Does phenazine form triplet excimer and dimer anion radical?

Laser flash photolysis of phenazine (PZ) solution reveals the existence of a stable species with a long lifetime at 380 nm in addition to the usual triplet PZ at 440 nm. The former is suggested to be due to formation of triplet PZ excimer. The triplet excimer also undergoes photoinduced electron transfer with some aromatic amines. The formation of PZ dimer anion radical and amine cation radicals are confirmed by external magnetic field effect studies. Measurement of B_1/2, which estimates hyperfine present in the system, also supports this assignment.     

Thermolyzable polymer networks and star polymers containing a novel,compact, degradable acylal‐based dimethacrylate cross‐linker: Synthesis,characterization, and thermolysis

A compact, cleavable acylal dimethacrylate cross‐linker, 1,1‐ethylenediol dimethacrylate (EDDMA), was synthesized from the anhydrous iron(III) chloride‐catalyzed reaction between methacrylic anhydride and acetaldehyde. The ability of EDDMA to act as cross‐linker was demonstrated by using it for the preparation of one neat cross‐linker network, four star polymers of methyl methacrylate (MMA), and four randomly cross‐linked MMA polymer networks using group transfer polymerization (GTP). For comparison, the corresponding polymer structures based on the commercially available ethylene glycol dimethacrylate (EGDMA) cross‐linker (isomer of EDDMA) were also prepared via GTP. The number of arms of the EDDMA‐based star polymers was lower than that of the corresponding EGDMA polymers, whereas the degrees of swelling in tetrahydrofuran of the EDDMA‐based MMA networks were higher than those of their EGDMA‐based counterparts. Although none of the EDDMA‐containing polymers could be cleanly hydrolyzed under basic or acidic conditions, they could be thermolyzed at 200 °C within 1 day giving lower molecular weight products. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5811–5823, 2007     

Measurement of Hartmann-Hahn cross-polarization dynamics with quenching of proton T1ρ relaxation dependence

A simple modification of the standard cross-polarization method designed for quenching the proton T_1ρ dependence when studying polarization transfer is presented. It is demonstrated that by using this simple procedure, new and subtle details of cross-polarization dynamics, previously hidden by the T_1ρ(¹H) effect, can be observed in dipolar-coupled spin systems.     

On the Buchstaber Subring in MS p

A formula is given to calculate the last n number of symplectic characteristic classes of the tensor product of the vector Spin(3)- and Sp(n)-bundles through its first 2n number of characteristic classes and through characteristic classes of Sp(n)-bundle. An application of this formula is given in symplectic cobordisms and in rings of symplectic cobordisms of generalized quaternion groups.     

Large-scale computer simulation of fully developed turbulent channel flow with heat transfer

Recently, with the advent of supercomputers, there has been considerable interest in the use of direct numerical simulation to obtain information about turbulent shear flow at low Reynolds number. This paper presents a pseudospectral technique to solve the full three-dimensional time-dependent Navier-Stokes and advection-diffusion equations without the use of subgrid-scale modelling. The technique has not been previously used for fully developed turbulent channel flow simulation and is based on methods applied in other contexts. The emphasis of this paper is to provide a reasonably detailed account of how the simulation is done rather than to present new calculations of turbulence. The details of an algorithm for turbulent channel flow simulation and the grid and time step sizes needed to integrate through transient behaviour to steady state turbulence have not been published before and are presented here. Results from a Cray-2 simulation of fully developed turbulent flow in a channel with heat transfer are presented along with a critical comparison between experiment and computation. The first- and second-order moments agree well with experimental measurements; the agreement is poor for higher-order moments such as the skewness and flatness near the walls of the channel. Detailed information given about the effects of spatial grid resolution on a computed results is important for estimating the size of the computation required to study various aspects of a turbulent flow.     

高速电视摄象系统的象质评价和动态计测精度

本文对高速摄象系统(包括电视摄象系统和光机式摄象系统)的象质评价方法予以讨论,并用实验方法对目前广泛使用的Kodak SP-2000、NAC HSV-200等高速电视摄象系统及我们自己开发的一维扫描电视摄象系统的象质,在新的定义下给出了评价,对它们的动态精度作了对比性测试,同时和光机式高速摄象系统作了比较。     

垂直上升管内液体横掠流动传热特性研究

本文对单相水和单相油横掠流动时的平均换热特性进行了实验研究,对试验的结果进行了分析和讨论,并对实验数据进行关联,得到了垂直上升管内单相水和单相油横掠流动时的换热准则关系式。结果表明,狭窄空间条件下的液体横掠柱体时的流动换热对液相Re数的依赖,较大空间条件下的流动换热相比明显减小,并对单相水和单相油横掠流动时的换热性能进行了比较。     

A density functional theory computational study of the role of ligand on the stability of CuI and CuII species associated with ATRP and SET‐LRP

Atom transfer radical polymerization (ATRP) and single electron‐transfer living radical polymerization (SET‐LRP) both utilize copper complexes of various oxidation states with N‐ligands to perform their respective activation and deactivation steps. Herein, we utilize DFT (B3YLP) methods to determine the preferred ligand‐binding geometries for Cu/N‐ligand complexes related to ATRP and SET‐LRP. We find that those ligands capable of achieving tetrahedral complexes with Cu^I and trigonal bipyramidal with axial halide complexes with [Cu^IIX]⁺ have higher energies of stabilization. We were able to correlate calculated preferential stabilization of [Cu^IIX]⁺ with those ligands that perform best in SET‐LRP. A crude calculation of energy of disproportionation revealed that the same preferential binding of [Cu^IIX]⁺ results in increased propensity for disproportionation. Finally, by examining the relative energies of the basic steps of ATRP and SET‐LRP, we were able to rationalize the transition from the ATRP mechanism to the SET‐LRP mechanism as we transition from typical nonpolar ATRP solvents to polar SET‐LRP solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4950–4964, 2007