卟啉类光电功能材料的研究进展

卟啉及其衍生物是一类具有优良的光电性能的有机半导体材料．引起人们广泛的关注。本文对卟啉类光电材料在模拟生物光合作用中心的光致电荷转移和能量转移，有机太阳能电池．分子光电器件。有机电致发光和光存储等领域的研究进展做一简要介绍。     

meso-四-(4-甲氧基-3-磺酸苯基)卟啉在测定痕量金属的应用—锌的分光光度法测定

本文研究了在咪唑存在下 meso—四—(4—甲氧基—3—磺酸苯基)卟啉(TMPPS_4)与锌显色反应的最佳条件,建立了测定锌的新方法,灵敏度高,锌量在0—1.2μg/10mL 范围内遵守比耳定律,用于测定粮食中的锌时结果满意     

A stochastic controller for a scalar linear system with additive Cauchy noise

A stochastic control scheme is developed for scalar, discrete-time, and linear-dynamic systems driven by Cauchy distributed process and measurement noises. When addressing the optimal control problem for such systems, the standard quadratic cost criteria cannot be used. In this study we introduce a new objective function that is functionally similar to the Cauchy probability density function. The performance index, defined as the expectation of this objective function with respect to the Cauchy densities, exists. The dynamic programming solution to the fixed and finite horizon optimal control problem that uses this performance index appears to be intractable. Therefore, a moving horizon optimal model predictive control problem is implemented, for which the conditional expected value of the objective function and its gradients can be computed in closed   form and without assumptions such as certainty equivalence. Numerical results are shown for this m$m$-step model predictive optimal controller and compared to a similar, Linear-Exponential-Gaussian model predictive controller. An essential difference between the Cauchy and Gaussian controllers when applied to a system with Cauchy noises is that, while the Gaussian controller is linear and reacts strongly to all noise pulses, the Cauchy controller can differentiate between measurement and process noise pulses by ignoring the former while responding to the latter. This property of the Cauchy controller occurs when an impulsive measurement noise is more likely than an impulsive process noise. The Cauchy and Gaussian controllers react similarly when applied to a system with Gaussian noises, demonstrating the robustness of the proposed control scheme.     

Pyrolysed carbon supported cobalt porphyrin: a potent catalyst for oxidation of hydrogen sulfide

Pyrolysed carbon supported cobalt porphyrin, an electrocatalyst that is frequently used for oxygen reduction in fuel cells, is evaluated for catalytic oxidation of hydrogen sulfide by dissolved dioxygen. The catalyst performs best after heat treatment at 880 °C_, at pH 8. Analysis of the reaction products reveals that sulfur is the dominant product throughout the investigated pH range 5–10. The catalyst performs much better than powdered activated carbon, granular activated carbon and different other forms of unmodified carbon catalysts. This is as far as we know the first time that heat treated cobalt porphyrins are evaluated for non-electrocatalytic applications.     

Self-assembled monolayers of a disulphide-derivatised cobalt-porphyrin on gold

A self-assembled monolayer (SAM) of a novel cobalt(II)porphyrin disulphide derivative was prepared on flat gold(1 1 1) electrode. Evidence for surface modification was provided by electrochemical reductive desorption of the monolayer and ellipsometry, consistent with a coverage of 2.5 × 10⁻¹⁰ mol cm⁻² and a thickness of 13 Å, respectively. Both results support the presence of SAMs where the molecules share an intermediate position between perpendicular and flat orientation. Scanning tunnelling microscopy have also proven the formation of CoPSS SAMs, however high-resolution images could only be obtained when the CoPSS molecules were diluted in an hexanethiol SAM. The electrocatalytic activity of the surface confined Co-porphyrin was evaluated for the oxygen reduction. Voltammetric data indicate that reaction involves two electrons consistent with the formation of hydrogen peroxide. Under similar experimental conditions the data obtained for an iron-porphyrin analogue points for a full reduction of dioxygen to water.     

基于荧光卟啉传感器阵列系统的肺癌标志物检测研究

针对肺癌呼出挥发性有机气体（VOCs）中的特定标志物,提出了一种新型的基于荧光卟啉传感器阵列检测系统,并对4种肺癌呼出标志物进行检测研究。通过小波分析等数学工具对测得的荧光光谱数据进行特征提取,然后采用层次聚类、主成分分析等统计学方法对特征向量进行分析。不同体积分数的各类标志物在聚类分析中能够完全正确的聚到一起。通过主成分分析得到的前3个主成分包含了标志物的88%的信息,便能对不同类别的标志物进行识别。研究表明：该荧光卟啉传感器阵列系统能够快速有效地对不同肺癌标志物进行识别,有望在临床中得到应用。     

葡萄糖键联卟啉的新合成方法

由5－（对溴丁氧基苯基）－10，15，20－三－（对甲氧基苯基）卟啉 或5，10，15，20－四－（对溴丁氧苯基）卟啉与α－D－葡萄糖经一步反应，得到相应的葡萄糖键联卟啉。该合成方法操作简便，反应条件温和，总产率高。     

两种新的水溶性卟啉的离解常数测定及酸碱诱导聚合

研究了ｍｅｓｏ－四卟啉和ｍｅｓｏ－四卟啉的离解常数。ＴＢＰｈＰ的离解常数为：ｐＫａ４＝１．１３．ｐＫａ３＝１．８８，ｐＫＡ２＝１２．２１；ＴＴＰＳ的离解常数为：ｐＫａ４＝４．４７，ｐＫａ３＝６．２６。外还发现了两卟啉的酸碱诱导聚合。     

Preparation and Characterization of a Chloroperoxidase-like Catalytic Antibody

The small molecule, meso-tetra(α,α,α,α-o-phenylacetamidophenyl) porphyrin (Mr1147.0) was used as complete antigen to elicit MAb through the immunization and cell fusion techniques. The MAb 1F2 obtained was demonstrated to be very pure by MALDI/TOFMS. The subtype of MAb 1F2 is IgG2a, which has a relative molecular weight of 156,678.8 Da.No significant change in the intensity of absorption peaks in UV and CD spectra was observed over a pH range between 6 and 12. The high stability of the abzyme and the tight binding between Fe porphyrin and antibody were also demonstrated. V_max, K_m, κcat, κcat/K_m for abzyme are 5.18 × 10⁻⁸ Ms⁻¹, 1.50 × 10⁻⁸ M, 0.518 s⁻¹, 3.45 × 10⁷ M⁻¹s⁻¹, respectively. The data obtained indicate that catalytic antibody has high catalytic activity. The chloroperoxidase activity of MAb 1F2-Fe porphyrin complex is stable from 10 °C to 60 °C.     

基于二氨基苯基卟啉的新型聚酰亚胺的合成与表征

卟啉类化合物的结构特征使其在很多领域受到广泛的关注,现在通常在卟啉上做修饰以获得更优的性能。以氨基苯基取代的卟啉化合物作为二胺单体和均苯四甲酸二酐为二酐单体,以苯甲酸为溶剂,通过反应合成粗产品新型的聚酰亚胺材料,用丙酮和氯仿洗涤得到纯产品,并进一步合成了Zn-卟啉聚酰亚胺。采用傅里叶红外吸收光谱、紫外-可见吸收光谱对产物进行了结构表征,对主要的紫外光谱、红外光谱吸收带进行了经验归属,以及原料与产物的对比分析,初步确定了合成产物的结构。结果表明,聚合产物是以卟啉骨架结构为主要聚合单元的聚酰亚胺类共聚物。