Syntheses of 4-(2-hydroperoxy-2,2-diarylethyl)-3,5-dimethylpyrazoles, 4-(2-hydroxy-2,2-diarylethyl)-3,5-dimethylpyrazoles and the related compounds

The reactions of 1,1-disubstituted ethenes with 2,4-pentanedione in the presence of manganese(III) acetate and atmospheric oxygen yielded 4-acetyl-6,6-diaryl-3-methyl-1,2-dioxan-3-ols. The latter gave 4-(2-hydroperoxy-2,2-diarylemyl)-3,5-dimethylpyrazoles by the reaction with hydrazines in methanol-acetic acid (1:1 v/v) at 50° in 15-77% yields, or 4-(2-hydroxy-2,2-diarylethyl)-3,5-dimethylpyrazoles by the reaction with hydrazines in methanol in 2-78% yields. The acid-catalyzed reaction of 4-(2-hydroperoxy-2,2-diarylethyl)-3,5-dimethylpyrazoles yielded 4-(aroylmethyl)-3,5-dimethylpyrazoles (15-55%) and 4-(2,2-diarylethenyl)-3,5-dimethylpyrazoles (9-29%).     

Two new tetranuclear complexes of the macrocyclic oxamide [MCu3] (M = Cd, Mn, macrocyclic oxamide = 1,4,8,11-tetraazacyclotradecanne-2,3-dione): syntheses, spectra and magnetic properties

Two new tetranuclear complexes of macrocyclic oxamide [Cd(CuL)₃](NO₃)₂·2.5H₂O 1, [Mn(CuL)₃(OH)₂](ClO₄)₂·Mn(H₂O)₆·4.5H₂O 2 (L = 1,4,8,11-tatraazacyclotradecanne-2,3-dione) have been synthesized, structurally characterized and preliminary investigated by magnetic studies. The structures of the title complexes consist of a tetranuclear units MCu₃ (M = Cd, Mn), the packing diagram shows two-dimensional and three-dimensional system through intermolecular weak interactions. The temperature-dependent magnetic susceptibilities of complex 2 were analyzed by an approximate treatment leading to J = −33 cm⁻¹, g_Cu = 2.10, g_Mn = 1.95 indicating antiferromagnetic exchange between Cu(II) and Mn(II) ions.     

扫描近场光学显微镜对纳米结构的观察

光学显微镜在人们认识微观世界的过程中一直扮演着非常重要的角色．随着认识的深入，对空间分辨率的要求也越来越高．但是众所周知，普通光学显微镜（远场情况下）的分辨率受光的衍射效应所限制，一般可表达为0．61A／N．A．（约等于A／2，A为照射光的波长，N．A．为数值孔径）     

弱碱性阴离子交换树脂分离1,6—二磷酸果糖的研究

采用弱碱性阴离子交换树脂HJ-30对发酵液中1，6-二磷酸果糖的分离进行了研究。详细地研究了树脂的吸附和脱附性能。实验结果表明，HJ-30树脂对FDP的吸附量达0．28gFDP／g湿树脂，以0．05mol／LNaCl洗脱光机磷和1mol／LNaCl洗脱1，6-二磷酸果糖，产品的收率和纯度分别为92％和99．4％。     

顺磁性聚酯金属配合物的合成及其驰豫性能的研究

本文通过二乙三胺五乙酸（ＤＴＰＡ）或乙二胺四乙酸（ＥＤＴＡ）的双酸酐与二元醇或二元酚进行聚合反应，制备了两个系列共１５种新的聚酯型大分子配体及其顺磁性金属配合物，用核磁、红外光谱以及元素分析表征了配体和配合物的结构。初步试验结果表明，与相应的小分子金属配合物相比，聚酯金属配合物具有较高的弛豫性能。     

不同介质凝胶体系中草酸钙结晶的研究

研究了五种不同介质（水、氯化钠、合成尿、正常人尿液和尿石患者尿液）的凝胶体系中草酸钙（CaC2O4）晶体的生长,及各种体系中防石药物柠檬酸钾（K3cit）对CaC2O4生长的影响.没有加K3cit时,CaC2O4晶体以一水草酸钙（calcium oxalate monohydrate, COM）为主要物相,但在氯化钠和合成尿的凝胶体系中同时出现了二水草酸钙（calcium oxalate dihydrate, COD）和三水草酸钙（calcium oxalate trihydrate, COT）,肾结石患者尿液中出现COD,而正常人尿液中没有COD和COT生成.加入K3cit后,水、氯化钠和合成尿介质的凝胶体系中,COT的含量显著增加,患者尿液中产生大量COD,而正常人尿液中出现了少量的COD和极个别的COT.COT的增加与低温、体系中高的离子强度及金属离子等因素有关.K3cit具有诱导COD和COT的生成、减小COM晶体比表面积的作用,从而有利于防治草酸钙结石的形成.     

Complexes formed between nitrilotris(methylenephosphonic acid) and M(2+) transition metals: isostructural organic-inorganic hybrids

Nitrilotris(methylenephosphonic acid) (NTP, [N(CH(2)PO(3)H(2))(3)]) recently has been found to form three-dimensional porous structures with encapsulation of templates as well as layered and linear structures with template intercalation. It was, therefore, of interest to examine the type of organic-inorganic hybrids that would form with metal cations. Mn(II) was found to replace two of the six acid protons, while a third proton bonds to the nitrilo nitrogen, forming a zwitter ion. Two types of compounds were obtained. When the ratio of acid to Mn(II) was less than 10, a trihydrate, Mn[HN(CH(2)PO(3)H)(3)(H(2)O)(3)] (2) formed. Compound 2 is monoclinic P2(1)/c, with a = 9.283(2) A, b = 16.027(3) A, c = 9.7742(2) A, beta = 115.209(3) degrees, V = 1315.0(5) A(3), and Z = 4. The Mn atoms form zigzag chains bridged by two of the three phosphonate groups. The third phosphonate group is only involved in hydrogen bonding. The metal atoms are octahedrally coordinated with three of the sites occupied by water molecules. Adjacent chains are hydrogen-bonded to each other through POH and HN donors, and the additional participation of all the water hydrogens in H-bonding results in a corrugated sheet-like structure. Use of excess NTP at a ratio to metal of 10 to 1 yields an anhydrous compound Mn[HN(CH(2)PO(3)H)(3)] (1), P2(1)/n, a = 9.129(1) A, b = 8.408(1) A, c = 13.453(1) A, beta = 97.830(2) degrees, V = 1023.0(2) A(3), and Z = 4. Manganese is five coordinate forming a distorted square pyramid with oxygens from five different phosphonate groups. The sixth oxygen is 2.85 A from an adjacent Mn, preventing octahedral coordination. All the protonated atoms, three phosphonate oxygens and N, form moderately strong hydrogen bonds in a compact three-dimensional structure. The open-structured trihydrate forms a series of isostructural compounds with other divalent transition metal ions as well as with mixed-metal compositions. This is indicative that the hydrogen bonding controls the type of structure formed irrespective of the cation.