首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   113篇
  免费   4篇
化学   65篇
力学   5篇
综合类   1篇
数学   6篇
物理学   40篇
  2024年   1篇
  2023年   2篇
  2022年   3篇
  2021年   1篇
  2020年   8篇
  2019年   9篇
  2018年   4篇
  2017年   7篇
  2016年   8篇
  2015年   3篇
  2014年   7篇
  2013年   11篇
  2012年   5篇
  2011年   2篇
  2010年   1篇
  2009年   4篇
  2008年   1篇
  2007年   2篇
  2006年   6篇
  2005年   1篇
  2003年   1篇
  2002年   1篇
  2001年   3篇
  2000年   2篇
  1999年   4篇
  1997年   1篇
  1996年   1篇
  1995年   1篇
  1994年   2篇
  1993年   2篇
  1991年   1篇
  1990年   1篇
  1988年   1篇
  1987年   1篇
  1985年   2篇
  1982年   1篇
  1980年   2篇
  1977年   1篇
  1976年   2篇
  1971年   1篇
排序方式: 共有117条查询结果,搜索用时 15 毫秒
11.
    
A semicrystalline inorganic–organic hybrid crosslinked network containing polyhedral oligomeric silsesquioxane (POSS) cores was constructed by the unusual hydrosilylation of the terminal vinyl groups of an internal acetylene‐containing silane linker by a POSS monomer. Products from the thermal treatments of this network in either argon or air at 250, 550, and 1000 °C, respectively, were characterized by Fourier transform infrared, Solid‐state 13C and 29Si magic angle spinning NMR, X‐ray diffraction and XPS analyses. The highly symmetrically functionalized POSS silica clusters, in the fluorite silica phase, in the network were found to remain unchanged on thermal treatment possibly due to the shielding of the silica core by the functionalities and a cancellation of thermal stresses on the silica core. Stabilization of the metastable α‐cristobalite phase, which is typically formed on cooling by a β‐ to α‐transition of the β‐cristobalite phase formed above 1400 °C, was observed in the amorphous regions in the network sample treated only to 1000 °C in air. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   
12.
13.
    
Official guidelines originating from a European Union directive regulate requirements for analytical methods used to identify chemical compounds in biological matrices. This study compared different liquid chromatography/electropray ionization mass spectrometry (LC/ESI‐MS) and tandem mass spectrometry (LC/ESI‐MS/MS) procedures for accurate determination of the conjugated ethanol metabolite and alcohol biomarker ethyl glucuronide (EtG) in urine, and the value of combined EtG and ethyl sulfate (EtS) measurement. Analysis was carried out on 482 urines following solid‐phase extraction (SPE) sample cleanup or using direct injection of a diluted sample. SPE combined with LC/MS/MS was demonstrated to be the most selective and sensitive method and was chosen as reference method. The EtG results by different methods showed good correlation (r = 0.96–0.98). When comparing five reporting limits for EtG in the range 0.10–1.00 mg/L, the overall agreement with the reference method (frequency of true positives plus true negatives) was 82–97% for direct‐injection LC/MS/MS, 90–97% for SPE‐LC/MS, 86–98% for direct‐injection LC/MS, and 86–98% for direct‐injection LC/MS analysis of EtG and EtS. Most deviations were attributable to uncertainty in quantitation, when the value was close to a cutoff but the respective results were slightly above and below, or vice versa, the critical limit. However, for direct‐injection LC/MS/MS, despite earning 4 identification points, equally many negative results were due to a product ion ratio outside the ±20% deviation accepted by the guidelines. These results indicate that the likelihood of different analytical methods to provide reliable analytical results depends on the reporting limit applied. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   
14.
    
Structural isomers of thermo‐oxidatively stable poly(carborane‐siloxane‐arylacetylene) (PCSAA), namely, m‐PCSAA and p‐PCSAA, were synthesized by the reaction of the dimagnesium salts of m‐diethynylbenzene or p‐diethynylbenzene with 1,7‐bis(chlorotetramethyldisiloxyl)‐m‐carborane. The developed polymers have exceptional thermo‐oxidative properties similar to their diacetylene counterpart poly(carborane‐siloxane‐acetylene), PCSA. Thermal treatment of either of the PCSAAs results in a fully crosslinked thermoset by 500 °C resulting from the cycloaddition reactions involving the acetylene and aryl functionalities and subsequent formation of bridging disilylmethylene entities as discerned from Fourier transform infrared, 13C and 29Si solid‐state NMR, and XPS studies. X‐ray diffraction analysis revealed that the thermosets obtained from p‐PCSAA possess enhanced crystallinity when compared to that obtained from m‐PCSAA possibly due to more efficient packing interactions of the p‐diethynylbenzene groups during thermoset formation. The presence of the aryl groups in the backbone of the PCSAAs' chains appeared to have enhanced the storage and bulk moduli of their thermosets when compared to the thermoset of PCSA. Dielectric studies of m‐PCSAA and p‐PCSAA revealed segmental relaxation peaks, α, above their glass transition temperatures with p‐PCSAA exhibiting a broader peak with a slower relaxation rate than m‐PCSAA. © 2013 Wiley Periodicals, Inc.? J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2638–2650  相似文献   
15.
Based on the different research approaches, econophysics can be divided into threedirections: empirical econophysics, computationaleconophysics, and experimental econophysics. Becauseempirical econophysics lacks controllability that is needed to studythe impacts of different external conditions and computational econophysicshas to adopt artificial decision-making processes that are often deviated fromthose of real humans, experimental econophysics tends to overcome theseproblems by offering controllability and using real humans in laboratory experiments.However, to our knowledge, the existing laboratory experiments have not convincinglyreappeared the stylized facts (say, scaling) that have been revealed for realeconomic/financial markets by econophysicists. A most important reason is that in theseexperiments, discrete trading time makes these laboratory markets deviated from realmarkets where trading time is naturally continuous. Here we attempt to overcome thisproblem by designing a continuous double-auction stock-trading market and conductingseveral human experiments in laboratory. As an initial work, the present artificialfinancial market can reproduce some stylized facts related to clustering and scaling.Also, it predicts some other scaling in human behavior dynamics that is hard to achieve inreal markets due to the difficulty in getting the data. Thus, it becomes possible to studyreal stock markets by conducting controlled experiments on such laboratory stock marketsproducing high frequency data.  相似文献   
16.
 以金刚石压腔高压装置为工具,用Ⅱ型金刚石作压砧兼红外窗口,对本征态聚苯胺进行了高压(0~8.4 GPa)就位红外光谱测试。结果表明:在4.8~5.2 GPa压力区间,代表醌环振动的吸收峰相对代表苯环振动的吸收峰变小,表明聚苯胺在此压力区间结构上发生了显著变化,且这种变化是不可逆的。聚苯胺的高压(0~14.5 GPa)电阻测量结果表明:当压力小于7.5 GPa时,电阻随压力升高而显著降低,据此认为聚苯胺为电子性导电物质;在7.5 GPa处电阻出现极小值,然后又缓慢升高,至10 GPa后基本不变。推测聚苯胺电阻极小值是由结构变化引起的。至于红外光谱与电阻测量结果反映聚苯胺结构变化的压力值不一致,可能是由于测试条件不同所致。  相似文献   
17.
We present infrared transient grating measurements of complexes of formic acid with pyridine and pyrazine at four excitation frequencies within the broad proton-stretching band. These experiments investigate the mechanism of the line broadening of the O-H stretching vibration. The transients show coherent oscillations that decay within a few hundred femtoseconds and population relaxation on two time scales. We fit the data using a simple model of three coupled oscillators that relax via sequential kinetics through an intermediate state. Based on this model, we conclude that the coherent oscillations result from superpositions of Fermi-resonance-coupled states involving formic acid overtone and combination states.  相似文献   
18.
    
Bacterial natural products in general, and non-ribosomally synthesized peptides in particular, are structurally diverse and provide us with a broad range of pharmaceutically relevant bioactivities. Yet, traditional natural product research suffers from rediscovering the same scaffolds and has been stigmatized as inefficient, time-, labour- and cost-intensive. Combinatorial chemistry, on the other hand, can produce new molecules in greater numbers, cheaper and in less time than traditional natural product discovery, but also fails to meet current medical needs due to the limited biologically relevant chemical space that can be addressed. Consequently, methods for the high throughput generation of new natural products would offer a new approach to identifying novel bioactive chemical entities for the hit to lead phase of drug discovery programs. As a follow-up to our previously published proof-of-principle study on generating bipartite type S non-ribosomal peptide synthetases (NRPSs), we now envisaged the de novo generation of non-ribosomal peptides (NRPs) on an unreached scale. Using synthetic zippers, we split NRPSs in up to three subunits and rapidly generated different bi- and tripartite NRPS libraries to produce 49 peptides, peptide derivatives, and de novo peptides at good titres up to 145 mg L−1. A further advantage of type S NRPSs not only is the possibility to easily expand the created libraries by re-using previously created type S NRPS, but that functions of individual domains as well as domain-domain interactions can be studied and assigned rapidly.  相似文献   
19.
20.
    
In a recent study, opposite enantiomer elution order was observed for ketoprofen enantiomers on two amylose-phenylcarbamate-based chiral columns with the same chemical composition of the chiral selector but in one case with coated while in the other with an immobilized chiral selector. In the present study, the influence of this uncommon effect on method validation parameters for the determination of minor enantiomeric impurity in dexketoprofen was studied. The validated methods with two alternative elution orders for enantiomers were applied for the evaluation of enantiomeric impurity in six marketed dexketoprofen formulations from various vendors. In most of these formulations except one the content of enantiomeric impurity exceeded 0.1% (w/w).  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号