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   26036篇
  免费   2647篇
  国内免费   5284篇
化学   28637篇
晶体学   178篇
力学   294篇
综合类   139篇
数学   460篇
物理学   4259篇
  2024年   70篇
  2023年   405篇
  2022年   801篇
  2021年   909篇
  2020年   1324篇
  2019年   1115篇
  2018年   1118篇
  2017年   1055篇
  2016年   1192篇
  2015年   1128篇
  2014年   1662篇
  2013年   2526篇
  2012年   1501篇
  2011年   1762篇
  2010年   1350篇
  2009年   1472篇
  2008年   1559篇
  2007年   1716篇
  2006年   1584篇
  2005年   1488篇
  2004年   1426篇
  2003年   1098篇
  2002年   714篇
  2001年   559篇
  2000年   572篇
  1999年   484篇
  1998年   443篇
  1997年   406篇
  1996年   359篇
  1995年   339篇
  1994年   279篇
  1993年   229篇
  1992年   223篇
  1991年   164篇
  1990年   126篇
  1989年   121篇
  1988年   98篇
  1987年   65篇
  1986年   54篇
  1985年   54篇
  1984年   49篇
  1983年   27篇
  1982年   39篇
  1981年   38篇
  1980年   33篇
  1979年   27篇
  1978年   30篇
  1977年   29篇
  1976年   38篇
  1974年   39篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
871.
载银缓释型抗菌敷料   总被引:1,自引:0,他引:1  
近10年来,载银缓释型抗菌敷料因其优良特性,在医药、卫生等领域引起科学家们的广泛关注。本文综述了银的抗菌机理和载银缓释型抗菌敷料的缓释机制;重点介绍了目前在国际市场上销售的代表性载银缓释型抗菌敷料的性能,并从不同的载体材料角度(如生物高分子、合成高分子、生物和合成高分子共用、有机硅材料)总结了新型载银抗菌敷料的研究进展;最后,讨论了载银抗菌医用敷料在研究和应用中需要解决的问题。  相似文献   
872.
铋纳米管的快速合成与表征   总被引:1,自引:0,他引:1  
以铁粉作还原剂在水溶液中通过置换反应在室温下成功地合成了铋纳米管,并采用透射电子显微镜、电子衍射、X射线粉末衍射仪和热重分析仪对样品进行了鉴定和表征.结果表明所合成的样品呈肩并肩式的管状结构,管径比较均一,并具有高的结晶性和相纯度.热重分析显示所制备的样品含有约3.2%的有机物,并具有良好的热稳定性能.  相似文献   
873.
Theoretical investigations are carried out on the multiple-channel reactions, CH(3) + SiH(CH(3))(3) → products and CF(3) + SiH(CH(3))(3) → products. The minimum energy paths (MEP) are calculated at the MP2/6-311 + G(d,p) level, and energetic information is further refined by the MC-QCISD (single point) method. The rate constants for major reaction channels are calculated by the canonical variational transition state theory (CVT) with small-curvature tunneling (SCT) correction over the temperature range 200-1500 K. The theoretical rate constants are in good agreement with the available experimental data and are found to be k(1a)(T) = 1.93 × 10(-24) T(3.15) exp(-1214.59/T) and k(2a)(T) = 1.33 × 10(-25) T(4.13) exp(-397.94/T) (in unit of cm(3) molecule(-1) s(-1)). Our calculations indicate that hydrogen abstraction channel from SiH group is the major channel due to the smaller barrier height among five channels considered.  相似文献   
874.
A stereoselective total synthesis of naturally occurring 20-epi cholanic acid derivatives has been realized, starting from readily available 16-dehydropregnenolone acetate. The key step of these syntheses involves an ionic hydrogenation of a C-20,22-ketene dithioacetal and deoxygenation of steroidal C-20 tert-alcohols, to set up the unnatural C(20R) configuration with 100% stereoselectivity. The unnatural C-22 aldehydes with C(20R) stereocenters thus obtained were elaborated to 20-epi cholanic acid derivatives. Two derivatives of 20-epi cholanic acid were synthesized and their structures have been confirmed by single crystal X-ray analysis. Catalytic hydrogenation of 16-dehydropregnenolone acetate and 16-dehydropregnenolone in ethanol affords C-5,C-16 tetrahydro products. Crystal structure analysis of one of these products revealed C-5α and C-17α configurations of the hydrogen atoms.  相似文献   
875.
A two-step convenient sequence for the synthesis of previously inaccessible mono-Boc-protected bis-N-heterocyclic alkyl substituted ether derivatives 4 is described. Mitsunobu protocol was applied to the preparation of pyridinyl ether precursor 5. The reduction of the electron rich pyridinyl system 5 has been achieved catalytically using the combination of PtO2-H2SO4 or PtO2-pTsOH under a hydrogen atmosphere maintained by a gas balloon at ambient temperature.  相似文献   
876.
A convergent and efficient synthesis of the 6,6-spiroketal core of the ionophore antibiotic CP-61,405 (routiennocin) is described. The synthesis required 10 steps from N-propionyl oxazolidinone (S)-8 and produced the desired spiroketal in 36% overall yield.  相似文献   
877.
旨在搞清CuSO4能否加快氢气生成速率,基于反应液质量递减法测定单位时间内氢气生成量,并用于反应速率表述。结果表明,CuSO4能否加快氢气生成速率取决于单质锌的形态。锌粒与CuSO4联用有利于氢气制备。  相似文献   
878.
What a core-ker! The title synthesis was achieved using a route featuring an intramolecular Mitsunobu reaction of a nosyl amide, stereoselective construction of the β-lactam, and formation of an enamide moiety by selenoxide elimination. The stereochemistry of the alkylation for the formation of the β-lactam was controlled by a secondary hydroxy group on the ten-membered ring. SEM=2-(trimethylsilyl)ethoxymethyl; TBS=tert-butyldimethylsilyl.  相似文献   
879.
Polarograms for the reduction of glycinate complexes of palladium(II) (5 × 10?5 M) are obtained in equilibrium solutions of pH 0.8–3.0 with different protonated-glycine concentrations c Hgly (supporting electrolyte, 0.5 M NaClO4). It is established that the irreversible wave of reduction of complexes Pd(gly)2 corresponds to the diffusion limiting current I d (2) . A similar wave at pH 1.5 and c Hgly = 0.005 M, as well as at pH 1.0 and c Hgly = 0.05–0.5 M is preceded by the diffusion limiting current I d (1) . Values of the I d (2) /I d (1) ratio are close to the ratio between equilibrium concentrations of Pd(gly)2] and [Pdgly+], calculated using the step stability constant for Pd(gly)2. This fact testifies to the reduction of complexes Pdgly+ in the vicinity of I d (1) and complexes Pd(gly)2, in the vicinity of I d (2) . At pH 0.8–1.2 and [H2gly+] = 1 × 10?4 to 5 × 10?3 there is observed the diffusion-kinetic limiting current of the first wave I 1 (1) , which increases with increasing [H+] and decreasing [H2gly+]. The nature of the slow preceding chemical stage that occurs during the reduction of complexes Pdgly+ is discussed.  相似文献   
880.
The reactions of p-(dimethylamino)benzaldehyde with 5-amino-3-methyl-1-phenylpyrazole and 2-RCOCH2-1H-benzimidazoles have produced 5-(1H-benzimidazol-2-yl)-1H-pyrazolo[3,4-b]pyridines. The transformation includes the formation of compounds in accordance with a Hantzsch reaction containing a 1,4-dihydropyridine ring, and is completed by the aromatization either by the splitting off of N,N-dimethylanyline or oxidation. The splitting is produced by acetic acid and the oxidation by a nitrocompound. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 578–584, April 2007.  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