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.     

四苯基卟啉制法的改进

传统合成四苯基卟啉(简称H_2TPP)的方法是将吡咯与等摩尔苯甲醛在丙酸中进行回流,产率仅20%,制得的H_2TPP中含3%～10%四苯基二氢卟啉(简称TPC),分离十分因难。 本文报道以丙酸为主的混合溶剂,并用亚硫酰氯代替过去采用的,毒性大的2,3-二氯-5,6-二氰苯醌作氧化剂进行氧化处理。H_2TTP产率达60%以上,纯化物收率38%。     

用X射线光电子能谱对热处理的四苯基钴卟啉修饰电极的表面表征

本文用XPS、DTA和TG分析了四苯基钴卟啉化学修饰电极的热分解行为, 它不同于四苯基铁卟啉. 由XPS谱图揭示了四苯基钴卟啉与玻璃碳电极之间的相互作用, 进而阐述了经热处理的四苯基钴卟啉化学修饰电极的表面结构与电催化稳定性的关系. 从Co2p_3/2和2p_(1/2)能级的自旋分裂间距及其Shake-up伴峰, 了解经热处理后的四苯基钴卟啉修饰电极中钴自旋态变化, 并且从Co的L_3VV俄歇跃迁计算出Co的双电离能, 其双电离能与电催化活性有一定关系。     

合成四苯基卟啉及其衍生物的新方法

目前文献中合成四苯基卟啉(TPPH_2)和取代四苯基卟啉都是采用 Adler 方法。在酸性介质中,一些对酸敏感的卟啉化合物的合成受     

四苯基卟啉锌J-聚集体的光谱与晶体结构分析

四苯基卟啉锌在完全无水的乙氰中发生自聚现象, 聚集体的形成可以通过稳态光谱来证实. 吸收光谱和荧光发射光谱的红移表明四苯基卟啉锌的聚集体是卟啉之间以头对头的方式排列, 即J-聚集体. 进一步研究表明聚集体的形成还依赖于溶剂. 光谱和激发态寿命的测定结果表明聚集体的辐射跃迁速率比单体快两倍, 这表明形成的J-聚集体存在超辐射. 四苯基卟啉锌的晶体呈现出杆状的结构. 通过X射线的结构分析, 提出了一个四苯基卟啉锌J-聚集体的结构模型. 四苯基卟啉锌中的一个苯基和相邻的四苯基卟啉锌中的吡咯垂直并通过C—H…π键相互作用. 最后讨论了乙氰配位后对四苯基卟啉锌中Zn—N键的影响.     

meso-四-(对甲氧基)苯基卟啉和meso-四-(对甲氧基)苯基卟啉的电化学性质

锌卟啉配合物;合成;meso-四-(对甲氧基)苯基卟啉和meso-四-(对甲氧基)苯基卟啉的电化学性质     

四苯基卟啉变色酸敏片

卟啉自由碱通常是紫或紫红色固体,遇酸则变成绿色,对光敏感。人工合成的卟啉最简单的是四苯基卟啉(H_2TPP)。美国专利曾将卟啉类化合物作为光氧化成象体系的增感剂。我们试图将H_2TPP作为VMD片(一种新型非银盐成象体系)的增感剂,未获成功。     

2-甲酰基-meso-四苯基卟啉的合成

研究了以金属四苯基卟啉为原料,经由Vilsmeier甲酰化反应制备2-甲酰基-meso-四苯基卟啉的合成方法。不同金属离子、溶剂以及Vilsmeier反应时间等因素对目标化合物的最终收率影响很大。在以铜四苯基卟啉为原料、氯仿为溶剂及Vilsmeier反应时间为5 h的反应体系中,目标化合物的收率可以高达99%以上。     

用于光动力治疗的四苯基卟啉衍生物研究进展

四苯基卟啉(TPP)衍生物的重要用途之一是用于光动力治疗(PDT)来破坏肿瘤组织.本文综述了近年来可用于光动力治疗的四苯基卟啉(TPP)衍生物的合成.通过对TPP衍生物进行官能团修饰,可以改善其物理、化学及生物性质,从而合成出可能用于PDT的卟啉衍生物.     

新型开环聚合催化剂—四苯基卟啉铝化物

四苯基卟啉氯化铝(TPPAICI)、四苯基卟啉烷氧基铝(TPPAIOR)等卟啉铝化物,能引发环氧化合物、内酯等话性聚合并进行嵌段共聚合,还能使酸酐、二氧化碳聚合。此类催化剂进行的活性聚合不被醇终止,相反,通过醇与活性链的快速交换反应,醇起到与催化剂相当的作用,从而能有效地调节聚合物的分子量。四苯基卟啉烷基铝(TPPAIR)在光照下可引发甲基丙烯酸甲酯等烯类单体进行活性聚合。     

四苯基卟啉镁的合成、表征及光化学性质

提出一种以乙酸镁和乙酸钠为原料合成四苯基卟啉镁(MgTPP)的新方法, 合成样品以柱层析法进行分离纯化. 分离产物经UV-Vis、1H-NMR、MALDI-TOF-MS(基质辅助激光解吸电离飞行时间质谱)等技术表征, 确定为MgTPP. UV-Vis光谱分析结果表明, 四苯基卟啉镁的Soret 吸收带为424 nm, Q 吸收带为563 nm 和602 nm. 此外, 光照对MgTPP的二氯甲烷溶液光谱性质的影响结果表明, 经光照射后MgTPP的UV-Vis光谱的Soret吸收带吸收强度明显降低, 同时, 经550 nm的光激发产生的荧光有明显的猝灭. 对光照后的MgTPP样品进行MALDI-TOF-MS分析, 发现有新的质核比(m/z)出现, 其为668, 这一结果表明, 在光照条件下, MgTPP分子可能与氧分子发生光化学作用, 形成MgTPP与氧的复合物MgTPP-O2.     

四苯硼钠滴定法快速测定钾

GB 1 50 63- 94四苯硼钠沉淀钾重量法测定钾 ,其分析方法精密度高、准确度好 ,被广泛应用于各种物料中常量钾的测定 ,但是操作繁琐、费时、易出错。本文提出的四苯硼钠滴定法 ,以四苯硼钠为标准滴定剂 ,在水和三氯甲烷的两相介质中 ,以溴酚蓝和季铵盐为指示剂 ,滴定钾离子直至三氯甲烷层中蓝色消失 ,水相呈色为终点 ,终点一滴变色明显 ,具有简便、快速、准确的特点。1　试验部分1 .1　主要试剂四苯硼钠标准溶液 :c[Na B(C6H5) 4]=0 .1 mol· L-1季铵盐溶液 :1 0 g· L-1氢氧化钠溶液 :1 0 0 g·L-1氯化钾溶液 :0 .1 mol· L-1溴酚蓝指示…     

示波极谱-四苯硼钠法的研究与应用

生物碱、季铵盐是重要的两大类药物。钾、铊、银、铜、铷、铯都是有重要用途的金属元素。其分析测试方法已报道的有重量法、萃取 -光度法、非水滴定法。本文依据四苯硼钠 ( Na TPB)与生物碱类药物、季铵盐类药物及 K+、Tl+、Ag+、Cu+、Rb+、Cs+一价金属离子在一定条件下均能发生定量地沉淀反应 ,又由于 Na TPB是示波活性物质 ,在交流示波极谱图上有敏锐的切口 ,可用 Na TPB切口的出现或消失指示滴定的终点 ,据此建立了示波极谱 -四苯硼钠测定法。方法具有准、快、简、省的特点     

示波极谱-四苯硼钠法的应用

示波极谱－四苯硼钠法是以示波极谱图形的突变来确定终点，其终点直观，不受溶液的颜色，沉淀，赋形剂的影响，可将重量分析，非水滴定，萃取－光度分析变为示波滴定分析，具有准，快，简，省的特点，有广泛的应用前景.     

Subcellular Localization of Sulfonated Tetraphenyl Porphines in Colon Carcinoma Cells by Spectrally Resolved Imaging

Subcellular localization of the dye, 5,10,15,20-tetra(4-sul-fonatophenyl)porphine (TPPS₄) and the more hydrophobic dye, 5,10,15,20-tetra(1-sulfonatophenyl)porphine (TPPS₁), in murine colon carcinoma cells was studied by spectrally resolved imaging (SRI) combined with image processing techniques. Spectrally resolved imaging enabled the acquisition of multipixel fluorescence spectra (>10⁴) from a single cell. Demarcation of specific localization sites and segregation of the irrelevant fluorescence were based on the pixel spectra and by operating the functions of spectral similarity mapping (SSM), principal component analysis (PCA) and spectral classification. The SRI revealed the fine details of the photochemical process that clarify some aspects of subcellular damage. The SRI depicted the differences between TPPS₄ and TPPS, with respect to their initial localization and their fate at the end of the photochemical effect. The dye TPPS₄ was localized initially in lysosomal vesicles, and upon irradiation fluorescence was seen in the nucleus as well as in vesicles. Some of the vesicles were closely related to the nucleus, as resolved by SSM, PCA and spectral classification. Additional light exposure stimulated relocalization of TPPS₄ into the nucleus as well as into the nucleolus, which was clearly depicted by SSM and PCA. Spectral classification showed a third, weak residual cytoplasmic array around the nucleus. The dye TPPS, concentrated in a Golgi-like complex and was resolved in the nuclear envelope and in small vesicles: it was not redistributed into other compartments upon photosensitization. Serum supplementation to the incubation media of colon carcinoma cells treated with TPPS₄ or TPPS, did not change the localization patterns. Pixel spectra of the two dyes in the cells showed spectral shifts and expanded shoulders due to microenvironmental effects. Thus, the chemical nature of the sulfonated phenyl porphines, and not their interaction with serum proteins, was the main determinant of their binding to the lysosomes, nucleus, nucleolus, nuclear envelope or Golgi.     

A High-Sensitivity Assay of Nucleic Acids with Tetraphenyl Porphyrin Cobalt Chlorine by Resonance Light Scattering Technique

Abstract

A novel probe, tetraphenyl porphyrin cobalt chlorine (CoTPPCl), is first applied to determine nucleic acids at the nanogram level based on the measurement of resonance light scattering (RLS) signals, which result from the interaction of CoTPPCl with nucleic acids. Under pH 6.37 conditions, the reaction between CoTPPCl and nucleic acid enhances the weak resonance light scattering (RLS) signal of CoTPPCl, and the enhanced light scattering intensity is proportional to the concentration of nucleic acid. The method is sensitive (3.45 ng/mL for ctDNA), simple (one step and a common fluorimeter), and tolerant of the metal ions and other coexistent substances. The mode of the combination between CoTPPCl and nucleic acids and the reasons for RLS enhancement are clearly clarified. Synthetic samples were determined with satisfactory results.     

The Electrochemistry of Tetraphenyl Porphyrin Iron(III) Within Immobilized Droplets Supported on Platinum Electrodes

For the first time, the voltammetry of an ensemble of immobilized benzonitrile microdroplets containing 5,10,15,20‐tetraphenyl‐21H,23H‐porphine iron (III) chloride, TPPFeCl immobilized at platinum electrodes immersed in various aqueous electrolytes has been explored. The reduction of TPPFeCl was observed with the voltammetric response seen to be highly dependent on the nature of ions in the surrounding aqueous phase. Unlike voltammetry in purely homogeneous solution the nature of the aqueous electrolyte can influence the voltammetry in the droplet phase. The electrochemical reduction of TPPFeCl contained within tetrabutylammonium chloride (TBACl) supported benzonitrile (PhCN) microdroplets immersed into an aqueous solution of TBACl was first studied. During TPPFeCl reduction the resulting [TPPFeCl]^? species is stabilized due to the excess of chloride anions inside the oil droplet. Voltammograms of homogeneous solutions of PhCN supported with TBACl show similar chemically reversible process which is also attributed to the stable [TPPFeCl]^? species. This anion stabilization was not observed when the oil droplets were supported with tetrabutylammonium perchlorate (TBAP) or when the PhCN solution bathing the microdroplet ensemble was supported with TBAP resulting in a chemically irreversible process. The voltammetry of unsupported droplets immobilized on a platinum electrode immersed in different aqueous electrolytes was also explored and the fate of the [TPPFeCl]^? species formed considered during the reduction sweep. Similarities and difference to voltammetry in purely homogeneous media are noted and the use of droplet voltammetry provides complimentary information.     

增强辣根过氧化物酶催化鲁米诺化学发光反应的新型增强剂四苯硼钠

报道了新型增强剂四苯硼钠对过氧化物酶催化鲁米诺－过氧化氢发光反应的增强作用，建立了流动注射化学发光测定或辣过氧化物酶（ＨＲＰ）的新体系。用该体系测定ＨＲＰ线性范围为１．０×１０－１２×１．２×１０－１３ｍｏｌ／Ｌ；检测限为０．６×１０－１３ｍｏｌ／Ｌ。对０．６×１０－１３ｍｍｏｌ／Ｌ的 ＨＲＰ进行１１次平行测定，相对标准偏差为 １． ５％。     

Study on the Inclusion Complex of C_(60) and Calix[8]arene Tetraphenyl Ether

Fullerenehasgeneratedarapidlygrowingandactiveresearchareal.InclusioncomplexesoffullerenehavebeenpreparedforCoowithavarietyofhostsystemsincludingcalixarenes,cyclotriveratrylene,andy-cyclodextrin.TheselectiveformationofaclathratefromCooandcall-c[8]areneswasexcellentlyutilizedfortheseparationofCooandC,,'.HereinwereportthatCoocanbeincludedinthecavityofanewkindoffunctionnedcalixlslarene,p-tert-butylcall-c[8]arenetetraphenylether(1).ThefixtureofCooand1(lfZmolarratio)wasrefluxedintoluenefor2--3h,d…