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   6073篇
  免费   810篇
  国内免费   502篇
化学   3248篇
晶体学   51篇
力学   236篇
综合类   23篇
数学   527篇
物理学   1473篇
无线电   1827篇
  2024年   14篇
  2023年   164篇
  2022年   190篇
  2021年   231篇
  2020年   206篇
  2019年   197篇
  2018年   176篇
  2017年   145篇
  2016年   241篇
  2015年   263篇
  2014年   318篇
  2013年   351篇
  2012年   422篇
  2011年   476篇
  2010年   302篇
  2009年   341篇
  2008年   393篇
  2007年   359篇
  2006年   340篇
  2005年   291篇
  2004年   226篇
  2003年   204篇
  2002年   168篇
  2001年   144篇
  2000年   124篇
  1999年   164篇
  1998年   140篇
  1997年   121篇
  1996年   122篇
  1995年   100篇
  1994年   72篇
  1993年   64篇
  1992年   57篇
  1991年   49篇
  1990年   35篇
  1989年   26篇
  1988年   21篇
  1987年   22篇
  1986年   16篇
  1985年   10篇
  1984年   19篇
  1983年   7篇
  1982年   7篇
  1981年   4篇
  1980年   9篇
  1979年   3篇
  1976年   9篇
  1975年   5篇
  1974年   4篇
  1970年   2篇
排序方式: 共有7385条查询结果,搜索用时 15 毫秒
991.
Reaction of K2[Ru(bipy)(CN)4] with MnCl2 produces a novel bimetallic compound {Mn(H2O)2[Ru(bipy)(CN)4]} (bipy = 2,2'-bipydine), exhibiting a CNT-like structure bridged by cyanide groups and high thermal stability, which has been first observed in coordination polymers.  相似文献   
992.
A polarized photon-pairs heterodyne polarimetry is proposed in order to measure in an ultrasensitive manner the circular birefringence of a chiral medium via optical rotation detection. A balanced detector is integrated into this polarimeter. Thus, shot-noise-limited detection by this polarimeter can be achieved. Experimentally, the detection sensitivity for the circular birefringence of a glucose-water solution up to partial differential |n(r) - n(l)| = 2 x 10(-11) at 10 mg/dL is verified. To our knowledge, this is the highest sensitivity ever measured of a chiral liquid solution based on single traveling sample cell geometry. Finally, when compared to a fiber loop ring-resonator in the frequency domain for a chiral liquid, this polarimeter shows an order of 10(4) enhancement on the sensitivity of natural optical activity measurement.  相似文献   
993.
Two novel hydroxyl- and carboxyl-functionalized cubane-like photodimers from methyl 2-naphthoate have been successfully achieved under mild conditions. X-ray crystal structures confirm that the cubane-like structure is well retained in these two derivatives and the intermolecular OH?O hydrogen bonding plays an important role in crystal packing. It is of significance that the isolated racemic mixture can be subsequently resolved into two optically pure enantiomers by high-performance liquid chromatography.  相似文献   
994.
Two novel μ-oxo-di-μ-carboxylato-bridged iron(III) complexes of [Fe2(bpea)2(PhCO2)2(μ-O)] (ClO4)2·C2H5OH (1) and [Fe2(bpma)2(ClCH2COO)2(μ-O)](ClO4)2· H2O (2) (bpea = N,N-bis(2-pyridylmethyl)ethylamine, bpma = N,N-bis(2-pyridylmethyl)methylamine), have been synthesized and determined by X-ray diffraction. Complex (1) crystallizes in the Orthorhombic space group P nma with d(Fe···Fe) of 3.094 Å and average d(Fe–Obbridge) of 1.805 Å; Complex (2) crystallizes in the Monoclinic space group C 2/c, with d(Fe···Fe) of 3.109 Å and average d(Fe–Obbridge) of 1.794 Å. The magnetic studies indicate a stronger antiferromagnetic interaction between iron(III) ions through μ-oxo-di-μ-carboxylato-bridge for complex (1), with J = ? 141.6 cm?1.  相似文献   
995.
With gold and platinum catalysts, cis-4,6-dien-1-yn-3-ols undergo cycloisomerizations that enable structural reorganization of cyclized products chemoselectively. The AuCl3-catalyzed cyclizations of 6-substituted cis-4,6-dien-1-yn-3-ols proceeded via a 6-exo-dig pathway to give allyl cations, which subsequently undergo a pinacol rearrangement to produce reorganized cyclopentenyl aldehyde products. Using chiral alcohol substrates, such cyclizations proceed with reasonable chirality transfer. In the PtCl2-catalyzed cyclization of 7,7-disubstituted cis-4,6-dien-1-yn-3-ols, we obtained exclusively either bicyclo[4.1.0]heptenones or reorganized styrene products with varied substrate structures. On the basis of the chemoselectivity/structure relationship, we propose that bicyclo[4.1.0]heptenone products result from 6-endo-dig cyclization, whereas reorganized styrene products are derived from the 5-exo-dig pathway. This proposed mechanism is supported by theoretic calculations.  相似文献   
996.
Hepatocellular carcinoma (HCC) is the most common malignant liver tumor. Analysis of human serum from HCC patients using two-dimensional gel electrophoresis (2DE) combined with nano-high-performance liquid chromatography electrospray ionization tandem mass spectrometry (nano-HPLC–ESI-MS/MS) identified fourteen different proteins differentially expressed between HCC patients and the control group. Twelve proteins were up-regulated and two down-regulated. By using nano-HPLC–MS/MS system to analyze proteome in human serum, 317 proteins were identified, twenty-nine of which to high confidence levels (protein matched at last two unique peptide sequences). Of these twenty-nine proteins, six were present only in HCC patients and may serve as biomarkers for HCC. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   
997.
Two unprecedented 2D entangled layers of warp-and-woof threads interwoven by left- and right-handed helical chains, {[Mn(salen)Au(CN)2]4(H2O)}n (salen = N,N'-ethylenebis(salicylideneaminato)) and {Mn(acacen)Ag(CN)2}n (acacen = N,N'-ethylenebis(acetylacetonylideneiminate)) 2, have been synthesized and characterized.  相似文献   
998.
2,7-Bis(4-tert-butylphenyl)-9,9'-spirobifluorene exhibits balanced electron and hole mobilities of up to 10(-3) cm(2) V(-1) s(-1), as measured using time-of-flight techniques.  相似文献   
999.
Su J  Wang Y  Yang S  Li G  Liao F  Lin J 《Inorganic chemistry》2007,46(20):8403-8409
Three new indium(III) compounds, In(HCOO)3 (1), In2(HCOO)5(OH) (2), and In(HCOO)2(OH) (3), were synthesized under hydrothermal conditions and characterized by single crystal and powder X-ray diffraction experiments, as well as by IR spectroscopy, elemental analysis, and coupled TG-DSC-MS measurement. All of these compounds adopt 3D framework structures consisting of InO6 octahedra and the 2.11 binding modes of formate with the (syn, syn-; syn, anti-; anti, anti-) configurations. The structural investigation of these indium formates reveals that the gradual introduction of the hydroxyl groups into the structures induces the polymerization of the InO6 octahedra, that is, InO6 is isolated in 1, becomes dimeric in 2, and finally forms 1D chains in 3. In addition, a simple formula that may be used for estimating the overall coordination number of the formate in Ma(HCOO)bLc is proposed.  相似文献   
1000.
Four new lanostane-type triterpenes, 24-ethyl-3beta-methoxylanost-9(11)-en-25-ol (1), 3beta-methoxy-24-methylenelanost-9(11)-en-25-ol (2), 3beta-methoxy-25-methyl-24-methylenelanost-9(11)-en-21-ol (3) and 3beta-methoxy-24-methyllanosta-9(11),25-dien-24-ol (4) together with three known triterpenes, betulinaldehyde, betulinic acid methyl ester, and ursaldehyde have been isolated from the methanol extract of the twigs of Diospyros discolor. The structures of those new compounds were elucidated by spectroscopic methods.  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