全文获取类型
收费全文 | 5062篇 |
免费 | 165篇 |
国内免费 | 1035篇 |
专业分类
化学 | 4464篇 |
晶体学 | 27篇 |
力学 | 124篇 |
综合类 | 4篇 |
数学 | 42篇 |
物理学 | 1601篇 |
出版年
2024年 | 20篇 |
2023年 | 168篇 |
2022年 | 161篇 |
2021年 | 168篇 |
2020年 | 212篇 |
2019年 | 156篇 |
2018年 | 138篇 |
2017年 | 182篇 |
2016年 | 222篇 |
2015年 | 195篇 |
2014年 | 234篇 |
2013年 | 375篇 |
2012年 | 309篇 |
2011年 | 416篇 |
2010年 | 313篇 |
2009年 | 452篇 |
2008年 | 379篇 |
2007年 | 435篇 |
2006年 | 319篇 |
2005年 | 240篇 |
2004年 | 195篇 |
2003年 | 164篇 |
2002年 | 93篇 |
2001年 | 106篇 |
2000年 | 66篇 |
1999年 | 61篇 |
1998年 | 85篇 |
1997年 | 89篇 |
1996年 | 56篇 |
1995年 | 40篇 |
1994年 | 28篇 |
1993年 | 29篇 |
1992年 | 37篇 |
1991年 | 19篇 |
1990年 | 13篇 |
1989年 | 18篇 |
1988年 | 14篇 |
1987年 | 7篇 |
1986年 | 11篇 |
1985年 | 11篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1981年 | 3篇 |
1977年 | 2篇 |
1973年 | 1篇 |
1971年 | 1篇 |
1970年 | 1篇 |
1968年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有6262条查询结果,搜索用时 15 毫秒
91.
Han Nim Choi Jee Hoon Han Ji Ae Park Joong Min Lee Won‐Yong Lee 《Electroanalysis》2007,19(17):1757-1763
A highly sensitive and selective glucose biosensor has been developed based on immobilization of glucose oxidase within mesoporous carbon nanotube–titania–Nafion composite film coated on a platinized glassy carbon electrode. Synergistic electrocatalytic activity of carbon nanotubes and electrodeposited platinum nanoparticles on electrode surface resulted in an efficient reduction of hydrogen peroxide, allowing the sensitive and selective quantitation of glucose by the direct reduction of enzymatically‐liberated hydrogen peroxide at ?0.1 V versus Ag/AgCl (3 M NaCl) without a mediator. The present biosensor responded linearly to glucose in the wide concentration range from 5.0×10?5 to 5.0×10?3 M with a good sensitivity of 154 mA M?1cm?2. Due to the mesoporous nature of CNT–titania–Nafion composite film, the present biosensor exhibited very fast response time within 2 s. In addition, the present biosensor did not show any interference from large excess of ascorbic acid and uric acid. 相似文献
92.
G.A.E. Mostafa 《Talanta》2007,71(4):1449-1454
The construction and general performance characteristics of two novel potentiometric carbon paste electrodes (CPE) responsive to antimony are described. These sensors are based on the use of the ion associate complexes of tetraiodoantimonate (TIA) anion with cetylpyridinium (CP) and triphenyl tetrazolium (TPT) counter cations as ion exchange site in a carbon paste matrix. The two sensors exhibits fast, stable and near-Nernstian for the mono charged TIA anion over the concentration range 1 × 10−3 to 10−6 M at 25 °C in the pH range 4-10 with anionic slope of 58.0 ± 0.5 and 55.0 ± 0.7 per concentration decade for TIA-CP and TIA-TPT, respectively. The lower detection limits are 4 and 5 × 10−6 M and response time are 20 and 30 s in the same order of both electrodes. Selectivity coefficients for antimony relative to a number of different cations and anions were investigated. There is negligible interference from many inorganic cation and anion except for Hg2+, Cd2+, and Bi3+; however, their effect were eliminated by EDTA. The determination of 1.0-120.0 μg/ml of antimony in aqueous solutions shows an average recovery of 99.0 and 97.5% with relative standard deviation of 2.0% for both electrodes at 40 μg/ml. The determination of antimony in wastewater and some antibilharzial compounds using the proposed electrodes gave results that compare favorably with those obtained by the atomic absorption spectrometric method. Precipitation titrations involving cetylpyridinium chloride as titrant are monitored with both electrodes with inflection point of 180 and 100 mV for TIA-CP and TIA-TPT, respectively. 相似文献
93.
Arno Behr 《Angewandte Chemie (International ed. in English)》1988,27(5):661-678
The carbon dioxide molecule has been of limited importance as a synthetic unit in organic chemistry. When it is coordinated to transition metals, however, completely new possibilities arise; CO2 can bond to metal complexes in a variety of ways and can enter into insertion and coupling reactions, or become catalytically attached to other substrates. The formation of C? C bonds between carbon dioxide and unsaturated hydrocarbons under conditions of homogeneous catalysis makes available new synthetic routes to industrially interesting organic compounds. 相似文献
94.
Summary Experimental results are presented on the application of Carbosieve S (Supelco) and Spherocarb (Analabs) spherical carbon molecular sieves for the gas chromatographic separation of mixtures of permanent gases and C1–C3 hydrocarbons using a single column or two columns in series. At a programmed temperature of 35–300°C, good separation of the sample components was obtained when using helium as the carrier gas. When hydrogen was used as the carrier gas and the analysis was carried out under isothermal conditions the elution sequence of oxygen and nitrogen reversed as the temperature was increased. This behaviour was observed within a temperature range of 35–225°C for Carbosieve S, and within a temperature range of 35–300°C for Spherocarb. 相似文献
95.
Octavio Surez-Iglesias Ignacio Medina Consuelo Pizarro Julio L. Bueno 《Fluid Phase Equilibria》2007,260(2):279-286
The Taylor–Aris chromatographic technique was employed for the determination of diffusion coefficients of 2-fluoroanisole, 2-bromoanisole, allylbenzene and 1,3-divinylbenzene at infinite dilution in supercritical carbon dioxide from 313.16 to 333.16 K and pressures between 15 and 35 MPa. As expected, the diffusivities rise when temperature increases and pressure decreases. Numerous predictive equations are compared with experimental data: Lai–Tan, Liu–Ruckenstein cluster formula, Woerlee, Hippler–Schubert–Troe, Catchpole–King, Eaton–Akgerman, He, He–Yu, Liu–Silva–Macedo, Funazukuri and coworkers, Dariva–Coelho–Oliveira, Zhu–Lu–Zhou–Wang–Shi and the Liu–Ruckenstein RHS formula. The equations of He, He–Yu and Catchpole–King are the best of all, but cannot be used in the whole range of temperatures and solvent densities. 相似文献
96.
氟钽酸钾中碳存在形式的探讨 总被引:2,自引:0,他引:2
本文从氟钽酸钾(K2TaF6)的生产工艺论述了有机物存在于D2TaF6的可能性。通过K2TaF6低温通氧燃烧前后测定碳的结果比较,以及X射线能谱仪表面分析结果,证实了碳的来源是残留的有机萃取剂。 相似文献
97.
Yajing Yin Ping Wu Yafen Lü Pan Du Yanmao Shi Chenxin Cai 《Journal of Solid State Electrochemistry》2007,11(3):390-397
A single-walled carbon nanotube (SWNT)-modified electrode was fabricated and characterized by SEM and ac impedance techniques.
The direct electrochemistry of cytochrome c (Cyt c), which was adsorbed on the surface of the SWNT, was studied by cyclic voltammetry. The results from cyclic voltammetry and
infrared spectroscopy indicated that Cyt c remained in its original structure and did not undergo structural change after its immobilization on the SWNT. Further results
demonstrated that the SWNT had promotional effects on the direct electron transfer of Cyt c and also indicated that the immobilized Cyt c retained its electrocatalytic activity to the reduction of H2O2. This modified electrode might be used in development of new biosensors and the biofuel cells. 相似文献
98.
99.
A density functional theory investigation on a series of sandwich-type transition metal complexes [(CBO)n]2M (n=4–6; M=transition metals) with carbon boronyls (CBO)n as effective aromatic ligands has been presented in this work at B3LYP level. The ground-states of these complexes possess staggered Dnd symmetries, while the corresponding eclipsed Dnh structures exist as transition states with slightly higher energies (within 5.8 kJ/mol). Carbon boronyl complexes [(CBO)n]2M are confirmed to be much more stable than their boron carbonyl isomers [(BCO)n]2M, which, on the other hand, take eclipsed ground-states with Dnh symmetries. The carbon boronyl complexes [(BCO)n]2M proposed in this work parallelize the well-known sandwich-type hydrocarbon complexes [CnHn]2M in coordination chemistry with boronyl groups –BO isolobal to –H atoms in corresponding ligands. 相似文献
100.
Static pressure usually increases the transition temperatures of polymers by decreasing their free volume. If the pressurizing medium is soluble in the polymer matrix, the opposing effect of increasing the free volume is possible. Those shifts of transition temperatures were monitored with a medium-pressure Differential Scanning Calorimetry (DSC) device. The influences of sorbed and surrounding gas molecules are demonstrated by changes occurring in the transition temperature regions. The results show the severe plasticizing effect of CO2 on poly(p-phenylene sulphide) (PPS). The glass transition temperature TG and the temperature of crystallization TC are influenced by sorbed gas molecules. They decrease due to sorbed CO2 molecules. Glass transition is lowered, but is difficult to interpret, as relaxation phenomena which diminish with increasing pressure occur during DSC runs. In crystallites no gas solution is usually possible, so that the melting point of PPS is mainly affected by influences other than plasticization. 相似文献