共查询到18条相似文献,搜索用时 93 毫秒
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提出了用薄层色谱分离四苯基卟啉和四苯基钴卟啉的方法.方法中以石油醚-二甲苯(体积比为2:1)二元溶剂体系为展开剂,在硅胶薄层板上分离了四苯基卟啉和四苯基钴卟啉,所得斑点清晰、无拖尾.应用此薄层色谱法跟踪检测了四苯基钴卟啉的合成. 相似文献
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壳聚糖固载的四苯基钴卟啉催化空气氧化环己烷 总被引:1,自引:0,他引:1
将金属卟啉吸附固载到壳聚糖上,在室温下制备了壳聚糖四苯基钴卟啉催化剂,并用紫外光谱技术测定了四苯基钴卟啉的固载量. 在未加入任何溶剂和还原剂的条件下,研究了壳聚糖四苯基钴卟啉催化空气氧化环己烷的性能. 在418 K和0.8 MPa的空气压力下,壳聚糖四苯基钴卟啉能够很好地催化空气氧化环己烷,环己烷转化率为11%,相应的主产物环己醇和环己酮的选择性为87%,转化数为2.9×105,与未固载的四苯基钴卟啉相比,其催化性能大大提高,环己烷转化率和转化数分别提高了10倍和27倍. 研究结果表明: 壳聚糖对四苯基钴卟啉不仅有明显的保护作用,使之免遭氧化破坏,而且还有重要的助催化作用. 相似文献
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亚硝酸根催化光度法的研究进展 总被引:7,自引:0,他引:7
目前国内外测定NO_2~-的标准方法仍为重氮偶合比色法,即在稀磷酸介质中,NO_2~-与对氨基苯酰胺(或对氨基苯磺酸)反应生成重氮盐,再与N-(1-萘)-乙二胺(或α-萘胺)偶联生成红色染料,用光度法进行测定,进而求出NO_2~-的量。该法虽然有较高的灵敏度和选择性,但是所需试剂和显色反应稳 相似文献
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研究了不同的有机溶剂中四苯基钴卟啉(Co(Ⅱ)TPP)的光助还原O2反应,详细讨论了溶剂效应和有机碱的轴向配位效应对光还原反应的影响,同时对反应机理进行了探讨。结果表明,溶剂的极性越大或有机碱的轴向配位能力越强时,光还原O2反应的速率越大。 相似文献
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亚硝酸根的催化光度法测定 总被引:11,自引:0,他引:11
本法基于甲酸介质中,亚硝酸根对溴酸钾氧化甲基橙褪色的催化效应,用正交法确定最佳测定条件。本法测定亚硝酸根的线性范围为0~0.20μg/mL灵敏度为2.83×10-10g/mL。用于测定水样中的亚硝酸根,结果良好。 相似文献
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7种中位—四取代苯基卟啉化合物的合成 总被引:3,自引:0,他引:3
卟啉是一类结构与生命物质(如血红素和维生素B_(12))相似的化合物,近年来曾被用于人体肿瘤的光动力学治疗;此外,在电化学、光物理学和光化学、放射医学、微量元素测定、纺织品漂洗等领域中的应用也相当广泛,已受到科技工作者的普遍关注和重视。本文按Rothemond法将相应的取代苯甲醛与新蒸吡咯在丙酸中缩合,制得具有酸性、中性和碱 相似文献
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钴卟啉催化剂的前线轨道能级与其催化活性的相关性研究 总被引:8,自引:1,他引:7
设计并合成了12种钴卟啉催化剂,在温和反应条件(55℃, 2.0 MPa氧压)下考察其催化氧气液相氧化对硝基甲苯制取对硝基苯甲酸的催化活性,发现其对上述反应均有显著的催化活性.采用PM3半经验分子轨道法对所设计的钴卟啉化合物模型体系进行了计算,将计算结果与实验结果相结合,探讨了钴卟啉分子前线轨道能级与其催化活性之间的关系.经研究发现,四配位或五配位钴卟啉催化剂的催化活性与EHOMO和ΔEL-H均有一定的相关性,且ΔEL-H对催化活性的影响大于EHOMO对催化活性的影响;EHOMO值越低、ΔEL-H越小,其催化活性越高. 相似文献
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Differential scanning calorimetry (DSC) was used to determine the molar enthalpies of dehydration and decomposition of CoC2O4·2H2O, Co(HCOO)2·2H2O and [Co(NH3)6]2(C2O4)3·4H2O. The first stage of dissociation of each compound is a single-step dehydration both in air and argon atmospheres. The next
stages are decomposition processes influenced by experimental parameters. The enthalpies of dehydration and decomposition
vary from compound to compound in each atmosphere. The obtained data have been related to the macromechanisms proposed for
the thermal decomposition and the parallel-consecutive decomposition-oxidation processes.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
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《Analytical letters》2012,45(17):2853-2863
Abstract Peroxynitrite (ONOO?), which is usually generated as a response of the immune system or in inflammatory processes, is a powerful oxidant species, while hemoglobin is an important peroxynitrite scavenger in vivo. In this work, we have studied the interaction between peroxynitrite and hemoglobin through an electrochemical method and UV-Vis spectroscopy. It is found that peroxynitrite, at a relatively high concentration level, may make the protein exhibit a concentration-dependent increase of its catalytic activity towards hydrogen peroxide, whereas peroxynitrite at low concentration will result in the slight decrease of the catalytic activity. Further studies reveal that the diversification of the enzymatic activity is ascribed to the different extent of tyrosine nitration and, accordingly, the spatial conformation of the protein. 相似文献
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采用密度泛函理论计算方法模拟了简单钴卟啉过氧中间体PCo-O2与环己烷C6H12的作用,分析了反应路径中各驻点能量和反应过渡态分子构型。研究结果表明,PCo-O2向底物环己烷夺氢的反应可以延正方向进行,二线态PCo-O2更具反应活性,反应过程中Co-O键得到加强,O-O键被削弱。依据理论计算结果,探讨了四苯基钴卟啉催化环己烷氧化生成环己醇和环己酮的反应机理,指出反应延Lyons高价金属氧代物机理生成环己醇,而反应循环中产生的烷基自由基可以延烷基过氧化过渡金属配合物反应机理进行生成环己酮。 相似文献
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Dr. Lin-Qiang Mo Xian-Fei Huang Guan Huang Guang-Ping Yuan Su-Juan Wei 《ChemistryOpen》2019,8(1):104-113
We aimed at elevating catalytic performances of cobalt tetrakis(pentafluorophenyl)porphyrin (Co TPFPP) through axial coordination, nanocavities, and covalently grafting action. The Co TPFPP was immobilized onto nanoporous and nonporous chitosan, forming Co TPFPP/np- and nonp-CTS catalysts, respectively. The catalysts were characterized by various spectroscopic techniques. The catalytic performances of these catalysts for cyclohexane oxidation under response-surface-methodology-optimized oxidation reaction conditions were estimated and compared. Co TPFPP/np-CTS was an excellent catalyst at aspect of catalytic activity, exhibiting the considerable potential reusability, 24.2 mol % yields (KA oil : cyclohexanone and cyclohexanol) in average, and total turnover frequencies (TOFs) of 3.25×106 h−1. This is attributed to the structural characteristics of the Co TPFPP/np-CTS catalyst: the cobalt porphyrin molecules could be highly scattered on CTS, forming the independent active sites, and were not leached. The axial coordination exerted the most important effect on the catalytic activity, and the covalent grafting action had a decisive effect on the increase of the total TOFs and on the reusability of the catalyst. 相似文献
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在体内NO和超氧阴离子生成的过氧亚硝酸根离子(ONOO-,peroxynitrite)是一种强氧化性物质,它可以诱导DNA单链断裂使DNA发生损伤。为了探讨ONOO-断裂DNA的作用机理,以质粒DNA pBR322为研究对象,采用琼脂糖凝胶和硫代巴比妥酸(TBA)显色反应等方法对ONOO-与DNA的反应进行研究。结果表明ONOO-能明显使DNA发生断裂,而且随着ONOO-浓度的增加,DNA断裂的程度增加,在酸性和中性条件下ONOO-断裂DNA的能力明显高于碱性介质,而CO2对该反应有显著的抑制作用,TBA显色反应进一步证实该反应为自由基机理,其机理为ONOO-与H+形成ONOOH,然后裂解为二氧化氮自由基(·NO2)和羟基自由基(·OH),继而对DNA造成损伤。 相似文献
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Pradip Ghosh Roland Schoch Matthias Bauer Axel Jacobi von Wangelin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2022,134(1):e202110821
Metal-catalyzed C?H activations are environmentally and economically attractive synthetic strategies for the construction of functional molecules as they obviate the need for pre-functionalized substrates and minimize waste generation. Great challenges reside in the control of selectivities, the utilization of unbiased hydrocarbons, and the operation of atom-economical dehydrocoupling mechanisms. An especially mild borylation of benzylic CH bonds was developed with the ligand-free pre-catalyst Co[N(SiMe3)2]2 and the bench-stable and inexpensive borylation reagent B2pin2 that produces H2 as the only by-product. A full set of kinetic, spectroscopic, and preparative mechanistic studies are indicative of a tandem catalysis mechanism of CH-borylation and dehydrocoupling via molecular CoI catalysts. 相似文献