Highly Mesoporous Metal‐Organic Frameworks as Synergistic Multimodal Catalytic Platforms for Divergent Cascade Reactions

Rational engineering and assimilation of diverse chemo‐ and biocatalytic functionalities in a single nanostructure is highly desired for efficient multistep chemical reactions but has so far remained elusive. Here, we design and synthesize multimodal catalytic nanoreactors (MCNRs) based on a mesoporous metal‐organic framework (MOF). The MCNRs consist of customizable metal nanocrystals and stably anchored enzymes in the mesopores, as well as coordinatively unsaturated cationic metal MOF nodes, all within a single nanoreactor space. The highly intimate and diverse catalytic mesoporous microenvironments and facile accessibility to the active site in the MCNR enables the cooperative and synergistic participation from different chemo‐ and biocatalytic components. This was shown by one‐pot multistep cascade reactions involving a heterogeneous catalytic nitroaldol reaction followed by a [Pd/lipase]‐catalyzed chemoenzymatic dynamic kinetic resolution to yield optically pure (>99 % ee) nitroalcohol derivatives in quantitative yields.     

2D Ising Model for Enantiomer Adsorption on Achiral Surfaces: L- and D-Aspartic Acid on Cu(111)

The 2D Ising model is well-formulated to address problems in adsorption thermodynamics. It is particularly well-suited to describing the adsorption isotherms predicting the surface enantiomeric excess, ees, observed during competitive co-adsorption of enantiomers onto achiral surfaces. Herein, we make the direct one-to-one correspondence between the 2D Ising model Hamiltonian and the Hamiltonian used to describe competitive enantiomer adsorption on achiral surfaces. We then demonstrate that adsorption from racemic mixtures of enantiomers and adsorption of prochiral molecules are directly analogous to the Ising model with no applied magnetic field, i.e., the enantiomeric excess on chiral surfaces can be predicted using Onsager’s solution to the 2D Ising model. The implication is that enantiomeric purity on the surface can be achieved during equilibrium exposure of prochiral compounds or racemic mixtures of enantiomers to achiral surfaces.     

Low-Temperature Processing of PZT Thick Film by Seeding and High-Energy Ball Milling and Studies on Electrical Properties

Lead zirconate titanate thick film with molecular formula PbZr_0.52Ti_0.42O₃ (PZT) was prepared by a modified conventional sol–gel method through seeding and high-energy ball milling, resulting in perovskite phase formation at lower temperatures. The ball-milling time was optimized by keeping the seed particle loading (5 wt.%) constant in the sol–gel solution. This methodology helped in reduction of the crystalline phase formation temperature to 300°C, which is much lower than that reported in the literature (450°C). The well-established perovskite phase was confirmed by x-ray diffraction (XRD) analysis. Scanning electron microscopy (SEM) of PZT films revealed uniform and crystalline microstructure. Film prepared by this methodology showed higher spontaneous polarization (2.22 μC/cm²), higher capacitance (1.17 nF), and low leakage current density (18 μA/cm²). The results obtained from ferroelectric characterization showed a strong correlation with the XRD and SEM results.     

Effect of guest-host interaction on the dynamics of ethylene glycol in H-ZSM5 zeolite

Dynamics of ethylene glycol (EG) adsorbed in H-ZSM5 zeolite as studied using quasielastic neutron scattering (QENS) technique is reported here. Analysis of QENS data revealed that observed dynamics correspond to isotropic rotational motion of EG. Rotational diffusion coefficient of EG adsorbed in H-ZSM5 zeolite is found to be slower compared to bulk and comparable to that of benzene adsorbed in the same host. Positron Annihilation Spectroscopy (PAS) technique is used to understand the nature of guest-host interaction and the results of both QENS and PAS are found to be consistent with each other.     

Volume of Hyperbolic 3-Manifolds with Iterated Pseudo-Anosov Amalgamations (Dedicated to Professor Mitsuyoshi Kato on his sixtieth birthday)

Let : be a pseudo-Anosov homeomorphism. We will study an asymptotic behaviour of the volume of closed hyperbolic 3-manifolds N _n obtained from certain 3-manifolds M, M by attaching their boundaries by the n-th iteration ⁿ of .     

Determination of thallium in water samples

This article illustrates the developments of effective preconcentration techniques and highly sensitive detection methods for accurate measurements of Tl species at extremely low concentration in aqueous solutions. The literature on this topic was taken from the Analytical Abstracts in the period 1990-2005.     

Surface analysis of environmental samples

The surface chemical compositions of solid samples from environmental sources can differ from bulk or average compositions. The processes of adsorption, desorption, precipitation, dissolution, reaction etc., change the surface composition thereby affecting the surface chemistry. Accordingly, surface analytical information is important for the understanding of environmental chemistry involving solid surfaces. Analysis of environmental solid samples with their complex composition is a challenge to rapidly developing surface analytical techniques.     

Temperature dependence of threshold and electrical characteristics of InGaAsP-InP d.h. lasers

Measurements are reported of the electrical characteristics and temperature dependence of threshold current of InGaAsP-InP d.h. lasers (? = 1.3 ?m). Analysis of the I dV/dI characteristics of these devices indicates that drift leakage of carriers from the active region is not responsible for the high temperature sensitivity of threshold in this material system.