全文获取类型
收费全文 | 5126篇 |
免费 | 0篇 |
国内免费 | 11篇 |
专业分类
化学 | 3310篇 |
晶体学 | 1篇 |
力学 | 3篇 |
数学 | 13篇 |
物理学 | 1620篇 |
无线电 | 190篇 |
出版年
2012年 | 337篇 |
2011年 | 523篇 |
2010年 | 79篇 |
2009年 | 14篇 |
2008年 | 458篇 |
2007年 | 439篇 |
2006年 | 490篇 |
2005年 | 512篇 |
2004年 | 379篇 |
2003年 | 286篇 |
2002年 | 237篇 |
2001年 | 151篇 |
2000年 | 205篇 |
1999年 | 37篇 |
1998年 | 14篇 |
1997年 | 6篇 |
1996年 | 86篇 |
1995年 | 74篇 |
1994年 | 124篇 |
1993年 | 149篇 |
1992年 | 133篇 |
1991年 | 63篇 |
1990年 | 67篇 |
1989年 | 66篇 |
1988年 | 40篇 |
1987年 | 36篇 |
1986年 | 39篇 |
1985年 | 43篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1976年 | 2篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1971年 | 1篇 |
1970年 | 1篇 |
1969年 | 6篇 |
1968年 | 3篇 |
1967年 | 4篇 |
1966年 | 1篇 |
1957年 | 1篇 |
1948年 | 13篇 |
1947年 | 3篇 |
1946年 | 1篇 |
排序方式: 共有5137条查询结果,搜索用时 218 毫秒
101.
Selection rules for helicate ligand component self-assembly: steric, pH, charge, and solvent effects
Nitschke JR Schultz D Bernardinelli G Gérard D 《Journal of the American Chemical Society》2004,126(50):16538-16543
The reaction between 1,10-phenanthroline-2,9-dicarboxaldehyde, copper(I), and certain primary amines was found to give quantitatively a dicopper double-helicate product (two of which were crystallographically characterized) by imine self-assembly around Cu(I) templates. The parameters of this reaction were investigated, and important roles were found to be played by (i) the steric bulk of the amine, (ii) the charge of the amine, (iii) the solvent used, and (iv) the pH of the solution. Water was found to allow the broadest range of structures to form, and ligand-component exchange reactions (involving the substitution of an aromatic for an aliphatic amine) were demonstrated to proceed readily in this solvent. 相似文献
102.
Evans PA Sawyer JR Lai KW Huffman JC 《Chemical communications (Cambridge, England)》2005,(31):3971-3973
The crossed intermolecular rhodium-catalyzed [2+2+2] carbocyclization of carbon and heteroatom tethered 1,6-enynes can be accomplished with symmetrical and unsymmetrical alkynes, to afford the corresponding bicyclohexadienes in an efficient and highly selective manner. 相似文献
103.
Kwac and Cho [J. Chem. Phys. 119, 2247 (2003)] have recently developed a combined electronic structure/molecular dynamics approach to vibrational spectroscopy in liquids. The method involves fitting ab initio vibrational frequencies for a solute in a cluster of solvent molecules to a linear combination of the electrostatic potentials on the solute atoms due to the charges on the solvent molecules. These authors applied their method to the N-methylacetamide-D/D(2)O system. We (S. A. Corcelli, C. P. Lawrence, and J. L. Skinner, [J. Chem. Phys. 120, 8107 (2004)]) have recently explored a closely related method, where instead of the electrostatic potential, the solute vibrational frequencies are fit to the components of the electric fields on the solute atoms due to the solvent molecules. We applied our method to the HOD/D(2)O and HOD/H(2)O systems. In order to make a direct comparison of these two approaches, in this paper we apply their method to the water system, and our method to the N-methylacetamide system. For the water system we find that the electric field method is superior to the potential approach, as judged by comparison with experiments for the absorption line shape. For the N-methylacetamide system the two methods are comparable. 相似文献
104.
Kimball DB Haley MM Mitchell RH Ward TR Bandyopadhyay S Williams RV Armantrout JR 《The Journal of organic chemistry》2002,67(25):8798-8811
The synthesis and study of dehydrobenzoannulene (DBA)-dimethyldihydropyrene (DDP) hybrids as models for the investigation of aromaticity in weakly diatropic systems is reported. Three new monofused DBA-DDP hybrids have been synthesized, and their NMR spectra are discussed with regard to quantifying the aromaticity remaining in multibenzene-fused DBAs. Nucleus-independent chemical shifts, determined at a series of locations for each compound, bond lengths, and (1)H and (13)C NMR chemical shifts were calculated and used to probe the aromaticity of these hybrids. Systems where more than one annulene/DBA is fused to the DDP core have also been obtained, and their potential use in photoinduced isomerization applications is discussed. 相似文献
105.
A gas chromatographic method for monitoring diacetyl guanfubase A in plasma is described. The procedure involved a single solvent extraction of drug from rabbit plasma into ethyl acetate with guanfubase A as an internal standard. The extract was analyzed subsequently on a gas chromatograph equipped with a hydrogen flame ionization detector. The recovery was 86.43% +/- 6.90% (+/- SD); the RSD of within-day and between-day was 2.81%-5.26% and 5.22%-8.24%, respectively; the regression line was linear over the concentration range of 25-200 micrograms/mL, the limit of detection was 10 micrograms/mL. No endogeneous interference was found in chromatograms of the biological samples. This method was applied to the pharmacokinetic study of diacetyl guanfubase A in rabbits. 相似文献
106.
Determination of the total nitrogen content of hard, semihard, and processed cheese by the Kjeldahl method: collaborative study 总被引:1,自引:0,他引:1
The objective of this collaborative study was to determine interlaboratory performance statistics for a modified and optimized version of AOAC Method 920.123 for the determination of the total nitrogen content of hard, semihard, and processed cheese by Kjeldahl analysis. Details included addressing the issues of material homogeneity, test portion size (1 g), quantitative transfer (weighing on to filter paper), ensuring system suitability (nitrogen recoveries), and using AOAC Method 991.20 as the basis for nitrogen analysis. Fifteen laboratories tested 18 pairs of blind duplicate cheese materials with a crude protein content between 18 and 36%. Materials represented hard, semihard, and processed commercial cheeses with a wide range of composition. Statistical performance parameters expressed as crude protein (nitrogen x 6.38), g/100 g, with invalid and outlier data removed were mean = 26.461, repeatability standard deviation (Sr) 0.111, reproducibility standard deviation (S(R)) = 0.153, repeatability relative standard deviation (RSDr) = 0.42%, reproducibility relative standard deviation (RSDR) = 0.58%, repeatability (r) = 0.312, and reproducibility (R) = 0.428. The interlaboratory study results were acceptable and comparable to those for the milk Kjeldahl nitrogen method on a relative nitrogen basis. The Study Directors recommend that this modified method for the determination of total nitrogen in hard, semihard, and processed cheese by Kjeldahl analysis be adopted First Action as an improved method to replace Method 920.123. 相似文献
107.
Immunoassays have traditionally relied on antibodies as diagnostic probes. Their use outside of a laboratory, however, may be problematic because antibodies are often unstable in severe environmental conditions. Environmental monitoring requires thermostable probes, such as landscape phage, that carry thousands of foreign peptides on their surfaces, are superior to antibodies, and can operate in non-controlled conditions. While parent wild-type phage are known to be extremely stable in various media at high temperatures, no work has been done to demonstrate the stability of landscape phage probes. We examined the thermostability of a landscape phage probe and a monoclonal antibody specific for -galactosidase in parallel in an enzyme-linked immunosorbent assay (ELISA) format. They were both stable for greater than six months at room temperature, but at higher temperatures the antibody degraded more rapidly than the phage probe. Phage retained detectable binding ability for more than six weeks at 63 °C, and three days at 76 °C. The activation energy of phage degradation was determined to be 1.34×105 J/mol. These results confirm that phage probes are highly thermostable and can function even after exposure to high temperatures during shipping, storage and operation. 相似文献
108.
Cross-validation of a solid-state NMR-derived membrane polypeptide structure is demonstrated. An initial structure has been achieved directly from solid-state NMR derived orientational restraints based on a variety of anisotropic nuclear spin interactions. Refining the molecular structure involves setting up a penalty function that incorporates all available solid-state NMR experimental data and an energy function. A validation method is required to choose the optimal weighting factor for the total penalty function to balance the contribution from the experimental restraints and the energy function. Complete cross-validation has been used to avoid over-fitting the orientational restraints. Such cross-validation involves partitioning of the experimental data into a test set and a working set followed by checking the free R-value during the refinement process. This approach is similar to the method used in crystallography and solution NMR. Optimizing the weighting factor on the penalty function by cross-validation will increase the quality of the refined structure from solid-state NMR data. The complete cross-validation and R-factor calculation is demonstrated using experimental solid-state NMR data from gramicidin A, a monovalent cation channel in lipid bilayers. 相似文献
109.
Hwu JR Jain ML Tsai FY Tsay SC Balakumar A Hakimelahi GH 《The Journal of organic chemistry》2000,65(17):5077-5088
Silica gel-supported ceric ammonium nitrate (CAN-SiO2) was found effective for rapid and selective cleavage of trityl (Tr), monomethoxytrityl (MMTr), and dimethoxytrityl (DMTr) groups from protected nucleosides and nucleotides under mild conditions. Efficiency of deprotections depended upon the stability of the resultant carbocationic species: DMTr+ > MMTr+ > Tr+. Use of a catalytic amount of this solid-supported reagent can also efficiently and selectively remove the tert-butyldimethylsilyl or the triisopropylsilyl group from a primary hydroxyl functionality in di- or trisilyl ethers of ribonucleosides. A comparative study of deprotection reactions by utilization of CAN alone or CAN-SiO2 indicates a remarkable increase in the rate of the reactions involving a solid support. The mechanism of electron-transfer processes is proposed for the use of CAN-SiO2 in the removal of these protective groups from organic molecules. 相似文献
110.
First-principles molecular dynamics simulations are carried out to study the structures, dynamics, and electronic properties of liquid Al88Si12 in the temperature ranging from 898 to 1298 K. The temperature dependence of static structure factors, pair correlation functions, and electronic density-of-states are investigated. The structural properties obtained from the simulations are in good agreement with the x-ray diffraction experimental results. 相似文献