Measurement of the absolute oscillator strengths of gadolinium using an atomic vapor produced by electron beam heating

The absolute values of the oscillator strength ƒ were measured for the six spectral lines of Gd by means of laser absorption spectroscopy with the atomic vapor produced by electron beam heating. The ƒ values obtained for the transition are 0–17381 cm⁻¹, 215–17750 cm⁻¹, 533–17795 cm⁻¹, 999–18070 cm⁻¹, 999–17931 cm⁻¹, 1719–18070 cm⁻¹ were obtained to be 0.0036, 0.012, 0.014, 0.019, 0.0075 and 0.039, respectively. The error of ƒ values was 24% due to uncertainty of metastable states' density.     

Apparent Production of Enzymatically Synthesized Amylose in DMSO by Means of Calcium Alginate Hydrogel Beads/DMSO System

In this paper, we describe the apparent production of enzymatically synthesized amylose in DMSO by means of the calcium alginate hydrogel beads/DMSO system as the reaction field of the phosphorylase-catalyzed enzymatic polymerization. When the calcium alginate hydrogel beads including glucose-1-phosphate, maltoheptaose, and phosphorylase were suspended in DMSO and the system was slowly stirred at 40°C for 12 h, the reaction proceeded to produce amylose, which eluted to the DMSO solution. The obtained amylose was purified by the treatment with ion-exchange resins, and its structure was confirmed by the ¹H NMR spectrum. The time-course experiment in the present system revealed that the phosphorylase-catalyzed enzymatic polymerization was carried out for 15 min on the inside of the calcium alginate hydrogel beads and the produced amylose was gradually eluted to the surrounding DMSO solution. The comparison of the present system with the general enzymatic polymerization in aqueous buffer solution suggested that the yield and the degree of polymerization of amylose in the present system were comparable to those in aqueous buffer solution.     

Polymerization-induced phase separation in silica sol-gel systems containing formamide

Silica gels with well-defined pores both in micrometer and nanometer ranges were obtained by acid-catalyzed hydrolysis and polymerization of tetramethoxysilane in the presence of formamide. The micrometer-range structures of these gels are studied in terms of the phase diagram of the quasi two-component system, namely solvent-rich and silica-rich end compositions. The resulting interconnected structures and aggregates of particles are related to the occurrence of spinodal phase separation. The composition region that gave interconnected structures for the present system was much more limited and their characteristic sizes were much smaller than those for the previously reported systems containing an organic polymer. These results could be explained qualitatively by the effect of the degree of polymerization on the Flory-Huggins' type free energy change of mixing.     

Synthesis of hetero- and carbocycles by nucleophilic substitution at sp carbon

Vinylic halides having alcohol, sulfonamide, active methine, and thiol moieties as nucleophiles cyclize to hetero- and carbocycles by intramolecular nucleophilic substitution at the sp² carbon centers. The density functional theory calculations suggest that the cyclization proceeds through S_N2-type substitution (the in-plane vinylic nucleophilic substitution, S_NVσ), when vinyl halides are substituted with oxygen, nitrogen, and carbon nucleophiles. The substitution with sulfur nucleophiles, in contrast, proceeds through both routes of S_NVσ and out-of-plane vinylic nucleophilic substitution (S_NVπ).     

Electrochemical impedance spectroscopy study of a hydrogen electrode reaction at a Zn electrode in a molten LiCl-KCl-LiH system

The hydrogen electrode reaction involving hydride ion, H-, at a Zn electrode is investigated in a molten LiCl-KCl-LiH system at 673 K. The charge-transfer resistances were measured by electrochemical impedance spectroscopy in the overpotential region of 0.10 < or = eta < or = 0.35 V and over the H- concentrations of 1.5 x 10(-4) < or = C(H)- < or = 1.2 x 10(-3) mol cm(-3). The logarithm plot of the charge-transfer resistance against the overpotential at C(H)- = 3.0 x 10(-4) mol cm(-3) gives the symmetry factor, beta, of 0.50 and the exchange current density, j0, of 5.8 x 10(-3)A cm(-2), respectively. Analysis of the dependence of j0 on H- concentration independently gives a beta of 0.55. The reasonable beta values indicate that the H- <==> H(ad)(M) + e- step is rate-determining.     

Metal assembly in novel dendrimers with porphyrin cores

A series of phenylazozmethine (DPA) dendrimers with a porphyrin core (PnH2) were synthesized by dehydration using TiCl4 from meso-tetrakis(4-aminophenyl)porphyrin and the DPA dendrons. The addition of SnCl2 to a dichloromethane/acetonitrile solution of dendritic cobalt porphyrin resulted in a stepwise spectral change. By using UV-vis spectroscopy to monitor the complexation of the P4CoIIICl until an equimolar amount of SnCl2 has been added, four changes in the position of the isosbestic point were observed during the addition of SnCl2. Titration results suggest that four different complexes are successively formed upon the SnCl2 addition and that the complexation proceeds in, not a random, but a stepwise fashion from the core imines to the terminal imines of P4CoIIICl. The electrochemical study reveals that their dendrimers with Tb ion act as a multielectron mediator in CO2 reduction at high applied potential on the electrode.     

Preparation of O-1∼C-6 and O-7∼C-14 fragments of colletodiol

(5S,2E)-5-Tetrahydropyranyloxy-2-hexenoic acid and p-toluenesulfonylethyl (4R,5R,7R,2E)-7-hydroxy-4,5-dimethylmethylenedioxy-2-octenoate were prepared from ethyl acetoacetate and D-glucose, respectively.     

Prediction of membrane protein structures by replica-exchange Monte Carlo simulations: case of two helices

We test our prediction method of membrane protein structures with glycophorin A transmembrane dimer and analyze the predicted structures in detail. Our method consists of two parts. In the first part, we obtain the amino-acid sequences of the transmembrane helix regions from one of existing WWW servers and use them as an input for the second part of our method. In the second part, we perform a replica-exchange Monte Carlo simulation of these transmembrane helices with some constraints that indirectly represent surrounding lipid and water effects and identify the predicted structure as the global-minimum-energy state. The structure obtained in the case for the dielectric constant epsilon=1.0 is very close to that from the nuclear magnetic resonance experiments, while that for epsilon=4.0 is more packed than the native one. Our results imply that the helix-helix interaction is the main driving force for the native structure formation and that the stability of the native structure is determined by the balance of the electrostatic term, van der Waals term, and torsion term, and the contribution of electrostatic energy is indeed important for correct predictions. The inclusion of atomistic details of side chains is essential for estimating this balance accurately because helices are tightly packed.     

Capillary high-performance liquid chromatography/electrospray ion trap time-of-flight mass spectrometry using a novel nanoflow gradient generator

A type of high-performance liquid chromatography (HPLC) based on a novel nanoflow gradient generator (Asymptotic-Trace-10-Port-Valve (AT10PV) nanoGR generator) was developed and coupled with an electrospray ion trap time-of-flight mass spectrometer (ESI-IT-TOF MS). Stability of the nanoflow GR HPLC system was tested at flow rates of 20 and 50 nL/min by using a nanoflow meter. Average flow rates in a 2-h run were 51.2 nL/min with RSD 0.7% and 21.0 nL/min with RSD 1.8%. Repeatability of analysis of the nanoHPLC/ESI-IT-TOF MS system was also tested by injecting 1.0 microL of trypsin digested bovine serum albumin (BSA) (100 fmol) into a monolithic silica-ODS column (30 microm i.d., 150 mm in length) through a packed silica-ODS trapping column (particle size 5 microm, 150 microm i.d., 10 mm in length). At a flow rate of 50 nL/min, the result demonstrated a reasonably good repeatability of peak retention times (RSD: 0.32-1.1%) and base-ion peak areas (RSD: 4.4-6.6%).