Intensity autocorrelation function for a flexible polymer

An exact expression for the autocorrelation function of the intensity of light scattered from a solution of large, flexible polymers is obtained using a simple “mean-force” model. A Q² dependence of the reciprocal relaxation time is found for both small values of QR_G and also very large values of QR_G. At small QR_G the relaxation time is proportional to the translational diffusion coefficient D of the entire polymer, while at large QR_G the relaxation time is proportional to the sum of D and an effective segment diffusion coefficient kt/f.     

Separation and identification of photodegradation products of benzoic acid by capillary zone electrophoresis

A capillary zone electrophoresis (CZE) method was developed for separation and identification of photodegradation products of benzoic acid under irradiation at a wavelength of 300 nm. Parameters such as run buffer, applied voltage and injection time were optimized for the separation of benzoic acid and its photodegradation products. Linearity, limit of detection, and repeatability of migration time as well as peak area of the method were examined. Four reaction products, including salicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid and 3,4-dihydroxybenzoic acid have been separated and identified by spiking the known compounds into the irradiated samples using the CZE method developed. The confirmation of the reaction products is one of the key steps for proposing the possible reaction mechanisms involved in the photodegradation of benzoic acid.     

Synthesis of Narrow Molecular Weight Distribution Copolymers for ArF Photoresist Materials by Nitroxide Mediated Polymerization

ArF candidate photoresist polymers have been synthesized by nitroxide mediated polymerization (NMP). Statistical copolymerizations of α‐gamma butyrolactone methacrylate, 3‐hydroxy‐1‐adamantyl methacrylate, and 2‐methyl 2‐adamantyl methacrylate with 5–10 mol% of controlling comonomers (i.e., styrene, p‐acetoxystyrene, 2‐vinyl naphthalene, acrylonitrile, and pentafluorostyrene), which are necessary for controlled polymerization of methacrylates by NMP with the unimolecular alkoxyamine initiator BlocBuilder, have been used. As little as 5 mol% controlling comonomer in the feed is demonstrated to be sufficient to produce linear evolution of number average molecular weight against conversion (X) up to X = 0.7 for relatively low target degrees of polymerization. All of the resulting copolymers have relatively low dispersities and show relatively low absorbance at 193 nm, comparable to other 193 nm candidate photoresists reported previously, with the exception of VN‐containing copolymer.

     

A Priori Estimation of Organic Reaction Yields

A thermodynamically guided calculation of free energies of substrate and product molecules allows for the estimation of the yields of organic reactions. The non‐ideality of the system and the solvent effects are taken into account through the activity coefficients calculated at the molecular level by perturbed‐chain statistical associating fluid theory (PC‐SAFT). The model is iteratively trained using a diverse set of reactions with yields that have been reported previously. This trained model can then estimate a priori the yields of reactions not included in the training set with an accuracy of ca. ±15 %. This ability has the potential to translate into significant economic savings through the selection and then execution of only those reactions that can proceed in good yields.     

Enhanced Electronic Conjugation in Anthracene-Linked Porphyrins

Despite their larger separation , the porphyrin groups in 1 are more strongly conjugated than in analogous compounds in which butadiyne is the bridging unit. This stronger electronic coupling in 1 results in a bathochromic shift in its absorption and emission spectra.     

Linked by loops: Network structure and switch integration in complex dynamical systems

Simple nonlinear dynamical systems with multiple stable stationary states are often taken as models for switchlike biological systems. This paper considers the interaction of multiple such simple multistable systems when they are embedded together into a larger dynamical “supersystem.” Attention is focused on the network structure of the resulting set of coupled differential equations, and the consequences of this structure on the propensity of the embedded switches to act independently versus cooperatively. Specifically, it is argued that both larger average and larger variance of the node degree distribution lead to increased switch independence. Given the frequency of empirical observations of high variance degree distributions (e.g., power-law) in biological networks, it is suggested that the results presented here may aid in identifying switch-integrating subnetworks as comparatively homogenous, low-degree, substructures. Potential applications to ecological problems such as the relationship of stability and complexity are also briefly discussed.     

Gradient shrinking Ricci solitons of half harmonic Weyl curvature

Gradient Ricci solitons and metrics with half harmonic Weyl curvature are two natural generalizations of Einstein metrics on four-manifolds. In this paper we prove that if a metric has structures of both gradient shrinking Ricci soliton and half harmonic Weyl curvature, then except for three examples, it has to be an Einstein metric with positive scalar curvature. Precisely, we prove that a four-dimensional gradient shrinking Ricci soliton with \(\delta W^{\pm }=0\) is either Einstein, or a finite quotient of \(S^3\times \mathbb {R}\), \(S^2\times \mathbb {R}^2\) or \(\mathbb {R}^4\). We also prove that a four-dimensional gradient Ricci soliton with constant scalar curvature is either Kähler–Einstein, or a finite quotient of \(M\times \mathbb {C}\), where M is a Riemann surface. The method of our proof is to construct a weighted subharmonic function using curvature decompositions and the Weitzenböck formula for half Weyl curvature, and the method was motivated by previous work (Gursky and LeBrun in Ann Glob Anal Geom 17:315–328, 1999; Wu in Einstein four-manifolds of three-nonnegative curvature operator 2013; Trans Am Math Soc 369:1079–1096, 2017; Yang in Invent Math 142:435–450, 2000) on the rigidity of Einstein four-manifolds with positive sectional curvature, and previous work (Cao and Chen in Trans Am Math Soc 364:2377–2391, 2012; Duke Math J 162:1003–1204, 2013; Catino in Math Ann 35:629–635, 2013) on the rigidity of gradient Ricci solitons.     

Steering in computational science: Mesoscale modelling and simulation

This paper outlines the benefits of computational steering for high performance computing applications. Lattice-Boltzmann mesoscale fluid simulations of binary and ternary amphiphilic fluids in two and three dimensions are used to illustrate the substantial improvements which computational steering offers in terms of resource efficiency and time to discover new physics. We discuss details of our current steering implementations and describe their future outlook with the advent of computational grids.     

First integrals and analytical solutions of the nonlinear fin problem with temperature-dependent thermal conductivity and heat transfer coefficient

Fin materials can be observed in a variety of engineering applications. They are used to ease the dissipation of heat from a heated wall to the surrounding environment. In this work, we consider a nonlinear fin problem with temperature-dependent thermal conductivity and heat transfer coefficient. The equation(s) under study are highly nonlinear. Both the thermal conductivity and the heat transfer coefficient are given as arbitrary functions of temperature. Firstly, we consider the Lie group analysis for different cases of thermal conductivity and the heat transfer coefficients. These classifications are obtained from the Lie group analysis. Then, the first integrals of the nonlinear straight fin problem are constructed by three methods, namely, Noether’s classical method, partial Noether approach and Ibragimov’s nonlocal conservation method. Some exact analytical solutions are also constructed. The obtained result is also compared with the result obtained by other methods.     

Preparation of non‐spherical particles from amphiphilic block copolymers

Simple self‐assembly techniques to fabricate non‐spherical polymer particles, where surface composition and shape can be tuned through temperature and the choice of non‐solvents was developed. A series of amphiphilic polystyrene‐b‐poly(2‐ethyl‐2‐oxazoline) block copolymers were prepared and through solvent exchange techniques using varying non‐solvent composition a range of non‐spherical particles were formed. Faceted phase separated particles approximately 300 nm in diameter were obtained when self‐assembled from tetrahydrofuran (THF) into water compared with unique large multivesicular particles of 1200 nm size being obtained when assembled from THF into ethanol (EtOH). A range of intermediate structures were also prepared from a three part solvent system THF/water/EtOH. These techniques present new tools to engineer the self‐assembly of non‐spherical polymer particles. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 750–757