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   49214篇
  免费   2841篇
  国内免费   7240篇
化学   39030篇
晶体学   892篇
力学   875篇
综合类   392篇
数学   9095篇
物理学   9011篇
  2024年   41篇
  2023年   356篇
  2022年   570篇
  2021年   841篇
  2020年   1116篇
  2019年   1099篇
  2018年   961篇
  2017年   1472篇
  2016年   1443篇
  2015年   1245篇
  2014年   1736篇
  2013年   3870篇
  2012年   3561篇
  2011年   2529篇
  2010年   2048篇
  2009年   2977篇
  2008年   3162篇
  2007年   3207篇
  2006年   2893篇
  2005年   2603篇
  2004年   2468篇
  2003年   2033篇
  2002年   2875篇
  2001年   1871篇
  2000年   1668篇
  1999年   1664篇
  1998年   1375篇
  1997年   1046篇
  1996年   839篇
  1995年   828篇
  1994年   738篇
  1993年   584篇
  1992年   622篇
  1991年   388篇
  1990年   355篇
  1989年   360篇
  1988年   240篇
  1987年   188篇
  1986年   203篇
  1985年   156篇
  1984年   166篇
  1983年   78篇
  1982年   140篇
  1981年   108篇
  1980年   139篇
  1979年   124篇
  1978年   112篇
  1977年   60篇
  1976年   41篇
  1973年   28篇
排序方式: 共有10000条查询结果,搜索用时 93 毫秒
971.
(R)-2-羟基-4-苯基丁酸乙酯的合成   总被引:4,自引:0,他引:4  
林文清  张晓梅  宓爱巧 《合成化学》2002,10(5):385-390,456
综述了血管紧张素转化酶抑制剂类治疗高血压和充血性心力衰竭药物的关键中间体(R)-2-羟基-4-苯基丁酸乙酯的合成方法。参考文献25篇。  相似文献   
972.
《Analytica chimica acta》2002,459(2):229-234
The ligand 1,4,8-tri(n-octyl)-1,4,8,11-tetraazacyclotetradecane (L1) containing pendant octyl groups has been synthesised. L1 is a tetraazamacrocycle derived from the well-known cyclam unit, and the Ni2+ and Co2+ complexes, [Ni(L1)]2+ and [Co(L1)]2+, have been isolated and characterised. The ability of the nickel(II) and cobalt(II) complexes to act as anion receptors has been studied by using them as ionophores in membrane-based ion-selective electrodes (ISEs). The PVC membrane containing the complex [Ni(L1)]2+ and 2-nitrophenyloctylether as plasticizer shows a Nernstian response against iodide in a concentration range from 1×10−1 to 4×10−5 M I with a detection limit of 1.6×10−5 M I and a slope of 58.6 mV/pI at pH 7 (25 °C). In comparison, the electrode containing [Co(L1)]2+ as ionophore gave a sub-Nernstian slope and a low lifetime. A comparison between the iodide-selective electrode containing [Ni(L1)]2+ and other reported iodide-selective electrodes is also reported.  相似文献   
973.
Amphiphilic AB‐type diblock copolymers composed of hydrophobic poly(L ‐lactide) (PLA) segments and hydrophilic poly(glycolic acid lysine) [poly(Glc‐Lys)] segments with amino side‐chain groups self‐associated to form PLA‐based polymeric micelles with amino surfaces in an aqueous solution. The average diameter of the loose core–shell polymeric micelles for poly(Glc‐Lys) [number‐average molecular weight (Mn) = 1240]‐b‐PLA (Mn = 7000) obtained by a dimethyl sulfoxide/water dialysis method was estimated to be about 50 nm in water by dynamic light scattering measurements. The size and shape of the obtained polymeric micelles were further observed with transmission electron microscopy and atomic force microscopy. To investigate the possibility of applying the obtained PLA‐based polymeric micelles as bioabsorbable vehicles for hydrophobic drugs, we tested the entrapment of drugs in poly(Glc‐Lys) (Mn = 1240)‐b‐PLA (Mn = 7000) micelles and their release with doxorubicin as a hydrophobic drug. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1426–1432, 2002  相似文献   
974.
Alternative Ligands. XXII. Rhodium(I) complexes with Donor/Acceptor Ligands of the Typs Me2PCH2CH2SiXnMe3?n(X = F, Cl, OMe) Donor/acceptor ligand of the type Me2PCH2SiXnMe3?n react with [Rh(CO)2Cl]2 ( 1 ) to give the mononuclear complexes RhCl(CO)(PMe2CH2CH2SiXnMe3?n)2 ( 2-6 , Table 1) with planar geometry of the donor atoms, one exception being Me2PCH2CH2CH2SiCl3, yielding the crystalline RhIII-complex RhCl2(CO)(PMe2CH2CH2SiCl2)(PMe2CH2CH2SiCl3) ( 7 ) by oxidative addition of one of the SiCl bonds to the Rh1 precursor. Structures with Rh → Si interaction between the basic central atoms and the acceptor group SiXnMe3?n could be detected in the isolated products neither spectroscopically nor by X-ray diffraction of the two representatives RhCl(CO)(PMe2CH2CH2SiF3)2 ( 2 ) and RhCl(CO)[PMe2CH2CH2siF3]2 ( 2 ) and RhCl(CO) [PMe2CH2CH2Si(OMe3]2 ( 6 ). The presence of such acid/base adducts in the reaction mixture is indicated for the more acidic acceptor groups SiXnMe3?n byvco values near 1990cm?1, (see Table 3). The complex RhCl(CO)PMe3)(PMe2CH2CH2SiF3 ( 8 ) is obtained by the reaction of RhCl(CO)(PMe3)2 ( 9 ) with Me2PCH2SiF3 and has been identified spectroscopically in a mixture with 2 and 9 .  相似文献   
975.
The conditions of formation and some properties of yttrium and lanthanide benzohydroxamates were studied. Simultaneous TG-DTG-DTA studies under non-isothermal conditions were carried out in air atmosphere in the temperature range 20-1000°C. The IR spectra and X-ray patterns of some thermal decomposition products were recorded. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   
976.
trans-RhCl(CO)(TPPTS)2 (TPPTS=tris(m-sulfonatophenyl)phosphine) has been intercalated into Zn-Al layered double hydroxides (LDHs) by the method of ion exchange. The structure, composition and thermal stability of the composite material have been characterized by powder X-ray diffraction, Fourier transform infrared and 31P solid-state magic-angle spinning nuclear magnetic resonance spectroscopy, elemental analysis, thermogravimetry, and differential thermal analysis. The geometry of trans-RhCl(CO)(TPPTS)2 was fully optimized using the PM3 semiempirical molecular orbital method, and a schematic model for the intercalated species has been proposed. The thermal stability of trans-RhCl(CO)(TPPTS)2 is significantly enhanced by intercalation, which suggests that such materials may have prospective application as the basis of a supported catalyst system for the hydroformylation of higher olefins.  相似文献   
977.
Composite nanoporous electrode SnO2/TiO2 was fabricated for the dye sensitized solar cell (DSSC) with N3 (Cis-Ru). After introducing of TiO2, the open-circuit photovoltage (Voc) was higher than that of the pure SnO2 electrode, while short-circuit photocurrent (Isc) was varied with the ratio of the TiO2. Appropriate content of the TiO2 can be beneficial to the efficiency of the solar cell, and it gives negative impact on the composite electrode when the content of TiO2 is higher.  相似文献   
978.
The kinetic study of ring-opening metathesis polymerization (ROMP) of a diester functionalised norbornene derivative, (±)-exo,endo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid diethyl ester, with a series of ruthenium benzylidene complexes revealed the applicability of these initiators for well defined polymerization reactions. Values for the rate of initiation as well as the rate of propagation of the initiators were determined and correlated to the molecular weight and polydispersity of the isolated polymers. As the only initiator providing an entry to virtually monodisperse polymers the classical “first generation Grubbs-catalyst” was identified, while N-heterocyclic carbene based initiators polymerized with a rate of propagation much higher than the rate of initiation yielding polymers with a broader molecular weight distribution.  相似文献   
979.
Quartz-homeotypic gallium (ortho-) phosphate, GaPO4, is of special interest for resonator applications asking for temperature compensated cuts with higher electro-mechanical coupling than quartz and operational temperatures up to 970°C. The crystal microbalance technique, well known for quartz (QCM) which can be used only at moderate temperatures, can now be extended to much higher temperatures using GaPO4 crystals, benefiting from all three advantages mentioned above. Two different experiments were done to demonstrate the advantages of a crystal microbalance based on GaPO4. First, the GaPO4 resonator was used for film thickness determination and compared with a commercial QCM. This experiment demonstrated that the measuring range can be extended by using GaPO4 resonators instead of quartz. The second experiment demonstrates the possibility for thermogravimetric analysis up to 720°C by using a new concept for resonator mounting.This revised version was published online in November 2005 with corrections to the Cover Date.  相似文献   
980.
N-Acylbenzotriazoles, when treated with samarium diiodide in THF, undergo self-coupling reaction to afford 1,2-diketones in good to excellent yields; while when treated with samarium diiodide in CH3CN, they undergo ring-opening reaction to afford 1-acylamido-2-alkyl (or aryl) benzimidazoles in reasonable to good yields. A plausible mechanism was suggested.  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