全文获取类型
收费全文 | 131788篇 |
免费 | 9302篇 |
国内免费 | 6028篇 |
专业分类
化学 | 62685篇 |
晶体学 | 1449篇 |
力学 | 9708篇 |
综合类 | 328篇 |
数学 | 37652篇 |
物理学 | 35296篇 |
出版年
2024年 | 185篇 |
2023年 | 1143篇 |
2022年 | 2168篇 |
2021年 | 2244篇 |
2020年 | 2333篇 |
2019年 | 2234篇 |
2018年 | 11877篇 |
2017年 | 11657篇 |
2016年 | 8536篇 |
2015年 | 3550篇 |
2014年 | 3522篇 |
2013年 | 4472篇 |
2012年 | 8745篇 |
2011年 | 15257篇 |
2010年 | 8921篇 |
2009年 | 9128篇 |
2008年 | 9971篇 |
2007年 | 11675篇 |
2006年 | 3070篇 |
2005年 | 3731篇 |
2004年 | 3356篇 |
2003年 | 3430篇 |
2002年 | 2372篇 |
2001年 | 1314篇 |
2000年 | 1253篇 |
1999年 | 1227篇 |
1998年 | 1075篇 |
1997年 | 976篇 |
1996年 | 1030篇 |
1995年 | 869篇 |
1994年 | 712篇 |
1993年 | 644篇 |
1992年 | 510篇 |
1991年 | 488篇 |
1990年 | 407篇 |
1989年 | 316篇 |
1988年 | 256篇 |
1987年 | 229篇 |
1986年 | 231篇 |
1985年 | 206篇 |
1984年 | 141篇 |
1983年 | 138篇 |
1982年 | 111篇 |
1981年 | 86篇 |
1980年 | 84篇 |
1979年 | 67篇 |
1978年 | 49篇 |
1977年 | 59篇 |
1976年 | 47篇 |
1973年 | 47篇 |
排序方式: 共有10000条查询结果,搜索用时 4 毫秒
951.
The folding landscapes of polypeptides and proteins exhibit a hierarchy of local minima. The causes range from proline isomerization all the way down to microstructure in the free energy caused by residual frustration inherent in even the best 20 amino acid design. The corresponding time scales range from hours to submicroseconds. The smallest microstructures are difficult to detect. We have measured the folding/unfolding kinetics of the engineered trpzip2 peptide at different tryptophan fluorescence wavelengths, each yielding a different rate. Wavelength-dependent folding kinetics on 0.1-2 mus time scales show that different microstructures with a range of solvent exposure and local dynamics are populated. We estimate a lower limit for the roughness of the free energy surface based on the range of rates observed. 相似文献
952.
Highly luminescent and photostable CdS:Mn/ZnS core/shell quantum dots are not water soluble because of their hydrophobicity. To create water-soluble quantum dots by an appropriate surface functionalization, CdS:Mn/ZnS quantum dots synthesized in a water-in-oil (W/O) microemulsion system (reverse micelles) were consecutively overcoated with a very thin silica layer ( approximately 2.5 nm thick) within the same reverse micellar system. The water droplet serves as a nanosized reactor for the controlled hydrolysis and condensation of a silica precursor, tetraethyl orthosilicate (TEOS), using an ammonium hydroxide (NH4OH) catalyst. Structural characterizations with transmission electron microscopy (TEM) and x-ray photoelectron spectroscopy (XPS) indicate that the silica-quantum dot nanocomposites consist of a layered structure. Owing to the amorphous, porous nature of a silica layer, the optical and photophysical properties of silica-overcoated CdS:Mn/ZnS quantum dots are found to remain close to those of uncoated counterparts. 相似文献
953.
在非水溶剂(二甲基亚砜(DMSO)及N,N_二甲基甲酰胺(DMF))中的伏安曲线.呈现三对电流峰,表明存在三个可逆或准可逆酞菁配体的单电子转移过程,而在水溶液中则不呈现准可逆行为,且波形改变很大.此外,还比较了四磺酸基酞菁锌的水溶液在自然光和红光(600~700nm)照射下的循环伏安曲线,其氧化还原峰的数目和峰电位基本不变,但在红光照射下比自然光照射下的峰电流明显增大. 相似文献
954.
The hydrothermal reaction of VOSO4, As2O3, CoC2O4·2H2O and 2,2-bipy yields a novel arsenic-vanadate [CoII(2,2-bpy)2]2[AsIII8VIV 14O42(H2O)]·H2O (1), which is characterized by IR, elemental analysis, TGA, magnetic susceptibility and single crystal X-ray diffraction analysis. X-ray diffraction shows that compound 1 is the first example of tubular arsenic–vanadium cluster containing infinite {[Co(2,2-bpy)2]2[As8V14O42(H2O)]} chain constructed from [As8V14O42(H2O)] clusters interconnected through [Co(2,2-bpy)]2+ units. Crystal data: 1, orthorhombic, P 212121, a=12.1401(2) Å, b=15.8722(1) Å, c=39.9533(5) Å, Z=4.Graphical Abstract: A novel polyoxoarsenicvanadate, [CoII(2,2-bipy)2]2 [AsIII8VIV 14O42(H2O)]·H2O, is depicted along with a tubular hybrid solid with a rhombic tube formed within the chain. 相似文献
955.
Raman mapping and in situ SERS spectroelectrochemical studies of 6-mercaptopurine SAMs on the gold electrode 总被引:1,自引:0,他引:1
Yang H Liu Y Liu Z Yang Y Jiang J Zhang Z Shen G Yu R 《The journal of physical chemistry. B》2005,109(7):2739-2744
The self-assembled monolayers (SAMs) of 6-mercaptopurine (6MP) were formed at the roughened polycrystalline gold surfaces in acid and alkaline media. The time-dependent Raman mapping spectral analysis in conjunction with the quantum calculations for the vibrational modes using ab initio BLYP/6-31G method suggested that both of the resulted 6MP SAMs adopted the same adsorption mode through the S atom of pyrimidine moiety and the N7 atom of the imidazole moiety anchoring the gold surface in a vertical way. The in situ surface-enhanced Raman scattering spectroelectrochemical experiment was conducted to examine the stability of the SAMs at various bias potentials. It was found that the detaching process of the 6MP SAMs from the surface involved one electron reduction as the voltage was applied at ca. 0.7 V vs a standard calomel electrode. 相似文献
956.
The goal of the present study is to test the hypothesis that LPA induces proliferation of astrocytes in hippocampus in vivo via phosphorylation of ERK 1/2. We first characterized the expression of GFAP, a special marker fiber protein of astrocytes,
in brain slices after direct injection of LPA into hippocampus by immunohistochemistry, and found that LPA induced a remarkable
proliferation of astrocytes. Then double-lablled immunofluorescence was used to detect GFAP and phosphorylation ERK 1/2 (p-ERK
1/2), LPA induced an immediate (10 min) and transient (<30 min) phosphorylation of ERK 1/2, and sequence sustained activation
of ERK 1/2 was observed, which last for at least 3 weeks after injection of LPA. Reactions are inhibited by U0126, a specific
pharmacological mitogen-activated protein kinase (MEK) inhibitor. Laser confocal scanning was used to study spatial relationship
of p-ERK and astrocytes. Amazingly, the early (<7 days) phosphorylation of ERK 1/2 is not expressed in astrocytes but in area
where neurons and/or in other cell type(s) occupied, expression of p-ERK 1/2 in astrocytes is not detected until 14 days after
LPA injection and lasts for at least 3 weeks. Taken together, these data suggest that LPA play an important role in proliferation
of astrocytes through phosphorylation of ERK 1/2 in hippocampus. It provides further proof for the functions of LPA in CNS
injury, and may contribute to clinical therapy for relative diseases. 相似文献
957.
A series of 2-benzyl-1,3-dicabonyl derivatives was synthesized.Their insulin-sensitizing activity was evaluated in 3T3-L1 preadipocyte cells.Compounds3,26 and 27 were found to possess strong insulin-sensitizing activity in vitro and were selected for further hypoglycemic evaluation in vivo. 相似文献
958.
J. Jung H. S. Jeong H. H. Chung M. J. Lee J. H. Jin K. B. Park 《Journal of Radioanalytical and Nuclear Chemistry》2003,255(3):543-546
The radioactive concentrations of radionuclides were measured in the soil and groundwater below the 12 GeV proton beam-line tunnel at KEK. Various long-lived radionuclides, (7Be, 22Na, 46Sc, 54Mn, 60Co, 134Cs, 152Eu and 154Eu) were observed in the soil samples by -ray spectra measurements, and 3H was also detected by liquid scintillation counting. On the other hand, 3H, 22Na and 54Mn, which were leached from the soil were measured in the groundwater below the EP2 beam line. 3H and 22Na were also found in slight amounts in groundwater collected in a well dug beside the East Counter Hall. From a comparison with the radioactive concentration in soil and groundwater, the order of the leaching percentages were 3H>22Na>54Mn. This tendency was in agreement with an experimental result of the RI laboratory. 相似文献
959.
A high-performance capillary electrophoretic (CE) method with electrochemical detection (ED) has been developed for determination of the pharmacologically active flavonoids in Ginkgo biloba L. and phytopharmaceuticals containing its extract. Epicatechin, catechin, rutin, apigenin, luteolin, and quercetin are important flavonoids in this plant. Operated in a wall-jet configuration, a 300 micro m diameter carbon-disk electrode was used as working electrode with good response to the six analytes at +1000 mV (relative to the SCE). Under the optimum conditions, the analytes were separated within 22 min in a borax buffer (pH 9.0). Excellent linearity was obtained over two orders of magnitude and detection limits (S/N=3) ranged from 1.4 x 10(-7) to 5.0 x 10(-7) g mL(-1) for all six analytes. The method was successfully used for assay of Ginkgo biloba L. and its phytopharmaceuticals after a relatively simple extraction procedure; the results obtained were satisfactory. 相似文献
960.
Direct trimethylsilylation1) of phenanthrene in different molar ratio of phenanthrene/sodium/trimethylchlorosilane is reported and discussed. Instead of the aromatic silyl compounds, such as 9-trimethylsilylphenanthrene (V), the hydroaromatic silyl compounds, such as 9, 10–bis (trimethylsilyl)-9, 10-dihydrophenanthrene (I) were obtained preferentially. Structure of these compounds are characterized and discussed. These silylated products have a general trend to change their properties during long time storage in the atmosphere under exposure to light. A significant difference of chemical shifts between silylated aromatic compound (V) and silylated hydroaromatic compound (I-IV) was observed. 相似文献