Multichannel autosampler for Curie-point pyrolysis capillary gas chromatography

A multichannel autosampler which can automatically analyze up to 20 samples in sequence has been developed for on-line Curie-point pyrolysis – capillary GC. The results obtained from the system show that the analysis of thermally labile samples could be performed without either thermal degradation or reaction during the waiting time before the final pyrolysis. The reproducibilities of the relative peak areas and retention times of the characteristic pyrolysates of a tricomponent copolymer were significantly better than those obtained by manual sample manipulation.     

Probing the shape and stereochemistry of molecular orbitals in locally flexible aromatic chains: a penning ionization electron spectroscopy and Green's function study of the electronic structure of biphenyl

We report on the results of an exhaustive study of the interplay between the valence electronic structure, the topology and reactivity of orbitals, and the molecular structure of biphenyl by means of Penning ionization electron spectroscopy in the gas phase upon collision with metastable He*(2(3)S) atoms. The measurements are compared with one-particle Green's function calculations of one-electron and shake-up valence ionization spectra employing the third-order algebraic diagrammatic construction scheme [ADC(3)]. Penning ionization intensities are also analyzed by means of the exterior electron-density model and comparison with photoelectron spectra: in contrast with the lines originating from sigma orbitals, ionization lines belonging to the pi-band system have large Penning ionization cross sections due to their greater extent outside the molecular van der Waals surface. The involved chemi-ionization processes are further experimentally investigated using collision-energy-resolved Penning ionization electron spectroscopy. The cross sections of pi-ionization bands exhibit a markedly negative collision-energy dependence and indicate that the interaction potential that prevails between the molecule and the He*(2(3)S) atom is strongly attractive in the pi-orbital region. On the other hand, the partial ionization cross sections pertaining to sigma-ionization channels are characterized by more limited collision-energy dependencies, as a consequence of rather repulsive interactions within the sigma-orbital region. A comparison of ADC(3) simulations with the Penning ionization electron spectra and UV photoelectron spectra measured by Kubota et al. [Chem. Phys. Lett. 1980, 74, 409] on thin films of biphenyl deposited at 170 and 109 K on copper demonstrates that biphenyl molecules lying at the surface of polycrystalline layers adopt predominantly a planar configuration, whereas within an amorphous sample most molecules have twisted structures similar to those prevailing in the gas phase.     

Stability test and improvement of hydrogen analyzer with trace reduction detector

We previously developed an analyzer able to detect hydrogen concentrations of less than 50 cm3/1000 m3. The analyzer uses a carrier gas purifier and a low temperature separation column to remove impurities preventing measurement of low concentrations from the carrier and sample gases. It uses a trace reduction detector with a mercuric oxide bed to detect the concentration of hydrogen based on the reduction reaction of mercuric oxide with hydrogen. We have now evaluated the performance of the analyzer by carrying out a series of tests that measured the spectrum peak and the retention time. We used three sample gases with hydrogen concentrations of 5, 20, and 50 cm3/1000 m3 in nitrogen dilution gas. The measured peak was stable (it was within a relative standard deviation of less than 10%), and there was a linear relationship between the peak and hydrogen concentration. However, the retention time gradually shortened as the measurements were repeated. The shortening was reduced by warming the low temperature separation column used in the analyzer; it was not observed when we used a hydrogen sample gas diluted by helium instead of nitrogen. Using nitrogen as a dilution gas apparently shortens the retention time. We thus added an MS-5A separation column and a thermal conductivity detector. The nitrogen and hydrogen in the sample/carrier gas are separated, and the nitrogen is efficiently removed by switching the pass line to a release line after the hydrogen has been sent to the low temperature separation column. An analyzer using this "after-cut method" was able to stably measure infinitesimal hydrogen concentrations and was not affected by nitrogen in the sample gas.     

Formal total synthesis of altohyrtin C (spongistatin 2). Part 1: Aldol approach to unite AB and CD spiroacetals

The Mukaiyama aldol coupling of the second-generation C1C14 (AB) fragment of altohyrtins (spongistatins) with the model α-methyl-β-alkoxyaldehydes revealed that the stereochemistry at the newly formed carbon centers was controlled by the β-alkoxy chiral center of the model aldehydes. The union of the AB fragment with the C15C28 (CD) fragment under the same conditions gave the fully elaborated C1C28 (ABCD) subunit in good yield.     

Copper(I) ion mediated self-organization of molecular rectangular boxes from 1,2-Bis(2-pyridylethynyl)benzene Ligands with bulky substituents

The reaction of chiral 1,2-bis(2-pyridylethynyl)benzene ligands with copper(I) ions in dichloromethane at room temperature gives rise to the formation of molecular rectangular boxes in high yields. The structures of these complexes were confirmed by X-ray crystallographic analysis. The compound CL1 crystallizes in the triclinic space group P1, with a = 13.707(4) A, b = 14.891(3) A, c = 12.030(1) A, alpha = 101.65(2) degrees, beta = 115.08(2) degrees, gamma = 97.66(1) degrees, V = 2110.8(2) A(3), Z = 1 (T = 288 K). The compound CL2 crystallizes in the triclinic space group P1, with a = 13.539(4) A, b = 14.755(2) A, c = 11.951(2) A, alpha = 101.70(1) degrees, beta = 115.11(1) degrees, gamma = 97.44(2) degrees, V = 2053.8(8) A(3), Z = 1 (T = 198 K). The formation of box-type structure is caused by steric hindrance between bulky substituents of the ligands.     

Spontaneous formation of core/shell bimetallic nanoparticles: a calorimetric study

We showed recently that low entropy core/shell structured nanoparticles form spontaneously from the physical mixture of a dispersion of Ag nanoparticles and that of another noble metal (Rh, Pd, or Pt) at room temperature. Here we use isothermal titration calorimetry (ITC) and show that the initial step of such a spontaneous process is strongly exothermic. When the alcohol dispersion of poly(N-vinyl-2-pyrrolidone) (PVP)-protected Rh nanoparticles (average diameter 2.3 nm) was titrated into the alcoholic dispersion of PVP-protected Ag nanoparticles, a strong exothermic enthalpy change, DeltaH, was observed: DeltaH = -908 kJ/mol for Ag(S) nanoparticle (average diameter 10.8 nm) and -963 kJ/mol for Ag(L) nanoparticles (average diameter 22.5 nm). The strength of interaction increases in the order of Rh/Ag > Pd/Ag > Pt/Ag. This strong exothermic interaction is considered as a driving force to from low entropy bimetallic nanoparticles by simple mixing of two kinds of monometallic nanoparticles. We show also that exothermic interactions occur between a pair of noble metal nanoparticles themselves by using ITC.     

Localization of Blepharismin Photosensors and Identification of a Photoreceptor Complex Mediating the Step-up Photophobic Response of the Unicellular Organism, Blepharisma

Abstract— Photosensitivity for the step-up photophobic response of Blepharisma is localized in the anterior 1/5 of the cell body. Blepharismin pigment, which is believed to be a photoreceptor pigment mediating the step-up photophobic response of the cells, was separated into five types of blepharismin (BL-1, -2, -3, -4 and -5). Blepharismin-1, -3, -4 and -5 were localized in the posterior 4/5, while BL-2 was located over the entire cell body; the anterior end, which is the photosensitive region, contained only BL-2. The results indicate that a functional photoreceptor pigment mediating the step-up photophobic response is BL-2. Hydroxylapatite chromatography revealed that BL-2 was bound to a 200 kDa membrane protein. We concluded that a photoreceptor mediating the step-up photophobic response was a BL-2/200 kDa protein complex.     

First total synthesis of (-)-AL-2

Treatment of the 3,4-dioxygenated-9-hydroxy-1-nonyn-5-one derivative, derived from diethyl l-tartrate, with a palladium catalyst in methanol under a CO atmosphere effected an intramolecular acetalization and a stereoselective construction of the (E)-methoxycarbonylmethylidene functionality resulting in formation of the core framework of the diacetylenic spiroacetal enol ether natural products. Chemical transformations of the 1,6-dioxaspiro[4.5]decane derivative thus formed led to the first total synthesis of (-)-AL-2. [reaction: see text]     

Translocation of a beta-peptide across cell membranes.

Short cationic peptides derived from DNA-binding proteins, of which HIV Tat is a prototype, can cross the membranes of living cells, and they can bring covalently attached moieties (proteins, drugs) along with them. We show that a beta-amino acid analogue of Tat 47-57 enters HeLa cells with comparable efficiency to Tat 47-57 itself (YGRKKRRQRRR). The beta-peptide is comprised of residues that bear the appropriate side chain at the beta-carbon. Both the alpha- and the beta-peptide were conjugated to fluorescein at the N terminus, and cell penetration was monitored by confocal fluorescence microscopy. Deletion of the three C-terminal arginine residues from the alpha-peptide abolished translocation activity, consistent with prior reports, and deletion of the three C-terminal beta3-homoarginine residues from the beta-peptide had a similarly adverse effect. Thus, alpha- and beta-peptide translocation processes show similar length/charge dependence. The beta-peptide appeared to be largely unfolded in water, which is consistent with the behavior of short Tat-derived alpha-peptides, but in methanol the beta-peptide adopted a helical conformation, in contrast to short Tat-derived alpha-peptides. Our results show that neither altering the oligomeric backbone (amide group spacing) nor increasing the intrinsic propensity to adopt a specific secondary structure affects translocation activity.     

Quater-, quinque-, and sexithiophene organogelators: unique thermochromism and heating-free sol-gel phase transition

A series of quater-, quinque-, and sexithiophene derivatives bearing two cholesteryl groups at the alpha-position, which are abbreviated as 4 T-(chol)(2), 5 T-(chol)(2), and 6 T-(chol)(2), respectively, have been synthesized. It has been found that these oligothiophene derivatives act as excellent organogelators for various organic fluids and show the unique thermochromic behaviors through the sol-gel phase transition. It was shown on the basis of extensive investigations, performed with UV-visible spectroscopy, circular dichroism (CD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM), that these gelators self-assemble into the one-dimensional structures in the organogels, in which the pi-block moieties of the oligothiophenes are stacked in an H-aggregation mode. Surprisingly, an AFM image shows that 4 T-(chol)(2) forms unimolecular fibers in a left-handed helical sense, whereby one pitch of the helical fiber is constructed by 400-540 4 T-(chol)(2) molecules. Very interestingly, the conformational change in the oligothiophene moieties can be visually detected: for example, 6 T-(chol)(2) shows a specific absorption maximum in the gel (lambda(max) = 389 nm) and in the solution (lambda(max) = 439 nm). In addition, a sol-gel phase transition of the 6 T-(chol)(2) gel was implemented by addition of oxidizing and reducing reagents such as FeCl(3) and ascorbic acid, respectively. The stimuli-responsive functionality of the oligothiophene-based organogels makes them promising candidates for switchable opto- and electronic soft materials.