全文获取类型
收费全文 | 7195篇 |
免费 | 360篇 |
国内免费 | 41篇 |
专业分类
化学 | 5264篇 |
晶体学 | 70篇 |
力学 | 204篇 |
数学 | 1004篇 |
物理学 | 1054篇 |
出版年
2023年 | 66篇 |
2022年 | 209篇 |
2021年 | 211篇 |
2020年 | 200篇 |
2019年 | 260篇 |
2018年 | 200篇 |
2017年 | 167篇 |
2016年 | 332篇 |
2015年 | 228篇 |
2014年 | 328篇 |
2013年 | 618篇 |
2012年 | 473篇 |
2011年 | 515篇 |
2010年 | 292篇 |
2009年 | 283篇 |
2008年 | 372篇 |
2007年 | 384篇 |
2006年 | 355篇 |
2005年 | 314篇 |
2004年 | 273篇 |
2003年 | 203篇 |
2002年 | 229篇 |
2001年 | 88篇 |
2000年 | 119篇 |
1999年 | 70篇 |
1998年 | 48篇 |
1997年 | 55篇 |
1996年 | 42篇 |
1995年 | 45篇 |
1994年 | 40篇 |
1993年 | 41篇 |
1992年 | 37篇 |
1991年 | 26篇 |
1990年 | 21篇 |
1989年 | 35篇 |
1988年 | 33篇 |
1987年 | 24篇 |
1986年 | 19篇 |
1985年 | 41篇 |
1984年 | 30篇 |
1983年 | 21篇 |
1982年 | 24篇 |
1981年 | 30篇 |
1980年 | 21篇 |
1979年 | 18篇 |
1978年 | 15篇 |
1977年 | 13篇 |
1976年 | 14篇 |
1975年 | 18篇 |
1959年 | 8篇 |
排序方式: 共有7596条查询结果,搜索用时 15 毫秒
31.
A. A. Abd El Raheem Abdel Aziz Amin A. S. Moustafa 《Fresenius' Journal of Analytical Chemistry》1960,172(5):347-356
Summary Omega Chrome Fast Blue 2G has been found to be a suitable indicator for the detection of the equivalence point of calcium, magnesium and manganese in the presence of cadmium, nickel, and aluminium, when they are masked by the addition of cyanide or triethanolamine. It is also a suitable indicator for the back titration of aluminium using calcium or magnesium as a back titrant.This dye has also been found to be a suitable reagent for the colorimetric determination of calcium, magnesium, manganese and thorium. 相似文献
32.
33.
The present work is dedicated to the XRD, ED and HREM characterization of a new bismuth copper oxyphosphate Bi∼6.2Cu∼6.2O8(PO4)5 (a=11.599(2)Å, , c=37.541(5)Å, R1=0.0755, Rw2=0.174, G.S Pn21a). The relatively long size of its c parameter is due to the arrangement along this direction of two kinds of ribbon-like polycations formed by edge sharing O(Bi, Cu)4 tetrahedra. The existence of such cations is characterized by the b∼5.2 Å value intrinsic to the ribbons structure and commonly found in bismuth oxyphosphate materials. In the title compound, 2-tetrahedra wide [Bi∼2.4Cu∼3.6O4]6.4+ and 3-tetrahedra wide [Bi∼5Cu∼3O6]9+ ribbons are isolated by phosphate groups and alternate along c. The interstitial site created between two different sizes ribbons is occupied by Cu2+ cations disordered over several close crystallographic sites. The mixed Bi3+/Cu2+ nature of certain edge-of-ribbons positions induces a disorder over several configurations of the phosphate groups. The concerned oxygen atoms form the environment of the disordered interstitial Cu2+ cations which occupy tunnels formed by the phosphate anions. The high-resolution electron microscope study enables a precise correlation between the observed images and the refined crystal structure, evidencing the polycations visualization. Furthermore, this material being the second example of partially disordered compound similar chemical system, some topological rules can be deduced. The b-axis doubling was observed by ED and HREM and is assigned to the ordering of interstitial Cu2+ within tunnels cations. A partial intra-tunnel ordering was also observed. 相似文献
34.
[reaction: see text] As a hybrid of the N,N-dibenzylammonium and 1,2-bis(pyridinium)ethane axles, various N-benzylanilinium cations were investigated as suitable axles for the formation of [2]pseudorotaxanes with the 24-membered crown ethers 24C8 and DB24C8. The effect of electron-donating OCH(3) and electron-withdrawing CF(3) groups on both the anilinium and benzyl aromatic rings was studied. Formation constants and structural details were compared to the [2]pseudorotaxanes formed by the two aforementioned dibenzylammonium and 1,2-bis(pyridinium)ethane axles. 相似文献
35.
1H NMR chemical shifts of solutions of the following cationic surfactants in D2O were determined as a function of their concentrations: cetyltrimethylammonium chloride, CTACl, a 1 : 1 molar mixture of
CTACl and toluene, cetylpyridinium chloride, CPyCl, cetyldimethylphenylam-monium chloride, CDPhACl, cetyldimethylbenzylammonium
chloride, CDBzACl, cetyldimethyl-2-phenylethylammonium chloride, CDPhEtACl, and cetyldimethyl-3-phenylpropylammonium chloride,
CDPhPrACl. Plots of observed chemical shifts versus [surfactant] are sigmoidal, and were fitted to a model based on the mass-action
law. Satisfactory fitting was obtained for the discrete protons of all surfactants. From these fits, we calculated the equilibrium
constant for micelle formation, K, the critical micelle concentration, CMC and the chemical shifts of the monomer, δmon and the micelle δmic. 1H NMR-based CMC values are in excellent agreement with those which we determined by surface tension measurements of surfactant
solutions in H2O, allowing for the difference in structure between D2O and H2O. Values of K increase as a function of increasing the size of the hydrophilic group, but the free energy of transfer per CH2 group of the phenylalkyl moiety from bulk water to the micellar interface is approximately constant, 1.9±0.1 kJ mol-1. Values of (δmic–δmon) for the surfactant groups at the interface, e.g., CH3–(CH2)15–N+(CH3)2 and within the micellar core, e.g., CH3–(CH2)15–N+ were used to probe the (average) conformation of the phenyl group in the interfacial region. The picture that emerges is
that the aromatic ring is perpendicular to the interface in CDPhACl and is more or less parallel to it in CDBzACl, CDPhEtACl,
and CDPhPrACl.
Received: 23 February 1996 Accepted: 29 August 1996 相似文献
36.
S. Allaoud H. Bitar M. El Mouhtadi B. Frange 《Journal of organometallic chemistry》1983,248(2):123-130
13C NMR spectra and complete assignment by means of coupled spectra and off resonance experiments, are reported for a new kind of organoboron heterocycle and the related borazine (o-CH3C6H4NBCH3)3; π-charge densities, obtained from LCAO-MO Hückel calculations, are in reasonable agreement with experimental chemical shifts for the former compound. 相似文献
37.
A fundamental study was made on the reduction of calcium phosphate by carbon. The mechanism of reduction was presented on applying different additions. Both silica and alumina increased the extent of reduction but with variable rates. The activation energies were calculated on the basis of first-order reactions. The phases formed during reduction were investigated by X-ray analysis. 相似文献
38.
Knaggs S Malkin H Osborn HM Williams NA Yaqoob P 《Organic & biomolecular chemistry》2005,3(21):4002-4010
Two novel tyrosinase mediated drug delivery pathways have been investigated for the selective delivery of cytotoxic units to melanocytes from urea and thiourea prodrugs. The synthesis of these prodrugs is reported, as well as oximetry data that illustrate that the targets are substrates for tyrosinase. The stability of each of the prodrugs in (i) phosphate buffer and (ii) bovine serum is discussed, and the urea prodrugs are identified as lead candidates for further studies. Finally, HPLC studies and preliminary cytotoxicity studies in a melanotic and an amelanotic cell line, that illustrate the feasibility of the approach, are presented. 相似文献
39.
Cowley AR Downs AJ Himmel HJ Marchant S Parsons S Yeoman JA 《Dalton transactions (Cambridge, England : 2003)》2005,(9):1591-1597
The novel adduct 1,1,3,3-tetramethylguanidine-gallane, (Me2N)2CN(H).GaH3, has been prepared by the reaction of [(Me2N)2CNH2]+Cl- with LiGaH4 in Et2O solution. Its spectroscopic properties indicate a monomeric species with an unusually strong coordinate link between the imido function and GaH3, an inference confirmed by the crystal structure at 150 K which also reveals significant secondary interactions through non-classical N-H...H-Ga bridges. Despite the intrinsic strength of the Ga-N bond, however, vaporisation at ca. 310 K occurs with partial dissociation, and decomposition via more than one pathway proceeds at temperatures >330-350 K to give a variety of products, including the free base, Me2NH, H2, and a novel gallium-nitrogen compound composed of a Ga4N4 cubane-like core bridged on three edges by -N{C(NMe2)2}GaH2- units. 相似文献
40.
Emulsion liquid membranes (ELM) with di-2-ethylhexylphosphoric acid in n-alkane, and dipicrylamine and cobalt(III) dicarbollide in nitrobenzene stabilized in double emulsions by SPAN 80/85 surfactant were used for preconcentration of radioactive fission products (137Cs,90Sr,139Ce, and152Eu) from slightly acidic nitrate solutions. The efficiency of sulfuric, phosphotungstic and silicotungstic acids as stripping agents, and picric acid as the bulky anion additive was investigated. A group separation of the fission products is possible by the ELM technique and can be considered for their removal from waste water solutions. 相似文献