Effects of Cationic Micelles on the Rate of Intramolecular General Base-Catalyzed Reaction of Ionized Phenyl Salicylate with DL-Proline

Pseudo-first order rate constants (k_obs) obtained for the reaction of ionized phenyl salicylate (PS^-) with anionic DL-proline (Prl^-) at a constant [NaOH] and [CTABr] (where CTABr represents cetyltrimethylammonium bromide) and 35°C, show a linear increase with increasing total concentration of Prl^-; Nucleophilic second-order rate constants (k_n ^obs) for the reactions of Prl^- with PS^- reveal a nearly 5-fold decrease with the increase in [CTABr] from 0.0 to 0.01 M.     

Kinetics of Alkaline Hydrolysis of Quaternary Phosphonium Salts. The Influence of Protic and Aprotic Solvents on the Hydrolysis of Alkyl Phenylphosphonium Salts

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.     

Effects of Nonionic and Mixed Cationic-Nonionic Micelles on the Rate of Alkaline Hydrolysis of 4-Nitrophthalimide

Pseudo-first-order rate constants (k_obs) for alkaline hydrolysis of 4-nitrophthalimide show a monotonic decrease with increase in [C₁₂E₂₃]_T (total concentration of Brij 35) at constant [CH₃CN] and [NaOH]. This micellar effect is explained in terms of a pseudophase micelle model. The rate of hydrolysis becomes too slow to monitor at [C₁₂E₂₃]_T≥0.03 M in the absence of cetyltrimethylammonium bromide (CTABr) and at [C₁₂E₂₃]_T≥0.04 M in the presence of 0.006–0.02 M CTABr at 0.01 M NaOH. The plots of k_obs versus [C₁₂E₂₃]_T show minima at 0.006 and 0.01 M CTABr, while such a minimum is not visible at 0.02 M CTABr.     

Effects of Various Schiff Base Ligands and Micelles on the Hydrolytic Kinetics of p-Nitrophenyl Picolinate

In this article, the effects of different micelles and Schiff base ligands on the hydrolytic kinetics of p-nitrophenyl picolinate (PNPP) were evaluated. The results reveal that the biggest rate enhancement for PNPP hydrolysis was given in Gemini 16-6-16 micellar solution relative to other four reaction media, that is, cetyltrimethylammonium bromide (CTAB), n-lauroylsarcosine sodium (LSS), polyoxyethylene (23) lauryl ether (Brij35) and pure buffer. Moreover, the hydrolytic rates of PNPP in other four media decreased in the order LSS > CTAB > Buffer > Brij35. The structural effects of Mn(III) catalysts clearly testify that a relatively open active site facilitates the formation of reactive substrate-catalyst complex.     

The Effect of Temperature on the Rate of Alkaline Hydrolysis of Esters in Concentrated Aqueous Solutions of Et4NCl

The rate of alkaline hydrolysis of 4-nitrophenyl toluenesulfonate, 4-nitrophenyl diethyl phosphate, and 4-nitrophenyl dimethylcarbamate (with Et₄NOH as reagent) in concentrated aqueous solutions of Et₄NCl (0-4.5 M) at 15, 25, 40, and 60 °C was studied. The nature of the effect of Et₄NCl on the reaction rate was explained by the action of the electrolyte on the structure of the water. It was shown that the increase in the rate results from change in the solvation component of the free energy of activation.     

阳、阴、非离子表面活性剂胶束对酯碱性水解的影响

应用紫外分光光度法和热动力学方法研究了芳香酸酯和正脂肪酸酯在表面活性剂ＤＴＡＢ、ＴＴＡＢ、ＣＴＡＢ、ＳＤＳ、Ｂｒｉｊ３５、ＴｒｉｔｏｎＸ－１００胶束中的碱性水解反应。阳、阴、非离子表面活性剂胶束对酯的碱性水解均有禁阻作用。讨论了胶束对酯碱性水解禁阻作用的原因。     

Binary Coalescence of Water Drops in Organic Media in Presence of Ionic Surfactants and Salts

Binary coalescence of water drops in o‐xylene and toluene, and ethylene glycol drops in toluene were studied in this work. The effects of cationic and anionic surfactants on coalescence time were studied. Cetyl trimethyl ammonium bromide (CTAB) and cetyl pyridinium bromide (CPyBr) were used as cationic surfactants. Sodium dodecyl benzene sulfonate (SDBS) was used as the anionic surfactant. The effects of salts (NaCl and CaCl₂) containing monovalent and divalent ions on coalescence were investigated. The coalescence time was found to follow distributions in each of these experiments. The minimum and maximum values of the distributions were largely different. The stochastic model developed earlier by us was used to fit the distributions. The effects of the physical properties of the system (such as density, size of the drops, interfacial tension, and surface excess of adsorbed surfactant) on the model parameters were discussed.     

基于IrYdium Chemistry Lab的可视化教学设计——以“盐类的水解”为例

利用虚拟化学实验软件IrYdium Chemistry Lab为基本工具，探讨其在“盐类的水解”一节进行可视化教学设计的具体方法和教学应用价值。说明基于虚拟化学实验的可视化教学设计，能兼顾表达思维可视化过程和结果，有利于强化学生的学科理解能力。     

基于认知模型建构的“盐类水解程度大小内因分析”的教学实验设计

从认知模型建构的角度对“盐类水解程度大小的内因分析”进行研究。在此基础上从同周期、同主族以及相同元素不同组成的物质3个维度出发,选用Na2CO3,Na2SiO3,Na2GeO3,NaHCO3,FeCl3,ZnCl2,CuCl2为基本物质,利用精密pH试纸结合浊度计为检测手段,设计相关的教学实验,为学生有效建构“盐类水解程度大小与盐的组成和结构有关”这一核心观念提供实验事实支撑。该组实验装置简单、操作简便、现象明显,能很好地帮助学生建构科学观念。     

Growth of Gemini Surfactant Micelles Under the Influence of Additives: DLS Studies

Results are presented on the first extensive study on the influence of additives on the growth of gemini; alkanediyl α, ω - bis(dimethylcetylammonium bromide) surfactant micelles (16-s-16, with s = 5, 6); as measured by dynamic light scattering technique at 30°C. The effect of adding n-butanol, n-pentanol, n-hexanol, and n-hexylamine in the absence or presence of general ionic salt potassium bromide on 0.03 M gemini solutions were observed. The tendency for micelles to grow from spherical to rodlike structures is decisively influenced by the spacer length s. At 30°C, the micellar growth was more for s being 5, which has been interpreted in terms of short spacer having strong propensity for micellar growth. Addition of KBr plays a role in screening of the electrostatic interactions, thus promoting a change of morphology of the aggregates and giving rise to high hydrodynamic diameter (D _h ) values. The micellar growth in presence of alcohols is interpreted in terms of the formation of the gemini–alcohol mixed micelles which followed the pattern C₆OH>C₅OH>C₄OH. For equal chain length additives C₆OH and C₆NH₂, the growth was more pronounced in case of alcohol. Also, in case of C₆NH₂, the value of D _h reached to almost constancy or decreased to some extent, which is discussed in terms of its partitioning in aqueous phase. A combined presence of KBr and n-alcohols or n-hexylamine produced favorable conditions for micellar growth due to synergistic effect.     

Photochemical Cleavage of the N—O Bond in 1-Benzoyloxy-4-[4-(dimethylamino)styryl]pyridinium Salts

The effect of UV or visible light on solutions of 1-benzoyloxy-4-[4-(dimethylamino)styryl]pyridinium salts in acetonitrile solution lead to cleavage of the N—O bond and formation of 4-[4-(dimethylamino)styryl]pyridine.     

Nucleophilic Substitution at Tricoordinate Sulfur—Alkaline Hydrolysis of Optically Active Dialkoxysulfonium Salts: Stereochemistry,Mechanism and Reaction Energetics

Optically active dialkoxyisopropylsulfonium salts were obtained by methylation (ethylation) of optically active alkyl isopropanesulfinates using methyl (ethyl) trifluoromethanesulfonate. Alkaline hydrolysis of a series of methoxy(alkoxy)sulfonium salts afforded the two sulfinate products methyl isopropanesulfinate and alkyl isopropanesulfinate, both formed with a slightly prevailing inversion of configuration at the sulfur atom. DFT calculations revealed that this substitution reaction proceeded stepwise according to an addition-elimination (A–E) mechanism involving the formation of high tetracoordinate S^IV sulfurane intermediates. In addition, the DFT calculations showed that recombination of the hydroxy anion with the methoxy(alkoxy)sulfonium cation—leading to the parallel formation of the two most stable primary sulfuranes, with the hydroxy and alkoxy groups in apical positions and their direct decomposition—is the most energetically favorable pathway.     

Effects of Sodium Salts Organic Acids Modification on the Microstructure and Dispersion Behavior of Palygorskite Nano-Powder via High-Pressure Homogenization Process

High-pressure homogenization could disaggregate the crystal bundles of palygorskite and favor the adsorption of electrolyte ions onto its surface through the produced cavitation, shear, and turbulence forces, and has evident influences on the micromorphologies and properties of clay. In this work, a series of palygorskite samples modified with sodium citrate, sodium benzoate, sodium lactate, sodium acetate, and sodium propionate were obtained under the condition of high-pressure homogenization. The effects of type and concentration of sodium salts organic acids on the microstructure, morphology, surface charge, and physicochemical property of palygorskite were studied through x-ray diffraction (XRD), N₂ adsorption–desorption isotherm, field emission scanning electron microscopy, zeta potential, rotational viscosity, and rheological measurements. XRD results confirmed that the crystal structure of homogenized palygorskite was not changed after introduction of sodium salts organic acids, but the aggregates were effectively disaggregated. Modification of palygorskite with sodium citrate made the surface more negatively charged, and the samples exhibited higher specific surface area and rheological properties. This work provided a method to improve the rheological properties of palygorskite suspension through dispersion of clay in sodium citrate solution followed by homogenization at 30 MPa.      

Abiotic Hydrolysis of Poly[(R)-3-hydroxybutyrate] in Acidic and Alkaline Media

Poly[(R)-3-hydroxybutyrate)], P(3HB), is the most common member of polyhydroxyalkanoates, the natural biopolyesters of intrinsic biodegradability and biocompatibility. Abiotic hydrolysis of P(3HB) was investigated in acid and base media by monitoring the formation of two monomer products, 3-hydroxybutyric acid (3HB) and crotonic acid (CA), from three types of P(3HB) samples, amorphous granules, irregular precipitates and solvent cast films. The soluble monomeric products were not detected in acid solutions (0.1 to 4 N H⁺), but measured as the major hydrolytic products in base solutions (0.1 to 4 N OH⁻). Unlike the protons as catalyst in both hydrolysis and esterification, hydroxyl anions were consumed during formation of carboxylate anions. The amorphous granules of P(3HB) were decomposed 80- to 100-fold faster than the precipitates and solvent cast films. The latter two had around 71% crystallinity. The hydrolysis of amorphous grannules exhibited a quasi 0^th-order reaction rate and the activation energy of saponification was 82.2 kJ/mol, silimar to those of the biotic hydrolysis of P(3HB) by enzymes and living cells.     

Formation of TiO2 Sols,Gels and Nanopowders from Hydrolysis of Ti(OiPr)4 in AOT Reverse Micelles

Titania sols, gels and nanopowders have been produced by the controlled hydrolysis of tetraisopropyltitanate (TPT) in sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reverse micelles. Particle formation and aggregation have been investigated by photon correlation spectroscopy, the crystal phases by FT-Raman spectroscopy, and the crystallite dimensions of the precipitates by transmission electron microscopy. Nanoparticles could be produced at relatively high Ti(IV) concentrations (up to 0.05 mol dm^–3). These nanoparticles aggregated into sols, with colloid sizes of 20–300 nm, eventually forming gelatinous precipitates. The kinetics of particle formation and aggregation were controlled by varying the primary process parameters [TPT], [H₂O]/[AOT] (w₀), and [H₂O]/[Ti(IV)] (R), yielding a range of products including stable, transparent sols, precipitates and monolithic gels. The aggregation kinetics and physical properties of the sols depended strongly on w₀. Different titania phases were produced, depending on w₀; w₀ 6 yielded amorphous particles, while w₀ 10 produced anatase. The dimensions of the crystallites were comparable to those of the parent reverse micelles. A model was developed to interpret the effect of the primary process parameters on colloidal stability: (1) nucleation to form primary crystallites occurs by rapid hydrolysis and condensation reactions within the reverse micelle and (2) subsequent colloidal growth by aggregation occurs by reverse micellar exchange, where the rate of growth is governed by electrostatic and steric stability factors which increase as [AOT]/[TPT] (S) and residual [H₂O]/[AOT] (w_r) increase.     

Effect of Different Saline,Alkaline Salts,Fertilizers and Surfactants on the Movement of Some Carbamoyl Group Containing Pesticides in Soils

Abstract

The influence of organic matter, calcium carbonate, flyash, saline and alkaline salts, inorganic fertilizers, surfactants and exchangeable ions on the mobility of five carbamoyl group containing pesticides has been studied using soil thin-layer chromatography. The variations in the R_f, R_B and R_M values of aldicarb, bavistin, carbofuran, dimecron and oxamyl under different treatments are reported and explained on the basis of adsorption and leachability.     

反胶束固定化乳酸脱氢酶的催化动力学性质研究

以十六烷基三甲基溴化铵(CATB)-辛烷-己醇反胶束体系对乳酸脱氢酶(LDH)进行固定化,试验了含水量、CTAB和己醇浓度对LDH固定化的影响。对游离酶和固定化酶的催化动力学性质研究表明:酶促反应的最适pH值分别为9.2和9.5,最适温度分别是37℃和43℃,对乳酸的米氏常数Km分别为1.4 mmol/L和2.3mmol/L。30℃时,游离酶存放2 h,约失活50%,而固定化酶仅失活10%,表明反胶束固定化LDH具有较好的热稳定性。     

丙烯酰胺-4-乙烯基吡啶胶束共聚合的动力学研究

以十二烷基苯磺酸钠为表面活性剂，过硫酸钾／亚硫酸氢钠为引发剂，丙烯酰胺／4－乙烯基吡啶胶束共聚合，并用^1H-NMR表征该共聚物。研究亲水单体用量、亲油单体用量、引发剂用量、表面活性剂用量对聚合反应动力学的影响。结果表明：Rp∝[M]^1.24,Rp∝[E]^-0.33,Rp∝[I]^0.28。     

Structural Effects in the Addition–Fragmentation Reaction of Allylic Onium Salts

Allylic onium salts with different hetero‐atoms and various substituent groups at the allylic double bond have been shown to be very efficient initiators for cationic polymerization. When attacked by a radical, they become radical cations, which are highly unstable species, and undergo fragmentation into smaller radical cations called onium radical cations. The reaction mechanism involves radical formation, addition and fragmentation. In our previous work, radical initiators generated in the same way and under the same conditions are studied experimentally for their ability to affect the polymerization efficiency. Here, the factors affecting the polymerization efficiency are discussed theoretically using semi‐empirical quantum mechanical techniques. The type of radical species, substituent group at the allylic side, the heteroatom at the onium side and the onium group itself are analyzed separately. For this purpose, the geometries of different onium radical cations to be fragmented are optimized and the strength of the C–heteroatom bond to be broken and the size of the radical cations after fragmentation are considered.