Effects of conformation and hydrogen bonding on the CC and NCN stretching Raman bands of N‐deuterated histidinium

Histidine is an important and versatile amino acid residue that plays a variety of structural and functional roles in proteins. Although the Raman bands of histidine are generally weak, histidine in the N‐deuterated cationic form with imidazole N_π D and N_τ D bonds (N‐deuterated histidinium) gives two strong Raman bands assignable to the C₄C₅ stretch (ν_CC) and the N_π C₂ N_τ symmetric stretch (ν_NCN) of the imidazole ring. We examined the Raman spectra of N‐deuterated histidinium in 12 crystals with known structures. The observed ν_CC and ν_NCN wavenumbers were analyzed to find empirical correlations with the conformation and hydrogen bonding. The effect of conformation on the vibrational wavenumber was expressed as a threefold cosine function of the C_α C_β C₄C₅ torsional angle. The effect of hydrogen bonding at N_π or N_τ was assumed to be proportional to the inverse sixth power of the distance between the hydrogen and acceptor atoms. Multiple linear regression analysis clearly shows that the conformational effect on the vibrational wavenumber is comparable for ν_CC and ν_NCN. The hydrogen bond at N_π weakly lowers the ν_CC wavenumber and substantially raises the ν_NCN wavenumber. On the other hand, the hydrogen bond at N_τ strongly raises the ν_CC wavenumber but does not affect the ν_NCN wavenumber. These empirical correlations may be useful in Raman spectral analysis of the conformation and hydrogen bonding states of histidine residues in proteins. Copyright © 2010 John Wiley & Sons, Ltd.     

Progress in muscular dystrophy research with special emphasis on gene therapy

Duchenne muscular dystrophy (DMD) is an X-linked, progressive muscle-wasting disease caused by mutations in the DMD gene. Since the disease was described by physicians in the 19th century, information about the subject has been accumulated. One author (Sugita) was one of the coworkers who first reported that the serum creatine kinase (CK) level is elevated in progressive muscular dystrophy patients. Even 50 years after that first report, an elevated serum CK level is still the most useful marker in the diagnosis of DMD, a sensitive index of the state of skeletal muscle, and useful to evaluate therapeutic effects. In the latter half of this article, we describe recent progress in the therapy of DMD, with an emphasis on gene therapies, particularly exon skipping.     

Non-existence of finite-time self-similar solutions of the Keller-Segel system in the scaling invariant class

Let us consider the problem whether there does exist a finite-time self-similar solution of the backward type to the semilinear Keller-Segel system. In the case of parabolic-elliptic type for n?3 we show that there is no such a solution with a finite mass in the scaling invariant class. On the other hand, in the case of parabolic-parabolic type for n?2, non-existence of finite-time self-similar solutions is proved in a larger class of a finite mass with some local bounds.     

MOVPE of AlN-free hexagonal GaN/cubic SiC/Si heterostructures for vertical devices

The heterostructures of GaN/SiC/Si were prepared without using AlN or AlGaN buffer layers (AlN buffers) in the metalorganic vapor phase epitaxy of GaN on SiC. GaN (0 0 0 1) with specular surface was obtained. The AlN buffers are usually used in the conventional growth of GaN on SiC due to the poor nucleation of GaN on SiC. Instead, the nucleation of GaN was controlled by varying the partial pressure of H₂ in the carrier gas, the mixture of H₂ and N₂, during the low-temperature (600 °C) growth of GaN (LT-GaN). After the LT-GaN, the high-temperature (1000 °C) growth of GaN was performed using pure H₂ as the carrier gas. The epitaxial film of cubic SiC (1 1 1) on a Si (1 1 1) substrate was used as the SiC template. Increasing the partial pressure of H₂ in the carrier gas decreased the coverage of SiC surface by LT-GaN. It is suggested that the hydrogen atoms adsorbed on the surface of SiC is preventing the nucleation of GaN.     

Protein adsorption and wetting of the protein adsorbed surfaces studied by a new type of laser reflectometer

We have devised a new type of laser reflectometer that can measure adsorption behavior of (bio)-polymers, such as proteins, on the substrate surface and also the wetting for the surface of adsorbed layer of such (bio)-polymers. The adsorption and the wetting experiments can be conducted in a sequential manner using the same sample by this apparatus. So, the wetting of the surface of protein-adsorbed layer can be measured in virtually intact state. The reflectometry is based on the traditional optical polarimetry and the wetting measurement is due to the dropping time method (DTM) that has been reported before by the authors. The two methods are combined in an apparatus and hence we can correlate the wetting of protein layer adsorbed on the substrate surfaces with the amounts of protein molecules on the surface. As a model case we demonstrate the adsorption of several typical water soluble globular proteins on stainless steel surfaces. For this combination of the adsorbent with adsorbates, it is found that the water wetting of the protein adsorbed surface is closely related with the adsorbed amounts of proteins not depending on species.     

"Beta-cis-SAr effect" on decarbonylation from alpha,beta-unsaturated acyl and aroyl complexes

Lone pair of heteroatom located at the beta-cis position in alpha,beta-unsaturated acyl and aroyl group 10 metal complexes dramatically facilitated the stoichiometric and catalytic decarbonylation reactions.     

An electron spin resonance study of gamma-ray irradiated ginseng

Using electron spin resonance (ESR) spectroscopy, we revealed the presence of four radical species in gamma-ray irradiated ginseng (Agaliaceae). Before irradiation, the representative ESR spectrum of ginseng is composed of a sextet centered at g = 2.0, a sharp singlet at the same g-value, and a singlet at about g = 4.0. The first one is attributable to a hyperfine (hf) signal of Mn2+ ion (hf constant: 7.4 mT). The second one is due to an organic free radical. The third one is originated from Fe3+. Upon gamma-ray irradiation, a new ESR (the fourth) signal was detectable in the vicinity of g = 2.0 region. The progressive saturation behaviors of the ESR signals at various microwave power levels were indicative of different relaxation time for those radicals. The anisotropic ESR spectra were detected by the angular rotation of the sample tube. This is due to the existence of anisotropic microcrystalline in the ginseng powder sample.     

Biotransformation of daidzein ditiglate by microorganisms

Biotransformation of the daidzein ditiglate (2) by fungi, Aspergillus niger and Glomerella cingulata was investigated. Compound 2 was transformed to daidzein (1) by A. niger and G. cingulata. This suggested that compound 2 was converted to compound 1 by hydrolysis at both of the C-7 and C-4' positions.     

Nuclear quadrupole resonance echoes from hexamethylenetetramine

We investigated the echo phenomenon of nuclear quadrupole resonance (NQR) from hexamethylenetetramine (HMT). We detected the pure NQR echo signal of HMT with a short pulse interval. The intensity of the echo signal increased as the pulse interval time was decreased. We observed that a clean echo signal was generated even when the pulse interval was shorter than the decay time constant T₂^*. Since the short interval time gives a strong echo, our result insists that shorter interval time is preferred for the NQR detection.     

Low-birefringent, chiral banana phase below calamitic nematic and/or smectic C phases in oxadiazole derivatives

Bent-shaped molecules based on the oxadiazole central core with various side wings and terminal chain groups have been synthesized, and their liquid-crystalline behavior was investigated by optical microscopic, X-ray, and electrooptic measurements. These molecules exhibit liquid-crystal polymorphism including both the calamitic and banana phases. Such a characteristic polymorphism is attributable to the larger bend angle of the oxadiazole core compared to that of the resorcinol core used in conventional banana molecules. Only one type of banana phase, designated as the Bx phase, is formed. It appears upon cooling from the nematic and smectic liquid crystals and exhibits chiral domains with a very weak birefringence (apparently optically isotropic). By applying an electric field, the Bx phase is altered to a high-birefringence B2 phase with a homochiral SmC(A)P(A) structure that exhibits an antiferroelectric response. From detailed analyses of the optical texture and X-ray patterns through the transformation from well-oriented calamitic phases, the Bx phase was found to exhibit a helical structure, which arises as a frustration from the ground-state B2 phase in such a manner that the blocks of B2 layers are twisted with respect to each other in a direction parallel to the layer plane similarly to the twisted grain boundary (TGB) phase.