Periodate oxidation analysis of carbohydrates: Part IV. Simultaneous determination of aldehydes in di-aldehyde fragments as 2,4-dinitrophenylhydrazones by thin-layer or liquid chromatography

A method for the simultaneous determination of aldehydes in dialdehyde fragments, obtained from carbohydrate samples by periodate oxidation, is proposed. Reaction mixtures obtained from the periodate oxidation of carbohydrate samples are deionized by resins, and evaporated to dryness. The syrupy residues are treated with 2,4-dinitrophenylhydrazine hydrochloride in 1.2-dimethoxyethane at 25°C for 3 h. The resultant mixtures of hydrazones are separated by t.l.c. or l.c., and individual hydrazones are determined by spectrophotometric measurement. Reliable analyses of carbohydrate linkages are possible with 50–250-μg samples.     

Creation of novel chiral synthons with enzymes and applications to natural product synthesis. 15. Efficient introduction of chiral centers into cyclohexane ring

The chiral half-ester 2 obtained by asymmetric hydrolysis of the symmetric diester 1 with pig liver esterase has been shown to be a versatile synthon for various chiral cyclohexane derivatives.     

Influence of amino acid side chain packing on Fe-methionine coordination in thermostable cytochrome C

Paramagnetic NMR and optical studies of the oxidized forms of mesophile Pseudomonas aeruginosa cytochrome c(551) and its quintuple mutant (F7A/V13M/F34Y/E43Y/V78I), and thermophile Hydrogenobacter thermophilus cytochrome c(552) demonstrated that the amino acid side chain packings in the protein interior influence the coordination bond between the heme iron and the axial methionine in the proteins. The strength of heme axial coordinations was found to correlate with the overall protein thermostability.     

Rational design and crystal structure determination of a 3-D metal-organic jungle-gym-like open framework

A new three-dimensional (3-D) jungle-gym-like open metal-organic framework has been synthesized from a two-dimensional (2-D) layer compound using a heterogeneous pillar insertion reaction. Both the starting 2-D layer and the resulting 3-D open compounds have been characterized using X-ray crystallography.     

A study of molecular vibrational relaxation mechanism in condensed phase based upon mixed quantum-classical molecular dynamics. I. A test of IBC model for the relaxation of a nonpolar solute in nonpolar solvent at high density

In order to investigate vibrational relaxation mechanism in condensed phase, a series of mixed quantum-classical molecular dynamics calculations have been executed for nonpolar solute in nonpolar solvent and polar solute in polar solvent. In the first paper (Paper I), relaxation mechanism of I2 in Ar, where Lennard-Jones force is predominant in the interaction, is investigated as a function of density and temperature, focusing our attention on the isolated binary collision (IBC) model. The model was originally established for the relaxation in gas phase. A key question, here, is "can we apply the IBC model to the relaxation in the high-density fluid?" Analyzing the trajectory of solvent molecule as well as its interaction with the solute, we found that collisions between them may be defined clearly even in the high-density fluid. Change of the survival probability of the vibrationally first excited state on collision was traced. The change caused by collisions with a particular solvent molecule was also traced together with the interaction between them. Each collision makes a contribution to the relaxation by a stepwise change in the probability. The analysis clearly shows that the relaxation is caused by collisions even in the high-density fluid. The difference between stepwise relaxation and the continuous one found for the total relaxation in the low-density fluid and in the high-density one, respectively, was clarified to come from just the difference in frequency of the collision. The stronger the intensity of the collision is, the greater the relaxation caused by the collision is. Further, the shorter the collision time is, the greater the resultant relaxation is. The discussion is followed by the succeeding paper (Paper II), where we report that molecular mechanism of the relaxation of a polar molecule in supercritical water is significantly different from that assumed in the IBC model despite that the density dependence of the relaxation rate showed a linear correlation with the local density of water around the solute, the linear correlation being apparently in good accordance with the IBC model. The puzzle will be solved in Paper II.     

Metal-complex assemblies constructed from the flexible hinge-like ligand H2bhnq: structural versatility and dynamic behavior in the solid state

Novel metal-complex assemblies constructed from the flexible hinge-like ligand H(2)bhnq (H(2)bhnq=2,2'-bi(3-hydroxy-1,4-naphthoquinone)) have been synthesized. The X-ray crystal structures of these compounds reveal that four types of architectures are accessible by variation of the metal ions. In copper(II) compounds 1-3, the chelating bhnq(2-) ions bridge copper(II) centers to form one-dimensional zigzag chains. The chains of 1-3 are arranged by hydrogen-bonding interactions and stacking interactions to produce porous structures. Cobalt(II) and zinc(II) compounds 4 and 5 form one-dimensional helical chains. In 4 and 5, the crystal packing induces spontaneous resolution of the helical chains with chiral cavities formed perpendicular to the helices. Nickel(II) compounds 6 and 7 form cyclic tetramers. The fourth architecture, a dimer (compound 8), is obtained by the reaction of zinc(II) and bhnq(2-) in MeOH. In these compounds, changes of the dihedral angles and the metal-coordination mode of the bhnq(2-) ion induce the structural versatility. The assemblies of the zigzag chains of the copper(II) compounds exhibit reversible vapochromic behavior. UV/Vis, powder X-ray diffraction, EPR, and adsorption isotherm measurements indicate that this vapochromic behavior is based on the hinge-like flexibility of the bhnq(2-) ion.     

De novo design, synthesis, and function of semiartificial myoglobin conjugated with coiled-coil two-alpha-helix peptides

The introduction of a flavin chromophore on the myoglobin (Mb) surface and an effective electron-transfer (ET) reaction through the flavin were successfully achieved by utilizing the self-assembly of heterostranded coiled-coil peptides. We have prepared a semiartificial Mb, named Mb-1alphaK, in which an amphiphilic and cationic alpha-helix peptide is conjugated at the heme propionate (Heme-1alphaK). Heme-1alphaK has a covalently bound iron-protoporphyrin IX (heme) at the N terminus of a 1alphaK peptide sequence. This sequence was designed to form a heterostranded coiled-coil in the presence of a counterpart amphiphilic and anionic 1alphaE peptide sequence in a parallel orientation. Two peptides, Fla(1)-1alphaE and Fla(31)-1alphaE, both incorporating a 10-methylisoalloxazine moiety as an artificial flavin molecule, were also prepared (Fla=2-[7-(10-methyl)isoalloxazinyl]-2-oxoethyl). Heme-1alphaK was successfully inserted into apomyoglobin to give Mb-1alphaK. Mb-1alphaK recognized the flavin-modified peptides and a two-alpha-helix structure was formed. In addition, an efficient ET from reduced nicotinamide adenine dinucleotide to the heme center through the flavin unit was observed. The ET rate was faster in the presence of Fla(1)-1alphaE than in the presence of Fla(31)-1alphaE or the equivalent molecule that has no peptide chain. These results demonstrate that the introduction of a functional chromophore on the Mb surface can be achieved by using specific peptide-peptide interactions. Moreover, the dependence of the ET rate on the position of the flavin indicated that the distance between the heme active site and the flavin chromophore was regulated by the three-dimensional structure of the designed polypeptide.     

Colominic acid: a novel chiral selector for capillary electrophoresis of basic drugs

Capillary zone electrophoresis was used for characterising nine samples of natural organic matter (NOM) using phosphate buffer (25 mM, pH 7) and various modifiers; methanol (50 mM), acetonitrile (10%,v/v), dimethyl sulfoxide (5%,v/v), and urea (5 M). Principal component analysis (PCA) was used to examine whether the electrophoretic profiles can be utilised as fingerprints for tracing the NOM samples to their source and/or type of location. It was found that all modifiers except methanol affect the electropherograms. Furthermore, it was found that the PCA analysis carried out on the electrophoretic profiles recorded in buffer solution modified by urea gave the best results for fingerprinting. The distribution of the fingerprints suggests a model for the humic substances in which all samples can be regarded as mixtures between two endmembers: autochtonous and allocthoneous NOM.     

Effect of Coriolis force on counter-current chromatographic separation by centrifugal partition chromatography

The effect of Coriolis force on the counter-current chromatographic separation was studied using centrifugal partition chromatography (CPC) with four different two-phase solvent systems including n-hexane-acetonitrile (ACN); tert-butyl methyl ether (MtBE)-aqueous 0.1% trifluoroacetic acid (TFA) (1:1); MtBE-ACN-aqueous 0.1% TFA (2:2:3); and 12.5% (w/w) polyethylene glycol (PEG) 1000-12.5% (w/w) dibasic potassium phosphate. Each separation was performed by eluting either the upper phase in the ascending mode or the lower phase in the descending mode, each in clockwise (CW) and counterclockwise column rotation. Better partition efficiencies were attained by the CW rotation in both mobile phases in all the two-phase solvent systems examined. The mathematical analysis also revealed the Coriolis force works favorably under the CW column rotation for both mobile phases. The overall results demonstrated that the Coriolis force produces substantial effects on CPC separation in both organic-aqueous and aqueous-aqueous two-phase systems.