An Efficient Synthesis of Sulfo Lewis X Analog Containing 1-Deoxynojirimycin 1

Abstract

Sulfo Lewis^x analog containing 1-deoxynojirimycin (13) has been efficiently synthesized. Glycosidation of ethyl 2,3,4-tri-O-benzyl-1-thio-β-D-fucopyranoside (5) with O-2,6-di-O-benzoyl-3,4-isopropylidene-β-D-galactopyranosyl)-(1→4)-2,6-di-O-benzoyl-N-benzyloxycarbonyl-1,5-dideoxy-1,5-imino-D-glucitol (4), prepared from O-β-D-galactopyranosyl-(1→4)-1,5-dideoxy-1,5-imino-D-glucitol (1) via 3 steps, and subsequent acid hydrolysis of the isopropylidene group gave the desired trisaccharide diol derivative (7) in good yield. Compound 7 was easily converted into 3′-O-sulfo Lewis^x analog (13) via 6 steps in high yield.

     

HPLC for stress-free screening of potential prostate cancer marker catechol estrogens in urine using a diamond-electrode electrochemical and a fluorescence detector

Improvement of the sensitivity and specificity of a simultaneous stress-free screening method for catechol estrogens as a potential prostate cancer marker in urine has been accomplished by HPLC with a diamond-electrode electrochemical detector and a fluorescence detector. Since taking urine samples generates less stress (or pain) than the drawing of blood, the method can readily be applied to almost any patient, and will also assist in improving the sensitivity and specificity of the prostatic specific antigen test. Catechol estrogens (2-hydroxyestrone, 4-hydroxyestrone, 2-methoxyestrone, 2-hydroxyestradiol, 4-hydroxyestradiol, 2-methoxyestradiol, and 2-hydroxyestriol) and estrogens (estrone, estradiol, estriol) were separated on an Inertsil ODS-II column with acetonitrile-potassium dihydrogen phosphate (pH 3.0). The diamond-electrode electrochemical detector used had the great advantage of being a maintenance-free system, and could sequentially analyze hundreds of samples. Fluorescence detection improved the sensitivity 10-500 times (e. g., the LOD of 2-hydroxyestriol was improved 250 times) compared to previous electrochemical detection reports, and dual detection improved peak identification in the urine samples. The proposed method was applied to the simultaneous determination of catechol estrogens in spiked urine in a preliminary study on estrogens and PSA values in biopsy and prostate cancer patients.     

Chiral separation with novel (S)-biotin-bonded silica gel for liquid chromatography

Liquid chromatographic separation of enantiomers was accomplished using a chiral stationary phase (CSP) derived from (S)-biotin on silica gel. In both nonaqueous and aqueous media, this CSP (1) permitted separation of racemic amino acid derivatives based on hydrogen bonding with a urea moiety of the biotin moiety.     

Electronic spectra of pure uranyl(V) complexes: characteristic absorption bands due to a U(V)O2+ core in visible and near-infrared regions

To clarify the electronic spectral properties of uranyl(V) complexes systematically, we measured absorption spectra of three types of pure uranyl(V) complexes: [U(V)O2(dbm)2DMSO]-, [U(V)O2(saloph)DMSO]-, and [U(V)O2(CO3)3]5- (dbm = dibenzoylmethanate, saloph = N,N'-disalicylidene-o-phenylenediaminate, DMSO = dimethyl sulfoxide). As a result, it was found that these uranyl(V) complexes have characteristic absorption bands in the visible-near-infrared (NIR) region, i.e., at around 640, 740, 860, 1470, and 1890 nm (molar absorptivity, epsilon = 150-900 M(-1).cm(-1)) for [U(V)O2(dbm)2DMSO]-, 650, 750, 900, 1400, and 1875 nm (epsilon = 100-300 M(-1).cm(-1)) for [U(V)O2(saloph)DMSO]-, and 760, 990, 1140, 1600, and 1800 nm (epsilon = 0.2-3.6 M(-1).cm(-1)) for [U(V)O2(CO3)3]5-. These characteristic absorption bands of the uranyl(V) complexes are attributable to the electronic transitions in the U(V)O2+ core because the spectral features are similar to each other despite the differences in the ligands coordinated to the equatorial plane of the U(V)O2+ moiety. On the other hand, the epsilon values of [U(V)O2(CO3)3]5- are quite smaller than those of [U(V)O2(dbm)2DMSO]- and [U(V)O2(saloph)DMSO]-. Such differences can be explained by the different coordination geometries around the center uranium in these uranyl(V) complexes. Consequently, the absorption bands of the uranyl(V) complexes in visible-NIR region were assigned to f-f transitions in the 5f1 configuration.     

Synthesis and X-ray structure study on new Au(I) polymer architectures based on multi-sulfur tentacles

Multi-thiolate ligands are used as a scaffold to construct a series of supramolecules, which cover the following entries; [(1,3-S₂-C₆H₄){AuP(C₆H₄-3-CF₃)₃}₂]_n (1), [(1,4-S₂-C₆H₄){AuP(C₆H₄-3-CF₃)₃}₂]_n (2), (1,4-S₂-C₆H₄){AuP(C₆H₅)₂(2-pyridine)}₂ (3), [(1,3,5-S₃-C₆H₃){AuP(C₆H₅)₂(2-pyridine)}₃]_n (4), and [(1,3,5-S₃-C₆H₃){AuP(C₆H₄-3-CF₃)₃}₃]_n (5). The molecular and crystal structures of these new derivatives have been elucidated by single crystal X-ray diffraction. Aurophilic interactions have been demonstrated for 1, 2, 4, and 5 to produce new supramolecular architectures. Nano-channels are formed by aurophilic and π-π interactions for 1, in which benzene molecules are trapped. An 8 (eight)-shaped loop is formed in solid state for 2. Infinite zigzag chains are constructed for 4 and 5.     

Chloride concentration and temperature effects on the hydration of Th(IV) ion: a molecular dynamics simulation

Molecular dynamics simulations have been performed to investigate the structural and dynamical properties of the second hydration shell of Th⁴⁺ ion at various chloride concentrations and temperatures. When the concentration increases (ca. 5 M), the hydration of Th⁴⁺ ion involves the displacement of the water molecules by Cl⁻ ligand and slightly decreases the total coordination number. The residence time of water molecules in the second hydration shell decreases as a function of increasing solution temperature.     

Topological inverse problem for oscillating systems and its application

This note is just an introduction to a problem to find a topological type of potentials from given data and a problem to see which data or experiment is necessary to obtain the topological classification of practical use. Here we propose a method of hysteresis on the space of Fourier coefficients, which reduces to the theory of resonance curves in a very special case. The direction of the hysteresis curve is proved to characterize the (first) topological type of potential. In contrast with the usual direction, which is common to the transistor oscillator, the unusual direction is found in EEG experiments (on humans) called photic driving experiments on rhythm.     

High Resolution Structure of Bacteriorhodopsin Determined by Electron Crystallography

Abstract— Bacteriorhodopsin pumps protons from the cytoplasm to the outside of halobacteria, Halobacterium salinarium , by using absorbed light energy. The newly observed density map at 3 Å resolution clarified nearly the entire structure; the resolution in the direction perpendicular to the membrane surface is 3.2 Å. The new structure clearly indicates the proton transfer pathway in bacteriorhodopsin. In particular, the location of key aspartic acid and glutamic acid residues in the derived structural model suggested funneling structures with different designs for input and output of protons on the cytoplasmic and extracellular sides, respectively, of the protein. This paper describes the major differences between the model based on the new observation and the former model obtained through crystallographic refinement by Grigorieff et al . ( J. Mol. Biol 259; 393-421, 1996).     

Heisenberg realization for U q (sl n ) on the flag manifold

We give the Heisenberg realization for the quantum algebra U _q (sl _n ), which is written by theq-difference operator on the flag manifold. We construct it from the action of U _q (sl _n ) on theq-symmetric algebraA _q (Mat _n ) by the Borel-Weil-like approach. Our realization is applicable to the construction of the free field realization for U _q [2].     

Human pre-interleukin 1 alpha and beta: structural features revealed by limited proteolysis

Both pre-interleukin 1 alpha and beta (pre IL 1 alpha and beta) are proteolytically processed into extracellular mature forms of IL 1 alpha and beta. Since pre IL 1 alpha is shown to be biologically active, there may be other reasons for the proteolytic processing of IL 1 alpha and presumably, for IL 1 beta also. In order to examine the possibility that structural stabilization may be associated with the proteolytic processing of pre IL 1 alpha and beta, we investigated the structural features of pre IL 1 alpha and beta by the combination of limited proteolysis and immunoprecipitation with antibodies to the NH2-terminal halves or COOH-terminal halves of pre IL 1 alpha or beta. Both trypsin and V8 protease digested the NH2-terminal halves of pre IL 1 alpha and beta more easily than the COOH-terminal halves of pre IL 1 alpha and beta, yielding structurally stabilized "mature" forms of IL 1. Both trypsin and V8 protease yielded a fragment similar in size to mature IL 1 alpha from pre IL 1 alpha. In contrast, trypsin digested pre IL 1 beta into fragments smaller in size than mature IL 1 beta, while V8 protease yielded a fragment similar in size to mature IL 1 beta. Furthermore, mature IL 1 beta, once processed and released from cells, was resistant to trypsin.(ABSTRACT TRUNCATED AT 250 WORDS)