Beyond Stereoselectivity,Switchable Catalysis: Some of the Last Frontier Challenges in Ring‐Opening Polymerization of Cyclic Esters

Metal‐based catalysts and initiators have played a pivotal role in the ring‐opening polymerization (ROP) of cyclic esters, thanks to their high activity and remarkable ability to control precisely the architectures of the resulting polyesters in terms of molar mass, dispersity, microstructure, or tacticity. Today, after two decades of extensive research, the field is slowly reaching maturity. However, several challenges remain, while original concepts have emerged around new types or new applications of catalysis. This Review is not intended to comprehensively cover all of these aspects. Rather, it provides a personal overview of the very recent progress achieved in some selected, important aspects of ROP catalysis—stereocontrol and switchable catalysis. Hence, the first part addresses the development of new metal‐based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselective ROP metal catalysts to control the monomer sequence in copolymers. A second part covers the development of ROP catalysts—primarily metal‐based catalysts, but also organocatalysts—that can be externally regulated by the use of chemical or photo stimuli to switch them between two states with different catalytic abilities. Current challenges and opportunities are highlighted.     

Structural and thermodynamic properties of AlB2 compound

We employ a first-principles plane wave method with the relativistic analytic pseudopotential of Hartwigsen, Goedecker and Hutter (HGH) scheme in the frame of DFT to calculate the equilibrium lattice parameters and the thermodynamic properties of AlB₂ compound with hcp structure. The obtained lattice parameters are in good agreement with the available experimental data and those calculated by others. Through the quasi-harmonic Debye model, obtained successfully are the dependences of the normalized lattice parameters a/a₀ and c/c₀ on pressure P, the normalized primitive cell volume V/V₀ on pressure P, the variation of the thermal expansion α with pressure P and temperature T, as well as the Debye temperature \Theta_D and the heat capacity C_V on pressure P and temperature T.     

Synthesis and Reactions of Some New Pyrrolylfuro[2,3‐d]Pyrimidines and Pyrrolopyrazinofuropyrimidines

5‐Amino‐4‐methyl‐2‐phenyl‐6‐substitutedfuro[2,3‐d]pyrimidines ( 2a‐c ) were reacted with 2,5‐dimethoxytetrahydrfuran to afford the pyrrolyl derivatives 3a‐c . Compound 3a was chosen as intermediate for the synthesis of poly fused heterocycles incorporated furopyrimidines moiety 4–11 . Some of the synthesized compounds were screened for their antibacterial and antifungal activities.     

Nanostructured thermoset epoxy resin templated by an amphiphilic poly(ethylene oxide)‐block‐poly(dimethylsiloxane) diblock copolymer

An amphiphilic poly(ethylene oxide)‐block‐poly(dimethylsiloxane) (PEO–PDMS) diblock copolymer was used to template a bisphenol A type epoxy resin (ER); nanostructured thermoset blends of ER and PEO–PDMS were prepared with 4,4′‐methylenedianiline (MDA) as the curing agent. The phase behavior, crystallization, hydrogen‐bonding interactions, and nanoscale structures were investigated with differential scanning calorimetry, Fourier transform infrared spectroscopy, transmission electron microscopy, and small‐angle X‐ray scattering. The uncured ER was miscible with the poly(ethylene oxide) block of PEO–PDMS, and the uncured blends were not macroscopically phase‐separated. Macroscopic phase separation took place in the MDA‐cured ER/PEO–PDMS blends containing 60–80 wt % PEO–PDMS diblock copolymer. However, the composition‐dependent nanostructures were formed in the cured blends with 10–50 wt % PEO–PDMS, which did not show macroscopic phase separation. The poly(dimethylsiloxane) microdomains with sizes of 10–20 nm were dispersed in a continuous ER‐rich phase; the average distance between the neighboring microdomains was in the range of 20–50 nm. The miscibility between the cured ER and the poly(ethylene oxide) block of PEO–PDMS was ascribed to the favorable hydrogen‐bonding interaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3042–3052, 2006     

On a class of new and practical performance indexes for approximation of fold bifurcations of nonlinear power flow equations

Efficient measurement of the performance index (the distance of a loading parameter from the voltage collapse point) is one of the key problems in power system operations and planning and such an index indicates the severity of a power system with regard to voltage collapse. There exist many interesting methods and ideas to compute this index. However, some successful methods are not yet mathematically justified while other mathematically sound methods are often proposed directly based on the bifurcation theory and they require the initial stationary state to be too close to the unknown turning point to make the underlying methods practical.This paper first gives a survey of several popular methods for estimating the fold bifurcation point including the continuation methods, bifurcation methods and the test function methods (Seydel's direct solution methods, the tangent vector methods and the reduced Jacobian method) and discuss their relative advantages and problems. Test functions are usually based on scaling of the determinant of the Jacobian matrix and it is generally not clear how to determine the behaviour of such functions. As the underlying nonlinear equations are of a particular type, this allows us to do a new analysis of the determinants of the Jacobian and its submatrices in this paper. Following the analysis, we demonstrate how to construct a class of test functions with a predictable analytical behaviour so that a suitable index can be produced. Finally, examples of two test functions from this class are proposed. For several standard IEEE test systems, promising numerical results have been achieved.