全文获取类型
收费全文 | 2071篇 |
免费 | 76篇 |
国内免费 | 16篇 |
专业分类
化学 | 1318篇 |
晶体学 | 43篇 |
力学 | 83篇 |
数学 | 284篇 |
物理学 | 435篇 |
出版年
2023年 | 11篇 |
2022年 | 55篇 |
2021年 | 49篇 |
2020年 | 57篇 |
2019年 | 60篇 |
2018年 | 71篇 |
2017年 | 69篇 |
2016年 | 88篇 |
2015年 | 69篇 |
2014年 | 86篇 |
2013年 | 200篇 |
2012年 | 126篇 |
2011年 | 185篇 |
2010年 | 108篇 |
2009年 | 110篇 |
2008年 | 132篇 |
2007年 | 130篇 |
2006年 | 97篇 |
2005年 | 76篇 |
2004年 | 60篇 |
2003年 | 56篇 |
2002年 | 58篇 |
2001年 | 25篇 |
2000年 | 19篇 |
1999年 | 6篇 |
1998年 | 16篇 |
1997年 | 12篇 |
1996年 | 16篇 |
1995年 | 5篇 |
1994年 | 5篇 |
1993年 | 11篇 |
1992年 | 13篇 |
1990年 | 4篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1987年 | 6篇 |
1986年 | 4篇 |
1985年 | 7篇 |
1984年 | 12篇 |
1983年 | 3篇 |
1982年 | 5篇 |
1981年 | 4篇 |
1980年 | 5篇 |
1979年 | 4篇 |
1977年 | 4篇 |
1975年 | 6篇 |
1974年 | 3篇 |
1973年 | 2篇 |
1967年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有2163条查询结果,搜索用时 169 毫秒
41.
The Claisen rearrangement of the N‐protected, silylated allyl glycinates 11 and 12 led to the formation of allyl/silyl‐functionalized amino acids 13 and 14 in yields up to 80%. The diastereoisomer ratio varied from 2 : 1 to 29 : 1 for 11mb , and from 2 : 1 to 46 : 1 (syn/anti) for 12mb , depending on reaction conditions, as shown by X‐ray crystallographic analysis of 14mb . The relationship between the size of the alkyl groups on the chlorosilane reagent (Me2R″SiCl, R″=Cl, Me, t‐Bu, Ph) used as an enolate trap and the observed stereoselectivity was investigated in the case of the Ireland–Claisen variant. Me3SiCl gave the best results. However, the size of the alkyl groups on the silylated ester (Me2R″Si, R=Me, t‐Bu, Ph, i‐Pr) did not exert a significant effect on the diastereoselectivity or yield of the rearrangement. 相似文献
42.
The adsorption of two different molecular weights of polyvinylpyrrolidone (PVP) (M(w)=44,000 and M(w)=360,000 g mol(-1)) from water on kaolinite saturated with sodium chloride has been studied. The adsorption of PVP increases slowly as temperature increases. The adsorption of PVP on the kaolinite was studied by considering Fourier transform infrared (FTIR) spectra, X-ray diffraction patterns, and dielectric constants. During the adsorption process, PVP interacts with saturating sodium cations and possibly forces some of them onto the edges of the kaolinite; thus, the dielectric constant of saturated kaolinite is reduced after PVP adsorption. Copyright 2001 Academic Press. 相似文献
43.
A total of seven pesticides and eight alkylphenols were monitored using this method for the determination of their trace levels in human cord blood. The pesticides are lindane, diazinon, α-endosulfan, β-endosulfan, endosulfan sulfate, chlorpyrifos and endrin; while the alkylphenols are 4-n-butylphenol, 4-n-pentylphenol, 4-n-hexylphenol, 4-t-octylphenol, 4-n-heptylphenol, nonylphenol, 4-n-octylphenol and bisphenol A. The pesticides and alkylphenols in the cord blood samples were extracted with solid phase extraction IST C18 cartridges and analyzed by selected ion monitoring mode using quadrapole detector in Shimadzu QP-5000 gas chromatograph-mass spectrometer. Trace levels of pesticide and alkylphenols in the range of non-detectable to 15.17 ng ml−1, were detected in the human cord blood samples. This technique of monitoring the levels of endocrine-disruptors in blood samples is consistent, reliable and cost effective while reducing wastage of time and solvents. 相似文献
44.
Yildiray Topcu Omer Andac Veysel T. Yilmaz William T. A. Harrison 《Journal of Molecular Structure》2002,610(1-3):99-103
The synthesis, molecular and crystal structure of bis(triethanolamine)Mn(II) saccharinate, [Mn(tea)2](sac)2 are reported. The configuration of the tea ligands results in an unusual example of coordination number seven for the Mn(II) ion. The two triethanolamine (tea) ligands coordinate to the Mn(II) ion forming a monocapped trigonal prism geometry, in which one of the tea ligands behaves as a tridentate ligand, while the other one acts as a tetradentate donor. The free and coordinated hydroxyl hydrogens of the tea ligands are involved in hydrogen bonding with the amine nitrogen, carbonyl and sulfonyl oxygens of the neighbouring sac ions to form a three-dimensional infinite network. A weak π–π interaction between the phenyl rings of the sac ions also occurs. 相似文献
45.
Two novel bidentate Schiff base ligands, 2-(2-hydroxy-3,5-dichloro/diboromo) benzaldehyde-[4-(3-methyl-3-mesitylcyclobutyl)-1,3-thiazol-2-yl]hydrazone,
L1H, L2H and their transition metal complexes are reported. The new ligands and their complexes have been characterized by elemental
analyses, ΛM, infrared, u.v.–vis, 1H- and 13C-n.m.r. spectroscopy, and magnetic susceptibility measurements. The thermal properties of all complexes have been investigated
by TG technique. The complexes contain two monoanionic, bidentate NO ligands. It was found that all the complexes are mononuclear.
Antimicrobial activities of the ligands and their complexes have been tested against five different microorganisms, and some
of the complexes were found to be active against some of the microorganisms studied. 相似文献
46.
3-Alkyl(Aryl)-4-amino-4,5-dihydro-1H-1,2,4-triazol-5-ones (2) reacted with 2-furoyl chloride and thiophene-2-carbonyl chloride to afford the corresponding 3- alkyl(aryl)-4-(2-furoylamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones (3) and 3-alkyl(aryl)- 4-(2-thienylcarbonylamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones (4), respectively. The new compounds synthesized were characterized by using IR, 1H-NMR, 13C-NMR and UV spectral data together with elemental analysis. In addition, to investigate the effects of solvents and molecular structure upon acidity, compounds 3 and 4 were titrated potentiometrically with tetrabutylammonium hydroxide in four non-aqueous solvents (isopropyl alcohol, tert-butyl alcohol, N,N-dimethylformamide and acetonitrile). The half-neutralization potential values and the corresponding pKa values were determined for all cases. 相似文献
47.
A simple and effective method is presented for the separation and preconcentration of thorium(IV) and uranium(VI) by solid phase extraction on Duolite XAD761 adsorption resin. Thorium(IV) and uranium(VI) 9-phenyl-3-fluorone chelates are formed and adsorbed onto the Duolite XAD761. Thorium(IV) and uranium(VI) are quantitatively eluted with 2 mol L−1 HCl and determined by inductively coupled plasma-mass spectrometry (ICP-MS). The influences of analytical parameters including pH, amount of reagents, amount of Duolite XAD761 and sample volume, etc. were investigated on the recovery of analyte ions. The interference of a large number of anions and cations has been studied and the optimized conditions developed have been utilized for the trace determination of uranium and thorium. A preconcentration factor of 30 for uranium and thorium was achieved. The relative standard deviation (N = 10) was 2.3% for uranium and 4.5% for thorium ions for 10 replicate determinations in the solution containing 0.5 μg of uranium and thorium. The three sigma detection limits (N = 15) for thorium(IV) and uranium(VI) ions were found to be 4.5 and 6.3 ng L−1, respectively. The developed solid phase extraction method was successively utilized for the determination of traces thorium(IV) and uranium(VI) in environmental samples by ICP-MS. 相似文献
48.
1-(2-pyridylazo) 2-naphtol (PAN) impregnated Ambersorb 563 resin was used as solid phase extractor of copper, nickel, cadmium, lead, chromium and cobalt ions in aqueous solutions prior to their atomic absorption spectrometric determinations. The parameters including pH, sample volume, matrix effects were also investigated. The relative standard deviation (R.S.D.) of the combined method of sample treatment, preconcentration and determination with atomic absorption spectrometry is generally lower than 10%. The limit of detection was between 0.21 and 1.4 μg l−1. The results were used for preconcentration of analyte ions from natural water samples. The method was also applied to a stream sediment standard reference material (GBW7309) for the determination of Cu, Ni, Cd, Pb, Cr and Co. 相似文献
49.
A CZE method was developed and validated for the analysis of Olmesartan medoxomil (OLMD) in tablets. The influences of pH, buffer concentration, applied voltage and capillary temperature on the migration time of OLMD were investigated. About 50 mM pH 6.5 phosphate buffer were used as background electrolyte. The optimum instrument parameters were found to be 30 °C temperature with 30 kV applied voltage and diode array detection was carried out at 210 nm. OLMD was hydrodynamically injected (P inj = 50 mbar, t inj = 3 s) and an internal standard, diflunisal (IS), was used to improve the precision and repeatability. Under these conditions, the migration time of OLMD was 2.32 min and the total analysis time was shorter than 5 min. Linearity range for the developed method was found to be 2.0–50.0 μg mL?1 and the limit of detection was 0.5 μg mL?1. The developed method was applied for the analysis of OLMD in pharmaceutical tablet formulations. 相似文献
50.
The divalent metal ion sorption (Cu(2+), Cd(2+), Ni(2+), and Pb(2+)) on chromium phosphate (CrPO(4)) was studied as a function of pH, temperature, and concentration of metal ions. The sorption of metal ions is observed to increase with the increase in pH, temperature, and concentration of metal ions in solution. The mechanism of sorption is found to be the exchange of the hydrolyzed metal cations with the protons from solid at high temperature. The sorption at low temperature is found to be accompanied by the precipitation of the corresponding metal phosphates such as Pb(3)(PO(4))(2). 相似文献