全文获取类型
收费全文 | 2094篇 |
免费 | 206篇 |
国内免费 | 4篇 |
专业分类
化学 | 1886篇 |
晶体学 | 16篇 |
力学 | 33篇 |
数学 | 124篇 |
物理学 | 245篇 |
出版年
2023年 | 16篇 |
2022年 | 26篇 |
2021年 | 39篇 |
2020年 | 45篇 |
2019年 | 57篇 |
2018年 | 34篇 |
2017年 | 28篇 |
2016年 | 89篇 |
2015年 | 99篇 |
2014年 | 107篇 |
2013年 | 173篇 |
2012年 | 140篇 |
2011年 | 174篇 |
2010年 | 137篇 |
2009年 | 103篇 |
2008年 | 128篇 |
2007年 | 116篇 |
2006年 | 100篇 |
2005年 | 83篇 |
2004年 | 71篇 |
2003年 | 81篇 |
2002年 | 71篇 |
2001年 | 47篇 |
2000年 | 40篇 |
1999年 | 11篇 |
1998年 | 11篇 |
1997年 | 7篇 |
1996年 | 17篇 |
1995年 | 13篇 |
1994年 | 11篇 |
1993年 | 9篇 |
1992年 | 8篇 |
1990年 | 7篇 |
1989年 | 6篇 |
1988年 | 6篇 |
1987年 | 7篇 |
1985年 | 7篇 |
1984年 | 10篇 |
1983年 | 7篇 |
1982年 | 12篇 |
1981年 | 11篇 |
1980年 | 8篇 |
1979年 | 5篇 |
1978年 | 13篇 |
1977年 | 9篇 |
1976年 | 11篇 |
1975年 | 10篇 |
1974年 | 7篇 |
1958年 | 7篇 |
1957年 | 6篇 |
排序方式: 共有2304条查询结果,搜索用时 15 毫秒
51.
Mihaylov M Chakarova K Hadjiivanov K Marie O Daturi M 《Langmuir : the ACS journal of surfaces and colloids》2005,21(25):11821-11828
Different carbonyls are formed after CO adsorption at ambient temperature on a Pt-Na-mordenite (Pt-Na-MOR) sample. Pt(3+)(CO)(2) dicarbonyls (nu(s) at 2205 cm(-1) and nu(as) at 2167 cm(-1)) are decomposed without formation of monocarbonyls. The respective mixed-ligand species, Pt(3+)((12)CO)((13)CO), formed after (12)CO-(13)CO coadsorption, display bands at 2192 and 2131 cm(-1), in excellent agreement with the theoretically calculated values. Pt(2+)-CO species absorb at 2145 cm(-1) and are not able to accept a second CO molecule. Pt(+)-CO carbonyls are characterized by a band at 2111 cm(-1). Under CO equilibrium pressure, these species are converted into dicarbonyls (nu(s) at 2135 cm(-1) and nu(as) at 2101 cm(-1)). The respective mixed-ligand species, Pt(+)((12)CO)((13)CO), manifest bands at 2123 and 2069 cm(-1), in good agreement again with the theory. Different carbonyls of metallic platinum are observed below 2100 cm(-)(1). In addition, weakly adsorbed CO was registered as Na(+)-CO complexes (2177 and 2165 cm(-1)) and Na(+)-OC-Na(+) species (2138 cm(-1)). It was found that during desorption of CO platinum was reduced, ultimately to metal. However, heating in a NO + O(2) mixture leads to reoxidation of the metal particles and restoration of the initial state of the sample. 相似文献
52.
Spyridon Divanis Tugce Kutlusoy Ida Marie Ingmer Boye Isabela Costinela Man Jan Rossmeisl 《Chemical science》2020,11(11):2943
Multiple strategies to overcome the intrinsic limitations of the oxygen evolution reaction (OER) have been proposed by numerous research groups. Despite the substantial efforts, the driving force required for water oxidation is largely making the reaction inefficient. In the present work, we collected published studies involving DFT calculations for the OER, with the purpose to understand why the progress made so far, for lowering the overpotential of the reaction, is relatively small. The data revealed that the universal scaling relationship between HO* and HOO* intermediates is still present and robust, despite the variety in methods and structures used for calculating the binding energies of the intermediates. On the other hand, the data did not show a clear trend line regarding the O* binding. Our analysis suggested that trends in doped semiconducting oxides behave very differently from those in other oxides. This points towards a computational challenge in describing doped oxides in a realistic manner. We propose a way to overcome these computational challenges, which can be applied to simulations corresponding to doped semiconductors in general.Multiple strategies to overcome the intrinsic limitations of the oxygen evolution reaction (OER) have been proposed by numerous research groups. 相似文献
53.
54.
Laurent Griffe Dr. Mary Poupot Dr. Patrice Marchand Dr. Alexandrine Maraval Dr. Cédric‐Olivier Turrin Dr. Olivier Rolland Pascal Métivier Dr. Gérard Bacquet Dr. Jean‐Jacques Fournié Dr. Anne‐Marie Caminade Dr. Rémy Poupot Dr. Jean‐Pierre Majoral Dr. 《Angewandte Chemie (International ed. in English)》2007,46(14):2334-2334
55.
Chiral separation method development is usually very time-consuming due to the diversity in chemical structures of pharmaceutical drug substances as well as the suitable separation conditions and the problem to choose the appropriate chiral selector. This paper shows capillary zone electrophoresis (CZE) which was developed for chiral separation of a basic compound - rivastigmine (RIV) using 30 cm × 50 μm i.d. polyacrylamide (PAA)-coated fused-silica capillary (effective length 20 cm), amine-modified phosphate buffer of pH 2.5 and sulfated-β-CD (S-β-CD) as chiral selector. Other selected native or derivatized cyclodextrins (CDs) were also tested: β-CD (5, 30 mM), carboxymethyl-β-CD (5, 30 mM), dimethyl-β-CD (15 mM), hydroxypropyl-β-CD (5, 30 mM), hydroxypropyl-α-CD (5, 30 mM) and hydroxypropyl-γ-CD (5, 30 mM). Complete enantiomeric separation of RIV was achieved at 20 kV, 18 °C and detection at 200 nm within 8 min with R.S.D. for the absolute migration time reproducibility of less than 2.1%. Rectilinear calibration range was 5.0-500.0 μM of each enantiomer (r = 0.9994-0.9995). The CZE method proposed was used for the control of chiral purity of pharmaceutically active S-RIV and for the analysis of Exelon caps preparation. 相似文献
56.
Frédérique Malbec René Milcent Patrick Vicart Anne Marie Bure 《Journal of heterocyclic chemistry》1984,21(6):1769-1774
Thirty new 2-substituted-4-amino-5-alkyl or aryl-2,4-dihydro-1,2,4-triazol-3-ones and ten 2-substituted-5-alkyl or aryl-4-(5-nitro-2-furfurylidene)amino-2,4-dihydro-1,2,4-triazol-3-ones were synthesized and characterised by their sharp melting points, elemental analysis, ir and 1H nmr spectra. These new derivatives of 5-nitro-2-furaldehyde were screened for their antibacterial activities. Most of the compounds showed good activity against one test organism, Staphylococcus aureus. For a few compounds, C.M.I. ranged from 4 to 8 μg/ml (higher results than nitrofurantoin). 相似文献
57.
58.
59.
Marie E Chevalier Y Brunel S Eydoux F Germanaud L Flores P 《Journal of colloid and interface science》2004,269(1):117-125
The mechanism of action of additives that control the sedimentation of paraffin crystals after their crystallization in model diesel oil has been studied by means of a new experimental approach. The chemical analysis of the crystals and detailed measurements of the sedimentation phenomenon give new insights into this complex process. Thus, the wax antisettling additives used for preventing wax crystal sedimentation adsorb at the surfaces of wax particles and provide them with enhanced colloidal stability. The settling rate is not related to the size of the crystals or the viscosity of the liquid medium, but to the ability of the additives to prevent the aggregation of wax crystals. The reported methodology makes it possible to investigate the fundamental mechanisms, but also to evaluate structure-activity relationships of the various additives used in the petroleum industry. 相似文献
60.
Vladimír Setni
ka Marie Urbanov Statis Pataridis Vladimír Krl Karel Volka 《Tetrahedron: Asymmetry》2002,13(24):2661-2666
A novel approach to study the sol-gel phase transition of a brucine–porphyrin based gelator, which uses vibrational circular dichroism (VCD) spectroscopy, is described. The gelation process leading to highly ordered chiral supramolecular assemblies was investigated in various solvents at the different temperatures and concentrations. The VCD spectra sensitively reveal the specific parts of molecule whose configuration is influenced by a sol-gel phase transition and chiral supramolecular aggregation and therefore indicate the parts of the molecule responsible for the chiral self-assembly formation. Temperature stability of the organogel studied is discussed on the basis of the VCD and IR absorption spectra. The scanning electron microscopy was used to visualize the structure of brucine–porphyrin conjugate in the gel phase. 相似文献