全文获取类型
收费全文 | 30957篇 |
免费 | 3333篇 |
国内免费 | 3979篇 |
专业分类
化学 | 12020篇 |
晶体学 | 296篇 |
力学 | 1026篇 |
综合类 | 288篇 |
数学 | 2015篇 |
物理学 | 6601篇 |
综合类 | 16023篇 |
出版年
2024年 | 95篇 |
2023年 | 340篇 |
2022年 | 698篇 |
2021年 | 861篇 |
2020年 | 752篇 |
2019年 | 738篇 |
2018年 | 688篇 |
2017年 | 750篇 |
2016年 | 899篇 |
2015年 | 1210篇 |
2014年 | 1627篇 |
2013年 | 1936篇 |
2012年 | 2179篇 |
2011年 | 2480篇 |
2010年 | 2060篇 |
2009年 | 2258篇 |
2008年 | 2531篇 |
2007年 | 2261篇 |
2006年 | 2091篇 |
2005年 | 1815篇 |
2004年 | 1371篇 |
2003年 | 1012篇 |
2002年 | 1183篇 |
2001年 | 1033篇 |
2000年 | 961篇 |
1999年 | 746篇 |
1998年 | 516篇 |
1997年 | 437篇 |
1996年 | 424篇 |
1995年 | 398篇 |
1994年 | 286篇 |
1993年 | 270篇 |
1992年 | 240篇 |
1991年 | 223篇 |
1990年 | 196篇 |
1989年 | 150篇 |
1988年 | 139篇 |
1987年 | 110篇 |
1986年 | 83篇 |
1985年 | 43篇 |
1984年 | 36篇 |
1983年 | 31篇 |
1982年 | 25篇 |
1981年 | 15篇 |
1980年 | 15篇 |
1979年 | 14篇 |
1978年 | 5篇 |
1974年 | 7篇 |
1972年 | 4篇 |
1959年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 10 毫秒
101.
Liu Q Fang D Zheng J 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(7):1453-1457
Infrared spectroscopy studies of methyl 4-hydroxybenzoate (MHB) in 17 different organic solvents and in ethanol/CCl4 binary solvent were undertaken to investigate the solvent-solute interactions. The frequencies of carbonyl stretching vibration nu(C=O) of MHB in single solvents were correlated with the solvent acceptor number (AN) and the linear solvation energy relationships (LSER). The assignments of the two bands of nu(C=O) of MHB in alcohols and the single one of that in non-alcoholic solvents were discussed. The shifts of nu(C=O) of MHB in ethanol/CCl4 binary solvents showed that several kinds of solute-solvent hydrogen bonding interactions coexisted in the mixture solvents, with a change in the mole fraction of ethanol in the binary solvents. 相似文献
102.
The flow-injection system combines on-line ion-exchange preconcentration with atomic absorption spectrometry (a.a.s.) for the determination of traces (μg l?1) of heavy metals in water samples. Miniature columns packed with 60–100 mesh chelating resin (122) with a salicylic acid functional group are used for preconcentration. A multifunctional rotary sampling valve which incorporated two parallel sampling columns allows sampling, exchange, elution and a.a.s. to be achieved sequentially. The increases in sensitivity for nickel, copper, lead and cadmium were 20–28-fold at a sampling rate of 40 h?1 with 5-ml samples. Relative standard deviations were 1.5–4.1%. The recoveries of these four metals added to tap, sea and polluted waters were generally satisfactory, except for cadmium in polluted water. The effects of column diameter and elution flow rates on sensitivity are discussed. Possible interferences are described. 相似文献
103.
The graft copolymers of chitosan with polycaprolactone (PCL) were prepared through a protection-graft-deprotection route using phthaloylchitosan as intermediate. PCL macromonomers terminated with isocyanate groups reacted with hydroxyl groups of phthaloyl-protected chitosan regioselectively, and then phthaloyl groups were deprotected to give the free amino groups. The graft reaction was carried out in homogeneous system and yielded copolymers with high grafting content due to solubilization. FTIR, NMR and XRD were detected to characterize the resultant chitosan-graft-PCL copolymers. 相似文献
104.
The electrochemical carbon dioxide reduction reaction (CO2RR) offers a promising solution to mitigate carbon emission and at the same time generate valuable carbonaceous chemicals/fuels. Single atom catalysts (SACs) are encouraging to catalyze the electrochemical CO2RR due to the tunable electronic structure of the central metal atoms, which can regulate the adsorption energy of reactants and reaction intermediates. Moreover, SACs form a bridge between homogeneous and heterogeneous catalysts, providing an ideal platform to explore the reaction mechanism of electrochemical reactions. In this review, we first discuss the strategies for promoting the CO2RR performance, including suppression of the hydrogen evolution reaction (HER), generation of C1 products and formation of C2+ products. Then, we summarize the recent developments in regulating the structure of SACs toward the CO2RR based on the above aspects. Finally, several issues regarding the development of SACs for the CO2RR are raised and possible solutions are provided.The electrochemical carbon dioxide reduction reaction (CO2RR) offers a promising solution to mitigate carbon emission and at the same time generate valuable carbonaceous chemicals/fuels. 相似文献
105.
Robert R Hudgins Fang Huang Gabriela Gramlich Werner M Nau 《Journal of the American Chemical Society》2002,124(4):556-564
A fluorescent amino acid derivative (Fmoc-DBO) has been synthesized, which contains 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) as a small, hydrophilic fluorophore with an extremely long fluorescence lifetime (325 ns in H2O and 505 ns in D2O under air). Polypeptides containing both the DBO residue and an efficient fluorescence quencher allow the measurement of rate constants for intramolecular end-to-end contact formation. Bimolecular quenching experiments indicated that Trp, Cys, Met, and Tyr are efficient quenchers of DBO (k(q) = 20, 5.1, 4.5, and 3.6 x 10(8) M(-1) x s(-1) in D2O), while the other amino acids are inefficient. The quenching by Trp, which was selected as an intrinsic quencher, is presumed to involve exciplex-induced deactivation. Flexible, structureless polypeptides, Trp-(Gly-Ser)n-DBO-NH2, were prepared by standard solid-phase synthesis, and the rates of contact formation were measured through the intramolecular fluorescence quenching of DBO by Trp with time-correlated single-photon counting, laser flash photolysis, and steady-state fluorometry. Rate constants of 4.1, 6.8, 4.9, 3.1, 2.0, and 1.1 x 10(7) s(-1) for n = 0, 1, 2, 4, 6, and 10 were obtained. Noteworthy was the relatively slow quenching for the shortest peptide (n = 0). The kinetic data are in agreement with recent transient absorption studies of triplet probes for related peptides, but the rate constants are significantly larger. In contrast to the flexible structureless Gly-Ser polypeptides, the polyproline Trp-Pro4-DBO-NH2 showed insignificant fluorescence quenching, suggesting that a high polypeptide flexibility and the possibility of probe-quencher contact is essential to induce quenching. Advantages of the new fluorescence-based method for measuring contact formation rates in biopolymers include high accuracy, fast time range (100 ps-1 micros), and the possibility to perform measurements in water under air. 相似文献
106.
Abstract— The primary and secondary electron transfer reactions which occurred upon laser flash photolysis of electrically neutral and positively-charged lipid bilayer vesicles containing chlorophyll, benzoquinone and cytochrome c were determined by time-resolved difference spectral and kinetic measurements, and compared with previous results obtained with negatively-charged vesicles (Y. Fang and G. Tollin, Photochem. Photobiol. 1988). The extent to which oxidized cytochrome c could function as an electron acceptor from triplet state chlorophyll, and reduced cytochrome c could act as an electron donor to chlorophyll cation radical, decreased from negatively-charged to electrically neutral to positively-charged vesicles, in agreement with expectations based on changes in the ability of cytochrome c to bind to the bilayer. In all three types of vesicles, cytochrome c reduction by benzoquinone anion radical occurred in the aqueous phase. 相似文献
107.
将计算机辅助设计技术、网络技术与机构设计相结合,以组合机构的尺寸综合理论为基础,以机构最小尺寸为优化目标,采用Java作为开发语言,应用模块化的面向对象的设计方法,研制开发了凸轮-连杆组合机构网上设计系统. 相似文献
108.
中厚板轧后快速冷却系统设计与应用 总被引:1,自引:0,他引:1
为了完善和丰富钢板的品种和规格,同时提高产品质量和轧制生产效率,针对武钢轧板厂生产线实际情况,设计了一套具有国内领先技术的中厚板轧后快速冷却系统.系统应用工业变频供水、高压水箱水量优化分配及高密度层流等先进技术,同时采用了西门子高性能控制器进行系统综合控制.该系统结构合理,功能完善,控制精度高,已成功投入使用,取得了良好效果. 相似文献
109.
水帘极板静电除尘模型的收集性能实验研究 总被引:1,自引:0,他引:1
建立了水帘极板电除尘器实验模型,研究了其电晕特性,以及极距、电场风速、水帘流量、供电电压、初始粉尘浓度等参数对除尘效率的影响.结果表明:水帘形成好坏对V-I特性曲线有一定影响,水帘流量影响形成水帘好坏的程度,因而影响除尘效率;极距对除尘效率有较大影响,极距300mm时除尘效率最高;供电电压对除尘效率的影响较为明显,随着电压的升高除尘效率也升高;风速增大除尘效率降低,初始粉尘浓度对除尘效率影响较小. 相似文献
110.
用均匀带电圆筒模拟带电弹壳分析了弹壳静电分布对微带天线谐振频率、方向图和增益的影响.首先,采用拉普拉斯方程法推导了均匀带电圆筒空间远场计算公式.然后,运用唯一性定理和场的迭加原理得到了合成场远场计算公式.最后,根据理论分析所得到的结果利用Matlab计算了微带天线辐射方向图,并分析了微带天线辐射方向图随着圆筒不同带电量的变化情况. 相似文献