Nuclear‐Spin Polarization in Electron‐Transfer Reactions of Amines

Chemically induced dynamic nuclear polarization (CIDNP) observed during electron transfer (ET) reactions of tertiary amines such as DABCO ( 1 ) or Et₃N ( 2 ) with a wide range of electron acceptors support the involvement of amine radical‐cations (e.g., 1^{. +} or 2^{. +} ) as key intermediates. Radical ions such as 2^{. +} may be deprotonated, generating neutral aminoalkyl radicals (e.g., 2^. ). When generated by reaction with an electron acceptor of energetically low triplet state such as naphthalene (¹Naph*), the resulting pair 2^{. +} /Naph^.? reacts mostly by reverse electron transfer (RET) from triplet pairs populating the naphthalene triplet state.     

HIPS／PP熔融反应共混及其动态力学性质

研究了高抗冲聚苯乙烯（HIPS）／聚丙烯（PP）共混物在过氧化二异丙苯（DCP）存在下的熔融反应过程及其动态力学性质．HIPS在DCP存在下以聚苯乙烯（PS）的降解为主，伴随着聚丁二烯（PB）的交联和接枝，PP在DCP存在下以降解为主，HIPS／PP在DCP存在下以PP同HIPS的反应接枝为主，这种原位生成的增容剂显著地改善了HIPS／PP两组份间的相容性，其分子运动特征较前两者发生明显变化，PS的Tg下降，PB和PP的Tg升高．     

Normalized Dynamic Characterization and Application of Multiple Heat Storage Materials Based on Standard Thermal Resistance北大核心CSCD

基于标准热阻和能量流法,推导出储热材料与换热流体的瞬态换热热阻,通过类比电路分析法,获得了储热-换热过程的瞬态热量流模型及动态响应时间常数。进一步引入节点温度,重新定义换热热阻,获得了储热与换热过程耦合的三阶电路瞬态热量流模型,求解得到了加热、储热和释热三类时间常数,可用于协同表征储热材料中储热与释热的快慢程度,从而实现了多类储热材料的归一化动态表征。通过数值模拟验证与应用对比分析,发现基于多时间常数的归一化动态模型用于表征储热材料的动态特性是可行的,可直接对不同换热、储热材料进行对比分析。案例分析发现与固体储热材料换热时,液态金属的动态换热能力优于熔融盐,而相比于水蒸气和CO₂,空气与陶瓷材料换热能更快达到稳态。     

Molecular dynamics of cyclic and linear poly(dimethylsiloxanes)

Dielectric spectroscopy (10^–1 Hz to 10⁷ Hz) has been employed to study the molecular dynamics of a series of cyclic and linear polydimethylsiloxanes (PDMS) of various molecular weights ranging from 300 to 10 000 g/mol in the temperature range above the glass transition (from 130 K to 190 K). The observed -relaxation depends strongly on both molecular weight and structure of the samples. For linear PDMS oligomers, the -relaxation shifts towards lower temperatures with decreasing molecular weight in good accordance with the Fox-Flory-model. Cyclic PDMS reveals a qualitatively different molecular weight dependence: for a given temperature the -relaxation time increases with decreasing ring length, but has a maximum for small oligomers (degree of polymerizationn6). The shape of relaxation curves and, with it, the relaxation time distribution is independent from length and architecture of the chains The observed experimental findings are in qualitative agreement with dynamic Monte-Carlo simulations.Dedicated to Prof. E.W. Fischer on the occasion of his 65th birthday Fast macht' das WLF ihn krank, jetzt raucht er wieder, Gott sei Dank! (frei nach Wilhelm Busch)     

Dynamic structure factor in a random diffusion model

Let {X _t:0} denote random walk in the random waiting time model, i.e., simple random walk with jump ratew ^–1(X _t), where {w(x):x^d} is an i.i.d. random field. We show that (under some mild conditions) theintermediate scattering function F(q,t)=E ₀ (q^d) is completely monotonic int (E ₀ denotes double expectation w.r.t. walk and field). We also show that thedynamic structure factor S(q, w)=2 ₀ cos(t)F(q, t) exists for 0 and is strictly positive. Ind=1, 2 it diverges as 1/||^1/2, resp. –ln(||), in the limit 0; ind3 its limit value is strictly larger than expected from hydrodynamics. This and further results support the conclusion that the hydrodynamic region is limited to smallq and small such that ||D |q|², whereD is the diffusion constant.     

聚苯醚砜在二甲基甲酰胺中稀溶液性质的研究(Ⅱ)

本文用广角及准弹性光散射法测定了聚苯醚砜各级分在DMF中和在θ溶剂中25℃时的均才半径R_G,第二维利系数A_2,流体力学半经R_H,扩散系数D_O,扩散系数的浓度依赖性k_F以及这些参数与分子量M的关系。它们的结果如下R_G=0.031MO~(0.55) D_O(θ)=0.906×10~(-4)M~(0.5) D_0=1.445×10~(-4)M~(0.55)A_2=0.033M~(-0.35) k_D(θ)=0.5M~(0.34) k_D=2.3×10~(-6)M~(1.36)α_H=R_H/R_H(θ)=0.63M~(0.05)R_H(θ)=0.0299M~(0.5)R_H=0.0188M~(0.55) 作者讨论了静态与动态两种高分子尺寸之间的关系;三种溶胀因子α_η和、α_H、α_G之间的关系;以及摩擦系数的浓度系数k_F与流体力学体积V_H之间的关系。它们的结果满足下面各关系式: R_H/R_G=[π(v+1)(2v+1)/3]~(1/2)(2-v)(1-v)/2, α_η~3=α_(G)~2α_H, k_F=1.2A_2M+N_AV_H/M,K_F(θ)=N_AV_H/M     

Analysis of grid file algorithms

Grid file algorithms were suggested in [12] to provide multi-key access to records in a dynamically growing file. We specify here two algorithms and derive the average sizes of the corresponding directories. We provide an asymptotic analysis. The growth of the indexes appears to be non-linear for uniform distributions:O(v ^c ) orO(v ), wherec=1+b^–1, =1+(s-1)/(sb+1),s is the number of attributes being used,v the file size, andb the page capacity of the system. Finally we give corresponding results for biased distributions and compare transient phases.     

A discrete method of optimal control based upon the cell state space concept

A discrete method of optimal control is proposed in this paper. The continuum state space of a system is discretized into a cell state space, and the cost function is discretized in a similar manner. Assuming intervalwise constant controls and using a finite set of admissible control levels (u) and a finite set of admissible time intervals (), the motion of the system under all possible interval controls (u, ) can then be expressed in terms of a family of cell-to-cell mappings. The proposed method extracts the optimal control results from these mappings by a systematic search, culminating in the construction of a discrete optimal control table.The possibility of expressing the optimal control results in the form of a control table seems to give this method a means to make systems real-time controllable.Dedicated to G. LeitmannThe material is based upon work supported by the National Science Foundation under Grant No. MEA-82-17471. The author is also indebted to Professor G. Leitmann for his many helpful comments.     

稀土离子(Gd3+,Eu3+)加载于纳米介孔ZrO2中的发光

水热合成法制备的高度有序多孔ZrO2具有规则六角排列，均匀纳米孔洞（约1．8nm)，丰富的表面，界面态及比表面积和强的蓝－（近）紫外光发射，使其较常规体材料有更优异的性质，以稀土离子为探针，研究了Gd^3 ,Eu^3 在这些纳米微孔中的发光行为，结果表明，500摄氏度下，介孔ZrO2与稀土离子相作用并有效地将能量传递给稀土离子，增进稀土离子发光，而在ZrO2:Gd-Eu体系中，Gd^3 在ZrO2与Eu3 间起桥梁作用，使基质ZrO2→Eu^3 的能量传递更为有效。     

Purification by solid layer melt crystallization

The application of solid layer crystallization techniques in industry is arousing ever more interest. One reason is the increasing demand for ultrapure products, and another is the energysaving potential of this separation technology.This article examines solid layer melt crystallization as concerns its purification efficiency. The crystallization process was carried out in two different modes, whereby the process parameters were varied and post-crystallization treatments were additionally applied. The experimental results were used as the basis for a mathematical fit of a semi-empirical expression which predicts the purification efficiency. It was used for a design of different multistage plants, which operate with different crystallization strategies. One result is that a comparable product quality is attainable with a simple process technique in combination with post-crystallization treatments, instead of a more complicated and therefore more expensive process technique.The authors wish to acknowledge support by the EU (JOULE program), which helped attainment of some results presented here.