Intramolecular photocycloaddition of β-stilbazoles tethered by silyl chains

Intramolecular (2+2) photocycloaddition of β-stilbazoles tethered by silyl chains took place with high efficiency. Complexation with dicarboxylic acid or catechol further enhanced both the efficiency and stereoselectivity.     

Ion-transfer voltammetry at a polarized room-temperature molten salt/water interface.

Tetraoctylammonium cation forms a room-temperature molten salt (RTMS) with 2,4,6-trinitrophenolate anion. The RTMS is immiscible with water (W) and forms a stable RTMS/W interface. It has been shown that the RTMS/W interface can be electrochemically polarized. A well-defined voltammetric wave due to the transfer of thiocyanate ion across the RTMS/W interface was observed within the potential window. This is the first example of a polarized RTMS/W interface.     

Rapid and sensitive determination of the conversion of UV-cured acrylic ester resins by pyrolysis-gas chromatography in the presence of an organic alkali.

The double-bond conversion of UV-cured resins prepared from pentaerythritol triacrylate (PETA) was determined by pyrolysis-gas chromatography in the presence of an organic alkali, tetramethylammonium hydroxide (TMAH). The pyrogram of the uncured prepolymer compound, consisting of PETA and a photoinitiator, 2,2-dimethoxy-2-phenylacetophenone, contained specific products reflecting the original acrylate structure, such as methyl acrylate (MA) and methyl ethers of pentaerithritol. Meanwhile, in pyrograms of the UV-cured PETA, the yields of MA considerably decreased. The double-bond conversions of the cured resins, irradiated with various UV dosages, were calculated based on the relative yields of MA among specific products in the pyrograms. The conversions determined by this approach were analyzed by comparing them with those estimated by Fourier-transform infrared spectroscopy.     

Polymorphy in the stereostructure of periodic polymer backbones

We theoretically investigated the polymorphy of the stereostructures of a periodic polymer. Using the polymer's internal conformation parameters of bond lengths, bond angles, and internal rotation angles, we extended the mathematical treatment for designing polymer backbones. We considered those periodic polymers whose unit cell consists of one (m = 1), two (m = 2), or three (m = 3) kinds of atoms. Moreover, for these three types of polymers, we supposed two catenation types for the skeleton atoms; one is a “homorotatory” sequence and the other is a “heterorotatory” one. To specify the backbone's stereostructure, we introduced several conformation parameters such as the helical pitch number n, the translation distance d, and the inclination angle of the skeleton plane Θ. By combining these parameters, we can systematically understand the variety and the possible polymorphy in the stereostructure of a periodic polymer backbone. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2829–2849, 2003     

WIDE RANGE DETECTOR USING PARABOLIC CYLINDRICAL MIRROR FOR THz APPLICATIONS

A new, wide-band, high-speed and high-sensitivity THz detector has been developed. The prototype detector consists of a parabolic cylindrical mirror, a long wire antenna and a Schottky barrier diode. Direct detection measurements have shown a stable sensitivity of 150 ± 50 V/W for 1–2 THz without any adjustments. The long wire antenna was fixed at the focus of parabolic cylindrical mirror then it has been realized less operation steps, easy coupling to the external THz signals and a dramatic enhancement in the practicality of this system. The optically polished mirror and frosted surface one showed comparable sensitivities, thus easy polishing and less cost mirror fabrication can be applied for this system. The radiation pattern showed a maximum radiation angle of approximately 23° with its dominant main lobe, which was attributed to the wire antenna character and confirmed good agreements with classical antenna theory.     

HCN laser scattering on the JIPP T-IIU tokamak

A 4-channel HCN laser scattering system has been developed and applied to the JIPP T-IIU tokamak. Main aim of this system is to study microturbulence excited in the plasma, especially in the high power ICRF heating experiment. The observed density fluctuations are in a frequency range of the electron diamagnetic drift wave and have broad frequency spectra. The main part of the wavenumber is found to satisfy the condition of . In the heating experiments, deterioration of the energy confinement time is observed, and the density fluctuation level increases with the increase of the heating power.     

New features in the catalytic cycle of cytochrome P450 during the formation of compound I from compound 0

Density functional theory (DFT) is applied to the dark section of the catalytic cycle of the enzyme cytochrome P450, namely, the formation of the active species, Compound I (Cpd I), from the ferric-hydroperoxide species (Cpd 0) by a protonation-assisted mechanism. The chosen 96-atom model includes the key functionalities deduced from experiment: Asp(251), Thr(252), Glu(366), and the water channels that relay the protons. The DFT model calculations show that (a) Cpd I is not formed spontaneously from Cpd 0 by direct protonation, nor is the process very exothermic. The process is virtually thermoneutral and involves a significant barrier such that formation of Cpd I is not facile on this route. (b) Along the protonation pathway, there exists an intermediate, a protonated Cpd 0, which is a potent oxidant since it is a ferric complex of water oxide. Preliminary quantum mechanical/molecular mechanical calculations confirm that Cpd 0 and Cpd I are of similar energy for the chosen model and that protonated Cpd 0 may exist as an unstable intermediate. The paper also addresses the essential role of Thr(252) as a hydrogen-bond acceptor (in accord with mutation studies of the OH group to OMe).     

Mechanisms of ATPases--a multi-disciplinary approach

ATPases are important molecular machines that convert the chemical energies stored in ATP to mechanical actions within the cell. ATPases are among the most abundant proteins with diverse functions involved in almost every cellular pathway. The well characterised ATPases include the various motor proteins responsible for cargo transfers, cell motilities, and muscle contractions; the protein degradation machinery - the proteasome; the ATP synthase, F-ATPase; and the chaperone systems. Other ATPases include DNA helicases and DNA replication complex; proteins responsible for protein/complex disassembly; and certain gene regulators. It is beyond the scope of this review to cover the complete range of ATPases. Instead, we will focus on a few representative ATPases, chosen based on their diverse mechanisms and properties. Furthermore, this review is by no means trying to cover comprehensively the literature for each ATPase nor the historical aspects in each field. We will focus on describing the various techniques being employed to derive the mechanisms and properties of the chosen ATPases. Among them, high and low resolution structural studies combined with biochemical assays seem to be the dominant technical advances adapted to reveal mechanisms for most of the ATPases except the bacterial sigma54 activators, whose mechanism of action is mostly derived from large amount of biochemical studies. A number of them, especially the F-ATPase and motor proteins, have been studied successfully by various single molecule and imaging techniques. We will therefore discuss them in greater details in order to describe the wide range techniques being utilised.