全文获取类型
收费全文 | 3147篇 |
免费 | 489篇 |
国内免费 | 426篇 |
专业分类
化学 | 2274篇 |
晶体学 | 31篇 |
力学 | 222篇 |
综合类 | 47篇 |
数学 | 319篇 |
物理学 | 1169篇 |
出版年
2024年 | 6篇 |
2023年 | 53篇 |
2022年 | 93篇 |
2021年 | 98篇 |
2020年 | 135篇 |
2019年 | 102篇 |
2018年 | 110篇 |
2017年 | 112篇 |
2016年 | 140篇 |
2015年 | 129篇 |
2014年 | 181篇 |
2013年 | 220篇 |
2012年 | 218篇 |
2011年 | 290篇 |
2010年 | 201篇 |
2009年 | 199篇 |
2008年 | 214篇 |
2007年 | 193篇 |
2006年 | 160篇 |
2005年 | 130篇 |
2004年 | 96篇 |
2003年 | 79篇 |
2002年 | 77篇 |
2001年 | 72篇 |
2000年 | 61篇 |
1999年 | 72篇 |
1998年 | 60篇 |
1997年 | 50篇 |
1996年 | 48篇 |
1995年 | 51篇 |
1994年 | 51篇 |
1993年 | 48篇 |
1992年 | 48篇 |
1991年 | 37篇 |
1990年 | 40篇 |
1989年 | 32篇 |
1988年 | 25篇 |
1987年 | 31篇 |
1986年 | 23篇 |
1985年 | 13篇 |
1984年 | 8篇 |
1983年 | 11篇 |
1982年 | 12篇 |
1981年 | 5篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1957年 | 4篇 |
排序方式: 共有4062条查询结果,搜索用时 15 毫秒
91.
The complex that forms between a boronic acid and a diol is often much more acidic than the starting boronic acid. In conditions where the solution pH is between the two pK(a) values, the boron atom will convert from a neutral trigonal form to an anionic tetrahedral form upon complexation. Such a change is likely to dramatically alter the electron density of neighboring groups. Utilizing this effect, we have designed and synthesized two nitrophenol-based boronic acid reporter compounds that change ionization states and therefore spectroscopic properties upon diol binding. Both compounds show significant UV changes upon addition of saccharides. For example, a blue shift of the absorption max from 373 to 332 nm was observed with the addition of D-fructose to 2-hydroxy-5-nitrophenylboronic acid at neutral pH. Such a reporter compound can be used as a recognition and signaling unit for the construction of polyboronic acid sensors for the selective and specific recognitions of saccharides of biological significance. 相似文献
92.
A mode of capillary electrochromatography (CEC), based on the dynamical adsorption of surfactants on the uncharged monolithic stationary phases has been developed. The monolithic stationary phase, obtained by the in situ polymerization of butyl methacrylate with ethylene dimethacrylate, was dynamically modified with an ionic surfactant such as the long-chain quaternary ammonium salt of cetyltrimethylammonium bromide (CTAB) and long-chain sodium sulfate of sodium dodecyl sulfate (SDS). The ionic surfactant was adsorbed on the surface of polymeric monolith by hydrophobic interaction, and the ionic groups used to generate the electroosmotic flow (EOF). The electroosmotic mobility through these capillary columns increased with increasing the content of ionic surfactants in the mobile phase. In this way, the synthesis of the monolithic stationary phase with binary monomers can be controlled more easily than that with ternary monomers, one of which should be an ionic monomer to generate EOF. Furthermore, it is more convenient to change the direction and magnitude of EOF by changing the concentration of cationic or anionic surfactants in this system. An efficiency of monolithic capillary columns with more than 140000 plates per meter for neutral compounds has been obtained, and the relative standard deviations observed for to and retention factors of neutral solutes were about 0.22% and less than 0.56% for ten consecutive runs, respectively. Effects of mobile phase composition on the EOF of the column and the retention values of the neutral solutes were investigated. Simultaneous separation of basic, neutral and acidic compounds has been achieved. 相似文献
93.
A new ion-pair complex, [1-(4′-chlorobenzyl)-4-aminopyridinium](+)bis(maleonitrile-dithiolato)nickel(−),[ClbzPyNH2][Ni(mnt)2] (1), has been prepared and characterized. X-ray single crystal structure conforms that the Ni(mnt)2− anions and [ClbzPyNH2]+ cations of 1 form completely segregated uniform stacking columns with the Ni?Ni distance 3.944 Å in the Ni(mnt)2− stacking column. The temperature dependence of the magnetic susceptibility reveals that 1 undergoes a magnetic transition, and exhibits ferromagnetic interaction in the high-temperature phase and spin gap system in the low-temperature phase. 相似文献
94.
Yu Mao Wenxuan Zhao Shuo Lu Lei Yu Yi Wang Yong Liang Shengyang Ni Yi Pan 《Chemical science》2020,11(19):4939
Redox-active esters (RAEs) as alkyl radical precursors have demonstrated great advantages for C–C bond formation. A decarboxylative cross-coupling method is described to afford substituted alkynes from various carboxylic acids using copper catalysts CuCl and Cu(acac)2. The photoexcitation of copper acetylides with electron-rich NEt3 as a ligand provides a general strategy to generate a range of alkyl radicals from RAEs of carboxylic acids, which can be readily coupled with a variety of aromatic alkynes. The scope of this cross-coupling reaction can be further expanded to aliphatic alkynes and alkynyl silanes using a catalytic amount of preformed copper-phenylacetylide. In addition, DFT calculations revealed the favorable reaction pathway and that the bidentate acetylacetonate ligand of the copper intermediate plays an important role in inhibiting the homo-coupling of the alkyne.Redox-active esters (RAEs) as alkyl radical precursors have demonstrated great advantages for Cu-catalysed C–C bond formation. 相似文献
95.
A selective and sensitive high-performance liquid chromatography-electrospray ionization mass spectrometry (MS) for the determination of nisoldipine in human plasma is first presented. With nimodipine as the internal standard, nisoldipine is extracted from plasma with ethyl acetate. The organic layer is evaporated and the residue is resuspended in the mobile phase of methanol-water (80:20, v/v). An aliquot of 40 microL is chromatographically analyzed on an Agilent ODS C18 reversed-phase column (5 microm, 250- x 4.6-mm i.d.) by means of selected-ion monitoring mode MS. The calibration curve of nisoldipine in plasma exhibits a linear range from 0.5 to 20.0 ng/mL with a correlation coefficient of 0.9995. The limit of detection is 0.2 ng/mL. The within- and between-day variations (relative standard deviation) are less than 9.28% and 11.13% (n = 5), respectively. The developed method is validated through successful use for the analysis of nisoldipine contained in biological fluids resulting from a phase-I human pharmacokinetic study. 相似文献
96.
Separation of the acidic compounds in the ion-exchange capillary electrochromatography (IE-CEC) with strong anion-exchange packing as the stationary phase was studied. It was observed that the electroosmotic flow (EOF) in strong anion-exchange CEC moderately changed with increase of the eluent ionic strength and decrease of the eluent pH, but the acetonitrile concentration in the eluent had almost no effect on the EOF. The EOF in strong anion-exchange CEC with eluent of low pH value was much larger than that in RP-CEC with Spherisorb-ODS as the stationary phase. The retention of acidic compounds on the strong anion-exchange packing was relatively weak due to only partial ionization of them, and both chromatographic and electrophoretic processes contributed to separation. It was observed that the retention values of acidic compounds decreased with the increase of phosphate buffer and acetonitrile concentration in the eluent as well as the decrease of the applied voltage, and even the acidic compounds could elute before the void time. These factors also made an important contribution to the separation selectivity for tested acidic compounds, which could be separated rapidly with high column efficiency of more than 220000 plates/m under the optimized separation conditions. 相似文献
97.
98.
讨论了沸点升高法测定混和溶剂化热和汽化熵的原理,并用拟静态法测定了乙醇-丙酮,并-四氯化碳和苯,甲苯三组混和溶剂在不同组成下的正常沸点,根据沸点数据求得了混和泶微分汽化热和汽化熵,实验结果表明,二元混和溶剂与理想溶液偏离不大时,其正常汽化熵符合Trouton规则。 相似文献
99.
298.1 K时脂肪酸钠盐对定组成水溶液中非水组分活度系数的影响 总被引:1,自引:0,他引:1
本文报告了298.1 K下甲酸钠(C_1), 乙酸钠(C_2)、丙酸钠(C_3)、丁酸钠(C_4)、戊酸钠(C_5)、已酸钠(C_6)和庚酸钠(C_7)七个盐对水溶液中乙醇、丙酮和乙腈三个溶质的活度系数的影响。实验方法是, 固定水溶液中乙醇、丙酮和乙腈的浓度(摩尔分数约为0.05), 用气相色谱法检测不同盐浓度下平衡气相中溶质分压的变化, 从而得出溶质的盐效应活度系数γ。本文给出了一个可以连续取样的气液平衡装置的设计。由实验结果可见, 不同碳链大小的脂肪酸根离子的盐效应作用差别很大。C_1、C_2的盐效应主要由于静电作用; 对C_3、C_4盐, 除静电作用外,它们的疏水基与溶质疏水基的相互作用对盐效应有显著影响; C_5、C_6和C_7的盐效应则反映了疏水离子的特色, 疏水水化、疏水相互作用、疏水离子形成的聚集体与不同官能团的特定相互作用等几项因素, 导致儿个溶质盐效应的差异。 相似文献
100.