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

Yan, Hao; Yang, Fan; Pan, Ding

Mechanical stimuli can modify the energy landscape of chemical reactions and enable reaction pathways, offering a synthetic strategy that complements conventional chemistry. These mechanochemical mechanisms have been studied extensively in one-dimensional polymers under tensile stress using ring-opening and reorganization, polymer unzipping and disulfide reduction as model reactions. In these systems, the pulling force stretches chemical bonds, initiating the reaction. Additionally, it has been shown that forces orthogonal to the chemical bonds can alter the rate of bond dissociation. Furthermore, these bond activation mechanisms have not been possible under isotropic, compressive stress (that is, hydrostatic pressure). Here we show that mechanochemistrymore » through isotropic compression is possible by molecularly engineering structures that can translate macroscopic isotropic stress into molecular-level anisotropic strain.« less

40 CFR 721.9285 - Reaction products of formalin (37%) with amine C12.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction products of formalin (37... Specific Chemical Substances § 721.9285 Reaction products of formalin (37%) with amine C12. (a) Chemical... as reaction products of formalin (37%) with amine C12 (PMN P-95-535) is subject to reporting under...

40 CFR 721.9285 - Reaction products of formalin (37%) with amine C12.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction products of formalin (37... Specific Chemical Substances § 721.9285 Reaction products of formalin (37%) with amine C12. (a) Chemical... as reaction products of formalin (37%) with amine C12 (PMN P-95-535) is subject to reporting under...

Perspective: Chemical reactions in ionic liquids monitored through the gas (vacuum)/liquid interface.

PubMed

Maier, F; Niedermaier, I; Steinrück, H-P

2017-05-07

This perspective analyzes the potential of X-ray photoelectron spectroscopy under ultrahigh vacuum (UHV) conditions to follow chemical reactions in ionic liquids in situ. Traditionally, only reactions occurring on solid surfaces were investigated by X-ray photoelectron spectroscopy (XPS) in situ. This was due to the high vapor pressures of common liquids or solvents, which are not compatible with the required UHV conditions. It was only recently realized that the situation is very different when studying reactions in Ionic Liquids (ILs), which have an inherently low vapor pressure, and first studies have been performed within the last years. Compared to classical spectroscopy techniques used to monitor chemical reactions, the advantage of XPS is that through the analysis of their core levels all relevant elements can be quantified and their chemical state can be analyzed under well-defined (ultraclean) conditions. In this perspective, we cover six very different reactions which occur in the IL, with the IL, or at an IL/support interface, demonstrating the outstanding potential of in situ XPS to gain insights into liquid phase reactions in the near-surface region.

One- and two-dimensional chemical exchange nuclear magnetic resonance studies of the creatine kinase catalyzed reaction

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

Gober, J.R.

1988-01-01

The equilibrium chemical exchange dynamics of the creatine kinase enzyme system were studied by one- and two-dimensional {sup 31}P NMR techniques. Pseudo-first-order reaction rate constants were measured by the saturation transfer method under an array of experimental conditions of pH and temperature. Quantitative one-dimensional spectra were collected under the same conditions in order to calculate the forward and reverse reaction rates, the K{sub eq}, the hydrogen ion stoichiometry, and the standard thermodynamic functions. The pure absorption mode in four quadrant two-dimensional chemical exchange experiment was employed so that the complete kinetic matrix showing all of the chemical exchange process couldmore » be realized.« less

In Situ Treatment and Management Strategies for 1,4-Dioxane-Contaminated Groundwater

DTIC Science & Technology

2017-05-05

microorganisms thrived during the biodegradation process. This was consistent with oxidation process that biodiversity was inhibited by the chemical reaction ...exhibit a strong inhibitory impact on CB1190-like bacteria (Figure 79). However, in well 8MNW54, inhibitory impacts of chemical reactions were clear...inhibited again, indicating that chemical reactions along with high CVOCs levels had widely-varying impacts on microorganisms. Specifically, under low DX

Population dynamics, information transfer, and spatial organization in a chemical reaction network under spatial confinement and crowding conditions

NASA Astrophysics Data System (ADS)

Bellesia, Giovanni; Bales, Benjamin B.

2016-10-01

We investigate, via Brownian dynamics simulations, the reaction dynamics of a generic, nonlinear chemical network under spatial confinement and crowding conditions. In detail, the Willamowski-Rossler chemical reaction system has been "extended" and considered as a prototype reaction-diffusion system. Our results are potentially relevant to a number of open problems in biophysics and biochemistry, such as the synthesis of primitive cellular units (protocells) and the definition of their role in the chemical origin of life and the characterization of vesicle-mediated drug delivery processes. More generally, the computational approach presented in this work makes the case for the use of spatial stochastic simulation methods for the study of biochemical networks in vivo where the "well-mixed" approximation is invalid and both thermal and intrinsic fluctuations linked to the possible presence of molecular species in low number copies cannot be averaged out.

A multi-purpose reaction cell for the investigation of reactions under solvothermal conditions

NASA Astrophysics Data System (ADS)

Heidenreich, N.; Rütt, U.; Köppen, M.; Inge, A. Ken; Beier, S.; Dippel, A.-C.; Suren, R.; Stock, N.

2017-10-01

A new versatile and easy-to-use remote-controlled reactor setup aimed at the analysis of chemical reactions under solvothermal conditions has been constructed. The reactor includes a heating system that can precisely control the temperature inside the reaction vessels in a range between ambient temperature and 180 °C. As reaction vessels, two sizes of commercially available borosilicate vessels (Vmax = 5 and 11 ml) can be used. The setup furthermore includes the option of stirring and injecting of up to two liquid additives or one solid during the reaction to initiate very fast reactions, quench reactions, or alter chemical parameters. In addition to a detailed description of the general setup and its functionality, three examples of studies conducted using this setup are presented.

Fundamental insights into interfacial catalysis.

PubMed

Gong, Jinlong; Bao, Xinhe

2017-04-03

Surface and interfacial catalysis plays a vital role in chemical industries, electrochemistry and photochemical reactions. The challenges of modern chemistry are to optimize the chemical reaction processes and understand the detailed mechanism of chemical reactions. Since the early 1960s, the foundation of surface science systems has allowed the study of surface and interfacial phenomena on atomic/molecular level, and thus brought a number of significant developments to fundamental and technological processes, such as catalysis, material science and biochemistry, just to name a few. This themed issue describes the recent advances and developments in the fundamental understanding of surface and interfacial catalysis, encompassing areas of knowledge from metal to metal oxide, carbide, graphene, hexagonal boron nitride, and transition metal dichalcogenides under ultrahigh vacuum conditions, as well as under realistic reaction conditions.

Experimental Study on Reaction Characteristics of PTFE/Ti/W Energetic Materials under Explosive Loading

PubMed Central

Li, Yan; Jiang, Chunlan; Wang, Zaicheng; Luo, Puguang

2016-01-01

Metal/fluoropolymer composites represent a new category of energetic structural materials that release energy through exothermic chemical reactions initiated under shock loading conditions. This paper describes an experiment designed to study the reaction characteristics of energetic materials with low porosity under explosive loading. Three PTFE (polytetrafluoroethylene)/Ti/W mixtures with different W contents are processed through pressing and sintering. An inert PTFE/W mixture without reactive Ti particles is also prepared to serve as a reference. Shock-induced chemical reactions are recorded by high-speed video through a narrow observation window. Related shock parameters are calculated based on experimental data, and differences in energy release are discussed. The results show that the reaction propagation of PTFE/Ti/W energetic materials with low porosity under explosive loading is not self-sustained. As propagation distance increases, the energy release gradually decreases. In addition, reaction failure distance in PTFE/Ti/W composites is inversely proportional to the W content. Porosity increased the failure distance due to higher shock temperature. PMID:28774056

Topical Hazard Evaluation Program of Candidate Insect Repellent A13-38349a US Department of Agriculture Proprietary Chemicals, July 1981-January 1983.

DTIC Science & Technology

1983-08-16

reaction (w/v) Oil of Bergamot irritation reaction under test (positive control) in 95% under test conditions and is ethyl alcohol was conditions, not...the rabbits, 0.05 mL cation and irradiation of the test chemical, caused greater irritant positive control (oil of effects than in un- Bergamot ) and

Consistency and Inconsistency in A Level Students' Understandings of a Number of Chemical Reactions.

ERIC Educational Resources Information Center

Kwen, Boo Hong

1996-01-01

Explores A level students' conceptions of some common chemical reactions. Findings indicate that students apply frameworks consistently across groups of events that they perceive to be similar. What was found to be lacking was the scientists' view of all the reactions being regarded as realizations of the same underlying conceptual model. Contains…

The Role of Electronic Excitations on Chemical Reaction Dynamics at Metal, Semiconductor and Nanoparticle Surfaces

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

Tully, John C.

Chemical reactions are often facilitated and steered when carried out on solid surfaces, essential for applications such as heterogeneous catalysis, solar energy conversion, corrosion, materials processing, and many others. A critical factor that can determine the rates and pathways of chemical reactions at surfaces is the efficiency and specificity of energy transfer; how fast does energy move around and where does it go? For reactions on insulator surfaces energy transfer generally moves in and out of vibrations of the adsorbed molecule and the underlying substrate. By contrast, on metal surfaces, metallic nanoparticles and semiconductors, another pathway for energy flow opensmore » up, excitation and de-excitation of electrons. This so-called “nonadiabatic” mechanism often dominates the transfer of energy and can directly impact the course of a chemical reaction. Conventional computational methods such as molecular dynamics simulation do not account for this nonadiabatic behavior. The current DOE-BES funded project has focused on developing the underlying theoretical foundation and the computational methodology for the prediction of nonadiabatic chemical reaction dynamics at surfaces. The research has successfully opened up new methodology and new applications for molecular simulation. In particular, over the last three years, the “Electronic Friction” theory, pioneered by the PI, has now been developed into a stable and accurate computational method that is sufficiently practical to allow first principles “on-the-fly” simulation of chemical reaction dynamics at metal surfaces.« less

Optimizing Chemical Reactions with Deep Reinforcement Learning.

PubMed

Zhou, Zhenpeng; Li, Xiaocheng; Zare, Richard N

2017-12-27

Deep reinforcement learning was employed to optimize chemical reactions. Our model iteratively records the results of a chemical reaction and chooses new experimental conditions to improve the reaction outcome. This model outperformed a state-of-the-art blackbox optimization algorithm by using 71% fewer steps on both simulations and real reactions. Furthermore, we introduced an efficient exploration strategy by drawing the reaction conditions from certain probability distributions, which resulted in an improvement on regret from 0.062 to 0.039 compared with a deterministic policy. Combining the efficient exploration policy with accelerated microdroplet reactions, optimal reaction conditions were determined in 30 min for the four reactions considered, and a better understanding of the factors that control microdroplet reactions was reached. Moreover, our model showed a better performance after training on reactions with similar or even dissimilar underlying mechanisms, which demonstrates its learning ability.

Catalytic and reactive polypeptides and methods for their preparation and use

DOEpatents

Schultz, Peter

1994-01-01

Catalytic and reactive polypeptides include a binding site specific for a reactant or reactive intermediate involved in a chemical reaction of interest. The polypeptides further include at least one active functionality proximate the binding site, where the active functionality is capable of catalyzing or chemically participating in the chemical reaction in such a way that the reaction rate is enhanced. Methods for preparing the catalytic peptides include chemical synthesis, site-directed mutagenesis of antibody and enzyme genes, covalent attachment of the functionalities through particular amino acid side chains, and the like. This invention was made with Government support under Grant Contract No. AI-24695, awarded by the Department of health and Human Services, and under Grant Contract No. N 00014-87-K-0256, awarded by the Office of Naval Research. The Government has certain rights in this invention.

Population dynamics, information transfer, and spatial organization in a chemical reaction network under spatial confinement and crowding conditions

DOE PAGES

Bellesia, Giovanni; Bales, Benjamin B.

2016-10-10

Here, we investigate, via Brownian dynamics simulations, the reaction dynamics of a generic, nonlinear chemical network under spatial confinement and crowding conditions. In detail, the Willamowski-Rossler chemical reaction system has been “extended” and considered as a prototype reaction-diffusion system. These results are potentially relevant to a number of open problems in biophysics and biochemistry, such as the synthesis of primitive cellular units (protocells) and the definition of their role in the chemical origin of life and the characterization of vesicle-mediated drug delivery processes. More generally, the computational approach presented in this work makes the case for the use of spatialmore » stochastic simulation methods for the study of biochemical networks in vivo where the “well-mixed” approximation is invalid and both thermal and intrinsic fluctuations linked to the possible presence of molecular species in low number copies cannot be averaged out.« less

Research on the Treatment of Aluminum Alloy Chemical Milling Wastewater with Fenton Process

NASA Astrophysics Data System (ADS)

Zong-liang, Huang; Ru, Li; Peng, Luo; Jun-li, Gu

2018-03-01

The aluminum alloy chemical milling wastewater was treated by Fenton method. The effect of pH value, reaction time, rotational speed, H2O2 dosage, Fe2+ dosage and the molar ratio between H2O2 and Fe2+ on the COD removal rate of aluminum alloy chemical milling wastewater were investigated by single factor experiment and orthogonal experiment. The results showed that the optimum operating conditions for Fenton oxidation were as follows: the initial pH value was 3, the rotational speed was 250r/min, the molar ratio of H2O2 and Fe2+ was 8, the reaction time was 90 min. Under the optimum conditions, the removal rate of the wastewater’s COD is about 72.36%. In the reaction kinetics that aluminum alloy chemical milling wastewater was oxidized and degraded by Fenton method under the optimum conditions, the reaction sequence of the initial COD was 0.8204.

Effect of Molecule–Surface Reaction Mechanism on the Electronic Characteristics and Photovoltaic Performance of Molecularly Modified Si

PubMed Central

2013-01-01

We report on the passivation properties of molecularly modified, oxide-free Si(111) surfaces. The reaction of 1-alcohol with the H-passivated Si(111) surface can follow two possible paths, nucleophilic substitution (SN) and radical chain reaction (RCR), depending on adsorption conditions. Moderate heating leads to the SN reaction, whereas with UV irradiation RCR dominates, with SN as a secondary path. We show that the site-sensitive SN reaction leads to better electrical passivation, as indicated by smaller surface band bending and a longer lifetime of minority carriers. However, the surface-insensitive RCR reaction leads to more dense monolayers and, therefore, to much better chemical stability, with lasting protection of the Si surface against oxidation. Thus, our study reveals an inherent dissonance between electrical and chemical passivation. Alkoxy monolayers, formed under UV irradiation, benefit, though, from both chemical and electronic passivation because under these conditions both SN and RCR occur. This is reflected in longer minority carrier lifetimes, lower reverse currents in the dark, and improved photovoltaic performance, over what is obtained if only one of the mechanisms operates. These results show how chemical kinetics and reaction paths impact electronic properties at the device level. It further suggests an approach for effective passivation of other semiconductors. PMID:24205409

Optimizing Chemical Reactions with Deep Reinforcement Learning

PubMed Central

2017-01-01

Deep reinforcement learning was employed to optimize chemical reactions. Our model iteratively records the results of a chemical reaction and chooses new experimental conditions to improve the reaction outcome. This model outperformed a state-of-the-art blackbox optimization algorithm by using 71% fewer steps on both simulations and real reactions. Furthermore, we introduced an efficient exploration strategy by drawing the reaction conditions from certain probability distributions, which resulted in an improvement on regret from 0.062 to 0.039 compared with a deterministic policy. Combining the efficient exploration policy with accelerated microdroplet reactions, optimal reaction conditions were determined in 30 min for the four reactions considered, and a better understanding of the factors that control microdroplet reactions was reached. Moreover, our model showed a better performance after training on reactions with similar or even dissimilar underlying mechanisms, which demonstrates its learning ability. PMID:29296675

Effects of Variable Thermal Conductivity and Non-linear Thermal Radiation Past an Eyring Powell Nanofluid Flow with Chemical Reaction

NASA Astrophysics Data System (ADS)

Ramzan, M.; Bilal, M.; Kanwal, Shamsa; Chung, Jae Dong

2017-06-01

Present analysis discusses the boundary layer flow of Eyring Powell nanofluid past a constantly moving surface under the influence of nonlinear thermal radiation. Heat and mass transfer mechanisms are examined under the physically suitable convective boundary condition. Effects of variable thermal conductivity and chemical reaction are also considered. Series solutions of all involved distributions using Homotopy Analysis method (HAM) are obtained. Impacts of dominating embedded flow parameters are discussed through graphical illustrations. It is observed that thermal radiation parameter shows increasing tendency in relation to temperature profile. However, chemical reaction parameter exhibits decreasing behavior versus concentration distribution. Supported by the World Class 300 Project (No. S2367878) of the SMBA (Korea)

Chemical Continuous Time Random Walks

NASA Astrophysics Data System (ADS)

Aquino, T.; Dentz, M.

2017-12-01

Traditional methods for modeling solute transport through heterogeneous media employ Eulerian schemes to solve for solute concentration. More recently, Lagrangian methods have removed the need for spatial discretization through the use of Monte Carlo implementations of Langevin equations for solute particle motions. While there have been recent advances in modeling chemically reactive transport with recourse to Lagrangian methods, these remain less developed than their Eulerian counterparts, and many open problems such as efficient convergence and reconstruction of the concentration field remain. We explore a different avenue and consider the question: In heterogeneous chemically reactive systems, is it possible to describe the evolution of macroscopic reactant concentrations without explicitly resolving the spatial transport? Traditional Kinetic Monte Carlo methods, such as the Gillespie algorithm, model chemical reactions as random walks in particle number space, without the introduction of spatial coordinates. The inter-reaction times are exponentially distributed under the assumption that the system is well mixed. In real systems, transport limitations lead to incomplete mixing and decreased reaction efficiency. We introduce an arbitrary inter-reaction time distribution, which may account for the impact of incomplete mixing. This process defines an inhomogeneous continuous time random walk in particle number space, from which we derive a generalized chemical Master equation and formulate a generalized Gillespie algorithm. We then determine the modified chemical rate laws for different inter-reaction time distributions. We trace Michaelis-Menten-type kinetics back to finite-mean delay times, and predict time-nonlocal macroscopic reaction kinetics as a consequence of broadly distributed delays. Non-Markovian kinetics exhibit weak ergodicity breaking and show key features of reactions under local non-equilibrium.

Coexistence of wave propagation and oscillation in the photosensitive Belousov-Zhabotinsky reaction on a circular route.

PubMed

Nakata, Satoshi; Morishima, Sayaka; Ichino, Takatoshi; Kitahata, Hiroyuki

2006-12-21

The photosensitive Belousov-Zhabotinsky (BZ) reaction was investigated on a circular ring, which was drawn using computer software and then projected on a film soaked with BZ solution using a liquid-crystal projector. Under the initial conditions, a chemical wave propagated with a constant velocity on the black ring under a bright background. When the background was rapidly changed to dark, coexistence of the oscillation on part of the ring and propagation of the chemical wave on the other part was observed. These experimental results are discussed in relation to the nature of the photosensitive BZ reaction and theoretically reproduced based on a reaction-diffusion system using the modified Oregonator model.

High speed turbulent reacting flows: DNS and LES

NASA Technical Reports Server (NTRS)

Givi, Peyman

1990-01-01

Work on understanding the mechanisms of mixing and reaction in high speed turbulent reacting flows was continued. Efforts, in particular, were concentrated on taking advantage of modern computational methods to simulate high speed turbulent flows. In doing so, two methodologies were used: large eddy simulations (LES) and direct numerical simulations (DNS). In the work related with LES the objective is to study the behavior of the probability density functions (pdfs) of scalar properties within the subgrid in reacting turbulent flows. The data base obtained by DNS for a detailed study of the pdf characteristics within the subgrid was used. Simulations are performed for flows under various initializations to include the effects of compressibility on mixing and chemical reactions. In the work related with DNS, a two-dimensional temporally developing high speed mixing layer under the influence of a second-order non-equilibrium chemical reaction of the type A + B yields products + heat was considered. Simulations were performed with different magnitudes of the convective Mach numbers and with different chemical kinetic parameters for the purpose of examining the isolated effects of the compressibility and the heat released by the chemical reactions on the structure of the layer. A full compressible code was developed and utilized, so that the coupling between mixing and chemical reactions is captured in a realistic manner.

Finding Chemical Reaction Paths with a Multilevel Preconditioning Protocol

PubMed Central

2015-01-01

Finding transition paths for chemical reactions can be computationally costly owing to the level of quantum-chemical theory needed for accuracy. Here, we show that a multilevel preconditioning scheme that was recently introduced (Tempkin et al. J. Chem. Phys.2014, 140, 184114) can be used to accelerate quantum-chemical string calculations. We demonstrate the method by finding minimum-energy paths for two well-characterized reactions: tautomerization of malonaldehyde and Claissen rearrangement of chorismate to prephanate. For these reactions, we show that preconditioning density functional theory (DFT) with a semiempirical method reduces the computational cost for reaching a converged path that is an optimum under DFT by several fold. The approach also shows promise for free energy calculations when thermal noise can be controlled. PMID:25516726

Chemical-Reaction-Controlled Phase Separated Drops: Formation, Size Selection, and Coarsening

NASA Astrophysics Data System (ADS)

Wurtz, Jean David; Lee, Chiu Fan

2018-02-01

Phase separation under nonequilibrium conditions is exploited by biological cells to organize their cytoplasm but remains poorly understood as a physical phenomenon. Here, we study a ternary fluid model in which phase-separating molecules can be converted into soluble molecules, and vice versa, via chemical reactions. We elucidate using analytical and simulation methods how drop size, formation, and coarsening can be controlled by the chemical reaction rates, and categorize the qualitative behavior of the system into distinct regimes. Ostwald ripening arrest occurs above critical reaction rates, demonstrating that this transition belongs entirely to the nonequilibrium regime. Our model is a minimal representation of the cell cytoplasm.

The mineralogic evolution of the Martian surface through time: Implications from chemical reaction path modeling studies

NASA Technical Reports Server (NTRS)

Plumlee, G. S.; Ridley, W. I.; Debraal, J. D.; Reed, M. H.

1993-01-01

Chemical reaction path calculations were used to model the minerals that might have formed at or near the Martian surface as a result of volcano or meteorite impact driven hydrothermal systems; weathering at the Martian surface during an early warm, wet climate; and near-zero or sub-zero C brine-regolith reactions in the current cold climate. Although the chemical reaction path calculations carried out do not define the exact mineralogical evolution of the Martian surface over time, they do place valuable geochemical constraints on the types of minerals that formed from an aqueous phase under various surficial and geochemically complex conditions.

Development of a Computational Chemical Vapor Deposition Model: Applications to Indium Nitride and Dicyanovinylaniline

NASA Technical Reports Server (NTRS)

Cardelino, Carlos

1999-01-01

A computational chemical vapor deposition (CVD) model is presented, that couples chemical reaction mechanisms with fluid dynamic simulations for vapor deposition experiments. The chemical properties of the systems under investigation are evaluated using quantum, molecular and statistical mechanics models. The fluid dynamic computations are performed using the CFD-ACE program, which can simulate multispecies transport, heat and mass transfer, gas phase chemistry, chemistry of adsorbed species, pulsed reactant flow and variable gravity conditions. Two experimental setups are being studied, in order to fabricate films of: (a) indium nitride (InN) from the gas or surface phase reaction of trimethylindium and ammonia; and (b) 4-(1,1)dicyanovinyl-dimethylaminoaniline (DCVA) by vapor deposition. Modeling of these setups requires knowledge of three groups of properties: thermodynamic properties (heat capacity), transport properties (diffusion, viscosity, and thermal conductivity), and kinetic properties (rate constants for all possible elementary chemical reactions). These properties are evaluated using computational methods whenever experimental data is not available for the species or for the elementary reactions. The chemical vapor deposition model is applied to InN and DCVA. Several possible InN mechanisms are proposed and analyzed. The CVD model simulations of InN show that the deposition rate of InN is more efficient when pulsing chemistry is used under conditions of high pressure and microgravity. An analysis of the chemical properties of DCVA show that DCVA dimers may form under certain conditions of physical vapor transport. CVD simulations of the DCVA system suggest that deposition of the DCVA dimer may play a small role in the film and crystal growth processes.

Development and application of bond cleavage reactions in bioorthogonal chemistry.

PubMed

Li, Jie; Chen, Peng R

2016-03-01

Bioorthogonal chemical reactions are a thriving area of chemical research in recent years as an unprecedented technique to dissect native biological processes through chemistry-enabled strategies. However, current concepts of bioorthogonal chemistry have largely centered on 'bond formation' reactions between two mutually reactive bioorthogonal handles. Recently, in a reverse strategy, a collection of 'bond cleavage' reactions has emerged with excellent biocompatibility. These reactions have expanded our bioorthogonal chemistry repertoire, enabling an array of exciting new biological applications that range from the chemically controlled spatial and temporal activation of intracellular proteins and small-molecule drugs to the direct manipulation of intact cells under physiological conditions. Here we highlight the development and applications of these bioorthogonal cleavage reactions. Furthermore, we lay out challenges and propose future directions along this appealing avenue of research.

Prediction of Hydrolysis Products of Organic Chemicals under Environmental pH Conditions

EPA Science Inventory

Cheminformatics-based software tools can predict the molecular structure of transformation products using a library of transformation reaction schemes. This paper presents the development of such a library for abiotic hydrolysis of organic chemicals under environmentally relevant...

Oxidation of dissolved iron under warmer, wetter conditions on Mars: Transitions to present-day arid environments

NASA Technical Reports Server (NTRS)

Burns, R. G.

1993-01-01

The copious deposits of ferric-iron assemblages littering the surface of bright regions of Mars indicate that efficient oxidative weathering reactions have taken place during the evolution of the planet. Because the kinetics of atmosphere-surface (gas-solid) reactions are considerably slower than chemical weathering reactions involving an aqueous medium, most of the oxidation products now present in the martian regolith probably formed when groundwater flowed near the surface. This paper examines how chemical weathering reactions were effected by climatic variations when warm, wet environments became arid on Mars. Analogies are drawn with hydrogeochemical and weathering environments on the Australian continent where present-day oxidation of iron is occurring in acidic ground water under arid conditions.

Modular verification of chemical reaction network encodings via serializability analysis

PubMed Central

Lakin, Matthew R.; Stefanovic, Darko; Phillips, Andrew

2015-01-01

Chemical reaction networks are a powerful means of specifying the intended behaviour of synthetic biochemical systems. A high-level formal specification, expressed as a chemical reaction network, may be compiled into a lower-level encoding, which can be directly implemented in wet chemistry and may itself be expressed as a chemical reaction network. Here we present conditions under which a lower-level encoding correctly emulates the sequential dynamics of a high-level chemical reaction network. We require that encodings are transactional, such that their execution is divided by a “commit reaction” that irreversibly separates the reactant-consuming phase of the encoding from the product-generating phase. We also impose restrictions on the sharing of species between reaction encodings, based on a notion of “extra tolerance”, which defines species that may be shared between encodings without enabling unwanted reactions. Our notion of correctness is serializability of interleaved reaction encodings, and if all reaction encodings satisfy our correctness properties then we can infer that the global dynamics of the system are correct. This allows us to infer correctness of any system constructed using verified encodings. As an example, we show how this approach may be used to verify two- and four-domain DNA strand displacement encodings of chemical reaction networks, and we generalize our result to the limit where the populations of helper species are unlimited. PMID:27325906

An Iodine Fluorescence Quenching Clock Reaction

ERIC Educational Resources Information Center

Weinberg, Richard B.; Muyskens, Mark

2007-01-01

Clock reactions based upon competing oxidation and reduction reactions of iodine and starch as the most popular type of chemistry example is presented to illustrate the redox phenomena, reaction kinetics, and principles of chemical titration. The examination of the photophysical principles underlying the iodine fluorescence quenching clock…

Toward a reaction rate model of condensed-phase RDX decomposition under high temperatures

NASA Astrophysics Data System (ADS)

Schweigert, Igor

2014-03-01

Shock ignition of energetic molecular solids is driven by microstructural heterogeneities, at which even moderate stresses can result in sufficiently high temperatures to initiate material decomposition and the release of the chemical energy. Mesoscale modeling of these ``hot spots'' requires a chemical reaction rate model that describes the energy release with a sub-microsecond resolution and under a wide range of temperatures. No such model is available even for well-studied energetic materials such as RDX. In this presentation, I will describe an ongoing effort to develop a reaction rate model of condensed-phase RDX decomposition under high temperatures using first-principles molecular dynamics, transition-state theory, and reaction network analysis. This work was supported by the Naval Research Laboratory, by the Office of Naval Research, and by the DOD High Performance Computing Modernization Program Software Application Institute for Multiscale Reactive Modeling of Insensitive Munitions.

40 CFR 721.10000 - Certain polybrominated diphenylethers.

Code of Federal Regulations, 2013 CFR

2013-07-01

... combination of these substances resulting from a chemical reaction are subject to reporting under this section...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10000 Certain polybrominated diphenylethers. (a) Chemical substances and...

40 CFR 721.10000 - Certain polybrominated diphenylethers.

Code of Federal Regulations, 2010 CFR

2010-07-01

... combination of these substances resulting from a chemical reaction are subject to reporting under this section...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10000 Certain polybrominated diphenylethers. (a) Chemical substances and...

40 CFR 721.10000 - Certain polybrominated diphenylethers.

Code of Federal Regulations, 2014 CFR

2014-07-01

... combination of these substances resulting from a chemical reaction are subject to reporting under this section...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10000 Certain polybrominated diphenylethers. (a) Chemical substances and...

40 CFR 721.10000 - Certain polybrominated diphenylethers.

Code of Federal Regulations, 2012 CFR

2012-07-01

... combination of these substances resulting from a chemical reaction are subject to reporting under this section...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10000 Certain polybrominated diphenylethers. (a) Chemical substances and...

40 CFR 721.10000 - Certain polybrominated diphenylethers.

Code of Federal Regulations, 2011 CFR

2011-07-01

... combination of these substances resulting from a chemical reaction are subject to reporting under this section...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10000 Certain polybrominated diphenylethers. (a) Chemical substances and...

Molecular Beam Studies of Hot Atom Chemical Reactions: Reactive Scattering of Energetic Deuterium Atoms

DOE R&D Accomplishments Database

Continetti, R. E.; Balko, B. A.; Lee, Y. T.

1989-02-01

A brief review of the application of the crossed molecular beams technique to the study of hot atom chemical reactions in the last twenty years is given. Specific emphasis is placed on recent advances in the use of photolytically produced energetic deuterium atoms in the study of the fundamental elementary reactions D + H{sub 2} -> DH + H and the substitution reaction D + C{sub 2}H{sub 2} -> C{sub 2}HD + H. Recent advances in uv laser and pulsed molecular beam techniques have made the detailed study of hydrogen atom reactions under single collision conditions possible.

Surface- and Tip-Enhanced Raman Spectroscopy in Catalysis

PubMed Central

2016-01-01

Surface- and tip-enhanced Raman spectroscopy (SERS and TERS) techniques exhibit highly localized chemical sensitivity, making them ideal for studying chemical reactions, including processes at catalytic surfaces. Catalyst structures, adsorbates, and reaction intermediates can be observed in low quantities at hot spots where electromagnetic fields are the strongest, providing ample opportunities to elucidate reaction mechanisms. Moreover, under ideal measurement conditions, it can even be used to trigger chemical reactions. However, factors such as substrate instability and insufficient signal enhancement still limit the applicability of SERS and TERS in the field of catalysis. By the use of sophisticated colloidal synthesis methods and advanced techniques, such as shell-isolated nanoparticle-enhanced Raman spectroscopy, these challenges could be overcome. PMID:27075515

Sterically controlled mechanochemistry under hydrostatic pressure

NASA Astrophysics Data System (ADS)

Yan, Hao; Yang, Fan; Pan, Ding; Lin, Yu; Hohman, J. Nathan; Solis-Ibarra, Diego; Li, Fei Hua; Dahl, Jeremy E. P.; Carlson, Robert M. K.; Tkachenko, Boryslav A.; Fokin, Andrey A.; Schreiner, Peter R.; Galli, Giulia; Mao, Wendy L.; Shen, Zhi-Xun; Melosh, Nicholas A.

2018-02-01

Mechanical stimuli can modify the energy landscape of chemical reactions and enable reaction pathways, offering a synthetic strategy that complements conventional chemistry. These mechanochemical mechanisms have been studied extensively in one-dimensional polymers under tensile stress using ring-opening and reorganization, polymer unzipping and disulfide reduction as model reactions. In these systems, the pulling force stretches chemical bonds, initiating the reaction. Additionally, it has been shown that forces orthogonal to the chemical bonds can alter the rate of bond dissociation. However, these bond activation mechanisms have not been possible under isotropic, compressive stress (that is, hydrostatic pressure). Here we show that mechanochemistry through isotropic compression is possible by molecularly engineering structures that can translate macroscopic isotropic stress into molecular-level anisotropic strain. We engineer molecules with mechanically heterogeneous components—a compressible (‘soft’) mechanophore and incompressible (‘hard’) ligands. In these ‘molecular anvils’, isotropic stress leads to relative motions of the rigid ligands, anisotropically deforming the compressible mechanophore and activating bonds. Conversely, rigid ligands in steric contact impede relative motion, blocking reactivity. We combine experiments and computations to demonstrate hydrostatic-pressure-driven redox reactions in metal-organic chalcogenides that incorporate molecular elements that have heterogeneous compressibility, in which bending of bond angles or shearing of adjacent chains activates the metal-chalcogen bonds, leading to the formation of the elemental metal. These results reveal an unexplored reaction mechanism and suggest possible strategies for high-specificity mechanosynthesis.

Non-invasive estimation of dissipation from non-equilibrium fluctuations in chemical reactions.

PubMed

Muy, S; Kundu, A; Lacoste, D

2013-09-28

We show how to extract an estimate of the entropy production from a sufficiently long time series of stationary fluctuations of chemical reactions. This method, which is based on recent work on fluctuation theorems, is direct, non-invasive, does not require any knowledge about the underlying dynamics and is applicable even when only partial information is available. We apply it to simple stochastic models of chemical reactions involving a finite number of states, and for this case, we study how the estimate of dissipation is affected by the degree of coarse-graining present in the input data.

The Effective Concepts on Students' Understanding of Chemical Reactions and Energy

ERIC Educational Resources Information Center

Ayyildiz, Yildizay; Tarhan, Leman

2012-01-01

The purpose of this study was to determine the relationship between the basic concepts related to the unit of "Chemical Reactions and Energy" and the sub-concepts underlying for meaningful learning of the unit and to investigate the effectiveness of them on students' learning achievements. For this purpose, the basic concepts of the unit…

Ephemeral collision complexes mediate chemically termolecular transformations that affect system chemistry [Ephemeral collision complexes induce chemically termolecular transformations that affect global chemistry

DOE PAGES

Burke, Michael P.; Klippenstein, Stephen J.

2017-08-14

Termolecular association reactions involve ephemeral collision complexes—formed from the collision of two molecules—that collide with a third and chemically inert ‘bath gas’ molecule that simply transfers energy to/from the complex. These collision complexes are generally not thought to react chemically on collision with a third molecule in the gas-phase systems of combustion and planetary atmospheres. Such ‘chemically termolecular’ reactions, in which all three molecules are involved in bond making and/or breaking, were hypothesized long ago in studies establishing radical chain branching mechanisms, but were later concluded to be unimportant. Here, with data from ab initio master equation and kinetic-transport simulations,more » we reveal that reactions of H+O 2 collision complexes with other radicals constitute major kinetic pathways under common combustion situations. These reactions are also found to influence flame propagation speeds, a common measure of global reactivity. As a result, analogous chemically termolecular reactions mediated by ephemeral collision complexes are probably of significance in various combustion and planetary environments.« less

Ephemeral collision complexes mediate chemically termolecular transformations that affect system chemistry [Ephemeral collision complexes induce chemically termolecular transformations that affect global chemistry

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

Burke, Michael P.; Klippenstein, Stephen J.

Termolecular association reactions involve ephemeral collision complexes—formed from the collision of two molecules—that collide with a third and chemically inert ‘bath gas’ molecule that simply transfers energy to/from the complex. These collision complexes are generally not thought to react chemically on collision with a third molecule in the gas-phase systems of combustion and planetary atmospheres. Such ‘chemically termolecular’ reactions, in which all three molecules are involved in bond making and/or breaking, were hypothesized long ago in studies establishing radical chain branching mechanisms, but were later concluded to be unimportant. Here, with data from ab initio master equation and kinetic-transport simulations,more » we reveal that reactions of H+O 2 collision complexes with other radicals constitute major kinetic pathways under common combustion situations. These reactions are also found to influence flame propagation speeds, a common measure of global reactivity. As a result, analogous chemically termolecular reactions mediated by ephemeral collision complexes are probably of significance in various combustion and planetary environments.« less

Ion-Molecule Reactions and Chemical Composition of Emanated from Herculane Spa Geothermal Sources

PubMed Central

Cosma, Constantin; Suciu, Ioan; Jäntschi, Lorentz; Bolboacă, Sorana D.

2008-01-01

The paper presents a chemical composition analysis of the gases emanated from geothermal sources in the Herculane Spa area (Romania). The upper homologues of methane have been identified in these gases. An ion-molecule reaction mechanism could be implicated in the formation of the upper homologues of methane. The CH4+ ions that appear under the action of radiation are the starting point of these reactions. The presence of hydrogen in the emanated gases may be also a result of these reactions. PMID:19325844

Cheminformatics and Computational Chemistry: A Powerful ...

EPA Pesticide Factsheets

The registration of new chemicals under the Toxicological Substances Control Act (TSCA) and new pesticides under the Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA) requires knowledge of the process science underlying the transformation of organic chemicals in natural ecosystems. The purpose of this presentation is to demonstrate how cheminformatics using chemical terms language in combination with the output of physicochemical property calculators can be employed to encode this knowledge and make it available to the appropriate decision makers. The encoded process science is realized through the execution of reaction libraries in simulators such as EPA’s Chemical Transformation Simulator (CTS). In support of the CTS, reaction libraries have or are currently being developed for a number of transformation processes including hydrolysis, abiotic reduction, photolysis and disinfection by-product formation. Examples of how the process science available in the peer-reviewed literature is being encoded will be presented. Presented at the 252nd American Chemical Society National Meeting:Aquatic Chemistry: Symposium in Honor of Professor Alan T. Stone

Recent advances in modeling Hugoniots with Cheetah

NASA Astrophysics Data System (ADS)

Glaesemann, Kurt

2005-07-01

The detonation of an energetic material is the result of a complex interaction between kinetic chemical reactions and thermodynamic chemical equilibrium. Unfortunately, little is known concerning the detailed chemical kinetics of reacting energetic materials. Cheetah uses rate laws to treat species with the slowest chemical reactions, while assuming other chemical species are in equilibrium. Cheetah supports a wide range of elements and condensed detonation products and can also be applied to gas phase reactions. Improvements have been made to Cheetah's equilibrium solver, that allow it to find a wider range of thermodynamic states. Many of the difficulties experienced by users in earlier versions of Cheetah have been fixed. New capabilities have also been added. The ultimate result is a code that can be applied to a wide range of shock problems involving both energetic and non-energetic materials. New experimental validations of Cheetah's equation of state methodology have been performed, including both reacted and unreacted Hugoniots. This work was performed under the auspices of the U.S. Department of Energy by the University of California Lawrence Livermore National Laboratory under contract No. W-7405-Eng-48.

Chemical Memory Reactions Induced Bursting Dynamics in Gene Expression

PubMed Central

Tian, Tianhai

2013-01-01

Memory is a ubiquitous phenomenon in biological systems in which the present system state is not entirely determined by the current conditions but also depends on the time evolutionary path of the system. Specifically, many memorial phenomena are characterized by chemical memory reactions that may fire under particular system conditions. These conditional chemical reactions contradict to the extant stochastic approaches for modeling chemical kinetics and have increasingly posed significant challenges to mathematical modeling and computer simulation. To tackle the challenge, I proposed a novel theory consisting of the memory chemical master equations and memory stochastic simulation algorithm. A stochastic model for single-gene expression was proposed to illustrate the key function of memory reactions in inducing bursting dynamics of gene expression that has been observed in experiments recently. The importance of memory reactions has been further validated by the stochastic model of the p53-MDM2 core module. Simulations showed that memory reactions is a major mechanism for realizing both sustained oscillations of p53 protein numbers in single cells and damped oscillations over a population of cells. These successful applications of the memory modeling framework suggested that this innovative theory is an effective and powerful tool to study memory process and conditional chemical reactions in a wide range of complex biological systems. PMID:23349679

Chemical memory reactions induced bursting dynamics in gene expression.

PubMed

Tian, Tianhai

2013-01-01

Memory is a ubiquitous phenomenon in biological systems in which the present system state is not entirely determined by the current conditions but also depends on the time evolutionary path of the system. Specifically, many memorial phenomena are characterized by chemical memory reactions that may fire under particular system conditions. These conditional chemical reactions contradict to the extant stochastic approaches for modeling chemical kinetics and have increasingly posed significant challenges to mathematical modeling and computer simulation. To tackle the challenge, I proposed a novel theory consisting of the memory chemical master equations and memory stochastic simulation algorithm. A stochastic model for single-gene expression was proposed to illustrate the key function of memory reactions in inducing bursting dynamics of gene expression that has been observed in experiments recently. The importance of memory reactions has been further validated by the stochastic model of the p53-MDM2 core module. Simulations showed that memory reactions is a major mechanism for realizing both sustained oscillations of p53 protein numbers in single cells and damped oscillations over a population of cells. These successful applications of the memory modeling framework suggested that this innovative theory is an effective and powerful tool to study memory process and conditional chemical reactions in a wide range of complex biological systems.

FACILITATED CHEMICAL SYNTHESIS UNDER ALTERNATE REACTION CONDITIONS

EPA Science Inventory

The chemical research in the late 1990's witnessed a paradigm shift towards "environmentally-friendly chemistry" more popularly known as "green chemistry" due to the increasing environmental concerns and legislative requirements to curb the release of chemical waste into the atmo...

40 CFR 721.10574 - Alkylcarboxy polyester acrylate reaction products with mixed metal oxides (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... reaction products with mixed metal oxides (generic). 721.10574 Section 721.10574 Protection of Environment... reaction products with mixed metal oxides (generic). (a) Chemical substance and significant new uses... reaction products with mixed metal oxides (PMN P-09-48) is subject to reporting under this section for the...

40 CFR 721.10574 - Alkylcarboxy polyester acrylate reaction products with mixed metal oxides (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... reaction products with mixed metal oxides (generic). 721.10574 Section 721.10574 Protection of Environment... reaction products with mixed metal oxides (generic). (a) Chemical substance and significant new uses... reaction products with mixed metal oxides (PMN P-09-48) is subject to reporting under this section for the...

40 CFR 721.9484 - Dimer acid/rosin amidoamine reaction product (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Dimer acid/rosin amidoamine reaction... Specific Chemical Substances § 721.9484 Dimer acid/rosin amidoamine reaction product (generic). (a... generically as Dimer acid/rosin amidoamine reaction product (PMN P-99-0143) is subject to reporting under this...

40 CFR 721.9484 - Dimer acid/rosin amidoamine reaction product (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Dimer acid/rosin amidoamine reaction... Specific Chemical Substances § 721.9484 Dimer acid/rosin amidoamine reaction product (generic). (a... generically as Dimer acid/rosin amidoamine reaction product (PMN P-99-0143) is subject to reporting under this...

Convective instabilities in traveling fronts of addition polymerization

NASA Technical Reports Server (NTRS)

Pojman, John A.; Jones, Chris E.; Khan, Akhtar M.

1993-01-01

An autocatalytic reaction in an unstirred vessel can support a constant velocity wavefront resulting from the coupling of diffusion to the chemical reaction. A flare front is a common example in which heat is the autocatalytic species that diffuses into unreacted regions stimulating a reaction that produces more heat. Traveling fronts were studied in synthetic polymerization reactions under high pressure by workers in the former USSR. More recently, propagating fronts of methacrylic acid polymerization were studied under ambient conditions, both with video techniques and by NMR.

CATALYST-FREE REACTIONS UNDER SOLVENT-FEE CONDITIONS: MICROWAVE-ASSISTED SYNTHESIS OF HETEROCYCLIC HYDRAZONES BELOW THE MELTING POINT OF NEAT REACTANTS: JOURNAL ARTICLE

EPA Science Inventory

NRMRL-CIN-1437 Jeselnik, M., Varma*, R.S., Polanc, S., and Kocevar, M. Catalyst-free Reactions under Solvent-fee Conditions: Microwave-assisted Synthesis of Heterocyclic Hydrazones below the Melting Point of Neat Reactants. Published in: Chemical Communications 18:1716-1717 (200...

Elucidating the alkaline oxygen evolution reaction mechanism on platinum

DOE PAGES

Favaro, M.; Valero-Vidal, C.; Eichhorn, J.; ...

2017-03-07

Understanding the interplay between surface chemistry, electronic structure, and reaction mechanism of the catalyst at the electrified solid/liquid interface will enable the design of more efficient materials systems for sustainable energy production. The substantial progress in operando characterization, particularly using synchrotron based X-ray spectroscopies, provides the unprecedented opportunity to uncover surface chemical and structural transformations under various (electro)chemical reaction environments. In this work, we study a polycrystalline platinum surface under oxygen evolution conditions in an alkaline electrolyte by means of ambient pressure X-ray photoelectron spectroscopy performed at the electrified solid/liquid interface. We elucidate previously inaccessible aspects of the surface chemistrymore » and structure as a function of the applied potential, allowing us to propose a reaction mechanism for oxygen evolution on a platinum electrode in alkaline solutions.« less

Nonequilibrium steady state of biochemical cycle kinetics under non-isothermal conditions

NASA Astrophysics Data System (ADS)

Jin, Xiao; Ge, Hao

2018-04-01

The nonequilibrium steady state of isothermal biochemical cycle kinetics has been extensively studied, but that under non-isothermal conditions has been much less extensively investigated. When the heat exchange between subsystems is slow, the isothermal assumption of the whole system breaks down, as is true for many types of living organisms. Here, starting with a four-state model of molecular transporter across the cell membrane, we generalize the nonequilibrium steady-state theory of isothermal biochemical cycle kinetics to the circumstances with non-uniform temperatures of subsystems in terms of general master equation models. We obtain a new thermodynamic relationship between the chemical reaction rates and thermodynamic potentials in non-isothermal circumstances, based on the overdamped dynamics along the continuous reaction coordinate. We show that the entropy production can vary up to 3% in real cells, even when the temperature difference across the cell membrane is only approximately 1 K. We then decompose the total thermodynamic driving force into its thermal and chemical components and predict that the net flux of molecules transported by the molecular transporter can potentially go against the temperature gradient in the absence of a chemical driving force. Furthermore, we demonstrate that the simple application of the isothermal transition-state rate formula for each chemical reaction in terms of only the reactant’ temperature is not thermodynamically consistent. Therefore, we mathematically derive several revised reaction rate formulas that are not only consistent with the new thermodynamic relationship but also approximate the exact reaction rate better than Kramers’ rate formula under isothermal conditions.

Modeling CO2 mass transfer in amine mixtures: PZ-AMP and PZ-MDEA.

PubMed

Puxty, Graeme; Rowland, Robert

2011-03-15

The most common method of carbon dioxide (CO(2)) capture is the absorption of CO(2) into a falling thin film of an aqueous amine solution. Modeling of mass transfer during CO(2) absorption is an important way to gain insight and understanding about the underlying processes that are occurring. In this work a new software tool has been used to model CO(2) absorption into aqueous piperazine (PZ) and binary mixtures of PZ with 2-amino-2-methyl-1-propanol (AMP) or methyldiethanolamine (MDEA). The tool solves partial differential and simultaneous equations describing diffusion and chemical reaction automatically derived from reactions written using chemical notation. It has been demonstrated that by using reactions that are chemically plausible the mass transfer in binary mixtures can be fully described by combining the chemical reactions and their associated parameters determined for single amines. The observed enhanced mass transfer in binary mixtures can be explained through chemical interactions occurring in the mixture without need to resort to using additional reactions or unusual transport phenomena such as the "shuttle mechanism".

Direct Monte Carlo simulation of chemical reaction systems: Simple bimolecular reactions

NASA Astrophysics Data System (ADS)

Piersall, Shannon D.; Anderson, James B.

1991-07-01

In applications to several simple reaction systems we have explored a ``direct simulation'' method for predicting and understanding the behavior of gas phase chemical reaction systems. This Monte Carlo method, originated by Bird, has been found remarkably successful in treating a number of difficult problems in rarefied dynamics. Extension to chemical reactions offers a powerful tool for treating reaction systems with nonthermal distributions, with coupled gas-dynamic and reaction effects, with emission and adsorption of radiation, and with many other effects difficult to treat in any other way. The usual differential equations of chemical kinetics are eliminated. For a bimolecular reaction of the type A+B→C+D with a rate sufficiently low to allow a continued thermal equilibrium of reactants we find that direct simulation reproduces the expected second order kinetics. Simulations for a range of temperatures yield the activation energies expected for the reaction models specified. For faster reactions under conditions leading to a depletion of energetic reactant species, the expected slowing of reaction rates and departures from equilibrium distributions are observed. The minimum sample sizes required for adequate simulations are as low as 1000 molecules for these cases. The calculations are found to be simple and straightforward for the homogeneous systems considered. Although computation requirements may be excessively high for very slow reactions, they are reasonably low for fast reactions, for which nonequilibrium effects are most important.

Multichannel quench-flow microreactor chip for parallel reaction monitoring.

PubMed

Bula, Wojciech P; Verboom, Willem; Reinhoudt, David N; Gardeniers, Han J G E

2007-12-01

This paper describes a multichannel silicon-glass microreactor which has been utilized to investigate the kinetics of a Knoevenagel condensation reaction under different reaction conditions. The reaction is performed on the chip in four parallel channels under identical conditions but with different residence times. A special topology of the reaction coils overcomes the common problem arising from the difference in pressure drop of parallel channels having different length. The parallelization of reaction coils combined with chemical quenching at specific locations results in a considerable reduction in experimental effort and cost. The system was tested and showed good reproducibility in flow properties and reaction kinetic data generation.

In Situ Monitoring of Chemical Reactions at a Solid-Water Interface by Femtosecond Acoustics.

PubMed

Shen, Chih-Chiang; Weng, Meng-Yu; Sheu, Jinn-Kong; Yao, Yi-Ting; Sun, Chi-Kuang

2017-11-02

Chemical reactions at a solid-liquid interface are of fundamental importance. Interfacial chemical reactions occur not only at the very interface but also in the subsurface area, while existing monitoring techniques either provide limited spatial resolution or are applicable only for the outmost atomic layer. Here, with the aid of the time-domain analysis with femtosecond acoustics, we demonstrate a subatomic-level-resolution technique to longitudinally monitor chemical reactions at solid-water interfaces, capable of in situ monitoring even the subsurface area under atmospheric conditions. Our work was proven by monitoring the already-known anode oxidation process occurring during photoelectrochemical water splitting. Furthermore, whenever the oxide layer thickness equals an integer  number of the effective atomic layer thickness, the measured acoustic echo will show higher signal-to-noise ratios with reduced speckle noise, indicating the quantum-like behavior of this coherent-phonon-based technique.

Models of glycolysis: Glyceraldehyde as a source of energy and monomers for prebiotic condensation reactions

NASA Technical Reports Server (NTRS)

Weber, A. L.

1986-01-01

All organisms require energy in a chemical form for maintenance and growth. In contemporary life this chemical energy is obtained by the synthesis of the phosphoanhydride bonds of ATP. Among the biological processes that yield ATP, fermentation is generally considered primitive, because it operates under anaerobic conditions by substrate-level phosphorylation which does not require compartmentation by membranes. Fermentation by the glycolytic pathway, which is found in almost every living cell, is an especially attractive energy source for primitive life. Glycolysis not only produces useful chemical energy (ATP), but intermediates of this pathway are also involved in amino acid synthesis and photosynthetic carbon-fixation. It is believed that energy and substrates needed for the origin of life were provided by nonenzymatic chemical reactions that resemble the enzyme-mediated reactions of glycolysis. These nonenzymatic reactions would have provided a starting point for the evolutionary development of glycolysis.

Michael Griffin | NREL

Science.gov Websites

production of high-value products Physical and chemical material characterization under reaction conditions Heterogeneous catalysis Design and operation of reactor systems Analysis of reaction kinetics and mechanisms labeled "major reaction products" at the top. On the right is a figure of blue spheres with a

A Qualitative Report of the Ways High School Chemistry Students Attempt to Represent a Chemical Reaction at the Atomic/Molecular Level

ERIC Educational Resources Information Center

Kern, Anne L.; Wood, Nathan B.; Roehrig, Gillian H.; Nyachwaya, James

2010-01-01

We report the findings of a large-scale (n = 1,337) qualitative descriptive analysis of U.S. high schools students' particulate representations of a chemical reaction, specifically, the combustion of methane. Data were collected as part of an end of course exam. Student representations were coded into 17 distinct subcategories under one of five…

Theory of First Order Chemical Kinetics at the Critical Point of Solution.

PubMed

Baird, James K; Lang, Joshua R

2017-10-26

Liquid mixtures, which have a phase diagram exhibiting a miscibility gap ending in a critical point of solution, have been used as solvents for chemical reactions. The reaction rate in the forward direction has often been observed to slow down as a function of temperature in the critical region. Theories based upon the Gibbs free energy of reaction as the driving force for chemical change have been invoked to explain this behavior. With the assumption that the reaction is proceeding under relaxation conditions, these theories expand the free energy in a Taylor series about the position of equilibrium. Since the free energy is zero at equilibrium, the leading term in the Taylor series is proportional to the first derivative of the free energy with respect to the extent of reaction. To analyze the critical behavior of this derivative, the theories exploit the principle of critical point isomorphism, which is thought to govern all critical phenomena. They find that the derivative goes to zero in the critical region, which accounts for the slowing down observed in the reaction rate. As has been pointed out, however, most experimental rate investigations have been carried out under irreversible conditions as opposed to relaxation conditions [Shen et al. J. Phys. Chem. A 2015, 119, 8784-8791]. Below, we consider a reaction governed by first order kinetics and invoke transition state theory to take into account the irreversible conditions. We express the apparent activation energy in terms of thermodynamic derivatives evaluated under standard conditions as well as the pseudoequilibrium conditions associated with the reactant and the activated complex. We show that these derivatives approach infinity in the critical region. The apparent activation energy follows this behavior, and its divergence accounts for the slowing down of the reaction rate.

Cheminformatics Applications and Physicochemical Property ...

EPA Pesticide Factsheets

The registration of new chemicals under the Toxic Substances Control Act (TSCA) and new pesticides under the Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA) requires knowledge of the process science underlying the transport and transformation of organic chemicals in natural ecosystems. The purpose of this presentation is to demonstrate how cheminformatics, using chemical terms language in combination with the output of physicochemical property calculators, can be employed to encode this knowledge and make it available to the appropriate decision makers. The encoded process science is realized through the execution of reaction libraries in simulators such as EPA’s Chemical Transformation Simulator (CTS). In support of the CTS, reaction libraries have, or are currently being developed for a number of transformation processes including hydrolysis, abiotic reduction, photolysis and disinfection by-product formation. Examples of how the process science in the peer-reviewed literature is being encoded will be presented. The purpose of this presentation is to demonstrate how cheminformatics, using chemical terms language in combination with the output of physicochemical property calculators, can be employed to encode this knowledge and make it available to the appropriate decision makers.

Computational Study of 3-D Hot-Spot Initiation in Shocked Insensitive High-Explosive

NASA Astrophysics Data System (ADS)

Najjar, F. M.; Howard, W. M.; Fried, L. E.

2011-06-01

High explosive shock sensitivity is controlled by a combination of mechanical response, thermal properties, and chemical properties. The interplay of these physical phenomena in realistic condensed energetic materials is currently lacking. A multiscale computational framework is developed investigating hot spot (void) ignition in a single crystal of an insensitive HE, TATB. Atomistic MD simulations are performed to provide the key chemical reactions and these reaction rates are used in 3-D multiphysics simulations. The multiphysics code, ALE3D, is linked to the chemistry software, Cheetah, and a three-way coupled approach is pursued including hydrodynamics, thermal and chemical analyses. A single spherical air bubble is embedded in the insensitive HE and its collapse due to shock initiation is evolved numerically in time; while the ignition processes due chemical reactions are studied. Our current predictions showcase several interesting features regarding hot spot dynamics including the formation of a ``secondary'' jet. Results obtained with hydro-thermo-chemical processes leading to ignition growth will be discussed for various pore sizes and different shock pressures. LLNL-ABS-471438. This work performed under the auspices of the U.S. Department of Energy by LLNL under Contract DE-AC52-07NA27344.

Prediction of Hydrolysis Products of Organic Chemicals under Environmental pH Conditions.

PubMed

Tebes-Stevens, Caroline; Patel, Jay M; Jones, W Jack; Weber, Eric J

2017-05-02

Cheminformatics-based software tools can predict the molecular structure of transformation products using a library of transformation reaction schemes. This paper presents the development of such a library for abiotic hydrolysis of organic chemicals under environmentally relevant conditions. The hydrolysis reaction schemes in the library encode the process science gathered from peer-reviewed literature and regulatory reports. Each scheme has been ranked on a scale of one to six based on the median half-life in a data set compiled from literature-reported hydrolysis rates. These ranks are used to predict the most likely transformation route when more than one structural fragment susceptible to hydrolysis is present in a molecule of interest. Separate rank assignments are established for pH 5, 7, and 9 to represent standard conditions in hydrolysis studies required for registration of pesticides in Organisation for Economic Co-operation and Development (OECD) member countries. The library is applied to predict the likely hydrolytic transformation products for two lists of chemicals, one representative of chemicals used in commerce and the other specific to pesticides, to evaluate which hydrolysis reaction pathways are most likely to be relevant for organic chemicals found in the natural environment.

Toward High-Level Theoretical Studies of Large Biodiesel Molecules: An ONIOM [QCISD(T)/CBS:DFT] Study of the Reactions between Unsaturated Methyl Esters (C nH2 n-1COOCH3) and Hydrogen Radical.

PubMed

Zhang, Lidong; Meng, Qinghui; Chi, Yicheng; Zhang, Peng

2018-05-31

A two-layer ONIOM[QCISD(T)/CBS:DFT] method was proposed for the high-level single-point energy calculations of large biodiesel molecules and was validated for the hydrogen abstraction reactions of unsaturated methyl esters that are important components of real biodiesel. The reactions under investigation include all the reactions on the potential energy surface of C n H 2 n-1 COOCH 3 ( n = 2-5, 17) + H, including the hydrogen abstraction, the hydrogen addition, the isomerization (intramolecular hydrogen shift), and the β-scission reactions. By virtue of the introduced concept of chemically active center, a unified specification of chemically active portion for the ONIOM (ONIOM = our own n-layered integrated molecular orbital and molecular mechanics) method was proposed to account for the additional influence of C═C double bond. The predicted energy barriers and heats of reaction by using the ONIOM method are in very good agreement with those obtained by using the widely accepted high-level QCISD(T)/CBS theory, as verified by the computational deviations being less than 0.15 kcal/mol, for almost all the reaction pathways under investigation. The method provides a computationally accurate and affordable approach to combustion chemists for high-level theoretical chemical kinetics of large biodiesel molecules.

Developing chemical strategies for the assembly of nanoparticles into mesoscopic objects.

PubMed

Maneeprakorn, Weerakanya; Malik, Mohammad A; O'Brien, Paul

2010-02-17

Nanoparticles of Au, Ag, CdS, and CdSe have been linked together by a chemical reaction to form controlled assemblies of similar or different types of nanoparticles through amido or azo linkage. The capping of nanoparticles was exchanged with bifunctional groups containing active functional groups at the tails. The reaction between the tails of the capping agents resulted in the formation of amido or azo linkages. These reactions were carried out under very dilute conditions to control the assembly and avoid the polymerization. The assemblies formed included the dimers, trimers, tetramers, and hexa- or heptamers. These reactions are the first examples for the systematic approach to establish the chemical route for the controlled assembly of nanoparticles and open the way for the fabrication of nanoparticle based devices for various application.

Diffusion-controlled reactions modeling in Geant4-DNA

NASA Astrophysics Data System (ADS)

Karamitros, M.; Luan, S.; Bernal, M. A.; Allison, J.; Baldacchino, G.; Davidkova, M.; Francis, Z.; Friedland, W.; Ivantchenko, V.; Ivantchenko, A.; Mantero, A.; Nieminem, P.; Santin, G.; Tran, H. N.; Stepan, V.; Incerti, S.

2014-10-01

Context Under irradiation, a biological system undergoes a cascade of chemical reactions that can lead to an alteration of its normal operation. There are different types of radiation and many competing reactions. As a result the kinetics of chemical species is extremely complex. The simulation becomes then a powerful tool which, by describing the basic principles of chemical reactions, can reveal the dynamics of the macroscopic system. To understand the dynamics of biological systems under radiation, since the 80s there have been on-going efforts carried out by several research groups to establish a mechanistic model that consists in describing all the physical, chemical and biological phenomena following the irradiation of single cells. This approach is generally divided into a succession of stages that follow each other in time: (1) the physical stage, where the ionizing particles interact directly with the biological material; (2) the physico-chemical stage, where the targeted molecules release their energy by dissociating, creating new chemical species; (3) the chemical stage, where the new chemical species interact with each other or with the biomolecules; (4) the biological stage, where the repairing mechanisms of the cell come into play. This article focuses on the modeling of the chemical stage. Method This article presents a general method of speeding-up chemical reaction simulations in fluids based on the Smoluchowski equation and Monte-Carlo methods, where all molecules are explicitly simulated and the solvent is treated as a continuum. The model describes diffusion-controlled reactions. This method has been implemented in Geant4-DNA. The keys to the new algorithm include: (1) the combination of a method to compute time steps dynamically with a Brownian bridge process to account for chemical reactions, which avoids costly fixed time step simulations; (2) a k-d tree data structure for quickly locating, for a given molecule, its closest reactants. The performance advantage is presented in terms of complexity, and the accuracy of the new algorithm is demonstrated by simulating radiation chemistry in the context of the Geant4-DNA project. Application The time-dependent radiolytic yields of the main chemical species formed after irradiation are computed for incident protons at different energies (from 50 MeV to 500 keV). Both the time-evolution and energy dependency of the yields are discussed. The evolution, at one microsecond, of the yields of hydroxyls and solvated electrons with respect to the linear energy transfer is compared to theoretical and experimental data. According to our results, at high linear energy transfer, modeling radiation chemistry in the trading compartment representation might be adopted.

Monitoring chemical reactions by low-field benchtop NMR at 45 MHz: pros and cons.

PubMed

Silva Elipe, Maria Victoria; Milburn, Robert R

2016-06-01

Monitoring chemical reactions is the key to controlling chemical processes where NMR can provide support. High-field NMR gives detailed structural information on chemical compounds and reactions; however, it is expensive and complex to operate. Conversely, low-field NMR instruments are simple and relatively inexpensive alternatives. While low-field NMR does not provide the detailed information as the high-field instruments as a result of their smaller chemical shift dispersion and the complex secondary coupling, it remains of practical value as a process analytical technology (PAT) tool and is complimentary to other established methods, such as ReactIR and Raman spectroscopy. We have tested a picoSpin-45 (currently under ThermoFisher Scientific) benchtop NMR instrument to monitor three types of reactions by 1D (1) H NMR: a Fischer esterification, a Suzuki cross-coupling, and the formation of an oxime. The Fischer esterification is a relatively simple reaction run at high concentration and served as proof of concept. The Suzuki coupling is an example of a more complex, commonly used reaction involving overlapping signals. Finally, the oxime formation involved a reaction in two phases that cannot be monitored by other PAT tools. Here, we discuss the pros and cons of monitoring these reactions at a low-field of 45 MHz by 1D (1) H NMR. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

Solid-state reactions to synthesize nanostructured lead selenide semiconductor powders by high-energy milling

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

Rojas-Chavez, H., E-mail: uu_gg_oo@yahoo.com.mx; Reyes-Carmona, F.; Jaramillo-Vigueras, D.

2011-10-15

Highlights: {yields} PbSe synthesized from PbO instead of Pb powder do not require an inert atmosphere. {yields} During high-energy milling oxygen has to be chemically reduced from the lead oxide. {yields} Solid-state and solid-gas chemical reactions promote both solid and gaseous products. -- Abstract: Both solid-solid and gas-solid reactions have been traced during high-energy milling of Se and PbO powders under vial (P, T) conditions in order to synthesize the PbSe phase. Chemical and thermodynamic arguments are postulated to discern the high-energy milling mechanism to transform PbO-Se micropowders onto PbSe-nanocrystals. A set of reactions were evaluated at around room temperature.more » Therefore an experimental campaign was designed to test the nature of reactions in the PbO-Se system during high-energy milling.« less

New instrumentation for the comprehension of chemical reactions under microwave and classical heating with the aid of a wide frequency band dielectric spectroscopy

NASA Astrophysics Data System (ADS)

Chevalier, S.; Meyer, O.; Weil, R.; Fourrierlamer, A.; Petit, A.; Loupy, A.; Maurel, F.

2001-09-01

An instrumentation system for measuring wide frequency band complex permittivity of a sample submitted to a microwave irradiation has been optimized in order to allow macroscopic temperature measurements. The reaction of saponification of aromatic esters is studied using this instrumentation. We take interest in the behavior of the ionic conductivity phenomenon occurring in the reactive medium during microwave heating, and we compare it with the results obtained under classical heating. We show that the activation energy associated with ionic conductivity is lower when the reaction is performed under microwaves than when it is performed under classical heating. We thus deduce that microwaves act on the reaction advancement as a catalyst, and thus makes the reaction easier.

Thermal-mechanical-chemical responses of polymer-bonded explosives using a mesoscopic reactive model under impact loading.

PubMed

Wang, XinJie; Wu, YanQing; Huang, FengLei

2017-01-05

A mesoscopic framework is developed to quantify the thermal-mechanical-chemical responses of polymer-bonded explosive (PBX) samples under impact loading. A mesoscopic reactive model is developed for the cyclotetramethylenetetranitramine (HMX) crystal, which incorporates nonlinear elasticity, crystal plasticity, and temperature-dependent chemical reaction. The proposed model was implemented in the finite element code ABAQUS by the user subroutine VUMAT. A series of three-dimensional mesoscale models were constructed and calculated under low-strength impact loading scenarios from 100m/s to 600m/s where only the first wave transit is studied. Crystal anisotropy and microstructural heterogeneity are responsible for the nonuniform stress field and fluctuations of the stress wave front. At a critical impact velocity (≥300m/s), a chemical reaction is triggered because the temperature contributed by the volumetric and plastic works is sufficiently high. Physical quantities, including stress, temperature, and extent of reaction, are homogenized from those across the microstructure at the mesoscale to compare with macroscale measurements, which will advance the continuum-level models. The framework presented in this study has important implications in understanding hot spot ignition processes and improving predictive capabilities in energetic materials. Copyright © 2016 Elsevier B.V. All rights reserved.

Reduction of chlorine radical chemical etching of GaN under simultaneous plasma-emitted photon irradiation

NASA Astrophysics Data System (ADS)

Liu, Zecheng; Imamura, Masato; Asano, Atsuki; Ishikawa, Kenji; Takeda, Keigo; Kondo, Hiroki; Oda, Osamu; Sekine, Makoto; Hori, Masaru

2017-08-01

Surface chemical reactions on the GaN surface with Cl radicals are thermally enhanced in the high-temperature Cl2 plasma etching of GaN, resulting in the formation of etch pits and thereby, a roughened surface. Simultaneous irradiation of ultraviolet (UV) photons in Cl2 plasma emissions with wavelengths of 258 and 306 nm reduces the surface chemical reactions because of the photodissociation of both Ga and N chlorides, which leads to a suppression of the increase in surface roughness. Compared with Si-related materials, we point out that photon-induced reactions should be taken into account during the plasma processing of wide-bandgap semiconductors.

Inner-shell chemistry under high pressure

NASA Astrophysics Data System (ADS)

Miao, Maosheng; Botana, Jorge; Pravica, Michael; Sneed, Daniel; Park, Changyong

2017-05-01

Chemistry at ambient conditions has implicit boundaries rooted in the atomic shell structure: the inner-shell electrons and the unoccupied outer-shell orbitals do not contribute as the major component to chemical reactions and in chemical bonds. These general rules govern our understanding of chemical structures and reactions. We review the recent progresses in high-pressure chemistry demonstrating that the above rules can be violated under extreme conditions. Using a first principles computation method and crystal structure search algorithm, we demonstrate that stable compounds involving inner shell electrons such as CsF3, CsF5, HgF3, and HgF4 can form under high external pressure and may present exotic properties. We also discuss experimental studies that have sought to confirm these predictions. Employing our recently developed hard X-ray photochemistry methods in a diamond anvil cell, we show promising early results toward realizing inner shell chemistry experimentally.

Ethylene Decomposition Initiated by Ultraviolet Radiation from Low Pressure Mercury Lamps: Kinetics Model Prediction and Experimental Verification.

NASA Astrophysics Data System (ADS)

Jozwiak, Zbigniew Boguslaw

1995-01-01

Ethylene is an important auto-catalytic plant growth hormone. Removal of ethylene from the atmosphere surrounding ethylene-sensitive horticultural products may be very beneficial, allowing an extended period of storage and preventing or delaying the induction of disorders. Various ethylene removal techniques have been studied and put into practice. One technique is based on using low pressure mercury ultraviolet lamps as a source of photochemical energy to initiate chemical reactions that destroy ethylene. Although previous research showed that ethylene disappeared in experiments with mercury ultraviolet lamps, the reactions were not described and the actual cause of ethylene disappearance remained unknown. Proposed causes for this disappearance were the direct action of ultraviolet rays on ethylene, reaction of ethylene with ozone (which is formed when air or gas containing molecular oxygen is exposed to radiation emitted by this type of lamp), or reactions with atomic oxygen leading to formation of ozone. The objective of the present study was to determine the set of physical and chemical actions leading to the disappearance of ethylene from artificial storage atmosphere under conditions of ultraviolet irradiation. The goal was achieved by developing a static chemical model based on the physical properties of a commercially available ultraviolet lamp, the photochemistry of gases, and the kinetics of chemical reactions. The model was used to perform computer simulations predicting time dependent concentrations of chemical species included in the model. Development of the model was accompanied by the design of a reaction chamber used for experimental verification. The model provided a good prediction of the general behavior of the species involved in the chemistry under consideration; however the model predicted lower than measured rate of ethylene disappearance. Some reasons for the model -experiment disagreement are radiation intensity averaging, the experimental technique, mass transfer in the chamber, and incompleteness of the set of chemical reactions included in the model. The work is concluded with guidelines for development of a more complex mathematical model that includes elements of mass transfer inside the reaction chamber, and uses a three dimensional approach to distribute radiation from the low pressure mercury ultraviolet tube.

The efficiency of driving chemical reactions by a physical non-equilibrium is kinetically controlled.

PubMed

Göppel, Tobias; Palyulin, Vladimir V; Gerland, Ulrich

2016-07-27

An out-of-equilibrium physical environment can drive chemical reactions into thermodynamically unfavorable regimes. Under prebiotic conditions such a coupling between physical and chemical non-equilibria may have enabled the spontaneous emergence of primitive evolutionary processes. Here, we study the coupling efficiency within a theoretical model that is inspired by recent laboratory experiments, but focuses on generic effects arising whenever reactant and product molecules have different transport coefficients in a flow-through system. In our model, the physical non-equilibrium is represented by a drift-diffusion process, which is a valid coarse-grained description for the interplay between thermophoresis and convection, as well as for many other molecular transport processes. As a simple chemical reaction, we consider a reversible dimerization process, which is coupled to the transport process by different drift velocities for monomers and dimers. Within this minimal model, the coupling efficiency between the non-equilibrium transport process and the chemical reaction can be analyzed in all parameter regimes. The analysis shows that the efficiency depends strongly on the Damköhler number, a parameter that measures the relative timescales associated with the transport and reaction kinetics. Our model and results will be useful for a better understanding of the conditions for which non-equilibrium environments can provide a significant driving force for chemical reactions in a prebiotic setting.

Hydrodynamic and Chemical Modeling of a Chemical Vapor Deposition Reactor for Zirconia Deposition

NASA Astrophysics Data System (ADS)

Belmonte, T.; Gavillet, J.; Czerwiec, T.; Ablitzer, D.; Michel, H.

1997-09-01

Zirconia is deposited on cylindrical substrates by flowing post-discharge enhanced chemical vapor deposition. In this paper, a two dimensional hydrodynamic and chemical modeling of the reactor is described for given plasma characteristics. It helps in determining rate constants of the synthesis reaction of zirconia in gas phase and on the substrate which is ZrCl4 hydrolysis. Calculated deposition rate profiles are obtained by modeling under various conditions and fits with a satisfying accuracy the experimental results. The role of transport processes and the mixing conditions of excited gases with remaining ones are studied. Gas phase reaction influence on the growth rate is also discussed.

Effect of local void morphology on the reaction initiation mechanism in the case of pressed HMX

NASA Astrophysics Data System (ADS)

Roy, Sidhartha; Rai, Nirmal; Udaykumar, H. S.

2017-06-01

The microstructural characteristics of pressed HMX has a significant effect on its sensitivity under shock loading. The microstructure of pressed HMX contains voids of various orientation and aspect ratio. Subject to shock loading, these voids can collapse forming hotspots and initiate chemical reaction. This work shows how the ignition and growth of chemical reaction is dependent on the local microstructural features of the voids. Morphological quantities like size, aspect ratio and orientations are extracted from the real microstructural images of Class III and Class V pressed HMX. These morphological quantities are correlated with the ignition and growth rates of the chemical reaction. The dependency of the sensitivity of a given HMX sample on the local morphological features shows that these local features can create a mocroscale physical response.

Different Models Used to Interpret Chemical Changes: Analysis of a Curriculum and Its Impact on French Students' Reasoning

ERIC Educational Resources Information Center

Kermen, Isabelle; Meheut, Martine

2009-01-01

We present an analysis of the new French curriculum on chemical changes describing the underlying models and highlighting their relations to the empirical level. The authors of the curriculum introduced a distinction between the chemical change of a chemical system and the chemical reactions that account for it. We specify the different roles of…

Force-induced chemical reactions on the metal centre in a single metalloprotein molecule.

PubMed

Zheng, Peng; Arantes, Guilherme M; Field, Martin J; Li, Hongbin

2015-06-25

Metalloproteins play indispensable roles in biology owing to the versatile chemical reactivity of metal centres. However, studying their reactivity in many metalloproteins is challenging, as protein three-dimensional structure encloses labile metal centres, thus limiting their access to reactants and impeding direct measurements. Here we demonstrate the use of single-molecule atomic force microscopy to induce partial unfolding to expose metal centres in metalloproteins to aqueous solution, thus allowing for studying their chemical reactivity in aqueous solution for the first time. As a proof-of-principle, we demonstrate two chemical reactions for the FeS4 centre in rubredoxin: electrophilic protonation and nucleophilic ligand substitution. Our results show that protonation and ligand substitution result in mechanical destabilization of the FeS4 centre. Quantum chemical calculations corroborated experimental results and revealed detailed reaction mechanisms. We anticipate that this novel approach will provide insights into chemical reactivity of metal centres in metalloproteins under biologically more relevant conditions.

Force-induced chemical reactions on the metal centre in a single metalloprotein molecule

PubMed Central

Zheng, Peng; Arantes, Guilherme M.; Field, Martin J.; Li, Hongbin

2015-01-01

Metalloproteins play indispensable roles in biology owing to the versatile chemical reactivity of metal centres. However, studying their reactivity in many metalloproteins is challenging, as protein three-dimensional structure encloses labile metal centres, thus limiting their access to reactants and impeding direct measurements. Here we demonstrate the use of single-molecule atomic force microscopy to induce partial unfolding to expose metal centres in metalloproteins to aqueous solution, thus allowing for studying their chemical reactivity in aqueous solution for the first time. As a proof-of-principle, we demonstrate two chemical reactions for the FeS4 centre in rubredoxin: electrophilic protonation and nucleophilic ligand substitution. Our results show that protonation and ligand substitution result in mechanical destabilization of the FeS4 centre. Quantum chemical calculations corroborated experimental results and revealed detailed reaction mechanisms. We anticipate that this novel approach will provide insights into chemical reactivity of metal centres in metalloproteins under biologically more relevant conditions. PMID:26108369

Tracking the behavior of Maillard browning in lysine/arginine-sugar model systems under high hydrostatic pressure.

PubMed

Ma, Xiao-Juan; Gao, Jin-Yan; Tong, Ping; Li, Xin; Chen, Hong-Bing

2017-12-01

High-pressure processing is gaining popularity in the food industry. However, its effect on the Maillard reaction during high-pressure-assisted pasteurization and sterilization is not well documented. This study aimed to investigate the effects of high hydrostatic pressure on the Maillard reaction during these processes using amino acid (lysine or arginine)-sugar (glucose or fructose) solution models. High pressure retarded the intermediate and final stages of the Maillard reaction in the lysine-sugar model. For the lysine-glucose model, the degradation rate of Amadori compounds was decelerated, while acceleration was observed in the arginine-sugar model. Increased temperature not only accelerated the Maillard reaction over time but also formed fluorescent compounds with different emission wavelengths. Lysine reacted with the sugars more readily than arginine under the same conditions. In addition, it was easier for lysine to react with glucose, whereas arginine reacted more readily with fructose under high pressure. High pressure exerts different effects on lysine-sugar and arginine-sugar models. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Kerosene combustion at pressures up to 40 atm: Experimental study and detailed chemical kinetic modeling

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

Dagaut, P.; Reuillon, M.; Boettner, J.C.

1994-12-31

The oxidation of TR0 kerosene (jet A1 aviation fuel) was studied in a jet-stirred reactor (JSR) at pressures extending from 10 to 40 atm, in the temperature range 750--1,150 K. A large number of reaction intermediates were identified, and their concentrations were followed for reaction yields ranging from low conversion to the formation of the final products. A reference hydrocarbon, n-decane, studied under the same experimental conditions gave very similar experimental concentration profiles for the main oxidation products. Because of the strong analogy between n-decane and kerosene oxidation kinetics, a detailed chemical kinetic reaction mechanisms describing the oxidation of n-decanemore » was built to reproduce the present experimental results. This mechanisms includes 573 elementary reactions, most of them being reversible, among 90 chemical species. A reasonably good prediction of the concentrations of major species was obtained by computation, covering the whole range of temperature, pressures, and equivalence ratios of the experiments. A kinetic analysis performed to identify the dominant reaction steps of the mechanism shows that, under the conditions of the present study (intermediate temperature and high pressure), HO{sub 2} radicals are important chain carriers leading to the formation of the branching agent H{sub 2}O{sub 2}.« less

Chemical compatibility between UO2 fuel and SiC cladding for LWRs. Application to ATF (Accident-Tolerant Fuels)

NASA Astrophysics Data System (ADS)

Braun, James; Guéneau, Christine; Alpettaz, Thierry; Sauder, Cédric; Brackx, Emmanuelle; Domenger, Renaud; Gossé, Stéphane; Balbaud-Célérier, Fanny

2017-04-01

Silicon carbide-silicon carbide (SiC/SiC) composites are considered to replace the current zirconium-based cladding materials thanks to their good behavior under irradiation and their resistance under oxidative environments at high temperature. In the present work, a thermodynamic analysis of the UO2±x/SiC system is performed. Moreover, using two different experimental methods, the chemical compatibility of SiC towards uranium dioxide, with various oxygen contents (UO2±x) is investigated in the 1500-1970 K temperature range. The reaction leads to the formation of mainly uranium silicides and carbides phases along with CO and SiO gas release. Knudsen Cell Mass Spectrometry is used to measure the gas release occurring during the reaction between UO2+x and SiC powders as function of time and temperature. These experimental conditions are representative of an open system. Diffusion couple experiments with pellets are also performed to study the reaction kinetics in closed system conditions. In both cases, a limited chemical reaction is observed below 1700 K, whereas the reaction is enhanced at higher temperature due to the decomposition of SiC leading to Si vaporization. The temperature of formation of the liquid phase is found to lie between 1850 < T < 1950 K.

Temperature dependence on plasma-induced damage and chemical reactions in GaN etching processes using chlorine plasma

NASA Astrophysics Data System (ADS)

Liu, Zecheng; Ishikawa, Kenji; Imamura, Masato; Tsutsumi, Takayoshi; Kondo, Hiroki; Oda, Osamu; Sekine, Makoto; Hori, Masaru

2018-06-01

Plasma-induced damage (PID) on GaN was optimally reduced by high-temperature chlorine plasma etching. Energetic ion bombardments primarily induced PID involving stoichiometry, surface roughness, and photoluminescence (PL) degradation. Chemical reactions under ultraviolet (UV) irradiation and chlorine radical exposure at temperatures higher than 400 °C can be controlled by taking into account the synergism of simultaneous photon and radical irradiations to effectively reduce PID.

Micro-scale thermal imaging of CO2 absorption in the thermochemical energy storage of Li metal oxides at high temperature

NASA Astrophysics Data System (ADS)

Morikawa, Junko; Takasu, Hiroki; Zamengo, Massimiliano; Kato, Yukitaka

2017-05-01

Li-Metal oxides (typical example: lithium ortho-silicate Li4SiO4) are regarded as a novel solid carbon dioxide CO2 absorbent accompanied by an exothermic reaction. At temperatures above 700°C the sorbent is regenerated with the release of the captured CO2 in an endothermic reaction. As the reaction equilibrium of this reversible chemical reaction is controllable only by the partial pressure of CO2, the system is regarded as a potential candidate for chemical heat storage at high temperatures. In this study, we applied our recent developed mobile type instrumentation of micro-scale infrared thermal imaging system to observe the heat of chemical reaction of Li4SiO4 and CO2 at temperature higher than 600°C or higher. In order to quantify the micro-scale heat transfer and heat exchange in the chemical reaction, the superimpose signal processing system is setup to determine the precise temperature. Under an ambient flow of carbon dioxide, a powder of Li4SiO4 with a diameter 50 micron started to shine caused by an exothermic chemical reaction heat above 600°C. The phenomena was accelerated with increasing temperature up to 700°C. At the same time, the reaction product lithium carbonate (Li2CO3) started to melt with endothermic phase change above 700°C, and these thermal behaviors were captured by the method of thermal imaging. The direct measurement of multiple thermal phenomena at high temperatures is significant to promote an efficient design of chemical heat storage materials. This is the first observation of the exothermic heat of the reaction of Li4SiO4 and CO2 at around 700°C by the thermal imaging method.

A Technical Approach to Marking Explosives, Propellants, and Precursor Chemicals

DTIC Science & Technology

1998-08-01

polymerase chain reaction (PCR) methods whereby small strands are cut and analyzed under specified temperature mediated enzymatic /molecular reactions (4...such as these are often overlooked. Several other companies have been investigating other methods including immunoassay techniques, microencapsulated

Synthesis Under 'Greener' Conditions: Role of Sustainable Nano-Catalysts

EPA Science Inventory

The presentation summarizes our recent activity in chemical synthesis involving benign alternatives, such as the use of supported reagents, and greener reaction medium in aqueous or solvent-free conditions.1 The synthesis of heterocyclic compounds, coupling reactions, and a varie...

Lagrangian descriptors of driven chemical reaction manifolds.

PubMed

Craven, Galen T; Junginger, Andrej; Hernandez, Rigoberto

2017-08-01

The persistence of a transition state structure in systems driven by time-dependent environments allows the application of modern reaction rate theories to solution-phase and nonequilibrium chemical reactions. However, identifying this structure is problematic in driven systems and has been limited by theories built on series expansion about a saddle point. Recently, it has been shown that to obtain formally exact rates for reactions in thermal environments, a transition state trajectory must be constructed. Here, using optimized Lagrangian descriptors [G. T. Craven and R. Hernandez, Phys. Rev. Lett. 115, 148301 (2015)PRLTAO0031-900710.1103/PhysRevLett.115.148301], we obtain this so-called distinguished trajectory and the associated moving reaction manifolds on model energy surfaces subject to various driving and dissipative conditions. In particular, we demonstrate that this is exact for harmonic barriers in one dimension and this verification gives impetus to the application of Lagrangian descriptor-based methods in diverse classes of chemical reactions. The development of these objects is paramount in the theory of reaction dynamics as the transition state structure and its underlying network of manifolds directly dictate reactivity and selectivity.

Diffusion-controlled reactions modeling in Geant4-DNA

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

Karamitros, M., E-mail: matkara@gmail.com; CNRS, INCIA, UMR 5287, F-33400 Talence; Luan, S.

2014-10-01

Context Under irradiation, a biological system undergoes a cascade of chemical reactions that can lead to an alteration of its normal operation. There are different types of radiation and many competing reactions. As a result the kinetics of chemical species is extremely complex. The simulation becomes then a powerful tool which, by describing the basic principles of chemical reactions, can reveal the dynamics of the macroscopic system. To understand the dynamics of biological systems under radiation, since the 80s there have been on-going efforts carried out by several research groups to establish a mechanistic model that consists in describing allmore » the physical, chemical and biological phenomena following the irradiation of single cells. This approach is generally divided into a succession of stages that follow each other in time: (1) the physical stage, where the ionizing particles interact directly with the biological material; (2) the physico-chemical stage, where the targeted molecules release their energy by dissociating, creating new chemical species; (3) the chemical stage, where the new chemical species interact with each other or with the biomolecules; (4) the biological stage, where the repairing mechanisms of the cell come into play. This article focuses on the modeling of the chemical stage. Method This article presents a general method of speeding-up chemical reaction simulations in fluids based on the Smoluchowski equation and Monte-Carlo methods, where all molecules are explicitly simulated and the solvent is treated as a continuum. The model describes diffusion-controlled reactions. This method has been implemented in Geant4-DNA. The keys to the new algorithm include: (1) the combination of a method to compute time steps dynamically with a Brownian bridge process to account for chemical reactions, which avoids costly fixed time step simulations; (2) a k–d tree data structure for quickly locating, for a given molecule, its closest reactants. The performance advantage is presented in terms of complexity, and the accuracy of the new algorithm is demonstrated by simulating radiation chemistry in the context of the Geant4-DNA project. Application The time-dependent radiolytic yields of the main chemical species formed after irradiation are computed for incident protons at different energies (from 50 MeV to 500 keV). Both the time-evolution and energy dependency of the yields are discussed. The evolution, at one microsecond, of the yields of hydroxyls and solvated electrons with respect to the linear energy transfer is compared to theoretical and experimental data. According to our results, at high linear energy transfer, modeling radiation chemistry in the trading compartment representation might be adopted.« less

Applications of Palladium-Catalyzed C-N Cross-Coupling Reactions.

PubMed

Ruiz-Castillo, Paula; Buchwald, Stephen L

2016-10-12

Pd-catalyzed cross-coupling reactions that form C-N bonds have become useful methods to synthesize anilines and aniline derivatives, an important class of compounds throughout chemical research. A key factor in the widespread adoption of these methods has been the continued development of reliable and versatile catalysts that function under operationally simple, user-friendly conditions. This review provides an overview of Pd-catalyzed N-arylation reactions found in both basic and applied chemical research from 2008 to the present. Selected examples of C-N cross-coupling reactions between nine classes of nitrogen-based coupling partners and (pseudo)aryl halides are described for the synthesis of heterocycles, medicinally relevant compounds, natural products, organic materials, and catalysts.

Applications of Palladium-Catalyzed C–N Cross-Coupling Reactions

PubMed Central

2016-01-01

Pd-catalyzed cross-coupling reactions that form C–N bonds have become useful methods to synthesize anilines and aniline derivatives, an important class of compounds throughout chemical research. A key factor in the widespread adoption of these methods has been the continued development of reliable and versatile catalysts that function under operationally simple, user-friendly conditions. This review provides an overview of Pd-catalyzed N-arylation reactions found in both basic and applied chemical research from 2008 to the present. Selected examples of C–N cross-coupling reactions between nine classes of nitrogen-based coupling partners and (pseudo)aryl halides are described for the synthesis of heterocycles, medicinally relevant compounds, natural products, organic materials, and catalysts. PMID:27689804

Intense Femtosecond Laser-Mediated Electrical Discharge Enables Preparation of Amorphous Nickel Phosphide Nanoparticles.

PubMed

Ma, Zhuo-Chen; Chen, Qi-Dai; Han, Bing; Li, He-Long; Wang, Lei; Zhang, Yong-Lai; Sun, Hong-Bo

2018-05-09

Reported here is a high-efficiency preparation method of amorphous nickel phosphide (Ni-P) nanoparticles by intense femtosecond laser irradiation of nickel sulfate and sodium hypophosphite aqueous solution. The underlying mechanism of the laser-assisted preparation was discussed in terms of the breaking of chemical bond in reactants via highly intense electric field discharge generated by the intense femtosecond laser. The morphology and size of the nanoparticles can be tuned by varying the reaction parameters such as ion concentration, ion molar ratio, laser power, and irradiation time. X-ray diffraction and transmission electron microscopy results demonstrated that the nanoparticles were amorphous. Finally, the thermogravimetric-differential thermal analysis experiment verified that the as-synthesized noncrystalline Ni-P nanoparticles had an excellent catalytic capability toward thermal decomposition of ammonium perchlorate. This strategy of laser-mediated electrical discharge under such an extremely intense field may create new opportunities for the decomposition of molecules or chemical bonds that could further facilitate the recombination of new atoms or chemical groups, thus bringing about new possibilities for chemical reaction initiation and nanomaterial synthesis that may not be realized under normal conditions.

Oxidation Numbers, Oxidants, and Redox Reactions: Variants of the Electrophilic Bromination of Alkenes and Variants of the Application of Oxone

ERIC Educational Resources Information Center

Eissen, Marco; Strudthoff, Merle; Backhaus, Solveig; Eismann, Carolin; Oetken, Gesa; Kaling, Soren; Lenoir, Dieter

2011-01-01

Oxidation-state and donor-acceptor concepts are important areas in the chemical education. Student worksheets containing problems that emphasize oxidation numbers, redox reactions of organic compounds, and stoichiometric reaction equations are presented. All of the examples are incorporated under one unifying topic: the production of vicinal…

LSENS - GENERAL CHEMICAL KINETICS AND SENSITIVITY ANALYSIS CODE

NASA Technical Reports Server (NTRS)

Bittker, D. A.

1994-01-01

LSENS has been developed for solving complex, homogeneous, gas-phase, chemical kinetics problems. The motivation for the development of this program is the continuing interest in developing detailed chemical reaction mechanisms for complex reactions such as the combustion of fuels and pollutant formation and destruction. A reaction mechanism is the set of all elementary chemical reactions that are required to describe the process of interest. Mathematical descriptions of chemical kinetics problems constitute sets of coupled, nonlinear, first-order ordinary differential equations (ODEs). The number of ODEs can be very large because of the numerous chemical species involved in the reaction mechanism. Further complicating the situation are the many simultaneous reactions needed to describe the chemical kinetics of practical fuels. For example, the mechanism describing the oxidation of the simplest hydrocarbon fuel, methane, involves over 25 species participating in nearly 100 elementary reaction steps. Validating a chemical reaction mechanism requires repetitive solutions of the governing ODEs for a variety of reaction conditions. Analytical solutions to the systems of ODEs describing chemistry are not possible, except for the simplest cases, which are of little or no practical value. Consequently, there is a need for fast and reliable numerical solution techniques for chemical kinetics problems. In addition to solving the ODEs describing chemical kinetics, it is often necessary to know what effects variations in either initial condition values or chemical reaction mechanism parameters have on the solution. Such a need arises in the development of reaction mechanisms from experimental data. The rate coefficients are often not known with great precision and in general, the experimental data are not sufficiently detailed to accurately estimate the rate coefficient parameters. The development of a reaction mechanism is facilitated by a systematic sensitivity analysis which provides the relationships between the predictions of a kinetics model and the input parameters of the problem. LSENS provides for efficient and accurate chemical kinetics computations and includes sensitivity analysis for a variety of problems, including nonisothermal conditions. LSENS replaces the previous NASA general chemical kinetics codes GCKP and GCKP84. LSENS is designed for flexibility, convenience and computational efficiency. A variety of chemical reaction models can be considered. The models include static system, steady one-dimensional inviscid flow, reaction behind an incident shock wave including boundary layer correction, and the perfectly stirred (highly backmixed) reactor. In addition, computations of equilibrium properties can be performed for the following assigned states, enthalpy and pressure, temperature and pressure, internal energy and volume, and temperature and volume. For static problems LSENS computes sensitivity coefficients with respect to the initial values of the dependent variables and/or the three rates coefficient parameters of each chemical reaction. To integrate the ODEs describing chemical kinetics problems, LSENS uses the packaged code LSODE, the Livermore Solver for Ordinary Differential Equations, because it has been shown to be the most efficient and accurate code for solving such problems. The sensitivity analysis computations use the decoupled direct method, as implemented by Dunker and modified by Radhakrishnan. This method has shown greater efficiency and stability with equal or better accuracy than other methods of sensitivity analysis. LSENS is written in FORTRAN 77 with the exception of the NAMELIST extensions used for input. While this makes the code fairly machine independent, execution times on IBM PC compatibles would be unacceptable to most users. LSENS has been successfully implemented on a Sun4 running SunOS and a DEC VAX running VMS. With minor modifications, it should also be easily implemented on other platforms with FORTRAN compilers which support NAMELIST input. LSENS required 4Mb of RAM under SunOS 4.1.1 and 3.4Mb of RAM under VMS 5.5.1. The standard distribution medium for LSENS is a .25 inch streaming magnetic tape cartridge (QIC-24) in UNIX tar format. It is also available on a 1600 BPI 9-track magnetic tape or a TK50 tape cartridge in DEC VAX BACKUP format. Alternate distribution media and formats are available upon request. LSENS was developed in 1992.

Laboratory Studies of Homogeneous and Heterogeneous Chemical Processes of Importance in the Upper Atmosphere

NASA Technical Reports Server (NTRS)

Molina, Mario J.

2003-01-01

The objective of this study was to conduct measurements of chemical kinetics parameters for reactions of importance in the stratosphere and upper troposphere, and to study the interaction of trace gases with ice surfaces in order to elucidate the mechanism of heterogeneous chlorine activation processes, using both a theoretical and an experimental approach. The measurements were carried out under temperature and pressure conditions covering those applicable to the stratosphere and upper troposphere. The main experimental technique employed was turbulent flow-chemical ionization mass spectrometry, which is particularly well suited for investigations of radical-radical reactions.

A unifying picture of gas-phase formation and growth of PAH (Polycyclic Aromatic Hydrocarbons), soot, diamond and graphite

NASA Technical Reports Server (NTRS)

Frenklach, Michael

1990-01-01

A variety of seemingly different carbon formation processes -- polycyclic aromatic hydrocarbons and diamond in the interstellar medium, soot in hydrocarbon flames, graphite and diamond in plasma-assisted-chemical vapor deposition reactors -- may all have closely related underlying chemical reaction mechanisms. Two distinct mechanisms for gas-phase carbon growth are discussed. At high temperatures it proceeds via the formation of carbon clusters. At lower temperatures it follows a polymerization-type kinetic sequence of chemical reactions of acetylene addition to a radical, and reactivation of the resultant species through H-abstraction by a hydrogen atom.

Thin liquid films with time-dependent chemical reactions sheared by an ambient gas flow

NASA Astrophysics Data System (ADS)

Bender, Achim; Stephan, Peter; Gambaryan-Roisman, Tatiana

2017-08-01

Chemical reactions in thin liquid films are found in many industrial applications, e.g., in combustion chambers of internal combustion engines where a fuel film can develop on pistons or cylinder walls. The reactions within the film and the turbulent outer gas flow influence film stability and lead to film breakup, which in turn can lead to deposit formation. In this work we examine the evolution and stability of a thin liquid film in the presence of a first-order chemical reaction and under the influence of a turbulent gas flow. Long-wave theory with a double perturbation analysis is used to reduce the complexity of the problem and obtain an evolution equation for the film thickness. The chemical reaction is assumed to be slow compared to film evolution and the amount of reactant in the film is limited, which means that the reaction rate decreases with time as the reactant is consumed. A linear stability analysis is performed to identify the influence of reaction parameters, material properties, and environmental conditions on the film stability limits. Results indicate that exothermic reactions have a stabilizing effect whereas endothermic reactions destabilize the film and can lead to rupture. It is shown that an initially unstable film can become stable with time as the reaction rate decreases. The shearing of the film by the external gas flow leads to the appearance of traveling waves. The shear stress magnitude has a nonmonotonic influence on film stability.

Essential chemistry for biochemists

PubMed Central

Jonsson, Amanda L.; Roberts, Mark A.J.; Kiappes, J.L.; Scott, Kathryn A.

2017-01-01

Within every living organism, countless reactions occur every second. These reactions typically occur more rapidly and with greater efficiency than would be possible under the same conditions in the chemical laboratory, and while using only the subset of elements that are readily available in nature. Despite these apparent differences between life and the laboratory, biological reactions are governed by the same rules as any other chemical reaction. Thus, a firm understanding of the fundamentals of chemistry is invaluable in biochemistry. There are entire textbooks devoted to the application of chemical principles in biological systems and so it is not possible to cover all of the relevant topics in depth in this short article. The aim is instead to provide a brief overview of those areas in chemistry that are most relevant to biochemistry. We summarize the basic principles, give examples of how these principles are applied in biological systems and suggest further reading on individual topics. PMID:28951470

Skating on thin ice: surface chemistry under interstellar conditions

NASA Astrophysics Data System (ADS)

Fraser, H.; van Dishoeck, E.; Tielens, X.

Solid CO2 has been observed towards both active star forming regions and quiescent clouds (Gerakines et. al. (1999)). The high abundance of CO2 in the solid phase, and its low abundance in the gas phase, support the idea that CO2 is almost exclusively formed in the solid state. Several possible formation mechanisms have been postulated (Ruffle &Herbst (2001): Charnley &Kaufman (2000)), and the detection of CO2 towards quiescent sources such as Elias 16 (Whittet et. al. (1998)) clearly suggests that CO2 can be produced in the absence of UV or electron mediated processes. The most likely route is via the surface reactions between O atoms, or OH radicals, and CO. The tools of modern surface- science offer us the potential to determine many of the physical and chemical attributes of icy interstellar grain mantles under highly controlled conditions, that closely mimic interstellar environments. The Leiden Surface Reaction Simulation Device ( urfreside) combines UHV (UltraS High Vacuum) surface science techniques with an atomic beam to study chemical reactions occurring on the SURFACE and in the BULK of interstellar ice grain mimics. By simultaneously combining two or more surface analysis techniques, the chemical kinetics, reaction mechanisms and activation energies can be determined directly. The experiment is aimed at identifying the key barrierless reactions and desorption pathways on and in H2 O and CO ices under interstellar conditions. The results from traditional HV (high vacuum) and UHV studies of the CO + O and CO + OH reactions will be presented in this paper. Charnley, S.B., & Kaufman, M.J., 2000, ApJ, 529, L111 Gerakines, P.A., 1999, ApJ, 522, 357 Ruffle, D.P., & Herbst, E., 2001, MNRAS, 324, 1054 Whittet, D.C.B., et.al., 1998, ApJ, 498, L159

Development of an alkaline/surfactant/polymer compositional reservoir simulator

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

Bhuyan, D.

1989-01-01

The mathematical formulation of a generalized three-dimensional compositional reservoir simulator for high-pH chemical flooding processes is presented in this work. The model assumes local thermodynamic equilibrium with respect to both reaction chemistry and phase behavior and calculates equilibrium electrolyte and phase compositions as a function of time and position. The reaction chemistry considers aqueous electrolytic chemistry, precipitation/dissolution of minerals, ion exchange reactions on matrix surface, reaction of acidic components of crude oil with the bases in the aqueous solution and cation exchange reactions with the micelles. The simulator combines this detailed reaction chemistry associated with these processes with the extensivemore » physical and flow property modeling schemes of an existing chemical flood simulator (UTCHEM) to model the multiphase, multidimensional displacement processes. The formulation of the chemical equilibrium model is quite general and is adaptable to simulate a variety of chemical descriptions. In addition to its use in the simulation of high-pH chemical flooding processes, the model will find application in the simulation of other reactive flow problems like the ground water contamination, reinjection of produced water, chemical waste disposal, etc. in one, two or three dimensions and under multiphase flow conditions. In this work, the model is used to simulate several hypothetical cases of high-pH chemical floods, which include cases from a simple alkaline preflush of a micellar/polymer flood to surfactant enhanced alkaline-polymer flooding and the results are analyzed. Finally, a few published alkaline, alkaline-polymer and surfactant-alkaline-polymer corefloods are simulated and compared with the experimental results.« less

Pump-shaped dump optimal control reveals the nuclear reaction pathway of isomerization of a photoexcited cyanine dye.

PubMed

Dietzek, Benjamin; Brüggemann, Ben; Pascher, Torbjörn; Yartsev, Arkady

2007-10-31

Using optimal control as a spectroscopic tool we decipher the details of the molecular dynamics of the essential multidimensional excited-state photoisomerization - a fundamental chemical reaction of key importance in biology. Two distinct nuclear motions are identified in addition to the overall bond-twisting motion: Initially, the reaction is dominated by motion perpendicular to the torsion coordinate. At later times, a second optically active vibration drives the system along the reaction path to the bottom of the excited-state potential. The time scales of the wavepacket motion on a different part of the excited-state potential are detailed by pump-shaped dump optimal control. This technique offers new means to control a chemical reaction far from the Franck-Condon point of absorption and to map details of excited-state reaction pathways revealing unique insights into the underlying reaction mechanism.

Rapid hybridization of nucleic acids using isotachophoresis

PubMed Central

Bercovici, Moran; Han, Crystal M.; Liao, Joseph C.; Santiago, Juan G.

2012-01-01

We use isotachophoresis (ITP) to control and increase the rate of nucleic acid hybridization reactions in free solution. We present a new physical model, validation experiments, and demonstrations of this assay. We studied the coupled physicochemical processes of preconcentration, mixing, and chemical reaction kinetics under ITP. Our experimentally validated model enables a closed form solution for ITP-aided reaction kinetics, and reveals a new characteristic time scale which correctly predicts order 10,000-fold speed-up of chemical reaction rate for order 100 pM reactants, and greater enhancement at lower concentrations. At 500 pM concentration, we measured a reaction time which is 14,000-fold lower than that predicted for standard second-order hybridization. The model and method are generally applicable to acceleration of reactions involving nucleic acids, and may be applicable to a wide range of reactions involving ionic reactants. PMID:22733732

Studying mechanism of radical reactions: From radiation to nitroxides as research tools

NASA Astrophysics Data System (ADS)

Maimon, Eric; Samuni, Uri; Goldstein, Sara

2018-02-01

Radicals are part of the chemistry of life, and ionizing radiation chemistry serves as an indispensable research tool for elucidation of the mechanism(s) underlying their reactions. The ever-increasing understanding of their involvement in diverse physiological and pathological processes has expanded the search for compounds that can diminish radical-induced damage. This review surveys the areas of research focusing on radical reactions and particularly with stable cyclic nitroxide radicals, which demonstrate unique antioxidative activities. Unlike common antioxidants that are progressively depleted under oxidative stress and yield secondary radicals, nitroxides are efficient radical scavengers yielding in most cases their respective oxoammonium cations, which are readily reduced back in the tissue to the nitroxide thus continuously being recycled. Nitroxides, which not only protect enzymes, cells, and laboratory animals from diverse kinds of biological injury, but also modify the catalytic activity of heme enzymes, could be utilized in chemical and biological systems serving as a research tool for elucidating mechanisms underlying complex chemical and biochemical processes.

Future Challenges in Heterogeneous Catalysis: Understanding Catalysts under Dynamic Reaction Conditions

PubMed Central

Kalz, Kai F.; Kraehnert, Ralph; Dvoyashkin, Muslim; Dittmeyer, Roland; Gläser, Roger; Krewer, Ulrike; Reuter, Karsten

2016-01-01

Abstract In the future, (electro‐)chemical catalysts will have to be more tolerant towards a varying supply of energy and raw materials. This is mainly due to the fluctuating nature of renewable energies. For example, power‐to‐chemical processes require a shift from steady‐state operation towards operation under dynamic reaction conditions. This brings along a number of demands for the design of both catalysts and reactors, because it is well‐known that the structure of catalysts is very dynamic. However, in‐depth studies of catalysts and catalytic reactors under such transient conditions have only started recently. This requires studies and advances in the fields of 1) operando spectroscopy including time‐resolved methods, 2) theory with predictive quality, 3) kinetic modelling, 4) design of catalysts by appropriate preparation concepts, and 5) novel/modular reactor designs. An intensive exchange between these scientific disciplines will enable a substantial gain of fundamental knowledge which is urgently required. This concept article highlights recent developments, challenges, and future directions for understanding catalysts under dynamic reaction conditions. PMID:28239429

Decontamination of chemical tracers in droplets by a submerging thin film flow

NASA Astrophysics Data System (ADS)

Landel, Julien R.; McEvoy, Harry; Dalziel, Stuart B.

2016-11-01

We investigate the decontamination of chemical tracers contained in small viscous drops by a submerging falling film. This problem has applications in the decontamination of hazardous chemicals, following accidental releases or terrorist attacks. Toxic droplets lying on surfaces are cleaned by spraying a liquid decontaminant over the surface. The decontaminant film submerges the droplets, without detaching them, in order to neutralize toxic chemicals in the droplets. The decontamination process is controlled by advection, diffusion and reaction processes near the drop-film interface. Chemical tracers dissolve into the film flow forming a thin diffusive boundary layer at the interface. The chemical tracers are then neutralized through a reaction with a chemical decontaminant transported in the film. We assume in this work that the decontamination process occurs mainly in the film phase owing to low solubility of the decontaminant in the drop phase. We analyze the impact of the reaction time scale, assuming first-order reaction, in relation with the characteristic advection and diffusion time scales in the case of a single droplet. Using theoretical, numerical and experimental means, we find that the reaction time scale need to be significantly smaller than the characteristic time scale in the diffusive boundary layer in order to enhance noticeably the decontamination of a single toxic droplet. We discuss these results in the more general case of the decontamination of a large number of droplets. This material is based upon work supported by the Defense Threat Reduction Agency under Contract No. HDTRA1-12-D-0003-0001.

Anomalous Hall effect assisted by interfacial chemical reaction in perpendicular Co/Pt multilayers

NASA Astrophysics Data System (ADS)

Liu, Qian; Jiang, Shaolong; Teng, Jiao

2018-05-01

To uncover the underlying mechanism of Mg effect on the improved anomalous Hall effect (AHE) of perpendicular [Pt/Co]3/Mg/HfO2 multilayers, the X-ray photoelectron spectroscopy analysis has been carried out. It is found that Mg interlayer at the Co/HfO2 interface could prevent the Co oxidation to some extent via interfacial chemical reaction. As a result, A large anomalous Hall resistivity (ρAH) is obtained in perpendicular [Pt/Co]3/Mg/HfO2 multilayers, with a maximum ρAH of 3.02 μΩ cm, which is 59% larger than that in Co/Pt multilayers without Mg insertion. This effective modification of the AHE based on interfacial chemical reaction provides a promising pathway for spintronic applications.

pH-Controlled Oxidation of an Aromatic Ketone: Structural Elucidation of the Products of Two Green Chemical Reactions

ERIC Educational Resources Information Center

Ballard, C. Eric

2010-01-01

A laboratory experiment emphasizing the structural elucidation of organic compounds has been developed as a discovery exercise. The "unknown" compounds are the products of the pH-controlled oxidation of 4'-methoxyacetophenone with bleach. The chemoselectivity of this reaction is highly dependent on the pH of the reaction media: under basic…

Optical fiber-based on-line UV/Vis spectroscopic monitoring of chemical reaction kinetics under high pressure in a capillary microreactor.

PubMed

Benito-Lopez, Fernando; Verboom, Willem; Kakuta, Masaya; Gardeniers, J Han G E; Egberink, Richard J M; Oosterbroek, Edwin R; van den Berg, Albert; Reinhoudt, David N

2005-06-14

With a miniaturized (3 microL volume) fiber-optics based system for on-line measurement by UV/Vis spectroscopy, the reaction rate constants (at different pressures) and the activation volumes (deltaV(not =)) were determined for a nucleophilic aromatic substitution and an aza Diels-Alder reaction in a capillary microreactor.

Method and apparatus for measuring coupled flow, transport, and reaction processes under liquid unsaturated flow conditions

DOEpatents

McGrail, Bernard P.; Martin, Paul F.; Lindenmeier, Clark W.

1999-01-01

The present invention is a method and apparatus for measuring coupled flow, transport and reaction processes under liquid unsaturated flow conditions. The method and apparatus of the present invention permit distinguishing individual precipitation events and their effect on dissolution behavior isolated to the specific event. The present invention is especially useful for dynamically measuring hydraulic parameters when a chemical reaction occurs between a particulate material and either liquid or gas (e.g. air) or both, causing precipitation that changes the pore structure of the test material.

Chemical Reactions of Molecules Promoted and Simultaneously Imaged by the Electron Beam in Transmission Electron Microscopy.

PubMed

Skowron, Stephen T; Chamberlain, Thomas W; Biskupek, Johannes; Kaiser, Ute; Besley, Elena; Khlobystov, Andrei N

2017-08-15

The main objective of this Account is to assess the challenges of transmission electron microscopy (TEM) of molecules, based on over 15 years of our work in this field, and to outline the opportunities in studying chemical reactions under the electron beam (e-beam). During TEM imaging of an individual molecule adsorbed on an atomically thin substrate, such as graphene or a carbon nanotube, the e-beam transfers kinetic energy to atoms of the molecule, displacing them from equilibrium positions. Impact of the e-beam triggers bond dissociation and various chemical reactions which can be imaged concurrently with their activation by the e-beam and can be presented as stop-frame movies. This experimental approach, which we term ChemTEM, harnesses energy transferred from the e-beam to the molecule via direct interactions with the atomic nuclei, enabling accurate predictions of bond dissociation events and control of the type and rate of chemical reactions. Elemental composition and structure of the reactant molecules as well as the operating conditions of TEM (particularly the energy of the e-beam) determine the product formed in ChemTEM processes, while the e-beam dose rate controls the reaction rate. Because the e-beam of TEM acts simultaneously as a source of energy for the reaction and as an imaging tool monitoring the same reaction, ChemTEM reveals atomic-level chemical information, such as pathways of reactions imaged for individual molecules, step-by-step and in real time; structures of illusive reaction intermediates; and direct comparison of catalytic activity of different transition metals filmed with atomic resolution. Chemical transformations in ChemTEM often lead to previously unforeseen products, demonstrating the potential of this method to become not only an analytical tool for studying reactions, but also a powerful instrument for discovery of materials that can be synthesized on preparative scale.

Computational Study of Field Initiated Surface Reactions for Synthesis of Diamond and Silicon

NASA Technical Reports Server (NTRS)

Musgrave, Charles Bruce

1999-01-01

This project involves using quantum chemistry to simulate surface chemical reactions in the presence of an electric field for nanofabrication of diamond and silicon. A field delivered by a scanning tunneling microscope (STM) to a nanometer scale region of a surface affects chemical reaction potential energy surfaces (PES) to direct atomic scale surface modification to fabricate sub-nanometer structures. Our original hypothesis is that the applied voltage polarizes the charge distribution of the valence electrons and that these distorted molecular orbitals can be manipulated with the STM so as to change the relative stabilities of the electronic configurations over the reaction coordinates and thus the topology of the PES and reaction kinetics. Our objective is to investigate the effect of applied bias on surface reactions and the extent to which STM delivered fields can be used to direct surface chemical reactions on an atomic scale on diamond and silicon. To analyze the fundamentals of field induced chemistry and to investigate the application of this technique for the fabrication of nanostructures, we have employed methods capable of accurately describing molecular electronic structure. The methods we employ are density functional theory (DFT) quantum chemical (QC) methods. To determine the effect of applied bias on surface reactions we have calculated the QC PESs in various applied external fields for various reaction steps for depositing or etching diamond and silicon. We have chosen reactions which are thought to play a role in etching and the chemical vapor deposition growth of Si and diamond. The PESs of the elementary reaction steps involved are then calculated under the applied fields, which we vary in magnitude and configuration. We pay special attention to the change in the reaction barriers, and transition state locations, and search for low energy reaction channels which were inaccessible without the applied bias.

Pyrite in contact with supercritical water: the desolation of steam.

PubMed

Stirling, András; Rozgonyi, Tamás; Krack, Matthias; Bernasconi, Marco

2015-07-14

The supercritical water-pyrite interface has been studied by ab initio molecular dynamics simulation. Extreme conditions are relevant in the iron-sulfur world (ISW) theory where prebiotic chemical reactions are postulated to occur at the mineral-water interface. We have investigated the properties of this interface under such conditions. We have come to the conclusion that hot-pressurized water on pyrite leads to an interface where a dry pyrite surface is in contact with the nearby SC water without significant chemical interactions. This picture is markedly different from that under ambient conditions where the surface is fully covered with adsorbed water molecules which is of relevance for the surface reactions of the ISW hypothesis.

Chemical treatment for silica-containing glass surfaces

DOEpatents

Grabbe, Alexis; Michalske, Terry Arthur; Smith, William Larry

1999-01-01

Dehydroxylated, silica-containing, glass surfaces are known to be at least partially terminated by strained siloxane rings. According to the invention, a surface of this kind is exposed to a selected silane compound or mixture of silane compounds under reaction-promoting conditions. The ensuing reaction results in opening of the strained siloxane rings, and termination of surface atoms by chemical species, such as organic or organosilicon species, having desirable properties. These species can be chosen to provide qualities such as hydrophobicity, or improved coupling to a polymeric coating.

Chemical treatment for silica-containing glass surfaces

DOEpatents

Grabbe, Alexis; Michalske, Terry Arthur; Smith, William Larry

1998-01-01

Dehydroxylated, silica-containing, glass surfaces are known to be at least partially terminated by strained siloxane rings. According to the invention, a surface of this kind is exposed to a selected silane compound or mixture of silane compounds under reaction-promoting conditions. The ensuing reaction results in opening of the strained siloxane rings, and termination of surface atoms by chemical species, such as organic or organosilicon species, having desirable properties. These species can be chosen to provide qualities such as hydrophobicity, or improved coupling to a polymeric coating.

Chemical treatment for silica-containing glass surfaces

DOEpatents

Grabbe, Alexis; Michalske, Terry Arthur; Smith, William Larry

1999-01-01

Dehydroxylated, silica-containing, glass surfaces are known to be at least partially terminated by strained siloxane rings. According to the invention, a surface of this kind is exposed to a selected silane compound or mixture of silane compounds under reaction-promoting conditons. The ensuing reaction results in opening of the strained siloxane rings, and termination of surface atoms by chemical species, such as organic or organosilicon species, having desirable properties. These species can be chosen to provide qualities such as hydrophobicity, or improved coupling to a polymeric coating.

Mechanisms and time-resolved dynamics for trihydrogen cation (H 3 +) formation from organic molecules in strong laser fields

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

Ekanayake, Nagitha; Nairat, Muath; Kaderiya, Balram

Strong-field laser-matter interactions often lead to exotic chemical reactions. Trihydrogen cation formation from organic molecules is one such case that requires multiple bonds to break and form. Here, we present evidence for the existence of two different reaction pathways for H 3 + formation from organic molecules irradiated by a strong-field laser. Assignment of the two pathways was accomplished through analysis of femtosecond time-resolved strong-field ionization and photoion-photoion coincidence measurements carried out on methanol isotopomers, ethylene glycol, and acetone. Ab initio molecular dynamics simulations suggest the formation occurs via two steps: the initial formation of a neutral hydrogen molecule, followedmore » by the abstraction of a proton from the remaining CHOH 2+ fragment by the roaming H 2 molecule. This reaction has similarities to the H 2+H 2 + mechanism leading to formation of H 3 + in the universe. These exotic chemical reaction mechanisms, involving roaming H 2 molecules, are found to occur in the ~100 fs timescale. Roaming molecule reactions may help to explain unlikely chemical processes, involving dissociation and formation of multiple chemical bonds, occurring under strong laser fields.« less

Mechanisms and time-resolved dynamics for trihydrogen cation (H 3 +) formation from organic molecules in strong laser fields

DOE PAGES

Ekanayake, Nagitha; Nairat, Muath; Kaderiya, Balram; ...

2017-07-05

Strong-field laser-matter interactions often lead to exotic chemical reactions. Trihydrogen cation formation from organic molecules is one such case that requires multiple bonds to break and form. Here, we present evidence for the existence of two different reaction pathways for H 3 + formation from organic molecules irradiated by a strong-field laser. Assignment of the two pathways was accomplished through analysis of femtosecond time-resolved strong-field ionization and photoion-photoion coincidence measurements carried out on methanol isotopomers, ethylene glycol, and acetone. Ab initio molecular dynamics simulations suggest the formation occurs via two steps: the initial formation of a neutral hydrogen molecule, followedmore » by the abstraction of a proton from the remaining CHOH 2+ fragment by the roaming H 2 molecule. This reaction has similarities to the H 2+H 2 + mechanism leading to formation of H 3 + in the universe. These exotic chemical reaction mechanisms, involving roaming H 2 molecules, are found to occur in the ~100 fs timescale. Roaming molecule reactions may help to explain unlikely chemical processes, involving dissociation and formation of multiple chemical bonds, occurring under strong laser fields.« less

Research Issues Underlying the Four-Lab Study: Integrated Disinfection Byproducts Mixtures Research

EPA Science Inventory

Chemical disinfection of drinking water is a major public health triumph of the 20th century, resulting in significant decreases in morbidity and mortality from waterborne diseases. Disinfection byproducts (DBPs) are chemicals formed by the reaction of oxidizing disinfectants wi...

Development of High-Speed Copper Chemical Mechanical Polishing Slurry for Through Silicon Via Application Based on Friction Analysis Using Atomic Force Microscope

NASA Astrophysics Data System (ADS)

Amanokura, Jin; Ono, Hiroshi; Hombo, Kyoko

2011-05-01

In order to obtain a high-speed copper chemical mechanical polishing (CMP) process for through silicon vias (TSV) application, we developed a new Cu CMP slurry through friction analysis of Cu reaction layer by an atomic force microscope (AFM) technique. A lateral modulation friction force microscope (LM-FFM) is able to measure the friction value properly giving a vibration to the layer. We evaluated the torsional displacement between the probe of the LM-FFM and the Cu reaction layer under a 5 nm vibration to cancel the shape effect of the Cu reaction layer. The developed Cu CMP slurry forms a frictionally easy-removable Cu reaction layer.

Assessment of PDF Micromixing Models Using DNS Data for a Two-Step Reaction

NASA Astrophysics Data System (ADS)

Tsai, Kuochen; Chakrabarti, Mitali; Fox, Rodney O.; Hill, James C.

1996-11-01

Although the probability density function (PDF) method is known to treat the chemical reaction terms exactly, its application to turbulent reacting flows have been overshadowed by the ability to model the molecular mixing terms satisfactorily. In this study, two PDF molecular mixing models, the linear-mean-square-estimation (LMSE or IEM) model and the generalized interaction-by-exchange-with-the-mean (GIEM) model, are compared with the DNS data in decaying turbulence with a two-step parallel-consecutive reaction and two segregated initial conditions: ``slabs" and ``blobs". Since the molecular mixing model is expected to have a strong effect on the mean values of chemical species under such initial conditions, the model evaluation is intended to answer the following questions: Can the PDF models predict the mean values of chemical species correctly with completely segregated initial conditions? (2) Is a single molecular mixing timescale sufficient for the PDF models to predict the mean values with different initial conditions? (3) Will the chemical reactions change the molecular mixing timescales of the reacting species enough to affect the accuracy of the model's prediction for the mean values of chemical species?

Microwave-Assisted Synthesis of Phenothiazine and Quinoline Derivatives

PubMed Central

Găină, Luiza; Cristea, Castelia; Moldovan, Claudia; Porumb, Dan; Surducan, Emanoil; Deleanu, Călin; Mahamoud, Abdalah; Barbe, Jacques; Silberg, Ioan A.

2007-01-01

Application of a dynamic microwave power system in the chemical synthesis of some phenothiazine and quinoline derivatives is described. Heterocyclic ring formation, aromatic nucleophilic substitution and heterocyclic aldehydes/ketones condensation reactions were performed on solid support, or under solvent free reaction conditions. The microwave-assisted Duff formylation of phenothiazine was achieved. Comparison of microwave-assisted synthesis with the conventional synthetic methods demonstrates advantages related to shorter reaction times and in some cases better reaction yields.

Amino Acids from Icy Amines: A Radiation-Chemical Approach to Extraterrestrial Synthesis

NASA Technical Reports Server (NTRS)

Dworkin, J. P.; Moore, M. H.

2010-01-01

Detections of amino acids in meteorites go back several decades, with at least 100 such compounds being reported for the Murchison meteorite alone. The presence of these extraterrestrial molecules raises questions as to their formation, abundance, thermal stability, racemization, and possible subsequent reactions. Although all of these topics have been studied in laboratories, such work often involves many variables and unknowns. This has led us to seek out model systems with which to uncover reaction products, test chemical predictions, and sited light on underlying reaction mechanisms. This presentation will describe one such study, focusing on amino-acid formation in ices.

Chemical Characterization and Reactivity of Fuel-Oxidizer Reaction Product

NASA Technical Reports Server (NTRS)

David, Dennis D.; Dee, Louis A.; Beeson, Harold D.

1997-01-01

Fuel-oxidizer reaction product (FORP), the product of incomplete reaction of monomethylhydrazine and nitrogen tetroxide propellants prepared under laboratory conditions and from firings of Shuttle Reaction Control System thrusters, has been characterized by chemical and thermal analysis. The composition of FORP is variable but falls within a limited range of compositions that depend on three factors: the fuel-oxidizer ratio at the time of formation; whether the composition of the post-formation atmosphere is reducing or oxidizing; and the reaction or post-reaction temperature. A typical composition contains methylhydrazinium nitrate, ammonium nitrate, methylammonium nitrate, and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. Thermal decomposition reactions of the FORP compositions used in this study were unremarkable. Neither the various compositions of FORP, the pure major components of FORP, nor mixtures of FORP with propellant system corrosion products showed any unusual thermal activity when decomposed under laboratory conditions. Off-limit thruster operations were simulated by rapid mixing of liquid monomethylhydrazine and liquid nitrogen tetroxide in a confined space. These tests demonstrated that monomethylhydrazine, methylhydrazinium nitrate, ammonium nitrate, or Inconel corrosion products can induce a mixture of monomethylhydrazine and nitrogen tetroxide to produce component-damaging energies. Damaging events required FORP or metal salts to be present at the initial mixing of monomethylhydrazine and nitrogen tetroxide.

Theoretical modeling of PEB procedure on EUV resist using FDM formulation

NASA Astrophysics Data System (ADS)

Kim, Muyoung; Moon, Junghwan; Choi, Joonmyung; Lee, Byunghoon; Jeong, Changyoung; Kim, Heebom; Cho, Maenghyo

2018-03-01

Semiconductor manufacturing industry has reduced the size of wafer for enhanced productivity and performance, and Extreme Ultraviolet (EUV) light source is considered as a promising solution for downsizing. A series of EUV lithography procedures contain complex photo-chemical reaction on photoresist, and it causes technical difficulties on constructing theoretical framework which facilitates rigorous investigation of underlying mechanism. Thus, we formulated finite difference method (FDM) model of post exposure bake (PEB) process on positive chemically amplified resist (CAR), and it involved acid diffusion coupled-deprotection reaction. The model is based on Fick's second law and first-order chemical reaction rate law for diffusion and deprotection, respectively. Two kinetic parameters, diffusion coefficient of acid and rate constant of deprotection, which were obtained by experiment and atomic scale simulation were applied to the model. As a result, we obtained time evolutional protecting ratio of each functional group in resist monomer which can be used to predict resulting polymer morphology after overall chemical reactions. This achievement will be the cornerstone of multiscale modeling which provides fundamental understanding on important factors for EUV performance and rational design of the next-generation photoresist.

Dynamic Responses and Initial Decomposition under Shock Loading: A DFTB Calculation Combined with MSST Method for β-HMX with Molecular Vacancy.

PubMed

He, Zheng-Hua; Chen, Jun; Ji, Guang-Fu; Liu, Li-Min; Zhu, Wen-Jun; Wu, Qiang

2015-08-20

Despite extensive efforts on studying the decomposition mechanism of HMX under extreme condition, an intrinsic understanding of mechanical and chemical response processes, inducing the initial chemical reaction, is not yet achieved. In this work, the microscopic dynamic response and initial decomposition of β-HMX with (1 0 0) surface and molecular vacancy under shock condition, were explored by means of the self-consistent-charge density-functional tight-binding method (SCC-DFTB) in conjunction with multiscale shock technique (MSST). The evolutions of various bond lengths and charge transfers were analyzed to explore and understand the initial reaction mechanism of HMX. Our results discovered that the C-N bond close to major axes had less compression sensitivity and higher stretch activity. The charge was transferred mainly from the N-NO2 group along the minor axes and H atom to C atom during the early compression process. The first reaction of HMX primarily initiated with the fission of the molecular ring at the site of the C-N bond close to major axes. Further breaking of the molecular ring enhanced intermolecular interactions and promoted the cleavage of C-H and N-NO2 bonds. More significantly, the dynamic response behavior clearly depended on the angle between chemical bond and shock direction.

Reaction front dynamics under shear flow for arbitrary Damköhler numbers

NASA Astrophysics Data System (ADS)

Bandopadhyay, Aditya; Méheust, Yves; Le Borgne, Tanguy

2016-04-01

Reaction fronts where two reactive fluids displace one another play an important role in a range of applications, including contaminant plume transport and reaction, soil and aquifer remediation, CO2 sequestration, geothermal dipoles and the development of hotspots of reaction in mixing zones. The background flow induces enhanced mixing, and therefore reaction, through interfacial shear. Hence the coupling of fluid flow with chemical reactions is pivotal in understanding and quantifying effective reaction kinetics in reaction fronts. While this problem has been addressed in the limit of fast reactions (e.g. de Simoni 2005, Le Borgne 2014), in natural systems reactions can span a large range of Damköhler numbers since their characteristic reaction times vary over a large range of typical values. Here the coupling of shear flow and reversible chemical reactions is studied for a reaction front with initially separated reactants at arbitrary Damköhler numbers. Approximate analytical expressions for the global production rate are derived based on a reactive lamella approach. We observe three distinct regimes, each of them characterized by different scalings of the global production rate and width of the reactive zone. We describe the dependency of these scalings and the associated characteristic transition times as a function of Damköhler and Péclet numbers. These results are validated against 2D numerical simulations. The study is expected to shed light on the inherently complex cases of reactive mixing with varying reaction rates under the influence of an imposed flow. de Simoni et al. (2005) Water Resour. Res., 41, W11410 Le Borgne et al. (2014) GRL, 41(22), 7898

Engaging unactivated alkyl, alkenyl and aryl iodides in visible-light-mediated free radical reactions

NASA Astrophysics Data System (ADS)

Nguyen, John D.; D'Amato, Erica M.; Narayanam, Jagan M. R.; Stephenson, Corey R. J.

2012-10-01

Radical reactions are a powerful class of chemical transformations. However, the formation of radical species to initiate these reactions has often required the use of stoichiometric amounts of toxic reagents, such as tributyltin hydride. Recently, the use of visible-light-mediated photoredox catalysis to generate radical species has become popular, but the scope of these radical precursors has been limited. Here, we describe the identification of reaction conditions under which photocatalysts such as fac-Ir(ppy)3 can be utilized to form radicals from unactivated alkyl, alkenyl and aryl iodides. The generated radicals undergo reduction via hydrogen atom abstraction or reductive cyclization. The reaction protocol utilizes only inexpensive reagents, occurs under mild reaction conditions, and shows exceptional functional group tolerance. Reaction efficiency is maintained upon scale-up and decreased catalyst loading, and the reaction time can be significantly shortened when the reaction is performed in a flow reactor.

An Analytical Framework for Studying Small-Number Effects in Catalytic Reaction Networks: A Probability Generating Function Approach to Chemical Master Equations

PubMed Central

Nakagawa, Masaki; Togashi, Yuichi

2016-01-01

Cell activities primarily depend on chemical reactions, especially those mediated by enzymes, and this has led to these activities being modeled as catalytic reaction networks. Although deterministic ordinary differential equations of concentrations (rate equations) have been widely used for modeling purposes in the field of systems biology, it has been pointed out that these catalytic reaction networks may behave in a way that is qualitatively different from such deterministic representation when the number of molecules for certain chemical species in the system is small. Apart from this, representing these phenomena by simple binary (on/off) systems that omit the quantities would also not be feasible. As recent experiments have revealed the existence of rare chemical species in cells, the importance of being able to model potential small-number phenomena is being recognized. However, most preceding studies were based on numerical simulations, and theoretical frameworks to analyze these phenomena have not been sufficiently developed. Motivated by the small-number issue, this work aimed to develop an analytical framework for the chemical master equation describing the distributional behavior of catalytic reaction networks. For simplicity, we considered networks consisting of two-body catalytic reactions. We used the probability generating function method to obtain the steady-state solutions of the chemical master equation without specifying the parameters. We obtained the time evolution equations of the first- and second-order moments of concentrations, and the steady-state analytical solution of the chemical master equation under certain conditions. These results led to the rank conservation law, the connecting state to the winner-takes-all state, and analysis of 2-molecules M-species systems. A possible interpretation of the theoretical conclusion for actual biochemical pathways is also discussed. PMID:27047384

Open quantum system approach to the modeling of spin recombination reactions.

PubMed

Tiersch, M; Steiner, U E; Popescu, S; Briegel, H J

2012-04-26

In theories of spin-dependent radical pair reactions, the time evolution of the radical pair, including the effect of the chemical kinetics, is described by a master equation in the Liouville formalism. For the description of the chemical kinetics, a number of possible reaction operators have been formulated in the literature. In this work, we present a framework that allows for a unified description of the various proposed mechanisms and the forms of reaction operators for the spin-selective recombination processes. On the basis of the concept that master equations can be derived from a microscopic description of the spin system interacting with external degrees of freedom, it is possible to gain insight into the underlying microscopic processes and develop a systematic approach toward determining the specific form of the reaction operator in concrete scenarios.

Entropy-driven loss of gas-phase Group 5 species from GOLD/3-5 compound semiconductor systems

NASA Astrophysics Data System (ADS)

Pugh, J. H.; Williams, R. S.

1986-02-01

Temperature dependent chemical interactions between Au and nine 3-5 compound semiconductors (3=A1, Ga, In and V=P, As, Sb) have been calculated using bulk thermodynamic properties. Enthalpic considerations alone are insufficient to predict metal/compound-semiconductor reactivities. The entropy of vaporization of the group 5 elements is shown to be an extremely important driving force for chemical reactions involving the 3-5's, since it enables several endothermic reactions to occur spontaneously under certain temperature and pressure conditions. Plots of either Gibb's free energies of reaction or equilibrium vapor pressure of the group 5 element versus temperature are used to predict critical reaction temperatures for each of the systems studied. These plots agree extremely well with previous experimental observations of thin film reactions of Au on GaAs.

Conifer defenses and xylophagous insects

Treesearch

Alexandr S. Rozhkov; Galina I. Massel

1991-01-01

The resistance of woody plants to phytophage damage consists of a universal system of mechanisms: 1) repellent chemicals, 2) defensive reactions both mechanical and chemical, 3) retention of viability under disturbed metabolism and low biomass accumulation, and 4) recuperative capacity. Siberian coniferous tree species, with the exception of Larix...

Digital isothermal quantification of nucleic acids via simultaneous chemical initiation of recombinase polymerase amplification reactions on SlipChip.

PubMed

Shen, Feng; Davydova, Elena K; Du, Wenbin; Kreutz, Jason E; Piepenburg, Olaf; Ismagilov, Rustem F

2011-05-01

In this paper, digital quantitative detection of nucleic acids was achieved at the single-molecule level by chemical initiation of over one thousand sequence-specific, nanoliter isothermal amplification reactions in parallel. Digital polymerase chain reaction (digital PCR), a method used for quantification of nucleic acids, counts the presence or absence of amplification of individual molecules. However, it still requires temperature cycling, which is undesirable under resource-limited conditions. This makes isothermal methods for nucleic acid amplification, such as recombinase polymerase amplification (RPA), more attractive. A microfluidic digital RPA SlipChip is described here for simultaneous initiation of over one thousand nL-scale RPA reactions by adding a chemical initiator to each reaction compartment with a simple slipping step after instrument-free pipet loading. Two designs of the SlipChip, two-step slipping and one-step slipping, were validated using digital RPA. By using the digital RPA SlipChip, false-positive results from preinitiation of the RPA amplification reaction before incubation were eliminated. End point fluorescence readout was used for "yes or no" digital quantification. The performance of digital RPA in a SlipChip was validated by amplifying and counting single molecules of the target nucleic acid, methicillin-resistant Staphylococcus aureus (MRSA) genomic DNA. The digital RPA on SlipChip was also tolerant to fluctuations of the incubation temperature (37-42 °C), and its performance was comparable to digital PCR on the same SlipChip design. The digital RPA SlipChip provides a simple method to quantify nucleic acids without requiring thermal cycling or kinetic measurements, with potential applications in diagnostics and environmental monitoring under resource-limited settings. The ability to initiate thousands of chemical reactions in parallel on the nanoliter scale using solvent-resistant glass devices is likely to be useful for a broader range of applications.

Digital Isothermal Quantification of Nucleic Acids via Simultaneous Chemical Initiation of Recombinase Polymerase Amplification Reactions on SlipChip

PubMed Central

Shen, Feng; Davydova, Elena K.; Du, Wenbin; Kreutz, Jason E.; Piepenburg, Olaf; Ismagilov, Rustem F.

2011-01-01

In this paper, digital quantitative detection of nucleic acids was achieved at the single-molecule level by chemical initiation of over one thousand sequence-specific, nanoliter, isothermal amplification reactions in parallel. Digital polymerase chain reaction (digital PCR), a method used for quantification of nucleic acids, counts the presence or absence of amplification of individual molecules. However it still requires temperature cycling, which is undesirable under resource-limited conditions. This makes isothermal methods for nucleic acid amplification, such as recombinase polymerase amplification (RPA), more attractive. A microfluidic digital RPA SlipChip is described here for simultaneous initiation of over one thousand nL-scale RPA reactions by adding a chemical initiator to each reaction compartment with a simple slipping step after instrument-free pipette loading. Two designs of the SlipChip, two-step slipping and one-step slipping, were validated using digital RPA. By using the digital RPA SlipChip, false positive results from pre-initiation of the RPA amplification reaction before incubation were eliminated. End-point fluorescence readout was used for “yes or no” digital quantification. The performance of digital RPA in a SlipChip was validated by amplifying and counting single molecules of the target nucleic acid, Methicillin-resistant Staphylococcus aureus (MRSA) genomic DNA. The digital RPA on SlipChip was also tolerant to fluctuations of the incubation temperature (37–42 °C), and its performance was comparable to digital PCR on the same SlipChip design. The digital RPA SlipChip provides a simple method to quantify nucleic acids without requiring thermal cycling or kinetic measurements, with potential applications in diagnostics and environmental monitoring under resource-limited settings. The ability to initiate thousands of chemical reactions in parallel on the nanoliter scale using solvent-resistant glass devices is likely to be useful for a broader range of applications. PMID:21476587

Impact of High Concentration Solutions on Hydraulic Properties of Geosynthetic Clay Liner Materials

PubMed Central

Xue, Qiang; Zhang, Qian; Liu, Lei

2012-01-01

This study focuses on the impact of landfill high concentration solutions erosion on geosynthetic clay liner (GCL) materials permeability. The permeation tests on the GCL, submerged using different kinds of solutions with different concentrations, were carried out systematically by taking these chemical solutions as permeant liquids. Based on seasonal variations of ion concentrations in Chenjiachong landfill leachate (Wuhan Province), CaCl2, MgCl2, NaCl, and KCl were selected as chemical attack solutions to carry out experimental investigations under three concentrations (50 mM, 100 mM, 200 mM) and soak times (5, 10, and 20 days). The variation law of the GCL hydraulic conductivity under different operating conditions was analyzed. The relationship between GCL hydraulic conductivity, chemical solutions categories, concentrations, and soak times were further discussed. The GCL hydraulic conductivity, when soaked and permeated with high concentration chemical solutions, increases several times or exceeds two orders of magnitude, as compared with the permeation test under normal conditions that used water as the permeant liquid. This reveals that GCL is very susceptible to chemical attack. For four chemical solutions, the chemical attack effect on GCL hydraulic conductivity is CaCl2 > MgCl2 > KCl > NaCl. The impact of soak times on GCL hydraulic conductivity is the cooperative contribution of the liner chemical attack reaction and hydration swelling. A longer soak time results in a more advantageous hydration swelling effect. The chemical attack reaction restrains the hydration swelling of the GCL. Moreover, the GCL hydraulic conductivity exponentially decreases with the increased amplitude of thickness.

Single-Molecule Fluorescence Imaging for Studying Organic, Organometallic, and Inorganic Reaction Mechanisms

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

Blum, Suzanne A.

2016-05-24

The reactive behavior of individual molecules is seldom observed, because we usually measure the average properties of billions of molecules. What we miss is important: the catalytic activity of less than 1% of the molecules under observation can dominate the outcome of a chemical reaction seen at a macroscopic level. Currently available techniques to examine reaction mechanisms (such as nuclear magnetic resonance spectroscopy and mass spectrometry) study molecules as an averaged ensemble. These ensemble techniques are unable to detect minor components (under ~1%) in mixtures or determine which components in the mixture are responsible for reactivity and catalysis. In themore » field of mechanistic chemistry, there is a resulting heuristic device that if an intermediate is very reactive in catalysis, it often cannot be observed (termed “Halpern’s Rule” ). Ultimately, the development of single-molecule imaging technology could be a powerful tool to observe these “unobservable” intermediates and active catalysts. Single-molecule techniques have already transformed biology and the understanding of biochemical processes. The potential of single-molecule fluorescence microscopy to address diverse chemical questions, such as the chemical reactivity of organometallic or inorganic systems with discrete metal complexes, however, has not yet been realized. In this respect, its application to chemical systems lags significantly behind its application to biophysical systems. This transformative imaging technique has broad, multidisciplinary impact with the potential to change the way the chemistry community studies reaction mechanisms and reactivity distributions, especially in the core area of catalysis.« less

Chemical Reactions of Portland Cement with Aqueous CO2 and Their Impacts on Cement's Mechanical Properties under Geologic CO2 Sequestration Conditions.

PubMed

Li, Qingyun; Lim, Yun Mook; Flores, Katharine M; Kranjc, Kelly; Jun, Young-Shin

2015-05-19

To provide information on wellbore cement integrity in the application of geologic CO2 sequestration (GCS), chemical and mechanical alterations were analyzed for cement paste samples reacted for 10 days under GCS conditions. The reactions were at 95 °C and had 100 bar of either N2 (control condition) or CO2 contacting the reaction brine solution with an ionic strength of 0.5 M adjusted by NaCl. Chemical analyses showed that the 3.0 cm × 1.1 cm × 0.3 cm samples were significantly attacked by aqueous CO2 and developed layer structures with a total attacked depth of 1220 μm. Microscale mechanical property analyses showed that the hardness and indentation modulus of the carbonated layer were 2-3 times greater than for the intact cement, but those in the portlandite-dissolved region decreased by ∼50%. The strength and elastic modulus of the bulk cement samples were reduced by 93% and 84%, respectively. The properties of the microscale regions, layer structure, microcracks, and swelling of the outer layers combined to affect the overall mechanical properties. These findings improve understanding of wellbore integrity from both chemical and mechanical viewpoints and can be utilized to improve the safety and efficiency of CO2 storage.

Unraveling the mysteries of microwave chemistry using silicon carbide reactor technology.

PubMed

Kappe, C Oliver

2013-07-16

In the past few years, the use of microwave energy to heat chemical reactions has become an increasingly popular theme in the scientific community. This nonclassical heating technique has slowly progressed from a laboratory curiosity to an established method commonly used both in academia and in industry. Because of its efficiency, microwave heating dramatically reduces reaction times (from days and hours to minutes and seconds) and improves product purities or material properties among other advantages. Since the early days of microwave chemistry, researchers have observed rate-accelerations and, in some cases, altered product distributions as compared with reactions carried out using classical oil-bath heating. As a result, researchers have speculated that so-called specific or nonthermal microwave effects could be responsible for these differences. Much of the debate has centered on the question of whether the electromagnetic field can exert a direct influence on a chemical transformation outside of the simple macroscopic change in bulk reaction temperature. In 2009, our group developed a relatively simple "trick" that allows us to rapidly evaluate whether an observed effect seen in a microwave-assisted reaction results from a purely thermal phenomenon, or involves specific or nonthermal microwave effects. We use a microwave reaction vessel made from silicon carbide (SiC) ceramic. Because of its high microwave absorptivity, the vessel shields its contents from the electromagnetic field. As a result, we can easily mimic a conventionally heated autoclave experiment inside a microwave reactor under carefully controlled reaction conditions. The switch from an almost microwave transparent glass (Pyrex) to a strongly microwave absorbing SiC reaction vial under otherwise identical reaction conditions (temperature profiles, pressure, stirring speed) then allows us to carefully evaluate the influence of the electromagnetic field on the particular chemical transformation. Over the past five years we have subjected a wide variety of chemical transformations, including organic reactions, preparations of inorganic nanoparticles, and the hydrolysis of proteins, to the "SiC test." In nearly all of the studied examples, we obtained identical results from reactions carried out in Pyrex vials and those carried out in SiC vials. The data obtained from these investigations confirm that in the overwhelming majority of cases a bulk temperature phenomenon drives the enhancements in microwave chemistry and that the electromagnetic field has no direct influence on the reaction pathway.

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

Bellesia, Giovanni; Bales, Benjamin B.

Here, we investigate, via Brownian dynamics simulations, the reaction dynamics of a generic, nonlinear chemical network under spatial confinement and crowding conditions. In detail, the Willamowski-Rossler chemical reaction system has been “extended” and considered as a prototype reaction-diffusion system. These results are potentially relevant to a number of open problems in biophysics and biochemistry, such as the synthesis of primitive cellular units (protocells) and the definition of their role in the chemical origin of life and the characterization of vesicle-mediated drug delivery processes. More generally, the computational approach presented in this work makes the case for the use of spatialmore » stochastic simulation methods for the study of biochemical networks in vivo where the “well-mixed” approximation is invalid and both thermal and intrinsic fluctuations linked to the possible presence of molecular species in low number copies cannot be averaged out.« less

An autonomous chemically fuelled small-molecule motor

NASA Astrophysics Data System (ADS)

Wilson, Miriam R.; Solà, Jordi; Carlone, Armando; Goldup, Stephen M.; Lebrasseur, Nathalie; Leigh, David A.

2016-06-01

Molecular machines are among the most complex of all functional molecules and lie at the heart of nearly every biological process. A number of synthetic small-molecule machines have been developed, including molecular muscles, synthesizers, pumps, walkers, transporters and light-driven and electrically driven rotary motors. However, although biological molecular motors are powered by chemical gradients or the hydrolysis of adenosine triphosphate (ATP), so far there are no synthetic small-molecule motors that can operate autonomously using chemical energy (that is, the components move with net directionality as long as a chemical fuel is present). Here we describe a system in which a small molecular ring (macrocycle) is continuously transported directionally around a cyclic molecular track when powered by irreversible reactions of a chemical fuel, 9-fluorenylmethoxycarbonyl chloride. Key to the design is that the rate of reaction of this fuel with reactive sites on the cyclic track is faster when the macrocycle is far from the reactive site than when it is near to it. We find that a bulky pyridine-based catalyst promotes carbonate-forming reactions that ratchet the displacement of the macrocycle away from the reactive sites on the track. Under reaction conditions where both attachment and cleavage of the 9-fluorenylmethoxycarbonyl groups occur through different processes, and the cleavage reaction occurs at a rate independent of macrocycle location, net directional rotation of the molecular motor continues for as long as unreacted fuel remains. We anticipate that autonomous chemically fuelled molecular motors will find application as engines in molecular nanotechnology.

Size-dependent chemical ageing of oleic acid aerosol under dry and humidified conditions

NASA Astrophysics Data System (ADS)

Al-Kindi, Suad S.; Pope, Francis D.; Beddows, David C.; Bloss, William J.; Harrison, Roy M.

2016-12-01

A chemical reaction chamber system has been developed for the processing of oleic acid aerosol particles with ozone under two relative humidity conditions: dry and humidified to 65 %. The apparatus consists of an aerosol flow tube, in which the ozonolysis occurs, coupled to a scanning mobility particle sizer (SMPS) and an aerosol time-of-flight mass spectrometer (ATOFMS) which measure the evolving particle size and composition. Under both relative humidity conditions, ozonolysis results in a significant decrease in particle size and mass which is consistent with the formation of volatile products that partition from the particle to the gas phase. Mass spectra derived from the ATOFMS reveal the presence of the typically observed reaction products: azelaic acid, nonanal, oxononanoic acid and nonanoic acid, as well as a range of higher molecular weight products deriving from the reactions of reaction intermediates with oleic acid and its oxidation products. These include octanoic acid and 9- and 10-oxooctadecanoic acid, as well as products of considerably higher molecular weight. Quantitative evaluation of product yields with the ATOFMS shows a marked dependence upon both particle size association (from 0.3 to 2.1 µm diameter) and relative humidity. Under both relative humidity conditions, the percentage residual of oleic acid increases with increasing particle size and the main lower molecular weight products are nonanal and oxononanoic acid. Under dry conditions, the percentage of higher molecular weight products increases with increasing particle size due to the poorer internal mixing of the larger particles. Under humidified conditions, the percentage of unreacted oleic acid is greater, except in the smallest particle fraction, with little formation of high molecular weight products relative to the dry particles. It is postulated that water reacts with reactive intermediates, competing with the processes which produce high molecular weight products. Whilst the oleic acid model aerosol system is of limited relevance to complex internally mixed atmospheric aerosol, the generic findings presented in this paper give useful insights into the nature of heterogeneous chemical processes.

Quantum Chemical Insight into the LiF Interlayer Effects in Organic Electronics: Reactions between Al Atom and LiF Clusters.

PubMed

Wu, Shui-Xing; Kan, Yu-He; Li, Hai-Bin; Zhao, Liang; Wu, Yong; Su, Zhong-Min

2015-08-06

It is well known that the aluminum cathode performs dramatically better when a thin lithium fluoride (LiF) layer inserted in organic electronic devices. The doping effect induced by the librated Li atom via the chemical reactions producing AlF3 as byproduct was previously proposed as one of possible mechanisms. However, the underlying mechanism discussion is quite complicated and not fully understood so far, although the LiF interlayer is widely used. In this paper, we perform theoretical calculations to consider the reactions between an aluminum atom and distinct LiF clusters. The reaction pathways of the Al-(LiF)n (n = 2, 4, 16) systems were discovered and the energetics were theoretically evaluated. The release of Li atom and the formation of AlF3 were found in two different chemical reaction routes. The undissociated Al-(LiF)n systems have chances to change to some structures with loosely bound electrons. Our findings about the interacted Al-(LiF)n systems reveal new insights into the LiF interlayer effects in organic electronics applications.

Laser-induced multi-energy processing in diamond growth

NASA Astrophysics Data System (ADS)

Xie, Zhiqiang

Laser-induced multi-energy processing (MEP) introduces resonant vibrational excitations of precursor molecules to conventional chemical vapor deposition methods for material synthesis. In this study, efforts were extended to explore the capability of resonant vibrational excitations for promotion of energy efficiency in chemical reactions, for enhancement of diamond deposition, and for control of chemical reactions. The research project mainly focused on resonant vibrational excitations of precursor molecules using lasers in combustion flame deposition of diamond, which led to: 1) promotion of chemical reactions; 2) enhancement of diamond growth with higher growth rate and better crystallizations; 3) steering of chemical reactions which lead to preferential growth of {100}-oriented diamond films and crystals; and 4) mode-selective excitations of precursor molecules toward bond-selective control of chemical reactions. Diamond films and crystals were deposited in open air by combustion flame deposition through resonant vibrational excitations of precursor molecules, including ethylene (C2H4) and propylene (C3H 6). A kilowatt wavelength-tunable CO2 laser with spectral range from 9.2 to 10.9 microm was tuned to match vibrational modes of the precursor molecules. Resonant vibrational excitations of these molecules were achieved with high energy efficiency as compared with excitations using a common CO2 laser (fixed wavelength at 10.591microm). With resonant vibrational excitations, the diamond growth rate was increased; diamond quality was promoted; diamond crystals with lengths up to 5 mm were deposited in open air; preferential growth of {100}-oriented diamond films and single crystals was achieved; mode-selective excitations of precursor molecules were investigated toward control of chemical reactions. Optical emission spectroscopy (OES), mass spectrometry (MS), and molecular dynamic simulations were conducted to obtain an in-depth understanding of the resonant vibrational excitations. Species concentrations in flames without and with laser excitations under different wavelengths were investigated both experimentally and theoretically. Detection of C2, CH, and OH radicals, as well as CxHy species and their oxides (CxH yO) (x=1, 2; y=0˜5) using OES and MS, together with reaction pathway simulations, were used to explain the effect of vibrational excitations of precursor molecules on chemical reactions and on diamond depositions.

Laser induced sonofusion: A new road toward thermonuclear reactions

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

Sadighi-Bonabi, Rasoul, E-mail: Sadighi@sharif.ir; Gheshlaghi, Maryam; Laser and optics research school, Nuclear Science and Technology Research Institute

2016-03-15

The Possibility of the laser assisted sonofusion is studied via single bubble sonoluminescence (SBSL) in Deuterated acetone (C{sub 3}D{sub 6}O) using quasi-adiabatic and hydro-chemical simulations at the ambient temperatures of 0 and −28.5 °C. The interior temperature of the produced bubbles in Deuterated acetone is 1.6 × 10{sup 6} K in hydro-chemical model and it is reached up to 1.9 × 10{sup 6} K in the laser induced SBSL bubbles. Under these circumstances, temperature up to 10{sup 7} K can be produced in the center of the bubble in which the thermonuclear D-D fusion reactions are promising under the controlled conditions.

Concordant Chemical Reaction Networks and the Species-Reaction Graph

PubMed Central

Shinar, Guy; Feinberg, Martin

2015-01-01

In a recent paper it was shown that, for chemical reaction networks possessing a subtle structural property called concordance, dynamical behavior of a very circumscribed (and largely stable) kind is enforced, so long as the kinetics lies within the very broad and natural weakly monotonic class. In particular, multiple equilibria are precluded, as are degenerate positive equilibria. Moreover, under certain circumstances, also related to concordance, all real eigenvalues associated with a positive equilibrium are negative. Although concordance of a reaction network can be decided by readily available computational means, we show here that, when a nondegenerate network’s Species-Reaction Graph satisfies certain mild conditions, concordance and its dynamical consequences are ensured. These conditions are weaker than earlier ones invoked to establish kinetic system injectivity, which, in turn, is just one ramification of network concordance. Because the Species-Reaction Graph resembles pathway depictions often drawn by biochemists, results here expand the possibility of inferring significant dynamical information directly from standard biochemical reaction diagrams. PMID:22940368

An equation-free probabilistic steady-state approximation: dynamic application to the stochastic simulation of biochemical reaction networks.

PubMed

Salis, Howard; Kaznessis, Yiannis N

2005-12-01

Stochastic chemical kinetics more accurately describes the dynamics of "small" chemical systems, such as biological cells. Many real systems contain dynamical stiffness, which causes the exact stochastic simulation algorithm or other kinetic Monte Carlo methods to spend the majority of their time executing frequently occurring reaction events. Previous methods have successfully applied a type of probabilistic steady-state approximation by deriving an evolution equation, such as the chemical master equation, for the relaxed fast dynamics and using the solution of that equation to determine the slow dynamics. However, because the solution of the chemical master equation is limited to small, carefully selected, or linear reaction networks, an alternate equation-free method would be highly useful. We present a probabilistic steady-state approximation that separates the time scales of an arbitrary reaction network, detects the convergence of a marginal distribution to a quasi-steady-state, directly samples the underlying distribution, and uses those samples to accurately predict the state of the system, including the effects of the slow dynamics, at future times. The numerical method produces an accurate solution of both the fast and slow reaction dynamics while, for stiff systems, reducing the computational time by orders of magnitude. The developed theory makes no approximations on the shape or form of the underlying steady-state distribution and only assumes that it is ergodic. We demonstrate the accuracy and efficiency of the method using multiple interesting examples, including a highly nonlinear protein-protein interaction network. The developed theory may be applied to any type of kinetic Monte Carlo simulation to more efficiently simulate dynamically stiff systems, including existing exact, approximate, or hybrid stochastic simulation techniques.

CO2 hydrogenation to methanol on supported Au catalysts under moderate reaction conditions: support and particle size effects.

PubMed

Hartadi, Yeusy; Widmann, Daniel; Behm, R Jürgen

2015-02-01

The potential of metal oxide supported Au catalysts for the formation of methanol from CO2 and H2 under conditions favorable for decentralized and local conversion, which could be concepts for chemical energy storage, was investigated. Significant differences in the catalytic activity and selectivity of Au/Al2 O3 , Au/TiO2 , AuZnO, and Au/ZrO2 catalysts for methanol formation under moderate reaction conditions at a pressure of 5 bar and temperatures between 220 and 240 °C demonstrate pronounced support effects. A high selectivity (>50 %) for methanol formation was obtained only for Au/ZnO. Furthermore, measurements on Au/ZnO samples with different Au particle sizes reveal distinct Au particle size effects: although the activity increases strongly with the decreasing particle size, the selectivity decreases. The consequences of these findings for the reaction mechanism and for the potential of Au/ZnO catalysts for chemical energy storage and a "green" methanol technology are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrathin Metallic Nanowire-Based Architectures as High-Performing Electrocatalysts

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

Li, Luyao; Wong, Stanislaus S.

Fuel cells (FCs) convert chemical energy into electricity through electrochemical reactions. They maintain desirable functional advantages that render them as attractive candidates for renewable energy alternatives. However, the high cost and general scarcity of conventional FC catalysts largely limit the ubiquitous application of this device configuration. For example, under current consumption requirements, there is an insufficient global reserve of Pt to provide for the needs of an effective FC for every car produced. Therefore, it is absolutely necessary in the future to replace Pt either completely or in part with far more plentiful, abundant, cheaper, and potentially less toxic firstmore » row transition metals, because the high cost-to-benefit ratio of conventional catalysts is and will continue to be a major limiting factor preventing mass commercialization. We and other groups have explored a number of nanowire-based catalytic architectures, which are either Pt-free or with reduced Pt content, as an energy efficient solution with improved performance metrics versus conventional, currently commercially available Pt nanoparticles that are already well established in the community. Specifically, in this Perspective, we highlight strategies aimed at the rational modification of not only the physical structure but also the chemical composition as a means of developing superior electrocatalysts for a number of small-molecule-based anodic oxidation and cathodic reduction reactions, which underlie the overall FC behavior. In particular, we focus on efforts to precisely, synergistically, and simultaneously tune not only the size, morphology, architectural motif, surface chemistry, and chemical composition of the as-generated catalysts but also the nature of the underlying support so as to controllably improve performance metrics of the hydrogen oxidation reaction, the methanol oxidation reaction, the ethanol oxidation reaction, and the formic acid oxidation reaction, in addition to the oxygen reduction reaction.« less

Chemical reactions induced by oscillating external fields in weak thermal environments

NASA Astrophysics Data System (ADS)

Craven, Galen T.; Bartsch, Thomas; Hernandez, Rigoberto

2015-02-01

Chemical reaction rates must increasingly be determined in systems that evolve under the control of external stimuli. In these systems, when a reactant population is induced to cross an energy barrier through forcing from a temporally varying external field, the transition state that the reaction must pass through during the transformation from reactant to product is no longer a fixed geometric structure, but is instead time-dependent. For a periodically forced model reaction, we develop a recrossing-free dividing surface that is attached to a transition state trajectory [T. Bartsch, R. Hernandez, and T. Uzer, Phys. Rev. Lett. 95, 058301 (2005)]. We have previously shown that for single-mode sinusoidal driving, the stability of the time-varying transition state directly determines the reaction rate [G. T. Craven, T. Bartsch, and R. Hernandez, J. Chem. Phys. 141, 041106 (2014)]. Here, we extend our previous work to the case of multi-mode driving waveforms. Excellent agreement is observed between the rates predicted by stability analysis and rates obtained through numerical calculation of the reactive flux. We also show that the optimal dividing surface and the resulting reaction rate for a reactive system driven by weak thermal noise can be approximated well using the transition state geometry of the underlying deterministic system. This agreement persists as long as the thermal driving strength is less than the order of that of the periodic driving. The power of this result is its simplicity. The surprising accuracy of the time-dependent noise-free geometry for obtaining transition state theory rates in chemical reactions driven by periodic fields reveals the dynamics without requiring the cost of brute-force calculations.

Ultrathin Metallic Nanowire-Based Architectures as High-Performing Electrocatalysts

DOE PAGES

Li, Luyao; Wong, Stanislaus S.

2018-03-19

Fuel cells (FCs) convert chemical energy into electricity through electrochemical reactions. They maintain desirable functional advantages that render them as attractive candidates for renewable energy alternatives. However, the high cost and general scarcity of conventional FC catalysts largely limit the ubiquitous application of this device configuration. For example, under current consumption requirements, there is an insufficient global reserve of Pt to provide for the needs of an effective FC for every car produced. Therefore, it is absolutely necessary in the future to replace Pt either completely or in part with far more plentiful, abundant, cheaper, and potentially less toxic firstmore » row transition metals, because the high cost-to-benefit ratio of conventional catalysts is and will continue to be a major limiting factor preventing mass commercialization. We and other groups have explored a number of nanowire-based catalytic architectures, which are either Pt-free or with reduced Pt content, as an energy efficient solution with improved performance metrics versus conventional, currently commercially available Pt nanoparticles that are already well established in the community. Specifically, in this Perspective, we highlight strategies aimed at the rational modification of not only the physical structure but also the chemical composition as a means of developing superior electrocatalysts for a number of small-molecule-based anodic oxidation and cathodic reduction reactions, which underlie the overall FC behavior. In particular, we focus on efforts to precisely, synergistically, and simultaneously tune not only the size, morphology, architectural motif, surface chemistry, and chemical composition of the as-generated catalysts but also the nature of the underlying support so as to controllably improve performance metrics of the hydrogen oxidation reaction, the methanol oxidation reaction, the ethanol oxidation reaction, and the formic acid oxidation reaction, in addition to the oxygen reduction reaction.« less

Analysis of chemical reaction kinetics of depredating organic pollutants from secondary effluent of wastewater treatment plant in constructed wetlands.

PubMed

Wang, Hao; Jiang, Dengling; Yang, Yong; Cao, Guoping

2013-01-01

Four subsurface constructed wetlands were built to treat the secondary effluent of a wastewater treatment plant in Tangshan, China. The chemical pollutant indexes of chemical oxygen demand (COD) were analyzed to evaluate the removal efficiency of organic pollutants from the secondary effluent of the wastewater treatment plant. In all cases, the subsurface constructed wetlands were efficient in treating organic pollutants. Under the same hydraulic loading condition, the horizontal flow wetlands exhibited better efficiency of COD removal than vertical flow wetlands: the removal rates in horizontal flow wetlands could be maintained at 68.4 ± 2.42% to 92.2 ± 1.61%, compared with 63.8 ± 1.19% to 85.0 ± 1.25% in the vertical flow wetlands. Meanwhile, the chemical reaction kinetics of organic pollutants was analyzed, and the results showed that the degradation courses of the four subsurface wetlands all corresponded with the first order reaction kinetics to a large extent.

Numerical investigation of biogas diffusion flames characteristics under several operation conditions in counter-flow configuration with an emphasis on thermal and chemical effects of CO2 in the fuel mixture

NASA Astrophysics Data System (ADS)

Mameri, A.; Tabet, F.; Hadef, A.

2017-08-01

This study addresses the influence of several operating conditions (composition and ambient pressure) on biogas diffusion flame structure and NO emissions with particular attention on thermal and chemical effect of CO2. The biogas flame is modeled by a counter flow diffusion flame and analyzed in mixture fraction space using flamelet approach. The GRI Mech-3.0 mechanism that involves 53 species and 325 reactions is adopted for the oxidation chemistry. It has been observed that flame properties are very sensitive to biogas composition and pressure. CO2 addition decreases flame temperature by both thermal and chemical effects. Added CO2 may participate in chemical reaction due to thermal dissociation (chemical effect). Excessively supplied CO2 plays the role of pure diluent (thermal effect). The ambient pressure rise increases temperature and reduces flame thickness, radiation losses and dissociation amount. At high pressure, recombination reactions coupled with chain carrier radicals reduction, diminishes NO mass fraction.

A polymer supported Cu(I) catalyst for the 'click reaction' in aqueous media.

PubMed

Ul Islam, Rafique; Taher, Abu; Choudhary, Meenakshi; Witcomb, Michael J; Mallick, Kaushik

2015-01-21

Polymer stabilized monovalent copper has been synthesized using an in situ chemical transformation route and was characterized by means of different microscopic, optical and surface characterization techniques, which offered information about the chemical structure of the polymer and the morphology of the complex. The supramolecular material, Cu(i)-poly(2-aminobenzoic acid), denoted Cu(i)-pABA, showed catalytic activity for the cycloaddition reaction between terminal alkynes and azides to synthesize 1,2,3-triazoles with excellent yields. The catalyst was recovered from the reaction mixture and recycled several times without an appreciable loss of catalytic activity. The whole strategy was done under ambient conditions and in the presence of water as a solvent.

Method for chemical surface modification of fumed silica particles

DOEpatents

Grabbe, Alexis; Michalske, Terry Arthur; Smith, William Larry

1999-01-01

Dehydroxylated, silica-containing, glass surfaces are known to be at least partially terminated by strained siloxane rings. According to the invention, a surface of this kind is exposed to a selected silane compound or mixture of silane compounds under reaction-promoting conditions. The ensuing reaction results in opening of the strained siloxane rings, and termination of surface atoms by chemical species, such as organic or organosilicon species, having desirable properties. These species can be chosen to provide qualities such as hydrophobicity, or improved coupling to a polymeric coating.

Remarkable nanoconfinement effects on chemical equilibrium manifested in nucleotide dimerization and H-D exchange reactions.

PubMed

Polak, Micha; Rubinovich, Leonid

2011-10-06

Nanoconfinement entropic effects on chemical equilibrium involving a small number of molecules, which we term NCECE, are revealed by two widely diverse types of reactions. Employing statistical-mechanical principles, we show how the NCECE effect stabilizes nucleotide dimerization observed within self-assembled molecular cages. Furthermore, the effect provides the basis for dimerization even under an aqueous environment inside the nanocage. Likewise, the NCECE effect is pertinent to a longstanding issue in astrochemistry, namely the extra deuteration commonly observed for molecules reacting on interstellar dust grain surfaces. The origin of the NCECE effect is elucidated by means of the probability distributions of the reaction extent and related variations in the reactant-product mixing entropy. Theoretical modelling beyond our previous preliminary work highlights the role of the nanospace size in addition to that of the nanosystem size, namely the limited amount of molecules in the reaction mixture. Furthermore, the NCECE effect can depend also on the reaction mechanism, and on deviations from stoichiometry. The NCECE effect, leading to enhanced, greatly variable equilibrium "constants", constitutes a unique physical-chemical phenomenon, distinguished from the usual thermodynamical properties of macroscopically large systems. Being significant particularly for weakly exothermic reactions, the effects should stabilize products in other closed nanoscale structures, and thus can have notable implications for the growing nanotechnological utilization of chemical syntheses conducted within confined nanoreactors.

Experimental Study on Impact-Induced Reaction Characteristics of PTFE/Ti Composites Enhanced by W Particles.

PubMed

Li, Yan; Wang, Zaicheng; Jiang, Chunlan; Niu, Haohao

2017-02-13

Metal/fluoropolymer composites are a category of energetic structural materials that release energy through exothermic chemical reactions initiated under highly dynamic loadings. In this paper, the chemical reaction mechanism of PTFE (polytetrafluoroethylene)/Ti/W composites is investigated through thermal analysis and composition analysis. These composites undergo exothermic reactions at 510 °C to 600 °C, mainly producing TiF x . The tungsten significantly reduces the reaction heat due to its inertness. In addition, the dynamic compression properties and impact-induced reaction behaviors of PTFE/Ti/W composites with different W content prepared by pressing and sintering are studied using Split Hopkinson Pressure Bar and high speed photography. The results show that both the mechanical strength and the reaction degree are significantly improved with the increasing strain rate. Moreover, as W content increases, the mechanical strength is enhanced, but the elasticity/plasticity is decreased. The PTFE/Ti/W composites tend to become more inert with the increasing W content, which is reflected by the reduced reaction degree and the increased reaction threshold for the impact ignition.

Experimental Study on Impact-Induced Reaction Characteristics of PTFE/Ti Composites Enhanced by W Particles

PubMed Central

Li, Yan; Wang, Zaicheng; Jiang, Chunlan; Niu, Haohao

2017-01-01

Metal/fluoropolymer composites are a category of energetic structural materials that release energy through exothermic chemical reactions initiated under highly dynamic loadings. In this paper, the chemical reaction mechanism of PTFE (polytetrafluoroethylene)/Ti/W composites is investigated through thermal analysis and composition analysis. These composites undergo exothermic reactions at 510 °C to 600 °C, mainly producing TiFx. The tungsten significantly reduces the reaction heat due to its inertness. In addition, the dynamic compression properties and impact-induced reaction behaviors of PTFE/Ti/W composites with different W content prepared by pressing and sintering are studied using Split Hopkinson Pressure Bar and high speed photography. The results show that both the mechanical strength and the reaction degree are significantly improved with the increasing strain rate. Moreover, as W content increases, the mechanical strength is enhanced, but the elasticity/plasticity is decreased. The PTFE/Ti/W composites tend to become more inert with the increasing W content, which is reflected by the reduced reaction degree and the increased reaction threshold for the impact ignition. PMID:28772534

Prebiotic Synthesis of Autocatalytic Products From Formaldehyde-Derived Sugars as the Carbon and Energy Source

NASA Technical Reports Server (NTRS)

Weber, Arthur L.

2003-01-01

Our research objective is to understand and model the chemical processes on the primitive Earth that generated the first autocatalytic molecules and microstructures involved in the origin of life. Our approach involves: (a) investigation of a model origin-of-life process named the Sugar Model that is based on the reaction of formaldehyde- derived sugars (trioses and tetroses) with ammonia, and (b) elucidation of the constraints imposed on the chemistry of the origin of life by the fixed energies and rates of C,H,O-organic reactions under mild aqueous conditions. Recently, we demonstrated that under mild aqueous conditions the Sugar Model process yields autocatalytic products, and generates organic micropherules (2-20 micron dia.) that exhibit budding, size uniformity, and chain formation. We also discovered that the sugar substrates of the Sugar Model are capable of reducing nitrite to ammonia under mild aqueous conditions. In addition studies done in collaboration with Sandra Pizzarrello (Arizona State University) revealed that chiral amino acids (including meteoritic isovaline) catalyze both the synthesis and specific handedness of chiral sugars. Our systematic survey of the energies and rates of reactions of C,H,O-organic substrates under mild aqueous conditions revealed several general principles (rules) that govern the direction and rate of organic reactions. These reactivity principles constrain the structure of chemical pathways used in the origin of life, and in modern and primitive metabolism.

Prediction of contaminant persistence in aqueous phase: a quantum chemical approach.

PubMed

Blotevogel, Jens; Mayeno, Arthur N; Sale, Tom C; Borch, Thomas

2011-03-15

At contaminated field sites where active remediation measures are not feasible, monitored natural attenuation is sometimes the only alternative for surface water or groundwater decontamination. However, due to slow degradation rates of some contaminants under natural conditions, attenuation processes and their performance assessment can take several years to decades to complete. Here, we apply quantum chemical calculations to predict contaminant persistence in the aqueous phase. For the test compound hexamethylphosphoramide (HMPA), P-N bond hydrolysis is the only thermodynamically favorable reaction that may lead to its degradation under reducing conditions. Through calculation of aqueous Gibbs free energies of activation for all potential reaction mechanisms, it is predicted that HMPA hydrolyzes via an acid-catalyzed mechanism at pH < 8.2, and an uncatalyzed mechanism at pH 8.2-8.5. The estimated half-lives of thousands to hundreds of thousands of years over the groundwater-typical pH range of 6.0 to 8.5 indicate that HMPA will be persistent in the absence of suitable oxidants. At pH 0, where the hydrolysis reaction is rapid enough to enable measurement, the experimentally determined rate constant and half-life are in excellent agreement with the predicted values. Since the quantum chemical methodology described herein can be applied to virtually any contaminant or reaction of interest, it is especially valuable for the prediction of persistence when slow reaction rates impede experimental investigations and appropriate QSARs are unavailable.

Effect of operating parameters on bio-fuel production from waste furniture sawdust.

PubMed

Uzun, Basak Burcu; Kanmaz, Gülin

2013-04-01

Fast pyrolysis is an effective technology for conversion of biomass into energy and value-added chemicals instead of burning them directly. In this study, fast pyrolysis of waste furniture sawdust (pine sawdust) was investigated under various reaction conditions (reaction time, pyrolysis temperature, heating rate, residence time and particle size) in a tubular reactor. The optimum reaction conditions for bio-oil production was found as reaction time of 5 min, pyrolysis temperature of 500 °C, heating rate of 300 °C min(-1) under nitrogen flow rate of 400 cm(3) min(-1). At these conditions, maximum bio-oil yield was obtained as 42.09%. Pyrolysis oils were characterized by using various elemental analyses, fourier - transformation infrared (FT-IR) spectrometry and gas chromatography-mass spectrometry (GC-MS). The results of the GC-MS showed that cracking of large molecular phenolics was followed by partial conversion into phenol and alkylated phenols (45%) during the pyrolysis. According to the experimental and characterization results; the liquid product could be used as feedstock for the chemical industry or petroleum crude for refinery.

Chemical reactions in reverse micelle systems

DOEpatents

Matson, Dean W.; Fulton, John L.; Smith, Richard D.; Consani, Keith A.

1993-08-24

This invention is directed to conducting chemical reactions in reverse micelle or microemulsion systems comprising a substantially discontinuous phase including a polar fluid, typically an aqueous fluid, and a microemulsion promoter, typically a surfactant, for facilitating the formation of reverse micelles in the system. The system further includes a substantially continuous phase including a non-polar or low-polarity fluid material which is a gas under standard temperature and pressure and has a critical density, and which is generally a water-insoluble fluid in a near critical or supercritical state. Thus, the microemulsion system is maintained at a pressure and temperature such that the density of the non-polar or low-polarity fluid exceeds the critical density thereof. The method of carrying out chemical reactions generally comprises forming a first reverse micelle system including an aqueous fluid including reverse micelles in a water-insoluble fluid in the supercritical state. Then, a first reactant is introduced into the first reverse micelle system, and a chemical reaction is carried out with the first reactant to form a reaction product. In general, the first reactant can be incorporated into, and the product formed in, the reverse micelles. A second reactant can also be incorporated in the first reverse micelle system which is capable of reacting with the first reactant to form a product.

Phase Analysis of Laser Direct Etching and Water Assisted Laser Combined Etching of SiC Ceramics

NASA Astrophysics Data System (ADS)

Yuan, Genfu; Cong, Qidong; Zhang, Chen; Xie, Bingbing

2017-12-01

In this study, to discover the etching mechanism of SiC ceramics under laser direct etching and water-jet assisted laser combined etching, the phenomena of substance change on the etched surface were investigated. Also, the rules of substance transfer in etching are discussed. The elemental content change and the phase change of the etching products on the etched surface were analyzed by energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD), respectively. These studies showed a high amount of carbon black on the etched surface, because of the decomposition of SiC ceramics under the high-power-density laser irradiation. SiC decomposed to Si under the laser irradiation, and the subsequent chemical reaction of Si and O2 easily produced SiO2. The SiO2 on the etched surface melted and vaporized, whereas most of SiO2 was removed through splashing, changing the chemical composition of the etched surface. Following the water jet introduction, an increased amount of O existed on the combined etching surface, because the chemical reaction of SiC and H2O easily produced SiO2 under the high-power-density laser irradiation.

MESOSCOPIC MODELING OF STOCHASTIC REACTION-DIFFUSION KINETICS IN THE SUBDIFFUSIVE REGIME

PubMed Central

BLANC, EMILIE; ENGBLOM, STEFAN; HELLANDER, ANDREAS; LÖTSTEDT, PER

2017-01-01

Subdiffusion has been proposed as an explanation of various kinetic phenomena inside living cells. In order to fascilitate large-scale computational studies of subdiffusive chemical processes, we extend a recently suggested mesoscopic model of subdiffusion into an accurate and consistent reaction-subdiffusion computational framework. Two different possible models of chemical reaction are revealed and some basic dynamic properties are derived. In certain cases those mesoscopic models have a direct interpretation at the macroscopic level as fractional partial differential equations in a bounded time interval. Through analysis and numerical experiments we estimate the macroscopic effects of reactions under subdiffusive mixing. The models display properties observed also in experiments: for a short time interval the behavior of the diffusion and the reaction is ordinary, in an intermediate interval the behavior is anomalous, and at long times the behavior is ordinary again. PMID:29046618

Symmetry Relations in Chemical Kinetics Arising from Microscopic Reversibility

NASA Astrophysics Data System (ADS)

Adib, Artur B.

2006-01-01

It is shown that the kinetics of time-reversible chemical reactions having the same equilibrium constant but different initial conditions are closely related to one another by a directly measurable symmetry relation analogous to chemical detailed balance. In contrast to detailed balance, however, this relation does not require knowledge of the elementary steps that underlie the reaction, and remains valid in regimes where the concept of rate constants is ill defined, such as at very short times and in the presence of low activation barriers. Numerical simulations of a model of isomerization in solution are provided to illustrate the symmetry under such conditions, and potential applications in protein folding or unfolding are pointed out.

The OH-initiated atmospheric chemical reactions of polyfluorinated dibenzofurans and polychlorinated dibenzofurans: A comparative theoretical study.

PubMed

Zeng, Xiaolan; Chen, Jing; Qu, Ruijuan; Pan, Xiaoxue; Wang, Zunyao

2017-02-01

The atmospheric chemical reactions of some polyfluorinated dibenzofurans (PFDFs) and polychlorinated dibenzofurans (PCDFs), initiated by OH radical, were investigated by performing theoretical calculations using density functional theory (DFT) and B3LYP/6-311++G(2df,p) method. The obtained results indicate that OH addition reactions of PFDFs and PCDFs occurring at C 1∼4 and C A sites are thermodynamic spontaneous changes and the branching ratio of the PF(C)DF-OH adducts is decided primarily by kinetic factor. The OH addition reactions of PFDFs taking place at fluorinated C 1∼4 positions are kinetically comparable with those occurring at nonfluorinated C 1∼4 positions, while OH addition reactions of PCDFs occurring at chlorinated C 1∼4 sites are negligible. The total rate constants of the addition reactions of PFDFs or PCDFs become smaller with consecutive fluorination or chlorination, and substituting at C 1 position has more adverse effects than substitution at other sites. The succedent O 2 addition reactions of PF(C)DF-OH adducts are thermodynamic nonspontaneous processes under the atmospheric conditions, and have high Gibbs free energies of activation (Δ r G ≠ ). The substituted dibenzofuranols are the primary oxidation products for PCDFs under the atmospheric conditions. However, other oxidative products may also be available for PFDFs besides substituted dibenzofuranols. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ionic screening and dissociation are crucial for understanding chemical self-propulsion in polar solvents.

PubMed

Brown, Aidan T; Poon, Wilson C K; Holm, Christian; de Graaf, Joost

2017-02-08

Polar solvents like water support the bulk dissociation of themselves and their solutes into ions, and the re-association of these ions into neutral molecules in a dynamic equilibrium, e.g., H 2 O 2 ⇌ H + + HO 2 - . Using continuum theory, we study the influence of these association-dissociation reactions on the self-propulsion of colloids driven by surface chemical reactions (chemical swimmers). We find that association-dissociation reactions should have a strong influence on swimmers' behaviour, and therefore should be included in future modelling. In particular, such bulk reactions should permit charged swimmers to propel electrophoretically even if all species involved in the surface reactions are neutral. The bulk reactions also significantly modify the predicted speed of chemical swimmers propelled by ionic currents, by up to an order of magnitude. For swimmers whose surface reactions produce both anions and cations (ionic self-diffusiophoresis), the bulk reactions produce an additional reactive screening length, analogous to the Debye length in electrostatics. This in turn leads to an inverse relationship between swimmer radius and swimming speed, which could provide an alternative explanation for recent experimental observations on Pt-polystyrene Janus swimmers [S. Ebbens et al., Phys. Rev. E: Stat., Nonlinear, Soft Matter Phys., 2012, 85, 020401]. We also use our continuum theory to investigate the effect of the Debye screening length itself, going beyond the infinitely-thin-screening-length approximation used by previous analytical theories. We identify significant departures from this limiting behaviour for micron-sized swimmers under typical experimental conditions and find that the approximation fails entirely for nanoscale swimmers.

A kinetic study on the chemical cleavage of nucleoside diphosphate sugars.

PubMed

Huhta, Eija; Parjanen, Atte; Mikkola, Satu

2010-03-30

Nucleoside diphosphate sugars serve in essential roles in metabolic processes. They have, therefore, been used in mechanistic studies on glycosylation reactions, and their analogues have been synthesised as enzyme and receptor inhibitors. Despite extensive biochemical research, little is known about their chemical reactions. In the present work the chemical cleavage of two different types of nucleoside diphosphate sugars has been studied. UDP-Glc is phosphorylated at the anomeric carbon, whereas in ADP-Rib C-1 is unsubstituted, allowing hence the equilibrium between cyclic hemiacetal and acyclic carbonyl forms. Due to the structural difference, these substrates react via different pathways under slightly alkaline conditions: while UDP-Glc reacts exclusively by a nucleophilic attack of a glucose hydroxyl group on the diphosphate moiety, ADP-Rib undergoes a complex reaction sequence that involves isomerisation processes of the acyclic ribose sugar and results in a release of ADP. Copyright 2009 Elsevier Ltd. All rights reserved.

Nitrous oxide production from reactive nitrification intermediates: a concerted action of biological and chemical processes

NASA Astrophysics Data System (ADS)

Brüggemann, Nicolas; Heil, Jannis; Liu, Shurong; Wei, Jing; Vereecken, Harry

2017-04-01

This contribution tries to open up a new perspective on biogeochemical N2O production processes, taking the term bio-geo-chemistry literally. What if a major part of N2O is produced from reactive intermediates of microbiological N turnover processes ("bio…") leaking out of the involved microorganisms into the soil ("…geo…") and then reacting chemically ("…chemistry") with the surrounding matrix? There are at least two major reactive N intermediates that might play a significant role in these coupled biological-chemical reactions, i.e. hydroxylamine (NH2OH) and nitrite (NO2-), both of which are produced during nitrification under oxic conditions, while NO2- is also produced during denitrification under anoxic conditions. Furthermore, NH2OH is assumed to be also a potential intermediate of DNRA and/or anammox. First, this contribution will summarize information about several chemical reactions involving NH2OH and NO2- leading to the formation of N2O. These abiotic reactions are: reactions of NO2- with reduced metal cations, nitrosation reactions of NO2- and soil organic matter (SOM), the reaction between NO2- and NH2OH, and the oxidation of NH2OH by oxidized metal ions. While these reactions can occur over a broad range of soil characteristics, they are ignored in most current N trace gas studies in favor of biological processes only. Disentangling microbiological from purely chemical N2O production is further complicated by the fact that the chemically formed N2O is either undiscernible from N2O produced during nitrification, or shows an intermediate 15N site preference between that of N2O from nitrification and denitrification, respectively. Results from experiments with live and sterilized soil samples, with artificial soil mixtures and with phenolic lignin decomposition model compounds will be presented that demonstrate the potential contribution of these abiotic processes to soil N trace gas emissions, given a substantial leakage rate of these reactive intermediates into the soil matrix. It will be shown that the magnitude of these chemically produced N2O fluxes is not only governed by soil nitrogen availability and soil water content, but also by organic matter content and composition, pH, redox conditions and redox-active metal ion content. The presented data reveal that the interplay between biological and chemical processes is relevant for soil N2O emissions. The integration of these processes and their additional controlling variables in soil N trace gas emission models would very likely have a great potential for reducing the uncertainty in emission model results and for facilitating the design of appropriate, site-specific N2O mitigation strategies.

Optimization of silicon oxynitrides by plasma-enhanced chemical vapor deposition for an interferometric biosensor

NASA Astrophysics Data System (ADS)

Choo, Sung Joong; Lee, Byung-Chul; Lee, Sang-Myung; Park, Jung Ho; Shin, Hyun-Joon

2009-09-01

In this paper, silicon oxynitride layers deposited with different plasma-enhanced chemical vapor deposition (PECVD) conditions were fabricated and optimized, in order to make an interferometric sensor for detecting biochemical reactions. For the optimization of PECVD silicon oxynitride layers, the influence of the N2O/SiH4 gas flow ratio was investigated. RF power in the PEVCD process was also adjusted under the optimized N2O/SiH4 gas flow ratio. The optimized silicon oxynitride layer was deposited with 15 W in chamber under 25/150 sccm of N2O/SiH4 gas flow rates. The clad layer was deposited with 20 W in chamber under 400/150 sccm of N2O/SiH4 gas flow condition. An integrated Mach-Zehnder interferometric biosensor based on optical waveguide technology was fabricated under the optimized PECVD conditions. The adsorption reaction between bovine serum albumin (BSA) and the silicon oxynitride surface was performed and verified with this device.

High temperature chemical kinetic study of the H2-CO-CO2-NO reaction system

NASA Technical Reports Server (NTRS)

Jachimowski, C. J.

1975-01-01

An experimental study of the kinetics of the H2-CO-CO2-NO reaction system was made behind incident shock waves at temperatures of 2460 and 2950 K. The overall rate of the reaction was measured by monitoring radiation from the CO + O yields CO2 + h upoilon reaction. Correlation of these data with a detailed reaction mechanism showed that the high-temperature rate of the reaction N + OH yields NO + H can be described by the low-temperature (320 K) rate coefficient. Catalytic dissociation of molecular hydrogen was an important reaction under the tests conditions.

Reaction monitoring using hyperpolarized NMR with scaling of heteronuclear couplings by optimal tracking

NASA Astrophysics Data System (ADS)

Zhang, Guannan; Schilling, Franz; Glaser, Steffen J.; Hilty, Christian

2016-11-01

Off-resonance decoupling using the method of Scaling of Heteronuclear Couplings by Optimal Tracking (SHOT) enables determination of heteronuclear correlations of chemical shifts in single scan NMR spectra. Through modulation of J-coupling evolution by shaped radio frequency pulses, off resonance decoupling using SHOT pulses causes a user-defined dependence of the observed J-splitting, such as the splitting of 13C peaks, on the chemical shift offset of coupled nuclei, such as 1H. Because a decoupling experiment requires only a single scan, this method is suitable for characterizing on-going chemical reactions using hyperpolarization by dissolution dynamic nuclear polarization (D-DNP). We demonstrate the calculation of [13C, 1H] chemical shift correlations of the carbanionic active sites from hyperpolarized styrene polymerized using sodium naphthalene as an initiator. While off resonance decoupling by SHOT pulses does not enhance the resolution in the same way as a 2D NMR spectrum would, the ability to obtain the correlations in single scans makes this method ideal for determination of chemical shifts in on-going reactions on the second time scale. In addition, we present a novel SHOT pulse that allows to scale J-splittings 50% larger than the respective J-coupling constant. This feature can be used to enhance the resolution of the indirectly detected chemical shift and reduce peak overlap, as demonstrated in a model reaction between p-anisaldehyde and isobutylamine. For both pulses, the accuracy is evaluated under changing signal-to-noise ratios (SNR) of the peaks from reactants and reaction products, with an overall standard deviation of chemical shift differences compared to reference spectra of 0.02 ppm when measured on a 400 MHz NMR spectrometer. Notably, the appearance of decoupling side-bands, which scale with peak intensity, appears to be of secondary importance.

Kinetics in the real world: linking molecules, processes, and systems.

PubMed

Kohse-Höinghaus, Katharina; Troe, Jürgen; Grabow, Jens-Uwe; Olzmann, Matthias; Friedrichs, Gernot; Hungenberg, Klaus-Dieter

2018-04-25

Unravelling elementary steps, reaction pathways, and kinetic mechanisms is key to understanding the behaviour of many real-world chemical systems that span from the troposphere or even interstellar media to engines and process reactors. Recent work in chemical kinetics provides detailed information on the reactive changes occurring in chemical systems, often on the atomic or molecular scale. The optimisation of practical processes, for instance in combustion, catalysis, battery technology, polymerisation, and nanoparticle production, can profit from a sound knowledge of the underlying fundamental chemical kinetics. Reaction mechanisms can combine information gained from theory and experiments to enable the predictive simulation and optimisation of the crucial process variables and influences on the system's behaviour that may be exploited for both monitoring and control. Chemical kinetics, as one of the pillars of Physical Chemistry, thus contributes importantly to understanding and describing natural environments and technical processes and is becoming increasingly relevant for interactions in and with the real world.

Sulfide chemiluminescence detection

DOEpatents

Spurlin, Stanford R.; Yeung, Edward S.

1985-01-01

A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction.

The combustion of Al-CuO powder mixture under shock wave initiation of the reaction

NASA Astrophysics Data System (ADS)

Ananev, S. Yu; Yankovsky, B. D.; Dolgoborodov, A. Yu

2018-01-01

The results of experiments on monitoring of manifestations of chemical transformation of Al-CuO powder mixture as a result of shock loading are given. Speeds of shift and expansion of chemical transformation area in free space are determined. The data about structure of combustion area of are received. The temperature of combustion area is measured. The duration of chemical transformation is determined.

Enhanced reaction kinetics and reactive mixing scale dynamics in mixing fronts under shear flow for arbitrary Damköhler numbers

NASA Astrophysics Data System (ADS)

Bandopadhyay, Aditya; Le Borgne, Tanguy; Méheust, Yves; Dentz, Marco

2017-02-01

Mixing fronts, where fluids of different chemical compositions mix with each other, are known to represent hotspots of chemical reaction in hydrological systems. These fronts are typically subjected to velocity gradients, ranging from the pore scale due to no slip boundary conditions at fluid solid interfaces, to the catchment scale due to permeability variations and complex geometry of the Darcy velocity streamlines. A common trait of these processes is that the mixing interface is strained by shear. Depending on the Péclet number Pe , which represents the ratio of the characteristic diffusion time to the characteristic shear time, and the Damköhler number Da , which represents the ratio of the characteristic diffusion time to the characteristic reaction time, the local reaction rates can be strongly impacted by the dynamics of the mixing interface. So far, this impact has been characterized mostly either in kinetics-limited or in mixing-limited conditions, that is, for either low or high Da. Here the coupling of shear flow and chemical reactivity is investigated for arbitrary Damköhler numbers, for a bimolecular reaction and an initial interface with separated reactants. Approximate analytical expressions for the global production rate and reactive mixing scale are derived based on a reactive lamella approach that allows for a general coupling between stretching enhanced mixing and chemical reactions. While for Pe < Da , reaction kinetics and stretching effects are decoupled, a scenario which we name "weak stretching", for Pe > Da , we uncover a "strong stretching" scenario where new scaling laws emerge from the interplay between reaction kinetics, diffusion, and stretching. The analytical results are validated against numerical simulations. These findings shed light on the effect of flow heterogeneity on the enhancement of chemical reaction and the creation of spatially localized hotspots of reactivity for a broad range of systems ranging from kinetic limited to mixing limited situations.

REACTION OF AMINO-ACIDS AND PEPTIDE BONDS WITH FORMALDEHYDE AS MEASURED BY CHANGES IN THE ULTRA-VIOLET SPECTRA,

DTIC Science & Technology

AMINO ACIDS , CHEMICAL REACTIONS), (*PEPTIDES, CHEMICAL REACTIONS), (*FORMALDEHYDE, CHEMICAL REACTIONS), (*ULTRAVIOLET SPECTROSCOPY, PROTEINS), ABSORPTION SPECTRA, CHEMICAL BONDS, AMIDES, CHEMICAL EQUILIBRIUM, REACTION KINETICS

Photochemistry of limonene secondary organic aerosol studied with chemical ionization mass spectrometry

NASA Astrophysics Data System (ADS)

Pan, Xiang

Limonene is one of the most abundant monoterpenes in the atmosphere. Limonene easily reacts with gas-phase oxidants in air such as NO3, ozone and OH. Secondary organic aerosol (SOA) is formed when low vapor pressure products condense into particles. Chemicals in SOA particles can undergo further reactions with oxidants and with solar radiation that significantly change SOA composition over the course of several days. The goal of this work was to characterize radiation induced reaction in SOA. To perform experiments, we have designed and constructed an Atmospheric Pressure Chemical Ionization Mass Spectrometer (APCIMS) coupled to a photochemical cell containing SOA samples. In APCIMS, (H2O)nH 3O+ clusters are generated in a 63Ni source and react with gaseous organic analytes. Most organic chemicals are not fragmented by the ionization process. We have focused our attention on limonene SOA prepared in two different ways. The first type of SOA is produced by oxidation of limonene by ozone; and the second type of SOA is formed by the NO3-induced oxidation of limonene. They model the SOA formed under daytime and nighttime conditions, respectively. Ozone initiated oxidation is the most important chemical sink for limonene both indoors, where it is used for cleaning purposes, and outdoors. Terpenes are primarily oxidized by reactions with NO3 at night time. We generated limonene SOA under different ozone and limonene concentrations. The resulting SOA samples were exposed to wavelength-tunable radiation in the UV-Visible range between 270 nm and 630 nm. The results show that the photodegradation rates strongly depend on radiation wavelengths. Gas phase photodegradation products such as acetone, formaldehyde, acetaldehyde, and acetic acid were shown to have different production rates for SOA formed in different concentration conditions. Even for SOA prepared under the lowest concentrations, the SOA photodegradation was efficient. The conclusion is that exposure of SOA to solar radiation causes significant chemical aging in SOA species.

The Corrosion Behavior of Pure Iron under Solid Na₂SO₄ Deposit in Wet Oxygen Flow at 500 °C.

PubMed

Tang, Yanbing; Liu, Li; Fan, Lei; Li, Ying; Wang, Fuhui

2014-08-27

The corrosion behavior of pure Fe under a Na₂SO₄ deposit in an atmosphere of O₂ + H₂O was investigated at 500 °C by thermo gravimetric, and electrochemical measurements, viz . potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and surface characterization methods viz . X-ray diffraction (XRD), and scanning electron microscope (SEM)/energy dispersive spectroscopy(EDS). The results showed that a synergistic effect occurred between Na₂SO₄ and O₂ + H₂O, which significantly accelerated the corrosion rate of the pure Fe. Briefly, NaFeO₂ was formed in addition to the customary Fe oxides; at the same time, H₂SO₄ gas was produced by introduction of water vapor. Subsequently, an electrochemical corrosion reaction occurred due to the existence of Na₂SO₄, NaFeO₂, and H₂O. When this coupled to the chemical corrosion reaction, the progress of the chemical corrosion reaction was promoted and eventually resulted in the acceleration of the corrosion of the pure Fe.

Ultrafast Chemistry under Nonequilibrium Conditions and the Shock to Deflagration Transition at the Nanoscale

DOE PAGES

Wood, Mitchell A.; Cherukara, Mathew J.; Kober, Edward M.; ...

2015-06-13

We use molecular dynamics simulations to describe the chemical reactions following shock-induced collapse of cylindrical pores in the high-energy density material RDX. For shocks with particle velocities of 2 km/s we find that the collapse of a 40 nm diameter pore leads to a deflagration wave. Molecular collisions during the collapse lead to ultrafast, multistep chemical reactions that occur under nonequilibrium conditions. WE found that exothermic products formed during these first few picoseconds prevent the nanoscale hotspot from quenching. Within 30 ps, a local deflagration wave develops. It propagates at 0.25 km/s and consists of an ultrathin reaction zone ofmore » only ~5 nm, thus involving large temperature and composition gradients. Contrary to the assumptions in current models, a static thermal hotspot matching the dynamical one in size and thermodynamic conditions fails to produce a deflagration wave indicating the importance of nonequilibrium loading in the criticality of nanoscale hot spots. These results provide insight into the initiation of reactive decomposition.« less

Electrical conductivity of a methane-air burning plasma under the action of weak electric fields

NASA Astrophysics Data System (ADS)

Colonna, G.; Pietanza, L. D.; D'Angola, A.; Laricchiuta, A.; Di Vita, A.

2017-02-01

This paper focuses on the calculation of the electrical conductivity of a methane-air flame in the presence of weak electric fields, solving the Boltzmann equation for free electrons self-consistently coupled with chemical kinetics. The chemical model GRI-Mech 3.0 has been completed with chemi-ionization reactions to model ionization in the absence of fields, and a database of cross sections for electron-impact-induced processes to account for reactions and transitions activated in the flame during discharge. The dependence of plasma properties on the frequency of an oscillating field has been studied under different pressure and gas temperature conditions. Fitting expressions of the electrical conductivity as a function of gas temperature and methane consumption are provided for different operational conditions in the Ansaldo Energia burner.

Chemical fate and changes in mutagenic activity of antibiotics nitrofurazone and furazolidone during aqueous chlorination.

PubMed

Nakamura, Hitomi; Kawakami, Tsuyoshi; Niino, Tatsuhiro; Takahashi, Yasuo; Onodera, Sukeo

2008-12-01

Reactions of nitrofuran antibiotics (nitrofurazone (NFZ) and frazolidone (FZD)) with hypochlorite in aqueous solution were investigated under the conditions that simulate wastewater disinfection. The chlorination byproducts were determined by high performance liquid chromatography. At the levels of 5 microM, NFZ reacted rapidly with free chlorine in neutral pH (7.0), while the FZD-hypochlorite reaction was reasonably slow under the same pH. Nevertheless, the strong mutagenic parents disappeared completely after the hypochlorite reactions, and the chlorination byproducts were observed to exert a weak mutagenic effect on Salmonella typhimurium TA100 without S9-mix. The extent of the reactions depended on the chlorine dose, solution pH and compound structures.

Method for the production of uranium chloride salt

DOEpatents

Westphal, Brian R.; Mariani, Robert D.

2013-07-02

A method for the production of UCl.sub.3 salt without the use of hazardous chemicals or multiple apparatuses for synthesis and purification is provided. Uranium metal is combined in a reaction vessel with a metal chloride and a eutectic salt- and heated to a first temperature under vacuum conditions to promote reaction of the uranium metal with the metal chloride for the production of a UCl.sub.3 salt. After the reaction has run substantially to completion, the furnace is heated to a second temperature under vacuum conditions. The second temperature is sufficiently high to selectively vaporize the chloride salts and distill them into a condenser region.

The influence of radiation-induced vacancy on the formation of thin-film of compound layer during a reactive diffusion process

NASA Astrophysics Data System (ADS)

Akintunde, S. O.; Selyshchev, P. A.

2016-05-01

A theoretical approach is developed that describes the formation of a thin-film of AB-compound layer under the influence of radiation-induced vacancy. The AB-compound layer is formed as a result of a chemical reaction between the atomic species of A and B immiscible layers. The two layers are irradiated with a beam of energetic particles and this process leads to several vacant lattice sites creation in both layers due to the displacement of lattice atoms by irradiating particles. A- and B-atoms diffuse via these lattice sites by means of a vacancy mechanism in considerable amount to reaction interfaces A/AB and AB/B. The reaction interfaces increase in thickness as a result of chemical transformation between the diffusing species and surface atoms (near both layers). The compound layer formation occurs in two stages. The first stage begins as an interfacial reaction controlled process, and the second as a diffusion controlled process. The critical thickness and time are determined at a transition point between the two stages. The influence of radiation-induced vacancy on layer thickness, speed of growth, and reaction rate is investigated under irradiation within the framework of the model presented here. The result obtained shows that the layer thickness, speed of growth, and reaction rate increase strongly as the defect generation rate rises in the irradiated layers. It also shows the feasibility of producing a compound layer (especially in near-noble metal silicide considered in this study) at a temperature below their normal formation temperature under the influence of radiation.

Irreversible xenon insertion into a small-pore zeolite at moderate pressures and temperatures

DOE PAGES

Seoung, Donghoon; Cynn, Hyunchae; Park, Changyong; ...

2014-09-01

Pressure drastically alters the chemical and physical properties of materials and allows structural phase transitions and chemical reactions to occur that defy much of our understanding gained under ambient conditions. Particularly exciting is the high-pressure chemistry of xenon, which is known to react with hydrogen and ice at high pressures and form stable compounds. Here, we show that Ag 16Al 16Si 24O 8·16H 2O (Ag-natrolite) irreversibly inserts xenon into its micropores at 1.7 GPa and 250 °C, while Ag + is reduced to metallic Ag and possibly oxidized to Ag 2+. In contrast to krypton, xenon is retained within themore » pores of this zeolite after pressure release and requires heat to desorb. This irreversible insertion and trapping of xenon in Ag-natrolite under moderate conditions sheds new light on chemical reactions that could account for the xenon deficiency relative to argon observed in terrestrial and Martian atmospheres.« less

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

Wiegel, Aaron A.; Liu, Matthew J.; Hinsberg, William D.

Multiphase chemical reactions (gas + solid/liquid) involve a complex interplay between bulk and interface chemistry, diffusion, evaporation, and condensation. Reactions of atmospheric aerosols are an important example of this type of chemistry: the rich array of particle phase states and multiphase transformation pathways produce diverse but poorly understood interactions between chemistry and transport. Their chemistry is of intrinsic interest because of their role in controlling climate. Their characteristics also make them useful models for the study of principles of reactivity of condensed materials under confined conditions. Previously, we have reported a computational study of the oxidation chemistry of a liquidmore » aliphatic aerosol. In this study, we extend the calculations to investigate nearly the same reactions at a semisolid gas-aerosol interface. A reaction-diffusion model for heterogeneous oxidation of triacontane by hydroxyl radicals (OH) is described, and its predictions are compared to measurements of aerosol size and composition, which evolve continuously during oxidation. Our results are also explicitly compared to those obtained for the corresponding liquid system, squalane, to pinpoint salient elements controlling reactivity. The diffusive confinement of the free radical intermediates at the interface results in enhanced importance of a few specific chemical processes such as the involvement of aldehydes in fragmentation and evaporation, and a significant role of radical-radical reactions in product formation. The simulations show that under typical laboratory conditions semisolid aerosols have highly oxidized nanometer-scale interfaces that encapsulate an unreacted core and may confer distinct optical properties and enhanced hygroscopicity. This highly oxidized layer dynamically evolves with reaction, which we propose to result in plasticization. The validated model is used to predict chemistry under atmospheric conditions, where the OH radical concentration is much lower. The oxidation reactions are more strongly influenced by diffusion in the particle, resulting in a more liquid-like character.« less

Study the effect of chemical reaction and variable viscosity on free convection MHD radiating flow over an inclined plate bounded by porous medium

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

Ali, M., E-mail: ali.mehidi93@gmail.com; Department of Mathematics, Chittagong University of Engineering and Technology, Chittagong-4349; Alim, M. A., E-mail: maalim@math.buet.ac.bd

An analysis is performed to study the free convection heat and mass transfer flow of an electrically conducting incompressible viscous fluid about a semi-infinite inclined porous plate under the action of radiation, chemical reaction in presence of magnetic field with variable viscosity. The dimensionless governing equations are steady, two-dimensional coupled and non-linear ordinary differential equation. Nachtsgeim-Swigert shooting iteration technique along with Runge-Kutta integration scheme is used to solve the non-dimensional governing equations. The effects of magnetic parameter, viscosity parameter and chemical reaction parameter on velocity, temperature and concentration profiles are discussed numerically and shown graphically. Therefore, the results of velocitymore » profile decreases for increasing values of magnetic parameter and viscosity parameter but there is no effect for reaction parameter. The temperature profile decreases in presence of magnetic parameter, viscosity parameter and Prandtl number but increases for radiation parameter. Also, concentration profile decreases for the increasing values of magnetic parameter, viscosity parameter and reaction parameter. All numerical calculations are done with respect to salt water and fixed angle of inclination of the plate.« less

Co/NHPI-mediated aerobic oxygenation of benzylic C–H bonds in pharmaceutically relevant molecules

DOE PAGES

Hruszkewycz, Damian P.; Miles, Kelsey C.; Thiel, Oliver R.; ...

2016-10-07

A simple cobalt(II)/N-hydroxyphthalimide catalyst system has been identified for selective conversion of benzylic methylene groups in pharmaceutically relevant (hetero)arenes to the corresponding (hetero)aryl ketones. The radical reaction pathway tolerates electronically diverse benzylic C–H bonds, contrasting recent oxygenation reactions that are initiated by deprotonation of a benzylic C–H bond. The reactions proceed under practical reaction conditions (1 M substrate in BuOAc or EtOAc solvent, 12 h, 90–100 °C), and they tolerate common heterocycles, such as pyridines and imidazoles. A cobalt-free, electrochemical, NHPI-catalyzed oxygenation method overcomes challenges encountered with chelating substrates that inhibit the chemical reaction. The utility of the aerobic oxidationmore » method is showcased in the multigram synthesis of a key intermediate towards a drug candidate (AMG 579) under process-relevant reaction conditions.« less

Bioorthogonal Chemistry: Fishing for Selectivity in a Sea of Functionality

PubMed Central

Sletten, Ellen M.

2010-01-01

The study of biomolecules in their native environments is a challenging task because of the vast complexity of cellular systems. Technologies developed in the last few years for the selective modification of biological species in living systems have yielded new insights into cellular processes. Key to these new techniques are bioorthogonal chemical reactions, whose components must react rapidly and selectively with each other under physiological conditions in the presence of the plethora of functionality necessary to sustain life. Herein we describe the bioorthogonal chemical reactions developed to date and how they can be used to study biomolecules. PMID:19714693

Bioorthogonal chemistry: fishing for selectivity in a sea of functionality.

PubMed

Sletten, Ellen M; Bertozzi, Carolyn R

2009-01-01

The study of biomolecules in their native environments is a challenging task because of the vast complexity of cellular systems. Technologies developed in the last few years for the selective modification of biological species in living systems have yielded new insights into cellular processes. Key to these new techniques are bioorthogonal chemical reactions, whose components must react rapidly and selectively with each other under physiological conditions in the presence of the plethora of functionality necessary to sustain life. Herein we describe the bioorthogonal chemical reactions developed to date and how they can be used to study biomolecules.

Surface modification of Cu metal particles by the chemical reaction between the surface oxide layer and a halogen surfactant

NASA Astrophysics Data System (ADS)

Yokoyama, Shun; Takahashi, Hideyuki; Itoh, Takashi; Motomiya, Kenichi; Tohji, Kazuyuki

2014-01-01

Surface oxides on small (2-5 μm) copper metal particles can be removed by chemical reaction with tris(2,3-dibromopropyl) isocyanurate (TIC) in diethylene glycol mono-n-hexyl ether (DGHE) solution under mild conditions where metal particles are not damaged. Surface oxides convert to copper bromide species and subsequently dissolve into the solvent. It was found that resultant surface species are resistant to re-oxidation due to remaining surface bromides. This finding opens up a possibility to create microclines based on cheap copper nanoparticles.

Metabolic assessment of E. coli as a Biofactory for commercial products.

PubMed

Zhang, Xiaolin; Tervo, Christopher J; Reed, Jennifer L

2016-05-01

Metabolic engineering uses microorganisms to synthesize chemicals from renewable resources. Given the thousands of known metabolites, it is unclear what valuable chemicals could be produced by a microorganism and what native and heterologous reactions are needed for their synthesis. To answer these questions, a systematic computational assessment of Escherichia coli's potential ability to produce different chemicals was performed using an integrated metabolic model that included native E.coli reactions and known heterologous reactions. By adding heterologous reactions, a total of 1777 non-native products could theoretically be produced in E. coli under glucose minimal medium conditions, of which 279 non-native products have commercial applications. Synthesis pathways involving native and heterologous reactions were identified from eight central metabolic precursors to the 279 non-native commercial products. These pathways were used to evaluate the dependence on, and diversity of, native and heterologous reactions to produce each non-native commercial product, as well as to identify each product׳s closest central metabolic precursor. Analysis of the synthesis pathways (with 5 or fewer reaction steps) to non-native commercial products revealed that isopentenyl diphosphate, pyruvate, and oxaloacetate are the closest central metabolic precursors to the most non-native commercial products. Additionally, 4-hydroxybenzoate, tyrosine, and phenylalanine were found to be common precursors to a large number of non-native commercial products. Strains capable of producing high levels of these precursors could be further engineered to create strains capable of producing a variety of commercial non-native chemicals. Copyright © 2016 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

Computational enzyme design: transitioning from catalytic proteins to enzymes.

PubMed

Mak, Wai Shun; Siegel, Justin B

2014-08-01

The widespread interest in enzymes stem from their ability to catalyze chemical reactions under mild and ecologically friendly conditions with unparalleled catalytic proficiencies. While thousands of naturally occurring enzymes have been identified and characterized, there are still numerous important applications for which there are no biological catalysts capable of performing the desired chemical transformation. In order to engineer enzymes for which there is no natural starting point, efforts using a combination of quantum chemistry and force-field based protein molecular modeling have led to the design of novel proteins capable of catalyzing chemical reactions not catalyzed by naturally occurring enzymes. Here we discuss the current status and potential avenues to pursue as the field of computational enzyme design moves forward. Published by Elsevier Ltd.

Toward a reaction rate model of condensed-phase RDX decomposition under high temperatures

NASA Astrophysics Data System (ADS)

Schweigert, Igor

2015-06-01

Shock ignition of energetic molecular solids is driven by microstructural heterogeneities, at which even moderate stresses can result in sufficiently high temperatures to initiate material decomposition and chemical energy release. Mesoscale modeling of these ``hot spots'' requires a reaction rate model that describes the energy release with a sub-microsecond resolution and under a wide range of temperatures. No such model is available even for well-studied energetic materials such as RDX. In this presentation, I will describe an ongoing effort to develop a reaction rate model of condensed-phase RDX decomposition under high temperatures using first-principles molecular dynamics, transition-state theory, and reaction network analysis. This work was supported by the Naval Research Laboratory, by the Office of Naval Research, and by the DoD High Performance Computing Modernization Program Software Application Institute for Multiscale Reactive Modeling of Insensitive Munitions.

Sulfide chemiluminescence detection

DOEpatents

Spurlin, S.R.; Yeung, E.S.

1985-11-26

A method is described for chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

Apparatus for use in sulfide chemiluminescence detection

DOEpatents

Spurlin, Stanford R.; Yeung, Edward S.

1987-01-01

A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction.

Elementary reaction profile and chemical kinetics study of [C(1D)/(3P) + SiH4] with the CCSD(T) method

NASA Astrophysics Data System (ADS)

Ranka, Karnamohit; Perera, Ajith; Bartlett, Rodney J.

2017-07-01

Carbon and silicon-based molecules are omnipresent in the fields of combustion, atmospheric, semiconductor, and astronomical chemistry, among others. This paper reports the underlying elementary reactions for the [C(1D) + SiH4] and [C(3P) + SiH4] reaction profiles, optimized geometries of the intermediates, transition states (at the CCSD(T) level), RRKM and TST rate constants, and the corresponding branching ratios. Previously unreported van der Waals complex intermediates have been found for both reactions.

15 CFR 710.1 - Definitions of terms used in the Chemical Weapons Convention Regulations (CWCR).

Code of Federal Regulations, 2010 CFR

2010-01-01

... chemical means its conversion into another chemical via a chemical reaction. Unreacted material must be... formed through chemical reaction that is subsequently reacted to form another chemical. ITAR. Means the... formation of a chemical through chemical reaction, including biochemical or biologically mediated reaction...

A polydimethylsiloxane-polycarbonate hybrid microfluidic device capable of generating perpendicular chemical and oxygen gradients for cell culture studies.

PubMed

Chang, Chia-Wen; Cheng, Yung-Ju; Tu, Melissa; Chen, Ying-Hua; Peng, Chien-Chung; Liao, Wei-Hao; Tung, Yi-Chung

2014-10-07

This paper reports a polydimethylsiloxane-polycarbonate (PDMS-PC) hybrid microfluidic device capable of performing cell culture under combinations of chemical and oxygen gradients. The microfluidic device is constructed of two PDMS layers with microfluidic channel patterns separated by a thin PDMS membrane. The top layer contains an embedded PC film and a serpentine channel for a spatially confined oxygen scavenging chemical reaction to generate an oxygen gradient in the bottom layer for cell culture. Using the chemical reaction method, the device can be operated with a small amount of chemicals, without bulky gas cylinders and sophisticated flow control schemes. Furthermore, it can be directly used in conventional incubators with syringe pumps to simplify the system setup. The bottom layer contains arrangements of serpentine channels for chemical gradient generation and a cell culture chamber in the downstream. The generated chemical and oxygen gradients are experimentally characterized using a fluorescein solution and an oxygen-sensitive fluorescent dye, respectively. For demonstration, a 48 hour cell-based drug test and a cell migration assay using human lung adenocarcinoma epithelial cells (A549) are conducted under various combinations of the chemical and oxygen gradients in the experiments. The drug testing results show an increase in A549 cell apoptosis due to the hypoxia-activated cytotoxicity of tirapazamine (TPZ) and also suggest great cell compatibility and gradient controllability of the device. In addition, the A549 cell migration assay results demonstrate an aerotactic behavior of the A549 cells and suggest that the oxygen gradient plays an essential role in guiding cell migration. The migration results, under combinations of chemokine and oxygen gradients, cannot be simply superposed with single gradient results. The device is promising to advance the control of in vitro microenvironments, to better study cellular responses under various physiological conditions for biomedical applications.

In situ loading of well-dispersed silver nanoparticles on nanocrystalline magnesium oxide for real-time monitoring of catalytic reactions by surface enhanced Raman spectroscopy.

PubMed

Zhang, Kaige; Li, Gongke; Hu, Yuling

2015-10-28

The surface-enhanced Raman spectroscopy (SERS) technique is of great importance for insight into the transient reaction intermediates and mechanistic pathways involved in heterogeneously catalyzed chemical reactions under actual reaction conditions, especially in water. Herein, we demonstrate a facile method for in situ synthesis of nanocrystalline magnesium oxide-Ag(0) (nano MgO-Ag(0)) hybrid nanomaterials with dispersed Ag nanoparticles (Ag NPs) on the surface of nanocrystalline magnesium oxide (nano MgO) via Sn(2+) linkage and reduction. As a benefit from the synergy effect of nano MgO and Ag NPs, the nano MgO-Ag(0) exhibited both excellent SERS and catalytic activities for the reduction of 4-nitrothiophenol in the presence of NaBH4. The nano MgO-Ag(0) was used for real-time monitoring of the catalytic reaction process of 4-nitrothiophenol to 4-aminothiophenol in an aqueous medium by observing the SERS signals of the reactant, intermediate and final products. The intrinsic reaction kinetics and reaction mechanism of this reaction were also investigated. This SERS-based synergy technique provides a novel approach for quantitative in situ monitoring of catalytic chemical reaction processes.

Tuning electronic properties by oxidation-reduction reactions at graphene-ruthenium interface

DOE PAGES

Kandyba, Viktor; Al-Mahboob, Abdullah; Giampietri, Alessio; ...

2018-06-06

Mass production of graphene is associated with the growth on catalysts used also in other chemical reactions. In this study, we exploit the oxidation-reduction to tailor the properties of single layer graphene domains with incorporated bi-layer patches on ruthenium. Using photoelectron spectromicroscopy techniques, we find that oxygen, intercalating under single layer and making it p-doped by the formation of Ru-O x, does not intercalate under the bilayer patches with n-doped upper layer, but decorates them under single layer surrounding creating lateral p-n junctions with chemical potential difference of 1.2 eV. O-reduction by thermal treatment in vacuum results in C-vacancy defectsmore » enhancing electronic coupling of remained graphene to Ru, whereas in H 2, vacancy formation is suppressed. Also, for the domains below 15–25 μm size, after O-reduction in H 2, graphene/Ru coupling is restored, while wrinkle pattern produced by O-intercalation is irreversible and can trap reaction products between the wrinkles and Ru surface step edges. In fact, in certain regions of bigger domains, the products, containing H 2O and/or its fragments, remain at the interface, making graphene decoupled and undoped.« less

Hydrothermal Testing of K Basin Sludge and N Reactor Fuel at Sludge Treatment Project Operating Conditions

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

Delegard, Calvin H.; Schmidt, Andrew J.; Thornton, Brenda M.

The Sludge Treatment Project (STP), managed for the U. S. DOE by Fluor Hanford (FH), was created to design and operate a process to eliminate uranium metal from K Basin sludge prior to packaging for Waste Isolation Pilot Plant (WIPP). The STP process uses high temperature liquid water to accelerate the reaction, produce uranium dioxide from the uranium metal, and safely discharge the hydrogen. Under nominal process conditions, the sludge will be heated in pressurized water at 185°C for as long as 72 hours to assure the complete reaction (corrosion) of up to 0.25-inch diameter uranium metal pieces. Under contractmore » to FH, the Pacific Northwest National Laboratory (PNNL) conducted bench-scale testing of the STP hydrothermal process in November and December 2006. Five tests (~50 ml each) were conducted in sealed, un-agitated reaction vessels under the hydrothermal conditions (e.g., 7 to 72 h at 185°C) of the STP corrosion process using radioactive sludge samples collected from the K East Basin and particles/coupons of N Reactor fuel also taken from the K Basins. The tests were designed to evaluate and understand the chemical changes that may be occurring and the effects that any changes would have on sludge rheological properties. The tests were not designed to evaluate engineering aspects of the process. The hydrothermal treatment affected the chemical and physical properties of the sludge. In each test, significant uranium compound phase changes were identified, resulting from dehydration and chemical reduction reactions. Physical properties of the sludge were significantly altered from their initial, as-settled sludge values, including, shear strength, settled density, weight percent water, and gas retention.« less

Ablation characteristics and reaction mechanism of insulation materials under slag deposition condition

NASA Astrophysics Data System (ADS)

Guan, Yiwen; Li, Jiang; Liu, Yang

2017-07-01

Current understanding of the physical and chemical processes involved in the ablation of insulation materials by highly aluminized solid propellants is limited. The study on the heat transfer and ablation principle of ethylene propylene diene monomer (EPDM) materials under slag deposition condition is essential for future design or modification of large solid rocket motors (SRMs) for launch application. In this paper, the alumina liquid flow pattern and the deposition principle in full-scale SRM engines are discussed. The interaction mechanism between the alumina droplets and the wall are analyzed. Then, an experimental method was developed to simulate the insulation material ablation under slag deposition condition. Experimental study was conducted based on a laboratory-scale device. Meanwhile, from the analysis of the cross-sectional morphology and chemical composition of the charring layer after ablation, the reaction mechanism of the charring layer under deposition condition was discussed, and the main reaction equation was derived. The numerical simulation and experimental results show the following. (i) The alumina droplet flow in the deposition section of the laboratory-scale device is similar to that of a full-scale SRM. (ii) The charring layer of the EPDM insulator displays a porous tight/loose structure under high-temperature slag deposition condition. (iii) A seven-step carbothermal reduction in the alumina is derived and established under high-pressure and high-temperature environment in the SRM combustion chamber. (iv) The analysis using thermodynamic software indicates that the reaction of the alumina and charring layer initially forms Al4C3 during the operation. Then, Al element and Al2OC compound are subsequently produced with the reduction in the release of gas CO as well with continuous environmental heating.

Modeling free energy availability from Hadean hydrothermal systems to the first metabolism.

PubMed

Simoncini, E; Russell, M J; Kleidon, A

2011-12-01

Off-axis Hydrothermal Systems (HSs) are seen as the possible setting for the emergence of life. As the availability of free energy is a general requirement to drive any form of metabolism, we ask here under which conditions free energy generation by geologic processes is greatest and relate these to the conditions found at off-axis HSs. To do so, we present a conceptual model in which we explicitly capture the energetics of fluid motion and its interaction with exothermic reactions to maintain a state of chemical disequilibrium. Central to the interaction is the temperature at which the exothermic reactions take place. This temperature not only sets the equilibrium constant of the chemical reactions and thereby the distance of the actual state to chemical equilibrium, but these reactions also shape the temperature gradient that drives convection and thereby the advection of reactants to the reaction sites and the removal of the products that relate to geochemical free energy generation. What this conceptual model shows is that the positive feedback between convection and the chemical kinetics that is found at HSs favors a greater rate of free energy generation than in the absence of convection. Because of the lower temperatures and because the temperature of reactions is determined more strongly by these dynamics rather than an external heat flux, the conditions found at off-axis HSs should result in the greatest rates of geochemical free energy generation. Hence, we hypothesize from these thermodynamic considerations that off-axis HSs seem most conducive for the emergence of protometabolic pathways as these provide the greatest, abiotic generation rates of chemical free energy.

Shock initiated thermal and chemical responses of HMX crystal from ReaxFF molecular dynamics simulation.

PubMed

Zhou, Tingting; Song, Huajie; Liu, Yi; Huang, Fenglei

2014-07-21

To gain an atomistic-level understanding of the thermal and chemical responses of condensed energetic materials under thermal shock, we developed a thermal shock reactive dynamics (TS-RD) computational protocol using molecular dynamics simulation coupled with ReaxFF force field. β-Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) was selected as a a target explosive due to its wide usage in the military and industry. The results show that a thermal shock initiated by a large temperature gradient between the "hot" region and the "cold" region results in thermal expansion of the particles and induces a thermal-mechanical wave propagating back and forth in the system with an averaged velocity of 3.32 km s(-1). Heat propagating along the direction of thermal shock leads to a temperature increment of the system and thus chemical reaction initiation. Applying a continuum reactive heat conduction model combined with the temperature distribution obtained from the RD simulation, a heat conduction coefficient is derived as 0.80 W m(-1) K(-1). The chemical reaction mechanisms during thermal shock were analyzed, showing that the reaction is triggered by N-NO2 bond breaking followed by HONO elimination and ring fission. The propagation rates of the reaction front and reaction center are obtained to be 0.069 and 0.038 km s(-1), based on the time and spatial distribution of NO2. The pressure effect on the thermal shock was also investigated by employing uniaxial compression before the thermal shock. We find that compression significantly accelerates thermal-mechanical wave propagation and heat conduction, resulting in higher temperature and more excited molecules and thus earlier initiation and faster propagation of chemical reactions.

Hydrothermal replacement of biogenic and abiogenic aragonite by Mg-carbonates - Relation between textural control on effective element fluxes and resulting carbonate phase

NASA Astrophysics Data System (ADS)

Jonas, Laura; Müller, Thomas; Dohmen, Ralf; Immenhauser, Adrian; Putlitz, Benita

2017-01-01

Dolomitization, i.e., the secondary replacement of calcite or aragonite (CaCO3) by dolomite (CaMg[CO3]2), is one of the most volumetrically important carbonate diagenetic processes. It occurs under near surface and shallow burial conditions and can significantly modify rock properties through changes in porosity and permeability. Dolomitization fronts are directly coupled to fluid pathways, which may be related to the initial porosity/permeability of the precursor limestone, an existing fault network or secondary porosity/permeability created through the replacement reaction. In this study, the textural control on the replacement of biogenic and abiogenic aragonite by Mg-carbonates, that are typical precursor phases in the dolomitization process, was experimentally studied under hydrothermal conditions. Aragonite samples with different textural and microstructural properties exhibiting a compact (inorganic aragonite single crystal), an intermediate (bivalve shell of Arctica islandica) and open porous structure (skeleton of coral Porites sp.) were reacted with a solution of 0.9 M MgCl2 and 0.015 M SrCl2 at 200 °C. The replacement of aragonite by a Ca-bearing magnesite and a Mg-Ca carbonate of non-stoichiometric dolomitic composition takes place via a dissolution-precipitation process and leads to the formation of a porous reaction front that progressively replaces the aragonite precursor. The reaction leads to the development of porosity within the reaction front and distinctive microstructures such as gaps and cavities at the reaction interface. The newly formed reaction rim consists of chemically distinct phases separated by sharp boundaries. It was found that the number of phases and their chemical variation decreases with increasing initial porosity and reactive surface area. This observation is explained by variations in effective element fluxes that result in differential chemical gradients in the fluid within the pore space of the reaction rim. Observed reaction rates are highest for the replacement of the initially highly porous coral and lowest for the compact structure of a single aragonite crystal. Therefore, the reaction progress equally depends on effective element fluxes between the fluid at the reaction interface and the bulk solution surrounding the test material as well as the reactive surface area. This study demonstrates that the textural and microstructural properties of the parent material have a significant influence on the chemical composition of the product phase. Moreover, our data highlight the importance of effective fluid-mediated element exchange between the fluid at the reaction interface and the bulk solution controlled by the local microstructure.

Application of chemical reaction mechanistic domains to an ecotoxicity QSAR model, the KAshinhou Tool for Ecotoxicity (KATE).

PubMed

Furuhama, A; Hasunuma, K; Aoki, Y; Yoshioka, Y; Shiraishi, H

2011-01-01

The validity of chemical reaction mechanistic domains defined by skin sensitisation in the Quantitative Structure-Activity Relationship (QSAR) ecotoxicity system, KAshinhou Tools for Ecotoxicity (KATE), March 2009 version, has been assessed and an external validation of the current KATE system carried out. In the case of the fish end-point, the group of chemicals with substructures reactive to skin sensitisation always exhibited higher root mean square errors (RMSEs) than chemicals without reactive substructures under identical C- or log P-judgements in KATE. However, in the case of the Daphnia end-point this was not so, and the group of chemicals with reactive substructures did not always have higher RMSEs: the Schiff base mechanism did not function as a high error detector. In addition to the RMSE findings, the presence of outliers suggested that the KATE classification rules needs to be reconsidered, particularly for the amine group. Examination of the dependency of the organism on the toxic action of chemicals in fish and Daphnia revealed that some of the reactive substructures could be applied to the improvement of the KATE system. It was concluded that the reaction mechanistic domains of toxic action for skin sensitisation could provide useful complementary information in predicting acute aquatic ecotoxicity, especially at the fish end-point.

Synthesis and materialization of a reaction-diffusion French flag pattern

NASA Astrophysics Data System (ADS)

Zadorin, Anton S.; Rondelez, Yannick; Gines, Guillaume; Dilhas, Vadim; Urtel, Georg; Zambrano, Adrian; Galas, Jean-Christophe; Estevez-Torres, André

2017-10-01

During embryo development, patterns of protein concentration appear in response to morphogen gradients. These patterns provide spatial and chemical information that directs the fate of the underlying cells. Here, we emulate this process within non-living matter and demonstrate the autonomous structuration of a synthetic material. First, we use DNA-based reaction networks to synthesize a French flag, an archetypal pattern composed of three chemically distinct zones with sharp borders whose synthetic analogue has remained elusive. A bistable network within a shallow concentration gradient creates an immobile, sharp and long-lasting concentration front through a reaction-diffusion mechanism. The combination of two bistable circuits generates a French flag pattern whose 'phenotype' can be reprogrammed by network mutation. Second, these concentration patterns control the macroscopic organization of DNA-decorated particles, inducing a French flag pattern of colloidal aggregation. This experimental framework could be used to test reaction-diffusion models and fabricate soft materials following an autonomous developmental programme.

Solid solution lithium alloy cermet anodes

DOEpatents

Richardson, Thomas J.

2013-07-09

A metal-ceramic composite ("cermet") has been produced by a chemical reaction between a lithium compound and another metal. The cermet has advantageous physical properties, high surface area relative to lithium metal or its alloys, and is easily formed into a desired shape. An example is the formation of a lithium-magnesium nitride cermet by reaction of lithium nitride with magnesium. The reaction results in magnesium nitride grains coated with a layer of lithium. The nitride is inert when used in a battery. It supports the metal in a high surface area form, while stabilizing the electrode with respect to dendrite formation. By using an excess of magnesium metal in the reaction process, a cermet of magnesium nitride is produced, coated with a lithium-magnesium alloy of any desired composition. This alloy inhibits dendrite formation by causing lithium deposited on its surface to diffuse under a chemical potential into the bulk of the alloy.

Microfluidic droplet trapping array as nanoliter reactors for gas-liquid chemical reaction.

PubMed

Zhang, Qingquan; Zeng, Shaojiang; Qin, Jianhua; Lin, Bingcheng

2009-09-01

This article presents a simple method for trapping arrays of droplets relying on the designed microstructures of the microfluidic device, and this has been successfully used for parallel gas-liquid chemical reaction. In this approach, the trapping structure is composed of main channel, lateral channel and trapping region. Under a negative pressure, array droplets can be generated and trapped in the microstructure simultaneously, without the use of surfactant and the precise control of the flow velocity. By using a multi-layer microdevice containing the microstructures, single (pH gradient) and multiple gas-liquid reactions (metal ion-NH3 complex reaction) can be performed in array droplets through the transmembrane diffusion of the gas. The droplets with quantitative concentration gradient can be formed by only replacing the specific membrane. The established method is simple, robust and easy to operate, demonstrating the potential of this device for droplet-based high-throughput screening.

Semiclassical Calculation of Reaction Rate Constants for Homolytical Dissociations

NASA Technical Reports Server (NTRS)

Cardelino, Beatriz H.

2002-01-01

There is growing interest in extending organometallic chemical vapor deposition (OMCVD) to III-V materials that exhibit large thermal decomposition at their optimum growth temperature, such as indium nitride. The group III nitrides are candidate materials for light-emitting diodes and semiconductor lasers operating into the blue and ultraviolet regions. To overcome decomposition of the deposited compound, the reaction must be conducted at high pressures, which causes problems of uniformity. Microgravity may provide the venue for maintaining conditions of laminar flow under high pressure. Since the selection of optimized parameters becomes crucial when performing experiments in microgravity, efforts are presently geared to the development of computational OMCVD models that will couple the reactor fluid dynamics with its chemical kinetics. In the present study, we developed a method to calculate reaction rate constants for the homolytic dissociation of III-V compounds for modeling OMCVD. The method is validated by comparing calculations with experimental reaction rate constants.

Use of hydrostatic pressure for modulation of protein chemical modification and enzymatic selectivity.

PubMed

Makarov, Alexey A; Helmy, Roy; Joyce, Leo; Reibarkh, Mikhail; Maust, Mathew; Ren, Sumei; Mergelsberg, Ingrid; Welch, Christopher J

2016-05-11

Using hydrostatic pressure to induce protein conformational changes can be a powerful tool for altering the availability of protein reactive sites and for changing the selectivity of enzymatic reactions. Using a pressure apparatus, it has been demonstrated that hydrostatic pressure can be used to modulate the reactivity of lysine residues of the protein ubiquitin with a water-soluble amine-specific homobifunctional coupling agent. Fewer reactive lysine residues were observed when the reaction was carried out under elevated pressure of 3 kbar, consistent with a pressure-induced conformational change of ubiquitin that results in fewer exposed lysine residues. Additionally, modulation of the stereoselectivity of an enzymatic transamination reaction was observed at elevated hydrostatic pressure. In one case, the minor diasteromeric product formed at atmospheric pressure became the major product at elevated pressure. Such pressure-induced alterations of protein reactivity may provide an important new tool for enzymatic reactions and the chemical modification of proteins.

Multiphase chemical kinetics of OH radical uptake by molecular organic markers of biomass burning aerosols: humidity and temperature dependence, surface reaction, and bulk diffusion.

PubMed

Arangio, Andrea M; Slade, Jonathan H; Berkemeier, Thomas; Pöschl, Ulrich; Knopf, Daniel A; Shiraiwa, Manabu

2015-05-14

Multiphase reactions of OH radicals are among the most important pathways of chemical aging of organic aerosols in the atmosphere. Reactive uptake of OH by organic compounds has been observed in a number of studies, but the kinetics of mass transport and chemical reaction are still not fully understood. Here we apply the kinetic multilayer model of gas-particle interactions (KM-GAP) to experimental data from OH exposure studies of levoglucosan and abietic acid, which serve as surrogates and molecular markers of biomass burning aerosol (BBA). The model accounts for gas-phase diffusion within a cylindrical coated-wall flow tube, reversible adsorption of OH, surface-bulk exchange, bulk diffusion, and chemical reactions at the surface and in the bulk of the condensed phase. The nonlinear dependence of OH uptake coefficients on reactant concentrations and time can be reproduced by KM-GAP. We find that the bulk diffusion coefficient of the organic molecules is approximately 10(-16) cm(2) s(-1), reflecting an amorphous semisolid state of the organic substrates. The OH uptake is governed by reaction at or near the surface and can be kinetically limited by surface-bulk exchange or bulk diffusion of the organic reactants. Estimates of the chemical half-life of levoglucosan in 200 nm particles in a biomass burning plume increase from 1 day at high relative humidity to 1 week under dry conditions. In BBA particles transported to the free troposphere, the chemical half-life of levoglucosan can exceed 1 month due to slow bulk diffusion in a glassy matrix at low temperature.

Sustainable Synthesis of Oxalic and Succinic Acid through Aerobic Oxidation of C6 Polyols Under Mild Conditions.

PubMed

Ventura, Maria; Williamson, David; Lobefaro, Francesco; Jones, Matthew D; Mattia, Davide; Nocito, Francesco; Aresta, Michele; Dibenedetto, Angela

2018-03-22

The sustainable chemical industry encompasses a shift from the use of fossil carbon to renewable carbon. The synthesis of chemicals from nonedible biomass (cellulosic or oil) represents one of the key steps for "greening" the chemical industry. In this paper, we report the aerobic oxidative cleavage of C6 polyols (5-HMF, glucose, fructose and sucrose) to oxalic acid (OA) and succinic acid (SA) in water under mild conditions using M@CNT and M@NCNT (M=Fe, V; CNT=carbon nanotubes; NCNT=N-doped CNT), which, under suitable conditions, were recoverable and reusable without any loss of efficiency. The influence of the temperature, O 2 pressure (PO2 ), reaction time and stirring rate are discussed and the best reaction conditions are determined for an almost complete conversion of the starting material and a good OA yield of 48 %. SA and formic acid were the only co-products. The former could be further converted into OA by oxidation in the presence of formic acid, resulting in an overall OA yield of >62 %. This process was clean and did not produce organic waste nor gas emissions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improving Density Functional Tight Binding Predictions of Free Energy Surfaces for Slow Chemical Reactions in Solution

NASA Astrophysics Data System (ADS)

Kroonblawd, Matthew; Goldman, Nir

2017-06-01

First principles molecular dynamics using highly accurate density functional theory (DFT) is a common tool for predicting chemistry, but the accessible time and space scales are often orders of magnitude beyond the resolution of experiments. Semi-empirical methods such as density functional tight binding (DFTB) offer up to a thousand-fold reduction in required CPU hours and can approach experimental scales. However, standard DFTB parameter sets lack good transferability and calibration for a particular system is usually necessary. Force matching the pairwise repulsive energy term in DFTB to short DFT trajectories can improve the former's accuracy for reactions that are fast relative to DFT simulation times (<10 ps), but the effects on slow reactions and the free energy surface are not well-known. We present a force matching approach to improve the chemical accuracy of DFTB. Accelerated sampling techniques are combined with path collective variables to generate the reference DFT data set and validate fitted DFTB potentials. Accuracy of force-matched DFTB free energy surfaces is assessed for slow peptide-forming reactions by direct comparison to DFT for particular paths. Extensions to model prebiotic chemistry under shock conditions are discussed. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

First-Principles Approach to Model Electrochemical Reactions: Understanding the Fundamental Mechanisms behind Mg Corrosion

NASA Astrophysics Data System (ADS)

Surendralal, Sudarsan; Todorova, Mira; Finnis, Michael W.; Neugebauer, Jörg

2018-06-01

Combining concepts of semiconductor physics and corrosion science, we develop a novel approach that allows us to perform ab initio calculations under controlled potentiostat conditions for electrochemical systems. The proposed approach can be straightforwardly applied in standard density functional theory codes. To demonstrate the performance and the opportunities opened by this approach, we study the chemical reactions that take place during initial corrosion at the water-Mg interface under anodic polarization. Based on this insight, we derive an atomistic model that explains the origin of the anodic hydrogen evolution.

Kinetics and Degradation Products of Trichloroethene.

DTIC Science & Technology

1986-05-01

34Several classes of hydrolyzable compounds have not been included in this review because some are hydrolytically inert under ordinary conditions and...Environmental Protection Agency (1975b), trichloroethene is not hydrolyzed by water under normal conditions." (Reference 3). 3. "The outstanding chemical...result under free radical conditions. The following sections provide a more detailed analysis of specific free radical reactions which have environmental

Apparatus for use in sulfide chemiluminescence detection

DOEpatents

Spurlin, S.R.; Yeung, E.S.

1987-01-06

A method is described for chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

Method of generating chemiluminescent light

DOEpatents

Spurlin, S.R.; Yeung, E.S.

1986-03-11

A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction that generates chemiluminescent light and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

Method of generating chemiluminescent light

DOEpatents

Spurlin, Stanford R.; Yeung, Edward S.

1986-01-01

A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction that generates chemiluminescent light and a specifically designed chemiluminescence detection cell for the reaction.

A theory of circular organization and negative feedback: defining life in a cybernetic context.

PubMed

Tsokolov, Sergey

2010-12-01

All life today incorporates a variety of systems controlled by negative feedback loops and sometimes amplified by positive feedback loops. The first forms of life necessarily also required primitive versions of feedback, yet surprisingly little emphasis has been given to the question of how feedback emerged out of primarily chemical systems. One chemical system has been established that spontaneously develops autocatalytic feedback, the Belousov-Zhabotinsky (BZ) reaction. In this essay, I discuss the BZ reaction as a possible model for similar reactions that could have occurred under prebiotic Earth conditions. The main point is that the metabolism of contemporary life evolved from primitive homeostatic networks regulated by negative feedback. Because life could not exist in their absence, feedback loops should be included in definitions of life.

A Theory of Circular Organization and Negative Feedback: Defining Life in a Cybernetic Context

NASA Astrophysics Data System (ADS)

Tsokolov, Sergey

2010-12-01

All life today incorporates a variety of systems controlled by negative feedback loops and sometimes amplified by positive feedback loops. The first forms of life necessarily also required primitive versions of feedback, yet surprisingly little emphasis has been given to the question of how feedback emerged out of primarily chemical systems. One chemical system has been established that spontaneously develops autocatalytic feedback, the Belousov-Zhabotinsky (BZ) reaction. In this essay, I discuss the BZ reaction as a possible model for similar reactions that could have occurred under prebiotic Earth conditions. The main point is that the metabolism of contemporary life evolved from primitive homeostatic networks regulated by negative feedback. Because life could not exist in their absence, feedback loops should be included in definitions of life.

Elementary Chemical Reactions in Surface Photocatalysis

NASA Astrophysics Data System (ADS)

Guo, Qing; Zhou, Chuanyao; Ma, Zhibo; Ren, Zefeng; Fan, Hongjun; Yang, Xueming

2018-04-01

Photocatalytic hydrogen evolution and organic degradation on oxide materials have been extensively investigated in the last two decades. Great efforts have been dedicated to the study of photocatalytic reaction mechanisms of a variety of molecules on TiO2 surfaces by using surface science methods under ultra-high vacuum (UHV) conditions, providing fundamental understanding of surface chemical reactions in photocatalysis. In this review, we summarize the recent progress in the study of photocatalysis of several important species (water, methanol, and aldehydes) on different TiO2 surfaces. The results of these studies have provided us deep insights into the elementary processes of surface photocatalysis and stimulated a new frontier of research in this area. Based on the results of these studies, a new dynamics-based photocatalysis model is also discussed.

Topical Hazard Evaluation Program of Candidate Insect Repellent AI3-30180-c, US Department of Agriculture Proprietary Chemical, April 1982 - September 1984.

DTIC Science & Technology

1985-01-10

irritation photochemical chemical and 10 percent reaction under test con- irritation in humans. (wlv) Oil of Bergamot ditions. 2 * - Study No. 75-51-0367-85...control (oil of Bergamot ), than unirradiated skin areas. a and diluent were applied to additional skin areas to serve as unirradiated control sites

Retention of phosphorus in highly weathered soils under a lowland Amazonian forest ecosystem

Treesearch

M. E. McGroddy; W. L. Silver; Jr. de Oliveira; W. Z. de Mello; M. Keller

2008-01-01

The low available phosphorus (P) pools typical of highly weathered tropical forest soils are thought to result from a combination of export of phosphorus via erosion and leaching as well as chemical reactions resulting in physically and chemically protected P compounds. Despite the low apparent P availability, these soils support some of the highest terrestrial net...

Flow Tube Studies of Gas Phase Chemical Processes of Atmospheric Importance

NASA Technical Reports Server (NTRS)

Molina, Mario J.

1997-01-01

The objective of this project is to conduct measurements of elementary reaction rate constants and photochemistry parameters for processes of importance in the atmosphere. These measurements are being carried out under temperature and pressure conditions covering those applicable to the stratosphere and upper troposphere, using the chemical ionization mass spectrometry turbulent flow technique developed in our laboratory.

Growth of fluorescence gold clusters using photo-chemically activated ligands

NASA Astrophysics Data System (ADS)

Mishra, Dinesh; Aldeek, Fadi; Michael, Serge; Palui, Goutam; Mattoussi, Hedi

2016-03-01

Ligands made of lipoic acid (LA) appended with a polyethylene glycol (PEG) chain have been used in the aqueous phase growth of luminescent gold clusters with distinct emission from yellow to near-IR, using two different routes. In the first route, the gold-ligand complex was chemically reduced using sodium borohydride in alkaline medium, which gave near- IR luminescent gold clusters with maximum emission around 745 nm. In the second method, LA-PEG ligand was photochemically modified to a mixture of thiols, oligomers and oxygenated species under UV-irradiation, which was then used as both reducing agent and stabilizing ligand. By adjusting the pH, temperature, and time of the reaction, we were able to obtain clusters with two distinct emission properties. Refluxing the gold-ligand complex in alkaline medium in the presence of excess ligand gave yellow emission within the first two hours and the emission shifted to red after overnight reaction. Mass spectrometry and chemical assay were used to understand the photo-chemical transformation of Lipoic Acid (LA). Mass spectroscopic studies showed the photo-irradiated product contains thiols, oligomers (dimers, trimers and tetramers) as well as oxygenated species. The amount of thiol formed under different conditions of irradiation was estimated using Ellman's assay.

The role of H-bond in the high-pressure chemistry of model molecules

NASA Astrophysics Data System (ADS)

Fanetti, Samuele; Citroni, Margherita; Dziubek, Kamil; Medre Nobrega, Marcelo; Bini, Roberto

2018-03-01

Pressure is an extraordinary tool to modify direction and strength of intermolecular interactions with important consequences on the chemical stability of molecular materials. The decrease of the distance among nearest neighbour molecules can give rise to reactive configurations reflecting the crystal arrangement and leading to association processes. In this context, the role of the H-bonds is very peculiar because their usual strengthening with rising pressure does not necessarily configure a decrease of the reaction activation energy but, on the contrary, can give rise to an anomalous stability of the system. In spite of this central role, the mechanisms by which a chemical reaction is favoured or prevented by H-bonding under high pressure conditions is a poorly explored field. Here we review a few studies where the chemical behaviour of simple molecular systems under static compression was related to the H-bonding evolution with pressure. These results are able to clarify a wealth of changes of the chemical and physical properties caused by the strengthening with pressure of the H-bonding network and provide additional tools to understand the mechanisms of high-pressure reactivity, a mandatory step to make these synthetic methods of potential interest for applicative purposes.

Recognition-driven chemical labeling of endogenous proteins in multi-molecular crowding in live cells.

PubMed

Amaike, Kazuma; Tamura, Tomonori; Hamachi, Itaru

2017-11-14

Endogenous protein labeling is one of the most invaluable methods for studying the bona fide functions of proteins in live cells. However, multi-molecular crowding conditions, such as those that occur in live cells, hamper the highly selective chemical labeling of a protein of interest (POI). We herein describe how the efficient coupling of molecular recognition with a chemical reaction is crucial for selective protein labeling. Recognition-driven protein labeling is carried out by a synthetic labeling reagent containing a protein (recognition) ligand, a reporter tag, and a reactive moiety. The molecular recognition of a POI can be used to greatly enhance the reaction kinetics and protein selectivity, even under live cell conditions. In this review, we also briefly discuss how such selective chemical labeling of an endogenous protein can have a variety of applications at the interface of chemistry and biology.

Influence of magnetic field on chemically reactive blood flow through stenosed bifurcated arteries

NASA Astrophysics Data System (ADS)

Hossain, Khan Enaet; Haque, Md. Mohidul

2017-06-01

Dynamic response of mass transfer in chemically reactive blood flow through bifurcated arteries under the stenotic condition is numerically studied in the present of a uniform magnetic field. The blood flowing through the artery is assumed an incompressible, fully developed and Newtonian. The nonlinear unsteady flow phenomena are governed by the Navier-Stokes and concentration equations. All these equations together with the appropriate boundary conditions describing the present biomechanical problem are transformed by using a radial transformation and the numerical results are obtained using a finite difference technique. Effects of stenosed bifurcation and externally applied magnetic field on the blood flow with chemical reaction are discussed with the help of graph. All the flow characteristics are found to be affected by the presence of chemical reaction and exposure of magnetic field of different intensities. Finally some important findings of the problem are concluded in this work.

Experimental simulation of marine meteorite impacts: Implications for astrobiology

NASA Astrophysics Data System (ADS)

Umeda, Y.; Suga, H.; Sekine, T.; Kobayashi, T.; Furukawa, Y.; Kakegawa, T.

2016-12-01

Early oceans on planets which had liquid water (e.g. Earth, Mars) might have contained certain amounts of organic compounds such as amino acids, and were subjected to meteorite impacts, especially during the late heavy bombardment (LHB). Therefore, it is necessary to know chemical reactions and products of amino acids in aqueous solution under shock conditions in order to elucidate the prebiotic chemistry and evolution of amino acids through marine meteorite impacts. In our study, we performed shock recovery experiments in order to simulate shock reactions of marine meteorite impacts among olivine as meteorite components and water and amino acids as oceanic components (Umeda et al., 2016). The analytical results on shocked products in the recovered sample showed (i) the formation of carbon-rich substances derived from amino acids and (ii) morphological changes of olivine to fiber and features of lumpy surfaces affected by hot water. These results suggest that marine meteorite impacts might be able to occur the formation of carbon-rich substances from amino acids and the interaction between minerals and water. Hereafter, we will conduct more detailed analyses to investigate the chemical bonding and the chemical composition of carbon-rich substances as the experimental product from amino acids by Scanning Transmission X-ray Microscopy (STXM) and to identify the morphological change of olivine by Scanning Transmission Electron Microscope (STEM). These informations such as the chemical bonding and the composition of carbon-rich substances may be useful to make the reaction and the transformation of amino acids under shock conditions clear in more detail. As a further implication, carbon-rich substances have been also found in solar system (e.g. comets, meteorites) as important materials related to origin of life, although the origin (precursors) and the formation mechanism (what kinds of reactions) of them are still unknown well. If carbon-rich substances between experimental products and extraterrestrial matters have similar features such as the structure, the chemical bonding, and valence, it may be able to give new understandings (e.g. origin, formation mechanism, and reactions) to the areas of astrobiology. The results and discussions of these analyses will be added in the presentation of this meeting.

Chemical Separation of Fe-Ni Particles after Impact

NASA Astrophysics Data System (ADS)

Miura, Y.; Fukuyama, S.; Kedves, M. A.; Yamori, A.; Okamoto, M.; Gucsik, A.

Tiny grains of Fe-Ni system originated from planetesimals or meteoroids can remain under solid (or melt)-solid impact reactions even after impact process, probably together with high pressure form of Fe phase. Impact fragment with major Fe-Si (-Ni) system can be formed under vapor condition of impact reaction from terrestrial and artificial impact craters and spherules, and those with Ni-Cl (-S) system in composi- tion are formed under vapor condition of artificial impact experiments on the Barringer iron meteorite. These impact grains of Fe-bearing composition or high pressure form of iron-rich phases will be found probably on the asteroids in future exploration

Delay chemical master equation: direct and closed-form solutions

PubMed Central

Leier, Andre; Marquez-Lago, Tatiana T.

2015-01-01

The stochastic simulation algorithm (SSA) describes the time evolution of a discrete nonlinear Markov process. This stochastic process has a probability density function that is the solution of a differential equation, commonly known as the chemical master equation (CME) or forward-Kolmogorov equation. In the same way that the CME gives rise to the SSA, and trajectories of the latter are exact with respect to the former, trajectories obtained from a delay SSA are exact representations of the underlying delay CME (DCME). However, in contrast to the CME, no closed-form solutions have so far been derived for any kind of DCME. In this paper, we describe for the first time direct and closed solutions of the DCME for simple reaction schemes, such as a single-delayed unimolecular reaction as well as chemical reactions for transcription and translation with delayed mRNA maturation. We also discuss the conditions that have to be met such that such solutions can be derived. PMID:26345616

Delay chemical master equation: direct and closed-form solutions.

PubMed

Leier, Andre; Marquez-Lago, Tatiana T

2015-07-08

The stochastic simulation algorithm (SSA) describes the time evolution of a discrete nonlinear Markov process. This stochastic process has a probability density function that is the solution of a differential equation, commonly known as the chemical master equation (CME) or forward-Kolmogorov equation. In the same way that the CME gives rise to the SSA, and trajectories of the latter are exact with respect to the former, trajectories obtained from a delay SSA are exact representations of the underlying delay CME (DCME). However, in contrast to the CME, no closed-form solutions have so far been derived for any kind of DCME. In this paper, we describe for the first time direct and closed solutions of the DCME for simple reaction schemes, such as a single-delayed unimolecular reaction as well as chemical reactions for transcription and translation with delayed mRNA maturation. We also discuss the conditions that have to be met such that such solutions can be derived.

Self-cleaning and surface chemical reactions during hafnium dioxide atomic layer deposition on indium arsenide.

PubMed

Timm, Rainer; Head, Ashley R; Yngman, Sofie; Knutsson, Johan V; Hjort, Martin; McKibbin, Sarah R; Troian, Andrea; Persson, Olof; Urpelainen, Samuli; Knudsen, Jan; Schnadt, Joachim; Mikkelsen, Anders

2018-04-12

Atomic layer deposition (ALD) enables the ultrathin high-quality oxide layers that are central to all modern metal-oxide-semiconductor circuits. Crucial to achieving superior device performance are the chemical reactions during the first deposition cycle, which could ultimately result in atomic-scale perfection of the semiconductor-oxide interface. Here, we directly observe the chemical reactions at the surface during the first cycle of hafnium dioxide deposition on indium arsenide under realistic synthesis conditions using photoelectron spectroscopy. We find that the widely used ligand exchange model of the ALD process for the removal of native oxide on the semiconductor and the simultaneous formation of the first hafnium dioxide layer must be significantly revised. Our study provides substantial evidence that the efficiency of the self-cleaning process and the quality of the resulting semiconductor-oxide interface can be controlled by the molecular adsorption process of the ALD precursors, rather than the subsequent oxide formation.

A steady-state continuous flow chamber for the study of daytime and nighttime chemistry under atmospherically relevant NO levels

NASA Astrophysics Data System (ADS)

Zhang, Xuan; Ortega, John; Huang, Yuanlong; Shertz, Stephen; Tyndall, Geoffrey S.; Orlando, John J.

2018-05-01

Experiments performed in laboratory chambers have contributed significantly to the understanding of the fundamental kinetics and mechanisms of the chemical reactions occurring in the atmosphere. Two chemical regimes, classified as high-NO vs. zero-NO conditions, have been extensively studied in previous chamber experiments. Results derived from these two chemical scenarios are widely parameterized in chemical transport models to represent key atmospheric processes in urban and pristine environments. As the anthropogenic NOx emissions in the United States have decreased remarkably in the past few decades, the classic high-NO and zero-NO conditions are no longer applicable to many regions that are constantly impacted by both polluted and background air masses. We present here the development and characterization of the NCAR Atmospheric Simulation Chamber, which is operated in steady-state continuous flow mode for the study of atmospheric chemistry under intermediate NO conditions. This particular chemical regime is characterized by constant sub-ppb levels of NO and can be created in the chamber by precise control of the inflow NO concentration and the ratio of chamber mixing to residence timescales. Over the range of conditions achievable in the chamber, the lifetime of peroxy radicals (RO2), a key intermediate from the atmospheric degradation of volatile organic compounds (VOCs), can be extended to several minutes, and a diverse array of reaction pathways, including unimolecular pathways and bimolecular reactions with NO and HO2, can thus be explored. Characterization experiments under photolytic and dark conditions were performed and, in conjunction with model predictions, provide a basis for interpretation of prevailing atmospheric processes in environments with intertwined biogenic and anthropogenic activities. We demonstrate the proof of concept of the steady-state continuous flow chamber operation through measurements of major first-generation products, methacrolein (MACR) and methyl vinyl ketone (MVK), from OH- and NO3-initiated oxidation of isoprene.

N-Heterocyclic Olefins as Robust Organocatalyst for the Chemical Conversion of Carbon Dioxide to Value-Added Chemicals.

PubMed

Saptal, Vitthal B; Bhanage, Bhalchandra M

2016-08-09

In this report, the activity of N-heterocyclic olefins (NHOs) as a newly emerging class of organocatalyst is investigated for the chemical fixation of carbon dioxide through reactions with aziridines to form oxazolidinones and the N-formylation of amines with polymethylhydrosiloxane (PMHS) or 9-borabicyclo[3.3.1]nonane (9-BBN) as the reducing agent under mild conditions. The exocyclic carbon atoms of NHOs are highly nucleophilic owing to the electron-donating ability of the two nitrogen atoms. This high nucleophilicity of the NHOs activates CO2 molecules to form zwitterionic NHO-carboxylate (NHO-CO2 ) adducts, which are active in formylation reactions as well as the carboxylation of aziridines to oxazolidinones. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Green polymer chemistry: enzyme catalysis for polymer functionalization.

PubMed

Sen, Sanghamitra; Puskas, Judit E

2015-05-21

Enzyme catalyzed reactions are green alternative approaches to functionalize polymers compared to conventional methods. This technique is especially advantageous due to the high selectivity, high efficiency, milder reaction conditions, and recyclability of enzymes. Selected reactions can be conducted under solventless conditions without the application of metal catalysts. Hence this process is becoming more recognized in the arena of biomedical applications, as the toxicity created by solvents and metal catalyst residues can be completely avoided. In this review we will discuss fundamental aspects of chemical reactions biocatalyzed by Candida antarctica lipase B, and their application to create new functionalized polymers, including the regio- and chemoselectivity of the reactions.

Microwaves in chemistry: Another way of heating reaction mixtures

NASA Astrophysics Data System (ADS)

Berlan, J.

1995-04-01

The question of a possible "microwave activation" of chemical reaction is discussed. In fact two cases should be distinguished: homogeneous or heterogeneous reaction mixtures. In homogeneous mixtures there are no (or very low) rate enhancements compared to a conventional heating, but some influence on chemioselectivity has been observed. These effects derive from fast and mass heating of microwaves, and probably, especially under reflux, from different boiling rates and/or overheating. With heterogeneous mixtures non conventional effects probably derive from mass heating and selective overheating. This is illustrated with several reactions: Diels-Alder, naphthalene sulphonation, preparation of cyanuric acid, hydrolysis of nitriles, transposition reaction on solid support.

Coding the Assembly of Polyoxotungstates with a Programmable Reaction System.

PubMed

Ruiz de la Oliva, Andreu; Sans, Victor; Miras, Haralampos N; Long, De-Liang; Cronin, Leroy

2017-05-01

Chemical transformations are normally conducted in batch or flow mode, thereby allowing the chemistry to be temporally or spatially controlled, but these approaches are not normally combined dynamically. However, the investigation of the underlying chemistry masked by the self-assembly processes that often occur in one-pot reactions and exploitation of the potential of complex chemical systems requires control in both time and space. Additionally, maintaining the intermediate constituents of a self-assembled system "off equilibrium" and utilizing them dynamically at specific time intervals provide access to building blocks that cannot coexist under one-pot conditions and ultimately to the formation of new clusters. Herein, we implement the concept of a programmable networked reaction system, allowing us to connect discrete "one-pot" reactions that produce the building block{W 11 O 38 } ≡ {W 11 } under different conditions and control, in real time, the assembly of a series of polyoxometalate clusters {W 12 O 42 } ≡ {W 12 }, {W 22 O 74 } ≡ {W 22 } 1a, {W 34 O 116 } ≡ {W 34 } 2a, and {W 36 O 120 } ≡ {W 36 } 3a, using pH and ultraviolet-visible monitoring. The programmable networked reaction system reveals that is possible to assemble a range of different clusters using {W 11 }-based building blocks, demonstrating the relationship between the clusters within the family of iso-polyoxotungstates, with the final structural motif being entirely dependent on the building block libraries generated in each separate reaction space within the network. In total, this approach led to the isolation of five distinct inorganic clusters using a "fixed" set of reagents and using a fully automated sequence code, rather than five entirely different reaction protocols. As such, this approach allows us to discover, record, and implement complex one-pot reaction syntheses in a more general way, increasing the yield and reproducibility and potentially giving access to nonspecialists.

Coding the Assembly of Polyoxotungstates with a Programmable Reaction System

PubMed Central

2017-01-01

Chemical transformations are normally conducted in batch or flow mode, thereby allowing the chemistry to be temporally or spatially controlled, but these approaches are not normally combined dynamically. However, the investigation of the underlying chemistry masked by the self-assembly processes that often occur in one-pot reactions and exploitation of the potential of complex chemical systems requires control in both time and space. Additionally, maintaining the intermediate constituents of a self-assembled system “off equilibrium” and utilizing them dynamically at specific time intervals provide access to building blocks that cannot coexist under one-pot conditions and ultimately to the formation of new clusters. Herein, we implement the concept of a programmable networked reaction system, allowing us to connect discrete “one-pot” reactions that produce the building block{W11O38} ≡ {W11} under different conditions and control, in real time, the assembly of a series of polyoxometalate clusters {W12O42} ≡ {W12}, {W22O74} ≡ {W22} 1a, {W34O116} ≡ {W34} 2a, and {W36O120} ≡ {W36} 3a, using pH and ultraviolet–visible monitoring. The programmable networked reaction system reveals that is possible to assemble a range of different clusters using {W11}-based building blocks, demonstrating the relationship between the clusters within the family of iso-polyoxotungstates, with the final structural motif being entirely dependent on the building block libraries generated in each separate reaction space within the network. In total, this approach led to the isolation of five distinct inorganic clusters using a “fixed” set of reagents and using a fully automated sequence code, rather than five entirely different reaction protocols. As such, this approach allows us to discover, record, and implement complex one-pot reaction syntheses in a more general way, increasing the yield and reproducibility and potentially giving access to nonspecialists. PMID:28414229

Cluster-based MOFs with accelerated chemical conversion of CO2 through C-C bond formation.

PubMed

Xiong, Gang; Yu, Bing; Dong, Jie; Shi, Ying; Zhao, Bin; He, Liang-Nian

2017-05-30

Investigations on metal-organic frameworks (MOFs) as direct catalysts have been well documented, but direct catalysis of the chemical conversion of terminal alkynes and CO 2 as chemical feedstock by MOFs into valuable chemical products has never been reported. We report here two cluster-based MOFs I and II assembled from a multinuclear Gd-cluster and Cu-cluster, displaying high thermal and solvent stabilities. I and II as heterogeneous catalysts possess active catalytic centers [Cu 12 I 12 ] and [Cu 3 I 2 ], respectively, exhibiting excellent catalytic performance in the carboxylation reactions of CO 2 with 14 kinds of terminal alkynes under 1 atm and mild conditions. For the first time catalysis of the carboxylation reaction of terminal alkynes with CO 2 by MOF materials without any cocatalyst/additive is reported. This work not only reduces greenhouse gas emission but also provides highly valuable materials, opening a wide space in seeking recoverable catalysts to accelerate the chemical conversion of CO 2 .

Electric Current Activated Combustion Synthesis and Chemical Ovens Under Terrestrial and Reduced Gravity Conditions

NASA Technical Reports Server (NTRS)

Unuvar, C.; Fredrick, D.; Anselmi-Tamburini, U.; Manerbino, A.; Guigne, J. Y.; Munir, Z. A.; Shaw, B. D.

2004-01-01

Combustion synthesis (CS) generally involves mixing reactants together (e.g., metal powders) and igniting the mixture. Typically, a reaction wave will pass through the sample. In field activated combustion synthesis (FACS), the addition of an electric field has a marked effect on the dynamics of wave propagation and on the nature, composition, and homogeneity of the product as well as capillary flow, mass-transport in porous media, and Marangoni flows, which are influenced by gravity. The objective is to understand the role of an electric field in CS reactions under conditions where gravity-related effects are suppressed or altered. The systems being studied are Ti+Al and Ti+3Al. Two different ignition orientations have been used to observe effects of gravity when one of the reactants becomes molten. This consequentially influences the position and concentration of the electric current, which in turn influences the entire process. Experiments have also been performed in microgravity conditions. This process has been named Microgravity Field Activated Combustion Synthesis (MFACS). Effects of gravity have been demonstrated, where the reaction wave temperature and velocity demonstrate considerable differences besides the changes of combustion mechanisms with the different high currents applied. Also the threshold for the formation of a stable reaction wave is increased under zero gravity conditions. Electric current was also utilized with a chemical oven technique, where inserts of aluminum with minute amounts of tungsten and tantalum were used to allow observation of effects of settling of the higher density solid particles in liquid aluminum at the present temperature profile and wave velocity of the reaction.

Experimental Demonstrations in Teaching Chemical Reactions.

ERIC Educational Resources Information Center

Hugerat, Muhamad; Basheer, Sobhi

2001-01-01

Presents demonstrations of chemical reactions by employing different features of various compounds that can be altered after a chemical change occurs. Experimental activities include para- and dia-magnetism in chemical reactions, aluminum reaction with base, reaction of acid with carbonates, use of electrochemical cells for demonstrating chemical…

The Corrosion Behavior of Pure Iron under Solid Na2SO4 Deposit in Wet Oxygen Flow at 500 °C

PubMed Central

Tang, Yanbing; Liu, Li; Fan, Lei; Li, Ying; Wang, Fuhui

2014-01-01

The corrosion behavior of pure Fe under a Na2SO4 deposit in an atmosphere of O2 + H2O was investigated at 500 °C by thermo gravimetric, and electrochemical measurements, viz. potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and surface characterization methods viz. X-ray diffraction (XRD), and scanning electron microscope (SEM)/energy dispersive spectroscopy(EDS). The results showed that a synergistic effect occurred between Na2SO4 and O2 + H2O, which significantly accelerated the corrosion rate of the pure Fe. Briefly, NaFeO2 was formed in addition to the customary Fe oxides; at the same time, H2SO4 gas was produced by introduction of water vapor. Subsequently, an electrochemical corrosion reaction occurred due to the existence of Na2SO4, NaFeO2, and H2O. When this coupled to the chemical corrosion reaction, the progress of the chemical corrosion reaction was promoted and eventually resulted in the acceleration of the corrosion of the pure Fe. PMID:28788182

Microbial production of metabolites and associated enzymatic reactions under high pressure.

PubMed

Dong, Yongsheng; Jiang, Hua

2016-11-01

High environmental pressure exerts an external stress on the survival of microorganisms that are commonly found under normal pressure. In response, many growth traits alter, including cell morphology and physiology, cellular structure, metabolism, physical and chemical properties, the reproductive process, and defense mechanisms. The high-pressure technology (HP) has been industrially utilized in pressurized sterilization, synthesis of stress-induced products, and microbial/enzymatic transformation of chemicals. This article reviews current research on pressure-induced production of metabolites in normal-pressure microbes and their enzymatic reactions. Factors that affect the production of such metabolites are summarized, as well as the effect of pressure on the performance of microbial fermentation and the yield of flavoring compounds, different categories of induced enzymatic reactions and their characteristics in the supercritical carbon dioxide fluid, effects on enzyme activity, and the selection of desirable bacterial strains. Technological challenges are discussed, and future research directions are proposed. Information presented here will benefit the research, development, and application of the HP technology to improve microbial fermentation and enzymatic production of biologically active substances, thereby help to meet their increasing demand from the ever-expanding market.

Chemical-garden formation, morphology, and composition. II. Chemical gardens in microgravity.

PubMed

Cartwright, Julyan H E; Escribano, Bruno; Sainz-Díaz, C Ignacio; Stodieck, Louis S

2011-04-05

We studied the growth of metal-ion silicate chemical gardens under Earth gravity (1 g) and microgravity (μg) conditions. Identical sets of reaction chambers from an automated system (the Silicate Garden Habitat or SGHab) were used in both cases. The μg experiment was performed on board the International Space Station (ISS) within a temperature-controlled setup that provided still and video images of the experiment downlinked to the ground. Calcium chloride, manganese chloride, cobalt chloride, and nickel sulfate were used as seed salts in sodium silicate solutions of several concentrations. The formation and growth of osmotic envelopes and microtubes was much slower under μg conditions. In 1 g, buoyancy forces caused tubes to grow upward, whereas a random orientation for tube growth was found under μg conditions.

Operando MAS NMR Reaction Studies at High Temperatures and Pressures

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

Walter, Eric D.; Qi, Long; Chamas, Ali

Operando MAS-NMR studies provide unique insights into the details of chemical reactions; comprehensive information about temperature- and time-dependent changes in chemical species is accompanied by similarly rich information about changes in phase and chemical environment. Here we describe a new MAS-NMR rotor (the WHiMS rotor) capable of achieving internal pressures up to 400 bar at 20 °C or 225 bar at 250 °C, a range which includes many reactions of interest. The MAS-NMR spectroscopy enabled by these rotors is ideal for studying the behavior of mixed-phase systems, such as reactions involving solid catalysts and volatile liquids, with the potential tomore » add gases at high pressure. The versatile operation of the new rotors is demonstrated by collecting operando 1H and 13C spectra during the hydrogenolysis of benzyl phenyl ether, catalyzed by Ni/-Al2O3 at ca. 250 ºC, both with and without H2 (g) supplied to the rotor. The 2-propanol solvent, which exists in the supercritical phase under these reaction conditions, serves as an internal source of H2. The NMR spectra provide detailed kinetic profiles for the formation of the primary products toluene and phenol, as well as secondary hydrogenation and etherification products.« less

40 CFR 710.3 - Definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... of a chemical reaction or occurring in nature, and any chemical element or uncombined radical; except... or in part in chemical reaction(s) used for the intentional manufacture of other chemical substance(s... chemical substance was manufactured and other equipment which is strictly ancillary to the reaction vessel...

CHAP III- CHARRING ABLATOR PROGRAM FOR ADVANCED INVESTIGATION OF THERMAL PROTECTION SYSTEMS FOR ENTRY

NASA Technical Reports Server (NTRS)

Stroud, C. W.

1994-01-01

The transient response of a thermal protection material to heat applied to the surface can be calculated using the CHAP III computer program. CHAP III can be used to analyze pyrolysis gas chemical kinetics in detail and examine pyrolysis reactions-indepth. The analysis includes the deposition of solid products produced by chemical reactions in the gas phase. CHAP III uses a modelling technique which can approximate a wide range of ablation problems. The energy equation used in CHAP III incorporates pyrolysis (both solid and gas reactions), convection, conduction, storage, work, kinetic energy, and viscous dissipation. The chemically reacting components of the solid are allowed to vary as a function of position and time. CHAP III employs a finite difference method to approximate the energy equations. Input values include specific heat, thermal conductivity, thermocouple locations, enthalpy, heating rates, and a description of the chemical reactions expected. The output tabulates the temperature at locations throughout the ablator, gas flow within the solid, density of the solid, weight of pyrolysis gases, and rate of carbon deposition. A sample case is included, which analyzes an ablator material containing several pyrolysis reactions subjected to an environment typical of entry at lunar return velocity. CHAP III is written in FORTRAN IV for batch execution and has been implemented on a CDC CYBER 170 series computer operating under NOS with a central memory requirement of approximately 102K (octal) of 60 bit words. This program was developed in 1985.

Reaction monitoring using hyperpolarized NMR with scaling of heteronuclear couplings by optimal tracking.

PubMed

Zhang, Guannan; Schilling, Franz; Glaser, Steffen J; Hilty, Christian

2016-11-01

Off-resonance decoupling using the method of Scaling of Heteronuclear Couplings by Optimal Tracking (SHOT) enables determination of heteronuclear correlations of chemical shifts in single scan NMR spectra. Through modulation of J-coupling evolution by shaped radio frequency pulses, off resonance decoupling using SHOT pulses causes a user-defined dependence of the observed J-splitting, such as the splitting of 13 C peaks, on the chemical shift offset of coupled nuclei, such as 1 H. Because a decoupling experiment requires only a single scan, this method is suitable for characterizing on-going chemical reactions using hyperpolarization by dissolution dynamic nuclear polarization (D-DNP). We demonstrate the calculation of [ 13 C, 1 H] chemical shift correlations of the carbanionic active sites from hyperpolarized styrene polymerized using sodium naphthalene as an initiator. While off resonance decoupling by SHOT pulses does not enhance the resolution in the same way as a 2D NMR spectrum would, the ability to obtain the correlations in single scans makes this method ideal for determination of chemical shifts in on-going reactions on the second time scale. In addition, we present a novel SHOT pulse that allows to scale J-splittings 50% larger than the respective J-coupling constant. This feature can be used to enhance the resolution of the indirectly detected chemical shift and reduce peak overlap, as demonstrated in a model reaction between p-anisaldehyde and isobutylamine. For both pulses, the accuracy is evaluated under changing signal-to-noise ratios (SNR) of the peaks from reactants and reaction products, with an overall standard deviation of chemical shift differences compared to reference spectra of 0.02ppm when measured on a 400MHz NMR spectrometer. Notably, the appearance of decoupling side-bands, which scale with peak intensity, appears to be of secondary importance. Copyright © 2016 Elsevier Inc. All rights reserved.

Selective desulfurization of cysteine in the presence of Cys(Acm) in polypeptides obtained by native chemical ligation.

PubMed

Pentelute, Brad L; Kent, Stephen B H

2007-02-15

Increased versatility for the synthesis of proteins and peptides by native chemical ligation requires the ability to ligate at positions other than Cys. Here, we report that Raney nickel can be used under standard conditions for the selective desulfurization of Cys in the presence of Cys(Acm). This simple and practical tactic enables the more common Xaa-Ala junctions to be used as ligation sites for the chemical synthesis of Cys-containing peptides and proteins. [reaction: see text].

Reciprocity theory of homogeneous reactions

NASA Astrophysics Data System (ADS)

Agbormbai, Adolf A.

1990-03-01

The reciprocity formalism is applied to the homogeneous gaseous reactions in which the structure of the participating molecules changes upon collision with one another, resulting in a change in the composition of the gas. The approach is applied to various classes of dissociation, recombination, rearrangement, ionizing, and photochemical reactions. It is shown that for the principle of reciprocity to be satisfied it is necessary that all chemical reactions exist in complementary pairs which consist of the forward and backward reactions. The backward reaction may be described by either the reverse or inverse process. The forward and backward processes must satisfy the same reciprocity equation. Because the number of dynamical variables is usually unbalanced on both sides of a chemical equation, it is necessary that this balance be established by including as many of the dynamical variables as needed before the reciprocity equation can be formulated. Statistical transformation models of the reactions are formulated. The models are classified under the titles free exchange, restricted exchange and simplified restricted exchange. The special equations for the forward and backward processes are obtained. The models are consistent with the H theorem and Le Chatelier's principle. The models are also formulated in the context of the direct simulation Monte Carlo method.

Covalent binding of aniline to humic substances. 2. 15N NMR studies of nucleophilic addition reactions

USGS Publications Warehouse

Thorn, K.A.; Pettigrew, P.J.; Goldenberg, W.S.; Weber, E.J.

1996-01-01

Aromatic amines are known to undergo covalent binding with humic substances in the environment. Although previous studies have examined reaction conditions and proposed mechanisms, there has been no direct spectroscopic evidence for the covalent binding of the amines to the functional groups in humic substances. In order to further elucidate the reaction mechanisms, the Suwannee River and IHSS soil fulvic and humic acids were reacted with 15N-labeled aniline at pH 6 and analyzed using 15N NMR spectrometry. Aniline underwent nucleophilic addition reactions with the quinone and other carbonyl groups in the samples and became incorporated in the form of anilinohydroquinone, anilinoquinone, anilide, imine, and heterocyclic nitrogen, the latter comprising 50% or more of the bound amine. The anilide and anilinohydroquinone nitrogens were determined to be susceptible to chemical exchange by ammonia. In the case of Suwannee River fulvic acid, reaction under anoxic conditions and pretreatment with sodium borohydride or hydroxylamine prior to reaction under oxic conditions resulted in a decrease in the proportion of anilinohydroquinone nitrogen incorporated. The relative decrease in the incorporation of anilinohydroquinone nitrogen with respect to anilinoquinone nitrogen under anoxic conditions suggested that inter- or intramolecular redox reactions accompanied the nucleophilic addition reactions.

Complex Chemical Reaction Networks from Heuristics-Aided Quantum Chemistry.

PubMed

Rappoport, Dmitrij; Galvin, Cooper J; Zubarev, Dmitry Yu; Aspuru-Guzik, Alán

2014-03-11

While structures and reactivities of many small molecules can be computed efficiently and accurately using quantum chemical methods, heuristic approaches remain essential for modeling complex structures and large-scale chemical systems. Here, we present a heuristics-aided quantum chemical methodology applicable to complex chemical reaction networks such as those arising in cell metabolism and prebiotic chemistry. Chemical heuristics offer an expedient way of traversing high-dimensional reactive potential energy surfaces and are combined here with quantum chemical structure optimizations, which yield the structures and energies of the reaction intermediates and products. Application of heuristics-aided quantum chemical methodology to the formose reaction reproduces the experimentally observed reaction products, major reaction pathways, and autocatalytic cycles.

Correcting ligands, metabolites, and pathways

PubMed Central

Ott, Martin A; Vriend, Gert

2006-01-01

Background A wide range of research areas in bioinformatics, molecular biology and medicinal chemistry require precise chemical structure information about molecules and reactions, e.g. drug design, ligand docking, metabolic network reconstruction, and systems biology. Most available databases, however, treat chemical structures more as illustrations than as a datafield in its own right. Lack of chemical accuracy impedes progress in the areas mentioned above. We present a database of metabolites called BioMeta that augments the existing pathway databases by explicitly assessing the validity, correctness, and completeness of chemical structure and reaction information. Description The main bulk of the data in BioMeta were obtained from the KEGG Ligand database. We developed a tool for chemical structure validation which assesses the chemical validity and stereochemical completeness of a molecule description. The validation tool was used to examine the compounds in BioMeta, showing that a relatively small number of compounds had an incorrect constitution (connectivity only, not considering stereochemistry) and that a considerable number (about one third) had incomplete or even incorrect stereochemistry. We made a large effort to correct the errors and to complete the structural descriptions. A total of 1468 structures were corrected and/or completed. We also established the reaction balance of the reactions in BioMeta and corrected 55% of the unbalanced (stoichiometrically incorrect) reactions in an automatic procedure. The BioMeta database was implemented in PostgreSQL and provided with a web-based interface. Conclusion We demonstrate that the validation of metabolite structures and reactions is a feasible and worthwhile undertaking, and that the validation results can be used to trigger corrections and improvements to BioMeta, our metabolite database. BioMeta provides some tools for rational drug design, reaction searches, and visualization. It is freely available at provided that the copyright notice of all original data is cited. The database will be useful for querying and browsing biochemical pathways, and to obtain reference information for identifying compounds. However, these applications require that the underlying data be correct, and that is the focus of BioMeta. PMID:17132165

Astrochem: Abundances of chemical species in the interstellar medium

NASA Astrophysics Data System (ADS)

Maret, Sébastien; Bergin, Edwin A.

2015-07-01

Astrochem computes the abundances of chemical species in the interstellar medium, as function of time. It studies the chemistry in a variety of astronomical objects, including diffuse clouds, dense clouds, photodissociation regions, prestellar cores, protostars, and protostellar disks. Astrochem reads a network of chemical reactions from a text file, builds up a system of kinetic rates equations, and solves it using a state-of-the-art stiff ordinary differential equation (ODE) solver. The Jacobian matrix of the system is computed implicitly, so the resolution of the system is extremely fast: large networks containing several thousands of reactions are usually solved in a few seconds. A variety of gas phase process are considered, as well as simple gas-grain interactions, such as the freeze-out and the desorption via several mechanisms (thermal desorption, cosmic-ray desorption and photo-desorption). The computed abundances are written in a HDF5 file, and can be plotted in different ways with the tools provided with Astrochem. Chemical reactions and their rates are written in a format which is meant to be easy to read and to edit. A tool to convert the chemical networks from the OSU and KIDA databases into this format is also provided. Astrochem is written in C, and its source code is distributed under the terms of the GNU General Public License (GPL).

On the Theory of Oxidation-Reduction Reactions Involving Electron Transfer. V. Comparison and Properties of Electrochemical and Chemical Rate Constants

DOE R&D Accomplishments Database

Marcus, R. A.

1962-01-01

Using a theory of electron transfers which takes cognizance of reorganization of the medium outside the inner coordination shell and of changes of bond lengths inside it, relations between electrochemical and related chemical rate constants are deduced and compared with the experimental data. A correlation is found, without the use of arbitrary parameters. Effects of weak complexes with added electrolytes are included under specified conditions. The deductions offer a way of coordinating a variety of data in the two fields, internally as well as with each those in another. For example, the rate of oxidation or reduction of a series of related reactants by one reagent is correlated with that of another and with that of the corresponding electrochemical oxidation-reduction reaction, under certain specified conditions. These correlations may also provide a test for distinguishing an electron from an atom transfer mechanism. (auth)

Probing fast ribozyme reactions under biological conditions with rapid quench-flow kinetics.

PubMed

Bingaman, Jamie L; Messina, Kyle J; Bevilacqua, Philip C

2017-05-01

Reaction kinetics on the millisecond timescale pervade the protein and RNA fields. To study such reactions, investigators often perturb the system with abiological solution conditions or substrates in order to slow the rate to timescales accessible by hand mixing; however, such perturbations can change the rate-limiting step and obscure key folding and chemical steps that are found under biological conditions. Mechanical methods for collecting data on the millisecond timescale, which allow these perturbations to be avoided, have been developed over the last few decades. These methods are relatively simple and can be conducted on affordable and commercially available instruments. Here, we focus on using the rapid quench-flow technique to study the fast reaction kinetics of RNA enzymes, or ribozymes, which often react on the millisecond timescale under biological conditions. Rapid quench of ribozymes is completely parallel to the familiar hand-mixing approach, including the use of radiolabeled RNAs and fractionation of reactions on polyacrylamide gels. We provide tips on addressing and preventing common problems that can arise with the rapid-quench technique. Guidance is also offered on ensuring the ribozyme is properly folded and fast-reacting. We hope that this article will facilitate the broader use of rapid-quench instrumentation to study fast-reacting ribozymes under biological reaction conditions. Copyright © 2017 Elsevier Inc. All rights reserved.

Probing fast ribozyme reactions under biological conditions with rapid quench-flow kinetics

PubMed Central

Bingaman, Jamie L.; Messina, Kyle J.; Bevilacqua, Philip C.

2017-01-01

Reaction kinetics on the millisecond timescale pervade the protein and RNA fields. To study such reactions, investigators often perturb the system with abiological solution conditions or substrates in order to slow the rate to timescales accessible by hand-mixing; however, such perturbations can change the rate-limiting step and obscure key folding and chemical steps that are found under biological conditions. Mechanical methods for collecting data on the millisecond timescale, which allow these perturbations to be avoided, have been developed over the last few decades. These methods are relatively simple and can be conducted on affordable and commercially available instruments. Here, we focus on using the rapid quench-flow technique to study the fast reaction kinetics of RNA enzymes, or ribozymes, which often react on the millisecond timescale under biological conditions. Rapid quench of ribozymes is completely parallel to the familiar hand-mixing approach, including the use of radiolabeled RNAs and fractionation of reactions on polyacrylamide gels. We provide tips on addressing and preventing common problems that can arise with the rapid-quench technique. Guidance is also offered on ensuring the ribozyme is properly folded and fast-reacting. We hope that this article will facilitate the broader use of rapid-quench instrumentation to study fast-reacting ribozymes under biological reaction conditions. PMID:28315484

40 CFR 710.3 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... whole or in part as a result of a chemical reaction or occurring in nature, and any chemical element or... or in part in chemical reaction(s) used for the intentional manufacture of other chemical substance(s... chemical substance was manufactured and other equipment which is strictly ancillary to the reaction vessel...

40 CFR 710.3 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... whole or in part as a result of a chemical reaction or occurring in nature, and any chemical element or... or in part in chemical reaction(s) used for the intentional manufacture of other chemical substance(s... chemical substance was manufactured and other equipment which is strictly ancillary to the reaction vessel...

40 CFR 710.3 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... whole or in part as a result of a chemical reaction or occurring in nature, and any chemical element or... or in part in chemical reaction(s) used for the intentional manufacture of other chemical substance(s... chemical substance was manufactured and other equipment which is strictly ancillary to the reaction vessel...

40 CFR 720.30 - Chemicals not subject to notification requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... purposes. (3) Any chemical substance which results from a chemical reaction that occurs incidental to..., microbial organisms, or sunlight. (4) Any chemical substance which results from a chemical reaction that... chemical substance which results from a chemical reaction that occurs upon end use of another chemical...

40 CFR 720.30 - Chemicals not subject to notification requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... purposes. (3) Any chemical substance which results from a chemical reaction that occurs incidental to..., microbial organisms, or sunlight. (4) Any chemical substance which results from a chemical reaction that... chemical substance which results from a chemical reaction that occurs upon end use of another chemical...

40 CFR 720.30 - Chemicals not subject to notification requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... purposes. (3) Any chemical substance which results from a chemical reaction that occurs incidental to..., microbial organisms, or sunlight. (4) Any chemical substance which results from a chemical reaction that... chemical substance which results from a chemical reaction that occurs upon end use of another chemical...

On the existence of and mechanism for microwave-specific reaction rate enhancement† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4sc03372h Click here for additional data file.

PubMed Central

Dudley, Gregory B.; Richert, Ranko

2015-01-01

The use of microwave radiation to drive chemical reactions has become ubiquitous in almost all fields of chemistry. In all of these areas it is principally due to rapid and convenient heating resulting in significantly higher rates of reaction, with other advantages including enhanced product selectivity and control of materials properties. Although microwave heating continues to grow as an enabling technology, fundamental research into the nature of microwave heating has not grown at the same rate. In the case of chemical reactions run in homogeneous solution, particularly synthetic organic reactions, there is considerable controversy over the origins of rate enhancement, with a fundamental question being whether there exist microwave-specific effects, distinct from what can be attained under conventional convective heating, that can accelerate a reaction rate. In this Perspective, we discuss unique aspects of microwave heating of molecules in solution and discuss the origin and nature of microwave-specific effects arising from the process of “selective heating” of reactants in solution. Integral to this discussion is work from the field of dielectric relaxation spectroscopy, which provides a model for selective heating by Debye relaxation processes. The Perspective also includes a critical discussion of hypotheses of non-thermal effects (alternatively classified here as resonant processes) and an outline of specific reaction parameters for chemical systems in which microwave-specific Debye relaxation processes can result in observable reaction rate enhancement. PMID:29308138

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

Vorotilin, V. P., E-mail: VPVorotilin@yandex.ru

A generalization of the theory of chemical transformation processes under turbulent mixing of reactants and arbitrary values of the rate of molecular reactions is presented that was previously developed for the variant of an instantaneous reaction [13]. The use of the features of instantaneous reactions when considering the general case, namely, the introduction of the concept of effective reaction for the reactant volumes and writing a closing conservation equation for these volumes, became possible due to the partition of the whole amount of reactants into “active” and “passive” classes; the reactants of the first class are not mixed and reactmore » by the mechanism of instantaneous reactions, while the reactants of the second class approach each other only through molecular diffusion, and therefore their contribution to the reaction process can be neglected. The physical mechanism of reaction for the limit regime of an ideal mixing reactor (IMR) is revealed and described. Although formally the reaction rate in this regime depends on the concentration of passive fractions of the reactants, according to the theory presented, the true (hidden) mechanism of the reaction is associated only with the reaction of the active fractions of the reactants with vanishingly small concentration in the volume of the reactor. It is shown that the rate constant of fast chemical reactions can be evaluated when the mixing intensity of reactants is much less than that needed to reach the mixing conditions in an IMR.« less

40 CFR 717.7 - Persons not subject to this part.

Code of Federal Regulations, 2013 CFR

2013-07-01

... produced are limited to: (i) Chemical substances that result from chemical reactions that occur incidental..., moisture, microbial organisms, or sunlight. (ii) Chemical substances that result from chemical reactions...) Chemical substances that result from chemical reactions that occur upon end use of other chemical...

40 CFR 717.7 - Persons not subject to this part.

Code of Federal Regulations, 2012 CFR

2012-07-01

... produced are limited to: (i) Chemical substances that result from chemical reactions that occur incidental..., moisture, microbial organisms, or sunlight. (ii) Chemical substances that result from chemical reactions...) Chemical substances that result from chemical reactions that occur upon end use of other chemical...

40 CFR 717.7 - Persons not subject to this part.

Code of Federal Regulations, 2014 CFR

2014-07-01

... produced are limited to: (i) Chemical substances that result from chemical reactions that occur incidental..., moisture, microbial organisms, or sunlight. (ii) Chemical substances that result from chemical reactions...) Chemical substances that result from chemical reactions that occur upon end use of other chemical...

Selective C-O Hydrogenolysis and Decarboxylation of Biomass-Derived Heterocyclic Compounds over Heterogeneous Catalysts

NASA Astrophysics Data System (ADS)

Chia, Mei

The catalytic deoxygenation of biomass-derived compounds through selective C-O hydrogenolysis, catalytic transfer hydrogenation and lactonization, and decarboxylation to value-added chemicals over heterogeneous catalysts was examined under liquid phase reaction conditions. The reactions studied involve the conversion or production of heterocyclic compounds, specifically, cyclic ethers, lactones, and 2-pyrones. A bimetallic RhRe/C catalyst was found to be selective for the hydrogenolysis of secondary C-O bonds for a broad range cyclic ethers and polyols. Results from experimentally-observed reactivity trends, NH3 temperature-programmed desorption, fructose dehydration reaction studies, and first-principles density functional theory (DFT) calculations are consistent with the hypothesis of a bifunctional catalyst which facilitates acid-catalyzed ring-opening and dehydration coupled with metal-catalyzed hydrogenation. C-O hydrogenolysis and fructose dehydration activities were observed to decrease with an increase in reduction temperature and a decrease in the number of surface metallic Re atoms measured by in situ X-ray absorption spectroscopy. No C-O hydrogenolysis activity was detected over RhRe/C under water-free conditions. The activation of water molecules by Re atoms on the surface of metallic Rh is suggested to result in the formation of Bronsted acidity over RhRe/C. The catalytic transfer hydrogenation and lactonization of levulinic acid and its esters to gamma-valerolactone was accomplished through the Meerwein-Ponndorf-Verley reaction over metal oxide catalysts using secondary alcohols as the hydrogen donor. ZrO2 was a highly active material for CTH under batch and continuous flow reaction conditions; the initial activity of the catalyst was repeatedly regenerable by calcination in air, with no observable loss in catalytic activity. Lastly, the 2-pyrone, triacetic acid lactone, is shown to be a promising biorenewable platform chemical from which a wide range of chemical intermediates and end products can be obtained using heterogeneous catalysts or by thermal decomposition. Mechanistic insights from experimentally-observed reactivity trends and results from DFT calculations indicate that 2-pyrones undergo reactions unique to their structure such as keto-enol tautomerization, retro Diels-Alder, and nucleophilic attack by water. Ring-opening and decarboxylation reactions were found to be governed by key structural features such as the degree of saturation in the ring (e.g., C4=C5 bond), nature of the solvent, and presence of an acid catalyst.

Aqueous organic geochemistry at high temperature/high pressure

NASA Technical Reports Server (NTRS)

Simoneit, Bernd R. T.

1992-01-01

A description of the fate and chemical alterations of organic matter under hydrothermal conditions is given, with a brief overview of the geographic localities where these processes have been investigated to date. Two major aspects are examined: (1) alteration and degradation processes and reactions, both reductive and oxidative; and (2) synthesis processes and reactions which are primarily reductive. Examples of industrial applications of the related supercritical fluid technology are discussed.

Free jet micromixer to study fast chemical reactions by small angle X-ray scattering.

PubMed

Marmiroli, Benedetta; Grenci, Gianluca; Cacho-Nerin, Fernando; Sartori, Barbara; Ferrari, Enrico; Laggner, Peter; Businaro, Luca; Amenitsch, Heinz

2009-07-21

We present the design, fabrication process, and the first test results of a high aspect ratio micromixer combined with a free jet for under 100 micros time resolved studies of chemical reactions. The whole system has been optimized for synchrotron small angle X-ray scattering (SAXS) experiments. These studies are of particular interest to understand the early stages of chemical reactions, such as the kinetics of nanoparticle formation. The mixer is based on hydrodynamic focusing and works in the laminar regime. The use of a free jet overcomes the fouling of the channels and simultaneously circumvents background scattering from the walls. The geometrical parameters of the device have been optimized using finite element simulations, resulting in smallest features with radius <1 microm, and a channel depth of 60 microm, thus leading to an aspect ratio >60. To achieve the desired dimensions deep X-ray lithography (DXRL) has been employed. The device has been tested. First the focusing effect has been visualized using fluorescein. Then the evolution and stability of the jet, which exits the mixer nozzle at 13 m s(-1), have been characterized. Finally SAXS measurements have been conducted of the formation of calcium carbonate from calcium chloride and sodium carbonate. The fastest measurement is 75 micros after the beginning of the mixing of the reagents. The nanostructural evolution of chemical reactions is clearly discernible.

Room-temperature and temperature-dependent QSRR modelling for predicting the nitrate radical reaction rate constants of organic chemicals using ensemble learning methods.

PubMed

Gupta, S; Basant, N; Mohan, D; Singh, K P

2016-07-01

Experimental determinations of the rate constants of the reaction of NO3 with a large number of organic chemicals are tedious, and time and resource intensive; and the development of computational methods has widely been advocated. In this study, we have developed room-temperature (298 K) and temperature-dependent quantitative structure-reactivity relationship (QSRR) models based on the ensemble learning approaches (decision tree forest (DTF) and decision treeboost (DTB)) for predicting the rate constant of the reaction of NO3 radicals with diverse organic chemicals, under OECD guidelines. Predictive powers of the developed models were established in terms of statistical coefficients. In the test phase, the QSRR models yielded a correlation (r(2)) of >0.94 between experimental and predicted rate constants. The applicability domains of the constructed models were determined. An attempt has been made to provide the mechanistic interpretation of the selected features for QSRR development. The proposed QSRR models outperformed the previous reports, and the temperature-dependent models offered a much wider applicability domain. This is the first report presenting a temperature-dependent QSRR model for predicting the nitrate radical reaction rate constant at different temperatures. The proposed models can be useful tools in predicting the reactivities of chemicals towards NO3 radicals in the atmosphere, hence, their persistence and exposure risk assessment.

Chemical modeling constraints on Martian surface mineralogies formed in an early, warm, wet climate, and speculations on the occurrence of phosphate minerals in the Martian regolith

NASA Technical Reports Server (NTRS)

Plumlee, Geoffrey S.; Ridley, W. Ian; Debraal, Jeffrey D.

1992-01-01

This is one in a series of reports summarizing our chemical modeling studies of water-rock-gas interactions at the martian surface through time. The purpose of these studies is to place constraints on possible mineralogies formed at the martian surface and to model the geochemical implications of martian surficial processes proposed by previous researchers. Plumlee and Ridley summarize geochemical processes that may have occurred as a result of inferred volcano- and impact-driven hydrothermal activity on Mars. DeBraal et al. model the geochemical aspects of water-rock interactions and water evaporation near 0 C, as a prelude to future calculations that will model sub-0 C brine-rock-clathrate interactions under the current martian climate. In this report, we discuss reaction path calculations that model chemical processes that may have occurred at the martian surface in a postulated early, warm, wet climate. We assume a temperature of 25 C in all our calculations. Processes we model here include (1) the reaction of rainwater under various ambient CO2 and O2 pressures with basaltic rocks at the martian surface, (2) the formation of acid rain by volcanic gases such as HCl and SO2, (3) the reactions of acid rain with basaltic surficial materials, and (4) evaporation of waters resulting from rainwater-basalt interactions.

Diffusive confinement of free radical intermediates in the OH radical oxidation of semisolid aerosols

DOE PAGES

Wiegel, Aaron A.; Liu, Matthew J.; Hinsberg, William D.; ...

2017-02-07

Multiphase chemical reactions (gas + solid/liquid) involve a complex interplay between bulk and interface chemistry, diffusion, evaporation, and condensation. Reactions of atmospheric aerosols are an important example of this type of chemistry: the rich array of particle phase states and multiphase transformation pathways produce diverse but poorly understood interactions between chemistry and transport. Their chemistry is of intrinsic interest because of their role in controlling climate. Their characteristics also make them useful models for the study of principles of reactivity of condensed materials under confined conditions. Previously, we have reported a computational study of the oxidation chemistry of a liquidmore » aliphatic aerosol. In this study, we extend the calculations to investigate nearly the same reactions at a semisolid gas-aerosol interface. A reaction-diffusion model for heterogeneous oxidation of triacontane by hydroxyl radicals (OH) is described, and its predictions are compared to measurements of aerosol size and composition, which evolve continuously during oxidation. Our results are also explicitly compared to those obtained for the corresponding liquid system, squalane, to pinpoint salient elements controlling reactivity. The diffusive confinement of the free radical intermediates at the interface results in enhanced importance of a few specific chemical processes such as the involvement of aldehydes in fragmentation and evaporation, and a significant role of radical-radical reactions in product formation. The simulations show that under typical laboratory conditions semisolid aerosols have highly oxidized nanometer-scale interfaces that encapsulate an unreacted core and may confer distinct optical properties and enhanced hygroscopicity. This highly oxidized layer dynamically evolves with reaction, which we propose to result in plasticization. The validated model is used to predict chemistry under atmospheric conditions, where the OH radical concentration is much lower. The oxidation reactions are more strongly influenced by diffusion in the particle, resulting in a more liquid-like character.« less

GREENER SYNTHETIC TRANSFORMATIONS USING MICROWAVES

EPA Science Inventory

Microwave irradiation has been used for a variety of organic transformations wherein chemical reactions are expedited because of selective adsorption of microwave (MW) energy by polar molecules, non-polar molecules being inert to the MW dielectric loss. The MW application under s...

Mass Transfer with Chemical Reaction.

ERIC Educational Resources Information Center

DeCoursey, W. J.

1987-01-01

Describes the organization of a graduate course dealing with mass transfer, particularly as it relates to chemical reactions. Discusses the course outline, including mathematics models of mass transfer, enhancement of mass transfer rates by homogeneous chemical reaction, and gas-liquid systems with chemical reaction. (TW)

Liquid-assisted grinding and ion pairing regulates percentage conversion and diastereoselectivity of the Wittig reaction under mechanochemical conditions.

PubMed

Denlinger, Kendra Leahy; Ortiz-Trankina, Lianna; Carr, Preston; Benson, Kingsley; Waddell, Daniel C; Mack, James

2018-01-01

Mechanochemistry is maturing as a discipline and continuing to grow, so it is important to continue understanding the rules governing the system. In a mechanochemical reaction, the reactants are added into a vessel along with one or more grinding balls and the vessel is shaken at high speeds to facilitate a chemical reaction. The dielectric constant of the solvent used in liquid-assisted grinding (LAG) and properly chosen counter-ion pairing increases the percentage conversion of stilbenes in a mechanochemical Wittig reaction. Utilizing stepwise addition/evaporation of ethanol in liquid-assisted grinding also allows for the tuning of the diastereoselectivity in the Wittig reaction.

Molecular dynamic simulation of thermite reaction of Al nanosphere/Fe2O3 nanotube

NASA Astrophysics Data System (ADS)

Zhu, Zhi-Yang; Ma, Bo; Tang, Cui-Ming; Cheng, Xin-Lu

2016-01-01

The letter presents thermite reactions of Al/Fe2O3 nanothermites simulated by using molecular dynamic method in combination with ReaxFF. The variations in chemical bonds are measured to elaborate reaction process and characterize ignition performance. It is found that the longer interval is, the higher ignition temperature and the longer ignition delay system has. Additionally, the heating rate has much effect on ignition temperature. Under the temperature of 1450 K, oxygen is directly released from hematite nanotube, thermite reaction is deemed as a multiphase process. And, release energy of System2 is about 3.96 kJ/g. However, much energy rises from alloy reaction. Thermite reactions do not follow the theoretical equation, but are a complicated process.

Photo-oxidation degradation mechanisms in P3HT for organic solar cells: Insights from first-principles simulations

NASA Astrophysics Data System (ADS)

Leung, Kevin; Sai, Na; Zador, Judit; Henkelman, Graeme

2014-03-01

Photo-oxidation is one of the leading chemical degradation mechanisms in polymer solar cells. In this work, using hybrid density functional theory and periodic boundary condition, we investigate reaction pathways that may lead to the sulfur oxidation in poly(3-hexylthiophene)(P3HT) as a step toward breaking the macromolecule backbone. We calculate energy barriers for reactions of P3HT backbone with oxidizing radicals suggested by infrared spectroscopy (IR) and XPS studies. Our results strongly suggest that an attack of hydroxyl radical on sulfur as proposed in the literature is unlikely to be thermodynamically favored. On the other hand, a reaction between the alkylperoxyl radical and the polymer backbone may provide low barrier reaction pathways to photo-oxidation of conjugated polymers with side chains. Our work paves way for future studies using ab-initio calculations in a condensed phase setting to model complex chemical reactions relevant to photochemical stability of novel polymers. Supported by the Energy Frontier Research Center funded by the U.S. DOE Office of Basic Energy Sciences under Award #DE-SC0001091.

Influence of vegetable oils fatty acid composition on reaction temperature and glycerides conversion to biodiesel during transesterification.

PubMed

Pinzi, S; Gandía, L M; Arzamendi, G; Ruiz, J J; Dorado, M P

2011-01-01

Presence of unreacted glycerides in biodiesel may reduce drastically its quality. This is why conversion of raw material in biodiesel through transesterification needs to readjust reaction parameter values to complete. In the present work, monitoring of glycerides transformation in biodiesel during the transesterification of vegetable oils was carried out. To check the influence of the chemical composition on glycerides conversion, selected vegetable oils covered a wide range of fatty acid composition. Reactions were carried out under alkali-transesterification in the presence of methanol. In addition, a multiple regression model was proposed. Results showed that kinetics depends on chemical and physical properties of the oils. It was found that the optimal reaction temperature depends on both length and unsaturation degree of vegetable oils fatty acid chains. Vegetable oils with higher degree of unsaturation exhibit faster monoglycerides conversion to biodiesel. It can be concluded that fatty acid composition influences reaction parameters and glycerides conversion, hence biodiesel yield and economic viability. Copyright © 2010 Elsevier Ltd. All rights reserved.

Direct numerical simulation of shear localization and decomposition reactions in shock-loaded HMX crystal

DOE PAGES

Austin, Ryan A.; Barton, Nathan R.; Reaugh, John E.; ...

2015-05-14

A numerical model is developed to study the shock wave ignition of HMX crystal. The model accounts for the coupling between crystal thermal/mechanical responses and chemical reactions that are driven by the temperature field. This allows for the direct numerical simulation of decomposition reactions in the hot spots formed by shock/impact loading. The model is used to simulate intragranular pore collapse under shock wave loading. In a reference case: (i) shear-enabled micro-jetting is responsible for a modest extent of reaction in the pore collapse region, and (ii) shear banding is found to be an important mode of localization. The shearmore » bands, which are filled with molten HMX, grow out of the pore collapse region and serve as potential ignition sites. The model predictions of shear banding and reactivity are found to be quite sensitive to the respective flow strengths of the solid and liquid phases. In this regard, it is shown that reasonable assumptions of liquid-HMX viscosity can lead to chemical reactions within the shear bands on a nanosecond time scale.« less

High-temperature water–rock interactions and hydrothermal environments in the chondrite-like core of Enceladus

PubMed Central

Sekine, Yasuhito; Shibuya, Takazo; Postberg, Frank; Hsu, Hsiang-Wen; Suzuki, Katsuhiko; Masaki, Yuka; Kuwatani, Tatsu; Mori, Megumi; Hong, Peng K.; Yoshizaki, Motoko; Tachibana, Shogo; Sirono, Sin-iti

2015-01-01

It has been suggested that Saturn's moon Enceladus possesses a subsurface ocean. The recent discovery of silica nanoparticles derived from Enceladus shows the presence of ongoing hydrothermal reactions in the interior. Here, we report results from detailed laboratory experiments to constrain the reaction conditions. To sustain the formation of silica nanoparticles, the composition of Enceladus' core needs to be similar to that of carbonaceous chondrites. We show that the presence of hydrothermal reactions would be consistent with NH3- and CO2-rich plume compositions. We suggest that high reaction temperatures (>50 °C) are required to form silica nanoparticles whether Enceladus' ocean is chemically open or closed to the icy crust. Such high temperatures imply either that Enceladus formed shortly after the formation of the solar system or that the current activity was triggered by a recent heating event. Under the required conditions, hydrogen production would proceed efficiently, which could provide chemical energy for chemoautotrophic life. PMID:26506464

Recovery of acetic acid from dilute aqueous solutions using catalytic dehydrative esterification with ethanol.

PubMed

Yagyu, Daisuke; Ohishi, Tetsuo; Igarashi, Takeshi; Okumura, Yoshikuni; Nakajo, Tetsuo; Mori, Yuichiro; Kobayashi, Shū

2013-03-01

We have developed a direct esterification of aqueous acetic acid with ethanol (molar ratio=1:1) catalyzed by polystyrene-supported or homogeneous sulfonic acids toward the recovery of acetic acid from wastewater in chemical plants. The equilibrium yield was significantly increased by the addition of toluene, which had a high ability to extract ethyl acetate from the aqueous phase. It was shown that low-loading and alkylated polystyrene-supported sulfonic acid efficiently accelerated the reaction. These results suggest that the construction of hydrophobic reaction environments in water was critical in improving the chemical yield. Addition of inorganic salts was also effective for the reaction under not only biphasic conditions (toluene-water) but also toluene-free conditions, because the mutual solubility of ethyl acetate and water was suppressed by the salting-out effect. Among the tested salts, CaCl(2) was found to be the most suitable for this reaction system. Copyright © 2012 Elsevier Ltd. All rights reserved.

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

Austin, Ryan A.; Barton, Nathan R.; Reaugh, John E.

A numerical model is developed to study the shock wave ignition of HMX crystal. The model accounts for the coupling between crystal thermal/mechanical responses and chemical reactions that are driven by the temperature field. This allows for the direct numerical simulation of decomposition reactions in the hot spots formed by shock/impact loading. The model is used to simulate intragranular pore collapse under shock wave loading. In a reference case: (i) shear-enabled micro-jetting is responsible for a modest extent of reaction in the pore collapse region, and (ii) shear banding is found to be an important mode of localization. The shearmore » bands, which are filled with molten HMX, grow out of the pore collapse region and serve as potential ignition sites. The model predictions of shear banding and reactivity are found to be quite sensitive to the respective flow strengths of the solid and liquid phases. In this regard, it is shown that reasonable assumptions of liquid-HMX viscosity can lead to chemical reactions within the shear bands on a nanosecond time scale.« less

High-temperature water-rock interactions and hydrothermal environments in the chondrite-like core of Enceladus.

PubMed

Sekine, Yasuhito; Shibuya, Takazo; Postberg, Frank; Hsu, Hsiang-Wen; Suzuki, Katsuhiko; Masaki, Yuka; Kuwatani, Tatsu; Mori, Megumi; Hong, Peng K; Yoshizaki, Motoko; Tachibana, Shogo; Sirono, Sin-iti

2015-10-27

It has been suggested that Saturn's moon Enceladus possesses a subsurface ocean. The recent discovery of silica nanoparticles derived from Enceladus shows the presence of ongoing hydrothermal reactions in the interior. Here, we report results from detailed laboratory experiments to constrain the reaction conditions. To sustain the formation of silica nanoparticles, the composition of Enceladus' core needs to be similar to that of carbonaceous chondrites. We show that the presence of hydrothermal reactions would be consistent with NH3- and CO2-rich plume compositions. We suggest that high reaction temperatures (>50 °C) are required to form silica nanoparticles whether Enceladus' ocean is chemically open or closed to the icy crust. Such high temperatures imply either that Enceladus formed shortly after the formation of the solar system or that the current activity was triggered by a recent heating event. Under the required conditions, hydrogen production would proceed efficiently, which could provide chemical energy for chemoautotrophic life.

Microfluidic chemical reaction circuits

DOEpatents

Lee, Chung-cheng [Irvine, CA; Sui, Guodong [Los Angeles, CA; Elizarov, Arkadij [Valley Village, CA; Kolb, Hartmuth C [Playa del Rey, CA; Huang, Jiang [San Jose, CA; Heath, James R [South Pasadena, CA; Phelps, Michael E [Los Angeles, CA; Quake, Stephen R [Stanford, CA; Tseng, Hsian-rong [Los Angeles, CA; Wyatt, Paul [Tipperary, IE; Daridon, Antoine [Mont-Sur-Rolle, CH

2012-06-26

New microfluidic devices, useful for carrying out chemical reactions, are provided. The devices are adapted for on-chip solvent exchange, chemical processes requiring multiple chemical reactions, and rapid concentration of reagents.

Control of Maillard Reactions in Foods: Strategies and Chemical Mechanisms.

PubMed

Lund, Marianne N; Ray, Colin A

2017-06-14

Maillard reactions lead to changes in food color, organoleptic properties, protein functionality, and protein digestibility. Numerous different strategies for controlling Maillard reactions in foods have been attempted during the past decades. In this paper, recent advances in strategies for controlling the Maillard reaction and subsequent downstream reaction products in food systems are critically reviewed. The underlying mechanisms at play are presented, strengths and weaknesses of each strategy are discussed, and reasonable reaction mechanisms are proposed to reinforce the evaluations. The review includes strategies involving addition of functional ingredients, such as plant polyphenols and vitamins, as well as enzymes. The resulting trapping or modification of Maillard targets, reactive intermediates, and advanced glycation endproducts (AGEs) are presented with their potential unwanted side effects. Finally, recent advances in processing for control of Maillard reactions are discussed.

Combustion Of Porous Graphite Particles In Oxygen Enriched Air

NASA Technical Reports Server (NTRS)

Delisle, Andrew J.; Miller, Fletcher J.; Chelliah, Harsha K.

2003-01-01

Combustion of solid fuel particles has many important applications, including power generation and space propulsion systems. The current models available for describing the combustion process of these particles, especially porous solid particles, include various simplifying approximations. One of the most limiting approximations is the lumping of the physical properties of the porous fuel with the heterogeneous chemical reaction rate constants [1]. The primary objective of the present work is to develop a rigorous modeling approach that could decouple such physical and chemical effects from the global heterogeneous reaction rates. For the purpose of validating this model, experiments with porous graphite particles of varying sizes and porosity are being performed under normal and micro gravity.

Assessing the Greenness of Chemical Reactions in the Laboratory Using Updated Holistic Graphic Metrics Based on the Globally Harmonized System of Classification and Labeling of Chemicals

ERIC Educational Resources Information Center

Ribeiro, M. Gabriela T. C.; Yunes, Santiago F.; Machado, Adelio A. S. C.

2014-01-01

Two graphic holistic metrics for assessing the greenness of synthesis, the "green star" and the "green circle", have been presented previously. These metrics assess the greenness by the degree of accomplishment of each of the 12 principles of green chemistry that apply to the case under evaluation. The criteria for assessment…

Preparing "Chameleon Balls" from Natural Plants: Simple Handmade pH Indicator and Teaching Material for Chemical Equilibrium

NASA Astrophysics Data System (ADS)

Kanda, Naoki; Asano, Takayuki; Itoh, Toshiyuki; Onoda, Makoto

1995-12-01

Anthocyanins are found in the flowers and fruits of natural plants. Since their color depends on pH, they are sometines used as a pH indicator. Since these sequences are reversible, they are also useful in demonstrating chemical equilibrium in the repetitive color changes of anthocyanins from flowers by controlling pH conditions. We prepared the polysaccharide beads conatining water extracts of red cabbage as calcium alginate. The beads showed a clear red color under acidic conditions, turned blue at neutral pH of 7, and orange-yellow at pH of 13. This color change could be demonstrated over and over. Because the color changes of these polysaccharide beads depended darmatically on pH, junior high students in science classes called them "chameleon balls" when we demonstrated this reaction for them. In this paper we describe how polysaccharide beads, which are made from calcium alginate with natural pigments, served as a teaching tool for the chemical equilibrium of anthocyanins under different pH conditions. Preparation of the chameleon ball is very easy. The most important thing is that making the chameleon ball is great fun. The ball should therefore be viewed not only as a handmade pH indicator but also an interesting teaching tool of the chemical equilibrium reaction.

40 CFR 710.4 - Scope of the inventory.

Code of Federal Regulations, 2013 CFR

2013-07-01

... not included. (3) Any chemical substance which results from a chemical reaction that occurs incidental... reaction that occurs incidental to storage of another chemical substance, mixture, or article. (5) Any chemical substance which results from a chemical reaction that occurs upon end use of other chemical...

40 CFR 710.4 - Scope of the inventory.

Code of Federal Regulations, 2014 CFR

2014-07-01

... not included. (3) Any chemical substance which results from a chemical reaction that occurs incidental... reaction that occurs incidental to storage of another chemical substance, mixture, or article. (5) Any chemical substance which results from a chemical reaction that occurs upon end use of other chemical...

40 CFR 710.4 - Scope of the inventory.

Code of Federal Regulations, 2012 CFR

2012-07-01

... not included. (3) Any chemical substance which results from a chemical reaction that occurs incidental... reaction that occurs incidental to storage of another chemical substance, mixture, or article. (5) Any chemical substance which results from a chemical reaction that occurs upon end use of other chemical...

Synthesis and DFT calculations of some 2-aminothiazoles

NASA Astrophysics Data System (ADS)

Rezania, Jafar; Behzadi, Hadi; Shockravi, Abbas; Ehsani, Morteza; Akbarzadeh, Elahe

2018-04-01

A series of 2-aminothiazole derivatives have been synthesized by the reaction of acetyl compounds with thiourea and iodine as catalyst under solvent-free condition, a green chemistry method. The quantum chemical calculations at the DFT/B3LYP level of theory in gas phase were carried out for starting acetyl derivatives. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) and related reactivity descriptor of acetyl derivatives, as well as, enthalpy of reactions are calculated in order to investigate the reaction properties of acetyl compounds and yields of the reactions. The calculated reactivity descriptors are well correlated to activity of different acetyl derivatives.

Allylic Amination and N-Arylation-Based Domino Reactions Providing Rapid Three-Component Strategies to Fused Pyrroles with Different Substituted Patterns

PubMed Central

Jiang, Bo; Li, Ying; Tu, Man-Su; Wang, Shu-Liang; Tu, Shu-Jiang; Li, Guigen

2012-01-01

New three-component domino reaction providing divergent approaches to multi-functionalized fused pyrroles with different substituted patterns have been established (40 examples). The direct C(sp3)–N bond formation was achieved through intermolecular allylic amination in a one-pot operation; and N-arylation of amines was realized by varying N-amino acid enaminones. The reaction is easy to perform simply by mixing three common reactants in acetic acid under microwave heating. The reaction proceeds at fast rates and can be finished within 30 min, which makes workup convenient to give good chemical yields. PMID:22852549

Base Oil-Extreme Pressure Additive Synergy in Lubricants

USDA-ARS?s Scientific Manuscript database

Extreme pressure (EP) additives are those containing reactive elements such as sulfur, phosphorus, and chlorine. In lubrication processes that occur under extremely severe conditions (e.g., high pressure and/or slow speed), these elements undergo chemical reactions generating new materials (tribofi...

Origins of the temperature dependence of hammerhead ribozyme catalysis.

PubMed Central

Peracchi, A

1999-01-01

The difficulties in interpreting the temperature dependence of protein enzyme reactions are well recognized. Here, the hammerhead ribozyme cleavage was investigated under single-turnover conditions between 0 and 60 degrees C as a model for RNA-catalyzed reactions. Under the adopted conditions, the chemical step appears to be rate-limiting. However, the observed rate of cleavage is affected by pre-catalytic equilibria involving deprotonation of an essential group and binding of at least one low-affinity Mg2+ion. Thus, the apparent entropy and enthalpy of activation include contributions from the temperature dependence of these equilibria, precluding a simple physical interpretation of the observed activation parameters. Similar pre-catalytic equilibria likely contribute to the observed activation parameters for ribozyme reactions in general. The Arrhenius plot for the hammerhead reaction is substantially curved over the temperature range considered, which suggests the occurrence of a conformational change of the ribozyme ground state around physiological temperatures. PMID:10390528

Coupling Glucose Dehydrogenation with CO2 Hydrogenation by Hydrogen Transfer in Aqueous Media at Room Temperature.

PubMed

Ding, Guodong; Su, Ji; Zhang, Cheng; Tang, Kan; Yang, Lisha; Lin, Hongfei

2018-05-08

Conversion of carbon dioxide into value-added chemicals and fuels provides a direct solution to reduce excessive CO2 in the atmosphere. Herein, a novel catalytic reaction system is presented by coupling the dehydrogenation of glucose with the hydrogenation of a CO2 derived salt, ammonium carbonate, in the ethanol-water mixture. For the first time, the hydrogenation of CO2 into formate by glucose has been achieved under ambient conditions. Under the optimal reaction conditions, the highest yield of formate reached ~ 46 %. We find that the apparent pH value in the ethanol-water mixture plays a central role in determining the performance of the hydrogen transfer reaction. Based on the 13C NMR and ESI-MS results, a possible pathway of the coupled glucose dehydrogenation and CO2 hydrogenation reactions was proposed. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Process characteristics for microwave assisted hydrothermal carbonization of cellulose.

PubMed

Zhang, Junting; An, Ying; Borrion, Aiduan; He, Wenzhi; Wang, Nan; Chen, Yirong; Li, Guangming

2018-07-01

The process characteristics of microwave assisted hydrothermal carbonization of cellulose was investigated and a first order kinetics model based on carbon concentration was developed. Chemical properties analysis showed that comparing to conventional hydrothermal carbonization, hydrochar with comparable energy properties can be obtained with 5-10 times decrease in reaction time with assistance of microwave heating. Results from kinetics study was in great agreement with experimental analysis, that they both illustrated the predominant mechanism of the reaction depend on variations in the reaction rates of two co-existent pathways. Particularly, the pyrolysis-like intramolecular dehydration reaction was proved to be the predominant mechanism for hydrochar generation under high temperatures. Finally, the enhancement effects of microwave heating were reflected under both soluble and solid pathways in this research, suggesting microwave-assisted hydrothermal carbonization as a more attracting method for carbon-enriched hydrochar recovery. Copyright © 2018 Elsevier Ltd. All rights reserved.

Molecular Dynamics Simulations of Chemical Reactions for Use in Education

ERIC Educational Resources Information Center

Qian Xie; Tinker, Robert

2006-01-01

One of the simulation engines of an open-source program called the Molecular Workbench, which can simulate thermodynamics of chemical reactions, is described. This type of real-time, interactive simulation and visualization of chemical reactions at the atomic scale could help students understand the connections between chemical reaction equations…

Automatized Assessment of Protective Group Reactivity: A Step Toward Big Reaction Data Analysis.

PubMed

Lin, Arkadii I; Madzhidov, Timur I; Klimchuk, Olga; Nugmanov, Ramil I; Antipin, Igor S; Varnek, Alexandre

2016-11-28

We report a new method to assess protective groups (PGs) reactivity as a function of reaction conditions (catalyst, solvent) using raw reaction data. It is based on an intuitive similarity principle for chemical reactions: similar reactions proceed under similar conditions. Technically, reaction similarity can be assessed using the Condensed Graph of Reaction (CGR) approach representing an ensemble of reactants and products as a single molecular graph, i.e., as a pseudomolecule for which molecular descriptors or fingerprints can be calculated. CGR-based in-house tools were used to process data for 142,111 catalytic hydrogenation reactions extracted from the Reaxys database. Our results reveal some contradictions with famous Greene's Reactivity Charts based on manual expert analysis. Models developed in this study show high accuracy (ca. 90%) for predicting optimal experimental conditions of protective group deprotection.

Quantum chemical study of the mechanism of reaction between NH (X 3sigma-) and H2, H2O, and CO2 under combustion conditions.

PubMed

Mackie, John C; Bacskay, George B

2005-12-29

Reactions of ground-state NH (3sigma-) radicals with H2, H2O, and CO2 have been investigated quantum chemically, whereby the stationary points of the appropriate reaction potential energy surfaces, that is, reactants, products, intermediates, and transition states, have been identified at the G3//B3LYP level of theory. Reaction between NH and H2 takes place via a simple abstraction transition state, and the rate coefficient for this reaction as derived from the quantum chemical calculations, k(NH + H2) = (1.1 x 10(14)) exp(-20.9 kcal mol(-1)/RT) cm3 mol(-1) s(-1) between 1000 and 2000 K, is found to be in good agreement with experiment. For reaction between triplet NH and H2O, no stable intermediates were located on the triplet reaction surface although several stable species were found on the singlet surface. No intersystem crossing seam between triplet NH + H2O and singlet HNO + H2 (the products of lowest energy) was found; hence there is no evidence to support the existence of a low-energy pathway to these products. A rate coefficient of k(NH + H2O) = (6.1 x 10(13)) exp(-32.8 kcal mol(-1)/RT) cm3 mol(-1) s(-1) between 1000 and 2000 K for the reaction NH (3sigma-) + H2O --> NH2 (2B) + OH (2pi) was derived from the quantum chemical results. The reverse rate coefficient, calculated via the equilibrium constant, is in agreement with values used in modeling the thermal de-NO(x) process. For the reaction between triplet NH and CO2, several stable intermediates on both triplet and singlet reaction surfaces were located. Although a pathway from triplet NH + CO2 to singlet HNO + CO involving intersystem crossing in an HN-CO2 adduct was discovered, no pathway of sufficiently low activation energy was discovered to compare with that found in an earlier experiment [Rohrig, M.; Wagner, H. G. Proc. Combust. Inst. 1994, 25, 993.].

Monitoring the dynamic photocatalytic activity of single CdS nanoparticles by lighting up H2 nanobubbles with fluorescent dyes.

PubMed

Su, Hua; Fang, Yimin; Chen, Fangyuan; Wang, Wei

2018-02-14

The capability of semiconductor nanomaterials to convert solar energy to chemical energy has led to many promising applications, for instance, photocatalyzed H 2 generation. Studying this important photocatalytic reaction at the single nanocatalyst level provides a great opportunity to understand the microscopic reaction kinetics and mechanism by overcoming the chemical and structural heterogeneity among individuals. Here we report a fluorescence (FL) labeling strategy to visualize individual H 2 nanobubbles that are generated at single CdS nanoparticles during photocatalysis. In operando imaging of nanobubble growth kinetics allows for determination of the photocatalytic activity of single nanocatalysts, which was found to randomly alternate among high activity, low activity and inactive states. In addition to H 2 nanobubbles, the present labeling strategy is also suitable for other types of gas nanobubbles. Since nanomaterial-catalyzed gas generation is widely involved in many important photochemical (water splitting), electrochemical (electrolysis) and chemical (nanomotors) reactions, the present work is promising for the general applicability of single nanoparticle catalysis in broad basic and industrial fields by lighting up nanobubbles under commercial and conventional FL microscopes.

Direct 3D Printing of Catalytically Active Structures

DOE PAGES

Manzano, J. Sebastian; Weinstein, Zachary B.; Sadow, Aaron D.; ...

2017-09-22

3D printing of materials with active functional groups can provide custom-designed structures that promote chemical conversions. Catalytically active architectures were produced by photopolymerizing bifunctional molecules using a commercial stereolithographic 3D printer. Functionalities in the monomers included a polymerizable vinyl group to assemble the 3D structures and a secondary group to provide them with active sites. The 3D-printed architectures containing accessible carboxylic acid, amine, and copper carboxylate functionalities were catalytically active for the Mannich, aldol, and Huisgen cycloaddition reactions, respectively. The functional groups in the 3D-printed structures were also amenable to post-printing chemical modification. And as proof of principle, chemically activemore » cuvette adaptors were 3D printed and used to measure in situ the kinetics of a heterogeneously catalyzed Mannich reaction in a conventional solution spectrophotometer. In addition, 3D-printed millifluidic devices with catalytically active copper carboxylate complexes were used to promote azide-alkyne cycloaddition under flow conditions. The importance of controlling the 3D architecture of the millifluidic devices was evidenced by enhancing reaction conversion upon increasing the complexity of the 3D prints.« less

Direct 3D Printing of Catalytically Active Structures

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

Manzano, J. Sebastian; Weinstein, Zachary B.; Sadow, Aaron D.

3D printing of materials with active functional groups can provide custom-designed structures that promote chemical conversions. Catalytically active architectures were produced by photopolymerizing bifunctional molecules using a commercial stereolithographic 3D printer. Functionalities in the monomers included a polymerizable vinyl group to assemble the 3D structures and a secondary group to provide them with active sites. The 3D-printed architectures containing accessible carboxylic acid, amine, and copper carboxylate functionalities were catalytically active for the Mannich, aldol, and Huisgen cycloaddition reactions, respectively. The functional groups in the 3D-printed structures were also amenable to post-printing chemical modification. And as proof of principle, chemically activemore » cuvette adaptors were 3D printed and used to measure in situ the kinetics of a heterogeneously catalyzed Mannich reaction in a conventional solution spectrophotometer. In addition, 3D-printed millifluidic devices with catalytically active copper carboxylate complexes were used to promote azide-alkyne cycloaddition under flow conditions. The importance of controlling the 3D architecture of the millifluidic devices was evidenced by enhancing reaction conversion upon increasing the complexity of the 3D prints.« less

Modeling microbiological and chemical processes in municipal solid waste bioreactor, Part II: Application of numerical model BIOKEMOD-3P.

PubMed

Gawande, Nitin A; Reinhart, Debra R; Yeh, Gour-Tsyh

2010-02-01

Biodegradation process modeling of municipal solid waste (MSW) bioreactor landfills requires the knowledge of various process reactions and corresponding kinetic parameters. Mechanistic models available to date are able to simulate biodegradation processes with the help of pre-defined species and reactions. Some of these models consider the effect of critical parameters such as moisture content, pH, and temperature. Biomass concentration is a vital parameter for any biomass growth model and often not compared with field and laboratory results. A more complex biodegradation model includes a large number of chemical and microbiological species. Increasing the number of species and user defined process reactions in the simulation requires a robust numerical tool. A generalized microbiological and chemical model, BIOKEMOD-3P, was developed to simulate biodegradation processes in three-phases (Gawande et al. 2009). This paper presents the application of this model to simulate laboratory-scale MSW bioreactors under anaerobic conditions. BIOKEMOD-3P was able to closely simulate the experimental data. The results from this study may help in application of this model to full-scale landfill operation.

A Pictet-Spengler ligation for protein chemical modification

PubMed Central

Agarwal, Paresh; van der Weijden, Joep; Sletten, Ellen M.; Rabuka, David; Bertozzi, Carolyn R.

2013-01-01

Aldehyde- and ketone-functionalized proteins are appealing substrates for the development of chemically modified biotherapeutics and protein-based materials. Their reactive carbonyl groups are typically conjugated with α-effect nucleophiles, such as substituted hydrazines and alkoxyamines, to generate hydrazones and oximes, respectively. However, the resulting C=N linkages are susceptible to hydrolysis under physiologically relevant conditions, which limits the utility of such conjugates in biological systems. Here we introduce a Pictet-Spengler ligation that is based on the classic Pictet-Spengler reaction of aldehydes and tryptamine nucleophiles. The ligation exploits the bioorthogonal reaction of aldehydes and alkoxyamines to form an intermediate oxyiminium ion; this intermediate undergoes intramolecular C–C bond formation with an indole nucleophile to form an oxacarboline product that is hydrolytically stable. We used the reaction for site-specific chemical modification of glyoxyl- and formylglycine-functionalized proteins, including an aldehyde-tagged variant of the therapeutic monoclonal antibody Herceptin. In conjunction with techniques for site-specific introduction of aldehydes into proteins, the Pictet-Spengler ligation offers a means to generate stable bioconjugates for medical and materials applications. PMID:23237853

Organic environments on Saturn's moon, Titan: simulating chemical reactions and analyzing products by FT-ICR and ion-trap mass spectrometry.

PubMed

Somogyi, Arpad; Oh, Chu-Ha; Smith, Mark A; Lunine, Jonathan I

2005-06-01

Laboratory simulations have been carried out to model chemical reactions that possibly take place in the stratosphere of Saturn's moon, Titan. The aerosol products of these reactions (tholin samples) have been systematically analyzed by mass spectrometry using electrospray ionization (ESI) and laser desorption (LD). A wide variety of ions with a general formula C(x)H(y)N(z) detected by ultrahigh resolution and accurate mass measurements in a Fourier transform/ion cyclotron resonance (FT-ICR) cell reflect the complexity of these polymeric products, both in chemical compositions and isomeric distributions. As a common feature, however, tandem mass spectral (MS/MS) data and H/D exchange products in the solution phase support the presence of amino and nitrile functionalities in these (highly unsaturated) "tholin" compounds. The present work demonstrates that ESI-MS coupled with FT-ICR is a suitable and "intact" method to analyze tholin components formed under anaerobic conditions; only species with C(x)H(y)N(z) are detected for freshly prepared and harvested samples. However, when intentionally exposed to water, oxygen-containing compounds are unambiguously detected.

Reaction Decoder Tool (RDT): extracting features from chemical reactions.

PubMed

Rahman, Syed Asad; Torrance, Gilliean; Baldacci, Lorenzo; Martínez Cuesta, Sergio; Fenninger, Franz; Gopal, Nimish; Choudhary, Saket; May, John W; Holliday, Gemma L; Steinbeck, Christoph; Thornton, Janet M

2016-07-01

Extracting chemical features like Atom-Atom Mapping (AAM), Bond Changes (BCs) and Reaction Centres from biochemical reactions helps us understand the chemical composition of enzymatic reactions. Reaction Decoder is a robust command line tool, which performs this task with high accuracy. It supports standard chemical input/output exchange formats i.e. RXN/SMILES, computes AAM, highlights BCs and creates images of the mapped reaction. This aids in the analysis of metabolic pathways and the ability to perform comparative studies of chemical reactions based on these features. This software is implemented in Java, supported on Windows, Linux and Mac OSX, and freely available at https://github.com/asad/ReactionDecoder : asad@ebi.ac.uk or s9asad@gmail.com. © The Author 2016. Published by Oxford University Press.

The mechanisms of hydrothermal deconstruction of lignocellulose: New insights from thermal–analytical and complementary studies

PubMed Central

Ibbett, Roger; Gaddipati, Sanyasi; Davies, Scott; Hill, Sandra; Tucker, Greg

2011-01-01

Differential Scanning Calorimetry, Dynamic Mechanical Thermal Analysis, gravimetric and chemical techniques have been used to study hydrothermal reactions of straw biomass. Exothermic degradation initiates above 195 °C, due to breakdown of the xylose ring from hemicellulose, which may be similar to reactions occurring during the early stage pyrolysis of dry biomass, though activated at lower temperature through water mediation. The temperature and magnitude of the exotherm reduce with increasing acid concentration, suggesting a reduction in activation energy and a change in the balance of reaction pathways. The presence of xylan oligomers in auto-catalytic hydrolysates is believed to be due to a low rate constant rather than a specific reaction mechanism. The loss of the lignin glass transition indicates that the lignin phase is reorganised under high temperature auto-catalytic conditions, but remains partially intact under lower temperature acid-catalytic conditions. This shows that lignin degradation reactions are activated thermally but are not effectively catalysed by aqueous acid. PMID:21763128

Rate kernel theory for pseudo-first-order kinetics of diffusion-influenced reactions and application to fluorescence quenching kinetics.

PubMed

Yang, Mino

2007-06-07

Theoretical foundation of rate kernel equation approaches for diffusion-influenced chemical reactions is presented and applied to explain the kinetics of fluorescence quenching reactions. A many-body master equation is constructed by introducing stochastic terms, which characterize the rates of chemical reactions, into the many-body Smoluchowski equation. A Langevin-type of memory equation for the density fields of reactants evolving under the influence of time-independent perturbation is derived. This equation should be useful in predicting the time evolution of reactant concentrations approaching the steady state attained by the perturbation as well as the steady-state concentrations. The dynamics of fluctuation occurring in equilibrium state can be predicted by the memory equation by turning the perturbation off and consequently may be useful in obtaining the linear response to a time-dependent perturbation. It is found that unimolecular decay processes including the time-independent perturbation can be incorporated into bimolecular reaction kinetics as a Laplace transform variable. As a result, a theory for bimolecular reactions along with the unimolecular process turned off is sufficient to predict overall reaction kinetics including the effects of unimolecular reactions and perturbation. As the present formulation is applied to steady-state kinetics of fluorescence quenching reactions, the exact relation between fluorophore concentrations and the intensity of excitation light is derived.

Some applications of equilibrium thermodynamic properties to continuum gasdynamics

NASA Technical Reports Server (NTRS)

1976-01-01

The speed of sound for the propagation of isentropic disturbances in a gas is developed, including corrections for chemical reaction. The term zero frequency is used to describe this isentropic limit sound speed; the term signifies that change in the gasdynamic variables are all very slow compared with the chemical rate changes in the gas. A faster, nonisentropic speed of propagation occurs for disturbances where the changes in gasdynamic variables are fast compared with the chemical rate changes. In the limit, this is known as the infinite frequency or frozen sound speed - the former term calling attention to the very high frequency of the disturbance, the latter term calling attention to the frozen character of the chemical reactions under such rapid changes of state. The true sound speed for a disturbance of finite frequency is shown to be between these two limits and is expressed in terms of the chemical relaxation time. The Riemann invariants that are useful in determining the changes in flow speed along characteristic directions in supersonic flow are derived in terms of integrations of acoustic impedance, and example results are given for air.

Atmosphere self-cleaning under humidity conditions and influence of the snowflakes and artificial light interaction for water dissociation simulated by the means of COMSOL

NASA Astrophysics Data System (ADS)

Cocean, A.; Cocean, I.; Cazacu, M. M.; Bulai, G.; Iacomi, F.; Gurlui, S.

2018-06-01

The self-cleaning of the atmosphere under humidity conditions is observed due to the change in emission intensity when chemical traces are investigated with DARLIOES - the advanced LIDAR based on space- and time-resolved RAMAN and breakdown spectroscopy in conditions of consistent humidity of atmosphere. The determination was performed during the night, in the wintertime under conditions of high humidity and snowfall, in urban area of Iasi. The change in chemical composition of the atmosphere detected was assumed to different chemical reactions involving presence of the water. Water dissociation that was registered during spectral measurements is explained by a simulation of the interaction between artificial light and snowflakes - virtually designed in a spherical geometry - in a wet air environment, using COMSOL Multiphysics software. The aim of the study is to explain the decrease or elimination of some of the toxic trace chemical compounds in the process of self-cleaning in other conditions than the sun light interaction for further finding application for air cleaning under artificial conditions.

Clustering mechanism of oxocarboxylic acids involving hydration reaction: Implications for the atmospheric models

NASA Astrophysics Data System (ADS)

Liu, Ling; Kupiainen-Määttä, Oona; Zhang, Haijie; Li, Hao; Zhong, Jie; Kurtén, Theo; Vehkamäki, Hanna; Zhang, Shaowen; Zhang, Yunhong; Ge, Maofa; Zhang, Xiuhui; Li, Zesheng

2018-06-01

The formation of atmospheric aerosol particles from condensable gases is a dominant source of particulate matter in the boundary layer, but the mechanism is still ambiguous. During the clustering process, precursors with different reactivities can induce various chemical reactions in addition to the formation of hydrogen bonds. However, the clustering mechanism involving chemical reactions is rarely considered in most of the nucleation process models. Oxocarboxylic acids are common compositions of secondary organic aerosol, but the role of oxocarboxylic acids in secondary organic aerosol formation is still not fully understood. In this paper, glyoxylic acid, the simplest and the most abundant atmospheric oxocarboxylic acid, has been selected as a representative example of oxocarboxylic acids in order to study the clustering mechanism involving hydration reactions using density functional theory combined with the Atmospheric Clusters Dynamic Code. The hydration reaction of glyoxylic acid can occur either in the gas phase or during the clustering process. Under atmospheric conditions, the total conversion ratio of glyoxylic acid to its hydration reaction product (2,2-dihydroxyacetic acid) in both gas phase and clusters can be up to 85%, and the product can further participate in the clustering process. The differences in cluster structures and properties induced by the hydration reaction lead to significant differences in cluster formation rates and pathways at relatively low temperatures.

Reduced Order Models for Reactions of Energetic Materials

NASA Astrophysics Data System (ADS)

Kober, Edward

The formulation of reduced order models for the reaction chemistry of energetic materials under high pressures is needed for the development of mesoscale models in the areas of initiation, deflagration and detonation. Phenomenologically, 4-8 step models have been formulated from the analysis of cook-off data by analyzing the temperature rise of heated samples. Reactive molecular dynamics simulations have been used to simulate many of these processes, but reducing the results of those simulations to simple models has not been achieved. Typically, these efforts have focused on identifying molecular species and detailing specific chemical reactions. An alternative approach is presented here that is based on identifying the coordination geometries of each atom in the simulation and tracking classes of reactions by correlated changes in these geometries. Here, every atom and type of reaction is documented for every time step; no information is lost from unsuccessful molecular identification. Principal Component Analysis methods can then be used to map out the effective chemical reaction steps. For HMX and TATB decompositions simulated with ReaxFF, 90% of the data can be explained by 4-6 steps, generating models similar to those from the cook-off analysis. By performing these simulations at a variety of temperatures and pressures, both the activation and reaction energies and volumes can then be extracted.

Plane wave density functional molecular dynamics study of exothermic reactions of Al/CuO thermites

NASA Astrophysics Data System (ADS)

Oloriegbe, Suleiman; Sewell, Thomas; Chen, Zhen; Jiang, Shan; Gan, Yong

2014-03-01

Exothermic reactions between nanosize aluminum (Al) and copper oxide (CuO) structures are of current interest because of their high reaction enthalpy and energy density which exceed those of traditional monomolecular energetic compounds such as TNT, RDX, and HMX. In this work, molecular dynamics simulations with forces obtained from plane wave density functional theory are used to investigate the atomic-scale and electronic processes that occur during the fast thermite reactions between Al and CuO nanostructures under adiabatic conditions. Aluminum surfaces in contact with O-exposed and Cu-exposed CuO surfaces are studied. Starting from initial temperature T = 800 K, we have observed: faster chemical reaction at the oxygen-rich interface during the initial 0.5 ps, linear temperature rise, and fast oxygen diffusion into the Al region with the rate 1.87 X 10-3 cm2/s. The density-derived electrostatic and chemical method is used to evaluate the net atomic charges and charge transfer during the important redox processes. High charge density around the oxygen-exposed interface may be responsible for the faster initial reactions at that interface. The overall reaction rate, determined using the time evolution of Cu-O charge orbital overlap population, is approximately first order.

Amine-functionalized Zn(ii) MOF as an efficient multifunctional catalyst for CO2 utilization and sulfoxidation reaction.

PubMed

Patel, Parth; Parmar, Bhavesh; Kureshy, Rukhsana I; Khan, Noor-Ul H; Suresh, Eringathodi

2018-06-19

Herein, a zinc(ii)-based 3D mixed ligand metal organic framework (MOF) was synthesized via versatile routes including green mechanochemical synthesis. The MOF {[Zn(ATA)(L)·H2O]}n (ZnMOF-1-NH2) has been characterized by various physico-chemical techniques, including SCXRD, and composed of the bipyridyl-based Schiff base (E)-N'-(pyridin-4-ylmethylene)isonicotinohydrazide (L) and 2-aminoterephthalic acid (H2ATA) ligands as linkers. The MOF material has been explored as a multifunctional heterogeneous catalyst for the cycloaddition of alkyl and aryl epoxides with CO2 and sulfoxidation reactions of aryl sulfides. The influence of various reaction parameters is examined to optimize the performance of the catalytic reactions. It is found that solvent-free catalytic reaction conditions offer good catalytic conversion in the case of cyclic carbonates, and for sulfoxide, good conversion and selectivity are achieved in the presence of DCM as a solvent medium under ambient reaction conditions. The chemical and thermal stability of the catalyst are excellent and it is active for up to four catalytic cycles without significant loss in activity. Furthermore, based on the catalytic activity and structural evidence, a plausible mechanism for both catalytic reactions is proposed.

Meso-scale investigation of anaerobic chemical reactivity of Ti-Al-B powder mixtures under impact loading

NASA Astrophysics Data System (ADS)

Gonzales, Manny; Gurumurthy, Ashok; Gokhale, Arun; Thadhani, Naresh N.

2011-06-01

Impact-initiated anaerobic chemical reactions in Ti-Al-B reactive powder mixtures under uniaxial stress conditions are investigated using a coupled experimental/computational approach. In particular, we characterize the effects of bulk composition on the threshold impact energy to initiate reaction using rod-on-anvil type tests performed on Ti-Al-B powder compacts. Statistical volume elements (SVEs) of different bulk compositions of the powder mixtures are analyzed using the continuum hydrocode CTH to quantify the effects of strain confinement and load configuration on the overall energy of the structure. These SVEs are also validated using one-point correlation functions to characterize the volume fraction and surface area of the constituents. Based on the deformation profiles from the continuum simulations, we investigate the effect of particle size distribution and clustering of Ti and B on the threshold energy required for observed reactivity. The deformation and threshold kinetic energy of the simulated system is compared with published values of the activation energy for Ti+B reactions and Al combustion in air to assess the extent of their impact-initiated reactivity. Funded by DTRA grant No. HDTRA1-10-1-0038

Diffusion approximations to the chemical master equation only have a consistent stochastic thermodynamics at chemical equilibrium

NASA Astrophysics Data System (ADS)

Horowitz, Jordan M.

2015-07-01

The stochastic thermodynamics of a dilute, well-stirred mixture of chemically reacting species is built on the stochastic trajectories of reaction events obtained from the chemical master equation. However, when the molecular populations are large, the discrete chemical master equation can be approximated with a continuous diffusion process, like the chemical Langevin equation or low noise approximation. In this paper, we investigate to what extent these diffusion approximations inherit the stochastic thermodynamics of the chemical master equation. We find that a stochastic-thermodynamic description is only valid at a detailed-balanced, equilibrium steady state. Away from equilibrium, where there is no consistent stochastic thermodynamics, we show that one can still use the diffusive solutions to approximate the underlying thermodynamics of the chemical master equation.

Diffusion approximations to the chemical master equation only have a consistent stochastic thermodynamics at chemical equilibrium.

PubMed

Horowitz, Jordan M

2015-07-28

The stochastic thermodynamics of a dilute, well-stirred mixture of chemically reacting species is built on the stochastic trajectories of reaction events obtained from the chemical master equation. However, when the molecular populations are large, the discrete chemical master equation can be approximated with a continuous diffusion process, like the chemical Langevin equation or low noise approximation. In this paper, we investigate to what extent these diffusion approximations inherit the stochastic thermodynamics of the chemical master equation. We find that a stochastic-thermodynamic description is only valid at a detailed-balanced, equilibrium steady state. Away from equilibrium, where there is no consistent stochastic thermodynamics, we show that one can still use the diffusive solutions to approximate the underlying thermodynamics of the chemical master equation.

A transformation theory of stochastic evolution in Red Moon methodology to time evolution of chemical reaction process in the full atomistic system.

PubMed

Suzuki, Yuichi; Nagaoka, Masataka

2017-05-28

Atomistic information of a whole chemical reaction system, e.g., instantaneous microscopic molecular structures and orientations, offers important and deeper insight into clearly understanding unknown chemical phenomena. In accordance with the progress of a number of simultaneous chemical reactions, the Red Moon method (a hybrid Monte Carlo/molecular dynamics reaction method) is capable of simulating atomistically the chemical reaction process from an initial state to the final one of complex chemical reaction systems. In the present study, we have proposed a transformation theory to interpret the chemical reaction process of the Red Moon methodology as the time evolution process in harmony with the chemical kinetics. For the demonstration of the theory, we have chosen the gas reaction system in which the reversible second-order reaction H 2 + I 2  ⇌ 2HI occurs. First, the chemical reaction process was simulated from the initial configurational arrangement containing a number of H 2 and I 2 molecules, each at 300 K, 500 K, and 700 K. To reproduce the chemical equilibrium for the system, the collision frequencies for the reactions were taken into consideration in the theoretical treatment. As a result, the calculated equilibrium concentrations [H 2 ] eq and equilibrium constants K eq at all the temperatures were in good agreement with their corresponding experimental values. Further, we applied the theoretical treatment for the time transformation to the system and have shown that the calculated half-life τ's of [H 2 ] reproduce very well the analytical ones at all the temperatures. It is, therefore, concluded that the application of the present theoretical treatment with the Red Moon method makes it possible to analyze reasonably the time evolution of complex chemical reaction systems to chemical equilibrium at the atomistic level.

Effect of electric signal frequency and form on physical-chemical oxidation of organic wastes

NASA Astrophysics Data System (ADS)

Morozov, Yegor; Tikhomirov, Alexander A.; Trifonov, Sergey V.; Kudenko, D.. Yurii A.

The behavior conditions of physical-chemical reactions securing organic wastes’ oxidation in H _{2}O _{2} aqueous medium aimed at an increase of mass exchange processes in a life support system (LSS) for a space purpose have been under study. The character of dependence of organic wastes oxidation rate in H _{2}O _{2} aqueous medium, activated with alternating current of different frequency and form have been considered. Ways of those parameters optimization for the purpose to efficiently increase the physical-chemical decomposition of organic wastes in LSS have been proposed. Specifically, power consumption and reaction time of wastes mineralization have been determined to reduce more than twice. Involvement ways of mineralized organic wastes received in intrasystem mass exchange have been shown. Application feasibility of the obtained results both for space and terrestrial purpose has been discussed. Key words: life support sustem, mineralization, turnover, frequency, organic wastes

A multi target approach to control chemical reactions in their inhomogeneous solvent environment

NASA Astrophysics Data System (ADS)

Keefer, Daniel; Thallmair, Sebastian; Zauleck, Julius P. P.; de Vivie-Riedle, Regina

2015-12-01

Shaped laser pulses offer a powerful tool to manipulate molecular quantum systems. Their application to chemical reactions in solution is a promising concept to redesign chemical synthesis. Along this road, theoretical developments to include the solvent surrounding are necessary. An appropriate theoretical treatment is helpful to understand the underlying mechanisms. In our approach we simulate the solvent by randomly selected snapshots from molecular dynamics trajectories. We use multi target optimal control theory to optimize pulses for the various arrangements of explicit solvent molecules simultaneously. This constitutes a major challenge for the control algorithm, as the solvent configurations introduce a large inhomogeneity to the potential surfaces. We investigate how the algorithm handles the new challenges and how well the controllability of the system is preserved with increasing complexity. Additionally, we introduce a way to statistically estimate the efficiency of the optimized laser pulses in the complete thermodynamical ensemble.

Influence of heating procedures on the surface structure of stabilized polyacrylonitrile fibers

NASA Astrophysics Data System (ADS)

Zhao, Rui-Xue; Sun, Peng-fei; Liu, Rui-jian; Ding, Zhan-hui; Li, Xiang-shan; Liu, Xiao-yang; Zhao, Xu-dong; Gao, Zhong-min

2018-03-01

The stabilized polyacrylonitrile (PAN) fibers were obtained after heating the precursor PAN fibers under air atmosphere by different procedures. The surface structures and compositions of as-prepared stabilized PAN fibers have been investigated by SEM, SSNMR, XPS and Raman spectroscopy. The results show that 200 °C, 220 °C, 250 °C, and 280 °C are key temperatures for the preparation of stabilized PAN fibers. The effect of heating gradient on the structure of stabilized PAN fibers has been studied. The possible chemical structural formulas for the PAN fibers is provided, which include the stable and unstable structure. The stable structure (α-type) could endure the strong chemical reactions and the unstable structure (β- or γ-type) could mitigate the drastic oxidation reactions. The inferences of chemical formula of stabilized PAN fibers are benefit to the design of appropriate surface structure for the production for high quality carbon fibers.

ENVIRONMENTALLY FRIENDLIER ALTERNATIVES TO ORGANIC SYNTHESIS USING MICROWAVES

EPA Science Inventory

Microwave irradiation has been used for a variety of organic transformations wherein chemical reactions are expedited because of selective adsorption of microwave (MW) energy by polar molecules, non-polar molecules being inert to the MW dielectric loss. The MW application under s...

GREENER APPROACH TO EFFICIENT ORGANIC SYNTHESES USING MICROWAVES

EPA Science Inventory

Microwave irradiation has been used for a variety of organic transformations wherein chemical reactions are expedited because of selective adsorption of microwave (MW) energy by polar molecules, non-polar molecules being inert to the MW dielectric loss. The MW application under s...

Tribological properties of limonene bisphosphonates

USDA-ARS?s Scientific Manuscript database

Limonene was chemically modified by reacting it with dialkyl phosphites of varying alkyl structures under inert atmosphere in the presence of free radical initiators. The reaction gave a mixture of mono- and di-adduct products, and was optimized to produce only the diadduct product limonene bisphosp...

21 CFR 178.3790 - Polymer modifiers in semirigid and rigid vinyl chloride plastics.

Code of Federal Regulations, 2011 CFR

2011-04-01

... chemical reactions, other than addition reactions, occur when they are mixed. (2) Polymers identified in...; provided that no chemical reactions, other than addition reactions, occur when they are combined. Such... weight-percent of polymer units derived from butadiene-styrene copolymers. (c) No chemical reactions...

21 CFR 178.3790 - Polymer modifiers in semirigid and rigid vinyl chloride plastics.

Code of Federal Regulations, 2010 CFR

2010-04-01

... chemical reactions, other than addition reactions, occur when they are mixed. (2) Polymers identified in...; provided that no chemical reactions, other than addition reactions, occur when they are combined. Such... weight-percent of polymer units derived from butadiene-styrene copolymers. (c) No chemical reactions...

Food Protein-polysaccharide Conjugates Obtained via the Maillard Reaction: A Review.

PubMed

de Oliveira, Fabíola Cristina; Coimbra, Jane Sélia Dos Reis; de Oliveira, Eduardo Basílio; Zuñiga, Abraham Damian Giraldo; Rojas, Edwin E Garcia

2016-05-18

The products formed by glycosylation of food proteins with carbohydrates via the Maillard reaction, also known as conjugates, are agents capable of changing and improving techno-functional characteristics of proteins. The Maillard reaction uses the covalent bond between a group of a reducing carbohydrates and an amino group of a protein. This reaction does not require additional chemicals as it occurs naturally under controlled conditions of temperature, time, pH, and moisture. Moreover, there is growing interest in modifying proteins for industrial food applications. This review analyses the current state of art of the Maillard reaction on food protein functionalities. It also discusses the influence of the Maillard reaction on the conditions and formulation of reagents that improve desirable techno-functional characteristics of food protein.

Thin layer chromatography coupled with surface-enhanced Raman scattering as a facile method for on-site quantitative monitoring of chemical reactions.

PubMed

Zhang, Zong-Mian; Liu, Jing-Fu; Liu, Rui; Sun, Jie-Fang; Wei, Guo-Hua

2014-08-05

By coupling surface-enhanced Raman spectroscopy (SERS) with thin layer chromatography (TLC), a facile and powerful method was developed for on-site monitoring the process of chemical reactions. Samples were preseparated on a TLC plate following a common TLC procedure, and then determined by SERS after fabricating a large-area, uniform SERS substrate on the TLC plate by spraying gold nanoparticles (AuNPs). Reproducible and strong SERS signals were obtained with substrates prepared by spraying 42-nm AuNPs at a density of 5.54 × 10(10) N/cm(2) on the TLC plate. The capacity of this TLC-SERS method was evaluated by monitoring a typical Suzuki coupling reaction of phenylboronic acid and 2-bromopyridine as a model. Results showed that this proposed method is able to identify reaction product that is invisible to the naked eye, and distinguish the reactant 2-bromopyridine and product 2-phenylpyridine, which showed almost the same retention factors (R(f)). Under the optimized conditions, the peak area of the characteristic Raman band (755 cm(-1)) of the product 2-phenylpyridine showed a good linear correlation with concentration in the range of 2-200 mg/L (R(2) = 0.9741), the estimated detection limit (1 mg/L 2-phenylpyridine) is much lower than the concentration of the chemicals in the common organic synthesis reaction system, and the product yield determined by the proposed TLC-SERS method agreed very well with that by UPLC-MS/MS. In addition, a new byproduct in the reaction system was found and identified through continuous Raman detection from the point of sample to the solvent front. This facile TLC-SERS method is quick, easy to handle, low-cost, sensitive, and can be exploited in on-site monitoring the processes of chemical reactions, as well as environmental and biological processes.

The Role of Grain Surface Reactions in the Chemistry of Star Forming Regions

NASA Technical Reports Server (NTRS)

Kress, M. E.; Tielens, A. G. G. M.; Roberge, W. G.

1998-01-01

The importance of reactions at the surfaces of dust grains has long been recognized to be one of the two main chemical processes that form molecules in cold, dark interstellar clouds where simple, saturated (fully-hydrogenated) molecules such as H2 water, methanol, H2CO, H2S, ammonia and CH4 are present in quantities far too high to be consistent with their extremely low gas phase formation rates. In cold dark regions of interstellar space, dust grains provide a substrate onto which gas-phase species can accrete and react. Grains provide a "third body" or a sink for the energy released in the exothermic reactions that form chemical bonds. In essence, the surfaces of dust grains open up alternative reaction pathways to form observed molecules whose abundances cannot be explained with gas-phase chemistry alone. This concept is taken one step further in this work: instead of merely acting as a substrate onto which radicals and molecules may physically adsorb, some grains may actively participate in the reaction itself, forming chemical bonds with the accreting species. Until recently, surface chemical reactions had not been thought to be important in warm circumstellar media because adspecies rapidly desorb from grains at very low temperatures; thus, the residence times of molecules and radicals on the surface of grains at all but the lowest temperatures are far too short to allow these reactions to occur. However, if the adspecies could adsorb more strongly, via a true chemical bond with surfaces of some dust grains, then grain surface reactions will play an important role in warm circumstellar regions as well. In this work, the surface-catalyzed reaction CO + 3 H2 yields CH4 + H2O is studied in the context that it may be very effective at converting the inorganic molecule CO into the simplest organic compound, methane. H2 and CO are the most abundant molecules in space, and the reaction converting them to methane, while kinetically inhibited in the gas phase under most astrophysical conditions, is catalyzed by iron, an abundant constituent of interstellar dust. At temperatures between 600 and 1000 K, which occur in the outflows from red giants and near luminous young stars, this reaction readily proceeds in the presence of an iron catalyst. Iron is one of the more abundant elements composing interstellar dust. Its abundance relative to hydrogen is almost that of silicon, and both of these heavy elements are primarily locked up in dust at all but the hottest regions of interstellar space.

Water Formation under Silica Thin Films: Real-Time Observation of a Chemical Reaction in a Physically Confined Space.

PubMed

Prieto, Mauricio J; Klemm, Hagen W; Xiong, Feng; Gottlob, Daniel M; Menzel, Dietrich; Schmidt, Thomas; Freund, Hans-Joachim

2018-04-16

Using low-energy electron microscopy and local photoelectron spectroscopy, water formation from adsorbed O and H 2 on a Ru(0001) surface covered with a vitreous SiO 2 bilayer (BL) was investigated and compared to the same reaction on bare Ru(0001). In both cases the reaction is characterized by moving reaction fronts. The reason for this might be related to the requirement of site release by O adatoms for further H 2 -dissociative adsorption. Apparent activation energies (Eaapp ) are found for the front motion of 0.59 eV without cover and 0.27 eV under cover. We suggest that the smaller activation energy but higher reaction temperature for the reaction on the SiO 2 BL covered Ru(0001) surface is due to a change of the rate-determining step. Other possible effects of the cover are discussed. Our results give the first values for Eaapp in confined space. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

The synthesis of highly functionalised pyridines using Ghosez-type reactions of dihydropyrazoles.

PubMed

Catti, Federica; Kiuru, Paula S; Slawin, Alexandra M Z; Westwood, Nicholas J

2008-09-29

The aza-Diels-Alder reaction of αβ-unsaturated hydrazones is a general methodology that has been applied both to the synthesis of natural products and in the development of multicomponent reactions. Trends have emerged as to the effect of substituents on the efficiency of this reaction with substituents at the C2 and C4-positions of the aza-diene in general suppressing the reaction. Here we report that 4,5-dihydropyrazoles can function as substrates in this process despite the presence of substituents at both of these positions. A one pot, four chemical step sequence carried out under standard thermal or microwave conditions results in the formation of the corresponding pyridine-containing compounds. The scope of the reaction is explored and additional insights into the proposed mechanism of this reaction are provided.

[Methods Used for Monitoring Cure Reactions in Real-time in an Autoclave

NASA Technical Reports Server (NTRS)

Cooper, John B.; Wise, Kent L.; Jensen, Brian J. (Technical Monitor)

2000-01-01

The goal of the research was to investigate methods for monitoring cure reactions in real-time in an autoclave. This is of particular importance to NASA Langley Research Center because polyimides were proposed for use in the High Speed Civil Transport (HSCT) program. Understanding the cure chemistry behind the polyimides would allow for intelligent processing of the composites made from their use. This work has led to two publications in peer-reviewed journals and a patent. The journal articles are listed as Appendix A which is on the instrument design of the research and Appendix B which is on the cure chemistry. Also, a patent has been awarded for the instrumental design developed under this grant which is given as Appendix C. There has been a significant amount of research directed at developing methods for monitoring cure reactions in real-time within the autoclave. The various research efforts can be categorized as methods providing either direct chemical bonding information or methods that provide indirect chemical bonding information. Methods falling into the latter category are fluorescence, dielectric loss, ultrasonic and similar type methods. Correlation of such measurements with the underlying chemistry is often quite difficult since these techniques do not allow monitoring of the curing chemistry which is ultimately responsible for material properties. Direct methods such as vibrational spectroscopy, however, can often be easily correlated with the underlying chemistry of a reaction. Such methods include Raman spectroscopy, mid-IR absorbance, and near-IR absorbance. With the recent advances in fiber-optics, these spectroscopic techniques can be applied to remote on-line monitoring.

Degradation of DEET and Caffeine under UV/Chlorine and Simulated Sunlight/Chlorine Conditions.

PubMed

Sun, Peizhe; Lee, Wan-Ning; Zhang, Ruochun; Huang, Ching-Hua

2016-12-20

Photoactivation of aqueous chlorine could promote degradation of chlorine-resistant and photochemically stable chemicals accumulated in swimming pools. This study investigated the degradation of two such chemicals, N,N-diethyl-3-methylbenzamide (DEET) and caffeine, by low pressure ultraviolet (UV) light and simulated sunlight (SS) activated free chlorine (FC) in different water matrices. Both DEET and caffeine were rapidly degraded by UV/FC and SS/FC but exhibited different kinetic behaviors. The degradation of DEET followed pseudo-first-order kinetics, whereas the degradation of caffeine accelerated with reaction. Mechanistic study revealed that, under UV/FC, ·OH and Cl· were responsible for degradation of DEET, whereas ClO· related reactive species (ClOrrs), generated by the reaction between FC and ·OH/Cl·, played a major role in addition to ·OH and Cl· in degrading caffeine. Reaction rate constants of DEET and caffeine with the respective radical species were estimated. The imidazole moiety of caffeine was critical for the special reactivity with ClOrrs. Water matrix such as pH had a stronger impact on the UV/FC process than the SS/FC process. In saltwater matrix under UV/FC and SS/FC, the degradation of DEET was significantly inhibited, but the degradation of caffeine was much faster than that in nonsalty solutions. The interaction between Br - and Cl - may play an important role in the degradation of caffeine by UV/FC in saltwater. Reaction product analysis showed similar product patterns by UV/FC and SS/FC and minimal formation of chlorinated intermediates and disinfection byproducts.

Mathematical modeling of chemical composition modification and etching of polymers under the atomic oxygen influence

NASA Astrophysics Data System (ADS)

Chirskaia, Natalia; Novikov, Lev; Voronina, Ekaterina

2016-07-01

Atomic oxygen (AO) of the upper atmosphere is one of the most important space factors that can cause degradation of spacecraft surface. In our previous mathematical model the Monte Carlo method and the "large particles" approximation were used for simulating processes of polymer etching under the influence of AO [1]. The interaction of enlarged AO particles with the polymer was described in terms of probabilities of reactions such as etching of polymer and specular and diffuse scattering of the AO particles on polymer. The effects of atomic oxygen on protected polymers and microfiller containing composites were simulated. The simulation results were in quite good agreement with the results of laboratory experiments on magnetoplasmadynamic accelerator of the oxygen plasma of SINP MSU [2]. In this paper we present a new model that describes the reactions of AO interactions with polymeric materials in more detail. Reactions of formation and further emission of chemical compounds such as CO, CO _{2}, H _{2}O, etc. cause the modification of the chemical composition of the polymer and change the probabilities of its consequent interaction with the AO. The simulation results are compared with the results of previous simulation and with the results of laboratory experiments. The reasons for the differences between the results of natural experiments on spacecraft, laboratory experiments and simulations are discussed. N. Chirskaya, M. Samokhina, Computer modeling of polymer structures degradation under the atomic oxygen exposure, WDS'12 Proceedings of Contributed Papers: Part III - Physics, Matfyzpress Prague, 2012, pp. 30-35. E. Voronina, L. Novikov, V. Chernik, N. Chirskaya, K. Vernigorov, G. Bondarenko, and A. Gaidar, Mathematical and experimental simulation of impact of atomic oxygen of the earth's upper atmosphere on nanostructures and polymer composites, Inorganic Materials: Applied Research, 2012, vol. 3, no. 2, pp. 95-101.

Combined Photoemission Spectroscopy and Electrochemical Study of a Mixture of (Oxy)carbides as Potential Innovative Supports and Electrocatalysts.

PubMed

Calvillo, Laura; Valero-Vidal, Carlos; Agnoli, Stefano; Sezen, Hikmet; Rüdiger, Celine; Kunze-Liebhäuser, Julia; Granozzi, Gaetano

2016-08-03

Active and stable non-noble metal materials, able to substitute Pt as catalyst or to reduce the Pt amount, are vitally important for the extended commercialization of energy conversion technologies, such as fuel cells and electrolyzers. Here, we report a fundamental study of nonstoichiometric tungsten carbide (WxC) and its interaction with titanium oxycarbide (TiOxCy) under electrochemical working conditions. In particular, the electrochemical activity and stability of the WxC/TiOxCy system toward the ethanol electrooxidation reaction (EOR) and hydrogen evolution reaction (HER) are investigated. The chemical changes caused by the applied potential are established by combining photoemission spectroscopy and electrochemistry. WxC is not active toward the ethanol electrooxidation reaction at room temperature but it is highly stable under these conditions thanks to the formation of a passive thin film on the surface, consisting mainly of WO2 and W2O5, which prevents the full oxidation of WxC. In addition, WxC is able to adsorb ethanol, forming ethoxy groups on the surface, which constitutes the first step for the ethanol oxidation. The interaction between WxC and TiOxCy plays an important role in the electrochemical stability of WxC since specific orientations of the substrate are able to stabilize WxC and prevent its corrosion. The beneficial interaction with the substrate and the specific surface chemistry makes tungsten carbide a good electrocatalyst support or cocatalyst for direct ethanol fuel cells. However, WxC is active toward the HER and chemically stable under hydrogen reduction conditions, since no changes in the chemical composition or dissolution of the film are observed. This makes tungsten carbide a good candidate as electrocatalyst support or cocatalyst for the electrochemical production of hydrogen.

Uptake of gaseous formaldehyde by soil surfaces: a combination of adsorption/desorption equilibrium and chemical reactions

NASA Astrophysics Data System (ADS)

Li, Guo; Su, Hang; Li, Xin; Kuhn, Uwe; Meusel, Hannah; Hoffmann, Thorsten; Ammann, Markus; Pöschl, Ulrich; Shao, Min; Cheng, Yafang

2016-08-01

Gaseous formaldehyde (HCHO) is an important precursor of OH radicals and a key intermediate molecule in the oxidation of atmospheric volatile organic compounds (VOCs). Budget analyses reveal large discrepancies between modeled and observed HCHO concentrations in the atmosphere. Here, we investigate the interactions of gaseous HCHO with soil surfaces through coated-wall flow tube experiments applying atmospherically relevant HCHO concentrations of ˜ 10 to 40 ppbv. For the determination of uptake coefficients (γ), we provide a Matlab code to account for the diffusion correction under laminar flow conditions. Under dry conditions (relative humidity = 0 %), an initial γ of (1.1 ± 0.05) × 10-4 is determined, which gradually drops to (5.5 ± 0.4) × 10-5 after 8 h experiments. Experiments under wet conditions show a smaller γ that drops faster over time until reaching a plateau. The drop of γ with increasing relative humidity as well as the drop over time can be explained by the adsorption theory in which high surface coverage leads to a reduced uptake rate. The fact that γ stabilizes at a non-zero plateau suggests the involvement of irreversible chemical reactions. Further back-flushing experiments show that two-thirds of the adsorbed HCHO can be re-emitted into the gas phase while the residual is retained by the soil. This partial reversibility confirms that HCHO uptake by soil is a complex process involving both adsorption/desorption and chemical reactions which must be considered in trace gas exchange (emission or deposition) at the atmosphere-soil interface. Our results suggest that soil and soil-derived airborne particles can either act as a source or a sink for HCHO, depending on ambient conditions and HCHO concentrations.

Study on Al2O3 extraction from activated coal gangue under different calcination atmospheres

NASA Astrophysics Data System (ADS)

Dong, Ling; Liang, Xinxing; Song, Qiang; Gao, Gewu; Song, Lihua; Shu, Yuanfeng; Shu, Xinqian

2017-12-01

Coal gangue was calcinated under air, nitrogen, carbon dioxide, air-hydrogen, and hydrogen atmospheres. The effects of different calcination temperatures and atmospheres on the mineral composition of activated coal gangue were investigated by X-ray diffraction. Moreover, the acid leaching kinetics of aluminum oxide from coal gangue was investigated with sulfuric acid. It showed that the air atmosphere promoted kaolinite decomposition during coal gangue calcination. The hydrogen atmosphere promoted the activation and decomposition of kaolinite at reaction temperatures exceeding 650°C. The carbon dioxide atmosphere eliminated the influence of residual carbon on coal gangue. When the ratio of acid/coal gangue was 1.5 and reaction temperature was 650°C, the sulfuric acid leaching rate under air, air-hydrogen, carbon dioxide, hydrogen and nitrogen atmospheres were 93.66%, 90.90%, 84.06%, 81.91% and 77.54% respectively. The acid leaching reaction process conformed to unreacted shrinking core model of particle unchanged, and was controlled by the interfacial chemical reaction. The reaction kinetic equation for the leaching process was 1-(1-x)1/3=kt with an apparent activation energy of 48.97 kJ/mol.

40 CFR 710.3 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... of a chemical reaction or occurring in nature, and any chemical element or uncombined radical; except... distribution in commerce, when used to describe an action taken with respect to a chemical substance or mixture... or in part in chemical reaction(s) used for the intentional manufacture of other chemical substance(s...

Smart, Sustainable, and Ecofriendly Chemical Design of Fully Bio-Based Thermally Stable Thermosets Based on Benzoxazine Chemistry.

PubMed

Froimowicz, Pablo; R Arza, Carlos; Han, Lu; Ishida, Hatsuo

2016-08-09

A smart synthetic chemical design incorporating furfurylamine, a natural renewable amine, into a partially bio-based coumarin-containing benzoxazine is presented. The versatility of the synthetic approach is shown to be flexible and robust enough to be successful under more ecofriendly reaction conditions by replacing toluene with ethanol as the reaction solvent and even under solventless conditions. The chemical structure of this coumarin-furfurylamine-containing benzoxazine is characterized by FTIR, (1) H NMR spectroscopy and two-dimensional (1) H-(1) H nuclear Overhauser effect spectroscopy (2D (1) H-(1) H NOESY). The thermal properties of the resin toward polymerization are characterized by differential scanning calorimetry (DSC) and the thermal stability of the resulting polymers by thermogravimetric analysis (TGA). The results reveal that the furanic moiety induces a co-operative activating effect, thus lowering the polymerization temperature and also contributes to a better thermal stability of the resulting polymers. These results, in addition to those of natural renewable benzoxazine resins reviewed herein, highlight the positive and beneficial implication of designing novel bio-based polybenzoxazine and possibly other thermosets with desirable and competitive properties. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extraterrestrial Radiation Chemistry and Molecular Astronomy

NASA Technical Reports Server (NTRS)

Hudson, Reggie L.; Moore, Marla H.

2009-01-01

Astronomical observations of both solar system and interstellar regions have revealed a rich chemical inventory that includes most classes of organic molecules and selected inorganics. For example, gas-phase ethylene glycol and SOz have been observed by astronomers, while solidphase detections include OCS, H2O2 , and the cyanate anion.' All of these are found in environments that are, by earthly standards, exceedingly hostile: temperatures of 10 - 100 K, miniscule densities, and near-ubiquitous ionizing-radiation fields. Beyond the simplest chemical species, these conditions have made it difficult-to-impassible to account for the observed molecular abundances using gas-phase chemistry, suggesting solid-phase reactions play an important role. In extraterrestrial environments, cosmic rays, UV photons, and magnetospheric radiation all drive chemical reactions, even at cryogenic temperatures. To study this chemistry, radiation astrochemists conduct experiments on icy materials, frozen under vacuum and exposed to sources such as keV electrons and MeV protons. Compositional changes usually are followed with IR spectroscopy and, in selected cases, more-sensitive mass-spectral techniques. This talk will review some recent results on known and suspected extraterrestrial molecules and ions. Spectra and reaction pathways will be presented, and predictions made for interstellar chemistry and the chemistry of selected solar system objects. Some past radiation-chemical contributions, and future needs, will be explored.

Enzyme-free and isothermal detection of microRNA based on click-chemical ligation-assisted hybridization coupled with hybridization chain reaction signal amplification.

PubMed

Oishi, Motoi

2015-05-01

An enzyme-free and isothermal microRNA (miRNA) detection method has been developed based on click-chemical ligation-assisted hybridization coupled with hybridization chain reaction (HCR) on magnetic beads (MBs). The click-chemical ligation between an azide-modified probe DNA and a dibenzocyclooctyne-modified probe DNA occurred through the hybridization of target miRNA (miR-141). HCR on MBs was performed by the addition of DNA hairpin monomers (H1 and H2). After magnetic separation and denaturation/rehybridization of HCR products ([H1/H2] n ), the resulting HCR products were analyzed by the fluorescence emitted from an intercalative dye, allowing amplification of the fluorescent signal. The proposed assay had a limit of detection of 0.55 fmol, which was 230-fold more sensitive than that of the HCR on the MBs coupled with a conventional sandwich hybridization assay (without click-chemical ligation) (limit of detection 127 fmol). Additionally, the proposed assay could discriminate between miR-141 and other miR-200 family members. In contrast to quantitative reverse transcription polymerase chain reaction techniques using enzymes and thermal cycling, this is an enzyme-free assay that can be conducted under isothermal conditions and can specifically detect miR-141 in fetal bovine serum.

Thermal Decomposition of the Solid Phase of Nitromethane: Ab Initio Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Chang, Jing; Lian, Peng; Wei, Dong-Qing; Chen, Xiang-Rong; Zhang, Qing-Ming; Gong, Zi-Zheng

2010-10-01

The Car-Parrinello molecular dynamics simulations were employed to investigate thermal decomposition of the solid nitromethane. It is found that it undergoes chemical decomposition at about 2200 K under ambient pressure. The initiation of reactions involves both proton transfer and commonly known C-N bond cleavage. About 75 species and 100 elementary reactions were observed with the final products being H2O, CO2, N2, and CNCNC. It represents the first complete simulation of solid-phase explosive reactions reported to date, which is of far-reaching implication for design and development of new energetic materials.

Continuous-flow processes for the catalytic partial hydrogenation reaction of alkynes

PubMed Central

Moreno-Marrodan, Carmen; Liguori, Francesca

2017-01-01

The catalytic partial hydrogenation of substituted alkynes to alkenes is a process of high importance in the manufacture of several market chemicals. The present paper shortly reviews the heterogeneous catalytic systems engineered for this reaction under continuous flow and in the liquid phase. The main contributions appeared in the literature from 1997 up to August 2016 are discussed in terms of reactor design. A comparison with batch and industrial processes is provided whenever possible. PMID:28503209

A solid-state nuclear magnetic resonance study of post-plasma reactions in organosilicone microwave plasma-enhanced chemical vapor deposition (PECVD) coatings.

PubMed

Hall, Colin J; Ponnusamy, Thirunavukkarasu; Murphy, Peter J; Lindberg, Mats; Antzutkin, Oleg N; Griesser, Hans J

2014-06-11

Plasma-polymerized organosilicone coatings can be used to impart abrasion resistance and barrier properties to plastic substrates such as polycarbonate. Coating rates suitable for industrial-scale deposition, up to 100 nm/s, can be achieved through the use of microwave plasma-enhanced chemical vapor deposition (PECVD), with optimal process vapors such as tetramethyldisiloxane (TMDSO) and oxygen. However, it has been found that under certain deposition conditions, such coatings are subject to post-plasma changes; crazing or cracking can occur anytime from days to months after deposition. To understand the cause of the crazing and its dependence on processing plasma parameters, the effects of post-plasma reactions on the chemical bonding structure of coatings deposited with varying TMDSO-to-O2 ratios was studied with (29)Si and (13)C solid-state magic angle spinning nuclear magnetic resonance (MAS NMR) using both single-pulse and cross-polarization techniques. The coatings showed complex chemical compositions significantly altered from the parent monomer. (29)Si MAS NMR spectra revealed four main groups of resonance lines, which correspond to four siloxane moieties (i.e., mono (M), di (D), tri (T), and quaternary (Q)) and how they are bound to oxygen. Quantitative measurements showed that the ratio of TMDSO to oxygen could shift the chemical structure of the coating from 39% to 55% in Q-type bonds and from 28% to 16% for D-type bonds. Post-plasma reactions were found to produce changes in relative intensities of (29)Si resonance lines. The NMR data were complemented by Fourier transform infrared (FTIR) spectroscopy. Together, these techniques have shown that the bonding environment of Si is drastically altered by varying the TMDSO-to-O2 ratio during PECVD, and that post-plasma reactions increase the cross-link density of the silicon-oxygen network. It appears that Si-H and Si-OH chemical groups are the most susceptible to post-plasma reactions. Coatings produced at a low TMDSO-to-oxygen ratio had little to no singly substituted moieties, displayed a highly cross-linked structure, and showed less post-plasma reactions. However, these chemically more stable coatings are less compatible mechanically with plastic substrates, because of their high stiffness.

Diagnostic studies of H2 Ar N2 microwave plasmas containing methane or methanol using tunable infrared diode laser absorption spectroscopy

NASA Astrophysics Data System (ADS)

Hempel, F.; Davies, P. B.; Loffhagen, D.; Mechold, L.; Röpcke, J.

2003-11-01

Tunable infrared diode laser absorption spectroscopy has been used to detect the methyl radical and nine stable molecules, CH4, CH3OH, C2H2, C2H4, C2H6, NH3, HCN, CH2O and C2N2, in H2-Ar-N2 microwave plasmas containing up to 7% of methane or methanol, under both flowing and static conditions. The degree of dissociation of the hydrocarbon precursor molecules varied between 20% and 97%. The methyl radical concentration was found to be in the range 1012-1013 molecules cm-3. By analysing the temporal development of the molecular concentrations under static conditions it was found that HCN and NH3 are the final products of plasma chemical conversion. The fragmentation rates of methane and methanol (RF(CH4) = (2-7) × 1015 molecules J-1, RF(CH3OH) = (6-9) × 1015 molecules J-1) and the respective conversion rates to methane, hydrogen cyanide and ammonia (RCmax(CH4) = 1.2 × 1015 molecules J-1, RCmax(HCN) = 1.3 × 1015 molecules J-1, RCmax(NH3) = 1 × 1014 molecules J-1) have been determined for different hydrogen to nitrogen concentration ratios. An extensive model of the chemical reactions involved in the H2-N2-Ar-CH4 plasma has been developed. Model calculations were performed by including 22 species, 145 chemical reactions and appropriate electron impact dissociation rate coefficients. The results of the model calculations showed satisfactory agreement between calculated and measured concentrations. The most likely main chemical pathways involved in these plasmas are discussed and an appropriate reaction scheme is proposed.

Reactive simulation of the chemistry behind the condensed-phase ignition of RDX from hot spots.

PubMed

Joshi, Kaushik L; Chaudhuri, Santanu

2015-07-28

Chemical events that lead to thermal initiation and spontaneous ignition of the high-pressure phase of RDX are presented using reactive molecular dynamics simulations. In order to initiate the chemistry behind thermal ignition, approximately 5% of RDX crystal is subjected to a constant temperature thermal pulse for various time durations to create a hot spot. After application of the thermal pulse, the ensuing chemical evolution of the system is monitored using reactive molecular dynamics under adiabatic conditions. Thermal pulses lasting longer than certain time durations lead to the spontaneous ignition of RDX after an incubation period. For cases where the ignition is observed, the incubation period is dominated by intermolecular and intramolecular hydrogen transfer reactions. Contrary to the widely accepted unimolecular models of initiation chemistry, N-N bond dissociations that produce NO2 species are suppressed in the condensed phase. The gradual temperature and pressure increase in the incubation period is accompanied by the accumulation of short-lived, heavier polyradicals. The polyradicals contain intact triazine rings from the RDX molecules. At certain temperatures and pressures, the polyradicals undergo ring-opening reactions, which fuel a series of rapid exothermic chemical reactions leading to a thermal runaway regime with stable gas-products such as N2, H2O and CO2. The evolution of the RDX crystal throughout the thermal initiation, incubation and thermal runaway phases observed in the reactive simulations contains a rich diversity of condensed-phase chemistry of nitramines under high-temperature/pressure conditions.

A new multiple-stage electrocoagulation process on anaerobic digestion effluent to simultaneously reclaim water and clean up biogas.

PubMed

Liu, Zhiguo; Stromberg, David; Liu, Xuming; Liao, Wei; Liu, Yan

2015-03-21

A new multiple-stage treatment process was developed via integrating electrocoagulation with biogas pumping to simultaneously reclaim anaerobic digestion effluent and clean up biogas. The 1st stage of electrocoagulation treatment under the preferred reaction condition led to removal efficiencies of 30%, 81%, 37% and >99.9% for total solids, chemical oxygen demand, total nitrogen and total phosphorus, respectively. Raw biogas was then used as a reactant and pumped into the effluent to simultaneously neutralize pH of the effluent and remove H2S in the biogas. The 2nd stage of electrocoagulation treatment on the neutralized effluent showed that under the selected reaction condition, additional 60% and 10% of turbidity and chemical oxygen demand were further removed. The study concluded a dual-purpose approach for the first time to synergistically combine biogas purification and water reclamation for anaerobic digestion system, which well addresses the downstream challenges of anaerobic digestion technology. Copyright © 2014 Elsevier B.V. All rights reserved.

Development of flame resistant treatment for Nomex fibrous structures

NASA Technical Reports Server (NTRS)

Toy, M. S.

1977-01-01

Flame resistant fibrous materials for space shuttle application were developed through chemical modification of commercially available aromatic polyamide fibrous products. The new surface treatment was achieved in the laboratory by ultraviolet activation of the fabric in the presence of fluoroolefin monomers and a diluent gas. The monomers grafted under these conditions provide the improved properties of the fabric in flame resistance, chemical inertness, and nonwettability without the sacrifice of color or physical properties. The laboratory reaction vessel was scaled-up to a batch continuous process, which treats ten yards of the commercial width textiles. The treated commercial width Nomex (HT-10-41) from the scaled-up reactor is self-extinguishing in an oxygen-enriched environment, water-repellent, soft, silky, and improved in chemical resistance. Unlike most textile processes, the grafting unit operates under dry conditions and no chemical by-products have to be washed out of the finished product.

CuAAC-Based Click Chemistry in Self-Healing Polymers.

PubMed

Döhler, Diana; Michael, Philipp; Binder, Wolfgang H

2017-10-17

Click chemistry has emerged as a significant tool for materials science, organic chemistry, and bioscience. Based on the initial concept of Barry Sharpless in 2001, the copper(I)-catalyzed azide/alkyne cycloaddition (CuAAC) reaction has triggered a plethora of chemical concepts for linking molecules and building blocks under ambient conditions, forming the basis for applications in autonomous cross-linking materials. Self-healing systems on the other hand are often based on mild cross-linking chemistries that are able to react either autonomously or upon an external trigger. In the ideal case, self-healing takes place efficiently at low temperatures, independent of the substrate(s) used, by forming strong and stable networks, binding to the newly generated (cracked) interfaces to restore the original material properties. The use of the CuAAC in self-healing systems, most of all the careful design of copper-based catalysts linked to additives as well as the chemical diversity of substrates, has led to an enormous potential of applications of this singular reaction. The implementation of click-based strategies in self-healing systems therefore is highly attractive, as here chemical (and physical) concepts of molecular reactivity, molecular design, and even metal catalysis are connected to aspects of materials science. In this Account, we will show how CuAAC reactions of multivalent components can be used as a tool for self-healing materials, achieving cross-linking at low temperatures (exploiting concepts of autocatalysis or internal chelation within the bulk CuAAC and systematic optimization of the efficiency of the used Cu(I) catalysts). Encapsulation strategies to separate the click components by micro- and nanoencapsulation are required in this context. Consequently, the examples reported here describe chemical concepts to realize more efficient and faster click reactions in self-healing polymeric materials. Thus, enhanced chain diffusion in (hyper)branched polymers, autocatalysis, or internal chelation concepts enable efficient click cross-linking already at 5 °C with a simultaneously reduced amount of Cu(I) catalyst and increased reaction rates, culminating in the first reported self-healing system based on click cycloaddition reactions. Via tailor-made nanocarbon/Cu(I) catalysts we can further improve the click cross-linking reaction in view of efficiency and kinetics, leading to the generation of self-healing graphene-based epoxy nanocomposites. Additionally, we have designed special CuAAC click methods for chemical reporting and visualization systems based on the detection of ruptured capsules via a fluorogenic click reaction, which can be combined with CuAAC cross-linking reactions to obtain simultaneous stress detection and self-healing within polymeric materials. In a similar concept, we have prepared polymeric Cu(I)-biscarbene complexes to detect (mechanical) stress within self-healing polymeric materials via a triggered fluorogenic reaction, thus using a destructive force for a constructive chemical response.

A Review of Study on Thermal Energy Transport System by Synthesis and Decomposition Reactions of Methanol

NASA Astrophysics Data System (ADS)

Liu, Qiusheng; Yabe, Akira; Kajiyama, Shiro; Fukuda, Katsuya

The study on thermal energy transport system by synthesis and decomposition reactions of methanol was reviewed. To promote energy conservation and global environment protection, a two-step liquid-phase methanol synthesis process, which starts with carbonylation of methanol to methyl formate, then followed by the hydrogenolysis of the formate, was studied to recover wasted or unused discharged heat from industrial sources for the thermal energy demands of residential and commercial areas by chemical reactions. The research and development of the system were focused on the following three points. (1) Development of low-temperature decomposition and synthetic catalysts, (2) Development of liquid phase reactor (heat exchanger accompanying chemical reaction), (3) Simulation of the energy transport efficiency of entire system which contains heat recovery and supply sections. As the result of the development of catalyst, promising catalysts which agree with the development purposes for the methyl formate decomposition reaction and the synthetic reaction are being developed though some studies remain for the methanol decomposition and synthetic reactions. In the fundamental development of liquid phase reactor, the solubilities of CO and H2 gases in methanol and methyl formate were measured by the method of total pressure decrease due to absorption under pressures up to 1500kPa and temperatures up to 140°C. The diffusivity of CO gas in methanol was determined by measuring the diameter and solution time of single CO bubbles in methanol. The chemical reaction rate of methanol synthesis by hydrogenolysis of methyl formate was measured using a plate-type of Raney copper catalyst in a reactor with rectangular channel and in an autoclave reactor. The reaction characteristics were investigated by carrying out the experiments at various temperatures, flow rates and at various catalyst development conditions. We focused on the effect of Raney copper catalyst thickness on the liquid-phase chemical reaction by varying the development time of the catalyst. Investigation results of the catalyst such as surface area, pore radius, lattice size, and photographs of scanning electron microscope (SEM) were also given. In the simulation of energy transport efficiency of this system, by simulating the energy transfer system using two-step liquid phase methanol decomposition and synthetic reactions, and comparing with the technology so far, it can be expected that an innovative energy transfer system is possible to realize.

Plant food allergy: Influence of chemicals on plant allergens.

PubMed

Shahali, Youcef; Dadar, Maryam

2018-05-01

Plant-derived foods are the most common allergenic sources in adulthood. Owing to the rapidly increasing prevalence of plant food allergies in industrialized countries, the environmental factors are suspected to play a key role in development of allergic sensitization. The present article provides an overview of ways by which chemicals may influence the development and severity of allergic reactions to plant foods, with especial focus on plant allergens up-regulated under chemical stress. In plants, a substantial part of allergens have defense-related function and their expression is highly influenced by environmental stress and diseases. Pathogenesis-related proteins (PR) account for about 25% of plant food allergens and some are responsible for extensive cross-reactions between plant-derived foods, pollen and latex allergens. Chemicals released by anthropogenic sources such as agriculture, industrial activities and traffic-related air pollutants are potential drivers of the increasing sensitization to allergenic PRs by elevating their expression and by altering their immunogenicity through post-translational modifications. In addition, some orally-taken chemicals may act as immune adjuvants or directly trigger non-IgE mediated food allergy. Taken together, the current literature provides an overwhelming body of evidence supporting the fact that plant chemical exposure and chemicals in diet may enhance the allergenic properties of certain plant-derived foods. Copyright © 2018 Elsevier Ltd. All rights reserved.

Advances in Quantum Mechanochemistry: Electronic Structure Methods and Force Analysis.

PubMed

Stauch, Tim; Dreuw, Andreas

2016-11-23

In quantum mechanochemistry, quantum chemical methods are used to describe molecules under the influence of an external force. The calculation of geometries, energies, transition states, reaction rates, and spectroscopic properties of molecules on the force-modified potential energy surfaces is the key to gain an in-depth understanding of mechanochemical processes at the molecular level. In this review, we present recent advances in the field of quantum mechanochemistry and introduce the quantum chemical methods used to calculate the properties of molecules under an external force. We place special emphasis on quantum chemical force analysis tools, which can be used to identify the mechanochemically relevant degrees of freedom in a deformed molecule, and spotlight selected applications of quantum mechanochemical methods to point out their synergistic relationship with experiments.

The Theory of Thermodynamics for Chemical Reactions in Dispersed Heterogeneous Systems

PubMed

Yongqiang; Baojiao; Jianfeng

1997-07-01

In this paper, the expressions of Gibbs energy change, enthalpy change, entropy change, and equilibrium constant for chemical reactions in dispersed heterogeneous systems are derived using classical thermodynamics theory. The thermodynamical relations for the same reaction system between the dispersed and the block state are also derived. The effects of degree of dispersion on thermodynamical properties, reaction directions, and chemical equilibria are discussed. The results show that the present equation of thermodynamics for chemical reactions is only a special case of the above-mentioned formulas and that the effect of the dispersity of a heterogeneous system on the chemical reaction obeys the Le Chatelier principle of movement of equilibria.

Exposure-time based modeling of nonlinear reactive transport in porous media subject to physical and geochemical heterogeneity.

PubMed

Sanz-Prat, Alicia; Lu, Chuanhe; Amos, Richard T; Finkel, Michael; Blowes, David W; Cirpka, Olaf A

2016-09-01

Transport of reactive solutes in groundwater is affected by physical and chemical heterogeneity of the porous medium, leading to complex spatio-temporal patterns of concentrations and reaction rates. For certain cases of bioreactive transport, it could be shown that the concentrations of reactive constituents in multi-dimensional domains are approximately aligned with isochrones, that is, lines of identical travel time, provided that the chemical properties of the matrix are uniform. We extend this concept to combined physical and chemical heterogeneity by additionally considering the time that a water parcel has been exposed to reactive materials, the so-called exposure time. We simulate bioreactive transport in a one-dimensional domain as function of time and exposure time, rather than space. Subsequently, we map the concentrations to multi-dimensional heterogeneous domains by means of the mean exposure time at each location in the multi-dimensional domain. Differences in travel and exposure time at a given location are accounted for as time difference. This approximation simplifies reactive-transport simulations significantly under conditions of steady-state flow when reactions are restricted to specific locations. It is not expected to be exact in realistic applications because the underlying assumption, such as neglecting transverse mixing altogether, may not hold. We quantify the error introduced by the approximation for the hypothetical case of a two-dimensional, binary aquifer made of highly-permeable, non-reactive and low-permeable, reactive materials releasing dissolved organic matter acting as electron donor for aerobic respiration and denitrification. The kinetically controlled reactions are catalyzed by two non-competitive bacteria populations, enabling microbial growth. Even though the initial biomass concentrations were uniform, the interplay between transport, non-uniform electron-donor supply, and bio-reactions led to distinct spatial patterns of the two types of biomass at late times. Results obtained by mapping the exposure-time based results to the two-dimensional domain are compared with simulations based on the two-dimensional, spatially explicit advection-dispersion-reaction equation. Once quasi-steady state has been reached, we find a good agreement in terms of the chemical-compound concentrations between the two approaches inside the reactive zones, whereas the exposure-time based model is not able to capture reactions occurring in the zones with zero electron-donor release. We conclude that exposure-time models provide good approximations of nonlinear bio-reactive transport when transverse mixing is not the overall controlling process and all reactions are essentially restricted to distinct reactive zones. Copyright © 2016 Elsevier B.V. All rights reserved.

The rate of the deoxygenation reaction limits myoglobin- and hemoglobin-facilitated O₂ diffusion in cells.

PubMed

Endeward, Volker

2012-05-01

A mathematical model describing facilitation of O(2) diffusion by the diffusion of myoglobin and hemoglobin is presented. The equations are solved numerically by a finite-difference method for the conditions as they prevail in cardiac and skeletal muscle and in red cells without major simplifications. It is demonstrated that, in the range of intracellular diffusion distances, the degree of facilitation is limited by the rate of the chemical reaction between myglobin or hemoglobin and O(2). The results are presented in the form of relationships between the degree of facilitation and the length of the diffusion path on the basis of the known kinetics of the oxygenation-deoxygenation reactions. It is concluded that the limitation by reaction kinetics reduces the maximally possible facilitated oxygen diffusion in cardiomyoctes by ∼50% and in skeletal muscle fibers by ∼ 20%. For human red blood cells, a reduction of facilitated O(2) diffusion by 36% is obtained in agreement with previous reports. This indicates that, especially in cardiomyocytes and red cells, chemical equilibrium between myoglobin or hemoglobin and O(2) is far from being established, an assumption that previously has often been made. Although the "O(2) transport function" of myoglobin in cardiac muscle cells thus is severely limited by the chemical reaction kinetics, and to a lesser extent also in skeletal muscle, it is noteworthy that the speed of release of O(2) from MbO(2), the "storage function," is not limited by the reaction kinetics under physiological conditions.

The HNC/HCN ratio in star-forming regions

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

Graninger, Dawn M.; Öberg, Karin I.; Herbst, Eric

2014-05-20

HNC and HCN, typically used as dense gas tracers in molecular clouds, are a pair of isomers that have great potential as a temperature probe because of temperature dependent, isomer-specific formation and destruction pathways. Previous observations of the HNC/HCN abundance ratio show that the ratio decreases with increasing temperature, something that standard astrochemical models cannot reproduce. We have undertaken a detailed parameter study on which environmental characteristics and chemical reactions affect the HNC/HCN ratio and can thus contribute to the observed dependence. Using existing gas and gas-grain models updated with new reactions and reaction barriers, we find that in staticmore » models the H + HNC gas-phase reaction regulates the HNC/HCN ratio under all conditions, except for very early times. We quantitatively constrain the combinations of H abundance and H + HNC reaction barrier that can explain the observed HNC/HCN temperature dependence and discuss the implications in light of new quantum chemical calculations. In warm-up models, gas-grain chemistry contributes significantly to the predicted HNC/HCN ratio and understanding the dynamics of star formation is therefore key to model the HNC/HCN system.« less

Mechanisms of stochastic focusing and defocusing in biological reaction networks: insight from accurate chemical master equation (ACME) solutions.

PubMed

Gursoy, Gamze; Terebus, Anna; Youfang Cao; Jie Liang

2016-08-01

Stochasticity plays important roles in regulation of biochemical reaction networks when the copy numbers of molecular species are small. Studies based on Stochastic Simulation Algorithm (SSA) has shown that a basic reaction system can display stochastic focusing (SF) by increasing the sensitivity of the network as a result of the signal noise. Although SSA has been widely used to study stochastic networks, it is ineffective in examining rare events and this becomes a significant issue when the tails of probability distributions are relevant as is the case of SF. Here we use the ACME method to solve the exact solution of the discrete Chemical Master Equations and to study a network where SF was reported. We showed that the level of SF depends on the degree of the fluctuations of signal molecule. We discovered that signaling noise under certain conditions in the same reaction network can lead to a decrease in the system sensitivities, thus the network can experience stochastic defocusing. These results highlight the fundamental role of stochasticity in biological reaction networks and the need for exact computation of probability landscape of the molecules in the system.

Impact of reaction products from building materials and furnishings on indoor air quality—A review of recent advances in indoor chemistry

NASA Astrophysics Data System (ADS)

Uhde, E.; Salthammer, T.

The variety of chemical substances present in modern building products, household products and furnishings provides potential for chemical reactions in the material (case 1), on the material surface (case 2) and in the gas phase (case 3). Such "indoor chemistry" is known as one of the main reasons for primary and secondary emissions. The conditions of production often cause unwanted side reactions and a number of new compounds can be found in finished products. Elevated temperatures are responsible for the degradation of cellulose, decomposition of non-heat-resistant additives and other thermally induced reactions like Diels-Alder synthesis. Heterogeneous chemistry takes place on the surface of materials. Well-known examples are the formation of aliphatic aldehydes from the oxidation of unsaturated fatty acids or the cleavage of photoinitiators under the influence of light. In case of composite flooring structures hydrolysis is one of the major pathways for the appearance of alcohols from esters. If different kinds of material are fixed together, emissions of new VOCs formed by inter-species reactions are possible. Other indoor air pollutants are formed by rearrangement of cleavage products or by metabolism. Compounds with -C dbnd C- bonds like terpenes, styrene, 4-phenylcyclohexene, etc. undergo gas phase reactions with O 3, NO x, OH and other reactive gases. It has been shown that such products derived from indoor-related reactions may have a negative impact on indoor air quality due to their low odor threshold or health-related properties. Therefore, the understanding of primary and secondary emissions and the chemical processes behind is essential for the evaluation of indoor air quality. This publication gives an overview on the current state of research and new findings regarding primary and secondary emissions from building products and furnishings.

Topical Hazard Evaluation Program of Candidate Insect Repellents AI3-38352a, AI3-38354a, AI3-38355a, US Department of Agriculture Proprietary Chemicals, May 1982 - November 1983.

DTIC Science & Technology

1983-11-01

irrita- chemical and of 10% (wv) A13-38357a, AI3-38360a, tion reaction under Oil of Bergamot (positive and Ar3-38361a did test conditions and control...caused a greater Irritant positive control (Oil of effect than In un- Bergamot ) and diluent were Irradiated skin areas. applied to additional skin

Mining chemical reactions using neighborhood behavior and condensed graphs of reactions approaches.

PubMed

de Luca, Aurélie; Horvath, Dragos; Marcou, Gilles; Solov'ev, Vitaly; Varnek, Alexandre

2012-09-24

This work addresses the problem of similarity search and classification of chemical reactions using Neighborhood Behavior (NB) and Condensed Graphs of Reaction (CGR) approaches. The CGR formalism represents chemical reactions as a classical molecular graph with dynamic bonds, enabling descriptor calculations on this graph. Different types of the ISIDA fragment descriptors generated for CGRs in combination with two metrics--Tanimoto and Euclidean--were considered as chemical spaces, to serve for reaction dissimilarity scoring. The NB method has been used to select an optimal combination of descriptors which distinguish different types of chemical reactions in a database containing 8544 reactions of 9 classes. Relevance of NB analysis has been validated in generic (multiclass) similarity search and in clustering with Self-Organizing Maps (SOM). NB-compliant sets of descriptors were shown to display enhanced mapping propensities, allowing the construction of better Self-Organizing Maps and similarity searches (NB and classical similarity search criteria--AUC ROC--correlate at a level of 0.7). The analysis of the SOM clusters proved chemically meaningful CGR substructures representing specific reaction signatures.

Diffusion approximations to the chemical master equation only have a consistent stochastic thermodynamics at chemical equilibrium

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

Horowitz, Jordan M., E-mail: jordan.horowitz@umb.edu

The stochastic thermodynamics of a dilute, well-stirred mixture of chemically reacting species is built on the stochastic trajectories of reaction events obtained from the chemical master equation. However, when the molecular populations are large, the discrete chemical master equation can be approximated with a continuous diffusion process, like the chemical Langevin equation or low noise approximation. In this paper, we investigate to what extent these diffusion approximations inherit the stochastic thermodynamics of the chemical master equation. We find that a stochastic-thermodynamic description is only valid at a detailed-balanced, equilibrium steady state. Away from equilibrium, where there is no consistent stochasticmore » thermodynamics, we show that one can still use the diffusive solutions to approximate the underlying thermodynamics of the chemical master equation.« less

Comparative simulation study of chemical synthesis of functional DADNE material.

PubMed

Liu, Min Hsien; Liu, Chuan Wen

2017-01-01

Amorphous molecular simulation to model the reaction species in the synthesis of chemically inert and energetic 1,1-diamino-2,2-dinitroethene (DADNE) explosive material was performed in this work. Nitromethane was selected as the starting reactant to undergo halogenation, nitration, deprotonation, intermolecular condensation, and dehydration to produce the target DADNE product. The Materials Studio (MS) forcite program allowed fast energy calculations and reliable geometric optimization of all aqueous molecular reaction systems (0.1-0.5 M) at 283 K and 298 K. The MS forcite-computed and Gaussian polarizable continuum model (PCM)-computed results were analyzed and compared in order to explore feasible reaction pathways under suitable conditions for the synthesis of DADNE. Through theoretical simulation, the findings revealed that synthesis was possible, and a total energy barrier of 449.6 kJ mol -1 needed to be overcome in order to carry out the reaction according to MS calculation of the energy barriers at each stage at 283 K, as shown by the reaction profiles. Local analysis of intermolecular interaction, together with calculation of the stabilization energy of each reaction system, provided information that can be used as a reference regarding molecular integrated stability. Graphical Abstract Materials Studio software has been suggested for the computation and simulation of DADNE synthesis.

Larnite powders and larnite/silica aerogel composites as effective agents for CO2 sequestration by carbonation.

PubMed

Santos, A; Ajbary, M; Morales-Flórez, V; Kherbeche, A; Piñero, M; Esquivias, L

2009-09-15

This paper presents the results of the carbonation reaction of two sample types: larnite (Ca(2)SiO(4)) powders and larnite/silica aerogel composites, the larnite acting as an active phase in a process of direct mineral carbonation. First, larnite powders were synthesized by the reaction of colloidal silica and calcium nitrate in the presence of ethylene glycol. Then, to synthesize the composites, the surface of the larnite powders was chemically modified with 3-aminopropyltriethoxysilane (APTES), and later this mixture was added to a silica sol previously prepared from tetraethylorthosilicate (TEOS). The resulting humid gel was dried in an autoclave under supercritical conditions for the ethanol. The textures and chemical compositions of the powders and composites were characterized.The carbonation reaction of both types of samples was evaluated by means of X-ray diffraction and thermogravimetric analysis. Both techniques confirm the high efficiency of the reaction at room temperature and atmospheric pressure. A complete transformation of the silicate into carbonate resulted after submitting the samples to a flow of pure CO(2) for 15 min. This indicates that for this reaction time, 1t of larnite could eliminate about 550 kg of CO(2). The grain size, porosity, and specific surface area are the factors controlling the reaction.

User`s guide for UTCHEM-5.32m a three dimensional chemical flood simulator. Final report, September 30, 1992--December 31, 1995

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

NONE

1996-07-01

UTCHEM is a three-dimensional chemical flooding simulator. The solution scheme is analogous to IMPES, where pressure is solved for implicitly, but concentrations rather than saturations are then solved for explicitly. Phase saturations and concentrations are then solved in a flash routine. An energy balance equation is solved explicitly for reservoir temperature. The energy balance equation includes heat flow between the reservoir and the over-and under-burden rocks. The major physical phenomena modeled in the simulator are: dispersion; dilution effects; adsorption; interfacial tension; relative permeability; capillary trapping; cation exchange; phase density; compositional phase viscosity; phase behavior (pseudoquaternary); aqueous reactions; partitioning of chemicalmore » species between oil and water; dissolution/precipitation; cation exchange reactions involving more than two cations; in-situ generation of surfactant from acidic crude oil; pH dependent adsorption; polymer properties: shear thinning viscosity; inaccessible pore volume; permeability reduction; adsorption; gel properties: viscosity; permeability reduction; adsorption; tracer properties: partitioning; adsorption; radioactive decay; reaction (ester hydrolization); temperature dependent properties: viscosity; tracer reaction; gel reactions The following options are available with UTCHEM: isothermal or non-isothermal conditions, a constant or variable time-step, constant pressure or constant rate well conditions, horizontal and vertical wells, and a radial or Cartesian geometry. Please refer to the dissertation {open_quotes}Field Scale Simulation of Chemical Flooding{close_quotes} by Naji Saad, August, 1989, for a more detailed discussion of the UTCHEM simulator and its formulation.« less

Study of Superbase-Based Deep Eutectic Solvents as the Catalyst in the Chemical Fixation of CO2 into Cyclic Carbonates under Mild Conditions

PubMed Central

García-Argüelles, Sara; Iglesias, Marta; Del Monte, Francisco

2017-01-01

Superbases have shown high performance as catalysts in the chemical fixation of CO2 to epoxides. The proposed reaction mechanism typically assumes the formation of a superbase, the CO2 adduct as the intermediate, most likely because of the well-known affinity between superbases and CO2, i.e., superbases have actually proven quite effective for CO2 absorption. In this latter use, concerns about the chemical stability upon successive absorption-desorption cycles also merits attention when using superbases as catalysts. In this work, 1H NMR spectroscopy was used to get further insights about (1) whether a superbase, the CO2 adduct, is formed as an intermediate and (2) the chemical stability of the catalyst after reaction. For this purpose, we proposed as a model system the chemical fixation of CO2 to epichlorohydrin (EP) using a deep eutectic solvent (DES) composed of a superbase, e.g., 2,3,4,6,7,8-hexahydro-1H-pyrimido[1,2-a]pyrimidine (TBD) or 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine (DBU), as a hydrogen acceptor and an alcohol as a hydrogen bond donor, e.g., benzyl alcohol (BA), ethylene glycol (EG), and methyldiethanolamine (MDEA), as the catalyst. The resulting carbonate was obtained with yields above 90% and selectivities approaching 100% after only two hours of reaction in pseudo-mild reaction conditions, e.g., 1.2 bars and 100 °C, and after 20 h if the reaction conditions of choice were even milder, e.g., 1.2 bars and 50 °C. These results were in agreement with previous works using bifunctional catalytic systems composed of a superbase and a hydrogen bond donor (HBD) also reporting good yields and selectivities, thus confirming the suitability of our choice to perform this study. PMID:28773128

A Second-Year Undergraduate Course in Applied Differential Equations.

ERIC Educational Resources Information Center

Fahidy, Thomas Z.

1991-01-01

Presents the framework for a chemical engineering course using ordinary differential equations to solve problems with the underlying strategy of concisely discussing the theory behind each solution technique without extensions to formal proofs. Includes typical class illustrations, student responses to this strategy, and reaction of the…

Using Games To Teach Chemistry: An Annotated Bibliography.

ERIC Educational Resources Information Center

Russell, Jeanne V.

1999-01-01

Lists 67 published or marketed chemistry games organized under the following categories: (1) general knowledge; (2) elements and atomic structure; (3) nomenclature, formulas, and equation writing; (4) chemical reactions; (5) solutions and solubilities; (6) organic chemistry, and (8) miscellaneous subjects. Includes a brief description of each…

40 CFR 704.3 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... of the article, and that result from a chemical reaction that occurs upon end use of other chemical... substance that is consumed, in whole or in part, in chemical reactions used for the intentional manufacture... altering the rates of such chemical reactions. Known to or reasonably ascertainable by means all...

40 CFR 704.3 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... of the article, and that result from a chemical reaction that occurs upon end use of other chemical... substance that is consumed, in whole or in part, in chemical reactions used for the intentional manufacture... altering the rates of such chemical reactions. Known to or reasonably ascertainable by means all...

40 CFR 704.3 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... of the article, and that result from a chemical reaction that occurs upon end use of other chemical... substance that is consumed, in whole or in part, in chemical reactions used for the intentional manufacture... altering the rates of such chemical reactions. Known to or reasonably ascertainable by means all...

Students' Visualisation of Chemical Reactions--Insights into the Particle Model and the Atomic Model

ERIC Educational Resources Information Center

Cheng, Maurice M. W.

2018-01-01

This paper reports on an interview study of 18 Grade 10-12 students' model-based reasoning of a chemical reaction: the reaction of magnesium and oxygen at the submicro level. It has been proposed that chemical reactions can be conceptualised using two models: (i) the "particle model," in which a reaction is regarded as the simple…

Diels-Alder reactions of 12-hydroxy-9(10®20)-5aH-abeo-abieta-1(10),8(9),12(13)-triene-11,14-dione.

PubMed

Majetich, George; Zhang, Yong; Tian, Xinrong; Zou, Ge; Li, Yang; Wang, Yangyang; Hu, Shougang; Huddleston, Eric

2013-06-14

12-Hydroxy-9(10-->20)-5aH-abeo-abieta-1(10),8(9),12(13)-triene-11,14-dione (quinone 2) served as the dienophile in numerous intermolecular Diels-Alder reactions. These cycloadditions were conducted either thermally (including microwave heating) or with Lewis acid activation. While most dienes reacted with quinone 2 in good chemical yield, others were incompatible under the experimental conditions used.

Combustion dynamics in liquid rocket engines

NASA Technical Reports Server (NTRS)

Mclain, W. H.

1971-01-01

A chemical analysis of the emission and absorption spectra in the combustion chamber of a nitrogen tetroxide/aerozine-50 rocket engine was conducted. Measurements were made under conditions of preignition, ignition, and post combustion operating periods. The cause of severe ignition overpressures sporadically observed during the vacuum startup of the Apollo reaction control system engine was investigated. The extent to which residual propellants or condensed intermediate reaction products remain after the engine has been operated in a pulse mode duty cycle was determined.

Stereochemical control factors in the Hantzsch thiazole synthesis: a Hammett substitution correlation analysis.

PubMed

Qiao, Q; So, S S; Goodnow, R A

2001-11-15

[reaction--see text] It is possible to correlate the distribution of stereochemical products produced during a Hantzsch thiazole synthesis according to the Hammett free-energy equation. This analysis confirms the presumed control of the rate of epimerization during thiazole formation due to stabilization of a cationic transition state intermediate during dehydration of the thiazoline ring system. In the chemical system under study, the stereochemical outcome of the reaction also appears to occur according to a kinetically controlled protonation of a thiazoline tautomer.

40 CFR 721.9300 - Reaction products of substituted hydroxy-alkanes and polyalkylpolyisocyanatocarbomono- cycle.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Reaction products of substituted... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9300 Reaction products of... significant new uses subject to reporting. (1) The chemical substance identified generically as reaction...

40 CFR 721.9300 - Reaction products of substituted hydroxy-alkanes and polyalkylpolyisocyanatocarbomono- cycle.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Reaction products of substituted... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9300 Reaction products of... significant new uses subject to reporting. (1) The chemical substance identified generically as reaction...

40 CFR 721.9300 - Reaction products of substituted hydroxy-alkanes and polyalkylpolyisocyanatocarbomono- cycle.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Reaction products of substituted... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9300 Reaction products of... significant new uses subject to reporting. (1) The chemical substance identified generically as reaction...

40 CFR 721.9300 - Reaction products of substituted hydroxy-alkanes and polyalkylpolyisocyanatocarbomono- cycle.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction products of substituted... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9300 Reaction products of... significant new uses subject to reporting. (1) The chemical substance identified generically as reaction...

40 CFR 721.9300 - Reaction products of substituted hydroxy-alkanes and polyalkylpolyisocyanatocarbomono- cycle.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction products of substituted... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9300 Reaction products of... significant new uses subject to reporting. (1) The chemical substance identified generically as reaction...

Diffusion and reactivity of ground-state nitrogen atoms N(4S) between 3 and 15 K: application to the hydrogen abstraction reaction from methane under non-energetic conditions

NASA Astrophysics Data System (ADS)

Nourry, Sendres; Krim, Lahouari

2015-07-01

We have characterized the CH4 + N(4S) reaction in solid phase, at very low temperature, under non-energetic conditions and where the CH4 and N reactants are in their ground states. A microwave-driven atomic source has been used to generate ground-state nitrogen atoms N(4S), and experiments have been carried out at temperatures as low as 3 K to reduce the mobility of the trapped species in solid phase and hence to freeze the first step of the CH4 + N reaction pathway. Leaving the formed solid sample in the dark for a while allows all trapped reactants to relax to the ground state, specifically radicals and excited species streaming from the plasma discharge. Such a method could be the only possibility of proving that the CH4 + N reaction occurs between CH4 and N reactants in their ground states without any additional energy to initiate the chemical process. The appearance of the CH3 reaction product, just by inducing the mobility of N atoms between 3 and 11 K, translates that a hydrogen abstraction reaction from methane, under non-energetic conditions, will start occurring at very low temperature. The formation of methyl radical, under these experimental conditions, is due to recombination processes N(4S)-N(4S) of ground-state nitrogen atoms without any contribution of cosmic ray particles or high-energy photons.

Influences of pH and CO2 on the formation of Metasilicate mineral water in Changbai Mountain, Northeast China

NASA Astrophysics Data System (ADS)

Yan, Baizhong; Xiao, Changlai; Liang, Xiujuan; Wu, Shili

2017-07-01

Mineral dissolution reactions actively participate in controlling the composition of mineral water. In this study, water soluble, acidic-alkaline and carbonated solution experiments were designed, and mineral reaction mechanisms were researched using chemical kinetics and the minimum free-energy method. The results showed that the release of metasilicate was controlled by pH, CO2, and rock characteristics. In the water soluble experiment, the release process of metasilicate in powdered rocks reached equilibrium after 40 days, while metasilicate in solid rocks took 170 days. The release process of metasilicate in solid rocks satisfied an asymptotic model, while in powdered rocks it accorded with the Stanford reaction kinetic model. In the acidic-alkaline experiment, metasilicate was released earlier under acidic conditions (2.46 < pH < 7) than under alkaline conditions (7 < pH < 10.61). The release process of metasilicate under acidic conditions reached equilibrium in 40 days, compared with 60 days for alkaline conditions. The addition of CO2 to the water solution was beneficial to the formation of metasilicate. Under neutral pH conditions, the reaction barely occurred. Under alkaline conditions, metasilicate was produced by the hydrolysis of metasilicate minerals. Under acidic and additional CO2 conditions, metasilicate formation was mainly via the reaction of H+, CO2, and metasilicate minerals. From these results, we concluded that the metasilicate mineral water from the Changbai Mountains, Jingyu County, is generated by a combination of the hydrolysis of metasilicate minerals and the reaction of H+, CO2, and metasilicate minerals. These results can contribute to a better development and protection of the mineral water resources in the Changbai Mountains.

40 CFR 717.7 - Persons not subject to this part.

Code of Federal Regulations, 2010 CFR

2010-07-01

... REACTIONS TO HEALTH OR THE ENVIRONMENT General Provisions § 717.7 Persons not subject to this part. (a... produced are limited to: (i) Chemical substances that result from chemical reactions that occur incidental..., moisture, microbial organisms, or sunlight. (ii) Chemical substances that result from chemical reactions...

40 CFR 717.7 - Persons not subject to this part.

Code of Federal Regulations, 2011 CFR

2011-07-01

... REACTIONS TO HEALTH OR THE ENVIRONMENT General Provisions § 717.7 Persons not subject to this part. (a... produced are limited to: (i) Chemical substances that result from chemical reactions that occur incidental..., moisture, microbial organisms, or sunlight. (ii) Chemical substances that result from chemical reactions...

40 CFR 372.3 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... or more chemicals, if the combination is not, in whole or in part, the result of a chemical reaction. However, if the combination was produced by a chemical reaction but could have been produced without a chemical reaction, it is also treated as a mixture. A mixture also includes any combination which consists...

40 CFR 712.3 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

...) Intermediate means any chemical substance that is consumed, in whole or in part, in chemical reactions used for... for the purpose of altering the rates of such chemical reactions. (See also paragraph (j) of this... of a chemical reaction; except that mixture does include (1) any combination which occurs, in whole...

40 CFR 712.3 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

...) Intermediate means any chemical substance that is consumed, in whole or in part, in chemical reactions used for... for the purpose of altering the rates of such chemical reactions. (See also paragraph (j) of this... of a chemical reaction; except that mixture does include (1) any combination which occurs, in whole...

40 CFR 712.3 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

...) Intermediate means any chemical substance that is consumed, in whole or in part, in chemical reactions used for... for the purpose of altering the rates of such chemical reactions. (See also paragraph (j) of this... of a chemical reaction; except that mixture does include (1) any combination which occurs, in whole...

40 CFR 712.3 - Definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

...) Intermediate means any chemical substance that is consumed, in whole or in part, in chemical reactions used for... for the purpose of altering the rates of such chemical reactions. (See also paragraph (j) of this... of a chemical reaction; except that mixture does include (1) any combination which occurs, in whole...

40 CFR 712.3 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

...) Intermediate means any chemical substance that is consumed, in whole or in part, in chemical reactions used for... for the purpose of altering the rates of such chemical reactions. (See also paragraph (j) of this... of a chemical reaction; except that mixture does include (1) any combination which occurs, in whole...

Force of crystallisation-development during CaO hydration: theory vs. experiment and the role of fluid transport

NASA Astrophysics Data System (ADS)

Wolterbeek, Tim; van Noort, Reinier; Spiers, Chris

2017-04-01

When chemical reactions that involve an increase in solid volume proceed in a confined space, this may under certain conditions lead to the development of a so-called force of crystallisation (FoC). In other words, reaction can result in stress being exerted on the confining boundaries of the system. In principle, any thermodynamic driving force that is able to produce a supersaturation with respect to a solid product can generate a FoC, as long as precipitation can occur under confined conditions, i.e. within load-bearing grain contacts. Well-known examples of such reactions include salt damage, where supersaturation is caused by evaporation and surface curvature effects, and a wide range of mineral reactions where the solid products comprise a larger volume than the solid reactants. Frost heave, where crystallisation is driven by fluid under-cooling, i.e. temperature change, is a similar process. In a geological context, FoC-development is widely considered to play an important role in pseudomorphic replacement, vein formation, and reaction-driven fracturing. Chemical reactions capable of producing a FoC such as the hydration of CaO (lime), which is thermodynamically capable of producing stresses in the GPa range, also offer obvious engineering potential. Despite this, relatively few studies have been conducted where the magnitude of the FoC is determined directly. Indeed, the maximum stress obtainable by CaO hydration has not been validated or determined experimentally. Here we report uni-axial compaction/expansion experiments performed in an oedometer-type apparatus on pre-compacted CaO powder, at 65 °C and at atmospheric pore fluid pressure. Using this set-up, the FoC generated during CaO hydration could be measured directly. Our results show FoC-induced stresses reaching up to 153 MPa, with the hydration reaction stopping or slowing down significantly before completion. Failure to achieve the GPa stresses predicted by thermodynamic theory is attributed to competition between FoC development and its inhibiting effect on reaction progress. Our microstructural observations indicate that hydration-induced stresses caused the shut-down of pathways for water into the sample, thereby hampering ongoing reaction and limiting the magnitude of stress build-up to the values observed.

Quantum dynamics of nuclear spins and spin relaxation in organic semiconductors

DOE PAGES

Mkhitaryan, V. V.; Dobrovitski, V. V.

2017-06-12

3D printing of materials with active functional groups can provide custom-designed structures that promote chemical conversions. Herein, catalytically active architectures were produced by photopolymerizing bifunctional molecules using a commercial stereolithographic 3D printer. Functionalities in the monomers included a polymerizable vinyl group to assemble the 3D structures and a secondary group to provide them with active sites. The 3D-printed architectures containing accessible carboxylic acid, amine, and copper carboxylate functionalities were catalytically active for the Mannich, aldol, and Huisgen cycloaddition reactions, respectively. The functional groups in the 3D-printed structures were also amenable to post-printing chemical modification. As proof of principle, chemically activemore » cuvette adaptors were 3D printed and used to measure in situ the kinetics of a heterogeneously catalyzed Mannich reaction in a conventional solution spectrophotometer. In addition, 3D-printed millifluidic devices with catalytically active copper carboxylate complexes were used to promote azide-alkyne cycloaddition under flow conditions. The importance of controlling the 3D architecture of the millifluidic devices was evidenced by enhancing reaction conversion upon increasing the complexity of the 3D prints.« less

State of Supported Nickel Nanoparticles during Catalysis in Aqueous Media

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

Chase, Zizwe; Kasakov, Stanislav; Shi, Hui

2015-11-09

The state of Ni supported on HZSM-5 zeolite, silica, and sulfonated carbon was determined during aqueous phase catalysis of phenol hydrodeoxygenation using in situ extended X-ray absorption fine structure spectroscopy (EXAFS). On sulfonated carbon and HZSM-5 supports, the NiO and Ni(OH)2 were readily reduced to Ni(0) under reaction conditions (~35 bar H2 in aqueous phenol solutions containing up to 0.5 wt. % phosphoric acid at 473 K). On the silica support, less than 70% of the Ni was converted to Ni(0) under reaction conditions, which is attributed to the formation of Ni phyllosilicates. Over a broad range of reaction conditionsmore » there was no leaching of Ni from the supports. In contrast, rapid leaching of the Ni(II) from HZSM-5 was observed, when 15 wt. % aqueous acetic acid was substituted for the aqueous phenol solution. Once the metallic state of Ni was established there was no leaching in 15 wt. % acetic acid at 473 K and 35 bar H2. This work was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Division of Chemical Sciences, Geosciences & Biosciences. The STEM was supported under the Laboratory Directed Research and Development Program: Chemical Imaging Initiative at Pacific Northwest National Laboratory (PNNL), a multi-program national laboratory operated for DOE by Battelle under Contract DE-AC05-76RL01830. STEM was performed at EMSL, a DOE Office of Science user facility sponsored by the Office of Biological and Environmental Research and located at PNNL.« less

Mechanisms of chemical vapor generation by aqueous tetrahydridoborate. Recent developments toward the definition of a more general reaction model

NASA Astrophysics Data System (ADS)

D'Ulivo, Alessandro

2016-05-01

A reaction model describing the reactivity of metal and semimetal species with aqueous tetrahydridoborate (THB) has been drawn taking into account the mechanism of chemical vapor generation (CVG) of hydrides, recent evidences on the mechanism of interference and formation of byproducts in arsane generation, and other evidences in the field of the synthesis of nanoparticles and catalytic hydrolysis of THB by metal nanoparticles. The new "non-analytical" reaction model is of more general validity than the previously described "analytical" reaction model for CVG. The non-analytical model is valid for reaction of a single analyte with THB and for conditions approaching those typically encountered in the synthesis of nanoparticles and macroprecipitates. It reduces to the previously proposed analytical model under conditions typically employed in CVG for trace analysis (analyte below the μM level, borane/analyte ≫ 103 mol/mol, no interference). The non-analytical reaction model is not able to explain all the interference effects observed in CVG, which can be achieved only by assuming the interaction among the species of reaction pathways of different analytical substrates. The reunification of CVG, the synthesis of nanoparticles by aqueous THB and the catalytic hydrolysis of THB inside a common frame contribute to rationalization of the complex reactivity of aqueous THB with metal and semimetal species.

Non-allergic cutaneous reactions in airborne chemical sensitivity--a population based study.

PubMed

Berg, Nikolaj Drimer; Linneberg, Allan; Thyssen, Jacob Pontoppidan; Dirksen, Asger; Elberling, Jesper

2011-06-01

Multiple chemical sensitivity (MCS) is characterised by adverse effects due to exposure to low levels of chemical substances. The aetiology is unknown, but chemical related respiratory symptoms have been found associated with positive patch test. The purpose of this study was to investigate the relationship between cutaneous reactions from patch testing and self-reported severity of chemical sensitivity to common airborne chemicals. A total of 3460 individuals participating in a general health examination, Health 2006, were patch tested with allergens from the European standard series and screened for chemical sensitivity with a standardised questionnaire dividing the participants into four severity groups of chemical sensitivity. Both allergic and non-allergic cutaneous reactions--defined as irritative, follicular, or doubtful allergic reactions--were analysed in relationship with severity of chemical sensitivity. Associations were controlled for the possible confounding effects of sex, age, asthma, eczema, atopic dermatitis, psychological and social factors, and smoking habits. In unadjusted analyses we found associations between allergic and non-allergic cutaneous reactions on patch testing and the two most severe groups of self-reported sensitivity to airborne chemicals. When adjusting for confounding, associations were weakened, and only non-allergic cutaneous reactions were significantly associated with individuals most severely affected by inhalation of airborne chemicals (odds ratio = 2.5, p = 0.006). Our results suggest that individuals with self-reported chemical sensitivity show increased non-allergic cutaneous reactions based on day 2 readings of patch tests. Copyright © 2011 Elsevier GmbH. All rights reserved.

Versatile Dual Photoresponsive System for Precise Control of Chemical Reactions.

PubMed

Xu, Can; Bing, Wei; Wang, Faming; Ren, Jinsong; Qu, Xiaogang

2017-08-22

A versatile method for photoregulation of chemical reactions was developed through a combination of near-infrared (NIR) and ultraviolet (UV) light sensitive materials. This regulatory effect was achieved through photoresponsive modulation of reaction temperature and pH values, two prominent factors influencing reaction kinetics. Photothermal nanomaterial graphene oxide (GO) and photobase reagent malachite green carbinol base (MGCB) were selected for temperature and pH regulation, respectively. Using nanocatalyst- and enzyme-mediated chemical reactions as model systems, we demonstrated the feasibility and high efficiency of this method. In addition, a photoresponsive, multifunctional "Band-aid"-like hydrogel platform was presented for programmable wound healing. Overall, this simple, efficient, and reversible system was found to be effective for controlling a wide variety of chemical reactions. Our work may provide a method for remote and sustainable control over chemical reactions for industrial and biomedical applications.

Influence of chemical reactions on the nonlinear dynamics of dissipative flows

NASA Astrophysics Data System (ADS)

Karimov, A. R.; Korshunov, A. M.; Beklemishev, V. V.

2015-08-01

The nonlinear dynamics of resistive flow with a chemical reaction is studied. Proceeding from the Lagrangian description, the influence of a chemical reaction on the development of fluid singularities is considered.

Flow chemistry using milli- and microstructured reactors-from conventional to novel process windows.

PubMed

Illg, Tobias; Löb, Patrick; Hessel, Volker

2010-06-01

The terminology Novel Process Window unites different methods to improve existing processes by applying unconventional and harsh process conditions like: process routes at much elevated pressure, much elevated temperature, or processing in a thermal runaway regime to achieve a significant impact on process performance. This paper is a review of parts of IMM's works in particular the applicability of above mentioned Novel Process Windows on selected chemical reactions. First, general characteristics of microreactors are discussed like excellent mass and heat transfer and improved mixing quality. Different types of reactions are presented in which the use of microstructured devices led to an increased process performance by applying Novel Process Windows. These examples were chosen to demonstrate how chemical reactions can benefit from the use of milli- and microstructured devices and how existing protocols can be changed toward process conditions hitherto not applicable in standard laboratory equipment. The used milli- and microstructured reactors can also offer advantages in other areas, for example, high-throughput screening of catalysts and better control of size distribution in a particle synthesis process by improved mixing, etc. The chemical industry is under continuous improvement. So, a lot of research is being done to synthesize high value chemicals, to optimize existing processes in view of process safety and energy consumption and to search for new routes to produce such chemicals. Leitmotifs of such undertakings are often sustainable development(1) and Green Chemistry(2).

A novel solid state photocatalyst for living radical polymerization under UV irradiation

NASA Astrophysics Data System (ADS)

Fu, Qiang; McKenzie, Thomas G.; Ren, Jing M.; Tan, Shereen; Nam, Eunhyung; Qiao, Greg G.

2016-02-01

This study presents the development of a novel solid state photocatalyst for the photoinduced controlled radical polymerization of methacrylates under mild UV irradiation (λmax ≈ 365 nm) in the absence of conventional photoinitiators, metal-catalysts or dye sensitizers. The photocatalyst design was based on our previous finding that organic amines can act in a synergistic photochemical reaction with thiocarbonylthio compounds to afford well controlled polymethacrylates under UV irradiation. Therefore, in the current contribution an amine-rich polymer was covalently grafted onto a solid substrate, thus creating a heterogeneous catalyst that would allow for facile removal, recovery and recyclability when employed for such photopolymerization reactions. Importantly, the polymethacrylates synthesized using the solid state photocatalyst (ssPC) show similarly excellent chemical and structural integrity as those catalysed by free amines. Moreover, the ssPC could be readily recovered and re-used, with multiple cycles of polymerization showing minimal effect on the integrity of the catalyst. Finally, the ssPC was employed in various photo-“click” reactions, permitting high yielding conjugations under photochemical control.

Chemical/Light-Powered Hybrid Micromotors with "On-the-Fly" Optical Brakes.

PubMed

Chen, Chuanrui; Tang, Songsong; Teymourian, Hazhir; Karshalev, Emil; Zhang, Fangyu; Li, Jinxing; Mou, Fangzhi; Liang, Yuyan; Guan, Jianguo; Wang, Joseph

2018-07-02

Hybrid micromotors capable of both chemically powered propulsion and fuel-free light-driven actuation and offering built-in optical brakes for chemical propulsion are described. The new hybrid micromotors are designed by combining photocatalytic TiO 2 and catalytic Pt surfaces into a Janus microparticle. The chemical reactions on the different surfaces of the Janus particle hybrid micromotor can be tailored by using chemical or light stimuli that generate counteracting propulsion forces on the catalytic Pt and photocatalytic TiO 2 sides. Such modulation of the surface chemistry on a single micromotor leads to switchable propulsion modes and reversal of the direction of motion that reflect the tuning of the local ion concentration and hence the dominant propulsion force. An intermediate Au layer (under the Pt surface) plays an important role in determining the propulsion mechanism and operation of the hybrid motor. The built-in optical braking system allows "on-the-fly" control of the chemical propulsion through a photocatalytic reaction on the TiO 2 side to counterbalance the chemical propulsion force generated on the Pt side. The adaptive dual operation of these chemical/light hybrid micromotors, associated with such control of the surface chemistry, holds considerable promise for designing smart nanomachines that autonomously reconfigure their propulsion mode for various on-demand operations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

PAH-Mineral Interactions. A Laboratory Approach to Astrophysical Catalysis

NASA Astrophysics Data System (ADS)

Adolfo Cruz Diaz, Gustavo; Mattioda, Andrew

2017-06-01

Polycyclic Aromatic Hydrocarbon (PAH) molecules carry the infrared emission features which dominate the spectra of most galactic and extragalactic sources. Our study investigates the chemical evolution, chemical properties, physical properties, thermal stability, and photostability of samples produced from the UV-irradiation of simulated mineral dust grains coated with aromatics and astrobiologically relevant ices, using infrared spectroscopy. We investigate the chemical evolution of aromatic organics via anhydrous (no H2O ice) and hydrous (H2O ice) mechanisms. The anhydrous mechanism involves UV-induced catalytic reactions between organics and dense-cloud mineral grains, whereas the hydrous mechanism incorporates H2O-rich ice mixtures with the minerals and organics. These investigations identify the chemical and physical interactions occurring between the organic species, the dust grains and water-rich ices.These laboratory simulations also generate observable IR spectroscopic parameters for future astronomical observations with infrared telescopes such as SOFIA and JWST as well as provide empirical parameters for input into astronomical models of the early stages of planetary formation. These studies give us a deeper understanding of the potential catalytic pathways mineral surfaces provide and a deeper understanding of the role of ice-organic compositions in the chemical reaction pathways and how these processes fit into the formation of new planetary systems.In order to achieve these goals we use the Harrick ‘Praying Mantis’ Diffuse Reflectance Accessory (DRIFTS), which allows FTIR measurements of dust samples under ambient conditions by measuring the light scattered by the dust sample. We have also incorporated a low -temperature reaction chamber permitting the DRIFTS measurements at low temperatures and high-vacuum. This set-up permits the analysis of the solid particles surfaces revealing the chemical species adsorbed as well as their chemical evolution via the introduction of reactant gases, UV irradiation, temperature change, etc.

Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities.

PubMed

Van Wyngarden, A L; Pérez-Montaño, S; Bui, J V H; Li, E S W; Nelson, T E; Ha, K T; Leong, L; Iraci, L T

Particles in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40-80 wt %) in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric aerosols and are potentially more important at the high acidities characteristic of UT/LS particles. In this study, experiments combining sulfuric acid (H 2 SO 4 ) with propanal and with mixtures of propanal with glyoxal and/or methylglyoxal at acidities typical of UT/LS aerosols produced highly colored surface films (and solutions) that may have implications for aerosol properties. In order to identify the chemical processes responsible for the formation of the surface films, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and 1 H nuclear magnetic resonance (NMR) spectroscopies were used to analyze the chemical composition of the films. Films formed from propanal were a complex mixture of aldol condensation products, acetals and propanal itself. The major aldol condensation products were the dimer (2-methyl-2-pentenal) and 1,3,5-trimethylbenzene that was formed by cyclization of the linear aldol condensation trimer. Additionally, the strong visible absorption of the films indicates that higher-order aldol condensation products must also be present as minor species. The major acetal species were 2,4,6-triethyl-1,3,5-trioxane and longer-chain linear polyacetals which are likely to separate from the aqueous phase. Films formed on mixtures of propanal with glyoxal and/or methylglyoxal also showed evidence of products of cross-reactions. Since cross-reactions would be more likely than self-reactions under atmospheric conditions, similar reactions of aldehydes like propanal with common aerosol organic species like glyoxal and methylglyoxal have the potential to produce significant organic aerosol mass and therefore could potentially impact chemical, optical and/or cloud-forming properties of aerosols, especially if the products partition to the aerosol surface.

Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities

PubMed Central

Van Wyngarden, A. L.; Pérez-Montaño, S.; Bui, J. V. H.; Li, E. S. W.; Nelson, T. E.; Ha, K. T.; Leong, L.; Iraci, L. T.

2016-01-01

Particles in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40–80 wt %) in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric aerosols and are potentially more important at the high acidities characteristic of UT/LS particles. In this study, experiments combining sulfuric acid (H2SO4) with propanal and with mixtures of propanal with glyoxal and/or methylglyoxal at acidities typical of UT/LS aerosols produced highly colored surface films (and solutions) that may have implications for aerosol properties. In order to identify the chemical processes responsible for the formation of the surface films, attenuated total reflectance–Fourier transform infrared (ATR-FTIR) and 1H nuclear magnetic resonance (NMR) spectroscopies were used to analyze the chemical composition of the films. Films formed from propanal were a complex mixture of aldol condensation products, acetals and propanal itself. The major aldol condensation products were the dimer (2-methyl-2-pentenal) and 1,3,5-trimethylbenzene that was formed by cyclization of the linear aldol condensation trimer. Additionally, the strong visible absorption of the films indicates that higher-order aldol condensation products must also be present as minor species. The major acetal species were 2,4,6-triethyl-1,3,5-trioxane and longer-chain linear polyacetals which are likely to separate from the aqueous phase. Films formed on mixtures of propanal with glyoxal and/or methylglyoxal also showed evidence of products of cross-reactions. Since cross-reactions would be more likely than self-reactions under atmospheric conditions, similar reactions of aldehydes like propanal with common aerosol organic species like glyoxal and methylglyoxal have the potential to produce significant organic aerosol mass and therefore could potentially impact chemical, optical and/or cloud-forming properties of aerosols, especially if the products partition to the aerosol surface. PMID:27212937

Explosion investigation of asphalt-salt mixtures in a reprocessing plant.

PubMed

Hasegawa, K; Li, Y

2000-12-15

Cause investigation of a fire and explosion at the nuclear fuel waste reprocessing plant indicated that self-heating ignition of an asphalt-salt-waste, bituminized, mixture (AS) caused the disaster. A 220l drum was filled with the AS at a temperature of about 180 degrees C. About 20h later the drum ignited and burned as it was being cooled. It is estimated that the AS contained approximately 55wt.% blown asphalt, 25wt.% NaNO(3), 5wt.% NaNO(2), 8wt.% Na(2)CO(3), 2wt.% NaH(2)PO(4), 1wt.% Ba (OH)(2), 1wt.% K(4)[Fe(CN)(6)], and possibly 3wt.% of other materials. To determine the reaction promoting factors and pertinent chemical reaction rates, self-reaction of the AS has been investigated by the use of a C80D heat flux reaction calorimeter. The oxidizing reactions with asphalt are ruled by NaNO(2) rather than by NaNO(3), in spite of a lower concentration of NaNO(2). The kinetic rates of the interfacial reaction between salt particles and asphalt for the reaction controlled and diffusion controlled steps have been formulated as a function of salt particle size for both NaNO(2) and NaNO(3). Numerical solution of the heat balance equations formulating the heterogeneous reaction scheme indicates that a runaway reaction occurs when the AS-filling temperature is 208 degrees C for a drum filled with an AS mixture produced under standard operating conditions. Molecules containing intramolecular hydrogen, such as Na(2)HPO(4) and NaHCO(3), do not oxidize asphalt directly, however, their presence chemically promotes the oxidizing reaction of NaNO(2). Moreover, NaHCO(3) decomposition which produces gases creates many micro holes in the interior of the salt particles. This in turn promotes the oxidizing reactions that are diffusion controlled. Finally, the consequence of a runaway reaction at 180 degrees C or lower is qualitatively explained by taking into account the chemical effect of intramolecular hydrogen and the physical effect of the NaHCO(3) decomposition gases.

Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit

DOE PAGES

Lucci, Felicia R.; Liu, Jilei; Marcinkowski, Matthew D.; ...

2015-10-09

Platinum is ubiquitous in the production sectors of chemicals and fuels; however, its scarcity in nature and high price will limit future proliferation of platinum-catalysed reactions. One definite approach to conserve platinum involves understanding the smallest number of platinum atoms needed to catalyse a reaction, then designing catalysts with the minimal platinum ensembles. Here we design and test a new generation of platinum–copper nanoparticle catalysts for the selective hydrogenation of 1,3-butadiene,, an industrially important reaction. Isolated platinum atom geometries enable hydrogen activation and spillover but are incapable of C–C bond scission that leads to loss of selectivity and catalyst deactivation.more » γ-Alumina-supported single-atom alloy nanoparticle catalysts with <1 platinum atom per 100 copper atoms are found to exhibit high activity and selectivity for butadiene hydrogenation to butenes under mild conditions, demonstrating transferability from the model study to the catalytic reaction under practical conditions.« less

X-ray induced chemical reaction revealed by in-situ X-ray diffraction and scanning X-ray microscopy in 15 nm resolution (Conference Presentation)

NASA Astrophysics Data System (ADS)

Ge, Mingyuan; Liu, Wenjun; Bock, David; De Andrade, Vincent; Yan, Hanfei; Huang, Xiaojing; Marschilok, Amy; Takeuchi, Esther; Xin, Huolin; Chu, Yong S.

2016-09-01

The detection sensitivity of synchrotron-based X-ray techniques has been largely improved due to the ever increasing source brightness, which have significantly advanced ex-situ and in-situ research for energy materials, such as lithium-ion batteries. However, the strong beam-matter interaction arisen from the high beam flux can significantly modify the material structure. The parasitic beam-induced effect inevitably interferes with the intrinsic material property, which brings difficulties in interpreting experimental results, and therefore requires comprehensive evaluation. Here we present a quantitative in-situ study of the beam-effect on one electrode material Ag2VO2PO4 using four different X-ray probes with different radiation dose rate. The material system we reported exhibits interesting and reversible radiation-induced thermal and chemical reactions, which was further evaluated under electron microscopy to illustrate the underlying mechanism. The work we presented here will provide a guideline in using synchrotron X-rays to distinguish the materials' intrinsic behavior from extrinsic structure changed induced by X-rays, especially in the case of in-situ and operando study where the materials are under external field of either temperature or electric field.

Imaging chemical reactions - 3D velocity mapping

NASA Astrophysics Data System (ADS)

Chichinin, A. I.; Gericke, K.-H.; Kauczok, S.; Maul, C.

Visualising a collision between an atom or a molecule or a photodissociation (half-collision) of a molecule on a single particle and single quantum level is like watching the collision of billiard balls on a pool table: Molecular beams or monoenergetic photodissociation products provide the colliding reactants at controlled velocity before the reaction products velocity is imaged directly with an elaborate camera system, where one should keep in mind that velocity is, in general, a three-dimensional (3D) vectorial property which combines scattering angles and speed. If the processes under study have no cylindrical symmetry, then only this 3D product velocity vector contains the full information of the elementary process under study.

Systematic trends in photonic reagent induced reactions in a homologous chemical family.

PubMed

Tibbetts, Katharine Moore; Xing, Xi; Rabitz, Herschel

2013-08-29

The growing use of ultrafast laser pulses to induce chemical reactions prompts consideration of these pulses as "photonic reagents" in analogy to chemical reagents. This work explores the prospect that photonic reagents may affect systematic trends in dissociative ionization reactions of a homologous family of halomethanes, much as systematic outcomes are often observed for reactions between homologous families of chemical reagents and chemical substrates. The experiments in this work with photonic reagents of varying pulse energy and linear spectral chirp reveal systematic correlations between observable ion yields and the following set of natural variables describing the substrate molecules: the ionization energy of the parent molecule, the appearance energy of each fragment ion, and the relative strength of carbon-halogen bonds in molecules containing two different halogens. The results suggest that reactions induced by photonic reagents exhibit systematic behavior analogous to that observed in reactions driven by chemical reagents, which provides a basis to consider empirical "rules" for predicting the outcomes of photonic reagent induced reactions.

40 CFR 721.9280 - Reaction product of ethoxylated fatty acid oils and a phenolic pentaerythritol tetraester.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Reaction product of ethoxylated fatty... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9280 Reaction product of... new uses subject to reporting. (1) The chemical substance identified generically as a reaction product...

40 CFR 721.9280 - Reaction product of ethoxylated fatty acid oils and a phenolic pentaerythritol tetraester.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Reaction product of ethoxylated fatty... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9280 Reaction product of... new uses subject to reporting. (1) The chemical substance identified generically as a reaction product...

40 CFR 721.9280 - Reaction product of ethoxylated fatty acid oils and a phenolic pentaerythritol tetraester.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Reaction product of ethoxylated fatty... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9280 Reaction product of... new uses subject to reporting. (1) The chemical substance identified generically as a reaction product...

40 CFR 721.9280 - Reaction product of ethoxylated fatty acid oils and a phenolic pentaerythritol tetraester.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of ethoxylated fatty... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9280 Reaction product of... new uses subject to reporting. (1) The chemical substance identified generically as a reaction product...

40 CFR 721.9280 - Reaction product of ethoxylated fatty acid oils and a phenolic pentaerythritol tetraester.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of ethoxylated fatty... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9280 Reaction product of... new uses subject to reporting. (1) The chemical substance identified generically as a reaction product...

Process for preparing a chemical compound enriched in isotope content

DOEpatents

Michaels, Edward D.

1982-01-01

A process to prepare a chemical enriched in isotope content which includes: (a) A chemical exchange reaction between a first and second compound which yields an isotopically enriched first compound and an isotopically depleted second compound; (b) the removal of a portion of the first compound as product and the removal of a portion of the second compound as spent material; (c) the conversion of the remainder of the first compound to the second compound for reflux at the product end of the chemical exchange reaction region; (d) the conversion of the remainder of the second compound to the first compound for reflux at the spent material end of the chemical exchange region; and the cycling of the additional chemicals produced by one conversion reaction to the other conversion reaction, for consumption therein. One of the conversion reactions is an oxidation reaction, and the energy that it yields is used to drive the other conversion reaction, a reduction. The reduction reaction is carried out in a solid polymer electrolyte electrolytic reactor. The overall process is energy efficient and yields no waste by-products.

REACTIONS OF FUEL NITROGEN COMPOUNDS UNDER CONDITIONS OF INERT PYROLYSIS

EPA Science Inventory

The paper describes the pyrolysis of fossil fuels and model nitrogen compounds in helium in a small quartz plow reactor, as part of a study of the chemical mechanisms involved in the conversion of fuel-nitrogen compounds to nitric oxide (NO) during combustion. Hydrogen cyanide (H...

Highly chemoselective esterification reactions and Boc/THP/TBDMS discriminating deprotections under samarium(III) catalysis.

PubMed

Gopinath, Pushparathinam; Nilaya, Surapaneni; Muraleedharan, Kannoth Manheri

2011-04-15

The usefulness of SmCl(3) as an excellent catalyst for chemoselective esterifications and selective removal of acid sensitive protecting groups such as Boc, THP, and TBDMS in the presence of one another is demonstrated through suitable examples. © 2011 American Chemical Society

AN ENVIRONMENTAL TECHNOLOGY VERIFICATION (ETV) TESTING OF ENZYMATIC TEST KITS FOR WARFARE AGENTS AND PESTICIDES IN DRINKING WATER

EPA Science Inventory

Enzymatic test kits, generally designed to be handheld and portable, detect the presence of chemical agents, carbamate pesticides, and/or organophosphate pesticides by relying on the reaction of the cholinesterase enzyme. Under normal conditions, the enzyme reacts as expected wi...

Reply to Comment on ‘The cancer Warburg effect may be a testable example of the minimum entropy production rate principle’

NASA Astrophysics Data System (ADS)

Sabater, Bartolomé; Marín, Dolores

2018-03-01

The minimum rate principle is applied to the chemical reaction in a steady-state open cell system where, under constant supply of the glucose precursor, reference to time or to glucose consumption does not affect the conclusions.

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...

Ab initio Quantum Chemical and Experimental Reaction Kinetics Studies in the Combustion of Bipropellants

DTIC Science & Technology

2017-03-24

NUMBER (Include area code) 24 March 2017 Briefing Charts 01 March 2017 - 31 March 2017 Ab initio Quantum Chemical and Experimental Reaction Kinetics...Laboratory AFRL/RQRS 1 Ara Road Edwards AFB, CA 93524 *Email: ghanshyam.vaghjiani@us.af.mil Ab initio Quantum Chemical and Experimental Reaction ...Clearance 17161 Zador et al., Prog. Energ. Combust. Sci., 37 371 (2011) Why Quantum Chemical Reaction Kinetics Studies? DISTRIBUTION A: Approved for

TOUGHREACT: a new code of the TOUGH Family for Non-Isothermal multiphase reactive geochemical transport in variably saturated geologic media

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

Xu, Tianfu; Sonnenthal, Eric; Spycher, Nicolas

Coupled modeling of subsurface multiphase fluid and heat flow, solute transport and chemical reactions can be used for the assessment of acid mine drainage remediation, waste disposal sites, hydrothermal convection, contaminant transport, and groundwater quality. We have developed a comprehensive numerical simulator, TOUGHREACT, which considers non-isothermal multi-component chemical transport in both liquid and gas phases. A wide range of subsurface thermo-physical-chemical processes is considered under various thermohydrological and geochemical conditions of pressure, temperature, water saturation, and ionic strength. The code can be applied to one-, two- or three-dimensional porous and fractured media with physical and chemical heterogeneity.

Chemical characterization of diesel and hydrotreated vegetable oil (HVO) soot after reactive gas probing using diffuse reflectance FTIR spectroscopy (DRIFTS).

PubMed

Tapia, A; Salgado, M S; Martín, M P; Rodríguez-Fernández, J; Rossi, M J; Cabañas, B

2017-03-01

A chemical characterization of diesel and hydrotreated vegetable oil (HVO) soot has been developed using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) before and after the reaction with different probe gases. Samples were generated under combustion conditions corresponding to an urban operation mode of a diesel engine and were reacted with probe gas-phase molecules in a Knudsen flow reactor. Specifically, NH 2 OH, O 3 and NO 2 were used as reactants (probes) and selected according to their reactivities towards specific functional groups on the sample surface. Samples of previously ground soot were diluted with KBr and were introduced in a DRIFTS accessory. A comparison between unreacted and reacted soot samples was made in order to establish chemical changes on the soot surface upon reaction. It was concluded that the interface of diesel and HVO soot before reaction mainly consists polycyclic aromatic hydrocarbons, nitro and carbonyl compounds, as well as ether functionalities. The main difference between both soot samples was observed in the band of the C=O groups that in diesel soot was observed at 1719 cm -1 but not in HVO soot. After reaction with probe gases, it was found that nitro compounds remain on the soot surface, that the degree of unsaturation decreases for reacted samples, and that new spectral bands such as hydroxyl groups are observed.

Thermal decomposition of the solid phase of nitromethane: ab initio molecular dynamics simulations.

PubMed

Chang, Jing; Lian, Peng; Wei, Dong-Qing; Chen, Xiang-Rong; Zhang, Qing-Ming; Gong, Zi-Zheng

2010-10-29

The Car-Parrinello molecular dynamics simulations were employed to investigate thermal decomposition of the solid nitromethane. It is found that it undergoes chemical decomposition at about 2200 K under ambient pressure. The initiation of reactions involves both proton transfer and commonly known C-N bond cleavage. About 75 species and 100 elementary reactions were observed with the final products being H2O, CO2, N2, and CNCNC. It represents the first complete simulation of solid-phase explosive reactions reported to date, which is of far-reaching implication for design and development of new energetic materials.

Fluorogenic Behaviour of the Hetero-Diels-Alder Ligation of 5-Alkoxyoxazoles with Maleimides and their Applications.

PubMed

Renault, Kévin; Jouanno, Laurie-Anne; Lizzul-Jurse, Antoine; Renard, Pierre-Yves; Sabot, Cyrille

2016-12-19

Fluorogenic reactions are largely underrepresented in the toolbox of chemoselective ligations despite their tremendous potential, particularly in chemical biology and biochemistry. In this respect, we have investigated in full detail the fluorescence behaviour of the azaphthalamide, a scaffold which is generated through a hetero-Diels-Alder reaction of 5-alkoxyoxazole and maleimide derivatives under mild conditions that are compatible with, among others, peptide chemistry. The scope and limitations of such a fluorogenic labelling strategy were examined through four distinct applications, which target enzymatic activities or bioorthogonal reactions. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

General Solutions for Hydromagnetic Free Convection Flow over an Infinite Plate with Newtonian Heating, Mass Diffusion and Chemical Reaction

NASA Astrophysics Data System (ADS)

Fetecau, Constatin; Shah, Nehad Ali; Vieru, Dumitru

2017-12-01

The problem of hydromagnetic free convection flow over a moving infinite vertical plate with Newtonian heating, mass diffusion and chemical reaction in the presence of a heat source is completely solved. Radiative and porous effects are not taken into consideration but they can be immediately included by a simple rescaling of Prandtl number and magnetic parameter. Exact general solutions for the dimensionless velocity and concentration fields and the corresponding Sherwood number and skin friction coefficient are determined under integral form in terms of error function or complementary error function of Gauss. They satisfy all imposed initial and boundary conditions and can generate exact solutions for any problem with technical relevance of this type. As an interesting completion, uncommon in the literature, the differential equations which describe the thermal, concentration and momentum boundary layer, as well as the exact expressions for the thicknesses of thermal, concentration or velocity boundary layers were determined. Numerical results have shown that the thermal boundary layer thickness decreases for increasing values of Prandtl number and the concentration boundary layer thickness is decreasing with Schmidt number. Finally, for illustration, three special cases are considered and the influence of physical parameters on some fundamental motions is graphically underlined and discussed. The required time to reach the flow according with post-transient solution (the steady-state), for cosine/sine oscillating concentrations on the boundary is graphically determined. It is found that, the presence of destructive chemical reaction improves this time for increasing values of chemical reaction parameter.

Degradation kinetics of aflatoxin B1 and B2 in solid medium by using pulsed light irradiation.

PubMed

Wang, Bei; Mahoney, Noreen E; Khir, Ragab; Wu, Bengang; Zhou, Cunshan; Pan, Zhongli; Ma, Haile

2018-04-10

Pulsed light (PL) is a new potential technology to degrade aflatoxin. The objective of this study was to investigate the degradation characters of aflatoxin B 1 (AFB 1 ) and B 2 (AFB 2 ) treated under PL irradiation. A kinetic degradation study of AFB 1 and AFB 2 in solid medium was performed under PL irradiation at different initial concentrations of AFB 1 (229.9, 30.7 and 17.8 μg kg -1 ) and AFB 2 (248.2, 32.2 and 19.5 μg kg -1 ) and irradiation intensities (2.86, 1.60 and 0.93 W cm -2 ) of PL. A second-order reaction model was applied to describe degradation of AFB 1 and AFB 2 . The results showed that the degradation of AFB 1 and AFB 2 followed the second-order reaction kinetic model well (R 2  > 0.97). The degradation rate was proportional to the intensities of PL irradiation and the initial concentrations of aflatoxins. It is concluded that the degradation of AFB 1 and AFB 2 with the use of PL could be accurately described using the second-order reaction kinetic model. © 2018 Society of Chemical Industry. © 2018 Society of Chemical Industry.

Chemical kinetics of multiphase reactions between ozone and human skin lipids: Implications for indoor air quality and health effects.

PubMed

Lakey, P S J; Wisthaler, A; Berkemeier, T; Mikoviny, T; Pöschl, U; Shiraiwa, M

2017-07-01

Ozone reacts with skin lipids such as squalene, generating an array of organic compounds, some of which can act as respiratory or skin irritants. Thus, it is important to quantify and predict the formation of these products under different conditions in indoor environments. We developed the kinetic multilayer model that explicitly resolves mass transport and chemical reactions at the skin and in the gas phase (KM-SUB-Skin). It can reproduce the concentrations of ozone and organic compounds in previous measurements and new experiments. This enabled the spatial and temporal concentration profiles in the skin oil and underlying skin layers to be resolved. Upon exposure to ~30 ppb ozone, the concentrations of squalene ozonolysis products in the gas phase and in the skin reach up to several ppb and on the order of ~10 mmol m -3 . Depending on various factors including the number of people, room size, and air exchange rates, concentrations of ozone can decrease substantially due to reactions with skin lipids. Ozone and dicarbonyls quickly react away in the upper layers of the skin, preventing them from penetrating deeply into the skin and hence reaching the blood. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Application of mixing-controlled combustion models to gas turbine combustors

NASA Technical Reports Server (NTRS)

Nguyen, Hung Lee

1990-01-01

Gas emissions were studied from a staged Rich Burn/Quick-Quench Mix/Lean Burn combustor were studied under test conditions encountered in High Speed Research engines. The combustor was modeled at conditions corresponding to different engine power settings, and the effect of primary dilution airflow split on emissions, flow field, flame size and shape, and combustion intensity, as well as mixing, was investigated. A mathematical model was developed from a two-equation model of turbulence, a quasi-global kinetics mechanism for the oxidation of propane, and the Zeldovich mechanism for nitric oxide formation. A mixing-controlled combustion model was used to account for turbulent mixing effects on the chemical reaction rate. This model assumes that the chemical reaction rate is much faster than the turbulent mixing rate.

Late-Stage Functionalization of Arylacetic Acids by Photoredox-Catalyzed Decarboxylative Carbon-Heteroatom Bond Formation.

PubMed

Sakakibara, Yota; Ito, Eri; Fukushima, Tomohiro; Murakami, Kei; Itami, Kenichiro

2018-05-02

The rapid transformation of pharmaceuticals and agrochemicals enables access to unexplored chemical space and thus has accelerated the discovery of novel bioactive molecules. Because arylacetic acids are regarded as key structures in bioactive compounds, new transformations of these structures could contribute to drug/agrochemical discovery and chemical biology. This work reports carbon-nitrogen and carbon-oxygen bond formation through the photoredox-catalyzed decarboxylation of arylacetic acids. The reaction shows good functional group compatibility without pre-activation of the nitrogen- or oxygen-based coupling partners. Under similar reaction conditions, carbon-chlorine bond formation was also feasible. This efficient derivatization of arylacetic acids makes it possible to synthesize pharmaceutical analogues and bioconjugates of pharmaceuticals and natural products. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical modification of cellulosic fibers for better convertibility in packaging applications.

PubMed

Vuoti, Sauli; Laatikainen, Elina; Heikkinen, Harri; Johansson, Leena-Sisko; Saharinen, Erkki; Retulainen, Elias

2013-07-25

Cellulose fiber has been modified by mechanical and chemical means in order to improve paper properties, which respond to moisture and temperature. When the cellulose is first refined and then etherified using hydroxypropylation under dry conditions, the paper sheets prepared from the hydroxypropylated cellulose show improved elongation. When the level of hydroxypropylation is high enough, the paper sheets also become transparent. Additionally, the effect of cellulose activation using different mechanical methods has been compared by esterification reactions. It is shown that removal of water is the most crucial step for the esterification reactions while other methods have a lesser impact. The paper sheets prepared from the esterified cellulose fibers show an increase in contact angles and high hydrophobicity. Copyright © 2012 Elsevier Ltd. All rights reserved.

Hot spot initiation and chemical reaction in shocked polymeric bonded explosives

NASA Astrophysics Data System (ADS)

An, Qi; Zybin, Sergey; Jaramillo-Botero, Andres; Goddard, William; Materials; Process Simulation Center, Caltech Team

2011-06-01

A polymer bonded explosive (PBX) model based on PBXN-106 is studied via molecular dynamics (MD) simulations using reactive force field (ReaxFF) under shock loading conditions. Hotspot is observed when shock waves pass through the non-planar interface of explosives and elastomers. Adiabatic shear localization is proposed as the main mechanism of hotspot ignition in PBX for high velocity impact. Our simulation also shows that the coupling of shear localization and chemical reactions at hotspot region play important rules at stress relaxtion for explosives. The phenomenon that shock waves are obsorbed by elastomers is also observed in the MD simulations. This research received supports from ARO (W911NF-05-1-0345; W911NF-08-1-0124), ONR (N00014-05-1-0778), and Los Alamos National Laboratory (LANL).

Silicon production process evaluations

NASA Technical Reports Server (NTRS)

1982-01-01

Chemical engineering analyses involving the preliminary process design of a plant (1,000 metric tons/year capacity) to produce silicon via the technology under consideration were accomplished. Major activities in the chemical engineering analyses included base case conditions, reaction chemistry, process flowsheet, material balance, energy balance, property data, equipment design, major equipment list, production labor and forward for economic analysis. The process design package provided detailed data for raw materials, utilities, major process equipment and production labor requirements necessary for polysilicon production in each process.

New Directions in X-Ray Light Sources or Fiat Lux: what's under the dome and watching atoms with x-rays (LBNL Summer Lecture Series)

ScienceCinema

Falcone, Roger [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS); Univ. of California, Berkeley, CA (United States). Dept. of Physics

2018-05-04

Summer Lecture Series 2008: Molecular movies of chemical reactions and material phase transformations need a strobe of x-rays, the penetrating light that reveals how atoms and molecules assemble in chemical and biological systems and complex materials. Roger Falcone, Director of the Advanced Light Source,will discuss a new generation of x ray sources that will enable a new science of atomic dynamics on ultrafast timescales.

Cross-linked chitosan aerogel modified with Au: Synthesis, characterization and catalytic application.

PubMed

Keshipour, Sajjad; Mirmasoudi, Seyyedeh Sahra

2018-09-15

Dimercaprol as the chelating agent of Au(III) was loaded on chitosan aerogel. Dimercaprol supported on chitosan aerogel efficiently was complexed with Au(III). The new organometallic compound showed good catalytic activity in the oxidation reaction of some aliphatic alcohols, benzyl alcohol, and ethylbenzene. High conversions and excellent selectivities were obtained in the solvent-free oxidation reactions under mild reaction conditions. Also, turnover numbers were calculated for the oxidation reactions with 203, 134, 308, 282, 392, and 153 for 1-pentanol, 1-octanol, 2-propanol, 2-butanol, benzyl alcohol, and ethylbenzene, respectively. The organometallic compound is applicable as a heterogeneous Au(III) catalyst with high chemical stabilityand recyclability up to 6 times. Copyright © 2018 Elsevier Ltd. All rights reserved.

Production of Organic Grain Coatings by Surface-Mediated Reactions and the Consequences of This Process for Meteoritic Constituents

NASA Technical Reports Server (NTRS)

Nuth, Joseph A., III; Johnson, Natasha M.

2011-01-01

When hydrogen, nitrogen and CO are exposed to amorphous iron silicate surfaces at temperatures between 500 - 900K, a carbonaceous coating forms via Fischer-Tropsch type reactions. Under normal circumstances such a catalytic coating would impede or stop further reaction. However, we find that this coating is a better catalyst than the amorphous iron silicates that initiate these reactions. The formation of a self-perpetuating catalytic coating on grain surfaces could explain the rich deposits of macromolecular carbon found in primitive meteorites and would imply that protostellar nebulae should be rich in organic material. Many more experiments are needed to understand this chemical system and its application to protostellar nebulae.

An efficient laser vaporization source for chemically modified metal clusters characterized by thermodynamics and kinetics

NASA Astrophysics Data System (ADS)

Masubuchi, Tsugunosuke; Eckhard, Jan F.; Lange, Kathrin; Visser, Bradley; Tschurl, Martin; Heiz, Ulrich

2018-02-01

A laser vaporization cluster source that has a room for cluster aggregation and a reactor volume, each equipped with a pulsed valve, is presented for the efficient gas-phase production of chemically modified metal clusters. The performance of the cluster source is evaluated through the production of Ta and Ta oxide cluster cations, TaxOy+ (y ≥ 0). It is demonstrated that the cluster source produces TaxOy+ over a wide mass range, the metal-to-oxygen ratio of which can easily be controlled by changing the pulse duration that influences the amount of reactant O2 introduced into the cluster source. Reaction kinetic modeling shows that the generation of the oxides takes place under thermalized conditions at less than 300 K, whereas metal cluster cores are presumably created with excess heat. These characteristics are also advantageous to yield "reaction intermediates" of interest via reactions between clusters and reactive molecules in the cluster source, which may subsequently be mass selected for their reactivity measurements.

Advanced functionalization of polyhydroxyalkanoate via the UV-initiated thiol-ene click reaction.

PubMed

Tajima, Kenji; Iwamoto, Kosuke; Satoh, Yasuharu; Sakai, Ryosuke; Satoh, Toshifumi; Dairi, Tohru

2016-05-01

Polyhydroxyalkanoates (PHAs) incorporating vinyl-bearing 3-hydroxyalkanoates were prepared in 8.5-12.9 g L(-1) yield. The molar ratios (0-16 mol%) of the vinyl-bearing 3-hydroxyalkanoate derivatives were controlled by the continuous feeding of undecylenate at various concentrations. Subsequently, the PHAs were functionalized by UV-initiated thiol-ene click reaction and chemical modification. (1)H NMR spectra suggested that 3-mercaptopropionic acid and 2-aminoethanethiol were successfully introduced into the vinyl-bearing PHA. Subsequently, chemical modification using fluorescein or a fibronectin active fragment (GRGDS) was attempted. The former yielded a PHA derivative capable of emitting fluorescence under UV irradiation, which was useful for determining the miscibility of PHA in a composite film comprising poly-ʟ-lactic acid (PLLA) and PHA. In the latter case, PHA bearing GRGDS peptides exhibited cell adhesiveness, suggesting that its biocompatibility was improved upon peptide introduction. Taken together, the UV-initiated thiol-ene click reaction was demonstrated to be useful in PHA modification.

Understanding and controlling the substrate effect on graphene electron-transfer chemistry via reactivity imprint lithography

NASA Astrophysics Data System (ADS)

Wang, Qing Hua; Jin, Zhong; Kim, Ki Kang; Hilmer, Andrew J.; Paulus, Geraldine L. C.; Shih, Chih-Jen; Ham, Moon-Ho; Sanchez-Yamagishi, Javier D.; Watanabe, Kenji; Taniguchi, Takashi; Kong, Jing; Jarillo-Herrero, Pablo; Strano, Michael S.

2012-09-01

Graphene has exceptional electronic, optical, mechanical and thermal properties, which provide it with great potential for use in electronic, optoelectronic and sensing applications. The chemical functionalization of graphene has been investigated with a view to controlling its electronic properties and interactions with other materials. Covalent modification of graphene by organic diazonium salts has been used to achieve these goals, but because graphene comprises only a single atomic layer, it is strongly influenced by the underlying substrate. Here, we show a stark difference in the rate of electron-transfer reactions with organic diazonium salts for monolayer graphene supported on a variety of substrates. Reactions proceed rapidly for graphene supported on SiO2 and Al2O3 (sapphire), but negligibly on alkyl-terminated and hexagonal boron nitride (hBN) surfaces, as shown by Raman spectroscopy. We also develop a model of reactivity based on substrate-induced electron-hole puddles in graphene, and achieve spatial patterning of chemical reactions in graphene by patterning the substrate.

Inactivation of phosphorylase b by potassium ferrate, a new reactive analogue of the phosphate group.

PubMed

Lee, Y M; Benisek, W F

1976-03-25

Rabbit muscle phosphorylase b reacts with the phosphate-like reagent potassium ferrate, K2FeO4, a potent oxidizing agent. The reaction results in inactivation of the enzyme and abolition of the ability of the enzyme to bind 5'-AMP. Activating and nonactivating nucleotides which bind at the 5'-AMP binding site such as 5'-AMP, 2'-AMP, 3'-AMP, and 5'-IMP substantially protect the enzyme from inactivation by ferrate. One to two residues of tyrosine and approximately 1 residue of cysteine are modified by ferrate under the conditions employed. Tyrosine is protected by 5-AMP, whereas cysteine is not. The tyrosine modification is suggested as the inactivating chemical reaction. The location of the inactivating reaction is suggested to be in or near the 5'-AMP binding site. The structural and chemical properties of ferrate ion are discussed and compared to those of phosphate. Ferrate ion may be a reagent useful for phosphate group binding site-directed modification of proteins.

Enhanced Photoreduction of Nitro-aromatic Compounds by Hydrated Electrons Derived from Indole on Natural Montmorillonite.

PubMed

Tian, Haoting; Guo, Yong; Pan, Bo; Gu, Cheng; Li, Hui; Boyd, Stephen A

2015-07-07

A new photoreduction pathway for nitro-aromatic compounds (NACs) and the underlying degradation mechanism are described. 1,3-Dinitrobenzene was reduced to 3-nitroaniline by the widely distributed aromatic molecule indole; the reaction is facilitated by montmorillonite clay mineral under both simulated and natural sunlight irradiation. The novel chemical reaction is strongly affected by the type of exchangeable cation present on montmorillonite. The photoreduction reaction is initiated by the adsorption of 1,3-dinitrobenzene and indole in clay interlayers. Under light irradiation, the excited indole molecule generates a hydrated electron and the indole radical cation. The structural negative charge of montmorillonite plausibly stabilizes the radical cation hence preventing charge recombination. This promotes the release of reactive hydrated electrons for further reductive reactions. Similar results were observed for the photoreduction of nitrobenzene. In situ irradiation time-resolved electron paramagnetic resonance and Fourier transform infrared spectroscopies provided direct evidence for the generation of hydrated electrons and the indole radical cations, which supported the proposed degradation mechanism. In the photoreduction process, the role of clay mineral is to both enhance the generation of hydrated electrons and to provide a constrained reaction environment in the galley regions, which increases the probability of contact between NACs and hydrated electrons.

Interplay between Reaction and Phase Behaviour in Carbon Dioxide Hydrogenation to Methanol.

PubMed

Reymond, Helena; Amado-Blanco, Victor; Lauper, Andreas; Rudolf von Rohr, Philipp

2017-03-22

Condensation promotes CO 2 hydrogenation to CH 3 OH beyond equilibrium through in situ product separation. Although primordial for catalyst and reactor design, triggering conditions as well as the impact on sub-equilibrium reaction behaviour remain unclear. Herein we used an in-house designed micro-view-cell to gain chemical and physical insights into reaction and phase behaviour under high-pressure conditions over a commercial Cu/ZnO/Al 2 O 3 catalyst. Raman microscopy and video monitoring, combined with online gas chromatography analysis, allowed the complete characterisation of the reaction bulk up to 450 bar (1 bar=0.1 MPa) and 350 °C. Dew points of typical effluent streams related to a parametric study suggest that the improving reaction performance and reverting selectivities observed from 230 °C strongly correlate with (i) a regime transition from kinetic to thermodynamic, and (ii) a phase transition from a single supercritical to a biphasic reaction mixture. Our results advance a rationale behind transitioning CH 3 OH selectivities for an improved understanding of CO 2 hydrogenation under high pressure. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Subsurface conditions in hydrothermal vents inferred from diffuse flow composition, and models of reaction and transport

NASA Astrophysics Data System (ADS)

Larson, B. I.; Houghton, J. L.; Lowell, R. P.; Farough, A.; Meile, C. D.

2015-08-01

Chemical gradients in the subsurface of mid-ocean ridge hydrothermal systems create an environment where minerals precipitate and dissolve and where chemosynthetic organisms thrive. However, owing to the lack of easy access to the subsurface, robust knowledge of the nature and extent of chemical transformations remains elusive. Here, we combine measurements of vent fluid chemistry with geochemical and transport modeling to give new insights into the under-sampled subsurface. Temperature-composition relationships from a geochemical mixing model are superimposed on the subsurface temperature distribution determined using a heat flow model to estimate the spatial distribution of fluid composition. We then estimate the distribution of Gibb's free energies of reaction beneath mid oceanic ridges and by combining flow simulations with speciation calculations estimate anhydrite deposition rates. Applied to vent endmembers observed at the fast spreading ridge at the East Pacific Rise, our results suggest that sealing times due to anhydrite formation are longer than the typical time between tectonic and magmatic events. The chemical composition of the neighboring low temperature flow indicates relatively uniform energetically favorable conditions for commonly inferred microbial processes such as methanogenesis, sulfate reduction and numerous oxidation reactions, suggesting that factors other than energy availability may control subsurface microbial biomass distribution. Thus, these model simulations complement fluid-sample datasets from surface venting and help infer the chemical distribution and transformations in subsurface flow.

Kinetic calorimetry in the study of the mechanism of low-temperature chemical reactions

NASA Astrophysics Data System (ADS)

Barkalov, I. M.; Kiryukhin, D. P.

Chemical reactions are always followed by a change in the reacting system enthalpy, hence, calorimetry as a method of enthalpy and heat capacity measuring is a universal and, sometimes, even the only possible way of studying chemical reaction kinetics. Throughout its long history, the calorimeter, having preserved the positions of the main method of thermodynamic studies, has conquered a new field of application: that of kinetic study of chemical reactions. The advantages and disadvantages of the kinetic calorimeter are now obvious. First, the advantages are: (1) the possibility of measuring the rate of a chemical reaction without any special requirements being imposed on the reaction medium (solid, viscous, multicomponent systems); (2) the high efficiency: a large volume of kinetic information in one experiment and a non-destructive character of changes; (3) the possibility of measuring directly in the field of ionizing radiation (γ-radiation, accelerated electrons) and light; and (4) recording of the chemical conversion directly at the time of its occurrence. The disadvantages of this method are: (1) the high inertia of standard calorimeter systems (τC⋍102-103S), which restricts the possibilities of studying fast processes; and (2) the complexity of the correct organization of the calorimeter experiment when the parameters of the process are changed (overheating in the sample, conversion of the process to explosive and auto wave regimens). One of the oldest and most universal methods of studying the mechanism of chemical reactions, calorimetry, is now passing through a period of turbulent development due to the advances in electronics and computerization. The wide variety of types of calorimeter set-ups and the large assortment of measurement schemes in the currently described methods complicate the experimental selection of the necessary instrument rather than facilitate it. The basic principles of the method, the types of calorimeters, and the measuring schemes are described [1-5]. However, despite the high working characteristics of modern calorimeters (Perkin-Elmer, Du Pont, LKB, etc.), all of them have one principal disadvantage: a cell with a sample is placed in them at room temperature. In cryochemical investigation, when the sample has metastable formations, the loading is made `from nitrogen to nitrogen', i.e. the sample prepared at 77 K should be loaded into a calorimeter at 77 K. Besides, the existing installations do not allow measurements at the temperatures <110K. For this reason, the Laboratory of Cryochemistry and Radiation Chemistry at the Institute of Chemical Physics in Chernogolovka has created original calorimetric techniques which allow: (1) the carrying out phase analysis and the determination of the main thermodynamic characteristic of individual substances and complicated systems in the temperature range 5 300 K. Sample loading can be conducted at 77 K that allows us to study the systems containing: tetrafiuoroethylene, hexafluoropropylene, ethylene, carbon monoxide, nitrogen, methane, hydrogen, oxygen, ozone, formaldehyde and many other gaseous substances; (2) the study of the dynamics of chemical reactions and to measure the main kinetic parameters of the processes-the elementary rate constants and the activation energies. The experiment can be conducted both under direct action of radiation and UV light and in the post-effect mode [5,6].

Analysis of large oxygenated and nitrated polycyclic aromatic hydrocarbons formed under simulated diesel engine exhaust conditions (by compound fingerprints with SPE/LC-API-MS)

PubMed Central

Adelhelm, Christoph; Niessner, Reinhard; Pöschl, Ulrich

2008-01-01

The analysis of organic compounds in combustion exhaust particles and the chemical transformation of soot by nitrogen oxides are key aspects of assessment and mitigation of the climate and health effects of aerosol emissions from fossil fuel combustion and biomass burning. In this study we present experimental and analytical techniques for efficient investigation of oxygenated and nitrated derivatives of large polycyclic aromatic hydrocarbons (PAHs), which can be regarded as well-defined soot model substances. For coronene and hexabenzocoronene exposed to nitrogen dioxide under simulated diesel exhaust conditions, several reaction products with high molecular mass could be characterized by liquid chromatography-atmospheric pressure chemical (and photo) ionization-mass spectrometry (LC-APCI-MS and LC-APPI-MS). The main products of coronene contained odd numbers of nitrogen atoms (m/z 282, 256, 338), whereas one of the main products of hexabenzocoronene exhibited an even number of nitrogen atoms (m/z 391). Various reaction products containing carbonyl and nitro groups could be tentatively identified by combining chromatographic and mass spectrometric information, and changes of their relative abundance were observed to depend on the reaction conditions. This analytical strategy should highlight a relatively young technique for the characterization of various soot-contained, semi-volatile, and semi-polar reaction products of large PAHs. Figure LC-APCI-MS analysis of nitrated coronene (and HBC): Total-Ion-Chromatogram (TIC), Extracted Ion Chromatograms (EICs) and corresponding mass spectrum (top). PMID:18560812

Survivability and reactivity of glycine and alanine in early oceans: effects of meteorite impacts.

PubMed

Umeda, Yuhei; Fukunaga, Nao; Sekine, Toshimori; Furukawa, Yoshihiro; Kakegawa, Takeshi; Kobayashi, Takamichi; Nakazawa, Hiromoto

2016-01-01

Prebiotic oceans might have contained abundant amino acids, and were subjected to meteorite impacts, especially during the late heavy bombardment. It is so far unknown how meteorite impacts affected amino acids in the early oceans. Impact experiments were performed under the conditions where glycine was synthesized from carbon, ammonia, and water, using aqueous solutions containing (13)C-labeled glycine and alanine. Selected amino acids and amines in samples were analyzed with liquid chromatography-mass spectrometry (LC/MS). In particular, the (13)C-labeled reaction products were analyzed to distinguish between run products and contaminants. The results revealed that both amino acids survived partially in the early ocean through meteorite impacts, that part of glycine changed into alanine, and that large amounts of methylamine and ethylamine were formed. Fast decarboxylation was confirmed to occur during such impact processes. Furthermore, the formation of n-butylamine, detected only in the samples recovered from the solutions with additional nitrogen and carbon sources of ammonia and benzene, suggests that chemical reactions to form new biomolecules can proceed through marine impacts. Methylamine and ethylamine from glycine and alanine increased considerably in the presence of hematite rather than olivine under similar impact conditions. These results also suggest that amino acids present in early oceans can contribute further to impact-induced reactions, implying that impact energy plays a potential role in the prebiotic formation of various biomolecules, although the reactions are complicated and depend upon the chemical environments as well.

Progression in High School Students' (Aged 16-18) Conceptualizations about Chemical Reactions in Solution.

ERIC Educational Resources Information Center

Boo, Hong-Kwen; Watson, J. R.

2001-01-01

Explores the development over time of students' understandings of the concept of chemical reaction in the context of two familiar reactions in solution. Based on interviews (n=48), results show that students made some progress in their understanding of the concept of chemical reaction but some fundamental misconceptions remained. (Author/MM)

Reactions. Learning in Science Project. Working Paper No. 37.

ERIC Educational Resources Information Center

Schollum, Brendan

The concept of a chemical reaction (as opposed to physical mixing, dissolution, or change of state) is developed in this five-part unit. In addition, the ideas that chemical reactions involve the formation of new substances and that mass is conserved in a chemical reaction are stressed. Part 1 discusses unit objectives and considers teachers'…

Phase-space reaction network on a multisaddle energy landscape: HCN isomerization.

PubMed

Li, Chun-Biu; Matsunaga, Yasuhiro; Toda, Mikito; Komatsuzaki, Tamiki

2005-11-08

By using the HCN/CNH isomerization reaction as an illustrative vehicle of chemical reactions on multisaddle energy landscapes, we give explicit visualizations of molecular motions associated with a straight-through reaction tube in the phase space inside which all reactive trajectories pass from one basin to another, with eliminating recrossing trajectories in the configuration space. This visualization provides us with a chemical intuition of how chemical species "walk along" the reaction-rate slope in the multidimensional phase space compared with the intrinsic reaction path in the configuration space. The distinct nonergodic features in the two different HCN and CNH wells can be easily demonstrated by a section of Poincare surface of section in those potential minima, which predicts in a priori the pattern of trajectories residing in the potential well. We elucidate the global phase-space structure which gives rise to the non-Markovian dynamics or the dynamical correlation of sequential multisaddle chemical reactions. The phase-space structure relevant to the controllability of the product state in chemical reactions is also discussed.

Citrus Juice: Green and Natural Catalyst for the Solvent-free Silica Supported Synthesis of β-Enaminones Using Grindstone Technique.

PubMed

Marvi, Omid; Fekri, Leila Zare

2018-01-01

Citrus Juice as an efficient, cost-effective and green catalyst employed for one-pot synthesis of various β-substituted enaminones through the reaction of β- dicarbonyl compounds with different primary amines in a solvent-free conditions on silica gel as solid surface using grindstone technique in high yields and short reaction times. The presented procedure is operationally simple, practical and green. The wide application of this procedure is demonstrated by the use of various substituted amines to react with β-dicarbonyl compounds. The method was successfully applied for primary amines (15 entries) and the related enaminones were well synthesized in good to excellent yields. Melting points were measured on an Electro thermal 9100 apparatus. 1HNMR and 13C NMR spectra were recorded on a FTNMR BRUKER DRX 500 Avence spectrometer. Chemical shifts were given in ppm from TMS as internal references and CDCl3 was used as the solvent as well. The IR spectra were recorded on a Perkin Elmer FT-IR GX instrument. The chemicals used in this work were purchased from Merck and Fluka chemical companies. Grinding synthesis of citrus juice catalyzed enamination of 1,3-dicarbonyls (acetylacetone, methyl and ethyl-3-oxobutanoate) with various primary amines (aromatic and aliphatic) under solvent-free silica supported conditions was examined and studied (15 entries) and the obtained enaminones were well synthesized in good to excellent yields. Furthermore, the effect of various catalysts on the yield and reaction time for grinding synthesis of 3-phenylamino- but- 2- enoic acid ethyl ester (1) by this method has evaluated as well. A novel, efficient and green protocol for the grinding synthesis of enaminones using citrus juice as natural catalyst has been presented. This methodology is user friendly, green and low cost procedure under mild reaction condition with faster reaction rates. The citrus juice is inexpensive and non-toxic which makes the process convenient, more economic and benign. Furthermore, applying grindstone technique in solvent-free conditions, use of silica gel as a solid and heterogeneous surface in reaction, high yields of products, cleaner reaction profiles, and availability of the reagents makes this method a better choice for synthetic chemists. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

The electrochemical generation of useful chemical species from lunar materials

NASA Technical Reports Server (NTRS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

1989-01-01

The current status of work on an electrochemical technology for the simultaneous generation of oxygen and lithium from a Li2O containing molten salt (Li2O-LiCl-LiF) is discussed. The electrochemical cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia, to effect separation between the oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700 to 800 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm, showing high reversibility for this reaction. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducting agent (compared to H2) for the chemical refining of lunar ores via the general reaction: 2Li + MO yields Li2O + M where MO represents a lunar ore. Emphasis to this time has been on the simulated lunar ore ilmenite (FeTiO3), which we have found becomes chemically reduced by Li at 432 C. Furthermore, both Fe2O3 and TiO2 have been reduced by Li to give the corresponding metal. This electrochemical approach provides a convenient route for producing metals under lunar conditions and oxygen for the continuous maintenance of human habitats on the Moon's surface. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery. This secondary lithium-oxygen battery system posses the highest theoretical energy density yet investigated.

The electrochemical generation of useful chemical species from lunar materials

NASA Astrophysics Data System (ADS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

1989-03-01

The current status of work on an electrochemical technology for the simultaneous generation of oxygen and lithium from a Li2O containing molten salt (Li2O-LiCl-LiF) is discussed. The electrochemical cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia, to effect separation between the oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700 to 800 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm, showing high reversibility for this reaction. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducting agent (compared to H2) for the chemical refining of lunar ores via the general reaction: 2Li + MO yields Li2O + M where MO represents a lunar ore. Emphasis to this time has been on the simulated lunar ore ilmenite (FeTiO3), which we have found becomes chemically reduced by Li at 432 C. Furthermore, both Fe2O3 and TiO2 have been reduced by Li to give the corresponding metal. This electrochemical approach provides a convenient route for producing metals under lunar conditions and oxygen for the continuous maintenance of human habitats on the Moon's surface. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery. This secondary lithium-oxygen battery system posses the highest theoretical energy density yet investigated.

Evaluating the Influence of Chemical Reactions on Wellbore Cement Integrity and Geochemical Tracer Behavior in Hydraulically-Fractured Shale Formations

NASA Astrophysics Data System (ADS)

Verba, C.; Lieuallen, A.; Yang, J.; Torres, M. E.; Hakala, A.

2014-12-01

Ensuring wellbore integrity for hydraulically-fractured shale reservoirs is important for maintaining zonal isolation of gases and fluids within the reservoir. Chemical reactions between wellbore cements, the shale formation, formation fluids, and fracturing fluids could affect the ability for cement to form an adequate seal. This study focuses on experimental investigations to evaluate how cement, rock, brines, and fracturing fluids react under conditions similar to the perforated zone associated with the Marcellus shale (Greene County, Pennsylvania). Two pressure/temperature regimes were investigated- moderate (25 MPa, 50oC) and high (27.5 MPa, 90oC). Shale collected from the Lower Marcellus section was encased in Class A cement, cured for 24 hours, and then exposed to simulated conditions in experimental autoclave reactors. The simulated formation fluid was a synthetic brine, modeled after a flowback fluid contained 187,000 mg/l total dissolved solids and had a pH of 7.6. The effect of pH was probed to evaluate the potential for cement reactivity under different pH conditions, and the potential for contaminant or geochemical tracer release from the shale (e.g. arsenic and rare earth elements). In addition to dissolution reactions, sorption and precipitation reactions between solutes and the cement are being evaluated, as the cement could bond with solute-phase species during continued hydration. The cements are expected to show different reactivity under the two temperature conditions because the primary cement hydration product, calcium silicate hydrate (C-S-H) is heavily influenced by temperature. Results from these experimental studies will be used both to inform the potential changes in cement chemistry that may occur along a wellbore in the hydraulically-fractured portion of a reservoir, and the types of geochemical tracers that may be useful in tracking these reactions.

Real-Time Optical Monitoring of Flow Kinetics and Gas Phase Reactions Under High-Pressure OMCVD Conditions

NASA Technical Reports Server (NTRS)

Dietz, N.; McCall, S.; Bachmann, K. J.

2001-01-01

This contribution addresses the real-time optical characterization of gas flow and gas phase reactions as they play a crucial role for chemical vapor phase depositions utilizing elevated and high pressure chemical vapor deposition (HPCVD) conditions. The objectives of these experiments are to validate on the basis of results on real-time optical diagnostics process models simulation codes, and provide input parameter sets needed for analysis and control of chemical vapor deposition at elevated pressures. Access to microgravity is required to retain high pressure conditions of laminar flow, which is essential for successful acquisition and interpretation of the optical data. In this contribution, we describe the design and construction of the HPCVD system, which include access ports for various optical methods of real-time process monitoring and to analyze the initial stages of heteroepitaxy and steady-state growth in the different pressure ranges. To analyze the onset of turbulence, provisions are made for implementation of experimental methods for in-situ characterization of the nature of flow. This knowledge will be the basis for the design definition of experiments under microgravity, where gas flow conditions, gas phase and surface chemistry, might be analyzed by remote controlled real-time diagnostics tools, developed in this research project.

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

Ilgen, A. G.; Kukkadapu, R. K.; Dunphy, D. R.

Heterogeneous redox reactions on clay mineral surfaces control mobility and bioavailability of redox-sensitive nutrients and contaminants. Iron (Fe) residing in clay mineral structures can either catalyze or directly participate in redox reactions; however, chemical controls over its reactivity are not fully understood. In our previous work we demonstrated that converting a minor portion of Fe(III) to Fe(II) (partial reduction) in the octahedral sheet of natural Fe-rich clay mineral nontronite (NAu-1) activates its surface, making it redox-active. In this study we produced and characterized synthetic ferric nontronite (SIP), highlighting structural and chemical similarities and differences between this synthetic nontronite and itsmore » natural counterpart NAu-1, and probed whether mineral surface is redox-active by reacting it with arsenic As(III) under oxic and anoxic conditions. We demonstrate that synthetic nontronite SIP undergoes the same activation as natural nontronite NAu-1 following the partial reduction treatment. Similar to NAu-1, SIP oxidized As(III) to As(V) under both oxic (catalytic pathway) and anoxic (direct oxidation) conditions. The similar reactivity trends observed for synthetic nontronite and its natural counterpart make SIP an appropriate analog for laboratory studies. The development of chemically pure analogs for ubiquitous soil minerals will allow for systematic research of the fundamental properties of these minerals.« less

Synthesis and characterization of redox-active ferric nontronite

DOE PAGES

Ilgen, A. G.; Kukkadapu, R. K.; Dunphy, D. R.; ...

2017-07-12

Heterogeneous redox reactions on clay mineral surfaces control mobility and bioavailability of redox-sensitive nutrients and contaminants. Iron (Fe) residing in clay mineral structures can either catalyze or directly participate in redox reactions; but, chemical controls over its reactivity are not fully understood. In our previous work we demonstrated that converting a minor portion of Fe(III) to Fe(II) (partial reduction) in the octahedral sheet of natural Fe-rich clay mineral nontronite (NAu-1) activates its surface, making it redox-active. In this study we produced and characterized synthetic ferric nontronite (SIP), highlighting structural and chemical similarities and differences between this synthetic nontronite and itsmore » natural counterpart NAu-1, and probed whether mineral surface is redox-active by reacting it with arsenic As(III) under oxic and anoxic conditions. Here, we demonstrate that synthetic nontronite SIP undergoes the same activation as natural nontronite NAu-1 following the partial reduction treatment. Similar to NAu-1, SIP oxidized As(III) to As(V) under both oxic (catalytic pathway) and anoxic (direct oxidation) conditions. The similar reactivity trends observed for synthetic nontronite and its natural counterpart make SIP an appropriate analog for laboratory studies. The development of chemically pure analogs for ubiquitous soil minerals will allow for systematic research of the fundamental properties of these minerals.« less

Evolution of Size and Chemical Composition of Copper Concentrate Particles Oxidized Under Simulated Flash Smelting Conditions

NASA Astrophysics Data System (ADS)

Pérez-Tello, Manuel; Parra-Sánchez, Víctor R.; Sánchez-Corrales, Víctor M.; Gómez-Álvarez, Agustín; Brown-Bojórquez, Francisco; Parra-Figueroa, Roberto A.; Balladares-Varela, Eduardo R.; Araneda-Hernández, Eugenia A.

2018-04-01

An experimental study was conducted to elucidate the evolution of size and chemical composition of La Caridad copper concentrate particles during oxidation under simulated flash smelting conditions. Input variables tested included particle size and oxygen concentration in the process gas. The response variables included the size distributions, chemical composition, and morphology of the reacted particles at seven locations along a laboratory reactor. Particles with initial size < 45 µm contained mostly chalcopyrite, they increased their mean size and decreased the amount of dust in the population during oxidation. This was explained by a reaction path involving rapid melting followed by collision and coalescence of reacting droplets during flight. Particles with sizes > 45 µm contained varying amounts of chalcopyrite and pyrite, and tended to either maintain or decrease their mean size upon oxidation. When size reduction was observed, dust was produced because of fragmentation, and the particles showed no evidence of collisions during flight. The main oxidation products detected in the particles consisted of matte, cuprospinel, and magnetite. A plot of the mean size divided by the mean size in the feed against the fraction of sulfur eliminated generalized the experimental data so far reported in the literature, and helped identify the reaction path followed by the particles.

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

Ilgen, A. G.; Kukkadapu, R. K.; Dunphy, D. R.

Heterogeneous redox reactions on clay mineral surfaces control mobility and bioavailability of redox-sensitive nutrients and contaminants. Iron (Fe) residing in clay mineral structures can either catalyze or directly participate in redox reactions; but, chemical controls over its reactivity are not fully understood. In our previous work we demonstrated that converting a minor portion of Fe(III) to Fe(II) (partial reduction) in the octahedral sheet of natural Fe-rich clay mineral nontronite (NAu-1) activates its surface, making it redox-active. In this study we produced and characterized synthetic ferric nontronite (SIP), highlighting structural and chemical similarities and differences between this synthetic nontronite and itsmore » natural counterpart NAu-1, and probed whether mineral surface is redox-active by reacting it with arsenic As(III) under oxic and anoxic conditions. Here, we demonstrate that synthetic nontronite SIP undergoes the same activation as natural nontronite NAu-1 following the partial reduction treatment. Similar to NAu-1, SIP oxidized As(III) to As(V) under both oxic (catalytic pathway) and anoxic (direct oxidation) conditions. The similar reactivity trends observed for synthetic nontronite and its natural counterpart make SIP an appropriate analog for laboratory studies. The development of chemically pure analogs for ubiquitous soil minerals will allow for systematic research of the fundamental properties of these minerals.« less

Hot-electron-mediated surface chemistry: toward electronic control of catalytic activity.

PubMed

Park, Jeong Young; Kim, Sun Mi; Lee, Hyosun; Nedrygailov, Ievgen I

2015-08-18

Energy dissipation at surfaces and interfaces is mediated by excitation of elementary processes, including phonons and electronic excitation, once external energy is deposited to the surface during exothermic chemical processes. Nonadiabatic electronic excitation in exothermic catalytic reactions results in the flow of energetic electrons with an energy of 1-3 eV when chemical energy is converted to electron flow on a short (femtosecond) time scale before atomic vibration adiabatically dissipates the energy (in picoseconds). These energetic electrons that are not in thermal equilibrium with the metal atoms are called "hot electrons". The detection of hot electron flow under atomic or molecular processes and understanding its role in chemical reactions have been major topics in surface chemistry. Recent studies have demonstrated electronic excitation produced during atomic or molecular processes on surfaces, and the influence of hot electrons on atomic and molecular processes. We outline research efforts aimed at identification of the intrinsic relation between the flow of hot electrons and catalytic reactions. We show various strategies for detection and use of hot electrons generated by the energy dissipation processes in surface chemical reactions and photon absorption. A Schottky barrier localized at the metal-oxide interface of either catalytic nanodiodes or hybrid nanocatalysts allows hot electrons to irreversibly transport through the interface. We show that the chemicurrent, composed of hot electrons excited by the surface reaction of CO oxidation or hydrogen oxidation, correlates well with the turnover rate measured separately by gas chromatography. Furthermore, we show that hot electron flows generated on a gold thin film by photon absorption (or internal photoemission) can be amplified by localized surface plasmon resonance. The influence of hot charge carriers on the chemistry at the metal-oxide interface are discussed for the cases of Au, Ag, and Pt nanoparticles on oxide supports and Pt-CdSe-Pt nanodumbbells. We show that the accumulation or depletion of hot electrons on metal nanoparticles, in turn, can also influence catalytic reactions. Mechanisms suggested for hot-electron-induced chemical reactions on a photoexcited plasmonic metal are discussed. We propose that the manipulation of the flow of hot electrons by changing the electrical characteristics of metal-oxide and metal-semiconductor interfaces can give rise to the intriguing capability of tuning the catalytic activity of hybrid nanocatalysts.

A Phosphine-mediated Synthesis of 2,3,4,5-tetra-substituted N-hydroxypyrroles from α-oximino Ketones and Dialkyl Acetylenedicarboxylates Under Ionic Liquid Green-media.

PubMed

Shahvelayati, Ashraf S; Ghazvini, Maryam; Yadollahzadeh, Khadijeh; Delbari, Akram S

2018-01-01

The development of multicomponent reactions (MCRs) in the presence of task-specific ionic liquids (ILs), used not only as environmentally benign reaction media, but also as catalysts, is a new approach that meet with the requirements of sustainable chemistry. In recent years, the use of ionic liquids as a green media for organic synthesis has become a chief study area. This is due to their unique properties such as non-volatility, non-flammability, chemical and thermal stability, immiscibility with both organic compounds and water and recyclability. Ionic liquids are used as environmentally friendly solvents instead of hazardous organic solvents. We report the condensation reaction between α-oximinoketone and dialkyl acetylene dicarboxylate in the presence of triphenylphosphine to afford substituted pyrroles under ionic liquid conditions in good yields. Densely functionalized pyrroles was easily prepared from reaction of α-oximinoketones, dialkyl acetylene dicarboxylate in the presence of triphenylphosphine in a quantitative yield under ionic liquid conditions at room temperature. In conclusion, ionic liquids are indicated as a useful and novel reaction medium for the selective synthesis of functionalized pyrroles. This reaction medium can replace the use of hazardous organic solvents. Easy work-up, synthesis of polyfunctional compounds, decreased reaction time, having easily available-recyclable ionic liquids, and good to high yields are advantages of present method. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Chemical potential and reaction electronic flux in symmetry controlled reactions.

PubMed

Vogt-Geisse, Stefan; Toro-Labbé, Alejandro

2016-07-15

In symmetry controlled reactions, orbital degeneracies among orbitals of different symmetries can occur along a reaction coordinate. In such case Koopmans' theorem and the finite difference approximation provide a chemical potential profile with nondifferentiable points. This results in an ill-defined reaction electronic flux (REF) profile, since it is defined as the derivative of the chemical potential with respect to the reaction coordinate. To overcome this deficiency, we propose a new way for the calculation of the chemical potential based on a many orbital approach, suitable for reactions in which symmetry is preserved. This new approach gives rise to a new descriptor: symmetry adapted chemical potential (SA-CP), which is the chemical potential corresponding to a given irreducible representation of a symmetry group. A corresponding symmetry adapted reaction electronic flux (SA-REF) is also obtained. Using this approach smooth chemical potential profiles and well defined REFs are achieved. An application of SA-CP and SA-REF is presented by studying the Cs enol-keto tautomerization of thioformic acid. Two SA-REFs are obtained, JA'(ξ) and JA'' (ξ). It is found that the tautomerization proceeds via an in-plane delocalized 3-center 4-electron O-H-S hypervalent bond which is predicted to exist only in the transition state (TS) region. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Pressure modulates the self-cleavage step of the hairpin ribozyme

NASA Astrophysics Data System (ADS)

Schuabb, Caroline; Kumar, Narendra; Pataraia, Salome; Marx, Dominik; Winter, Roland

2017-03-01

The ability of certain RNAs, denoted as ribozymes, to not only store genetic information but also catalyse chemical reactions gave support to the RNA world hypothesis as a putative step in the development of early life on Earth. This, however, might have evolved under extreme environmental conditions, including the deep sea with pressures in the kbar regime. Here we study pressure-induced effects on the self-cleavage of hairpin ribozyme by following structural changes in real-time. Our results suggest that compression of the ribozyme leads to an accelerated transesterification reaction, being the self-cleavage step, although the overall process is retarded in the high-pressure regime. The results reveal that favourable interactions between the reaction site and neighbouring nucleobases are strengthened under pressure, resulting therefore in an accelerated self-cleavage step upon compression. These results suggest that properly engineered ribozymes may also act as piezophilic biocatalysts in addition to their hitherto known properties.

The role of proton shuttling mechanisms in solvent-free and catalyst-free acetalization reactions of imines.

PubMed

Lillo, Victor J; Mansilla, Javier; Saá, José M

2018-06-06

Proton transfer is central to the understanding of chemical processes. More so in addition reactions of the type NuH + E → Nu-EH taking place under solvent-free and catalyst-free conditions. Herein we show that the addition of alcohols or amines (the NuH component) to imine derivatives (the E component), in 1 : 1 ratio, under solvent-free and catalyst-free conditions, are efficient methods to access N,O and N,N-acetal derivatives. In addition, computational studies reveal that they are catalyzed reactions involving two or even three NuH molecules operating in a cooperative manner as H-bonded NuH(NuH)nNuH associates (many body effects) in the transition state through a concerted proton shuttling mechanism (addition of alcohols) or stepwise proton shuttling mechanism (addition of amines), thereby facilitating the key proton transfer step.

An ab initio molecular dynamics and density functional theory study of the formation of phosphate chains from metathiophosphates.

PubMed

Mosey, Nicholas J; Woo, Tom K

2006-09-04

The reactions that occur between metathiophosphate (MTP) molecules are identified and examined through ab initio molecular dynamics simulations and static quantum chemical calculations at the density functional level of theory. The simulations show that certain types of MTPs can react to yield phosphate chains, while others only dimerize. These differences are rationalized in terms of reaction energies and the electronic structures of these molecules. In the reaction leading to the formation of phosphate chains, the reactive center, a tri-coordinate phosphorus atom, is continually regenerated. A polymerization mechanism linking MTPs to phosphate chains is developed on the basis of these results. This information sheds light on the underlying processes that may be responsible for the formation of phosphates under high-temperature conditions and may prove useful in the development of protocols for the rational synthesis of complex phosphate structures.

A ribonucleotide Origin for Life - Fluctuation and Near-ideal Reactions

NASA Astrophysics Data System (ADS)

Yarus, Michael

2013-02-01

Oligoribonucleotides are potentially capable of Darwinian evolution - they may replicate and can express an independent chemical phenotype, as embodied in modern enzymatic cofactors. Using quantitative chemical kinetics on a sporadically fed ribonucleotide pool, unreliable supplies of unstable activated ribonucleotides A and B at low concentrations recurrently yield a replicating AB polymer with a potential chemical phenotype. Self-complementary replication in the pool occurs during a minority (here ≈ 35 %) of synthetic episodes that exploit coincidental overlaps between 4, 5 or 6 spikes of arbitrarily arriving substrates. Such uniquely productive synthetic episodes, in which near-ideal reaction sequences recur at random, account for most AB oligonucleotide synthesis, and therefore underlie the emergence of net replication under realistic primordial conditions. Because overlapping substrate spikes are unexpectedly frequent, and in addition, complex spike sequences appear disproportionately, a sporadically fed pool can host unexpectedly complex syntheses. Thus, primordial substrate fluctuations are not necessarily a barrier to Darwinism, but instead can facilitate early evolution.

Allergic reactions to indoor air pollutants.

PubMed Central

Karol, M H

1991-01-01

Inhalation of airborne chemicals can result in allergic sensitization with episodic pulmonary responses occurring on subsequent exposures. Responses may occur in the upper respiratory tract (rhinitis), the lower respiratory tract (wheeze, bronchospasm) or systemically, for example, a febrile response. The mechanisms underlying these responses are not always clear but include production of reaginic antibody, activation of T-lymphocyte subsets, and release of spasmogenic and inflammatory mediators from pulmonary cell populations. A variety of agents have been associated with elicitation of these reactions including chemical vapors, dusts and particulates, and microbial organisms. As a result of the widespread occurrence of allergy in indoor environments, conditions conducive to development of allergy have received close attention. Agent-related factors include the nature of the chemical, its concentration, and the frequency and length of exposure to the agent. Host-related factors include the sex, age, and race of the host, as well as the general physical well being. The interactive nature of the host's immune system with the environment is the ultimate determinant of allergic disease. PMID:1821377

A ribonucleotide Origin for Life--fluctuation and near-ideal reactions.

PubMed

Yarus, Michael

2013-02-01

Oligoribonucleotides are potentially capable of Darwinian evolution - they may replicate and can express an independent chemical phenotype, as embodied in modern enzymatic cofactors. Using quantitative chemical kinetics on a sporadically fed ribonucleotide pool, unreliable supplies of unstable activated ribonucleotides A and B at low concentrations recurrently yield a replicating AB polymer with a potential chemical phenotype. Self-complementary replication in the pool occurs during a minority (here ≈ 35 %) of synthetic episodes that exploit coincidental overlaps between 4, 5 or 6 spikes of arbitrarily arriving substrates. Such uniquely productive synthetic episodes, in which near-ideal reaction sequences recur at random, account for most AB oligonucleotide synthesis, and therefore underlie the emergence of net replication under realistic primordial conditions. Because overlapping substrate spikes are unexpectedly frequent, and in addition, complex spike sequences appear disproportionately, a sporadically fed pool can host unexpectedly complex syntheses. Thus, primordial substrate fluctuations are not necessarily a barrier to Darwinism, but instead can facilitate early evolution.

Rare earth separations by selective borate crystallization

PubMed Central

Yin, Xuemiao; Wang, Yaxing; Bai, Xiaojing; Wang, Yumin; Chen, Lanhua; Xiao, Chengliang; Diwu, Juan; Du, Shiyu; Chai, Zhifang; Albrecht-Schmitt, Thomas E.; Wang, Shuao

2017-01-01

Lanthanides possess similar chemical properties rendering their separation from one another a challenge of fundamental chemical and global importance given their incorporation into many advanced technologies. New separation strategies combining green chemistry with low cost and high efficiency remain highly desirable. We demonstrate that the subtle bonding differences among trivalent lanthanides can be amplified during the crystallization of borates, providing chemical recognition of specific lanthanides that originates from Ln3+ coordination alterations, borate polymerization diversity and soft ligand coordination selectivity. Six distinct phases are obtained under identical reaction conditions across lanthanide series, further leading to an efficient and cost-effective separation strategy via selective crystallization. As proof of concept, Nd/Sm and Nd/Dy are used as binary models to demonstrate solid/aqueous and solid/solid separation processes. Controlling the reaction kinetics gives rise to enhanced separation efficiency of Nd/Sm system and a one-step quantitative separation of Nd/Dy with the aid of selective density-based flotation. PMID:28290448

Detection of Singlet Oxygen Formation inside Photoactive Biohybrid Composite Material.

PubMed

Hajdu, Kata; Ur Rehman, Ateeq; Vass, Imre; Nagy, László

2017-12-26

Photosynthetic reaction center proteins (RCs) are the most efficient light energy converter systems in nature. The first steps of the primary charge separation in photosynthesis take place in these proteins. Due to their unique properties, combining RCs with nano-structures promising applications can be predicted in optoelectronic systems. In the present work RCs purified from Rhodobacter sphaeroides purple bacteria were immobilized on multiwalled carbon nanotubes (CNTs). Carboxyl-and amine-functionalised CNTs were used, so different binding procedures, physical sorption and chemical sorption as well, could be applied as immobilization techniques. Light-induced singlet oxygen production was measured in the prepared photoactive biocomposites in water-based suspension by histidine mediated chemical trapping. Carbon nanotubes were applied under different conditions in order to understand their role in the equilibration of singlet oxygen concentration in the suspension. CNTs acted as effective quenchers of ¹O₂ either by physical (resonance) energy transfer or by chemical (oxidation) reaction and their efficiency showed dependence on the diffusion distance of ¹O₂.

Reactivity of Dazomet, a Hydraulic Fracturing Additive: Hydrolysis and Interaction with Pyrite

NASA Astrophysics Data System (ADS)

Consolazio, N.; Lowry, G. V.; Karamalidis, A.; Hakala, A.

2015-12-01

The Marcellus Shale is currently the largest shale gas formation in play across the world. The low-permeability formation requires hydraulic fracturing to be produced. In this process, millions of gallons of water are blended with chemical additives and pumped into each well to fracture the reservoir rock. Although additives account for less than 2% of the fracking fluid mixture, they amount to hundreds of tons per frack job. The environmental properties of some of these additives have been studied, but their behavior under downhole conditions is not widely reported in the peer-reviewed literature. These compounds and their reaction products may return to the surface as produced or waste water. In the event of a spill or release, this water has the potential to contaminate surface soil and water. Of these additives, biocides may present a formidable challenge to water quality. Biocides are toxic compounds (by design), typically added to the Marcellus Shale to control bacteria in the well. An assessment of the most frequently used biocides indicated a need to study the chemical dazomet under reservoir conditions. The Marcellus Shale contains significant deposits of pyrite. This is a ubiquitous mineral within black shales that is known to react with organic compounds in both oxic and anoxic settings. Thus, the objective of our study was to determine the effect of pyrite on the hydrolysis of dazomet. Liquid chromatography-triple quadrupole mass spectrometry (LC-QQQ) was used to calculate the loss rate of aqueous dazomet. Gas chromatography-mass spectrometry (GC-MS) was used to identify the reaction products. Our experiments show that in water, dazomet rapidly hydrolyses in water to form organic and inorganic transformation products. This reaction rate was unaffected when performed under anoxic conditions. However, with pyrite we found an appreciable increase in the removal rate of dazomet. This was accompanied by a corresponding change in the distribution of observed reaction products. Our results indicate the need to determine specific mineral-additive interactions to evaluate the potential risks of chemical use in hydraulic fracturing.

Investigation of Embedded Si/C System Exposed to a Hybrid Reaction of Centrifugal-Assisted Thermite Method

PubMed Central

Mahmoodian, Reza; Yahya, Rosiyah; Dabbagh, Ali; Hamdi, Mohd; Hassan, Mohsen A.

2015-01-01

A novel method is proposed to study the behavior and phase formation of a Si+C compacted pellet under centrifugal acceleration in a hybrid reaction. Si+C as elemental mixture in the form of a pellet is embedded in a centrifugal tube. The pellet assembly and tube are exposed to the sudden thermal energy of a thermite reaction resulted in a hybrid reaction. The hybrid reaction of thermite and Si+C produced unique phases. X-ray diffraction pattern (XRD) as well as microstructural and elemental analyses are then investigated. XRD pattern showed formation of materials with possible electronic and magnetic properties. The cooling rate and the molten particle viscosity mathematical model of the process are meant to assist in understanding the physical and chemical phenomena took place during and after reaction. The results analysis revealed that up to 85% of materials converted into secondary products as ceramics-matrix composite. PMID:26641651

Beyond the conventional understanding of water-rock reactivity

NASA Astrophysics Data System (ADS)

Fischer, Cornelius; Luttge, Andreas

2017-01-01

A common assumption is that water-rock reaction rates should converge to a mean value. There is, however, an emerging consensus on the genuine nature of reaction rate variations under identical chemical conditions. Thus, the further use of mean reaction rates for the prediction of material fluxes is environmentally and economically risky, manifest for example in the management of nuclear waste or the evolution of reservoir rocks. Surface-sensitive methods and resulting information about heterogeneous surface reactivity illustrate the inherent rate variability. Consequently, a statistical analysis was developed in order to quantify the heterogeneity of surface rates. We show how key components of the rate combine to give an overall rate and how the identification of those individual rate contributors provide mechanistic insight into complex heterogeneous reactions. This generates a paradigm change by proposing a new pathway to reaction model parameterization and for the prediction of reaction rates.