全文获取类型
收费全文 | 2330篇 |
免费 | 93篇 |
国内免费 | 7篇 |
专业分类
化学 | 1628篇 |
晶体学 | 25篇 |
力学 | 58篇 |
数学 | 333篇 |
物理学 | 386篇 |
出版年
2022年 | 13篇 |
2021年 | 25篇 |
2020年 | 23篇 |
2019年 | 25篇 |
2018年 | 21篇 |
2017年 | 10篇 |
2016年 | 57篇 |
2015年 | 53篇 |
2014年 | 66篇 |
2013年 | 148篇 |
2012年 | 118篇 |
2011年 | 144篇 |
2010年 | 94篇 |
2009年 | 68篇 |
2008年 | 122篇 |
2007年 | 131篇 |
2006年 | 141篇 |
2005年 | 120篇 |
2004年 | 128篇 |
2003年 | 100篇 |
2002年 | 88篇 |
2001年 | 22篇 |
2000年 | 29篇 |
1999年 | 23篇 |
1998年 | 26篇 |
1997年 | 28篇 |
1996年 | 34篇 |
1995年 | 26篇 |
1994年 | 29篇 |
1993年 | 25篇 |
1992年 | 18篇 |
1991年 | 19篇 |
1990年 | 20篇 |
1989年 | 27篇 |
1988年 | 21篇 |
1987年 | 13篇 |
1986年 | 21篇 |
1985年 | 34篇 |
1984年 | 33篇 |
1983年 | 25篇 |
1982年 | 22篇 |
1981年 | 29篇 |
1980年 | 30篇 |
1979年 | 21篇 |
1978年 | 17篇 |
1977年 | 23篇 |
1976年 | 15篇 |
1975年 | 22篇 |
1974年 | 12篇 |
1973年 | 20篇 |
排序方式: 共有2430条查询结果,搜索用时 15 毫秒
101.
102.
103.
104.
Dr. Christophe Kahlfuss Dr. Raymond Grüber Prof. Elise Dumont Prof. Guy Royal Floris Chevallier Dr. Saioa Cobo Prof. Eric Saint-Aman Dr. Christophe Bucher 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(6):1573-1580
A dynamic supramolecular approach is developed to promote the π-dimerization of viologen radicals at room temperature and in standard concentration ranges. The approach involves cis- or trans-protected palladium centers serving as inorganic hinges linking two functionalized viologens endowed with metal-ion coordinating properties. Based on detailed spectroscopic, electrochemical and computational data, we show that the one-electron electrochemical reduction of the viologen units in different dynamic metal/ligand mixtures leads to the formation of the same intramolecular π-dimer, regardless of the initial environment around the metallic precursor and of the relative ratio between metal and ligand initially introduced in solution. The large-scale electron-triggered reorganization of the building blocks introduced in solution thus involves drastic changes in the stoichiometry and stereochemistry of the palladium/viologen complexes proceeding in some cases through a palladium centered trans→cis isomerization of the coordinated ligands. 相似文献
105.
In 1977 the celebrated theorem of B. Dahlberg established that the harmonic measure is absolutely continuous with respect to the Hausdorff measure on a Lipschitz graph of dimension in , and later this result has been extended to more general non-tangentially accessible domains and beyond.In the present paper we prove the first analogue of Dahlberg's theorem in higher co-dimension, on a Lipschitz graph Γ of dimension d in , , with a small Lipschitz constant. We construct a linear degenerate elliptic operator L such that the corresponding harmonic measure is absolutely continuous with respect to the Hausdorff measure on Γ. More generally, we provide sufficient conditions on the matrix of coefficients of L which guarantee the mutual absolute continuity of and the Hausdorff measure. 相似文献
106.
107.
AbstractThe reactions of methyl radicals with MII-(ntp)(H2O)2 complexes were studied. The formation of an unstable intermediate (ntp)(H2O)MIII-CH3 is observed. This reaction is an equilibrium process, i.e. the MIII-C bond decomposes via homolysis. The (ntp)(H2O)MIII-CH3 complexes isomerize to a more stable form. The results compared to those obtained in analogous reactions of the MII-(nta)(H2O)2 complexes were shown to be similar with one exception – for the nta complexes no isomerization process is observed. 相似文献
108.
Jing Zhao Yanan Zhu Xuehong Song Yuanyuan Xiao Guowei Su Xinyue Liu Zhangjie Wang Yongmei Xu Jian Liu David Eliezer Trudy F. Ramlall Guy Lippens James Gibson Fuming Zhang Robert J. Linhardt Lianchun Wang Chunyu Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(5):1834-1843
Prion-like transcellular spreading of tau in Alzheimer's Disease (AD) is mediated by tau binding to cell surface heparan sulfate (HS). However, the structural determinants for tau–HS interaction are not well understood. Microarray and SPR assays of structurally defined HS oligosaccharides show that a rare 3-O-sulfation (3-O-S) of HS significantly enhances tau binding. In Hs3st1−/− (HS 3-O-sulfotransferase-1 knockout) cells, reduced 3-O-S levels of HS diminished both cell surface binding and internalization of tau. In a cell culture, the addition of a 3-O-S HS 12-mer reduced both tau cell surface binding and cellular uptake. NMR titrations mapped 3-O-S binding sites to the microtubule binding repeat 2 (R2) and proline-rich region 2 (PRR2) of tau. Tau is only the seventh protein currently known to recognize HS 3-O-sulfation. Our work demonstrates that this rare 3-O-sulfation enhances tau–HS binding and likely the transcellular spread of tau, providing a novel target for disease-modifying treatment of AD and other tauopathies. 相似文献
109.
Steffen H. Symoens Syam Ukkandath Aravindakshan Florence H. Vermeire Kevin De Ras Marko R. Djokic Guy B. Marin Marie-Françoise Reyniers Kevin M. Van Geem 《国际化学动力学杂志》2019,51(11):872-885
Automatically generated kinetic networks are ideally validated against a large set of accurate, reproducible, and easy-to-model experimental data. However, although this might seem simple, it proves to be quite challenging. QUANTIS, a publicly available Python package, is specifically developed to evaluate both the precision and accuracy of experimental data and to ensure a uniform, quick processing, and storage strategy that enables automated comparison of developed kinetic models. The precision is investigated with two clustering techniques, PCA and t-SNE, whereas the accuracy is probed with checks for the conservation laws. First, the developed tool processes, evaluates, and stores experimental yield data automatically. All data belonging to a given experiment, both unprocessed and processed, are stored in the form of an HDF5 container. The demonstration of QUANTIS on three different pyrolysis cases showed that it can help in identifying and overcoming instabilities in experimental datasets, reduce mass and molar balance closure discrepancies, and, by evaluating the visualized correlation matrices, increase understanding in the underlying reaction pathways. Inclusion of all experimental data in the HDF5 file makes it possible to automate simulating the experiment with CHEMKIN. Because of the employed InChI string identifiers for molecules, it is possible to automate the comparison experiment/simulation. QUANTIS and the concepts demonstrated therein is a potentially useful tool for data quality assessment, kinetic model validation, and refinement. 相似文献
110.
Large‐Scale Synthesis of Enantiopure Molecular Cages: Chiroptical and Recognition Properties 下载免费PDF全文
Sara Lefevre Dawei Zhang Estelle Godart Marion Jean Dr. Nicolas Vanthuyne Jean‐Christophe Mulatier Dr. Jean‐Pierre Dutasta Dr. Laure Guy Prof. Alexandre Martinez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(6):2068-2074
A convenient and efficient gram‐scale synthesis for enantiopure hemicryptophane–tren (tren=tris(2‐aminoethyl)amine) derivatives has been developed. The four‐step synthesis is based on the optical resolution of a key intermediate, cyclotriveratrylene, for which the energy barrier for racemization has been measured to ensure that no racemization occurs during the two last steps of the synthetic pathway. The assignments of the absolute configurations have been performed by electronic circular dichroism and the enantiopurity was determined by NMR spectroscopy in the presence of enantiopure camphor sulfonic acid. To highlight the interest of such compounds, the recognition of norephedrine neurotransmitter was investigated and showed a remarkable enantioselectivity towards the C3 symmetrical hosts. Finally, this highly modular synthetic pathway was used to provide eight enantiopure hemicryptophanes with different sizes, shapes, and functionalities. These results underline the high potential of this approach, which could lead to many applications in chiral recognition or asymmetric supramolecular catalysis. 相似文献