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   4173篇
  免费   312篇
  国内免费   432篇
化学   1417篇
晶体学   8篇
力学   89篇
综合类   87篇
数学   2641篇
物理学   675篇
  2024年   5篇
  2023年   54篇
  2022年   84篇
  2021年   138篇
  2020年   127篇
  2019年   139篇
  2018年   144篇
  2017年   149篇
  2016年   167篇
  2015年   95篇
  2014年   230篇
  2013年   412篇
  2012年   200篇
  2011年   251篇
  2010年   184篇
  2009年   248篇
  2008年   241篇
  2007年   270篇
  2006年   229篇
  2005年   220篇
  2004年   199篇
  2003年   177篇
  2002年   147篇
  2001年   110篇
  2000年   108篇
  1999年   98篇
  1998年   104篇
  1997年   58篇
  1996年   66篇
  1995年   43篇
  1994年   33篇
  1993年   29篇
  1992年   25篇
  1991年   16篇
  1990年   12篇
  1989年   17篇
  1988年   13篇
  1987年   11篇
  1986年   3篇
  1985年   19篇
  1984年   9篇
  1983年   2篇
  1982年   5篇
  1981年   4篇
  1980年   8篇
  1979年   3篇
  1978年   2篇
  1976年   4篇
  1955年   1篇
  1936年   1篇
排序方式: 共有4917条查询结果,搜索用时 406 毫秒
121.
The objectives of this study were to address uncertainties in the solubility product of (UO2)3(PO4)2⋅4H2O(c) and in the phosphate complexes of U(VI), and more importantly to develop needed thermodynamic data for the Pu(VI)-phosphate system in order to ascertain the extent to which U(VI) and Pu(VI) behave in an analogous fashion. Thus studies were conducted on (UO2)3(PO4)2⋅4H2O(c) and (PuO2)3(PO4)2⋅4H2O(am) solubilities for long-equilibration periods (up to 870 days) in a wide range of pH values (2.5 to 10.5) at fixed phosphate concentrations of 0.001 and 0.01 M, and in a range of phosphate concentrations (0.0001–1.0 M) at fixed pH values of about 3.5. A combination of techniques (XRD, DTA/TG, XAS, and thermodynamic analyses) was used to characterize the reaction products. The U(VI)-phosphate data for the most part agree closely with thermodynamic data presented in Guillaumont et al.,(1) although we cannot verify the existence of several U(VI) hydrolyses and phosphate species and we find the reported value for formation constant of UO2PO4 is in error by more than two orders of magnitude. A comprehensive thermodynamic model for (PuO2)3(PO4)2⋅4H2O(am) solubility in the H+-Na+-OH-Cl-H2PO4-HPO2−4-PO3−4-H2O system, previously unavailable, is presented and the data shows that the U(VI)-phosphate system is an excellent analog for the Pu(VI)-phosphate system.  相似文献   
122.
Concise construction of the trans-fused 7/7/6/6 tetracyclic ether part of hemibrevetoxin B (1) was achieved by a convergent strategy based on coupling reaction of an acyl anion equivalent, reductive cyclization of an α,ε-dihydroxyketone, and introduction of a methyl group at the central ring junction by the Nicolaou method. The resultant tetracyclic ether was transformed into the known intermediate, which was already converted to 1 by the Yamamoto group, thereby completing the formal total synthesis of 1.  相似文献   
123.
A new approach for the stereoselective synthesis of (2R,3S)-2-amino-3,4-dihydroxybutyric acid, an α-amino acid from Lyophyllum ulmarium, has been accomplished using an ether directed aza-Claisen rearrangement. On investigation of optimal conditions for this key step it was shown for the first time that Au(I) can be used to catalyse this transformation.  相似文献   
124.
The combination of attenuated total reflectance-fourier transform mid-infrared spectrometry (ATR-FTMIR) and multivariate pattern recognition is presented as a fast and convenient methodology to ascertain the source product an oil slick comes from and to evaluate the extent of its weathering. Different types of hydrocarbons (including crude oils, several heavy distillates and the Prestige's heavy fuel oil) were spilled on metallic containers designed ad hoc and their fate monitored by ATR-FTMIR. Not only environmental conditions were considered for weathering but artificial IR- and UV-irradiation. Pattern-recognition studies revealed that the different hydrocarbons clustered at different locations on the score plots and that the samples corresponding to each oil became ordered according to the extent of their weathering. Among them, fuel oil samples coming from the recent disaster of the Prestige tanker off the Galician shoreline showed a distinctive behaviour. Comparison of natural-, IR- and UV-weathering of a crude oil showed that IR solar radiation can be important in oil-weathering, in addition to broadly-reported UV degradation.  相似文献   
125.
The first synthesis of the fungal natural product (−)-xylariamide A 1 is reported. N,O-Bis(trimethylsilyl)acetamide induced coupling of d-tyrosine with (E)-but-2-enedioic acid 2,5-dioxo-pyrrolidin-1-yl ester methyl ester 5 produced the dechloro natural product 6, which was subsequently monochlorinated using oxone and KCl to yield synthetic 1. (−)-Xylariamide A 1, (+)-xylariamide A 2 and (−)-dechloroxylariamide A 6 displayed no cytotoxic or antimicrobial activity.  相似文献   
126.
127.
《Arabian Journal of Chemistry》2020,13(10):7289-7301
Black pepper oils have been investigated frequently in the recent years. However, there is a significant variation in physicochemical properties and bioactivity of oils depended on extraction techniques. In this study, the systemic investigation of four various extraction methods was performed to evaluate the physicochemical characterizations, antioxidant and antibacterial activity. The investigation of 1H NMR, FTIR and UV–Vis spectra confirmed presence of non-volatile components in oils extracted through supercritical CO2 and hexane-soaking extractions which induced their typical thermal properties. The isothermal behaviour of extracted oils related to evaporation was within range of 3.2–7.3% (w/w) at 27 °C. The SEM images of the black pepper confirmed different operation manners of mechanism between extractions using the solvents and heating process. The lowest MIC for both essential oils from conventional hidrodistillation and microwave-assisted hidrodistillation against two bacteria including E. coli and B. subtilis were found to be 137 µg mL−1. The non-isothermal decomposition kinetics were investigated on the essential oil of microwave-assisted hydrodistillation extraction. The activation energies and pre-exponent factors of non-isothermal decomposition were found to be in range of 36.5–73.7 KJ mol−1 and 4.98 × 103–1.97 × 108 s−1, respectively, dependent on conversional fractions of the oil. The results revealed that chemical components, physicochemical properties and bioactivity of black pepper essential oils depended on the extraction techniques.  相似文献   
128.
Silicon nitride powders were synthesized in an atmospheric-pressure convection-stabilized arc using silicon and ammonia as reactants. The morphology and particle size distributions of the silicon nitride particles were characterized by SEM, TEM, and electron diffraction analyses. The silicon nitride particles collected in the plasma reactor were formed by either gas-condensed phase reactions or chemical vapor reactions. The morphologies of the particles formed by gas-condensed phase reactions consisted of -Si3N4 prisms, -Si3N4 matte, -Si3N4 needles, and spaghetti-like whiskers. For the homogeneously nucleated particles, the morphologies included dendrites, needles, platelets, and amorphous particles. Most of the particles formed were aggregates with particle size distributions ranging from 500 to 1500 Å depending on the location of injection of the reactants.  相似文献   
129.
Approaches toward the synthesis of iridoids and 9-isocyanopupukeanane starting from cy-clopentadiene are discussed.  相似文献   
130.
建立了毛细管气相色谱法同时测定水产品中多氯联苯和有机氯农药的方法,用高氯酸与冰乙酸的混合溶液消化样品,以石油醚提取,浓硫酸净化后,用毛细管气相色谱法测定,方法的回收法为88%-110%,相对标准偏差为8%-19%(n=6),检出限为0.08-0.60ug/kg,方法简便,快速,结果准确。  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