Recent advances in capillary isoelectric focusing: 1997-2001

The methodological developments in the field of capillary isoelectric focusing (CIEF) published between 1997-2001 are reviewed as a continuation of the previous review by Rodriguez-Diaz et al. (Electrophoresis 1997, 18, 2134-2144). The applications are summarized and the progress in CIEF technologies, including experimental setup with coated and uncoated capillaries, remedies for the presence of salts in samples, additives to reduce precipitation of samples during the focusing process, calibration of the pH gradients, issues of reproducibility, carrier ampholyte-free CIEF, and a computer simulation of focusing process are discussed. Developments of IEF separations in fabricated microchannels and the advances in detection schemes, i.e., imaging, fluorescence and chemiluminescence, are summarized. The progress in micropreparation was noted, and the massive works for two-dimensional separations are described for the coupling with size-exclusion chromatography and mass spectrometry, in which the developments aimed at proteomics are discussed separately. The applications for the detection of noncovalent complexes and the separations of microorganisms are reviewed.     

Radical-initiated homopolymerization and copolymerization of ethyl α-hydroxymethylacrylate

Ethyl α-hydroxymethylacrylate (EHMA) was synthesized and homopolymerized in bulk and in solution. The poly(EHMA) is readily soluble in alcohol, acetone, tetrahydrofuran, and methylene chloride at room temperature. Intramolecular lactone formation occurred when poly(EHMA) was heated to 180–230°C. The kinetics of EHMA homopolymerization was investigated in ethyl acetate, using α,α′-azobisisobutylonitrile as an initiator. The rate of polymerization R_p was expressed by R_p = k[AIBN]^0.50[EHMA]^1.4 and the overall activation energy was calculated as 71.9 kJ/mol. Kinetic constants for EHMA polymerization were obtained as follows: k_p/k = 0.17L^0.9mol^?0.9s^?0.5; 2fk_d = 1.5 × 10^?5 s^?1. The relative reactivity ratios of EHMA(M₂) copolymerization with styrene (r₁ = 0.472, r₂ = 0.564) in ethyl acetate were obtained. Applying the Q-e scheme led to Q = 0.84 and e = 0.35 for EHMA.     

Metallic Na formation in/on NaCl crystals with irradiation by electron or vacuum ultraviolet photons

Metallic Na was formed in/on NaCl single crystals by irradiating them with a variety of radiation sources, namely, 21 MeV electron pulses, an electron beam of 30 keV and photon fluxes in the VUV region. The physical states were analysed using several methods, optical absorption, lifetime measurement of positron annihilation, Auger electron spectroscopy and UV photoelectron spectroscopy. Metallic Na was obtained in different physical states; clusters were formed in bulk, thin layers (islands) and thick layers on the surface.     

Growth of single-layer carbon tubes assisted with iron-group metal catalysts in carbon arc

Single-layer (SL) carbon tubes were produced by arc evaporation of graphite rods containing iron-group metals (Fe, Co, Ni, Fe/Co, Co/Ni, Fe/Ni) under He and Ar gas. Transmission electron microscopy (TEM) revealed that these elemental and binary metals, excluding Fe which need a special atmosphere (a mixture of Ar and CH₄), showed catalytic activity producing SL tubes under pure inactive gases. Fe/Ni alloy was the most effectual catalysts for producing SL tubes. The highest abundance of SL tubes in raw soot was estimated to be ～ 10% from TEM observation. Smoke particles directly caught on TEM grids near an evaporation source during arcburning were also investigated, and it was suggested that small metal particles were first formed in the gas phase and then SL tubes grew from them.     

Melting points and thermal expansivities of proton-disordered hexagonal ice with several model potentials

A method of free energy calculation is proposed, which enables to cover a wide range of pressure and temperature. The free energies of proton-disordered hexagonal ice (ice Ih) and liquid water are calculated for the TIP4P [J. Chem. Phys. 79, 926 (1983)] model and the TIP5P [J. Chem. Phys. 112, 8910 (2000)] model. From the calculated free energy curves, we determine the melting point of the proton-disordered hexagonal ice at 0.1 MPa (atmospheric pressure), 50 MPa, 100 MPa, and 200 MPa. The melting temperatures at atmospheric pressure for the TIP4P ice and the TIP5P ice are found to be about T(m)=229 K and T(m)=268 K, respectively. The melting temperatures decrease as the pressure is increased, a feature consistent with the pressure dependence of the melting point for realistic proton-disordered hexagonal ice. We also calculate the thermal expansivity of the model ices. Negative thermal expansivity is observed at the low temperature region for the TIP4P ice, but not for the TIP5P ice at the ambient pressure.     

On the thermodynamic stability and structural transition of clathrate hydrates

Gas mixtures of methane and ethane form structure II clathrate hydrates despite the fact that each of pure methane and pure ethane gases forms the structure I hydrate. Optimization of the interaction potential parameters for methane and ethane is attempted so as to reproduce the dissociation pressures of each simple hydrate containing either methane or ethane alone. An account for the structural transitions between type I and type II hydrates upon changing the mole fraction of the gas mixture is given on the basis of the van der Waals and Platteeuw theory with these optimized potentials. Cage occupancies of the two kinds of hydrates are also calculated as functions of the mole fraction at the dissociation pressure and at a fixed pressure well above the dissociation pressure.     

Cationic ring-opening polymerization of 1,4-anhydro-2,3-di-O-benzyl-α-L-arabinopyranose and synthesis of L-arabinofuranan

1,4-Anhydro-2,3-di-O-benzyl-α-L -arabinopyranose (=1,5-anhydro-2,3-di-O-benzyl-β-L -arabinofuranose) (ABAP) was synthesized and underwent cationic ring-opening polymerization with several kinds of Lewis acids. All the polylmers prepared by Lewis acids as catalyst were found to consist of two different structural units, α-furanosidic and β-furanosidic units, and the structure of the polymers greatly depended on the polymerization conditions. Polymerization of ABAP with antimony pentachloride catalyst at 0°C for 42 h gave a polymer with the highest α content of 93%, and that at ?20°C for 3 h gave a polymer with the lowest (25%) α content. The other catalysts such as phosphorus pentafluoride, boron trifluoride etherate, niobium pentafluoride, and tantalum pentafluoride also afforded polymers with mixed structure of α-and β-furanosides. After debenzylation of poly(ABAP), a new polysaccharide, L -arabinofuranan was obtained.     

Broad spectrum and mode of action of an antibiotic produced byScytonema sp. TISTR 8208 in a seaweed-type bioreactor

A photobioreactor was constructed using anchored polyurethane foam strips (1 x 1 x 40 cm) fixed onto a stainless-steel ring to prevent flotation, as a biomass support material (BSM). This type of reactor was named a seaweed-type bioreactor. A filamentous cyanobacterium, Scytonema sp. TISTR 8208, which produces a novel cyclic dodecapeptide antibiotic, was immobilized in seaweed-type photobioreactor and cultivated with air containing 5% CO₂ sparged at a gas flow rate of 250 mL/min under illumination at a light intensity of 200 μmol photon m^-2s^-1. The antibiotic produced in the seaweed-type photobioreactor was purified by HPLC and examined regarding its spectrum and mode of action. The antibiotic effectively inhibited the growth of Gram-positive bacteria, pathogenic yeasts, and filamentous fungi, but it had only a weak effect on Gram-negative bacteria. Scanning electron micrograph analysis showed that the most characteristic change was swelling of the cells after exposure to the antibiotic. The antibiotic seems to alter the conformation of the microbial cell membrane, thereby changing its permeability, leading to osmotic shock.     

Lannotinidines A-G, new alkaloids from two species of Lycopodium

Seven new Lycopodium alkaloids, lannotinidines A-G (1-7), have been isolated from the club moss Lycopodium annotinum and L. annotinum var. acrifolium. Stereochemistry of 1-7 was elucidated by combination of NOESY correlations and chemical transformation. Lannotinidines B-E (2-5) elevated NGF mRNA expression.