Vinyl Sulfonates: A Click Function for Coupling‐and‐Decoupling Chemistry and their Applications

The term coupling‐and‐decoupling (CAD) chemistry refers to applications in which efficient bond formation and subsequent cleavage between two moieties is required. Within this context, the scope of the vinyl sulfonate (VSO) group as an efficient tool for CAD chemistry is reported. The coupling step relies on the click features of the Michael‐type addition of diverse nucleophiles to vinyl sulfonates as a valuable methodology. The feasibility of this strategy has been proved by the high yields obtained in mild conditions with model VSO derivatives. Cleavage of the resulting sulfonate adducts either through nucleophilic substitution with different nucleophiles (for alkyl VSO groups) or through hydrolysis (for both alkyl and aryl VSO) are successful strategies for the decoupling step, the former being the most promising, as the reaction proceeds under milder conditions with thiol nucleophiles. Moreover, the click VSO coupling chemistry proves to be orthogonal with the click CuAAC reaction, which enables the VSO‐CAD methodology for the preparation of hetero‐bifunctional clickable and cleavable linkers for double click modular strategies. The potential of the VSO‐CAD chemistry is demonstrated in two biologically relevant examples: the decoupling of sulfonates with glutathione (GSH) under conditions compatible with those of living systems; and the synthesis of homo‐ and heterogeneous multivalent glycosylated systems from 1‐thio and 1‐azido or 1‐azidoethyl sugar derivatives and bis‐vinyl sulfonates (homo systems) or alkynyl‐VSO bifunctional clickable‐cleavable linkers (hetero systems). As proof of concept, the cleavable character of these multivalent systems was demonstrated by using one of them as a reversible linker for the non‐covalent assembling and chemical decoupling of two model lectins.

     

脂肪酸甲酯磺酸盐的产业化开发

介绍了脂肪酸甲酯磺酸盐(MES)的生产技术和国内外发展的概况,指出MES生产过程的技术关键,提倡自主创新开发这一新的产品。     

糖基表面活性剂和不含硫酸盐的香波配方

从个人护理品配方中除去月桂基硫酸钠（SLS）和月桂基醚硫酸钠（SLES）的研究已进行了多年,讨论了一种新的受专利保护的基于糖原料的阴离子产品。     

Studies on surface activity of petroleum sulfonates prepared from extracts of solvent refining

Petroleum sulfonates with the active substance content from 21 to 32.5 % wt were prepared from four extracts of solvent refining by phenol and N-methylpyrrolidone (oil side streams II and III) in laboratory conditions. Their average molecular weight, composition, and surface activity were evaluated using a rotating drop test. The sulfonated products were characterized by NMR, IR spectroscopy, and HPLC methods.     

Synthesis,surface activity,and composition of dimeric petroleum sulfonates from low quality hydrocarbon feedstock

In the article we discuss the results of a comparison of interfacial activity and component composition data for petroleum sulfonates (PS) synthesized from an extract of selective N-MP refining of side stream II and for dimeric PS prepared from the same source in the presence of paraform (paraformaldehyde)—a component responsible for the formation of disulfonic acids. The prepared technical anionic PS are characterized by a higher molecular mass (688 g/mol) and lower CMC values (40-fold for the mass 120 concentration and 500-fold for the molar concentration) relative to paraform-free sulfonation of hydrocarbons. Surfactants with low CMC values sourced from the low-quality multitonnage hydrocarbon feedstock are promising in a search of formulations for chemical flooding of reservoirs.     

纳米铁还原TNT红水中二硝基甲苯磺酸(钠)的影响因素研究

考察了纳米铁的投加量、二硝基甲苯磺酸钠(DNTS)初始浓度、初始pH、纳米铁超声、干燥处理等因素对纳米铁还原TNT红水中DNTS效果的影响。结果表明:考察范围内,纳米铁/DNTS质量比越大,DNTS的去除率越高,单位质量纳米铁去除DNTS总质量越小;当初始pH<10时,去除率受pH影响不大,但准一级反应速率常数随pH上升而接近直线下降,酸性条件下还原更彻底,碱性条件下吸附沉淀作用更明显;干燥处理使纳米铁被部分氧化,还原能力下降;超声有助于促进纳米铁的充分分散和表面氧化层的剥离,提高反应活性。去除率随时间变化曲线表明,2,4-DNT-5-SO3Na(H)比2,4-DNT-3-SO3Na(H)容易被还原。     

磺酸盐表面活性剂与疏水缔合聚合物作用的热力学

采取物理涂敷的方式将疏水缔合聚合物(HAWP)直接涂敷到硅胶表面制备了HAWP涂敷硅胶固定相。对该固定相的元素分析结果表明HAWP被成功的涂敷到了硅胶表面。分别用蒸馏水、不同矿化度的试液作流动相,测定了不同碳数的单链苯磺酸盐、萘磺酸盐和双链苯磺酸盐在该固定相上的色谱保留参数,并对不同种类磺酸盐类表面活性剂和固载疏水缔合聚合物间的相互作用进行了热力学研究。结果表明,在蒸馏水溶液中,疏水缔合聚合物处于舒展状态,与磺酸盐表面活性剂之间的相互作用主要表现为疏水效应和位阻效应的竞争;在盐水溶液中,疏水缔合聚合物处于收缩状态,与磺酸盐表面活性剂之间的相互作用主要表现为疏水效应,且盐水的矿化度越高,HAWP收缩越严重,与磺酸盐之间的疏水效应也就越小。     

Fatty acid ecological tracers highlight the role of diet in perfluoroalkyl acid contaminant exposure in eggs of an omnivorous bird

Herring gulls (Larus argentatus) are generalist feeders; contaminant levels in their eggs reflect chemical exposure and uptake due to foraging in both aquatic and terrestrial environments. Hence, contaminant levels in their eggs provide insights into sources and relative importance of aquatic versus terrestrial pathways of chemical transfer. Here, perfluoroalkyl acids (PFAAs) known to be bioaccumulative were measured in individual herring gull eggs from one site on Lake Superior, Ontario, Canada. Thirteen perfluorinated carboxylates (PFCA, C₄-C₁₈) and four perfluorinated sulfonates (PFSA, C₄-C₁₀) were measured. Total PFCA and total PFSA concentrations varied 4- and 5-fold, respectively, among eggs. To understand these differences, stable carbon and nitrogen isotopes and fatty acid dietary tracers were measured in the same eggs. Stable isotopes were not useful in explaining inter-egg differences in PFAA concentrations. However, a variety of omega 3 (n-3) and omega 6 (n-6) fatty acid measures were correlated with C₉-C₁₃ PFCAs as well as the PFSAs: perfluoro-1-hexanesulfonic acid (PFHxS) and perfluoro-1-octanesulfonic acid (PFOS). In general, n-3 fatty acids were positively correlated with egg PFAA concentrations while only the n-6 fatty acids exhibited negative relationships with egg PFAA levels. Proportions of n-3 and n-6 fatty acids in eggs would be expected to increase and decrease, respectively, with increased aquatic food in the gull diet. Results indicate that increased use of aquatic food led to heightened PFAA exposure in these generalist consumers sampled in a relatively remote area. They also highlight the utility of employing a variety of dietary markers for understanding contaminant exposure and accumulation.     

Biological and electrochemical oxidation of naphthalenesulfonates

A biofilm airlift suspension (BAS) reactor and an undivided flow cell equipped with a boron‐doped diamond (BDD) anode and a stainless‐steel cathode were used to investigate the effects of varying operating conditions on process performance in the biological and electrochemical oxidation of a mixture of naphthalenesulfonates contained in the infiltration water of a contaminated industrial site. The experiments were aimed at evaluating the feasibility of process integration and the criteria for optimization (i.e. how to maximize degradation efficiency with minimum energy consumption) in combined biological and electrochemical oxidation of scarcely biodegradable compounds. Because of high reactor biomass concentration and long biomass retention time, the BAS reactor achieved a high degradation capacity (up to 6.8 kg COD m^?3 d^?1). On the other hand, owing to the recalcitrant character of some of the aromatic sulfonates in the leachate, the overall degradation efficiency did not exceed 70% based on COD measurements. All naphthalene‐mono‐ and ‐disulfonates (except naphthalene‐1,5‐disulfonate) were completely degraded in the BAS reactor, whereas more complex molecules (e.g. naphthalenetrisulfonates) were more recalcitrant to biological oxidation. These compounds were completely mineralized by electrochemical oxidation using a boron‐doped diamond anode. The energy consumption and the time required for the complete mineralization of the infiltration water decreased from 80 kWh m^?3 and 4 h to 61 kWh m^?3 and 3 h for the oxidation of raw and biologically pretreated leachate, respectively. Copyright © 2005 Society of Chemical Industry     

利用混合C9重芳烃回收磺酸盐装置技术经济分析

介绍了回收磺酸盐生产工艺，对其装置的产品成本进行了测算，并对盈亏平衡及其敏感性进行了分析，进而确定了主要经济指标。