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131.
Jun-ichi Azuma Nam-Hun Kim Laurent Heux Roger Vuong Henri Chanzy 《Cellulose (London, England)》2000,7(1):3-19
The cellulose system of the viscous fibrous cellulosic polysaccharide (viscan) in the viscin tissue of the European mistletoe, Viscum album L., was analyzed by chemical and physicochemical techniques including sugar analysis, optical and transmission electron microscopy, X-ray and electron diffraction together with solid state CP/MAS 13C-NMR spectroscopy. The results confirmed that in the elongated thin viscin cells, the cellulose microfibrils (having a diameter of around 3 nm) were tightly coiled with their axes perpendicular to the long axis of the cell. Upon stretching these cells became deformed by more than a hundred fold. In such a deformation, the cellulose microfibrils became unwound to be perfectly aligned along the stretching direction. Based on solid-state CP/MAS 13C-NMR spectroscopic analysis of the viscin tissue, it was found that its cellulose consisted of I and I polymorphs in the ratio 1:1. 相似文献
132.
Vincent Lapinte Laurent Fontaine Vronique Montembault Irne Campistron Danile Reyx 《Journal of molecular catalysis. A, Chemical》2002,190(1-2):117-129
ROMP and retro-acyclic diene metathesis (ADMET) were used for the synthesis of new functional polymers and functional oligomers, respectively. Purely exo and enantiomerically pure norbornene and 7-oxanorbornene derivatives were prepared using stereospecific synthesis, effective fractionation and high yield condensation reactions. Successful ROMPs of those monomers were performed using either the new carbenic Schrock’s or Grubb’s catalysts or in some cases a classical bicomponent catalyst. New functional polymers such as optically active poly(norbornene-2-carboxylic acid), reactive poly(norbornene-2-azlactone), and side-chain liquid crystal polyoxanorbornenes were fully characterized. On the other hand, successful depolymerizations of 1,4-polyisoprene and of epoxidized 1,4-polybutadiene via cross-metathesis with 4-octene were performed using a stabilized bicomponent catalyst and the Grubb’s catalyst, respectively. Conditions for the controlled synthesis of epoxidized oligobutadienes and of epoxydienic monomers via retro-ADMET were clearly defined. 相似文献
133.
N. SanzJ. Zaccaro L. DelmotteC. Le Luyer A. Ibanez 《Journal of solid state chemistry》2002,165(1):25-34
Organic nanocrystals of N-4-nitrophenyl-l-prolinol (NPP) have been grown in sol-gel matrices prepared from silicon alkoxide precursors. Our process is based on the control of the nucleation and growth kinetics of the dye in the pores of dense gels. Nanocomposites gel-glasses are obtained with a high optical quality due to the small size of the nanocrystals (10-20 nm). Differential scanning calorimetry experiments evidenced clearly the melting point of NPP nanocrystals, which is registered 51°C above that of NPP powder. Micro-Raman and solid state NMR spectroscopies allowed us to demonstrate that our nanocrystallization process does not chemically modify NPP molecules. We specified also the nature of interactions existing between the NPP nanocrystals and the xerogels. These strong interactions, which explain the important increase of the melting point of the nanocrystals in comparison to the NPP powder, are hydrogen bonds between nitro groups of NPP and uncondensed silanol functions of the silicate network. 相似文献
134.
Jarmila Štetinová Rudolf Kada Miloslava Dandárová Marcela Krublová Ján Leśko 《Chemistry of Heterocyclic Compounds》1995,31(10):1231-1233
Substituted ]-(6-methoxy-2-benzothiazolyt)-2-pyridones were prepared from 2-amino-6-methoxybenzathiazate through N-(6-methoxy-2-benzothiazotyl) cyanvorearmileaznd-3-aryl-N-(6-methoxy-2-benzothiazolyt)-2-cyano-2-propenamides. The cyclization of the latter with malonodinitrile in the presence of piperidine gave the corresponding pyridones. The structures of the synthesized compounds were confirmed by1H NMR and mass spectral data.Department of Organic Chemistry, Mass Spectrometry Laboratory, Slovak Technical University, 812 37 Bratislava, Slovakia. Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1402–1404, October, 1995. Original article submitted August 24, 1995. 相似文献
135.
Paul Servin Régis Laurent Anne-Marie Caminade Jean-Pierre Majoral 《Tetrahedron letters》2007,48(4):579-583
A series of densely functionalized dendrimers is synthesized using two branched monomers of type AB2 and CD2, in which the A function (NH2) reacts with D (CHO) and the B function (Cl) reacts with C (OH). The reaction has been carried out up to the fourth generation possessing 96 end groups and has been obtained in only four steps. 相似文献
136.
Elizabeth Dinand Michel Vignon Henri Chanzy Laurent Heux 《Cellulose (London, England)》2002,9(1):7-18
The mercerization of homogenized primary wall cellulose extracted fromsugar beet pulp was investigated by transmission electron microscopy (TEM),X-ray diffraction together with 13C CP-MAS NMR, and FT-IR spectroscopy.For samples resulting from acid extraction, mercerization began at 9% NaOH, whereasfor samples purified by alkaline treatment, the mercerization started at 10%NaOH. The change in morphology when going from cellulose I to cellulose II wasspectacular, as all the microfibrillar cellulose morphology disappeared duringthe treatment. This change in morphology was very drastic as soon as the NaOHconcentrations were increased beyond 8 and 9% for the acid and alkalinepreparedsamples, respectively. On the other hand, the conversion was found to be moreprogressive in terms of increasing NaOH concentration when the transformationwas analyzed by X-ray diffraction or spectroscopy. Our observations of themercerization of isolated cellulose microfibrils are consistent with theconceptof cellulose microfibrils made of parallel chains in cellulose I and crystalsofcellulose II consisting of antiparallel chains. 相似文献
137.
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
138.
Ascorbic acid (AA) is determined by amperometric detection based on the photochemical reduction of Methylene Blue (MB(+)) in 0.1 M phthalate buffer at pH 3.8. In this medium, MB(+) using flow-injection analysis. The carrier stream is 1 mM MB(+) is reduced quasi-reversibly at a glassy carbon electrode at -0.34 V vs. Ag/AgCl, while AA is oxidized irreversibly at about 0.3 V. The reactor is irradiated with a 500 W halogen lamp to facilitate the development of the photochemical reaction. A laboratory-built wall-jet electrode system was used. The Leucomethylene Blue formed in the reaction is detected at +0.050 V. At 2.2 ml min(-1) and using a sample loop of 43 mul, the method allows the determination of AA in the range 5.0-90.0 mug ml(-1), with a relative standard deviation of 1.3-4.8%, a detection limit of 1.9 mug ml(-1) and a sampling frequency of 45-50 h(-1). 相似文献
139.
Immobilization of protein on ferromagnetic Dacron 总被引:1,自引:0,他引:1
A. M. A. Carneiro LeÃo E. A. Oliveira L. B. Carvalho 《Applied biochemistry and biotechnology》1991,31(1):53-58
Ferromagnetic Dacron (polyethyleneterephthalate) is proposed as a matrix to immobilize proteins covalently. Dacron in powder was magnetized by reacting ferrous (Fe+2) and ferric (Fe+3) ions with its hydrazide form at pH 8.3. Ferromagnetic hydrazide Dacron was converted to ferromagnetic azide Dacron and amyloglucosidase (E.C. 3.2.1.3) was covalently bound through the latter group. The catalytic property of the enzyme was preserved (8% of the specific activity estimated for the soluble enzyme) and all the magnetic amyloglucosidase Dacron derivative was recovered by using a magnetic field. No activity was detected in the supernatant. 相似文献
140.
Cantat T Jaroschik F Nief F Ricard L Mézailles N Le Floch P 《Chemical communications (Cambridge, England)》2005,(41):5178-5180
New samarium carbene complexes have been synthesized and characterized by X-ray diffraction analysis; the carbenic nature was assessed by reactivity studies. 相似文献