Structural investigation of an antibiotic sporaviridin II.1 application of 13C-NMR to the structural elucidation of viridopentaose B

A new heteropentasaccharide named viridopentaose B was obtained by aqueous ammonia hydrolysis of N-acetylsporaviridin and the structure was established by he detailed analysis of ¹³C-NMR specra with those of further degradation products.     

Hall effect and transverse magnetoresistance in a low-dimensional conductor HfTe5

Temperature dependence of Hall coefficient and transverse magnetoresistance of a low-dimensional conductor HfTe₅ with 1.5 wt. % Zr is reported for the first time up to 12 kOe in magnetic field. Hall coefficient changes sign from positive to negative at the temperature at which the peak of the resistivity has been observed. Temperature dependence of the transverse magnetoresistance has an anomaly. Two-carrier model has been proposed to explain the data qualitatively. These results suggest the change of the electronic structure associated with the charge density wave formation or some other kind of phase transition. Simple chemical bonding consideration shows that the carrier originates from p-like bands.     

Comparison of FAIR technique with different inversion times and post contrast dynamic perfusion MRI in chronic occlusive cerebrovascular disease

The purpose of this study was to examine the signal change occurring with different inversion times (TIs) of the flow-sensitive alternating inversion recovery (FAIR) technique and to compare with the perfusion image obtained with Gd-DTPA injection. The subjects were 11 patients with unilateral occlusive cerebrovascular disease. Two FAIR images with different TIs (800 ms and 1600 ms) were measured for each patient and dynamic perfusion MRI was performed to produce four kinds of parameter maps: mean transit time (MTT), time to peak (TTP), relative cerebral blood flow (rCBF) and relative cerebral blood volume (rCBV) maps. Asymmetry ratios (ARs) between the affected and contra-lateral vascular sides were measured in both FAIR images and the four dynamic parameter maps. The AR of the MTT map of the four parameters showed the highest correlation with that of the FAIR images, especially with that of TI = 1600 ms (r = 0.829), and the AR of the rCBV map revealed the worst correlation with the FAIR images. The AR of the FAIR image with TI = 800 ms was less correlated with that of MTT than that with TI = 1600 ms. These results suggested that the signal intensity of the FAIR image was influenced by flow transition time and the change in TI could be used to select the flow with a different transition time. Our study suggested that a longer TI in the FAIR technique might be more useful than a shorter TI for evaluating chronic occlusive cerebrovascular disease in the clinical setting.     

Enhanced detection of sulfo-peptides as onium salts in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

A new two-component system, consisting of a matrix and an onium salt as comatrix, is described for detection of sulfo-peptides in the positive mode by matrix-assisted desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). Binary iodonium salts were superior to quaternary phosphonium salts in terms of suppression of desulfation and salt formation with the carboxyl group. Of the iodonium salts examined, bis(4-tert-butylphenyl)iodonium (BTI) hexafluorophosphate and bromide were most effective in giving intensive molecular ion signals in the form of [M(BTI)+BTI](+). The conditions optimized for O-sulfated tyrosine-containing peptides could be applicable for O-sulfated serine- and threonine-containing peptides. In the case of a phospho-peptide, a molecular ion appeared more intensively as a proton adduct than as a BTI adduct.     

Self-threading of a poly(ethylene glycol) chain in a cyclodextrin-ring: control of the exchange dynamics by chain length

Poly(ethylene glycol) (PEG)-substituted cyclodextrins (CDs) with different chain lengths have been synthesized. PEG-substituted CDs formed self-threading complexes in aqueous solutions, and the conformational exchange dynamics between self-threading and dethreading could be regulated by its chain length.     

Sparsity‐weighted outlier FLOODing (OFLOOD) method: Efficient rare event sampling method using sparsity of distribution

As an extension of the Outlier FLOODing (OFLOOD) method [Harada et al., J. Comput. Chem. 2015, 36, 763], the sparsity of the outliers defined by a hierarchical clustering algorithm, FlexDice, was considered to achieve an efficient conformational search as sparsity‐weighted “OFLOOD.” In OFLOOD, FlexDice detects areas of sparse distribution as outliers. The outliers are regarded as candidates that have high potential to promote conformational transitions and are employed as initial structures for conformational resampling by restarting molecular dynamics simulations. When detecting outliers, FlexDice defines a rank in the hierarchy for each outlier, which relates to sparsity in the distribution. In this study, we define a lower rank (first ranked), a medium rank (second ranked), and the highest rank (third ranked) outliers, respectively. For instance, the first‐ranked outliers are located in a given conformational space away from the clusters (highly sparse distribution), whereas those with the third‐ranked outliers are nearby the clusters (a moderately sparse distribution). To achieve the conformational search efficiently, resampling from the outliers with a given rank is performed. As demonstrations, this method was applied to several model systems: Alanine dipeptide, Met‐enkephalin, Trp‐cage, T4 lysozyme, and glutamine binding protein. In each demonstration, the present method successfully reproduced transitions among metastable states. In particular, the first‐ranked OFLOOD highly accelerated the exploration of conformational space by expanding the edges. In contrast, the third‐ranked OFLOOD reproduced local transitions among neighboring metastable states intensively. For quantitatively evaluations of sampled snapshots, free energy calculations were performed with a combination of umbrella samplings, providing rigorous landscapes of the biomolecules. © 2015 Wiley Periodicals, Inc.     

Glutathione oxidase-like activity of glass beads, silica gel and anion-exchange resin modified with cobalt(III)-tetrakis(4-carboxyphenyl)porphine

Silica gel and glass beads were modified by using acid chloride of metal–tetrakis(4-carboxyphenyl)porphine (M–TCPP) through a peptide bond, and an anion-exchange resin with M–TCPP by ion-exchange reaction and physical adsorption. The carriers modified with Co³⁺–TCPP proved to accelerate the redox reaction which is catalyzed by glutathione oxidase (GSHOx), while those modified with Mn³⁺–TCPP exhibited no activity. Formation of GS-SG and hydrogen peroxide was confirmed by means of mass spectroscopy and colored reaction, respectively. The silica gel modified with Co³⁺–TCPP exhibited the strongest activity among the tested carriers, and was expected to be useful practically as a solid catalyst for the determination of glutathione.     

Optical resolution of mandelic acid derivatives by column chromatography on crosslinked cyclodextrin gels

Crosslinked α- and β-cyclodextrin gels (α-CD-E and β-CD-E) were used for the chromatographic resolution of racemic mandelic acid and its derivatives. β-CD-E bound L -(+)-isomers preferentially over D -(?)-isomers and resolved DL -methyl mandelate to give a D -(?)-isomer of 100% optical purity in the first fraction. Mandelic acid, ethyl mandelate, and O-methylated mandelic acid yielded resolutions of 65–83% in initial fractions. α-CD-E, on the contrary, bound D -(?)-isomers more strongly than L -(+)-isomers, resolving DL -methyl mandelate to a smaller extent than β-CD-E. Binding of DL -mandelic acid and DL -methyl mandelate on β-CD-E was studied quantitatively by the equilibrium method. β-CD-E has a similar binding capacity to starch with 1:1 stoichiometry but bound much more strongly than starch. β-CD-E has the same mode of selectivity as starch for the asymmetric binding of the mandelic acid derivatives, but α-CD-E has a reverse selectivity to β-CD-E and starch.