Direct Addition of Amides to Glycals Enabled by Solvation‐Insusceptible 2‐Haloazolium Salt Catalysis

The direct 2‐deoxyglycosylation of nucleophiles with glycals leads to biologically and pharmacologically important 2‐deoxysugar compounds. Although the direct addition of hydroxyl and sulfonamide groups have been well developed, the direct 2‐deoxyglycosylation of amide groups has not been reported to date. Herein, we show the first direct 2‐deoxyglycosylation of amide groups using a newly designed Brønsted acid catalyst under mild conditions. Through mechanistic investigations, we discovered that the amide group can inhibit acid catalysts, and the inhibition has made the 2‐deoxyglycosylation reaction difficult. Diffusion‐ordered two‐dimensional NMR spectroscopy analysis implied that the 2‐chloroazolium salt catalyst was less likely to form aggregates with amides in comparison to other acid catalysts. The chlorine atom and the extended π‐scaffold of the catalyst played a crucial role for this phenomenon. This relative insusceptibility to inhibition by amides is more responsible for the catalytic activity than the strength of the acidity.     

A Hydroperoxide-Mediated Decarboxylation of α-Ketoacids Enables the Chemoselective Acylation of Amines

Strategies for the formation of amide bonds, that is, one of the most basic and important transformations in organic synthesis, have so far focused predominantly on dehydration reactions. Herein, we report and demonstrate the practical utility of a novel decarboxylative amidation of α-ketoacids by using inexpensive tert-butyl hydroperoxide (TBHP), which is characterized by high yields, a broad substrate scope, mild reaction conditions, and a unique chemoselectivity. These features enable the synthesis of peptides from amino acid derived α-ketoacids under preservation of the stereochemical information.     

Dominant modes of submerged thin cylindrical shells

The relationship between the dominant mode of the submerged thin cylindrical shell and the flexural wave velocity is investigated. The natural frequency corresponding to the vibration mode is obtained as the solution of characteristic equation of thin cylindrical shell. However, it is difficult to estimate the dominant mode, especially if two or more vibration modes are involved. To estimate the dominant mode of a thin shell in vacuo, the concept of “modified bending stiffness” has been introduced. In this paper, the concept of modified bending stiffness is extended to estimate the dominant mode of a submerged thin cylindrical shell. The dominant mode of a submerged thin cylindrical shell is theoretically discriminated from the other mode based on the smallness of the modified bending stiffness of the submerged shell. The validity of our theory is confirmed by a good agreement between theoretical and experimental results on flexural wave velocity.     

Nonrelativistic limit in the energy space for nonlinear Klein-Gordon equations

We study the nonrelativistic limit of the Cauchy problem for the nonlinear Klein-Gordon equation and prove that any finite energy solution converges to the corresponding solution of the nonlinear Schr?dinger equation in the energy space, after the infinite oscillation in time is removed. We also derive the optimal rate of convergence in . Received: 13 July 2000 / Published online: 1 February 2002     

Status of heavy element research using a gas-filled recoil separator at RIKEN

A gas-filled type of recoil separator for heavy element research was installed at an experimental hall of RIKEN Linear Accelerator facility to realize getting higher intensity of primary beam and long beam time. Performance of the separator was studied using target recoils and various nuclear reactions. The results show the high performance of the separator for heave element research. As an application of the GARIS, production and identification of an isotope of the 110th element ²⁷¹[110] have been performed using the ²⁰⁸Pb(⁶⁴Ni,1n)²⁷¹[110] reaction. Three decay chains coincide well both in decay times and energies with the ones reported by the group of SHIP experiment at GSI, Germany. Our results provide a confirmation of the synthesis of an isotope ²⁷¹[110] of element 110.     

DNA-conjugated polymers for self-assembled DNA chip fabrication.

We developed two DNA-conjugated polymers, one based on polyallylamine and the other on polyacrylic acid, for use in DNA chips. A 30-mer single-stranded DNA probe and thioctic acid were covalently attached to polyallylamine as sidechains. The same single-stranded DNA and 3-(pyridyldithio)propionyl hydrazide were covalently attached to polyacrylic acid as sidechains. Both DNA-conjugated polymers could be specifically immobilized onto a gold sensor substrate by a self-assembly technique. The interactions between fully matched DNA and each DNA-conjugated polymer were investigated by surface plasmon resonance. A gold surface modified with either DNA-conjugated polymer recognized fully matched DNA much better than unmatched DNA. The hybridization selectivity and efficiency of DNA-conjugated polyallylamine was optimized by adjusting the pH so as to reduce the effects of cationic polymer sidechains. The hybridization selectivity and efficiency of DNA-conjugated polymers were higher than those of a conventional immobilized thiol-based DNA. The coating of DNA-conjugated polymers reduced nonspecific adsorption of DNA by the gold substrate. DNA-conjugated polyacrylic acid was more selective toward fully matched DNA than was DNA-conjugated polyallylamine. Therefore, DNA-conjugated polymers show promise for application in novel DNA chips.     

Design and synthesis of labeling reagents (MS probes) for highly sensitive electrospray ionization mass spectrometry and their application to the detection of carbonyl, alcohol, carboxylic acid and primary amine samples.

Novel labeling reagents, called MS probes, which possess a positively charged quaternary amine moiety and can transform a neutral analyte into a charged compound by simply mixing with the analyte and allowing the mixture to stand from several minutes to 30 min at room temperature or while heating to 50 degrees C, were designed and synthesized for the highly sensitive detection of carbonyl, alcohol, carboxylic acid and primary amine samples by electrospray ionization mass spectrometry (ESI-MS). The positively charged products can be detected with high sensitivity in an ESI-MS system, which is the most popular liquid MS instrument. All of the labeled products showed a remarkably large increase in the molecular-ion peak abundance detection sensitivity of over 500-fold at picomolar concentration levels compared to that of unlabeled analytes in an ESI-MS system. These MS probes, used together with liquid MS detection, are widely applicable as a convenient method for the highly sensitive detection of less than picomolar levels of analytes, and therefore greatly enhance the power of ESI-MS analysis.     

Simultaneous determination of serotonin and 5-hydroxyindole-3-acetic acid in human urine by automated precolumn derivatization and semi-microbore column liquid chromatography with fluorescence detection.

An improved high-performance liquid-chromatographic (HPLC) assay for the simultaneous determination of serotonin (5-HT) and 5-hydroxyindole-3-acetic acid (5-HIAA) in human urine is reported. Following the automated precolumn derivatization of urinary 5-HT and 5-HIAA with benzylamine, the derivatives are separated by isocratic elution on a reversed-phase C18 semi-microbore column, and are fluorometrically detected at an excitation wavelength of 345 nm and an emission wavelength of 480 nm. The detection limits of 5-HT and 5-HIAA are 7 and 5 nmol/l in urine (0.7 and 0.5 fmol/20-microl injection). The proposed automatic method permits a highly selective and sensitive determination of 5-HT and 5-HIAA in human urine without any sample purification.