酮缺陷对中性和带电六卟啉芳香性影响的直接可视化研究

利用含时密度泛函理论研究了酮缺陷对中性和带电六卟啉芳香性的影响,并使用多维可视化技术给出了该体系基态电荷分布和电子跃迁的直观图像. 研究结果表明,芳香性是决定这类体系基态密立根电荷分布的主要因素;酮缺陷效应使得体系基态的密立根电荷分布更多地局域在六卟啉基团上,在这类体系的五氟苯基取代基上密立根电荷布居较少,同时使得体系的芳香性发生改变. 进一步,通过计算体系的跃迁密度和电荷差分密度,可视化了酮缺陷对中性和带电六卟啉芳香性的影响. 结果表明,酮缺陷加强了体系电荷转移的能力.     

基于FT-ICR质谱仪的光解离光谱自动化谱图采集程序的开发与应用

光解离光谱在气相离子结构及动力学研究中发挥着重要的作用.这种方法非常灵活,可在实验室中利用不同种类的激光器及质谱仪的结合来开展相应的研究.但也存在一些问题,例如,自动化水平低,费时,长时间的操作容易引入人为错误,使实验结果的可信度降低.为解决此类问题,该工作开发了一套可用于光谱自动采集和分析的程序AutoMS.该程序包...     

锰卟啉/钒取代杂多酸配合物的合成、表征和性能研究

利用碘化四对(4-三甲氨基苯基)锰卟啉与钒取代杂多酸H5 PMo10 V2O40,在水溶液中,室温下反应合成了锰卟啉/钒取代杂多酸配合物,用红外和紫外光谱技术对其结构进行了表征,发现该配合物中包含着金属卟啉的环状结构与杂多酸的笼状结构,并且二者以化学键的形式键合在一起.以该化合物作为催化剂,以过氧化氢水溶液为氧化剂,在温和的条件下研究了锰卟啉/钒杂多酸配合物对苯的羟基化反应的影响,考察了催化剂的催化活性,探讨了催化剂对苯羟基化反应的活性中心.研究结果表明,杂多酸中的钒原子是其主要的催化活性中心,锰卟啉的存在可以有效地提高其催化活性.     

几种新型手性季铵盐-卟啉化合物的合成与表征(Ⅰ)

本文合成了四个新的Ｎ－甲基麻黄素或奎宁手性季铵盐－卟啉化合物,并用元素分析、红外光谱、紫外可见光谱、核磁共振谱、质谱确定了其结构。     

两种新型卟啉吡啶季铵盐的合成

合成了两种新型卟啉吡啶季铵盐:溴化5-[4-N-(对硝基)苄铵基吡啶基]-10,15,20-三(4-N吡啶基)卟啉和氯化5-[4-N-(对甲氧基)苄铵基吡啶基]-10,15,20-三(4-N-吡啶基)卟啉.这两种化合物尚未见文献报道,它们的结构分别由紫外可见光谱、红外光谱、核磁共振谱、质谱、元素分析得到确证.     

meso-四(4-甲氧基苯基)卟啉分光光度法测定痕量铅的研究

研究了在 p H12和 Tween- 80存在下非水溶性试剂 meso-四 (4 -甲氧基苯基 )卟啉与铅的络合反应条件 ,形成的络合物的最大吸收波长为 4 6 7nm,组成摩尔比为 1∶ 1。铅含量在 0 .1— 8μg/ 10 m L范围内有较好的线性关系 ,表观摩尔吸光系数为 1.12× 10 5L· mol-1· cm-1。本方法应用于环境水样中痕量铅的测定 ,结果令人满意     

卟啉超分子化合物在分子器件中的应用

分子电子器件已成为近年来的一个研究热点，卟啉类化合物因为光敏性好、性能稳定、易于修饰等优点成为分子器件研究的理想模型化合物。本文着重介绍了它在分子器件中的最新应用进展。     

Visible Light Photocatalytic Activity of Porphyrin Tin(IV) Sensitized TiO2 Nanoparticles for the Degradation of 4-Nitrophenol and Methyl Orange

A stable metalloporphyrin sensitized TiO₂ (Degussa P25) photocatalyst was prepared by using trans-dihydroxo[5,10,15,20-tetraphenylporphyrin]tin(IV) (SnP) as a sensitizer in a simple impregnation process. The solid diffuse reflectance ultraviolet-visible (UV-vis) spectrum of the SnP sensitized TiO₂ photocatalyst (SnP-TiO₂) indicated that there existed interaction between SnP and TiO₂. It was found that SnP-TiO₂ exhibited an enhanced visible light photocatalytic activity as compared with that over P25 for the degradation of 4-nitrophenol (4-NP) and methyl orange (MO) in aqueous solutions. The mechanism exploration showed that the degradation of MO and 4-NP experienced two different ways, that is, MO was photodegraded by reactive oxygen species and 4-NP was directly photodegraded by the excited state of SnP. Furthermore, it was found that the loading content of SnP had an important influence on the photocatalytic activity of TiO₂. The maximum photocatalytic efficiency was achieved when the contents of SnP were 25 mg and 30 mg per gram TiO₂ for MO and 4-NP, respectively. Importantly, SnP-TiO₂ was particularly stable and the photocatalytic activity was hardly decreased after being recycled seven times in the presence of oxygen, which could be attributed to the easy reductive regeneration of SnP.     

Spectroelectrochemical Investigation of TPPMn(III/II)‐Driven Liquid | Liquid | Electrode Triple Phase Boundary Anion Transfer into 4‐(3‐Phenylpropyl)‐Pyridine: ClO4−, CO3H−, Cl−, and F−

The triple phase boundary transfer of anions from the aqueous into an organic phase can be driven electrochemically here with the tetraphenylporphyrinato‐Mn(III/II) (or TPPMn) redox system in 4‐(3‐phenylpropyl)‐pyridine) (or PPP). Anions investigated are perchlorate, chloride, fluoride, and bicarbonate. The bicarbonate and fluoride transfer processes are shown to be chemically more complex compared to the perchlorate and chloride cases with UV‐vis‐spectroelectrochemical measurements indicating a combination of HCO₃^?/CO₃^2? transfer processes and association of fluoride with TPPMn(III)⁺, respectively. In situ spectroelectrochemistry is developed for ion‐transfer voltammetry into sub‐microliter organic phase regions on mesoporous ITO conducting film electrodes.     

Methoxy-isoporphyrins of water-soluble porphyrins: synthesis,characterization and electrochemical properties

Abstract

Methoxy-isoporphyrins of zinc [5,10,15,20-tetrakis(4-sulfonatophenyl)]porphyrin, ZnTSPP (1a) and zinc [5,10,15,20-tetrakis(4-carboxyphenyl)]porphyrin, ZnTCPP (1b) have been synthesized and characterized using standard spectroscopic techniques (Uv-visible, ¹H NMR) , ESI-mass spectrometry and powder X-ray diffraction studies. The isoporphyrins [5-(methoxy)-5,10,15,20-tetrakis(4-sulfonatophenyl)-5H,15H-porphinato]zinc(II) (2a) and [5-(methoxy)-5,10,15,20-tetrakis(4-carboxyphenyl)-5H,21H-porphinato]zinc(II) (2b) are formed due to nucleophilic attack of the methanol to the zinc porphyrin dication. Ceric ammonium nitrate (CAN) was used to oxidize zinc porphyrin and to form zinc porphyrin dication. The electronic spectra of the isoporphyrin complexes 2a and 2b exhibit an intense peak at near IR region . Electrochemical measurements of the synthesized isoporphyrins showed a typical irreversible reduction peak at lower potential. S-containing nucleophiles, which work as reducing agents, convert the zinc isoporphyrins to their parent porphyrins, which supports the electrochemical observations. Their structural properties have been studied using powder X-ray diffraction. The luminescence properties of isoporphyrins were compared with the parent zinc porphyrins.