全文获取类型
收费全文 | 3563篇 |
免费 | 449篇 |
国内免费 | 410篇 |
专业分类
化学 | 2988篇 |
晶体学 | 41篇 |
力学 | 9篇 |
综合类 | 14篇 |
数学 | 8篇 |
物理学 | 1362篇 |
出版年
2024年 | 5篇 |
2023年 | 27篇 |
2022年 | 87篇 |
2021年 | 77篇 |
2020年 | 129篇 |
2019年 | 114篇 |
2018年 | 75篇 |
2017年 | 105篇 |
2016年 | 135篇 |
2015年 | 133篇 |
2014年 | 151篇 |
2013年 | 317篇 |
2012年 | 203篇 |
2011年 | 212篇 |
2010年 | 161篇 |
2009年 | 206篇 |
2008年 | 233篇 |
2007年 | 251篇 |
2006年 | 228篇 |
2005年 | 187篇 |
2004年 | 164篇 |
2003年 | 159篇 |
2002年 | 116篇 |
2001年 | 147篇 |
2000年 | 93篇 |
1999年 | 115篇 |
1998年 | 93篇 |
1997年 | 71篇 |
1996年 | 63篇 |
1995年 | 59篇 |
1994年 | 45篇 |
1993年 | 36篇 |
1992年 | 30篇 |
1991年 | 23篇 |
1990年 | 20篇 |
1989年 | 24篇 |
1988年 | 14篇 |
1987年 | 16篇 |
1986年 | 12篇 |
1985年 | 6篇 |
1984年 | 9篇 |
1983年 | 9篇 |
1982年 | 9篇 |
1981年 | 8篇 |
1980年 | 11篇 |
1979年 | 7篇 |
1978年 | 4篇 |
1976年 | 5篇 |
1974年 | 3篇 |
1973年 | 5篇 |
排序方式: 共有4422条查询结果,搜索用时 93 毫秒
41.
Hanns‐Dieter Amberger Lixin Zhang Hauke Reddmann Christos Apostolidis Olaf Walter 《无机化学与普通化学杂志》2006,632(15):2467-2470
Electronic Structures of Organometallic Compounds of f Elements. 64 Does the Zwitterionic Nature of the Triphenylphosphine Oxide Ligand Manifest itself in its Spectrochemical Properties? The triphenylphosphine oxide mono adducts of the moiety tris(η5‐cyclopentadienyl)lanthanide(III) (Ln(Cp)3; Ln = Pr ( 1 ), La ( 2 )) were synthesized and structurally characterized. The Ln–O distances of these compounds are noticeably shorter than those of the corresponding THF adducts. A crystal field (CF) analysis of the optical spectra of 1 leads to a low absolute value of the quadratic CF parameter which is comparable with those of [Pr(Cp)3(L)]? adducts with anionic bases but not with [Pr(Cp)3(MeTHF)]. Reasons for the latter finding are presented. 相似文献
42.
Bagiyan G. A. Koroleva I. K. Soroka N. V. Ufimtsev A. V. 《Russian Chemical Bulletin》2003,52(5):1135-1141
Side self-oxidation of thiols was studied. It was found that these reactions in neutral and alkaline solutions are induced by impurities of variable-valence metals. The ability of transition metals to catalyze oxidation of thiols changes in the order Cu > Mn > Fe > Ni Co. The plot of the self-oxidation rate vs. pH passes through a maximum whose position on the pH scale depends on both the nature of metal and the structure of the thiol oxidized. For thiols having different structures, the kinetic orders in reactions catalyzed by copper ions differently vary with pH, which is apparently associated with the formation of complexes possessing different catalytic activity. 相似文献
43.
Microcolumns containing 8-hydroxyquinoline azo-immobilized on controlled pore glass were incorporated in a field sampler for on-site collection, isolation and preconcentration of trace metal ions in waters of the Okavango Delta, Botswana. Sequestered trace metal ions were recovered by elution with 0.5 ml of 1.5 M nitric acid, and determined by graphite furnace atomic absorption spectrometry (GFAAS). This sampling and enrichment method minimizes sample contamination, and collection of large volumes of water samples for transporting, over long distances, to analytical laboratories is avoided.Data reported comprise one of the initial surveys on trace metal ion concentrations in waters of the Okavango Delta, Botswana. In waters with more efficient mixing, dissolved metal ion concentrations found were generally low with slightly elevated levels of manganese (7-19 μg l−1), zinc (2.7-4.8 μg l−1), nickel (0.2-2.5 μg l−1) and copper (0.3-2.1 μg l−1). For each trace metal ion, concentration levels seem to reflect zones of varying water conveyance, and show no obvious temporal and spatial variations apart from a slight increment from the inlet in the upper Delta to the outlets in the lower Delta. 相似文献
44.
水中痕量酚的富集和紫外分光光度测定法的研究 总被引:2,自引:0,他引:2
本文研究了用微型树脂柱快速富集,分离,紫外分光光度测定水中痕量酚的方法。结果表明,以GDX-502为吸附剂,水样pH为1~3并含0.2mol/L氯化钠,以每分种15~20ml的速度通过吸附柱,以热的1%氢氧化钠水溶液为淋洗剂时,在291nm处测定苯酚的回收率为89~98%。此外探讨了干扰物的消除方法。吸附柱对苯酚的富集倍数达300倍,最低检测限为0.001ppm。方法精密度为0.3(%),相对标准偏差为3.18%。本法对实际水样进行了测定。结果满意。 相似文献
45.
The formation of negative hydrogen ions in a conventional hollow cathode discharge has been investigated. A mixture of Ne and H2 proved to be more advantageous compared to pure hydrogen. The study has been performed by solving the electron Boltzmann equation, coupled with a system of balance equations for neon and hydrogen neutral and charged particles. The vibrational distribution function of hydrogen has been calculated. Our calculations show unusually high population of vibrationally excited hydrogen molecules in a Ne–H2 mixture, which explains the high density of negative hydrogen ions under optimal conditions (total gas pressure of few Torr, hydrogen number mole fraction of 1–10% and discharge current of 10–100 mA). Line intensities originating from highly excited neon states vs. hydrogen pressure have been calculated and a comparison with existing experimental results has been made. 相似文献
46.
Eugenio?Garcia-Pa?eda Pilar?Guardado Alfredo?MaestreEmail author 《Journal of solution chemistry》2004,33(10):1277-1293
Partial molar volumes at infinite dilution, V02, of alkali–metal halides (LiCl, NaCl KCl RbCl CsCl, NaBr, KBr, KI), tetra-n-alkylammonium bromides, R4NBr (R=Me, Et, n-Pr, n-Bu, n-Pen), NaBPh4, and Ph4PCl have been determined in binary solvent mixtures of water with 2-methyl-2-butanol covering the water-rich region and the alcohol-rich region at 298.15 K. V02 for alkali–metal halides show relatively little dependence on the solvent composition. However, in the case of hydrophobic electrolytes the observed effects are more pronounced. A good linear dependence between V02(R4NBr) and the molecular weight of the tetra-n-alkylammonium cation is found. Limiting single-ion volumes have been obtained using the assumption that V0(Ph4P+)–V0(BPh–4)=2.0 cm3-mol–1. The trends in the single-ion volumes are discussed in both solvent regions. 相似文献
47.
Radiation-chemical transformations of chloride solutions in the presence of iodide additives were studied by pulse radiolysis.
Radical anion Cl2
⋅− oxidize I− ion, while in the secondary reactions Cl2 reacts with I− to form a mixed trihalide ion ICl2
−. A reaction model that satisfactorily describes the experimental data was proposed.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1336–1340, June, 2005. 相似文献
48.
《Electroanalysis》2004,16(8):633-639
A potentiometric sensor constructed from a mixture of 25% (m/m) spinel‐type manganese oxide (lambda‐MnO2), 50% (m/m) graphite powder and 25% (m/m) mineral oil is used for the determination of lithium ions in a flow injection analysis system. Experimental parameters, such as pH of the carrier solution, flow rate, injection sample volume, and selectivity for Li+ against other alkali and alkaline‐earth ions and the response time of this sensor were investigated. The sensor response to lithium ions was linear in the concentration range 8.6×10?5–1.0×10?2 mol L?1 with a slope 78.9±0.3 mV dec?1 over a wide pH range 7–10 (Tris buffer), without interference of other alkali and alkaline‐earth metals. For a flow rate of 5.0 mL min?1 and a injection sample volume of 408.6 μL, the relative standard deviation for repeated injections of a 5.0×10?4 mol L?1 lithium ions was 0.3%. 相似文献
49.
The separation procedure for Ag, B, Cd, Dy, Eu and Sm as impurities in Gd matrix using ICP-AES technique with an extraction chromatographic column has been developed. The spectral interference of the Gd matrix on the elements was eliminated using a chromatography technique with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC-88A) as the mobile phase and XAD-16 resin as the stationary phase. Ag+, B4O72−, and Cd2+ were eluted with 0.1 M HNO3, while rare earth ions were not. The best eluent for separating Eu and Sm in the Gd matrix was 0.3 M HNO3. The limit of quantitation for these elements was 0.6-3.0 ng mL−1. The recovery of Ag, B, and Cd was 90-104% using 0.1 M HNO3 as the eluent, while that of Eu, Gd, and Sm ranged from 100 to 102% with 0.3 M HNO3. Dy was recovered quantitatively with 4 M HNO3. The relative standard deviation of the methods for a set of three replicates was between 1.0 and 15.4% for the synthetic and standard Gd solutions. The proposed separation procedure was used to measure Ag, B, Cd, Dy, Eu, and Sm in a standard Gd solution. 相似文献
50.
Chronoamperograms for gold in solutions containing 0.1 M thiourea, 0.5 M H2SO4, and catalytically active sulfide ions at the concentration c 1 from 1 × 10?5 to 4 × 10?5 M are obtained at different potentials with the aid of an automated setup intended for renewing the electrode surface directly in the solution by cutting off a thin surface layer of the metal. It is shown that the results of measurements of the current practically coincide at a constant value of the product c 1 t, where t is the time period elapsed after the renewal of the electrode surface. Such a coincidence testifies to a diffusion nature of processes that hamper accumulation of sulfide ions at the gold surface. This fact permitted the use of a procedure developed previously for the calculation of polarization curves at constant values of surface coverage θ by catalytically active ions. At θ = const, the voltammetric curves for gold in sulfide-containing thiourea solutions are shown to correspond to the Tafel equation. With the surface coverage increasing, the effective values of the exchange current i 0, transfer coefficient α, and anodic reaction order with respect to thiourea P a increase from the values i }~ 10?5 A cm?2, α }~ 0.12, and P a = 0.2, which are characteristic of pure solutions, to 2 × 10?4 A cm?2, α }~ 0.5, and P a = 1.1 (at θ }~ 0.5). An interpretation to the established regularities is given. 相似文献