全文获取类型
收费全文 | 178736篇 |
免费 | 17761篇 |
国内免费 | 10412篇 |
专业分类
化学 | 93009篇 |
晶体学 | 1924篇 |
力学 | 13039篇 |
综合类 | 533篇 |
数学 | 42765篇 |
物理学 | 55639篇 |
出版年
2024年 | 369篇 |
2023年 | 2133篇 |
2022年 | 3644篇 |
2021年 | 4052篇 |
2020年 | 4248篇 |
2019年 | 4138篇 |
2018年 | 13045篇 |
2017年 | 12645篇 |
2016年 | 10745篇 |
2015年 | 5716篇 |
2014年 | 6291篇 |
2013年 | 8062篇 |
2012年 | 12934篇 |
2011年 | 19590篇 |
2010年 | 11677篇 |
2009年 | 11785篇 |
2008年 | 12760篇 |
2007年 | 14286篇 |
2006年 | 5666篇 |
2005年 | 5839篇 |
2004年 | 4841篇 |
2003年 | 4530篇 |
2002年 | 3371篇 |
2001年 | 2211篇 |
2000年 | 2044篇 |
1999年 | 2219篇 |
1998年 | 2032篇 |
1997年 | 1856篇 |
1996年 | 2080篇 |
1995年 | 1614篇 |
1994年 | 1531篇 |
1993年 | 1257篇 |
1992年 | 1121篇 |
1991年 | 1045篇 |
1990年 | 840篇 |
1989年 | 621篇 |
1988年 | 522篇 |
1987年 | 439篇 |
1986年 | 431篇 |
1985年 | 364篇 |
1984年 | 283篇 |
1983年 | 190篇 |
1982年 | 183篇 |
1981年 | 144篇 |
1980年 | 122篇 |
1979年 | 88篇 |
1978年 | 68篇 |
1976年 | 52篇 |
1974年 | 56篇 |
1973年 | 56篇 |
排序方式: 共有10000条查询结果,搜索用时 10 毫秒
251.
The Si clusters are prepared by inert gas condensation method and then softly land on the mother skeleton of the porous silicon (PS), and thus quasi-free clusters are formed. Several new Raman peaks are observed and identified as surface modes of Si clusters and their combination with TA modes for the first time. Good agreement is achieved between the experimental observations and the calculated results. 相似文献
252.
253.
Interaction of tetrandrine with human serum albumin: a fluorescence quenching study. 总被引:4,自引:0,他引:4
Chun Wang Qiu-Hua Wu Cai-Rui Li Zhi Wang Jing-Jun Ma Xiao-Huan Zang Na-Xin Qin 《Analytical sciences》2007,23(4):429-433
The interaction of tetrandrine with human serum albumin (HSA) was studied by measuring fluorescence quenching spectra, synchronous fluorescence spectra and ultra-violet spectra. The fluorescence quenching spectra of HSA in the presence of tetrandrine showed that tetrandrine quenched the fluorescence of HSA. The quenching constants of tetrandrine on HSA were determined using the Stern-Volmer equation. Static quenching and non-radiation energy transfer were the two main reasons leading to the fluorescence quenching of HSA by tetrandrine. According to the F?rster theory of non-radiation energy transfer, the binding distances (r) and the binding constants (K(A)) were obtained. The thermodynamic parameters obtained in this study revealed that the interaction between tetrandrine and HSA was mainly driven by a hydrophobic force. The conformational changes of HSA were investigated by synchronous spectrum studies. 相似文献
254.
Ion mobility spectrometry (IMS) was used as a flow-injection detector to quantitatively examine the ionization chemistry of aniline in hexane. A 5-microl sample was vaporized at 15-90-sec intervals in a flowing air stream and analyzed with an IMS equipped with acetone reactant ion chemistry, ambient temperature drift tube and membrane-based inlet. Precision was 3-11% relative standard deviation for 1-100 ppm aniline in hexane with 90-sec injection intervals and detection limits were ca. 0.5 ppm with 5-microl injections. Matrix effects with amine and organic solvent mixtures were observed and corrected for low and medium proton affinity interferences with standard addition methods. Pronounced fouling of the IMS occurred when a continuous water flow was introduced for aqueous flow injection-IMS. Continuous water monitoring without degraded IMS performance was possible by sampling air flow through a Silastic tube immersed in an aqueous sample. 相似文献
255.
Adsorption of NH3 onto activated carbon prepared from palm shells impregnated with H2SO4 总被引:3,自引:0,他引:3
Adsorption of ammonia (NH3) onto activated carbons prepared from palm shells impregnated with sulfuric acid (H2SO4) was investigated. The effects of activation temperature and acid concentration on pore surface area development were studied. The relatively large micropore surface areas of the palm-shell activated carbons prepared by H2SO4 activation suggest their potential applications in gas adsorption. Adsorption experiments at a fixed temperature showed that the amounts of NH3 adsorbed onto the chemically activated carbons, unlike those prepared by CO2 thermal activation, were not solely dependent on the specific pore surface areas of the adsorbents. Further adsorption tests for a wide range of temperatures suggested combined physisorption and chemisorption of NH3. Desorption tests at the same temperature as adsorption and at an elevated temperature were carried out to confirm the occurrence of chemisorption due to the interaction between NH3 and some oxygen functional groups via hydrogen bonding. The surface functional groups on the adsorbent surface were detected by Fourier transform infrared spectroscopy. The amounts of NH3 adsorbed by chemisorption were correlated with the contents of elemental oxygen present in the adsorbents. Mechanisms for chemical activation and adsorption processes are proposed based on the observed phenomena. 相似文献
256.
[chemical reaction: see text]. Direct addition of Grignard reagents to acid chlorides in the presence of bis[2-(N,N-dimethylamino)ethyl] ether proceeds selectively to provide aryl ketones in high yields. A possible tridentate interaction between Grignard reagents and bis[2-(N,N-dimethylamino)ethyl] ether moderates the reactivity of Grignard reagents, preventing the newly formed ketones from nucleophilic addition by Grignard reagents. 相似文献
257.
Fresh grapes and grape products, such as grape wine and grape juice, were analyzed for proanthocyanidins (PACs) using liquid chromatography with electrospray ionization mass spectrometric (MS) detection. PACs were successfully separated and analyzed on the basis of their protonated molecules, allowing the identification of PACs in different degrees of polymerization from monomers to oligomers (up to 7 units), and in various isomeric forms. Using reversed-phase high-performance liquid chromatography (HPLC) combined with MS detection, the PAC monomers, (+)-catechin (C), (-)-epicatechin (EC), (-)-catechin gallate (CG), and (-)-epicatechin gallate (ECG), were successfully quantified using selected ion monitoring (SIM) mode. Standard curves were fitted for each PAC ranging from 43.8 to 5600 ng/mL for C, from 42.2 to 5400 ng/mL for EC, from 36.7 to 4700 ng/mL for CG, and from 39.8 to 5100 ng/mL for ECG. Good linearity (r2>0.999) was achieved for each analyte. The accuracy and precision (RSD) were within 10% (n=8) at the limit of detection. This method allows direct quantification of monomeric PACs in fresh grapes and grape-derived products. Additionally, flow injection analysis (FIA) was applied to estimate the concentration levels of PAC oligomers by comparing their FIA-MS peak areas, which were well correlated (r2=0.936) to the total concentrations of PAC monomers. 相似文献
258.
In this study, the determination of 4-Bromoaniline (4-BA) in green algae Chlamydomonas reinhardtii (C. reinhardtii) was investigated by applying continuous-flow microextraction (CFME) combined with high-performance liquid chromatography
(HPLC). Continuous-flow microextraction was conducted in a homemade glass chamber, i.e. the sample solution flowed through
a constant volume drop of solvent in the chamber at a constant flow rate. The effects of different factors on extraction efficiencies
were also investigated and these factors included the kind of extraction solvent, solvent drop volume, sample flow rate, extraction
time and addition amount of salt. Under the optimum extraction conditions (extraction solvent, carbon tetrachloride; solvent
drop volume, 3.5 μL; sample flow rate, 1.0 mL min−1; extraction time, 10 min; no addition of salt), the calibration plot was set up by plotting peak area against a series of
4-Bromoaniline concentrations (0.01–10 μg mL−1) in aqueous solution. The correlation coefficient (r) was 0.9990. The limit of detection (LOD) was 0.6 ng mL−1. The precision of this method was obtained by successive five time analyses of 100-ng mL−1 standard solution of 4-Bromoaniline, and the relative standard deviation (RSD) was 3.5%. The concentration factor was calculated
by the ratio of peak area of the analyte obtained after and before extraction and found to be 10.6. 4-Bromoaniline residues
in Chlamydomonas. reinhardtii cells and tap water samples were satisfactorily analyzed according to the method described above. 相似文献
259.
Ni(OH)2 hollow microspheres with beta-Ni(OH)2 nanosheets as the in situ formed building units were fabricated via a novel template-free approach in a strong alkaline solution of glycine, and can be converted into NiO hollow microspheres by a thermal decomposition process. 相似文献
260.
High-level computations at G3, CBS-Q, and G3B3 levels were conducted, and good-quality C-H and N-H bond dissociation energies (BDEs) were obtained for a variety of saturated and unsaturated strained hydrocarbons and amines for the first time. From detailed NBO analyses, we found that the C-H BDEs of hydrocarbons are determined mainly by the hybridization of the parent compound, the hybridization of the radical, and the extent of spin delocalization of the radical. The ring strain has a significant effect on the C-H BDE because it forces the parent compound and radical to adopt certain undesirable hybridization. A structure-activity relationship equation (i.e., BDE (C-H) = 61.1-227.8 (p(parent)% - 0.75)(2) + 152.9 (p(radical)% - 1.00)(2) + 40.4 spin) was established, and it can predict the C-H BDEs of a variety of saturated and unsaturated strained hydrocarbons fairly well. For the C-H BDEs associated with the bridgehead carbons of the highly rigid strained compounds, we found that the strength of the C-H bond can also be predicted from the H-C-C bond angles of the bridgehead carbon. Finally, we found that N-H BDEs show less dependence on the ring strain than C-H BDEs. 相似文献