全文获取类型
收费全文 | 536篇 |
免费 | 14篇 |
国内免费 | 1篇 |
专业分类
化学 | 429篇 |
晶体学 | 2篇 |
力学 | 10篇 |
数学 | 70篇 |
物理学 | 40篇 |
出版年
2023年 | 2篇 |
2022年 | 5篇 |
2021年 | 8篇 |
2020年 | 3篇 |
2019年 | 12篇 |
2018年 | 8篇 |
2017年 | 8篇 |
2016年 | 14篇 |
2015年 | 14篇 |
2014年 | 12篇 |
2013年 | 28篇 |
2012年 | 20篇 |
2011年 | 46篇 |
2010年 | 22篇 |
2009年 | 21篇 |
2008年 | 30篇 |
2007年 | 23篇 |
2006年 | 24篇 |
2005年 | 20篇 |
2004年 | 18篇 |
2003年 | 16篇 |
2002年 | 15篇 |
2001年 | 18篇 |
2000年 | 8篇 |
1999年 | 7篇 |
1998年 | 10篇 |
1997年 | 8篇 |
1996年 | 14篇 |
1995年 | 7篇 |
1994年 | 4篇 |
1993年 | 5篇 |
1992年 | 8篇 |
1991年 | 5篇 |
1990年 | 7篇 |
1989年 | 9篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1986年 | 6篇 |
1985年 | 10篇 |
1984年 | 8篇 |
1983年 | 6篇 |
1982年 | 5篇 |
1978年 | 3篇 |
1974年 | 5篇 |
1970年 | 5篇 |
1968年 | 2篇 |
1914年 | 1篇 |
1913年 | 3篇 |
1911年 | 1篇 |
1909年 | 1篇 |
排序方式: 共有551条查询结果,搜索用时 15 毫秒
21.
LiTiCl3 is obtained as one example within an ample solid solution, Li24–2nTinCl24 (?4?n?10), by synpropotionation of TiCl3 and Ti in the presence of LiCl (2:1:3 molar ratio) in sealed tantalum tubes at 750°C. It crystallizes with the inverse spinel-type structure according to (Li0.67)[4](Li0.67Ti1.33)[4]Cl4 with, at 25°C, a = 1048.62(4) pm, space group Fd3m. Thermal expansion is linear with α = 4.85 × 10?5K?1 up to about 300°C and thereafter, when the migration of Li+ from tetrahedral to octahedral interstices becomes increasingly important, it exhibits a relative decrease resulting, finally, in the phase transition to a NaCl-type structure that is observed for the first time at about 575°C. 相似文献
22.
23.
24.
Gerhard Schomburg Alfred Deege Heike Hinrichs Eduard Hübinger Heribert Husmann 《Journal of separation science》1992,15(9):579-584
Methods of alkylation of α-, β- and γ-cyclodextrins have been optimized with regard to the parameters of reaction, degree of alkylation and yields. The analysis of the reaction mixtures and of the isolated single species has been performed by high temperature GC and HPLC. The phase systems of the preferably applied HPLC have been carefully adjusted by variation of both the stationary and mobile phases to the very different hydrophobicities of the various alkylated CD species which have been synthesized. Several partially or fully alkylated CD species were isolated from preparative scale HPLC separations in high purity. 相似文献
25.
Syntheses, Structure Determination and Reactions of Phosphine Substituted Derivatives of Fe3(CO)9(μ3-CF)2 Photolysis of Fe3(CO)9(μ3-CF)2 1 in the presence of acetonitrile 2a or benzoenitrile 2b results in the substitution of a single carbonyl ligand by a nitrile ligand yielding Fe3(CO)8(CH3CN)(μ3-CF)2 3a and Fe3(CO)8(C6H5CN)(μ3-CF)2 3b, respectively. The acetonitrile ligand in 3a can be easily replaced by trimethyl-phosphine 4a or triphenylphosphine 4b . The monosubstituted compounds Fe3(CO)8(PR3)(μ3-CF)25, R = CH3 a, R = C6H5, b are obtained as major products besides a small amount of the disubsituted products Fe3(CO)7(PR3)2(μ3-CF)2 6. The structure of 5a has been elucidated by a single crystal X-ray structure determination. Thermal ligand substitution in 1, however, results in the formation of a mixture of mono-, disubstituted, and trisubstituted products, in which 6b is the major product for diphenylphosphine. 5a reacts with ethyne 7 forming a phosphine substituted diferra-allyl-cluster Fe3(CO)7(PR3)(μ3-CF)(μ3? CF? CH? CH) 8. The structure of one isomere of 8 has been determinated by X-ray crystallography. 相似文献
26.
Suwa Y Matsuura S Fujimori M Heike S Onogi T Kajiyama H Hitosugi T Kitazawa K Uda T Hashizume T 《Physical review letters》2003,90(15):156101
Novel atomic structures on a H-terminated Si(100)-(2x1)-H surface were found using scanning tunneling microscopy (STM). The structures are distinguishable only from Si dimers in empty-state STM images. They were observed on arsenic- and phosphorus-doped substrates, but not on boron-doped substrates. Surface density of these structures was found to be proportional to the dopant density in the substrate. First-principles calculations clarify that they are consisting of dopant pairs that are segregated from the bulk material. Hydrogen atoms attached to the dopant pair are found to flip between two positions on the surface due to a quantum effect. 相似文献
27.
28.
Franziska Schulte Klaus‐Werner Brzezinka Karin Lutzenberger Heike Stege Ulrich Panne 《Journal of Raman spectroscopy : JRS》2008,39(10):1455-1463
Raman microscopy allows a non‐destructive characterisation of inorganic and organic painting materials such as pigments and organic dyestuffs. The objectives of this study are the more recent organic pigments typically present in paintings and other art works from the 20th century. More than 20 organic synthetic pigments from different chemical classes could be identified by Raman spectroscopy using different excitation wavelengths (457.9, 476.5, 487.9, 514.5, 632.8, and 1064 nm). To evaluate the performance for real paint samples, varying paint mixtures of the Hansa Yellow pigment PY 3 and the binding medium Mowilith, a polyvinyl acetate (PVAC) compound, were characterised; PY 3 was determined at a 1 wt% level in the binder. In addition, commercial tube paints containing the quinacridone violet PV 19 were studied. The pigment was clearly identified in all of these more complex oil and acrylic paints. Finally, alizarin (PR 83) and a green copper phthalocyanine pigment (PG 7) could unambiguously be identified by Raman microscopy in the painting ‘Woman with mandolin in yellow and red’ of Max Beckmann dating 1950. The discovery of a red naphthol AS pigment by Raman spectroscopy in a sample from the ‘Three field workers’ by Georg Baselitz (1964/1965) demonstrated that in some cases complementary chromatographic methods are needed for a comprehensive identification of the organic pigments. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
29.
Hennig A Hoffmann A Borcherding H Thiele T Schedler U Resch-Genger U 《Chemical communications (Cambridge, England)》2011,47(27):7842-7844
We introduce a method to determine the number of accessible functional groups on a polymer microsphere surface based on the interaction between the macrocyclic host cucurbit[7]uril (CB7) and a guest reacted to the microsphere surface. After centrifugation, CB7 in the supernatant is quantified by addition of a fluorescent dye. The difference between added and detected CB7 affords the number of accessible surface functional groups. 相似文献
30.
Two decades ago, it has been observed experimentally that hydrogels immersed in a bath solution swells or shrinks under external stimulations (Ric?ka et al., Macromolecules 17:2916?C2921, 1984). Recently, this fact has received renewed interest, since understanding the precise mechanisms underlying that kind of behavior has the potential to tailor most sensitive drug delivery systems based on hydrogels (Segalman and Witkowski, Mater Sci Eng C 2:243?C249, 1995). Here we contribute to a precise understanding of the mechanisms responsible for the hydrogels?? swelling kinetics as well as dynamics by proposing for the first time a model approach that can resolve the inherent short-range correlation effects along the hydrogel?Csolution interface jointly with the long-range ionic transport fields. To that end, we investigate the swelling dynamics of hydrogels, which is a moving boundary problem, by a phase field model, which couples the Nernst?CPlanck equation for the concentration of mobile ions, Poisson equation for the electric potential, mechanical equation for the displacement, and an equation for the phase field variable. Simulation for two-dimensional case reveals that under the chemical stimulation, the hydrogel will swell or shrink if the concentration of mobile ions inside bath solution decreases or increases. This is in agreement with the experimental results qualitatively and validates our new model approach. 相似文献