13 resultados para Well-established biomarkers
em Chinese Academy of Sciences Institutional Repositories Grid Portal
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There is a unidirectional, ipsilateral and monosynaptic projection from the hippocampus to the prefrontal cortex. The cognitive function of hippocampal-prefrontal cortical circuit is not well established. In this paper, we use muscimol treated rats to inv
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A computer program, QtUCP, has been developed based on several well-established algorithms using GCC 4.0 and Qt (R) 4.0 (Open Source Edition) under Debian GNU/Linux 4.0r0. it can determine the unit-cell parameters from an electron diffraction tilt series obtained from both double-tilt and rotation-tilt holders. In this approach, two or more primitive cells of the reciprocal lattice are determined from experimental data, in the meantime, the measurement errors of the tilt angles are checked and minimized. Subsequently, the derived primitive cells are converted into the reduced form and then transformed into the reduced direct primitive cell. Finally all the patterns are indexed and the least-squares refinement is employed to obtain the optimized results of the lattice parameters. Finally, two examples are given to show the application of the program, one is based on the experiment, the other is from the simulation. (C) 2008 Elsevier B.V. All rights reserved.
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We investigate the annealing behavior of InAs layers with different thicknesses in a GaAs matrix. The diffusion enhancement by strain, which is well established in strained quantum wells, occurs in InAs/GaAs quantum dots (QDs). A shift of the QD luminescence peak toward higher energies results from this enhanced diffusion. In the case of structures where a significant portion of the strain is relaxed by dislocations, the interdiffusion becomes negligible, and there is a propensity to generate additional dislocations. This results in a decrease of the QD luminescence intensity, and the QD peak energy is weakly affected.
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A novel heavy-metal chalcogenide glass doped with a high dysprosium ion (Dy(3+)) concentration was prepared by the well-established melt-quenching technique from high-purity elements. The results show that when Cadmium (Cd) is introduced into chalcogenide glass, the concentration of Dy(3+) ions doped in GeGaCdS glasses is markedly increased, the thermodynamic performance improves, and the difference between T(g) and T(x) is >120 degrees C. The Vickers microhardness is also modified greatly, about 245 kgf/mm(2). The optical spectra indicate that all absorption and emission bands of Dy(3+) are clearly observed and red-shifted with increasing Dy(3+) concentration.
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过去十多年,世界手性药物市场需求迅速增长,手性制药工业的发展壮大,已经引起了各国政府、学术界,特别是企业界的高度重视。手性药物中含有大量的手性胺单元,因此研究高效构建手性胺结构单元的方法具有重要的意义和实用价值,而亚胺的不对称还原是合成手性胺最便捷的方法。 手性有机小分子路易斯碱催化三氯氢硅不对称还原亚胺是最近几年才发展起来的一类新的亚胺不对称还原方法。尽管在对映选择性和底物适用范围等方面已经获得了突破性的进展,但是,高性能的路易斯碱催化剂仅局限于N-甲酰氨基酸酰胺一种类型,而且其底物适用范围和催化活性仍不够理想。因此,发展新型催化剂很有必要。 手性硫氧化物作为手性诱导剂的应用已经有数十年的时间,广泛应用在不对称合成及天然产物的全合成中。理论上,硫氧结构单元也可以作为路易斯碱,对硅烷类试剂进行活化,而且硫氧键还有碳氧键难以比拟的先天优势,硫原子自带手性特征,在反应过程中,手性中心离反应位点更近,因此,从手性硫氧化合物出发,极有可能开发出新的高效手性路易斯碱催化剂。最近,Kobayashi和Khiar在亚胺的不对称烯丙基化反应中用手性亚砜活化烯丙基三氯硅烷,获得了较好的ee值,但反应中手性亚砜的用量都需要化学计量以上,因此还不能算做真正意义上的催化剂,进一步的文献调研也未见真正意义上的硫手性有机小分子催化剂。 本文首次成功将硫手性亚磺酰胺衍生物应用于催化三氯氢硅对亚胺的不对称还原,在经过对亚磺酰胺衍生物的多次结构优化,开发出了合成容易,催化活性和立体选择性都很优良,并且有着前所未有的底物普适性的新型手性路易斯碱催化剂。 我们首先尝试将商品化的20mol%叔丁基亚磺酰胺和对甲基亚磺酰胺直接用作催化剂催化三氯氢硅对亚胺的不对称还原,尽管仅获得中等的收率和很低的对映选择性,但证明我们的设计思路是可行的。在此基础上,我们以叔丁基亚磺酰胺为原料和基本骨架,设计合成了一系列的亚磺酰胺类催化剂,通过对催化剂的结构改造,发现当催化剂中存在较强酸性的酚羟基时,催化效果得到大幅提高。随着对催化剂的进一步结构优化,我们找到了一个结构简单,催化效果还不错的催化剂,经过反应条件优化以后,催化反应的收率最高能达到98%,对映选择性最高达93%,并且这个催化剂的底物适应范围比之前报道的催化剂都要广泛。针对酚羟基在催化剂中的重要作用,我们进行了仔细的机理研究后发现,在催化反应中,催化剂极有可能是通过双分子机理去活化三氯氢硅从而实现不对称催化的,而酚羟基的作用就是通过分子间氢键促进双分子催化剂与三氯氢硅的络合。受此启发,我们设计了一系列具有双齿结构的催化剂,通过对双齿催化剂的结构优化,最终筛选出了一个结构更加简单,但催化效果更好的双齿催化剂。10mol%该催化剂催化亚胺还原最高获得95%的收率和96%的ee值。这一结果也进一步验证了我们先前对催化剂机理的推测。 随后,我们还尝试将这些催化剂用于二级胺和芳香酮的直接还原胺化反应中,虽然能获得不错的收率,但对映选择性却很差,我们对反应条件进行了仔细的摸索,仍然没有获得突破。但这些实验为进一步研究二级胺和酮的不对称直接还原胺化反应奠定了良好的基础。 In the past decade, the rapid growth of the global chiral drug market and the significant development of the chiral pharmaceutical industry have attracted a great deal of attention from government, academia and enterprises. Chiral amine is an important structural motif of chiral drugs. Therefore, development of methods for the construction of this motif is of great importance. Catalytic enantioselective reduction of imines represents one of the most straightforward and efficient methods for the preparation of chiral amines. The chiral Lewis base organocatalysts promoted asymmetric reduction of imines by HSiCl3 has recently achieved significant advancements. Although big breakthroughs have been made in terms of substrate generality and enantioselectivity, the highly effective catalysts are limited to N-formyl amino acid amides, of which the efficiency and substrate scope remain unsatisfactory. Therefore, development of novel organocatalysts for this transformation is in great demand. Chiral sulfoxides have been well established as efficient and versatile stereocontrollers and have been extensively used in asymmetric synthesis and total synthesis of natural products. The S=O structural motif of sulfoxide could also behave as Lewis base activator for cholorsilane reagents, which, moreover, could be even better than caboxamide considering that the sulfur atom is chiral and thus the chirality center is closer to the reaction center. There exist great potentials that highly effective novel Lewis base organocatalysts could be developed starting from S-chiral sulfoxides. Recently, several S-chiral sulfoxides were reported by Kobayashi and Khiar to be used as Lewis base catalyst to activate allyltrichlorosilanes in asymmetric allylations and good enantioselectivities were obtained. However, these S-chiral sulfoxides were all used at a more than stoichiometric amount and were thus not authentically catalytic. A careful literature survey further revealed that there has been so far no S-chiral organocatalyst available. In this study, we, for the first time, successfully used S-chiral sulfinamides as Lewis base organocatalysts for the asymmetric reduction of ketimines by HSiCl3. After several rounds of structural optimization, we developed the first example of highly effective S-chiral organocatalysts, which promoted the asymmetric reduction of ketimines with trichlorosilane in high yield and excellent enantioselectivity with unprecedented substrate spectrum. In our initial practice, we examined 20mol% of the commercially available (R)-tert-butanesulfinamide and (S)-toluenesulfinamide as the catalyst in the hydrosilylation of ketimine. Although the product was only furnished in moderate yield and low ee, these results demonstrated that our strategy of catalyst design is on the right way. Next, starting from chiral tert-butanesulfinamide, we prepared a series of tert-butanesulfinamide derivatives via simple reductive amination and examined their catalytic efficiencies in the reduction of ketimine. We found that the catalyst bearing a phenolic hydroxyl group exhibited good reactivity and enantioselectivity. On the basis of which, we obtained a structurally simple and highly effective novel organocatalyst, affording the product in 98% yield and 93% ee under optimal reaction conditions. After careful exploration on the role of phenolic hydroxyl group in the catalyst, we speculated that two molecules of the catalyst be involved in the course of reaction, of which the assembly around the silicon center is facilitated by the intermolecular hydrogen bonding through the phenolic hydroxyl groups. Thus, we incorporated two units of sulfonamide into one molecular and prepared a new type of bissulfinamides organocatalysts and examined their catalytic efficiencies in the reduction of ketimine. After optimizing the structure of these catalysts, we finally obtained a novel organocatalyst which has even simpler molecular structure but showed better efficacies, 10mol% of which afforded up to 97% yield and 96% ee under optimal reaction conditions. These results further proved our speculation about the catalytic mechanism. We also examined the newly developed S-chiral organocatalysts in direct asymmetric reductive amination of secondary amines with aromatic ketone. The product was furnished in good yield but in low ee. No better results could be obtained despite our intense opimization efforts. Nevertheless, these experiments laid excellent foundations for eventual success.
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The synthesis of monodisperse nanocrystals is an important topic in the field of nanomaterials not only for practical applications, but also for scientific interest in fundamental research. In this feature article, we mainly focus on synthesis of monodisperse nanocrystals by a two-phase approach without the separation of nucleation and growth processes, and report some progress made recently in the observation and understanding of nucleation and growth of semiconductor nanocrystals. Firstly, a novel two-phase approach to monodisperse nanocrystals, which is different from the well-established synthesis models, is discussed. We demonstrate that the two-phase approach has a quite lengthy nucleation process, and can be applied to the synthesis of many kinds of binary monodisperse nanocrystals.
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A new strategy for preparing ammonium-type ionic liquid (IL) by acid/base neutralization reaction was proposed. The method contributed to preparing hydroxide-based ammonium IL and resulting task specific ionic liquid (TSIL) with high purity using a low-costly and environment-friendly synthetic. route. Halide contamination in the prepared ILs could be markedly decreased than those prepared by well-established anion metathesis method. Moreover, some novel TSILs composed of cations and anions with big steric hindrances could be prepared by this method. Physicochemical properties of the bifunctional TSILs, i.e., density, water content, decomposition temperature, and munal solubility, were also studied in this article.
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(NH4)(2)Na-3(V3W3O19).12H(2)O, diammonium trisodium nonadecaoxo(tritungsto)trivanadate dodecahydrate, is a mixed V/W salt in which each site has an approximately equal population of V and W atoms. The centrosymmetric polyanion consists of six (V/W)O-6 edge-sharing distorted octahedra and has a well established structure. Each of the three Na+ cations is surrounded by six water molecules in a distorted octahedron. The (V/W)-O distances are between 1.644(14) and 2.2885 (10) Angstrom.
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The impact of transient wind events on an established zooplankton community was observed during a, field survey in a, coastal region off northern Norway in May 2002. A transient wind event induced a coastal jet/filament intrusion of warm, saline water into our survey area where a semi-permanent eddy was present. There was an abrupt change in zooplankton community structure within 4-7 days of the wind event, with a change in the size structure, an increase in lower size classes less than 1 mm in equivalent spherical diameter (ESD) and a decrease in larger size classes greater than 1.5 mm in ESD. The slope of zooplankton biovolume spectra changed from -0.6 to -0.8, consistent with the size shifting towards smaller size classes. This study shows that even well established zooplankton communities are susceptible to restructuring during transient wind events, and in particular when wind forcing induces horizontal currents or filaments.
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Eighteen novel triazole compounds containing thioamide were designed and synthesized. Their structures were confirmed by elemental analysis, H-1 NMR, IR, and MS. The title compounds exhibited certain antifungal activity. And the geometry structures of the title compounds were optimized by means of the density functional theory (DFT) method at B3LYP/6-31G* level. The quantitative structure-activity relationship (QSAR) of the title compounds was systematically investigated. A correlative equation between FA and DELH, V was well established by using the multiple linear regression (MLR). (c) 2006 Elsevier Ltd. All rights reserved.
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Job Burnout has been a focus of the Occupational Stress Research. As a typical,helping occupation, teacher has attracted widely attention and researches in the areas of pedagogy and psychology. The special subgroup of teacher, headmasters who are the elites of the Basic Education, is ignored. The research about principals’ Job Burnout is nearly blank after analyzing related documents and information. With the development of the society, people pay more and more attention to the education and put more demands on the headmasters, especially middle-school principals. They are required not only to be good educators, who are equipped with all the inner qualities as a teacher, but also good managers. So the main purpose of this research was to compare the principal group with ordinary teacher group, and reveal underling factors, such as background variables and psychological protection variables. A representative sample of Wenzhou middle school principals sized 192 and a sample of middle school teacher sized 302 were sampled from various schools. The educational version of burnout inventory, self consistency scale, and interpersonal trust scale were administrated to the two samples, together with some demographic variables of interest. The applicability and equivalence of the three instruments used in this study were checked. Based on well-established reliability and cross-sample congruence of measures, the difference between principals and teachers was test. Then the contributing factors were analysis gradually. The five background variables were examined one by one in the two samples separately. A multiple covariance analysis was conducted to test whether there remained any difference between these two samples on the variables of interest. Regression analysis was used to further control the effect of self harmony and interpersonal trust to test the difference between two samples. Mediating analysis was conducted to build the relationship among the three constructs. The main results of the research were stated as following: 1. The internal consistency coefficients of all the scales were good, and no difference exited between the two groups. The measurement equivalence of three instruments was established well. The measures could be applied to and comparing the two samples. 2. The self-harmony, and interpersonal trust of principals were better than the ordinary middle-school teachers. Job Burnout of principals was significant lower than teachers. 3. Demographic variables like the gender, age groups, income levels, disricts, and the type of school, were important influencing factors. The difference patterns of the variables on these five variables in two samples had similarity and distinction. 4. After controlling the background variables, there remained significant difference between principals and teachers on the variables of interest. 5. Job Burnout negatively correlated with self-harmony and interpersonal trust. That is to say,the lower the degree of self-harmony and interpersonal are, the serious of the Job Burnout is, The correlation between the self-harmony and the interpersonal trust was positive. 6. After statistically controlling the background variables and psychological variables, there still exited significant difference between two groups of this study. Also, self harmony and interpersonal trust were significant protection predictors to different aspect of job burnout. 7. Mediating analysis was conducted to the residual score of the three constructs after controlling the five variables and group membership. Self harmony partially mediated the relationship between interpersonal trust and job burnout. That is, interpersonal trust had indirect effect to burnout mediated by self harmony, also had direct effect to burnout.
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In the history of psychology research, more attention had been focused on the relation between local processing and global processing. For the global information and the local information, which is processed earlier? And which is processed faster? Precedence of the global over the local level in visual perception has been well established by Navon with compound stimuli, and Navon’s original study gave rise to many publications, including replications, generalization to other kinds of stimuli (nonverbal material, digits), populations (infants, children, brain-damaged subjects), and tasks (lateral visual hemifield presentation, copy drawing, memory recognition, and recall), and triggered some debate about the conditions in which global precedence is and is not observed (number, size, sparsity, and goodness of the stimuli, exposure duration, etc.). However, whether there is a global advantage or precedence in other cognitive processes was less tested. Most researches had suggested that there was a functional equivalency between visual perception and visual image processing. However, it’s still unknown whether there will be a global advantage on mental rotation. In the present study, we combined the mental rotation task with the compound stimuli to explore whether the global or local advantage also existed at the mental imagery transformation stages. In two pilot studies, the perceptual global precedence was found to be present in a normal/mirror-image judgment task when the stimuli exposure time was short; while the stimuli exposure time was prolonged (stimuli kept available till subjects’ response) the perceptual global precedence was showed to be eliminated. In all of the subsequent experiments, stimili would be presented till subjects’ response. Then mental rotation was added in normal/mirror-image judgment (some of the stimuli were rotated to certain angles from upright) in normal experiments, experiment 1 and 2 observed a global advantage on mental rotation both with a focused-attention design (Experiment 1) and divided-attention design (Experiment 2). Subjects’ reaction times were increased with rotation angles, and the accuracy was decreased with rotation angles, suggesting that subject need a mental rotation to make a normal/mirror judgment. The most important results were that subjects’ response to global rotation was faster than that to local rotation. The analysis of slope of rotation further indicated that, to some extend, the speed of global rotation was faster than that of local rotation. These results suggest a global advantage on mental rotation. Experiment 3 took advantage of the high temporal resolution of event-related potentials to explore the temporal pattern of global advantage on mental rotation. Event-related potential results indicated the parietal P300 amplitude was inversely related to the character orientation, and the local rotation task delayed the onset of the mental-rotation-related negativity at parietal electrodes. None clear effect was found for occipital N150. All these results suggested that the global rotation was not only processed faster than local rotation, but also occurred earlier than local rotation. Experiments 4 and 5 took the effect size of global advantage as the main dependent variable, and visual angle and exposure duration of the stimuli as independent variables, to examine the relationship between perceptual global precedence and global advantage on mental rotation. Results indicated that visual angle and exposure duration did not influence the effect size of global advantage on mental rotation. The global advantage on mental rotation and the perceptual global advantage seemed to be independent but their effects could be accumulated at some condition. These findings not only contribute to revealing a new processing property of mental rotation, but also deepen our understanding of the problem of global/local processing and shed light on the debate on locus of global precedence.
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It is well established that memory functioning deteriorates with advancing age. However, research indicates that the magnitude of age-related memory deficits varies across different types of memory, and broad individual differences can be observed in the rate and timing of memory aging. The general aim of this study was to investigate the selectivity and variability of memory functioning in relation to anxiety. Firstly, memory effectiveness was assessed in episodic memory tasks with reality monitoring and external source monitoring paradigms, semantic memory tasks referred to general knowledge and word fluency, and perceptual priming task reflected in word completion. According to the scores on trait version of STAI, the high-trait and low-trait anxious subjects were screened respectively from young and old participants matched for educational level. Secondly, based on the results of the first part, concurrent primary and secondary tasks with probe technique assessing spare processing capacity were used to explore the relation between memory efficiency and anxiety. The first main findings were that: (a) there were no age-related differences in semantic memory assessed by general knowledge and PRS, whereas age effects were observed in episodic memory and semantic memory assessed by word fluency with stringent time restraints. (b) Furthermore, comparison of age-related deficits in source and item was not related to the presentation ways and encoding effort for source, but was affected by types of source. Specifically, memory was more sensitive to aging than item memory in external source monitoring processes involved in discriminating two external sources (i.e., female vs. male voices), but not in reality monitoring processes in discriminating between internal and external sources (i.e., acting vs. listening). The second main findings were that: (a) Anxiety had no effects on the effectiveness and efficiency of semantic memory in recall of general knowledge and PRS, but impaired those of semantic memory in word fluency. (b) The effects of anxiety on episodic memory were different between the old and the young. Both the effectiveness and the efficiency of episodic memory of the old were affected adversely by anxiety. More importantly, source recall in external source monitoring processes was observed to be more vulnerable to anxiety than item memory. The effectiveness of episodic memory of the young was relatively unrelated to anxiety, while anxiety might have adverse effect on their memory efficiency. These results indicated that: First, the selectivity of age-related memory deficits existed not only between memory systems, but also within episodic memory system. The tendency to forget the source even when the fact was retained in external source monitoring was suggested to be a specific feature of cognitive aging. Second, anxiety had adverse impact on the individual differences in memory aging, and mediated partial age-related differences in episodic memory performance.