Active site structure and redox processes of cytochrome c oxidase immobilised in a novel biomimetic lipid membrane on an electrode

Membrane-bound cytochrome c oxidase was attached to an electrode via a His-tag linker and studied by surface enhanced resonance Raman spectroscopy, demonstrating intact redox site structures and electron transfer between the electrode and the immobilized enzyme.     

Photoemission and ionization of He+ under simultaneous irradiation of fundamental laser and high-order harmonic pulses

We theoretically study the response of He+ exposed simultaneously to an intense Ti:sapphire laser and its 27th or 13th harmonic pulses. High-order harmonic emission from He+ is enhanced by many orders of magnitude compared with the case of the fundamental pulse alone. Moreover, while an individual 10 fs laser (wavelength lambda(F)=800 nm) or its 27th harmonic pulse with a peak intensity of 3 x 10(14) and 10(13) W/cm(2), respectively, ionizes no more than 5 x 10(-6) of He+, their combined pulse leads to a surprisingly high He2+ yield of 17%.     

Solid-phase synthesis of HTLV-1 protease inhibitors containing hydroxyethylamine dipeptide isostere

An efficient method has been developed for the first solid-phase synthesis of HTLV-1 protease inhibitors that contain hydroxyethylamine isostere as a transition-state mimetic. The synthetic procedure was designed to allow the evaluation of stereostructure-activity relationships at the scissile site. All the possible configurations at the hydroxy- and side chain-bearing asymmetric centers of the isostere were constructed by an ester-derived asymmetric aldol reaction. Each inhibitor containing the isostere backbone was synthesized on solid support by using the newly developed succinate ester linker. The configuration at the hydroxy- and side chain-bearing asymmetric center showed remarkable effects on the inhibitory activity; the K(i) value changed with approximately 2 orders of magnitude. The described approach enables an efficient preparation of the inhibitors containing secondary alcohol as a transition-state mimetic.     

The first oxovanadium ring in [[O[double bond]V(salen)]2(mu-F)][VO(salen)][BF4].(CH2Cl2)x crystals

The crystal structure of [{O=VV(salen)}2(mu-F)][VIVO(salen)][BF4].(CH2Cl2)x revealed a hollow cavity with a diameter of 5.3 A that penetrates through the crystal, and a remarkable cyclic chain of the [VO(salen)] unit, a motif that has never been fashioned from oxometal building blocks. These features endow the crystal with a molecular sievelike property for the rapid, reversible, and size-selective absorption of guest CH2Cl2 molecules.     

Massadine,a novel geranylgeranyltransferase type I inhibitor from the marine sponge Stylissa aff. massa

Massadine, a highly oxygenated alkaloid, was isolated from the marine sponge Stylissa aff. massa as an inhibitor of geranylgeranyltransferase type I (GGTase I). The structure of massadine has been deduced from spectral data. Massidine inhibited GGTase I from Candida albicans with an IC(50) value of 3.9 microM. [structure: see text]     

The multiple server effect: Optimal allocation of servers to stations with different service‐time distributions in tandem queueing networks

Traditionally, studies on tandem queueing networks concentrate on systems with infinite buffers, exponential service times, and/or single servers where solutions are more tractable. Less research can be found on more general, less tractable systems. We examine multipleserver systems with finite buffers and nonexponential service times, studying the effects of coefficient of variation (cv) of the servicetime distribution on the throughput of these systems, where cv differs among stations.Starting with the single station, we examine the effects of cv and the number of servers at the station on the distribution of interdeparture times. This insight helps explain the differences in throughput seen in the single (fast) server vs. multiple (slow) server problem. These results, in turn, shed light on the server allocation problem when cv differs among stations. We present some observations, as well as the intuition behind them.     

Ignition enhancement by addition of NO and NO2 from a N2/O2 plasma torch in a supersonic flow

The effects of NO and NO₂ produced by using a plasma jet (PJ) of a N₂/O₂ mixture on ignition of hydrogen, methane, and ethylene in a supersonic airflow were experimentally and numerically investigated. Numerical analysis of ignition delay time showed that the addition of a small amount of NO or NO₂ drastically reduced ignition delay times of hydrogen and hydrocarbon fuels at a relatively low initial temperature. In particular, NO and NO₂ were more effective than O radicals for ignition of a CH₄/air mixture at 1200 K or lower. These ignition enhancement effects were examined by including the low temperature chemistry. Ignition tests by a N₂/O₂ PJ in a supersonic flow (M = 1.7) for using hydrogen, methane, and ethylene injected downstream of the PJ were conducted. The results showed that the ignitability of the N₂/O₂ PJ is affected by the composition of the feedstock and that pure O₂ is not the optimum condition for downstream fuel injection. This result of ignition tests with downstream fuel injection demonstrated a significant difference in ignition characteristics of the PJ from the ignition tests with upstream fuel injection.     

Solubilization of C60 by micellization with a thermoresponsive block copolymer in water: Characterization,singlet oxygen generation,and DNA photocleavage

Water‐soluble diblock copolymer, poly(N‐isopropylacrylamide)‐block‐poly(N‐vinyl‐2‐pyrroridone) (PNIPAM_m‐b‐PNVP_n), was found to associate with fullerene (C₆₀), and thus C₆₀ can be solubilized in water. The 63C₆₀/PNIPAM_m‐b‐PNVP_n micelle formed a core‐shell micelle‐like aggregate comprising a C₆₀/PNVP hydrophobic core and a thermoresponsive PNIPAM shell. The C₆₀‐containing polymer micelle formation and its thermoresponsive behavior were characterized using light scattering and ¹H NMR techniques. The hydrodynamic radius (R_h) of the C₆₀‐bound polymer micelle increased with increasing temperature, which was ascribed to the hydrophobic association between dehydrated PNIPAM shells above lower critical solution temperature (LCST). ¹H NMR data suggest that the motion of the PNIPAM block is restricted above LCST due to the dehydration of the PNIPAM shell in water. The generation of singlet oxygen by photosensitization by the C₆₀‐bound polymer micelle was confirmed from photooxidation of 9,10‐anthracenedipropionic acid. Furthermore, DNA was found to be cleaved by visible light irradiation in the presence of the C₆₀‐bound polymer micelle. Therefore, there may be a hope for a pharmaceutical application of the C₆₀‐bound polymer micelle to cancer photodynamic therapy. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.