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191.
Gregory B. Kharas Matthew J. Lazzarotto Kara A. Ledin Michelle M. Mulvaney Jason R. Nazarof Jean E. Pineda 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(8):1127-1133
Electrophilic trisubstituted ethylene monomers, akyl and alkoxy ring‐trisubstituted methyl 2‐cyano‐3‐phenyl‐2‐propenoates, RC6H2CH[dbnd]C(CN)CO2CH3, (where R is 2,3‐dimethyl‐4‐methoxy, 2,5‐dimethyl‐4‐methoxy‐, 2,3,4‐trimethoxy‐, 2,4,5‐trimethoxy, 2,4,6‐trimethoxy, and 2,4‐dimethoxy‐3‐methyl), were synthesized by the piperidine catalyzed Knoevenagel condensation of ring‐substituted benzaldehydes and methyl cyanoacetate, and characterized by CHN elemental analysis, IR, 1H‐ and 13C‐NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator (AIBN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, 1H and 13C NMR, GPC, DSC, and TGA. High Tg of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the copolymers decompose in the 283–306°C range. 相似文献
192.
193.
Pretransitional fluctuations in the isotropic phase of liquid crystalline and non‐liquid crystalline alkyl cyanobiphenyls have been investigated using light scattering and magnetic birefringence measurements. We find evidence for a virtual isotropic‐nematic phase transition in short‐chain alkyl cyanobiphenyls with no observable nematic phase. The measured temperature dependence of fluctuations is well‐described by mean‐field theory. Virtual phase transition temperatures extrapolated from separate light scattering and magnetic birefringence experiments are in good agreement. Landau–de Gennes model parameters for the compounds investigated are calculated from the experimental results. 相似文献
194.
The liquid crystalline behaviour of methyl-6-O-(n-dodecanoyl)-α-D-glucopyranoside, 1, has been characterised using X-ray diffraction and variable temperature Fourier transform infrared (FTIR spectroscopy). 1 exhibits a monotropic interdigitated smectic A phase consisting of bilayers in which the alkyl chains are overlapped. The crystal–isotropic transition is accompanied by a pronounced decrease in the strength of the hydrogen bonding network involving the sugar groups resulting in a marked change in the environment of the alkyl chains. The isotropic phase consists of disordered smectic-like domains stabilised via hydrogen bonding between the sugar groups. At the transition to the smectic A phase, a subtle change in hydrogen bonding is observed which is manifested by a change in the temperature dependence of the OH stretching peak position in the FTIR spectrum. On crystallisation, the strong hydrogen bonding network is re-established accompanied by a change in the conformational distribution of the alkyl chains. A model is proposed in which a combination of hydrogen bonding (enthalpic effects) and conformational arrangements (entropic effects) promotes initially the formation of smectic-like domains in the isotropic phase and subsequently stabilises the smectic A phase by inhibiting the microphase separation leading to the crystal phase. 相似文献
195.
Supramolecular main-chain liquid crystalline polymers and networks with competitive hydrogen bonding
A series of supramolecular polymers and networks with variable liquid crystalline characteristics have been created. These species are formed though the benzoic acid/pyridine associations of a flexible bisacid and a mixture of a rigid bispyridyl and a non-mesogenic tetrapyridyl. The networked systems displayed liquid crystalline characteristics up to and including 22.5% netpoint inclusion. Above this concentration, only crystalline and melting behaviours were observed. This observed phenomenon would seem to be linked to the statistical correlation of hydrogen bond acceptors and donors. There was also no observed phase segregation of the species after multiple heat/cool cycles and extended periods of time in the isotropic state. This would indicate that the thermodynamically more stable mesogenic phase cannot out-compete the non-liquid crystalline network. Computational analysis indicates no significant difference in hydrogen bond strength between the two different hydrogen bond acceptors. 相似文献
196.
Jason E. Bara Evan S. Hatakeyama Brian R. Wiesenauer Xiaohui Zeng Richard D. Noble 《Liquid crystals》2013,40(12):1587-1599
Thermotropic ionic liquid crystals (LCs) are useful for a number of applications such as anisotropic ion transport and as organised reaction media/solvents because of their ordered fluid properties and intrinsic charge units. A large number of different ionic LC architectures are known, but only a handful of examples of gemini (i.e. paired or dimeric) ionic LCs have been prepared and studied. In this work, a series of 20 new symmetric, imidazolium-based, gemini cationic LCs containing two bridged imidazolium cations and two pendant alkyl chains was synthesised, and the thermotropic LC behaviours were characterised. The imidazolium unit provides a highly tunable and modular platform for the design and synthesis of gemini cationic LCs which offers excellent structure control. As expected, the thermotropic LC properties of these new amphilphilic, gemini ionic LCs were found to be strongly influenced by the length of the spacer between the imidazolium units, the length of the pendant alkyl tails, and the nature of the anion. Smectic A (SmA) thermotropic LC phases were observed in more than half of the gemini imidazolium LC systems studied. 相似文献
197.
Dr. Paul Smart Dr. Charles A. Mason Jason R. Loader Dr. Anthony J. H. M. Meijer Prof. Alastair J. Florence Dr. Kenneth Shankland Dr. Ashleigh J. Fletcher Dr. Stephen P. Thompson Dr. Michela Brunelli Dr. Adrian H. Hill Prof. Lee Brammer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(11):3552-3557
198.
Ryan Gianatassio Shuhei Kawamura Cecil L Eprile Klement Foo Jason Ge Aaron C. Burns Michael R. Collins Phil S. Baran 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(37):10009-10013
A simple method to convert readily available carboxylic acids into sulfinate salts by employing an interrupted Barton decarboxylation reaction is reported. A medicinally oriented panel of ten new sulfinate reagents was created using this method, including a key trifluoromethylcyclopropanation reagent, TFCS‐Na. The reactivity of six of these salts towards C H functionalization was field‐tested using several different classes of heterocycles. 相似文献
199.
Stacey N. Anderson Mark Noble Katarzyna Grubel Brooks Marshall Atta M. Arif 《Journal of Coordination Chemistry》2014,67(23-24):4061-4075
The visible light-induced CO-release reactivity of the zinc flavonolato complex [(6-Ph2TPA)Zn(3-Hfl)]ClO4 (1) has been investigated in 1?:?1 H2O?:?DMSO. Additionally, the effect of ligand secondary microenvironment on the aqueous stability and visible light-induced CO-release reactivity of zinc flavonolato species has been evaluated through the preparation, characterization, and examination of the photochemistry of compounds supported by chelate ligands with differing secondary appendages, [(TPA)Zn(3-Hfl)]ClO4 (3; TPA = tris-2-(pyridylmethyl)amine) and [(bnpapa)Zn(3-Hfl)]ClO4 (4; bnpapa = N,N-bis((6-neopentylamino-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine)). Compound 3 undergoes reaction in 1?:?1 H2O?:?DMSO resulting in the release of the free neutral flavonol. Irradiation of acetonitrile solutions of 3 and 4 at 419 nm under aerobic conditions results in quantitative, photoinduced CO-release. However, the reaction quantum yields under these conditions are lower than that exhibited by 1, with 4 exhibiting an especially low quantum yield. Overall, the results of this study indicate that positioning a zinc flavonolato moiety within a hydrophobic microenvironment is an important design strategy toward further developing such compounds as CO-release agents for use in biological systems. 相似文献
200.
Samuel Piña Jr. Diana M. Cedillo Carlos Tamez Nezhueyotl Izquierdo Jason G. Parsons Jose J. Gutierrez 《Tetrahedron letters》2014
Reported here is the reduction of aromatic nitro compounds using sodium borohydride and transition metal sulfides as catalysts. The reaction conditions were optimized using the reduction of nitrobenzene as a model reaction. The catalysts studied were iron sulfide (Fe3S4), copper sulfide (CuS), zinc sulfide (ZnS), cobalt sulfide (Co3S4), and nickel sulfide (NiS). The reduction was monitored using gas chromatography. Quantitative conversions were achieved using Co3S4 and NiS, representing a ten-fold increase in reactivity compared to the non-catalyzed reaction. Fe3S4 and ZnS had no apparent effect on the reduction of nitrobenzene while the reduction using CuS showed a marginal increase. The reduction method was applied to several aryl-nitro derivatives containing either electron-withdrawing or electron-donating groups. Halogen containing aryl-nitro compounds were reduced without dehalogenation. The reduction had no effect on other functional groups such as carboxylic acids, esters, amides, or alkenes, indicating that the reduction is highly chemoselective. 相似文献