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101.
Perfluorooctanoyl modified poly(vinyl alcohol)s (FPVA) were prepared by means of substituting a small amountof hydroxyl groups on the backbone of poly(vinyl alcohol), for which the initial degree of polymerization is equal to 1750.The substitution extent, defined by the number of substituting units in a chain, for the four FPVA samples was in the range of0.5-5 perfluorooctanoyl groups per chain. The FPVA samples with the highest substitution extent still had good solubility inwater. It was shown by experimental measurement at 30.0±0.1℃ that the surface tension of the aqueous solution of thehighest substituted FPVA decreased to 16.6 mN/In at a higher concentration, e.g about 0.1 g/mL. Obviously,macromolecules of FPVA exhibit a very strong tendency to adsorb at the air-water interface, because the hydrophobicperfluorooctanoyl groups in FPVA have a very high surface activity as they are in small molecular fluorinated surfactants.The chain conformation of such a model polymer adsorbed on the air-water interface was also discussed. 相似文献
102.
The conformations of poly(l-glutamic acid) [P(Glu)] in solutions of the bipolar amphiphile 1,20-icosanediylbis(alkylammonium chloride) [C20(RA)2], where RA includes trimethylammonium (TMA), dimethylammonium (DMA), or methylammonium (MA), were investigated with measurements
of the circular dichroism spectra at 10–35 °C. All C20(RA)2 induced an α-helix of P(Glu) in the aqueous solutions. The residue molar ellipticity at 222 nm showed a similar dependence
on the amphiphile concentration (C
s) below 0.5 of the ratio of 2C
s to the residue concentration (C
p) of P(Glu), but it separated into three directions at 2C
s/C
p>0.5. C20(MA)2 induced an α-helix of P(Glu) at 2C
s/C
p<0.5 followed by a helix aggregate at 2C
s/C
p>0.5. C20(DMA)2 and C20(TMA)2 also induced an α-helix, but a helix aggregate. C20(TMA)2 indicated a strong temperature dependence and did not induce a complete α-helix at 35 °C.
Received: 20 June 2001 Accepted: 6 September 2001 相似文献
103.
Studies on the Molecular Chain Conformation Stability of Aminated Konjac Glucomannan 总被引:2,自引:0,他引:2
Konjac glucomannan (KGM) was aminated by 2-chloroethyl-amine (CEA) as reagent so as to study the influence of concentration of CEA (based on the amount of KGM), concentration of NaOH, reaction time and temperature on the extent of amination. And the molecular simulation technology was adopted to analyze the conformation stability of aminate (AKGM). The results indicate that when the amount of CEA is higher, the extent of amination is higher. The optimum concentration of NaOH, reaction time and temperature are 10% NaOH, 70 ℃ and 45 rain, respectively. IR shows KGM is successfully aminated. The conformation of AKGM is in a random clew-like shape. 相似文献
104.
Fluorinated Musk Fragrances: The CF2 Group as a Conformational Bias Influencing the Odour of Civetone and (R)‐Muscone 下载免费PDF全文
Dr. Ricardo Callejo Dr. Michael J. Corr Mingyan Yang Prof. Mingan Wang Dr. David B. Cordes Prof. Alexandra M. Z. Slawin Prof. David O'Hagan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(24):8137-8151
The difluoromethylene (CF2) group has a strong tendency to adopt corner over edge locations in aliphatic macrocycles. In this study, the CF2 group has been introduced into musk relevant macrocyclic ketones. Nine civetone and five muscone analogues have been prepared by synthesis for structure and odour comparisons. X‐ray studies indeed show that the CF2 groups influence ring structure and they give some insight into the preferred ring conformations, triggering a musk odour as determined in a professional perfumery environment. The historical conformational model of Bersuker and co‐workers for musk fragrance generally holds, and structures that become distorted from this consensus, by the particular placement of the CF2 groups, lose their musk fragrance and become less pleasant. 相似文献
105.
Tomasz Laskowski Zbigniew Rafiński Paweł Sowiński Jan Pawlak 《Magnetic resonance in chemistry : MRC》2012,50(5):347-349
The relative configurations of four stereogenic centers of the C33‐C42 fragment of niphimycin A were assigned as 2S*, 3R*, 4S* and 6S*, based upon 1H NMR analysis with double‐quantum filtered COSY and nuclear Overhauser spectroscopy experiments. These data were then correlated with absolute configurations at C36 and C38 of niphimycin A, which were declared previously as 36S and 38S [3]. This allowed for the assignment of the absolute configurations at C34 and C35 of niphimycin A as 34S and 35R. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
106.
《Acta Crystallographica. Section C, Structural Chemistry》2017,73(10):780-783
The molecular conformation and supramolecular architecture of cocaethylene [systematic name: ethyl (1R ,2R ,3S ,5S )‐3‐benzoyloxy‐8‐methyl‐8‐azabicyclo[3.2.1]octane‐2‐carboxylate], C18H23NO4, have been determined for the first time. Cocaethylene is a narcotic produced in vivo when cocaine and ethanol are administered concomitantly. The intra‐ and intermolecular features of cocaethylene and its less potent narcotic precursor cocaine are very similar. The only molecular difference is in the conformation of the methyl group of the ethoxycarbonyl group. Similar to cocaine, the carboxylate atoms and the α‐C atom are coplanar in cocaethylene, but the methyl C atom of the ethyl group is bent by ca 90° away from this plane in the narcotic reported here. The main supramolecular motif is a one‐dimensional chain stabilized by weak C—H…O contacts. 相似文献
107.
Andrew J. Thompson Dr. Jerome Dabin Javier Iglesias‐Fernández Dr. Albert Ardèvol Dr. Zoran Dinev Assoc. Prof. Spencer J. Williams Dr. Omprakash Bande Dr. Aloysius Siriwardena Carl Moreland Dr. Ting‐Chou Hu David K. Smith Prof. Harry J. Gilbert Prof. Carme Rovira Prof. Gideon J. Davies 《Angewandte Chemie (International ed. in English)》2012,51(44):11171-11171
108.
Edyta M. Greer Christopher V. Cosgriff Olga Lavinda 《Journal of Physical Organic Chemistry》2012,25(12):1293-1298
Pentamethylene chain conformational effects for the Bergman cyclization of the 11‐membered ring enediyne, (3Z)‐3‐cycloundecene‐1,5‐diyne, 2, are examined theoretically with unrestricted Becke, three‐parameter, Lee–Yang–Parr/6‐31 G(d,p) calculations. A C1 symmetric enediyne conformation was found to be the global minimum, where its nonsymmetric pentamethylene chain prevented π‐orbital alignment of the acetylene groups for C–C σ bond product formation. The Bergman cyclization of 2 was found to be conformationally dependent. In a Curtin–Hammett type process, the C1 symmetric 2 inverts to one of the CS or C2 symmetric conformers required for the Bergman cyclization, which produced a CS or C2 symmetric 1,4‐diradical intermediate. The activation energy for the cyclization is slightly higher to reach the C2 symmetry diradical compared with the CS symmetry diradical. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
109.
In the polymerization of chiral allene by using chiral phosphine complex, the polymerization rate of L-1 is approximately 1.9 times that of D-1. This catalyst has enantiomer-selectivity for the polymerization of chiral allene derivative monomer. 相似文献
110.
Tilman Krauch Bernd Schweizer 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):207-209
Abstract Through a direct and selective deprotection of 1 (R=methyl) with boron tribromide substituted o-hydroxy-dithiophosphinic acid 1 was prepared under mild conditions in excellent yield. 相似文献