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   10697篇
  免费   1540篇
  国内免费   925篇
化学   5770篇
晶体学   103篇
力学   516篇
综合类   37篇
数学   1011篇
物理学   3226篇
无线电   2499篇
  2024年   45篇
  2023年   261篇
  2022年   315篇
  2021年   400篇
  2020年   449篇
  2019年   354篇
  2018年   327篇
  2017年   341篇
  2016年   490篇
  2015年   542篇
  2014年   579篇
  2013年   724篇
  2012年   932篇
  2011年   888篇
  2010年   658篇
  2009年   635篇
  2008年   680篇
  2007年   521篇
  2006年   594篇
  2005年   469篇
  2004年   333篇
  2003年   277篇
  2002年   226篇
  2001年   177篇
  2000年   210篇
  1999年   220篇
  1998年   202篇
  1997年   160篇
  1996年   174篇
  1995年   150篇
  1994年   120篇
  1993年   104篇
  1992年   96篇
  1991年   93篇
  1990年   55篇
  1989年   43篇
  1988年   51篇
  1987年   36篇
  1986年   31篇
  1985年   24篇
  1984年   23篇
  1983年   20篇
  1982年   10篇
  1981年   16篇
  1980年   9篇
  1977年   6篇
  1976年   10篇
  1975年   9篇
  1973年   8篇
  1972年   6篇
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
51.
A new metal-organic coordination polymer [Zn(Pydc)(Dppz)] n (I) (H2Pydc = 2,6-pyridinedicarboxylic acid, Dppz = dipyrido[3,2-a:2′,3′-c]phenazine) was hydrothermally synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The X-ray diffraction analysis reveals that I crystallizes in the monoclinic system, space group P21/c. The Pydc2? ligands adopt O,N,O′-tridentate chelating and monodentate bridging coordination mode to link two adjacent Zn2+ ions to form a one-dimensional (1D) zigzag chain. The adjacent chains are further linked through hydrogen bonds and π-π stacking interactions, forming a three-dimensional (3D) supramolecular framework. The unit cell parameters for I: a = 7.332(3) Å, b = 36.023(9) Å, c = 7.8838(13) Å, β = 105.65(3), V = 2005.1(10) Å3, Z = 4.  相似文献   
52.
An approximate method has been established to calculate the depth of the potential acting on an electron in a molecule at the saddle point along a chemical bond, denoted by Dpb. It is a new indicator which can be used for predicting the strength of a chemical bond. In this work, as a practical application for demonstrating thismethod, we calculated the Dpb of deoxyribonucleosides and ribonucleosides along all C-H and N-H chemical bonds using the method. The results are in fair agreement with those results of previously reported experimental and theoretical observations.  相似文献   
53.
A reactive template method was used to fabricate alginate‐based hydrogel microcapsules. The uniform and well‐dispersed hydrogel capsules have a high drug loading capacity. After they are coated by a folate‐linked lipid mixture on the surface, the capsules possess higher cell uptake efficiency by the molecule recognition between folate and the folate‐receptor overexpressed by the cancer cells. Moreover, in this bioconjugate, the lipid could remarkably reduce the release rate of hydrophilic doxorubicin from the hydrogel microcapsules and encapsulate the hydrophobic photosensitizer hypocrellin B. The biointerfaced capsules could be used as drug carriers for combined treatment against cancer cell proliferation in vitro; this was much more effective than chemotherapy or photodynamic therapy alone.  相似文献   
54.
Li-Hua Du  Xi-Ping Luo 《合成通讯》2013,43(19):2880-2886
A green, efficient method for the synthesis of various 2-aryl-benzimidazoles in the presence of hypervalent iodine as the oxidant at room temperature under solvent-free conditions is reported. The salient features of this method include mild conditions, short reaction times (3–5 min), excellent yields, and simple procedure.  相似文献   
55.
Y. Hu  Z. Du    Y. Xi  S. Gu 《合成通讯》2013,43(18):3299-3304
Aluminium powder has been used to reduce titanium tetrachloride to generate the low valent titanium (LVT)reagent which can induce the reductive coupling of aldehydes and ketones to form the corresponding pinacols or olefins. However, arylsulfonyl chlorides will give diaryldisulfides under the same condition.  相似文献   
56.
Potassium tert-butoxide (0.1 mol%) catalyzed a vinylogous Mukaiyama aldol reaction between aromatic and aliphatic aldehydes with 2-(trimethylsilyloxy)furan. The corresponding γ-butenolides were obtained in good yields with good diastereoselectivities.  相似文献   
57.
Gold nanospheres modified with bifunctional molecules have been separated and characterized by using agarose gel electrophoresis as well as optical spectroscopy and electron microscopy. The electrophoretic mobility of a gold nanosphere capped with 11‐mercaptoundecanoic acid (MUA) has been found to depend on the number of MUA molecules per gold nanosphere, indicating that it increases with the surface charge of the nanoparticle. The extinction spectrum of gold nanospheres capped with MUA at an MUA molecules per gold nanosphere value of 1000 and connected via 1,6‐hexanedithiol (HDT) decreases by 33% in magnitude and shifts to the red as largely as 22 nm with the increase of the molar ratio of HDT to MUA (RHM). Gold nanospheres capped with MUA and connected via HDT have been separated successfully using gel electrophoresis and characterized by measuring reflectance spectra of discrete electrophoretic bands directly in the gel and by monitoring transmission electron microscope images of gold nanoparticles collected from the discrete bands. Electrophoretic mobility has been found to decrease substantially with the increment of HDT to MUA, indicating that the size of aggregated gold nanoparticles increases with the concentration of HDT.  相似文献   
58.
The kinetics for the reaction between potassium ferricyanide (K3Fe(CN)6) and cobalt chloride (CoCl2) in aqueous solution and water/bis(2-ethylhexyl) sodium sulfosuccianate (AOT)/isooctane microemulsions were studied by three-wavelength spectrophotometry at 298.2 K. The second-order rate constants (k2) were calculated from the time dependence of the concentration of reactant K3Fe(CN)6. The result showed that the reaction rates in water/AOT/isooctane microemulsions were slower than that in the aqueous solution, and k2 decreased with molar ratio (ω) of water to AOT in microemulsions, which was interpreted by the transition state theory and confirmed that the reaction took place at the interfaces of the microemulsion water pools.  相似文献   
59.
杜乐  曹鹏  廖建 《化学学报》2013,(9):1239-1242
研究双亚砜膦配体(BiSO-P)亚砜基团的Bronsted碱性在协同催化反应中的作用.1H NMR研究表明双亚砜膦与醇和胺等质子试剂形成氢键;并将此类配体应用于钯催化的不对称醚化和胺化反应,最高获得99%ee.研究发现氢键的存在能有效提高反应的ee值,配体亚砜基团在反应过程中同时起着Lewis和Bronsted碱的作用.  相似文献   
60.
A method for concurrent synthesis of vanillin and isovanillin has been developed by a nonregioselective Vilsmeier–Haack reaction of O-alkyl guaiacols. O-Alkylation of guaiacol provided the corresponding O-alkyl guaiacol (1), which was then formylated with N-methylformanilide/phosphorus oxychloride to give a mixture of 4-alkoxy-3-methoxy-benzaldehyde (2) and 3-alkoxy-4-methoxybenzaldehyde (3). Finally, the obtained mixture underwent a selective dealkylation by anhydrous aluminium trichloride, while leaving methyl groups intact to simultaneously achieve the significant fine chemicals vanillin and isovanillin.  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