生物活性小分子过亚硝酸根

过亚硝酸根可产生于生物系统,是一种强氧化剂、过氧化引发剂和硝化剂,可与多种生物物质反应,在许多生物过程中都起着重要作用。     

薄层色谱法分离四苯基卟啉和四苯基钴卟啉

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.     

壳聚糖固载的四苯基钴卟啉催化空气氧化环己烷

 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.     

动力学光度法检测过亚硝酸根分解产生的羟自由基

羟自由基与苯甲酸发生羟化反应后生成的羟基苯甲酸能抑制碘催化的锰（Ⅲ）氧化亚砷酸的反应,基于此,提出了一种用动力学光度法测定过严硝酸根分解产生的羟自由基的新方法。用动力学光度法测定羟基苯甲酸含量可间接测定羟自由基生成量。拟定的方法简单、灵敏。应用该方法测定了几种浓度的过亚硝酸根分解时羟自由基的生成量以及当一些羟自由基清除剂存在时羟自由基的生成量,结果满意。     

亚硝酸根催化光度法的研究进展

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     

金属卟啉化合物光催化反应研究（Ⅳ）：—四苯基钴卟啉光…

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。     

四(对羟基苯基)钴卟啉的合成新方法

本研究用丙酸和DMF混合液作为溶剂,采用溶剂热合成的方法这一新型的合成方法,由吡咯,对羟基苯甲醛,以及CoCl2.6H2O直接合成四羟基苯基钴卟啉配合物。探讨了诸因素对反应的影响,找出最佳的反应过程以及最适宜的反应条件:在140℃时,吡咯,对羟基苯甲醛,金属盐CoCl2.6H2O,丙酸,DMF的摩尔比为4∶4∶1∶134∶86时得最高产率,达到43.2%,这相比于传统方法的10%～30%有了一定的提高。     

亚硝酸根的催化光度法测定

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。     

四苯基卟啉合钴电化学催化还原二卤代乙烷的研究

本文以电化学、薄层电化学,可见·紫外现场光谱电化学和计算机数字模拟等方法,研究了四苯基卟啉合钻在N,N-二甲基甲酰胺和1,2-二氯乙烷溶液中电化学催化还原1,2-二澳乙烷和1,2-二氯乙烷的电极过程,测定了平行催化反应速率常数分别为1.2×10~3和5mol~(-1)·dm~3·S~(-1).     

7种中位—四取代苯基卟啉化合物的合成

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     

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

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E_HOMO和ΔE_L-H均有一定的相关性,且ΔE_L-H对催化活性的影响大于E_HOMO对催化活性的影响;EHOMO值越低、ΔE_L-H越小,其催化活性越高.     

Thermochemistry of the Decomposition of Some Cobalt Compounds

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.     

Study of the Interaction Between Peroxynitrite and Hemoglobin

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.     

钴卟啉过氧中间体向环己烷夺氢的密度泛函计算

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。     

Highly Active Catalysis of Cobalt Tetrakis(pentafluorophenyl)porphyrin Promoted by Chitosan for Cyclohexane Oxidation in Response-Surface-Methodology-Optimized Reaction Conditions

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.     

过氧亚硝酸根离子诱导DNA断裂机理的研究

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。     

四苯基卟啉衍生物质子化热力学

用光度法六种四苯基卟啉衍生物的表 观质子化常数及质子化热力学函数,并用半经验量子化学计算方法PM3计算了卟啉环中两个氮原子（ ＝N－）的净电荷,探讨了取代基的电子效应及空间效应对质子化常数的影响。     

Selective Benzylic CH-Borylations by Tandem Cobalt Catalysis

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 Co^I catalysts.