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   3211篇
  免费   531篇
  国内免费   334篇
化学   2100篇
晶体学   34篇
力学   260篇
综合类   27篇
数学   386篇
物理学   1269篇
  2024年   3篇
  2023年   71篇
  2022年   83篇
  2021年   140篇
  2020年   140篇
  2019年   124篇
  2018年   103篇
  2017年   103篇
  2016年   176篇
  2015年   164篇
  2014年   205篇
  2013年   235篇
  2012年   318篇
  2011年   321篇
  2010年   224篇
  2009年   222篇
  2008年   202篇
  2007年   183篇
  2006年   179篇
  2005年   142篇
  2004年   117篇
  2003年   79篇
  2002年   69篇
  2001年   64篇
  2000年   48篇
  1999年   68篇
  1998年   42篇
  1997年   37篇
  1996年   35篇
  1995年   31篇
  1994年   25篇
  1993年   21篇
  1992年   20篇
  1991年   18篇
  1990年   23篇
  1989年   10篇
  1988年   6篇
  1987年   6篇
  1986年   7篇
  1985年   3篇
  1984年   2篇
  1983年   1篇
  1981年   3篇
  1974年   1篇
  1971年   1篇
  1959年   1篇
排序方式: 共有4076条查询结果,搜索用时 46 毫秒
51.
The refolding of the reduced-denatured insulin from bovine pancreas was investigated with the size exclusion chromatography (SEC). It was shown that the reduced-denatured insulin originally denatured with 7.0 mol L?1 guanidine hydrochloride (GuHCI) or 8.0 mol L?1 urea could not be refolded with a non-oxidized mobile phase. Although the oxidized and reduced glutathione (GSSG and GSH) were employed in the oxidized mobile phase, the reduced-denatured insulin still could not be renatured. However, in the presence of 2.0 mol Lt-1 urea in the oxidized mobile phase employed, the reduced-denatured insulin can be refolded with SEC, and the aggregation of denatured insulin can be diminished by urea. In addition, the disulfide exchange of reduced-denatured insulin also can be accelerated with GSSG/GSH in the oxidized mobile phase. The three disulfide bridges of insulin were formed correctly and the reduced-unfolded insulin can be renatured completely. The results were further tested with reversed-phase liquid chromatography (RPLC) and hydrophobic interaction chromatography (HIC).  相似文献   
52.
Because of the effect of pyridine on the substituent position on the TTF group, TTF derivatives exhibit different assembly structures at the interface, which will be of great significance to the construction of functional nanostructures from the molecular design point of view.  相似文献   
53.
比值光谱导数法同时测定铝合金中铁,铜,锌   总被引:6,自引:0,他引:6  
刘葵  耿玉珍 《分析化学》1998,26(10):1201-1204
用比值光谱-导数分光光度法,在pH5.5缓冲溶液中,利用金属-2-(5-溴-2-吡啶偶氮)-5-二乙氨基酚(5-Br-PADAP)-OP三元络合物显色体系,对混合物中铁,铜,锌三组分进行了同时测定。合成试样5次测定回收率在97.3%-104.4%之间。应用于铝合金中铁,铜,锌的测定,各6次测定的RSD分别为3.66%,1.38%,2.03%。  相似文献   
54.
时亚丽  耿信笃 《分析化学》1994,22(2):143-145
反相高效液相色谱(RPLC)中小分子极性溶质的极性是可以用液相色谱中溶质计量置换保留模型中的Z值(1mol溶质被固定相吸附时,在固定相与溶质子间释放出置换剂的mol数)来表征的,其大小可用带有该极性端基的同系物的Z值对碳原子数线性作图的截距求得。这些检性基的Z测量定值与疏水性片段指数1gf间有极好的线性关系。依此关系还可测出一些用其他实验方法无法测得的某些基团的1gf值。  相似文献   
55.
Parallel solution combustion synthesis for combinatorial materials studies   总被引:1,自引:0,他引:1  
A parallel solution combustion synthesis technique was developed for combinatorial materials studies. The vigorous combustion reactions were successfully limited in the microreactors by using a substrate-net-mask microreactor system and the lowest adoptable furnace temperature. Using this technique, a luminescent materials library of Y3Al5O12/Tb(chi) was synthesized with the aid of an ink-jet delivery system. Structure and luminescence characterizations were implemented using X-ray diffraction and UV/X-ray spectroscopies, respectively. The results show that this technique is reliable and applicable to combinatorial study of powder materials with high synthesis temperature.  相似文献   
56.
Synthetic gp120331-335 glycopeptide fragments carrying hybrid and high-mannose type N-linked glycans were evaluated for binding to broadly neutralizing antibody 2G12 using surface plasmon resonance technology. None of the hybrid-type constructs demonstrated binding to 2G12. In the high-mannose series, the "Cys dimer" construct, presenting two undecasaccharide glycans, showed significantly higher binding than the Cys-protected monomer. The binding of the dimeric structure was further investigated in competition with recombinant gp120. The data suggest that gp120 and its designed synthetic epitope construct bind to the same site on 2G12.  相似文献   
57.
A series of novel liquid crystalline epoxides with lateral substituents were cured with anhydrides and the cure kinetics was investigated by non-isothermal DSC technique. The results showed that the lengths of lateral substituents have great effect on the value of Ea. The curing reaction became less active, when the liquid crystalline epoxides have long lateral substituents and were controlled by diffusion at the late stage of cure. A nematic structure was observed by POM and XRD.  相似文献   
58.
An oligosaccharide homologue named SnS-2 was isolated from the root of Scrophularia ningpoensis Hemsl.SnS-2 was purified by means of gel-permeation chromatography and ion-exchange chromatography. Its physicochemical properties, including carbohydrate content and molecular weight were determined. The structure of SnS-2 was elucidated by chemical methods along with ^1H and ^13C NMR spectroscopy, including two-dimensional DQCOSY and H-detected ^1H, ^13C HMQC experiments. These results show that SnS-2 possesses a backbone consisting of terminal α-Galp-(1→, α-Galp-(1→6), α-Glcp-(1→6) and nonreducing end β-Fruf-(2→. The bioactive assay showed that it could inhibit the growth of Lewis pulmonary carcinoma implanted in mice.  相似文献   
59.
流动注射—化学发光法测定苯甲醛   总被引:1,自引:0,他引:1  
姚公安  刘谦光 《分析化学》1996,24(12):1441-1443
依据苯甲醛增强没食子酸-过氧化氢-氢氧化钠体系化学发光的性质,建立了苯甲醛的流动注射化学发光分析法。  相似文献   
60.
David Zhigang Wang 《Tetrahedron》2005,61(30):7134-7143
In the framework of a helix theory recently developed for molecular chiralities and chiral interactions, it is further proposed that for an asymmetric reaction to be highly enantioselective, the helical characters, that is, the local energies of electrons on the helices, of the catalyst and the substrate complexed with it in the corresponding enantioselection-determining step must be matched. These helical characters can be analyzed on the basis of molecular polarizability and structure properties under a given reaction mechanism. This proposal highlights the importance of polarizability matching in three-dimension chiral space and in essence is a chiral version of the classical hard and soft acid-base theory. It also from an electronic effect angle sheds light on the nature of the conventional lock-and-key origin of high enantioselection and carries the message that, to design a good catalyst (the key), rather than focusing on the rigidity, bulkiness or C2-symmetry of the catalyst, one should focus more on the helical character of the substrate (the lock) with which the catalyst will interact. It is generally easier to discover a highly enantioselective catalyst for a substrate of a large helical character than for a substrate of a small helical character. The proposal is supported by theoretical modeling as well as numerous experiments and is used to understanding various aspects of current asymmetric catalysis.  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