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141.
R. G. Stebbins T. Roy T. R. Doane 《International journal of environmental analytical chemistry》2013,93(3):127-137
Abstract The 1-ethylmonocarboxylic acid of Malathion (MCA) was identified as a metabolite of Malathion in the gut of golden shiners (N. Chrysoleucas) (7.11 × 102±0.66 × 102 ng/g tissue). As noted in the literature the rate of hydrolysis of Malathion above pH 7 is first order with respect to Malathion and pH dependent. In addition, the rate of hydrolysis of Malathion in aquaria housing these fish was found to be dependent on the concentration of Ca+2; sparging the aquaria with air affected the rate. Some of the hydrolysis products of Malathion were identified by gc/ms and found to be pH dependent above pH 7. The half-life of Malathion under different conditions, the identification of some hydrolytic products and a general scheme for the analysis of Malathion, along with some of its metabolic and hydrolytic products are included in this paper. 相似文献
142.
A degradable atom transfer radical polymerization inimer: Synthesis,polymerization, and cleavage of the resulting polymer products 下载免费PDF全文
Marios Elladiou Costas S. Patrickios 《Journal of polymer science. Part A, Polymer chemistry》2017,55(17):2831-2839
A novel degradable inimer for atom transfer radical polymerization (ATRP), 2‐(6‐(2‐((2‐bromo‐2‐methylpropanoyl)oxy)ethyl)pyridin‐2‐yl)ethyl methacrylate (PyDEBrMΑ), was synthesized by the two‐step esterification of 2,6‐pyridinediethanol, first with α‐bromoisobutyryl bromide in order to introduce the initiator moiety, and then with methacryloyl chloride in order to introduce the monomer moiety. PyDEBrMA was subsequently used to initiate the self‐condensing ATRP of methyl methacrylate (MMA) to obtain a hyperbranched MMA homopolymer which could be cleaved at the PyDEBrMA residue either by treatment under mildly alkaline hydrolysis conditions (sodium deuteroxide in d6‐DMSO at room temperature) or thermolysis at 150 °C. The lability of the PyDEBrMA residue arises from the presence in its structure of two 2‐(pyridin‐2‐yl)ethyl ester moieties. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2831–2839 相似文献
143.
J. Graham Dawber R. Glynn Skerratt John C. Tebby Albert A. C. Waite 《Phosphorus, sulfur, and silicon and the related elements》2013,188(10):1261-1268
Abstract Third order rate constants have been determined for the alkaline hydrolysis of four series of alkylphenylphosphonium salts and alkylphenylbenzylphosphonium salts at various temperatures in 50%–70% v/v aqueous tetrahydrofuran and 70% v/v aqueous methanol. Thermodynamic activation parameters have been calculated for the reactions of each substrate and the effects of varying the ratio of alkyl to phenyl groups have been compared, as well as the effects of changes in the nature of the alkyl group. Solvation, as revealed by trends in entropy of activation, plays a largely counter-balancing role with respect to enthalpy and energy of activation. The role of the isokinetic effect is discussed. In aqueous tetrahydrofuran, solvation effects on the hydrolyses of phosphonium salts change as the mole fraction of water changes, and for aqueous methanol the trends in the thermodynamic activation parameters actually reverse. 相似文献
144.
Mrityunjoy Datta Alan J. Buglass 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6):691-700
Abstract The hydrolysis of some N,N-dibenzylalkanesulfinamides (RSONH(CH2Ph)2; 1, R = Me; 2, R = iPr; 3, R = tBu; 4, R = 1-adamantyl) has been studied in 50% (v:v) acetonitrile–water solutions of hydrobromic and hydrochloric acids, mainly at 44.8 °C, using ultraviolet (UV) spectrophotometry to determine pseudo first-order rate constants. The compounds were found to hydrolyze by concurrent bimolecular neutral, acid-catalyzed, and acid-dependent nucleophilic (halide ion) catalysis pathways. The last-named is predominant in reactions in HBr solutions, but in HCl solutions, the acid-catalyzed pathway is predominant. The results indicate that both steric and electronic effects are important in these reactions. There appears to be no mechanistic switchover in the series 1→4. 相似文献
145.
Marie-Christine Brochier Salon Mohamed Naceur Belgacem 《Phosphorus, sulfur, and silicon and the related elements》2013,188(2):240-254
Abstract The hydrolysis kinetics of 14 alkoxy silane coupling agents were carried out in an ethanol:water 80:20 (w/w) solution under acidic conditions and were monitored by 1H, 13C, and 29Si NMR spectroscopy. Acidic conditions were selected in order to enhance the silanol formation and to slow down the self-condensation between the resulting hydrolysed silanol groups. In situ 29Si NMR spectroscopy allowed the determination of the intermediate species as a function of the reaction time. Thus, the following silane coupling agents were studied: 3-methacryloxypropyl trimethoxy silane (MPMS), 3-mercaptopropyl trimethoxy silane (MRPMS), 3-cyanopropyl triethoxy silane (CPES), triethoxy vinyl silane (VES), trimethoxy (2-phenylethyl) silane (PEMS), octyl triethoxy silane (OES), trimethoxy (7-octen-1-yl) silane (OEMS), 3-aminopropyl triethoxy silane (APES), 3-aminopropyl trimethoxy silane (APMS), 3-(2-aminoethylamino)propyl trimethoxy silane, (DAMS), 3-[2-(2-aminoethylamino)-ethylamino]propyl trimethoxy silane (TAMS), 4-amino-3,3-dibutyl trimethoxy silane (ADBMS), trimethoxy [3-(phenylamino)propyl] silane (PAPMS), and triethoxy-3-(2-imidazolin-1-yl) propyl silane (IZPES). A parameter quantifying the grafting potentiality of each silane coupling agent towards OH-rich solid substrates (such as cellulose) was established as a function of the nature of the alkoxy groups (methoxy or ethoxy), as well as that of the fourth substituent (vinyl, aminopropyl, etc.) of the silane studied. GRAPHICAL ABSTRACT 相似文献
146.
M. Qasim H. Fredrickson P. Honea J. Furey J. Leszczynski S. Okovytyy 《SAR and QSAR in environmental research》2013,24(5):495-515
Highest occupied and lowest unoccupied molecular orbital energies, formation energies, bond lengths and FTIR spectra all suggest competing CL-20 degradation mechanisms. This second of two studies investigates recalcitrant, toxic, aromatic CL-20 intermediates that absorb from 370 to 430?nm. Our earlier study (Struct. Chem., 15, 2004) revealed that these intermediates were formed at high OH? concentrations via the chemically preferred pathway of breaking the C–C bond between the two cyclopentanes, thereby eliminating nitro groups, forming conjugated π bonds, and resulting in a pyrazine three-ring aromatic intermediate. In attempting to find and make dominant a more benign CL-20 transformation pathway, this current research validates hydroxylation results from both studies and examines CL-20 transformations via photo-induced free radical reactions. This article discusses CL-20 competing modes of degradation revealed through: computational calculation; UV/VIS and SF spectroscopy following alkaline hydrolysis; and photochemical irradiation to degrade CL-20 and its byproducts at their respective wavelengths of maximum absorption. 相似文献
147.
A simple synthetic route to 1-p-methoxyphenyl and 1-p-methoxyphenyl-4-methylbicyclo [2.2.1]heptan-7-one 6b,a has been developed through benzilic acid rearrangement of the bicyclo[2.2.1]octandiones 2b,a. The oxidation of 7-hydroxy-1-p-methoxyphenyl-4-methylbicyclo[2.2.1]heptan-7-carboxylic acid 3a with lead tetraacetate gives the carbolactone 7a which is also formed by the reaction of the ketone 6a with m-chloroperbenzoic acid. 相似文献
148.
Aasif Helal Hyun Gon Kim Manik Kumer Ghosh Cheol-Ho Choi Sung-Hong Kim Hong-Seok Kim 《Tetrahedron》2013
Two new reactive and highly selective turn-on fluorescent chemosensors based on the position of ring annulation of the naphthalene–thiazole moiety for aluminum ions in ethanol, were synthesized and investigated. It was found that sensors 2 and 4 exhibited a remarkable enhancement of emission upon complexation with Al3+. A TD-B3LYP/6-31G(d,p) calculation was performed to characterize the nature of the fluorescence behavior of sensors 2 and 4 upon Al3+ complexation. The mechanism of fluorescence was based on the cation promoted hydrolysis of ester and subsequent complexation. The combination of experimental and computational analyses provides a more complete understanding of the molecular level origin of these types of unique photophysical properties. 相似文献
149.
M. Sh. Ramadan S. A. Senior G. M. Nabil E. A. Hamed 《Journal of Dispersion Science and Technology》2013,34(12):1752-1760
Reaction rate for alkaline hydrolysis of the substrates 3,5-dinitro-2-chloro benzotriflouride (DNCBTF) (1) at 30°C and 2,4-dinitrochloro benzene (DNCB) (2) at 50°C separetely with NaOH as nucleophile is carried out spectrophotometrically in mixed aqueous-acetonitrile solvents. In each system, cationic surfactant as dodecyltrimethyl ammonium bromide (DoTAB), or anionic one as sodium dodecyle sulfate (SDS) is used in wide range of concentrations to study the effect of micelle on the reaction rate. The micellar effect is explained in term of modified pseudo phase ion exchange model. Pseudo first order rate constant, kobs is obtained for each of the nucleophile and for both substrates 1 and 2 at all range of XAN · kobs at given [OH?] and in presence of any substrate is found to increase with the increase of DoTAB,while decrease with the increase of SDS as micellar phases. Critical micelle concentrations (CMCs) in similar trend are observed to increase in DoTAB while decrease in SDS systems by increasing acetonitrile (AN) content. Micellar binding constant (KS) between any type of given substrate and the formed micelle, is found to decrease in presence of DoTAB and increase in SDS micellar phases by increasing AN content. Finally, the ratios between pseudo first order rate constants for hydrolysis in micellar phase kM to that in the bulk phase kw for DoTAB and SDS systems are found to be greater than and smaller than unity respectively at any given XAN where the data indicated for (1) is always higher than those for (2). The results concluded that micelle DoTAB is working as a catalyst for the reaction rate, while that for SDS is considered as an inhibitor. 相似文献
150.
Xia Dong 《Journal of Dispersion Science and Technology》2013,34(6):750-755
A series of dye-polyether derivatives, supposedly to be used as dispersants for parent dye, were synthesized by grafting poly(oxyalkylene)-amines based on differing both molecular weights and degrees of hydrophilicity/hydrophobicity, onto C.I. disperse red 60 via a stable urea linkage. The structures of the dye-polyether derivatives were characterized by FTIR, 1H NMR, and SEC. The influence of pH on the hydrolysis behaviors of the dye-polyether derivatives were studied in buffered aqueous solutions within the pH range of 4 to 10. The hydrolysis of dye-polyether derivatives was pH dependent and relatively faster in mild alkaline buffer solution than in acidic one. The influence of poly(oxyalkylene)-amine structure on the hydrolysis behavior was also investigated; it was found that the hydrolysis rate is affected little by the molecular weight and increases with the increasing hydrophilicity of the poly(oxyalkylene)-amine. 相似文献