非水层状液晶的稳定性与相行为

水体系层状液晶已研究较久,非水层状液晶则是近十年来才得到发展。本文以层状液晶的相行为和~2H NMR测量,研究并比较了非水层状液晶十二烷基硫酸钠/正癸醇溶剂以甘油或甲酰胺为溶剂时体系的结构与稳定性。 表面活性剂十二烷基硫酸钠(BDH,简写SDS)经无水乙醇重结晶两次提纯。用铂环法测     

用共轭亚油酸构筑层状液晶的药物传递系统

在水相中用共轭亚油酸(CLA)及其钠盐(SCL)构筑层状液晶相, 并考察了其药物缓释行为. 借助偏光显微镜并辅以目测确定CLA/SCL/H₂O三元相图中的层状液晶相区, 然后用偏光显微镜、 小角X射线散射仪和旋转流变仪获得层状液晶的偏光织构、 相参数和流变参数等, 证实其适用于药物传递系统(DDS). 采用透析法研究了负载亲水性药物5-氟尿嘧啶或亲油性药物姜黄素的层状液晶的释药曲线, 结果表明, 该类层状液晶对2种药物均有良好的缓释能力.     

水与非水体系层状液晶稳定性的研究

水体系层状液晶已有较长的研究历史,非水层状液晶则是近年来才得发展.本文以层状液晶的相行为和~2H NMR测量,研究以极性有机物甘油代替水为溶剂后,对十二烷基硫酸钠/正癸醇/溶剂体系层状液晶稳定性的影响。1 实验试剂C_(12)H_(25)SO_4Na(SDS),正癸醇(C_(10)H_(21)OH,简为C_(10)OH),甘油(简为Gly)均同文献,水为二次蒸馏水.氚代物SDS_(-d25)和C_(10)OH_(-d21)均出自Cambridge Isotopes. 层状液晶单相区域的确定和~2H NMR测量见文献[92].     

CTMAB-C5H11OH-H2O体系微乳液、液晶及其增溶特性

微乳液、液晶及其增溶作用具有重要的理论意义及应用价值,已引起重视与关注。本文研究了CTMAB-C_5H_(11)OH-H_2O体系微乳液、层状液晶及其对C_7H_(16)的增溶特性。1 实验方法十六烷基三甲基溴化铵(分析纯,简称CTMAB)、正戊醇、正庚烷,皆为分析纯,H_2O为二次蒸馏水。1.2 各向同性区域的测定先以滴定法粗略确定单相区域的相界线,然后在相界线两侧均匀选点配样,于25.0±     

壬基酚聚氧乙烯醚(10)/水体系层状液晶的流变性

采用应力控制流变仪,研究了非离子表面活性剂壬基酚聚氧乙烯醚(10)(NP-10)/水体系层状液晶在不同温度和表面活性剂质量分数的流变性。 在线性黏弹区内,其储能模量和损耗模量与频率的关系不符合Maxwell模型,并用滑移模型、范德华力、水化作用解释了非离子表面活性剂层状液晶表现此类流变性的原因;用Burgers模型解释了蠕变-回复实验的结论,其结果与线性的振荡实验一致。     

直链醇链长对层状液晶结构与稳定性的影响

作为助表面活性剂,直链醇在层状溶致液晶的制备中是非常重要的。本文以层状液晶的相行为和小角度X射线衍射测量,研究了直链醇链长对层状液晶结构与稳定的影响。     

辛基三甲基溴化铵与辛基硫酸钠混合水溶液的相行为

对辛基三甲基溴化铵(OTAB)与辛基硫酸钠(SOS)正、负离子混合表面活性剂水溶液的相行为进行了研究.在高浓度的溶液中,混合表面活性剂形成液晶相,随着混合摩尔比OTAB/SOS接近于1,液晶结构由六角相转层状相,同时夹杂少量沉淀物;在中等浓度时,任意混合摩尔比例下皆为均相透明溶液;在低浓度下,在很宽的OTAB/SOS混合摩尔比的范围,出现双水相,其中的表面活性剂稀薄相,为不同大小的胶团与囊泡组成的稀溶液,另一表面活性剂富集相中则为数密度很大的囊泡聚集体,富集相对油溶性染料的增溶作用比非富集相高得多.     

油酸/三乙醇胺/液体石蜡水体系层状润滑性能

层状液晶;油酸/三乙醇胺/液体石蜡水体系层状润滑性能     

SDS/苯甲醇/H2O体系的相行为与结构

SDS／苯甲醇／H2O体系能生成胶束、微乳液、层状液晶、六角状液晶等分子有序组合作，它们之间转换关系可以从凝聚能理论得到解释．来甲酸在O／W微乳液中的分配系数K＝168，表明绝大多数苯甲醇被增溶于SDS胶束相内．随重量比本甲醇／SDS增加，层状液晶中的do值几乎不变，溶剂渗透率略有增加，六角状液晶中圆柱缔合体的半径r值几乎不变，溶剂渗透率增加．     

溶致液晶模板电化学沉积束状铂纳米材料

以非离子型三嵌段共聚物EO106PO70EO106 (F127)/正丁醇/氯铂酸水溶液构建的溶致液晶层状相为模板, 电化学沉积制备铂纳米材料. 透射电镜和扫描电镜显示, 产物为具有高长径比的纳米线形成的束状结构, 能量弥散谱与电极电势分析证实产物为铂单质, 而循环伏安测量表明产物的比表面积约为53 m2•g−1. 对影响产物形貌的因素和产物生成的可能机理进行了分析.     

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%.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

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.