On the Image Regularity Condition

In this paper, we continue the analysis of the image regularity condition (IRC) as introduced in a previous paper where we have proved that IRC implies the existence of generalized Lagrange-John multipliers with first component equal to 1. The term generalized is connected with the fact that the separation (in the image space) is not necessarily linear (when we have classic Lagrange-John multipliers), but it can be also nonlinear. Here, we prove that the IRC guarantees, also in the nondifferentiable case, the fact that 0 is a solution of the first-order homogeneized (linearized) problem obtained by means of the Dini-Hadamard derivatives.     

Symmetry specified enumeration of substituted derivatives: an easy solution to the complex problem

Several sophisticated methods to solution of symmetry specified enumeration problems are available in the modern literature. In this paper we propose a simple technique that allows one to manually compute the exact numbers of fixed-symmetry derivatives for a given structure either with inclusion or ignoring the substitution patterns. The basic idea of the method suggested consists in the derivation of Pólya-like cycle indices for the automorphism groups of specially constructed orbit partition graphs; the expansion of these indices and subsequent simple calculations result in the desired numbers of substituted derivatives with achiral substituents. Limitations of the new technique (and a method suggested earlier) depend on the relevance of the orbit partitions for particular subgroups of the point symmetry group. For illustration purposes, the results obtained for the prismane (D _3h ) and adamantane (T _d ) structures are discussed. In the former case the numbers of substituted derivatives can be found for all subgroups of the D _3h group, whereas in the latter case these numbers can be determined for eight out of eleven subgroups of the T _d point symmetry group. This work is based on the text of the lecture presented by the authors at the 5th All-Russia Conference on Molecular Modeling (Moscow, April 2007). The paper deals with the methodology and detailed treatment of applied aspects related to solution of enumeration problems for substituted derivatives with prescribed symmetry groups. Unlike the known methods of symmetry specified enumeration, the technique suggested is simple enough and may be regarded as generalization of the Pólya methodology, which is widely used by chemists. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 227–245, February, 2008.     

Solid state NMR characterization of formation of poly(ϵ‐caprolactone)/maghnite nanocomposites by in situ polymerization

Results of multinuclear MAS NMR spectroscopy are reported for poly (ε‐caprolactone)/maghnite nanocomposite formation, with ε‐caprolactone in situ polymerized in the presence of maghnite, a proton exchanged montmorillonite clay. Exfoliated and intercalated materials with different maghnite loading in the range 3–15 wt % were investigated. ¹H NMR evidences Brønsted acid hydroxyl groups in the silicate layers and shows that their broad signal at 7.6 ppm present in the parent clay disappears in the nanocomposite material. ²⁷Al MAS NMR results show that beside the hexacoordinated aluminum signal, two additional peaks corresponding to two different tetrahedral Al sites are present in the clay framework. The NMR signal intensity of only one of them was found to be affected in the nanocomposites compared with the parent maghnite, suggesting that these specific aluminum sites are the reactive ones at the initial stages of the polymerization. However almost no changes occurred in the ²⁹Si NMR spectra, confirming that the polymer grafting, as indicated earlier by atomic force microscopy, took place on the aluminum tetracoordinated sites rather than on the silicon sites. A mechanism of maghnite surface catalyzed polymerization of ε‐caprolactone was proposed, involving Brønsted and Lewis acid sites. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3060–3068, 2007     

5-(对羧基苯偶氮)-8-羟基喹啉与钍的显色反应及应用

研究了钍与5-(对羧基苯偶氮)-8-羟基喹啉(5-CPAHQ)的显色反应条件:在阳离子表面活性剂十六烷基三甲基溴化铵(CTMAB)存在下,pH4.4-5.4缓冲介质中,形成稳定的橙红色络合物,最大吸收波长为490nm,ε=1.10×105L·mol-1·cm-1,钍在0-9μg/25mL范围内符合比尔定律。用TBP萃淋树脂分离,该方法可用于测定矿石中的微量钍。     

Fe-ZSM-5杂原子分子筛的合成与表征

采用静态水热法分别以正丁胺、四丙基溴化铵为模板剂合成ZSM-5分子筛及Fe-ZSM-5杂原子分子筛；利用XRD与FT-IR对其结构进行表征；考察了Mo改性后分子筛催化剂上甲烷脱氢芳构化的反应性能。结果表明，Fe部分进入了分子筛的骨架，导致分子筛的结晶度及表面酸强度的下降，使Mo／Fe-ZSM-5催化剂的反应性能较Mo／HZSM-5显著下降。     

1-Benzopyran-4(4H)-ones as novel activated alkenes in the Baylis-Hillman reaction: a simple and facile synthesis of indolizine-fused-chromones

1-Benzopyran-4(4H)-one derivatives have been successfully employed as novel activated alkenes in the Baylis-Hillman coupling with heteroaromatic-aldehydes, nitrobenzaldehydes and isatin-derivatives and the corresponding adducts, derived from pyridine-2-carboxaldehyde, have been transformed into a novel indolizine-fused-chromone framework.     

Sugar conjugates of fulvestrant (ICI 182,780): efficient general procedures for glycosylation of the fulvestrant core

We have prepared glucose and cellobiose conjugates at the phenolic 3- and hydroxylic 17-positions of the pure anti-estrogenic compound fulvestrant (ICI 182,780), which has recently been approved in the USA for the treatment of advanced postmenopausal breast cancer. Glycosylation at the 17-position was achieved most effectively using pivaloyl protection of the sugar imidates employed, which we found suppressed the competing transacylation reaction and led to improved yields of the product glycosides.     

Crystallographic report: Crystal structure of 1‐bromo‐1′‐[(2S)‐N‐(1‐hydroxy‐3‐methylbutane‐2‐yl)]‐ferroceneamide

For the unsymmetrical title compound, 1‐bromo‐1′‐[(2S)‐N‐(1‐hydroxy‐3‐methylbutane‐2‐yl)]‐ferroceneamide, two independent molecules were found in the asymmetric unit. Copyright © 2003 John Wiley & Sons, Ltd.     

三嗪类光学探针与标记分析

评述了以三聚氰氯作桥联剂或骨架而合成的三嗪类衍生物、特别是其光学标记探针的研究进展及分析应用。