Dibenzomethanopentacene-Based Polymers of Intrinsic Microporosity for Use in Gas-Separation Membranes

Dibenzomethanopentacene (DBMP) is shown to be a useful structural component for making Polymers of Intrinsic Microporosity (PIMs) with promise for making efficient membranes for gas separations. DBMP-based monomers for PIMs are readily prepared using a Diels–Alder reaction between 2,3-dimethoxyanthracene and norbornadiene as the key synthetic step. Compared to date for the archetypal PIM-1, the incorporation of DBMP simultaneously enhances both gas permeability and the ideal selectivity for one gas over another. Hence, both ideal and mixed gas permeability data for DBMP-rich co-polymers and an amidoxime modified PIM are close to the current Robeson upper bounds, which define the state-of-the-art for the trade-off between permeability and selectivity, for several important gas pairs. Furthermore, long-term studies (over ≈3 years) reveal that the reduction in gas permeabilities on ageing is less for DBMP-containing PIMs relative to that for other high performing PIMs, which is an attractive property for the fabrication of membranes for efficient gas separations.     

A Molecular‐Dynamics Study of Size and Chirality Effects on Glass‐Transition Temperature and Ordering in Carbon Nanotube‐Polymer Composites

Molecular‐dynamics simulations of single‐walled carbon nanotubes (CNTs) embedded in a coarse‐grained amorphous monodisperse polyethylene‐like model system have been carried out. The roles of nanotube diameter and chirality on the physical and structural properties of the composite are thoroughly discussed for several CNTs with different diameter and chirality. It is shown that the glass‐transition temperature of the polymer matrix increases with the diameter of the CNT while chirality effects are negligible. A denser and ordered layered region of polymer matrix is found in the vicinity of the nanotube surface. The density and ordering of this layer increases with the CNT diameter. All simulations indicate that chirality does not affect the atomic structure of the highly ordered layer surrounding the CNTs. Despite the simplicity of the polymer model, results of this study are qualitatively comparable with those obtained from experiments and numerical simulations that consider a chemically specific polymer matrix.

     

Bifurcation analysis of a circular arch under hydrostatic pressure

Summary In this paper the bifurcation analysis of a circular arch under hydrostatic pressure in the elastic postbuckling range is performed by means of a geometrically exact beam model. The relevant nonlinear field equations are solved by utilizing a perturbation technique. A number of numerical results regarding the dependence of the critical load and the second order load parameter on the geometric and mechanical parameters are plotted in diagrams.

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Sommario Nel presente lavoro si studia la biforcazione di un arco circolare soggetto a pressione idrostatica nel campo elastico facendo uso di un modello di trave cinematicamente esatto. Le corrispondenti equazioni di campo nonlineari vengono risolte utilizzando una tecnica perturbativa. Vengono riportati in diagramma una serie di risultati numerici riguardanti la dipendenza del carico critico e del parametro di carico del secondo ordine dai parametri geometrici e meccanici.

     

Polyimide Dendrimers Containing Multiple Electron Donor–Acceptor Units and Their Unique Photophysical Properties

A high‐yielding synthesis of a series of polyimide dendrimers, including decacyclene‐ and perylene‐containing dendrimer D6 , in which two types of polyimide dyes are present, is reported. In these constructs, the branching unit is represented by trisphenylamine, and the solubilizing chains by N‐9‐heptadecanyl‐substituted perylene diimides. The photophysical properties of the dendrimers have been studied by absorption, steady‐state, and time‐resolved emission spectroscopy and pump–probe transient absorption spectroscopy. Photoinduced charge‐separated (CS) states are formed on the femtosecond timescale upon visible excitation. In particular, in D6 , two different CS states can be formed, involving different subunits that decays independently with different lifetimes (ca. 10–100 ps).     

Clickable 2,2-bis(hydroxymethyl)propionic acid-derived AB2 monomers: Hyperbranched polyesters through the CuAAC cycloaddition (click) reaction

We present the synthesis and characterization of two aliphatic AB₂ monomers derived from the readily available 2,2-bis(hydroxymethyl)propionic acid and containing one alkyne group and two azide functionalities. The distance between the polymerizable groups differs in the two monomers by the insertion of an additional carbon atom in the aliphatic structure that addresses the steric demand during polymerization. The synthetic procedure for the monomers is relatively simple and scalable, and the monomers are able to polymerize through the Copper(I)-catalyzed Azide-Alkyne Cycloaddition (CuAAC reaction). The polymerization affords hyperbranched polymers in good yields and molecular weights and moderate degrees of branching. Copyright © 2021 John Wiley & Sons, Ltd.     

Thermal convection and related instabilities in models of crystal growth from the melt on earth and in microgravity: Past history and current status

The paper presents a comparative study of a number of theoretical/experimental/numerical results concerning the dynamics of natural (gravitational), Marangoni and related mixed convection in various geometrical models of widely‐used technologies for the production of single‐crystalline materials (Horizontal and vertical Bridgman growth, Czochralski method, Floating Zone Technique). Emphasis is given to fundamental knowledge provided over the years by landmark analyses as well as to very recent contributions. Such a knowledge is of paramount importance since it is validating new, more complex models, accelerating the current trend towards predictable and reproducible phenomena and finally providing an adequate scientific foundation to industrial processes which are still conducted on a largely empirical basis. A deductive approach is followed with fluid‐dynamic systems of growing complexity being treated as the discussion progresses. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Non parabolic band transport in semiconductors: closure of the moment equations

The problem of the closure of the moment equations of the semiconductor Boltzmann equation is studied in the framework of the Kane dispersion relation (therefore avoiding the limitations of the parabolic band approximation). By using the maximum entropy ansatz for the closure one obtains, in the limit of small anisotropy, explicit constitutive relations for the stress tensor and the flux of energy flux tensor. The results obtained are in remarkable agreement with those arising from Monte Carlo simulations. Received October 27, 98     

Low Field (10 mT) Pulsed Dynamic Nuclear Polarization

EPR irradiation by a train of inverting pulses has potential advantages over continuous-wave EPR irradiation in DNP applications; however, it has previously been used only at high field (5 T). This paper presents the design and testing of an apparatus for performing pulsed DNP experiments at 10 mT with large samples (17 ml). Experimental results using pulsed DNP with an aqueous solution of a narrow-linewidth paramagnetic probe are presented. A maximum DNP enhancement of about -36 with a train of inverting pulses (width 500 ns, repetition time 4 micros) was measured. A preliminary comparison showed that, when the same enhancement value is considered, the pulsed DNP technique requires an average power that is about three times higher than that required with the CW irradiation. However, for in vivo DNP applications it is very important to minimize the average power deposited in the sample. From the experimental results reported in this work, when considering the maximum enhancement, the pulsed technique requires only 2% of the average power necessary with the CW DNP technique. We believe that this reduction in the average power can be important for future DNP studies with large biological samples.