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21.
Ioan Paraschiv Paul Delforterie Marcel Giesbers Maarten A. Posthumus 《Liquid crystals》2013,40(8):977-983
The synthesis and phase behaviour of a new series of unsymmetrically substituted hexaalkoxytriphenylene‐based liquid crystals are reported. One of the hexyloxy chains in hexahexyloxytriphenylene (HAT6) is replaced by either a shorter or a longer chain, HAT‐(OC6H13)5(OC n H2n+1). Compounds with chain lengths n of 2–14, 16 and 18 were prepared and investigated. Compounds with n?13 were not liquid crystalline. For all compounds with n?12 Colh textures were observed by polarizing microscopy. X‐ray investigations showed that the intercolumnar distance gradually increased with n from n = 2 to n = 12, while the interdisk distance (3.6 Å) remained constant. A small odd–even effect on the increase of the intercolumn distance with n was observed. This effect was also found in the change of ΔH of isotropization with n. 相似文献
22.
Low-field nuclear magnetic resonance techniques are employed to extract information about the effects introduced by the interaction with the surface on the rotational and translational dynamics of molecules confined inside a mesoporous carbon xerogel. The molecules under study were water, cyclohexane, and hexane. They were chosen due to their different interaction strength with the carbonaceous matrix. Frequency dependent longitudinal relaxation measurements, using the fast field cycling technique, allowed extraction of the fractal dimension of the carbon xerogel surface. It was observed that the measured value is influenced by the molecule affinity to the surface. Diffusion measurements, using the pulse field gradient technique, have revealed that the stronger interaction with the surface of cyclohexane and hexane molecules leads to an increased diffusive tortuosity, as compared with water. 相似文献
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Mihai Dimonie Nguyen viet Bac Gheorghe Dragan Ioan Neguluscu 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(4):629-649
Trioxane was copolymerized with small amounts of dioxolane in benzene in the presence of a boron trifluoride:a crylonitrile complex as initiator. The kinetics of reactions was expressed in terms of topoenergetic principles. The copolymerizations had no induction periods and the maximum reaction rate was found proportional to the square of both the initiator and monomers concentrations. A zwitterionic mechanism is suggested for initiation. The activation energy for the system with 5% dioxolane was determined as 18.3 kcal/mol. The melting behavior of the copolymers is briefly discussed as a function of the dioxolane initial content, and is indicative of the amorphous-crystalline coupling phenomenon. The copolymers with ~ 5% dioxolane are thermostable in air up to 250%deg; and are recommended for practical purposes. 相似文献
26.
Frederick H. Roos William H. Daly Marietta N. Aniano-Ilao Ioan I. Negulescu 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(3):275-290
Abstract The synthesis of a variety of substituted bisphenol A polysulfones, including nitro, amino, aminomethyl, ethyl, and methyl derivatives, is described. Nuclear magnetic resonance (NMR) (both proton and carbon, and several 2-D experiments) data confirm conclusions on the substitution site based on arguments on inductive effects in the phenyl rings. The proton ortho to the oxygen in the bisphenol A (BPA) residue is replaced in electrophilic substitution reactions. The degree of substitution was also calculated from the NMR results. The ethyl and methyl derivatives were expected, from the starting reactants, to each have a BPA ring substituted. The NMR data showed that, on the average, this is true. The nitro derivative also has substitution in every BPA ring, while the amino and aminomethyl derivatives have only intermittent BPA rings substituted. Measured degrees of substitution (DS) varied from 0.11 to 2.25. 相似文献
27.
Chelate polymers derived from bis(2,4-dihydroxybenzaldehyde)propyl-enediimine M and bis(2,4-dihydroxyacetophenone)propylenediimine M (M = Fe2+, Co2+, Ni2+, Cu2+, Zn2+) with aromatic acid chlorides were prepared by interfacial polycondensation. Also, chelate polysiloxanes were obtained from the same monomers and α,ω-dichloropolydimethyl-siloxane. The spectral, thermal, magnetic, and electrical properties of the polychelates were studied. 相似文献
28.
Yannick Weesepoel Jean‐Paul Vincken Raluca Maria Pop Kun Liu Harry Gruppen 《Journal of mass spectrometry : JMS》2013,48(7):862-874
The microalga Haematococcus pluvialis produces the pigment astaxanthin mainly in esterified form with a multitude of fatty acids, which results in a complex mixture of carotenol mono‐ and diesters. For rapid fingerprinting of these esters, matrix‐assisted laser desorption ionization time of flight mass spectrometry (MALDI‐TOF/TOF‐MS) might be an alternative to traditional chromatographic separation combined with MS. Investigation of ionization and fragmentation of astaxanthin mono‐ and diester palmitate standards in MALDI‐TOF/TOF‐MS showed that sodium adduct parent masses [M + Na]+ gave much simpler MS2 spectra than radical / protonated [M]+● / [M + H]+ parents. [M + Na]+ fragments yielded diagnostic polyene‐specific eliminations and fatty acid neutral losses, whereas [M]+● / [M + H]+ fragmentation resulted in a multitude of non‐diagnostic daughters. For diesters, a benzonium fragment, formed by polyene elimination, was required for identification of the second fatty acid attached to the astaxanthin backbone. Parents were forced into [M + Na]+ ionization by addition of sodium acetate, and best signal‐to‐noise ratios were obtained in the 0.1 to 1.0 mM range. This method was applied to fingerprinting astaxanthin esters in a crude H. pluvialis extract. Prior to MALDI‐TOF/TOF‐MS, the extract was fractionated by normal phase Flash chromatography to obtain fractions enriched in mono‐ and diesters and to remove pheophytin a, which compromised monoester signals. All 12 types of all‐trans esterified esters found in LC were identified with MALDI‐TOF/TOF‐MS, with the exception of two minor monoesters. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
29.
Ioan Paraschiv Alistair Tomkinson Marcel Giesbers Ernst J. R. Sudh?lter Han Zuilhof Antonius T. M. Marcelis 《Liquid crystals》2013,40(9):1029-1038
The synthesis and thermotropic properties are reported for a series of hexaalkoxytriphenylenes that contain an amide, urea or thiourea group in one of their alkoxy tails. The intermolecular hydrogen bonding abilities of these molecules have a disturbing influence on the formation and stability of the columnar liquid crystalline phases. The stronger the hydrogen bonding the more the liquid crystallinity is suppressed, probably due to disturbance of the π–π stacking of the triphenylene discs. As a direct result, urea‐ and amide‐containing triphenylene derivatives are not liquid crystalline, but several thiourea derivatives show hexagonal columnar mesophases. 相似文献
30.
Nicoleta Gabriela Hădărugă Daniel Ioan Hădărugă Heinz-Dieter Isengard 《Journal of inclusion phenomena and macrocyclic chemistry》2013,75(3-4):297-302
Cyclodextrins are some of the most used carriers for bioactive compounds (as host–guest complex) and many factors influence the association–dissociation of this complex, some of them being related to hydrophobicity. In the solid state, cyclodextrins contain two types of water molecules: “surface” water molecules (especially close to the crystal surface) and “strong-bonded” water molecules (especially from the cyclodextrin cavity), but the classification is hard to do, and the concentration of these water molecules are relatively difficult to estimate by simple methods. In the present study we used the volumetric Karl Fischer titration to estimate these types of water molecules in cyclodextrins by means of the rate of water reaction (related to diffusion from cyclodextrin crystals). “Surface” water molecules are titrated with rates between 1.8–2.8 mM/s for α-cyclodextrin, while for β-cyclodextrin these rates are little bit higher (2.9–3.4 mM/s). The rates corresponding to “strong-bonded” water molecules are approximately tens fold lower (0.05–0.3 mM/s for α-cyclodextrin and 0.15–0.33 mM/s for β-cyclodextrin). The approximate ratio between “surface” and “strong-bonded” water molecules could also be estimated by this simple and rapid method. 相似文献