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   66993篇
  免费   10646篇
  国内免费   7339篇
化学   47482篇
晶体学   812篇
力学   3813篇
综合类   418篇
数学   7266篇
物理学   25187篇
  2024年   226篇
  2023年   1348篇
  2022年   2508篇
  2021年   2683篇
  2020年   2791篇
  2019年   2675篇
  2018年   2313篇
  2017年   2195篇
  2016年   3255篇
  2015年   3256篇
  2014年   3849篇
  2013年   5003篇
  2012年   6025篇
  2011年   5991篇
  2010年   4159篇
  2009年   3931篇
  2008年   4274篇
  2007年   3826篇
  2006年   3424篇
  2005年   2974篇
  2004年   2316篇
  2003年   1864篇
  2002年   1801篇
  2001年   1394篇
  2000年   1177篇
  1999年   1320篇
  1998年   1076篇
  1997年   1004篇
  1996年   981篇
  1995年   882篇
  1994年   746篇
  1993年   623篇
  1992年   532篇
  1991年   484篇
  1990年   392篇
  1989年   292篇
  1988年   215篇
  1987年   190篇
  1986年   191篇
  1985年   173篇
  1984年   107篇
  1983年   108篇
  1982年   69篇
  1981年   56篇
  1980年   38篇
  1979年   19篇
  1976年   24篇
  1975年   27篇
  1973年   21篇
  1972年   21篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
A new short synthesis of 3-substituted 5-amino-1-(chloromethyl)-1,2-dihydro-3H-benzo[e]indoles from Martius Yellow is disclosed. The key steps of the synthesis were three efficient regioselective reactions (iodination, 5-exo-trig aryl radical-alkene cyclization and carboxylation).  相似文献   
102.
The UV and visible spectra of six model compounds were studied. These compounds can be considered as models of polyaniline in the reduced, cation radical, partially oxidized and oxidized forms. After treatment of a mixture of equal molar quantities of the reduced form (DPPD) and the oxidized form (QDIM) with acid, the following reaction was observed: DPPD(I)+QDIM(III)+2H+=2DPPD+(II) After similar treatment of the partially oxidized form (V) with acid, the radical cation salt formed. The UV and visible spectra of polyaniline in the reduced form, oxidized form and conductive form are similar to the spectra of DPPD, QDIM and DPPD+ or radical cation salt of V respectively. We propose that the polyaniline synthesized by chemical oxidation of aniline consists of oxidized and reduced repeat units. Upon protonation a redox reaction (or electron rearrangement) occurs and forms delocalized radical cations (polarons) in the polymer chain which are highly conductive.  相似文献   
103.
对1993年6月至1996年6月因体弱多病,生长发育矮小等来诊的351例儿童作了血铅测查和临床全征分析,以期引起儿科临床医师重视。  相似文献   
104.
Nitropyridines reacted with an excess of vinyl Grignard reagent to produce 4- or 6-azaindoles. Improved yields were obtained when a halogen atom was present at the position alpha to the nitrogen atom in the pyridine ring.  相似文献   
105.
本文采用XRD,NH_3-TPD,IR以及TEM等方法考察了Pt/BaKL沸石中Ba~(2+)的作用。NH_3-TPD结果表明,交换Ba~(2+)后的L型沸石的酸性,由于阳离子的作用仅在弱酸范围内有些改变,但与载铂的沸石的催化活性无明显的对应关系。IR及XRD谱线表明,BaKL沸石中Ba~(2+)在最佳交换度(26.3%)时,随预培烧温度的提高,使Ba~(2+)处于沸石孔道中B、C、D位置,接近于最佳分布,此时IR谱线上1421cm~(-1)处有一新峰。当沸石负载铂后,因铂与Ba~(2+)的相互作用,新峰消失,导致铂粒在沸石上分布更加均匀;铂粒在1.5—3.0nm之间占有最大比例,使得Pt/BaKL沸石呈现芳构化活性及选择性高于Pt/KL沸石,分别为~98%和~95%。  相似文献   
106.
We investigate the role that local motions and slow cooperative fluctuations have on the relaxation of the intrapair dipolar order in the nematic 5CB. With this purpose we present a theoretical and experimental systematic study which allow us to quantify the contribution from each type of molecular fluctuation to the intrapair dipolar order relaxation time, T(1D). The experimental work includes measurements of Zeeman and intrapair dipolar order relaxation times (T(1Z) and T(1D)) as a function of temperature at conventional NMR frequencies, in three complementary samples: normal and chain deuterated 4-n-pentyl-4(')-cyanobiphenyl (5CB and 5CB(d11)) and a mixture of normal 5CB and fully deuterated 4-n-pentyl-4'-cyanobiphenyl (5CB(d19)), 50% in weight. Additionally we perform T(1Z) field-cycling Larmor frequency-dependent measurements to obtain the spectral density of the cooperative fluctuations. The obtained results are as follows. (a) The cooperative molecular fluctuations have a strong relative weight in the relaxation of the intrapair dipolar order state, even at Larmor frequencies in the range of conventional NMR. (b) Alkyl chain rotations are an important relaxation mechanism of the intrapair dipolar order at megahertz frequencies. (c) Intermolecular fluctuations mediated by translational self-diffusion of the molecules is not an efficient mechanism of relaxation of the intrapair dipolar order.  相似文献   
107.
Oxidation of cysteine residues to cysteic acids in C-terminal arginine-eontaining peptides (such as those derived by tryptic digestion of proteins) strongly promotes the formation of multiple members of the Y? series of fragment ions following low energy collision-activated decomposition (CAD) of the protonated peptides, Removal of the arginine residue abolishes the effect, which is also attenuated by conversion of the arginine to dimethylpyrim-idylornithine. The data indicate the importance of an intraionic interaction between the cysteic acid and arginine side-chains. Low energy CAD of peptides which include cysteic acid and histidine residues, also provides evidence for intraionic interactions. It is proposed that these findings are consistent with the general hypothesis that an increased heterogeneity (with respect to location of charge) of the protonated peptide precursor ion population is beneficial to the generation of a high yield of product ions via several charge-directed, low energy fragmentation pathways. Furthermore, these data emphasize the significance of gas-phase conformations of protonated peptides in determining fragmentation pathways.  相似文献   
108.
Since hydration forces become very strong at short range and are particularly important for determining the magnitude of the adhesion between two surfaces or interaction energy, the influences of the hydration force and elastic strain energy due to hydration-induced layering of liquid molecules close to a solid film surface on the stability of a solid film in a solid-on-liquid (SOL) nanostructure are studied in this paper. The liquid of this thin SOL structure is a kind of water solution. Since the surface forces play an important role in the structure, the total free energy change of SOL structures consists of the changes in the bulk elastic energy within the solid film, the surface energy at the solid-liquid interface and the solid-air interface, and highly nonlinear volumetric component associated with interfacial forces. The critical wavelength of one-dimensional undulation, the critical thickness of the solid film, and the critical thickness of the liquid layer are studied, and the stability regions of the solid film have been determined. Emphasis is placed on calculation of critical values, which are the basis of analyzing the stability of the very thin solid film.  相似文献   
109.
The thermal behaviors of chelates of oxine, 8-hydroxyquinaldine and their derivatives (DCQ, 5, 7-dichloro-8-hydroxyquinoline; DCQ', 5, 7-dichloro-8-hydroxyquinaldine) in an air atmosphere have been studied. The order of heat stability of chelates, decreased with decreasing basicity of the ligand, i.e. oxine<DCQ<DCQ'. The presence of water or proton-containing compounds in the chelates seemed to lower heat stabilities,  相似文献   
110.
In this study, the determination of 4-Bromoaniline (4-BA) in green algae Chlamydomonas reinhardtii (C. reinhardtii) was investigated by applying continuous-flow microextraction (CFME) combined with high-performance liquid chromatography (HPLC). Continuous-flow microextraction was conducted in a homemade glass chamber, i.e. the sample solution flowed through a constant volume drop of solvent in the chamber at a constant flow rate. The effects of different factors on extraction efficiencies were also investigated and these factors included the kind of extraction solvent, solvent drop volume, sample flow rate, extraction time and addition amount of salt. Under the optimum extraction conditions (extraction solvent, carbon tetrachloride; solvent drop volume, 3.5 μL; sample flow rate, 1.0 mL min−1; extraction time, 10 min; no addition of salt), the calibration plot was set up by plotting peak area against a series of 4-Bromoaniline concentrations (0.01–10 μg mL−1) in aqueous solution. The correlation coefficient (r) was 0.9990. The limit of detection (LOD) was 0.6 ng mL−1. The precision of this method was obtained by successive five time analyses of 100-ng mL−1 standard solution of 4-Bromoaniline, and the relative standard deviation (RSD) was 3.5%. The concentration factor was calculated by the ratio of peak area of the analyte obtained after and before extraction and found to be 10.6. 4-Bromoaniline residues in Chlamydomonas. reinhardtii cells and tap water samples were satisfactorily analyzed according to the method described above.  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