全文获取类型
收费全文 | 84525篇 |
免费 | 6885篇 |
国内免费 | 7746篇 |
专业分类
化学 | 73707篇 |
晶体学 | 920篇 |
力学 | 4064篇 |
综合类 | 440篇 |
数学 | 4152篇 |
物理学 | 15873篇 |
出版年
2024年 | 113篇 |
2023年 | 866篇 |
2022年 | 1798篇 |
2021年 | 1876篇 |
2020年 | 2516篇 |
2019年 | 2381篇 |
2018年 | 2271篇 |
2017年 | 2950篇 |
2016年 | 3451篇 |
2015年 | 2983篇 |
2014年 | 3321篇 |
2013年 | 6233篇 |
2012年 | 5039篇 |
2011年 | 4984篇 |
2010年 | 4163篇 |
2009年 | 5185篇 |
2008年 | 4542篇 |
2007年 | 4963篇 |
2006年 | 4342篇 |
2005年 | 4066篇 |
2004年 | 3764篇 |
2003年 | 3092篇 |
2002年 | 3067篇 |
2001年 | 2201篇 |
2000年 | 1994篇 |
1999年 | 1796篇 |
1998年 | 1574篇 |
1997年 | 1436篇 |
1996年 | 1460篇 |
1995年 | 1416篇 |
1994年 | 1236篇 |
1993年 | 957篇 |
1992年 | 860篇 |
1991年 | 781篇 |
1990年 | 613篇 |
1989年 | 557篇 |
1988年 | 601篇 |
1987年 | 548篇 |
1986年 | 423篇 |
1985年 | 406篇 |
1984年 | 415篇 |
1983年 | 194篇 |
1982年 | 368篇 |
1981年 | 309篇 |
1980年 | 288篇 |
1979年 | 278篇 |
1978年 | 132篇 |
1977年 | 95篇 |
1976年 | 84篇 |
1973年 | 50篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
911.
Publications on the binding characteristics of metals with humic acid (HA) are sparse. Here we investigated the release of nickel from Ni(II)-HA complexes using model solutions of three different [Ni(II)]/[HA] mole ratios at three different pH values; we also compared the results with those of [Ni(II)]/[FA] complexes from previous work in this laboratory. Ligand exchange kinetics using the competing ligand exchange method (CLEM) were studied using two different techniques: graphite furnace atomic absorption spectrometry (GFAAS) with Chelex 100 resin as the competing ligand, and adsorptive cathodic stripping voltammetry (AdCSV) with dimethylglyoxime as the competing ligand to measure the rate of dissociation of Ni(II)-HA complexes. The results of the kinetic studies showed that as the [Ni(II)]/[HA] mole ratio was decreased, the rate of dissociation of Ni(II)-HA complexes decreased, and the proportion of free Ni2+ ions plus very labile nickel complexes decreased while the proportion of the less labile kinetically distinguishable components increased. Generally, the rate of dissociation of Ni(II)-HA complexes was slower than that of Ni(II)-FA complexes. Studies on the validity of the kinetic model showed that the concentrations of chemical species varied in a reasonable way with pH and the [Ni(II)]/[HA] mole ratios, indicating that the kinetically distinguishable components have chemical significance and the kinetic model is valid. 相似文献
912.
气相-质谱法测定粮谷中恶草酮的残留量 总被引:6,自引:0,他引:6
应用微量化学法和固相萃取技术 ,建立了粮谷中恶草酮残留量的气相 质谱 (GC MS)测定方法。用苯 正己烷 (体积比为 1∶1)萃取 ,中性氧化铝小柱净化。净化液用GC MS测定 ,采用外标法定量。恶草酮在大米中的回收率为 90 4%~ 115 .7% ,RSD为 2 %~ 6 % ,在玉米中的回收率为 81 3%~ 10 9 7% ,RSD为 4%~ 9% ,最低定量检出限为 0 0 0 5mg/kg。该法快速、灵敏、准确 ,各项技术指标均满足农药残留检测的要求。 相似文献
913.
A method combining the techniques of liquid – solid disk extraction (LSDE) and supercritical fluid elution (SFE) has been developed for the phenols regulated by the Clean Water Act. LSDE uses a disk or membrane made of polytetrafluoroethylene (PTFE) fibrils impregnated with small particles, e.g. styrene divinylbenzene (SDB) resin, to extract phenols from water. After disk extraction the retained analytes are eluted from the disk using SFE. SFE is used as an alternative to liquid solvent elution with an organic solvent. Analytes are separated, identified, and quantified using gas chromatography – ion trap detector mass spectrometry (GC-ITDMS). The method is capable of sub parts per billion detection limits, and precision of 5–28% RSD. Evaluation of various disks or membranes, such as C18-silica disks, SDB disks, and ion exchange membranes, has also been performed for the extraction of phenols from water. The results obtained from the in-situ aqueous acetylation of phenols and extraction of their acetates are quantitative. The utilization of LSDE and SFE techniques has proven to be a more effective approach than liquid – liquid extraction in minimizing air pollution and solvent waste. 相似文献
914.
915.
Alternative Ligands. XXIII Rhodium(I) Complexes with Donor/Acceptor Ligands of the Type (Me2PCH2CH2)2SiX2 and (2-Me2PC6H4)SiXMe2 (X = F, Cl) Donor/acceptor ligands of the type (Me2PCH2CH2)2SiX2 and (2-Me2PC6H4)SiXMe2 (X = F, Cl) react with [Rh(CO)2Cl]2 (1) to give the mononuclear complexes RhCl(CO)(Me2PCH2CH2)2SiX2 [X = F( 4 ), Cl ( 5 )] and RhCl(CO)[2-Me2PC6H4)SixMe2]2 [X = F ( 8 ), Cl ( 9 )], respectively. In case of the ligands (Me2PCH2CH2)2SiCl2 ( 3 ) and (2-Me2PC6H6)SiClMe2 ( 7 ) the Rh(I) complexes formed in the first step partly undergo oxidative addition reactions of SiCl bonds yielding rhodium(III) compounds of low solubility. Only for 8 the coordination shifts Δδ = δ(complex)?δ(ligand) and coupling constants give some indication to possible Rh→Si interactions. However, the molecular structure of 8 determined by X-ray diffraction does not show RhSi or RhF bonding contacts. The new compounds were characterized by analytical (C, H) and spectroscopic investigations (MS, IR,-NMR). 相似文献
916.
Recent developments in quantitative surface analysis by Auger (AES) and x-ray photoelectron (XPS) spectroscopies are reviewed and problems relating to a more accurate quantitative interpretation of AES/XPS experimental data are discussed. Special attention is paid to consideration of elementary physical processes involved and influence of multiple scattering effects on signal line intensities. In particular, the major features of core-shell ionization by electron impact, Auger transitions and photoionization are considered qualitatively and rigorous approaches used to calculate the respective transition probabilities are analysed. It is shown that, in amorphous and polycrystalline targets, incoherent scattering of primary and signal Auger and photoelectrons can be described by solving analytically a kinetic equation with appropriate boundary conditions. The analytical results for the angular and energy distribution, the mean escape depth, and the escape probability as a function of depth of origin of signal electrons as well as that for the backscattering factor in AES are in good agreement with the corresponding Mote Carlo simulation data. Methods for inelastic background subtraction, surface composition determination and depth-profile reconstructions by angle-resolved AES/XPS are discussed. Examples of novel techniques based on x-ray induced photoemission are considered. 相似文献
917.
Aggregated aromatic molecule--cyclodextrin-precipitant complexes exhibit long-lived phosphorescence at room temperature in water after the chemical binding of oxygen. The temperature dependences of the phosphorescence lifetimes of naphthalene-h8, naphthalene-de, and phenanthrene in the aggregates were measured. For example, the phosphorescence lifetimes of naphthalene-d8 aggregated with -cyclodextrin and cyclohexane are equal to 25.1, 17.6, and 6.8 s at 77, 276, and 347 K, respectively, and that of phenanthrene aggregated with isooctane and -cyclodextrin are 3.24, 3.06, and 1.26 s at 268, 274, and 335 K, respectively. The temperature dependences of the phosphorescence lifetimes at room temperature are determined by the rate constants of the radiative and nonradiative transitions from the triplet state of an aromatic molecule.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2225–2228, September, 1996. 相似文献
918.
Xin-hua Wan Hui-lin Tu Ying-feng Tu Dong Zhang Ling Sun Qi-feng Zhou Yu-ping Dong Mao Tang Department of Polymer Science & Engineering College of Chemistry Peking University Beijing China Department of Materials & Chemical Engineering Beijing Institute of Technology Beijing China 《高分子科学》1999,(2):189-192
The first TEMPO-mediated "living" free radical polymerization of liquid crystallinemonomer, 2, 5-bis[(4-methoxyphenyl)oxycarbonyl]styrene(MPCS), was carried out at 130℃ withBPO as an initiator. The molecular weight of the polymer can be varied from rather low values to highvalues while maintaining narrow polydispersity. It was observed that the polymerization of MPCSproceeded much faster than that of styrene. A tentative explanation for this fast polymerization wassuggested. 相似文献
919.
Itsuo Furuoya 《Catalysis Surveys from Japan》1999,3(1):71-73
The vapor phase catalytic reaction between aromatic carboxylic acid and acetic acid was investigated. Many metal oxides catalyzed the reaction between 2methylbenzoic acid (OTA) and acetic acid (AA) to produce 2methylacetophenone (OMA), and weakly acidic oxides such as Th, U, Ce, and La oxide exhibited higher yield of OMA. The OMA yield depended on the catalyst support. SiO2, Al2O3, TiO2, and ZrO2 with a surface area of less than 200 m2 g–1 appeared to be suitable as industrial catalyst supports. CeO2 on Al2O3was chosen as an industrial catalyst for the synthesis of OMA because of higher productivity, longer catalyst life, and lifting of legal restrictions on catalyst handling. This catalyst system can also be applied to the syntheses of acetophenone, nitroacetophenone, and chloroacetophenone. 相似文献
920.
Summary High-performance liquid chromatography and ultraviolet spectroscopy methods were applied to the studies on the influence of
temperature on the complexation of β-cyclodextrin with naphthalene and its derivatives. The strong nonlinearity of Van't Hoff
plots suggests, that the retention mechanism of hydrocarbons investigated might be different in high and low temperature region.
The total lack of correlation (r=−0.230) between chromatographic data (capacity factors ratio:k
PAH/k
PAH×CD) and spectrophotometric data (ΔA) at high temperature (60°) as well as a significant correlation (r=0.922) at subambient temperature (15°C) suggest, that the inclusion mechanism starts to be important at low temperature region
and the predominant mechanism for chromatographic retention is the formation of an inclusion complexes in the mobile phase. 相似文献