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.     

在BEPC上建造γ束线站的分析

考虑电子的反冲并利用康普顿散射,研究了激光同步辐射光源(LSS)辐射的光子波长、光子能量。结果表明,对于不同的γ,LSS辐射的光子波长和能量有不同的近似公式。当γ<<λ1/4λe时,LSS辐射的光子波长λ2≈λ1/4γ2,能量(εc2≈4γ2εc1;当γ>>λ1/4λe时,LSS辐射的光子波长λ2≈λe/γ,能量cε2≈m0γc2;结果表明,LSS辐射的条件是种子激光的波长λ1大于电子的物质波波长λm;LSS辐射的极值波长是λ2m ax=h/m0γv,极值能量是cε2m ax=βeε;本文后半部分提出了利用北京正负电子对撞机的强流高亮度电子束与激光的康普顿背散射产生单色γ射线的建议。     

一种新型可调谐锁模光纤激光器

利用法布里-珀罗腔的激光二极管作为调制器件，实现环形腔光纤激光器的主动锁模。并利用法布里-珀罗腔的激光二极管的多纵模特性，把激光二极管当作一梳状滤波器，通过偏振控制器来调整入射到激光二极管内光的偏振态，同时均衡腔内增益，得到波长大范围可调谐的锁模激光，其脉冲宽度约为48ps，脉冲重复速率2GHz。     

光纤光栅激光器激射波长的研究

一般认为，用光纤光栅作选频元件的光纤激光器，激射波长与光纤光栅中心反射波长一致，本文报道了不同的实验研究结果。通过细致的实验研究，发现光纤光栅激光器激射波长相对于光纤光栅中心反射波长有一定的偏移。激射波长可以出现在光栅中心反射波长的长波端，也可以出现在其短波端。对不同腔结构的掺镱、掺铒光纤光栅激光器的深入研究证明，谐振腔的各向异性对激光器的激射波长偏移起到决定性的作用，波长最大偏移量主要受限于光纤光栅的反射带宽。通过激光腔内的偏振控制器改变谐振腔的各向异性，可以在光纤光栅的反射带宽内控制激射波长的位置。     

一种不等带宽光学梳状滤波器

提出了一种新型—Michelson—三面镜FabryPerot型50GHz不等带宽光学梳状滤波器设计方案,分析和模拟表明:该器件将一路信道间隔为50GHz的输入信号分离成信道间隔为100GHz的奇偶两路输出信号,其中在3dB处,奇数信道带宽大于30GHz用于10Gb/s传输,偶数信道带宽大于60GHz用于40Gb/s传输对于将来的40Gb/s系统,该器件具有优势.     

一种新型波长转换器的模块化设计

对一种新型结构全光波长转换器进行了高精度、高稳定度的模块化设计，并利用该模块实现对波长转换器参数的监控。结果表明这种新型模块对波长转换器的实现提供了可靠的保证，表现出较高的稳定度和实用性。     

Single to 16-Channel Wavelength Conversion at 10 Gb/s Based on Cross-Gain Modulation of ASE Spectrum in SOA

A simple scheme for single to multi-channel wavelength conversion based on cross-gain modulation of amplified spontaneous emission (ASE) spectrum in semiconductor optical amplifier (SOA) is described. Single to 16-channel wavelength conversion at 10 Gb/s is first demonstrated without any additional probe lights, the modulation information carried by input signal could be converted into arbitrary many channels if only the demultiplexer with enough channels is exploited. Output performance and pattern effects are investigated experimentally.     

光突发交换的交换控制策略和光缓存配置

光突发交换是面向下一代互联网的光交换模式.讨论了异步光突发交换系统的交换控制策略以及相应光缓存的优化配置策略.除了传统预约模式的交换策略,还研究了非预约和改进型预约模式,它们的性能评估由计算机仿真给出.结果表明:在条件相当情况下,改进型预约模式具有最低的丢包率.同时光缓存的配置对上述几类交换控制策略的性能都有很大影响,仿真结果指出:光缓存的粒度对系统性能具有重要影响,所讨论的几类交换模式都存在最佳时延粒度,研究结果对光交换矩阵的设计有指导意义.     

强流束晕-混沌的外部磁场开关控制

研究了强流离子束在周期聚焦磁场通道中束晕-混沌的外部磁场开关参数控制方法. 将该方法应用在多粒子模型中，实现了对5种不同初始分布质子束的束晕-混沌的有效控制，得到了消除束晕及其再生现象的理想结果.在强流加速器系统中，由于外部磁场是可测和可调 的物理量，因此该控制方法有利于实验研究，可为强流质子加速器中周期聚焦磁场的设计和实验提供参考. 关键词： 强流离子束 周期聚焦磁场通道 束晕_混沌 混沌控制 开 关控制     

Multimode optical fiber demultiplexer-star coupler using a single gradient-index-rod lens and a multi-facet grating

An optical fiber multi-function device consisting of a single gradient-index-rod lens and a multi-facet blazed reflection grating is proposed to simultaneously realize functions of wavelength demultiplexing and optical signal distribution in a multimode optical fiber transmission system. We analyzed the demultiplexing characteristics and the tolerance of optical components using the ray trace method. This device can realize not only low loss optical signal distribution but also offers improved demultiplexing characteristics in comparison with the previously proposed demultiplexer-multiposition switch. The following characteristics are expected from the design using commercially available optical components: a working band of 0.64–0.88 μm, channel separation of 34–36 nm, 3 dB bandwidth of 27–28 nm, channel cross-talk of less than - 40 dB and minimum excess insertion loss of 0.9–2.1 dB.