The first total synthesis of ganglioside GalNAc-GD1a, a target molecule for autoantibodies in Guillain-Barré syndrome

The first synthesis of ganglioside GalNAc-GD1a, featuring efficient glycan assembly and a cyclic glucosyl ceramide as a versatile unit for ganglioside synthesis is described. Although ganglioside GalNAc-GD1a was first found as a brain ganglioside, IgG autoantibodies to GalNAc-GD1a were subsequently found to be closely related to a human peripheral-nerve disorder, Guillain-Barré syndrome, which is the commonest cause of acute flaccid paralysis worldwide. In this study, the characteristic hexasaccharide part carrying two sialic acid residues was synthesized efficiently by use of a readily accessible GM2-core unit as a common unit. The potentially difficult coupling of the oligosaccharide and ceramide moieties was carried out by using a cyclic glucosyl ceramide as a coupling partner for the hexasaccharide part, thereby successfully providing the framework of the target compound. Global deprotection delivered the homogenous ganglioside GalNAc-GD1a. An enzyme-linked immunosorbent assay showed that sera from patients with Guillain-Barré syndrome reacted both with natural and with synthetic GalNAc-GD1a.     

Preconcentration of trace aluminum from environmental water samples with 5'-chloro-5-dodecyl-2,4,2'-trihydroxyazobenzene impregnated macroporous resin.

5'-Chloro-5-dodecyl-2,4,2'-trihydroxyazobenzene (CDTA) impregnated XAD-4 resin (CDTA resin) was prepared, and applied to the preconcentration of trace aluminum from environmental water samples with satisfactory results. Aluminum was measured by flow-injection analysis (FIA) with fluorescence detection by using lumogallion after the preconcentration of aluminum with CDTA resin. Fe3+ and other coexisting substances had no interference on the determination of aluminum by the present method. Chemical speciation of trace aluminum in environmental water was carried out by using the CDTA resin after the separation of aluminum species with ionic exchangers without changing the pH. About 50% of water-soluble aluminum in Lake Biwa was found to be aluminum organic species (anion species).     

Status of bubble detectors for high-energy heavy ions

Five types of bubble detectors (T-15, T-34, T-12, T-24 and T-14) of large volume and different sensitivities were developed in the China Institute of Atomic Energy for the purpose of heavy ion research. Calibrations were carried out with beams of high-energy protons, He, C, Si, Ar, Fe, Kr and Xe, at accelerators in the energy region 150–650 MeV/u. The bubble detectors were demonstrated to be a family of detectors for recording tracks of high-energy heavy ions with atomic numbers from Z=1 (proton) to all the numbers in the whole periodic table of elements. The threshold levels of the detectors differ from each other with values 0.05±0.01 (T-15), 1.62±0.05 (T-34), 1.68±0.03 (T-12), 2.24±0.06 (T-24) and 6.04±0.80 (T-14) MeVmg⁻¹ cm², respectively, which are about the same or even lower than the levels of plastic track detectors for recording heavy ions. The distinguishing features of bubble detectors are high sensitivity, active recording, real-time display, volume registration and background discriminating capacities. Bubble detectors are a new type of high sensitivity detectors and are very promising for detection of heavy ions, neutrons and exotic particles.     

Determinations of humic substances and other dissolved organic matter and their effects on the increase of COD in Lake Biwa.

Humic substances and other dissolved organic matter (DOM) in Lake Biwa and the surrounding rivers were investigated to elucidate their origins and behavior. An annual increase in chemical oxygen demand (COD) has been observed in the northern basin of Lake Biwa since 1985. The concentrations of dissolved organic carbon (DOC) in the northern and southern basins of Lake Biwa were 1.7-2.4 mgC/l and 1.9-2.6 mgC/l, respectively. The DOC concentrations tended to be high in summer and low in winter, and the seasonal changes in the concentrations of humic substances were small. The humic substances content of DOM was considered to be comparatively small because the ratio of the concentration of humic substances to DOC was in the range of 0.14-0.32. From the results of the fractionation of DOM in lake waters, it was estimated that hydrophobic acids, such as humic substances and hydrophilic acids, were about 25% and 45%, respectively. The main origin of hydrophobic acids in Lake Biwa may be humic substances from soils around the rivers that flow into Lake Biwa, while hydrophilic acids may be due to the inner production by phytoplankton. Therefore, the increase of COD in the northern basin of Lake Biwa may be attributed to the contributions of not only humic substances but also hydrophilic acids.     

A Structurally Robust Chiral Borate Ion: Molecular Design,Synthesis, and Asymmetric Catalysis

Catalysis by chiral weakly-coordinating anions (WCAs) remains underdeveloped due to the lack of a molecular design strategy for exploiting their characteristics, such as the non-nucleophilic nature. Here, we report the development of a chiral borate ion comprising an O,N,N,O-tetradentate backbone, which ensures hitherto unattainable structural robustness. Upon pairing with a proton, the hydrogen borate acts as an effective catalyst for the asymmetric Prins-type cyclization of vinyl ethers, providing access to structurally and stereochemically defined dihydropyrans. The key to selectivity control is the distinct ability of the borate ion to discriminate the prochiral faces of the acyclic oxonium ion intermediate and dictate the regiochemical outcome. We anticipate that this study paves the way for exploring the untapped potential of WCA catalysis for selective chemical synthesis.     

Efficient Amide Bond Formation through a Rapid and Strong Activation of Carboxylic Acids in a Microflow Reactor

The development of highly efficient amide bond forming methods which are devoid of side reactions, including epimerization, is important, and such a method is described herein and is based on the concept of rapid and strong activation of carboxylic acids. Various carboxylic acids are rapidly (0.5 s) converted into highly active species, derived from the inexpensive and less‐toxic solid triphosgene, and then rapidly (4.3 s) reacted with various amines to afford the desired peptides in high yields (74 %–quant.) without significant epimerization (≤3 %). Our process can be carried out at ambient temperature, and only CO₂ and HCl salts of diisopropylethyl amine are generated. In the long history of peptide synthesis, a significant number of active coupling reagents have been abandoned because the highly active electrophilic species generated are usually susceptible to side reactions such as epimerization. The concept presented herein should renew interest in the use of these reagents.     

Four-electron shell structures and an interacting two-electron system in carbon-nanotube quantum dots

Low-temperature transport measurements have been carried out on single-wall carbon-nanotube quantum dots in a weakly coupled regime in magnetic fields. Four-electron shell filling was observed, and the magnetic field evolution of each Coulomb peak was investigated. Excitation spectroscopy measurements have revealed Zeeman splitting of single particle states for one electron in the shell, and demonstrated singlet and triplet states with direct observation of the exchange splitting at zero-magnetic field for two electrons in the shell, the simplest example of Hund's rule.     

Local magnetic fields in the Mo layer of Mo/Fe multilayer

Using time-differential perturbed-angular-correlation technique, hyperfine fields at ⁹⁹Tc (←⁹⁹Mo) in the Mo layers in polyimide/Fe (10 nm)/[Mo (t _Mo)/Fe (2.0 nm)]₁₂₀, where t _Mo is in the range between 0.4 and 1.5 nm, were measured at room temperature. The values of the magnetic hyperfine field at the Mo/Fe interface were extracted. Its dependence on the Mo layer thickness suggests that the oscillatory interlayer exchange coupling is due to conduction electron spin polarization in the Mo layer, which in turn is produced via an RKKY-type mechanism.