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   1475篇
  免费   97篇
  国内免费   217篇
化学   1163篇
晶体学   20篇
力学   4篇
综合类   18篇
物理学   85篇
综合类   499篇
  2024年   5篇
  2023年   10篇
  2022年   42篇
  2021年   45篇
  2020年   48篇
  2019年   41篇
  2018年   34篇
  2017年   45篇
  2016年   56篇
  2015年   56篇
  2014年   42篇
  2013年   136篇
  2012年   99篇
  2011年   69篇
  2010年   52篇
  2009年   78篇
  2008年   71篇
  2007年   92篇
  2006年   80篇
  2005年   84篇
  2004年   74篇
  2003年   56篇
  2002年   59篇
  2001年   49篇
  2000年   46篇
  1999年   47篇
  1998年   53篇
  1997年   32篇
  1996年   31篇
  1995年   31篇
  1994年   22篇
  1993年   21篇
  1992年   19篇
  1991年   13篇
  1990年   5篇
  1989年   11篇
  1988年   6篇
  1987年   6篇
  1986年   5篇
  1985年   3篇
  1984年   2篇
  1982年   5篇
  1980年   2篇
  1978年   1篇
  1977年   1篇
  1976年   1篇
  1975年   1篇
  1973年   1篇
  1972年   1篇
排序方式: 共有1789条查询结果,搜索用时 15 毫秒
951.
圆弧青霉突变株HB01碱性脂肪酶基因的克隆和表达   总被引:1,自引:0,他引:1  
圆弧青霉(Peniciuium cyclopium)突变株可产生一种具有工业价值的碱性脂肪酶(alkaline lipase,PEL),通过RT-PCR基因克隆及序列测定,获得了PEL完整的基因序列,该基因全长855bp,编码1个由285个氨基酸残基组成的酶蛋白,根据氨基酸组成推导该脂肪酶蛋白的分子量约为30kD.  相似文献   
952.
The synthesis, structural, and spectral characterization as well as a theoretical study of a family of alkaline‐earth‐metal acetylides provides insights into synthetic access and the structural and bonding characteristics of this group of highly reactive compounds. Based on our earlier communication that reported unusual geometry for a family of triphenylsilyl‐substituted alkaline‐earth‐metal acetylides, we herein present our studies on an expanded family of target derivatives, providing experimental and theoretical data to offer new insights into the intensively debated theme of structural chemistry in heavy alkaline‐earth‐metal chemistry.  相似文献   
953.
A new family in town! Treatment of a rare‐earth metal (Ln) and either a potential divalent rare‐earth metal (Ln′) or an alkaline earth metal (Ae) with 2,6‐diphenylphenol (HOdpp) at elevated temperatures (200–250 °C) afforded heterobimetallic aryloxo complexes (see figure). Both a charge‐separated species, [(Ln′/Ae)2(Odpp)3][Ln(Odpp)4], and a neutral species, [AeEu(Odpp)4], were obtained and crystallographically characterised.

  相似文献   

954.
刘丹  周荫庄 《无机化学学报》2009,25(10):1797-1804
本文报道了新型铜配合物[Cu(PyPt)(NO3)2](HPyPt是N-2-吡啶基-N'-苯基硫脲)的合成、结构、波谱表征及其与DNA相互作用研究.该配合物属三斜品系P1空间群,其中a=0.761 52(15)nm,b=0.80957(16)nm,c=1.311 3(3)nm,α=76.01(3)°,β=89.59(3)°,γ=68.24(3)°,V=0.7255(2)nm3,Z=2.利用荧光光谱法、紫外光谱法和粘度法初步研究了[Cu(PyPt)(NO3)2]与小牛胸腺DNA的相互作用,计算其与DNA结合常数Kb为1.63×103 L·mol-1.  相似文献   
955.
A new solid substrate room temperature phosphorimetry (SSRTP) for the determination of trace mercury has been established, using Triton X‐100 as a sensitizer. The regression equation of working curve was ΔIp=11.40m(Hg2+)+1.569 (ag·spot?1, n=6, ΔIp=Ip1?Ip2, Ip1 and Ip2 referred to the phosphorescence intensity of the blank reagent and the test solution, respectively), and correlation coefficient (r) was 0.9984. The RSD valus of the determination of 0.016 and 8.0 ag·spot?1 Hg2+ were 4.1% and 1.7% (n=8), respectively, indicating that the method had good repeatability. The limit of detection (LOD) calculated by 3Sb/k was 7.0 zg·spot?1 Hg2+ (corresponding concentration: 1.8×10?17 g·mL?1, Sb=0.025, n=11). This method has high sensitivity, selectivity and precision, which was applied to determination of trace mercury in water samples with the result being agreed very well with that of dithizone extraction spectrophotometry.  相似文献   
956.
An environmentally benign method has been developed for the synthesis of novel chiral thiourea derivatives in high yields in ionic liquid [Bmim]PF6. The ionic solvent can be recovered and reused without any loss of its activity. The target compounds were characterized by elemental analysis, IR, 1H NMR and 13C NMR spectral data. According to the preliminary bioassay, some of the chiral thiourea analogues exhibited moderate in vivo antiviral activities against TMV at a concentration of 500 mg/L. Title chiral compound 3i was found to possess good in vivo protection, inactivation and curative activities of 57.0%, 96.4% and 55.0%, respectively against TMV with an inhibitory concentration at 500 mg/L. The title chiral compound 3i revealed better inactivation effect on TMV (EC50=50.8 µg/mL) than Ningnanmycin (EC50=60.2 µg/mL).  相似文献   
957.
The relative stability of different clusters of thiourea dioxide (TDO) in water is examined using gas phase quantum chemical calculations at the MP2 and B3LYP level with 6‐311++G(d,p) basis set. The possible equilibrium structures and other energetic and geometrical data of the thiourea dioxide clusters, TDO‐(H2O)n (n is the number of water molecules), are obtained. The calculation results show that a strong interaction exists between thiourea dioxide and water molecules, as indicated by the binding energies of the TDO clusters progressively increased by adding water molecules. PCM model is used to investigate solvent effect of TDO. We obtained a negative hydration energy of ?20.6 kcal mol?1 and free‐energy change of ?21.0 kcal mol?1 in hydration process. On the basis of increasing binding energies with adding water molecules and a negative hydration energy by PCM calculation, we conclude thiourea dioxide can dissolve in water molecules. Furthermore, the increases of the C? S bond distance by the addition of water molecules show that the strength of the C? S bonds is attenuated. We find that when the number of water molecules was up to 5, the C? S bonds of the clusters, TDO‐(H2O)5 and TDO‐(H2O)6 were ruptured. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009  相似文献   
958.
A series of new N-acylsubstituted thioureas, the compositions and structures of which were determined by IR and PMR spectroscopy and mass spectrometry, were synthesized from the alkaloid anabasine. The crystal structure of one of the products, N-(anabasino-1-thiocarbonyl)furan-2-carboxamide, was confirmed by x-ray structure analysis. It was also shown that this compound exhibited moderate antibacterial activity. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 183–185, March–April, 2009.  相似文献   
959.
二氨基硫脲与芳香醛(酮)反应,合成了3个三齿Schiff碱配体;配体与二苄基二氯化锡或三苄基氯化锡反应合成了6个未见文献报道的三齿配体杂环有机锡(Ⅳ)配合物,其结构经1H NMR, IR和元素分析表征.  相似文献   
960.
采用循环伏安、线性扫描和恒电位阶跃电化学方法结合扫描电镜研究了不同浓度的丙烯基硫脲(ATU)对NH3-NH4Cl-H2O体系镍在玻碳电极上的电沉积过程的影响. 循环伏安测试、线性扫描以及恒电位暂态曲线一致表明ATU的加入对镍电沉积具有阻化作用,并且随着ATU浓度的增加其阻化作用增强;恒电位暂态曲线结果表明,镍的电结晶是按瞬时形核三维生长机理进行的,随外加电位负移,晶体向外生长速率增大;ATU的加入没有改变镍的形核方式,但形核数密度增大,并且减小晶体向外生长的速率;扫描电镜结果表明,ATU的加入可以细化晶粒,得到整平、致密的镍沉积层.  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