全文获取类型
收费全文 | 93072篇 |
免费 | 942篇 |
国内免费 | 514篇 |
专业分类
化学 | 34549篇 |
晶体学 | 883篇 |
力学 | 7115篇 |
数学 | 34466篇 |
物理学 | 17515篇 |
出版年
2023年 | 140篇 |
2022年 | 255篇 |
2021年 | 330篇 |
2020年 | 402篇 |
2019年 | 387篇 |
2018年 | 10600篇 |
2017年 | 10403篇 |
2016年 | 6611篇 |
2015年 | 1304篇 |
2014年 | 841篇 |
2013年 | 1162篇 |
2012年 | 4841篇 |
2011年 | 11688篇 |
2010年 | 6249篇 |
2009年 | 6571篇 |
2008年 | 7490篇 |
2007年 | 9608篇 |
2006年 | 1130篇 |
2005年 | 2113篇 |
2004年 | 2227篇 |
2003年 | 2446篇 |
2002年 | 1512篇 |
2001年 | 416篇 |
2000年 | 427篇 |
1999年 | 299篇 |
1998年 | 306篇 |
1997年 | 271篇 |
1996年 | 361篇 |
1995年 | 220篇 |
1994年 | 186篇 |
1993年 | 212篇 |
1992年 | 137篇 |
1991年 | 155篇 |
1990年 | 120篇 |
1989年 | 130篇 |
1988年 | 142篇 |
1987年 | 129篇 |
1986年 | 124篇 |
1985年 | 145篇 |
1984年 | 146篇 |
1983年 | 97篇 |
1982年 | 156篇 |
1981年 | 160篇 |
1980年 | 143篇 |
1979年 | 127篇 |
1978年 | 147篇 |
1977年 | 110篇 |
1976年 | 89篇 |
1975年 | 87篇 |
1973年 | 93篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
111.
Daniel G. Shimshak Georghios P. Sphicas 《The Journal of the Operational Research Society》1982,33(8):745-750
An analysis taking into account the dependencies in the departure process from the first station of the M/E k /1→./M/1 system is conducted. Arrivals to the second station are approximated as a general independent distribution, and the waiting times in this station are compared to those found through computer simulation. 相似文献
112.
Lewis K. Panell Henry M. Fales John P. Scovill Daniel L. Klayman Douglas X. West Ramon L. Tate 《Transition Metal Chemistry》1985,10(4):141-147
Summary Californium-252 plasma desorption mass spectra were recorded for complexes of the anions of various thio-and seleno-semicarbazones of 3-acetylpyridines(1–4) with the transition metal ions iron(III) and cobalt(II). Positive ion spectra gave clear evidence of the cation present and fragmentation with loss of ligands or parts of ligands was straightforward. Negative ion spectra likewise provided evidence of the intact anion except with tetracoordinate metal halide systems [MX4]– which lost one or more halide atoms. Evidence of fragmentation of the ligand and recombination of the fragments with the metal ion was also observed in the negative ion mode. Spectra were used to revise the structure of a complex previously reported as [FeLCl2](1) to [FeL2]+[FeCl4]–. 相似文献
113.
Jorge Pavez Maritza Páez Armelle Ringuedé Fethi Bedioui José H. Zagal 《Journal of Solid State Electrochemistry》2005,9(1):21-29
We studied the electrocatalytic activity of cobalt tetra-aminophthalocyanine (CoTAPc) for the reduction of molecular oxygen (O2) on adsorbed monomeric and on electropolymerized films of different thicknesses on glassy carbon (GC) electrode. The polymeric films, denoted poly-CoTAPc, were first characterized by electrochemical impedance spectroscopy and it appears that the types of phenomena revealed to be occurring depend less on the film thickness in basic than in acid media. For O2 reduction, the results showed that poly-CoTAPc is more active than the monomeric CoTAPc adsorbed on GC. Indeed, rotating ring-disk electrode data showed that polymeric CoTAPc promotes the four-electron reduction of O2 to water in parallel to a two-electron reduction to give peroxide. On monomeric and thin films of poly-CoTAPc, a two-electron reduction mechanism predominates. In basic media the activity increases very slightly with thickness, whereas in acid media this increase is more pronounced. This parallels the observed behavior revealed by electrochemical impedance spectroscopy. 相似文献
114.
Sorption of uranium by non-living water hyacinth roots 总被引:1,自引:0,他引:1
S. Shawky M. Abdel Geleel Ashraf Aly 《Journal of Radioanalytical and Nuclear Chemistry》2005,265(1):81-84
Summary Many studies have shown that water hyacinth (Eichhornia crassipes) roots can be used to accumulate high concentrations of organic as well as inorganic pollutants. They are currently used to remediate aquatic environments and aqueous solutions. In the present study, sorption of uranium from aqueous solutions by using dried roots of water hyacinth has been investigated. The sorption of uranium was examined as a function of initial concentration, pH, weight of roots and contact time. Five different concentrations 20, 40, 60, 80, and 100 μg . ml-1 were used. Sorption proves to be very rapid and depend on pH, weight of roots and concentration of uranium. Maximum sorption capacity of water hyacinth roots was 64,000 U6+ μg/g. The sorption of uranium by water hyacinth roots follows a Langmuir isotherm. 相似文献
115.
L. F. Brum Malta Marta Eloisa Medeiros 《Journal of Thermal Analysis and Calorimetry》2005,81(1):149-152
Summary This work reports the room-temperature stabilization of the Bi4V2-xFexIIO11-1.5x γ ‘ phase, a promising ionic conductive material that finds application in solid oxide fuel cell and oxygen sensor devices. The Fe(II) cation proved to be a better stabilizer than Fe(III), which was previously used, since a lower substitution degree of V5+ is needed for the former. Powder X-ray diffraction, Fourier-transform infrared spectroscopy and differential scanning calorimetry were used in these experiments. 相似文献
116.
Obrecht D Altorfer M Lehmann C Schönholzer P Müller K 《The Journal of organic chemistry》1996,61(12):4080-4086
A novel strategy for the synthesis of (R)- and (S)-alpha-methyl(alkyl)serine-containing peptides is presented. Using (S)-phenylalanine cyclohexylamide 6 as chiral auxiliary, the optically pure azlactones (R)- and (S)-2 were synthesized via a novel azlactone/oxazoline interconversion reaction (Figures 3 and 6). These azlactones constitute fully protected and activated synthetic equivalents of (R)- and (S)-alpha-methylserine and can be directly incorporated into peptides without further protective group manipulations. Like other alpha,alpha-dialkylated glycines, optically pure alpha-alkylserines can be used to stabilize beta-turn and alpha-helical conformations in short peptides. 相似文献
117.
The K-Selectride reduction at low temperature (-45°C) of 7-oxo-5α-holestan-3β-yl acetate and methyl 7-oxo-3α-hydroxy-5(β-cholanoate resulted in almost quantitative yield of the 7α-alcohol in the 5α-compound but only moderate yield of the 5β-analog. The simultaneous reduction of two carbonyl groups in the 3 and 7 positions afforded good to excellent yields of the diaxial diol in planar steroids (methyl 3,7-dioxo-5α-cholanoate, 3,7-dioxo-5α-cholestane and methyl 3,7-dioxo-5α-cholestan-27-oate) and only 14% of 3α,7α-(OH)2 from methyl 3,7-dioxo-5β-cholanoate. 相似文献
118.
Hans König 《Analytical and bioanalytical chemistry》1973,266(2):119-124
The separation of a mixture of 22 bactericides has been achieved by gas chromatography on columns with silicone rubber W-982 as stationary phase with temperatures between 100° and 300°C. The unchanged compounds as well as their silylation products have been used. The latter are more conveniently used especially for the quantitative determination. To be able to calculate the retention indices after Kovats gas chromatography has been performed isothermally at 180°C for the more volatile compounds and at 250°C for all other bactericides.The retention indices obtained under these conditions are tabulated together with the limits of detection. 相似文献
119.
Paloma Sevillano Sven Koenig Daniel Himmel Olaf Fuhr Dieter Fenske 《无机化学与普通化学杂志》2005,631(11):2236-2240
The reactions of [Co2(CO)8] with E(SiMe3)2 (E = Se, Te) in CH2Cl2 result in the formation of the compounds [Co4Se2(CO)10]> ( 1 ) and [Co4Te2(CO)11] ( 2 ), respectively. Both cluster complexes have similar molecular structures in which the cobalt atoms form four‐membered rings with μ4‐bridging chalcogen atoms (Se and Te) above and below the plane of the metal atoms and the carbonyl ligands as either terminal or μ2‐bridging ligands. DFT‐calculations for both compounds have been carried out in order to obtain some more information about their electronic distribution. In the presence of the phosphine Ph2PC≡CPPh2 (dppa), the reaction of [Co2(CO)8] with Se(SiMe3)2 leads to the formation of [Co8Se4(CO)16(μ‐dppa)2] ( 3 ). During the reaction two molecules of [Co2(CO)8] have been added to the acetylene groups of the dppa ligands, whilst the remaining cobalt atoms coordinate to the phosphorus atoms of the phosphine. In this compounds the selenium atoms act as μ3‐ligands, bridging the metal atoms bonded to the phosphorus with those bonded to the acetylene groups. 相似文献
120.
Allison M. Mills Daniel Brunling Michael Ruck 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(8):i70-i72
A redetermination of the structure of `La32.66Fe11S60' in the trigonal space group Rm led to the new formula La52Fe12S90 and to a redefinition of the structure type. In the structure, the Fe2+ cations occur in Fe2S9 dimers of face‐sharing octahedra (with 3m symmetry). The dimers are linked by face‐ and vertex‐sharing bi‐ and tricapped LaS6 trigonal prisms (with m symmetry) to form a three‐dimensional network containing two types of cuboctahedral cavities. The larger cavities remain empty, while the smaller ones accommodate alternative sites for disordered La3+ cations. 相似文献