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.     

Long-wavelength light emission from InAs quantum dots covered by GaAsSb grown on GaAs substrates

We fabricated InAs quantum dots (QDs) with a GaAsSb strain-reducing layer (SRL) on a GaAs(0 0 1) substrate. The wavelength of emission from InAs QD is shown to be controllable by changing the composition and thickness of the SRL. An increase in photoluminescence intensity with increasing compositions of Sb and thickness of the GaAsSb SRL is also seen. The efficiency of radiative recombination was improved under both conditions because the InAs/GaAsSb/GaAs hetero-interface band structure more effectively suppressed carrier escape from the InAs QDs.     

A new luciferase reporter gene assay for the detection of androgenic and antiandrogenic effects based on a human prostate specific antigen promoter and PC3/AR human prostate cancer cells.

We developed a new mammalian cell-based luciferase reporter gene assay for androgenic and antiandrogenic activities of chemicals and environmental samples. Environmental samples usually have a complex matrix that may contain the constituents acting as androgen receptor (AR) agonists, AR antagonists or aryl hydrocarbon receptor (AhR) agonists. AhR agonists are known to elicit the antiandrogenic effect through cross-talk between AR and AhR signal transduction pathways. In this study, PC3/AR human prostate carcinoma cells were transiently transfected with a prostate-specific antigen (PSA) promoter-driven luciferase expression plasmid. The cells were treated with a test compound or an environmental sample for 24 h at 37 degrees C and then measured for luciferase activity. The luciferase activity was induced by dihydrotestosterone (DHT) in a concentration-dependent manner in a concentration range from 10 fM to 1 nM. R1881, a synthetic androgen receptor agonist, induced luciferase activity and its inductive effects was additive to that of DHT. The luciferase activity was not induced by cortisol, a glucocorticoid, progesterone, a progestin, and 17beta-estradiol, an estrogen in a concentration range of up to 1 microM. DHT-induced luciferase activity was reduced by bicalutamide and cyproterone acetate, AR antagonists, and also by benzo[a]pyrene, an aryl hydrocarbon receptor agonist, through AhR-mediated pathways. All of these findings indicate that the present assay system correctly responds to AR agonists, AR antagonists and AhR agonist and, therefore, it is a powerful tool for the sensitive and selective screening of chemicals and environmental samples for their androgenic and antiandrogenic activities. We developed the first assay system, in which the expression of luciferase was driven by the promoter of a prostate-specific antigen gene, a typical human androgen-regulated gene.     

‘Me2CuLi·TMSCl in CH2Cl2’. The most powerful methylating agent for sterically congested α,β-enoates

The reaction of Me₂CuLi with sterically congested α,β-unsaturated esters in the presence of TMSCl in CH₂Cl₂ proceeded very smoothly to produce the conjugate addition products in high yields.     

Computation of the quasi-stationary distributions inM(n)/GI/1/K andGI/M(n)/1/K queues

In this paper, we provide numerical means to compute the quasi-stationary (QS) distributions inM/GI/1/K queues with state-dependent arrivals andGI/M/1/K queues with state-dependent services. These queues are described as finite quasi-birth-death processes by approximating the general distributions in terms of phase-type distributions. Then, we reduce the problem of obtaining the QS distribution to determining the Perron-Frobenius eigenvalue of some Hessenberg matrix. Based on these arguments, we develop a numerical algorithm to compute the QS distributions. The doubly-limiting conditional distribution is also obtained by following this approach. Since the results obtained are free of phase-type representations, they are applicable for general distributions. Finally, numerical examples are given to demonstrate the power of our method.     

Experimental Study on Time-Spread/Wavelength-Hop Optical Code Division Multiplexing with Dispersion-Compensating En/Decoder

10Gbit/s time-spread/wavelength-hop optical code generation and decoding are performed by dispersion-compensating fiber Bragg grating (FBG) en/decoder pair. Error-free 10km single mode fiber (SMF) transmission of 10Gbit/s optical code division multiplexing (OCDM) has been experimentally demonstrated.     

Numerical reconstruction of an infrared wavefront utilizing an optical phase modulation device

We utilize nitroanisole, that absorbs infrared (IR) radiation as heat, as an optical modulation device based on a thermal process. The nitroanisole exhibits a thermal lens effect, i.e. a temperature dependent refractive index. Hence, the nitroanisole can induce phase modulation to visible light, in direct response to intensity of the incident IR radiation. The proposed method can be used to obtain the phase modulation distribution that corresponds to the IR intensity distribution, i.e. the IR hologram itself, on the nitroanisole by examining the phase map of visible light that is modulated upon passing through the nitroanisole. The IR wavefront can be reconstructed by calculating extracted IR holograms through the Fresnel transform. It is verified that both the amplitude and the phase of the IR wavefront can be reconstructed accurately by proposed method.     

Malyngamide X: The First (7R)‐Lyngbic Acid that Connects to a New Tripeptide Backbone from the Thai Sea Hare Bursatella leachii

Malyngamide X ( 1 ), the first (7R)‐lyngbic acid connected to a new tripeptide backbone, was isolated from the Thai sea hare Bursatella leachii. The gross structure of 1 was established on the basis of 1D and 2D NMR and mass spectroscopic data. Combination of the NMR spectroscopic experiments with α‐methoxy‐α‐(trifluoromethyl)phenylacetic acid esters, 2,2,2‐trifluoro‐1‐(9‐anthryl)ethanol chiral solvating agent, and molecular mechanics of 1 and the synthetic molecular fragments allowed us to determine the absolute stereochemistry of all six stereogenic centers without hydrolytic degradation of the compound. Compound 1 displayed moderate cytotoxic, antitubercular, and antimalarial properties.