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   46518篇
  免费   8158篇
  国内免费   6194篇
化学   33368篇
晶体学   666篇
力学   2934篇
综合类   437篇
数学   5544篇
物理学   17921篇
  2024年   88篇
  2023年   848篇
  2022年   991篇
  2021年   1386篇
  2020年   1774篇
  2019年   1704篇
  2018年   1510篇
  2017年   1387篇
  2016年   2211篇
  2015年   2170篇
  2014年   2682篇
  2013年   3335篇
  2012年   3979篇
  2011年   4297篇
  2010年   3021篇
  2009年   3010篇
  2008年   3326篇
  2007年   2941篇
  2006年   2783篇
  2005年   2179篇
  2004年   1818篇
  2003年   1503篇
  2002年   1579篇
  2001年   1265篇
  2000年   1230篇
  1999年   1038篇
  1998年   876篇
  1997年   789篇
  1996年   808篇
  1995年   708篇
  1994年   612篇
  1993年   502篇
  1992年   466篇
  1991年   370篇
  1990年   324篇
  1989年   256篇
  1988年   225篇
  1987年   189篇
  1986年   164篇
  1985年   166篇
  1984年   112篇
  1983年   79篇
  1982年   63篇
  1981年   44篇
  1980年   19篇
  1979年   19篇
  1978年   6篇
  1977年   4篇
  1974年   3篇
  1957年   3篇
排序方式: 共有10000条查询结果,搜索用时 62 毫秒
971.
Bian HD  Gu W  Xu JY  Bian F  Yan SP  Liao DZ  Jiang ZH  Cheng P 《Inorganic chemistry》2003,42(14):4265-4267
The first mu(3)-oxalato-bridged copper(II) complex, [[Cu(3)(L)(3)(mu(3)-C(2)O(4))][Cu(L)(H(2)O)](ClO(4))(2)] x 0.5(H(2)O) x 0.5(CH(3)OH), where HL = N-ethyl-N'-salicylidene-1,2-diaminoethane, has been synthesized and characterized by variable-temperature magnetic susceptibility measurement. The complex exhibits ferromagnetic coupling between the oxalato-bridged copper atoms and antiferromagnetic coupling between the oxygen-bridged copper atoms.  相似文献   
972.
The anodic oxidation of caffeic acid in the presence of acetylacetone or methyl acetoacetate in aqueous solution has been studied by cyclic voltammetry and controlled-potential electrolysis techniques. The result showed that caffeic acid was oxidized to the corresponding o-benzoquinone, which underwent further Michael-addition with acetylacetone or methyl acetoacetate to produce caffeic acid derivative 3,4-dihydroxy-6-(1-acetylacetone)-yl cinnamic acid 4a or 3,4-dihydroxy-6-(1-acetyl-methylacetate)-yl cinnamic acid 4b.  相似文献   
973.
A new method for the determination of antithrombotic activity of egg white protein hydrolysate(EWPH)was developed using amicroplate reader.Reaction was carried out at 37℃ and pH 7.2 with fibrinogen concentration 0.1%.Microplate reading wasconducted at 405 nm.Inhibition rate of EWPH on thrombin activity showed linearity(R~2=0.9971),when the inhibition rate was inthe range of 10-90%.The lower limit of detection(LLD,at 99.7%probability)and the biological limit of detection(BLD,at 99.7%probability)of the method were 10.643 and 40 mg/mL,respectively.The repeatability standard deviation(R.S.D.)was 1.08%.Thestandard deviation of the method was 0.027 AT-U.  相似文献   
974.
Recently the research on structures with an ordered two-dimensional(2D) pattern has attracted great attention due to its versatile applications in the fields of microelectronic and optoelectronic devices, displays, biochips and sensors, enzymatic immobilization, drug carriers, and photonic band gap materials. Various well-arrayed 2D structures have been made by the modern technique such as laser writing pattern fabrication, photoetching technique, micro-electromechanical systems based on scann…  相似文献   
975.
A series of pure silica MSU and carboxylic-modified MSU materials were prepared. The formation of mesoporous silica materials with terminal carboxylic groups on pore surface was performed by the acid-catalyzed hydrolysis of cyano to carboxylic. Then their potential applications in controlled drug delivery carriers were investigated. Drug famotidine was selected as a model molecule out of the consideration of the terminal amino groups in its molecule. The adsorption experiments show significant adsorption of famotidine on the carboxylic-modified MSU materials. And, the functionalization level of carboxylic groups has been found to be the key factor affecting the adsorption capacities of the modified MSU materials for famotidine. Subsequently, three kinds of release fluids, including simulated gastric medium, simulated intestinal medium, and simulated body fluid, were used to test the famotidine release rate from the carboxylic-modified MSU material. Obvious delayed effect has been observed for the famotidine release from the carboxylic-modified mesoporous silica material under the in vitro assays.  相似文献   
976.
乳状液法制备憎液溶胶Ⅰ.BaCO_3均匀粒子的制备   总被引:1,自引:0,他引:1  
均匀胶体粒子的形成,除与反应条件(反应物浓度、陈化时间和温度、介质种类等)有关外,反应体系的环境也影响最终产物的形态,《至结晶结构.气溶胶法和微乳液法正是利用微环境中的‘水池效应”;分别制备出球形亚微米和纳米级的均匀粒子[‘-‘]、这些方法与水解法和相转化法等方法比较,反应物浓度要大几个数量级,而反应时间却短很多,因而受到研究人员的关注.乳状液也能提供亚微米、微米及以上级的微环境,因此,可以应用O/W乳状液乳液中的聚合反应制备亲液的分散体系.然而,极少有关利用w/O乳状液制备僧液溶胶的报导问;最近…  相似文献   
977.
A combined femtosecond Kerr gated time-resolved fluorescence (fs-KTRF) and picosecond Kerr gated time-resolved resonance Raman (ps-KTR(3)) study is reported for two p-hydroxyphenacyl (pHP) caged phototriggers, HPDP and HPA, in neat acetonitrile and water/acetonitrile (1:1 by volume) solvents. Fs-KTRF spectroscopy was employed to characterize the spectral properties and dynamics of the singlet excited states, and the ps-KTR(3) was used to monitor the formation and subsequent reaction of triplet state. These results provide important evidence for elucidation of the initial steps for the pHP deprotection mechanism. An improved fs-KTRF setup was developed to extend its detectable spectral range down to the 270 nm UV region while still covering the visible region up to 600 nm. This combined with the advantage of KTRF in directly monitoring the temporal evolution of the overall fluorescence profile enables the first time-resolved observation of dual fluorescence for pHP phototriggers upon 267 nm excitation. The two emitting components were assigned to originate from the (1)pipi (S(3)) and (1)npi (S(1)) states, respectively. This was based on the lifetime, the spectral location, and how these varied with the type of solvent. By correlating the dynamics of the singlet decay with the triplet formation, a direct (1)npi --> (3)pipi ISC mechanism was found for these compounds with the ISC rate estimated to be approximately 5 x 10(11) s(-)(1) in both solvent systems. These photophysical processes were found to be little affected by the kind of leaving group indicating the common local pHP chromophore is largely responsible for the fluorescence and relevant deactivation processes. The triplet lifetime was found to be approximately 420 and 2130 ps for HPDP and HPA, respectively, in the mixed solvent compared to 150 and 137 ns, respectively, in neat MeCN. The solvent and leaving group dependent quenching of the triplet is believed to be associated with the pHP deprotection photochemistry and indicates that the triplet is the reactive precursor for pHP photorelease reactions for the compounds examined in this study.  相似文献   
978.
To study Pseudomonas putida CZ1, having high tolerance to copper and zinc on the removal of toxic metals from aqueous solutions, the biosorption of Cu(II) and Zn(II) by living and nonliving P. putida CZ1 were studied as functions of reaction time, initial pH of the solution and metal concentration. It was found that the optimum pH for Zn(II) removal by living and nonliving cells was 5.0, while it was 5.0 and 4.5, respectively, for Cu(II) removal. At the optimal conditions, metal ion biosorption was increased as the initial metal concentration increased. The adsorption data with respect to both metals provide an excellent fit to the Langmuir isotherm. The binding capacity of living cells is significantly higher than that of nonliving cells at tested conditions. It demonstrated that about 40-50% of the metals were actively taken up by P. putida CZ1, with the remainder being passively bound to the bacterium. Moreover, desorption efficiency of Cu(II) and Zn(II) by living cells was 72.5 and 45.6% under 0.1M HCl and it was 95.3 and 83.8% by nonliving cells, respectively. It may be due to Cu(II) and Zn(II) uptake by the living cells enhanced by intracellular accumulation.  相似文献   
979.
粉煤灰与几种酸固相反应特性的表面分析   总被引:1,自引:0,他引:1  
用扫描电镜.能量色散谱研究了粉煤灰与酸的固相反应过程中表面形貌和化学组成变化特性。室温下粉煤灰分别与HCI、HNO3、H2SO4、HCIO4固相反应后,表面产生直径20—200nm的结晶颗粒或晶柱。反应生成的水溶物结晶体的扫描电镜图像分别呈手指状、龟背形、蛛蛛状、蝙蝠态,分别为氯化铝铁混晶、硝酸铝铁混晶、硫酸铝铁混晶和高氯酸铝铁混晶。粉煤灰是硅、铝、铁等元素的氧化物聚集体,铁铝等氧化物主要分布在颗粒表面,氧化硅主要分布在颗粒内层。用少量酸进行固相反应这些氧化物聚集体可相互剥离,用H2SO4处理粉煤灰优先将铁铝氧化物转化成可溶性硫酸盐。  相似文献   
980.
In this study, we developed an analytical method for the enantioseparation of ofloxacin, using capillary electrophoresis with fluorescence detection. The optimum background electrolyte was obtained to be 60 mM hydroxylpropyl‐β‐cyclodextrin (HP‐β‐CD) in 50 mM phosphate buffer at pH 2.30. Under these conditions, the (+) and (‐) ofloxacin were completely separated, with the detection limit of 10 nM when the sample was prepared in deionized water. The linear ranges of levofloxacin in deionized water and untreated urine were 10?7 to 5 × 10?3 M with R2 = 0.9989 and 5 × 10?6to 5 × 10?3 M with R2 = 0.9943, respectively. We also applied this method to investigate the purity of a commercial drug. The results revealed that the ratio between (+)‐ofloxacin and (‐)‐ofloxacin (levofloxacin) was 99.9:0.1, and there is about 93 mg levofloxacin per tablet (200 mg). The concentration of levofloxacin in patient's urine was founded to be 7.9 × 10?4M, and the ratio between the two optical isomers was 99.3:0.7.  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