A novel tridentate nitrogen donor as ligand in copper catalyzed ATRP of methyl methacrylate

A tridentate ligand, BPIEP: 2,6‐bis[1‐(2,6‐diisopropyl phenylimino) ethyl] pyridine, having central pyridine unit and two peripheral imine coordination sites was effectively employed in controlled/“living” radical polymerization of MMA at 90°C in toluene as solvent, Cu^IBr as catalyst, and ethyl‐2‐bromoisobutyrate (EBiB) as initiator resulting in well‐defined polymers with polydispersities M_w/M_n ≤ 1.23. The rate of polymerization follows first‐order kinetics, k_app = 3.4 × 10^?5 s^?1, indicating the presence of low radical concentration ([P*] ≤ 10^?8) throughout the reaction. The polymerization rate attains a maximum at a ligand‐to‐metal ratio of 2:1 in toluene at 90°C. The solvent concentration (v/v, with respect to monomer) has a significant effect on the polymerization kinetics. The polymerization is faster in polar solvents like, diphenylether, and anisole, as compared to toluene. Increasing the monomer concentration in toluene resulted in a better control of polymerization. The molecular weights (M_n,SEC) increased linearly with conversion and were found to be higher than predicted molecular (M_n,Cal). However, the polydispersity remained narrow, i.e., ≤1.23. The initiator efficiency at lower monomer concentration approaches a value of 0.7 in 110 min as compared to 0.5 in 330 min at higher monomer concentration. The aging of the copper salt complexed with BPIEP had a beneficial effect and resulted in polymers with narrow polydispersitities and higher conversion. PMMA obtained at room temperature in toluene (33%, v/v) gave PDI of 1.22 (M_n = 8500) in 48 h whereas, at 50°C the PDI is 1.18 (M_n = 10,300), which is achieved in 23 h. The plot of lnk_app versus 1/T gave an apparent activation energy of polymerization as (ΔE^≠_app) 58.29 KJ/mol and enthalpy of equilibrium (ΔH⁰_eq) to 28.8 KJ/mol. Reverse ATRP of MMA was successfully performed using AIBN in bulk as well as solution. The controlled nature of the polymerization reaction was established through kinetic studies and chain extension experiments. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4996–5008, 2005     

Förster energy transfer from poly(arylene–ethynylene)s to an erbium–porphyrin complex

We study the infrared emission at 1.54 μm of an organolanthanide complex, Er(III)-tetraphenylporphyrin [Er(TPP)acac], both as a result of direct optical excitation and via energy transfer from host π-conjugate polymers of type poly(arylene–ethynylene) [PAE]. In the first case, the emission of the neat complex is characterized in inert transparent materials and a value of the quantum yield at 1.54 μm φ_IR=4×10⁻⁴ is measured. Then, fluorescence resonance transfer is investigated in blends of Er(TPP)acac with PAEs by monitoring the quenching of the polymer fluorescence along with the enhancement of both the visible emission of the ligand and the near-infrared band of Er³⁺. These different procedures allow a detailed analysis of the transfer efficiency within a specific implementation of the Förster model for polymeric donors. The experimental values of the critical radius R₀, ranging from 1.3 to 2.5 nm for the different blends, are in good agreement with theory for a wide interval of the physical and spectroscopic parameters. This suggests that other mechanisms for excitation transfer do not play a significant role in these materials.     

Besov-Morrey spaces: Function space theory and applications to non-linear PDE

This paper is devoted to the analysis of function spaces modeled on Besov spaces and their applications to non-linear partial differential equations, with emphasis on the incompressible, isotropic Navier-Stokes system and semi-linear heat equations. Specifically, we consider the class, introduced by Hideo Kozono and Masao Yamazaki, of Besov spaces based on Morrey spaces, which we call Besov-Morrey or BM spaces. We obtain equivalent representations in terms of the Weierstrass semigroup and wavelets, and various embeddings in classical spaces. We then establish pseudo-differential and para-differential estimates. Our results cover non-regular and exotic symbols. Although the heat semigroup is not strongly continuous on Morrey spaces, we show that its action defines an equivalent norm. In particular, homogeneous BM spaces belong to a larger class constructed by Grzegorz Karch to analyze scaling in parabolic equations. We compare Karch's results with those of Kozono and Yamazaki and generalize them by obtaining short-time existence and uniqueness of solutions for arbitrary data with subcritical regularity. We exploit pseudo-differential calculus to extend the analysis to compact, smooth, boundaryless, Riemannian manifolds. BM spaces are defined by means of partitions of unity and coordinate patches, and intrinsically in terms of functions of the Laplace operator.

     

Diffusion Structural Analysis Study of Titania Films Deposited by Sol-Gel Technique on Silica Glass

The diffusion structural analysis (DSA) was used to characterize microstructure changes of hydrous titania gel films under in situ conditions of heating. TG and DTA were used in order to elucidate the processes controlling the formation of anatase film during heating of hydrous titania gel film. The annealing of porosity and near surface structure defects of the dehydrated titania films was indicated by DSA in the temperature range 255–700°C as the decrease of radon release rate. It was demonstrated that the annealing was enhanced on heating in oxygen in comparison with heating in argon. The DSA experimental results were compared with model curves describing the radon diffusion mobility and the annealing of radon diffusion paths.     

辐射传递蒙特卡洛法精度分析及数值试验

本文建立了蒙特卡洛法模拟散射参与性介质内辐射传递计算模型。对蒙特卡洛法的计算精度及运行时间进行了较为详细的分析,提出了几种判断计算精度的方法。同时,借助蒙特卡洛法模拟辐射传递过程,进行数值“辐射实验”。利用该“实验结果”进行了物性反问题研究。在已知光学厚度的前提下,得到散射反照率与后半球辐射热流之间的单值函数关系。     

Sensitivity analysis of an optimized bar-spring model with hill-top branching

Summary Characteristics of optimal solutions under nonlinear buckling constraints are investigated by using a bar-spring model. It is demonstrated that optimization under buckling constraints of a symmetric system often leads to a structure with hill-top branching, where a limit point and bifurcation points coincide. A general formulation is derived for imperfection sensitivity of the critical load factor corresponding to a hill-top branching point. It is shown that the critical load is not imperfection-sensitive even for the case where an asymmetric bifurcation point exists at the limit point.     

从像上提取非旋转对称系统的传递函数制作解卷空间滤波器

本文提出从高分辨电子显微像中,利用光学、全息和部分相干等方法,提取传递函数,制作相位和振幅滤波器,实现解卷,提高高分辨电子显微像的分辨率.     

The method of lines solution of discrete ordinates method for radiative heat transfer in cylindrical enclosures

A radiation code based on method of lines solution of discrete ordinates method for radiative heat transfer in axisymmetric cylindrical enclosures containing absorbing-emitting medium was developed and tested for predictive accuracy by applying it to (i) test problems with black and grey walls (ii) a gas turbine combustor simulator enclosing a non-homogeneous absorbing-emitting medium and benchmarking its steady-state predictions against exact solutions and measurements. Comparisons show that it provides accurate solutions for radiative heat fluxes and can be used with confidence in conjunction with CFD codes based on the same approach.     

Living/controlled radical copolymerization of N‐substituted maleimides with styrene in 1‐butyl‐3‐methylimidazolium hexafluorophosphate and anisole

The atom transfer radical copolymerization of N‐substituted maleimides such as N‐phenylmaleimide (PhMI), N‐cyclohexylmaleimide (ChMI), and N‐butylmaleimide (NBMI) with styrene initiated with dendritic polyarylether 2‐bromoisobutyrates in an ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([bmim][PF₆]), at room temperature and anisole at 110 °C was investigated. The dendritic‐linear block copolymers obtained in ionic liquid possessed well‐defined molecular weight and low polydispersity (1.05 < M_w/M_n < 1.32) and could be used as a macroinitiator for chain‐extension polymerization, suggesting the living nature of the reaction system. The ionic liquids containing catalyst could be recycled in the atom transfer radical polymerization systems without further treatment. Compared with polymerization conducted in anisole, the polymerization in ionic liquid had a stronger tendency for alternation. The tendency for alternation decreased in the order PhMI > NBMI > ChMI in [bmim][PF₆] and PhMI > ChMI > NBMI in anisole. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2156–2165, 2003     

Rotational analysis ofA 1Π-X 1Σ+ bands of P14N and P15N: Perturbatio studies in theA 1Π state

The ultraviolet band systemsA ¹Π-X ¹Σ⁺ of P¹⁴N and P¹⁵N were excited in an electrodeless tube containing traces of phosphorus specpure nitrogen and neon using a microwave discharge (2450 MHz). Bands of the isotopic species, P¹⁵N, were obtained using¹⁵N₂ enriched to 95.5%. Rotational analyses of eleven bands of P¹⁴N and sixteen bands of P¹⁵N were carried out. Three perturbing statese ³Σ⁻,d ³Δ andb ³Π, arising from the lower valence configurations were identified from the observed perturbations in thev′=0–4 levels of theA ¹Π state. Deperturbation studies led to the determination of molecular constants of the perturbing states. Vibrational assignments of the perturbing states were made from isotope shift studies.