Showing papers on "Reaction rate constant published in 2010"

Cytochrome P450 Compound I: Capture, Characterization, and C-H Bond Activation Kinetics

Abstract: Cytochrome P450 enzymes are responsible for the phase I metabolism of approximately 75% of known pharmaceuticals. P450s perform this and other important biological functions through the controlled activation of C-H bonds. Here, we report the spectroscopic and kinetic characterization of the long-sought principal intermediate involved in this process, P450 compound I (P450-I), which we prepared in approximately 75% yield by reacting ferric CYP119 with m-chloroperbenzoic acid. The Mossbauer spectrum of CYP119-I is similar to that of chloroperoxidase compound I, although its electron paramagnetic resonance spectrum reflects an increase in |J|/D, the ratio of the exchange coupling to the zero-field splitting. CYP119-I hydroxylates the unactivated C-H bonds of lauric acid [D(C-H) ~ 100 kilocalories per mole], with an apparent second-order rate constant of k(app) = 1.1 × 10(7) per molar per second at 4°C. Direct measurements put a lower limit of k ≥ 210 per second on the rate constant for bound substrate oxidation, whereas analyses involving kinetic isotope effects predict a value in excess of 1400 per second.

Thiol-yne click chemistry: A powerful and versatile methodology for materials synthesis

Abstract: Radical mediated thiol-yne polymerization reactions complement the more well-known thiol-ene radical polymerization processes, with the added advantage of increased functionality. In one system studied, the rate constant for the addition of the thiol to the vinyl sulfide created by the initial reaction of the thiol with the alkyne is three times faster than the initial reaction. When hydrocarbon based dialkynes and dithiols were copolymerized, the resulting thiol-alkyne networks containing only hydrocarbon and sulfide linking groups exhibited refractive index values tunable above 1.65, with the refractive index directly related to the sulfur content. The thiol-yne reaction was also found to be useful in functionalizing thiol-terminated polymer chain ends via sequential Michael thiol-ene addition followed by the thiol-yne reaction: the result is the dual functionalization of the polymer chain end. A thermally responsive polymer hydrogel network was formed when an yne terminated water-soluble homopolymer was polymerized with a tetrafunctional thiol.

Rotational quenching of co due to h2 collisions

Abstract: Rate coefficients for state-to-state rotational transitions in CO induced by both para- and ortho-H2 collisions are presented. The results were obtained using the close-coupling method and the coupled-states approximation, with the CO-H2 interaction potential of Jankowski & Szalewicz. Rate coefficients are presented for temperatures between 1 and 3000 K, and for CO(v = 0, j) quenching from j = 1-40 to all lower j' levels. Comparisons with previous calculations using an earlier potential show some discrepancies, especially at low temperatures and for rotational transitions involving large |Δj|. The differences in the well depths of the van der Waals interactions and the anisotropy of the two potential surfaces lead to different resonance structures in the energy dependence of the cross sections which influence the low temperature rate coefficients. Applications to far infrared observations of astrophysical environments are briefly discussed.

Nucleophile-Initiated Thiol-Michael Reactions: Effect of Organocatalyst, Thiol, and Ene

Abstract: A detailed evaluation of the kinetics of the thiol-Michael reaction between hexanethiol and hexyl acrylate is described. It is shown that primary amines are more effective catalysts than either secondary or tertiary amines with, for example, quantitative conversion being achieved within 500 s in the case of hexylamine with an apparent rate constant of 53.4 mol L−1 s−1 at a catalyst loading of 0.057 mol %. Certain tertiary phosphines, and especially tri-n-propylphosphine and dimethylphenylphosphine, are shown to be even more effective species even at concentrations 2 orders of magnitude lower than employed for hexylamine and performed in solution with quantitative conversions reached within ca. 100 s for both species and apparent rate constants of 1810 and 431 mol L−1 s−1, respectively. The nature of the thiol is also demonstrated to be an important consideration with mercaptoglycolate and mercaptopropionate esters being significantly more reactive than hexanethiol with reactivity mirroring the pKa of the ...

Glyoxal processing by aerosol multiphase chemistry: towards a kinetic modeling framework of secondary organic aerosol formation in aqueous particles

Abstract: . This study presents a modeling framework based on laboratory data to describe the kinetics of glyoxal reactions that form secondary organic aerosol (SOA) in aqueous aerosol particles. Recent laboratory results on glyoxal reactions are reviewed and a consistent set of empirical reaction rate constants is derived that captures the kinetics of glyoxal hydration and subsequent reversible and irreversible reactions in aqueous inorganic and water-soluble organic aerosol seeds. Products of these processes include (a) oligomers, (b) nitrogen-containing products, (c) photochemical oxidation products with high molecular weight. These additional aqueous phase processes enhance the SOA formation rate in particles and yield two to three orders of magnitude more SOA than predicted based on reaction schemes for dilute aqueous phase (cloud) chemistry for the same conditions (liquid water content, particle size). The application of the new module including detailed chemical processes in a box model demonstrates that both the time scale to reach aqueous phase equilibria and the choice of rate constants of irreversible reactions have a pronounced effect on the predicted atmospheric relevance of SOA formation from glyoxal. During day time, a photochemical (most likely radical-initiated) process is the major SOA formation pathway forming ∼5 μg m−3 SOA over 12 h (assuming a constant glyoxal mixing ratio of 300 ppt). During night time, reactions of nitrogen-containing compounds (ammonium, amines, amino acids) contribute most to the predicted SOA mass; however, the absolute predicted SOA masses are reduced by an order of magnitude as compared to day time production. The contribution of the ammonium reaction significantly increases in moderately acidic or neutral particles (5 Glyoxal uptake into ammonium sulfate seed under dark conditions can be represented with a single reaction parameter keffupt that does not depend on aerosol loading or water content, which indicates a possibly catalytic role of aerosol water in SOA formation. However, the reversible nature of uptake under dark conditions is not captured by keffupt, and can be parameterized by an effective Henry's law constant including an equilibrium constant Kolig = 1000 (in ammonium sulfate solution). Such reversible glyoxal oligomerization contributes Sensitivity tests reveal five parameters that strongly affect the predicted SOA mass from glyoxal: (1) time scales to reach equilibrium states (as opposed to assuming instantaneous equilibrium), (2) particle pH, (3) chemical composition of the bulk aerosol, (4) particle surface composition, and (5) particle liquid water content that is mostly determined by the amount and hygroscopicity of aerosol mass and to a lesser extent by the ambient relative humidity. Glyoxal serves as an example molecule, and the conclusions about SOA formation in aqueous particles can serve for comparative studies of other molecules that form SOA as the result of multiphase chemical processing in aerosol water. This SOA source is currently underrepresented in atmospheric models; if included it is likely to bring SOA predictions (mass and O/C ratio) into better agreement with field observations.

3-D Carbon Nanotube Structures Used as High Performance Catalyst for Oxygen Reduction Reaction

Abstract: We report a high performance oxygen reduction reaction (ORR) catalyst based on vertically aligned, nitrogen-doped carbon nanotube (VA-NCNT) arrays. Characterization in conditions analogous to the operation of a polymer electrolyte membrane fuel cell show ORR taking place on the catalyst at a favorable reduction potential with a superior current density and greater rate constant.

New catalytic route: Hydrogels as templates and reactors for in situ Ni nanoparticle synthesis and usage in the reduction of 2- and 4-nitrophenols

Abstract: Nickel nanoparticles inside poly(2-acrylamido-2-methyl-1-propansulfonic acid) (p(AMPS)) hydrogel were prepared by reduction of Ni(II) ions absorbed within hydrogel network. TEM images confirmed that in situ formed nickel particle in p(AMPS) hydrogel networks are about 100 nm. These nickel metal nanoparticles containing hydrogel-composites were utilized as catalysts and reaction media for the reduction reactions of aromatic nitro compounds, 2- and 4-nitrophenols with aqueous NaBH 4 . The reduction rate constants at four different temperatures (30, 40, 50 and 60 °C) and activation parameters were calculated. The activation energies ( E a ) for 4- and 2-nitrophenols are 25.70 and 38.69 kJ mol −1 , respectively. It was found that these types of hydrogel-composite catalyst systems can be used repetitively up to five times with 100% conversion and only with 25% reduction in the initial reduction rate.

Experimental evidence for the nanocage effect in catalysis with hollow nanoparticles.

Abstract: Five different hollow cubic nanoparticles with wall length of 75 nm were synthesized from platinum and/or palladium elements. The five nanocatalysts are pure platinum nanocages (PtNCs), pure palladium nanocages (PdNCs), Pt/Pd hollow shell-shell nanocages (NCs) (where Pd is defined as the inner shell around the cavity), Pd/Pt shell-shell NCs, and Pt-Pd alloy NCs. These are used to catalyze the reduction of 4-nitrophenol with sodium borohydride. The kinetic parameters (rate constants, activation energies, frequency factors, and entropies of activation) of each shell/shell NCs are found to be comparable to that of pure metal NCs made of the same metal coating the cavity in the shell-shell NCs. These results strongly suggest that the catalytic reaction takes place inside the cavity of the hollow nanoparticles. Because of the nanoreactor confinement effect of the hollow nanocatalysts, the frequency factors obtained from the Arrhenius plots are found to be the highest ever reported for this reduction reaction. This is the reason for enhanced rate of this reaction inside the cavity. The importance of mechanism of the homogeneous and the heterogeneous nanocatalytic reactions occurring on the external surface of a solid nanoparticle are contrasted with those occurring on the nanocavity surface.

Catalytic hydrothermal deoxygenation of palmitic acid

Abstract: We herein report a new approach to convert fatty acids to hydrocarbons in near- or supercritical water. We tested several different metal salts, bases, and high-surface-area supported metal catalysts for activity toward deoxygenation of palmitic acid in a hydrothermal reaction medium. Two heterogeneous catalysts, 5% platinum on activated carbon (Pt/C) and 5% palladium on activated carbon (Pd/C), proved to be very effective for hydrothermal deoxygenation of palmitic acid. The reactions were done in water with no added H2. The catalysts can be reused without significant activity loss, and the selectivity was more than 90% toward pentadecane, the deoxygenation product. We examined the effect of the catalyst loading, reactant loading, batch holding time, and reaction temperature on the Pt/C-catalyzed deoxygenation rate. The results show that the reaction is first-order in palmitic acid, and the rate constants displayed Arrhenius behavior with an activation energy of 79 kJ mol−1.

Dissociation rates of urea in the presence of NiOOH catalyst: a DFT analysis.

Abstract: Single molecule reactions have been studied between nickel oxyhydroxide, urea, and the hydroxide ion to understand the process of urea dissociation into ammonia, isocyanic acid, cyanate ion, carbon dioxide, and nitrogen. In the absence of hydroxide ions, nickel oxyhydroxide will catalyze urea to form ammonia and isocyanic acid with the rate-limiting step being the formation of ammonia with a rate constant of 1.5 × 10⁻⁶ s⁻¹. In the presence of hydroxide, the evolution of ammonia was also the rate-limiting step with a rate constant of 1.4 × 10⁻²⁶ s⁻¹. In addition, desorption of the cyanate ion presented an energy barrier of 6190 kJ mol⁻¹ suggesting that the cyanate ion cannot be separated from NiOOH unless further reactions occurred. Finally, elementary dissociation reactions with hydroxide ions deprotonating urea to produce nitrogen and carbon dioxide were analyzed. These elementary reactions were investigated along three paths differing in the order that protons were removed and the nitrogen atoms were rotated. The rate-limiting step was found to be the removal of carbon dioxide with a rate constant of 4.3 × 10⁻⁶⁵ s⁻¹. Therefore, the catalyst could be deactivated by the surface blockage caused by carbon dioxide adsorption.

Rapid reaction of hydrogen sulfide with the neutrophil oxidant hypochlorous acid to generate polysulfides.

Abstract: H₂S has been recognized as a signaling molecule and mediator of inflammation. Here, we report the kinetics and mechanism of its reaction with the neutrophil oxidant hypochlorous acid. Stopped flow studies, carried out at high pH, showed this reaction to be extremely fast, with a second-order rate constant extrapolated to be 2 × 10⁹ M⁻¹ s⁻¹ at pH 7.4. The reaction produces polysulfides rather than polythionates and may represent a novel pathway for protein Cys-sulfhydration, a recently proposed mechanism for H₂S signaling.

SET‐LRP of N,N‐dimethylacrylamide and of N‐isopropylacrylamide at 25 °C in protic and in dipolar aprotic solvents

Abstract: The single-electron transfer living radical polymerization (SET-LRP) of water-soluble monomers, N,N-dimethylacrylamide (DMA) and N-isopropylacrylamide (NIPAM), initiated with 2-methylchloropropionate (MCP) in dipolar aprotic and protie solvents is reported. The radical polymerization of acrylamides is characterized by higher rate constants of propagation and bimolecular termination than acrylates. Therefore, the addition of CuCl Is required to mediate deactivation in the early stages of the reaction. Through the use of Cu(0)-wire/Me-TREN catalysis, conditions were optimized to minimize the amount of externally added CuCl required to maintain a linear evolution of molecular weight and narrow molecular weight distribution. By using less CuCl additive, the amount of soluble copper species that must ultimately be removed from the reaction mixture is reduced.

Role of Chain Transfer Agents in Free Radical Polymerization Kinetics

Abstract: This study deals with modeling the propagation and the chain transfer reactions in the free radical polymerization of ethylene, methyl methacrylate (MMA), and acrylamide (AM). The chain transfer agents modeled in the free radical polymerization of ethylene are the experimentally widely used species such as ethylene, methane, ethane, propane, trimethylamine, dimethylamine, chloroform, and carbon tetrachloride. The role of 4-X-thiophenols as chain transfer agents in the polymerization of MMA and AM has been investigated. Geometry optimizations have been carried out with the B3LYP/6-31+G(d) methodology. Reaction rate constants are calculated via the standard transition-state theory with the B3LYP/6-311+G(3df,2p)//B3LYP/6-31+G(d), MPWB1K/6-311+G(3df,2p)//B3LYP/6-31+G(d), and M05-2X/6-311+G(3df,2p)//B3LYP/6-31+G(d) methodologies, which reproduce qualitatively the experimental trends for the chain transfer rate constants. The usage of simple continuum models with the MPWB1K/6-311+G(3df,2p)//B3LYP/6-31+G(d) meth...

Accurate modelling of Pd(0) + PhX oxidative addition kinetics

Abstract: We have used dispersion-corrected DFT (DFT-D) together with solvation to examine possible mechanisms for reaction of PhX (X = Cl, Br, I) with Pd(PtBu3)2 and compare our results to recently published kinetic data (F. Barrios-Landeros, B. P. Carrow and J. F. Hartwig, J. Am. Chem. Soc., 2009, 131, 8141–8154).1 The calculated activation free energies agree near-quantitatively with experimentally observed rate constants.

Copper-Catalyzed Enantioselective Propargylic Amination of Propargylic Esters with Amines: Copper−Allenylidene Complexes as Key Intermediates

Abstract: The scope and limitations of the copper-catalyzed propargylic amination of various propargylic esters with amines are presented, where optically active diphosphines such as Cl-MeO-BIPHEP and BINAP work as good chiral ligands. A variety of secondary amines are available as nucleophiles for this catalytic reaction to give the corresponding propargylic amines with a high enantioselectivity. The results of some stoichiometric and catalytic reactions indicate that the catalytic amination proceeds via copper−allenylidene complexes formed in situ, where the attack of amines to the electrophilic γ-carbon atom in the allenylidene complex is an important step for the stereoselection. Investigation of the relative rate constants for the reaction of several para-substituted propargylic acetates with N-methylanilines reveals that the formation of the copper−allenylidene complexes is involved in the rate-determining step. The result of the density functional theory calculation on a model reaction also supports the prop...

What Factors Influence the Rate Constant of Substrate Epoxidation by Compound I of Cytochrome P450 and Analogous Iron(IV)-Oxo Oxidants?

Abstract: The cytochromes P450 are a versatile range of mono-oxygenase enzymes that catalyze a variety of different chemical reactions, of which the key reactions include aliphatic hydroxylation and C═C double bond epoxidation. To establish the fundamental factors that govern substrate epoxidation by these enzymes we have done a systematic density functional theory study on substrate epoxidation by the active species of P450 enzymes, namely the iron(IV)-oxo porphyrin cation radical oxidant or Compound I. We show here, for the first time, that the rate constant of substrate epoxidation, and hence the activation energy, correlates with the ionization potential of the substrate as well as with intrinsic electronic properties of the active oxidant such as the polarizability volume. To explain these findings we present an electron-transfer model for the reaction mechanism that explains the factors that determine the barrier heights and developed a valence bond (VB) curve crossing mechanism to rationalize the observed tr...

Kinetics and Mechanisms of N-Nitrosodimethylamine Formation upon Ozonation of N,N-Dimethylsulfamide-Containing Waters: Bromide Catalysis

Abstract: N,N-Dimethylsulfamide (DMS), a newly identified, ubiquitous degradation product of the fungicide tolylfluanide, has been shown to be a N-nitrosodimethylamine (NDMA) precursor during ozonation. In this study, batch ozonation experiments in ultrapure buffered water, surface water, and tap water were performed to determine the kinetics and elucidate the mechanism of NDMA formation from DMS. It was found that at circumneutral pH, DMS reacts slowly with ozone (k ≈ 20 M−1 s−1) and moderately with hydroxyl radicals (k = 1.5 × 109 M−1s−1). The reaction of DMS with these oxidants does not lead to NDMA. NDMA was only formed if bromide was present during ozonation of DMS-containing waters. Bromide is oxidized to hypobromous acid (HOBr) by ozone which then reacts with the primary amine of DMS to form a Br−DMS species. The rate limiting step of the formation of Br−DMS is the formation of HOBr. The reaction to form Br−DMS has an apparent second order rate constant at pH 8 of >3 × 104 M−1s−1. The Br−DMS is transformed b...

Rate constants for the thermal decomposition of ethanol and its bimolecular reactions with OH and D: reflected shock tube and theoretical studies.

Abstract: The thermal decomposition of ethanol and its reactions with OH and D have been studied with both shock tube experiments and ab initio transition state theory-based master equation calculations. Dissociation rate constants for ethanol have been measured at high T in reflected shock waves using OH optical absorption and high-sensitivity H-atom ARAS detection. The three dissociation processes that are dominant at high T are C2H5OH--> C2H4+H2O (A) -->CH3+CH2OH (B) -->C2H5+OH (C).The rate coefficient for reaction C was measured directly with high sensitivity at 308 nm using a multipass optical White cell. Meanwhile, H-atom ARAS measurements yield the overall rate coefficient and that for the sum of reactions B and C , since H-atoms are instantaneously formed from the decompositions of CH(2)OH and C(2)H(5) into CH(2)O + H and C(2)H(4) + H, respectively. By difference, rate constants for reaction 1 could be obtained. One potential complication is the scavenging of OH by unreacted ethanol in the OH experiments, and therefore, rate constants for OH+C2H5OH-->products (D)were measured using tert-butyl hydroperoxide (tBH) as the thermal source for OH. The present experiments can be represented by the Arrhenius expression k=(2.5+/-0.43) x 10(-11) exp(-911+/-191 K/T) cm3 molecule(-1) s(-1) over the T range 857-1297 K. For completeness, we have also measured the rate coefficient for the reaction of D atoms with ethanol D+C2H5OH-->products (E) whose H analogue is another key reaction in the combustion of ethanol. Over the T range 1054-1359 K, the rate constants from the present experiments can be represented by the Arrhenius expression, k=(3.98+/-0.76) x10(-10) exp(-4494+/-235 K/T) cm3 molecule(-1) s(-1). The high-pressure rate coefficients for reactions B and C were studied with variable reaction coordinate transition state theory employing directly determined CASPT2/cc-pvdz interaction energies. Reactions A , D , and E were studied with conventional transition state theory employing QCISD(T)/CBS energies. For the saddle point in reaction A , additional high-level corrections are evaluated. The predicted reaction exo- and endothermicities are in good agreement with the current Active Thermochemical Tables values. The transition state theory predictions for the microcanonical rate coefficients in ethanol decomposition are incorporated in master equation calculations to yield predictions for the temperature and pressure dependences of reactions A - C . With modest adjustments (<1 kcal/mol) to a few key barrier heights, the present experimental and adjusted theoretical results yield a consistent description of both the decomposition (1-3) and abstraction kinetics (4 and 5). The present results are compared with earlier experimental and theoretical work.

SET-LRP of acrylates in air

Abstract: Single Electron Transfer-Living Radical Polymerization (SET-LRP) represents a robust and versatile method for the rapid synthesis of macromolecules with well defined topology. In SET-LRP, certain combinations of solvents and ligands facilitate the disproportionation of in situ generated Cu(I) species into “nascent” Cu(0) and Cu(II) species. A combination of heterogeneous and “nascent” Cu(0) activation yields polymers with very high chain end functionality. Under suitable conditions the tolerance toward oxygen must be increased since Cu(0), the activator in SET-LRP, acts as an oxygen scavenger in all inert gas purification systems. Here we demonstrate that SET-LRP of methyl acrylate can be conducted in the presence of air. The addition of a small amount of reducing agent hydrazine hydrate to the reaction mixture reduces Cu2O generated by the oxidation of Cu(0) with air, regenerating Cu(0) and allowing for the synthesis of polymers with predictable molecular weight and perfect retention of chain end functionality. The kinetics plots obtained under these conditions were identical to these generated by degassed samples. High conversions were achieved within a very short reaction time. In these SET-LRP experiments, the reagents were not deoxygenated or subjected to standard degassing procedures such as freeze-pump-thaw or nitrogen sparging. This simple SET-LRP procedure provides an efficient and economical approach to the synthesis of functional macromolecules. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1190–1196, 2010

Selenium and sulfur in exchange reactions: a comparative study.

Abstract: Cysteamine reduces selenocystamine to form hemiselenocystamine and then cystamine. The rate constants are k1 = 1.3 × 105 M−1 s−1; k−1 = 2.6 × 107 M−1 s−1; k2 = 11 M−1 s−1; and k−2 = 1.4 × 103 M−1 s−1, respectively. Rate constants for reactions of cysteine/selenocystine are similar. Reaction rates of selenium as a nucleophile and as an electrophile are 2−3 and 4 orders of magnitude higher, respectively, than those of sulfur. Sulfides and selenides are comparable as leaving groups.