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91.
Morphological studies of a hydrogen-bonded LC polymer obtained by photopolymerization in LC solvents
Hideyuki Kihara Corresponding author Toshiaki Miura Ryoichi Kishi Takashi Yoshida Mitsuhiro Shibata Ryutoku Yosomiya 《Liquid crystals》2013,40(7):799-809
Anisotropic morphologies and the phase behaviour of a hydrogen-bonded LC polymer obtained by photopolymerization in two kinds of LC solvent are discussed. The hydrogen-bonded LC monomer, 4-(6-acryloyloxyhexyloxy) benzoic acid (A6OBA), was photopolymerized in 4-cyano-4′-hexyloxybiphenyl (6OCB) and in 4-cyano-4′-undecyloxybiphenyl (11OCB), which show a nematic phase and a smectic A phase, respectively. After photo-polymerization, the LC media were removed by extraction and the pure polymer was observed by scanning electron microscopy. SEM images showed that the polymer possessed fibrous morphology with a fibre diameter of a few micrometers, based on polymerization-induced phase separation. The overall geometries reflected typical LC characteristics such as schlieren and focal-conic fan textures. It was found that the hydrogen bond between benzoic acid groups in the monomer was rigid enough to fix the anisotropic phase-separated structure forming during the early stage of phase separation; however, it could not permanently maintain the fibre structure due to dissociation at elevated temperature. X-ray measurements revealed that a well developed layer structure of the hydrogen-bonded mesogen existed in the polymer obtained from the smectic phase of 11OCB, whereas a polymer layer structure could develop only partially from the nematic phase of 6OCB. 相似文献
92.
Yutaka Nishiyama Hiroshi KawabataToshiki Nishino Kouji HashimotoNoboru Sonoda 《Tetrahedron》2003,59(34):6609-6614
It was found that lanthanum metal caused the dehalogenation of o-dihalogen substituted arenes and α,α′-dihalogen substituted o-xylenes to generate the corresponding benzynes and o-quinodimethanes. When o-dihalogen substituted arenes were allowed to react with lanthanum metal in the presence of dienes, the Diels-Alder products between benzyne and dienes were formed in moderate to good yields. Similarly, the Diels-Alder adducts of o-quinodimethane with dienophiles were obtained, in the reaction of α,α′-dibromo-o-xylenes with lanthanum metal in the presence of dienophiles. 相似文献
93.
[6n]Paracyclophenediynes 2a-d (n = 3-6) having [4.3.2]propellatriene units were prepared as precursors of the corresponding [6n]paracyclophynes. Laser irradiation of 2a-d produced the negative ions of [6n]paracyclophynes 1a-d (n = 3-6) by extrusion of the indan fragments, which were detected by time-of-flight mass spectrometry. 相似文献
94.
Chitrakar R Tezuka S Sonoda A Sakane K Ooi K Hirotsu T 《Journal of colloid and interface science》2005,290(1):45-51
Adsorptive properties of MgMn-3-300 (MgMn-type layered double hydroxide with Mg/Mn mole ratio of 3, calcined at 300 degrees C) for phosphate were investigated in phosphate-enriched seawater with a concentration of 0.30 mg-P/dm3. It showed the highest phosphate uptake from the seawater among the inorganic adsorbents studied (hydrotalcite, calcined hydrotalcite, activated magnesia, hydrous aluminum oxide, manganese oxide (delta-MnO2)). The phosphate uptake by MgMn-3-300 reached 7.3 mg-P/g at an adsorbent/solution ratio of 0.05 g/2 dm3. The analyses of the uptakes of other constituents (Na+, K+, Ca(+, Cl-, and SO(2-)4) of seawater showed that the adsorbent had a markedly high selectivity for the adsorption of phosphate ions. Effects of initial phosphate concentration, temperature, pH, and salinity on phosphate uptake were investigated in detail by a batch method. The phosphate uptake increased slightly with an increase in the adsorption temperature. The adsorption isotherm followed Freundlich's equation with constants of logK(F)=1.25 and 1/n=0.65, indicating that it could effectively remove phosphate even from a solution of markedly low phosphate concentration as well as with large numbers of coexisting ions. The pH dependence showed a maximum phosphate uptake around pH 8.5. The pH dependence curve suggested that selective phosphate adsorption progresses mainly by the ion exchange of HPO(2-)4. The study on the effect of salinity suggested the presence of two kinds of adsorption sites in the adsorbent: one nonspecific site with weak interaction and one specific site with strong interaction. The effective desorption of phosphate could be achieved using a mixed solution of 5 M NaCl + 0.1 M NaOH (1 M = 1 mol/dm3), with negligible dissolution of adsorbent. The adsorbent had high chemical stability against the adsorption/desorption cycle; it kept a good phosphate uptake even after the repetition of the seventh cycle. 相似文献
95.
Osaki T Suzuki Y Hirokawa K Shimada R 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,83(1):175-179
The hydrogen bond formations between pyrazine and formic acids and between pyrazine and trichloroacetic acids were studied through observation of the Raman and infrared spectra for mixture of pyrazine and formic acid and also mixture of pyrazine and trichloroacetic acid at 77 K. It was observed that the mutual exclusion principle held for the Raman and infrared spectra of both mixtures, even for the spectra of the samples whose mixing mole ratio of acids was very low. This fact clearly indicates that the hydrogen bonded molecule does not exist in the form of formic acid-pyrazine or trichloroacetic acid-pyrazine whose geometry belongs to the Cs point group, but exists in the form of formic acid-pyrazine-formic acid or trichloroacetic acid-pyrazine-trichloroacetic acid belonging to the C(i) point group. 相似文献
96.
97.
An automatic HPLC system for analyzing nitropolycyclic aromatic hydrocarbons (NPAHs, nitroarenes) in airborne particulates was previously described (Anal. Chim. Acta, 2001, 445, 20). Some problems with this system were that it generated a peak originating from an ascorbic acid solution that elutes at a retention time close to that of 1,6-dinitropyrene (DNP), and that it was able to analyze only 1,3-, 1,6-, 1,8-DNPs and 1-nitropyrene (I-NP). Here, we describe an improved system that effectively removes the interfering peak by introducing an ODS column just after the pump for the ascorbic acid solution, and which is capable of analyzing several additional compounds (2-, 4-NPs, 2-nitrofluorene. 6-nitrochrysene, 7-nitrobenz[a]anthracene, 3-nitroperylene and 6-nitrobenzo[a]pyrene etc.). The improved sensitivities were achieved by concentrating the compounds in a benzene-ethanol extract from airborne particulates, by increasing the loading time of the sample solution from 20 to 38 min, and by increasing the flow rate of an ascorbic acid solution from 1.3 to 1.8 mL/min. 相似文献
98.
A high performance liquid chromatographic (HPLC) method for the quantification of 2-hydroxyfluorene (2-OHF) in normal human urine was established using deuterated 2-hydroxyfluorene (2-OHF-d9) as an internal standard with column-switching and fluorescence detection. The 2-OHF-d9 was synthesized by the metabolism of deuterated fluorene with cytochrome P450. The analytes were cleaned up on an ODS pre-column, via column-switching, and separated on an alkylamide-type reversed phase column. The internal standard eluted immediately prior to non-deuterated 2-OHF on the HPLC system and had nearly the same fluorescence characteristics as the non-deuterated 2-OHF. The detection limit was 0.03 nmol l(-1) (S/N = 3) and the calibration range of urine sample was from 0.2 to 50 nmol l(-1). The urine sample treatment involved enzymatic hydrolysis followed by solid phase extraction using a Sep-Pak C18 cartridge. 2-OHF was observed in the form of conjugates such as glucuronide and/or sulfate in human urine, and urinary metabolites were completely hydrolyzed for 2 h with beta-glucuronidase/aryl sulfatase. The proposed method was used to determine urinary 2-OHF in smokers and non-smokers, and showed that the urinary concentrations of 2-OHF in smokers were significantly higher than those in non-smokers (P < 0.01). Thus, the data suggest that urinary 2-OHF might be a sensitive and specific biological marker for the assessment of the exposure to polycyclic aromatic hydrocarbons. 相似文献
99.
A potentiometric flow injection determination method for iodide ion in a photographic developing solution was proposed by utilizing a flow-through type iodide ion-selective electrode detector. The sensing membrane of the electrode was Ag2S–AgI membrane. The response of the electrode detector as a peak-shape signal was obtained for injected iodide ion in a photographic developing solution. A linear relationship in the subnernstian zone was found to exist between peak height and the concentration of the iodide ion in a photographic developing solution in a concentration range from 0 to 6.0×10−5 mol l−1. The relative standard deviation for ten injections of 2×10−5 mol l−1 iodide ion in a photographic developing solution was 0.96% and the sampling rate was approximately 12–13 samples h−1. The iodide ion could be determined under coexisting of an organic reducing reagent and inorganic electrolytes of high concentration in a photographic developing solution sample solution by the present method. 相似文献
100.
Tobe Y Utsumi N Kawabata K Nagano A Adachi K Araki S Sonoda M Hirose K Naemura K 《Journal of the American Chemical Society》2002,124(19):5350-5364
m-Diethynylbenzene macrocycles (DBMs), buta-1,3-diyne-bridged [4(n)]metacyclophanes, have been synthesized and their self-association behaviors in solution were investigated. Cyclic tetramers, hexamers, and octamers of DBMs having exo-annular octyl, hexadecyl, and 3,6,9-trioxadecyl ester groups were prepared by intermolecular oxidative coupling of dimer units or intramolecular cyclization of the corresponding open-chain oligomers. The aggregation properties were investigated by two methods, the (1)H NMR spectra and the vapor pressure osmometry (VPO). Although some discrepancies were observed between the association constants obtained from the two methods, the qualitative view was consistent with each other. The analysis of self-aggregation by VPO revealed unique aggregation behavior of DBMs in acetone and toluene, which was not elucidated by the NMR method. Namely, the association constants for infinite association are several times larger than the dimerization constant, suggesting that the aggregation is enhanced by the formation of dimers (a nucleation mechanism). In polar solvents, DBMs aggregate more strongly than in chloroform due to the solvophobic interactions between the macrocyclic framework and the solvents. Moreover, DBMs self-associate in aromatic solvents such as toluene and o-xylene more readily than in chloroform. In particular, the hexameric DBM having a large macrocyclic cavity exhibits extremely large association constants in aromatic solvents. By comparing the aggregation properties of DBMs with the corresponding acyclic oligomers, the effect of the macrocyclic structure on the aggregation propensity was clarified. Finally, it turned out that DBMs tend to aggregate more readily than the corresponding phenylacetylene macrocycles, acetylene-bridged [2(n)]metacyclophanes, owing to the withdrawal of the electron density from the aromatic rings by the butadiyne linkages which facilitates pi-pi stacking interactions. 相似文献