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11.
The forms of responses of substituents to strongly changing pi-electron demands have been investigated using molecular orbital calculations at the STO-3G level of approximation; the non-parallel responses depend strongly upon the nature of the substituent. For example, CN, CHO, and NO2 act as pi electron donors in strongly electron deficient systems. 相似文献
12.
13.
13C NMR NT1 and NOE have been calculated by using composite spectral density functions describing polymer chain segmental motion and internal rotation of a hydrocarbon side chain attached to the polymer backbone. Numerical results at two magnetic fields are presented as a function of the various motional parameters characterizing the various models. NT1 and NOE relaxation parameters are well behaved and appear to have practical value for describing the dynamics of these systems. The models have been applied to the relaxation data of poly(n-butyl methacrylate) and poly(n-hexyl methacrylate) in toluene solutions. The dynamics of the two polymers are characterized by a very localized backbone motion and restricted internal rotation about successive C? C bonds of the side chains. © 1995 John Wiley & Sons, Inc. 相似文献
14.
Virginia A. Dais D. B. Priddy Bruce Bell Kevin D. Sikkema Pat Smith 《Journal of polymer science. Part A, Polymer chemistry》1993,31(4):901-908
A variety of 1,1-disubstituted ethylenes, having an electron-withdrawing (capto) and an electron-donor (dative) substituent on the same carbon, were synthesized and added to styrene polymerizations. The dative substituents investigated were alkoxy or alkylcarbonate. After the addition of a polystyryl radical to a disubstituted ethylene, the resulting alkoxy or carbonate radicals could potentially fragment, resulting in chain termination and the formation of alkyl radicals. This process is called addition-fragmentation chain transfer (AFCT). The polymers produced during this study were examined for evidence of copolymerization and AFCT. The relative stability of the radicals generated by the fragmentation process appears to be the predominant factor controlling the ratio of copolymerization versus AFCT. © 1993 John Wiley & Sons, Inc. 相似文献
15.
C. M. Paleos G. P. Evagelatos Photis Dais G. Kipouros 《Journal of polymer science. Part A, Polymer chemistry》1979,17(6):1611-1618
In the present study the polymerization of 4-vinyl-N-methylpyridinium methylsulfate at liquid–liquid interfaces is investigated. Various experimental procedures that may favor the interfacial mode of polymerization over the isotropic one are discussed. The effectiveness of the methods was evaluated by physical characterization studies and particularly polymer tacticity. This last property is directly associated with the achieved organization of the monomers at interfaces. 13C-NMR technique was used for tacticity determination. According to tacticity, random polymers are primarily obtained that result from an isotropic polymerization in the aqueous phase, where the monomer is extremely soluble. The small predominance of the syndiotactic triad over the isotactic one is explained by the occurrence of an interfacial polymerization induced by the orientation of the monomers. A polymerization model is proposed that justifies the stereospecificity modification of polymerization. 相似文献
16.
Phase-sensitive nuclear Overhauser enhancement spectroscopy (NOESY) experiments, (3)J couplings and computational molecular modeling (MM2* and MMFF force fields) were employed to examine the conformational properties of verrucarin A in chloroform solutions. The MMFF force field calculations resulted in a family of 12 low-energy structures along with their populations, the latter being determined by the NMR analysis of molecular flexibility in solution(NAMFIS) deconvolution analysis. The concluded model was capable of reproducing successfully the experimental NOESY cross-peak volumes and the proton-coupling constants. Among the 12 conformers, the one which was similar to the structure of verrucarin A in the solid state was the predominant accounting for 75% of the total relative population, although other low-energy conformations contributed to a lesser degree in order to explain the experimental data. 相似文献
17.
18.
Dimitrios I. Dais 《manuscripta mathematica》2001,105(2):143-174
An explicit computation of the so-called string-theoretic E-function of a normal complex variety X with at most log-terminal singularities can be achieved by constructing one snc-desingularization of X, accompanied with the intersection graph of the exceptional prime divisors, and with the precise knowledge of their structure.
In the present paper, it is shown that this is feasible for the case in which X is the underlying space of a class of absolutely isolated singularities (including both usual ?
n
-singularities and Fermat singularities of arbitrary dimension). As byproduct of the exact evaluation of lim, for
this class of singularities, one gets counterexamples to a conjecture of Batyrev concerning the boundedness of the string-theoretic
index. Finally, the string-theoretic Euler number is also computed for global complete intersections in ℙℂ
N
with prescribed singularities of the above type.
Received: 2 January 2001 / Revised version: 22 May 2001 相似文献
19.
Nuclear Magnetic Resonance (NMR) Spectroscopy has been extensively used for the analysis of olive oil and it has been established as a valuable tool for its quality assessment and authenticity. To date, a large number of research and review articles have been published with regards to the analysis of olive oil reflecting the potential of the NMR technique in these studies. In this critical review, we cover recent results in the field and discuss deficiencies and precautions of the three NMR techniques (1H, 13C, 31P) used for the analysis of olive oil. The two methodological approaches of metabonomics, metabolic profiling and metabolic fingerprinting, and the statistical methods applied for the classification of olive oils will be discussed in critical way. Some useful information about sample preparation, the required instrumentation for an effective analysis, the experimental conditions and data processing for obtaining high quality spectra will be presented as well. Finally, a constructive criticism will be exercised on the present methodologies used for the quality control and authentication of olive oil. 相似文献
20.
A. Spyros Photis Dais R. H. Marchessault 《Journal of Polymer Science.Polymer Physics》1995,33(3):367-378
Variable-temperature 13C NMR spin-lattice relaxation times (T1) and Nuclear Overhauser Enhancements (NOE) at two magnetic fields have been used to study the dynamics of the amorphous part of a semicrystalline sample (33% of crystallinity) of poly(β-hydroxyoctanoate) (PHO). The interpretation of the relaxation data of the backbone carbons was made by employing a number of motional models. Among these, the DLM model offered the best interpretation of the relaxation data in terms of conformational transitions and librational motions of the backbone C? H vectors, and proved to be superior to unimodal distribution functions. The interpretation of temperature- and frequency-dependent T1 and NOE data of the carbon nuclei in the n-pentyl side chain was made by employing a newly developed composite spectral density function for multiple internal C? C bond rotations of restricted amplitude and chain segmental motion. The temperature dependence of the linewidths of the various protonated carbon resonances of PHO has been discussed in terms of the semicrystalline character of this polymer. © 1995 John Wiley & Sons, Inc. 相似文献