First observation of a smectic A-cholesteric phase transition in a thermotropic liquid crystal consisting of a rigid-rod helical polysilane

A smectic A-cholesteric phase transition for a rigid-rod helical polymer, poly[n-decyl-(S)-2-methylbutylsilane] (PD2MBS), with a narrow molecular weight distribution, has been observed for the first time. Polarizing optical microscopy showed that the fan-shaped texture of the smectic A phase turned into the characteristic planar texture of the cholesteric phase upon heating. The positive CD band, which corresponds to the reflection band of the cholesteric phase, gradually decreased in intensity within a range 30°C below the transition temperature on cooling, while the peak maximum shifted towards shorter wavelengths. It was concluded that the system has a very wide temperature region over which the cholesteric-smectic A phase transition occurs and in which the cholesteric pitch varies with temperature.     

Latticelike smectic liquid crystal phase in a rigid-rod helical polyisocyanide with mesogenic pendants

We report a unique macromolecule consisting of a rodlike helical polyisocyanide backbone with a narrow molecular weight distribution and rigid mesogenic chiral pendants linked via a flexible spacer that exhibits lyotropic nematic and latticelike new smectic (lat-Sm) liquid crystal phases at different concentrations. The unprecedented lat-Sm phase is associated with the smectic ordering of both the stiff polymer backbone and the rigid-rod side groups. A detailed investigation of the films using X-ray scattering and atomic force microscopy revealed a novel tilted smectic layer structure of the polymer backbone aligned perpendicular to the smectic layer of the mesogenic pendants, which arrange in an antiparallel overlapping interdigitated manner.     

Use of the MALDI BioTyper system with MALDI–TOF mass spectrometry for rapid identification of microorganisms

In a clinical diagnosis microbiology laboratory, the current method of identifying bacterial isolates is based mainly on phenotypic characteristics, for example growth pattern on different media, colony morphology, Gram stain, and various biochemical reactions. These techniques collectively enable great accuracy in identifying most bacterial isolates, but are costly and time-consuming. In our clinical microbiology laboratory, we prospectively assessed the ability of matrix-assisted laser desorption ionization–time of flight mass spectrometry (MALDI–TOF MS) to identify bacterial strains that were routinely isolated from clinical samples. Bacterial colonies obtained from a total of 468 strains of 92 bacterial species isolated at the Department of Clinical Laboratory at Chiba University were directly placed on target MALDI plates followed by addition of CHCA matrix solution. The plates were then subjected to MALDI–TOF MS measurement and the microorganisms were identified by pattern matching with the libraries in the BioTyper 2.0 software. Identification success at the species and genus levels was 91.7% (429/468) and 97.0% (454/468), respectively. MALDI–TOF MS is a rapid, simple, and high-throughput proteomic technique for identification of a variety of bacterial species. Because colony-to-colony differences and effects of culture duration on the results are minimal, it can be implemented in a conventional laboratory setting. Although for some pathogens, preanalytical processes should be refined, and the current database should be improved to obtain more accurate results, the MALDI–TOF MS based method performs, in general, as well as conventional methods and is a promising technology in clinical laboratories.     

Identification and stereochemical assignment of the beta-hydroxytryptophan intermediate in the echinomycin biosynthetic pathway

[reaction: see text] Little is known about how quinoxaline-2-carboxylic acid (QC) is synthesized in nature. On the basis of analysis of echinomycin biosynthetic gene clusters as well as feeding experiments with labeled precursors, we have proposed a biosynthetic pathway to QC and identified the (2S,3S)-beta-hydroxytryptophan as a key intermediate.     

A 116-Nuclear Metallosupramolecular Cage-of-Cage Showing Multistep Single-Crystal-to-Single-Crystal Transformation

Here a unique single-crystal-to-single-crystal (SCSC) transformation of a 116-nuclear Au^I₇₂Cd^II₄₀Na^I₄ cage-of-cage ( 2 _CdNa) is reported, which was created from a trigold(I) metalloligand with d -penicillamine by way of a 9-nuclear Au^I₆Cd^II₃ cage ( 1 ). Cage-of-cage 2 _CdNa is composed of 12 cages of 1 that are linked by 4 Cd²⁺ and 4 Na⁺ ions, with its surface being covered by 12 NO₃⁻ ions to form a discrete, spherical molecule with a diameter ca. 4.7 nm. In crystal 2 _CdNa, the cage-of-cage molecules are packed in a cubic lattice with a huge cell volume of ca. 4.5×10⁵ ų_, so as to have large interstices with diameters of more than 3 nm. Upon soaking crystals 2 _CdNa in aqueous Cu(NO₃)₂, all Cd²⁺ and Na⁺ were quickly exchanged by Cu²⁺ to produce an analogous Au^I₇₂Cu^II₄₄ cage-of-cage ( 2 _Cu) in a SCSC manner. Prolonged soaking led to the SCSC transformation to another supramolecular structure ( 2′ _Cu) consisting of 152-nuclear Au^I₇₂Cu^II₈₀ cage-of-cages that are alternately H-bonded with the Au^I₇₂Cu^II₄₄ cage-of-cages. 2′ _Cu showed the accommodation of MoO₄²⁻ and the conversion of MoO₄²⁻ to β-Mo₈O₂₆⁴⁻ in the crystal, with retention of single-crystallinity.     

Control of chain ends of polyesters in polycondensation of AA and BB monomers by use of solid‐phase reagent

For selective synthesis of linear polyester having a functional group at one end, polycondensation between 1,4‐butanediol ( 1a ) and sebacoyl chloride ( 2a ) and between 1,12‐dodecanediol ( 1b ) and isophthaloyl chloride ( 2b ) was conducted in the presence of oxime resin or oxime silica gel, followed by cleavage of the formed polyester from the solid‐phase support with aniline. Matrix‐assisted laser desorption ionization time‐of‐flight mass spectra and ¹H NMR spectra of the cleaved polyester showed that the products contained not only polyester with anilide at one end ( poly 1 ), but also polyester with anilides at both ends ( poly 2 ). The product ratio of poly 1 to poly 2 ( poly 1 / poly 2 ) was dependent on monomers, monomer concentration, feed ratio of monomer to oxime moiety in the support, oxime content in the support, reaction solvent, and the nature of the support. Polyester with a high poly 1 / poly 2 ratio of 81/21 and moderate molecular weight (M_n = 1430 g/mol) was obtained by polycondensation of 1b and 2b in the presence of oxime silica gel in dichloromethane. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1379–1386     

Helix-sense controlled polymerization of a single phenyl isocyanide enantiomer leading to diastereomeric helical polyisocyanides with opposite helix-sense and cholesteric liquid crystals with opposite twist-sense

We report the unprecedented helix-sense controlled polymerization of enantiomerically pure phenyl isocyanides bearing an l- or d-alanine pendant with a long alkyl chain. The polymerization with an achiral nickel catalyst diastereoselectively proceeds, resulting in either a right- or left-handed helical polymer, whose helix-sense can be controlled by the polymerization solvent and temperature. Both the diastereomeric right- and left-handed helical polymers further self-assemble into lyotropic cholesteric liquid crystals with opposite twist-senses. Consequently, the macromolecular helicity and mesoscopic, supramolecular cholesteric twist can be controlled by the molecular chirality of the pendant of a single enantiomeric phenyl isocyanide through the polymerization under either kinetic or thermodynamic control assisted by hydrogen bonds. High-resolution atomic force microscopy revealed their helical conformations and enabled the determination of the helical sense.     

Dynamics of a bilayer membrane with membrane-solvent partial slip boundary conditions

We discuss the dynamics of a bilayer membrane with partial slip boundary conditions between the monolayers and the bulk fluid. Using Onsager’s variational principle to account for the associated dissipations, we derive the coupled dynamic equations for the membrane height and the excess lipid density. The newly introduced friction coe?cients appear in the renormalized fluid viscosities. For ordinary lipid bilayer membranes, we find that it is generally justified to ignore the e?ects of permeation and parallel slip at the membrane surface.