全文获取类型
收费全文 | 4763篇 |
免费 | 243篇 |
国内免费 | 33篇 |
专业分类
化学 | 3378篇 |
晶体学 | 17篇 |
力学 | 121篇 |
数学 | 860篇 |
物理学 | 663篇 |
出版年
2023年 | 41篇 |
2022年 | 27篇 |
2021年 | 74篇 |
2020年 | 116篇 |
2019年 | 110篇 |
2018年 | 68篇 |
2017年 | 55篇 |
2016年 | 154篇 |
2015年 | 139篇 |
2014年 | 177篇 |
2013年 | 277篇 |
2012年 | 312篇 |
2011年 | 358篇 |
2010年 | 252篇 |
2009年 | 199篇 |
2008年 | 313篇 |
2007年 | 314篇 |
2006年 | 301篇 |
2005年 | 300篇 |
2004年 | 231篇 |
2003年 | 198篇 |
2002年 | 173篇 |
2001年 | 53篇 |
2000年 | 46篇 |
1999年 | 40篇 |
1998年 | 34篇 |
1997年 | 56篇 |
1996年 | 58篇 |
1995年 | 43篇 |
1994年 | 36篇 |
1993年 | 23篇 |
1992年 | 19篇 |
1991年 | 31篇 |
1990年 | 18篇 |
1989年 | 29篇 |
1988年 | 18篇 |
1986年 | 19篇 |
1985年 | 28篇 |
1984年 | 30篇 |
1983年 | 27篇 |
1982年 | 33篇 |
1981年 | 23篇 |
1980年 | 25篇 |
1979年 | 18篇 |
1978年 | 33篇 |
1977年 | 20篇 |
1976年 | 15篇 |
1975年 | 12篇 |
1974年 | 18篇 |
1973年 | 10篇 |
排序方式: 共有5039条查询结果,搜索用时 26 毫秒
31.
32.
Understanding the activity and selectivity of molecular catalysts for CO2 reduction to fuels is an important scientific endeavour in addressing the growing global energy demand. Cobalt–terpyridine compounds have been shown to be catalysts for CO2 reduction to CO while simultaneously producing H2 from the requisite proton source. To investigate the parameters governing the competition for H+ reduction versus CO2 reduction, the cobalt bisterpyridine class of compounds is first evaluated as H+ reduction catalysts. We report that electronic tuning of the ancillary ligand sphere can result in a wide range of second-order rate constants for H+ reduction. When this class of compounds is next submitted to CO2 reduction conditions, a trend is found in which the less active catalysts for H+ reduction are the more selective towards CO2 reduction to CO. This represents the first report of the selectivity of a molecular system for CO2 reduction being controlled through turning off one of the competing reactions. The activities of the series of catalysts are evaluated through foot-of-the-wave analysis and a catalytic Tafel plot is provided. 相似文献
33.
This paper shows that monotone self-dual Boolean functions in irredundant disjuntive normal form (IDNF) do not have more variables than disjuncts. Monotone self-dual Boolean functions in IDNF with the same number of variables and disjuncts are examined. An algorithm is proposed to test whether a monotone Boolean function in IDNF with n variables and n disjuncts is self-dual. The runtime of the algorithm is O(n3). 相似文献
34.
Reis Thaiene A. Matos Breno N. Lima Eliana M. Chaker Juliano A. Gratieri Tais Cunha-Filho Marcílio S. S. Gelfuso Guilherme M. 《Journal of Thermal Analysis and Calorimetry》2017,128(3):1671-1682
Journal of Thermal Analysis and Calorimetry - The objectives of this study were to verify the viability of the photoinitiating system using curcumin as a photoinitiator and glycerol as a... 相似文献
35.
Marc P. Renault 《Central European Journal of Operations Research》2017,25(4):953-966
This paper studies the problem of maximizing the number of items packed into n bins, known as the dual bin packing problem, in the advice per request model. In general, no online algorithm has a constant competitive ratio for this problem. An online algorithm with 1 bit of advice per request is shown to be 3/2-competitive. Next, for \(0< \varepsilon < 1{/}2\), an online algorithm with advice that is \((1/(1-\varepsilon ))\)-competitive and uses \({O}(1/\varepsilon )\) bits of advice per request is presented. 相似文献
36.
Caitlin E. Shields Dr. Xue Wang Dr. Thomas Fellowes Rob Clowes Dr. Linjiang Chen Prof. Graeme M. Day Prof. Anna G. Slater Dr. John W. Ward Dr. Marc A. Little Prof. Andrew I. Cooper 《Angewandte Chemie (International ed. in English)》2023,62(34):e202303167
Hydrogen-bonded organic frameworks (HOFs) with low densities and high porosities are rare and challenging to design because most molecules have a strong energetic preference for close packing. Crystal structure prediction (CSP) can rank the crystal packings available to an organic molecule based on their relative lattice energies. This has become a powerful tool for the a priori design of porous molecular crystals. Previously, we combined CSP with structure-property predictions to generate energy-structure-function (ESF) maps for a series of triptycene-based molecules with quinoxaline groups. From these ESF maps, triptycene trisquinoxalinedione (TH5) was predicted to form a previously unknown low-energy HOF (TH5-A) with a remarkably low density of 0.374 g cm−3 and three-dimensional (3D) pores. Here, we demonstrate the reliability of those ESF maps by discovering this TH5-A polymorph experimentally. This material has a high accessible surface area of 3,284 m2 g−1, as measured by nitrogen adsorption, making it one of the most porous HOFs reported to date. 相似文献
37.
Matthijs P. J. M. van der Ham Ellis van Keulen Prof. Dr. Marc T. M. Koper Dr. Akbar Asadi Tashvigh Prof. Dr. Johannes H. Bitter 《Angewandte Chemie (International ed. in English)》2023,62(33):e202306701
Electrocatalytic glucose oxidation can produce high value chemicals, but selectivity needs to be improved. Here we elucidate the role of the Pt oxidation state on the activity and selectivity of electrocatalytic oxidation of glucose with a new analytical approach, using high-pressure liquid chromatography and high-pressure anion exchange chromatography. It was found that the type of oxidation, i.e. dehydrogenation of primary and secondary alcohol groups or oxygen transfer to aldehyde groups, strongly depends on the Pt oxidation state. Pt0 has a 7-fold higher activity for dehydrogenation reactions than for oxidation reactions, while PtOx is equally active for both reactions. Thus, Pt0 promotes glucose dialdehyde formation, while PtOx favors gluconate formation. The successive dehydrogenation of gluconate is achieved selectively at the primary alcohol group by Pt0, while PtOx also promotes the dehydrogenation of secondary alcohol groups, resulting in more complex reaction mixtures. 相似文献
38.
Iuliana-Marilena Andrei Dmytro Strilets Dr. Shixin Fa Marc Baaden Prof. Tomoki Ogoshi Dr. Mihail Barboiu 《Angewandte Chemie (International ed. in English)》2023,62(42):e202310812
Artificial water channels (AWCs) that selectively transport water and reject ions through bilayer membranes have potential to act as synthetic Aquaporins (AQPs). AWCs can have a similar osmotic permeability, better stability, with simpler manufacture on a larger-scale and have higher functional density and surface permeability when inserted into the membrane. Here, we report the screening of combinatorial libraries of symmetrical and unsymmetrical rim-functionalized PAs A – D that are able to transport ca. 107–108 water molecules/s/channel, which is within 1 order of magnitude of AQPs’ and show total ion and proton rejection. Among the four channels, C and D are 3–4 times more water permeable than A and B when inserted in bilayer membranes. The binary combinations of A – D with different molar ratios could be expressed as an independent (linear ABA ), a recessive (inhibition AB , AC , DB , ACA ), or a dominant (amplification, DBD ) behavior of the water net permeation events. 相似文献
39.
Enno Aeissen Aaron R. von Seggern Dr. Marc Schmidtmann Prof. Dr. Jens Christoffers 《European journal of organic chemistry》2023,26(14):e202300180
Cyclopenta-, benzo-, and cyclohepta[b]-annulated azepane scaffolds were prepared in two steps from optically active cyclic α-allyl-β-oxoesters. The first step was ruthenium-catalyzed olefin cross metathesis with acrylonitrile. The second step was palladium-catalyzed dihydrogenation which consists of three consecutive processes: The hydrogenation of the C−C double and C−N triple bonds was followed by the reductive amination via the iminium ion formed in situ from the primary amino function and the endocyclic carbonyl group. This last step gave, stereoselectively, the annulated azepanes with relative trans-configuration. The amino function and the ester group define two points for further diversification of the scaffolds. The trifluoroacetyl derivatives allowed to establish the enantiopurity of the products to be 97–98 % ee by GLC on a chiral phase. The relative trans-configurations and in one case also the absolute (R,R)-configuration was established by X-ray crystallography. 相似文献
40.
Marine Pinaud Leïla Vaïtilingom Gayathiri Gnanalingam Dr. Tania Xavier Prof. Erwan Le Gall Dr. Marc Presset 《European journal of organic chemistry》2023,26(18):e202300198
The use of N-alkyl imines in decarboxylative Mannich reaction with substituted malonic acids half oxyesters (SMAHOs) has been developed to afford a direct access to secondary β2,3-aminoesters. The transformation occurs under very practical conditions (DABCO as a catalyst in bulk toluene and open to air) and can be performed with a broad range of each substrate in yields of 36 to 97 %. Importantly, the reaction was found to require the use of acidic additives in combination with the organocatalyst to limit the competitive olefination reaction. 相似文献