ABSTRACT
The enantioselective synthesis (3.7% overall yield in nine steps from 2) and biological screening of the ethyl analog of the macrocyclic marine alkaloid haliclorensin C (compound 5) are reported. Amino alcohol 3, generated by a LiNH2BH3-promoted reductive ring-opening/debenzylation sequence from phenylglycinol-derived lactam 2, was used as the starting chiral linear building block. Incorporation of the undecene chain via the nosyl derivative 12, methylenation of the pentanol moiety, and a ring-closing metathesis are the key steps of the synthesis.
Subject(s)
Alkaloids/chemistry , Alkaloids/chemical synthesis , Aquatic Organisms/chemistry , Ethyl Chloride/chemistry , StereoisomerismSubject(s)
Ethyl Chloride , Patient Care Management/methods , Psychotropic Drugs , Substance-Related Disorders , Anesthetics, Local/chemistry , Anesthetics, Local/pharmacology , Anesthetics, Local/toxicity , Central Nervous System/drug effects , Ethyl Chloride/chemistry , Ethyl Chloride/pharmacology , Ethyl Chloride/toxicity , Humans , Inhalation , Male , Medical History Taking , Neurologic Examination , Psychotropic Drugs/chemistry , Psychotropic Drugs/pharmacology , Psychotropic Drugs/toxicity , Substance-Related Disorders/etiology , Substance-Related Disorders/physiopathology , Substance-Related Disorders/psychology , Substance-Related Disorders/therapy , Treatment Outcome , Volatilization , Young AdultABSTRACT
Vicinal stereocenters are found in many natural and unnatural compounds. Although metal-catalyzed cross-coupling reactions of unactivated alkyl electrophiles are emerging as a powerful tool in organic synthesis, there have been virtually no reports of processes that generate, much less control, vicinal stereocenters. In this investigation, we establish that a chiral nickel catalyst can mediate doubly stereoconvergent alkyl-alkyl cross-coupling, specifically, reactions of a racemic pyrrolidine-derived nucleophile with cyclic alkyl halides (as mixtures of stereoisomers) to produce vicinal stereocenters with very good stereoselectivity.
Subject(s)
Nickel/chemistry , Seed Storage Proteins/chemistry , Alkylation , Catalysis , Ethyl Chloride/chemistry , Molecular Structure , StereoisomerismABSTRACT
Three ethyl chitosans (ECSs) have been prepared using the ethyl chloride (AA) that was obtained in situ. Each ECS was applied on a 100% cotton fabric through a pad-dry-cure technology. Using the ANOVA as statistic method, the wrinkle-proofing effects have been determined varying the concentrations of AA (0.1-2.1mmol) and chitosan (CS) (0.1-2.1mmol). Alkylation and grafting mechanisms have been confirmed by the results of FTIR, (1)H NMR, XPS, SEM, DSC and termogravimetric analyses. The performances of each ECS as wrinkle-proofing agent have been revealed through quantitative methods (taking-up degree, wrinkle-recovering angle, tensile strength and effect's durability). The ECSs confer wrinkle-recovering angle and tensile strength higher than those of the witness sample. Durability of ECSs grafted on cotton have been demonstrated by a good capacity of dyeing with non-specific (acid/anionic and cationic) dyes under severe working conditions (100°C, 60min) and a good antimicrobial capacity.
Subject(s)
Chitosan/chemistry , Alkylation , Analysis of Variance , Cellulose/chemistry , Ethyl Chloride/chemistry , Spectroscopy, Fourier Transform Infrared , Tensile Strength , ThermogravimetryABSTRACT
The coupling of tertiary carbon radicals with alkene acceptors is an underdeveloped strategy for uniting complex carbon fragments and forming new quaternary carbons. The scope and limitations of a new approach for generating nucleophilic tertiary radicals from tertiary alcohols and utilizing these intermediates in fragment coupling reactions is described. In this method, the tertiary alcohol is first acylated to give the tert-alkyl N-phthalimidoyl oxalate, which in the presence of visible-light, catalytic Ru(bpy)3(PF6)2, and a reductant fragments to form the corresponding tertiary carbon radical. In addition to reductive coupling with alkenes, substitution reactions of tertiary radicals with allylic and vinylic halides is described. A mechanism for the generation of tertiary carbon radicals from tert-alkyl N-phthalimidoyl oxalates is proposed that is based on earlier pioneering investigations of Okada and Barton. Deuterium labeling and competition experiments reveal that the reductive radical coupling of tert-alkyl N-phthalimidoyl oxalates with electron-deficient alkenes is terminated by hydrogen-atom transfer.
Subject(s)
Carbon/chemistry , Onium Compounds/chemical synthesis , Oxalates/chemistry , Phthalimides/chemistry , Catalysis , Ethyl Chloride/analogs & derivatives , Ethyl Chloride/chemistry , Imidazoles/chemistry , Light , Molecular Structure , Onium Compounds/chemistry , Photochemical Processes , Pyrroles/chemistryABSTRACT
Enhanced photodecomposition of ethyl chloride (EC) adsorbed on SiO2/Si (100) supported silver nanoparticles (Ag NPs) under ultrahigh vacuum (UHV) conditions has been studied in order to assess the potential contribution of plasmonic effects. The cross section for photodecomposition of EC and overall photoyield were found to increase with increasing photon energy regardless of the plasmon resonant wavelength and with Ag coverage without any noticeable particle size effect. The influence of EC-Ag NPs separation distance on the rate of EC decomposition was studied in order to examine potential local electric field influence on the photodissociation process. Long (â¼5 nm) photoactivity decay distance has been observed which excludes local surface plasmon dominance in the photodecomposition event. These findings suggest that the alignment of excited electron energy and adsorbate affinity levels is central for efficient photochemical reactions, whereas short-range electric field enhancement by plasmon excitation on top and at the immediate vicinity of silver nanoparticles does not have any measurable effect.
Subject(s)
Ethyl Chloride/chemistry , Gold/chemistry , Metal Nanoparticles/chemistry , Photochemical Processes , Surface Plasmon ResonanceABSTRACT
Understanding the process of membrane insertion is an essential step in developing a detailed mechanism, for example, for peripheral membrane protein association and membrane fusion. The highly mobile membrane mimetic (HMMM) has been used to accelerate the membrane association and binding of peripheral membrane proteins in simulations by increasing the lateral diffusion of phospholipid headgroups while retaining an atomistic description of the interface. Through a comparative study, we assess the difference in insertion rate of a free phospholipid into an HMMM as well as into a conventional phospholipid bilayer and develop a detailed mechanistic model of free phospholipid insertion into biological membranes. The mechanistic insertion model shows that successful irreversible association of the free phospholipid to the membrane interface, which results in its insertion, is the rate-limiting step. Association is followed by independent, sequential insertion of the acyl tails of the free phospholipid into the membrane, with splayed acyl tail intermediates. Use of the HMMM is found to replicate the same intermediate insertion states as in the full phospholipid bilayer; however, it accelerates overall insertion by approximately a factor of 3, with the probability of successful association of phospholipid to the membrane being significantly enhanced.
Subject(s)
Biomimetic Materials/chemistry , Lipid Bilayers/chemistry , Membranes, Artificial , Models, Molecular , Phospholipids/chemistry , Ethyl Chloride/analogs & derivatives , Ethyl Chloride/chemistry , Linear Models , Molecular Dynamics Simulation , Phosphatidylcholines/chemistry , Probability , Time FactorsABSTRACT
This systematic investigation examines gas transport in the lung for two sets of chlorohydrocarbons (CHCs): the chloromethanes (C1) and chloroethanes (C2). The C1 series includes chloromethane, methylene chloride, chloroform, and carbon tetrachloride, and the C2 series includes chloroethane, 1,2-dichloroethane, 1, 1, 2-trichloroethane, and 1, 1, 2, 2-tetrachloroethane. Most CHC gases cause narcosis. The comprehensive narcosis work of Lehmann and colleagues on CHCs was used as a basis for the narcosis endpoint in the present examination. The sites for narcosis are located in the brain (midline cortex and posterior parietal area), the spine, and at many peripheral nerve sites. Central nervous system (CNS) exposure executes a multisite, neural transmission set of inhibitions that promotes rapid loss of consciousness, sensory feeling, and current and stored memory while providing temporary amnesia. Absorption into the system requires dissolution into many lipid membranes and binding to lipoproteins. Lipophilicity is a CHC property shared with many anesthetics according to the Meyer-Overton Rule. Many structurally different lipid chemicals produce the narcosis response when the lipid concentration exceeds -67 mM. This suggests narcotic or anesthetic dissolution into CNS membranes until the lipid organization is disrupted or perturbed. This perturbation includes loading of Na(+)- and K(+)-channel transmembrane lipoprotein complexes and disrupting their respective channel functional organizations. The channel functions become attenuated or abrogated until the CHC exposure ceases and CHC loading reverses. This investigation demonstrates how the CHC physical and chemical properties influence the absorption of these CHCs via the lung and the alveolar system on route to the blood. Narcosis in test animals was used here as an objective biological endpoint to study the effects of the physical factors Bp, Vp, Kd (oil: gas) partition, Henry's constant (HK), and water solubility (S%) on gas transport. Narcosis is immediate after gas exposure and requires no chemical activation only absorption into the blood and circulation to CNS narcotic sites. The three physical factors Bp, K(d) (oil: air), and S% vary directly with unitary narcosis (UN) whereas Vp and HK vary inversely with UN in linear log-log relationships for the C2 series but not for the C1 series. Physicochemical properties of C1 series gases indicate why they depart from what is usually assumed to be an Ideal Gas. An essential discriminating process in the distal lung is the limiting alveolar film layer (AFL) and the membrane layer of the alveolar acini. The AFL step influences gas uptake by physically limiting the absorption process. Interaction with and dissolution into aqueous solvent of the AFL is required for transport and narcotic activity. Narcotics or anesthetics must engage the aqueous AFL with sufficient strength to allow transport and absorption for downstream CNS binding. CHCs that do not engage well with the AFL are not narcotic. Lipophilicity and amphipathicity are also essential solvency properties driving narcotics' transport through the alveolar layer, delivery to the blood fats and lipoproteins, and into critical CNS lipids, lipoproteins, and receptor sites that actuate narcosis. AFL disruption is thought to be strongly related to a number of serious pulmonary diseases such acute respiratory distress syndrome, infant respiratory distress syndrome, emphysema, chronic obstructive pulmonary disease, asthma, chronic bronchitis, pneumonia, pulmonary infections, and idiopathic pulmonary fibrosis. The physical factors (Bp, Vp, Kd [oil: gas] partition, Henry's constant, and water solubility [S%]) combine to affect a specific transport through the AFL if lung C > C(0) (threshold concentration for narcosis). The degree of blood CHC absorption depends on dose, lipophilicity, and lung residence time. AFL passage can be manipulated by physical factors of increased pressure (kPa) or increased gas exposure (moles). Molecular lipophilicity facilitates narcosis but lipophilicity alone does not explain narcosis. Vapor pressure is also required for narcosis. Narcotic activity apparently requires stereospecific processing in the AFL and/or down-stream inhibition at stereospecific lipoproteins at CNS inhibitory sites. It is proposed that CHCs likely cannot proceed through the AFL without perturbation or disruption of the integrity of the AFL at the alveoli. CHC physicochemical properties are not expected to allow their transport through the AFL as physiological CO(2) and O(2) naturally do in respiration. This work considers CHC inspiration and systemic absorption into the blood with special emphasis on the CHC potential perturbation effects on the lipid, protein liquid layer supra to the alveolar membrane (AFL). A heuristic gas transport model for the CHCs is presented as guidance for this examination. The gas transport model can be used to study absorption for other gas delivery endpoints of environmental concern such as carcinogens.
Subject(s)
Hydrocarbons, Chlorinated/chemistry , Hydrocarbons, Chlorinated/pharmacokinetics , Lung/drug effects , Stupor/chemically induced , Administration, Inhalation , Animals , Cats , Ethane/analogs & derivatives , Ethane/pharmacology , Ethyl Chloride/chemistry , Ethyl Chloride/pharmacokinetics , Ethyl Chloride/toxicity , Gases/metabolism , Gases/toxicity , Hydrocarbons, Chlorinated/metabolism , Hydrocarbons, Chlorinated/pharmacology , Hydrocarbons, Chlorinated/toxicity , Lipids/chemistry , Lung/physiology , Methyl Chloride/chemistry , Methyl Chloride/pharmacokinetics , Methyl Chloride/toxicity , Models, Biological , Pulmonary Alveoli/chemistry , Pulmonary Alveoli/drug effects , Stupor/etiologyABSTRACT
INTRODUCTION: Chlorinated ethanes and ethenes are among the most frequently detected organic pollutants of water. Their physicochemical properties are such that they can contaminate aquifers for decades. In favourable conditions, they can undergo degradation. In anaerobic conditions, chlorinated solvents can undergo reductive dechlorination. DEGRADATION PATHWAYS: Abiotic dechlorination is usually slower than microbial but abiotic dechlorination is usually complete. In favourable conditions, abiotic reactions bring significant contribution to natural attenuation processes. Abiotic agents that may enhance the reductive dechlorination of chlorinated ethanes and ethenes are zero-valent metals, sulphide minerals or green rusts. OXIDATION: At some sites, permanganate and Fenton's reagent can be used as remediation tool for oxidation of chlorinated ethanes and ethenes. SUMMARY: Nanoscale iron or bimetallic particles, due to high efficiency in degradation of chlorinated ethanes and ethenes, have gained much interest. They allow for rapid degradation of chlorinated ethanes and ethenes in water phase, but they also give benefit of treating dense non-aqueous phase liquid.
Subject(s)
Ethyl Chloride/chemistry , Vinyl Chloride/chemistry , Water Pollutants, Chemical/chemistry , Ethyl Chloride/analogs & derivatives , Iron/chemistry , Metal Nanoparticles/chemistry , Palladium/chemistry , Porphyrins/chemistry , Vinyl Chloride/analogs & derivatives , Water , Zinc/chemistryABSTRACT
PURPOSE: Lack of focus on the treatment of wastewaters bearing potentially hazardous pollutants like 1,1,2 trichloroethane and 1,1,2,2 tetrachloroethane in anaerobic reactors has provided an impetus to undertake this study. The objective of this exercise was to quantify the behavior of upflow anaerobic sludge blanket reactors and predict their performance based on the overall organic substrate removal. METHODS: The reactors (wastewater-bearing TCA (R2), and wastewater-bearing TeCA (R3)) were operated at different hydraulic retention times (HRTs), i.e., 36, 30, 24, 18, and 12 h corresponding to food-to-mass ratios varying in the range of 0.20.7 mg chemical oxygen demand (COD) mg−1 volatile suspended solids day−1. The process kinetics of substrate utilization was evaluated on the basis of experimental results, by applying three mathematical models namely first order, Grau second order, and Michaelis-Menten type kinetics. RESULTS: The results showed that the lowering of HRT below 24 h resulted in reduced COD removal efficiencies and higher effluent pollutant concentrations in the reactors. The Grau second-order model was successfully applied to obtain the substrate utilization kinetics with high value of R 2 (>0.95). The Grau second-order substrate removal constant (K 2) was calculated as 1.12 and 7.53 day−1 for reactors R2 and R3, respectively. CONCLUSION: This study demonstrated the suitability of Grau second-order kinetic model over other models, for predicting the performance of reactors R2 and R3, in treating wastewaters containing chlorinated ethanes under different organic and hydraulic loading conditions.
Subject(s)
Ethyl Chloride/chemistry , Waste Disposal, Fluid/methods , Water Pollutants, Chemical/chemistry , Ethane/analogs & derivatives , Ethane/analysis , Ethane/chemistry , Ethyl Chloride/analysis , Hydrocarbons, Chlorinated/analysis , Hydrocarbons, Chlorinated/chemistry , Kinetics , Models, Chemical , Trichloroethanes/analysis , Trichloroethanes/chemistry , Water Pollutants, Chemical/analysisABSTRACT
Bare metal anions K(-), Rb(-), Cs(-), Fe(-), Co(-), Ni(-), Cu(-), and Ag(-), generated by electrospray ionization of the corresponding oxalate or tricarballylate solutions, were allowed to react with methyl and ethyl chloride, methyl bromide, nitromethane, and acetonitrile in the collision hexapole of a triple-quadrupole mass spectrometer. Observed reactions include (a) the formation of halide, nitride, and cyanide anions, which was shown to be likely due to the insertion of the metal into the C-X, C-N, and C-C bonds, (b) transfer of H(+) from the organic molecule, which is demonstrated to most likely be due to the simple transfer of a proton to form neutral metal hydride, and (c) in the case of nitromethane, direct electron transfer to form the nitromethane radical anion. Interestingly, Co(-) was the only metal anion to transfer an electron to acetonitrile. Differences in the reactions are related to the differences in electron affinity of the metals and the Δ(acid)H° of the metals and organic substrates. Density functional theory calculations at the B3-LYP/6-311++G(3df,2p)//B3-LYP/6-31+G(d) level of theory shed light on the relative energetics of these processes and the mechanisms by which they take place.
Subject(s)
Anions/chemistry , Chemistry, Physical , Gases/chemistry , Metals/chemistry , Protons , Acetonitriles/chemistry , Electron Transport , Electrons , Ethyl Chloride/chemistry , Methane/analogs & derivatives , Methane/chemistry , Methyl Chloride/chemistry , Nitroparaffins/chemistry , Oxalates/chemistry , Quantum Theory , Solutions , Spectrometry, Mass, Electrospray Ionization , Thermodynamics , Tricarboxylic Acids/chemistryABSTRACT
The enhanced reactivity exhibited by six pseudo-alpha-bases, RC[triple bond]CZ(-) (R = H and Cl; Z = O, S, and Se) in gas-phase E2 reactions with ethyl chloride was examined at the G2(+) level. It is found that anomalous reactivity is observed despite the fact that these chalcogen bases do not possess adjacent lone-pair electrons. The influence of the halide leaving groups on the alpha-effect and the origin of the alpha-effect in the E2 reactions of ethyl halides are investigated and discussed.
Subject(s)
Chlorine/chemistry , Gases/chemistry , Hydrogen/chemistry , Oxygen/chemistry , Sulfur/chemistry , Ethyl Chloride/chemistry , Molecular Structure , Selenium/chemistry , ThermodynamicsABSTRACT
The photocatalytic degradation of chlorinated ethanes was studied in a tubular photoreactor packed with TiO(2) pellets prepared by sol-gel method. The steady-state condition was not obtained, but the deterioration in the photocatalytic activity was observed during the irradiation. Effects of mole fractions of water vapor, O(2), and C(2)H(5)Cl or C(2)H(4)Cl(2) and reaction temperature on the photodegradation of C(2)H(5)Cl or C(2)H(4)Cl(2) were examined, and these data were compared with those obtained by the photodegradation of chlorinated ethylenes. On the basis of the products detected with and without oxygen in the reactant's gas stream, we proposed the degradation mechanism. Measurement of diffuse reflectance infrared Fourier transform spectroscopy of pyridine adsorbed on the catalysts showed that decrease in the conversion for the photodegradation of C(2)H(5)Cl was attributable to the formation of Brønsted acid sites. Comparison of the data obtained with the TiO(2) and the sulfated TiO(2) (SO(4)(2-)/TiO(2)) pellets indicated that the photodegradation of C(2)H(5)Cl was suppressed by the presence of the Brønsted sites, but that of trichloroethylene was not affected. Such a difference is attributable to the adsorption process of these reactants on the acid sites on the catalyst surface.
Subject(s)
Ethyl Chloride/chemistry , Gases/chemistry , Photolysis , Titanium/chemistry , Catalysis , Hydrogen-Ion Concentration , Porosity , Spectroscopy, Fourier Transform Infrared , Surface PropertiesABSTRACT
1,1,1-Trichloroethane (1,1,1-TCA) is a common groundwater contaminant that can be reductively dechlorinated to 1,1-dichloroethane (1,1-DCA) and monochloroethane, and can support the growth of certain dehalorespiring strains of Dehalobacter We used reductive dehalogenase cell-free extract assays (with reduced methyl viologen) and whole cell suspension dechlorination assays (with hydrogen) and a Dehalobacter-containing enrichment culture to explore the kinetics of l,1,1-TCA and 1,1-DCA reductive dechlorination in the presence of the common co-contaminants trichloroethene (TCE), cis-dichloroethene (cDCE), and vinyl chloride (VC). These chlorinated ethenes were most significant inhibitors of 1,1,1-TCA dechlorination in cell-free extracts, indicating direct effects on the reductive dehalogenase enzyme(s). The inhibition was present but less pronounced in whole cell suspension assays. None of the chlorinated ethenes inhibited 1,1-DCA dechlorination in cell-free extract assays, yet cDCE and particularly VC were inhibitors in whole cell assays, indicating an effect on Dehalobacter, but not on the dehalogenase enzyme(s). Marked differences in kinetic parameters for 1,1,1-TCA and 1,1-DCA, and an uncoupling of these two activities in cultures grown on 1,1-DCA compared to those grown on 1,1,1-TCA was strong evidence for the existence of distinct 1,1,1-TCA and 1,1-DCA reductive dehalogenase enzymes.
Subject(s)
Ethyl Chloride/analogs & derivatives , Peptococcaceae/growth & development , Trichloroethanes/analysis , Water Pollutants, Chemical/analysis , Biodegradation, Environmental , Culture Media , Ethyl Chloride/analysis , Ethyl Chloride/chemistry , Ethylene Dichlorides/chemistry , Models, Theoretical , Oxidation-Reduction , Trichloroethanes/chemistry , Trichloroethylene/chemistry , Vinyl Chloride/chemistry , Water Pollutants, Chemical/chemistryABSTRACT
A field study was performed to evaluate the potential for in-situ aerobic cometabolism of 1,1,1-trichloroethane (1,1,1-TCA) through bioaugmentation with a butane enrichment culture containing predominantly two Rhodococcus sp. strains named 179BP and 183BP that could cometabolize 1,1,1-TCA and 1,1-dicholoroethene (1,1-DCE). Batch tests indicated that 1,1-DCE was more rapidly transformed than 1,1,1-TCA by both strains with 183BP being the most effective organism. This second in a series of bioaugmentation field studies was conducted in the saturated zone at the Moffett Field In Situ Test Facility in California. In the previous test, bioaugmentation with an enrichment culture containing the 183BP strain achieved short term in situ treatment of 1,1-DCE, 1,1,1-TCA, and 1,1-dichloroethane (1,1-DCA). However, transformation activity towards 1,1,1-TCA was lost over the course of the study. The goal of this second study was to determine if more effective and long-term treatment of 1,1,1-TCA could be achieved through bioaugmentation with a highly enriched culture containing 179BP and 183BP strains. Upon bioaugmentation and continuous addition of butane and dissolved oxygen and or hydrogen peroxide as sources of dissolved oxygen, about 70% removal of 1,1,1-TCA was initially achieved. 1,1-DCE that was present as a trace contaminant was also effectively removed (approximately 80%). No removal of 1,1,1-TCA resulted in a control test leg that was not bioaugmented, although butane and oxygen consumption by the indigenous populations was similar to that in the bioaugmented test leg. However, with prolonged treatment, removal of 1,1,1-TCA in the bioaugmented leg decreased to about 50 to 60%. Hydrogen pexoxide (H2O2) injection increased dissolved oxygen concentration, thus permitting more butane addition into the test zone, but more effective 1,1,1-TCA treatment did not result. The results showed bioaugmentation with the enrichment cultures was effective in enhancing the cometabolic treatment of 1,1,1-TCA and low concentrations of 1,1-DCE over the entire period of the 50-day test. Compared to the first season of testing, cometabolic treatment of 1,1,1-TCA was not lost. The better performance achieved in the second season of testing may be attributed to less 1,1-DCE transformation product toxicity, more effective addition of butane, and bioaugmentation with the highly enriched dual culture.
Subject(s)
Butanes/chemistry , Butanes/metabolism , Ethyl Chloride/analogs & derivatives , Trichloroethanes/chemistry , Trichloroethanes/metabolism , Water Microbiology , Ethyl Chloride/chemistry , Ethyl Chloride/metabolism , Microscopy, Electron, Scanning , Oxygen/metabolism , Time Factors , Water/chemistry , Water/metabolismABSTRACT
Caging and photo-induced decomposition of ethyl chloride molecules (EC) within a layer of amorphous solid water (ASW) on top of clean and oxygen-covered Ru(001) under ultra-high vacuum (UHV) conditions are presented. The caged molecules were estimated to reside 1.5 +/- 0.2 nm above the solid surface, based on parent molecule thermal decomposition on the clean ruthenium. Dissociative electron attachment (DEA) of the caged molecules following 193 nm laser irradiation, result in initial fragmentation to ethyl radical and chloride anion. It was found that photoreactivity on top of the clean ruthenium surface (Ru) is twenty times faster than on the oxygen-covered surface (O/Ru), with DEA cross sections: sigma(Ru) = (3.8 +/- 1) x 10(-19) cm(2) and sigma(O/Ru) = (2.1 +/- 0.3) x 10(-20) cm(2). This difference is attributed to the higher work function of oxygen-covered ruthenium, leading to smaller electron attachment probability due to mismatch of the ruthenium photo-electron energy with the adsorbed EC excited electron affinity levels. EC molecules fragmented within the cage, result in post-irradiation TPD spectra that reveal primarily C(4)H(8), C(3)H(5) and C(3)H(3), without any oxygen-containing molecules. Unique stabilization of the photoproducts has been observed with the first layer of water molecules in direct contact with the substrate, desorbing near 180 K, a significantly higher temperature than the desorption of fully caged molecules. This study may contribute for understanding stratospheric photochemistry and processes in interstellar space.
Subject(s)
Chemistry, Physical/methods , Ethyl Chloride/chemistry , Photochemistry/methods , Water/chemistry , Cations , Electrons , Hydrogen/chemistry , Hydrogen Bonding , Molecular Structure , Oxygen/chemistry , Ruthenium/chemistry , Surface Properties , TemperatureABSTRACT
Nucleophile (11)C/ (14)C [ k (11)/ k (14)] and secondary alpha-deuterium [( k H/ k D) alpha] kinetic isotope effects (KIEs) were measured for the S N2 reactions between tetrabutylammonium cyanide and ethyl iodide, bromide, chloride, and tosylate in anhydrous DMSO at 20 degrees C to determine whether these isotope effects can be used to determine the structure of S N2 transition states. Interpreting the experimental KIEs in the usual fashion (i.e., that a smaller nucleophile KIE indicates the Nu-C alpha transition state bond is shorter and a smaller ( k H/ k D) alpha is found when the Nu-LG distance in the transition state is shorter) suggests that the transition state is tighter with a slightly shorter NC-C alpha bond and a much shorter C alpha-LG bond when the substrate has a poorer halogen leaving group. Theoretical calculations at the B3LYP/aug-cc-pVDZ level of theory support this conclusion. The results show that the experimental nucleophile (11)C/ (14)C KIEs can be used to determine transition-state structure in different reactions and that the usual method of interpreting these KIEs is correct. The magnitude of the experimental secondary alpha-deuterium KIE is related to the nucleophile-leaving group distance in the S N2 transition state ( R TS) for reactions with a halogen leaving group. Unfortunately, the calculated and experimental ( k H/ k D) alpha's change oppositely with leaving group ability. However, the calculated ( k H/ k D) alpha's duplicate both the trend in the KIE with leaving group ability and the magnitude of the ( k H/ k D) alpha's for the ethyl halide reactions when different scale factors are used for the high and the low energy vibrations. This suggests it is critical that different scaling factors for the low and high energy vibrations be used if one wishes to duplicate experimental ( k H/ k D) alpha's. Finally, neither the experimental nor the theoretical secondary alpha-deuterium KIEs for the ethyl tosylate reaction fit the trend found for the reactions with a halogen leaving group. This presumably is found because of the bulky (sterically hindered) leaving group in the tosylate reaction. From every prospective, the tosylate reaction is too different from the halogen reactions to be compared.
Subject(s)
Computer Simulation , Deuterium/chemistry , Hydrocarbons, Halogenated/chemistry , Models, Chemical , Quantum Theory , Thermodynamics , Carbon Radioisotopes/chemistry , Ethyl Chloride/chemistry , Hydrocarbons, Brominated/chemistry , Hydrocarbons, Iodinated/chemistry , Kinetics , Quaternary Ammonium Compounds/chemistry , Tosyl Compounds/chemistryABSTRACT
The purge-and-trap (P&T) gas extraction method combined with gas chromatography was studied for its suitability for quantitative residual solvents determination in a water-soluble active pharmaceutical ingredient (API). Some analytical method performance characteristics were investigated, namely, the repeatability, the accuracy and the detection limit of determination. The results show that the P&T technique is--as expected--more sensitive than the static headspace, thus it can be used for the determination of residual solvents pertaining to the ICH Class 1 group. It was found that it could be an alternative sample preparation method besides the static headspace (HS) method.
Subject(s)
Chromatography, Gas/methods , Flame Ionization/methods , Pharmaceutical Preparations/analysis , Research Design , Solvents/analysis , Benzene/chemistry , Carbon Tetrachloride/chemistry , Chromatography, Gas/instrumentation , Chromatography, Gas/standards , Dimethylformamide , Drug Contamination , Ethyl Chloride/analogs & derivatives , Ethyl Chloride/chemistry , Flame Ionization/instrumentation , Flame Ionization/standards , Formamides/chemistry , Methylene Chloride/chemistry , Nitrogen/chemistry , Pharmaceutical Preparations/chemistry , Reference Standards , Reproducibility of Results , Sensitivity and Specificity , Software , Solvents/chemistry , Solvents/classification , Temperature , Water/chemistryABSTRACT
Degradation of 1,1- and 1,2-dichloroethane (1,1-DCA, 1,2-DCA) and carbon tetrachloride (CCl4) on Zn0 was investigated using compound specific isotope analysis (CSIA) to measure isotopic fractionation factors for chloroalkane degradation by hydrogenolysis, by alpha-elimination, and by beta-elimination. Significant differences in enrichment factors (epsilon) and associated apparent kinetic isotope effects (AKIE) were measured for these different reaction pathways, suggesting that carbon isotope fractionation by beta-elimination is substantially larger than fractionation by hydrogenolysis or by alpha-elimination. Specifically, for 1,1-DCA, the isotopic composition of the reductive alpha-elimination product (ethane) and the hydrogenolysis product (chloroethane) were the same, indicating that cleavage of a single C-Cl bond was the rate-limiting step in both cases. In contrast, for 1,2-DCA, epsilon = epsilon(reactive position) = -29.7 +/- 1.5% per hundred, and the calculated AKIE (1.03) indicated that beta-elimination was likely concerted, possibly involving two C-Cl bonds simultaneously. Compared to 1,1-DCA hydrogenolysis, the AKIE of 1.01 for hydrogenolysis of CCl4 was much lower, indicating that, for this highly reactive organohalide, mass transfer to the surface was likely partially rate-limiting. These findings are a first step toward delineating the relative contribution of these competing pathways in other abiotic systems such as the degradation of chlorinated ethenes on zerovalent iron (ZVI), iron sulfide, pyrite, or magnetite, and, potentially, toward distinguishing between degradation of chlorinated ethenes by abiotic versus biotic processes.
Subject(s)
Carbon Tetrachloride/chemistry , Ethyl Chloride/analogs & derivatives , Ethylene Dichlorides/chemistry , Carbon Isotopes/analysis , Environmental Pollutants/chemistry , Ethyl Chloride/chemistry , Zinc/chemistryABSTRACT
The objective of this research was to study the dechlorination of 1,2-dichloroethane (1,2-DCA) in a synthetic wastewater with lab-scale anaerobic sequencing batch (ASBR) reactors. Anaerobic sludge was used as a biocatalyst. Sodium acetate and dextrose served as the main methanogenic substrate. Experimental studies were conducted at wide-range of volumetric (0.25-1.25 g COD/L.d) and specific (0.0362-0.181 g COD/ g VSS.d) loading rates and influent wastewater CODs (500-2500 mg/L). During 266 days of reactor operation, the mixed culture degraded 1,2 dichloroethane at concentrations of up to 50 mg/L, with an HRT of 48 hrs. No chlorinated intermediates or residues were found. 1,2-DCA degradation resulted in ethene and ethane formation. Acetate was the most effective electron donor for dechlorination, although, dextrose was also effective, but to a lesser extent. The mixed culture degraded 1,2 Dichloroethane in the temperature range of 28+/-4 degrees C, with the pH range of 7.25 to 7.95. The 1,2-DCA removal rates achieved, and the safe nature of the end products, signify the anaerobic sequencing batch (ASBR) reactor technology for practical decontamination of waters containing such types of organochlorines. The COD removal efficiencies were in the range of 95 to 98% depending on volumetric and specific loading rates applied.