Laser ablation mechanism and plume dynamics of polyarylsulfone films studied by laser ionization time-of-flight mass spectrometry

The KrF laser ablation of polyarylsulfone (PAS) was investigated for fluences between 90 and 200 mJ/cm². Neutral fragments were probed using laser post ionization (193 nm) time-of-flight (TOF) mass spectrometry. Decomposition of PAS was found to occur mainly through scission of C-S and C-O bonds as well as via decomposition of the phenylene rings in the chain. The dependencies of both the flight velocities and the Knudsen layer temperature of the fragments on fluence suggest that PAS ablation is a photothermal process. In contrast, the high average translational energies (up to a few tens of eV) indicate the existence of a non-thermal component in the process. In terms of the plume dynamics, the fitting of the arrival profiles of the fragments with a shifted Maxwell-Boltzmann distribution over the full fluence range indicates the existence of a collision during the adiabatic expansion process.     

Structural characterization of hierarchically porous alumina aerogel and xerogel monoliths

Detailed nanostructures have been investigated for hierarchically porous alumina aerogels and xerogels prepared from ionic precursors via sol–gel reaction. Starting from AlCl₃·6H₂O and poly(ethylene oxide) (PEO) dissolved in a H₂O/EtOH mixed solvent, monolithic wet gels were synthesized using propylene oxide (PO) as a gelation initiator. Hierarchically porous alumina xerogels and aerogels were obtained after evaporative drying and supercritical drying, respectively. Macroporous structures are formed as a result of phase separation, while interstices between the secondary particles in the micrometer-sized gel skeletons work as mesoporous structures. Alumina xerogels exhibit considerable shrinkage during the evaporative drying process, resulting in relatively small mesopores (from 5.4 to 6.2 nm) regardless of the starting composition. For shrinkage-free alumina aerogels, on the other hand, the median mesopore size changes from 13.9 to 33.1 nm depending on the starting composition; the increases in PEO content and H₂O/EtOH volume ratio both contribute to producing smaller mesopores. Small-angle X-ray scattering (SAXS) analysis reveals that variation of median mesopore size can be ascribed to the change in agglomeration state of primary particles. As PEO content and H₂O/EtOH ratio increase, secondary particles become small, which results in relatively small mesopores. The results indicate that the agglomeration state of alumina primary particles is influenced by the presence of weakly interacting phase separation inducers such as PEO.     

A preliminary step toward molecular spring driven by cooperative guest binding

A macrocyclic host molecule that comprised two different rotating modules, cerium(IV) bis(porphyrinate)s and ferrocenyl rotating units, exhibiting contraction/expansion motion was synthesized, which can be regarded as a prototype of artificial molecular spring driven by cooperative guest binding in 1:6 stoichiometry.     

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     

Development of Highly Selective Process for Mono-Ethylene Glycol Production from Ethylene Oxide via Ethylene Carbonate Using Phosphonium Salt Catalyst

A new process for the production of mono-ethylene glycol (MEG; HOCH₂CH₂OH) was developed by Mitsubishi Chemical Corporation (MCC) to meet its growing demand in the world. While the MEG selectivity of conventional non-catalyzed process is around 89% under typical conditions, that of the new process exceeds 99%. The key of the high selectivity is the two-step synthesis via ethylene carbonate. The first step reaction is catalyzed by phosphonium salts and generates ethylene carbonate as an intermediate. This is followed by hydrolysis of ethylene carbonate in the second step. Several commercial plants of the new process have already been operated world-wide.     

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.     

Enantioselective reductive aldol reaction using tertiary amine as hydride donor

An efficient method was developed for the enantioselective reductive aldol reaction of α,β-unsaturated ketones with aldehydes in the presence of a Lewis base catalyst; conjugate reduction using a tertiary amine and trichlorosilyl triflate, followed by an aldol reaction with BINAP dioxide (BINAPO) as an organocatalyst, gave the corresponding product in high yield with high stereoselectivity.     

High‐performance liquid chromatography separation of unsaturated organic compounds by a monolithic silica column embedded with silver nanoparticles

The optimization of a porous structure to ensure good separation performances is always a significant issue in high‐performance liquid chromatography column design. Recently we reported the homogeneous embedment of Ag nanoparticles in periodic mesoporous silica monolith and the application of such Ag nanoparticles embedded silica monolith for the high‐performance liquid chromatography separation of polyaromatic hydrocarbons. However, the separation performance remains to be improved and the retention mechanism as compared with the Ag ion high‐performance liquid chromatography technique still needs to be clarified. In this research, Ag nanoparticles were introduced into a macro/mesoporous silica monolith with optimized pore parameters for high‐performance liquid chromatography separations. Baseline separation of benzene, naphthalene, anthracene, and pyrene was achieved with the theoretical plate number for analyte naphthalene as 36 000 m^?1. Its separation function was further extended to cis/trans isomers of aromatic compounds where cis/trans stilbenes were chosen as a benchmark. Good separation of cis/trans‐stilbene with separation factor as 7 and theoretical plate number as 76 000 m^?1 for cis‐stilbene was obtained. The trans isomer, however, is retained more strongly, which contradicts the long‐ established retention rule of Ag ion chromatography. Such behavior of Ag nanoparticles embedded in a silica column can be attributed to the differences in the molecular geometric configuration of cis/trans stilbenes.     

Inertial instability of the Stewartson -layer

Inertial stability of a vertical shear layer (Stewartson E^1/4-layer) on the sidewall of a cylindrical tank with respect to stationary axisymmetric perturbations is inverstigated by means of a linear theory. The stability is determined by two non-dimensional parameters, the Rossby number Ro = U/2ΩL and Ekman number E = v/ΩH², where U and L = (E/4)1/4H are the characteristic velocity and width of the shear layer, respectively, Ω the angular velocity of the basic rotation, v the kinematic viscosity and H the depth of the tank.

For a given Ekman number, the flow is more unstable for larger values of the Rossby number. For E = 10⁻⁴, which is a typical value of the Ekman number realized in rotating tank experiments, the critical Rossby number Ro_c for instability and the critical axial wavenumber m_c non-dimensionalized by L⁻¹ are found to be 1.3670 and 8.97, respectively. The value of Ro_c increases and that of m_c decreases with increasing E.