紫细菌光合作用原初反应中的超快光动力学过程研究 (Ⅰ)--紫细菌捕光天线系统LH2

主要综述了紫细菌捕光天线系统LH2中的超快光动力学过程及相关的物理机制等方面的研究进展。     

New structure model of oxygen-evolving center and mechanism for oxygen evolution in photosynthesis

So far, many important questions and problems concerning the structure and mechanism of photosynthetic oxygen evolution are still unsolved. On the basis of recent achievements in this field, a new structure model is proposed whereby two H2O molecules bind asymmetrically to two manganese ions (Mn1Ⅱ and Mn4Ⅲ) at the open end of "C" shaped cluster and keep rather large distance. Two histidine residues coordinate to the other two manganese ions in higher oxidation state (Mn2Ⅳ and Mn3Ⅳ ) through their nitrogen atoms of the imidazole. Cl bound as terminal ligand to Mn4Ⅲl is connected to Ca, and the latter is needed to maintain the special configuration of two Mn2O2 units by bridged-oxo and bridged-carboxylate ligands. The whole structure of oxygen evolution center is asymmetry. A new mechanism for oxygen evolution invokes predictions of asymmetric oxidation of two H2O molecules, dynamic structural changes of oxygen e-volving center and indirect proton transport, etc. Only in S2 state, could Mn1Ⅳ = O. intermediate with high oxidation potential be formed. The S2→S3 process occurs with significant structural changes, as well as intramolecular and intermolecular hydrogen transfer. The S3 state corresponds to intermediate of Mn1Ⅳ-O… H… O-Mn4Ⅳ . During S3→ [S4] →S0, the O-O bond is formed only in S4 state. The change of nucleophilic interaction between Cl and manganese ions different oxidation states has consequence for the significant structural changes in H2O oxidation process.     

茜素红荷移反应测定多潘立酮

在水溶液和室温下,电子给体多潘立酮与电子受体茜素红发生电荷转移反应形成稳定的1:2荷移配合物.该配合物的λmax=521 nm,在此波长下,溶液吸光度(A)与溶液中多潘立酮浓度(C)成正比关系,表观摩尔吸光系数为7.0×103 L/(mol·cm).据此建立了多潘立酮的分光光度测定法,线性回归方程为A=0.0269C+0.1201,多潘立酮浓度在1.5～200μg/mL范围内与吸光度呈线性关系,相关系数,r=0.9990.方法检出限为0.426 μg/mL.用该方法测定吗丁啉药片样品中的多潘立酮含量,相对标准偏差为0.20%(n=11),结果与药片标示量一致,方法回收率在97%～98%之间.     

Effect of calcium ions on the secondary structures of photosystem II and its relations with photoinhibition

Calcium ions play an important role in the oxygen-evolving process of photosystem II as demonstrated in many experiments. The changes of the secondary structures of PS II induced by the depletion of Ca²⁺ were reported. The results indicated that the removal of Ca²⁺ led to the transition of ahelix to turns and sheet structures. While Ca²⁺ was re-added to the media, only the structures changed to turns could be recovered. The protein conformational changes of PS II during the donor side photoinhibition induced by the depletion of ca²⁺ were also studied. This showed that the protein conformational changes differed between the control and Ca²⁺-depleted samples in a short period of illumination (within 10 min). However, the changes became similar when the illumination time was increased.     

An Arabidopsis ctpA homologue is involved in the repair of photosystem II under high light

A T-DNA insertion mutant AtctpA1 was identified to study the physiological roles of a carboxyl-terminal processing protease (CtpA) homologue in Arabidopsis. Under normal growth conditions, disruption of AtctpA1 did not result in any apparent alterations in growth rate and thylakoid membrane protein components. However the mutant plants exhibited increased sensitivity to high irradiance. Degradation of PSII reaction center protein D1 was accelerated in the mutant during photoinhibition. These results demostrated that AtctpA1 was required for efficient repair of PSII in Arabidopsis under high irradiance.     

Effect of Mn cluster on the formation of superoxide radicals in photoinhibition of photosystem Ⅱ

To further realize the action of superoxide radicals (O₂^{− .}) in photoinhibition of photosystem Ⅱ (PSⅡ), we employed 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a spin trap, associated with EPR spectroscopy, to study the effect of illumination time on O₂^{− .} formation during high light photoinhibition in PSⅡ membranes and Mn-depleted PSⅡ membranes. Results indicated that the removal of Mn cluster from PS
membranes has a strong influence on the dynamics of superoxide formation. The relative mechanism was also discussed. These novel findings may further promote the studies of the structure and function of PSⅡ and the mechanism of photoinhibition.     

环丙沙星和四氰基乙烯的荷移反应及其荧光特性的研究

研究了以四氰基乙烯(TCNE)为电子受体对环丙沙星(CPFX)的电荷荷转移效应,并确立形成该荷移络合物的最佳条件.实验结果表明,CPFX与TCNE在丙酮-甲醇体系中,40℃水浴中恒温40 min即可形成稳定的n-π络合物,其荧光发射强度较之CPFX有显著的增强.对形成的电荷转移络合物的机理进行了探讨.     

Excitation energy transfer mechanisms in allophycocyanin (I)

The mechanisms of excitation energy transfer within allophycocyanin monomer with the theory of generalized master equation (GME) and the technique of time-resobed fluorescence anisotropic spectroscopy are studied. In the case of known information of its structure and spectra, the theory applied is based on the assumption that the coupling interaction between two chromophores is fairly weak. The theory correctly predicts the experimentlly observed rate for excitation energy transfer in allophycocyanin monomer. Based on the results, the energy transfer mechanism can be described as Förster and these processes cannot take place from the high vibrational levels of donor to acceptor.     

Depletion of phosphatidyl-glycerol head-group induces changes in oxygen evolution and protein secondary struc-tures of photosystem Ⅱ

The techniques of oxygen electrode polarogra-phy and Fourier transform infrared (FT-IR) spectroscopy were employed to explore the roles of polar head-group of phosphatidylglycerol (PG) molecules in the functional and structural aspects of photosystem Ⅱ (PS Ⅱ) through enzymatic approach. It was shown that the depletion of PG by treatment of phospholipase C (PLC) on PS Ⅱ particles caused the inhibition of oxygen evolving activity in PS Ⅱ. This effect also gave rise to changes in the protein secondary structures of PS Ⅱ, that is, an increase in a-helical conformation which is compensated by the loss of p-strand structures. It revealed that the head-group of PG molecules plays an important structural role in the maintenance of normal structure of PS Ⅱ proteins, which is required to maintain the appropriate physiological activity of the PS Ⅱ complex such as the oxygen evolving activity. It is suggested that there most probably exist hydrogen-bonding interactions between PG molecules and PS Ⅱ proteins.     

电量与反应进度的关系式

将反应进度概念用于电极反应,得出了电量与反应进度的关系式Δq=Δξ.zF。通过比较和应用表明,关系式能够全面、确切地解释法拉第定律。该关系式不仅能用于电极反应,对电解的反应物和产物的数量进行计算,而且还能用于电池反应,对电池过程的热力学函数变化进行辅助计算。     

电荷比特的超强藕合实现及量子态转移

基于超导量子电路中光与物质相互作用强度的可调性, 研究了库珀对盒子(Cooper-pair box, CPB)与LC谐振电路耦合的电路模型, 证明了可以通过减小CPB的约瑟夫森能量和增加LC谐振子阻抗, 实现光与物质的超强耦合(ultra-strong coupling, USC)和深度强耦合(deep-strong coupling, DSC)相互作用. 在此基础上, 进一步提出了具有一定抗噪性的 USC 双比特超导电路模型, 并以该模型作为非相干中介实现了两个Transmon系统间的量子态转移(quantum-state transfer, QST). 研究结果为在超导量子系统中实现USC相互作用提供了新的方案, 并有望进一步应用于量子调控、量子模拟和量子信息处理等领域.     

Distribution of lanthanum among the chloroplast subcomponents of spinach and its biological effects on photosynthesis： location of the lanthanum binding sites in photosystem Ⅱ

The effects of lanthanum at different concentrations on the related photosynthetic activities of Hill reaction, Mg^2＋-ATPase and Ca^2＋-ATPase in spinach chloroplast were studied. Experimental results showed that lanthanum can increase all the activities at suitable concentration （15-30 mg· L^-1）, however, it behaves toxically on them when over used （60 mg. L^-1）. To get an improved understanding of the mechanism of lanthanum effects on the photosynthesis of spinach, the different subcomponents in the chloroplast of the cultured spinach were isolated, and the content of lanthanum in each subcomponent was determined by ICP-MS. The results obtained indicated that among these different subcomponents, about 90% out of the total chloroplast lanthanum was located in photosystem Ⅱ （PS Ⅱ） while there was little lanthanum in photosystem Ⅰ （PS Ⅰ）. Moreover, size exclusion high performance liquid chromatography （SE-HPLC） coupled with online UV and ICP-MS detections was novelly used for locating lanthanum binding sites in PS Ⅱ proteins for the first time. It was found that lanthanum has two binding sites in PS Ⅱ： La associates with chlorophyll together with magnesium in PS Ⅱ by partly replacing magnesium and also shares the common binding sites of PS Ⅱ proteins together with the inorganic cofactors of calcium and manganese, influencing the process of photosynthesis.     

Thermal stability of oxygen evolution in photosystem Ⅱ core complex in the presence of digalactosyl diacylglyceroli

The influence of digalactosyldiacylglycerol (DGDG), one of the photosynthetic membrane lipids, on heat inactivation of the process of oxygen evolution has been studied in vitro in photosystem Ⅱ (PSⅡ) core complex. It was found that the temperature of semi-inactivation of oxygen evolution in the complex increased from 40.0 to about 43.0℃ in the presence of DGDG with 5-min heat treatment in the dark. Furthermore, when PSⅡ core complex was incubated for 5 min at 45.0℃, the oxygen evolution in the complex was completely lost, whilst the DGDG-complexed PSⅡ core complex still retained a 16% of activity (100% for 25.0℃). In addition, a 1-h incubation at 38.0℃ inactivated absolutely the oxygen evolution for the PSⅡ core complex. By contrast, there remained about 20% of activity (zero time for 100%) for the complex in the presence of DGDG under the same condition. These results indicate a new role of DGDG in the protection of PSⅡ core complex against the deleterious effects of temperature. It was most likely that DGDG-mediated stability toward thermal denaturation of oxygen evolution in PSⅡ core complex is due to the protective effect of DGDG on the release of the 33 kD protein from PSⅡ core complex.     

Distribution of lanthanum among the chloroplast subcomponents of spinach and its biological effects on photosynthesis:location of the lanthanum binding sites in photosystem II

Positive, nil and/or negative effects of REEs on crops’ growth and yield were observed by room cultivation or field experiments in many countries. Especially in China, rare earth elements (REEs) containing fertilizers were applied to more than 300 species of field crops, and re-sulted in a mean productivity increase of 5%―15%[1]. Since the 1970s many approaches in the understanding of physiological and biochemical effects of REEs on plantmetabolism, yield and quality have been made[2―4]…     

The v-v energy transfer of highly vibrationally excited states (II)

The vibrational energy transfer from highly vibrationally excited CO to H₂O molecules is studied by time-resolved Fourier transform infrared emission spectroscopy (TR FTIR). Following the 193 nm laser photolysis of CHBr₃ and O₂ the secondary reactions generate CO(v). The infrared emission of CO(v → v−1) is detected by TR FTIR. The excitation of H₂O molecules is not observed. By the method of the spectral simulation and the differential technique, 8 rate constants for CO(v)/H₂O system are obtained: (1.7 ±0.1), (3.4 ±0.2), (6.2 ±0.4), (8.0 ±1.0), (9.0 ±2.0), (12 ±3), (16 ±4) and (18 ±7) (10¹³cm³ · molecule^-1· s^-1). At least two reasons lead to the efficient energy transfer. One is the contributions of the rotational energy to the vibational energy defect and the other is the result of the complex collision. With the SSH andab initio calculations, the quenching mechanism of CO(v) by H₂O is suggested.     

墙体不稳定传热计算中反应系数项数的分析与确定

从反应系数的基本原理出发,以我国常用的24墙和37墙为例,利用计算机辅助分析的方法,对其围护结构的不稳定传热进行数值计算,并考察了不同反应系数项数对其能耗计算精度的影响。研究了进一步完善传热反应系数法,为此理论的实际应用提供了保障。     

含钼、钨和钒的Keggin结构杂多酸荷移配合物的合成与表征

合成了 2个Keggin结构混合多阴离子的喹啉电荷转移配合物 .经元素分析和热重分析 ,确定了其元素构成和配合物的分子组成 .并对其进行了IR ,UV ,DRUV Vis,XPS和ESR表征 .结果表明 ,在受体多酸和给体喹啉之间存在较强的相互作用并发生了电子转移 ,(C9H7N) 4 H3 PMo6W6O40 ·9H2 O中Mo+ 6为电子受体并被部分还原为Mo+ 5,而 (C9H7N) 5 5H5PMo1 0V2 O40 ·5 5H2 O·CH3 CN中V+ 5为电子受体并被部分还原为V+ 4 ,2种电荷转移配合物中杂多阴离子都仍然保持Keggin结构     

羟胺氧化反应活化能的测定

在磷酸介质中,羟胺对溴酸钾氧化溴甲酚紫具有催化作用,在此催化动力学体系中,测得不同温度下羟胺氧化的剩余量,建立了测定羟胺氧化反应活化能的方法。