全文获取类型
收费全文 | 937篇 |
免费 | 57篇 |
国内免费 | 7篇 |
专业分类
化学 | 709篇 |
晶体学 | 1篇 |
力学 | 10篇 |
数学 | 180篇 |
物理学 | 101篇 |
出版年
2024年 | 5篇 |
2023年 | 5篇 |
2022年 | 13篇 |
2021年 | 17篇 |
2020年 | 34篇 |
2019年 | 36篇 |
2018年 | 19篇 |
2017年 | 17篇 |
2016年 | 39篇 |
2015年 | 38篇 |
2014年 | 41篇 |
2013年 | 65篇 |
2012年 | 52篇 |
2011年 | 60篇 |
2010年 | 54篇 |
2009年 | 23篇 |
2008年 | 85篇 |
2007年 | 48篇 |
2006年 | 53篇 |
2005年 | 42篇 |
2004年 | 26篇 |
2003年 | 24篇 |
2002年 | 24篇 |
2001年 | 12篇 |
2000年 | 15篇 |
1999年 | 16篇 |
1998年 | 6篇 |
1997年 | 12篇 |
1996年 | 7篇 |
1995年 | 6篇 |
1994年 | 13篇 |
1993年 | 3篇 |
1992年 | 3篇 |
1989年 | 4篇 |
1988年 | 7篇 |
1987年 | 4篇 |
1984年 | 3篇 |
1983年 | 4篇 |
1981年 | 6篇 |
1980年 | 5篇 |
1979年 | 5篇 |
1978年 | 4篇 |
1977年 | 5篇 |
1976年 | 3篇 |
1975年 | 6篇 |
1974年 | 8篇 |
1973年 | 3篇 |
1972年 | 4篇 |
1965年 | 2篇 |
1964年 | 2篇 |
排序方式: 共有1001条查询结果,搜索用时 15 毫秒
71.
Perovskites as Precursors for Ni/La2O3 Catalysts in the Dry Reforming of Methane: Synthesis by Constant pH Co‐Precipitation,Reduction Mechanism and Effect of Ru‐Doping
下载免费PDF全文
![点击此处可从《无机化学与普通化学杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Stefanie Kühl Hendrik Düdder Frank Girgsdies Kevin Kähler Martin Muhler Malte Behrens 《无机化学与普通化学杂志》2017,643(16):1088-1095
LaNiO3 perovskite is an interesting precursor for Ni/La2O3 catalysts for the dry reforming of methane at high temperatures. Precursors have been synthesized by co‐precipitation without, with 2.5 at %, and with 5 at % Ru doping. The presence of Ru leads to a stabilization of the perovskite structure and hinders the decomposition into NiO and Ruddlesden‐Popper mixed oxides Lan+1NinO3n+1, which was observed for the Ru‐free sample upon calcination at 1000 °C (n = 3). Upon reduction in hydrogen, a mechanism involving at least two steps was observed and the first major step was identified as the partial reduction of the precursor leading to a LaNiO2.5‐like intermediate. The second major step is the reduction to Ni metal supported on La2O3 independent of the Ru content of the catalyst. In the presence of Ru, indications for Ni‐Ru alloy formation and for a higher dispersion of the metallic phase were found. The catalytic activity in DRM of the catalyst containing 2.5 % Ru was superior to the catalysts with more or without Ru. Furthermore, the propensity of coke formation was reduced by the presence of Ru. 相似文献
72.
Meinert C de Marcellus P d'Hendecourt Lle S Nahon L Jones NC Hoffmann SV Bredehöft JH Meierhenrich UJ 《Physics of life reviews》2011,8(3):307-330
Proteins of all living organisms including plants, animals, and humans are made up of amino acid monomers that show identical stereochemical L-configuration. Hypotheses for the origin of this symmetry breaking in biomolecules include the absolute asymmetric photochemistry model by which interstellar ultraviolet (UV) circularly polarized light (CPL) induces an enantiomeric excess in chiral organic molecules in the interstellar/circumstellar media. This scenario is supported by a) the detection of amino acids in the organic residues of UV-photo-processed interstellar ice analogues, b) the occurrence of L-enantiomer-enriched amino acids in carbonaceous meteorites, and c) the observation of CPL of the same helicity over large distance scales in the massive star-forming region of Orion. These topics are of high importance in topical biophysical research and will be discussed in this review. Further evidence that amino acids and other molecules of prebiotic interest are asymmetrically formed in space comes from studies on the enantioselective photolysis of amino acids by UV-CPL. Also, experiments have been performed on the absolute asymmetric photochemical synthesis of enantiomer-enriched amino acids from mixtures of astrophysically relevant achiral precursor molecules using UV-circularly polarized photons. Both approaches are based on circular dichroic transitions of amino acids that will be highlighted here as well. These results have strong implications on our current understanding of how life's precursor molecules were possibly built and how life selected the left-handed form of proteinogenic amino acids. 相似文献
73.
Carlo Garoni Carla Manni Francesca Pelosi Stefano Serra-Capizzano Hendrik Speleers 《Numerische Mathematik》2014,127(4):751-799
We study the spectral properties of stiffness matrices that arise in the context of isogeometric analysis for the numerical solution of classical second order elliptic problems. Motivated by the applicative interest in the fast solution of the related linear systems, we are looking for a spectral characterization of the involved matrices. In particular, we investigate non-singularity, conditioning (extremal behavior), spectral distribution in the Weyl sense, as well as clustering of the eigenvalues to a certain (compact) subset of \(\mathbb C\) . All the analysis is related to the notion of symbol in the Toeplitz setting and is carried out both for the cases of 1D and 2D problems. 相似文献
74.
75.
The crystal structure of [Co(nta)(N,N-Et2en)] (nta = nitrilotriacetate and N,N-Et2en = N,N-diethylethylenediamine) was determined from three-dimensional X-ray diffraction data. The substituted nitrogen of N,N-diethylethylenediamine is bonded trans to the nta nitrogen with the Co—N(N,N Et2en)= 2.011(5) and Co—N(nta) = 1.950(4) Å while the cis Co—N bond is 1.953(4) Å. The Co—O bond lengths are 1.905(2) and 1.884(4) Å respectively. 相似文献
76.
Rahul B. Kawthekar Sai Kumar Chakka Vivian Francis Pher G. Andersson Hendrik G. Kruger Glenn E.M. Maguire Thavendran Govender 《Tetrahedron: Asymmetry》2010,21(7):846-852
A novel family of eleven new tetrahydroisoquinoline (TIQ)–oxazoline intermediates and five corresponding copper(II) catalysts has been developed and applied to the catalytic asymmetric Henry reaction of various aldehydes with nitromethane to provide β-hydroxy nitroalkanes in high conversion (>99%). This paper describes the synthesis of the TIQ compounds from l-dihydroxyphenylalanine (l-DOPA) as the starting material. The chiral ligands were complexed in situ with various transition metals such as Cu, Sc, Co, Zn, Ni and Mn and tested as a chiral catalyst for the Henry reaction. The reaction was optimized in terms of the metal, counter ion, solvent, temperature and over a range of substrates. The corresponding catalyst with copper(II) acetate and 2-propanol as the solvent provides the best enantioselectivities (up to 77% ee) of the corresponding nitroalcohol for 4-chlorobenzaldehyde. 相似文献
77.
78.
Byron K. Peters Sai Kumar Chakka Tricia Naicker Glenn E.M. Maguire Hendrik G. Kruger Pher G. Andersson Thavendran Govender 《Tetrahedron: Asymmetry》2010,21(6):679-687
The use of the tetrahydroisoquinoline scaffold is well documented in biologically active compounds. However, reports of the utilisation of tetrahydroisoquinoline compounds in asymmetric catalysis are limited. The synthesis of novel diamine ligands possessing the tetrahydroisoquinoline (tetrahydroisoquinoline) backbone and evaluation of their activity in the asymmetric transfer hydrogenation of acetophenone are presented. The diamine ligands in conjunction with i-PrOH as the hydrogen source and [RhCl2(Cp1)]2 as the metal precursor proved to be the most effective of the tetrahydroisoquinoline derivatives for this catalytic system. Water was found to have a profound influence on the enantioselectivity of the reaction. Optimisation of the amount water, i-PrOH and catalytic loading content rendered the best result of 70% enantioselectivity for the (S)-1-phenylethanol isomer product. 相似文献
79.
80.
Oluseye K. Onajole Patrick Govender Thavendran Govender Glenn E. M. Maguire Hendrik G. Kruger 《Structural chemistry》2010,21(6):1203-1209
The NMR elucidation of five novel SQ109 analogues including SQ109 is reported herein. These derivatives were synthesized as
potential anti-tuberculosis candidates. One-dimensional NMR (1H and 13C) techniques show a series of overlapping signals from the methine and methylene groups of these compounds, thereby making
it extremely difficult to assign all NMR signals. Two-dimensional (2D) NMR techniques were instrumental in overcoming these
challenges. This paper appears to be a rare report on the complete structure elucidation of mono-substituted adamantane moieties. 相似文献