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.     

Stability of O3 + N2, O3 + O2 and O3 + CO2 double hydrates: DFT study

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Frequency Insertion Strategy for Channel Assignment Problem

This paper presents a new heuristic method for quickly finding a good feasible solution to the channel assignment problem (CAP). Like many other greedy-type heuristics for CAP, the proposed method also assigns a frequency to a call, one at a time. Hence, the method requires computational time that increases only linear to the number of calls. However, what distinguishes the method from others is that it starts with a narrow enough frequency band so as to provoke violations of constraints that we need to comply with in order to avoid radio interference. Each violation is then resolved by inserting frequencies at the most appropriate positions so that the band of frequencies expands minimally. An extensive computational experiment using a set of randomly generated problems as well as the Philadelphia benchmark instances shows that the proposed method perform statistically better than existing methods of its kind and even yields optimum solutions to most of Philadelphia benchmark instances among which two cases are reported for the first time ever, in this paper. Won-Young Shin was born in Busan, Korea in 1978. He received B.S. in industrial engineering from Pohang University of Science and Technology (POSTECH) in 2001 and M.S in operation research and applied statistics from POSTECH in 2003. Since 2003 he has been a researcher of Agency for Defense Development (ADD) in Korea. He is interested in optimization of communication system and applied statistics. Soo Y. Chang is an associate professor in the Department of Industrial Engineering at Pohang University of Science and Technology (POSTECH), Pohang, Korea. He teaches linear programming, discrete optimization, network flows and operations research courses. His research interests include mathematical programming and scheduling. He has published in several journals including Discrete Applied Mathematics, Computers and Mathematics with Application, IIE Transactions, International Journal of Production Research, and so on. He is a member of Korean IIE, and ORMSS. Jaewook Lee is an assistant professor in the Department of Industrial Engineering at Pohang University of Science and Technology (POSTECH), Pohang, Korea. He received the B.S. degree in mathematics with honors from Seoul National University, and the Ph.D. degree from Cornell University in applied mathematics in 1993 and 1999, respectively. He is currently an assistant professor in the department of industrial engineering at the Pohang University of Science and Technology (POSTECH). His research interests include nonlinear systems, neural networks, nonlinear optimization, and their applications to data mining and financial engineering. Chi-Hyuck Jun was born in Seoul, Korea in 1954. He received B.S. in mineral and petroleum engineering from Seoul National University in 1977, M.S. in industrial engineering from Korea Advanced Institute of Science and Technology in 1979 and Ph.D. in operations research from University of California, Berkeley, in 1986. Since 1987 he has been with the department of industrial engineering, Pohang University of Science and Technology (POSTECH) and he is now a professor and the department head. He is interested in performance analysis of communication and production systems. He has published in several journals including IIE Transactions, IEEE Transactions, Queueing Systems and Chemometrics and Intelligent Laboratory Systems. He is a member of IEEE, INFORMS and ASQ.     

Comprehensive heat exchange model for a semiconductor laser diode

By measuring the total energy flow from an optical device, we can develop new design strategies for thermal stabilization. Here we present a comprehensive model for heat exchange between a semiconductor laser diode and its environment that includes the mechanisms of conduction, convection, and radiation. We perform quantitative measurements of these processes for several devices, deriving parameters such as a laser's heat transfer coefficient, and then demonstrate the feasibility of thermal probing for the nondestructive wafer-scale characterization of optical devices.     

Note on B-splines, wavelet scaling functions, and Gabor frames

Let g be a continuous, compactly supported function on such that the integer translates of g constitute a partition of unity. We show that the Gabor system (g,a,b), with window g and time-shift and frequency-shift parameters a,b>0 has no lower frame bound larger than 0 if b=2,3,... and a>0. In particular, (g,a,b) is not a Gabor frame if g is a continuous, compactly supported wavelet scaling function and if b=2,3,... and a>0. We give an example for our result for the case that g=B/sub 1/, the triangle function supported by [-1,1], by showing pictures of the canonical dual corresponding to (g,a,b) where ab=1/4 and b crosses the lines N=2,3,.     

State of polarization changes: Classification and measurement

We propose a standardization procedure that provides a convenient, quantitative and reproducible laboratory-based method for measuring the state of polarization (SOP) fluctuations produced by polarization varying devices. This method is based on the SOP distributions generated by commercial polarization scramblers. We show that these devices generate distributions of the maximum change of the SOP (in a given sample time) that follow Rayleigh statistics, which scale linearly with scrambling frequency and the sample time. We use this procedure to measure the SOP fluctuations in a short length of coiled fiber subject to mechanical perturbations.     

Cover Picture: Arresting,Fixing, and Separating Dimers Composed of Uniform Silica Colloidal Spheres (Adv. Funct. Mater. 12/2006)

In colloidal suspensions of silica, particles undergo constant collisions. By controlling various parameters, the repulsive barrier can be reduced, thereby substantially increasing the number of collision‐induced dimerization events. Xia and co‐workers report on p. 1627 that the dimers could be arrested and then permanently fixed by introducing a small amount of fresh tetraethylorthosilicate into the colloidal suspension, with monodisperse dimer yields of up to 50 %. This yield could be increased to 80 % by centrifugation in a density gradient medium. When fresh tetraethylorthosilicate is introduced into a colloidal suspension of silica spheres, it hydrolyzes and condenses in situ to arrest and fix the dimers resulting from constant collisions between the spheres. By optimizing the experimental parameters (including the length of aging time) and the diameter of the silica spheres, as well as the concentrations of counterions, water, and ammonia, it is possible to routinely produce monodisperse dimers with a yield as high as 50 %. When combined with centrifugation using a density gradient medium, the yield of such dimers could be further increased to 80 %. It is believed that this method will provide a simple and versatile approach to the high‐volume production of dimers from spherical colloids composed of different materials. These dimers may find widespread use in a range of applications such as fabrication of photonic crystals and fundamental studies related to colloidal science.     

A redundant multivalued logic for a 10-Gb/s CMOS demultiplexer IC

A redundant multivalued logic is proposed for high-speed communication ICs. In this logic, serial binary data are received and converted into parallel redundant multivalued data. Then they are restored into parallel binary data. Because of the multivalued data conversion, this logic makes it possible to achieve higher operating speeds than that of a conventional binary logic. Using this logic, a 1:4 demultiplexer (DEMUX, serial-parallel converter) IC was fabricated using a 0.18-/spl mu/m CMOS process. The IC achieved an operating speed of 10 Gb/s with a supply voltage of only 1.3 V and with power consumption of 38 mW. This logic may achieve CMOS communication ICs with an operating speed several times greater than 10 Gb/s.     

Unified Systolic-Like Architecture for DCT and DST Using Distributed Arithmetic

A common computing-core representation of the discrete cosine transform and discrete sine transform is derived and a reduced-complexity algorithm is developed for computation of the proposed computing-core. A parallel architecture based on the principle of distributed arithmetic is designed further for the computation of these transforms using the common-core algorithm. The proposed scheme not only leads to a systolic-like regular and modular hardware for computing these transforms, but also offers significant improvement in area-time efficiency over the existing structures. The structure proposed here is devoid of complicated input/output mapping and does not involve any complex control. Unlike the convolution-based structures, it does not restrict the transform length to be a prime or multiple of prime and can be utilized as a reusable core for cost-effective, memory-efficient, high-throughput implementation of either of these transforms     

A New Comb Circular Polarizer Suitable for Millimeter‐Band Application

This letter presents a new polarizer which has a simple comb structure inside a circular waveguide. The electrical performance of the proposed comb polarizer is optimized by a circular waveguide radius and by the physical parameters of the comb plates. This polarizer is suitable for providing good performance in millimeter‐band application because of its simple structure and low fabrication cost. In our experiments the dual‐band comb polarizer designed in band 1(K) and band 2(Ka) showed good electrical performance without any tuning elements.