全文获取类型
收费全文 | 4720篇 |
免费 | 259篇 |
国内免费 | 23篇 |
专业分类
化学 | 3689篇 |
晶体学 | 46篇 |
力学 | 124篇 |
数学 | 240篇 |
物理学 | 903篇 |
出版年
2024年 | 5篇 |
2023年 | 26篇 |
2022年 | 34篇 |
2021年 | 133篇 |
2020年 | 94篇 |
2019年 | 106篇 |
2018年 | 86篇 |
2017年 | 97篇 |
2016年 | 165篇 |
2015年 | 159篇 |
2014年 | 209篇 |
2013年 | 312篇 |
2012年 | 458篇 |
2011年 | 468篇 |
2010年 | 261篇 |
2009年 | 226篇 |
2008年 | 356篇 |
2007年 | 316篇 |
2006年 | 294篇 |
2005年 | 271篇 |
2004年 | 197篇 |
2003年 | 178篇 |
2002年 | 148篇 |
2001年 | 69篇 |
2000年 | 50篇 |
1999年 | 33篇 |
1998年 | 20篇 |
1997年 | 29篇 |
1996年 | 21篇 |
1995年 | 21篇 |
1994年 | 10篇 |
1993年 | 16篇 |
1992年 | 8篇 |
1991年 | 11篇 |
1990年 | 8篇 |
1989年 | 9篇 |
1988年 | 6篇 |
1987年 | 8篇 |
1986年 | 7篇 |
1985年 | 7篇 |
1984年 | 4篇 |
1983年 | 8篇 |
1982年 | 6篇 |
1981年 | 4篇 |
1979年 | 5篇 |
1978年 | 3篇 |
1977年 | 8篇 |
1976年 | 7篇 |
1975年 | 4篇 |
1973年 | 3篇 |
排序方式: 共有5002条查询结果,搜索用时 875 毫秒
81.
Pyun DK Kim BJ Jung HJ Kim JH Lee JS Lee WK Lee CH 《Chemical & pharmaceutical bulletin》2002,50(3):415-418
A new series of 1beta-methylcarbapenems 1a-d bearing 5-methyl-4-mercaptopyrrolidinone rings has been prepared and evaluated for in vitro antibacterial activity and pharmacokinetic parameters. Most compounds showed excellent antibacterial activity and high stability to dehydropeptidase-1. We have synthesized optically active 5-methyl-4-hydroxypyrrolidinones from enantiomerically pure aziridine esters. 相似文献
82.
Kim MS Seo KS Khang G Lee HB 《Langmuir : the ACS journal of surfaces and colloids》2005,21(9):4066-4070
A gradient polyethylene (PE) surface was created through corona treatment, in which the corona power increased along the 5 cm length of the PE. The gradient surface was treated with polyethyleneimine and then biotin. Fluorescein-conjugated streptavidin (SAV) caged within 5-carboxymethoxy-2-nitrobenzyl (CMNB) adsorbed onto the biotinylated gradient PE surface following molecular recognition principles. Photoirradiation decomposed the CMNB cage and allowed the fluorescein-conjugated SAV to fluoresce, the intensity of which increased gradually along the PE surface. 相似文献
83.
Dong Won Kim Young Shin Jeon Young Kyu Jeong Moo Yul Suh Kih Soo Joe 《Journal of Radioanalytical and Nuclear Chemistry》1995,189(2):219-227
The chromatographic separation of lithium isotopes was investigated by chemical exchange with the recently synthesized polymer-bound dibenzo pyridino diamide azacrown (DBPDA) and reduced dibenzo pyridino diamide azacrown (RDBPDA). Column chromatography was employed for the determination of the effect of solvents and ligand conformation on the separation coefficients. The maximum separation coefficients, , for the DBPDA and RDBPDA at 20.0±0.02°C with acetonitrile as eluent, were found to be 0.034±0.002 and 0.035±0.002, respectively. The isotope separation coefficient and adsorption capability of the lithium ion on the DBPDA and RDBPDA were only slightly dependent on ligand structure, but strongly dependent on the solvent. DBPDA and RDBPDA appeared to have almost the same value for the isotope separation coefficient of lithium. 相似文献
84.
Jung-Hoon Oh Mun-Chual Rho Hyeong Kyu Lee Jae Nyoung Kim Sang-Hun Jung 《Tetrahedron letters》2004,45(38):7077-7079
Asymmetric synthesis of four possible stereoisomers of (9,10)-epoxyheptadecan-4,6-diyn-3-one was accomplished, and the absolute configuration of the naturally occurring (9R,10S)-epoxyheptadecan-4,6-diyn-3-one (1) was elucidated. 相似文献
85.
The structures of hydrated 1-hydroxyanthraquinone complexes (1-HAQ), 1-HAQ(H2O)n=1,2, with intramolecular and intermolecular hydrogen bonding interactions were studied using laser spectroscopic methods such as laser induced fluorescence, fluorescence-detected infrared, infrared-visible hole burning, and visible-visible hole burning spectroscopy. In the 1:1 complex 1-HAQ(H2O)1, the water binds to the free carbonyl group of 1-HAQ not associated with intramolecular hydrogen bond. The second water in the 1:2 complex, 1-HAQ(H2O)2, binds to the first water of the 1:1 complex rather than other hydrogen bonding sites of 1-HAQ. A pair of two geometric isomers was produced in a supersonic jet for each of the 1:1 and 1:2 complexes. Both isomers of each complex have the same vibrational spectra in the region of the OH stretching vibration of water, but have different energies for the 0-0 band of vibronic transition due to the asymmetry of the two phenyl rings in 1-HAQ. The 0-0 bands for all four species of 1-HAQ(H2O)n=1,2 were unambiguously assigned by comparing with the results of ab initio calculations, which yielded the structures, vibrational frequencies, and relative energies of the frontier molecular orbitals. 相似文献
86.
Lee JS Kim DH Liu KH Oh TK Lee CH 《Rapid communications in mass spectrometry : RCM》2005,19(23):3539-3548
Searchable MS/MS spectra libraries, constructed using the results of liquid chromatography coupled with electrospray ionization (ESI) tandem mass spectrometry (LC/MS/MS) with data-dependent acquisition on an ion trap mass spectrometer, are presented with regard to the identification and confirmation of a variety of closely related flavonoids in a set of biological samples. Flavonoids were found to exhibit a maximum amount of structurally specific MS/MS spectra at 45% of normalized collision energy on the instrument used, without wideband activation. These MS/MS spectra were then searched automatically against a 297-substance MS/MS library that contains many previously acquired spectra of standard flavonoids. The possible applications of this powerful technique to biological samples are also discussed. Daidzein and genistein were identified through the MS/MS spectra library while searching through LC/MS/MS data for plant and microbial extracts. Moreover, these compounds proved completely distinguishable from other flavonoids of closely related structures in the MS/MS spectra library, using the NIST MS search program. The applicability of the library-searchable spectra at low concentrations was demonstrated by successful identification of daidzein and genistein at 0.05 and 0.5 microg/mL, respectively. 相似文献
87.
Top layers of γ-Al2O3 composite membranes have been modified by the silane coupling technique using phenyltriethoxysilane for improving the separation factor of CO2 to N2. The separation efficiency of the modified membranes was strongly dependent upon the hydroxylation tendency of the support materials and the amount of the special functional group (i.e. phenyl radical) which was coupled onto a top layer. The separation factor through the TiO2 supported γ-Al2O3 membrane was found to be fairly enhanced by silane coupling, but in case of the -Al2O3 supported membrane was not. The CO2/N2 separation factor through the modified γ-Al2O3/TiO2 composite membrane is 1.7 at 90°C and ΔP = 2 × 105 Pa for the binary mixture containing 50 vol% CO2. The separation factor is proportional to the CO2 concentration in the gas mixture, and the modified membrane is stable up to 100°C. The main mechanism of the CO2 transport through the modified γ-Al2O3 layer is known to be a surface diffusion. 相似文献
88.
We have developed a strategy of signal generation for immunosensors that transduces biospecific affinity recognition reactions into electrochemical signals. The cyclic voltammetric method, tracking the precipitation of insoluble products onto the sensing surface and the subsequent decrement in the electrode area, was chosen for signal registration. Precipitation of insolubilities was induced by the catalytic reaction of enzymes, which were labeled to the biospecifically attached protein or antibody molecules. As a model system for affinity recognition, we have investigated the functionalization of biotin groups to the sensing monolayer and their biospecific interactions with anti-biotin antibody molecules. The immunosensing interface was developed onto the dendrimer-activated self-assembled monolayers (SAMs), as the base template for the functionalization of the antigen moiety and signal generation. The advantages of using dendrimer-activated SAMs in comparison to the plain modified thiolate SAMs for the sensing surface were shown in terms of sensing performances, and the analytical characteristics of the resulting immunosensor were examined. Additionally, the sensing system was applied for biotin/(strept)avidin couples, extending the applicability of the developed strategy. 相似文献
89.
Hye-Young Seo Jun-Hyoung Kim Hyun-Pa Song Dong-Ho Kim Myung-Woo Byun Joog-Ho Kwon Kyong-Su Kim 《Radiation Physics and Chemistry》2007,76(11-12):1869-1874
The study was carried out to determine the effects of gamma irradiation on the volatile flavor components including essential oils, of Angelica gigas Nakai. The volatile organic compounds from non- and irradiated A. gigas Nakai at doses of 1, 3, 5, 10 and 20 kGy were extracted by a simultaneous steam distillation and extraction (SDE) method and identified by GC/MS analysis. A total of 116 compounds were identified and quantified from non- and irradiated A. gigas Nakai. The major volatile compounds were identified 2,4,6-trimethyl heptane, α-pinene, camphene, α-limonene, β-eudesmol, α-murrolene and sphatulenol. Among these compounds, the amount of essential oils in non-irradiated sample were 77.13%, and the irradiated samples at doses of 1, 3, 5, 10 and 20 kGy were 84.98%, 83.70%, 83.94%, 82.84% and 82.58%, respectively. Oxygenated terpenes such as β-eudesmol, α-eudesmol, and verbenone were increased after irradiation but did not correlate with the irradiation dose. The yields of active substances such as essential oil were increased after irradiation; however, the yields of essential oils and the irradiation dose were not correlated. Thus, the profile of composition volatiles of A. gigas Nakai did not change with irradiation. 相似文献
90.
S. M. Jeong S.-B. Park S.-S. Hong C.-S. Seo S.-W. Park 《Journal of Radioanalytical and Nuclear Chemistry》2006,268(2):349-356
Summary The
electrolytic reduction of U3O8 powder was carried out
using LiCl-Li2O molten salt in a 20-kg U3O8
batch cell to verify the feasibility of the process. As the current passes the
cell, the decomposition of Li2O and the reduction of U3O8
occur simultaneously in a cathode assembly and oxygen gas evolvs at the anode.
The results from a 20-kg U3O8 scale cell were compared
with data obtained from a bench scale cell. The results suggest a successful
demonstration of this process, exhibiting a reduction conversion of U3O8
of more than 99% in a batch.</p>
</p> 相似文献