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161.
A novel transesterification reaction between acetylated maritime pine sapwood (Pinus pinaster Soland) and methyl benzoate (MB), in the presence of dibutyltin oxide (DBTO) as a catalyst, was performed. Reaction was confirmed by Fourier-transform infrared spectroscopy (FTIR) and 13C nuclear magnetic resonance cross-polarisation with magic-angle spinning (NMR CP MAS) analysis: signals corresponding to benzoylated wood were identified and, when transesterification was performed with ethyl trimethylsilylacetate (ETMSA), characteristic trimethylsilyl groups were detected. The acetyl/benzoyl exchange rate was found to increase with increasing amount of DBTO, temperature and reaction time and a concurrent deterioration of the woody material was evidenced. 相似文献
162.
163.
M. A. Desando Y. P. Handa R. E. Hawkins C. I. Ratcliffe J. A. Ripmeester 《Journal of inclusion phenomena and macrocyclic chemistry》1990,8(1-2):3-16
The structure I clathrate hydrate of carbon monoxide has been studied using dielectric measurements and13C NMR spectroscopy. Broad, weak dielectric absorption curves with maxima at 2.2–3.8 K yieldE
a
= 0.14 kJ mol–1 for the average Arrhenius activation energy associated with the reorientation of the low polarity guest. Except for H2S this represents the fastest reorienting polar guest known among the clathrate hydrates. The low temperature dielectric absorption curves can best be fitted with a Cole-Davidson asymmetric distribution of relaxation times and activation energies (with = 0.06 at 4 × 106 Hz), which at 107 Hz has been resolved into a double symmetric distribution of discrete relaxation times for CO in the small and large cages. The cross-polarization magic angle spinning13C NMR spectra indicate identical chemical shifts for CO in the small and large cages, in contrast to other hydrates. The static spectra show that the CO molecules undergo anisotropic reorientation in the large cages and that there is still considerable mobility at 77 K. One possible model for the anisotropic motion has the CO rapidly moving among sites over each of the 14 faces of the cage with the CO axis orientated towards the cage centre. The cage occupancy ratio at 220 K,
s/
L = 1.11, indicates slightly greater preference of CO for the small cage.Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena. 相似文献
164.
Zoran Vondraček 《Journal of Theoretical Probability》1991,4(2):457-464
Let (Y
t, Qx) be a strong Markov process in a bounded Lipschitz domainD with continuous paths up to its lifetime , and let (X
t, Px) be a Brownian motion inD. IfY
– exists in D andQ
x(Y– C)=Px(X– C) for all Borel subsetsC of D and allx, thenY is a time change ofX. 相似文献
165.
This study applies the theory of stochastic processes to the equilibrium statistical physics of polymers in solution. The topics treated include random copolymers and randomly branching polymers, with self-consistent mean field effects. A new and more natural way of dealing with Boltzmann weighting is discussed, which makes it possible from the beginning of a calculation to consider only the physical polymer conformations. We also show that in general the random copolymer problem can be reduced to the ordinary polymer problem, and treat the self-consistent field problem for a general branching polymer. 相似文献
166.
G. G. Kasparov 《K-Theory》1991,5(1):47-49
We provide a straightforward proof of one of the main results of the Baum-Douglas K-homology theory: If A is a separable nuclear C
*-algebra and I an ideal of A, then the natural restriction map K
0(A, I) K
0(I) is an isomorphism of Abelian groups. 相似文献
167.
Christian K. Riener Andreas Ebner Alex A. Gall Yuri L. Lyubchenko Hermann J. Gruber 《Analytica chimica acta》2003,479(1):59-75
We have established an easy-to-use test system for detecting receptor-ligand interactions on the single molecule level using atomic force microscopy (AFM). For this, avidin-biotin, probably the best characterized receptor-ligand pair, was chosen. AFM sensors were prepared containing tethered biotin molecules at sufficiently low surface concentrations appropriate for single molecule studies. A biotin tether, consisting of a 6 nm poly(ethylene glycol) (PEG) chain and a functional succinimide group at the other end, was newly synthesized and covalently coupled to amine-functionalized AFM tips. In particular, PEG800 diamine was glutarylated, the mono-adduct NH2-PEG-COOH was isolated by ion exchange chromatography and reacted with biotin succinimidylester to give biotin-PEG-COOH which was then activated as N-hydroxysuccinimide (NHS) ester to give the biotin-PEG-NHS conjugate which was coupled to the aminofunctionalized AFM tip. The motional freedom provided by PEG allows for free rotation of the biotin molecule on the AFM sensor and for specific binding to avidin which had been adsorbed to mica surfaces via electrostatic interactions. Specific avidin-biotin recognition events were discriminated from nonspecific tip-mica adhesion by their typical unbinding force (∼40 pN at 1.4 nN/s loading rate), unbinding length (<13 nm), the characteristic nonlinear force-distance relation of the PEG linker, and by specific block with excess of free d-biotin. The convenience of the test system allowed to evaluate, and compare, different methods and conditions of tip aminofunctionalization with respect to specific binding and nonspecific adhesion. It is concluded that this system is well suited as calibration or start-up kit for single molecule recognition force microscopy. 相似文献
168.
K. Yu. Chegaev A. N. Kravchenko O. V. Lebedev Yu. A. Strelenko P. A. Belyakov 《Chemistry of Heterocyclic Compounds》2002,38(10):1250-1252
N-Trimethylsilyl derivatives of 2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-diones have been prepared for the first time and the electrophilic substitution reaction of the trimethylsilyl group has been studied. 相似文献
169.
Anand Pal Singh P. Ramos Cabrer E. Alvarez-Parrilla F. Meijide J. Vázquez Tato 《Journal of inclusion phenomena and macrocyclic chemistry》1999,35(1-2):335-348
In order to study its guest binding and the inclusion phenomena, 6-deoxy-6-(aminoethyl)amino--cyclodextrin (CDN) was synthesised and its binding properties examined. The complexation phenomena of sodium cholate (NaC) and sodium deoxycholate (NaDC) with CDN has been monitored by the NMR method using 13C chemical shift data. The method of continuous variation Job's method has been used to determine the stoichiometry of these supramolecular complexes. The Job's plot confirms the 1 : 1 supramolecular complex for NaC: CDN and the 1 : 2 supramolecular complex for NaDC: CDN. The interaction of NaC and NaDC with CDN has been obtained through two-dimensional Rotational Nuclear Overhauser Effect Spectroscopy (ROESY) NMR. Equilibrium constants were also obtained from 13C chemical shift data (C-1, C-3 & C-4) at different pH values (7, 9, & 11). 相似文献
170.
In spite of Sinai's result that the decay of the velocity autocorrelation function for a random walk on
d
(d=2) can drastically change if local impurities are present, it is shown that local impurities can not abolish weak convergence to the Brownian motion if d2. 相似文献