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101.
Synthesis, characterization and crystal structures of two polyphilic mesogenic compounds 总被引:1,自引:0,他引:1
Philippe Kromm Michel Cotrait Jean Claude Rouillon Philippe Barois Huu Tinh Nguyen 《Liquid crystals》1996,21(1):121-131
Three homologous series of semi-perfluorinated liquid crystals: 4-(2,2,3,3,4,4,4-heptafluoro-butyloxycarbonyl)phenyl, 4-(2,2,3,3,4,4,5,5-octafluoropentyloxycarbonyl)phenyl and 4-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyloxycarbonyl)phenyl 4-[(n-perfluoroalkyl)alkyloxy]benzoates have been synthesized. Their mesomorphic properties were studied by DSC, microscopic observation and X-ray diffraction. Their layer spacings are smaller than the molecular length (L). The ratio dSA/L is about 0.7. The crystal structure of two derivatives of the first family have also been investigated. In both structures the molecules pack in smectic C-like sheets where neighbouring molecules are antiparallel, interacting through dipolar and van der Waals forces. The interactions between contiguous sheets, through the ends of perfluorinated chains are very weak. The X-ray diffraction results on the mesophases and on the crystalline structures of two compounds of the first family are compared. From this, we propose a model of the smectic phases with a zig-zag structure. 相似文献
102.
Claude Balny Jennifer Canva Pierre Douzou Jean Bourdon 《Photochemistry and photobiology》1969,10(6):375-382
Abstract— Chemiluminescence and photochemiluminescence of systems generating excited (singlet) molecular oxygen has been studied at low temperature in fluid media. A possible interpretation is proposed: that dimers of singlet oxygen are directly or indirectly responsible for the observed emission, the species [1 δg +1 σg+ ] predominating. Energy transfer to a fluorescent molecule is possible only when conditions of spectral overlap, required for transfer by inductive resonance, are fulfilled. Evidence is also presented for the formation of a transient complex between oxygen and a sensitiser or acceptor molecule [S…O2 ], which is the precursor of singlet oxygen in these systems. However, other possible mechanisms cannot be excluded. 相似文献
103.
Amino‐alcohol derivatives of fragrant, volatile aldehydes and ketones were synthesized in a one‐pot procedure by sequential cyanohydrin formation with trimethylsilyl cyanide and reduction with lithium aluminium hydride, or by ammonolysis of epoxide precursors. The amino alcohols are nonvolatile, stable properfumes releasing fragrant carbonyls by oxidation with sodium periodate or sodium bismuthate. Examples include amino alcohol properfumes of citronellal, Lilial®, lauryl aldehyde, menthone, benzaldehyde, and anisaldehyde. 相似文献
104.
The gas-phase decomposition of diallylvinylphosphine 1 into C5H5P 12 is studied by DFT/6-311+G(d,p) calculations with the B3LYP functional, followed by single-point energy-only calculations at the CCSD(T)/6-311+G(d,p) level. According to these calculations, the first step involves a retro-ene elimination that yields 3-phosphahexatrienes 2Z and 2E. Both compounds equilibrate through the formation of 1,2- and 3,4-dihydrophosphetes 3 and 4, and it is shown that the formation of 2Z is favored by the exothermic formation of the 3,4-dihydrophosphinine 5 through a 6pi-electrocyclization. Though 5 can easily isomerize into 2,3- (6) and 1,2-diyhydrophosphinines (7) by successive 1,5-hydrogen shifts, the formation of 12 from 5, 6, or 7 through an elimination of H2 is found to be a high energy process. It is also shown that the elimination of H2 from lambda5-phosphinine 8 following a C2v pathway is a symmetry-forbidden process. Finally, 1,4-dihydrophosphinine 9, which can be formed through a 1,4-hydrogen shift from lambda5-phosphinine 8, is found to be a convenient precursor of 12 through a 1,4-elimination of H2. The formation of 9 from 5 involves the intermediary formation of 3-phosphabicyclo[3.1.0]hex-2-ene 10. The mechanism eventually proposed for the formation of 12 from 2Z is given in Scheme 16 at the CCSD(T) level. 相似文献
105.
The system BaF2/AlF3 is investigated by X-ray and D.T.A., and the liquid-solid phase diagram is established. Five ternary fluorides are disclosed: trimorphic BaAlF5, Ba3Al2F12, Ba5AlF19, polymorphic Ba3AlF9 and Ba5AlF13. Neutron thermodiffractometry experiments are performed to specify some parts of the diagram. The cell parameters of the fluorides are given and the results are discussed and compared with those of the previous works. 相似文献
106.
Dense membranes were prepared from poly(vinyl alcohol)–poly(N-vinyl pyrrolidone) (PVA–PVP) blends of different compositions and studied in swelling and dehydration by pervaporation of three organic solvents contaminated by 5 wt% water. The swelling generally increases with the PVP content. No extraction occurs in water–tetrahydrofuran (THF) and water–methyl ethyl ketone (MEK) mixtures. In ethanol containing 10 wt% of water, there is no extraction for blends containing less than 40 wt% PVP and an increasing extraction beyond this PVP content. The pervaporation flux of the water–ethanol mixture increases drastically at the same threshold whereas the water permselectivity falls to a low level. The values of the diffusion and permeability coefficients determined from transient permeation of the test water–ethanol mixture exhibit a similar sudden increase at the same PVP content threshold. This singular behavior of the blend membranes is interpreted by a strong affinity of the PVP component to ethanol, combined with a disappearance of crystallites in the blend at this threshold. Consequently the amorphous membrane can swell freely according to the affinity of the PVP component, leading to the observed behavior. 相似文献
107.
Self-replicating peptide systems hold great promise for a wide range of technological applications, as well as to address fundamental questions pertaining to the molecular origins of life. The development of self-replicating compounds capable of high efficiency, however, has remained elusive. Here we disclose a successful strategy whereby modulation of coiled-coil stability results in remarkable catalytic efficiency for self-replication. By shortening the peptide to the minimum length necessary for coiled-coil formation a highly efficient self-replicating system was obtained due to very low background reaction rates, bringing the efficiency close to naturally occurring enzymes. 相似文献
108.
Hétérocycles à fonction quinone. 7. Benzo[f]quinazolinediones-7,10 à action antitumorale potentielle
Hlne Parrot-Lopez Jean-Michel Delacotte Jean Renault Suzanne Cros 《Journal of heterocyclic chemistry》1986,23(4):1039-1043
Few benzo[f]quinazoline-7,10-diones 4a-c are prepared by oxidation, with potassium nitrosodisulfonate, of the corresponding benzo[f]quinazolinamines, made by reduction of the nitro analogues which were obtained from 8-methoxybenzo[f]quinazolin-1(2H)-one. The compound 4a shows an interesting cytotoxicity. 相似文献
109.
3-Hydroperoxy-1,3,6-trimethyl-2-phenyl indolines coming from the sensitized photooxygenation of the indoles in presence of KBH4 rearrange partially in basic methanol into the corresponding 3-hydroxy-6-methoxymethyL indolines. 相似文献
110.
The examination of 19F chemical shifts for ca. 650 F-alkylated compounds of general formula CF3(CF2)nCF2X led to the following conclusions: the CF2 groups α to X are very sensitive to the nature of X, and are spread over a range of 85 ppm. The effect of the length of the F-alkyl chain decreases rapidly, so that δCF2(α) can already be considered as characteristic of X for n = 1 or 2 for most practical purposes. Solvent effects (in 9 different solvents having ε = 1.8 to 52.1) were found to be rather small except for the F-alkyl iodides. A chart which indicates the domain in which the CF2(α) resonance signal is to be expected is given for 42 different series of F-alkylated compounds; it is expected to provide the synthetic chemist with a useful tool for the identification and characterization of such compounds. 相似文献