对称正-负离手表面活性剂的胶团化和表面吸附自由能

根据所建议的表面活性剂疏水碳氢基在水溶液中自卷曲的分子构型和碳氢链/水界面自由能降低模型导出了对称正-负离子表面活性剂胶团化和表面吸附自由能及疏水自由能公式,计算结果支持上述理论模型。     

表面活性剂胶团形成的自由能改变——碳氢链卷曲构象证据之一

用两种方法对各种类型表面活性剂水溶液胶团形成的碳氢链部分的标准自由能改变进行了计算: 一种是根据表面活性剂同系物的临界胶团浓度实验数据; 另一种是按照分子结构与碳氢链构象的模型。两种计算结果相符, 说明假设的分子结构与构象模型合理, 首次提供了表面活性剂长碳氢链在水中自卷曲的一种证据。     

表面活性剂和四烷基溴化铵的复配 Ⅲ.四烷基溴化铵碳氢链长对离子型表面活性剂在气/液表面吸附行为的影响

本文考察了四烷基澳化铵(TAAB)碳氢链长对离子型表面活性剂SDS和DTAB在气/液表面吸附行为的影响.实验结果表明,与表面活性剂离子对应的添加剂反离子是影响其水溶液表面活性的主要因素,因而TAAB对SDS表现出明显的效应,对DTAB影响效果则和同浓度的NaBr类似.除了对表面活性离子头基电荷的静电屏蔽外,TAA+的碳氢基团和SD-碳氢链间还可能发生疏水相互作用,但后者受TAA+离子体积制约.TAAB对SDS在气/液表面吸附行为的影响是上述几个因素的综合作用结果.     

碳氢表面活性剂在超临界CO_2中形成微乳液的研究进展

在超临界CO2中形成微乳液可以克服CO2对高分子量和亲水性物质溶解能力差的缺点。碳氢表面活性剂成本低,对环境友好,利用碳氢表面活性剂形成超临界CO2微乳液有利于工业应用,但绝大部分碳氢表面活性剂不能形成微乳液,所以需要对碳氢表面活性剂进行选择和设计。本文介绍了微乳液的形成、表征和评价,从表面活性剂的亲CO2性能和界面活性两方面,综述了碳氢表面活性剂的设计思路和进展。另外介绍了助表面活性剂对形成超临界CO2微乳液的作用,并对常规碳氢表面活性剂在助表面活性剂的作用下形成超临界CO2微乳液的体系进行了综述。最后,介绍了含碳氢表面活性剂的混合表面活性剂在形成超临界CO2微乳液方面的研究情况。     

表面活性剂和四烷基溴化铵的复配：Ⅲ.四烷基溴化铵碳氢链长对 …

本文考察了四烷基溴化铵（ＴＡＡＢ）碳氢链长对离子型表面活性剂ＳＤＳ和ＤＴＡＢ在气／液表面吸附行为的影响。实验结果表明：与表面活性剂离子对应的添加剂反离子是影响其水溶液表面活性的主要因素,因而ＴＡＡＢ对ＳＤＳ表现出明显的效应,对ＤＴＡＢ影响效果则是同浓度的ＮａＢｒ类似,除了对表面活性离子头基电荷的静电屏蔽外,ＴＡＡ＾＋的碳氢基团和ＳＤ＾－碳氢链间还可能发生疏水相互作用,但后者受ＴＡＡ＾＋离子体积制约     

碳氢表面活性剂在超临界CO2中形成微乳液的研究进展

在超临界CO₂中形成微乳液可以克服CO₂对高分子量和亲水性物质溶解能力差的缺点。碳氢表面活性剂成本低,对环境友好,利用碳氢表面活性剂形成超临界CO₂微乳液有利于工业应用,但绝大部分碳氢表面活性剂不能形成微乳液,所以需要对碳氢表面活性剂进行选择和设计。本文介绍了微乳液的形成、表征和评价,从表面活性剂的亲CO₂性能和界面活性两方面,综述了碳氢表面活性剂的设计思想和进展。另外介绍了助表面活性剂对形成超临界CO₂微乳液的作用,并对常规碳氢表面活性剂在助表面活性剂的作用下形成超临界CO₂微乳液的体系进行了综述。最后,介绍了含碳氢表面活性剂的混合表面活性剂在形成超临界CO₂微乳液方面的研究情况。     

四乙铵离子对阴离子表面活性剂及其混合体系的表面活性和胶团形成的影响

研究了溴化四乙铵介质中十二烷基硫酸四乙铵、全氟辛基磺酸四乙铵及其混合体系的表面化学性质。四乙铵离子在浓度较小时主要起电解质反离子作用,在浓度较大时则明显参与表面吸附和胶团的形成,其作用相当于在表面活性离子的疏水链上“引入”碳氢链,从而导致表面活性提高和碳氢/碳氟表面活性剂混合体系中碳氢/碳氟链间的互疏作用减弱等。     

表面活性剂对污泥脱水性能影响的机理研究:Gemini表面活性剂与聚电解质相互作用的分子动力学模拟

表面活性剂可以与污泥表面的胞外聚合物(EPS)吸附形成胶束,释放出自由水和结合水,从而达到改善污泥脱水性能的目的.本文采用粗粒化的分子动力学模拟方法,研究了Gemini表面活性剂与EPS形成复合物的过程和结构.聚电解质链的亲疏水性对吸附过程有显著影响,亲水聚电解质链与Gemini表面活性剂吸附的主要驱动力为静电吸引,Gemini表面活性剂头基吸附在链上,尾链朝向溶剂;疏水聚电解质链与Gemini表面活性剂吸附过程由静电作用与疏水作用共同促进,Gemini表面活性剂以平行于聚电解质链的构型存在.Gemini表面活性剂联结基团长度对吸附过程的影响甚微;聚电解质链的电荷密度对亲水聚电解质链的吸附产生协同作用,对疏水聚电解质链的吸附不产生作用.     

碳氟-碳氢表面活性剂混合水溶液在油面上铺展

本文研究RfCONH(CH2)3N(C2H5)2CH3I/CnH2n 1,COONa及RfCOONa/CmH2m 1N(CH3)3Br(Rf=F[CF(CF3)CF2O]2CF(CF3);n=7,8.11,13;m=8,10,12)两类正，负离子碳氟－碳氢表面活性剂混合水溶液在油面上的铺展及对油面的密封性能。研究表明在碳氟表面活性剂中加入异电性碳氢表面活性剂可大大降低碳氟表面活性剂水溶液的铺展浓度，也可使一些因素表面张力较高而不能铺展的碳氟表面活性剂水溶液在油面上铺展。在碳氟表面活性剂中加入异电性碳氢表面活性剂可提高水膜对油面的密封性。若在混合表面活性剂中加入黄原胶，水膜的密封性能更好。     

正、负离子碳氟-碳氢表面活性剂混合水溶液的表面活性

1　前言碳氟表面活性剂是目前所有表面活性剂中表面活性最高的一类 ,具有很多碳氢表面活性剂无法取代的特殊用途[1] 。但是碳氟表面活性剂由于合成困难 ,价格昂贵 ,实际应用受到限大限制。研究表明 ,通过碳氟表面活性剂与碳氢表面活性剂的复配 ,有可能减少碳氟表面活性剂的用量而保持其表面活性 [1] 。在所有表面活性剂混合体系中 ,正、负离子表面活性剂混合体系具有最强的协同效应 [2 ] 。但由于正、负离子表面活性剂混合溶液一般在很低浓度即形成沉淀 ,对碳氟表面活性剂更是如此。因此目前有关碳氟—碳氢混合表面活性剂的研究主要集中在同…     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.