Theory of chemical bonds in metalloenzymes XXII: a concerted bond-switching mechanism for the oxygen–oxygen bond formation coupled with one electron transfer for water oxidation in the oxygen-evolving complex of photosystem II

ABSTRACT

QM(UB3LYP)/MM(AMBER) calculations were performed for the locations of the transition structure (TS) of the oxygen–oxygen (O–O) bond formation in the S₄ state of the oxygen-evolving complex (OEC) of photosystem II (PSII). The natural orbital (NO) analysis of the broken-symmetry (BS) solutions was also performed to elucidate the nature of the chemical bonds at TS on the basis of several chemical indices defined by the occupation numbers of NO. The computational results revealed a concerted bond switching (CBS) mechanism for the oxygen–oxygen bond formation coupled with the one-electron transfer (OET) for water oxidation in OEC of PSII. The orbital interaction between the σ-HOMO of the Mn(IV)₄–O₍₅₎ bond and the π*-LUMO of the Mn(V)₁=O₍₆₎ bond plays an important role for the concerted O–O bond formation for water oxidation in the CaMn₄O₆ cluster of OEC of PSII. One electron transfer (OET) from the π-HOMO of the Mn(V)₁=O₍₆₎ bond to the σ*-LUMO of the Mn(IV)₄–O₍₅₎ bond occurs for the formation of electron transfer diradical, where the generated anion radical [Mn(IV)₄–O₍₅₎]^-? part is relaxed to the ?Mn(III)₄?…?O₍₅₎^- structure and the cation radical [O₍₆₎=Mn(V)₁]⁺ ? part is relaxed to the ⁺O₍₆₎–Mn(IV)₁? structure because of the charge-spin separation for the electron-and hole-doped Mn–oxo bonds. Therefore, the local spins are responsible for the one-electron reductions of Mn(IV)₄->Mn(III)₄ and Mn(V)₁->Mn(IV)₁. On the other hand, the O₍₅₎^- and O₍₆₎⁺ sites generated undergo the O–O bond formation in the CaMn₄O₆ cluster. The Ca(II) ion in the cubane- skeleton of the CaMn₄O₆ cluster assists the above orbital interactions by the lowering of the orbital energy levels of π*-LUMO of Mn(V)₁=O₍₆₎ and σ*-LUMO of Mn(IV)₄–O₍₅₎, indicating an important role of its Lewis acidity. Present CBS mechanism for the O–O bond formation coupled with one electron reductions of the high-valent Mn ions is different from the conventional radical coupling (RC) and acid-base (AB) mechanisms for water oxidation in artificial and native photosynthesis systems. The proton-coupled electron transfer (PC-OET) mechanism for the O–O bond formation is also touched in relation to the CBS-OET mechanism.     

pH Dependence of Chlorophyll States, Protein Structures and Function of the PSII Membranes

IntroductionPhotosystem II ( PSII) is a pigment- proteincomplex in the thylakoid membrane. Its reactioncenter( PSII- RC) ,which is composed of D1 andD2 proteins,generates the highly positive oxidantrequired for the oxidation of water by light- drivencharge separation. Water oxidation occurs at theMn4cluster positioned atthe center of the oxygen-evolving complex on the lumenal surface of PSII.In green plants,the highly reactive Mn4cluster isshielded by a number of extrinsic proteins( 33…     

DLC多层膜对9Cr18微动磨损性能的影响

采用等离子体源离子注入（PSII）技术在9Cr18不锈钢基体上制备类金刚石碳膜（DLC）多层膜，比较了该多层膜与N注入层对基体微动磨损性能的影响，结果表明，注入N后，改性层内形成了CrN,Cr2N和Fe3N等氮化物相；PSII技术能够提高9Cr18不锈钢的抗微动磨损性能，实验所制备的DLC多层膜比N注入层具有更好的抗微动磨损性，这与最外层LDC膜的高硬度和低摩擦系数有关。     

Natural and artificial light-harvesting systems utilizing the functions of carotenoids

Carotenoids are essential pigments in natural photosynthesis. They absorb in the blue–green region of the solar spectrum and transfer the absorbed energy to (bacterio-)chlorophylls, and so expand the wavelength range of light that is able to drive photosynthesis. This process is an example of singlet–singlet energy transfer and so carotenoids serve to enhance the overall efficiency of photosynthetic light reactions. Carotenoids also act to protect photosynthetic organisms from the harmful effects of excess exposure to light. In this case, triplet–triplet energy transfer from (bacterio-)chlorophyll to carotenoid plays a key role in this photoprotective reaction. In the light-harvesting pigment–protein complexes from purple photosynthetic bacteria and chlorophytes, carotenoids have an additional role, namely the structural stabilization of those complexes. In this article we review what is currently known about how carotenoids discharge these functions. The molecular architecture of photosynthetic systems will be outlined to provide a basis from which to describe the photochemistry of carotenoids, which underlies most of their important functions in photosynthesis. Then, the possibility to utilize the functions of carotenoids in artificial photosynthetic light-harvesting systems will be discussed. Some examples of the model systems are introduced.     

Synthesis and Crystal Structure of Ethoxyethyl 3-(2-chloro-5-pyridyl methylamino)-2-cyano-3-methylthio acrylate

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Theory of chemical bonds in metalloenzymes XXI. Possible mechanisms of water oxidation in oxygen evolving complex of photosystem II

ABSTRACT

Possible mechanisms for water cleavage in oxygen evolving complex (OEC) of photosystem II (PSII) have been investigated based on broken-symmetry (BS) hybrid DFT (HDFT)/def2 TZVP calculations in combination with available XRD, XFEL, EXAFS, XES and EPR results. The BS HDFT and the experimental results have provided basic concepts for understanding of chemical bonds of the CaMn₄O₅ cluster in the catalytic site of OEC of PSII for elucidation of the mechanism of photosynthetic water cleavage. Scope and applicability of the hybrid DFT (HDFT) methods have been examined in relation to relative stabilities of possible nine intermediates such as Mn-hydroxide, Mn-oxo, Mn-peroxo, Mn-superoxo, etc., in order to understand the O–O (O–OH) bond formation in the S₃ and/or S₄ states of OEC of PSII. The relative stabilities among these intermediates are variable, depending on the weight of the Hartree–Fock exchange term of HDFT. The Mn-hydroxide, Mn-oxo and Mn-superoxo intermediates are found to be preferable in the weak, intermediate and strong electron correlation regimes, respectively. Recent different serial femtosecond X-ray (SFX) results in the S₃ state are investigated based on the proposed basic concepts under the assumption of different water-insertion steps for water cleavage in the Kok cycle. The observation of water insertion in the S₃ state is compatible with previous large-scale QM/MM results and previous theoretical proposal for the chemical equilibrium mechanism in the S₃ state . On the other hand, the no detection of water insertion in the S₃ state based on other SFX results is consistent with previous proposal of the O–OH (or O–O) bond formation in the S₄ state . Radical coupling and non-adiabatic one-electron transfer (NA-OET) mechanisms for the OO-bond formation are examined using the energy diagrams by QM calculations and by QM(UB3LYP)/MM calculations . Possible reaction pathways for the O–O and O–OH bond formations are also investigated based on two water-inlet pathways for oxygen evolution in OEC of PSII. Future perspectives are discussed in relation to post HDFT calculations of the energy diagrams for elucidation of the mechanism of water oxidation in OEC of PSII.     

中心电极射频感应等离子体管件内表面改性

本文利用中心电极射频感应等离子体对金属管件内壁进行表面改性处理,验证了该方法的合理性以及可行性.利用该方法制备出了类金刚石(DLC)薄膜,为管型和瓶型样品的内壁强化提供新的手段.     

Research progress in the inner surface modification of metal tubes by plasma processing

The recent progress in inner surface hardening of tubes by plasma processing is summerized. Several techniques of inner surface plasma source ion implantation and deposition are introduced, and their advantages and disadvantages are discussed. The basic principles, technical features and new progress of inner surface plasma source ion implantation methods for metal tubes, which were developed in our laboratory, are described in detail. And perspectives of the future technical development for inner surface ion implantation of tubes are presented.     

菠菜PSII核心复合物激发能传递与温度的关系

采用基于延时分次扫描单光子计数器为探测装置的皮秒时间分辨荧光光谱测试系统研究了菠菜光系统 (PSⅡ )核心复合物光能传递与温度的关系。分别对PSII核心复合物样品在 2 0℃、42℃、48℃下做温浴处理 ,然后以脉宽为 1 2 0 ps,重复率为 4MHz ,波长为 5 1 4nm的Ar+激光作为光源分别激发处理后样品的荧光。通过对测量结果进行数据处理 ,分析比较发现 :同一温度下 ,呈荧光带的激发能传递速度比副荧光带处的快 ;同一波长下 ,慢组分的时间常量随温度升高而变慢 ,而快速组分的时间常数则变化不大 ;做 42℃温浴处理的样品接近于蛋白质解体的临界状态     

Heat Denaturation of Protein Structures and Chlorophyll States in PSII Membranes

IntroductionPhotosystem II (PSII) is a large supramolecularpigment-protein complex found in the thylakoidmembranes of green plants,algae andcyanobacteria.Its main role is to drive light-induced electron transfer from water toplastoquinone with a concomitant production ofmolecular oxygen.PSII membranes consist of anouter antenna portion of light-harvestingchlorophyll (Chl) a/b binding complexes (LHCII)and a core fraction.The core fraction is composedof an inner antenna of membrane-bound …