Mössbauer spectroscopic study of gamma-ray irradiated potassium phosphate glasses

A Mössbauer spectroscopic study was performed to investigate the effect of γ-ray irradiation on the formation of non-bridging oxygens in the potassium phosphate glasses denoted by the formula x K₂O · (100 ? x)P₂O₅ · 7 Fe₂O₃ (0 ? x ? 50 mol.%). Mössbauer spectra for these glass samples consisted of two kinds of doublets due to Fe²⁺ and Fe³⁺ ions of octahedral symmetries. Only small changes occurred in the Mössbauer parameters as a result of irradiation at room temperature in a dry nitrogen atmosphere, except for the decrease in the absorption area for the Fe²⁺ ions. The decrease in the absorption area was attributed to the electron transfer from the Fe²⁺ ions to the neighboring oxygens. Thermal annealing experiments for a few non-irradiated glass samples indicated that the decrease in the absorption area was confirmed to be due to γ-rays rather than heating during the irradiation.     

Triple helicate constructed by covalent bondings: crystal structure and effective synthesis based on propeller-like substructures

A triple helicate, having a macrocyclic aromatic amide structure, was synthesized in high yield because of a preorganized component of the tertiary benzenetrianilide moieties in a propeller-like syn conformation at both ends. The helicity was derived from tilted T-shaped aromatic-aromatic (CH-pi) interactions between each of the N-phenyl rings. [structure: see text]     

Spectrophotometric determination of urinary protein with o-sulfophenylfluorone-metal complex.

A simple and sensitive spectrophotometric method for the determination of human serum albumin (HSA) was established based on the ternary complex-formation reaction of HSA with o-sulfophenylfluorone (SPF) as a xanthene dye and metal ion (niobium(V) and bismuth(III)) in the presence of a dispersion agent. This new method enabled the determination of HSA in the range of 1 - 15 microg/ml HSA by measuring the difference of the absorbance at 530 nm between HSA-SPF-metal ion and SPF-metal ion solutions. In the determination of HSA, this method is about 2-times more sensitive than the Pyrogallol Red-molybdenum(VI) method (PR method), which accounts for more than 80% of the quantification methods for urinary protein assays in Japan. There was no significant difference between the results obtained by the present method and the PR method for human urine samples. The binding process between the SPF-metal complex and HSA was studied by determining the binding parameters and the thermodynamic parameters.     

Isolation and characterization of N-alkyl-N- (hydroxymethyl)nitrosamines from N-alkyl-N- (hydroperoxymethyl)nitrosamines by deoxygenation

N-Alkyl-N- (hydroxymethyl)nitrosamines, postulated intermediates in the metabolic activation of carcinogenic nitrosamines, were prepared by deoxygenation of the corresponding hydroperoxymethyl nitrosamines and characterized.     

Rhodium-catalyzed approach to Mannich-type products using aldimine,alpha,beta-unsaturated ester,and hydrosilane

A rhodium-catalyzed method for the synthesis of beta-amino esters was accomplished in a one-pot procedure from aldimine, alpha,beta-unsaturated ester and hydrosilane.     

Synthetic Studies on Sialoglycoconjugates 81: Synthesis of Positional Isomers of Sialyl Lewis X Epitope Containing 1-Deoxy-d Glucose in Place of N-Acetylglucosamine,and Their Inhibitory Activity to Selectin-Mediated Adhesion

Abstract

Three sialyl-Le^x epitope analogs, which carry fucose and α-sialyl-(2→3)-galactose residues at O-2 and O-3, O-3 and O-2, and O-4 and O-6 positions of 1-deoxy-D-glucose backbone, respectively, have been synthesized. Glycosylation of 1,5-anhydro-4,6-O-benzylidene-D-glucitol (1) or 1,5-anhydro-6-O-benzoyl-2,3-di-O-benzyl-d-glucitol (4) prepared from 1,5-anhydro-d-glucitol, with methyl 2,3,4-tri-O-benzyl-1-thio-β-L-fucopyranoside (5) using dimethyl(methylthio)sulfonium triflate (DMTST) as a promoter, afforded the corresponding fucosyl 1,5-anhydro-d-glucitol derivatives 7, 8 and 9. Glycosylation of 7, 8 or 10 derived from 9, with methyl O-(methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-d-glyceroα-d-galacto-2-nonulopyranosylonate)-(2→3)-2,4,6-tri-O-benzoyl-1-thio-β-d-galactopyranoside (11) in the presence of DMTST gave the expected tetrasaccharide derivatives 12, 16 and 20. Hydrolysis of the benzylidene group in 12 and 16 gave compounds 13 and 17. Finally 13, 17 and 20 were transformed, by reductive removal of the benzyl groups, O-deacylation and subsequent hydrolysis of the methyl ester, into the sialyl-Le^x epitope analogs 15, 19 and 22, respectively.     

Chiral recognition by cyclic oligosaccharides. Enantioselective complexation of binaphthyl derivatives with cyclodextrins

Abstract

Chiral recognition of binaphthyl derivatives, such as 1,1′-bi-2-naphthol (1), 1,1′-binaphthyl-2,2′-diyl hydrogen phosphate (2), and 2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dicarboxylic acid (3), by cyclodextrins (CDxs) has been studied. The S enantiomers of 1 and 2 are bound to heptakis(2,3,6-tri-O-methyl)-β-CDx (TMe-β-CDx) as well as β-CDx more strongly than the R enantiomers. The molecular mechanics and molecular dynamics calculations for the 1:1 complex of 1 and β-CDx suggest that more effective van der Waals contacts and intermolecular hydrogen bonding stabilize the complex of S-1 compared with that of R-1. Meanwhile the R enantiomer of 3 is the preferable guest for β- and TMe-β-CDxs. Circular dichroism spectroscopy suggests that the complex of S-3 is more unstable than that of R-3 because the dihedral angle of the naphthalene planes of S-3 needs to be reduced for forming the inclusion complex. The enantiomers of the guest binaphthyls are completely separated by means of capillary zone electrophoresis (CZE) when TMe-β-CDx is used as a separating agent. The results of the CZE correspond well with those of the binding constants of the inclusion complexes.     

Synthesis of a base-stabilized silanone-coordinated complex by oxygenation of a (silyl)(silylene)tungsten complex

Base-stabilized silanone complex Cp*(OC)(2)W(SiMe(3)){O═SiMes(2)(DMAP)} (2) was synthesized by the reaction of (silyl)(silylene)tungsten complex Cp*(OC)(2)W(SiMe(3))(═SiMes(2)) (1) with 1 equiv of pyridine-N-oxide (PNO) in the presence of 4-(dimethylamino)pyridine (DMAP). Further oxygenation of 2 with 3 equiv of PNO at 80 °C resulted in the formation of a W-O-Si-O-Si framework to give disiloxanoxy complex Cp*(O)(2)W{OSiMes(2)(OSiMe(3))} (3). Complex 3 was also obtained by the direct reaction of complex 1 with 4 equiv of PNO at 80 °C.     

Assembly of amphiphilic poly[2‐(methacryloyloxy)ethyl phosphorylcholine] with cholesteryl moieties as terminal groups

Poly[2‐(methacryloyloxy)ethyl phosphorylcholine]s (PMPCs) with one pendant cholesteryl moiety at the polymer end (PMPC‐Chol‐I and PMPC‐Chol‐II) and two pendant cholesteryl moieties at both polymer ends as terminal groups (PMPC‐2Chol‐I and PMPC‐2Chol‐II) were prepared by the radical polymerization of 2‐(methacryloyloxy)ethyl phosphorylcholine initiated with 4,4′‐azobis[(3‐cholesteryl)‐4‐cyanopentanoate] in the presence of 2‐mercaptoethanol or thiocholesterol as chain‐transfer reagents, respectively. The self‐organization of PMPC‐Chol and PMPC‐2Chol was analyzed with fluorescence and ¹H NMR measurements. The critical micelle concentrations of PMPC‐Chol‐I with a degree of polymerization (P_n) of 91 and of PMPC‐2Chol‐I with a P_n value of 165 were 250 and 27 mg L^?1, respectively. The blood compatibility of PMPC‐2Chol was evaluated from the Michaelis constant (K_m) for the enzymatic reaction of thrombin and a synthetic substrate, S‐2238, in the presence of PMPC‐2Chol. K_m was 0.07, 0.05, and 0.56 for PMPC‐2Chol‐I with P_n = 165, PMPC‐2Chol‐II with P_n = 38, and PMPC (an intrinsic viscosity of 0.54 dL g^?1) initiated with 2,2′‐azobisisobutyronnitrile in the absence of chain transfer agent, respectively. A mixture of PMPC‐2Chol‐II and cholesterol as a drug model formed a lamellar type of complex with an interplanar spacing of d = 35.2 Å. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1992–2000, 2003