壳聚糖液晶溶液的性能

制备了聚糖液晶溶液,并采用偏光显微镜(POM)、流变仪、差示扫描量热仪(DSC)等分别对液晶织构、黏度、相转变性能进行了研究.结果表明:壳聚糖呈现典型的胆甾相液晶织构;其溶液黏度随浓度及剪切力的变化规律符合高分子液晶溶液的变化规律;在DSC升、降温曲线上分别存在吸热峰和放热峰.     

席夫碱型液晶冠醚的合成与性质

以4-(4'-烷氧基联苯基-4-羧基)苯甲醛和二氨基二苯并-14-冠-4为原料,通过溶液缩合反应,合成了一系列席夫碱型液晶冠醚.并用元素分析、旋光仪、核磁共振、红外光谱、快原子轰击质谱、基质辅助激光解析电离飞行时间质谱、示差扫描量热法和偏光显微镜对其进行了表征.发现化合物2,4,8I和8Ⅱ加热至各自的熔点以上都能形成液晶态,在液晶态可以观察到手性近晶C相、近晶相、胆甾相和向列相的典型织构.随分子末端烷氧基碳原子数增加,化合物(除2A和4A外)的熔点(Tm)和液晶态的清亮点(Ti)呈规律性变化,近晶相范围渐增,而近晶相-向列相转变温度和向列相温度范围递减.     

丁酸壳聚糖液晶的织构研究

用偏光显微镜研究了一种新的液晶高分子－丁酸壳聚糖液晶的织构。丁酸壳聚糖能溶于十多种溶剂中形成胆甾型液晶相。指纹状织构是主要织构，此外还观察到鲜偏振场织构、滴状织构、平面织构和条带织构等，与纤维素衍生物的液晶态结构很相似。     

5-{[(4′-正戊基氧-4-联苯基基)羰基]氧}-1-戊炔的相转变与相结构

采用差示扫描量热(DSC)、一维(1D)广角X射线衍射(WAXD)、热台偏光显微镜(PLM-hotstage)等研究手段对含联苯液晶基元的侧链液晶聚炔单体5-{[(4′-正戊基氧-4-联苯基基)羰基]氧}-1-戊炔(A3EO5)的本体相转变和相结构进行了研究.DSC和1D-WAXD实验结果表明,A3EO5在升温和降温过程中均呈现四个相转变过程,形成双向性液晶.样品从各向同性态降温至室温过程中,首先形成近晶A相,随后进入层内排列具有准长程有序的近晶B相,继续降温将形成层内为正交排列的近晶E相,在此之后样品进入晶相.PLM结果指出样品在各向同性态降温过程中分别形成球状织构、角锥织构和同心圆弧织构.     

一代树状碳硅烷液晶研究－端基含12个丁氧基偶氮苯介晶基元

用发散法合成周边含12个丁氧基偶氮苯介晶基元（M5）端基新的一代树状碳硅 烷（D1）。并用元素分析、核磁共振、激光解吸电离飞行时间质谱、红外、紫外、 偏光显微镜、差示扫描量热（DSC）和广角X射线衍射（WAXD）表征。D1为向列相与 M5相同，树状物相态由介晶基元相态决定，D1相行为：K82N133I132N67K，D1熔点 比M5降低30－43℃，D1清亮点比M5增加9－11℃，D1介晶相区比M5加宽39－54℃， 观察到8条黑刷的树状物的高强向错（S＝＋2），D1清亮焓值略低于通常液晶n-i相 变清亮焓值，原因是枝化的树状物核心不易完全变形为液晶态的各向异性结构。     

三代树状碳硅烷液晶研究——端基含丁氧基偶氮苯介晶基元

用发散法合成周边含丁氧基偶氮苯介晶基元(M5)端基新的三代树状碳硅烷(D3) 液晶,并用元素分析,核磁共振,激光解吸电离飞行时间质谱(MALDI-TOF-MS),红外、 紫外、偏光显微镜、差示扫描量热（DSC）和广角X射线衍射（WAXD）表征，D3为向 列相与M5相同，树状物相态由介晶基元相态决定，D3相行为；K79N1261116N，D3熔 点比M5降低33℃，D3清亮点比M5增加2℃，D3液晶态温区比M5加宽35℃。     

二代树状碳硅烷液晶研究I.端基含36个丁氧基偶氮苯介晶基元

用发散法合成周边含36个丁氧基偶氮苯介晶基元（M5）端基新的二代树状碳硅 烷液晶（D_2），并用元素分析，氢谱，激光质谱，红外，紫外，偏光显微镜，DSC和WAXD法表 征D2为向列相，与M5相同，二代树状物相态由介晶基定．D2液晶态相行为是 K85N107I103N69K，其熔点比M5降低27-41℃，清亮点比M5降低17-18宽10-23℃．二 代碳硅烷（D2）与一代碳硅烷（D1）相比熔点增加2-3℃，清亮点降低26-29℃，液 晶态温区减少℃．在二代树状物中观察到S＝＋3／2的高强向错．     

二代树状碳硅烷液晶研究I.端基含36个丁氧基偶氮苯介晶基元

用发散法合成周边含36个丁氧基偶氮苯介晶基元（M5）端基新的二代树状碳硅 烷液晶（D_2），并用元素分析，氢谱，激光质谱，红外，紫外，偏光显微镜，DSC和WAXD法表 征D2为向列相，与M5相同，二代树状物相态由介晶基定．D2液晶态相行为是 K85N107I103N69K，其熔点比M5降低27-41℃，清亮点比M5降低17-18宽10-23℃．二 代碳硅烷（D2）与一代碳硅烷（D1）相比熔点增加2-3℃，清亮点降低26-29℃，液 晶态温区减少℃．在二代树状物中观察到S＝＋3／2的高强向错．     

胶原液晶膜的制备及对细胞生长的影响

从仿生角度出发, 制备了一系列液晶态胶原薄膜. 采用偏光显微镜、扫描电镜和原子力显微镜分别研究了各种膜的液晶织构和拓扑结构, 并通过3-(4,5-二甲基噻唑-2)-2,5-二苯基四氮唑溴盐(MTT)法及细胞骨架荧光染色观察研究了各种膜对鼠成纤维细胞3T3的黏附、增殖以及形貌的影响. 结果表明, 胶原液晶薄膜呈现典型的胆甾型液晶织构, 与非液晶薄膜相比, 它不仅能更好地促进细胞的黏附、生长及增殖, 而且其拓扑结构对细胞生长具有接触引导效应.     

一种侧链液晶高分子的合成与表征

合成了一种主链为甲基丙烯酸酯 ,侧链是三个苯环以酯键相连的介晶基元 ,柔性间隔段为两个亚甲基的新的侧链液晶高分子 .聚合物和单体的化学结构、液晶相转变和液晶态织构采用红外光谱、核磁共振、偏光显微镜、差热分析和广角X光衍射进行了表征 .研究表明 ,单体呈现近晶相和向列相两个液晶相 ,聚合物在很宽的温度范围内呈向列相 .该单体和聚合物在一定条件下可形成固化诱导条带织构     

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.     

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.     

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.     

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.