含偶氮苯生色团的聚醚的合成与热致液晶性质

β－氯乙基缩水甘油醚（ＧＣＥ）和ＧＣＥ／羟丁基乙烯基醚（ＨＢＶＥ）分别通过阳离子聚合、光引发共聚合,获得两种聚醚,然后再分别与４－硝基－４’－羟基偶氦苯（ＮＨＡ）反应,制备了两种侧链含偶氦苯生色团的液晶聚合物（ＰＡＥＧ、ＰＡＶ）。用ＦＴＩＲ、＾１Ｈ－ＮＭＲ和ＥＡ对其化学结构及生色团含量进行了表征,以ＰＯＭ,ＤＳＣ、ＴＧＡ和ＷＡＸＤ对聚合物介晶相转变温度、织构、热稳定性及相行为进行了研究。结果表明,     

聚对苯二甲酸乙二酯／热致液晶聚合物共混体系中液晶组分的诱导结晶效应

用差示扫描量热法对聚对苯二甲酸乙二酯（ＰＥＴ）／热致液晶高分子（ＬＣＰ）共混体系的等温和非等温结晶行为进行了研究．结果表明，由于液晶组分的加入，共混体系中ＰＥＴ的结晶速率和结晶度均得到提高．说明ＬＣＰ具有ＰＥＴ结晶成核剂的作用．在较低的ＬＣＰ组分含量下（～２ｗｔ％），这一效果最为明显，说明ＬＣＰ是以很小的微区或某些ＬＣＰ分子链介晶微束的形式对ＰＥＴ的结晶起成核剂的作用．     

SYNTHESIS AND PROPERTIES OF THERMOTROPIC LIQUID CRYSTALLINE COPOLYESTERS CONTAINING BIS（4－HYDROXYPHENYL）METHANONE（Ⅵ）

ＳＹＮＴＨＥＳＩＳＡＮＤＰＲＯＰＥＲＴＩＥＳＯＦＴＨＥＲＭＯＴＲＯＰＩＣＬＩＱＵＩＤＣＲＹＳＴＡＬＬＩＮＥＣＯＰＯＬＹＥＳＴＥＲＳＣＯＮＴＡＩＮＩＮＧＢＩＳ（４－ＨＹＤＲＯＸＹＰＨＥＮＹＬ）ＭＥＴＨＡＮＯＮＥ（Ⅵ）ＳＹＮＴＨＥＳＩＳＡＮＤＰＲＯＰＥＲ...     

引入离子基团改善聚苯乙烯和热致液晶聚合物的相容性 Ⅰ热性能和形态

ＤＳＣ和ＳＥＭ研究结果表明聚苯乙烯（ＰＳ）与一种热致液晶聚合物（ＬＣＰ）（ＰＨＢ／ＰＥＴ（６０／４０）共聚酯）完全不相容．共混体系具有与组分无关的Ｔｇ，并且表现出明显的两相结构．将ＰＳ进行化学改性（引入磺酸基团）制备成磺化聚苯乙烯（ＳＰＳ），随中和盐离子的变化有：酸式、Ｌｉ、Ｎａ、Ｚｎ和Ｍｎ盐五种形式．用ＤＳＣ和ＳＥＭ对ＬＣＰ与ＳＰＳ共混物的热性能和形态进行了分析和表征．共混体系有一个与组成相关，且明显低于纯ＳＰＳ的Ｔｇ．这表明了ＰＳ与ＬＣＰ的相容性因为磺酸基团的引入而得到了改善．同时用Ｆｏｘ方程计算了ＬＣＰ的Ｔｇ．当ＳＰＳ含量较低时（不大于５０％）在各个共混体系中，所估算的ＬＣＰ的Ｔｇ相互吻合．表明共混体系满足Ｆｏｘ方程的前提条件，即ＬＣＰ与ＳＰＳ形成相容体系．当ＳＰＳ含量较低时（２５％），ＬＣＰ／ＳＰＳ的共混物为较均一体系，断面光滑；而ＳＰＳ含量较高时，在脆断面可以观察到纳米级的颗粒．电子能谱分析证明了这些颗粒是ＳＰＳ负离子的聚集体．     

热可逆性共价交联热塑性弹性体的研究

本文以丙烯酸环戊二烯基已酯（ＣＰＤＥＡ）、烯丙基环成二烯（Ａ－ＣＰ）与丙烯酸乙酯（ＥＡ）进行乳液共聚，制得了含环成二烯侧基的共聚物．研究了工艺条件对转化率的影响，测定了共聚物的溶解性能和热转化行为．     

SYNTHESIS OF THERMOTROPIC LIQUID CRYSTAL AROMATIC COPOLYESTERS AND COPOLY （ESTER－AMIDE）S CONTAINING DI （ETHYLOXY－ETHER） AS THE SPACER

ＳＹＮＴＨＥＳＩＳ　ＯＦ　ＴＨＥＲＭＯＴＲＯＰＩＣ　ＬＩＱＵＩＤ　ＣＲＹＳＴＡＬ　ＡＲＯＭＡＴＩＣ　ＣＯＰＯＬＹＥＳＴＥＲＳ　ＡＮＤ　ＣＯＰＯＬＹ　（ＥＳＴＥＲ－ＡＭＩＤＥ）Ｓ　ＣＯＮＴＡＩＮＩＮＧ　ＤＩ　（ＥＴＨＹＬＯＸＹ－ＥＴＨＥＲ）　ＡＳ　ＴＨ...     

APPLICATIONS OF ULTRASONICALLY DISPERSED POTASSIUM（UDP）PART 4：REDUCTIVE COUPLING OF CHALCONES IN THE PRESENCE OF UDP，COMMENTS ON THE MECHANISM OF ALKALIMETAL REDUCTION OF α，β－UNSATURATED ENONES

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SYNTHESIS AND CHARACTERIZATION OF NEIV PICKET FENCE CROWN－PORPHYRIN AND ITS Zn（Ⅱ），Fe（Ⅲ） COMIPLEXES

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Thermal transitions of DODAB vesicular dispersions

Two endothermic transitions, at 36°C and 44°C, were observed with differential scanning calorimetry (DSC) upon heating dioctadecyldimethylammonium bromide vesicle dispersions that were equilibrated below 15°C while in samples kept at 25°C there was only the transition at 44°C, which was shown to be the gel to liquid–crystalline transition by ¹H-NMR measurements. The transition at 36°C was reversed in an exothermic transition around 13°C upon cooling. The slowness of this transition at ambient temperatures suggests that the presence of the transition at 36°C in a DSC upscan depends strongly on the sample history.     

Theoretical studies on Myers-Saito and Schmittel cyclization mechanisms of hepta-1,2,4-triene-6-yne

The mechanisms of the Myers-Saito cyclization and the Schmittel cyclization of hepta-1,2,4-triene-6-yne are studied by ab initio multireference MO methods (CASSCF and MRMP2 methods). For the Myers-Saito cyclization, two transition states with C(s) and C? symmetries are located. The transition state with C1 symmetry is only 1.5 kcal/mol lower in energy than that with C(s) symmetry at the MRMP2 calculation level. The obtained activation energy at the transition state with C? symmetry and the reaction energy are 16.6 and 16.2 kcal/mol exothermic, respectively. For the Schmittel cyclization, two transition states with C(s) and C? symmetry are also obtained. The transition state with C? symmetry is 7.9 kcal/mol lower in energy than that with C(s) symmetry. The transition state with C? symmetry for Schmittel cyclization is 6.7 kcal/mol higher in energy than that for the Myers-Saito cyclization. The reaction mechanisms are analyzed by a CiLC-IRC method. The interactions of orbitals for the Myers-Saito and Schmittel cyclizations can be distinguished.     

Structural change of water by gelation of curdlan suspension

Phase transition of water restrained by curdlan suspension annealed at a temperature from 20 to 110°C was investigated by differential scanning calorimetry (DSC). The melting temperature of water restrained by annealed curdlan discontinuously decreased at around 60°C, while the amount of bound water calculated from enthalpy of melting increased at 60°C, regardless of water content. Using a highly sensitive DSC, curdlan suspension with various concentrations was studied. It was found that an endothermic transition was observed at ca. 58°C in a wide range of concentrations. The transition observed at 60°C is thermo-reversible and both temperature and transition enthalpy are constant even after gel formation. Well equilibrated suspension at a temperature lower than 60°C formed no gel.     

Hydrostatic pressure reveals bilayer phase behavior of dioctadecyldimethylammonium bromide and chloride

Bilayer phase transitions of dioctadecyldimethylammonium bromide (2C(18)Br) and chloride (2C(18)Cl) were observed by differential scanning calorimetry and high-pressure light-transmittance measurements. The 2C(18)Br bilayer membrane showed different kinds of transitions depending on preparation methods of samples under atmospheric pressure. Under certain conditions, the 2C(18)Br bilayer underwent three kinds of transitions, the metastable transition from the metastable lamellar crystal (L(c(2))) phase to the metastable lamellar gel (L(β)) phase at 35.4 °C, the metastable main transition from the metastable L(β) phase to the metastable liquid crystalline (L(α)) phase at 44.5 °C, and the stable transition from the stable lamellar crystal (L(c(1))) phase to the stable L(α) phase at 52.8 °C. On the contrary, the 2C(18)Cl bilayer underwent two kinds of transitions, the stable transition from the stable L(c) phase to the stable L(β) phase at 19.7 °C and the stable main transition from the stable L(β) phase to the stable L(α) phase at 39.9 °C. The temperatures of the phase transitions of the 2C(18)Br and 2C(18)Cl bilayers were almost linearly elevated by applying pressure. It was found from the temperature (T)-pressure (p) phase diagram of the 2C(18)Br bilayer that the T-p curves for the main transition and the L(c(1))/L(α) transition intersect at ca. 130 MPa because of the larger slope of the former transition curve. On the other hand, the T-p phase diagram of the 2C(18)Cl bilayer took a simple shape. The thermodynamic properties for the main transition of the 2C(18)Br and 2C(18)Cl bilayers were comparable to each other, whereas those for the L(c(1))/L(α) transition of the 2C(18)Br bilayer showed considerably high values, signifying that the L(c(1)) phase of the 2C(18)Br bilayer is extremely stable. These differences observed in both bilayers are attributable to the difference in interaction between a surfactant and its counterion.     

Temperature dependence of the conformation of isotactic polystyrene in toluene

In order to obtain information about a possible helix–coil transition of isotactic polystyrene (i-PS) at 80°C in toluene, as has been reported in other solvents, solution properties were examined at temperatures between 10 and 110°C. Use was made of viscometry, high-resolution nuclear magnetic resonance, infrared spectroscopy, calorimetry, and light scattering. No distinct transition was found at 80°C but rather a second-order transition between 62 and 65°C. A similar transition occurred in toluene solutions of atactic polystyrene. The transition may be attributed to a sudden change in the mobility of the phenyl side-group of the polymer. From this study it is concluded that i-PS has a helical conformation in toluene, the mean helix length decreasing smoothly with increasing temperature.     

Thermophysical Properties of Cholesteryl Oleyl Carbonate Determined with Microscopic Ftir/Dsc System

A microscopic Fourier transform infrared spectrometer (Micro FTIR) equipped for differential scanning calorimetry (DSC) was used to measure simultaneously the chemical structural variation and the thermal response of phase transition of cholesteryl oleyl carbonate (COC). The differential scanning calorimeter served also to determine the phase transitions of COC during heating or cooling. Two endothermic features due to phase transition were found in the thermogram: 18. 3 °C for a smectic-cholesteric transition and 37.5 °C for a cholesteric-isotropic transition during heating; 35.1 °C for an isotropic-cholesteric transition and 15.8 °C for a cholesteric-smectic transition during cooling. The breadth of the feature indicated sluggish phase transitions. The three-dimensional plot indicated that the intensities of lines due to the C-H stretching and scissoring deformation modes and C=O stretching mode of COC decreased suddenly near the temperature of phase transition during heating but the intensity of the line dues to the C-O stretching mode of carbonate ester of COC increased. Lattice vibrations or coupling of vibrational modes might be responsible for the result. These intensities in the cooling process varied inversely to those in heating process.     

Thermotropic and barotropic phase transitions of dialkyldimethylammonium bromide bilayer membranes: effect of chain length

The bilayer phase transitions of dialkyldimethylammonium bromides (2C(n)Br; n = 12, 14, 16) were observed by differential scanning calorimetry and high-pressure light-transmittance measurements. Under atmospheric pressure, the 2C(12)Br bilayer membrane underwent the stable transition from the lamellar crystal (L(c)) phase to the liquid crystalline (L(α)) phase. The 2C(14)Br bilayer underwent the main transition from the metastable lamellar gel (L(β)) phase to the metastable L(α) phase in addition to the stable L(c)/L(α) transition. For the 2C(16)Br bilayer, moreover, three kinds of phase transitions were observed: the metastable main transition, the metastable transition from the metastable lamellar crystal (L(c(2))) phase to the metastable L(α) phase, and the stable lamellar crystal (L(c(1)))/L(α) transition. The temperatures of all the phase transitions elevated almost linearly with increasing pressure. The temperature (T)-pressure (p) phase diagrams of the 2C(12)Br and 2C(14)Br bilayers were simple, but that of the 2C(16)Br bilayer was complex; that is, the T-p curves for the metastable main transition and the L(c(2))/L(α) transition intersect at ca. 25 MPa, which means the inversion of the relative phase stability between the metastable phases of L(β) and L(c(2)) above and below the pressure. Moreover, the T-p curve of the L(c(2))/L(α) transition was separated into two curves under high pressure, and as a result, the pressure-induced L(c(2P)) phase appeared in between. Thermodynamic quantities for phase transitions of the 2C(n)Br bilayers increased with an increase in alkyl-chain length. The chain-length dependence of the phase-transition temperature for all kinds of transitions observed suggests that the stable L(c(1))/L(α) transition incorporates the metastable L(c(2))/L(α) transition in the bilayers of 2C(n)Br with shorter alkyl chains, and the main-transition of the 2C(12)Br bilayer would occur at a temperature below 0 °C.     

Solid State Nuclear Magnetic Resonance Studies of the Thermochromic Phase Transition of the Polydiacetylene from the Bis-n-Propylurethane of 5,7-Dodecadiyne-1,12-diol

The polydiacetylene (PDA) from the bis-n-propylurethane of 5,7-dodecadiyne-1,12-diol (PUDO) undergoes a first order phase transition near 135°C that is associated with a color change from blue at temperatures below the transition to red at temperatures above the transition. We have studied PDA-PUDO by solid state ¹³C nuclear magnetic resonance (NMR) spectra using cross polarization and magic angle spinning (CP-MAS) techniques at temperatures between 25° and 140°C. As observed previously, the acetylene carbon shift moves up field as the temperature is raised above the transition temperature. In addition, near 130°C, the oxymethylene carbon shows 3 resonances, indicating multiple side chain conformations as the PDA undergoes the phase transition.     

Switching of spin states triggered by a phase transition: spin-crossover properties of self-assembled iron(II) complexes with alkyl-tethered triazole ligands

Iron(II) complexes of triazole derivatives having two C12 and C16 long alkyl chains, (C12trz)FeII and (C16trz)FeII, serve as novel spin-crossover materials, which display a spin-state transition in response to a phase transition. In contrast, a triazole complex with two C8 alkyl chains ((C8trz)FeII) exhibits only a poor response. EXAFS and XRD analyses of (C16trz)FeII indicate an interdigitating self-assembled structure of polynuclear iron(II) species. According to DSC, VT-IR, and VT-XRD profiles, the spin-state transition is triggered by melting of the interdigitating alkyl chains, which is likely responsible for the "lock-and-release" feature of the spin state. By virtue of the thermoreversibility of the phase transition, the spin crossover could be repeated without deterioration.     

Transition‐metal‐catalyzed Chelation‐assisted C–H Functionalization of Aromatic Substrates

In the past decade, transition‐metal‐catalyzed C–H activations have been very popular in the research field of organometallic chemistry, and have been considered as efficient and convenient strategies to afford complex natural products, functional advanced materials, fluorescent compounds, and pharmaceutical compounds. In this account, we begin with a brief introduction to the development of transition‐metal‐catalyzed C–H activation, especially the development of transition‐metal‐catalyzed chelation‐assisted C–H activation. Then, a more detailed discussion is directed towards our recent studies on the transition‐metal‐catalyzed chelation‐assisted oxidative C–H/C–H functionalization of aromatic substrates bearing directing functional groups.