全文获取类型
收费全文 | 1514篇 |
免费 | 70篇 |
国内免费 | 4篇 |
专业分类
化学 | 1197篇 |
晶体学 | 1篇 |
力学 | 25篇 |
数学 | 168篇 |
物理学 | 197篇 |
出版年
2023年 | 10篇 |
2022年 | 11篇 |
2021年 | 17篇 |
2020年 | 35篇 |
2019年 | 30篇 |
2018年 | 14篇 |
2017年 | 9篇 |
2016年 | 68篇 |
2015年 | 54篇 |
2014年 | 64篇 |
2013年 | 75篇 |
2012年 | 128篇 |
2011年 | 115篇 |
2010年 | 73篇 |
2009年 | 54篇 |
2008年 | 106篇 |
2007年 | 84篇 |
2006年 | 95篇 |
2005年 | 72篇 |
2004年 | 95篇 |
2003年 | 70篇 |
2002年 | 53篇 |
2001年 | 35篇 |
2000年 | 21篇 |
1999年 | 16篇 |
1998年 | 13篇 |
1997年 | 13篇 |
1996年 | 22篇 |
1995年 | 17篇 |
1994年 | 21篇 |
1993年 | 4篇 |
1992年 | 8篇 |
1991年 | 4篇 |
1990年 | 5篇 |
1986年 | 3篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 8篇 |
1980年 | 6篇 |
1978年 | 6篇 |
1976年 | 3篇 |
1975年 | 3篇 |
1973年 | 4篇 |
1970年 | 3篇 |
1968年 | 3篇 |
1966年 | 3篇 |
1965年 | 3篇 |
1963年 | 4篇 |
1962年 | 3篇 |
排序方式: 共有1588条查询结果,搜索用时 15 毫秒
11.
Synthesis and Crystal Structure Determination of Lead(II) Oxide Halide Alcoholates with Different Connectivity of Pb4O4 Heterocubane‐like Subunits The reaction of red lead(II) oxide (Litharge) and lead(II) halide (Cl? and Br?) with diethylene glycole at a temperature of 180 °C leads to the isotypic compounds [Pb6(C4H8O3)O2Cl6] (1) and [Pb6(C4H8O3)O2Br6] (2) . In a similar synthesis with PbI2 as educt at temperature of 160 °C the two modifications β‐[Pb6(C4H8O3)O2I6] (3) and α‐[Pb6(C4H8O3)O2I6] (4) were found, whereas at a reaction temperature of 180 °C [Pb9(C2H4O2)(C4H8O3)O3I8] (5) was surprisingly obtained as product. The X‐ray diffraction data show that at a temperature of 180 °C a splitting of the ether took place. The cited compounds show cubane like subunits built by lead and oxygen atoms. These fragments are connected by alkoholate molecules. In 5 additionally an I6 octahedra centered by lead is observed. 相似文献
12.
A facile synthesis of 2-formyl-1,8-naphthalenediol is reported. Its potential as a general precursor for the preparation of unsymmetrical multidentate chelating ligand systems based on 1,8-naphthalenediol is demonstrated by the synthesis of the dinucleating ligand L(4-)(H(4)L=N,N'-bis(2-(1,8-naphthalenediol)methylidene)propylenediamine). Reaction of H(4) L with copper acetate results in the formation of the unsymmetrical dinuclear Cu(II) complex [LCu(2)](3), which has been structurally characterized by single-crystal X-ray diffraction. One Cu(II) ion is coordinated by a N(2)O(2) compartment of L(4-) and the other Cu(II) ion is coordinated by an O(4) compartment of L(4-) while they are bridged by two aryloxide functions of L(4-). A dimerization of two molecules of 3 to a tetranuclear entity 3(2) occurs through formation of weak apical Cu--O interactions. Analysis of the temperature dependent magnetic susceptibility measurements (2--290 K) established a strong intradimer exchange coupling J(12)=-371 cm(-1). This strong superexchange interaction fits nicely in a magneto-structural correlation which has been established for dinuclear bis(phenoxide)-bridged Cu(II) complexes demonstrating the electronic equivalence of the aryloxides of a phenol and 1,8-naphthalenediol. 相似文献
13.
The aggregation behavior of a novel class of surfactants, p-n-alkylbenzamidinium chlorides, has been investigated. The thermodynamics of aggregation of p-n-decylbenzamidinium chloride mixed with cationic and anionic cosurfactants has been studied using isothermal titration calorimetry. For mixtures of p-n-decylbenzamidinium chloride with n-alkyltrimethylammonium chlorides, the aggregation process is enthalpically more favorable than for the pure n-alkyltrimethylammonium chlorides, probably caused by diminished headgroup repulsion due to charge delocalization in the amidinium headgroup. A critical aggregation concentration between 3 and 4 mM has been extrapolated for p-n-decylbenzamidinium chloride at 40 degrees C, around two times lower than that of similar surfactants without charge delocalization in the headgroup and well comparable to that of similar surfactants with charge delocalization in the headgroup. In mixtures of p-n-decylbenzamidinium chloride with either sodium n-alkylsulfates or sodium dodecylbenzenesulfonate, evidence is found for the formation of bilayer aggregates by the pseudo-double-tailed catanionic surfactants composed of p-n-decylbenzamidinium and the anionic surfactant. These aggregates are solubilized to mixed micelles by excess free anionic surfactant at the measured critical aggregation concentration. 相似文献
14.
Chiral carbenium ions can be attacked by arene nucleophiles with high facial diastereoselectivity (dr >/= 94/6). Benzylic cations, such as 2, were generated under acidic conditions and reacted with arenes in intra- and intermolecular Friedel-Crafts alkylation reaction. The depicted reaction 1 --> 3 represents one example for the unprecedented, highly diastereoselective intermolecular Friedel-Crafts alkylation reactions which were observed in this study. 相似文献
15.
Thorsten Oldag Thomas Aussieker Hans‐Lothar Keller Christian Preitschaft Arno Pfitzner 《无机化学与普通化学杂志》2005,631(4):677-682
Solvothermal Synthesis and Crystal Structure Determination of AgBiI4 and Ag3BiI6 AgBiI4 and Ag3BiI6 were synthesized by solvothermal reaction from AgI and BiI3 in diluted HI‐solution (20 %) at a temperature of 160 °C. The greyish‐black crystals grow as octahedra (AgBiI4) or hexagonal/trigonal platelets (Ag3BiI6). AgBiI4 crystallizes in space group Fd3¯m with a = 1222.3(1) pm (300 K) and Z = 8 whereas Ag3BiI6 shows the space group R3¯m with a = 435.37(6) pm, c = 2081.0(4) pm (300 K) and Z = 1. Both crystal structures show stacking sequence abcabc… of hexagonal layers containing Iodine. Bismuth and silver are sharing octahedral sites with different mass ratio in both structures. The part of silver which could be localized varies with temperature. This behaviour indicates mobility of silver within the crystal structure. The ionic conductivity of AgBiI4 is explored. AgBiI4 and Ag3BiI6 show close structural relationship, with AgBiI4 as a variant with a higher degree of order. 相似文献
16.
A model compound containing a thymine oxetane moiety linked to a flavin chromophore was investigated regarding (6-4)-photolyase activity. The need for a charge shift reaction was demonstrated by a detailed pH-dependent kinetic analysis. 相似文献
17.
Reductive photoinduced electron transfer (PET) reactions have been performed with various bicyclic alpha-cyclopropyl-substituted ketones and tertiary amines. The reaction resulted in a regioselective cleavage of one cyclopropyl bond under formation of an exocyclic radical with an endocyclic enolate unit. In the case of bicyclic ketones with an unsaturated side chain, various bicyclic, spirocyclic, and tricyclic products are accessible via radical cyclization, depending on the position of the alkenyl substituent. In addition to triethylamine, N-silylated amines have also been used as electron donors, leading to a variety of compounds, among them are silylated fragmentation products, indicating that a proton is transferred from not only the amine radical cation but also the cationic silyl group. The intramolecular Paternó-Büchi reaction has also been studied for cyclopropane derivatives of the jasmone type leading to tetracyclic oxetanes. Finally, alpha-epoxy-substituted ketones have been investigated under PET conditions, yielding ring-opened products. 相似文献
18.
19.
Steffen Wolf Benedikt Sohmen Bjrn Hellenkamp Johann Thurn Gerhard Stock Thorsten Hugel 《Chemical science》2021,12(9):3350
We report on a study that combines advanced fluorescence methods with molecular dynamics (MD) simulations to cover timescales from nanoseconds to milliseconds for a large protein. This allows us to delineate how ATP hydrolysis in a protein causes allosteric changes at a distant protein binding site, using the chaperone Hsp90 as test system. The allosteric process occurs via hierarchical dynamics involving timescales from nano- to milliseconds and length scales from Ångstroms to several nanometers. We find that hydrolysis of one ATP is coupled to a conformational change of Arg380, which in turn passes structural information via the large M-domain α-helix to the whole protein. The resulting structural asymmetry in Hsp90 leads to the collapse of a central folding substrate binding site, causing the formation of a novel collapsed state (closed state B) that we characterise structurally. We presume that similar hierarchical mechanisms are fundamental for information transfer induced by ATP hydrolysis through many other proteins.We report on a study that combines advanced fluorescence methods with molecular dynamics simulations to cover timescales from nanoseconds to milliseconds for a large protein, the chaperone Hsp90. 相似文献
20.
A series ofc-axis oriented YBa2Cu3O
x
-films with different oxygen content were prepared by laser deposition. The oxygen contentx was determined by X-ray diffraction and by resonant Rutherford-back-scattering (RRBS) measurements. Thec-axis length in these films of YBa2Cu3O
x
is about 0.5% larger compared to bulk values. We describe transport measurements in magnetic fields up to 7 Tesla between room temperature andT
c
in samples with an oxygen content between the orthorhombic-to-tetragonal transition (x6.4) and full oxygenation (x7). The ratio /R
H
was investigated with respect to the two-dimensional Luttinger liquid theory and the model of the two-dimensional ionic metal. We report on deviations from the expected quadratic temperature behaviour of /R
H
, especially in films with high oxygen content. 相似文献