Low temperature properties of acetonitrile confined in MCM-41

The effect of confinement on the phase changes and dynamics of acetonitrile in mesoporous MCM-41 was studied by use of adsorption, FT-IR, DSC, and quasi-elastic neutron scattering (QENS) measurements. Acetonitrile molecules in a monolayer interact strongly with surface hydroxyls to be registered and perturb the triple bond in the C[triple bond]N group. Adsorbed molecules above the monolayer through to the central part of the cylindrical pores are capillary condensed molecules (cc-acetonitrile), but they do not show the hysteresis loop in adsorption-desorption isotherms, i.e., second order capillary condensation. FT-IR measurements indicated that the condensed phase is very similar to the bulk liquid. The cc-acetonitrile freezes at temperatures that depend on the pore size of the MCM-41 down to 29.1 A (C14), below which it is not frozen. In addition, phase changes between alpha-type and beta-type acetonitriles were observed below the melting points. Application of the Gibbs-Thomson equation, assuming the unfrozen layer thickness to be 0.7 nm, gave the interface free energy differences between the interfaces, i.e., Deltagamma(l/alpha) = 22.4 mJ m(-2) for the liquid/pore surface (ps) and alpha-type/ps, and Deltagamma(alpha/beta) = 3.17 mJ m(-2) for alpha-type/ps and beta-type/ps, respectively. QENS experiments substantiate the differing behaviors of monolayer acetonitrile and cc-acetonitrile. The monolayer acetonitrile molecules are anchored so as not to translate. The two Lorentzian analysis of QENS spectra for cc-acetonitriles showed translational motion but markedly slowed. However, the activation energy for cc-acetonitrile in MCM-41 (C18) is 7.0 kJ mol(-1) compared to the bulk value of 12.7 kJ mol(-1). The relaxation times for tumbling rotational diffusion of cc-acetonitrile are similar to bulk values.     

An efficient solid‐state polycondensation method for synthesizing stereocomplexed poly(lactic acid)s with high molecular weight

Simultaneous solid‐state polycondensation (SSP) of the powdery prepolymers of poly(L ‐lactic acid) (PLLA) and poly(D ‐lactic acid) (PDLA) can produce entire stereocomplexed poly(lactic acid)s (sc‐PLA) with high molecular weight and can be an alternative synthetic route to sc‐PLA. Ordinary melt polycondensations of L ‐ and D ‐lactic acids gave the PLLA and PDLA prepolymers having medium molecular weight which were pulverized for blending in 1:1 ratio. The resultant powder blends were then subjected to SSP at 130–160 °C for 30 h under a reduced pressure of 0.5 Torr. Some of the products thus obtained attained a molecular weight (M_w) as high as 200 kDa, consisting of stereoblock copolymer of PLLA and PDLA. A small amount of the stereocomplex should be formed in the boundaries of the partially melted PLLA and PDLA where the hetero‐chain connection is induced to generate the blocky components. The resultant SSP products showed predominant stereocomplexation after their melt‐processing in the presence of the stereoblock components in spite of containing a small amount of racemic sequences in the homo‐chiral PLLA and PDLA chains. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3714–3722, 2008     

Monte carlo simulations for blue-phase structure in liquid crystals

Blue-phase liquid crystals form three-dimensional structures in a self-organizing manner and are similar to living tissue structures such as the teeth of mice and collagen tissues. This study presents numerical results regarding the conditions under which blue-phase liquid crystals occur. The Monte Carlo simulations are performed by employing an improved Lennard–Jones potential that considers anisotropy and chirality. The conditions for the formation of the blue phase, which vary with respect to the chirality, are examined first. The relationship between the anisotropic parameters and the chiral parameter for the formation of the blue phase is discussed. Identical blue-phase structures are obtained, even when the cell size and molecular number are varied drastically. This discussion is useful for considering the scale-up problem, which is almost always a difficult issue for molecular-scale simulations.     

A topological splitting theorem for sub-Riemannian manifolds

We prove an analogue of the Cheeger–Gromoll splitting theorem for sub-Riemannian manifolds with the measure contraction property instead of the nonnegativity of the Ricci curvature. If such a sub-Riemannian manifold contains a straight line, then the manifold splits diffeomorphically, where the splitting is not necessarily isometric. We prove that such a sub-Riemannian manifold containing a straight line cannot split isometrically under some typical condition in sub-Riemannian geometry. Heisenberg groups are such examples.     

Development of Yellow-to-Orange Photoluminescence Molecules Based on Alterations in the Donor Units of Fluorinated Tolanes

Since the aggregation-induced emission (AIE) phenomenon was first reported by Tang et al., much effort has been devoted to the development of solid-state luminescent molecules by chemists worldwide. Our group successfully developed fluorinated tolanes as novel compact π-conjugated luminophores with blue photoluminescence (PL) in the crystalline state. Moreover, we reported the yellow-green PL molecules based on their electron-density distributions. In the present study, we designed and synthesized fluorinated tolanes with various amine-based donors and evaluated their photophysical properties. The carbazole-substituted fluorinated tolane exhibited strong PL in the solution state, whereas piperidine- or phenothiazine-substituted fluorinated tolanes showed a dramatic decrease in PL efficiency. Notably, fluorinated tolanes with piperidine or phenothiazine substituents displayed yellow-to-orange PL in the crystalline state; this may have occurred because these tolanes exhibited tightly packed structures formed by intermolecular interactions, such as H···F hydrogen bonds, which suppressed the non-radiative deactivation process. Moreover, fluorinated tolanes with amine-based donors exhibited AIE characteristics. We believe that these yellow-to-orange solid PL molecules can contribute to the development of new solid luminescent materials.     

Altered posttranslational modification on U1 small nuclear ribonucleoprotein 68k in systemic autoimmune diseases detected by 2D Western blot

Anti-ribonucleoprotein (anti-RNP) antibodies are one of the representative autoantibodies detectable in patients with systemic lupus erythematosus (SLE) and mixed connective tissue disease (MCTD). Generally, posttranslational modifications (PTMs) on autoantigens are proposed to be involved in the production of autoantibodies. In this study, we tried to detect the alteration in PTMs on a U1 small nuclear RNP 68k subunit (U1-68k), a major antigen of anti-RNP antibodies. Peripheral blood mononuclear cells (PBMCs) were obtained from patients with MCTD, SLE, and rheumatoid arthritis (RA), and from healthy donors. U1-68ks in the PBMCs were detected by 2D Western blot (WB), where extracted nuclear proteins were separated by 2DE, followed by the detection of U1-68k using WB. More than 20 PTM isoforms were detected with different molecular weights of 65.0 , 66.5, and 68.0kDa, and different pIs between 6.0 and 8.5. Importantly, the relative intensity of the spot with 66.5 kDa and pI 7.5 was significantly increased in the MCTD and SLE groups compared to the RA and healthy groups. Further, this U1-68k isoform, in particular, in its RS domain, was found to have significantly decreased phosphorylation compared to the other isoforms. The PTM alternation may be one of the steps to generate the anti-RNP antibodies.     

Chemical constituents of Bolbostemma paniculatum (Maxim) Franquet: III. Structure of tubeimoside I

From the bulbs of Bolbostemma paniculatum (Maxim) Franquet (Cucurbitaceae), five glycosides: tubeimosides I, II, III, IV, and V were isolated. The structure of the tubeimoside I was elucidated by degradation and spectral analyses. It has inter-saccharide chain bridgied by a dicrotalic acid to form a unique macrocyclic structure.     

Carbamate mediated functionalization of unsaturated alcohols II. Regio- and stereo-selective synthesis of 1,3-syn and 1,2-anti amino alcohol derivatives via iodocarbamation

A regio- and stereo-selective introduction of nitrogen functions to double bonds of acyclic, allylic and homoallylic alcohols was achieved via iodocyclization of the corresponding N-sulfonylated O-carbamates.