金属卟啉催化氧化环己烷反应的研究进展

为了筛选仿生催化氧化环己烷反应的优异催化剂。重点归纳总结了用做仿生催化空气氧化环己烷反应的金属卟啉化合物的类型和种类。其中,研究最为活跃的是中位取代（meso-）四苯基卟啉及其衍生物的金属配合物,络合的金属种类主要是过渡金属Fe、Mn、Co。金属卟啉仿酶催化剂品种中,主要有单金属卟啉、双核金属卟啉和固载金属卟啉等3种类型,其中研究较为成熟的是单金属卟啉催化剂,且苯环上取代吸电子基团的金属卟啉仿酶催化剂的催化活性较高。     

两种氧膦配体的合成与表征

文中合成了两种新型氧膦配体，２，２’－联萘酚基苯基膦和二（β萘酚基）苯基膦。并用ＩＲ、’ＨＮＭＲ、３’ＰＮＭＲ、元素分析技术表征了两种配体。     

金属卟啉在手性识别中的应用

从结构上分析了金属卟啉作为手性分子识别受体的优点,阐述了判断化合物绝对构型的激子手性方法机理,按照单卟啉体系和多卟啉体系介绍了金属卟啉与手性客体分子的识别机理和相关研究成果。初步系统化地对金属卟啉在手性识别中的应用进行综述,意为在相关领域工作的研究者提供参考。     

Meso-取代卟啉及其金属配合物的合成进展

为了筛选仿生催化氧化环己烷的催化剂,通过查阅相关文献,重点概述了Meso-取代卟啉及其金属配合物的合成方法。合成卟啉的方法有Rothemund法、Adler法及其改进法、Lindsey法等,合成金属卟啉的方法有＂一步法＂和：＂两步法＂,目前,＂两步法＂被普遍使用。     

Electrocatalytic Oxidation of Amines on Platinum Electrodes. Part III. Oxidation Of Ethylenediamine Via Higher Oxidation States of Nickel

The voltammetric behaviour of aqueous nickel ethylenediamine solutions has been studied. Electrocatalytic oxidation waves were obtained which are attributed to the formation of trivalent and possibly also tetravalent nickel ethylenediamine complexes as intermediates. The mechanism of the electrocatalytic process is discussed.     

Exploratory Characterization of Phenolic Compounds with Demonstrated Anti-Diabetic Activity in Guava Leaves at Different Oxidation States

Psidium guajava L. is widely used like food and in folk medicine all around the world. Many studies have demonstrated that guava leaves have anti-hyperglycemic and anti-hyperlipidemic activities, among others, and that these activities belong mainly to phenolic compounds, although it is known that phenolic composition in guava tree varies throughout seasonal changes. Andalusia is one of the regions in Europe where guava is grown, thus, the aim of this work was to study the phenolic compounds present in Andalusian guava leaves at different oxidation states (low, medium, and high). The phenolic compounds in guava leaves were determined by HPLC-DAD-ESI-QTOF-MS. The results obtained by chromatographic analysis reported that guava leaves with low degree of oxidation had a higher content of flavonols, gallic, and ellagic derivatives compared to the other two guava leaf samples. Contrary, high oxidation state guava leaves reported the highest content of cyanidin-glucoside that was 2.6 and 15 times higher than guava leaves with medium and low oxidation state, respectively. The QTOF platform permitted the determination of several phenolic compounds with anti-diabetic properties and provided new information about guava leaf phenolic composition that could be useful for nutraceutical production.     

阳极氧化处理对碳纤维强度离散性的影响及表征

采用阳极氧化法对碳纤维进行了表面处理,并探讨了表面处理后碳纤维接触角、强度的变化和碳纤维强度离散性的表征方法。研究发现:碳纤维在阳极氧化表面处理后,接触角变小,说明浸润性增强,强度略有下降,离散性略有增大;表面处理后随放置时间延长,接触角有一定程度增大,强度继续下降,离散性继续增大。用强度CV值和韦伯分布拟合强度所得的韦伯模数两种不同指标表征了表面处理后碳纤维的强度离散性,经验证,两种表征方法的一致性好。     

Metalloporphyrins in Oxidative Catalysis. Oxygen Transfer Reactions of Oxochromium Porphyrins

The oxidation of chloro-5-10,15,20-tetramesitylporphyrinotoiron(III) with peroxyacids affords a reactive oxoiron(IV)-porphyrin cation radical species 2. The characterization of 2 and its oxochromium analogs 3, 4 and 5 are reviewed. The nature of reactive oxochromium species derived from chromyl reagents is also reviewed. The oxidation of triphenylphosphine by CrOTPP (11), CrOTTP (13) and CrOTMP (14) is described. Variations in the rate constants indicate that steric factors affect the rate of oxygen atom transfer. Activation parameters for the oxidation of triphenylphosphine by 14 are ΔH^≠ = 6.96 kcal/mol and ΔS^≠ = −39 eu. The oxidation of t-butylphenylcarbinol (18) by CrOTPP gave predominantly benzaldehyde via carbon—carbon bond cleavage while the chromium(III) porphyrin-catalyzed oxidation of 18 by iodosylbenzene afforded t-butylphenylketone.     

Optical Absorption and Oxidation States of Uranium in Alkali Aluminoborate Glasses

The optical absorption spectra of 22R₂O.13Al₂O₃.65B₂O₃ (mol%) glasses contain ing uranium indicate the presence of U⁶⁺, U⁵⁺, and U⁴⁺. The presence of U⁶⁺ in the uranyl group is favored as alkali ion (R) is replaced in the direction Li6+ coordinated diflerently from that in uranyl groups (possibly 4-coordinated). A suggestion for making use of such findings in estimating the uranium content of a sample is given.     

5-氨基四唑为配体的锌离子配合物的结构表征及荧光

利用水热法合成配合物的优点,构筑了一个具有特定结构的5-氨基四唑为配体与锌金属离子配位聚合物,用红外光谱、X-射线单晶衍射等技术对配合物进行了结构表征和性能研究。单晶X-射线衍射显示配合物为2D双层结构。每一个锌离子与周围的四个5-氨基四唑配体进行配位,由键长和键角的数据可以看出锌离子的配位构型是有些扭曲的四面体构型。该配合物属于正交晶系,Cmcm空间群,a=1.7973(4)nm,b=1.0348(2)nm,c=2.0206(4)nm,Z=4,V=3.7580(13)nm3,D=1.651(mg/m3),μ=2.589(mm-1)。对配合物的固态的发光性质进行了研究。结果表明,在室温342nm激发下,配合物在397nm处有最大发谢。     

过氧钒有机配合物的合成及其催化降解水中有机污染物的研究

合成并用1H NMR和51VNMR以及IR等谱学表征了3种过氧钒有机配合物：草酸过氧钒[pV（ox）],三乙醇胺过氧钒[pV（teoa）],双（二乙烯三胺）过氧钒[pV（beta）].用分光光度法研究了这些过氧钒有机配合物对水中少量或微量有机染料污染物氧化降解的催化性能,并将这三种配合物的氧化降解的催化作用进行比较,发现它们的催化活性顺序为：pV（ox）〉pV（teoa）〉pV（beta）.     

Synthesis and Characterization of Dendrimer-Templated Mesoporous Oxidation Catalysts

We report here the use of 4th and 5th generation dendrimers poly(propylene)imine (CU-D32 and CU-D64) as templating agents for the synthesis of mesoporous titanosilicate and vanadosilicate oxidation catalysts via solgel techniques. The physical properties of these mesoporous materials were characterized by TGA, BET, PXD and SEM/EDX analyses and these showed that the transition metals are evenly distributed throughout these silicates, which have interconnected spherical pores (approx. 12Å in diameter) and high surface areas of about 650m²g^–1. Kinetic studies showed that all transition metal-doped catalysts were highly selective at oxidizing cyclohexene to the corresponding epoxide. Additionally, CU-D64-templated catalysts were more catalytically active for cyclohexene epoxidation than CU-D32-templated catalysts as a result of differences in pore size. All CU-D64-templated catalysts exhibited epoxidation catalytic activity comparable to that of titanium doped MCM-41 materials.     

金属卟啉在新型材料领域的应用进展

作为新型材料其中一员,卟啉及金属卟啉在光电器件、医药和功能材料等领域具有重要的研究意义和广泛的应用前景。本文综述了近年来卟啉及金属卟啉化合物在新型材料方面的研究,重点介绍了金属卟啉化合物在电化学、分子自组装及催化等方面的应用新进展,并对其未来在新型材料领域的研究进行了展望。     

4-甲基水杨酸铜(Ⅱ)配合物的合成与表征

采用溶剂热法合成了一个配合物[Cu(4-Me-SA)(Phen)]•2H2O(Phen = 1,10-邻菲啰啉,4-Me-SA = 4-甲基水杨酸）,用X-射线单晶衍射仪测定了该化合物的晶体结构,通过元素分析(EA),红外光谱(FTIR),紫外-可见光谱(UV-Vis),热分析(DSC-TGA)和荧光光谱(FS)对其结构和性质进行了分析与表征。结果表明：晶体属于单斜晶系,P2(1)/c空间群,晶胞参数a = 0.8324(3) nm,b = 1.2644(5) nm,c = 1.7493(7) nm,α = 90.00°,β = 100.404(7)°,γ = 90.00°,V = 1810.8(12) nm3, Z = 4。配位原子分别来自于1个4-甲基水杨酸配体的2个氧原子和1个邻菲啰啉配体的2个氮原子,形成配位数为4的稳定结构。配合物中的氢键和π-π堆积作用使其自组装成1个稳定的三维立体结构。发光性能测试表明该配合物具有荧光性质。     

新癸酸钴中不同氧化态钴的分离及测定

研究新癸酸钴中不同氧化态钴分离及测定的方法。根据二价钴和三价钴与乙酰丙酮形成的配合物溶解性的不同,实现不同氧化态钴的有效分离;根据配合物稳定常数的不同,利用络合滴定法,测定新癸酸钴中二价钴含量。用本方法对自制及市售新癸酸钴样品的进行分离及测定取得满意的效果。     

4-甲基水杨酸铜(Ⅱ)配合物的合成与表征

采用溶剂热法合成了一个配合物[Cu(4-Me-SA)(Phen)]·2H2O(Phen=1,10-邻菲啰啉,4-Me-SA=4-甲基水杨酸),用X射线单晶衍射仪测定了该化合物的晶体结构,通过元素分析(EA),红外光谱(FTIR),紫外-可见光谱(UV-Vis),热分析(DSC-TGA)和荧光光谱(FS)对其结构和性质进行了分析与表征。结果表明:晶体属于单斜晶系,P2(1)/c空间群,晶胞参数a=0.8324(3)nm,b=1.2644(5)nm,c=1.7493(7)nm,α=90.00°,β=100.404(7)°,γ=90.00°,V=1 810.8(12)nm3,Z=4。配位原子分别来自于1个4-甲基水杨酸配体的2个氧原子和1个邻菲啰啉配体的2个氮原子,形成配位数为4的稳定结构。配合物中的氢键和π-π堆积作用使其自组装成1个稳定的三维立体结构。发光性能测试表明,该配合物具有荧光性质。     

新型氨基硫脲类Schiff碱配体的合成及结构表征

用 0 .0 5mol烯丙基异硫氰酸酯和 9.5mL质量分数为 5 0 %的水合肼溶液反应 ,制得 6 3g新的烃基取代的氨基硫脲类化合物——— 4 烯丙基氨基硫脲 (Ⅰ)白色晶体。首先用 0 0 1mol联乙酰分别与 0 0 2mol化合物Ⅰ及 0 0 2mol氨基硫脲缩合 ,合成了收率为 71%的联乙酰双缩 ( 4 烯丙基氨基硫脲 ) (Ⅱ)和收率为 70 %的联乙酰双缩氨基硫脲 (Ⅲ)两种新的含硫脲基Schiff碱。其次用 10mmol环己酮与 10mmol化合物Ⅰ在 30mL无水乙醇中 ,电磁搅拌 ,回流反应 2h ,合成出 1 8g环己酮缩烯丙基氨基硫脲 (Ⅳ )淡黄色晶体。最后将 0 0 1mol化合物Ⅰ分别与 0 0 0 5mol水合茚三酮及 1 0g乙二醛缩合 ,合成了两种新的含硫脲基的双Schiff碱型配体——— 1 6g茚三酮二缩 ( 4 烯丙基氨基硫脲 ) (Ⅴ)桔红色晶体和 1 2g乙二醛二缩 ( 4 烯丙基氨基硫脲 ) (Ⅵ )浅黄色粉末。对所合成的 5种新的含硫脲基Schiff碱配体 ,通过元素分析 ,IR ,1HNMR和MS表征了它们的结构。初步测试了它们对部分金属离子的配位性能。该合成方法具有操作简便、反应条件温和、产率高等优点     

The Effect of Salts on Ozone Oxidation Processes

Much research on ozone oxidation is performed using model wastewaters, containing a number of organic compounds to be degraded. In some cases they contain low concentrations of inorganic buffers to stabilize the pH during the experiments. In practical applications, however, salts and detergents may be present as well. The effect of such compounds on the process has to be investigated to prevent unexpected results in pilot- or full-scale applications. To quantify these effects, experiments have been performed on model waste waters in the absence and the presence of high concentrations of several inorganic salts. The oxidation selectivity in these experiments was interpreted using Hammett free-energy relationships. The effect of the different salt concentrations on the oxidation selectivity when considering reactions in the bulk of the liquid was seen to be small. This implicates the design of an ozone-based oxidation system can often be based on literature or calculated data regarding reaction rates. However, the effect of increased salt concentrations on ozone solubility and bubble size distribution may have implications for the reactor design, as these factors affect the mass transfer efficiency.     

The Cell Surface Receptor CD44: NMR‐Based Characterization of Putative Ligands

The cell surface receptor CD44 is a glycoprotein belonging to the hyaluronan‐binding proteins, termed hyaladherins. CD44 is expressed in a wide variety of isoforms in many cells and, in particular, is present on the surface of malignant cells where it is involved in the onset and progression of cancer. In a first attempt to identify novel CD44‐binding agents, we first characterized, with NMR spectroscopic techniques, several agents that were reported to bind to human CD44 (hCD44). To our surprise, however, none of these putative CD44‐binding agents, including a peptide that is in phase 2 clinical trials (A6 peptide) and a recently reported fragment hit, were found to interact significantly with recombinant hCD44(21–178). Nonetheless, we further report that a fragment‐screening campaign, with solution NMR spectroscopy as the detection method, identified a viable fragment hit that bound in a potentially functional pocket on the surface of CD44, opposite to the hyaluronic acid binding site. We hypothesize that this pocket could be indirectly associated with the cellular and in vivo activity of the A6 peptide, which would provide a novel framework for the possible development of therapeutically viable CD44 antagonists.     

Ti-HMS合成、表征及其催化氧化性能研究

以有机金属二氯二茂钛为钛源,六方介孔二氧化硅分子筛(HMS)为载体,采用嫁接法合成了含钛量(mol)分别为2.8%、3.8%和4.8%的Ti-HMS,HMS合成原料组成中H2O/EtOH(v/v)分别为0.5、1、2、5、9.合成材料用X射线粉末衍射(XRD)、N2吸附-脱附等温线、漫反射紫外可见光谱(UV-VIS)进行了表征,并考察了它们以叔丁基过氧化物(TBHP)为氧化剂在对叔丁基甲苯液相氧化中的催化性能.结果表明,表面钛嫁接后的HMS介孔结构有所损失,比表面积和孔体积减少.载体HMS合成原料中的H2O/EtOH(v/v)影响介孔织构和钛的配位环境.UV-VIS资料表明,H2O/EtOH(v/v)=0.5和9时不利于钛着床于分子筛骨架,H2O/EtOH(v/v)=1、2和5的HMS适合作为嫁接钛的载体.催化剂的活性主要受四配位Ti、介孔织构的影响.钛嫁接的HMS在氧化反应中表现出较好的催化活性,载钛量为4.8%Ti、H2O/EtOH(v/v)=1的Ti-HMS显示最好催化活性,对叔丁基甲苯转化率为21.8%.