Probe electrode study of cathodically polarized PtIr-YSZ interfaces

Journal of Solid State Electrochemistry - Local cathodic polarizations of yttria-stabilized zirconia were carried out with a PtIr probe as the working electrode in a controlled atmosphere high...     

木质素在塑料中的应用

总结了国内外近10年来木质素在塑料中的应用进展，重点对木质素在PVC、PP、PE、PF、PU等5个方面的研究成果进行了系统阐述，并对该技术的发展方向进行了分析预测。     

The mapping properties of the radiosity operator along an edge

In this article we study the radiosity operator along an edge between two adjacent half‐planes. First we show that the radiosity operator is invertible in a whole scale of anisotropic Sobolev spaces. In the absence of any shadows we are able to derive regularity properties of the solution, which depend only on the angle between the half‐planes, the reflectivity coefficients and the right‐hand side. This work can be considered as a supplement to the article of Rathsfeld (Mathematical Methods in the Applied Sciences 1999; 22 : 217–241). Copyright © 2002 John Wiley & Sons, Ltd.     

Temperature coefficient of NH chemical shifts of thioamides and amides in relation to structure

NH chemical shift temperature coefficients have been measured in a large series of N-substituted-3-piperidinethiopropionamides in which the NN distances are short but of varied length, as well as in a couple of the corresponding amides and in some simpler amides and thioamides. Geometries are calculated by means of ab initio DFT methods. The N-substituted-3-piperidinethiopropionamides show in most cases strong intramolecular N–HN hydrogen bonds according to IR spectra and ab initio calculations. For compounds with rather short NN distances the S=C–N–H moiety is non-planar. Dihedral angles as small as 160° are found. The NH chemical shift coefficients measured in non-polar solvents in all the N-substituted-3-piperidinethiopropionamides are more negative (−8 to −17 ppb/K) than in non-hydrogen bonded thioamides. For the latter in non-polar solvents like CDCl₃ and toluene the temperature coefficients are as small as −1 to −4 ppb/K. The large negative effects can be related not only to the non-planarity of the thioamide group in a way that the more pronounced the non-planarity the more negative the temperature coefficients, but also to strong hydrogen bonding and the fact that the acceptor is a nitrogen. For similar amides with non-planar amide groups and nitrogen acceptor large negative temperature coefficients are likewise seen. In polar solvents like DMF the effects in simple thioamides are uniform and close to −6 ppb/K, whereas in the more complex compound like 4p(t) the temperature coefficient is close to 0. An essential feature of measuring temperature coefficients of compounds without strong intramolecular hydrogen bonds in non-polar solvents and at low temperatures is to keep the concentration low enough to avoid dimerisation.     

关于1+1维可积系统的代数结构与Riemann-Hilbert变换

1+1维经典可积系统的隐代数结构用Riemann-Hilbert变换进行一般性讨论。新的Loop代数用Yang-Baxter等式的解给出,并指出它与基本Poisson-Lie括号的一致性。系统的Virasoro代数结构由系统的共形不变性导出。     

Organocatalysis: quantum chemical modeling of nucleophilic addition to α,β‐unsaturated carbonyl compounds

One of the successful transformations within the field of organocatalysis, the organocatalytic asymmetric addition of nitromethane to α,β‐unsaturated aldehydes and ketones, has been studied by quantum chemical modeling. The level of accuracy of the hybrid density functional theory method B3LYP/6‐31G(d) was compared to a high level ab initio benchmark for this reaction. It is concluded that B3LYP/6‐31G(d) performs very well for this reaction type, giving good estimates of critical energies. The reaction between acrolein and nitromethane was studied in detail. The reaction mechanism revealed an intermediate oxazolidin structure, which is currently unknown. Alkyl substitution in various positions on the amine catalyst or α,β‐unsaturated carbonyl compound influences the reactivity in a predictive fashion. The iminium ion, prop‐2‐en‐iminium, is less activated towards nucleophilic attack compared to protonated acrolein. Copyright © 2007 John Wiley & Sons, Ltd.