锰、铑原卟啉IX-二甲酯配合物共振拉曼光谱研究

合成了MnPPCl,RhPPCl,RhPPN3,RhPP(CO)Cl四种配合物 (PP =ProtophyrinIXDimethy1Ester) ,用元素分析、红外吸收光谱及紫外吸收光谱确定了配合物的组成 ,测定了它们的共振拉曼光谱 ,对特征谱带进行了归属。分析了拉曼谱带和电子吸收谱带变化的原因 ,提出了谱带频率的变化受金属离子外层d电子和轴配体的影响。     

铂电极上自组装铁原卟啉单分子层的表面增强振动光谱初探(英文)

应用现场表面增强拉曼光谱和衰减全反射表面增强红外光谱初步研究了0.1mol·L-1HClO4溶液中Pt电极表面铁原卟啉(FePP)自组装单层的电化学和结构特性.以514nm波长为激发线,得到了增强因子约为40的粗糙Pt电极上FePP在不同电位下的表面增强拉曼光谱.分析0.5～-0.3V(SCE)区间内谱峰变化,得到近似的吸附等温式,由此可估算出Fe3+/Fe2+的式量电位大约为-0.2V.原位表面增强红外光谱的测试结果表明,FePP分子主要以斜立方式吸附在Pt膜电极表面,其中一个环外羧酸根与电极表面相接触,而另一羧酸基团以氢键与相邻的FePP分子相连.这样的吸附结构在-0.1～0.9V(SCE)的电位区间内并没有显著的变化.     

血清一阶导数荧光光谱诊断早期恶性肿瘤

利用Wistar大鼠接种恶性肉瘤模拟人患上癌症。取Wistar大鼠眼静脉血制备血清,并用乙醇简单处理得上层清液,扫描获得其一阶导数荧光光谱,确定上层清液原卟啉发射带(630 nm附近)的峰高,观察到健康Wistar大鼠与癌变大鼠的血清样存在明显差异,10例癌变样假阳性率为0,而20例正常样中仅有1例假阳性达到了恶性肿瘤早期诊断的目的。     

Photodynamic Therapy for Cancer Cells Using a Flash Wave Light Xenon Lamp

We determined photodynamic therapy (PDT) efficacy using a flash wave (FW) and a continuous wave (CW) light, of which the fluence rate was 70 W/cm², for murine thymic lymphoma cells (EL-4) cultivated in vitro. The irradiation frequency and the pulse width of the FW light were in the range of 1–32 Hz and less than one millisecond, respectively. 5-Aminolevulinic acid-induced protoporphyrin IX (ALA-PpIX) was used as a photosensitizer. When EL-4 with ALA administration was irradiated by the light for 4 h (irradiation fluence: 1.0J/cm²), the survival rate of EL-4 by the FW light was lower than that by the CW light, except for the FW light with irradiation frequency of 32 Hz, and decreased gradually with decreasing irradiation frequency. Moreover, the FW light, especially at lower irradiation frequency, was superior to the CW light for the generation of singlet oxygen in an aqueous PpIX solution. Therefore, thehigher PDT efficacy for EL-4 of the FW light would be caused by the greater generation of singlet oxygen in the cells.     

Characterization of porphyrins of rat Harderian gland by thin layer chromatography and mass spectrometry: no evidence for a tricarboxylic acid porphyrin

Reversed-phase TLC systems using ion-pairing reagents are described for the separation without prior derivatization of the porphyrins of rat Harderian gland. Porphyrins with R(f) values greater than protoporphyrin but smaller than coproporphyrin, representing harderoporphyrin, were labile to 1 m NaOH, which converted them to protoporphyrin, inconsistent with the established literature that harderoporphyrin is a tricarboxylic acid porphyrin. It was confirmed by HPLC/electrospray ionization MS that this 'harderoporphyrin' fraction consists of the recently characterized glycoconjugate, protoporphyrin-1-O-acyl beta-xyloside, with trace amounts of protoporphyrin-1-O-acyl beta-glucoside.     

锌原卟啉与儿童铅中毒和贫血关系的研究

[目的 ]探讨锌原卟啉测定诊断儿童铅中毒与贫血可能性。 [方法 ]测定了 2 3 5名儿童血ZPP、Hb、BPb。 [结果 ]ZPP值 2 3 9± 1 0 2 μg/gHb ,增高率 1 3 61 % ;血铅水平 8 94± 4 62 μg/dL ,铅中毒率 41 0 7%。Hb平均浓度 1 1 2 5 0± 1 0 5 5g/L ,贫血患病率 3 1 48%。ZPP与Hb呈高度负相关 (P <0 0 1 ) ,与BPb无相关性 (P >0 0 5 )。血铅水平正常组与铅中毒组ZPP值差异无显著意义(P >0 0 5 )。Hb正常组与贫血组ZPP值差异有显著意义 (P <0 0 1 )。 [结论 ]ZPP升高可作为缺铁性贫血的诊断指标 ,但在血铅水平较低的地区 ,则不宜用ZPP作为儿童铅中毒的筛查指标。     

Coordination Studies of Iron(II) Protoporphyrin IX and Iron(II) Hematoporphyrin IX with 4,4′-Dipyridyl and other Nitrogenous Bases

Abstract

The results of spectral studies of iron(II) protopor-phyrin IX and iron(II) hematoporphyrin IX with several substituted pyridines are reported. The existence in solution of an iron(II) porphyrin complex coordinated to a water molecule and to a substituted pyridine was shown by isolation of the complex from solution. The complex isolated was dimeric inono-4,4′-dipyridyl diaquo iron(II) hematoporphyrin. Addition of ethanol to the aqueous solvent inhibits coordination of iron(II) porphyrins with substituted pyridines. The protoporphyrin ring enhances coordination relative to the hematoporphyrin ring.     

Quantitative HPLC of pigments of irregularly coloured eggshells: application to aliquots of powdered shell from quail

Twelve quail eggshells from farmed Coturnix coturnix japonica were separately ground to fine powder and two aliquots of each (average weights 13.86 mg and 51.90 mg) were extracted with formic acid. Biliverdin (38–284 pmol/mg) and protoporphyrin (841–1666 pmol/mg) were measured by HPLC. There was good agreement between the values for the corresponding samples and with those for two entire eggshells from the same source. The preparation of a homogenate as a powder from heterogeneously pigmented eggshells has the advantage that not all of the sample needs to be initially extracted for analysis and residual material can be stored in a stable form and used for repeat measurements and for longitudinal studies. Copyright © 2012 John Wiley & Sons, Ltd.     

Supramolecular self-assembled nanowires by the aggregation of a protoporphyrin derivative in low-polarity solvents

The self-assembly of a simple tetraalkyl-substituted protoporphyrin derivative into fibril wire-like nanostructures from CHCl₃/cyclohexane solvent mixes is explored. The protoporphyrin IX derivative is synthesised in two efficient steps by amidation of the two propylenic acid groups followed by a cross metathesis of the vinyl groups using Grubbs' second-generation catalyst. The self-assembly of the functionalised protoporphyrin is sensitive to solvent and under favourable conditions forms ‘nanowires’ of micrometre length. The nanowires were characterised by absorption and fluorescence spectroscopy, transmission electron microscopy and atomic force microscopy.     

Organometallic complexes with biological molecules. I. Diorganotin(IV)chloro protoporphyrin IX complexes: Solid-state and solution-phase characterization

Protoporphyrin IX (H₄PPIX) complexes of diorganotin(IV)chloro moieties with formula (R₂SnCl)₂H₂PPIX (R?Me, Bu and Ph) have been obtained and their solid-state and solution-phase configurations have been studied through spectroscopic investigations. Coordination of the side-chain carboxylates of H₄PPIX to R₂Sn(IV)Cl moieties, with bridging carboxylate (COO^?) has been inferred by comparison of the free and coordinated H₄PPIX IR spectra, while the occurrence of a five-coordinated tin(IV) atom in a cis-R₂ trigonal bipyramidal structure has been deduced, for all of the synthesized complexes, by rationalization of the nuclear quadrupole splitting parameters, according to the point-charge model formalism. Fanally, the solution-phase spectral features of (R₂SnCl)₂^?H₂PPIX are in agreement with the monomeric character of the protoporphyrin IX, under the experimental conditions used.