分子内氢键对屏蔽酚抗氧化活性的影响

采用基于密度泛函理论的量子化学从头算法计算了不同分子结构屏蔽酚的O-H键解离能(E_BD),采用压力差示扫描量热仪测定了屏蔽酚在润滑油基础油中的抗氧化活性,考察了屏蔽酚的E_BD与其抗氧化活性之间的关系,并重点探究了结构因素对邻位桥联屏蔽双酚E_BD的影响。结果表明,屏蔽酚的活性构象E_BD越小,其抗氧化活性越高。分子内氢键对邻位桥联屏蔽双酚的E_BD可以产生显著影响。对于邻位桥联屏蔽双酚分子而言,其最低能量构象存在2个O-H┅π氢键,E_BD较高,并非抗氧化活性构象;存在1个O-H┅O氢键的局部最低能量构象,E_BD相对较低,为抗氧化活性构象。邻位亚甲基桥联屏蔽双酚分子的内旋转能垒较低,容易形成E_BD较低的活性构象,这是其抗氧化效果突出的主要原因。     

Electronic Structure and Geminate Pair Energetics at Organic–Organic Interfaces: The Case of Pentacene/C60 Heterojunctions

Organic semiconductors are characterized by localized states whose energies are predominantly determined by electrostatic interactions with their immediate molecular environment. As a result, the details of the energy landscape at heterojunctions between different organic semiconductors cannot simply be deduced from those of the individual semiconductors, and they have so far remained largely unexplored. Here, microelectrostatic computations are performed to clarify the nature of the electronic structure and geminate pair energetics at the pentacene/C₆₀ interface, as archetype for an interface between a donor molecule and a fullerene electron acceptor. The size and orientation of the molecular quadrupole moments, determined by material choice, crystal orientation, and thermodynamic growth parameters of the semiconductors, dominate the interface energetics. Not only do quadrupoles produce direct electrostatic interactions with charge carriers, but, in addition, the discontinuity of the quadrupole field at the interface induces permanent interface dipoles. That discontinuity is particularly striking for an interface with C₆₀ molecules, which by virtue of their symmetry possess no quadrupole. Consequently, at a pentacene/C₆₀ interface, both the vacuum‐level shift and geminate pair dissociation critically depend on the orientation of the pentacene π‐system relative to the adjacent C₆₀.     

Dissociations of the night: Individual differences in sleep-related experiences and their relation to dissociation and schizotypy.

The author examined the associations among sleep-related experiences (e.g., hypnagogic hallucinations, nightmares, waking dreams, and lucid-dreams), dissociation, schizotypy, and the Big Five personality traits in 2 large student samples. Confirmatory factor analyses indicated that (a) dissociation and schizotypy are strongly correlated—yet distinguishable—constructs, and (b) the differentiation between them can be enhanced by eliminating detachment/depersonalization items from the dissociation scales. A general measure of sleep experiences was substantially correlated with both schizotypy and dissociation (especially the latter) and more weakly related to the Big Five. In contrast, an index of lucid dreaming was weakly related to all of these other scales. These results suggest that measures of dissociation, schizotypy, and sleep-related experiences all define a common domain characterized by unusual cognitions and perceptions. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

390.60nm激光作用下Si(CH3)4的多光子解离与硅原子的(1+1)电离

在390.60nm的紫外激光作用下，利用超声分子束技术与飞行时间（TOF）质谱仪相结合的方法研究了气相四甲基硅分子多光子电离（MPI）的TOF质谱，在较低能量的激光作用下主要检测到了Si(CH3)^ 、Si^ 、C2^ 等离子的信号，有时甚至只检测到了Si^ 离子的信号：在较高能量的激光作用下主要检测到Si(CH3)^ n(n=1,2,3,4)、Si^ 、C2^ 甚至还有SiC3^ ,SiC2^ 等离子的信号。据此并结合以前得到的结论，讨论了四甲基硅分子可能的MPI过程。得出了Si^ 主要来自于Si(CH3)4的多光子解离－Si原子的（1＋1）电离、Si(CH3)n^ (n=1,2,3)的（3＋1）电离、Si(CH3)^ 4来自于Si(CH3)4的（3＋1）电离的结论。     

Judgment dissociation theory: An analysis of differences in causal, counterfactual and covariational reasoning.

Research suggests that causal judgment is influenced primarily by counterfactual or covariational reasoning. In contrast, the author of this article develops judgment dissociation theory (JDT), which predicts that these types of reasoning differ in function and can lead to divergent judgments. The actuality principle proposes that causal selections focus on antecedents that are sufficient to generate the actual outcome. The substitution principle proposes that ad hoc categorization plays a key role in counterfactual and covariational reasoning such that counterfactual selections focus on antecedents that would have been sufficient to prevent the outcome or something like it and covariational selections focus on antecedents that yield the largest increase in the probability of the outcome or something like it. The findings of 4 experiments support JDT but not the competing counterfactual and covariational accounts. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

The influence of the filament temperature on the structure of hot-wire deposited silicon

Exposure to hydrogen significantly cools the filament from the set temperature. This can mainly be explained by the power dissipation due to dissociation of hydrogen. The effect of silane on the filament temperature is more complicated. Below a certain threshold temperature (1850 K for W, 1750 K for Ta) a silicon-rich silicide is deposited on the filament, partially shielding it for further dissociation reactions. A drop in deposition rate accompanies this. Above another but higher threshold temperature (2000 K for W and 1950 K for Ta) the silicon-rich silicide is evaporated from the filament and the dissociation reactions occurred and thus the deposition rate are restored. Below these threshold temperatures (2 2 0) oriented materials can be produced.     

Ultrasonically-Induced Interfacial Changes

The ultrasonic wirebond failure mechanism associated with interfacial changes in a thin-film device was studied. The thin-film device was fabricated on a ferrite substrate and composed of a gold layer on top with titanium, nickel-iron and aluminum oxide underneath. The chemical changes at the nickel-iron/aluminum oxide interface, induced by the transfer of ultrasonic energy through the gold and the titanium layers were investigated by Auger electron spectroscopy. The applied ultrasonic energy promoted preferential migration of iron to the interface resulting in weakening of the bond between the nickel-iron and its adjacent aluminum oxide layer.     

Predicting users' return to virtual worlds: a social perspective

Virtual worlds or three‐dimensional computer‐based simulated environments have received considerable attention as platforms for entertainment, education and commerce. In contrast to a web site, for example, where a user interacts with a two‐dimensional site, virtual worlds provide a platform in which users can interact with other individuals, sometimes including strangers, within three‐dimensional environments. Virtual worlds afford a form of ‘socialness’ unlike many other technologies, often motivating a user – by virtue of these social experiences – to return. Drawing on the Spatial Model of Interaction and Awareness‐Attention Theory, we demonstrate that besides social aspects, which include social awareness and social perception, flow experience, which is the mental state of being fully absorbed and somewhat lost in time, is an essential ingredient in an individual's decision to return to a virtual world. We also demonstrate how characteristics of the technology are linked to the social aspects experienced in virtual worlds. A laboratory study conducted in a virtual world, Second Life, supports our assertions and identifies state predictors of flow that influence individuals' intentions to return to the virtual world environment.