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   27550篇
  免费   5227篇
  国内免费   10595篇
化学   20031篇
晶体学   1303篇
力学   2159篇
综合类   1160篇
数学   3894篇
物理学   14825篇
  2024年   80篇
  2023年   253篇
  2022年   1015篇
  2021年   950篇
  2020年   951篇
  2019年   878篇
  2018年   834篇
  2017年   1285篇
  2016年   969篇
  2015年   1376篇
  2014年   1686篇
  2013年   2138篇
  2012年   2056篇
  2011年   2388篇
  2010年   2456篇
  2009年   2608篇
  2008年   2868篇
  2007年   2468篇
  2006年   2550篇
  2005年   2246篇
  2004年   1689篇
  2003年   1244篇
  2002年   1226篇
  2001年   1350篇
  2000年   1417篇
  1999年   772篇
  1998年   427篇
  1997年   346篇
  1996年   313篇
  1995年   281篇
  1994年   279篇
  1993年   276篇
  1992年   302篇
  1991年   164篇
  1990年   186篇
  1989年   159篇
  1988年   152篇
  1987年   135篇
  1986年   97篇
  1985年   86篇
  1984年   76篇
  1983年   70篇
  1982年   44篇
  1981年   46篇
  1980年   37篇
  1979年   57篇
  1978年   17篇
  1966年   8篇
  1965年   9篇
  1959年   10篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
11.
大孔吸附树脂对邻甲酚的吸附行为研究   总被引:14,自引:0,他引:14  
研究了大孔吸附树脂NDA—909吸附水溶液中邻甲酚的热力学特征,并与Amberlite XAD—4树脂进行了比较.通过吸附动力学实验,初步探讨了初始温度对吸附过程的影响。结果表明,NDA—909对邻甲酚的吸附符合Freundlich经验公式,表现为放热的物理吸附过程.此外吸附速率受颗粒内扩散和其它类型扩散的共同控制。  相似文献   
12.
New binuclear copper(Ⅱ) complexes, [Cu(samen)Cu(NO_2-phen)]·H_2O and [Cu(sampn)-Cu(NO_2-phen)]·2H_2O have been synthesized, where samen~(4-), sampn~(4-) and NO_2-phen denote N, N′-ethylenedisalicylamidate anion, N, N′-1, 2-propanedisalicylamidate anion and 5-nitro-1, 10-phenanthroline respectively. 3ased on IR, elemental analyses and electronic spectra, the complexes are proposed to have a phenoxy-bridged structure and to consist of the Cu(Ⅱ)ion in distorted planar environment. The complexes have been characterized with varlable-temperature magnetic susceptibility (4—300 K) and the observed data were fit to those from a modified Bleaney-Bowers equation by least-squares method, giving the exchange integral J=-63.0 cm~(-1) (samen) and J=-46.5cm~(-1) (sampn). This indicates the existence of antiferromagnetic spin exchange interaction among the metal ions.  相似文献   
13.
A novel 5-deoxyflavone compound, 7, 8-dimethoxy-3′, 4′-methylene-dioxyflavone (1), was in 2002 isolated from the root bark of Albizia Odoratissima. [1] The compound 1 was preparaed from pyrogallic acid (2) and piperonal(5) in four steps (Scheme 1). [2] The spectroscopic data (1H NMR, 13C NMR, MS and IR) of 1 were in good agreement with those of natural product. [ 1]  相似文献   
14.
The phenomenon of migration of the silyl groups from α-oxygen to β-oxygen in sodium aldol reaction was observed for the first time in this paper.  相似文献   
15.
Chen C  Huang D  Zhang X  Chen F  Zhu H  Liu Q  Zhang C  Liao D  Li L  Sun L 《Inorganic chemistry》2003,42(11):3540-3548
A reaction system consisting of terephthalic acid, NaOH, inorganic Mn(II) or Mn(III) salt, and salicylidene alkylimine resulted in dinuclear manganese complexes (salpn)(2)Mn(2)(mu-phth)(CH(3)OH)(2) (1, salpn = N,N'-1,3-propylene-bis(salicylideneiminato); phth = terephthalate dianion), (salen)(2)Mn(2)(mu-phth)(CH(3)OH)(2) (2, salen = N,N'-ethylene-bis(salicylideneiminato)), (salen)(2)Mn(2)(mu-phth)(CH(3)OH)(H(2)O) (3), and (salen)(2)Mn(2)(mu-phth) (4), while the absence of NaOH in the reaction led to a mononuclear Mn complex (salph)Mn(CH(3)OH)(NO(3)) (5, salph = N,N'-1,2-phenylene-bis(salicylideneiminato)). In addition, a trinuclear mixed metal complex H[Mn(2)Na(salpn)(2)(mu-OAc)(2)(H(2)O)(2)](OAc)(2) (6) was obtained from the reaction system by using maleic acid instead of terephthalic acid. Five-coordinate Mn ions were found in 4 giving rise to an intermolecular interaction and constructing a one-dimensional linear structure. Antiferromagnetic exchange interactions were observed for 1-3, and a total ferromagnetic exchange of 4 was considered to stem from intermolecular magnetic coupling. (1)H NMR signals of phenolate ring and alkylene (or phenylene) backbone of the diamine are similar to those reported in the literature, and the phth protons are at -2.3 to -10.1 ppm. Studies on structure, bond valence sum analysis, and magnetic properties indicate the oxidation states of the Mn ions in 6 to be +3, which are also indicated by ESR spectra in dual mode. Ferromagnetic exchange interaction between the Mn(III) sites was observed with J = 1.74 cm(-1). A quasireversible redox pair at -0.29V/-0.12V has been assigned to the redox of Mn(2)(III)/Mn(III)Mn(II), implying the intactness of the complex backbone in solution.  相似文献   
16.
The surface basicity of Ti-La-Li multicoinponent oxides has been investigated by means of CO2-TPD. The experiment results show that C2 (C2H6 C2H4) selectivity is related to surface basic strength. The surface active oxygen species have also been characterized by means of XPS, O2-TPD and so on. It has been indicated that C2 selectivity and CH4 conversion are correlated with lattice oxygen and the adsorbed oxygen on the surface of the catalyst respectively In the O2-TPD experiments, it has also been found that there are three kinds of oxygen species on the surface of the series catalvsts, which are a (100℃ 750℃) Among them α-oxvgen causes deep oxidation whileβand γ oxygen species are related to oxidalive coupling of methane (OCM).  相似文献   
17.
电化学合成铜配合物的研究   总被引:3,自引:0,他引:3  
采用金属铜为"牺牲"阳极,首次在无隔膜电解槽中,电化学溶解金属铜一步制备了纳米CuO前体Cu(OEt)2, Cu(OBu)2, Cu(acac)2, Cu(OEt)(acac), Cu(OBu)(acac) (acac为乙酰丙酮基).产物通过红外光谱(FT-IR)、拉曼光谱(Raman spectrum)进行表征.同时讨论了影响电合成铜醇盐及其配合物的关键因素.实验表明,防止阳极钝化,温度控制在30~50 ℃,采用有机胺溴化物为导电盐, 电极电位控制在0.8~1.2 V之间,可以提高电合成效率.实验同时表明Cu(acac)2, Cu(OEt)(acac), Cu(OBu)(acac)可作为制备含铜纳米材料前驱体.  相似文献   
18.
The Kringle-1 structure of plasminogen (PGK-1), the Kringle-2 structure of tissue plasminogen activator (PAK-2) and the Kringle structure of prourokinase (UKK) has been modeled on the basis of the three-dimensional structure of Kringle-1 of prothrombin (PTK-1) at 2.8 resolution. The predicted three-dimensional structure of these Kringles shows that the binding site of PGK-1 is characterized by an apparent dipolar site, the polar parts of which are separated by a hydrophobic region. PAK-2 possesses the anionic center but has not a cationic binding center which might be provided by a guanidinium group from Arg-69 located adjacent to the Arg-71 position. UKK possesses neither the anionic binding center nor the cationic center which are probably the main reason for the poor fibrin specificity of urokinase.  相似文献   
19.
A one-pot procedure for the efficient synthesis of a small library of t-RNA inhibitor analogues was developed. Thus,Rh2(OAc)4 catalyzed three-component 1,3-dipolar cycloaddition reactions of carbonyl ylides derived from diazoindan-1,3-dione and aldehydes with other dipolarophiles in 1,1,2,2-tetrachloroethane at 80 ℃ gave ring fused tetrahydrofurans having three stereocenters in good yield.  相似文献   
20.
Following the previous paperr, we examined the kinetics of the irreversible modification of enzyme activity in coupled assay when the modifier reacted with both primary and auxiliary enzymes. It was shown that Tsou's kinetic method can also be used in the present situation in some conditions.  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