全文获取类型
收费全文 | 1894篇 |
免费 | 23篇 |
国内免费 | 2篇 |
专业分类
化学 | 1244篇 |
晶体学 | 5篇 |
力学 | 17篇 |
数学 | 190篇 |
物理学 | 463篇 |
出版年
2016年 | 27篇 |
2015年 | 17篇 |
2014年 | 22篇 |
2013年 | 42篇 |
2012年 | 52篇 |
2011年 | 48篇 |
2010年 | 37篇 |
2009年 | 28篇 |
2008年 | 36篇 |
2007年 | 46篇 |
2006年 | 44篇 |
2005年 | 48篇 |
2004年 | 47篇 |
2003年 | 27篇 |
2002年 | 31篇 |
2001年 | 43篇 |
2000年 | 41篇 |
1999年 | 28篇 |
1998年 | 30篇 |
1997年 | 16篇 |
1996年 | 16篇 |
1995年 | 26篇 |
1994年 | 24篇 |
1993年 | 34篇 |
1992年 | 24篇 |
1991年 | 31篇 |
1990年 | 31篇 |
1989年 | 19篇 |
1988年 | 33篇 |
1987年 | 20篇 |
1986年 | 18篇 |
1985年 | 23篇 |
1984年 | 19篇 |
1982年 | 20篇 |
1980年 | 27篇 |
1979年 | 34篇 |
1978年 | 30篇 |
1977年 | 52篇 |
1976年 | 37篇 |
1975年 | 37篇 |
1974年 | 40篇 |
1973年 | 39篇 |
1972年 | 38篇 |
1971年 | 29篇 |
1970年 | 21篇 |
1969年 | 30篇 |
1968年 | 31篇 |
1967年 | 38篇 |
1966年 | 28篇 |
1933年 | 16篇 |
排序方式: 共有1919条查询结果,搜索用时 15 毫秒
81.
Hans‐Peter Kormann Günter Schmid Katrin Pelzer K. Philippot Bruno Chaudret 《无机化学与普通化学杂志》2004,630(12):1913-1918
Nanoporous alumina membranes, loaded with palladium and ruthenium nanoparticles of various size, were used for gas phase hydrogenation of 1, 3‐butadiene and for oxidation of carbon monoxide, respectively. Those membranes contain 109 ‐ 1011 pores per cm2, all running perpendicular to the surface. Membrane discs of 20 mm in diameter and only 60 μm thick, incorporated in a reactor in which the reactants can be pumped in a closed circuit through the pores, turned out to very actively catalyze hydrogenation of butadiene (Pd) and oxidation of CO (Ru). The activity of the Pd catalysts depends characteristically on the particles size, the gas flow, and of the educts ratio. As could be expected, larger particles are less active than smaller ones, whereas increasing gas flows in case of hydrogenation accelerates the reactions. Excessive hydrogen reduces selectivity with respect to the various butenes, but favours formation of butane. 相似文献
82.
83.
In recent years, cathinone derivatives have entered the global drug market and caused serious social problems in many European countries. Modification of the basic structure of cathinone leads to a multitude of derivatives, including the most popular representative mephedrone. All those substances contain a stereogenic center and therefore two isoforms exist. As it is the case with many chiral active pharmaceutical ingredients, even the pharmacological effect of the enantiomers of those psychoactive compounds may differ. During this research, an easy-to-prepare chiral capillary zone electrophoresis method for the enantioseparation of a set of 19 cathinone derivatives was developed. Testing different types of cyclodextrin (CD), including native-β-CD, carboxymethyl-β-CD, 2-hydroxypropyl-β-CD, sulfated-β-CD, and native γ-CD, best results were obtained with the negatively charged sulfated-β-CD. The effect of the CD concentration, the temperature, and the addition of ACN to the BGE on the enantioseparation is shown by three model compounds. Under optimal conditions, using 20 mg/mL sulfated-β-CD in 50 mM ammonium acetate buffer pH?= 4.5 containing 10% v/v ACN at a cassette temperature of 40°C and with an applied voltage of 20 kV, all derivatives except methedrone were resolved in their enantiomers within 20 min. 相似文献
84.
Dr. Debangshu Chaudhuri Dr. Eva Sigmund Annemarie Meyer Lisa Röck Philippe Klemm Sebastian Lautenschlager Agnes Schmid Shane R. Yost Prof. Dr. Troy Van Voorhis Dr. Sebastian Bange Prof. Dr. Sigurd Höger Prof. Dr. John M. Lupton 《Angewandte Chemie (International ed. in English)》2013,52(50):13449-13452
85.
Gerhard Schmid 《Journal of membrane science》1998,150(2):151-157
In capillary systems with narrow pores the Helmholtz electrochemical double layer located at the pore wall extends over the entire cross section of the pores. It loses its character as the “charge on the wall”. It will be shown that not only the electrokinetic phenomena but also the electrical conductivity and the dialysis potential of membranes with narrow pores can be understood from the same point of view, namely: the electrolyte solution in the pores of a membrane with narrow pores is considered to be an approximately homogeneous solution in contact with immobilised charges located at the pore wall. In this case the electrochemical equations contain the fixed ion concentration as a parameter instead of the ζ potential. This makes it possible to describe quantitatively to a good approximation data on the electroosmosis, the electrical conductivity, the streaming potential and the dialysis potential taken from the literature, as well as results of our own measurements, by using a single membrane constant. 相似文献
86.
Magnesium dicyanamide tetrahydrate Mg[N(CN)2]2 · 4 H2O was synthesized by aqueous ion exchange starting from Na[N(CN)2] and Mg(NO3)2 · 6 H2O. The crystal structure was solved and refined on the basis of powder X‐ray diffraction data (P21/c, Z = 2, a = 737.50(2), b = 732.17(1), c = 971.67(2) pm, β = 98.074(1)°, wRp = 0.059, Rp = 0.046, RF = 0.075). In the crystal there are neutral complexes [Mg[N(CN)2]2(H2O)4] which are only connected via hydrogen bonds. Above 40 °C the tetrahydrate decomposes into anhydrous Mg[N(CN)2]2. 相似文献
87.
Summary A new simplified version of a closed on-column injector is introduced. Because of its design isobaric injection conditions do not have to be followed and a wide range of injection temperatures above the boiling point of the sample solvent can be chosen for on-column injections in capillary gas chromatography. Also, when following certain basic injection rules, injections of large sample volumes (20 l or more) give accurate and reproducible results without further problems.Presented at the 17th International Symposium on Chromatography, September 25–30, 1988, Vienna, Austria. 相似文献
88.
Jochen Lutz The Vinh Ho Richard H. Fish Andreas Schmid 《Journal of organometallic chemistry》2004,689(25):4783-4790
The biocatalytic, regioselective hydroxylation of 2-hydroxybiphenyl to the corresponding catechol was accomplished utilizing the monooxygenase 2-hydroxybiphenyl 3-monooxygenase (HbpA). The necessary natural 1,4-dihydronicotinamde adenine dinucleotide (NADH) co-factor for this biocatalytic process was replaced by a biomimetic co-factor, N-benzyl-1,4-dihydronicotinamide, 1b. The interaction between the flavin (FAD) containing HbpA enzyme and the corresponding biomimetic NADH compound, N-benzyl-1,4-dihdronicotinamide, 1b, for hydride transfer, was shown to readily occur. The in situ recycling of the reduced NADH biomimic 1b from 1a was accomplished with [Cp*Rh(bpy)H](Cl); however, productive coupling of this regeneration reaction to the enzymatic hydroxylation reaction was not totally successful, due to a deactivation process concerning the HbpA enzyme peripheral groups; i.e., -SH or -NH2 possibly reacting with the precatalyst, [Cp*Rh(bpy)(H2O)](Cl)2, and thus inhibiting the co-factor regeneration process. The deactivation mechanism was studied, and a promising strategy of derivatizing these peripheral -SH or -NH2 groups with a polymer containing epoxide was successful in circumventing the undesired interaction between HbpA and the precatalyst. This latter strategy allowed tandem co-factor regeneration using 1a or 2a, [Cp*Rh(bpy)(H2O)](Cl)2, and formate ion, in conjunction with the polymer bound, FAD containing HbpA enzyme to provide the catechol product. 相似文献
89.
Recent advances in chiral separation principles in capillary electrophoresis and capillary electrochromatography 总被引:3,自引:0,他引:3
This review summarizes recent developments in chiral separation in capillary zone electrophoresis (CZE), electrokinetic chromatography (EKC), and capillary electrochromatography (CEC) covering literature published since the year 2000. New chiral selectors and innovative approaches for CE and CEC are introduced. Recent progress in column technology for CEC is highlighted and the development of new chiral stationary phases is discussed. This review is not dedicated to list applications but will focus on new developments. 相似文献
90.