Synthesis of DTPA-conjugated (1,4)-linked 2-aminoglycosides varying in the anomeric configuration and their MRI contrast effect

We describe the efficient synthesis of DTPA-conjugated oligosaccharides composed of alpha- and/or beta-linked tri to monoglucosamines. Gd(iii) complex with DTPA-conjugated chitotriitol has been reported to be an effective MRI contrast agent. In order to elucidate the structure-property relationships, we planned to synthesize the DTPA-conjugated 2-amino-tri-, di-, and monosaccharides varying in configuration at the anomeric positions and the C2 position on the reducing end. Our strategy for the synthesis of the DTPA-conjugated oligosaccharides involves O-perbenzyl protected 2-amino-tri-, di-, and monosaccharides as key intermediates. The 2-aminoglycosides were prepared by non-selective glycosidation of 2-azido-2-deoxyglycosyl donors, followed by separation of two anomeric isomers. Although the synthesis involves separation of the stereoisomers, it circumvents not only the careful tuning of reaction conditions, but also the time-consuming preparation of glycosyl donors attached to different protecting groups. The protected 2-aminoglycosides were converted to the fully deprotected DTPA-conjugated tri- to monosaccharides by the same operation. MRI phantom study using the Gd(III) complexes of DTPA-conjugated oligosaccharides indicates that the number of the monosaccharide units was critical for enhancing the relative signal intensity of water protons per Gd, and various stereoisomers would be candidate scaffolds for MRI contrast agents.     

Evidence for muon neutrino oscillation in an accelerator-based experiment

We present results for nu(mu) oscillation in the KEK to Kamioka (K2K) long-baseline neutrino oscillation experiment. K2K uses an accelerator-produced nu(mu) beam with a mean energy of 1.3 GeV directed at the Super-Kamiokande detector. We observed the energy-dependent disappearance of nu(mu), which we presume have oscillated to nu(tau). The probability that we would observe these results if there is no neutrino oscillation is 0.0050% (4.0 sigma).     

A relation between the zeros of an <Emphasis Type="Italic">L</Emphasis>-function belonging to the Selberg class and the zeros of an associated <Emphasis Type="Italic">L</Emphasis>-function twisted by a Dirichlet character

Let F (s) be a function belonging to the Selberg class. For a primitive Dirichlet character , we can define the -twist F(s) of F (s). If F(s) also belongs to the Selberg class and satisfies some other conditions then there is a relation between the zeros of F (s) and the zeros F(s). Further we give an operator theoretic interpretation of this relation according to A. Connes study.Received: 5 January 2004     

Single-particle light scattering study of polyethyleneglycol-grafted poly(ureaurethane) microcapsule in ethanol

Microcapsules having polyethyleneglycol-grafted poly(ureaurethane) (PUU) membrane and di-2ethylhexyl phthalate core have been prepared, and the structure when they were suspended in dispersing ethanol have been studied by means of single-particle light scattering method. The PUU membrane was synthesized from monomers with aromatic functional groups (microcapsule MC110) and hexamethylene functional groups (microcapsule MC160). Because the outer and inner solvent passed through the membrane easily, the outside and inside of the membrane were the same at the equilibrium state. The thickness of the wall membrane was significantly smaller than that calculated from the overall weight ratio of the wall-forming material and the core solvents. It was attributed to low affinity of PUU membranes and ethanol.     

1,8-bis(diphenylmethylium)naphthalenediyl dication as an organic oxidant: synthesis of benzidines via self-coupling of N,N-dialkylanilines

1,8-Bis(diphenylmethylium)naphthalenediyl dications promoted oxidative coupling of various N,N-dialkylanilines to afford the corresponding para-coupled bisanilines, benzidines, in good to excellent yield. The dications were readily prepared from a cyclic ether precursor, derived from 1,8-dibromonaphthalene, via deoxygenation with a silylating reagent in 1,1,1,3,3,3-hexafluoro-2-propanol under anhydrous conditions. [reaction: see text]     

STM-based molecular detection of "catch-and-release" of protons for bipyridine bound to phenylene-ethynylene thiol

The protonation/deprotonation response of a novel bipyridine containing (phenylene-ethynylene) thiol adsorbed to a Au surface was investigated with scanning tunneling microscopy (STM), showing reversible changes in the average heights (approximately 50 spots) and the height distribution arising from protonation/deprotonation.     

High-speed separation system of randomly suspended single living cells by laser trap and dielectrophoresis

We developed a new system for random separation of a single microorganism, such as a living cell and a microbe, in the microfluidic device under the microscope by integrating the laser-trapping force and dielectrophoretic (DEP) force. An arbitrarily selected single microbe could be isolated in a microchannel, despite the presence of a large number of microbes in solution. Once the target microbe is trapped at the focal point of the laser, we can easily realize exclusion of excess microbes around the target by controlling the electric field, while keeping the target trapped by the laser at the focal point. To realize an efficient separation system, we proposed a new separation cell and produced it by microfabrication. Flow speed in the microchannel is adjusted and balanced to realize high-speed and high-purity extraction of the target. Some preliminary experiments are conducted to show the effectiveness. The target is trapped by the laser, transported, and is taken out from the extraction port. Total separation time is less than 20 s. Our method is extremely useful in the pure cultivation of the cell and will be a promising method for biologists in screening useful microbes.     

Formation and Characterization of Reversed Micelles Composed of Phospholipids and Fatty Acids

The formation of reversed micellar systems composed of phosphatidylcholine (PC) and fatty acid was newly demonstrated by a significant increase in water content in the organic ethyl oleate phase when the micelles were prepared by the contact method. The solubilized water concentration in the reversed micellar organic phase reached 3 wt%. The new systems are expected to be used as highly biocompatible reversed micellar systems. The structure of the reversed micelles composed of PC and oleic acid was characterized by determining the water concentration and by small-angle X-ray scattering analysis. The reversed micelles composed of PC and oleic acid formed in ethyl oleate were spherical. The radius of gyration was between 30 and 50 Å. The size of the reversed micelles decreased with an increase in the oleic acid concentration and was independent of the PC concentration. Experimental results indicated that the structure of the reversed micellar system was determined by the oleic acid concentration. An increase in the PC concentration caused an increase in the number of reversed micelles of the same size. These reversed micellar systems are expected to be used as solubilization media in pharmaceutical and food industries because they are not toxic.