全文获取类型
收费全文 | 1280篇 |
免费 | 31篇 |
国内免费 | 8篇 |
专业分类
化学 | 906篇 |
晶体学 | 17篇 |
力学 | 21篇 |
数学 | 135篇 |
物理学 | 240篇 |
出版年
2022年 | 9篇 |
2021年 | 26篇 |
2020年 | 36篇 |
2019年 | 24篇 |
2018年 | 16篇 |
2017年 | 8篇 |
2016年 | 27篇 |
2015年 | 21篇 |
2014年 | 12篇 |
2013年 | 67篇 |
2012年 | 72篇 |
2011年 | 77篇 |
2010年 | 41篇 |
2009年 | 21篇 |
2008年 | 68篇 |
2007年 | 53篇 |
2006年 | 70篇 |
2005年 | 56篇 |
2004年 | 52篇 |
2003年 | 38篇 |
2002年 | 41篇 |
2001年 | 15篇 |
2000年 | 19篇 |
1999年 | 17篇 |
1998年 | 11篇 |
1997年 | 19篇 |
1996年 | 14篇 |
1995年 | 19篇 |
1994年 | 11篇 |
1993年 | 10篇 |
1992年 | 7篇 |
1991年 | 10篇 |
1990年 | 7篇 |
1989年 | 17篇 |
1988年 | 11篇 |
1987年 | 11篇 |
1986年 | 13篇 |
1985年 | 22篇 |
1984年 | 18篇 |
1983年 | 22篇 |
1982年 | 21篇 |
1981年 | 22篇 |
1980年 | 22篇 |
1979年 | 17篇 |
1978年 | 22篇 |
1977年 | 17篇 |
1976年 | 24篇 |
1975年 | 17篇 |
1974年 | 8篇 |
1973年 | 8篇 |
排序方式: 共有1319条查询结果,搜索用时 250 毫秒
31.
In the 1B2u-1Ag system of naphthalene in a supersonic jet, rotational contour calculations show rotational temperatures of 2–60 K for argon carrier gas pressures of 1520-120 Torr. The b1u vibration v24 shows a high vibrational temperature which corresponds to the seeding temperature for pressures <400 Torr. 相似文献
32.
Gillitzer E Willits D Young M Douglas T 《Chemical communications (Cambridge, England)》2002,(20):2390-2391
Here we present generalized methods for chemically modifying the surface of a viral protein cage; this exploits the chemistry of native and engineered surface exposed functional groups for multivalent presentation of ligands. 相似文献
33.
Doris J. Bates Myron Rosenblum Sari B. Samuels 《Journal of organometallic chemistry》1981,209(3):C55-C59
CpFe(CO)2[C(OEt)R]BF4 complexes can be prepared by reaction of CpFe(CO)2(isobutylene)BF4 with monoalkylated acetylenes in methylene chloride/ethanol solutions. Methyl propiolate yields methyl trans-2-ethoxy-acrylate, in a reaction catalytic in CpFe(CO)2(isobutylene)BF4, and internal acetylenes can be transformed to CpFe(CO)2(vinyl ether)BF4 complexes. 相似文献
34.
Earlier work by Lindenbaum and Boyd has demonstrated the important role of hydrophobic interactions involving the water solvent in determining the osmotic coefficients and properties of aqueous solutions of the tetraalkylammonium halides. Osmotic coefficients of solutions of tetramethyl-, tetraethyl-, tetrapropyl-, and tetrabutylammonium bromides in the more highly structured solvent D2O have now been determined by the gravimetric isopiestic method, using reference solutions of NaCl in D2O. The data were fitted to the Rush-Johnson and Pitzer equations. Satisfactory agreement with the results for aqueous solutions at comparable concentrations indicates that the solution chemistry of these quaternary ammonium bromides is not highly dependent on the degree of structure of the pure solvents. Supplementary data for mixtures of Me4NBr with Et4NBr, Pr4NBr, or Bu4NBr in both H2O and D2O are consistent with this conclusion.On leave 1980–82 from Banaras Hindu University, India 相似文献
35.
Alan P. Marchand Anna Hazlewood Zilin Huang Satish Kumar Vadlakonda John-David R. Rocha Trevor D. Power Kata Mlinarić-Majerski Lada Klaić Goran Kragol Jeffrey C. Bryan 《Structural chemistry》2003,14(3):279-288
Bis-cage-annulated 18-crown-6 and 20-crown-6 macrocyclic ethers (i.e., 1 and 2, respectively) have been synthesized, and their alkali metal picrate extraction profiles have been determined. Host system 1 proved to be a significantly more avid alkali metal cation complexant than 2 and somewhat more avid than 18-crown-6. Both 1 and 18-crown-6 display modest selectivity toward K+ and Rb+. A stable host–guest complex was prepared by slow evaporation of a CH2Cl2–hexane solution of an equimolar mixture of 2 and potassium picrate. The X-ray crystal structure of this complex reveals that picrate anion functions as a bidentate ligand therein. The gas-phase interaction energy between the 2 K+ complex and picrate anion was calculated to be ca. –64.9 kcal mol–1, thereby indicating that participation of picrate anion as an additional bidentate ligand results in significant stabilization of complex 10. 相似文献
36.
The IR and resonance Raman spectra of the nickel(II) complexes of dibenzo[b,i][1,4,8,11]tetraaza[14]annulene (TAA) and 5,7,12,14-tetramethyldibenzo[b,i][1,4,8,11]tetraaza[14]annulene (TMTAA) have been measured and compared with ab initio calculations of the vibrational wavenumbers at the B3-LYP level using the LanL2DZ basis set. An excellent fit is found between the experimental and calculated data, enabling precise vibrational assignments to be made. Surface-enhanced resonance Raman spectra were obtained following adsorption on Ag electrodes, with potentials in the range -0.1 to -1.1 V vs Ag/AgCl. There is evidence for contributions from both the electromagnetic and charge transfer (CT) surface enhancement mechanisms. The data indicate that variations in band intensities with electrode potential can be interpreted in terms of the CT mechanism. 相似文献
37.
Liane M. Moreau Alexandre Herve Mark D. Straub Dominic R. Russo Rebecca J. Abergel Selim Alayoglu John Arnold Augustin Braun Gauthier J. P. Deblonde Yangdongling Liu Trevor D. Lohrey Daniel T. Olive Yusen Qiao Julian A. Rees David K. Shuh Simon J. Teat Corwin H. Booth Stefan G. Minasian 《Chemical science》2020,11(18):4648
We report the structural properties of ultra-small ThO2 and UO2 nanoparticles (NPs), which were synthesized without strong binding surface ligands by employing a covalent organic framework (COF-5) as an inert template. The resultant NPs were used to observe how structural properties are affected by decreasing grain size within bulk actinide oxides, which has implications for understanding the behavior of nuclear fuel materials. Through a comprehensive characterization strategy, we gain insight regarding how structure at the NP surface differs from the interior. Characterization using electron microscopy and small-angle X-ray scattering indicates that growth of the ThO2 and UO2 NPs was confined by the pores of the COF template, resulting in sub-3 nm particles. X-ray absorption fine structure spectroscopy results indicate that the NPs are best described as ThO2 and UO2 materials with unpassivated surfaces. The surface layers of these particles compensate for high surface energy by exhibiting a broader distribution of Th–O and U–O bond distances despite retaining average bond lengths that are characteristic of bulk ThO2 and UO2. The combined synthesis and physical characterization efforts provide a detailed picture of actinide oxide structure at the nanoscale, which remains highly underexplored compared to transition metal counterparts.ThO2 and UO2 nanoparticles synthesized using a COF-5 template exhibit unpassivated surfaces and provide insight into nanoscale properties of actinides. 相似文献
38.
Resonance Raman and infrared absorption spectra of ClO3 radicals have been observed from measurements of crystalline NaClO3 irradiated at 77 K with 1.5 MeV electrons. The ClO3 radicals occupy two sets of nonequivalent sites; radicals at one site are observed from resonance scattering using 6328 Å excitation while those at the other site are observed from resonance scattering with 5145 Å excitation. The red sensitive radicals decompose at 77 K with a half-life of ≈29 min while the green sensitive radicals are more stable at this temperature. 相似文献
39.
During 1998 and early 1999, shellfish samples from sites in Scotland were found to contain the amnesic shellfish poisoning toxin, domoic acid (DA). Two different techniques, liquid chromatography (LC) with UV diode-array detection and LC with mass spectrometric (MS) detection, were used to detect and confirm DA in shellfish extracts. The LC/UV method was validated for routine monitoring by recovery experiments on spiked mussel and scallop tissues with a certified mussel tissue used as reference material. Crude extracts of selected samples as well as extracts cleaned with strong anion exchange (SAX) were analyzed by both LC/UV and LC/MS. Good correlation (linear regression r2 = 0.996, slope = 0.93) between the 2 methods was found for cleaned extracts. Analyses of crude extracts by LC/UV produced false-positive results in 2 crab samples, whereas LC/MS analyses gave accurate results. It was concluded that LC/UV is a valid approach for routine monitoring of DA in shellfish when cleanup is performed with a SAX cartridge to prevent false positives. A variety of shellfish species were surveyed for DA content, including Pecten maximus (king scallops), Chlamys opercularis (queen scallop), Mytilus edulis (blue mussels), Cancer pugaris (crab), and Ensis ensis (razor fish). The highest concentration of DA was 105 microg/g in Pecten maximus. 相似文献
40.
Hydrous amorphous Al (HAO), Fe (HFO), and Mn (HMO) oxides are ubiquitous in the subsurface as both discrete particles and coatings and exhibit a high affinity for heavy metal contaminants. To assess risks associated with heavy metals, such as Pb, to the surrounding environment and manage remedial activities requires accurate mechanistic models with well-defined transport parameters that represent sorption processes. Experiments were conducted to evaluate Pb sorption to microporous Al, Fe, and Mn oxides, as well as to montmorillonite and HAO-coated montmorillonite. Intraparticle diffusion, a natural attenuating process, was observed to be the rate-limiting mechanism in the sorption process, where best-fit surface diffusivities ranged from 10(-18) to 10(-15) cm(2) s(-1). Specifically, diffusivities of Pb sorption to discrete aluminum oxide, aluminum oxide-coated montmorillonite, and montmorillonite indicated substrate surface characteristics influence metal mobility where diffusivity increased as affinity decreased. Furthermore, the diffusivity for aluminum oxide-coated montmorillonite was consistent with the concentrations of the individual minerals present and their associated particle size distributions. These results suggest that diffusivities for other coated systems can be predicted, and that oxide coatings and montmorillonite are effective sinks for heavy metal ions. 相似文献