全文获取类型
收费全文 | 145232篇 |
免费 | 21008篇 |
国内免费 | 16293篇 |
专业分类
化学 | 76839篇 |
晶体学 | 1203篇 |
力学 | 6520篇 |
综合类 | 728篇 |
数学 | 13669篇 |
物理学 | 42305篇 |
无线电 | 41269篇 |
出版年
2024年 | 581篇 |
2023年 | 3317篇 |
2022年 | 4443篇 |
2021年 | 5661篇 |
2020年 | 5486篇 |
2019年 | 4956篇 |
2018年 | 4649篇 |
2017年 | 4416篇 |
2016年 | 6226篇 |
2015年 | 6632篇 |
2014年 | 8071篇 |
2013年 | 10381篇 |
2012年 | 12092篇 |
2011年 | 12329篇 |
2010年 | 9161篇 |
2009年 | 9077篇 |
2008年 | 9383篇 |
2007年 | 8439篇 |
2006年 | 8095篇 |
2005年 | 7046篇 |
2004年 | 5154篇 |
2003年 | 4306篇 |
2002年 | 3895篇 |
2001年 | 3320篇 |
2000年 | 3048篇 |
1999年 | 3152篇 |
1998年 | 2697篇 |
1997年 | 2364篇 |
1996年 | 2333篇 |
1995年 | 2050篇 |
1994年 | 1741篇 |
1993年 | 1462篇 |
1992年 | 1274篇 |
1991年 | 1072篇 |
1990年 | 902篇 |
1989年 | 649篇 |
1988年 | 505篇 |
1987年 | 411篇 |
1986年 | 420篇 |
1985年 | 317篇 |
1984年 | 239篇 |
1983年 | 207篇 |
1982年 | 158篇 |
1981年 | 87篇 |
1980年 | 72篇 |
1979年 | 28篇 |
1978年 | 29篇 |
1976年 | 24篇 |
1975年 | 24篇 |
1957年 | 28篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
LIU Xin GUAN Li HE Cheng-yan ZHANG Xiao-jing XU Li-na SHANG De-jing MA Tong-hui YANG Hong 《高等学校化学研究》2008,24(2)
Cystic fibrosis(CF)is a severe genetic disease caused by the gene mutation of the cystic fibrosis transmembrane conductance regulator(CFTR)chloride channel.The most common point mutation △F508,which leads to impaired intracellular processing and channel gating of CFTR, appears in about 90? patients.The natural compound curcumin was reported to correct the processing defect of △F508-CFTR and proposed as a potential therapeutic drug to cure CF.In the present study.we analyzed the efrect of curcumin on △F508-CFTR and demonstrated that curcumin can restore the impaired chloride conductance of △F508 mutant CFTR.The activity is rapid,reversible and cAMP-dependent.However,we couldn't reproduce the previously reported correction of the defective membrane trafficking of △F508-CFTR by curcumin.Therefore,curcumin may not be a superior lead compound for developing anti-CF drugs. 相似文献
992.
993.
Persistent organic pollutants (POPs) are greatly noxious chemicals in environment, and they can cumulate in organisms and transfer between different species. Therefore, it is significant to detect POPs for both environmental evaluation and further treatment. However, developing facile approach for the detection of POPs still remains a challenge so far. In this paper, we report an innovative method for facile detection of POPs using gas sensor for the first time. Porous SnO2 nanostructures with a special tri-walled structure prepared via hydrothermal route and annealing process, were employed as gas-sensing materials. Through gas measurements, it was revealed that the as-fabricated gas sensor exhibited highly sensitive performance towards target POPs, including methoxychlor, mirex, p,p′-DDT, and aldrin. Moreover, we found that target POPs were distinguishable by extracting characteristics in kinetic curves of gas adsorption-desorption. As the presented detecting approach is facile without the requirements of complex operations, expensive and bulky instruments, it is expected that it would be developed as a promising method for the detection of POPs, and thereby showing its significance for environmental monitoring. 相似文献
994.
运用量子化学密度泛函B3LYP方法,在6-311++G(d,p)基组水平上对邻位和间位取代1-氯葸醌的分子内卤键进行了研究.用电子定域函数和“分子中的原子,,理论对分子内卤键的性质进行了电子密度拓扑分析.通过对计算得到的密度矩阵进行σ-π兀分离,得到了π-键的键径和分子图,并讨论了。电荷密度和兀电荷密度对卤键的影响.结果表明,键鞍点和环鞍点处的电子密度拓扑性质均可作为衡量分子内卤键强度的量度.键鞍点和环鞍点处的电荷密度P越大,键鞍点与环鞍点的距离越大,卤键强度越大.除σ电荷密度外,π电荷密度对分子内卤键的性质也有明显影响. 相似文献
995.
The interaction between[Hg(SCN)4]2- and hemoglobin(Hb) under conditions that simulate a physiological environment was investigated by UV-vis spectroscopy,fluorescence spectroscopy,resonance Rayleigh scattering(RRS) spectroscopy and circular dichroism(CD) spectroscopy.The results obtained from the change of UV-vis and CD spectra,the quenching of Hb fluorescence and the enhancement of RRS intensity proved that a 10:1 type complex was formed between[Hg(SCN)4]2- and Hb.The possible mechanism suggested for the interaction was that ten Hg(SCN)4]2- anions entered the four subunits of a Hb molecule to react with some residues to form an adduct by coordination and electrostatic forces.The coordination of[Hg(SCN)4]2- with Trp was the major cause of the fluorescence quenching of Hb. 相似文献
996.
H Fu C Qin Y Lu ZM Zhang YG Li ZM Su WL Li EB Wang 《Angewandte Chemie (International ed. in English)》2012,51(32):7985-7989
Pretty porous POMs: Ionothermal synthesis was applied to prepare porous POM-based open frameworks. The structural integrity remains unchanged until 300?°C; most importantly, the bulky tetrabutylammonium cations within their nanosized channels can be replaced by transition-metal ions through a cation-exchange process, and subsequent gas adsorption measurements confirm their permanent porosity. 相似文献
997.
Liquid chromatography-mass spectrometry identification of imidacloprid photolysis products 总被引:2,自引:0,他引:2
Photolysis of imidacloprid by near ultraviolet (UV) radiation was investigated using reversed phase liquid chromatography (RPLC) and liquid chromatography-electrospray ionization/mass spectrometry (LC-ESI/MS) operated in the positive ion mode. The decomposition of imidacloprid by near UV light is first order with a half life of 10.18 h. Photo-degradation products of imidacloprid identified in this study included imidacloprid urea, imidacloprid olefin, and imidacloprid desnitro. A degradation pathway is proposed for imidacloprid from an examination of the product decay curves obtained in this monitoring study which was performed in a batch test mode. 相似文献
998.
A commercially-available sulfonphthalein derivative was demonstrated to be a chemodosimeter for Fe2+ and its sensing behavior was further investigated by UV-vis spectroscopy in aqueous media under the optimum conditions. In the presence of chlorophenol red (CPR) and H2O2, the absorption maximum at 435 nm decreased upon addition of Fe2+, resulting in a significant color change of the CPR solution from yellow to colorless. The chemosensor system did not show significant responses to a series of other metal ions including Al3+, Zn2+, Cd2+, Hg2+, Mn2+, Co2+, Fe3+, Ni2+, Cu2+, La3+, Ce4+, Th4+, Pd2+, Pb2+, Sb3+, Cr3+, Au3+, Ag+, Nd3+, Sm3+, alkali and alkaline earth metal cations, allowing for highly selective naked-eye detection of Fe2+. Quantitative analysis was carried out kinetically for practicable the Fe2+ assay when either fixed time method or the initial rate method was applied. When the detecting time was set, the decrease of absorbance signal was linear with Fe2+ concentration in the range of 0 to 7.50 × 10?5 mol L?1 and the regression equation was ΔA = 0.00759 + 0.00593C Fe with a correlation coefficient r = 0.9953. The chemodosimetric system has employed an irreversible Fenton reagent-promoted oxidation of the CPR free chromophore and the hydroxyl radicals were generated in the presence of both Fe2+ and hydrogen peroxide. The mechanistic interpretation of the signaling process was partially confirmed by the radical scavenging experiment and the FT-IR analysis of the intermediates formed at different reaction periods. 相似文献
999.
Yue W Gao J Li Y Jiang W Di Motta S Negri F Wang Z 《Journal of the American Chemical Society》2011,133(45):18054-18057
Tetracene tetracarboxylic diimides have been synthesized based on direct double ring extension of electron-deficient naphthalene diimides involving metallacyclopentadienes. Atomic structure and electronic transitions responsible for their NIR absorption spectra are investigated with quantum-chemical calculations. In light of their unique structure and admirable photophysical and electronic properties, this new molecular skeleton is promising candidate for n-type semiconductors. 相似文献
1000.
An ethylene glycol solution was used as the electrophoretic running buffer in unmodified cyclic olefin copolymer (COC) microchips to minimize the interactions between the analytes and the hydrophobic walls of the plastic microchannels, enhance the resolution of the analytes and eliminate the uncontrollable dispersion caused by uneven liquid levels and non-uniform surfaces of the separation channels. Five amino acids that were labeled with fluorescein isothiocyanate (FITC) were used as model analytes to examine the separation efficiency. The effects of ethylene glycol concentration, pH and sodium tetraborate concentration were systematically investigated. The five FITC-labeled amino acids were effectively resolved using a COC microchip with an effective length of 2.5 cm under optimum conditions, which included using a running buffer of 20 mmol/L sodium tetraborate in ethylene glycol:water (80:20, v/v), pH 6.7. A theoretical plate number of 4.8 × 10(5)/m was obtained for aspartic acid. The system exhibited good repeatability, and the relative standard deviations (n=5) of the peak areas and migration times were no more than 3.4% and 0.7%, respectively. Furthermore, the system was successfully applied to elucidate these five amino acids in human saliva. 相似文献