < 3 or pH > 11). In terms of kinetics, the leaching of Cr, Ni, Cu, Zn, and As within the spent catalyst was dominated by erosion and dissolution processes, which were rapid reaction processes. V was released in large amounts within 1 h, but its leaching amount sharply decreased with time due to readsorption. Copyright © 2018 Elsevier Ltd. All rights reserved.

Ultrafast Transient Absorption Spectroscopy of Polymer-Based Organophotoredox Catalysts Mimicking Transition-Metal Complexes

NASA Astrophysics Data System (ADS)

Jamhawi, Abdelqader; Paul, Anam C.; Smith, Justin D.; Handa, Sachin; Liu, Jinjun

2017-06-01

Transition-metal complexes of rare earth metals including ruthenium and iridium are most commonly employed as visible-light photocatalysts. Despite their highly important and broad applications, they have many disadvantages including high cost associated with low abundance in earth crust, potential toxicity, requirement of specialized ligands for desired activity, and difficulty in recycling of metal contents as well as associated ligands. Polymer-based organophotoredox catalysts are promising alternatives and possess unique advantages such as easier synthesis from inexpensive starting material, longer excited state life time, broad range of activity, sustainability, and recyclability. In this research talk, time-resolved photoluminescence and femtosecond transient absorption (TA) spectroscopy measurements of three novel polymer-based organophotoredox catalysts will be presented. By our synthetic team, their catalytic activity has been proven in some highly valuable chemical transformations, that otherwise require transition metal complexes. Time-resolved spectroscopic investigations have demonstrated that photoinduced processes in these catalysts are similar to the transition metal complexes. Especially, intramolecular vibrational relaxation, internal conversion, and intersystem crossing from the S1 state to the T1 state all occur on a sub-picosecond timescale. The long lifetime of the T1 state ( 2-3 microsecond) renders these polymers potent oxidizing and reducing agents. A spectroscopic and kinetic model has been developed for global fitting of TA spectra in both the frequency and time domains. Implication of the current ultrafast spectroscopy studies of these novel molecules to their roles in photocatalysis will be discussed.

Evaluation of the toxic properties of naturally weathered Exxon Valdez crude oil to surrogate wildlife species

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

Stubblefield, W.A.; Hancock, G.A.; Ford, W.H.

1995-12-31

The toxic properties of naturally weathered Exxon Valdez crude oil (WEVC) to avian and mammalian wildlife species were evaluated using the surrogate species, mallard duck, Anas platyrhynchos, and European ferret, Mustela putorius. This study was conducted to evaluate the potential for toxic (rather than physical) injury to wildlife species that may have been exposed to WEVC, either through external contact or through dietary uptake. Previous studies have assessed the toxicity of unweathered crude oils, including Alaska North Slope Crude, but little information exists regarding the toxicity of a naturally weathered crude oil, typical of that encountered following a spill. Amore » battery of laboratory toxicity tests was conducted, in compliance with standard and published test procedures, to evaluate acute and subchronic toxicity of WEVC. These included tests of food avoidance, reproductive effects, and direct eggshell application toxicity. Naturally weathered EVC, recovered postspill from Prince William Sound, was used as the test material. 36 refs., 7 figs., 4 tabs.« less

Recurrent Streptococcus agalactiae Toxic Shock Syndrome Triggered by a Tumor Necrosis Factor-α Inhibitor

PubMed Central

Yoshida, Masataka; Takazono, Takahiro; Tashiro, Masato; Saijo, Tomomi; Morinaga, Yoshitomo; Yamamoto, Kazuko; Nakamura, Shigeki; Imamura, Yoshifumi; Miyazaki, Taiga; Sawai, Toyomitsu; Nishino, Tomoya; Izumikawa, Koichi; Yanagihara, Katsunori; Mukae, Hiroshi; Kohno, Shigeru

2016-01-01

Streptococcal toxic shock syndrome caused by group B streptococcus (GBS) is a rare, but lethal disease. We experienced a 45-year-old woman with pustular psoriasis who developed toxic shock-like syndrome during infliximab treatment. Surprisingly, similar episodes recurred three times in one year with restarting of infliximab treatments. In the third episode, GBS were detected in blood, urine, and vaginal secretion cultures. These episodes of shock syndrome were possibly due to GBS. To the best of our knowledge, this is the first case report of recurrent streptococcal toxic shock syndrome possibly caused by GBS which was induced by anti-TNF-α inhibitor therapy. The restarting of biological agents in patients with a history of toxic shock syndrome should therefore be avoided as much as possible. PMID:27803422

Recurrent Streptococcus agalactiae Toxic Shock Syndrome Triggered by a Tumor Necrosis Factor-α Inhibitor.

PubMed

Yoshida, Masataka; Takazono, Takahiro; Tashiro, Masato; Saijo, Tomomi; Morinaga, Yoshitomo; Yamamoto, Kazuko; Nakamura, Shigeki; Imamura, Yoshifumi; Miyazaki, Taiga; Sawai, Toyomitsu; Nishino, Tomoya; Izumikawa, Koichi; Yanagihara, Katsunori; Mukae, Hiroshi; Kohno, Shigeru

Streptococcal toxic shock syndrome caused by group B streptococcus (GBS) is a rare, but lethal disease. We experienced a 45-year-old woman with pustular psoriasis who developed toxic shock-like syndrome during infliximab treatment. Surprisingly, similar episodes recurred three times in one year with restarting of infliximab treatments. In the third episode, GBS were detected in blood, urine, and vaginal secretion cultures. These episodes of shock syndrome were possibly due to GBS. To the best of our knowledge, this is the first case report of recurrent streptococcal toxic shock syndrome possibly caused by GBS which was induced by anti-TNF-α inhibitor therapy. The restarting of biological agents in patients with a history of toxic shock syndrome should therefore be avoided as much as possible.

General aspects of metal toxicity.

PubMed

Kozlowski, H; Kolkowska, P; Watly, J; Krzywoszynska, K; Potocki, S

2014-01-01

This review is focused on the general mechanisms of metal toxicity in humans. The possible and mainly confirmed mechanisms of their action are discussed. The metals are divided into four groups due to their toxic effects. First group comprises of metal ions acting as Fenton reaction catalyst mainly iron and copper. These types of metal ions participate in generation of the reactive oxygen species. Metals such as nickel, cadmium and chromium are considered as carcinogenic agents. Aluminum, lead and tin are involved in neurotoxicity. The representative of the last group is mercury, which may be considered as a generally toxic metal. Fenton reaction is a naturally occurring process producing most active oxygen species, hydroxyl radical: Fe(2+) + He2O2 ↔ Fe(3+) + OH(-) + OH(•) It is able to oxidize most of the biomolecules including DNA, proteins, lipids etc. The effect of toxicity depends on the damage of molecules i.e. production site of the hydroxyl radical. Chromium toxicity depends critically on its oxidation state. The most hazardous seems to be Cr(6+) (chromates) which are one of the strongest inorganic carcinogenic agents. Cr(6+) species act also as oxidative agents damaging among other nucleic acids. Redox inactive Al(3+), Cd(2+) or Hg(2+) may interfere with biology of other metal ions e.g. by occupying metal binding sites in biomolecules. All these aspects will be discussed in the review.

50 CFR 600.510 - Gear avoidance and disposal.

Code of Federal Regulations, 2011 CFR

2011-10-01

... any marine resource, including marine mammals and birds, except in cases of emergency involving the..., fishing gear, net scraps, bale straps, plastic bags, oil drums, petroleum containers, oil, toxic chemicals...

Development of Metal-impregnated Single Walled Carbon Nanotubes for Toxic Gas Contaminant Control in Advanced Life Support Systems

NASA Technical Reports Server (NTRS)

Cinke, Martin; Li, Jing; Chen, Bin; Wignarajah, Kanapathipillai; Pisharody, Suresh A.; Fisher, John W.; Delzeit, Lance; Meyyappan, Meyya; Partridge, Harry; Clark, Kimberlee

2003-01-01

The success of physico-chemical waste processing and resource recovery technologies for life support application depends partly on the ability of gas clean-up systems to efficiently remove trace contaminants generated during the process with minimal use of expendables. Highly purified metal-impregnated carbon nanotubes promise superior performance over conventional approaches to gas clean-up due to their ability to direct the selective uptake gaseous species based both on the nanotube s controlled pore size, high surface area, and ordered chemical structure that allows functionalization and on the nanotube s effectiveness as a catalyst support material for toxic contaminants removal. We present results on the purification of single walled carbon nanotubes (SWCNT) and efforts at metal impregnation of the SWCNT's.

Formation of N-alkylpyrroles via intermolecular redox amination.

PubMed

Pahadi, Nirmal K; Paley, Miranda; Jana, Ranjan; Waetzig, Shelli R; Tunge, Jon A

2009-11-25

A wide variety of aldehydes, ketones, and lactols undergo redox amination when allowed to react with 3-pyrroline in the presence of a mild Brønsted acid catalyst. This reaction utilizes the inherent reducing power of 3-pyrroline to perform the equivalent of a reductive amination to form alkyl pyrroles. In doing so, the reaction avoids stoichiometric reducing agents that are typically associated with reductive aminations. Moreover, the redox amination protocol allows access to alkyl pyrroles that cannot be made via standard reductive amination.

Emissions of toxic pollutants from compressed natural gas and low sulfur diesel-fueled heavy-duty transit buses tested over multiple driving cycles.

PubMed

Kado, Norman Y; Okamoto, Robert A; Kuzmicky, Paul A; Kobayashi, Reiko; Ayala, Alberto; Gebel, Michael E; Rieger, Paul L; Maddox, Christine; Zafonte, Leo

2005-10-01

The number of heavy-duty vehicles using alternative fuels such as compressed natural gas (CNG) and new low-sulfur diesel fuel formulations and equipped with after-treatment devices are projected to increase. However, few peer-reviewed studies have characterized the emissions of particulate matter (PM) and other toxic compounds from these vehicles. In this study, chemical and biological analyses were used to characterize the identifiable toxic air pollutants emitted from both CNG and low-sulfur-diesel-fueled heavy-duty transit buses tested on a chassis dynamometer over three transient driving cycles and a steady-state cruise condition. The CNG bus had no after-treatment, and the diesel bus was tested first equipped with an oxidation catalyst (OC) and then with a catalyzed diesel particulate filter (DPF). Emissions were analyzed for PM, volatile organic compounds (VOCs; determined on-site), polycyclic aromatic hydrocarbons (PAHs), and mutagenic activity. The 2000 model year CNG-fueled vehicle had the highest emissions of 1,3-butadiene, benzene, and carbonyls (e.g., formaldehyde) of the three vehicle configurations tested in this study. The 1998 model year diesel bus equipped with an OC and fueled with low-sulfur diesel had the highest emission rates of PM and PAHs. The highest specific mutagenic activities (revertants/microg PM, or potency) and the highest mutagen emission rates (revertants/mi) were from the CNG bus in strain TA98 tested over the New York Bus (NYB) driving cycle. The 1998 model year diesel bus with DPF had the lowest VOCs, PAH, and mutagenic activity emission. In general, the NYB driving cycle had the highest emission rates (g/mi), and the Urban Dynamometer Driving Schedule (UDDS) had the lowest emission rates for all toxics tested over the three transient test cycles investigated. Also, transient emissions were, in general, higher than steady-state emissions. The emissions of toxic compounds from an in-use CNG transit bus (without an oxidation catalyst) and from a vehicle fueled with low-sulfur diesel fuel (equipped with DPF) were lower than from the low-sulfur diesel fueled vehicle equipped with OC. All vehicle configurations had generally lower emissions of toxics than an uncontrolled diesel engine. Tunnel backgrounds (measurements without the vehicle running) were measured throughout this study and were helpful in determining the incremental increase in pollutant emissions. Also, the on-site determination of VOCs, especially 1,3-butadiene, helped minimize measurement losses due to sample degradation after collection.

Prenatal Care

MedlinePlus

... and prescription medicines you are using. These include dietary or herbal supplements. Some medicines are not safe during pregnancy. At the same time, stopping medicines you need also can be harmful. Avoid contact with toxic substances or materials at ...

Minimally Adhesive, Advanced Non-toxic Coatings of Dendrimeric Catalysts in Sol-Gel Matrices

DTIC Science & Technology

2015-10-19

PD Summary of Research Highlights Supported by ONR N00014-09-1-0217 1) Hydrophobie xerogel coatings are "robust" - good adhesion to glass , aluminum...that none of the xerogels leach materials that cause increased mortality relative to leachates from glass slides. 6) Xerogels can be tailored to...with high surface area, high surface roughness, and chemical segregation of functionality. 10) Monoliths of 5 mole-% V2O5 or 0=V(0-/Pr)3 in

Review of desulfurization process for biogas purification

NASA Astrophysics Data System (ADS)

Xiao, Cong; Ma, Yunqian; Ji, Dandan; Zang, Lihua

2017-12-01

Hydrogen sulfide (H2S) is a toxic and odorous compound present in biogas produced by the anaerobic digestion of biosolids and other organic materials. Elimination of H2S is necessary as it is extremely hazardous to human health, poisonous to process catalysts and corrosive to equipment. The desulfurization technology is an important part for efficient utilization of biogas. In this paper, the traditional wet and dry desulfurization technology for biogas was reviewed, and the new research progress of biological desulfurization technologies are also introduced.

Microwave-Assisted Condensation Reactions of Acetophenone Derivatives and Activated Methylene Compounds with Aldehydes Catalyzed by Boric Acid under Solvent-Free Conditions.

PubMed

Brun, Elodie; Safer, Abdelmounaim; Carreaux, François; Bourahla, Khadidja; L'helgoua'ch, Jean-Martial; Bazureau, Jean-Pierre; Villalgordo, Jose Manuel

2015-06-23

We here disclosed a new protocol for the condensation of acetophenone derivatives and active methylene compounds with aldehydes in the presence of boric acid under microwave conditions. Implementation of the reaction is simple, healthy and environmentally friendly owing to the use of a non-toxic catalyst coupled to a solvent-free procedure. A large variety of known or novel compounds have thus been prepared, including with substrates bearing acid or base-sensitive functional groups.

Web-Based Toxic Gas Dispersion Model for Shuttle Launch Operations

NASA Technical Reports Server (NTRS)

Bardina, Jorge; Thirumalainambi, Rajkumar

2004-01-01

During the launch of the Space Shuttle vehicle, the burning of liquid hydrogen fuel with liquid oxygen at extreme high temperatures inside the three space shuttle main engines, and the burning of the solid propellant mixture of ammonium perchlorate oxidizer, aluminum fuel, iron oxide catalyst, polymer binder, and epoxy curing agent in the two solid rocket boosters result in the formation of a large cloud of hot, buoyant toxic exhaust gases near the ground level which subsequently rises and entrains into ambient air until the temperature and density of the cloud reaches an approximate equilibrium with ambient conditions. In this paper, toxic gas dispersion for various gases are simulated over the web for varying environmental conditions which is provided by rawinsonde data. The model simulates chemical concentration at ground level up to 10 miles (1 KM grids) in downrange up to an hour after launch. The ambient concentration of the gas dispersion and the deposition of toxic particles are used as inputs for a human health risk assessment model. The advantage of the present model is the accessibility and dissemination of model results to other NASA centers over the web. The model can be remotely operated and various scenarios can be analyzed.

Electro-catalytic biodiesel production from canola oil in methanolic and ethanolic solutions with low cost stainless steel and hybrid ion-exchange resin grafted electrodes

NASA Astrophysics Data System (ADS)

Allioux, Francois-Marie; Holland, Brendan J.; Kong, Lingxue; Dumée, Ludovic F.

2017-07-01

Biodiesel is a growing alternative to petroleum fuels and is produced by the catalysed transesterification of fats in presence of an alcohol base. Transesterification processes using homogeneous catalysts are considered to be amongst the most efficient methods but rely on the feedstock quality and low water content in order to avoid undesirable saponification reactions. In this work, the electro-catalytic conversion of canola oil to biodiesel in a 1% aqueous methanolic and ethanolic reaction mixture was performed without the addition of external catalyst or co-solvent. An inexpensive stainless steel electrode and a hybrid stainless steel electrode coated with an ion-exchange resin catalyst were used as cathode materials while the anode was composed of a plain carbon paper. The cell voltages were varied from 10 to 40 V and the reaction temperature maintained at 20 or 40°C. The canola oil conversion rates were found to be superior at 40°C without saponification reactions for cell voltages below 30 V. The conversion rates were as high as 87% for the hybrid electrode and 81% for the plain stainless steel electrode. This work could inspire new process development for the conversion of high water content feedstock for the production of second-generation biodiesel.

One-pot deposition of palladium on hybrid TiO2 nanoparticles and catalytic applications in hydrogenation.

PubMed

Mehri, Afef; Kochkar, Hafedh; Daniele, Stéphane; Mendez, Violaine; Ghorbel, Abdelhamid; Berhault, Gilles

2012-03-01

One-pot deposition of Pd onto TiO(2) has been achieved through directly contacting palladium(II) salt with nanosized functionalized TiO(2) support initially obtained by sol-gel process using titanium isopropoxide and citric acid. Citrate groups act as functional moieties able to directly reduce the Pd salt avoiding any further reducing treatment. Various palladium salts (Na(2)PdCl(4) and Pd(NH(3))(4)Cl(2)·H(2)O) and titanium to citrate (Ti/CA) ratios (20, 50, and 100) were used in order to study the effect of the nature of the precursor and of the citrate content on the final Pd particle size and catalytic properties of the as-obtained Pd/TiO(2) systems. Characterization was performed using N(2) adsorption-desorption isotherms, ICP-AES, FTIR, XRD, XPS, and TEM. The as-obtained hybrid Pd/TiO(2) catalysts were tested in the selective hydrogenation (HYD) of an α,β-unsaturated aldehyde, i.e. cinnamaldehyde. Citrate-free Pd/TiO(2)-based catalysts present lower selectivity into saturated alcohol. However, citrate-functionalized Pd/TiO(2) catalyst seems to control the selectivity, the particle size and dispersion of Pd NPs leading to high intrinsic activity. Copyright © 2011 Elsevier Inc. All rights reserved.

A peroxidase mimic with atom transfer radical polymerization activity constructed through the grafting of heme onto metal-organic frameworks.

PubMed

Jiang, Wei; Pan, Yue; Yang, Jiebing; Liu, Yong; Yang, Yan; Tang, Jun; Li, Quanshun

2018-07-01

Atom transfer radical polymerization (ATRP) has been considered to be an efficient strategy for constructing functional macromolecules owing to its simple operation and versatile monomers, and thus it is of great significance to develop ideal catalysts with higher activity and perfect reusability. We constructed a peroxidase mimic through the grafting of heme onto metal-organic frameworks UiO-66-NH 2 (ZrMOF), namely Heme-ZrMOF. After the systematic characterization of structure, the composite Heme-ZrMOF was demonstrated to possess high peroxidase activity using 2,2'-azinobis-(3-ethylbenzthiazoline-6-sulphonate) and 3,3',5,5'-tetramethylbenzidine as substrates. The enzyme mimic was then used as catalysts in the ATRP reactions of different monomers, in which favorable monomer conversion (44.6-98.0%) and product molecular weight (8600-25,600 g/mol) could be obtained. Compared to free heme, Heme-ZrMOF could efficiently achieve the easy separation of heme from the catalytic system and facilitate the ATRP reaction in an aqueous environment to avoid the utilization of organic solvents. In conclusion, the enzyme mimic Heme-ZrMOF could be potentially used as an effective catalyst for preparing well-defined polymers with biomedical applications. Copyright © 2018 Elsevier Inc. All rights reserved.

The repellent and persistent toxic effects of essential oils against the poultry red mite, Dermanyssus gallinae.

PubMed

Nechita, I S; Poirel, M T; Cozma, V; Zenner, L

2015-12-15

The economic impact of the poultry red mite, Dermanyssus gallinae, the lack of new acaricides, the occurrence of resistance and tighter legislation have all led to the need to find new ways to control this pest. One promising alternative method of control focuses on employing repellent and/or toxic effects of selected plant essential oils against D. gallinae. Ten essential oils (basil, thyme, coriander, eucalyptus, lavender, lemon, fir tree, oregano, mint, and juniper) were tested for the persistence of toxic and repellent effects. In filter-paper toxicity bioassays against D. gallinae, the best results were observed for lavender (more than 97% mortality after 48 and 72 h) and thyme (84% at 72 h) at a dose of 0.12 mg/cm(2). In addition, two oils showed significant persistent toxic effects 15 and 30 days post application to filter papers. Thyme was the most effective (100% mortality at 72 h), followed by lavender (nearly 80% mortality after 72 h). Out of the ten oils tested for their repellent effect, thyme was the strongest, with nearly 80% of the tested area avoided by mites; oregano caused a 60% avoidance and lavender exhibited an effect close to 40%. All other oils exhibited a repellent effect of less than 30%. None of the experiments showed a repellent effect for HM (commercial alimentary oil) or negative controls. We found that the thyme and lavender essential oils exhibited promising results when tested in vitro for toxic and repellent effects against D. gallinae; thus, we suggest that future experiments focus on in vivo tests using these oils in farm units. Copyright © 2015 Elsevier B.V. All rights reserved.

Catalytic Properties of Fe-containing Layered Aluminosilicates in Photo-oxidation of Dye “Methyl Green”

NASA Astrophysics Data System (ADS)

Shadrina, O. A.; Dashinamzhilova, E. Ts; Khankhasaeva, S. Ts

2017-11-01

The iron-containing materials with an iron content of 40 mg/g and 52.5 mg/g, a specific surface area of 107 m2/g and 96 m2/g are developed on the basis of natural layered aluminosilicate (montmorillonite) and polyhydroxo complexes of iron. It is shown that the materials exhibit high catalytic activity in the photo-oxidation of dye “Methyl Green”. The influence of physicochemical parameters (loading of the catalyst, a ratio of initial concentrations [H2O2]/[MG] on the efficiency of the dye photo-oxidation was established. The optimum conditions, which made it possible to achieve high mineralization and 100 % the dye oxidation efficiency were determined: the catalyst loading equal to 1.0 g/l and the ratio of [H2O2] and [MG] equal to stoichiometric ratio (55 mol/mol). The decrease of the total organic carbon content after photo-oxidation reaction was 56.5%. The average value of the quantum yield of the dye photo-oxidation was to 0.30 mol/Einstein. The results of the conducted research show that the developed iron-containing materials are the promising catalysts for photo-Fenton processes of oxidative degradation of organic compounds. The materials are of interest for use in wastewater treatment processes from toxic organic pollutants.

Performance of a passive direct ethanol fuel cell

NASA Astrophysics Data System (ADS)

Pereira, J. P.; Falcão, D. S.; Oliveira, V. B.; Pinto, A. M. F. R.

2014-06-01

Ethanol emerges as an attractive fuel since it is less toxic and has higher energy density than methanol and can be produced from biomass. Direct ethanol fuel cells (DEFCs) appear as a good choice for producing sustainable energy for portable applications. However, they are still far from attaining acceptable levels of power output, since their performance is affected by the slow electrochemical ethanol oxidation and water and ethanol crossover. In the present work, an experimental study on the performance of a passive DEFC is described. Tailored MEAs (membrane electrode assembly) with different catalyst loadings, anode diffusion layers and membranes were tested in order to select optimal working conditions at high ethanol concentrations and low ethanol crossover. The performance increased with an increase of membrane and anode diffusion layer thicknesses and anode catalyst loading. A maximum power density of 1.33 mW cm-2, was obtained using a Nafion 117 membrane, 4 mg cm-2 of Pt-Ru and 2 mg cm-2 of Pt on the anode and cathode catalyst layers, ELAT as anode diffusion layer, carbon cloth as cathode diffusion layer and an ethanol concentration of 2 M. As far as the authors are aware this is the first work reporting an experimental optimization of passive DEFCs.

Effective heterogeneous transition metal glycerolates catalysts for one-step biodiesel production from low grade non-refined Jatropha oil and crude aqueous bioethanol

PubMed Central

Lau, Pak-Chung; Kwong, Tsz-Lung; Yung, Ka-Fu

2016-01-01

The utilization of bioethanol as the alcohol source for biodiesel production is more environmentally advantageous over methanol owing to its lower toxicity, lower flammability and its sustainable supply from renewable agricultural resources. However, as the presence of water in crude bioethanol is the critical factor limiting the biodiesel production process, the energy-intensive and costly purification of bioethanol is necessary for biodiesel application. Manganese glycerolate (MnGly) is reported the first time here as a robust heterogeneous catalyst that exhibited over 90% conversion by using aqueous ethanol containing 80 wt.% of water in the production of fatty acid ethyl ester (FAEE). The employment of 95 wt.% ethanol with respect to water could achieve 99.7% feedstock conversion in 6 hours under the optimal reaction conditions: reaction temperature (150 °C), feedstock-to-ethanol molar ratio (1:20) and catalyst loading (6 wt.%). Commercially available low grade crude bioethanol with the presence of impurities like sugars were applied which demonstrated remarkable catalytic activity in 24 hours. The high water tolerance of MnGly towards biodiesel production could eventually simplify the purification of bioethanol that consumes less energy and production cost. PMID:27029238

TiO2 Nanorods Decorated with Pd Nanoparticles for Enhanced Liquefied Petroleum Gas Sensing Performance.

PubMed

Dhawale, Dattatray S; Gujar, Tanaji P; Lokhande, Chandrakant D

2017-08-15

Development of highly sensitive and selective semiconductor-based metal oxide sensor devices to detect toxic, explosive, flammable, and pollutant gases is still a challenging research topic. In the present work, we systematically enhanced the liquefied petroleum gas (LPG) sensing performance of chemical bath deposited TiO 2 nanorods by decorating Pd nanoparticle catalyst. Surface morphology with elemental mapping, crystal structure, composition and oxidation states, and surface area measurements of pristine TiO 2 and Pd:TiO 2 nanorods was examined by high resolution transmission electron microscopy with energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and nitrogen adsorption-desorption characterization techniques. LPG sensing performance of pristine TiO 2 and Pd:TiO 2 nanorods was investigated in different LPG concentration and operating temperature ranges. The LPG response of 21% for pristine TiO 2 nanorods is enhanced to 49% after Pd catalyst decoration with reasonably fast response and recovery times. Further, the sensor exhibited long-term stability, which could be due to the strong metal support (Pd:TiO 2 ) interaction and catalytic properties offered by the Pd nanoparticle catalyst. The work described herein demonstrates a general and scalable approach that provides a promising route for rational design of variety of sensor devices for LPG detection.

Effective heterogeneous transition metal glycerolates catalysts for one-step biodiesel production from low grade non-refined Jatropha oil and crude aqueous bioethanol

NASA Astrophysics Data System (ADS)

Lau, Pak-Chung; Kwong, Tsz-Lung; Yung, Ka-Fu

2016-03-01

The utilization of bioethanol as the alcohol source for biodiesel production is more environmentally advantageous over methanol owing to its lower toxicity, lower flammability and its sustainable supply from renewable agricultural resources. However, as the presence of water in crude bioethanol is the critical factor limiting the biodiesel production process, the energy-intensive and costly purification of bioethanol is necessary for biodiesel application. Manganese glycerolate (MnGly) is reported the first time here as a robust heterogeneous catalyst that exhibited over 90% conversion by using aqueous ethanol containing 80 wt.% of water in the production of fatty acid ethyl ester (FAEE). The employment of 95 wt.% ethanol with respect to water could achieve 99.7% feedstock conversion in 6 hours under the optimal reaction conditions: reaction temperature (150 °C), feedstock-to-ethanol molar ratio (1:20) and catalyst loading (6 wt.%). Commercially available low grade crude bioethanol with the presence of impurities like sugars were applied which demonstrated remarkable catalytic activity in 24 hours. The high water tolerance of MnGly towards biodiesel production could eventually simplify the purification of bioethanol that consumes less energy and production cost.

Atmospheric pressure reaction cell for operando sum frequency generation spectroscopy of ultrahigh vacuum grown model catalysts

NASA Astrophysics Data System (ADS)

Roiaz, Matteo; Pramhaas, Verena; Li, Xia; Rameshan, Christoph; Rupprechter, Günther

2018-04-01

A new custom-designed ultrahigh vacuum (UHV) chamber coupled to a UHV and atmospheric-pressure-compatible spectroscopic and catalytic reaction cell is described, which allows us to perform IR-vis sum frequency generation (SFG) vibrational spectroscopy during catalytic (kinetic) measurements. SFG spectroscopy is an exceptional tool to study vibrational properties of surface adsorbates under operando conditions, close to those of technical catalysis. This versatile setup allows performing surface science, SFG spectroscopy, catalysis, and electrochemical investigations on model systems, including single crystals, thin films, and deposited metal nanoparticles, under well-controlled conditions of gas composition, pressure, temperature, and potential. The UHV chamber enables us to prepare the model catalysts and to analyze their surface structure and composition by low energy electron diffraction and Auger electron spectroscopy, respectively. Thereafter, a sample transfer mechanism moves samples under UHV to the spectroscopic cell, avoiding air exposure. In the catalytic cell, SFG spectroscopy and catalytic tests (reactant/product analysis by mass spectrometry or gas chromatography) are performed simultaneously. A dedicated sample manipulation stage allows the model catalysts to be examined from LN2 temperature to 1273 K, with gaseous reactants in a pressure range from UHV to atmospheric. For post-reaction analysis, the SFG cell is rapidly evacuated and samples are transferred back to the UHV chamber. The capabilities of this new setup are demonstrated by benchmark results of CO adsorption on Pt and Pd(111) single crystal surfaces and of CO adsorption and oxidation on a ZrO2 supported Pt nanoparticle model catalyst grown by atomic layer deposition.

The potential for increasing the use of catalytic carbons in commercial applications

USGS Publications Warehouse

Kruse, C.W.

1996-01-01

A carbon catalyst, prepared either by oxidizing activated carbon with air at 500-700??C or by oxidizing activated carbon with boiling nitric acid followed by heating it to 500-700??C, is the subject of this paper. This catalyst, designated OAC500-700, catalyzes the removal of hydrogen chloride from alkyl halides. Because OAC500-700 retains adsorptive properties of an activated carbon it can be used both to adsorb pollutants from liquid or gaseous streams and to convert them to recyclable products. A highly-developed micropore structure is not required for all uses of activated carbon or a catalyst produced from it. A comparatively inexpensive ($325/ton projected) low surface area (<300 m2/g) carbon has been developed at the Illinois State Geological Survey (ISGS) for cleaning incinerator flue gas. This grade of activated carbon is widely used in Europe for flue gas cleaning and for other applications. Activated carbon adsorbers of some type are required by recently passed U.S. Environmental Protection Agency (EPA) regulations for municipal waste combustors to control emission of cadmium, mercury, lead, dioxins, furans and acid gases (U.S. EPA, 1995). Similar regulations are expected for hospital and hazardous waste incinerators. The marketing of less costly activated carbons of the type used widely in Europe is expected in the United States. Low cost OAC500-700 made from less expensive grades of activated carbon may become available for large scale adsorbent/catalyst systems designed to both remove and decompose toxic pollutants found in liquid and gaseous streams, chlorinated organic compounds in particular.

Nickel-doped cobalt ferrite nanoparticles: efficient catalysts for the reduction of nitroaromatic compounds and photo-oxidative degradation of toxic dyes.

PubMed

Singh, Charanjit; Goyal, Ankita; Singhal, Sonal

2014-07-21

This study deals with the exploration of NixCo₁-xFe₂O₄ (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0) ferrite nanoparticles as catalysts for reduction of 4-nitrophenol and photo-oxidative degradation of Rhodamine B. The ferrite samples with uniform size distribution were synthesized using the reverse micelle technique. The structural investigation was performed using powder X-ray diffraction, high-resolution transmission electron microscopy, energy dispersive X-ray and scanning tunneling microscopy. The spherical particles with ordered cubic spinel structure were found to have the crystallite size of 4-6 nm. Diffused UV-visible reflectance spectroscopy was employed to investigate the optical properties of the synthesized ferrite nanoparticles. The surface area calculated using BET method was found to be highest for Co₀.₄Ni₀.₆Fe₂O₄ (154.02 m(2) g(-1)). Co₀.₄Ni₀.₆Fe₂O₄ showed the best catalytic activity for reduction of 4-nitrophenol to 4-aminophenol in the presence of NaBH4 as reducing agent, whereas CoFe₂O₄ was found to be catalytically inactive. The reduction reaction followed pseudo-first order kinetics. The effect of varying the concentration of catalyst and NaBH₄ on the reaction rates was also scrutinized. The photo-oxidative degradation of Rhodamine B, enhanced oxidation efficacy was observed with the introduction of Ni(2+) in to the cobalt ferrite lattice due to octahedral site preference of Ni(2+). Almost 99% degradation was achieved in 20 min using NiFe₂O₄ nanoparticles as catalyst.

Silver/iron oxide/graphitic carbon composites as bacteriostatic catalysts for enhancing oxygen reduction in microbial fuel cells

NASA Astrophysics Data System (ADS)

Ma, Ming; You, Shijie; Gong, Xiaobo; Dai, Ying; Zou, Jinlong; Fu, Honggang

2015-06-01

Biofilms from anode heterotrophic bacteria are inevitably formed over cathodic catalytic sites, limiting the performances of single-chamber microbial fuel cells (MFCs). Graphitic carbon (GC) - based nano silver/iron oxide (AgNPs/Fe3O4/GC) composites are prepared from waste pomelo skin and used as antibacterial oxygen reduction catalysts for MFCs. AgNPs and Fe3O4 are introduced in situ into the composites by one-step carbothermal reduction, enhancing their conductivity and catalytic activity. To investigate the effects of Fe species on the antibacterial and catalytic properties, AgNPs/Fe3O4/GC is washed with sulfuric acid (1 mol L-1) for 0.5 h, 1 h, and 5 h and marked as AgNPs/Fe3O4/GC-x (x = 0.5 h, 1 h and 5 h, respectively). A maximum power density of 1712 ± 35 mW m-2 is obtained by AgNPs/Fe3O4/GC-1 h, which declines by 4.12% after 17 cycles. Under catalysis of all AgNP-containing catalysts, oxygen reduction reaction (ORR) proceeds via the 4e- pathway, and no toxic effects to anode microorganisms result from inhibiting the cathodic biofilm overgrowth. With the exception of AgNPs/Fe3O4/GC-5 h, the AgNPs-containing composites exhibit remarkable power output and coulombic efficiency through lowering proton transfer resistance and air-cathode biofouling. This study provides a perspective for the practical application of MFCs using these efficient antibacterial ORR catalysts.

Multimetallic Catalysis Enabled Cross-Coupling of Aryl Bromides with Aryl Triflates

PubMed Central

Ackerman, Laura K.G.; Lovell, Matthew M.

2015-01-01

Transition metal-catalyzed strategies for the formation of new C-C bonds have revolutionized the field of organic chemistry, enabling the efficient synthesis of ligands, materials, and biologically active molecules.1–3 In cases where a single metal fails to promote a selective or efficient transformation, the synergistic cooperation4 of two distinct catalysts – multimetallic catalysis – can be employed instead. Many important reactions rely on multimetallic catalysis,5 including the Wacker oxidation of olefins6–8 and the Sonogashira coupling of alkynes with aryl halides.9–10 However, the application of this strategy, even in recently developed methods11, has largely been limited to the use of metals with distinct reactivities, with only one metal catalyst undergoing an oxidative addition.12 In this manuscript, we demonstrate that cooperativity between two d10 metal catalysts, (bipyridine)nickel and (1,3-bis(diphenylphosphino)propane)palladium, enables a general cross-Ullman reaction.13–15 Our method couples aryl bromides with aryl triflates directly, eliminating the use of arylmetal reagents and avoiding the challenge of differentiating between multiple C–H bonds that is required for many C–H activation methods.16–17 The selectivity does not require an excess of either substrate and originates from the orthogonal activity of the two catalysts and the relative stability of the two arylmetal intermediates. While (dppp)Pd reacts preferentially with aryl triflates to afford a persistent intermediate, (bpy)Ni reacts preferentially with aryl bromides to form a transient, reactive intermediate. Although each catalyst forms less than 5% cross product in isolation, together they are able to achieve up to 94% yield. Our results reveal a new, general method for the synthesis of biaryls, heteroaryls, and dienes, as well as a new mechanism for selective transmetalation between two catalysts. We anticipate that this reaction will simplify the synthesis of pharmaceutical agents, many of which are currently made with pre-formed organometallic reagents,1–3 and lead to the discovery of new multimetallic reactions. PMID:26280337

Environmental assessment of depleted uranium used in military armor-piercing rounds in terrestrial systems.

PubMed

Stanley, Jacob K; Coleman, Jessica G; Brasfield, Sandra M; Bednar, Anthony J; Ang, Choo Y

2014-06-01

Depleted uranium (DU) from the military testing and use of armor-piercing kinetic energy penetrators has been shown to accumulate in soils; however, little is known about the toxicity of DU geochemical species created through corrosion or weathering. The purpose of the present study was to assess the toxic effects and bioaccumulation potential of field-collected DU oxides to the model terrestrial invertebrates Eisenia fetida (earthworm) and Porcellio scaber (isopod). Earthworm studies were acute (72 h) dermal exposures or 28-d spiked soil exposures that used noncontaminated field-collected soils from the US Army's Yuma and Aberdeen Proving Grounds. Endpoints assessed in earthworm testing included bioaccumulation, growth, reproduction, behavior (soil avoidance), and cellular stress (neutral red uptake in coelomocytes). Isopod testing used spiked food, and endpoints assessed included bioaccumulation, survival, and feeding behavior. Concentration-dependent bioaccumulation of DU in earthworms was observed with a maximum bioaccumulation factor of 0.35; however, no significant reductions in survival or impacts to cellular stress were observed. Reproduction lowest-observed-effect concentrations (LOEC) of 158 mg/kg and 96 mg/kg were observed in Yuma Proving Ground and a Mississippi reference soil (Karnac Ferry), respectively. Earthworm avoidance of contaminated soils was not observed in 48-h soil avoidance studies; however, isopods were shown to avoid food spiked with 12.7% by weight DU oxides through digital tracking studies. © 2014 SETAC.

Taking action on developmental toxicity: Scientists’ duties to protect children

PubMed Central

2012-01-01

Background Although adaptation and proper biological functioning require developmental programming, pollutant interference can cause developmental toxicity or DT. Objectives This commentary assesses whether it is ethical for citizens/physicians/scientists to allow avoidable DT. Methods Using conceptual, economic, ethical, and logical analysis, the commentary assesses what major ethical theories and objectors would say regarding the defensibility of allowing avoidable DT. Results The commentary argues that (1) none of the four major ethical theories (based, respectively, on virtue, natural law, utility, or equity) can consistently defend avoidable DT because it unjustifiably harms, respectively, individual human flourishing, human life, the greatest good, and equality. (2) Justice also requires leaving “as much and as good” biological resources for all, including future generations possibly harmed if epigenetic change is heritable. (3) Scientists/physicians have greater justice-based duties, than ordinary/average citizens, to help stop DT because they help cause it and have greater professional abilities/opportunities to help stop it. (4) Scientists/physicians likewise have greater justice-based duties, than ordinary/average citizens, to help stop DT because they benefit more from it, given their relatively greater education/consumption/income. The paper shows that major objections to (3)-(4) fail on logical, ethical, or scientific grounds, then closes with practical suggestions for implementing its proposals. Conclusions Because allowing avoidable DT is ethically indefensible, citizens---and especially physicians/scientists---have justice-based duties to help stop DT. PMID:22963689

Taking action on developmental toxicity: scientists' duties to protect children.

PubMed

Shrader-Frechette, Kristin

2012-09-10

Although adaptation and proper biological functioning require developmental programming, pollutant interference can cause developmental toxicity or DT. This commentary assesses whether it is ethical for citizens/physicians/scientists to allow avoidable DT. Using conceptual, economic, ethical, and logical analysis, the commentary assesses what major ethical theories and objectors would say regarding the defensibility of allowing avoidable DT. The commentary argues that (1) none of the four major ethical theories (based, respectively, on virtue, natural law, utility, or equity) can consistently defend avoidable DT because it unjustifiably harms, respectively, individual human flourishing, human life, the greatest good, and equality. (2) Justice also requires leaving "as much and as good" biological resources for all, including future generations possibly harmed if epigenetic change is heritable. (3) Scientists/physicians have greater justice-based duties, than ordinary/average citizens, to help stop DT because they help cause it and have greater professional abilities/opportunities to help stop it. (4) Scientists/physicians likewise have greater justice-based duties, than ordinary/average citizens, to help stop DT because they benefit more from it, given their relatively greater education/consumption/income. The paper shows that major objections to (3)-(4) fail on logical, ethical, or scientific grounds, then closes with practical suggestions for implementing its proposals. Because allowing avoidable DT is ethically indefensible, citizens---and especially physicians/scientists---have justice-based duties to help stop DT.

Pyrrolizidine alkaloid-containing toxic plants (Senecio, Crotalaria, Cynoglossum, Amsinckia, Heliotropium, and Echium spp.).

PubMed

Stegelmeier, Bryan L

2011-07-01

Pyrrolizidine alkaloid (PA)-containing plants are found throughout the world and are probably the most common plant cause of poisoning of livestock, wildlife, and humans. PAs are potent liver toxins that under some conditions can be carcinogenic. This article briefly introduces high-risk North American PA-containing plants, summarizing their toxicity and subsequent pathology. Current diagnostic techniques, treatments, and strategies to avoid losses to PA poisoning are also reviewed. Published by Elsevier Inc.

Lethal and sub-lethal effects of five pesticides used in rice farming on the earthworm Eisenia fetida.

PubMed

Rico, Andreu; Sabater, Consuelo; Castillo, María-Ángeles

2016-05-01

The toxicity of five pesticides typically used in rice farming (trichlorfon, dimethoate, carbendazim, tebuconazole and prochloraz) was evaluated on different lethal and sub-lethal endpoints of the earthworm Eisenia fetida. The evaluated endpoints included: avoidance behaviour after an exposure period of 2 days; and mortality, weight loss, enzymatic activities (cholinesterase, lactate dehydrogenase and alkaline phosphatase) and histopathological effects after an exposure period of 14 days. Carbendazim was found to be highly toxic to E. fetida (LC50=2mg/kg d.w.), significantly reducing earthworm weight and showing an avoidance response at soil concentrations that are close to those predicted in rice-fields and in surrounding ecosystems. The insecticide dimethoate showed a moderate acute toxicity (LC50=28mg/kg d.w.), whereas the rest of tested pesticides showed low toxicity potential (LC50 values above 100mg/kg d.w.). For these pesticides, however, weight loss was identified as a sensitive endpoint, with NOEC values approximately 2 times or lower than the calculated LC10 values. The investigated effects on the enzymatic activities of E. fetida and the observed histopathological alterations (longitudinal and circular muscle lesions, edematous tissues, endothelial degeneration and necrosis) proved to be sensitive biomarkers to monitor pesticide contamination and are proposed as alternative measures to evaluate pesticide risks on agro-ecosystems. Copyright © 2016 Elsevier Inc. All rights reserved.

Assessment of the use of red mud as a catalyst for photodegradation of bisphenol A in wastewater treatment.

PubMed

Busto, Raquel Vieira; Gonçalves, Maraisa; Coelho, Lúcia Helena Gomes

2016-09-01

This study aimed to investigate the use of red mud (RM) - a byproduct of aluminum production, as a photocatalyst, which was characterized physical-chemically and used in the photodegradation of the target compound bisphenol A (BPA). Chemical processing was performed in the RM (acid treatment, chemical reduction and calcination) to verify the most active catalyst. From the results obtained, a complete degradation kinetics of BPA was carried out using a synthetic matrix (BPA in deionized water) and a real matrix (BPA in wastewater) using natural RM/calcined and TiO 2 for comparison. The results indicated the potential use of the RM/calcined, which was able to degrade between 88 and 100% of the pollutant in a synthetic sample. Tests on a real effluent sample resulted in degradation rates that ranged from 59 to 100% with chemical oxygen demand reductions of up to 23% using natural RM/calcined in comparison to TiO 2 . The blank system (irradiation of the solution without the use of a photocatalyst) and the natural RM/calcined one, resulted in reductions of the toxicity in the effluent sample (measured by EC 20 using the marine bacteria Vibrio fischeri) of about 12 times, whereas the same treatment using TiO 2 resulted in a toxicity reduction of only seven times. Within these results, the RM/calcined showed potential to be used in wastewater treatment in polishing processes.

Toxicity of smelter slag-contaminated sediments from Upper Lake Roosevelt and associated metals to early life stage White Sturgeon (Acipenser transmontanus Richardson, 1836)

USGS Publications Warehouse

Little, E.E.; Calfee, R.D.; Linder, G.

2014-01-01

The toxicity of five smelter slag-contaminated sediments from the upper Columbia River and metals associated with those slags (cadmium, copper, zinc) was evaluated in 96-h exposures of White Sturgeon (Acipenser transmontanus Richardson, 1836) at 8 and 30 days post-hatch. Leachates prepared from slag-contaminated sediments were evaluated for toxicity. Leachates yielded a maximum aqueous copper concentration of 11.8 μg L−1 observed in sediment collected at Dead Man's Eddy (DME), the sampling site nearest the smelter. All leachates were nonlethal to sturgeon that were 8 day post-hatch (dph), but leachates from three of the five sediments were toxic to fish that were 30 dph, suggesting that the latter life stage is highly vulnerable to metals exposure. Fish maintained consistent and prolonged contact with sediments and did not avoid contaminated sediments when provided a choice between contaminated and uncontaminated sediments. White Sturgeon also failed to avoid aqueous copper (1.5–20 μg L−1). In water-only 96-h exposures of 35 dph sturgeon with the three metals, similar toxicity was observed during exposure to water spiked with copper alone and in combination with cadmium and zinc. Cadmium ranging from 3.2 to 41 μg L−1 or zinc ranging from 21 to 275 μg L−1 was not lethal, but induced adverse behavioral changes including a loss of equilibrium. These results suggest that metals associated with smelter slags may pose an increased exposure risk to early life stage sturgeon if fish occupy areas contaminated by slags.

Ecotoxicity of boric acid in standard laboratory tests with plants and soil organisms.

PubMed

Princz, Juliska; Becker, Leonie; Scheffczyk, Adam; Stephenson, Gladys; Scroggins, Rick; Moser, Thomas; Römbke, Jörg

2017-05-01

To verify the continuous sensitivity of ecotoxicological tests (mainly the test organisms), reference substances with known toxicity are regularly tested. Ideally, this substance(s) would lack specificity in its mode action, be bioavailable and readily attainable with cost-effective means of chemical characterization. Boric acid has satisfied these criteria, but has most recently been characterized as a substance of very high concern, due to reproductive effects in humans, thus limiting its recommendation as an ideal reference toxicant. However, there is probably no other chemical for which ecotoxicity in soil has been so intensively studied; an extensive literature review yielded lethal (including avoidance) and sublethal data for 38 taxa. The ecotoxicity data were evaluated using species sensitivity distributions, collectively across all taxa, and separately according to species type, endpoints, soil type and duration. The lack of specificity in the mode of action yielded broad toxicity among soil taxa and soil types, and provided a collective approach to assessing species sensitivity, while taking into consideration differences in test methodologies and exposure durations. Toxicity was species-specific with Folsomia candida and enchytraied species demonstrating the most sensitivity; among plants, the following trend occurred: dicotyledonous (more sensitive) ≫ monocotyledonous ≫ gymnosperm species. Sensitivity was also time and endpoint specific, with endpoints such as lethality and avoidance being less sensitive than reproduction effects. Furthermore, given the breadth of data and toxicity demonstrated by boric acid, lessons learned from its evaluation are discussed to recommend the properties required by an ideal reference substance for the soil compartment.

Oxygen toxicity.

PubMed

Stogner, S W; Payne, D K

1992-12-01

The objective of this article is to provide an overview of the biochemistry of oxygen metabolism, including the formation of free radicals and the role of endogenous antioxidants. Pathophysiologic correlates underlying the clinical manifestations of oxygen toxicity are reviewed and management strategies are outlined. References from basic science and clinical journals were selected from the authors' files and from a search of a computerized database of the biomedical literature. Articles selected for review included both historical and current literature concerning the biochemistry and pathophysiology of oxygen toxicity in animals and humans. The benefits of oxygen therapy have been known for many years; however, its potential toxicity has not been recognized until the last two decades. The lungs, the eyes, and, under certain conditions, the central nervous system are the organs most affected by prolonged exposure to hyperoxic environments. Free radical formation during cellular metabolism under hyperoxic conditions is recognized as the biochemical basis of oxygen injury to cells and organs. Endogenous antioxidants are a primary means of detoxifying reactive oxygen species and preventing hyperoxia-induced cellular damage. When this defense fails or is overwhelmed by the excessive production of hyperoxia-induced free-radical species, distinctive morphologic changes occur at the cellular level. The amount of hyperoxia required to cause cellular damage and the time course of these changes vary from species to species and from individual to individual within the same species. Age, nutritional status, presence of underlying diseases, and certain drugs may influence the development of oxygen toxicity. There is currently no reliably effective drug for preventing or delaying the development of oxygen toxicity in humans. Use of the lowest effective oxygen concentration, the avoidance of certain drugs, and attention to nutritional and metabolic factors remain the best means currently available to avoid or minimize oxygen toxicity. Research is continuing into more effective ways to prevent, diagnose, and treat this disorder.

Decoloration and detoxification of effluents by ionizing radiation

NASA Astrophysics Data System (ADS)

Borrely, Sueli I.; Morais, Aline V.; Rosa, Jorge M.; Badaró-Pedroso, Cintia; da Conceição Pereira, Maria; Higa, Marcela C.

2016-07-01

Three distinct textile samples were investigated for color and toxicity (S1-chemical/textile industry; S2-final textile effluent; S3 - standard textile produced effluent-untreated blue). Radiation processing of these samples were carried out at Dynamitron Electron Beam Accelerator and color and toxicity removal were determined: color removal by radiation was 96% (40 kGy, S1); 55% (2.5 kGy, S2) and 90% (2.5 kGy, S3). Concerning toxicity assays, Vibrio fischeri luminescent bacteria demonstrated higher reduction after radiation than the other systems: removal efficiencies were 33% (20 kGy, S1); 55% (2.5 kGy, S2) and 33% (2.5 kGy, S3). Daphnia similis and Brachionus plicatilis fitted well for S3 effluents. Hard toxic volumes into biological treatment plant may be avoided if radiation would be previously applied in a real plant. Results reveled how indispensable is to run toxicity to more than one living-organism.

Active avoidance from a crude oil soluble fraction by an Andean paramo copepod.

PubMed

Araújo, Cristiano V M; Moreira-Santos, Matilde; Sousa, José P; Ochoa-Herrera, Valeria; Encalada, Andrea C; Ribeiro, Rui

2014-09-01

Several oil spills due to ruptures in the pipeline oil systems have occurred at the Andean paramo. A sample of this crude oil was mixed with water from a nearby Andean lagoon and the toxicity of the soluble fraction was assessed through lethal and avoidance assays with a locally occurring copepod (Boeckella occidentalis intermedia). The integration of mortality and avoidance aimed at predicting the immediate decline of copepod populations facing an oil leakage. The 24-h median lethal PAH concentration was 42.7 (26.4-91.6) µg L(-1). In the 12-h avoidance assay, 30% avoidance was recorded at the highest PAH concentration (19.4 µg L(-1)). The mortality at this PAH concentration would be of 25% and, thus, the population immediate decline would be of 55%. The inclusion of non-forced exposure testing with the quantification of the avoidance response in environmental risk assessments is, therefore, supported due to underestimation of the lethal assays.

Towards Carbon-Neutral CO2 Conversion to Hydrocarbons.

PubMed

Mattia, Davide; Jones, Matthew D; O'Byrne, Justin P; Griffiths, Owen G; Owen, Rhodri E; Sackville, Emma; McManus, Marcelle; Plucinski, Pawel

2015-12-07

With fossil fuels still predicted to contribute close to 80 % of the primary energy consumption by 2040, methods to limit further CO2 emissions in the atmosphere are urgently needed to avoid the catastrophic scenarios associated with global warming. In parallel with improvements in energy efficiency and CO2 storage, the conversion of CO2 has emerged as a complementary route with significant potential. In this work we present the direct thermo-catalytic conversion of CO2 to hydrocarbons using a novel iron nanoparticle-carbon nanotube (Fe@CNT) catalyst. We adopted a holistic and systematic approach to CO2 conversion by integrating process optimization-identifying reaction conditions to maximize conversion and selectivity towards long chain hydrocarbons and/or short olefins-with catalyst optimization through the addition of promoters. The result is the production of valuable hydrocarbons in a manner that can approach carbon neutrality under realistic industrial process conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermosensitive polymer stabilized core-shell AuNR@Ag nanostructures as "smart" recyclable catalyst

NASA Astrophysics Data System (ADS)

Li, Dongxiang; Liu, Na; Gao, Yuanyuan; Lin, Weihong; Li, Chunfang

2017-11-01

Core-shell AuNR@Ag nanostructures were synthesized and surface-grafted with thermosensitive poly( N-isopropylacrylamide) to enhance stability and endow stimuli-responsive property. The AuNR cores showed average dimensions of 8-nm diameter and 33-nm length, while the anisotropic silver shells displayed 1-2 nm thin side and maximal 8 nm fat side. The obtained polymer-stabilized AuNR@Ag nanostructures as catalysts showed normal Arrhenius change of apparent rate constant, k app, in catalyzed reaction between 20 and 30 °C, but displayed a decrease of k app with respect to the temperature increasing between 32.5-40 °C, showing self-inhibition of the observed catalytic activity. Such "smart" self-inhibition of catalytic activity at enhanced temperature can be attributed to the thermosensitive response of the grafted polymer molecules and should be significant to control the reaction rate and avoid superheat for exothermic reactions. Such polymer-stabilized nanocatalyst also could be recovered and reused in the catalytic system. [Figure not available: see fulltext.

Oxygen-aided synthesis of polycrystalline graphene on silicon dioxide substrates.

PubMed

Chen, Jianyi; Wen, Yugeng; Guo, Yunlong; Wu, Bin; Huang, Liping; Xue, Yunzhou; Geng, Dechao; Wang, Dong; Yu, Gui; Liu, Yunqi

2011-11-09

We report the metal-catalyst-free synthesis of high-quality polycrystalline graphene on dielectric substrates [silicon dioxide (SiO(2)) or quartz] using an oxygen-aided chemical vapor deposition (CVD) process. The growth was carried out using a CVD system at atmospheric pressure. After high-temperature activation of the growth substrates in air, high-quality polycrystalline graphene is subsequently grown on SiO(2) by utilizing the oxygen-based nucleation sites. The growth mechanism is analogous to that of growth for single-walled carbon nanotubes. Graphene-modified SiO(2) substrates can be directly used in transparent conducting films and field-effect devices. The carrier mobilities are about 531 cm(2) V(-1) s(-1) in air and 472 cm(2) V(-1) s(-1) in N(2), which are close to that of metal-catalyzed polycrystalline graphene. The method avoids the need for either a metal catalyst or a complicated and skilled postgrowth transfer process and is compatible with current silicon processing techniques.

Stellate macroporous silica nanospheres in bio-macromolecules encapsulation and delivery

NASA Astrophysics Data System (ADS)

Chi, Hao-Hsin

This project focused on using mesoporous silica as a solid support to encapsulate enzymes for operating a highly economic, and recyclable biomass processing system. The main objective is to turn non-food biomass sources into food products. Enzymes are macromolecules with the structural backbone of proteins or ribonucleic acid sequences (RNAs) which work as catalysts in living organisms. Enzymes have the advantage of being the least contaminating catalyst due to normal catalyst might generate toxic by-product, and preferable to organic and inorganic catalysts, especially when used for product related to human used, which require biocompatibility of final product. However, there are several disadvantages in enzyme utilization. Their fabrication is time-consuming and requires elaborated molecular biology processes. Most of the enzymes need well-defined reaction conditions to be functional and operate at high yield. Unfortunately, although they are reusable as normal catalysts, it proves difficult to extract or reuse the enzymes from a reaction. Also, enzyme molecules are easily degradable and demand proper storage. To overcome some of the disadvantages, especially regarding stability to degradation, recovery, and reusability, immobilization of enzyme on solid support has become a thriving methodology. In recent years, mesoporous silica nanomaterials(MSN) have been at the forefront of enzyme immobilization given their extensive surface area, which provides capability to increase enzyme loading and for their demonstrate ability to protect enzyme from degradation, thus enabling high recyclability. Mesoporous silica is biocompatible and has already been used for several applications included. Catalysis, drug delivery, and Bio-imaging. Previously published research utilized mesoporous silica to deliver drugs, DNAs, RNAs or encapsulate single enzyme. The objective of this research is completed to develop a new porous silica platform that is unique in its porosity structure and develop it into a dual-enzyme platform with the scope of demonstrating a multi-reaction bio nanocatalyst. In regard to the further applications, the stellate MSN can be used as drug delivery or become a package of the biomacromolecule delivery system kit.

Adverse interaction between colchicine and ketoconazole in a Chinese shar pei.

PubMed

McAlister, Amber; Center, Sharon A; Bender, Hannah; McDonough, Sean P

2014-01-01

A Chinese shar pei with a 2 yr history of episodic fever, lethargy, and shifting lameness was presumptively diagnosed with familial shar pei fever but had never been treated for the syndrome. After being presented for a superficial pyoderma with possible dermatophyte coinfection, treatment with a cephalosporin and ketoconazole were prescribed. One wk later, colchicine was initiated for familial shar pei fever using cautious dose escalation. Nevertheless, gastrointestinal toxicity, skeletal muscle myopathy, and hepatotoxicity developed within 2 wk. Abrupt resolution of gastrointestinal toxicity and myopathy followed drug withdrawal. However, escalating liver enzyme activity and hyperbilirubinemia led to liver biopsy to rule out an antecedent hepatopathy. Biopsy characterized canalicular cholestasis and colchicine-associated metaphase arrest and ring mitoses reflecting repression of mitotic spindle formation. Signs of illness completely resolved 3 mo after drug discontinuation. Although avoidable adverse interactions between ketoconazole and drugs reliant on cytochrome oxidase biotransformation and/or drug efflux mediated by multiple drug-resistant transporters are well documented in humans, these are rarely reported in veterinary patients. This case exemplifies an important and avoidable ketoconazole/colchicine drug interaction from which the patient completely recovered. The dog tested negative for the canine MDR1 loss of function mutation that also might potentiate colchicine toxicity.

Mitochondrial toxicity in human pregnancy: an update on clinical and experimental approaches in the last 10 years.

PubMed

Morén, Constanza; Hernández, Sandra; Guitart-Mampel, Mariona; Garrabou, Glòria

2014-09-22

Mitochondrial toxicity can be one of the most dreadful consequences of exposure to a wide range of external agents including pathogens, therapeutic agents, abuse drugs, toxic gases and other harmful chemical substances. However, little is known about the effects of mitochondrial toxicity on pregnant women exposed to these agents that may exert transplacental activity and condition fetal remodeling. It has been hypothesized that mitochondrial toxicity may be involved in some adverse obstetric outcomes. In the present study, we investigated the association between exposure to mitochondrial toxic agents and pathologic conditions ranging from fertility defects, detrimental fetal development and impaired newborn health due to intra-uterine exposure. We have reviewed data from studies in human subjects to propose mechanisms of mitochondrial toxicity that could be associated with the symptoms present in both exposed pregnant and fetal patients. Since some therapeutic interventions or accidental exposure cannot be avoided, further research is needed to gain insight into the molecular pathways leading to mitochondrial toxicity during pregnancy. The ultimate objective of these studies should be to reduce the mitochondrial toxicity of these agents and establish biomarkers for gestational monitoring of harmful effects.

Heavy metal toxicity to bacteria - are the existing growth media accurate enough to determine heavy metal toxicity?

PubMed

Rathnayake, I V N; Megharaj, Mallavarapu; Krishnamurti, G S R; Bolan, Nanthi S; Naidu, Ravi

2013-01-01

A new minimal medium was formulated considering the limitations of the existing media for testing heavy metal sensitivity to bacteria. Toxicity of cadmium and copper to three bacteria was investigated in the new medium and compared with three other media commonly used to study the effect of the toxic metals. Based on speciation data arrived at using ion-selective electrodes, the available free-metal concentration in solution was highest in the MES-buffered medium. This finding was strongly supported by the estimated EC(50) values for the metals tested based on the toxicity bioassays. The free-ionic cadmium and copper concentrations in the medium provide more accurate determination of metal concentrations that affects the bacteria, than with most of other existing media. This will avoid doubts on other media and misleading conclusions relevant to the toxicity of heavy metals to bacteria and provides a better option for the study of metal-bacteria interactions. Copyright © 2012 Elsevier Ltd. All rights reserved.

Evaluation of an alternative in vitro test battery for detecting reproductive toxicants in a grouping context.

PubMed

Kroese, E Dinant; Bosgra, Sieto; Buist, Harrie E; Lewin, Geertje; van der Linden, Sander C; Man, Hai-yen; Piersma, Aldert H; Rorije, Emiel; Schulpen, Sjors H W; Schwarz, Michael; Uibel, Frederik; van Vugt-Lussenburg, Barbara M A; Wolterbeek, Andre P M; van der Burg, Bart

2015-08-01

Previously we showed a battery consisting of CALUX transcriptional activation assays, the ReProGlo assay, and the embryonic stem cell test, and zebrafish embryotoxicity assay as 'apical' tests to correctly predict developmental toxicity for 11 out of 12 compounds, and to explain the one false negative [7]. Here we report on applying this battery within the context of grouping and read across, put forward as a potential tool to fill data gaps and avoid animal testing, to distinguish in vivo non- or weak developmental toxicants from potent developmental toxicants within groups of structural analogs. The battery correctly distinguished 2-methylhexanoic acid, monomethyl phthalate, and monobutyltin trichloride as non- or weak developmental toxicants from structurally related developmental toxicants valproic acid, mono-ethylhexyl phthalate, and tributyltin chloride, respectively, and, therefore, holds promise as a biological verification model in grouping and read across approaches. The relevance of toxicokinetic information is indicated. Copyright © 2014 Elsevier Inc. All rights reserved.

Stereotactic Radiosurgery of the Postoperative Resection Cavity for Brain Metastases: Prospective Evaluation of Target Margin on Tumor Control

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

Choi, Clara Y.H.; Chang, Steven D.; Gibbs, Iris C.

2012-10-01

Purpose: Given the neurocognitive toxicity associated with whole-brain irradiation (WBRT), approaches to defer or avoid WBRT after surgical resection of brain metastases are desirable. Our initial experience with stereotactic radiosurgery (SRS) targeting the resection cavity showed promising results. We examined the outcomes of postoperative resection cavity SRS to determine the effect of adding a 2-mm margin around the resection cavity on local failure (LF) and toxicity. Patients and Methods: We retrospectively evaluated 120 cavities in 112 patients treated from 1998-2009. Factors associated with LF and distant brain failure (DF) were analyzed using competing risks analysis, with death as a competingmore » risk. The overall survival (OS) rate was calculated by the Kaplan-Meier product-limit method; variables associated with OS were evaluated using the Cox proportional hazards and log rank tests. Results: The 12-month cumulative incidence rates of LF and DF, with death as a competing risk, were 9.5% and 54%, respectively. On univariate analysis, expansion of the cavity with a 2-mm margin was associated with decreased LF; the 12-month cumulative incidence rates of LF with and without margin were 3% and 16%, respectively (P=.042). The 12-month toxicity rates with and without margin were 3% and 8%, respectively (P=.27). On multivariate analysis, melanoma histology (P=.038) and number of brain metastases (P=.0097) were associated with higher DF. The median OS time was 17 months (range, 2-114 months), with a 12-month OS rate of 62%. Overall, WBRT was avoided in 72% of the patients. Conclusion: Adjuvant SRS targeting the resection cavity of brain metastases results in excellent local control and allows WBRT to be avoided in a majority of patients. A 2-mm margin around the resection cavity improved local control without increasing toxicity compared with our prior technique with no margin.« less

Iron-catalyzed urea synthesis: dehydrogenative coupling of methanol and amines† †Electronic supplementary information (ESI) available: Experimental details, characterization data, and select NMR spectra. See DOI: 10.1039/c8sc00775f

PubMed Central

Lane, Elizabeth M.; Hazari, Nilay

2018-01-01

Substituted ureas have numerous applications but their synthesis typically requires the use of highly toxic starting materials. Herein we describe the first base-metal catalyst for the selective synthesis of symmetric ureas via the dehydrogenative coupling of methanol with primary amines. Using a pincer supported iron catalyst, a range of ureas was generated with isolated yields of up to 80% (corresponding to a catalytic turnover of up to 160) and with H2 as the sole byproduct. Mechanistic studies indicate a stepwise pathway beginning with methanol dehydrogenation to give formaldehyde, which is trapped by amine to afford a formamide. The formamide is then dehydrogenated to produce a transient isocyanate, which reacts with another equivalent of amine to form a urea. These mechanistic insights enabled the development of an iron-catalyzed method for the synthesis of unsymmetric ureas from amides and amines. PMID:29780531

[Microbial denitrogenation of fuel oil].

PubMed

Li, Shan-shan; Ma, Ting; Li, Guo-qiang; Liang, Feng-lai; Liu, Ru-lin

2006-12-01

The amount of organic nitrides contained in fuel oil is smaller than the one of organic sulfur compounds, but the existence of them is enough to affect the invariability of oil product greatly , and has a big effect on the color of oil. They also contribute to catalyst poisoning during the refining of crude oil, thus reducing the catalyzing rate of the catalyst and increasing process costs. Further more, some nitrogen organic compounds possess mutagenic and toxic activities. The combustion of these contaminants form nitrogen oxides (NOx), releasing of which to the air will cause the formation of acid rain and hence to air pollution. The classical hydroprocessing methods of nitrogen removal are costly and complicated, so the scientists are more and more interested in microbial denitrogenation. The aspects as follows are introduced, including the aromatic nitrogen compounds of fuel oil, the varieties of denitrogenation techincs, the classes of microbial denitrogenation and its biochemical pathways, molecular genetics developments of carbazole-degradative genes, and our opinion of the research direction in the future.

l-Glutamic acid assisted eco-friendly one-pot synthesis of sheet-assembled platinum-palladium alloy networks for methanol oxidation and oxygen reduction reactions.

PubMed

Shi, Ya-Cheng; Mei, Li-Ping; Wang, Ai-Jun; Yuan, Tao; Chen, Sai-Sai; Feng, Jiu-Ju

2017-10-15

In this work, bimetallic platinum-palladium sheet-assembled alloy networks (PtPd SAANs) were facilely synthesized by an eco-friendly one-pot aqueous approach under the guidance of l-glutamic acid at room temperature, without any additive, seed, toxic or organic solvent involved. l-Glutamic acid was served as the green shape-director and weak-stabilizing agent. A series of characterization techniques were employed to examine the morphology, structure and formation mechanism of the product. The architectures exhibited improved electrocatalytic activity and durable ability toward methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) in contrast with commercial Pt black and Pd black catalysts. This is ascribed to the unique structures of the obtained PtPd SAANs and the synergistic effects of the bimetals. These results demonstrate the potential application of the prepared catalyst in fuel cells. Copyright © 2017 Elsevier Inc. All rights reserved.

A nanoparticle catalyst for heterogeneous phase para-hydrogen-induced polarization in water.

PubMed

Glöggler, Stefan; Grunfeld, Alexander M; Ertas, Yavuz N; McCormick, Jeffrey; Wagner, Shawn; Schleker, P Philipp M; Bouchard, Louis-S

2015-02-16

Para-hydrogen-induced polarization (PHIP) is a technique capable of producing spin polarization at a magnitude far greater than state-of-the-art magnets. A significant application of PHIP is to generate contrast agents for biomedical imaging. Clinically viable and effective contrast agents not only require high levels of polarization but heterogeneous catalysts that can be used in water to eliminate the toxicity impact. Herein, we demonstrate the use of Pt nanoparticles capped with glutathione to induce heterogeneous PHIP in water. The ligand-inhibited surface diffusion on the nanoparticles resulted in a (1) H polarization of P=0.25% for hydroxyethyl propionate, a known contrast agent for magnetic resonance angiography. Transferring the (1) H polarization to a (13) C nucleus using a para-hydrogen polarizer yielded a polarization of 0.013%. The nuclear-spin polarizations achieved in these experiments are the first reported to date involving heterogeneous reactions in water. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Asymmetric transfer hydrogenation by synthetic catalysts in cancer cells

NASA Astrophysics Data System (ADS)

Coverdale, James P. C.; Romero-Canelón, Isolda; Sanchez-Cano, Carlos; Clarkson, Guy J.; Habtemariam, Abraha; Wills, Martin; Sadler, Peter J.

2018-03-01

Catalytic anticancer metallodrugs active at low doses could minimize side-effects, introduce novel mechanisms of action that combat resistance and widen the spectrum of anticancer-drug activity. Here we use highly stable chiral half-sandwich organometallic Os(II) arene sulfonyl diamine complexes, [Os(arene)(TsDPEN)] (TsDPEN, N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine), to achieve a highly enantioselective reduction of pyruvate, a key intermediate in metabolic pathways. Reduction is shown both in aqueous model systems and in human cancer cells, with non-toxic concentrations of sodium formate used as a hydride source. The catalytic mechanism generates selectivity towards ovarian cancer cells versus non-cancerous fibroblasts (both ovarian and lung), which are commonly used as models of healthy proliferating cells. The formate precursor N-formylmethionine was explored as an alternative to formate in PC3 prostate cancer cells, which are known to overexpress a deformylase enzyme. Transfer-hydrogenation catalysts that generate reductive stress in cancer cells offer a new approach to cancer therapy.

VUV photo-oxidation of gaseous benzene combined with ozone-assisted catalytic oxidation: Effect on transition metal catalyst

NASA Astrophysics Data System (ADS)

Huang, Haibao; Lu, Haoxian; Zhan, Yujie; Liu, Gaoyuan; Feng, Qiuyu; Huang, Huiling; Wu, Muyan; Ye, Xinguo

2017-01-01

Volatile organic compounds (VOCs) cause the major air pollution concern. In this study, a series of ZSM-5 supported transition metals were prepared by impregnation method. They were combined with vacuum UV (VUV) photo-oxidation in a continuous-flow packed-bed reactor and used for the degradation of benzene, a typical toxic VOCs. Compared with VUV photo-oxidation alone, the introduction of catalysts can greatly enhance benzene oxidation under the help of O3, the by-products from VUV irradiation, via ozone-assisted catalytic oxidation (OZCO). The catalytic activity of transition metals towards benzene oxidation followed the order: Mn > Co > Cu > Ni > Fe. Mn achieved the best catalytic activity due to the strongest capability for O3 catalytic decomposition and utilization. Benzene and O3 removal efficiency reached as high as 97% and 100% after 360 min, respectively. O3 was catalytically decomposed, generating highly reactive oxidants such as rad OH and rad O for benzene oxidation.

Plant Insecticide L-Canavanine Repels Drosophila via the Insect Orphan GPCR DmX

PubMed Central

Framery, Bérénice; Bockaert, Joël; Parmentier, Marie-Laure; Grau, Yves

2009-01-01

For all animals, the taste sense is crucial to detect and avoid ingesting toxic molecules. Many toxins are synthesized by plants as a defense mechanism against insect predation. One example of such a natural toxic molecule is l-canavanine, a nonprotein amino acid found in the seeds of many legumes. Whether and how insects are informed that some plants contain l-canavanine remains to be elucidated. In insects, the taste sense relies on gustatory receptors forming the gustatory receptor (Gr) family. Gr proteins display highly divergent sequences, suggesting that they could cover the entire range of tastants. However, one cannot exclude the possibility of evolutionarily independent taste receptors. Here, we show that l-canavanine is not only toxic, but is also a repellent for Drosophila. Using a pharmacogenetic approach, we find that flies sense food containing this poison by the DmX receptor. DmXR is an insect orphan G-protein–coupled receptor that has partially diverged in its ligand binding pocket from the metabotropic glutamate receptor family. Blockade of DmXR function with an antagonist lowers the repulsive effect of l-canavanine. In addition, disruption of the DmXR encoding gene, called mangetout (mtt), suppresses the l-canavanine repellent effect. To avoid the ingestion of l-canavanine, DmXR expression is required in bitter-sensitive gustatory receptor neurons, where it triggers the premature retraction of the proboscis, thus leading to the end of food searching. These findings show that the DmX receptor, which does not belong to the Gr family, fulfills a gustatory function necessary to avoid eating a natural toxin. PMID:19564899

Granular activated carbon based microbial fuel cell for simultaneous decolorization of real dye wastewater and electricity generation.

PubMed

Kalathil, Shafeer; Lee, Jintae; Cho, Moo Hwan

2011-12-15

Decolorization of dye wastewater before discharge is pivotal because of its immense color and toxicities. In this study, a granular activated carbon based microbial fuel cell (GACB-MFC) was used without using any expensive materials like Nafion membrane and platinum catalyst for simultaneous decolorization of real dye wastewater and bioelectricity generation. After 48 hours of GACB-MFC operation, 73% color was removed at anode and 77% color was removed at cathode. COD removal was 71% at the anode and 76% at the cathode after 48 hours. Toxicity measurements showed that cathode effluent was almost nontoxic after 24 hours. The anode effluent was threefold less toxic compared to original dye wastewater after 48 hours. The GACB-MFC produced a power density of 1.7 W/m(3) with an open circuit voltage 0.45 V. One of the advantages of the GACB-MFC system is that pH was automatically adjusted from 12.4 to 7.2 and 8.0 at the anode and cathode during 48 hours operation. Copyright © 2011 Elsevier B.V. All rights reserved.

Reduction of carbon content in waste-tire combustion ashes by bio-thermal treatment.

PubMed

Chen, Chun-Chi; Lee, Wen-Jhy; Shih, Shun-I; Mou, Jin-Luh

2009-11-01

Application of bio-catalyst (NOE-7F) in thermal treatment can adequately dispose dark-black fly ashes from co-combustion of both waste tires and coal. After thermal treatment of fly ashes by adding 10% NOE-7F, the carbon contents reduced by 37.6% and the weight losses increased by 405%, compared with the fly ashes without mixing with NOE-7F. The combustion behaviors of wasted tires combustion fly ashes with NOE-7F were also investigated by both thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The results verify that NOE-7F has positive effects on the combustion of residual carbon and toxic polycyclic aromatic hydrocarbons (PAHs) enhance the energy release and reduce the toxicity during the process of thermal treatment. Furthermore, using NOE-7F to dispose high-carbon content fly ashes did improve the compressive strength of fly ashes and concrete mixtures. Therefore, NOE-7F is a promising additive which could decrease treatment cost of high-carbon content fly ashes and reduce the amount of survival toxic PAHs.

Reduction of carbon content in waste-tire combustion ashes by bio-thermal treatment

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

Chen, C.C.; Lee, W.J.; Shih, S.I.

2009-07-01

Application of bio-catalyst (NOE-7F) in thermal treatment can adequately dispose dark-black fly ashes from co-combustion of both waste tires and coal. After thermal treatment of fly ashes by adding 10% NOE-7F, the carbon contents reduced by 37.6% and the weight losses increased by 405%, compared with the fly ashes without mixing with NOE-7F. The combustion behaviors of wasted tires combustion fly ashes with NOE-7F were also investigated by both thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The results verify that NOE-7F has positive effects on the combustion of residual carbon and toxic polycyclic aromatic hydrocarbons (PAHs) enhance the energymore » release and reduce the toxicity during the process of thermal treatment. Furthermore, using NOE-7F to dispose high-carbon content fly ashes did improve the compressive strength of fly ashes and concrete mixtures. Therefore, NOE-7F is a promising additive which could decrease treatment cost of high-carbon content fly ashes and reduce the amount of survival toxic PAHs.« less

[Production technology and use of composite materials in the aeronautics industry, risks and pathology in the manufacturing workers].

PubMed

Franco, G; Candura, F

1985-01-01

The type and applications of composite materials have increased greatly during the last forty years, particularly in the aircraft and aerospace industries. The foreseeable increase of the employment of composite materials in future needs an adequate engagement in finding out health risks involved with technological processes. Composite materials - considered as a close union between a continuous glass, aramid or carbon reinforcing fibre and a epoxy matrix - present several advantages over traditional materials. Structural epoxy adhesives are defined as complex formulated systems. By mixing a large number of ingredients a formulated resin is obtained, which represents the start of the production process for adhesive manufacture. The most important ingredients such as catalysts, accelerators, the groups of epoxy monomers and oligomers, additives most used and their role into the epoxy matrices are illustrated. Of the various technologies existing for the fabrication of aircraft structures the one so called "vacuum bag" is described. The knowledge of the chemical composition of the substances used in the production of composite materials and epoxy adhesives allows to verify the possible existence of hazard for workers health. Among the potentially dangerous chemicals, epoxy monomers and oligomers, catalysts, accelerators are to be considered. The metabolism and the mechanisms of toxicity of epoxides are summarized. However the toxic effects of most epoxides are far from being wholly investigated. In man epoxides ingestion, inhalation or absorption through the skin can lead to several toxic effects: irritation and sensitisation, alterations of liver and nervous function. Finally some epoxides are considered to be carcinogenic in animals and in man; however for many compounds, the results are not yet conclusive. From what it is said above come out the necessity of a careful sanitary control of the workers exposed to these hazards, control that is made difficult by the lack of adequate biological indices for the risks found.

Mechanistic Insight Facilitates Discovery of a Mild and Efficient Copper-Catalyzed Dehydration of Primary Amides to Nitriles Using Hydrosilanes.

PubMed

Liu, Richard Y; Bae, Minwoo; Buchwald, Stephen L

2018-02-07

Metal-catalyzed silylative dehydration of primary amides is an economical approach to the synthesis of nitriles. We report a copper-hydride(CuH)-catalyzed process that avoids a typically challenging 1,2-siloxane elimination step, thereby dramatically increasing the rate of the overall transformation relative to alternative metal-catalyzed systems. This new reaction proceeds at ambient temperature, tolerates a variety of metal-, acid-, or base-sensitive functional groups, and can be performed using a simple ligand, inexpensive siloxanes, and low catalyst loading.

A new method to synthesize complicated multi-branched carbon nanotubes with controlled architecture and composition.

PubMed

Wei, Dacheng; Liu, Yunqi; Cao, Lingchao; Fu, Lei; Li, Xianglong; Wang, Yu; Yu, Gui; Zhu, Daoben

2006-02-01

Here we develop a simple method by using flow fluctuation to synthesize arrays of multi-branched carbon nanotubes (CNTs) that are far more complex than those previously reported. The architectures and compositions can be well controlled, thus avoiding any template or additive. A branching mechanism of fluctuation-promoted coalescence of catalyst particles is proposed. This finding will provide a hopeful approach to the goal of CNT-based integrated circuits and be valuable for applying branched junctions in nanoelectronics and producing branched junctions of other materials.

An efficient synthesis of 3,4-Dihydropyrimidin-2(1H)-ones and thiones catalyzed by a novel Brønsted acidic ionic liquid under solvent-free conditions.

PubMed

Zhang, Yonghong; Wang, Bin; Zhang, Xiaomei; Huang, Jianbin; Liu, Chenjiang

2015-02-26

We report here an efficient and green method for Biginelli condensation reaction of aldehydes, β-ketoesters and urea or thiourea catalyzed by Brønsted acidic ionic liquid [Btto][p-TSA] under solvent-free conditions. Compared to the classical Biginelli reaction conditions, the present method has the advantages of giving good yields, short reaction times, near room temperature conditions and the avoidance of the use of organic solvents and metal catalyst.

New targeted therapies and diagnostic methods for iron overload diseases.

PubMed

Kolnagou, Annita; Kontoghiorghe, Christina N; Kontoghiorghes, George John

2018-01-01

Millions of people worldwide suffer from iron overload toxicity diseases such as transfusional iron overload in thalassaemia and hereditary haemochromatosis. The accumulation and presence of toxic focal iron deposits causing tissue damage can also be identified in Friedreich's ataxia, Alzheimer's, Parkinson's, renal and other diseases. Different diagnostic criteria of toxicity and therapeutic interventions apply to each disease of excess or misplaced iron. Magnetic resonance imaging relaxation times T2 and T2* for monitoring iron deposits in organs and iron biomarkers such as serum ferritin and transferrin iron saturation have contributed in the elucidation of iron toxicity mechanisms and pathways, and also the evaluation of the efficacy and mode of action of chelating drugs in the treatment of diseases related to iron overload, toxicity and metabolism. Similarly, histopathological and electron microscopy diagnostic methods have revealed mechanisms of iron overload toxicity at cellular and sub-cellular levels. These new diagnostic criteria and chelator dose adjustments could apply in different or special patient categories e.g. thalassaemia patients with normal iron stores, where iron deficiency and over-chelation toxicity should be avoided.

"Nanorust"-catalyzed benign oxidation of amines for selective synthesis of nitriles.

PubMed

Jagadeesh, Rajenahally V; Junge, Henrik; Beller, Matthias

2015-01-01

Organic nitriles constitute key precursors and central intermediates in organic synthesis. In addition, nitriles represent a versatile motif found in numerous medicinally and biologically important compounds. Generally, these nitriles are synthesized by traditional cyanation procedures using toxic cyanides. Herein, we report the selective and environmentally benign oxidative conversion of primary amines for the synthesis of structurally diverse aromatic, aliphatic and heterocyclic nitriles using a reusable "nanorust" (nanoscale Fe2 O3 )-based catalysts applying molecular oxygen. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical Cobalt-Catalyzed C-H Activation.

PubMed

Sauermann, Nicolas; Meyer, Tjark H; Ackermann, Lutz

2018-06-19

Carbon-heteroatom bonds represent omnipresent structural motifs of the vast majority of functionalized materials and bioactive compounds. C-H activation has emerged as arguably the most efficient strategy to construct C-Het bonds. Despite of major advances, these C-H transformations were largely dominated by precious transition metal catalysts, in combination with stoichiometric, toxic metal oxidants. Herein, we discuss the recent evolution of cobalt-catalyzed C-H activations that enable C-Het formations with electricity as the sole sustainable oxidant until May 2018. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coupling of exothermic and endothermic reactions in oxidative conversion of natural gas into ethylene/olefins over diluted SrO/La{sub 2}O{sub 3}/SA5205 catalyst

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

Choudhary, V.R.; Mulla, S.A.R.

1997-09-01

In the oxidative conversion of natural gas to ethylene/lower olefins over SrO (17.3 wt.%)/La{sub 2}O{sub 3} (17.9 wt.%)/SA5205 catalyst diluted with inert solid particles (inerts/catalyst(w/w) = 2.0) in the presence of limited O{sub 2}, the exothermic oxidative conversion reactions of natural gas are coupled with the endothermic C{sub 2+} hydrocarbon thermal cracking reactions for avoiding hot spot formation and eliminating heat removal problems. Because of this, the process is operated in the most energy-efficient and safe manner. The influence of various process variables (viz. temperature, NG/O{sub 2} and steam/NG ratios in feed, and space velocity) on the conversion of carbonmore » and also of the individual hydrocarbons in natural gas, the selectivity for C{sub 2}-C{sub 4} olefins, and also on the net heat of reactions in the process has been thoroughly investigated. By carrying out the process at 800--850 C in the presence of steam (H{sub 2}O/NG {le} 0.2) and using limited O{sub 2} in the feed (NG/O{sub 2} = 12--18), high selectivity for ethylene (about 60%) or C{sub 2}-C{sub 4} olefins (above 80%) at the carbon conversion (>15%) of practical interest could be achieved at high space velocity ({ge}34,000 cm{sup 3}/g (catalyst) h), requiring no external energy and also without forming coke or tar-like products. The net heat of reactions can be controlled and the process can be made mildly exothermic or even close to thermoneutral by manipulating the O{sub 2} concentration in the feed.« less

Electrocatalysts for oxygen electrodes in fuel cells and water electrolyzers for space applications

NASA Technical Reports Server (NTRS)

Prakash, Jai; Tryk, Donald; Yeager, Ernest

1989-01-01

In most instances separate electrocatalysts are needed to promote the reduction of O2 in the fuel cell mode and to generate O2 in the energy storage-water electrolysis mode in aqueous electrochemical systems operating at low and moderate temperatures (T greater than or equal to 200 C). Interesting exceptions are the lead and bismuth ruthenate pyrochlores in alkaline electrolytes. These catalysts on high area carbon supports have high catalytic activity for both O2 reduction and generation (1,2). Rotating ring-disk electrode measurements provide evidence that the O2 reduction proceeds by a parallel four-electron pathway. The ruthenates can also be used as self-supported catalysts to avoid the problems associated with carbon oxidation, but the electrode performance so far achieved in the research at Case Western Reserve University (CWRU) is considerably less. At the potentials involved in the anodic mode the ruthenate pyrochlores have substantial equilibrium solubility in concentrated alkaline electrolyte. This results in the loss of catalyst into the bulk solution and a decline in catalytic activity. Furthermore, the hydrogen generation counter electrode may become contaminated with reduction products from the pyrochlores (lead, ruthenium). A possible approach to this problem is to immobilize the pyrochlore catalyst within an ionic-conducting solid polymer, which would replace the fluid electrolyte within the porous gas diffusion O2 electrode. For bulk alkaline electrolyte, an anion-exchange polymer is needed with a transference number close to unity for the Oh(-) ion. Preliminary short-term measurements with lead ruthenates using a commercially available partially-fluorinated anion-exchange membrane as an overlayer on the porous gas-fed electrode indicate lower anodic polarization and virtually unchanged cathodic polarization.

Exploring the Impact of Toxic Attitudes and a Toxic Environment on the Veterinary Healthcare Team.

PubMed

Moore, Irene C; Coe, Jason B; Adams, Cindy L; Conlon, Peter D; Sargeant, Jan M

2015-01-01

The objective of this qualitative study was to compare veterinarians' and Registered Veterinary Technicians' (RVT's) perceptions of the veterinary healthcare team with respect to the impact of toxic attitudes and a toxic environment. Focus group interviews using a semi-structured interview guide and follow up probes were held with four veterinarian groups (23 companion animal veterinarians) and four Registered Veterinary Technician groups (26 RVTs). Thematic analysis of the discussions indicated both veterinarian and RVT participants felt team members with manifestations of toxic attitudes negatively impacted veterinary team function. These manifestations included people being disrespectful, being resistant to change, always wanting to be the "go to person," avoiding conflict, and lacking motivation. When conflict was ignored, or when people with toxic attitudes were not addressed, a toxic environment often resulted. A toxic environment sometimes manifested when "broken communication and tension between staff members" occurred as a result of employees lacking confidence, skills, or knowledge not being managed properly. It also occurred when employees did not feel appreciated, when there was difficulty coping with turnover, and when there were conflicting demands. The presence of people manifesting a toxic attitude was a source of frustration for both veterinarian and RVT participants. Prompt and consistent attention to negative behaviors is recommended to reduce the development of a toxic environment.

Oxidized starch solutions for environmentally friendly aircraft deicers.

PubMed

Plahuta, Joseph M; Teel, Amy L; Ahmad, Mushtaque; Beutel, Mark W; Rentz, Jeremy A; Watts, Richard J

2011-09-01

Deicers currently used for aircraft deicing, including ethylene glycol and propylene glycol, pose significant threats to surface waters, as a result of high biochemical oxygen demand (BOD) and toxicity to aquatic organisms. Oxidized starch may provide a less toxic deicer with lower BOD. The freezing point depression of starch formulations oxidized using hydrogen peroxide and catalysts (i.e., catalyzed hydrogen peroxide [H2O2] propagations-CHP) was 28 degrees C, and viscosities similar to those of commercial deicers were achieved after post-treatment with granular activated carbon. The most effective oxidized starch formulation exerted a 5-day BOD up to 6 times lower than glycol deicers (103 versus 400 to 800 g O2/L). Toxicity to Ceriodaphnia dubia for this formulation (48-hour lethal concentration, 50% [LC50] of 2.73 g/L) was greater than pure propylene glycol (13.1 g/ L), but lower than propylene glycol deicer formulations (1.02 g/L). Organic acids were identified by gas chromatography/mass spectrometry as the primary constituents in the oxidized starch solution. The proposed deicing system would provide effective deicing while exerting minimal environmental effects (e.g., lower toxicity to aquatic organisms and lower BOD). Furthermore, these deicers could be made from waste starch, promoting sustainability.

Photodegradation applied to the treatment of phenol and derived substances catalyzed by TiO2/BiPO4 and biological toxicity analysis.

PubMed

Zaidan, Léa Elias Mendes Carneiro; de Lima Sales, Renata Vitória; de Almeida Salgado, Júlia Barbosa; da Silva, Ana Maria Ribeiro Bastos; Napoleão, Daniella Carla; Rodríguez-Díaz, Joan Manuel; Marques, Olga Martins; Benachour, Mohand; da Silva, Valdinete Lins

2017-03-01

For this work, a phenol solution model was treated by an advanced oxidation process (AOPs), using the heterogeneous catalyst TiO 2 /BiPO 4 and hydrogen peroxide combined with UVA for 240 min. An annular reactor containing a UVA lamp (80 W) was employed. A central composite rotacional design was developed employing a TiO 2 /BiPO 4 concentration of 87 mg L -1 and a hydrogen peroxide concentration of 1800 mg L -1 , being evaluated by the degradation percentage and phenol mineralization percentage as responses; 94.30 and 67.00 % were obtained for the phenol degradation and total organic carbon (TOC) conversion, respectively. The lumped kinetic model (LKM) was applied and a satisfactory profile of the residual fractions of the organic compounds present in the liquid phase as a time function with a determination coefficient (R 2  = 0.9945). The toxicity tests employing microbiological species indicated that the organisms tested for the evaluation of the toxic compounds present in the contaminated samples presented a practical low cost test, rapid execution, and high sensibility as an indicator of the presence of toxic substances in liquid effluents.

A Cu/Pt Near-Surface Alloy for Water-Gas Shift Catalysis.

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

Knudsen, Jan; Nilekar, Anand U.; Vang, Ronnie T.

2007-05-01

The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The primary route to hydrogen production from fossil fuels involves the water-gas shift (WGS) reaction, and an improvement in the efficiency of WGS catalysts could therefore lead to a major leap forward in the realization of hydrogen economy. On the basis of a combination of high-resolution scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory (DFT) calculations, we suggestmore » the existence of a new thermodynamically stable Cu/Pt near-surface alloy (NSA). Temperature-programmed desorption and DFT reveal that this Cu/Pt NSA binds CO significantly more weakly than does Pt alone, thereby implying a considerable reduction in the potential for CO poisoning of the Cu/Pt NSA surface as compared to that of pure Pt. In addition, DFT calculations show that this Cu/Pt NSA is able to activate H2O easily, which is the rate-determining step for the WGS on several metal surfaces, and, at the same time, to bind the products of that reaction and formate intermediates rather weakly, thus avoiding possible poisoning of the catalyst surface. The Cu/Pt NSA is thus a promising candidate for an improved WGS catalyst.« less

Chemical activation of commercial CNTs with simultaneous surface deposition of manganese oxide nano flakes for the creation of CNTs-graphene supported oxygen reduction ternary composite catalysts applied in air fuel cell

NASA Astrophysics Data System (ADS)

Sun, Ling; Liu, Danxian

2018-07-01

To elevate power performance is crucial for commercally potential metal air fuel cells. Non-precious metal oxide-based oxygen reduction catalytic electrode is much desirable. Rational combination with low-dimension nanomaterials are greatly expected as the supports. Herein, carbon nanotubes (CNTs)-graphene supported manganese oxides composite catalysts (CMnCs) were obtained through activating commercial CNTs, namely, immersing them in acidic KMnO4 solution at room condition. It avoided conventional hydrothermal process and template surfactants. CMnCs-based air cathodes were made via pilot manufacture technology and equipped in fuel cells. Through characterizations, CNTs was found structurally defective and their outer walls suffered cracking into graphene nano pieces during processing, which further enhanced oxygen reduction reaction (ORR). Nano sized manganese oxide flakes were simulataneously grown on the CNTs-graphene surfaces, identified as the manganite. The areal distribution was found closely related to the additive amount of KMnO4 with regard to CNTs, somewhat influencing catalytic performance. The ORR activities of these CMnCs exceeded raw CNTs and referred manganese catalysts under identical conditions, and also the CMnCs air fuel cells were capable of outputting ∼15% more power at 100 mA/cm2. This reseach provided an inspiring pilot evidence for updating air fuel cell power from economical carbon as well as industrialization.

A lyophilized and thermal two step synthesis of CoFe alloy nanoparticles embedded in N-doped carbon nanosheets/carbon nanotubes for highly-efficient oxygen evolution reaction.

PubMed

Liu, Yang; Li, Feng; Yang, Haidong; Li, Jing; Ma, Ping; Zhu, Yan; Ma, Jiantai

2018-05-22

There is a vital need to explore highly-efficient and stable nonprecious-metal catalysts for oxygen evolution reaction (OER) to reduce the overpotential and further improve the energy conversion efficiency. Herein, we report a unique and cost-effective lyophilized and thermal two step procedure to synthesize high-performance CoFe alloy nanoparticles embedded in N-doped carbon nanosheets interspersed with carbon nanotubes (CoFe-N-CN/CNTs) hybrid. The lyophilization step during catalysts preparation is beneficial to uniform the dispersion of carbon-like precursors and avoid the agglomeration of metal particles. Meanwhile, the inserted CNTs and doped N in this hybrid provide better electrical conductivity, more chemically active sites, improved mass transport capability and effective gas adsorption/release channels. And all these lead to a high specific surface area of 240.67 m2 g-1, favorable stability and remarkable OER activities with an overpotential of only 285 mV at the current density of 10 mA cm-2 and a Tafel slope of 51.09 mV dec-1 in 1.0 M KOH electrolyte, which is even superior to commercial IrO2 catalysts. The CoFe-N-CN/CNTs hybrid thus exhibits great potential as a highly efficient and earth-abundant anode OER electrocatalyst. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of novel ternary Au/CeO2@g-C3N4 nanocomposite: kinetics and mechanism investigation of 4-nitrophenol reduction, and benzyl alcohol oxidation

NASA Astrophysics Data System (ADS)

Kohantorabi, Mona; Gholami, Mohammad Reza

2018-06-01

Au nanoparticles supported on cerium oxide/graphitic carbon nitride (CeO2@g-C3N4) was synthesized and used as heterogeneous catalyst in redox reaction. The catalyst was characterized by different techniques such as FT-IR, XRD, FE-SEM, EDS, TEM, BET, TGA, and ICP. The as-prepared ternary nanocomposite was used as an effective catalyst for the reduction of toxic 4-nitrophenol to useful 4-aminophenol by NaBH4. The rate constant value of reduction reaction reached up to 0.106 s-1 by Au/CeO2@g-C3N4, which was 3.8, and 8.8 times higher than that of Au@CeO2 (0.028 s-1), and Au@g-C3N4 (0.012 s-1) nanocomposites, respectively. The superior catalytic performance of as-prepared catalyst in 4-NP reduction can be attributed to synergistic effect between Au nanoparticles and CeO2@g-C3N4 support, and efficient electron transfer. The reduction reaction was carried out at different temperatures, and the energy of activation ({Ea}), and thermodynamic parameters including, activation of entropy (Δ S^ ≠), enthalpy (Δ H^ ≠), and Gibbs free energy (Δ G^ ≠) were determined. Additionally, the mechanism of reaction was studied in details, and equilibrium constants of 4-NP ( K 4-NP), and {BH}4^{ - } ({K_{{BH}4^{{ - }} }}) were calculated using Langmuir-Hinshelwood model. Furthermore, this nanocomposite exhibited excellent catalytic activity in oxidation of benzyl alcohol by molecular oxygen as a green oxidant. This study revealed that the ternary Au/CeO2@g-C3N4 nanocomposite is an attractive candidate for catalytic applications.

Nickel-doped cobalt ferrite nanoparticles: efficient catalysts for the reduction of nitroaromatic compounds and photo-oxidative degradation of toxic dyes

NASA Astrophysics Data System (ADS)

Singh, Charanjit; Goyal, Ankita; Singhal, Sonal

2014-06-01

This study deals with the exploration of NixCo1-xFe2O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0) ferrite nanoparticles as catalysts for reduction of 4-nitrophenol and photo-oxidative degradation of Rhodamine B. The ferrite samples with uniform size distribution were synthesized using the reverse micelle technique. The structural investigation was performed using powder X-ray diffraction, high-resolution transmission electron microscopy, energy dispersive X-ray and scanning tunneling microscopy. The spherical particles with ordered cubic spinel structure were found to have the crystallite size of 4-6 nm. Diffused UV-visible reflectance spectroscopy was employed to investigate the optical properties of the synthesized ferrite nanoparticles. The surface area calculated using BET method was found to be highest for Co0.4Ni0.6Fe2O4 (154.02 m2 g-1). Co0.4Ni0.6Fe2O4 showed the best catalytic activity for reduction of 4-nitrophenol to 4-aminophenol in the presence of NaBH4 as reducing agent, whereas CoFe2O4 was found to be catalytically inactive. The reduction reaction followed pseudo-first order kinetics. The effect of varying the concentration of catalyst and NaBH4 on the reaction rates was also scrutinized. The photo-oxidative degradation of Rhodamine B, enhanced oxidation efficacy was observed with the introduction of Ni2+ in to the cobalt ferrite lattice due to octahedral site preference of Ni2+. Almost 99% degradation was achieved in 20 min using NiFe2O4 nanoparticles as catalyst.

Control of harmful hydrocarbon species in the exhaust of modern advanced GDI engines

NASA Astrophysics Data System (ADS)

Hasan, A. O.; Abu-jrai, A.; Turner, D.; Tsolakis, A.; Xu, H. M.; Golunski, S. E.; Herreros, J. M.

2016-03-01

A qualitative and quantitative analysis of toxic but currently non-regulated hydrocarbon compounds ranging from C5-C11, before and after a zoned three-way catalytic converter (TWC) in a modern gasoline direct injection (GDI) engine has been studied using gas chromatography-mass spectrometry (GC-MS). The GDI engine has been operated under conventional and advanced combustion modes, which result in better fuel economy and reduced levels of NOx with respect to standard SI operation. However, these fuel-efficient conditions are more challenging for the operation of a conventional TWC, and could lead to higher level of emissions released to the environment. Lean combustion leads to the reduction in pumping losses, fuel consumption and in-cylinder emission formation rates. However, lean HCCI will lead to high levels of unburnt HCs while the presence of oxygen will lower the TWC efficiency for NOx control. The effect on the catalytic conversion of the hydrocarbon species of the addition of hydrogen upstream the catalyst has been also investigated. The highest hydrocarbon engine-out emissions were produced for HCCI engine operation at low engine load operation. The catalyst was able to remove most of the hydrocarbon species to low levels (below the permissible exposure limits) for standard and most of the advanced combustion modes, except for naphthalene (classified as possibly carcinogenic to humans by the International Agency for Research on Cancer) and methyl-naphthalene (which has the potential to cause lung damage). However, when hydrogen was added upstream of the catalyst, the catalyst conversion efficiency in reducing methyl-naphthalene and naphthalene was increased by approximately 21%. This results in simultaneous fuel economy and environmental benefits from the effective combination of advanced combustion and novel aftertreatment systems.

Nanocrystalline semiconductor doped rare earth oxide for the photocatalytic degradation studies on Acid Blue 113: A di-azo compound under UV slurry photoreactor.

PubMed

Suganya Josephine, G A; Mary Nisha, U; Meenakshi, G; Sivasamy, A

2015-11-01

Preventive measures for the control of environmental pollution and its remediation has received much interest in recent years due to the world-wide increase in the contamination of water bodies. Contributions of these harmful effluents are caused by the leather processing, pharmaceutical, cosmetic, textile, agricultural and other chemical industries. Nowadays, advanced oxidation processes considered to be better option for the complete destruction of organic contaminants in water and wastewater. Acid Blue 113 is a most widely used di-azo compound in leather, textile, dying and food industry as a color rending compound. In the present study, we have reported the photo catalytic degradation of Acid Blue 113 using a nanocrystalline semiconductor doped rare earth oxide as a photo catalyst under UV light irradiation. The photocatalyst was prepared by a simple precipitation technique and were characterized by XRD, FT-IR, UV-DRS and FE-SEM analysis. The experimental results proved that the prepared photo catalyst was nanocrystalline and highly active in the UV region. The UV-DRS results showed the band gap energy was 3.15eV for the prepared photo catalyst. The photodegradation efficiency was analyzed by various experimental parameters such as pH, catalyst dosage, variation of substrate concentration and effect of electrolyte addition. The photo degradation process followed a pseudo first order kinetics and was continuously monitored by UV-visible spectrophotometer. The experimental results proved the efficacy of the nanocrystalline zinc oxide doped dysprosium oxide which are highly active under UV light irradiations. It is also suggested that the prepared material would find wider applications in environmental remediation technologies to remove the carcinogenic and toxic moieties present in the industrial effluents. Copyright © 2015 Elsevier Inc. All rights reserved.

Effects of Jatropha curcas oil in Lactuca sativa root tip bioassays.

PubMed

Andrade-Vieira, Larissa F; Botelho, Carolina M; Laviola, Bruno G; Palmieri, Marcel J; Praça-Fontes, Milene M

2014-03-01

Jatropha curcas L. (Euphorbiaceae) is important for biofuel production and as a feed ingredient for animal. However, the presence of phorbol esters in the oil and cake renders the seeds toxic. The toxicity of J. curcas oil is currently assessed by testing in animals, leading to their death. The identification of toxic and nontoxic improved varieties is important for the safe use of J. curcas seeds and byproducts to avoid their environmental toxicity. Hence, the aim of this study was to propose a short-term bioassay using a plant as a model to screen the toxicity of J. curcas oil without the need to sacrifice any animals. The toxicity of J. curcas oil was evident in germination, root elongation and chromosomal aberration tests in Lactuca sativa. It was demonstrated that J. curcas seeds contain natural compounds that exert phyto-, cyto- and genotoxic effects on lettuce, and that phorbol esters act as aneugenic agents, leading to the formation of sticky chromosomes and c-metaphase cells. In conclusion, the tests applied have shown reproducibility, which is important to verify the extent of detoxification and to determine toxic doses, thus reducing the numbers of animals that would be used for toxicity tests.

Avoidance behaviour response and esterase inhibition in the earthworm, Lumbricus terrestris, after exposure to chlorpyrifos.

PubMed

Martínez Morcillo, S; Yela, J L; Capowiez, Y; Mazzia, C; Rault, M; Sanchez-Hernandez, Juan C

2013-05-01

The avoidance response of earthworms to polluted soils has been standardised using a simple and low-cost test, which facilitates soil toxicity screening. In this study, the avoidance response of Lumbricus terrestris was quantified in chlorpyrifos-spiked soils, depending on the pesticide concentration and exposure duration. The inhibition of acetylcholinesterase (AChE) and carboxylesterase (CbE) activities was also determined as indirect measures of pesticide bioavailability. The effects of different chlorpyrifos concentrations were examined in a standardised test (two-chamber system) with 0.6, 3 and 15 mg/kg chlorpyrifos. A modification of the test involved a pre-exposure step (24, 48 or 72 h) in soils spiked with 15 mg/kg. In both protocols, earthworms were unable to avoid the contaminated soils. However, the esterase activities showed that all earthworms were exposed to chlorpyrifos. Acetylcholinesterase activity did not change in earthworms in the standardised behavioural test (0.58 ± 0.20 U/mg protein, mean ± SD; n = 72), whereas the CbE activity was significantly inhibited (62-87 % inhibition) in earthworms exposed to 3 and 15 mg/kg. In the modified test, earthworms had greatly inhibited AChE activity (0.088 ± 0.034 U/mg protein, n = 72), which was supported by reactivation of the inhibited enzyme activity in the presence of pralidoxime (2-PAM). Similarly, the CbE activity was significantly inhibited in earthworms with all treatments. This study suggests that the avoidance behaviour test for organophosphorus-contaminated soils could be supported by specific biomarkers to facilitate a better understanding of pesticide exposure and toxicity during this test.

Contaminants as habitat disturbers: PAH-driven drift by Andean paramo stream insects.

PubMed

Araújo, Cristiano V M; Moreira-Santos, Matilde; Sousa, José P; Ochoa-Herrera, Valeria; Encalada, Andrea C; Ribeiro, Rui

2014-10-01

Contaminants can behave as toxicants, when toxic effects are observed in organisms, as well as habitat disturbers and fragmentors, by triggering avoidance responses and generating less- or uninhabited zones. Drift by stream insects has long been considered a mechanism to avoid contamination by moving to most favorable habitats. Given that exploration and transportation of crude oil represent a threat for surrounding ecosystems, the key goal of the present study was to assess the ability of autochthonous groups of aquatic insects from the Ecuadorian paramo streams to avoid by drift different concentrations of polycyclic aromatic hydrocarbons (PAH) contained in the soluble fraction of locally transported crude oil. In the laboratory, different groups of insects were exposed to PAH for 12h. Three different assays, which varied in taxa and origin of the organisms, concentrations of PAH (0.6-38.8µgL(-1)), and environment settings (different levels of refuge and flow) were performed. For Anomalocosmoecus palugillensis (Limnephilidae), drift was a major cause of population decline in low concentration treatments but at higher concentrations mortality dominated. PAH was highly lethal, even at lower concentrations, for Chironomidae, Grypopterygidae (Claudioperla sp.) and Hydrobiosidae (Atopsyche sp.), and, therefore, no conclusion about drift can be drawn for these insects. Contamination by PAH showed to be a threat for benthic aquatic insects from Ecuadorian paramo streams as it can cause a population decline due to avoidance by drift and mortality. Copyright © 2014 Elsevier Inc. All rights reserved.

Postconditioning Effectively Prevents Trimethyltin Induced Neuronal Damage in the Rat Brain.

PubMed

Lalkovicova, Maria; Burda, Jozef; Nemethova, Miroslava; Burda, Rastislav; Danielisova, Viera

Trimethyltin (TMT) is a toxic substance formerly used as a catalyst in the production of organic substances, as well as in industry and agriculture. TMT poisoning has caused death or severe injury in many dozens of people. The toxicity of TMT is mediated by dose dependent selective damage to the limbic system in humans and other animals, specifically the degeneration of CA1 neurons in the hippocampus. The typical symptoms include memory loss and decreased learning ability. Using knowledge gained in previous studies of global ischaemia, we used delayed postconditioning after TMT intoxication (8 mg/kg i.p.), consisting of applying a stressor (BR, bradykinin 150 μg/kg i.p.) 24 or 48 hours after the injection of TMT. We found that BR had preventive effects on neurodegenerative changes as well as learning and memory deficits induced by TMT intoxication.

Green synthesis, characterization and catalytic activity of the Pd/TiO2 nanoparticles for the ligand-free Suzuki-Miyaura coupling reaction.

PubMed

Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad

2016-03-01

A green synthesis process was developed for production of the Pd/TiO2 nanoparticles (NPs) without using toxic, hazardous and dangerous materials. Myrtus communis L. leaf extract serves as a mild, renewable and non-toxic reducing agent. The advantages of this biosynthesis method include use of cheap, clean, nontoxic and environmentally benign precursors and simple procedures without time-consuming polymerization and problems with treatment of a highly viscous polymeric resin. More importantly, the synthesized Pd/TiO2 NPs presented excellent catalytic activity for ligand-free Suzuki-Miyaura coupling which could be easily separated from the reaction mixture and reused many times with no loss of activity. Therefore, these properties indicate demonstrative benefits of the catalyst. The Pd/TiO2 NPs was characterized by FESEM, TEM, FT-IR, UV-vis spectroscopy and EDS. Copyright © 2015 Elsevier Inc. All rights reserved.

Decontamination of unsymmetrical dimethylhydrazine waste water by hydrodynamic cavitation-induced advanced Fenton process.

PubMed

Torabi Angaji, Mahmood; Ghiaee, Reza

2015-03-01

A pilot scale hydrodynamic cavitation (HC) reactor, using iron metal blades, as the heterogeneous catalyst, with no external source of H₂O₂ was developed for catalytic decontamination of unsymmetrical dimethylhydrazine (UDMH) waste water. In situ generation of Fenton reagents suggested an induced advanced Fenton process (IAFP) to explain the enhancing effect of the used catalyst in the HC process. The effects of the applied catalyst, pH of the initial solution (1.0-9.7), initial UDMH concentration (2-15 mg/l), inlet pressure (5.5-7.8bar), and downstream pressure (2-6 bar), have been investigated. The results showed that the highest cavitation yield can be obtained at pH 3 and initial UDMH concentration of 10mg/l. Also, an increase in the inlet pressure would lead to an increase in the extent of UDMH degradation. In addition, the optimum value of 3 bar was determined for the downstream pressure that resulted to 98.6% degradation of UDMH after 120 min of processing time. Neither n-nitrosodimethylamine (NDMA) nor any other toxic byproduct (/end-product) was observed in the investigated samples. Formic acid and acetic acid, as well as nitromethane, were identified as oxidation by-products. The present work has conclusively established that hydrodynamic cavitation in combination with Fenton's chemistry can be effectively used for the degradation of UDMH. Copyright © 2014 Elsevier B.V. All rights reserved.

Water oxidation catalysed by manganese compounds: from complexes to 'biomimetic rocks'.

PubMed

Wiechen, Mathias; Berends, Hans-Martin; Kurz, Philipp

2012-01-07

One of the most fundamental processes of the natural photosynthetic reaction sequence is the light-driven oxidation of water to molecular oxygen. In vivo, this reaction takes place in the large protein ensemble Photosystem II, where a μ-oxido-Mn(4)Ca- cluster, the oxygen-evolving-complex (OEC), has been identified as the catalytic site for the four-electron/four-proton redox reaction of water oxidation. This Perspective presents recent progress for three strategies which have been followed to prepare functional synthetic analogues of the OEC: (1) the synthesis of dinuclear manganese complexes designed to act as water-oxidation catalysts in homogeneous solution, (2) heterogeneous catalysts in the form of clay hybrids of such Mn(2)-complexes and (3) the preparation of manganese oxide particles of different compositions and morphologies. We discuss the key observations from the studies of such synthetic manganese systems in order to shed light upon the catalytic mechanism of natural water oxidation. Additionally, it is shown how research in this field has recently been motivated more and more by the prospect of finding efficient, robust and affordable catalysts for light-driven water oxidation, a key reaction of artificial photosynthesis. As manganese is an abundant and non-toxic element, manganese compounds are very promising candidates for the extraction of reduction equivalents from water. These electrons could consecutively be fed into the synthesis of "solar fuels" such as hydrogen or methanol.

Palladium Supported on Titanium Carbide: A Highly Efficient, Durable, and Recyclable Bifunctional Catalyst for the Transformation of 4-Chlorophenol and 4-Nitrophenol

PubMed Central

Fan, Guangyin; Li, Xiaojing; Xu, Caili; Jiang, Weidong; Zhang, Yun; Gao, Daojiang; Bi, Jian; Wang, Yi

2018-01-01

Developing highly efficient and recyclable catalysts for the transformation of toxic organic contaminates still remains a challenge. Herein, Titanium Carbide (Ti3C2) MXene modified by alkali treatment process was selected as a support (designated as alk-Ti3C2X2, where X represents the surface terminations) for the synthesis of Pd/alk-Ti3C2X2. Results show that the alkali treatment leads to the increase of surface area and surface oxygen-containing groups of Ti3C2X2, thereby facilitating the dispersion and stabilization of Pd species on the surface of alk-Ti3C2X2. The Pd/alk-Ti3C2X2 catalyst shows excellent catalytic activity for the hydrodechlorination of 4-chlorophenol and the hydrogenation of 4-nitrophenol in aqueous solution at 25 °C and hydrogen balloon pressure. High initial reaction rates of 216.6 and 126.3 min−1·gpd−1 are observed for the hydrodechlorination of 4-chlorophenol and hydrogenation of 4-nitrophenol, respectively. Most importantly, Pd/alk-Ti3C2X2 exhibits excellent stability and recyclability in both reactions without any promoters. The superior property of Pd/alk-Ti3C2X2 makes it as a potential material for practical applications. PMID:29498652

Ni0 encapsulated in N-doped carbon nanotubes for catalytic reduction of highly toxic hexavalent chromium

NASA Astrophysics Data System (ADS)

Yao, Yunjin; Zhang, Jie; Chen, Hao; Yu, Maojing; Gao, Mengxue; Hu, Yi; Wang, Shaobin

2018-05-01

N-doped carbon nanotubes encapsulating Ni0 nanoparticles (Ni@N-C) were fabricated via thermal reduction of dicyandiamide and NiCl2·6H2O, and used to remove CrVI in polluted water. The resultant products present an excellent catalytic activity for CrVI reduction using formic acid under relatively mild conditions. The CrVI reduction efficiency of Ni@N-C was significantly affected by the preparation conditions including the mass of nickel salt and synthesis temperatures. The impacts of several reaction parameters, such as initial concentrations of CrVI and formic acid, solution pH and temperatures, as well as inorganic anions in solution on CrVI reduction efficiency were also evaluated in view of scalable industrial applications. Owing to the synergistic effects amongst tubes-coated Ni0, doped nitrogen, oxygen containing groups, and the configuration of carbon nanotubes, Ni@N-C catalysts exhibit excellent catalytic activity and recyclable capability for CrVI reduction. Carbon shell can efficiently protect inner Ni0 core and N species from corrosion and subsequent leaching, while Ni0 endows the Ni@N-C catalysts with ferromagnetism, so that the composites can be easily separated via a permanent magnet. This study opens up an avenue for design of N-doped carbon nanotubes encapsulating Ni0 nanoparticles with high CrVI removal efficiency and magnetic recyclability as low-cost catalysts for industrial applications.

Fe-Based Nano-Materials in Catalysis

PubMed Central

Konstantopoulos, Christos

2018-01-01

The role of iron in view of its further utilization in chemical processes is presented, based on current knowledge of its properties. The addition of iron to a catalyst provides redox functionality, enhancing its resistance to carbon deposition. FeOx species can be formed in the presence of an oxidizing agent, such as CO2, H2O or O2, during reaction, which can further react via a redox mechanism with the carbon deposits. This can be exploited in the synthesis of active and stable catalysts for several processes, such as syngas and chemicals production, catalytic oxidation in exhaust converters, etc. Iron is considered an important promoter or co-catalyst, due to its high availability and low toxicity that can enhance the overall catalytic performance. However, its operation is more subtle and diverse than first sight reveals. Hence, iron and its oxides start to become a hot topic for more scientists and their findings are most promising. The scope of this article is to provide a review on iron/iron-oxide containing catalytic systems, including experimental and theoretical evidence, highlighting their properties mainly in view of syngas production, chemical looping, methane decomposition for carbon nanotubes production and propane dehydrogenation, over the last decade. The main focus goes to Fe-containing nano-alloys and specifically to the Fe–Ni nano-alloy, which is a very versatile material. PMID:29772842

Toxicity of the organophosphate chemical warfare agents GA, GB, and VX: Implications for public protection

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

Munro, N.B.; Ambrose, K.R.; Watson, A.P.

1994-01-01

The nerve agents, GA, GB, and VX are organophosphorus esters that form a major portion of the total agent volume contained in the U.S. stockpile of unitary chemical munitions. Congress has mandated the destruction of these agents, which is currently slated for completion in 2004. The acute, chronic, and delayed toxicity of these agents is reviewed in this analysis. The largely negative results from studies of genotoxicity, carcinogenicity, developmental, and reproductive toxicity are also presented. Nerve agents show few or delayed effects. At supralethal doses, GB can cause delayed neuropathy in antidote-protected chickens, but there is not evidence that itmore » causes this syndrome in humans at any dose. Agent VX shows no potential for inducing delayed neuropathy in any species. In view of their lack of genotoxicity, the nerve agent exposure is the extraordinarily high acute toxicity of these substances. Futhermore, acute effects of moderate exposure such as nausea, diarrhea, inability to perform simple mental tasks, and respiratory effects may render the public unable to respond adequately to emergency instructions in the unlikely event of agent release, making early warning and exposure avoidance important. Likewise, exposure or self-contamination of first responders and medical personnel must be avoided. Control limits for exposure via surface contact of drinking water are needed, as are detection methods for low levels in water or foodstuffs. 187 refs., 3 figs., 7 tabs.« less

Toxicity of the Organophosphate Chemical Warfare Agents GA, GB, and VX: Implications for Public Protection.

PubMed Central

Munro, N

1994-01-01

The nerve agents, GA, GB, and VX are organophosphorus esters that form a major portion of the total agent volume contained in the U.S. stockpile of unitary chemical munitions. Congress has mandated the destruction of these agents, which is currently slated for completion in 2004. The acute, chronic, and delayed toxicity of these agents is reviewed in this analysis. The largely negative results from studies of genotoxicity, carcinogenicity, developmental, and reproductive toxicity are also presented. Nerve agents show few or delayed effects. At supralethal doses, GB can cause delayed neuropathy in antidote-protected chickens, but there is no evidence that it causes this syndrome in humans at any dose. Agent VX shows no potential for inducing delayed neuropathy in any species. In view of their lack of genotoxcity, the nerve agents are not likely to be carcinogens. The overreaching concern with regard to nerve agent exposure is the extraordinarily high acute toxicity of these substances. Furthermore, acute effects of moderate exposure such as nausea, diarrhea, inability to perform simple mental tasks, and respiratory effects may render the public unable to respond adequately to emergency instructions in the unlikely event of agent releaase, making early warning and exposure avoidance important. Likewise, exposure or self-contamination of first responders and medical personnel must be avoided. Control limits for exposure via surface contact of drinking water are needed, as are detection methods for low levels in water or foodstuffs. Images Figure 2. PMID:9719666

Comparative ecotoxicity of chlorantraniliprole to non-target soil invertebrates.

PubMed

Lavtižar, Vesna; Berggren, Kristina; Trebše, Polonca; Kraak, Michiel H S; Verweij, Rudo A; van Gestel, Cornelis A M

2016-09-01

The insecticide chlorantraniliprole (CAP) is gaining importance in agricultural practice, but data on its possible negative effects on non-target organisms is severely deficient. This study therefore determined CAP toxicity to non-target soil invertebrates playing a crucial role in ecosystem functioning, including springtails (Folsomia candida), isopods (Porcellio scaber), enchytraeids (Enchytraeus crypticus) and oribatid mites (Oppia nitens). In sublethal toxicity tests in Lufa 2.2 soil, chronic exposure to CAP concentrations up to 1000 mg/kgdw did not affect the survival and reproduction of E. crypticus and O. nitens nor the survival, body weight and consumption of P. scaber. In contrast, the survival and reproduction of F. candida was severely affected, with an EC50 for effects on reproduction of 0.14 mg CAP/kgdw. The toxicity of CAP to the reproduction of F. candida was tested in four different soils following OECD guideline 232, and additionally in an avoidance test according to ISO guideline 17512-2. A significantly lower toxicity in soils rich in organic matter was observed, compared to low organic soils. Observations in the avoidance test with F. candida suggest that CAP acted in a prompt way, by affecting collembolan locomotor abilities thus preventing them from escaping contaminated soil. This study shows that CAP may especially pose a risk to non-target soil arthropods closely related to insects, while other soil invertebrates seem rather insensitive. Copyright © 2016 Elsevier Ltd. All rights reserved.

Proof of Principle of Ocular sparing in dogs with sinonasal tumors treated with intensity-modulated radiation therapy

PubMed Central

Lawrence, Jessica A.; Forrest, Lisa J.; Turek, Michelle M.; Miller, Paul E.; Mackie, T. Rockwell; Jaradat, Hazim A.; Vail, David M.; Dubielzig, Richard R.; Chappell, Richard; Mehta, Minesh P.

2010-01-01

Intensity modulated radiation therapy (IMRT) allows optimization of radiation dose delivery to complex tumor volumes with rapid dose drop-off to surrounding normal tissues. A prospective study was performed to evaluate the concept of conformal avoidance using IMRT in canine sinonasal cancer. The potential of IMRT to improve clinical outcome with respect to acute and late ocular toxicity was evaluated. Thirty-one dogs with sinonasal cancer were treated definitively with IMRT using helical tomotherapy and/or dynamic multileaf collimator (DMLC) delivery. Ocular toxicity was evaluated prospectively and compared to a comparable group of historical controls treated with conventional two-dimensional radiotherapy (2D-RT) techniques. Treatment plans were devised for each dog using helical tomotherapy and DMLC that achieved the target dose to the planning treatment volume and limited critical normal tissues to the prescribed dose-volume constraints. Overall acute and late toxicities were limited and minor, detectable by an experienced observer. This was in contrast to the profound ocular morbidity observed in the historical control group treated with 2D-RT. Overall median survival for IMRT treated and 2D treated dogs was 420 days and 411 days, respectively. Compared with conventional techniques, IMRT reduced dose delivered to eyes and resulted in bilateral ocular sparing in the dogs reported herein. These data provide proof-of-principle that conformal avoidance radiotherapy can be delivered through high conformity IMRT, resulting in decreased normal tissue toxicity as compared to historical controls treated with 2D-RT. PMID:20973393

Ecotoxicological characterization of sugarcane vinasses when applied to tropical soils.

PubMed

Alves, Paulo Roger L; Natal-da-Luz, Tiago; Sousa, José Paulo; Cardoso, Elke J B N

2015-09-01

The impact of sugarcane vinasse on soil invertebrates was assessed through ecotoxicological assays. Increasing concentrations of two vinasses from different distillery plants (VA and VB), and a vinasse from a laboratory production (VC), were amended on two natural tropical Oxisols (LV and LVA) and a tropical artificial soil (TAS) to characterize the effects of the vinasses on earthworms (Eisenia andrei), enchytraeids (Enchytraeus crypticus), mites (Hypoaspis aculeifer) and collembolans (Folsomia candida). The highest concentrations of VA and VB were avoided by earthworms in all soils and by collembolans especially in the natural soils. The presence of VC in all of the tested soils did not cause avoidance behavior in these species. The reproduction of earthworms, enchytraeids and collembolans was decreased in the highest concentrations of VA and VB in the natural soils. In TAS, VB reduced the reproduction of all test species, whereas VA was toxic exclusively to E. andrei and E. crypticus. The vinasse VC only reduced the number of earthworms in TAS and enchytraeids in LVA. The reproduction of mites was reduced by VB in TAS. Vinasses from distillery plants were more toxic than the vinasse produced in laboratory. The vinasse toxicities were influenced by soil type, although this result was most likely because of the way the organisms are exposed to the contaminants in the soils. Toxicity was attributed to the vinasses' high salt content and especially the high potassium concentrations. Data obtained in this study highlights the potential risk of vinasse disposal on tropical soils to soil biota. The toxic values estimated are even more relevant when considering the usual continuous use of vinasses in crop productions. Copyright © 2015 Elsevier B.V. All rights reserved.

The Effect of Cerium Oxide Nanoparticle Valence State on Reactive Oxygen Species and Toxicity.

PubMed

Dunnick, Katherine M; Pillai, Rajalekshmi; Pisane, Kelly L; Stefaniak, Aleksandr B; Sabolsky, Edward M; Leonard, Stephen S

2015-07-01

Cerium oxide (CeO2) nanoparticles, which are used in a variety of products including solar cells, gas sensors, and catalysts, are expected to increase in industrial use. This will subsequently lead to additional occupational exposures, making toxicology screenings crucial. Previous toxicology studies have presented conflicting results as to the extent of CeO2 toxicity, which is hypothesized to be due to the ability of Ce to exist in both a +3 and +4 valence state. Thus, to study whether valence state and oxygen vacancy concentration are important in CeO2 toxicity, CeO2 nanoparticles were doped with gadolinium to adjust the cation (Ce, Gd) and anion (O) defect states. The hypothesis that doping would increase toxicity and decrease antioxidant abilities as a result of increased oxygen vacancies and inhibition of +3 to +4 transition was tested. Differences in toxicity and reactivity based on valence state were determined in RLE-6TN rat alveolar epithelial and NR8383 rat alveolar macrophage cells using enhanced dark field microscopy, electron paramagnetic resonance (EPR), and annexin V/propidium iodide cell viability stain. Results from EPR indicated that as doping increased, antioxidant potential decreased. Alternatively, doping had no effect on toxicity at 24 h. The present results imply that as doping increases, thus subsequently increasing the Ce(3+)/Ce(4+) ratio, antioxidant potential decreases, suggesting that differences in reactivity of CeO2 are due to the ability of Ce to transition between the two valence states and the presence of increased oxygen vacancies, rather than dependent on a specific valence state.

SU-C-BRA-06: Developing Clinical and Quantitative Guidelines for a 4DCT-Ventilation Functional Avoidance Clinical Trial

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

Vinogradskiy, Y; Waxweiler, T; Diot, Q

Purpose: 4DCT-ventilation is an exciting new imaging modality that uses 4DCTs to calculate lung ventilation. Because 4DCTs are acquired as part of routine care, calculating 4DCT-ventilation allows for lung function evaluation without additional cost or inconvenience to the patient. Development of a clinical trial is underway at our institution to use 4DCT-ventilation for thoracic functional avoidance with the idea that preferential sparing of functional lung regions can decrease pulmonary toxicity. The purpose of our work was to develop the practical aspects of a 4DCT-ventilation functional avoidance clinical trial including: 1.assessing patient eligibility 2.developing trial inclusion criteria and 3.developing treatment planningmore » and dose-function evaluation strategies. Methods: 96 stage III lung cancer patients from 2 institutions were retrospectively reviewed. 4DCT-ventilation maps were calculated using the patient’s 4DCTs, deformable image registrations, and a density-change-based algorithm. To assess patient eligibility and develop trial inclusion criteria we used an observer-based binary end point noting the presence or absence of a ventilation defect and developed an algorithm based on the percent ventilation in each lung third. Functional avoidance planning integrating 4DCT-ventilation was performed using rapid-arc and compared to the patient’s clinically used plan. Results: Investigator-determined clinical ventilation defects were present in 69% of patients. Our regional/lung-thirds ventilation algorithm identified that 59% of patients have lung functional profiles suitable for functional avoidance. Compared to the clinical plan, functional avoidance planning was able to reduce the mean dose to functional lung by 2 Gy while delivering comparable target coverage and cord/heart doses. Conclusions: 4DCT-ventilation functional avoidance clinical trials have great potential to reduce toxicity, and our data suggest that 59% of lung cancer patients have lung function profiles suitable for functional avoidance. Our study used a retrospective evaluation of a large lung cancer patient database to develop the practical aspects of a 4DCT-ventilation functional avoidance clinical trial. (R.C., E.C., T.G.), NIH Research Scientist Development Award K01-CA181292 (R.C.), and State of Colorado Advanced Industries Accelerator Grant (Y.V.)« less

Degradation of 2,4-dichlorophenol using combined approach based on ultrasound, ozone and catalyst.

PubMed

Barik, Arati J; Gogate, Parag R

2017-05-01

The present work investigates the application of ultrasound and ozone operated individually and in combination with catalyst (ZnO and CuO) for establishing the possible synergistic effects for the degradation of 2,4-dichlorophenol. The dependency of extent of degradation on the operating parameters like temperature (over the range of 30-36°C), initial pH (3-9), catalyst as ZnO (loading of 0.025-0.15g/L) and CuO (loading of 0.02-0.1g/L) and initial concentration of 2,4-DCP (20-50ppm) has been established to maximize the efficacy of ultrasound (US) induced degradation. Using only US, the maximum degradation of 2,4-DCP obtained was 28.85% under optimized conditions of initial concentration as 20ppm, pH of 5 and temperature of 34°C. Study of effect of ozone flow rate for approach of only ozone revealed that maximum degradation was obtained at 400mg/h ozone flow rate. The combined approaches such as US+O 3 , US+ZnO, US+CuO, O 3 +ZnO, O 3 +CuO, US+O 3 +ZnO and US+O 3 +CuO have been subsequently investigated under optimized conditions and observed to be more efficient as compared to individual approaches. The maximum extent of degradation for the combined operation of US+O 3 (400mg/h)+ZnO (0.1g/L) and US+O 3 (400mg/h)+CuO (0.08g/L) has been obtained as 95.66% and 97.03% respectively. The degradation products of 2,4-DCP have been identified using GC-MS analysis and the toxicity analysis has also been performed based on the anti-microbial activity test (agar-well diffusion method) for the different treatment strategies. The present work has conclusively established that the combined approach of US+O 3 +CuO was the most efficient treatment scheme resulting in near complete degradation of 2,4-DCP with production of less toxic intermediates. Copyright © 2016 Elsevier B.V. All rights reserved.

Sunlight-assisted Fenton reaction catalyzed by gold supported on diamond nanoparticles as pretreatment for biological degradation of aqueous phenol solutions.

PubMed

Navalon, Sergio; Martin, Roberto; Alvaro, Mercedes; Garcia, Hermenegildo

2011-05-23

Gold nanoparticles supported on Fenton-treated diamond nanoparticles (Au/DNPs) have been reported as one of the most efficient solid catalysts effecting the Fenton reaction, achieving a turnover number (TON) as high as 321,000. However, at room temperature the main limitation for the catalytic activity of Au/DNPs is the pH of the solution, which should be less than 5. In this paper, we report that exposure of Au/DNPs to sunlight enhances the catalytic activity of Au/DNPs up to the point that it can promote the Fenton reaction at room temperature even at slightly basic pH values. Also, in addition to performing a deep Fenton treatment and considering that the excess of H(2)O(2) used in the process should be minimized, we have achieved in our study, using a mild Fenton reaction promoted by Au/DNPs under sunlight irradiation, an optimum in the biodegradability, a minimum in the ecotoxicity, and no toxicity for the Vibrio fischeri test. The results have shown that, by using an H(2)O(2) -to-phenol molar ratio of 5.5 or higher, it is possible to achieve a high biodegradability as well as a complete lack of ecotoxicity and of Vibrio fischeri toxicity. The stability of Au/DNPs was confirmed by analyzing the gold leached to the solution and by performing four consecutive reuses of the catalyst with initial pH values ranging from 4 to 8. It was observed that, after finishing the reaction and exhaustive washings with basic aqueous solutions, the initial reaction rate of the used catalyst is recovered to the value exhibited by the fresh solid. Overall, our study shows that the synergism between catalysis and photocatalysis can overcome the limitations found for dark catalytic reactions and that the reaction parameters can be optimized to effect mild Fenton reactions aimed at increasing biodegradability in biorecalcitrant waste waters. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionogel Electrolytes through Sol-Gel Processing

NASA Astrophysics Data System (ADS)

Horowitz, Ariel I.

Electrical energy needs have intensified due to the ubiquity of personal electronics, the decarbonization of energy services through electrification, and the use of intermittent renewable energy sources. Despite developments in mechanical and thermal methods, electrochemical technologies are the most convenient and effective means of storing electrical energy. These technologies include both electrochemical cells, commonly called batteries, and electrochemical double-layer capacitors, or "supercapacitors", which store energy electrostatically. Both device types require an ion-conducting electrolyte. Current devices use solutions of complex salts in organic solvents, leading to both toxicity and flammability concerns. These drawbacks can be avoided by replacing conventional electrolytes with room-temperature molten salts, known as ionic liquids (ILs). ILs are non-volatile, non-flammable, and offer high conductivity and good electrochemical stability. Device mass can be reduced by combining ILs with a solid scaffold material to form an "ionogel," further improving performance metrics. In this work, sol-gel chemistry is explored as a means of forming ionogel electrolytes. Sol-gel chemistry is a solution-based, industrially-relevant, well-studied technique by which solids such as silica can be formed in situ. Previous works used a simple acid-catalyzed sol-gel reaction to create brittle, glassy ionogels. Here, both the range of products that can be accomplished through sol-gel processing and the understanding of interactions between ILs and the sol-gel reaction network are greatly expanded. This work introduces novel ionogel materials, including soft and compliant silica-supported ionogels and PDMS-supported ionogels. The impacts of the reactive formulation, IL identity, and casting time are detailed. It is demonstrated that variations in formulation can lead to rapid gelation and open pore structures in the silica scaffold or slow gelation and more dense silica morphologies. The IL identity is shown to have an impact on the apparent strength of the acid catalyst, leading to significant shifts in gelation time. Delayed casting is proven to be an optimal technique for avoiding pore blockage when combining ionogels with high surface area electrodes for supercapacitor applications. Finally, a simple recycling process is proposed, establishing that ILs can be easily reclaimed from silica-supported ionogels and reused, thereby validating the reputation of ILs as "green" materials.

Toxicological properties of emission particles from heavy duty engines powered by conventional and bio-based diesel fuels and compressed natural gas.

PubMed

Jalava, Pasi I; Aakko-Saksa, Päivi; Murtonen, Timo; Happo, Mikko S; Markkanen, Ari; Yli-Pirilä, Pasi; Hakulinen, Pasi; Hillamo, Risto; Mäki-Paakkanen, Jorma; Salonen, Raimo O; Jokiniemi, Jorma; Hirvonen, Maija-Riitta

2012-09-29

One of the major areas for increasing the use of renewable energy is in traffic fuels e.g. bio-based fuels in diesel engines especially in commuter traffic. Exhaust emissions from fossil diesel fuelled engines are known to cause adverse effects on human health, but there is very limited information available on how the new renewable fuels may change the harmfulness of the emissions, especially particles (PM). We evaluated the PM emissions from a heavy-duty EURO IV diesel engine powered by three different fuels; the toxicological properties of the emitted PM were investigated. Conventional diesel fuel (EN590) and two biodiesels were used - rapeseed methyl ester (RME, EN14214) and hydrotreated vegetable oil (HVO) either as such or as 30% blends with EN590. EN590 and 100% HVO were also operated with or without an oxidative catalyst (DOC + POC). A bus powered by compressed natural gas (CNG) was included for comparison with the liquid fuels. However, the results from CNG powered bus cannot be directly compared to the other situations in this study. High volume PM samples were collected on PTFE filters from a constant volume dilution tunnel. The PM mass emission with HVO was smaller and with RME larger than that with EN590, but both biofuels produced lower PAH contents in emission PM. The DOC + POC catalyst greatly reduced the PM emission and PAH content in PM with both HVO and EN590. Dose-dependent TNFα and MIP-2 responses to all PM samples were mostly at the low or moderate level after 24-hour exposure in a mouse macrophage cell line RAW 264.7. Emission PM from situations with the smallest mass emissions (HVO + cat and CNG) displayed the strongest potency in MIP-2 production. The catalyst slightly decreased the PM-induced TNFα responses and somewhat increased the MIP-2 responses with HVO fuel. Emission PM with EN590 and with 30% HVO blended in EN590 induced the strongest genotoxic responses, which were significantly greater than those with EN590 + cat or 100% HVO. The emission PM sample from the CNG bus possessed the weakest genotoxic potency but had the strongest oxidative potency of all the fuel and catalyst combinations. The use of 100% HVO fuel had slightly weaker and 100% RME somewhat stronger emission PM induced ROS production, when compared to EN590. The harmfulness of the exhaust emissions from vehicle engines cannot be determined merely on basis of the emitted PM mass. The study conditions and the engine type significantly affect the toxicity of the emitted particles. The selected fuels and DOC + POC catalyst affected the PM emission from the heavy EURO IV engine both qualitative and quantitative ways, which influenced their toxicological characteristics. The plain HVO fuel performed very well in emission reduction and in lowering the overall toxicity of emitted PM, but the 30% blend of HVO in EN590 was no better in this respect than the plain EN590. The HVO with a DOC + POC catalyst in the EURO IV engine, performed best with regard to changes in exhaust emissions. However some of the toxicological parameters were significantly increased even with these low emissions.

Toxicological properties of emission particles from heavy duty engines powered by conventional and bio-based diesel fuels and compressed natural gas

PubMed Central

2012-01-01

Background One of the major areas for increasing the use of renewable energy is in traffic fuels e.g. bio-based fuels in diesel engines especially in commuter traffic. Exhaust emissions from fossil diesel fuelled engines are known to cause adverse effects on human health, but there is very limited information available on how the new renewable fuels may change the harmfulness of the emissions, especially particles (PM). We evaluated the PM emissions from a heavy-duty EURO IV diesel engine powered by three different fuels; the toxicological properties of the emitted PM were investigated. Conventional diesel fuel (EN590) and two biodiesels were used − rapeseed methyl ester (RME, EN14214) and hydrotreated vegetable oil (HVO) either as such or as 30% blends with EN590. EN590 and 100% HVO were also operated with or without an oxidative catalyst (DOC + POC). A bus powered by compressed natural gas (CNG) was included for comparison with the liquid fuels. However, the results from CNG powered bus cannot be directly compared to the other situations in this study. Results High volume PM samples were collected on PTFE filters from a constant volume dilution tunnel. The PM mass emission with HVO was smaller and with RME larger than that with EN590, but both biofuels produced lower PAH contents in emission PM. The DOC + POC catalyst greatly reduced the PM emission and PAH content in PM with both HVO and EN590. Dose-dependent TNFα and MIP-2 responses to all PM samples were mostly at the low or moderate level after 24-hour exposure in a mouse macrophage cell line RAW 264.7. Emission PM from situations with the smallest mass emissions (HVO + cat and CNG) displayed the strongest potency in MIP-2 production. The catalyst slightly decreased the PM-induced TNFα responses and somewhat increased the MIP-2 responses with HVO fuel. Emission PM with EN590 and with 30% HVO blended in EN590 induced the strongest genotoxic responses, which were significantly greater than those with EN590 + cat or 100% HVO. The emission PM sample from the CNG bus possessed the weakest genotoxic potency but had the strongest oxidative potency of all the fuel and catalyst combinations. The use of 100% HVO fuel had slightly weaker and 100% RME somewhat stronger emission PM induced ROS production, when compared to EN590. Conclusions The harmfulness of the exhaust emissions from vehicle engines cannot be determined merely on basis of the emitted PM mass. The study conditions and the engine type significantly affect the toxicity of the emitted particles. The selected fuels and DOC + POC catalyst affected the PM emission from the heavy EURO IV engine both qualitative and quantitative ways, which influenced their toxicological characteristics. The plain HVO fuel performed very well in emission reduction and in lowering the overall toxicity of emitted PM, but the 30% blend of HVO in EN590 was no better in this respect than the plain EN590. The HVO with a DOC + POC catalyst in the EURO IV engine, performed best with regard to changes in exhaust emissions. However some of the toxicological parameters were significantly increased even with these low emissions. PMID:23021308

Final Technical Report on Development of an Economic and Efficient Biodiesel production Process (NC)

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

Tirla, Cornelia; Dooling, Thomas A.; Smith, Rachel B.

The Biofuels Team at The University of North Carolina at Pembroke and North Carolina A&T State University carried out a joint research project aimed at developing an efficient process to produce biodiesel. In this project, the team developed and tested various types of homogeneous and heterogeneous catalysts which could replace the conventionally used soluble potassium hydroxide catalyst which, traditionally, must be separated and disposed of at the end of the process. As a result of this screening, the homogeneous catalyst choline hydroxide was identified as a potential replacement for the traditional catalyst used in this process, potassium hydroxide, due tomore » its decreased corrosiveness and toxicity. A large number of heterogeneous catalysts were produced and tested in order to determine the scaffold, ion type and ion concentration which would produce optimum yield of biodiesel. The catalyst with 12% calcium on Zeolite β was identified as being highly effective and optimal reaction conditions were identified. Furthermore, a packed bed reactor utilizing this type of catalyst was designed, constructed and tested in order to further optimize the process. An economic analysis of the viability of the project showed that the cost of an independent farmer to produce the fuelstock required to produce biodiesel exceeds the cost of petroleum diesel under current conditions and that therefore without incentives, farmers would not be able to benefit economically from producing their own fuel. An educational website on biodiesel production and analysis was produced and a laboratory experiment demonstrating the production of biodiesel was developed and implemented into the Organic Chemistry II laboratory curriculum at UNCP. Five workshops for local farmers and agricultural agents were held in order to inform the broader community about the various fuelstock available, their cultivation and the process and advantages of biodiesel use and production. This project fits both Universities’ goals in the Biofuels Research Initiative, since it uses an alternative fuelstock: namely canola. The outcomes of this project may eventually aid in reducing the state’s consumption of corn and soybean, which are important food crops. The project will also encourage regional farmers to grow alternative crops for biofuel production. The success of this project has contributed towards the development of Robeson County, an economically disadvantaged region. Additionally it should be noted that Robeson County serves a large Native American population. Therefore, training and engaging this minority group in the energy industry was an important accomplishment.« less

Development of a detection sensor for lethal H2S gas.

PubMed

Park, Young-Ho; Kim, Yong-Jae; Lee, Chang-Seop

2012-07-01

The gas which may be lethal to human body with short-term exposure in common industrial fields or workplaces in LAB may paralyze the olfactory sense and impose severe damages to central nervous system and lung. This study is concerned with the gas sensor which allows individuals to avoid the toxic gas that may be generated in the space with residues of organic wastes under 50 degrees C or above. This study investigates response and selectivity of the sensor to hydrogen sulfide gas with operating temperatures and catalysts. The thick-film semiconductor sensor for hydrogen sulfide gas detection was fabricated WO3/SnO2 prepared by sol-gel and precipitation methods. The nanosized SnO2 powder mixed with the various metal oxides (WO3, TiO2, and ZnO) and doped with transition metals (Au, Ru, Pd Ag and In). Particle sizes, specific surface areas and phases of sensor materials were investigated by SEM, BET and XRD analyses. The metal-WO3/SnO2 thick films were prepared by screen-printing method. The measured response to hydrogen sulfide gas is defined as the ratio (Ra/R,) of the resistance of WO3ISnO2 film in air to the resistance of WO3/SnO2 film in a hydrogen sulfide gas. It was shown that the highest response and selectivity of the sensor for hydrogen sulfide by doping with 1 wt% Ru and 10 wt% WO3 to SnO2 at the optimum operating temperature of 200 degrees C.

Impregnation of Catalytic Metals in Single-Walled Carbon Nanotubes for Toxic Gas Conversion in Life Support System

NASA Technical Reports Server (NTRS)

Li, Jing; Wignarajah, Kanapathipillai; Cinke, Marty; Partridge, Harry; Fisher, John

2004-01-01

Carbon nanotubes (CNTs) possess extraordinary properties such as high surface area, ordered chemical structure that allows functionalization, larger pore volume, and very narrow pore size distribution that have attracted considerable research attention from around the world since their discovery in 1991. The development and characterization of an original and innovative approach for the control and elimination of gaseous toxins using single walled carbon nanotubes (SWNTs) promise superior performance over conventional approaches due to the ability to direct the selective uptake of gaseous species based on their controlled pore size, increased adsorptive capacity due to their increased surface area and the effectiveness of carbon nanotubes as catalyst supports for gaseous conversion. We present our recent investigation of using SWNTs as catalytic supporting materials to impregnate metals, such as rhodium (Rh), palladium (Pd) and other catalysts. A protocol has been developed to oxidize the SWNTs first and then impregnate the Rh in aqueous rhodium chloride solution, according to unique surface properties of SWNTs. The Rh has been successfully impregnated in SWNTs. The Rh-SWNTs have been characterized by various techniques, such as TGA, XPS, TEM, and FTIR. The project is funded by a NASA Research Announcement Grant to find applications of single walled nanocarbons in eliminating toxic gas Contaminant in life support system. This knowledge will be utilized in the development of a prototype SWNT KO, gas purification system that would represent a significant step in the development of high efficiency systems capable of selectively removing specific gaseous for use in regenerative life support system for human exploration missions.

Elimination of radiocontrast agent diatrizoic acid by photo-Fenton process and enhanced treatment by coupling with electro-Fenton process.

PubMed

Bocos, Elvira; Oturan, Nihal; Pazos, Marta; Sanromán, M Ángeles; Oturan, Mehmet A

2016-10-01

The removal of radiocontrast agent diatrizoic acid (DIA) from water was performed using photo-Fenton (PF) process. First, the effect of H2O2 dosage on mineralization efficiency was determined using ultraviolet (UV) irradiation. The system reached a maximum mineralization degree of 60 % total organic carbon (TOC) removal at 4 h with 20 mM initial H2O2 concentration while further concentration values led to a decrease in TOC abatement efficiency. Then, the effect of different concentrations of Fenton's reagents was studied for homogeneous Fenton process. Obtained results revealed that 0.25 mM Fe(3+) and 20 mM H2O2 were the best conditions, achieving 80 % TOC removal efficiency at 4 h treatment. Furthermore, heterogeneous PF treatment was developed using iron-activated carbon as catalyst. It was demonstrated that this catalyst is a promising option, reaching 67 % of TOC removal within 4 h treatment without formation of iron leachate in the medium. In addition, two strategies of enhancement for process efficiency are proposed: coupling of PF with electro-Fenton (EF) process in two ways: photoelectro-Fenton (PEF) or PF followed by EF (PF-EF) treatments, achieving in both cases the complete mineralization of DIA solution within only 2 h. Finally, the Microtox tests revealed the formation of more toxic compounds than the initial DIA during PF process, while, it was possible to reach total mineralization by both proposed alternatives (PEF or PF-EF) and thus to remove the toxicity of DIA solution.

Recent advances in investigations of toxicity of automotive exhaust

PubMed Central

Stupfel, Maurice

1976-01-01

The influence of auto exhaust on man's health is difficult to gauge considering the intricacy of human environmental urban stresses and particularly of other air polluting (industrial, domestic) emissions. Epidemiological surveys made in road tunnel employees and in traffic officers have not demonstrated specific effects and have often been complicated by cigarette smoking as a factor. Long-term animal experiments run mostly on small rodents give evidence of little effect of the pathological actions of dilutions such as those encountered in high polluted cities. However the acute toxicity of gasoline exhaust emission is well known and mostly due to carbon monoxide. Considering the different types of cycles and operating conditions of vehicles (gasoline and diesel), auto exhaust gases constitute no more a chemical entity than they show, a definite toxicity. A great number of substances that they contain (nitrogen oxides, aldehydes, antiknock additives, heavy metals, possible catalysts are highly toxic as shown by in vivo and in vitro (mutagenic) tests. Interactions of the components are for the moment ignored or poorly understood. Besides, the evolution of the physicochemical properties and natures of the auto exhaust emission in the gaseous biotope of man under determined conditions of ultraviolet irradiation, temperature, and hygrometry provoke the formation of secondary products such as oxidants and ozone. Several experiments show clearly that irradiation increases the toxicity of auto exhaust significantly. For these reasons, geographical, meteorological, and chronological (circadian and seasonal) factors should be taken into consideration, especially with regard to emission standards. PMID:67944

Intracellular and extracellular microtubule associated protein tau as a therapeutic target in Alzheimer disease and other tauopathies.

PubMed

Avila, Jesús; Pallas, Noemí; Bolós, Marta; Sayas, C Laura; Hernandez, Felix

2016-06-01

Microtubule associated protein tau, a protein mainly expressed in neurons, plays an important role in several diseases related to dementia, named tauopathies. Alzheimer disease is the most relevant tauopathy. The role of tau protein in dementia is now a topic under discussion, and is the focus of this review. We have covered two major areas: tau pathology and tau as a therapeutic target. Tau pathology is mainly related to a gain of toxic function due to an abnormal accumulation, aberrant modifications (such as hyperphosphorylation and truncation, among others) and self-aggregation of tau into oligomers or larger structures. Also, tau can be found extracellularly in a toxic form. Tau-based therapy is mainly centered on avoiding the gain of these toxic functions of tau. Tau therapies are focused on lowering tau levels, mainly of modified tau species that could be toxic for neurons (phosphorylated, truncated or aggregated tau), in intracellular or extracellular form. Decreasing the levels of those toxic species is a possible therapeutic strategy.

Lead toxicity as an etiology for abdominal pain in the emergency department.

PubMed

Moriarity, Risa S; Harris, James T; Cox, Robert D

2014-02-01

Abdominal pain is an uncommon presentation of lead toxicity in the emergency department (ED). However, making the diagnosis is important in avoiding unnecessary testing and the long-term sequelae of lead toxicity. To illustrate possible presentations of abdominal pain secondary to lead toxicity and highlight the importance of taking a thorough patient history. We report 2 patients who presented to the ED with abdominal pain and underwent extensive evaluations that did not reveal an etiology. At follow-up visits, their occupational histories revealed possible lead exposures from working for a bullet-recycling company. Tests revealed that each patient had extremely high lead levels and they were both treated for lead toxicity. Their abdominal pain resolved as their lead levels decreased. These cases demonstrate a rare but significant cause of abdominal pain in the ED. Although history-taking in the ED is necessarily brief, these cases underscore the importance of obtaining an occupational history. Copyright © 2014 Elsevier Inc. All rights reserved.

[Pharmacogenomics in neuro-oncology].

PubMed

Riese-Jorda, H H; Baez, J M

Chemotherapy protocols for treatment of brain tumors use toxic molecules for killing cancer cells in a similar way that protocols for treating other cancers. Therefore, secondary effects and poor response are the major handicaps. Technological developments based on pharmacogenomics and pharmacoproteomics will predict response and toxicity giving rise to a personalized medicine. However, there are only few studies that correlate chemotherapeutical molecules for brain tumor treatment and prediction of response and toxicity. The development of new technologies based on high-density microarrays allows the progressive identification of genes whose presence will predict the efficacy of therapeutic protocols. Once identified, specific equipments based on low-density arrays will detect exclusively in an easy and fast way the presence of genes in order to predict patient's response and avoid toxicity. Other more sophisticated techniques at present still at an experimental step based on proteomics as MALDI (Matrix-Assisted Laser Desorption Ionization) and SELDI (Surface-Enhanced Laser Desorption Ionization) will allow the identification of proteins that could predict response and toxicity.

Mutagenicity and Acute Oral Toxicity Test for Herbal Poultry Feed Supplements.

PubMed

Srinivasa Rao, Boddapati; Chandrasekaran, C V; Srikanth, H S; Sasikumar, Murugan; Edwin Jothie, R; Haseena, Begum; Bharathi, Bethapudi; Selvam, Ramasamy; Prashanth, D'Souza

2018-01-01

Herbal products are being used and trusted globally for thousands of years for their health benefits and limited side effects. Globally, a general belief amongst the consumers is that herbal supplements are always safe because they are "natural." But later, research reveals that they may not be safe. This raises concern on their safety and implications for their use as feed supplement or medicine. Toxicity testing can reveal some of the risks that may be associated with use of herbs, therefore avoiding potential harmful effects. The present study was designed to investigate five poultry feed supplements (PFS), EGMAX® (to revitalize ovarian activity), FEED-X ™ (feed efficiency enhancer), KOLIN PLUS ™ (natural replacer of synthetic choline chloride), PHYTOCEE® (natural defence enhancer), and STODI® (to prevent and control loose droppings), for their possible mutagenicity and toxicity. Bacterial reverse mutation (BRMT) and acute oral toxicity tests were employed to assess the PFS for their possible mutagenicity and toxicity. Results indicated that the PFS were devoid of mutagenic effects in BRMT and showed higher safety profile in rodent acute oral toxicity test.

[Household gas poisonings].

PubMed

Maloca, Ivana; Macan, Jelena; Varnai, Veda Marija; Turk, Rajka

2006-12-01

Exposure to toxic gases which can induce serious health effects, can occur in the working as well as in general environment, including home. The severity of gas poisoning is determined by its physical and chemical characteristics, intensity and duration of exposure, and concomitant diseases and injuries in the poisoned person. Manifestations of gas toxic action involve simple asphyxia, local irritation of respiratory mucosa, systemic toxicity, and a combination of these mechanisms. This article describes the characteristics, modes of exposure and health effects of most common gases causing poisoning at home. These include gas fuels, carbon monoxide, ammonia, chlorine, and fire gases such as nitrogen and sulphur oxides, hydrogen cyanide and phosgene. First aid as well as preventive measures to avoid exposure to toxic gases and prevent fire at home are also given. The Croatian Poison Control Centre gathered data on toxic gas exposures in households between November 2005 and July 2006. During this period 30 persons (3 % of the total number of cases) were exposed to toxic gases at home, including carbon monoxide, irritating vapours from cleaning agents and disinfectants, gas fuels, septic tank gases, tear-gas, and chlorofluorocarbons from refrigerators.

Classification of baseline toxicants for QSAR predictions to replace fish acute toxicity studies.

PubMed

Nendza, Monika; Müller, Martin; Wenzel, Andrea

2017-03-22

Fish acute toxicity studies are required for environmental hazard and risk assessment of chemicals by national and international legislations such as REACH, the regulations of plant protection products and biocidal products, or the GHS (globally harmonised system) for classification and labelling of chemicals. Alternative methods like QSARs (quantitative structure-activity relationships) can replace many ecotoxicity tests. However, complete substitution of in vivo animal tests by in silico methods may not be realistic. For the so-called baseline toxicants, it is possible to predict the fish acute toxicity with sufficient accuracy from log K ow and, hence, valid QSARs can replace in vivo testing. In contrast, excess toxicants and chemicals not reliably classified as baseline toxicants require further in silico, in vitro or in vivo assessments. Thus, the critical task is to discriminate between baseline and excess toxicants. For fish acute toxicity, we derived a scheme based on structural alerts and physicochemical property thresholds to classify chemicals as either baseline toxicants (=predictable by QSARs) or as potential excess toxicants (=not predictable by baseline QSARs). The step-wise approach identifies baseline toxicants (true negatives) in a precautionary way to avoid false negative predictions. Therefore, a certain fraction of false positives can be tolerated, i.e. baseline toxicants without specific effects that may be tested instead of predicted. Application of the classification scheme to a new heterogeneous dataset for diverse fish species results in 40% baseline toxicants, 24% excess toxicants and 36% compounds not classified. Thus, we can conclude that replacing about half of the fish acute toxicity tests by QSAR predictions is realistic to be achieved in the short-term. The long-term goals are classification criteria also for further groups of toxicants and to replace as many in vivo fish acute toxicity tests as possible with valid QSAR predictions.

Therapy of primary CNS lymphoma with methotrexate-based chemotherapy and deferred radiotherapy: preliminary results.

PubMed

Cher, L; Glass, J; Harsh, G R; Hochberg, F H

1996-06-01

Disease-free survival in primary CNS lymphoma has improved with the advent of methotrexate-based pre-irradiation chemotherapy. Prolonged response durations have been noted in six of eight patients refusing radiation therapy in two of our prior series. We have treated an additional 11 patients with methotrexate-based chemotherapy without subsequent planned irradiation. Some received maintenance chemotherapy. Most have had durable responses with little or no toxicity. Prolonged responses can be maintained without radiation therapy, thus avoiding potential long-term radiation toxicity.

Hydrogen sulfide-powered solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Liu, Man

2004-12-01

The potential utilization of hydrogen sulfide as fuel in solid oxide fuel cells has been investigated using an oxide-ion conducting YSZ electrolyte and different kinds of anode catalysts at operating temperatures in the range of 700--900°C and at atmospheric pressure. This technology offers an economically attractive alternative to present methods for removing toxic and corrosive H2S gas from sour gas streams and a promising approach for cogenerating electrical energy and useful chemicals. The primary objective of the present research was to find active and stable anode materials. Fuel cell experimental results showed that platinum was a good electrocatalyst for the conversion of H2S, but the Pt/YSZ interface was physically unstable due to the reversible formation and decomposition of PtS in H 2S streams at elevated temperatures. Moreover, instability of the Pt/YSZ interface was accelerated significantly by electrochemical reactions, and ultimately led to the detachment of the Pt anode from the electrolyte. It has been shown that an interlayer of TiO2 stabilized the Pt anode on YSZ electrolyte, thereby prolonging cell lifetime. However, the current output for a fuel cell using Pt/TiO2 as anode was not improved compared to using Pt alone. It was therefore necessary to investigate novel anode systems for H 2S-air SOFCs. New anode catalysts comprising composite metal sulfides were developed. These catalysts exhibited good electrical conductivity and better catalytic activity than Pt. In contrast to MoS2 alone, composite catalysts (M-Mo-S, M = Fe, Co, Ni) were not volatile and had superior stability. However, when used for extended periods of time, detachment of Pt current collecting film from anodes comprising metal sulfides alone resulted in a large increase in contact resistance and reduction in cell performance. Consequently, a systematic investigation was conducted to identify alternative electronic conductors for use with M-Mo-S catalysts. Anode catalysts comprising Co-Mo-S admixed with up to 10% Ag powder were found to have excellent performance and longevity, as well as improved electrical contact when compared with Pt/M-Mo-S anode systems. The highest current density of 450 mA/cm2 and power density of 115 mW/cm2 were achieved with an anode that consisted of 95% (Co-Mo-S) and 5% Ag.

Biodegradable polymers as non-viral carriers for plasmid DNA delivery.

PubMed

Luten, Jordy; van Nostrum, Cornelus F; De Smedt, Stefaan C; Hennink, Wim E

2008-03-03

Gene therapy holds a great promise for the treatment of acquired and inherited diseases with a genetic origin that are currently incurable. Non-viral gene delivery systems are gaining recognition as an alternative to viral gene vectors for their potential in avoiding immunogenicity and toxicity problems inherently associated with the use of viral systems. Many cationic polymers have been studied both in vitro and in vivo for gene delivery purposes. However, in recent years there has been a focus on biodegradable carrier systems. The potential advantage of biodegradable carriers as compared to their non-degradable counterparts is their reduced toxicity and the avoidance of accumulation of the polymer in the cells after repeated administration. Also, the degradation of the polymer can be used as a tool to release the plasmid DNA into the cytosol. In this article the recent results obtained with two classes of degradable gene delivery systems, namely those based on water-soluble cationic polymers and on micro- and nanoparticles will be summarized and discussed.

The preservation of living cells with biocompatible microparticles

NASA Astrophysics Data System (ADS)

Yang, Jing; Zhu, Yingnan; Xu, Tong; Pan, Chao; Cai, Nana; Huang, He; Zhang, Lei

2016-07-01

Biomedical applications of living cells have rapidly expanded in many fields such as toxic detection, drug screening, and regenerative medicine, etc. Efficient methods to support cell survival and maintain activity in vitro have become increasingly important. However, traditional cryopreservation for living cell-based applications is limited by several problems. Here, we report that magnetic hydrogel microparticles can physically assemble into a 3D environment for efficient cell preservation in physiological conditions, avoiding any chemical reactions that would damage the cells. Two representative cell lines (loosely and firmly adherent) were tested to evaluate the versatility of this method. The results showed that cell longevity was significantly extended to at least 15 days, while the control cell samples without microparticles quickly died within 3 days. Moreover, after preservation, cells can be easily retrieved by applying a magnet to separate the magnetic particles. This strategy can also inhibit cell over-proliferation while avoiding the use of temperature extremes or toxic cryoprotectants that are essential in cryopreservation.

Can Batesian mimicry help plants to deter herbivores?

PubMed

Massei, Giovanna; Cotterill, Jane V; Coats, Julia C; Bryning, Gareth; Cowan, Dave P

2007-06-01

Several authors have suggested that edible plants could avoid herbivory by mimicking olfactory cues of toxic plants. However, very few studies have been carried out to test this hypothesis. The aims of the present study were to identify the volatiles of three clover species and to test whether a species lacking chemical defences, such as red clover, could avoid being grazed by rabbits by mimicking the volatiles of the cyanogenic white clover. Two main volatiles were identified in all three clover species, and a further two volatiles were present in white clover only. Rabbits presented with a choice between white clover, red clover and red clover sprayed with white clover extract ate significantly more red clover than white or white-flavoured red clover. The results suggest that the volatiles of toxic plants could be used and exploited as a source of natural, safe and effective repellents to control the impact of pest herbivores on plants. Copyright 2007 Society of Chemical Industry.

Exploring the Impact of Toxic Attitudes and a Toxic Environment on the Veterinary Healthcare Team

PubMed Central

Moore, Irene C.; Coe, Jason B.; Adams, Cindy L.; Conlon, Peter D.; Sargeant, Jan M.

2015-01-01

The objective of this qualitative study was to compare veterinarians’ and Registered Veterinary Technicians’ (RVT’s) perceptions of the veterinary healthcare team with respect to the impact of toxic attitudes and a toxic environment. Focus group interviews using a semi-structured interview guide and follow up probes were held with four veterinarian groups (23 companion animal veterinarians) and four Registered Veterinary Technician groups (26 RVTs). Thematic analysis of the discussions indicated both veterinarian and RVT participants felt team members with manifestations of toxic attitudes negatively impacted veterinary team function. These manifestations included people being disrespectful, being resistant to change, always wanting to be the “go to person,” avoiding conflict, and lacking motivation. When conflict was ignored, or when people with toxic attitudes were not addressed, a toxic environment often resulted. A toxic environment sometimes manifested when “broken communication and tension between staff members” occurred as a result of employees lacking confidence, skills, or knowledge not being managed properly. It also occurred when employees did not feel appreciated, when there was difficulty coping with turnover, and when there were conflicting demands. The presence of people manifesting a toxic attitude was a source of frustration for both veterinarian and RVT participants. Prompt and consistent attention to negative behaviors is recommended to reduce the development of a toxic environment. PMID:26779492

Vitamin D, Essential Minerals, and Toxic Elements: Exploring Interactions between Nutrients and Toxicants in Clinical Medicine

PubMed Central

Schwalfenberg, Gerry K.; Genuis, Stephen J.

2015-01-01

In clinical medicine, increasing attention is being directed towards the important areas of nutritional biochemistry and toxicant bioaccumulation as they relate to human health and chronic disease. Optimal nutritional status, including healthy levels of vitamin D and essential minerals, is requisite for proper physiological function; conversely, accrual of toxic elements has the potential to impair normal physiology. It is evident that vitamin D intake can facilitate the absorption and assimilation of essential inorganic elements (such as calcium, magnesium, copper, zinc, iron, and selenium) but also the uptake of toxic elements (such as lead, arsenic, aluminum, cobalt, and strontium). Furthermore, sufficiency of essential minerals appears to resist the uptake of toxic metals. This paper explores the literature to determine a suitable clinical approach with regard to vitamin D and essential mineral intake to achieve optimal biological function and to avoid harm in order to prevent and overcome illness. It appears preferable to secure essential mineral status in conjunction with adequate vitamin D, as intake of vitamin D in the absence of mineral sufficiency may result in facilitation of toxic element absorption with potential adverse clinical outcomes. PMID:26347061

ADDME – Avoiding Drug Development Mistakes Early: central nervous system drug discovery perspective

PubMed Central

Tsaioun, Katya; Bottlaender, Michel; Mabondzo, Aloise

2009-01-01

The advent of early absorption, distribution, metabolism, excretion, and toxicity (ADMET) screening has increased the attrition rate of weak drug candidates early in the drug-discovery process, and decreased the proportion of compounds failing in clinical trials for ADMET reasons. This paper reviews the history of ADMET screening and its place in pharmaceutical development, and central nervous system drug discovery in particular. Assays that have been developed in response to specific needs and improvements in technology that result in higher throughput and greater accuracy of prediction of human mechanisms of absorption and toxicity are discussed. The paper concludes with the authors' forecast of new models that will better predict human efficacy and toxicity. PMID:19534730

The weaker points of fish acute toxicity tests and how tests on embryos can solve some issues.

PubMed

Wedekind, Claus; von Siebenthal, Beat; Gingold, Ruth

2007-07-01

Fish acute toxicity tests play an important role in environmental risk assessment and hazard classification because they allow for first estimates of the relative toxicity of various chemicals in various species. However, such tests need to be carefully interpreted. Here we shortly summarize the main issues which are linked to the genetics and the condition of the test animals, the standardized test situations, the uncertainty about whether a given test species can be seen as representative to a given fish fauna, the often missing knowledge about possible interaction effects, especially with micropathogens, and statistical problems like small sample sizes and, in some cases, pseudoreplication. We suggest that multi-factorial embryo tests on ecologically relevant species solve many of these issues, and we shortly explain how such tests could be done to avoid the weaker points of fish acute toxicity tests.

Synthesis and functionalization of coiled carbon filaments

NASA Astrophysics Data System (ADS)

Hikita, Muneaki

Coiled carbon filaments have one of the most attractive three-dimensional forms in carbon materials due to their helical morphologies. Because of their shape and carbon structure, they exhibit excellent mechanical and electrical properties such as superelasticity, low Young's modulus, relatively high electrical conductivity, and good electromagnetic (EM) wave absorption. Therefore, they are good candidates as fillers in composite materials for tactile sensor and electromagnetic interference shielding. In medical areas of interests, coiled carbon filaments can be used as micro and nano heaters or trigger for thermotherapy and biosensors using EM wave exposure because absorbed EM waves by coiled carbon filaments are converted into heat. Although various shapes of coiled carbon filaments have been discovered, optimum synthesis conditions and growth mechanisms of coiled carbon filaments are poorly understood. The study of growth kinetics is significant not only to analyze catalyst activity but also to establish the growth mechanisms of coiled carbon filaments. The establishment of growth mechanisms would be useful for determining optimum synthesis conditions and maximizing the quantity of carbon filaments synthesized for a given application. In the first study, tip grown single helical carbon filaments or carbon nanocoils (CNCs) were synthesized by a chemical vapor deposition method using tin-iron-oxide (Sn-Fe-O) xerogel film catalyst. The Sn-Fe-O catalyst was prepared by a low-cost sol-gel method using stannous acetate and ferric acetate as precursors. The growth kinetics of CNCs were monitored by a thermogravimetric analyzer, and the experimental result was correlated using a one-dimensional kinetic model, corresponding to one-dimensional tip growth. In the second study, bidirectionally grown double helical filaments or carbon microcoils (CMCs) were synthesized using a chemical vapor deposition method. CMCs obtained at two reaction temperatures were compared. CMCs grown at the higher temperature had smaller fiber size and coil diameter, and longer lifetime of catalyst. For in-depth analysis, growth kinetics of CMCs were studied using an exponential decay model for catalyst poisoning. In the third study, CMCs were functionalized for improvement of water dispersion, optical properties and self-assembly. As-grown CMCs were hydrophobic. To improve water dispersion for biological applications, the surface of as-grown CMCs were oxidized by concentrated nitric acid at room temperature. After the oxidation, the acid-treated CMCs were well dispersed in water. For optical property, CMCs were functionalized with octadecylamine (ODA). Upon photoexcitation, the functionalized CMCs exhibited photoluminescence in the visible region. Similar to carbon based nanoparticles, the photoluminescence of CMCs was attributed to electron-hole radiative recombination after surface passivation. The results suggest that these functionalized CMCs might be used as a new class of optical agents for biological applications. As a primary experiment to study Au-S bonding, aminoethanethiol (HSCH2CH2NH2) was attached to the surface of gold-coated CMCs. Energy dispersive X-ray (EDX) mapping shows gold, sulfur and nitrogen on the surface of CMCs. Then, a thiol-modified ssDNA attachment experiment was performed using a similar functionalization procedure as aminoethanethiol. The existence of phosphorus, nitrogen, oxygen and sulfur on surface of Au-coated CMCs immersed in thiol-modified ssDNA solution was confirmed by the EDX spectrum. The result indicates that ssDNA was fixed on their surface. In the fourth study, the effect of oxidized CMCs on mouse embryonic stem (MES) cells was examined to determine their toxicity. Mouse embryonic stem cells represent a unique cell population with the ability to undergo both self-renewal and differentiation. Results indicate that oxidized CMCs had very little toxicity on stem cell viability. There was no observed loss of alkaline phosphatase (AP) as a stem cell marker and mitochondrial membrane potential (MMP) of oxidized CMC-treated MES cells was unaffected. Oxidized CMCs did not show toxicity to MES cells at the cellular level.

Spiritual energy of Islamic prayers as a catalyst for psychotherapy.

PubMed

Henry, Hani M

2015-04-01

Islamic prayers can produce spiritual energy that may yield many psychological benefits, such as amelioration of stress and improvement in subjective well-being, interpersonal sensitivity, and mastery. Islamic prayers can also be integrated into mainstream therapeutic interventions with religious Muslim clients, and this integration can mobilize, transform, and invigorate the process of psychotherapy. This paper provides methods that can be used for the explicit integration of Islamic prayers into traditional psychotherapy. Further, the paper offers strategies for avoiding potential pitfalls that may hamper this process. Finally, a case study illustrating this therapeutic integration and its psychological benefits will be presented.

Cyclic process for producing methane from carbon monoxide with heat removal

DOEpatents

Frost, Albert C.; Yang, Chang-lee

1982-01-01

Carbon monoxide-containing gas streams are converted to methane by a cyclic, essentially two-step process in which said carbon monoxide is disproportionated to form carbon dioxide and active surface carbon deposited on the surface of a catalyst, and said carbon is reacted with steam to form product methane and by-product carbon dioxide. The exothermic heat of reaction generated in each step is effectively removed during each complete cycle so as to avoid a build up of heat from cycle-to-cycle, with particularly advantageous techniques being employed for fixed bed, tubular and fluidized bed reactor operations.

Cyclic process for producing methane in a tubular reactor with effective heat removal

DOEpatents

Frost, Albert C.; Yang, Chang-Lee

1986-01-01

Carbon monoxide-containing gas streams are converted to methane by a cyclic, essentially two-step process in which said carbon monoxide is disproportionated to form carbon dioxide and active surface carbon deposited on the surface of a catalyst, and said carbon is reacted with steam to form product methane and by-product carbon dioxide. The exothermic heat of reaction generated in each step is effectively removed during each complete cycle so as to avoid a build up of heat from cycle-to-cycle, with particularly advantageous techniques being employed for fixed bed, tubular and fluidized bed reactor operations.

Scalable synthesis of palladium icosahedra in plug reactors for the production of oxygen reduction reaction catalysts

DOE PAGES

Wang, Helan; Niu, Guangda; Zhou, Ming; ...

2016-03-10

We have synthesized Pd icosahedra with uniform, controllable sizes in plug reactors separated by air. The oxygen contained in the air segments not only contributed to the generation of a reductant from diethylene glycol in situ, but also oxidized elemental Pd back to the ionic form by oxidative etching and thus slowed down the reduction kinetics. Compared to droplet reactors involving silicone oil or fluorocarbon, the use of air as a carrier phase could reduce the production cost by avoiding additional procedures for the separation of products from the oil. The average diameters of the Pd icosahedra could be readilymore » controlled in the range of 12–20 nm. The Pd icosahedra were further employed as seeds for the production of Pd@Pt 2–3L core-shell icosahedra, which could serve as a catalyst toward the oxygen reduction reaction with greatly enhanced activity. As a result, we believe that the plug reactors could be extended to other types of noble-metal nanocrystals for their scale-up production.« less

Alkali metal recovery from carbonaceous material conversion process

DOEpatents

Sharp, David W.; Clavenna, LeRoy R.; Gorbaty, Martin L.; Tsou, Joe M.

1980-01-01

In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced in the gasifier or similar reaction zone, alkali metal constitutents are recovered from the particles by withdrawing and passing the particles from the reaction zone to an alkali metal recovery zone in the substantial absence of molecular oxygen and treating the particles in the recovery zone with water or an aqueous solution in the substantial absence of molecular oxygen. The solution formed by treating the particles in the recovery zone will contain water-soluble alkali metal constituents and is recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. Preventing contact of the particles with oxygen as they are withdrawn from the reaction zone and during treatment in the recovery zone avoids the formation of undesirable alkali metal constituents in the aqueous solution produced in the recovery zone and insures maximum recovery of water-soluble alkali metal constituents from the alkali metal residues.

Controlling First-Row Catalysts: Amination of Aryl and Heteroaryl Chlorides and Bromides with Primary Aliphatic Amines Catalyzed by a BINAP-Ligated Single-Component Ni(0) Complex

PubMed Central

2015-01-01

First-row metal complexes often undergo undesirable one-electron redox processes during two-electron steps of catalytic cycles. We report the amination of aryl chlorides and bromides with primary aliphatic amines catalyzed by a well-defined, single-component nickel precursor (BINAP)Ni(η2-NC-Ph) (BINAP = 2,2′-bis(biphenylphosphino)-1,1′-binaphthalene) that minimizes the formation of Ni(I) species and (BINAP)2Ni. The scope of the reaction encompasses electronically varied aryl chlorides and nitrogen-containing heteroaryl chlorides, including pyridine, quinoline, and isoquinoline derivatives. Mechanistic studies support the catalytic cycle involving a Ni(0)/Ni(II) couple for this nickel-catalyzed amination and are inconsistent with a Ni(I) halide intermediate. Monitoring the reaction mixture by 31P NMR spectroscopy identified (BINAP)Ni(η2-NC-Ph) as the resting state of the catalyst in the amination of both aryl chlorides and bromides. Kinetic studies showed that the amination of aryl chlorides and bromides is first order in both catalyst and aryl halide and zero order in base and amine. The reaction of a representative aryl chloride is inverse first order in PhCN, but the reaction of a representative aryl bromide is zero order in PhCN. This difference in the order of the reaction in PhCN indicates that the aryl chloride reacts with (BINAP)Ni(0), formed by dissociation PhCN from (BINAP)Ni(η2-NC-Ph), but the aryl bromide directly reacts with (BINAP)Ni(η2-NC-Ph). The overall kinetic behavior is consistent with turnover-limiting oxidative addition of the aryl halide to Ni(0). Several pathways for catalyst decomposition were identified, such as the formation of the catalytically inactive bis(amine)-ligated arylnickel(II) chloride, (BINAP)2Ni(0), and the Ni(I) species [(BINAP)Ni(μ-Cl)]2. By using a well-defined nickel complex as catalyst, the formation of (BINAP)2Ni(0) is avoided and the formation of the Ni(I) species [(BINAP)Ni(μ-Cl)]2 is minimized. PMID:24397570

Monolayer formation of human osteoblastic cells on vertically aligned multiwalled carbon nanotube scaffolds.

PubMed

Lobo, Anderson O; Antunes, Erica F; Palma, Mariana Bs; Pacheco-Soares, Cristina; Trava-Airoldi, Vladimir J; Corat, Evaldo J

2010-03-12

Monolayer formation of SaOS-2 (human osteoblast-like cells) was observed on VACNT (vertically aligned multiwalled carbon nanotubes) scaffolds without purification or functionalization. The VACNT were produced by a microwave plasma chemical vapour deposition on titanium surfaces with nickel or iron as catalyst. Cell viability and morphology studies were evaluated by LDH (lactate dehydrogenase) release assay and SEM (scanning electron microscopy), respectively. The non-toxicity and the flat spreading with monolayer formation of the SaOs-2 on VACNT scaffolds surface indicate that they can be used for biomedical applications.

Hydrous pyrolysis/oxidation process for in situ destruction of chlorinated hydrocarbon and fuel hydrocarbon contaminants in water and soil

DOEpatents

Knauss, Kevin G.; Copenhaver, Sally C.; Aines, Roger D.

2000-01-01

In situ hydrous pyrolysis/oxidation process is useful for in situ degradation of hydrocarbon water and soil contaminants. Fuel hydrocarbons, chlorinated hydrocarbons, polycyclic aromatic hydrocarbons, petroleum distillates and other organic contaminants present in the soil and water are degraded by the process involving hydrous pyrolysis/oxidation into non-toxic products of the degradation. The process uses heat which is distributed through soils and water, optionally combined with oxygen and/or hydrocarbon degradation catalysts, and is particularly useful for remediation of solvent, fuel or other industrially contaminated sites.

Porous Silica Sol-Gel Glasses Containing Reactive V2O5 Groups

NASA Technical Reports Server (NTRS)

Stiegman, Albert E.

1995-01-01

Porous silica sol-gel glasses into which reactive vanadium oxide functional groups incorporated exhibit number of unique characteristics. Because they bind molecules of some species both reversibly and selectively, useful as chemical sensors or indicators or as scrubbers to remove toxic or hazardous contaminants. Materials also oxidize methane gas photochemically: suggests they're useful as catalysts for conversion of methane to alcohol and for oxidation of hydrocarbons in general. By incorporating various amounts of other metals into silica sol-gel glasses, possible to synthesize new materials with broad range of new characteristics.

Non-aqueous primary cell

NASA Astrophysics Data System (ADS)

James, S. D.; Smith, P. H.; Oneill, K. M.; Wilson, M. H.

1986-05-01

This patent application relates to electrochemical cells and especially to high-energy, liquid cathode, non-aqueous lithium electrochemical cells free from highly toxic materials. A non-aqueous lithium electrochemical cell is described which includes a halocarbon cathode depolarizer which is 1,2-dichloroethane, 1.1,2-trichloroethane, 1,1,2,2-tetrachloroethane, 1,2-dichloro-1,1-difluoroethane or mixtures thereof and a cathode catalyst which is copper, rhodium, palladium, cobalt phthalocyanine, nickel phthalocyanine, iron phthalocyanine, a cobalt tetraaza-(14)-annulene, a nickel tetraaza-(14)-annulene, a iron tetraaza-(14)-annulene, a cobalt porphyrin, a nickel porphyrin, a iron porphyrin, or a mixture thereof.

Development studies of a novel wet oxidation process

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

Rogers, T.W.; Dhooge, P.M.

1995-10-01

Many DOE waste streams and remediates contain complex and variable mixtures of organic compounds, toxic metals, and radionuclides. These materials are often dispersed in organic or inorganic matrices, such as personal protective equipment, various sludges, soils, and water. Incineration and similar combustive processes do not appear to be viable options for treatment of these waste streams due to various considerations. The objective of this project is to develop a novel catalytic wet oxidation process for the treatment of multi-component wastes. The DETOX process uses a unique combination of metal catalysts to increase the rate of oxidation of organic materials.

Development of a novel wet oxidation process for hazardous and mixed wastes

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

Dhooge, P.M.

1994-11-01

This article describes and evaluates the DETOX{sup sm} process for processing of mixed wastes. Many DOE waste streams and remediates contain complex and variable mixtures of organic compounds, toxic metals, and radionuclides, often dispersed in organic or inorganic matrices, such as personal protective equipment, various sludges, soils, and water. The DETOX{sup sm} process, patented by Delphi Research, uses a unique combination of metal catalysts to increase the rate of oxidation of organic materials. Included are the following subject areas: project description (phases I-IV); results of all phases; and future work. 5 figs., 1 tab.

Establishment of a bioassay for the toxicity evaluation and quality control of Aconitum herbs.

PubMed

Qin, Yi; Wang, Jia-bo; Zhao, Yan-ling; Shan, Li-mei; Li, Bao-cai; Fang, Fang; Jin, Cheng; Xiao, Xiao-he

2012-01-15

Currently, no bioassay is available for evaluating the toxicity of Aconitum herbs, which are well known for their lethal cardiotoxicity and neurotoxicity. In this study, we established a bioassay to evaluate the toxicity of Aconitum herbs. Test sample and standard solutions were administered to rats by intravenous infusion to determine their minimum lethal doses (MLD). Toxic potency was calculated by comparing the MLD. The experimental conditions of the method were optimized and standardized to ensure the precision and reliability of the bioassay. The application of the standardized bioassay was then tested by analyzing 18 samples of Aconitum herbs. Additionally, three major toxic alkaloids (aconitine, mesaconitine, and hypaconitine) in Aconitum herbs were analyzed using a liquid chromatographic method, which is the current method of choice for evaluating the toxicity of Aconitum herbs. We found that for all Aconitum herbs, the total toxicity of the extract was greater than the toxicity of the three alkaloids. Therefore, these three alkaloids failed to account for the total toxicity of Aconitum herbs. Compared with individual chemical analysis methods, the chief advantage of the bioassay is that it characterizes the total toxicity of Aconitum herbs. An incorrect toxicity evaluation caused by quantitative analysis of the three alkaloids might be effectively avoided by performing this bioassay. This study revealed that the bioassay is a powerful method for the safety assessment of Aconitum herbs. Copyright © 2011 Elsevier B.V. All rights reserved.

Platinum-paper micromotors: an urchin-like nanohybrid catalyst for green monopropellant bubble-thrusters.

PubMed

Claussen, Jonathan C; Daniele, Michael A; Geder, Jason; Pruessner, Marius; Mäkinen, Antti J; Melde, Brian J; Twigg, Mark; Verbarg, Jasenka M; Medintz, Igor L

2014-10-22

Platinum nanourchins supported on microfibrilated cellulose films (MFC) were fabricated and evaluated as hydrogen peroxide catalysts for small-scale, autonomous underwater vehicle (AUV) propulsion systems. The catalytic substrate was synthesized through the reduction of chloroplatinic acid to create a thick film of Pt coral-like microstructures coated with Pt urchin-like nanowires that are arrayed in three dimensions on a two-dimensional MFC film. This organic/inorganic nanohybrid displays high catalytic ability (reduced activation energy of 50-63% over conventional materials and 13-19% for similar Pt nanoparticle-based structures) during hydrogen peroxide (H2O2) decomposition as well as sufficient propulsive thrust (>0.5 N) from reagent grade H2O2 (30% w/w) fuel within a small underwater reaction vessel. The results demonstrate that these layered nanohybrid sheets are robust and catalytically effective for green, H2O2-based micro-AUV propulsion where the storage and handling of highly explosive, toxic fuels are prohibitive due to size-requirements, cost limitations, and close person-to-machine contact.

Solid-state synthesis of ordered mesoporous carbon catalysts via a mechanochemical assembly through coordination cross-linking

PubMed Central

Zhang, Pengfei; Wang, Li; Yang, Shize; Schott, Jennifer A.; Liu, Xiaofei; Mahurin, Shannon M.; Huang, Caili; Zhang, Yu; Fulvio, Pasquale F.; Chisholm, Matthew F.; Dai, Sheng

2017-01-01

Ordered mesoporous carbons (OMCs) have demonstrated great potential in catalysis, and as supercapacitors and adsorbents. Since the introduction of the organic–organic self-assembly approach in 2004/2005 until now, the direct synthesis of OMCs is still limited to the wet processing of phenol-formaldehyde polycondensation, which involves soluble toxic precursors, and acid or alkali catalysts, and requires multiple synthesis steps, thus restricting the widespread application of OMCs. Herein, we report a simple, general, scalable and sustainable solid-state synthesis of OMCs and nickel OMCs with uniform and tunable mesopores (∼4–10 nm), large pore volumes (up to 0.96 cm3 g−1) and high-surface areas exceeding 1,000 m2 g−1, based on a mechanochemical assembly between polyphenol-metal complexes and triblock co-polymers. Nickel nanoparticles (∼5.40 nm) confined in the cylindrical nanochannels show great thermal stability at 600 °C. Moreover, the nickel OMCs offer exceptional activity in the hydrogenation of bulky molecules (∼2 nm). PMID:28452357

Remediation of trichloroethylene by bio-precipitated and encapsulated palladium nanoparticles in a fixed bed reactor.

PubMed

Hennebel, Tom; Verhagen, Pieter; Simoen, Henri; De Gusseme, Bart; Vlaeminck, Siegfried E; Boon, Nico; Verstraete, Willy

2009-08-01

Trichloroethylene is a toxic and recalcitrant groundwater pollutant. Palladium nanoparticles bio-precipitated on Shewanella oneidensis were encapsulated in polyurethane, polyacrylamide, alginate, silica or coated on zeolites. The reactivity of these bio-Pd beads and zeolites was tested in batch experiments and trichloroethylene dechlorination followed first order reaction kinetics. The calculated k-values of the encapsulated catalysts were a factor of six lower compared to non-encapsulated bio-Pd. Bio-Pd, used as a catalyst, was able to dechlorinate 100 mgL(-1) trichloroethylene within a time period of 1h. The main reaction product was ethane; yet small levels of chlorinated intermediates were detected. Subsequently polyurethane cubes empowered with bio-Pd were implemented in a fixed bed reactor for the treatment of water containing trichloroethylene. The influent recycle configuration resulted in a cumulative removal of 98% after 22 h. The same reactor in a flow through configuration achieved removal rates up to 1059 mg trichloroethylene g Pd(-1)d(-1). This work showed that fixed bed reactors with bio-Pd polyurethane cubes can be instrumental for remediation of water contaminated with trichloroethylene.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Natural Magnetite: an efficient catalyst for the degradation of organic contaminant

NASA Astrophysics Data System (ADS)

He, Hongping; Zhong, Yuanhong; Liang, Xiaoliang; Tan, Wei; Zhu, Jianxi; Yan Wang, Christina

2015-05-01

Iron (hydr)oxides are ubiquitous earth materials that have high adsorption capacities for toxic elements and degradation ability towards organic contaminants. Many studies have investigated the reactivity of synthetic magnetite, while little is known about natural magnetite. Here, we first report the reactivity of natural magnetites with a variety of elemental impurities for catalyzing the decomposition of H2O2 to produce hydroxyl free radicals (•OH) and the consequent degradation of p-nitrophenol (p-NP). We observed that these natural magnetites show higher catalytic performance than that of the synthetic pure magnetite. The catalytic ability of natural magnetite with high phase purity depends on the surface site density while that for the magnetites with exsolutions relies on the mineralogical nature of the exsolved phases. The pleonaste exsolution can promote the generation of •OH and the consequent degradation of p-NP; the ilmenite exsolution has little effect on the decomposition of H2O2, but can increase the adsorption of p-NP on magnetite. Our results imply that natural magnetite is an efficient catalyst for the degradation of organic contaminants in nature.

Surface grafting of Eu3+ doped luminescent hydroxyapatite nanomaterials through metal free light initiated atom transfer radical polymerization for theranostic applications.

PubMed

Zeng, Guangjian; Liu, Meiying; Jiang, Ruming; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

2017-08-01

We reported a simple and efficient method to prepare the hydrophilic luminescent HAp polymer nanocomposites through the combination of ligand exchange and metal free light initiated surface-initiated atom transfer radical polymerization (SI-ATRP) using 10-phenylphenothiazine (PTH) as organic catalyst and 2-methacryloyloxyethyl phosphorylcholine (MPC) and itaconic acid (IA) as monomers. The biological imaging and drug delivery performance of HAp-poly(MPC-IA) nanorods were examined to evaluate their potential for biomedical applications. Results suggested that hydrophilic HAp-poly(MPC-IA) nanorods can be successfully prepared. More importantly, the HAp-poly(MPC-IA) exhibited excellent water dispersibility, desirable biocompatibility and good performance for biological imaging and controlled drug delivery applications. As compared with other controlled living polymerization reactions, the metal free light initiated SI-ATRP displayed many advantages such as easy for handle, mild reaction conditions, toxicity and fluorescence quenching from metal catalysts. Therefore, we believe that this strategy should be a useful and effective strategy for preparation of HAp nanomaterials for biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Evaluation and refinement of a field-portable drinking water toxicity sensor utilizing electric cell-substrate impedance sensing and a fluidic biochip.

PubMed

Widder, Mark W; Brennan, Linda M; Hanft, Elizabeth A; Schrock, Mary E; James, Ryan R; van der Schalie, William H

2015-07-01

The US Army's need for a reliable and field-portable drinking water toxicity sensor was the catalyst for the development and evaluation of an electric cell-substrate impedance sensing (ECIS) device. Water testing technologies currently available to soldiers in the field are analyte-specific and have limited capabilities to detect broad-based water toxicity. The ECIS sensor described here uses rainbow trout gill epithelial cells seeded on fluidic biochips to measure changes in impedance for the detection of possible chemical contamination of drinking water supplies. Chemicals selected for testing were chosen as representatives of a broad spectrum of toxic industrial compounds. Results of a US Environmental Protection Agency (USEPA)-sponsored evaluation of the field portable device were similar to previously published US Army testing results of a laboratory-based version of the same technology. Twelve of the 18 chemicals tested following USEPA Technology Testing and Evaluation Program procedures were detected by the ECIS sensor within 1 h at USEPA-derived human lethal concentrations. To simplify field-testing methods further, elimination of a procedural step that acclimated cells to serum-free media streamlined the test process with only a slight loss of chemical sensitivity. For field use, the ECIS sensor will be used in conjunction with an enzyme-based sensor that is responsive to carbamate and organophosphorus pesticides. Copyright © 2014 John Wiley & Sons, Ltd.

Determination and toxicity evaluation of the generated products in sulfamethoxazole degradation by UV/CoFe(2)O(4)/TiO(2).

PubMed

Gong, Han; Chu, Wei

2016-08-15

The photodegradation of sulfamethoxazole (SMX) under UV radiation with a recyclable catalyst CoFe2O4/TiO2 was examined. The reaction mechanism during the treatment was determined. The toxicity of the degradation intermediates to aquatic organisms, including the green alga Chlorella vulgaris and the brine shrimp Artemia salina was investigated. SMX was completely removed and about 50% TOC was degraded in 5h. Sixteen intermediates were detected, from which four of them were reported for the first time in this study. Four main decay pathways, i.e., hydroxylation, cleavage of SN bond, nitration of amino group, and isomerization were proposed. About 45% of the total mass sulfur source transformed to sulfate ion, and around 25%, 1%, and 0.25% of the total nitrogen transformed to ammonium, nitrogen, and nitrite ions. The toxicity of the treated solution was significantly reduced compared to that of the parent compound SMX. A variation of the algae growth was observed, which was due to the combination of generation of toxic intermediates (i.e., sulfanilamide) and the release of inorganic substances and carbon source as additional nutrients. The adverse effect on the clearance rate of the brine shrimp was also observed, but it can be eliminated if longer degradation time is used. Copyright © 2016 Elsevier B.V. All rights reserved.

Porous media for catalytic renewable energy conversion

NASA Astrophysics Data System (ADS)

Hotz, Nico

2012-05-01

A novel flow-based method is presented to place catalytic nanoparticles into a reactor by sol-gelation of a porous ceramic consisting of copper-based nanoparticles, silica sand, ceramic binder, and a gelation agent. This method allows for the placement of a liquid precursor containing the catalyst into the final reactor geometry without the need of impregnating or coating of a substrate with the catalytic material. The so generated foam-like porous ceramic shows properties highly appropriate for use as catalytic reactor material, e.g., reasonable pressure drop due to its porosity, high thermal and catalytic stability, and excellent catalytic behavior. The catalytic activity of micro-reactors containing this foam-like ceramic is tested in terms of their ability to convert alcoholic biofuel (e.g. methanol) to a hydrogen-rich gas mixture with low concentrations of carbon monoxide (up to 75% hydrogen content and less than 0.2% CO, for the case of methanol). This gas mixture is subsequently used in a low-temperature fuel cell, converting the hydrogen directly to electricity. A low concentration of CO is crucial to avoid poisoning of the fuel cell catalyst. Since conventional Polymer Electrolyte Membrane (PEM) fuel cells require CO concentrations far below 100 ppm and since most methods to reduce the mole fraction of CO (such as Preferential Oxidation or PROX) have CO conversions of up to 99%, the alcohol fuel reformer has to achieve initial CO mole fractions significantly below 1%. The catalyst and the porous ceramic reactor of the present study can successfully fulfill this requirement.

Photocatalytic degradation of humic acid in saline waters. Part 1. Artificial seawater: influence of TiO2, temperature, pH, and air-flow.

PubMed

Al-Rasheed, Radwan; Cardin, David J

2003-06-01

We report the first systematic study on the photocatalytic oxidation of humic acid (HA) in artificial seawater (ASW). TiO(2) (Degussa P25) dispersions were used as the catalyst with irradiation from a medium-pressure mercury lamp. The optimum quantity of catalyst was found to be between 2 and 2.5 gl(-1); while the decomposition was fastest at low pH values (pH 4.5 in the range examined), and the optimum air-flow, using an immersion well reactor with a capacity of 400 ml, was 850 ml min(-1). Reactivity increased with air-flow up to this figure, above which foaming prevented operation of the reactor. Using pure oxygen, an optimal flow rate was observed at 300 ml min(-1), above which reactivity remains essentially constant. Following treatment for 1 h, low-salinity water (2700 mg l(-1)) was completely mineralised, whereas ASW (46000 mg l(-1)) had traces of HA remaining. These effects are interpreted and kinetic data presented. To avoid problems of precipitation due to change of ionic strength humic substances were prepared directly in ASW, and the effects of ASW on catalyst suspension and precipitation have been taken into account. The Langmuir-Hinshelwood kinetic model has been shown to be followed only approximately for the catalytic oxidation of HA in ASW. The activation energy for the reaction derived from an Arrhenius treatment was 17 (+/-0.6) kJ mol(-1).

Preparation and characterization of nanostructured metal oxides for application to biomass upgrading Polar (111) metal oxide surfaces for pyrolysis oil upgrading and lignin depolymerization

NASA Astrophysics Data System (ADS)

Finch, Kenneth

2013-01-01

Pyrolysis oil, or bio-oil, is one of the most promising methods to upgrade a variety of biomass to transportation fuels. Moving toward a more "green" catalytic process requires heterogeneous catalysis over homogeneous catalysis to avoid extraction solvent waste. Nanoscale catalysts are showing great promise due to their high surface area and unusual surfaces. Base catalyzed condensation reactions occur much quicker than acid catalyzed condensation reactions. However, MgO is slightly soluble in water and is susceptible to degradation by acidic environments, similar to those found in fast-pyrolysis oil. Magnesium oxide (111) has a highly active Lewis base surface, which can catalyze Claisen-Schmidt condensation reactions in the organic phase. It has been shown previously that carbon coating a catalyst, such as a metal oxide, provides integrity while leaving the catalytic activity intact. Here, carbon-coated MgO(111) will be discussed with regards to synthesis, characterization and application to bio-oil upgrading through model compounds. Raman spectroscopy and HR-TEM are used to characterize the thickness and carbon-bonding environment of the carbon coating. Propanal self-condensation reactions have been conducted in the aqueous phase with varying amounts of acetic acid present. Quantitative analysis by gas chromatography was completed to determine the catalytic activity of CC-MgO(111). ICP-OES analysis has been conducted to measure the magnesium concentration in the product solution and give insight into the leaching of the catalyst into the reaction solution.

Gold(I)-assisted catalysis - a comprehensive view on the [3,3]-sigmatropic rearrangement of allyl acetate

NASA Astrophysics Data System (ADS)

Freindorf, Marek; Cremer, Dieter; Kraka, Elfi

2018-03-01

The unified reaction valley approach (URVA) combined with the local mode, ring puckering and electron density analysis is applied to elucidate the mechanistic differences of the non-catalysed and the Au[I]-N-heterocyclic carbene (NHC)-catalysed [3,3]-sigmatropic rearrangement of allyl acetate. Using a dual-level approach (DFT and DLPNO-CCSD(T)), the influence of solvation, counter-ions, bulky and electron withdrawing/donating substituents as well as the exchange of the Au[I]-NHC with a Au[I]-phosphine catalyst is investigated. The catalyst breaks up the rearrangement into two steps by switching between Au[I]-π and Au[I]-σ complexation, thus avoiding the energy-consuming CO cleavage in the first step. Based on local stretching force constants ka(C=C), we derive for the first time a quantitative measure of the π-acidity of the Au[I] catalyst; in all catalysed reactions, the bond order n(C=C) drops from 2 to 1.65. The ring puckering analysis clarifies that all reactions start and end via a six-membered ring with a boat form. All Au[I]-σ-complex intermediates show a considerable admixture of the chair form. The non-catalysed [3,3]-sigmatropic rearrangement goes through a maximum of charge separation between the allyl and acetate units at the transition state, while all catalysed reactions proceed via a minimum of charge separation reached in the region of the Au[I]-σ-complex.

A categorical structure-activity relationship analysis of the developmental toxicity of antithyroid drugs.

PubMed

Cunningham, Albert R; Carrasquer, C Alex; Mattison, Donald R

2009-01-01

The choice of therapeutic strategies for hyperthyroidism during pregnancy is limited. Surgery and radioiodine are typically avoided, leaving propylthiouracil and methimazole in the US. Carbimazole, a metabolic precursor of methimazole, is available in some countries outside of the US. In the US propylthiouracil is recommended because of concern about developmental toxicity from methimazole and carbimazole. Despite this recommendation, the data on developmental toxicity of all three agents are extremely limited and insufficient to support a policy given the broad use of methimazole and carbimazole around the world. In the absence of new human or animal data we describe the development of a new structure-activity relationship (SAR) model for developmental toxicity using the cat-SAR expert system. The SAR model was developed from data for 323 compounds evaluated for human developmental toxicity with 130 categorized as developmental toxicants and 193 as nontoxicants. Model cross-validation yielded a concordance between observed and predicted results between 79% to 81%. Based on this model, propylthiouracil, methimazole, and carbimazole were observed to share some structural features relating to human developmental toxicity. Thus given the need to treat women with Graves's disease during pregnancy, new molecules with minimized risk for developmental toxicity are needed. To help meet this challenge, the cat-SAR method would be a useful in screening new drug candidates for developmental toxicity as well as for investigating their mechanism of action.

Investigation of the Alkaline Electrochemical Interface and Development of Composite Metal/Metal-Oxides for Hydrogen and Oxygen Electrodes

NASA Astrophysics Data System (ADS)

Bates, Michael

Understanding the fundamentals of electrochemical interfaces will undoubtedly reveal a path forward towards a society based on clean and renewable energy. In particular, it has been proposed that hydrogen can play a major role as an energy carrier of the future. To fully utilize the clean energy potential of a hydrogen economy, it is vital to produce hydrogen via water electrolysis, thus avoiding co-production of CO2 inherent to reformate hydrogen. While significant research efforts elsewhere are focused on photo-chemical hydrogen production from water, the inherent low efficiency of this method would require a massive land-use footprint to achieve sufficient hydrogen production rates to integrate hydrogen into energy markets. Thus, this research has primarily focused on the water splitting reactions on base-metal catalysts in the alkaline environment. Development of high-performance base-metal catalysts will help move alkaline water electrolysis to the forefront of hydrogen production methods, and when paired with solar and wind energy production, represents a clean and renewable energy economy. In addition to the water electrolysis reactions, research was conducted to understand the de-activation of reversible hydrogen electrodes in the corrosive environment of the hydrogen-bromine redox flow battery. Redox flow batteries represent a promising energy storage option to overcome the intermittency challenge of wind and solar energy production methods. Optimization of modular and scalable energy storage technology will allow higher penetration of renewable wind and solar energy into the grid. In Chapter 1, an overview of renewable energy production methods and energy storage options is presented. In addition, the fundamentals of electrochemical analysis and physical characterization of the catalysts are discussed. Chapter 2 reports the development of a Ni-Cr/C electrocatalyst with unprecedented mass-activity for the hydrogen evolution reaction (HER) in alkaline electrolyte. The HER kinetics of numerous binary & ternary Ni-alloys and composite Ni/metal-oxide/C samples were evaluated in aqueous 0.1 M KOH electrolyte. Furthermore a model of the double layer interface is proposed, which helps explain the observed ensemble effect in the presence of AEI. In Chapter 3, Ni-Fe and Ni-Fe-Co mixed-metal-oxide (MMO) films were investigated for oxygen evolution reaction (OER) activity in 0.1M KOH on high surface area Raney-Nickel supports. During investigations of MMO activity, aniline was identified as a useful "capping agent" for synthesis of high-surface area MMO-polyaniline (PANI) composite materials. A Ni-Fe-Co/PANI-Raney-Ni catalyst was developed which exhibits enhanced mass-activity compared to state-of-the-art Ni-Fe OER electrocatalysts reported to date. The morphology of the MMO catalyst film on PANI/Raney-Ni support provides excellent dispersion of active-sites and should maintain high active-site utilization for catalyst loading on gas-diffusion electrodes. In Chapter 4, the de-activation of reversible-hydrogen electrode catalysts was investigated and the development of a Pt-Ir-Nx/C catalyst is reported, which exhibits significantly increased stability in the HBr/Br 2 electrolyte. In contrast a Pt-Ir/C catalyst exhibited increased tolerance to high-voltage cycling and in particular showed recovery of electrocatalytic activity after reversible de-activation (presumably from bromide adsorption and subsequent oxidative bromide stripping). Under the harshest testing conditions of high-voltage cycling or exposure to Br2 the Pt-based catalyst showed a trend in stability: Pt < Pt-Ir < Pt-Ir-Nx. (Abstract shortened by UMI.).

Plasmonic photocatalysts based on silver nanoparticles - layered double hydroxides for efficient removal of toxic compounds using solar light

NASA Astrophysics Data System (ADS)

Gilea, Diana; Radu, Teodora; Muresanu, Mihaela; Carja, Gabriela

2018-06-01

Plasmon-enhanced photocatalysis holds important promise for chemical processes and outcomes. We present here the self-assemblies of silver nanoparticles (AgNP)/layered double hydroxides (LDHs: MeAlLDHs with Me2+ = Zn2+;Mg2+) and their derived AgNP/MMOs (type AgNP/MgAl2O4; AgNP/ZnO/ZnAl2O4) as novel plasmonic photocatalysts exhibiting activity for phenol photodegradation from aqueous solution by solar-light. The fabrication procedure of AgNP/LDHs assemblies is simple and cost effective and is based on the in-situ synthesis of AgNP on the LDHs matrices during the reconstruction of MgAlLDH and ZnAlLDH in the aqueous solution of Ag2SO4. The tested catalysts were thoroughly investigated - techniques to obtain information on their crystalline structure (XRD), surface properties (XPS), morphological features (TEM) and optical properties (UV-vis). The results show that the solar photocatalytic response of the catalysts is ascribed to the plasmonic response of AgNP though the catalytic efficiency is strongly influenced by the composition of the MeAlLDHs. The best photocatalytic performance was obtained on AgNP/ZnAlLDH750 catalyst that degraded 100% of phenol after 80 min of irradiation with solar light. The results reveal the high potential to tailor AgNP/LDHs and AgNP/MMOs as efficient photo-functional plasmonic hybrids for waste-water cleaning.

Photodegradation of estrogenic endocrine disrupting steroidal hormones in aqueous systems: Progress and future challenges.

PubMed

Sornalingam, Kireesan; McDonagh, Andrew; Zhou, John L

2016-04-15

This article reviews different photodegradation technologies used for the removal of four endocrine disrupting chemicals (EDCs): estrone (E1), 17β-estradiol (E2), estriol (E3) and 17α-ethinylestradiol (EE2). The degradation efficiency is greater under UV than visible light; and increases with light intensity up to when mass transfer becomes the rate limiting step. Substantial rates are observed in the environmentally relevant range of pH7-8, though higher rates are obtained for pH above the pKa (~10.4) of the EDCs. The effects of dissolved organic matter (DOM) on EDC photodegradation are complex with both positive and negative impacts being reported. TiO2 remains the best catalyst due to its superior activity, chemical and photo stability, cheap commercial availability, capacity to function at ambient conditions and low toxicity. The optimum TiO2 loading is 0.05-1gl(-1), while higher loadings have negative impact on EDC removal. The suspended catalysts prove to be more efficient in photocatalysis compared to the immobilised catalysts, while the latter are considered more suitable for commercial scale applications. Photodegradation mostly follows 1st or pseudo 1st order kinetics. Photodegradation typically eradicates or moderates estrogenic activity, though some intermediates are found to exhibit higher estrogenicity than the parent EDCs; the persistence of estrogenic activity is mainly attributed to the presence of the phenolic moiety in intermediates. Copyright © 2016 Elsevier B.V. All rights reserved.

Nitrous Oxide-dependent Iron-catalyzed Coupling Reactions of Grignard Reagents.

PubMed

Döhlert, Peter; Weidauer, Maik; Enthaler, Stephan

2015-01-01

The formation of carbon-carbon bonds is one of the fundamental transformations in chemistry. In this regard the application of palladium-based catalysts has been extensively investigated during recent years, but nowadays research focuses on iron catalysis, due to sustainability, costs and toxicity issues; hence numerous examples for iron-catalyzed cross-coupling reactions have been established, based on the coupling of electrophiles (R(1)-X, X = halide) with nucleophiles (R(2)-MgX). Only a small number of protocols deals with the iron-catalyzed oxidative coupling of nucleophiles (R(1)-MgX + R(2)-MgX) with the aid of oxidants (1,2-dihaloethanes). However, some issues arise with these oxidants; hence more recently the potential of the industrial waste product nitrous oxide (N(2)O) was investigated, because the unproblematic side product N(2) is formed. Based on that, we demonstrate the catalytic potential of easily accessible iron complexes in the oxidative coupling of Grignard reagents. Importantly, nitrous oxide was essential to obtain yields up to >99% at mild conditions (e.g. 1 atm, ambient temperature) and low catalyst loadings (0.1 mol%) Excellent catalyst performance is realized with turnover numbers of up to 1000 and turnover frequencies of up to 12000 h(-1). Moreover, a good functional group tolerance is observed (e.g. amide, ester, nitrile, alkene, alkyne). Afterwards the reaction of different Grignard reagents revealed interesting results with respect to the selectivity of cross-coupling product formation.

Bushy sphere dendrites with husk-shaped branches axially spreading out from the core for photo-catalytic oxidation/remediation of toxins.

PubMed

Shenashen, Mohamed A; Kawada, Satoshi; Selim, Mahmoud M; Morsy, Wafaa M; Yamaguchi, Hitoshi; Alhamid, Abdulaziz A; Ohashi, Naoki; Ichinose, Izumi; El-Safty, Sherif A

2017-06-14

This work describes densely interlinked bushy "tree-like chains" characterized by neatly branched sphere dendrites (bushy sphere dendrites, BSD) with long fan-like, husk-shaped branching paths that extend longitudinally from the core axis of the {110}-exposed plane. We confirmed that the hierarchical dendrite surfaces created bowls of swirled caves along the tree-tube in the mat-like branches. These surfaces had high-index catalytic site facets associated with the formation of ridges/defects on the dominant {110}-top-cover surface. These swirled caves along the branches were completely filled with 50-100 nm poly-CN nano-sphere-fossils with orb-like appearance. Such structural features are key issues of the inherent surface reactivity of a powerful catalyst/trapper, enabling photocatalytic oxidation and trapping of extremely toxic arsenite (AsO 3 3- ) species and photo-induced recovery of arsenate (AsO 4 3- ) products from catalyst surfaces. The light-induced release of produced AsO 4 3- from BSD indicates (i) highly controlled waste collection/management (i.e., recovery), (ii) low cost and ecofriendly photo-adsorbent, (iii) selective trapping of real sample water to produce water-free arsenite species; (iv) multiple reuse cycles of catalysts (i.e., reduced waste volume). Matrixed dendrites, covered with 3D microscopic sphere cores that capture solar-light, trap toxins, and are triggered by light, were designed. These dendrites can withstand indoor and outdoor recovery of toxins from water sources.

Gallium-67-citrate uptake in a case of acne vulgaris

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

Kipper, M.S.; Taylor, A.; Ashburn, W.L.

1981-09-01

A case of increased Ga-67 uptake in a patient with active acne vulgaris is reported. The scan was requested in a search for metastatic testicular carcinoma or bleomycin pulmonary toxicity. Careful clinical evaluation including physical examination was necessary in order to avoid an erroneous scan interpretation.

Release and toxicity comparison between industrial- and sunscreen-derived nano-ZnO particles

EPA Science Inventory

Many consumer products containing ZnO have raised concern for safety in regards toenvironmental impact and the public health. Widely used sunscreens for protectingagainst UV and avoiding sunburns represent a great exposure to nano-ZnO, one of theingredients commonly applied in su...

Nano-structured Platinum-based Catalysts for the Complete Oxidation of Ethylene Glycol and Glycerol

NASA Astrophysics Data System (ADS)

Falase, Akinbayowa

Direct alcohol fuel cells are a viable alternative to the traditional hydrogen PEM fuel cell. Fuel versatility, integration with existing distribution networks, and increased safety when handling these fuels increases their appeal for portable power applications. In order to maximize their utility, the liquid fuel must be fully oxidized to CO2 so as to harvest the full amount of energy. Methanol and ethanol are widely researched as potential fuels to power these devices, but methanol is a toxic substance, and ethanol has a much lower energy density than other liquids such as gasoline or glucose. Oxidation of complex fuels is difficult to realize, due to difficulty in breaking carbon-carbon bonding and poisoning of the catalysts by oxidative byproducts. In order to achieve the highest efficiency, an anode needs to be engineered in such a way as to maximize activity while minimizing poisoning effects of reaction byproducts. We have engineered an anode that uses platinum-based catalysts that is capable of completely oxidizing ethylene glycol and glycerol in neutral and alkaline media with little evidence of CO poisoning. We have constructed a hybrid anode consisting of a nano-structured PtRu electrocatayst with an NAD-dependent alcohol dehydrogenase for improved oxidation of complex molecules. A nano-structured PtRu catalyst was used to oxidize ethylene glycol and glycerol in neutral media. In situ infrared spectroscopy was used to verify complete oxidation via CO2 generation. There was no evidence of poisoning by CO species. A pH study was performed to determine the effect of pH on oxidative current. The peak currents did not trend at 60 mV/pH unit as would be expected from the Nernst equation, suggesting that adsorption of fuel to the surface of the electrode is not an electron-transfer step. We synthesized nano-structured PtRu, PtSn, and PtRuSn catalysts for oxidation of ethylene glycol and glycerol in alkaline media. The PtRu electrocatalyst the highest oxidative currents and highest stability compared to a nano-structured platinum, PtSn, and PtRuSn catalyst. In situ infrared spectroscopy showed complete oxidation of each fuel occurred by the presence of CO 2, with very little poisoning CO species present. In order to increase oxidative performance in neutral media, a hybrid anode based on nano-structured PtRu and a NAD-dependent alcohol dehydrogenase for the oxidation of ethanol and ethylene glycol was developed. Steady state polarization showed that the hybrid anode had higher current densities than the enzyme or the PtRu electrocatalyst alone. The hybrid anode had higher current densities at concentrations up to 3 M while oxidizing ethanol and ethylene glycol. The catalyst synthesis, characterization, and experimental results demonstrate the feasibility of fuel cells that can oxidize higher order fuels that platinum based catalysts or enzymes cannot oxidize alone. The cooperative mechanism from co-catalysis using inorganic and organic catalysts will allow for deep oxidation and improved power generation.

The conversion of CO 2 to methanol on orthorhombic β-Mo 2C and Cu/β-Mo 2C catalysts: Mechanism for admetal induced change in the selectivity and activity

DOE PAGES

Posada-Pérez, Sergio; Ramírez, Pedro J.; Gutiérrez, Ramón A.; ...

2016-02-01

Here, the conversion of CO 2 into methanol catalyzed by β-Mo 2C and Cu/β-Mo 2C surfaces has been investigated by means of a combined experimental and theoretical study. Experiments have shown the direct activation and dissociation of the CO 2 molecule on bare β-Mo 2C, whereas on Cu/β-Mo 2C, CO 2 must be assisted by hydrogen for its conversion. Methane and CO are the main products on the clean surface and methanol production is lower. However, the deposition of Cu clusters avoids methane formation and increases methanol production even above that corresponding to a model of the technical catalyst. DFTmore » calculations on surface models of both possible C- and Mo-terminations corroborate the experimental observations. Calculations for the clean Mo-terminated surface reveal the existence of two possible routes for methane production (C + 4H → CH 4; CH 3O + 3H → CH 4 + H 2O) which are competitive with methanol synthesis, displaying slightly lower energy barriers. On the other hand, a model for Cu deposited clusters on the Mo-terminated surface points towards a new route for methanol and CO production avoiding methane formation. The new route is a direct consequence of the generation of a Mo 2C–Cu interface. The present experimental and theoretical results entail the interesting catalytic properties of Mo 2C as an active support of metallic nanoparticles, and also illustrate how the deposition of a metal can drastically change the activity and selectivity of a carbide substrate for CO 2 hydrogenation.« less

Pre-treatment of Stegomyia aegypti mosquitoes with a sublethal dose of imidacloprid impairs behavioural avoidance induced by lemon oil and DEET.

PubMed

Thany, S H; Tong, F; Bloomquist, J R

2015-03-01

The present study was conducted to determine whether imidacloprid can impair the avoidance behaviour of the mosquito Stegomyia aegypti. Laboratory investigations using a T-maze apparatus showed that St. aegypti mosquitoes present long term avoidance behaviour when they are exposed to repetitive trials with lemon oil and DEET. The present study tested the effect of a sublethal dose of imidacloprid on the avoidance behaviour of St. aegypti mosquitoes over a 48 h period. Data suggest that 0.5 ng of imidacloprid/mosquito reduces the avoidance behaviour of mosquitoes exposed to lemon oil, on the first day of exposure, after the second trial; whereas imidacloprid affected DEET repellency only the first day of exposure, after the second trial. Imidacloprid was toxic against St. aegypti mosquitoes, and at sublethal doses was able to impair the repellency induced by lemon oil and DEET. The present data were consistent with the finding that St. aegypti mosquitoes exhibit long term avoidance behaviour, and treatment of mosquitoes with a sublethal dose of imidacloprid under DEET application can affect the repellency of DEET against St. aegypti. © 2014 The Royal Entomological Society.

Lessons learned from vivo-morpholinos: How to avoid vivo-morpholino toxicity

PubMed Central

Ferguson, David P.; Dangott, Lawrence J.; Lightfoot, J. Timothy

2014-01-01

Vivo-morpholinos are a promising tool for gene silencing. These oligonucleotide analogs transiently silence genes by blocking either translation or pre-mRNA splicing. Little to no toxicity has been reported for vivo-morpholino treatment. However, in a recent study conducted in our lab, treatment of mice with vivo-morpholinos resulted in high mortality rates. We hypothesized that the deaths were the result of oligonucleotide hybridization, causing an increased cationic charge associated with the dendrimer delivery moiety of the vivo-morpholino. The cationic charge increased blood clot formation in whole blood treated with vivo-morpholinos, suggesting that clotting could have caused cardiac arrest in the deceased mice. Therefore, we investigate the mechanism by which some vivo-morpholinos increase mortality rates and propose techniques to alleviate vivo-morpholino toxicity. PMID:24806225

Mild forms of toxic shock syndrome toxin-1-mediated exanthematous disease related to Staphylococcus aureus infection.

PubMed

Moriguchi, Naohiko; Kano, Tomowa; Yoshimatsu, Yutaka; Yanagida, Hidehiko

2016-08-01

The present report describes three patients with toxic shock syndrome toxin (TSST)-1-associated exanthematous disease. In all patients, fever and systemic erythema without hemodynamic disturbance occurred following cellulitis of the lower limbs. At the site of infection, TSST-1 producing Methicillin-susceptible Staphylococcus aureus was detected. They defervesced and erythema resolved in response to administration of an antimicrobial drug, thereby avoiding severe illness. These patients did not meet the criteria for a clinical diagnosis of toxic shock syndrome. Measurement of T-cell receptor Vβ2-positive T cells in the peripheral blood early after onset of symptoms was useful for diagnosis. Copyright © 2016 Japanese Society of Chemotherapy and The Japanese Association for Infectious Diseases. Published by Elsevier Ltd. All rights reserved.

Chloride: from Nutrient to Toxicant.

PubMed

Geilfus, Christoph-Martin

2018-05-01

In salinized soils in which chloride (Cl-) is the dominant salt anion, growth of plants that tolerate only low concentrations of salt (glycophytes) is disturbed by Cl- toxicity. Chlorotic discolorations precede necrotic lesions, causing yield reductions. Little is known about the effects of Cl- toxicity on these dysfunctions. A lack of understanding exists regarding (i) the molecular and physiological mechanisms that lead to Cl--induced damage and (ii) the adaptive aspects of induced tolerance to Cl- salinity. Here, mechanistic explanations for the Cl--induced stress responses are proposed and novel ideas and strategies by which glycophytic plants avoid the excessive accumulation of Cl- are reviewed. New experiments are suggested to test the proposed hypotheses. Cl- salinity constrains global food security and thus we urgently need more research into the causes and consequences of Cl- salinity.

Disentangling taste and toxicity in aposematic prey

PubMed Central

Holen, Øistein Haugsten

2013-01-01

Many predators quickly learn to avoid attacking aposematic prey. If the prey vary in toxicity, the predators may alternatively learn to capture and taste-sample prey carefully before ingesting or rejecting them (go-slow behaviour). An increase in prey toxicity is generally thought to decrease predation on prey populations. However, while prey with a higher toxin load are more harmful to ingest, they may also be easier to recognize and reject owing to greater distastefulness, which can facilitate a taste-sampling foraging strategy. Here, the classic diet model is used to study the separate effects of taste and toxicity on predator preferences. The taste-sampling process is modelled using signal detection theory. The model is applicable to automimicry and Batesian mimicry. It shows that when the defensive toxin is sufficiently distasteful, a mimicry complex may be less profitable to the predator and better protected against predation if the models are moderately toxic than if they are highly toxic. Moreover, taste mimicry can reduce the profitability of the mimicry complex and increase protection against predation. The results are discussed in relation to the selection pressures acting on prey defences and the evolution of mimicry. PMID:23256198

Disentangling taste and toxicity in aposematic prey.

PubMed

Holen, Øistein Haugsten

2013-02-22

Many predators quickly learn to avoid attacking aposematic prey. If the prey vary in toxicity, the predators may alternatively learn to capture and taste-sample prey carefully before ingesting or rejecting them (go-slow behaviour). An increase in prey toxicity is generally thought to decrease predation on prey populations. However, while prey with a higher toxin load are more harmful to ingest, they may also be easier to recognize and reject owing to greater distastefulness, which can facilitate a taste-sampling foraging strategy. Here, the classic diet model is used to study the separate effects of taste and toxicity on predator preferences. The taste-sampling process is modelled using signal detection theory. The model is applicable to automimicry and batesian mimicry. It shows that when the defensive toxin is sufficiently distasteful, a mimicry complex may be less profitable to the predator and better protected against predation if the models are moderately toxic than if they are highly toxic. Moreover, taste mimicry can reduce the profitability of the mimicry complex and increase protection against predation. The results are discussed in relation to the selection pressures acting on prey defences and the evolution of mimicry.

Serotonin toxicity caused by moclobemide too soon after paroxetine-selegiline.

PubMed

Wu, Ming-Ling; Deng, Jou-Fang

2009-08-01

Serotonin toxicity is an iatrogenic complication of serotonergic drug therapy. It is due to an overstimulation of central and peripheral serotonin receptors that lead to neuromuscular, mental and autonomic changes. Moclobemide is a reversible inhibitor of monoamine oxidase (MAO)-A, selegiline is an irreversible selective inhibitor of MAO-B, and paroxetine is a selective serotonin reuptake inhibitor. Combined use of these agents is known to cause serotonin toxicity. A 53-year-old woman had been treated with paroxetine and selegiline. After moclobemide was prescribed in place of paroxetine without a washout period, she quickly developed confusion, agitation, ataxia, diaphoresis, tremor, mydriasis, ocular clonus, hyperreflexia, tachycardia, moderately elevated blood pressure and high fever, symptoms that were consistent with serotonin toxicity. Discontinuation of the drugs, hydration and supportive care were followed by remarkable improvement of baseline status within 3 days. This case demonstrates that serotonin toxicity may occur even with small doses of paroxetine, selegiline and moclobemide in combination. Physicians managing patients with depression must be aware of the potential for serotonin toxicity and should be able to recognize and treat or, ideally, anticipate and avoid this pharmacodynamically-mediated interaction that may occur between prescribed drugs.

Experiential avoidance as a generalized psychological vulnerability: comparisons with coping and emotion regulation strategies.

PubMed

Kashdan, Todd B; Barrios, Velma; Forsyth, John P; Steger, Michael F

2006-09-01

Extending previous work, we conducted two studies concerning the toxic influences of experiential avoidance (EA) as a core mechanism in the development and maintenance of psychological distress, and disruption of pleasant, engaging, and spontaneous activity. Of particular interest was whether EA accounted for relationships between coping and emotion regulation strategies on anxiety-related pathology (Study 1) and psychological distress and hedonic functioning over the course of a 21-day monitoring period (Study 2). In Study 1, EA mediated the effects of maladaptive coping, emotional responses styles, and uncontrollability on anxiety-related distress (e.g., anxiety sensitivity, trait anxiety, suffocation fears, and body sensation fears). In Study 2, EA completely mediated the effects of two emotion regulation strategies (i.e., suppression and reappraisal) on daily negative and positive experiences and was associated with diminished daily positive affective experiences and healthy life appraisals, diminished frequency of positive events and more frequent negative life events, and greater negative affective experiences. The present data show that cognitive reappraisal, a primary process of traditional cognitive-behavior therapy, was much less predictive of the quality of psychological experiences and events in everyday life compared with EA. Further consideration of experiential avoidance as a generalized diathesis and toxic process will be useful in improving our understanding of the etiology, phenomenology, and treatment of anxiety conditions, general human suffering, and disruptions in hedonic capacity.

Photobiodegradation of chlorinated water pollutants by a combined TiO2-polyaniline-enzyme catalytic system

NASA Astrophysics Data System (ADS)

Campanella, Luigi; Crescentini, G.; Militerno, S.

1995-10-01

The removal of xenobiotic compounds, such as chlorophenols and pesticides, from municipal and industrial wastewaters is an important task because of the toxicity and the tendency to bioaccumulation of these compounds. Among the several methods proposed, photodegradation catalyzed by suspended inorganic semiconductors (i.e. TiO2) has lately received wide attention because this process is fast, leads to non-toxic final products and shows a high degradation efficiency. In this work, the results obtained in the photodegradation of monochlorophenols using a new catalyst, made of TiO2 and polyaniline both immobilized on a polyvinylchloride (PVC) membrane, in presence (and in absence) of an enzyme are presented. Different enzymes have been tested by adding 5, 10 or 15 U/mL to 50 mL of aqueous solution (1 multiplied by 10-4 mol/L) of o-chloro-phenol containing the catalytic membrane. The samples were irradiated using a QUV panel accelerated weathering tester, which simulates very well the solar radiation up to lambda equals 400 nm and HPLC was used to measure the variation of the compound's concentration with the time. While some enzymes (i.e., peroxidase) do not improve the photodegradation process since they do not survive under the irradiation conditions used, some of them show marked effect both in terms of rate degradation and time required to reach the total degradation of the compound examined. For example, the addition of Laccase reduces the 100% degradation time from 35 hrs to about 20 hrs. Attempts to immobilize the enzyme on the catalytic membrane (by adsorption) have been carried out and the performance of the catalyst with non-immobilized and immobilized enzyme has been studied.

Ozone-UV-catalysis based advanced oxidation process for wastewater treatment.

PubMed

Tichonovas, Martynas; Krugly, Edvinas; Jankunaite, Dalia; Racys, Viktoras; Martuzevicius, Dainius

2017-07-01

A bench-scale advanced oxidation (AO) reactor was investigated for the degradation of six pollutants (2-naphthol, phenol, oxalic acid, phthalate, methylene blue, and D-glucose) in a model wastewater at with the aim to test opportunities for the further upscale to industrial applications. Six experimental conditions were designed to completely examine the experimental reactor, including photolysis, photocatalysis, ozonation, photolytic ozonation, catalytic ozonation, and photocatalytic ozonation. The stationary catalyst construction was made from commercially available TiO 2 nanopowder by mounting it on a glass support and subsequently characterized for morphology (X-ray diffraction analysis and scanning electron microscopy) as well as durability. The ozone was generated in a dielectrical barrier discharge reactor using air as a source of oxygen. The degradation efficiency was estimated by the decrease in total organic carbon (TOC) concentration as well as toxicity using Daphnia magna, and degradation by-products by ultra-performance liquid chromatography-mass spectrometry. The photocatalytic ozonation was the most effective for the treatment of all model wastewater. The photocatalytic ozonation was most effective against ozonation and photolytic ozonation at tested pH values. A complete toxicity loss was obtained after the treatment using photocatalytic ozonation. The possible degradation pathway of the phthalate by oxidation was suggested based on aromatic ring opening reactions. The catalyst used at this experiment confirmed as a durable for continuous use with almost no loss of activity over time. The design of the reactor was found to be very effective for water treatment using photocatalytic ozonation. Such design has a high potential and can be further upscaled to industrial applications due to the simplicity and versatility of manufacturing and maintenance.

Detoxification of kraft pulp ECF bleaching effluents by catalytic hydrotreatment.

PubMed

Calvo, L; Gilarranz, M A; Casas, J A; Mohedano, A F; Rodríguez, J J

2007-02-01

Two different effluents from the D(1) and E(1) stages of the ECF bleaching of Eucalyptus globulus kraft pulp were treated by catalytic hydrogenation in a trickle bed reactor using commercial and homemade Pd/AC catalysts. The reactor was fed with the bleaching effluent and a H(2)/N(2) gas stream. The variables studied were space-time (1.4-5g(cat)min/mL), gas to liquid flow ratio (286-1000vol.), gas feed concentration (H(2):N(2), 1:1-1:7.3vol.), temperature (25-100 degrees C) and pressure (1-11bar). Hydrotreatment performance was evaluated in terms of ecotoxicity, adsorbable organic halogen (AOX), chemical oxygen demand (COD), biological oxygen demand (BOD(5)) and colour removal. In all the runs, the ecotoxicity of the effluents decreased as a result of the treatment, achieving reductions that ranged from 70% to 98%. Simultaneously to the reduction of toxicity, the hydrotreatment led to a decrease of the colour of the effluents, being the decrease significantly higher in the case of E(1) effluent. The AOX content was reduced by 85% and 23% for E(1) and D(1) effluents, respectively. In the case of D(1) effluent the removal of ecotoxicity was significantly higher than that of AOX, which indicates that much of the toxicity of the effluent must be associated to non-chlorinated organics. In spite of the important reduction of ecotoxicity, the biodegradability of the effluents only increased slightly. The homemade catalysts, prepared from activated carbons with a high external or non-microporous surface area and mesopore volume and a convenient surface chemistry showed a higher efficiency than the commercial one.

Natural soil mediated photo Fenton-like processes in treatment of pharmaceuticals: Batch and continuous approach.

PubMed

Changotra, Rahil; Rajput, Himadri; Dhir, Amit

2017-12-01

This paper manifests the potential viability of soil as a cost-free catalyst in photo-Fenton-like processes for treating pharmaceuticals at large scale. Naturally available soil without any cost intensive modification was utilized as a catalyst to degrade pharmaceuticals, specifically ornidazole (ORZ) and ofloxacin (OFX). Soil was characterized and found enriched with various iron oxides like hematite, magnetite, goethite, pyrite and wustite, which contributes toward enhanced dissolution of Fe 3+ than Fe 2+ in the aqueous solution resulting in augmented rate of photo-Fenton reaction. The leached iron concentration in solution was detected during the course of experiments. The degradation of ORZ and OFX was assessed in solar induced batch experiments using H 2 O 2 as oxidant and 95% ORZ and 92% OFX removal was achieved. Elevated efficiencies were achieved due to Fe 2+ /Fe 3+ cycling, producing more hydroxyl radical leading to the existence of homogeneous and heterogeneous reactions simultaneously. The removal efficiency of solar photo-Fenton like process was also compared to photo-Fenton process with different irradiation sources (UV-A and UV-B) and were statistically analysed. Continuous-scale studies were conducted employing soil either in the form of soil beads or as a thin layer spread on the surface of baffled reactor. Soil beads were found to have satisfactory reusability and stability. 84 and 79% degradation of ORZ and OFX was achieved using soil as thin layer while with soil beads 71 and 68% degradation, respectively. HPLC and TOC study confirmed the efficient removal of both the compounds. Toxicity assessment demonstrates the inexistence of toxic intermediates during the reaction. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effects of particulate oxidation catalyst on unregulated pollutant emission and toxicity characteristics from heavy-duty diesel engine.

PubMed

Feng, Xiangyu; Ge, Yunshan; Ma, Chaochen; Tan, Jianwei

2015-01-01

To evaluate the effects of particulate oxidation catalyst (POC) on unregulated pollutant emission and toxicity characteristics, polycyclic aromatic hydrocarbons (PAHs), volatile organic compounds (VOCs), soot, soluble organic fractions (SOF) and sulphate emissions emitted from a heavy-duty diesel engine retrofitted with a POC were investigated on a diesel bench. The particulate matter (PM) in the exhaust was collected by Teflon membrane, and the PAHs and VOCs were analysed by a gas chromatography/mass spectrometer (GC/MS). The results indicate that the POC exhibits good performance on the emission control of VOCs, PAHs and PM. The POC and the diesel particulate filters (DPF) both show a good performance on reducing the VOCs emission. Though the brake-specific emission (BSE) reductions of the total PAHs by the POC were lower than those by the DPF, the POC still removed almost more than 50% of the total PAHs emission. After the engine was retrofitted with the POC, the reductions of the PM mass, SOF and soot emissions were 45.2-89.0%, 7.8-97.7% and 41.7-93.3%, respectively. The sulphate emissions decreased at low and medium loads, whereas at high load, the results were contrary. The PAHs emissions were decreased by 32.4-69.1%, and the contributions of the PAH compounds were affected by the POC, as well as by load level. The benzo[a]pyrene equivalent (BaPeq) of PAHs emissions were reduced by 35.9-97.6% with the POC. The VOCs emissions were reduced by 21.8-94.1% with the POC, and the reduction was more evident under high load.

Ferrous ions reused as catalysts in Fenton-like reactions for remediation of agro-food industrial wastewater.

PubMed

Leifeld, Vanessa; Dos Santos, Tâmisa Pires Machado; Zelinski, Danielle Wisniewski; Igarashi-Mafra, Luciana

2018-09-15

Cassava is the most important tuberous root in tropical and subtropical regions of the world, being the third largest source of carbohydrates. The root processing is related to the production of starch, an important industrial input, which releases a highly toxic liquid wastewater due to its complex composition, which inhibits high performances of conventional effluent treatments. This study aims to evaluate Fenton-like and photo-Fenton-like reactions for treatment of cassava wastewater, reusing ferrous ions from the preliminary coagulation stage. Pre-treated cassava wastewater was submitted to oxidation in three variations of hydrogen peroxide concentrations, with more relevant analytical responses verified in color, turbidity, COD (Chemical Oxygen Demand), and acute toxicity in Artemia salina, besides the action of radicals during Fenton-like reactions. At higher peroxide concentrations, a decrease of 68% in turbidity and 70% in COD on the photo-Fenton-like system was observed, even at slow reaction rates (fastest rate constant k = 2 × 10 -4 min -1 ). Inclusion of UV increases the viability of the Fenton-like reactions by supplementing the reaction medium with hydroxyl radicals, verified by the tert-butanol tests. The oxidation process leads to high EC 50 values in 24 h of incubation in Fenton-like reactions and 48 h in photo-Fenton-like reactions. Final COD and turbidity suggests that the reuse of iron, which remains in the preliminary treatment step shows a great potential as a catalyst for Fenton-like advanced oxidation processes. Tertiary treatment can be less expensive and harmful to the environment, reducing production of residual sludge and metal content in the final effluent, which reduces polluting potential of the effluent regarding solid waste. Copyright © 2018 Elsevier Ltd. All rights reserved.

Best Practices in Cancer Nanotechnology – Perspective from NCI Nanotechnology Alliance

PubMed Central

Zamboni, William C.; Torchilin, Vladimir; Patri, Anil; Hrkach, Jeff; Stern, Stephen; Lee, Robert; Nel, Andre; Panaro, Nicholas J.; Grodzinski, Piotr

2014-01-01

Historically, treatment of patients with cancer using chemotherapeutic agents has been associated with debilitating and systemic toxicities, poor bioavailability, and unfavorable pharmacokinetics. Nanotechnology-based drug delivery systems, on the other hand, can specifically target cancer cells while avoiding their healthy neighbors, avoid rapid clearance from the body, and be administered without toxic solvents. They hold immense potential in addressing all of these issues which has hampered further development of chemotherapeutics. Furthermore, such drug delivery systems will lead to cancer therapeutic modalities which are not only less toxic to the patient but also significantly more efficacious. In addition to established therapeutic modes of action, nanomaterials are opening up entirely new modalities of cancer therapy, such as photodynamic and hyperthermia treatments. Furthermore, nanoparticle carriers are also capable of addressing several drug delivery problems which could not be effectively solved in the past and include overcoming formulation issues, multi-drug-resistance phenomenon and penetrating cellular barriers that may limit device accessibility to intended targets such as the blood-brain-barrier. The challenges in optimizing design of nanoparticles tailored to specific tumor indications still remain; however, it is clear that nanoscale devices carry a significant promise towards new ways of diagnosing and treating cancer. This review focuses on future prospects of using nanotechnology in cancer applications and discusses practices and methodologies used in the development and translation of nanotechnology-based therapeutics. PMID:22669131

Liver transplantation from a deceased donor with β-thalassemia intermedia is not contraindicated: A case report.

PubMed

Gumus, Ersin; Abbasoglu, Osman; Tanyel, Cahit; Gumruk, Fatma; Ozen, Hasan; Yuce, Aysel

2017-05-01

The use of extended criteria donors who might have previously been deemed unsuitable is an option to increase the organ supply for transplantation. This report presents a pediatric case of a successful liver transplantation from a donor with β-thalassemia intermedia. A patient, 6-year-old female, with a diagnosis of cryptogenic liver cirrhosis underwent deceased donor liver transplantation from a thalassemic donor. Extreme hyperferritinemia was detected shortly after transplantation. The most probable cause of hyperferritinemia was iron overload secondary to transplantation of a hemosiderotic liver. Hepatocellular injury due to acute graft rejection might have contributed to elevated ferritin levels by causing release of stored iron from the hemosiderotic liver graft. Iron chelation and phlebotomy therapies were started simultaneously in the early postoperative period to avoid iron-related organ toxicity and transplant failure. Follow-up with monthly phlebotomies after discharge yielded a favorable outcome with normal transplant functions. Thalassemia intermedia patients can be candidates of liver donors to decrease pretransplant waitlist mortality. After transplantation of a hemosiderotic liver, it is important to monitor the recipient in terms of iron overload and toxicity. Early attempts to lower iron burden including chelation therapy and/or phlebotomy should be considered to avoid organ toxicity and transplant failure. © 2017 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

The Role of Therapeutic Drugs on Acquired Mitochondrial Toxicity.

PubMed

Morén, Constanza; Juárez-Flores, Diana Luz; Cardellach, Francesc; Garrabou, Glòria

2016-01-01

Certain therapeutic drugs used in medical practice may trigger mitochondrial toxicity leading to a wide range of clinical symptoms including deafness, neuropathy, myopathy, hyperlactatemia, lactic acidosis, pancreatitis and lipodystrophy, among others, which could even compromise the life of the patient. The aim of this work is to review the potential mitochondrial toxicity derived from drugs used in health care, including anesthetics, antiepileptics, neuroleptics, antidepressants, antivirals, antibiotics, antifungals, antimalarics, antineoplastics, antidiabetics, hypolipemiants, antiarrhythmics, anti-inflammatories and nitric oxide. We herein have reviewed data from experimental and clinical studies to document the molecular mitochondrial basis, potential biomarkers and putative clinical symptoms associated to secondary effects of drugs. One hundred and forty-five articles were selected and the information was organized by means of the primary target to which pharmacologic drugs were directed. Adverse toxic events were classified depending on the mitochondrial offtarget effect and whether they had been demonstrated in the experimental or clinical setting. Since treatment of acquired mitochondriopathies remains supportive and therapeutic interventions cannot be avoided, information of molecular and clinical consequences of toxic exposure becomes fundamental to assess riskbenefit imbalance of treatment prescription. Additionally, there is a crucial need to develop less mitochondrial toxic compounds, novel biomarkers to follow up mitochondrial toxicity (or implement those already proposed) and new approaches to prevent or revert unintended mitochondrial damage.

A Predictive Model for Toxicity Effects Assessment of Biotransformed Hepatic Drugs Using Iterative Sampling Method.

PubMed

Tharwat, Alaa; Moemen, Yasmine S; Hassanien, Aboul Ella

2016-12-09

Measuring toxicity is one of the main steps in drug development. Hence, there is a high demand for computational models to predict the toxicity effects of the potential drugs. In this study, we used a dataset, which consists of four toxicity effects:mutagenic, tumorigenic, irritant and reproductive effects. The proposed model consists of three phases. In the first phase, rough set-based methods are used to select the most discriminative features for reducing the classification time and improving the classification performance. Due to the imbalanced class distribution, in the second phase, different sampling methods such as Random Under-Sampling, Random Over-Sampling and Synthetic Minority Oversampling Technique are used to solve the problem of imbalanced datasets. ITerative Sampling (ITS) method is proposed to avoid the limitations of those methods. ITS method has two steps. The first step (sampling step) iteratively modifies the prior distribution of the minority and majority classes. In the second step, a data cleaning method is used to remove the overlapping that is produced from the first step. In the third phase, Bagging classifier is used to classify an unknown drug into toxic or non-toxic. The experimental results proved that the proposed model performed well in classifying the unknown samples according to all toxic effects in the imbalanced datasets.

Laccase-syringaldehyde-mediated degradation of trace organic contaminants in an enzymatic membrane reactor: Removal efficiency and effluent toxicity.

PubMed

Nguyen, Luong N; van de Merwe, Jason P; Hai, Faisal I; Leusch, Frederic D L; Kang, Jinguo; Price, William E; Roddick, Felicity; Magram, Saleh F; Nghiem, Long D

2016-01-01

Redox-mediators such as syringaldehyde (SA) can improve laccase-catalyzed degradation of trace organic contaminants (TrOCs) but may increase effluent toxicity. The degradation performance of 14 phenolic and 17 non-phenolic TrOCs by a continuous flow enzymatic membrane reactor (EMR) at different TrOC and SA loadings was assessed. A specific emphasis was placed on the investigation of the toxicity of the enzyme (laccase), SA, TrOCs and the treated effluent. Batch tests demonstrated significant individual and interactive toxicity of the laccase and SA preparations. Reduced removal of resistant TrOCs by the EMR was observed for dosages over 50μg/L. SA addition at a concentration of 10μM significantly improved TrOC removal, but no removal improvement was observed at the elevated SA concentrations of 50 and 100μM. The treated effluent showed significant toxicity at SA concentrations beyond 10μM, providing further evidence that higher dosage of SA must be avoided. Copyright © 2015 Elsevier Ltd. All rights reserved.

A comparative experimental approach to ecotoxicology in shallow-water and deep-sea holothurians suggests similar behavioural responses.

PubMed

Brown, Alastair; Wright, Roseanna; Mevenkamp, Lisa; Hauton, Chris

2017-10-01

Exploration of deep-sea mineral resources is burgeoning, raising concerns regarding ecotoxicological impacts on deep-sea fauna. Assessing toxicity in deep-sea species is technologically challenging, which promotes interest in establishing shallow-water ecotoxicological proxy species. However, the effects of temperature and hydrostatic pressure on toxicity, and how adaptation to deep-sea environmental conditions might moderate these effects, are unknown. To address these uncertainties we assessed behavioural and physiological (antioxidant enzyme activity) responses to exposure to copper-spiked artificial sediments in a laboratory experiment using a shallow-water holothurian (Holothuria forskali), and in an in situ experiment using a deep-sea holothurian (Amperima sp.). Both species demonstrated sustained avoidance behaviour, evading contact with contaminated artificial sediment. However, A. sp. demonstrated sustained avoidance of 5mgl -1 copper-contaminated artificial sediment whereas H. forskali demonstrated only temporary avoidance of 5mgl -1 copper-contaminated artificial sediment, suggesting that H. forskali may be more tolerant of metal exposure over 96h. Nonetheless, the acute behavioural response appears consistent between the shallow-water species and the deep-sea species, suggesting that H. forskali may be a suitable ecotoxicological proxy for A. sp. in acute (≤24h) exposures, which may be representative of deep-sea mining impacts. No antioxidant response was observed in either species, which was interpreted to be the consequence of avoiding copper exposure. Although these data suggest that shallow-water taxa may be suitable ecotoxicological proxies for deep-sea taxa, differences in methodological and analytical approaches, and in sex and reproductive stage of experimental subjects, require caution in assessing the suitability of H. forskali as an ecotoxicological proxy for A. sp. Nonetheless, avoidance behaviour may have bioenergetic consequences that affect growth and/or reproductive output, potentially impacting fecundity and/or offspring fitness, and thus influencing source-sink dynamics and persistence of wider deep-sea populations. Copyright © 2017 Elsevier B.V. All rights reserved.

Large-Area Chemical and Biological Decontamination Using a High Energy Arc Lamp (HEAL) System.

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

Duty, Chad E; Smith, Rob R; Vass, Arpad Alexander

2008-01-01

Methods for quickly decontaminating large areas exposed to chemical and biological (CB) warfare agents can present significant logistical, manpower, and waste management challenges. Oak Ridge National Laboratory (ORNL) is pursuing an alternate method to decompose CB agents without the use of toxic chemicals or other potentially harmful substances. This process uses a high energy arc lamp (HEAL) system to photochemically decompose CB agents over large areas (12 m2). Preliminary tests indicate that more than 5 decades (99.999%) of an Anthrax spore simulant (Bacillus globigii) were killed in less than 7 seconds of exposure to the HEAL system. When combined withmore » a catalyst material (TiO2) the HEAL system was also effective against a chemical agent simulant, diisopropyl methyl phosphonate (DIMP). These results demonstrate the feasibility of a rapid, large-area chemical and biological decontamination method that does not require toxic or corrosive reagents or generate hazardous wastes.« less

Olfactory toxicity in fishes.

PubMed

Tierney, Keith B; Baldwin, David H; Hara, Toshiaki J; Ross, Peter S; Scholz, Nathaniel L; Kennedy, Christopher J

2010-01-21

Olfaction conveys critical environmental information to fishes, enabling activities such as mating, locating food, discriminating kin, avoiding predators and homing. All of these behaviors can be impaired or lost as a result of exposure to toxic contaminants in surface waters. Historically, teleost olfaction studies have focused on behavioral responses to anthropogenic contaminants (e.g., avoidance). More recently, there has been a shift towards understanding the underlying mechanisms and functional significance of contaminant-mediated changes in fish olfaction. This includes a consideration of how contaminants affect the olfactory nervous system and, by extension, the downstream physiological and behavioral processes that together comprise a normal response to naturally occurring stimuli (e.g., reproductive priming or releasing pheromones). Numerous studies spanning several species have shown that ecologically relevant exposures to common pollutants such as metals and pesticides can interfere with fish olfaction and disrupt life history processes that determine individual survival and reproductive success. This represents one of the pathways by which toxic chemicals in aquatic habitats may increasingly contribute to the decline and at-risk status of many commercially and ecologically important fish stocks. Despite our emerging understanding of the threats that pollution poses for chemical communication in aquatic communities, many research challenges remain. These include: (1) the determination of specific mechanisms of toxicity in the fish olfactory sensory epithelium; (2) an understanding of the impacts of complex chemical mixtures; (3) the capacity to assess olfactory toxicity in fish in situ; (4) the impacts of toxins on olfactory-mediated behaviors that are still poorly understood for many fish species; and (5) the connections between sublethal effects on individual fish and the long-term viability of wild populations. This review summarizes and integrates studies on fish olfaction-contaminant interactions, including metrics ranging from the molecular to the behavioral, and highlights directions for future research. 2009 Elsevier B.V. All rights reserved.

Nail toxicity induced by cancer chemotherapy.

PubMed

Gilbar, Peter; Hain, Alice; Peereboom, Veta-Marie

2009-09-01

To provide a comprehensive literature review of chemotherapy-induced nail toxicity, including clinical presentation, implicated drugs and approaches for prevention and management. A search of MEDLINE and EMBASE (1966-2008) databases was conducted using the terms (and variations of the terms) antineoplastic agents, nails, nail toxicity, onycholysis, and paronychia. Bibliographies from selected articles were reviewed for appropriate references. The retrieved literature was reviewed to include all articles relevant to the clinical presentation, diagnosis, incidence, prevention, and treatment of chemotherapy-induced nail toxicity. Nail toxicity is a relatively uncommon adverse effect linked to a number of chemotherapeutic agents. Clinical presentation varies, depending on which nail structure is affected and the severity of the insult. Nail changes may involve all or some nails. Toxicity may be asymptomatic and limited to cosmetic concerns, however, more severe effects, involving pain and discomfort can occur. Taxanes and anthracyclines are the antineoplastic drug groups most commonly implicated. It is suggested that the administration schedule may influence the incidence of nail abnormalities, for example reported cases linked to the weekly administration of paclitaxel.Before instituting chemotherapy, patients should be educated regarding potential nail toxicities and strategies for prevention implemented. Management includes appropriate nail cutting, avoiding potential irritants, topical, or oral antimicrobials, and possibly cessation or dose reduction of the offending agent. Cryotherapy, through the application of frozen gloves or socks, has been beneficial in reducing docetaxel-induced nail toxicity and may be effective for other drugs.

Process simulation and economic analysis of biodiesel production from waste cooking oil with membrane bioreactor

NASA Astrophysics Data System (ADS)

Abdurakhman, Yuanita Budiman; Putra, Zulfan Adi; Bilad, Muhammad Roil

2017-10-01

Pollution and shortage of clean energy supply are among major problems that are caused by rapid population growth. Due to this growth, waste cooking oil is one of the pollution sources. On the other hand, biodiesel appears to be one of the most promising and feasible energy sources as it emits less toxic pollutants and greenhouse gases than petroleum diesel. Thus, biodiesel production using waste cooking oil offers a two-in-one solution to cater pollution and energy issues. However, the conventional biodiesel production process using homogeneous base catalyst and stirred tank reactor is unable to produce high purity of biodiesel from waste cooking oil. It is due its sensitivity to free fatty acid (FFA) content in waste cooking oil and purification difficulties. Therefore, biodiesel production using heterogeneous acid catalyst in membrane reactor is suggested. The product of this process is fatty acid methyl esters (FAME) or biodiesel with glycerol as by-product. This project is aimed to study techno-economic feasibility of biodiesel production from waste cooking oil via heterogeneous acid catalyst in membrane reactor. Aspen HYSYS is used to accomplish this aim. Several cases, such as considering different residence times and the production of pharmaceutical (USP) grade glycerol, are evaluated and compared. Economic potential of these cases is calculated by considering capital expenditure, utilities cost, product and by-product sales, as well as raw material costs. Waste cooking oil, inorganic pressure-driven membrane and WAl is used as raw material, type of membrane and heterogeneous acid catalyst respectively. Based on literature data, FAME yield formulation is developed and used in the reactor simulation. Simulation results shows that economic potential increases by 30% if pharmaceutical (USP) grade glycerol is produced regardless the residence time of the reactor. In addition, there is no significant effect of residence time on the economic potential.

Investigations on the effect of chlorine in lubricating oil and the presence of a diesel oxidation catalyst on PCDD/F releases from an internal combustion engine.

PubMed

Dyke, Patrick H; Sutton, Mike; Wood, David; Marshall, Jonathan

2007-04-01

This paper reports on an intensive study into releases of polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated furans (PCDF) and polychlorinated biphenyls (PCB) from a diesel engine and the analysis of PCDD/F and PCB in crankcase lubricating oil. Experimental conditions were set and carefully controlled in order to maximize the possible impact of, and our ability to measure the effect of, changes in the levels of chlorine in the lubricant. Emissions to air were measured using modified EPA methods following the principles of the European EN 1948 standards. A series of 40 experimental runs were completed using three reference lubricants formulated to have three levels of chlorine present as a residual component (at levels of 12, 131 and 259 mg kg(-1) or ppm). The engine was run with and without the diesel oxidation catalyst. All lubricants were realistic oils and the use of unrealistic additives or doping of components - particularly chlorine - in the fuel and lubricant was carefully avoided. Analysis of fuel and lubricant (before and after testing) samples required strenuous attention to achieve acceptable recoveries and showed non-detectable levels of PCB and PCDD/F at a detection limit of around 1.5 ng I-TEQ kg(-1) (ppt), indistinguishable from the laboratory blank. The testing demonstrated the need for extreme care to be taken in developing measurement methods that are sufficiently sensitive for measuring chlorine content of fluids and PCDD/F in oils, the latter being particularly challenging. Mean emissions of PCDD/F with the diesel oxidation catalyst in place were 23 pg I-TEQ l(-1) of fuel and with the diesel oxidation catalyst removed 97 pg I-TEQ l(-1) of fuel. The results of this testing showed that the emissions of PCDD/F were greatly reduced by the presence of a diesel oxidation catalyst in the exhaust, a finding that has not been explicitly tested in previous work. They also show that emissions from the engine were not controlled by the level of chlorine in the lubricant and that emissions did not change in response to a much greater step change in the total chlorine entering the combustion chamber due to a change in the level of chlorine in the fuel. Emissions when the engine was configured with a diesel oxidation catalyst showed a consistent pattern that appears to be unique in the experience of the authors.

Research progress of nanoparticles as enzyme mimetics

NASA Astrophysics Data System (ADS)

Hu, XiaoNa; Liu, JianBo; Hou, Shuai; Wen, Tao; Liu, WenQi; Zhang, Ke; He, WeiWei; Ji, YingLu; Ren, HongXuan; Wang, Qi; Wu, XiaoChun

2011-10-01

Natural enzymes as biological catalysts possess remarkable advantages, especially their highly efficient and selective catalysis under mild conditions. However, most natural enzymes are proteins, thus exhibiting an inherent low durability to harsh reaction conditions. Artificial enzyme mimetics have been pursued extensively to avoid this drawback. Quite recently, some inorganic nanoparticles (NPs) have been found to exhibit unique enzyme mimetics. In addition, their much higher stability overcomes the inherent disadvantage of natural enzymes. Furthermore, easy mass-production and low cost endow them more benefits. As a new member of artificial enzyme mimetics, they have received intense attention. In this review article, major progress in this field is summarized and future perspectives are highlighted.

Vertical epitaxial wire-on-wire growth of Ge/Si on Si(100) substrate.

PubMed

Shimizu, Tomohiro; Zhang, Zhang; Shingubara, Shoso; Senz, Stephan; Gösele, Ulrich

2009-04-01

Vertically aligned epitaxial Ge/Si heterostructure nanowire arrays on Si(100) substrates were prepared by a two-step chemical vapor deposition method in anodic aluminum oxide templates. n-Butylgermane vapor was employed as new safer precursor for Ge nanowire growth instead of germane. First a Si nanowire was grown by the vapor liquid solid growth mechanism using Au as catalyst and silane. The second step was the growth of Ge nanowires on top of the Si nanowires. The method presented will allow preparing epitaxially grown vertical heterostructure nanowires consisting of multiple materials on an arbitrary substrate avoiding undesired lateral growth.

Inhibition of methyldigoxin-induced arrhythmias by pentadecapeptide BPC 157: a relation with NO-system.

PubMed

Balenovic, Dijana; Bencic, Martina Lovric; Udovicic, Mario; Simonji, Karol; Hanzevacki, Jadranka Separovic; Barisic, Ivan; Kranjcevic, Stjepan; Prkacin, Ingrid; Coric, Vedran; Brcic, Luka; Coric, Marijana; Brcic, Iva; Borovic, Suzana; Radic, Bozo; Drmic, Domagoj; Vrcic, Hrvoje; Seiwerth, Sven; Sikiric, Predrag

2009-08-07

Pentadecapeptide BPC 157 (GEPPPGKPADDAGLV, MW 1419) reversed congestive heart failure and various arrhythmias, influenced the NO-system and showed no proarrhythmic effect. In therapy analogy, we challenged rats with digitalis, to show attenuation by BPC 157 and the relation between the NO-system and digitalis toxicity. (i). BPC 157 prophylactic effect. Development of cumulative intravenous digitalis toxicity, BPC 157 (50 microg, 10 microg, 10 ng/kg applied intravenously immediately before a methyldigoxin increment regimen (2.0/1.5/1.5/1.0 mg/kg at 15 min-intervals, total dose 6.0 mg/kg/45 min)) reduced the number of ventricular premature beats, prolonged the time before onset of ventricular tachycardia, reduced ventricular tachycardia and AV-block duration (microg-regimes) or reduced mainly the AV-block duration (ng-regimen). (ii). BPC 157 therapy. Advanced methyldigoxin toxicity (6.0 mg/kg i.v. bolus). BPC 157 applied at the 20th second of the grade 3 AV-block shortened AV-blocks, mitigated a further digitalis toxicity course. Ventricular tachycardias were either avoided (50 microg), or markedly reduced (10 microg, 10 ng). Fatal outcome was either avoided (50 microg), reduced (10 microg), or only delayed (10 ng) (iii) BPC 157, L-NAME, l-arginine, L-NAME+l-arginine application. L-NAME-application (5 mg/kg i.p.) aggravated methyldigoxin-arrhythmias. l-arginine (200 mg/kg i.p.) alone had no effect but blunted L-NAME-exaggeration (L-NAME+l-arginine). In this respect, BPC 157 (50 microg/kg i.p.) was prophylactically and therapeutically more effective: the antagonism of L-NAME with BPC 157 produced an effect similar to BPC 157 alone. In conclusion, digitalis-induced arrhythmias in rats could be prevented and counteracted by pentadecapeptide BPC 157, mainly through an interaction with the NO-system.

Bioassays with terrestrial and aquatic species as monitoring tools of hydrocarbon degradation.

PubMed

Bori, Jaume; Vallès, Bettina; Ortega, Lina; Riva, Maria Carme

2016-09-01

In this study chemical analyses and ecotoxicity tests were applied for the assessment of a heavily hydrocarbon-contaminated soil prior and after the application of a remediation procedure that consisted in the stimulation of soil autochthonous populations of hydrocarbon degraders in static-ventilated biopiles. Terrestrial bioassays were applied in mixtures of test soils and artificial control soil and studied the survival and reproduction of Eisenia fetida and the avoidance response of E. fetida and Folsomia candida. Effects on aquatic organisms were studied by means of acute tests with Vibrio fischeri, Raphidocelis subcapitata, and Daphnia magna performed on aqueous elutriates from test soils. The bioremediation procedure led to a significant reduction in the concentration of hydrocarbons (from 34264 to 3074 mg kg(-1), i.e., 91 % decrease) and toxicity although bioassays were not able to report a percentage decrease of toxicity as high as the percentage reduction. Sublethal tests proved the most sensitive terrestrial bioassays and avoidance tests with earthworms and springtails showed potential as monitoring tools of hydrocarbon remediation due to their high sensitivity and short duration. The concentrations of hydrocarbons in water extracts from test soils were 130 and 100 μg L(-1) before and after remediation, respectively. Similarly to terrestrial tests, most aquatic bioassays detected a significant reduction in toxicity, which was almost negligible at the end of the treatment. D. magna survival was the most affected by soil elutriates although toxicity to the crustacean was associated to the salinity of the samples rather than to the concentration of hydrocarbons. Ecotoxicity tests with aqueous soil elutriates proved less relevant in the assessment of hydrocarbon-contaminated soils due to the low hydrosolubility of hydrocarbons and the influence of the physicochemical parameters of the aquatic medium.

PBPK Models, BBDR Models, and Virtual Tissues: How Will They Contribute to the Use of Toxicity Pathways in Risk Assessment?

EPA Science Inventory

Accuracy in risk assessment, which is desirable in order to ensure protection of the public health while avoiding over-regulation of economically-important substances, requires quantitatively accurate, in vivo descriptions of dose-response and time-course behaviors. This level of...

40 CFR 104.7 - Powers of Presiding Officer.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 21 2010-07-01 2010-07-01 false Powers of Presiding Officer. 104.7... HEARINGS ON EFFLUENT STANDARDS FOR TOXIC POLLUTANTS § 104.7 Powers of Presiding Officer. The Presiding...) of the Act. He shall take all necessary action to avoid delay and to maintain order. He shall have...

40 CFR 104.7 - Powers of Presiding Officer.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 22 2011-07-01 2011-07-01 false Powers of Presiding Officer. 104.7... HEARINGS ON EFFLUENT STANDARDS FOR TOXIC POLLUTANTS § 104.7 Powers of Presiding Officer. The Presiding...) of the Act. He shall take all necessary action to avoid delay and to maintain order. He shall have...

Spider mite infestations reduce Bacillus thuringiensis toxin concentration in corn leaves and predators avoid spider mites that have fed on Bacillus thuringiensis corn

USDA-ARS?s Scientific Manuscript database

Transgenic crops containing pyramid-stacked genes for Bacillus thuringiensis derived toxins for controlling coleopteran and lepidopteran pests are increasingly common. As part of environmental risk assessments, these crops are evaluated for toxicity against non-target organisms, and for their poten...

Destruction of VX by aqueous-phase oxidation using peroxydisulfate (direct chemical oxidation)

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

Cooper, J.F.; Krueger, R.; Farmer, J.C.

1995-10-11

Chemical warfare agents may be completely destroyed (converted to H{sub 2}O, CO{sub 2}, salts) by oxidation at 90--100 C using acidified ammonium peroxydisulfate, with recycle of NH{sub 4}SO{sub 4} byproduct. The process requires no toxic or expended catalysts and produces no secondary wastes other than the precipitated inorganic content of the agents. To determine oxidative capability of peroxydisulfate at low reductant contents, we measured rate data for oxidation of 20 diverse compounds with diverse functional groups; 4 of these have bonds similar to those found in VX, HD, and GB. On an equivalence basis, integral first-order rate constants for 100more » C oxidation are 0.012{plus_minus}0.005 min{sup {minus}1} for di-isopropyl-methyl-phosphonate, methyl phosphonic acid, triethylamine, and 2,2{prime}-thiodiethanol at low initial concentrations of 50 ppM(as carbon) and pH 1.5. To provide scale-up equations for a bulk chemical agent destruction process, we measured time-dependent oxidation of bulk model chemicals at high concentrations (0.5 N) and developed and tested a quantitative model. A practical process for bulk VX destruction would begin with chemical detoxification by existing techniques (eg, hydrolysis or mild oxidation using oxone), followed by mineralization of the largely detoxified products by peroxydisulfate. Secondary wastes would be avoided by use of commercial electrolysis equipment to regenerate the oxidant. Reagent requirements, mass balance and scaleup parameters are given for VX destruction, using peroxydisulfate alone, or supplemented with hydrogen peroxide. For the use of 2.5 N peroxydisulfate as the oxidant, a 1 m{sup 3} digester will process about 200 kg (as C) per day. The process may be extended to total destruction of HD and hydrolysis products of G agents.« less

Significance of Intratracheal Instillation Tests for the Screening of Pulmonary Toxicity of Nanomaterials.

PubMed

Morimoto, Yasuo; Izumi, Hiroto; Yoshiura, Yukiko; Fujisawa, Yuri; Fujita, Katsuhide

Inhalation tests are the gold standard test for the estimation of the pulmonary toxicity of respirable materials. Intratracheal instillation tests have been used widely, but they yield limited evidence of the harmful effects of respirable materials. We reviewed the effectiveness of intratracheal instillation tests for estimating the hazards of nanomaterials, mainly using research papers featuring intratracheal instillation and inhalation tests centered on a Japanese national project. Compared to inhalation tests, intratracheal instillation tests induced more acute inflammatory responses in the animal lung due to a bolus effect regardless of the toxicity of the nanomaterials. However, nanomaterials with high toxicity induced persistent inflammation in the chronic phase, and nanomaterials with low toxicity induced only transient inflammation. Therefore, in order to estimate the harmful effects of a nanomaterial, an observation period of 3 months or 6 months following intratracheal instillation is necessary. Among the endpoints of pulmonary toxicity, cell count and percentage of neutrophil, chemokines for neutrophils and macrophages, and oxidative stress markers are considered most important. These markers show persistent and transient responses in the lung from nanomaterials with high and low toxicity, respectively. If the evaluation of the pulmonary toxicity of nanomaterials is performed in not only the acute but also the chronic phase in order to avoid the bolus effect of intratracheal instillation and inflammatory-related factors that are used as endpoints of pulmonary toxicity, we speculate that intratracheal instillation tests can be useful for screening for the identification of the hazard of nanomaterials through pulmonary inflammation.

QSAR modeling of acute toxicity on mammals caused by aromatic compounds: the case study using oral LD50 for rats.

PubMed

Rasulev, Bakhtiyor; Kusić, Hrvoje; Leszczynska, Danuta; Leszczynski, Jerzy; Koprivanac, Natalija

2010-05-01

The goal of the study was to predict toxicity in vivo caused by aromatic compounds structured with a single benzene ring and the presence or absence of different substituent groups such as hydroxyl-, nitro-, amino-, methyl-, methoxy-, etc., by using QSAR/QSPR tools. A Genetic Algorithm and multiple regression analysis were applied to select the descriptors and to generate the correlation models. The most predictive model is shown to be the 3-variable model which also has a good ratio of the number of descriptors and their predictive ability to avoid overfitting. The main contributions to the toxicity were shown to be the polarizability weighted MATS2p and the number of certain groups C-026 descriptors. The GA-MLRA approach showed good results in this study, which allows the building of a simple, interpretable and transparent model that can be used for future studies of predicting toxicity of organic compounds to mammals.

Method For Selective Catalytic Reduction Of Nitrogen Oxides

DOEpatents

Mowery-Evans, Deborah L.; Gardner, Timothy J.; McLaughlin, Linda I.

2005-02-15

A method for catalytically reducing nitrogen oxide compounds (NO.sub.x, defined as nitric oxide, NO, +nitrogen dioxide, NO.sub.2) in a gas by a material comprising a base metal consisting essentially of CuO and Mn, and oxides of Mn, on an activated metal hydrous metal oxide support, such as HMO:Si. A promoter, such as tungsten oxide or molybdenum oxide, can be added and has been shown to increase conversion efficiency. This method provides good conversion of NO.sub.x to N.sub.2, good selectivity, good durability, resistance to SO.sub.2 aging and low toxicity compared with methods utilizing vanadia-based catalysts.

Method for selective catalytic reduction of nitrogen oxides

DOEpatents

Mowery-Evans, Deborah L [Broomfield, CO; Gardner, Timothy J [Albuquerque, NM; McLaughlin, Linda I [Albuquerque, NM

2005-02-15

A method for catalytically reducing nitrogen oxide compounds (NO.sub.x, defined as nitric oxide, NO, +nitrogen dioxide, NO.sub.2) in a gas by a material comprising a base metal consisting essentially of CuO and Mn, and oxides of Mn, on an activated metal hydrous metal oxide support, such as HMO:Si. A promoter, such as tungsten oxide or molybdenum oxide, can be added and has been shown to increase conversion efficiency. This method provides good conversion of NO.sub.x to N.sub.2, good selectivity, good durability, resistance to SO.sub.2 aging and low toxicity compared with methods utilizing vanadia-based catalysts.

Niobium(V) saponite clay for the catalytic oxidative abatement of chemical warfare agents.

PubMed

Carniato, Fabio; Bisio, Chiara; Psaro, Rinaldo; Marchese, Leonardo; Guidotti, Matteo

2014-09-15

A Nb(V)-containing saponite clay was designed to selectively transform toxic organosulfur chemical warfare agents (CWAs) under extremely mild conditions into nontoxic products with reduced environmental impact. Thanks to the insertion of Nb(V) sites within the saponite framework, a bifunctional catalyst with strong oxidizing and acid properties was obtained. Remarkable activity and high selectivity were observed for the oxidative abatement of (2-chloroethyl)ethyl sulfide (CEES), a simulant of sulfur mustard, at room temperature with aqueous hydrogen peroxide. This performance was significantly better compared to a conventional commercial decontamination powder. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimizing Metalloporphyrin-Catalyzed Reduction Reactions for In Situ Remediation of DOE Contaminants

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

Schlautman, Mark A.

2013-07-14

Past activities have resulted in a legacy of contaminated soil and groundwater at Department of Energy facilities nationwide. Uranium and chromium are among the most frequently encountered and highest-priority metal and radionuclide contaminants at DOE installations. Abiotic chemical reduction of uranium and chromium at contaminated DOE sites can be beneficial because the reduced metal species are less soluble in water, less mobile in the environment, and less toxic to humans and ecosystems. Although direct biological reduction has been reported for U(VI) and Cr(VI) in laboratory studies and at some field sites, the reactions can sometimes be slow or even inhibitedmore » due to unfavorable environmental conditions. One promising approach for the in-situ remediation of DOE contaminants is to develop electron shuttle catalysts that can be delivered precisely to the specific subsurface locations where contaminants reside. Previous research has shown that reduction of oxidized organic and inorganic contaminants often can be catalyzed by electron shuttle systems. Metalloporphyrins and their derivatives are well known electron shuttles for many biogeochemical systems, and thus were selected to study their catalytic capabilities for the reduction of chromium and uranium in the presence of reducing agents. Zero valent iron (ZVI) was chosen as the primary electron donor in most experimental systems. Research proceeded in three phases and the key findings of each phase are reported here. Phase I examined Cr(VI) reduction and utilized micro- and nano-sized ZVI as the electron donors. Electron shuttle catalysts tested were cobalt- and iron-containing metalloporphyrins and Vitamin B12. To aid in the recycle and reuse of the nano-sized ZVI and soluble catalysts, sol-gels and calcium-alginate gel beads were tested as immobilization/support matrices. Although the nano-sized ZVI could be incorporated within the alginate gel beads, preliminary attempts to trap it in sol-gels were not successful. Conversely, the water-soluble catalysts could be trapped within sol-gel matrices but they tended to leach out of the alginate gel beads during use. In general, immobilization of the nano-sized ZVI in gel beads and of the catalysts in sol-gels tended to result in slower rates of Cr(VI) reduction, but these effects could be overcome to some extent by using higher reactant/catalyst concentrations. In addition, the lowering of their effectiveness would likely be offset by the benefits obtained when recycling and reusing the materials because they were immobilized. Addition of the catalytic electron shuttles will be most useful when the micro-sized or nano-sized ZVI becomes less reactive with reaction time. Continued work in Phase II in the area of nano-sized ZVI immobilization led to procedures that were successful in incorporating the iron particles in sol-gel matrices. The water-soluble reductants sodium dithionite and L-ascorbic acid were also tested, but their use appeared to lead to formation of complexes with the uranyl cation which limited their effectiveness. Also, although the sol-gel supported nano-sized ZVI showed some promise at reducing uranium, the fluoride used in the sol-gel synthesis protocol appeared to lead to formation of uranyl-fluoride complexes that were less reactive. Because hexavalent chromium is an anion which does not form complexes with fluoride, it was used to demonstrate the intrinsic reactivity of the sol-gel immobilized nano-sized ZVI. Consistent with our observations in Phase I, the sol-gel matrix once again slowed down the reduction reaction but the expected benefits of recycle/reuse should outweigh this adverse effect. The major emphasis in Phase III of this study was to simultaneously incorporate nano-sized ZVI and water-soluble catalysts in the same sol-gel matrix. The catalysts utilized were cobalt complexes of uroporphyrin and protoporphyrin and Cr(VI) reduction was used to test the efficacy of the combined "catalyst + reductant" sol-gel matrix. When enough catalyst was added to the sol-gels, enhancement of the Cr(VI) reduction reaction was observed. At the lowest levels of catalyst addition, however, the rates of Cr(VI) reduction were similar to those systems which only used sol-gel immobilized nano-sized ZVI without any catalyst present. These findings suggest future areas of research that should be pursued to further optimize abiotic reduction reactions of metals with combined "catalyst + reductant" matrices.« less

Effects of soot by-product from the synthesis of engineered metallofullerene nanomaterials on terrestrial invertebrates.

PubMed

Johnson, David R; Boyd, Robert E; Bednar, Anthony J; Weiss, Charles A; Hull, Matt S; Coleman, Jessica G; Kennedy, Alan J; Banks, Cynthia J; Steevens, Jeffery A

2018-02-23

The synthesis of carbon-based nanomaterials is often inefficient, generating large amounts of soot with metals as waste by-product. Currently, there are no specific regulations for disposal of engineered nanomaterials or the waste by-products resulting from their synthesis, so it is presumed that by-products are disposed of in the same way as the parent (bulk) materials. We studied the terrestrial toxicity of soot from gadolinium metallofullerene nanomanufacturing on earthworms (Eisenia fetida) and isopods (Porcellio scaber). The metallofullerene soot consisted of carbon particle agglomerates in the nanometer and submicrometer ranges (1-100 and 101-999 nm, respectively), with metals used during nanomanufacturing detectable on the particles. Despite high metal concentrations (>100 000 mg/kg) in the soot, only a relatively small amount of metals leached out of a spiked field soil, suggesting only moderate mobility. Seven- and 14-d exposures in field soil demonstrated that the soot was only toxic to earthworms at high concentrations (>10 000 mg/kg); however, earthworms avoided spiked soils at lower concentrations (as low as 500 mg/kg) and at lower soil pH. The presence of soot in food and soil did not cause isopod avoidance. These data demonstrate that metallofullerene soot from nanomanufacturing may only be toxic to earthworms at high concentrations representative of improper disposal or accidental spills. However, our results indicate that terrestrial invertebrates may avoid soils contaminated with soot at sublethal concentrations. Environ Toxicol Chem 2018;9999:1-12. Published 2018 Wiley Periodicals, Inc. on behalf of SETAC. This article is a US government work, and as such, is in the public domain in the United States of America. Published 2018 Wiley Periodicals, Inc. on behalf of SETAC. This article is a US government work, and as such, is in the public domain in the United States of America.

Potential Toxicity and Underlying Mechanisms Associated with Pulmonary Exposure to Iron Oxide Nanoparticles: Conflicting Literature and Unclear Risk

PubMed Central

Kornberg, Tiffany G.; Antonini, James M.; Rojanasakul, Yon; Castranova, Vincent; Rojanasakul, Liying W.

2017-01-01

Fine/micron-sized iron oxide particulates are incidentally released from a number of industrial processes, including iron ore mining, steel processing, welding, and pyrite production. Some research suggests that occupational exposure to these particulates is linked to an increased risk of adverse respiratory outcomes, whereas other studies suggest that iron oxide is biologically benign. Iron oxide nanoparticles (IONPs), which are less than 100 nm in diameter, have recently surged in use as components of novel drug delivery systems, unique imaging protocols, as environmental catalysts, and for incorporation into thermoplastics. However, the adverse outcomes associated with occupational exposure to IONPs remain relatively unknown. Relevant in vivo studies suggest that pulmonary exposure to IONPs may induce inflammation, pulmonary fibrosis, genotoxicity, and extra-pulmonary effects. This correlates well with in vitro studies that utilize relevant dose, cell type(s), and meaningful end points. A majority of these adverse outcomes are attributed to increased oxidative stress, most likely caused by particle internalization, dissolution, release of free iron ions, and disruption of iron homeostasis. However, because the overall toxicity profile of IONPs is not well understood, it is difficult to set safe exposure limit recommendations that would be adequate for the protection of at-risk workers. This review article will focus on known risks following IONPs exposure supported by human, animal, and cell culture-based studies, the potential challenges intrinsic to IONPs toxicity assessment, and how these may contribute to the poorly characterized IONPs toxicity profile. PMID:28984829

Apparatus and method for simultaneous recovery of hydrogen from water and from hydrocarbons

DOEpatents

Willms, R. Scott; Birdsell, Stephen A.

2000-01-01

Apparatus and method for simultaneous recovery of hydrogen from water and from hydrocarbon feed material. The feed material is caused to flow over a heated catalyst which fosters the water-gas shift reaction (H.sub.2 O+COH.sub.2 +CO.sub.2) and the methane steam reforming reaction (CH.sub.4 +H.sub.2 O3 H.sub.2 +CO). Both of these reactions proceed only to partial completion. However, by use of a Pd/Ag membrane which is exclusively permeable to hydrogen isotopes in the vicinity of the above reactions and by maintaining a vacuum on the permeate side of the membrane, product hydrogen isotopes are removed and the reactions are caused to proceed further toward completion. A two-stage palladium membrane reactor was tested with a feed composition of 28% CQ.sub.4, 35% Q.sub.2 O (where Q=H, D, or T), and 31% Ar in 31 hours of continuous operation during which 4.5 g of tritium were processed. Decontamination factors were found to increase with decreasing inlet rate. The first stage was observed to have a decontamination factor of approximately 200, while the second stage had a decontamination factor of 2.9.times.10.sup.6. The overall decontamination factor was 5.8.times.10.sup.8. When a Pt/.alpha.-Al.sub.2 O.sub.3 catalyst is employed, decoking could be performed without catalyst degradation. However, by adjusting the carbon to oxygen ratio of the feed material with the addition of oxygen, coking could be altogether avoided.

Silylation of C-H bonds in aromatic heterocycles by an Earth-abundant metal catalyst

NASA Astrophysics Data System (ADS)

Toutov, Anton A.; Liu, Wen-Bo; Betz, Kerry N.; Fedorov, Alexey; Stoltz, Brian M.; Grubbs, Robert H.

2015-02-01

Heteroaromatic compounds containing carbon-silicon (C-Si) bonds are of great interest in the fields of organic electronics and photonics, drug discovery, nuclear medicine and complex molecule synthesis, because these compounds have very useful physicochemical properties. Many of the methods now used to construct heteroaromatic C-Si bonds involve stoichiometric reactions between heteroaryl organometallic species and silicon electrophiles or direct, transition-metal-catalysed intermolecular carbon-hydrogen (C-H) silylation using rhodium or iridium complexes in the presence of excess hydrogen acceptors. Both approaches are useful, but their limitations include functional group incompatibility, narrow scope of application, high cost and low availability of the catalysts, and unproven scalability. For this reason, a new and general catalytic approach to heteroaromatic C-Si bond construction that avoids such limitations is highly desirable. Here we report an example of cross-dehydrogenative heteroaromatic C-H functionalization catalysed by an Earth-abundant alkali metal species. We found that readily available and inexpensive potassium tert-butoxide catalyses the direct silylation of aromatic heterocycles with hydrosilanes, furnishing heteroarylsilanes in a single step. The silylation proceeds under mild conditions, in the absence of hydrogen acceptors, ligands or additives, and is scalable to greater than 100 grams under optionally solvent-free conditions. Substrate classes that are difficult to activate with precious metal catalysts are silylated in good yield and with excellent regioselectivity. The derived heteroarylsilane products readily engage in versatile transformations enabling new synthetic strategies for heteroaromatic elaboration, and are useful in their own right in pharmaceutical and materials science applications.

[Prevention and multimodal therapy of hyperthyroidism].

PubMed

Palitzsch, K-D

2008-12-01

Subclinical and overt hyperthyroidism have been associated with various negative clinical outcomes as for example an increased risk of atrial fibrillation or increased cardiovascular mortality, especially in old age. In order to avoid hyperthyroidism it is strongly recommended not to start any iodine containing drug therapy or to avoid application of contrast agents unless the patient presents with an unremarkable clinical course. TSH suppressive therapy for the treatment of endemic goiter or differentiated low risk thyroid carcinoma is unnecessary, since it favours the development of subclinical hyperthyroidism. Overt hyperthyroidism is treated with antithyroid drugs and/or radioiodine therapy or surgery according to the underlying disease (toxic nodular goiter, Graves' disease).

Transition-Metal-Controlled Inorganic Ligand-Supported Non-Precious Metal Catalysts for the Aerobic Oxidation of Amines to Imines.

PubMed

Yu, Han; Zhai, Yongyan; Dai, Guoyong; Ru, Shi; Han, Sheng; Wei, Yongge

2017-10-09

Most state-of-art transition-metal catalysts usually require organic ligands, which are essential for controlling the reactivity and selectivity of reactions catalyzed by transition metals. However, organic ligands often suffer from severe problems including cost, toxicity, air/moisture sensitivity, and being commercially unavailable. Herein, we show a simple, mild, and efficient aerobic oxidation procedure of amines using inorganic ligand-supported non-precious metal catalysts 1, (NH 4 ) n [MMo 6 O 18 (OH) 6 ] (M=Cu 2+ ; Fe 3+ ; Co 3+ ; Ni 2+ ; Zn 2+ , n=3 or 4), synthesized by a simple one-step method in water at 100 °C, demonstrating that the catalytic activity and selectivity can be significantly improved by changing the central metal atom. In the presence of these catalysts, the catalytic oxidation of primary and secondary amines, as well as the coupling of alcohols and amines, can smoothly proceed to afford various imines with O 2 (1 atm) as the sole oxidant. In particular, the catalysts 1 have transition-metal ion core, and the planar arrangement of the six Mo VI centers at their highest oxidation states around the central heterometal can greatly enhance the Lewis acidity of catalytically active sites, and also enable the electrons in the center to delocalize onto the six edge-sharing MO 6 units, in the same way as ligands in traditional organometallic complexes. The versatility of this methodology maybe opens a path to catalytic oxidation through inorganic ligand-coordinated metal catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mitigation of PAH and nitro-PAH emissions from nonroad diesel engines.

PubMed

Liu, Z Gerald; Wall, John C; Ottinger, Nathan A; McGuffin, Dana

2015-03-17

More stringent emission requirements for nonroad diesel engines introduced with U.S. Tier 4 Final and Euro Stage IV and V regulations have spurred the development of exhaust aftertreatment technologies. In this study, several aftertreatment configurations consisting of diesel oxidation catalysts (DOC), diesel particulate filters (DPF), Cu zeolite-, and vanadium-based selective catalytic reduction (SCR) catalysts, and ammonia oxidation (AMOX) catalysts are evaluated using both Nonroad Transient (NRTC) and Steady (8-mode NRSC) Cycles in order to understand both component and system-level effects of diesel aftertreatment on emissions of polycyclic aromatic hydrocarbons (PAH) and their nitrated derivatives (nitro-PAH). Emissions are reported for four configurations including engine-out, DOC+CuZ-SCR+AMOX, V-SCR+AMOX, and DOC+DPF+CuZ-SCR+AMOX. Mechanisms responsible for the reduction, and, in some cases, the formation of PAH and nitro-PAH compounds are discussed in detail, and suggestions are provided to minimize the formation of nitro-PAH compounds through aftertreatment design optimizations. Potency equivalency factors (PEFs) developed by the California Environmental Protection Agency are then applied to determine the impact of aftertreatment on PAH-derived exhaust toxicity. Finally, a comprehensive set of exhaust emissions including criteria pollutants, NO2, total hydrocarbons (THC), n-alkanes, branched alkanes, saturated cycloalkanes, aromatics, aldehydes, hopanes and steranes, and metals is provided, and the overall efficacy of the aftertreatment configurations is described. This detailed summary of emissions from a current nonroad diesel engine equipped with advanced aftertreatment can be used to more accurately model the impact of anthropogenic emissions on the atmosphere.

Continuous process for singlet oxygenation of hydrophobic substrates in microemulsion using a pervaporation membrane.

PubMed

Caron, Laurent; Nardello, Véronique; Mugge, José; Hoving, Erik; Alsters, Paul L; Aubry, Jean-Marie

2005-02-15

Chemically generated singlet oxygen (1O2, 1Deltag) is able to oxidize a great deal of hydrophobic substrates from molybdate-catalyzed hydrogen peroxide decomposition, provided a suitable reaction medium such as a microemulsion system is used. However, high substrate concentrations or poorly reactive organics require large amounts of H2O2 that generate high amounts of water and thus destabilize the system. We report results obtained on combining dark singlet oxygenation of hydrophobic substrates in microemulsions with a pervaporation membrane process. To avoid composition alterations after addition of H2O2 during the peroxidation, the reaction mixture circulates through a ceramic membrane module that enables a partial and selective dewatering of the microemulsion. Optimization phase diagrams of sodium molybdate/water/alcohol/anionic surfactant/organic solvent have been elaborated to maximize the catalyst concentration and therefore the reaction rate. The membrane selectivity towards the mixture constituents has been investigated showing that a high retention is observed for the catalyst, for organic solvents and hydrophobic substrates, but not for n-propanol (cosurfactant) and water. The efficiency of such a process is illustrated with the peroxidation of a poorly reactive substrate, viz., beta-pinene.

The Role of Electrode-Catalyst Interactions in Enabling Efficient CO2 Reduction with Mo(bpy)(CO)4 As Revealed by Vibrational Sum-Frequency Generation Spectroscopy.

PubMed

Neri, Gaia; Donaldson, Paul M; Cowan, Alexander J

2017-10-04

Group 6 metal carbonyl complexes ([M(bpy)(CO) 4 ], M = Cr, Mo, W) are potentially promising CO 2 reduction electrocatalysts. However, catalytic activity onsets at prohibitively negative potentials and is highly dependent on the nature of the working electrode. Here we report in situ vibrational SFG (VSFG) measurements of the electrocatalyst [Mo(bpy)(CO) 4 ] at platinum and gold electrodes. The greatly improved onset potential for electrocatalytic CO 2 reduction at gold electrodes is due to the formation of the catalytically active species [Mo(bpy)(CO) 3 ] 2- via a second pathway at more positive potentials, likely avoiding the need for the generation of [Mo(bpy)(CO) 4 ] 2- . VSFG studies demonstrate that the strength of the interaction between initially generated [Mo(bpy)(CO) 4 ] •- and the electrode is critical in enabling the formation of the active catalyst via the low energy pathway. By careful control of electrode material, solvent and electrolyte salt, it should therefore be possible to attain levels of activity with group 6 complexes equivalent to their much more widely studied group 7 analogues.

New Directions for the Photocatalytic Reduction of CO2: Supramolecular, scCO2 or Biphasic Ionic Liquid-scCO2 Systems

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

Grills, D.C.; Fujita, E.

2010-09-02

There is an urgent need for the discovery of carbon-neutral sources of energy to avoid the consequences of global warming caused by ever-increasing atmospheric CO{sub 2} levels. An attractive possibility is to use CO{sub 2} captured from industrial emissions as a feedstock for the production of useful fuels and precursors such as carbon monoxide and methanol. An active field of research to achieve this goal is the development of catalysts capable of harnessing solar energy for use in artificial photosynthetic processes for CO{sub 2} reduction. Transition-metal complexes are excellent candidates, and it has already been shown that they can bemore » used to reduce CO{sub 2} with high quantum efficiency. However, they generally suffer from poor visible light absorption, short catalyst lifetimes, and poor reaction rates. In this Perspective, the field of photocatalytic CO{sub 2} reduction is introduced, and recent developments that seek to improve the efficiency of such catalytic processes are highlighted, especially CO{sub 2} reduction with supramolecules and molecular systems in supercritical CO{sub 2} (scCO{sub 2}) or biphasic ionic liquid-scCO{sub 2} mixtures.« less

Interactions of platinum metals and their complexes in biological systems.

PubMed Central

LeRoy, A F

1975-01-01

Platinum-metal oxidation catalysts are to be introduced in exhaust systems of many 1975 model-year automobiles in the U.S. to meet Clean Air Act standards. Small quantities of finely divided catalyst have been found issuing from prototype systems; platinum and palladium compounds may be found also. Although platinum exhibits a remarkable resistance to oxidation and chemical attack, it reacts chemically under some conditions producing coordination complex compounds. Palladium reacts more readily than platinum. Some platinum-metal complexes interact with biological systems as bacteriostatic, bacteriocidal, viricidal, and immunosuppressive agents. Workers chronically exposed to platinum complexes often develop asthma-like respiratory distress and skin reactions called platinosis. Platinum complexes used alone and in combination therapy with other drugs have recently emerged as effective agents in cancer chemotherapy. Understanding toxic and favorable interactions of metal species with living organisms requires basic information on quantities and chemical characteristics of complexes at trace concentrations in biological materials. Some basic chemical kinetic and thermodynamic data are presented to characterize the chemical behavior of the complex cis-[Pt(NH3)2Cl2] used therapeutically. A brief discussion of platinum at manogram levels in biological tissue is discussed. PMID:50943

Catalytic degradation of organophosphorous nerve agent simulants by polymer beads@graphene oxide with organophosphorus hydrolase-like activity based on rational design of functional bimetallic nuclear ligand.

PubMed

Ma, Xuejuan; Zhang, Lin; Xia, Mengfan; Zhang, Xiaohong; Zhang, Yaodong

2018-05-15

The degradation of organophosphorous nerve agents is of primary concern due to the severe toxicity of these agents. Based on the active center of organophosphorus hydrolase (OPH), a bimetallic nuclear ligand, (5-vinyl-1,3-phenylene)bis(di(1H-imidazol-2-yl) methanol) (VPIM), was designed and synthesized, which contains four imidazole groups to mimic the four histidines at OPH active center. By grafting VPIM on graphene oxide (GO) surface via polymerization, the VPIM-polymer beads@GO was produced. The obtained OPH mimics has an impressive activity in dephosphorylation reactions (turnover frequency (TOF) towards paraoxon: 2.3 s -1 ). The synergistic catalytic effect of the bimetallic Zn 2+ nuclear center and carboxyl groups on surface of GO possibly contributes to the high hydrolysis on organophosphate substrate. Thus, a biomimetic catalyst for efficient degradation of some organophosphorous nerve agent simulants, such as paraoxon and chlorpyrifos, was prepared by constructing catalytic active sites. The proposed mechanism and general synthetic strategy open new avenues for the engineering of functional GOs for biomimetic catalysts. Copyright © 2018 Elsevier B.V. All rights reserved.

Heterogeneous activation of H2O2 by defect-engineered TiO(2-x) single crystals for refractory pollutants degradation: A Fenton-like mechanism.

PubMed

Zhang, Ai-Yong; Lin, Tan; He, Yuan-Yi; Mou, Yu-Xuan

2016-07-05

The heterogeneous catalyst plays a key role in Fenton-like reaction for advanced oxidation of refractory pollutants in water treatment. Titanium dioxide (TiO2) is a typical semiconductor with high industrial importance due to its earth abundance, low cost and no toxicity. In this work, it is found that TiO2 can heterogeneously activate hydrogen peroxide (H2O2, E°=1.78 eV), a common chemical oxidant, to efficiently generate highly-powerful hydroxyl radical, OH (E(0)=2.80 eV), for advanced water treatment, when its crystal shape, exposed facet and oxygen-stoichiometry are finely tuned. The defect-engineered TiO2 single crystals exposed by high-energy {001} facets exhibited an excellent Fenton-like activity and stability for degrading typical refractory organic pollutants such as methyl orange and p-nitrophenol. Its defect-centered Fenton-like superiority is mainly attributed to the crystal oxygen-vacancy, single-crystalline structure and exposed polar {001} facet. Our findings could provide new chance to utilize TiO2 for Fenton-like technology, and develop novel heterogeneous catalyst for advanced water treatment. Copyright © 2016 Elsevier B.V. All rights reserved.

Release and toxicity comparison between industrial- and ...

EPA Pesticide Factsheets

Many consumer products containing ZnO have raised concern for safety in regards toenvironmental impact and the public health. Widely used sunscreens for protectingagainst UV and avoiding sunburns represent a great exposure to nano-ZnO, one of theingredients commonly applied in sunscreens. Applying nano-products on beaches mayrelease nanoparticles unintentionally into the ocean. Despite the accumulation of suchnano-products in the ocean harming or being detrimental to critical marine organisms,few studies have investigated the release and potential toxicity of nanoparticlesextracted from products and compared them with those from industrial-typenanoparticles. Results show that the cytotoxicity of both industrial- and sunscreenderivednano-ZnO to the marine diatom algae, Thalassiosira pseudonana, increasedas exposure increases over time, as measured by growth inhibition (%) of the algae ata constant concentration of nano-ZnO (10 mg/L). The extent of toxicity appeared to behigher from industrial-type nano-ZnO compared to sunscreen-extracted nano-ZnO,though the extent becomes similar when concentrations increase to 50 mg/L. On theother hand, at a fixed exposure time of 48 hrs, the cytotoxicity increases asconcentrations increase with the higher toxicity shown from the industrial-typecompared to sunscreen-induced nano-ZnO. Results indicate that while industrial-typenano-ZnO shows higher toxicity than sunscreen-derived nano-ZnO, the release andextent of toxicity from n

40 CFR Appendix V to Part 265 - Examples of Potentially Incompatible Waste

Code of Federal Regulations, 2010 CFR

2010-07-01

... pressure, (2) fire or explosion, (3) violent reaction, (4) toxic dusts, mists, fumes, or gases, or (5... analyze his wastes so that he can avoid creating uncontrolled substances or reactions of the type listed... mixed in a way that precludes a reaction (e.g., adding acid to water rather than water to acid) or that...

40 CFR Appendix V to Part 265 - Examples of Potentially Incompatible Waste

Code of Federal Regulations, 2011 CFR

2011-07-01

... pressure, (2) fire or explosion, (3) violent reaction, (4) toxic dusts, mists, fumes, or gases, or (5... analyze his wastes so that he can avoid creating uncontrolled substances or reactions of the type listed... mixed in a way that precludes a reaction (e.g., adding acid to water rather than water to acid) or that...

40 CFR Appendix V to Part 264 - Examples of Potentially Incompatible Waste

Code of Federal Regulations, 2011 CFR

2011-07-01

... explosion, (3) violent reaction, (4) toxic dusts, mists, fumes, or gases, or (5) flammable fumes or gases... can avoid creating uncontrolled substances or reactions of the type listed below, whether they are... precludes a reaction (e.g., adding acid to water rather than water to acid) or that neutralizes them (e.g...

Conditioned food aversion to control outbreaks of intoxication by Ipomoea carnea and Turbina cordata in goats

USDA-ARS?s Scientific Manuscript database

Conditioned food aversion is used to train livestock to avoid the ingestion of toxic plants. This technique was used to control Turbina cordata poisoning in goats in one farm, and to control Ipomoea carnea subsp. istulosa poisoning in another farm. The goats were penned at night and the next mornin...

Toxicological and chemical screening of Antarctica sediments: Use of whole sediment toxicity tests, microtox, mutatox and semipermeable membrane devices (SPMDs)

USGS Publications Warehouse

Cleveland, Laverne; Little, Edward E.; Petty, Jimmie D.; Johnson, B. Thomas; Lebo, Jon A.; Orazio, Carl E.; Dionne, Jane

1997-01-01

Eight whole sediment samples from Antarctica (four from Winter Quarters Bay and four from McMurdo Sound) were toxicologically and chemically evaluated. Also, the influence of ultraviolet radiation on the toxicity and bioavailability of contaminants associated with the sediment samples was assessed. The evaluations were accomplished by use of a 10-day whole sediment test with Leptocheirus plumulosus, Microtox®, Mutatox® and semipermeable membrane devices (SPMDs). Winter Quarters Bay sediments contained about 250 ng g−1 (dry weight) total PCBs and 20 μg g−1 total PAHs. These sediments elicited toxicity in the Microtox test and avoidance and inhibited burrowing in the L. plumulosus test. The McMurdo Sound sediment samples contained only trace amounts of PCBs and no PAHs, and were less toxic in both the L. plumulosus and Microtox tests compared to the Winter Quarters Bay sediments. The sediments from McMurdo Sound apparently contained some unidentified substance which was photolytically modified to a more toxic form. The photolytic modification of sediment-associated contaminants, coupled with the polar ozone hole and increased incidence of ultraviolet radiation could significantly increase hazards to Antarctic marine life.

Assessment of Crystal Morphology on Uptake, Particle Dissolution, and Toxicity of Nanoscale Titanium Dioxide on Artemia salina

PubMed Central

Johnson, Martha; Ates, Mehmet; Arslan, Zikri; Farah, Ibrahim; Bogatu, Coneliu

2017-01-01

Knowledge of nanomaterial toxicity is critical to avoid adverse effects on human and environment health. In this study, the influences of crystal morphology on physico-chemical and toxic properties of nanoscale TiO2 (n-TiO2) were investigated. Artemia salina were exposed to anatase, rutile and mixture polymorphs of n-TiO2 in seawater. Short-term (24 h) and long-term (96 h) exposures were conducted in 1, 10 and 100 mg/L suspensions of n-TiO2 in the presence and absence of food. Anatase form had highest accumulation followed by mixture and rutile. Presence of food greatly reduced accumulation. n-TiO2 dissolution was not significant in seawater (p<0.05) nor was influenced from crystal structure. Highest toxic effects occurred in 96h exposure in the order of anatase > mixture > rutile. Mortality and oxidative stress levels increased with increasing n-TiO2 concentration and exposure time (p<0.05). Presence of food in the exposure medium alleviated the oxidative stress, indicating that deprivation from food could promote toxic effects of n-TiO2 under long-term exposure. PMID:29333492

Preclinical evaluations of norcantharidin-loaded intravenous lipid microspheres with low toxicity.

PubMed

Lin, Xia; Zhang, Bo; Zhang, Keru; Zhang, Yu; Wang, Juan; Qi, Na; Yang, Shenshen; He, Haibing; Tang, Xing

2012-12-01

The aim of this study was to perform a systematic preclinical evaluation of norcantharidin (NCTD)-loaded intravenous lipid microspheres (NLM). Pharmacokinetics, biodistribution, antitumor efficacy and drug safety assessment (including acute toxicity, subchronic toxicity, hemolysis testing, intravenous stimulation and injection anaphylaxis) of NLM were carried out in comparison with the commercial product disodium norcantharidate injection (NI). The pharmacokinetics of NLM in rats was similar to that of NI, and a non-linear correlation was observed between AUC and dose. A comparable antitumor efficacy of NLM and NI was observed in mice inoculated with A549, BEL7402 and BCAP-37 cell lines. It was worth noting that the NLM produced a lower drug concentration in heart compared with NI, and significantly reduced the cardiac and renal toxicity. The LD(50) of NLM was twice higher than that of NI. In NLM, over 80% of NCTD was loaded in the lipid phase or bound with phospholipids. Thus, NCTD was sequestered by direct contacting with body fluids and largely avoided distribution into tissues, consequently leading to significantly reduced cardiac and renal toxicity. These preclinical results suggested that NLM could be a useful potential carrier for parenteral administration of NCTD, while providing a superior safety profile.

Linking waterlogging tolerance with Mn²⁺ toxicity: a case study for barley.

PubMed

Huang, X; Shabala, S; Shabala, L; Rengel, Z; Wu, X; Zhang, G; Zhou, M

2015-01-01

Vast agricultural areas are affected by flooding, causing up to 80% yield reduction and resulting in multibillion dollar losses. Up to now, the focus of plant breeders was predominantly on detrimental effects of anoxia, while other (potentially equally important) traits were essentially neglected; one of these is soil elemental toxicity. Excess water triggers a progressive decrease in soil redox potential, thus increasing the concentration of Mn(2+) that can be toxic to plants if above a specific threshold. This work aimed to quantify the relative contribution of Mn(2+) toxicity to waterlogging stress tolerance, using barley as a case study. Twenty barley (Hordeum vulgare) genotypes contrasting in waterlogging stress tolerance were studied for their ability to cope with toxic (1 mm) amounts of Mn(2+) in the root rhizosphere. Under Mn(2+) toxicity, chlorophyll content of most waterlogging-tolerant genotypes (TX9425, Yerong, CPI-71284-48 and CM72) remained above 60% of the control value, whereas sensitive genotypes (Franklin and Naso Nijo) had 35% less chlorophyll than 35% of controls. Manganese concentration in leaves was not related to visual Mn(2+) toxicity symptoms, suggesting that various Mn(2+) tolerance mechanisms might operate in different tolerant genotypes, i.e. avoidance versus tissue tolerance. The overall significant (r = 0.60) correlation between tolerance to Mn(2+) toxicity and waterlogging in barley suggests that plant breeding for tolerance to waterlogging traits may be advanced by targeting mechanisms conferring tolerance to Mn(2+) toxicity, at least in this species. © 2014 German Botanical Society and The Royal Botanical Society of the Netherlands.

Daily chlorhexidine bathing does not increase skin toxicity after remission induction or stem cell transplantation.

PubMed

Deeren, Dries; Dewulf, Evelyne; Verfaillie, Lydie

2016-12-01

A recent multicenter study demonstrated that bathing with chlorhexidine reduces the transmission of resistant organisms and the risk of hospital-acquired bloodstream infections in ICUs. We wanted to confirm the feasibility of this strategy in a cohort of patients in a typical intensive haematology unit. Patients treated with remission induction chemotherapy, autologous or allogeneic stem cell transplantation received daily chlorhexidine bathing. To avoid deshydratation of skin, we used prophylactic application of hydrating lotion, replaced by corticosteroid cream in case of skin toxicity of chemotherapy or conditioning. We studied 15 consecutive admissions of 12 patients. Daily chlorhexidine bathing never needed to be interrupted, even though 53% of patients were treated with intravenous cytarabine. Patients were satisfied with the skin treatment and reported few unwanted effects. Daily chlorhexidine bathing was feasible in our intensive haematology unit in all patients and did not increase skin toxicity, even when treated with IV cytarabine.

Management of toxic cyanobacteria for drinking water production of Ain Zada Dam.

PubMed

Saoudi, Amel; Brient, Luc; Boucetta, Sabrine; Ouzrout, Rachid; Bormans, Myriam; Bensouilah, Mourad

2017-07-01

Blooms of toxic cyanobacteria in Algerian reservoirs represent a potential health problem, mainly from drinking water that supplies the local population of Ain Zada (Bordj Bou Arreridj). The objective of this study is to monitor, detect, and identify the existence of cyanobacteria and microcystins during blooming times. Samples were taken in 2013 from eight stations. The results show that three potentially toxic cyanobacterial genera with the species Planktothrix agardhii were dominant. Cyanobacterial biomass, phycocyanin (PC) concentrations, and microcystin (MC) concentrations were high in the surface layer and at 14 m depth; these values were also high in the treated water. On 11 May 2013, MC concentrations were 6.3 μg/L in MC-LR equivalent in the drinking water. This study shows for the first time the presence of cyanotoxins in raw and treated waters, highlighting that regular monitoring of cyanobacteria and cyanotoxins must be undertaken to avoid potential health problems.

Heterogeneous photocatalysis using TiO2 modified with hydrotalcite and iron oxide under UV-visible irradiation for color and toxicity reduction in secondary textile mill effluent.

PubMed

Arcanjo, Gemima Santos; Mounteer, Ann H; Bellato, Carlos Roberto; Silva, Laís Miguelina Marçal da; Brant Dias, Santos Henrique; Silva, Priscila Romana da

2018-04-01

The objective of this study was to evaluate ADMI color removal from a biologically treated textile mill effluent by heterogeneous photocatalysis with UV-visible irradiation (UV-vis) using a novel catalyst composed of TiO 2 supported on hydrotalcite and doped with iron oxide (HT/Fe/TiO 2 ). Simulated biological treatment of solutions of the dyes (50 mg/L) used in the greatest amounts at the mill where the textile effluent was collected resulted in no color removal in reactive dye solutions and about 50% color removal in vat dye solutions, after 96 h, indicating that the secondary effluent still contained a large proportion of anionic reactive dyes. Photocatalytic treatments were carried out with TiO 2 and HT/Fe/TiO 2 of Fe:Ti molar ratios of 0.25, 0.5, 0.75 and 1, with varying catalyst doses (0-3 mg/L), initial pH values (4-10) and UV-vis times (0-6 h). The highest ADMI color removal with unmodified TiO 2 was found at a dose of 2 g/L and pH 4, an impractical pH value for industrial application. The most efficient composite was HT/Fe/TiO 2 1 at pH 10, also at a dose of 2 g/L, which provided more complete ADMI color removal, from 303 to 9 ADMI color units (96%), than unmodified TiO 2 , from 303 to 37 ADMI color units (88%), under the same conditions. Hydroxyl radicals were responsible for the color reduction, since when 2-propanol, an OH scavenger, was added color removal was very low. For this reason, the HT/Fe/TiO 2 1 composite performed better at pH 10, because the higher concentration of hydroxide ions present at higher pH favored hydroxyl radical formation. COD reductions were relatively low and similar, approximately 20% for both catalysts after 6 h under UV-vis, because of the low initial COD (78 mg/L). Secondary effluent toxicity to Daphnia similis (EC 50  = 70.7%) was reduced by photocatalysis with TiO 2 (EC 50  = 95.0%) and the HT/Fe/TiO 2 1 composite (EC 50  = 78.6%). HT/Fe/TiO 2 1 was reused five times and still lowered secondary effluent ADMI color below local discharge limits. Benefits of the HT/Fe/TiO 2 1 catalyst compared to TiO 2 include its lower bandgap energy (2.34 eV vs 3.25 eV), higher ADMI color removal and its magnetic nature that facilitated its recovery and would reduce treatment costs. Copyright © 2018 Elsevier Ltd. All rights reserved.

Asymmetric synthesis of N-allylic indoles via regio- and enantioselective allylation of aryl hydrazines

PubMed Central

Xu, Kun; Gilles, Thomas; Breit, Bernhard

2015-01-01

The asymmetric synthesis of N-allylic indoles is important for natural product synthesis and pharmaceutical research. The regio- and enantioselective N-allylation of indoles is a true challenge due to the favourable C3-allylation. We develop here a new strategy to the asymmetric synthesis of N-allylic indoles via rhodium-catalysed N-selective coupling of aryl hydrazines with allenes followed by Fischer indolization. The exclusive N-selectivities and good to excellent enantioselectivities are achieved applying a rhodium(I)/DTBM-Segphos or rhodium(I)/DTBM-Binap catalyst. This method permits the practical synthesis of valuable chiral N-allylated indoles, and avoids the N- or C-selectivity issue. PMID:26137886

Carbon dioxide electrolysis with solid oxide electrolyte cells for oxygen recovery in life support systems

NASA Technical Reports Server (NTRS)

Isenberg, Arnold O.; Cusick, Robert J.

1988-01-01

The direct electrochemical reduction of carbon dioxide (CO2) is achieved without catalysts and at sufficiently high temperatures to avoid carbon formation. The tubular electrolysis cell consists of thin layers of anode, electrolyte, cathode and cell interconnection. The electrolyte is made from yttria-stabilized zirconia which is an oxygen ion conductor at elevated temperatures. Anode and cell interconnection materials are complex oxides and are electronic conductors. The cathode material is a composite metal-ceramic structure. Cell performance characteristics have been determined using varying feed gas compositions and degrees of electrochemical decomposition. Cell test data are used to project the performance of a three-person CO2-electrolysis breadboard system.