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   698篇
  免费   37篇
  国内免费   64篇
化学   698篇
晶体学   4篇
力学   13篇
综合类   15篇
数学   1篇
物理学   68篇
  2024年   1篇
  2023年   8篇
  2022年   12篇
  2021年   95篇
  2020年   41篇
  2019年   31篇
  2018年   20篇
  2017年   24篇
  2016年   38篇
  2015年   39篇
  2014年   35篇
  2013年   56篇
  2012年   49篇
  2011年   28篇
  2010年   35篇
  2009年   31篇
  2008年   25篇
  2007年   28篇
  2006年   33篇
  2005年   23篇
  2004年   20篇
  2003年   18篇
  2002年   18篇
  2001年   17篇
  2000年   10篇
  1999年   8篇
  1998年   11篇
  1997年   5篇
  1996年   4篇
  1995年   6篇
  1994年   7篇
  1993年   4篇
  1991年   3篇
  1990年   4篇
  1989年   1篇
  1988年   4篇
  1987年   2篇
  1986年   1篇
  1983年   2篇
  1979年   2篇
排序方式: 共有799条查询结果,搜索用时 218 毫秒
1.
An innovative volatolomic approach employs the detection of biomarkers present in cerumen (earwax) to identify cattle intoxication by Stryphnodendron rotundifolium Mart., Fabaceae (popularly known as barbatimão). S. rotundifolium is a poisonous plant with the toxic compound undefined and widely distributed throughout the Brazilian territory. Cerumen samples from cattle of two local Brazilian breeds (‘Curraleiro Pé-Duro’ and ‘Pantaneiro’) were collected during an experimental intoxication protocol and analyzed using headspace (HS)/GC–MS followed by multivariate analysis (genetic algorithm for a partial least squares, cluster analysis, and classification and regression trees). A total of 106 volatile organic metabolites were identified in the cerumen samples of bovines. The intoxication by S. rotundifolium influenced the cerumen volatolomic profile of the bovines throughout the intoxication protocol. In this way, it was possible to detect biomarkers for cattle intoxication. Among the biomarkers, 2-octyldecanol and 9-tetradecen-1-ol were able to discriminate all samples between intoxicated and nonintoxicated bovines. The cattle intoxication diagnosis by S. rotundifolium was accomplished by applying the cerumen analysis using HS/GC–MS, in an easy, accurate, and noninvasive way. Thus, the proposed bioanalytical chromatography protocol is a useful tool in veterinary applications to determine this kind of intoxication.  相似文献   
2.
Metabolomics is a potential tool for the discovery of new biomarkers in the early diagnosis of diseases. An ultra-fast gas chromatography system equipped to an electronic nose detector (FGC eNose) was used to identify the metabolomic profile of Volatile Organic Compounds (VOCs) in type 2 diabetes (T2D) urine from Mexican population. A cross-sectional, comparative, and clinical study with translational approach was performed. We recruited twenty T2D patients and twenty-one healthy subjects. Urine samples were taken and analyzed by FGC eNose. Eighty-eight compounds were identified through Kovats's indexes. A natural variation of 30% between the metabolites, expressed by study groups, was observed in Principal Component 1 and 2 with a significant difference (p < 0.001). The model, performed through a Canonical Analysis of Principal coordinated (CAP), allowed a correct classification of 84.6% between healthy and T2D patients, with a 15.4% error. The metabolites 2-propenal, 2-propanol, butane- 2,3-dione and 2-methylpropanal, were increased in patients with T2D, and they were strongly correlated with discrimination between clinically healthy people and T2D patients. This study identified metabolites in urine through FGC eNose that can be used as biomarkers in the identification of T2D patients. However, more studies are needed for its implementation in clinical practice.  相似文献   
3.
A model is developed for the formation and propagation of cracks in a material sample that is heated at its top surface, pyrolyses, and then thermally degrades to form char. In this work the sample is heated uniformly over its entire top surface by a hypothetical flame (a heat source). The pyrolysis mechanism is described by a one-step overall reaction that is dependent nonlinearly on the temperature (Arrhenius form). Stresses develop in response to the thermal degradation of the material by means of a shrinkage strain caused by local mass loss during pyrolysis. When the principal stress exceeds a prescribed threshold value, the material forms a local crack. Cracks are found to generally originate at the surface in response to heating, but occasionally they form in the bulk, away from ever-changing material boundaries. The resulting cracks evolve and form patterns whose characteristics are described. Quantities examined in detail are: the crack spacing in the pyrolysis zone; the crack length evolution; the formation and nature of crack loops which are defined as individual cracks that have joined to form loops that are disconnected from the remaining material; the formation of enhanced pyrolysis area; and the impact of all of the former quantities on mass flux. It is determined that the mass flux from the sample can be greatly enhanced over its nominal (non-cracking) counterpart. The mass efflux profile qualitatively resembles those observed in Cone Calorimeter tests.  相似文献   
4.
Landfill gas, cryotrapped on a loop fashioned from a length of a capillary gas chromatography (GC) column, was examined for volatile organometallic compounds (VOMCs) and for volatile organic compounds (VOCs) by using GC–mass spectrometry (MS). A large number of organic components were present and many were identified, but the only VOMCs present in high enough concentrations to be detected were trimethylstibine and tetramethyltin. The use of inductively coupled plasma (ICP)‐MS as an element‐specific detector allowed the identification of a number of other organometallic species in the landfill gas, including trimethylarsine and trimethylbismuth, and, for the first time, butyltrimethyltin and dibutyldimethyltin. The presence of molybdenum hexacarbonyl was confirmed. Gas from a large‐scale compost heap and from compost incubated in the laboratory contained iodomethane but no common VOMCs (GC–ICP‐MS). Only VOCs were present in forest air (GC–MS). Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   
5.
李红军  蒋琴 《分析化学》1993,21(1):117-120
本文设计了直接蒸馏-顶空分析-预柱低温富集-毛细管色谱-质谱联机分析技术,有效地提取、浓缩、分离和鉴定了藿香的香气成分。实现了天然产物微量多组分的联机快速分析。并首次在霍香的头香成分中发现了乙酸甲酯、3-甲基丁酮、3-甲基-3-丁烯酮等一系列分子量小、易挥发的成分。  相似文献   
6.
本文在无氧条件下利用ESR分别观察了肝脏和晶状体的微粒体及线粒体酶在NADPH存在下还原三硝基甲苯(TNT)的过程,检测到参数为g=2.0048±0.0005,A_对位~N=1.215mT,A~N=0.800±0.010mT,A~H=0.122±0.0206mT的自由基信号,并通过电子计算机对ESR谱的模拟证明该自由基信号为TNT硝基阴离子自由基,根据其超精细分裂常数认为,其不配对电子的电子云密度主要分布在对位硝基上。  相似文献   
7.
华中五味子挥发性成份的研究   总被引:6,自引:0,他引:6  
华中五味子有收敛、止咳、止汗、止泻、活血和健胃等作用。近年来已分离到约15种非挥发性成份,但关于它的挥发性成份迄今未见报道。我们用毛细管气相色谱法分离出  相似文献   
8.
肉苁蓉挥发性化学成分分析   总被引:10,自引:3,他引:10  
报道了用同时蒸馏—萃取法提取肉苁蓉挥发性物质,测得肉苁蓉挥发油的含量为3.5%;利用GC/MS法分离确认出24种化学成分;用峰面积归一化法得出各化学成分在挥发油中的相对百分含量,其中主要成分为丁香酚,占总挥发油的83.60%;又用单离子法分离出丁香酚,并用IR,EI-MS法对其进行分析确认。  相似文献   
9.
烟草及烟草制品总挥发酸的测定--连续流动法   总被引:11,自引:0,他引:11  
采用连续流动方法测定烟草及其制品中的总挥发酸,详细研究了测定条件.结果表明最大吸收波长为350 nm,标准乙酸溶液在0.086~4.0 μg/mL的范围内服从比尔定律,摩尔吸光系数为1.174×104L·mol-1·cm-1,对烟草中挥发酸的检出限为0.012mg/g,相关系数为0.999 5,测定范围为0.12~5.0mg/g.方法具有很好的灵敏度和较高的精密度.  相似文献   
10.
We report a simple and versatile approach for the conjugation of luminescent CdSe-ZnS core-shell quantum dots (QDs) to proteins through coordination of engineered C-terminal oligohistidine sequences. Several histidine tail containing proteins were self-assembled onto the QD surface using this method. A recombinant antibody specific for the high explosive 2,4,6-trinitrotoluene (TNT) was conjugated to QDs through a carboxy terminal histidine tail and the bioconjugate used to detect TNT by competitive immunoassay. TNT was detected over the range of 10 μg/ml down to 41 ng/ml using the scFv conjugated to QDs. These results open up the possibility to conjugate luminescent QDs to a whole range of proteins to form QD bioconjugates that can be effectively used in bio-oriented applications, such as sensing, imaging, immunoassay and other diagnostics.  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