关于RNP和SCS的若干等价条件

使用切片方法，讨论了Banach空间中有界闭凸子集的RNP和SCS的若干等价条件．     

取代基效应(SCS)与乙烯-α-烯烃共聚物的序列结构Ⅲ.定量分析

本文在分析乙烯-α-烯烃共聚物序列结构时,把代表共单体反接单元的亚甲基(CH₂)βγ和γδ分别归属给了二元组VV和三元组EEV。与此同时,CH₂-δδ和δδ⁺归属给了二元组EE。表征乙烯长序列的CH₂-δ⁺δ⁺分属二元组EE和三元组EEE,对应峰强度在EE和EEE之间的分配是处理序列分布的关键。在本文中运用序列结构的Bovey关系和Randall统计进行演算,求得了修正值△的数学表达式,严格解和近似解。在规则链条件下得到的近似解与G.J.Ray的结果完全相同。当共单体含量较少时,谱峰强度Iδ⁺δ⁺的分配接近相等。在二元组和三元组的水平上,乙烯-α-稀烃共聚物的¹³C NMR谱中共有十三个峰,属于CH₂的有十个,属于CH的有三个。利用这些谱峰的强度数据可以建立一套计算公式,由此提供共聚物序列结构的全部信息。因此这是一个研究乙烯-α-烯烃共聚物序列结构的普适方法。     

3（或）4—取代苯甲亚氨酸酯中取代基效应的^13C—NMR研究

本文测定了三个3(或4)-取代苯甲亚氨酸乙酯(1)和八个N-氰甲基-3(或4)-取代苯甲亚氨酸乙酯(2)的~(13)C-NMR谱。归属了1 和2和各碳化学位移。求得了的取代基化学位移(substituent Chemical Shift,SCS)。碳-13化学位移与单取代苯的取代基化学位移(SCS)的相关分析表明:4-取代苯甲亚氨酸酯1 b～g和2b～e中,除C_(2,6)外,其他各芳碳的化学位移值与加和规则基本相符;3-取代苯甲亚氨酸酯1h～j和2f～h中,除C_1外,其他各芳碳的化学位移值与加和规则基本相符。另外,本文还进行了碳-13化学位移与σ_(I)/σ_(R)~O和F/M的双参数相关分析。     

Hydroxyl Substituent Chemical Shift (SCS) Effects in Alcohols: The 17O NMR of Diols

The ¹⁷O NMR spectra for a series of saturated diols were investigated. From these studies both hydroxyl induced substituent chemical shift (SCS) effects of hydroxyl oxygen ¹⁷O NMR chemical shifts were determined. In addition, linear correlations between the ¹⁷O chemical shift of the hydroxyl oxygen (ROH) and the ¹³C chemical shift for the methyl group in the corresponding hydrocarbon (RCH₃) were obtained.

     

13C NMR Investigation of Si-alkylsubstituted 1,3,5-Trisilacyclohexanes

¹³C NMR spectra of Si-alkylsubstituted derivatives of 1,3,5-trisilacyclohexanes have been recorded and analyzed. A systematic preparation of alkyl derivatives with mixed substituents made it possible to evaluate substituent-induced chemical shift (SCS) values for the ring carbon atoms in β and δ position. It is found that the β_e effect decreases in the order Me > Et > i-Pr > t-Bu. For the alkyl groups Me, Et, and i-Pr the β_a effect is smaller than the β_e effect. Axial SCS values for the t-Bu group are not accessible because chair conformations with an axial t-Bu group are unfavourable and tend to escape into a twisted boat form. The observed δ effects are small and do not show any obvious tendencies.     

壁流动中的转捩

对壁流动的不同实验结果做了对比,这些实验结果来自于流动显示、热膜测量以及PIV测量, 对比的同时,还总结了与此相应的理论方面的进展.这些进展是在对所选大约120篇文献中内容归纳提炼的基础上给出的.尽管实验中所使用的初始扰动条件不同,但所发现的流动结构几乎是完全一样的. 在对壁流动转捩的认识方面,认为下列所观察到的流动结构是最基本最重要的:在边界层和管流中被称为类孤子相干结构(SCS)的三维非线性涡包、$\Lambda$涡、二次涡环和涡环链.近期的实验中发现了这些结构形成和转捩的动力学过程,具体包括以下内容: (1) $\Lambda$ 涡和二次涡环间持续的相互作用过程.该过程决定了涡环链的产生方式, 总是从壁面区域周期性地形成,并进入到边界层的外部区域; (2)高频涡的生成,这是理解转捩和湍流边界层(以及其他流动)发展的关键问题之一.尽管已经提出了一些解释,但是二次涡环的实验发现将对此提供一个特别清晰的解释.(3)在所有湍流猝发中SCS所起的关键作用.这一点被看做是低雷诺数湍流边界层中湍流产生的关键机制.与猝发直接相关联的是低速条带. 基于SCS的动力学过程, 针对壁流动情况,可以比以前更清晰地解释低速条带的形成机制及其与流动结构的关系.在实验中所观察到的SCS和二次涡环,不仅能使我们重温壁面流动转捩中的经典故事, 同时还开辟一条新的途径,可以基于此建立壁面流动转捩可能具有的普适性的动力学过程.      

基于尺度质心统计的纹理分析

结合目前纹理分析的三类算法,提出了尺度质心统计的分析算法。该算法以具有多分辨率特性的小波包为基础,结合结构法的纹理元分析方式,采用区域质心完成局部特征提取,最后使用投影法进行整体的特征提取。实验证明,尺度质心统计取得了令人满意的纹理分析效果。     

The statistical generation of SCS values and interaction factors for the13C NMR spectra of arenes

A new methodology which statistically determines substituent chemical shifts (SCS) and interaction factors of adjacent groups for use in the³C NMR spectroscopy of arenes is described. From a data base of 15,255 signals we have computed several hundred of thesestatistical SCS values (SSCS values), and interaction factors for many common pairs of groups. Some interaction factors for 1,2,3-substitution are also reported. When these SSCS values and interaction factors are used to predict the signal position they are found to give a correlation coefficient of predicted verses observed values of 0.994 with a standard deviation of 1.5 ppm.     

15N NMR chemical shifts of ring substituted benzonitriles

15N chemical shifts in an extensive series of para (15) and meta (15) as well as ortho (8) substituted benzonitriles, X-C6H4-CN, were measured in deuteriochloroform solutions, using three different methods of referencing. The standard error of the average chemical shift was less than 0.03 ppm in most cases. The results are discussed for both empirical correlations with substituent parameters and quantum chemical calculations. The 15N chemical shifts calculated at the GIAO/B3LYP/6-31 + G*//B3LYP/6-31 + G* level reproduce the experimental values well, and include nitrogen atoms in the substituent groups (range of 300 ppm with slope 0.98 and R = 0.998, n = 43). The 15N shifts in hydroxybenzonitriles are affected by interaction with the OH group. Therefore, these derivatives are excluded from the correlation analysis. The resultant 15N chemical shift correlates well with substituent constants, both in the simple Hammett or DSP relationships and the 13C substituent-induced chemical shifts of the CN carbon.     

Conformational analysis of p-X-anilino dioxaphosphinanes. Substituent effects on P and N NMR signals and on negative hyperconjugation (n-σ*)

The conformational analysis of anancomeric cis-ax and cis-eq 2-p-X-anilino-2-thio-4,6-dimethyl-1,3,2λ⁵-dioxaphosphinanes (X=OCH₃, C₆H₁₁, H, Cl, CN and NO₂) is informed. In accordance with ³J_HH, ³J_HP, ⁴J_HP, and ³J_CP coupling constants the preferred conformation in solution is a chair in both series of compounds. Structural parameters obtained through X-ray diffraction studies of the series of cis-ax and cis-eq diastereomers 1-6, suggest that the stabilization of the axial and equatorial diastereomers in chair conformation rely on stereoelectronic n_πO-σ*_P-N and n_πN-σ*_P-O interactions, respectively. Theoretical Kohn-Sham DFT calculations support the participation of the cited stereoelectronic interactions not only to understand the conformational behavior of these systems but also to give an explanation of the observed substituent-induced chemical shift (SCS) on ³¹P and ¹⁵N NMR signals.