全文获取类型
收费全文 | 1316篇 |
免费 | 32篇 |
国内免费 | 6篇 |
专业分类
化学 | 936篇 |
晶体学 | 5篇 |
力学 | 25篇 |
数学 | 203篇 |
物理学 | 185篇 |
出版年
2023年 | 9篇 |
2022年 | 31篇 |
2021年 | 34篇 |
2020年 | 30篇 |
2019年 | 22篇 |
2018年 | 32篇 |
2017年 | 21篇 |
2016年 | 48篇 |
2015年 | 28篇 |
2014年 | 41篇 |
2013年 | 71篇 |
2012年 | 57篇 |
2011年 | 68篇 |
2010年 | 43篇 |
2009年 | 39篇 |
2008年 | 64篇 |
2007年 | 49篇 |
2006年 | 42篇 |
2005年 | 44篇 |
2004年 | 37篇 |
2003年 | 42篇 |
2002年 | 34篇 |
2001年 | 16篇 |
2000年 | 11篇 |
1999年 | 7篇 |
1998年 | 11篇 |
1997年 | 18篇 |
1996年 | 17篇 |
1995年 | 8篇 |
1994年 | 7篇 |
1993年 | 15篇 |
1992年 | 10篇 |
1991年 | 11篇 |
1990年 | 7篇 |
1988年 | 7篇 |
1987年 | 8篇 |
1985年 | 7篇 |
1984年 | 11篇 |
1983年 | 8篇 |
1981年 | 11篇 |
1980年 | 7篇 |
1979年 | 10篇 |
1976年 | 8篇 |
1918年 | 8篇 |
1905年 | 6篇 |
1901年 | 11篇 |
1895年 | 6篇 |
1894年 | 6篇 |
1888年 | 6篇 |
1885年 | 9篇 |
排序方式: 共有1354条查询结果,搜索用时 0 毫秒
41.
Heinz Falk Helmut Marko Norbert Müller Wolfgang Schmitzberger Hugo Stumpe 《Monatshefte für Chemie / Chemical Monthly》1990,121(11):893-901
Summary Apomyoglobin was reconstituted with bile pigments of the verdinoid, 2,3-dihydroverdinoid, pterobilinoid, and violinoid type. Absorption and circular dichroism data as well as formation constants of the complexes were measured. From these results it was concluded that chromophore binding and induced chirality of these pigments are mainly governed by a lipophilic region opposite to the propionic side chain(s) and the asymmetric position of the hydrogen bonding acceptors of the propionic acid side chain(s) at the entrance of the protein pocket.Dedicated to Prof. Dr. A. Eschenmoser on occasion of his 65th birthday 相似文献
42.
Lauri J. Missio Hugo S. Braibante Mara E. F. Braibante 《Journal of heterocyclic chemistry》1996,33(4):1243-1245
The reactivity of the enamino compounds 4-amino-3-phenylamino(thio)carbonyl-3-penten-2-one 1 and 2 and ethyl 3-amino-2-phenylamino(thio)carbonyl-2-butyrate 7 and 8 was studied using the reaction with hydrazine hydrate and hydrazine hydrochloride to evaluate the 1,3 electrophilic center of the compounds by the formation of the pyrazole rings. The pyrazoles 3, 4, 5, 9, 11 and 13 were obtained depending on the reaction conditions employed. 相似文献
43.
Yulia Shenberger Ortal Marciano Hugo E. Gottlieb 《Journal of Coordination Chemistry》2018,71(11-13):1985-2002
AbstractCopper transporter 1 (CTR1) is the main copper transporter in the eukaryotic system. CTR1 has several important roles: It binds Cu(II) ions that are present in the blood; it reduces those Cu(II) ions to Cu(I); and it subsequently transfers Cu(I) to the cytoplasmic domain, where the ion is delivered to various cellular pathways. Here, we seek to identify CTR1 binding sites for Cu(II) and Cu(I) and to shed light on the Cu(II)-to-Cu(I) reduction process. We focus on the first 14 amino acids of CTR1. This N-terminal segment is rich with histidine and methionine residues, which are known to bind Cu(II) and Cu(I), respectively; thus, this region has been suggested to have an important function in recruiting Cu(II) and reducing it to Cu(I). We utilize electron paramagnetic resonance (EPR) spectroscopy together with nuclear magnetic resonance (NMR) and UV-VIS spectroscopy and alanine substitution to reveal Cu(II) and Cu(I) binding sites in the focal 14-amino-acid segment. We show that H5 and H6 directly coordinate to Cu(II), whereas M7, M9, and M12 are involved in Cu(I) binding. This research is another step on the way to a complete understanding of the cellular copper regulation mechanism in humans. 相似文献
44.
Douglas L. Cassimiro Leonardo M. B. Ferreira Ana Luiza R. de Souza Mariana Fonseca Suzy S. S. Kurokawa Jovan D. Alonso Victor Hugo V. Sarmento Clovis Augusto Ribeiro 《Journal of Thermal Analysis and Calorimetry》2018,134(3):1599-1609
Supramolecular gels are soft materials formed mainly by low molecular weight units held together by intermolecular interactions. Stabilizing these kinds of materials is quite a challenge due to the influence of multiple factors interfering with the integrity of the supramolecular structure. In our previous studies, we have shown that the aminocarbohydrate meglumine (MEG) interacts with organic acids by ion-pairing leading to the formation of MEG–carboxylate adducts. These adducts undergo supramolecular polymerization by heat treatment, but the macromolecular assembly was stable for a short period due to hydrogen bond (H-bond) breakup. Herein, we attempt to study the influence of hydrophobic building blocks on the formation of these compounds aiming to stabilize H-bonds to produce polymerizable supra-amphiphiles in water. Oleic acid and stearic acid are two analogous fatty acids differing only in the presence of unsaturation that were used in our studies. Results demonstrated that the presence of unsaturation hinders gelation in water by interfering with the self-assembly behavior of supra-amphiphiles. Thus, unsaturated supra-amphiphiles behave like traditional surfactants and gelify water at high concentrations (above 30% w/w). On the other hand, supramolecular gels with a polymer-like behavior could be produced with a saturated supra-amphiphile in water (above 4% w/w). The material was characterized by a lamellar arrangement that facilitates the alignment of H-bonds necessary to stabilize the self-assembled structure. These results have pivotal importance on the design of polymerizable supra-amphiphiles and demonstrate that the double bond of hydrophobic building blocks is an important design factor to be considered by scientists studying similar materials. 相似文献
45.
46.
Viviana Heguaburu Hugo do Carmo Florencia Parpal María Eugenia Amorós Andrés González 《Tetrahedron letters》2017,58(18):1738-1741
The synthesis of 3-hydroxy-2-hexanone and 2,3-hexanediol, two components of the aggregation pheromone of several cerambycid species, is disclosed in here. Starting from 2-hexanone, through an α-hydroxylation using (diacetoxyiodo)benzene, 3-hydroxy-2-hexanone is obtained in good yield. Further reduction of this compound, gives 2,3-hexanediol in excellent yield. A study of the α-hydroxylation reaction of several alkylketones using an hypervalent iodine reagent is also disclosed in here. The synthesis of optically active compounds (R)- and (S)-3-hydroxy-2-hexanone was achieved starting from 2-hexanone with nitrosobenzene and l- and d-proline respectively, in several reaction media. 相似文献
47.
48.
Hugo M. Ortner 《Fresenius' Journal of Analytical Chemistry》1992,343(11):825-826
Conclusion Analytical Chemistry, as we have seen, is quite an established science but also a very vivid and young one. Its boundaries have always been and will be at the very frontiers of natural science: we are approaching the detection of single atoms as well as the analysis of matter at the very fringes of our universe. Analytical Chemistry is essential for the development of taylor-made high-tech materials and equally for the evolution of our knowledge about the toxicity of elements and compounds. It needs specialists with a profound insight in certain fields, for methods development or the handling of very complex instrumentation as e.g. a high resolution secondary ion mass spectrometer. But it also needs allrounders with a broad view not only of the capability of Analytical Chemistry as a whole but with an understanding for the complexity of modern social and economic structures. Frequently new ideas, new concepts and progress are forming on the seams between disciplines, on the grain boundaries of scientific fields too often kept strictly separated from each other. Analytical Chemistry is certainly a discipline which is predestinated for scientific communication collaborating with practically all fields of natural science as well as politics and economics.As a branch of natural science it is neutral in its moral value and therefore needs responsible and courageous analysts to use it for the benefit of mankind. 相似文献
49.
[reaction: see text] The copper metallomicellar hydrolysis of O-methyl O-4-nitrophenyl phenylphosphonothioate to O-methyl phenylphosphonothioic acid takes place with effectively complete inversion at phosphorus. 相似文献
50.
It has been shown theoretically that a light amplifier working on the physical principle of stimulated emission should achieve optimal quantum cloning of the polarization state of light. We demonstrate close-to-optimal universal quantum cloning of polarization in a standard fiber amplifier for telecom wavelengths. For cloning 1-->2 we find a fidelity of 0.82, the optimal value being 5 / 6=0.83. 相似文献