全文获取类型
收费全文 | 1087篇 |
免费 | 46篇 |
国内免费 | 4篇 |
专业分类
化学 | 759篇 |
晶体学 | 1篇 |
力学 | 31篇 |
数学 | 196篇 |
物理学 | 150篇 |
出版年
2023年 | 6篇 |
2022年 | 18篇 |
2021年 | 26篇 |
2020年 | 24篇 |
2019年 | 21篇 |
2018年 | 16篇 |
2017年 | 12篇 |
2016年 | 47篇 |
2015年 | 25篇 |
2014年 | 41篇 |
2013年 | 61篇 |
2012年 | 87篇 |
2011年 | 87篇 |
2010年 | 56篇 |
2009年 | 33篇 |
2008年 | 70篇 |
2007年 | 55篇 |
2006年 | 44篇 |
2005年 | 56篇 |
2004年 | 48篇 |
2003年 | 36篇 |
2002年 | 43篇 |
2001年 | 13篇 |
2000年 | 13篇 |
1999年 | 7篇 |
1998年 | 13篇 |
1997年 | 15篇 |
1996年 | 11篇 |
1995年 | 6篇 |
1994年 | 6篇 |
1993年 | 8篇 |
1992年 | 6篇 |
1991年 | 6篇 |
1990年 | 7篇 |
1989年 | 5篇 |
1988年 | 5篇 |
1987年 | 6篇 |
1986年 | 12篇 |
1985年 | 8篇 |
1984年 | 6篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1980年 | 8篇 |
1979年 | 5篇 |
1977年 | 4篇 |
1974年 | 3篇 |
1971年 | 3篇 |
1967年 | 5篇 |
1870年 | 2篇 |
排序方式: 共有1137条查询结果,搜索用时 250 毫秒
61.
Antonio Doménech-Carbó Monserrat Lastras Francisco Rodríguez Emilio Cano Juan Piquero-Cilla Laura Osete-Cortina 《Journal of Solid State Electrochemistry》2014,18(2):399-409
A methodology for monitoring washing procedures applied to stabilize archaeological iron is described. It is based on the combination of voltammetry of microparticles (VMP) with electrochemical impedance spectroscopy (EIS). A semi-empirical approach is used where the impedances at low and high frequencies were related with the fraction areas of passive and corrosion layers generated during the stabilizing treatment, the thickness, and the porosity of the corrosion layer. The variation of such parameters with the time of washing was determined from EIS data for four types of desalination procedures using concentrated NaOH and/or Na2SO3 aqueous solutions on archaeological iron artifacts. After 2 months of treatment, EIS data indicate that an essentially identical “stable” state was attained in all cases, as confirmed by the formation of a passive magnetite layer identified in VMP measurements while the rate of variation of corroded surface and porosity at short washing times varied significantly from one stabilization procedure to another. 相似文献
62.
Probing the CH⋅⋅⋅π Weak Hydrogen Bond in Anesthetic Binding: The Sevoflurane–Benzene Cluster
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Nathan A. Seifert Dr. Daniel P. Zaleski Dr. Cristóbal Pérez Dr. Justin L. Neill Prof. Brooks H. Pate Montserrat Vallejo‐López Prof. Alberto Lesarri Dr. Emilio J. Cocinero Prof. Fernando Castaño Prof. Isabelle Kleiner 《Angewandte Chemie (International ed. in English)》2014,53(12):3210-3213
Cooperativity between weak hydrogen bonds can be revealed in molecular clusters isolated in the gas phase. Here we examine the structure, internal dynamics, and origin of the weak intermolecular forces between sevoflurane and a benzene molecule, using multi‐isotopic broadband rotational spectra. This heterodimer is held together by a primary C? H???π hydrogen bond, assisted by multiple weak C? H???F interactions. The multiple nonbonding forces hinder the internal rotation of benzene around the isopropyl C? H bond in sevoflurane, producing detectable quantum tunneling effects in the rotational spectrum. 相似文献
63.
Dr. Helena Isla Dr. Emilio M. Pérez Prof. Dr. Nazario Martín 《Angewandte Chemie (International ed. in English)》2014,53(22):5629-5633
Supramolecular polymers based on dispersion forces typically show lower molecular weights (MW) than those based on hydrogen bonding or metal–ligand coordination. We present the synthesis and self‐assembling properties of a monomer featuring two complementary units, a C60 derivative and an exTTF‐based macrocycle, that interact mainly through π–π, charge‐transfer, and van der Waals interactions. Thanks to the preorganization in the host part, a remarkable log Ka=5.1±0.5 in CHCl3 at room temperature is determined for the host–guest couple. In accordance with the large binding constant, the monomer self‐assembles in the gas phase, in solution, and in the solid state to form linear supramolecular polymers with a very high degree of polymerization. A MW above 150 kDa has been found experimentally in solution, while in the solid state the monomer forms extraordinarily long, straight, and uniform fibers with lengths reaching several microns. 相似文献
64.
65.
Rodrigo D. Tosso Oscar Parravicini M. Natalia C. Zarycz Emilio Angelina Marcela Vettorazzi Nélida Peruchena Sebastián Andujar Ricardo D. Enriz 《Journal of computational chemistry》2020,41(21):1898-1911
We report an exhaustive conformational and electronic study on dopamine (DA) interacting with the D2 dopamine receptor (D2DR). For the first time, the complete surface of the conformational potential energy of the complex DA/D2DR is reported. Such a surface was obtained through the use of QM/MM calculations. A detailed study of the molecular interactions that stabilize and destabilize the different molecular complexes was carried out using two techniques: Quantum Theory of Atoms in Molecules computations and nuclear magnetic shielding constants calculations. A comparative study of the behavior of DA in the gas phase, aqueous solution, and in the active site of D2DR has allowed us to evaluate the degree of deformation suffered by the ligand and, therefore, analyze how rustic are the lock-key model and the induced fit theory in this case. Our results allow us to propose one of the conformations obtained as the “biologically relevant” conformation of DA when it is interacting with the D2DR. 相似文献
66.
The decoration of SWNTs with supramolecular motifs is a common strategy for their subsequent noncovalent functionalization. However, due to the lack of a standard methodology, there are no quantitative measurements showing the extent to which the supramolecular equilibria are affected by one of the host-guest couple being anchored to the SWNT. Here, we use a method we initially developed to quantify association of small organic molecules to the walls of SWNTs to compare association constants of two host-guest systems, a Hamilton receptor-cyanuric acid derivative and a crown ether-ammonium couple, in solution and when the host is covalently attached to the SWNTs. Our data show that association does occur, but the stability of the complexes is significantly affected, as reflected in a sizable reduction in their association constant, when compared to solution. 相似文献
67.
Luis Palomo Rafael Rodríguez Samara Medina Emilio Quio Juan Casado Flix Freire Francisco J. Ramírez 《Angewandte Chemie (International ed. in English)》2020,59(23):9080-9087
Poly(phenylacetylene)s are a family of helical polymers constituted by conjugated double bonds. Raman spectra of these polymers show a structural fingerprint of the polyene backbone which, in combination with its helical orientation, makes them good candidates to be studied by Raman optical activity (ROA). Four different well‐known poly(phenylacetylene)s adopting different scaffolds and ten different helical senses have been prepared. Raman and ROA spectra were recorded and allowed to establish ROA‐spectrum/helical‐sense relationships: a left/right‐handed orientation of the polyene backbone (Mhelix/Phelix) produces a triplet of positive/negative ROA bands. Raman and ROA spectra of each polymer exhibited the same profile, and the sign of the ROA spectrum was opposite to the lowest‐energy electronic circular dichroism (ECD) band, indicating a resonance effect. Resonance ROA appears then as an indicator of the helical sense of poly(phenylacetylene)s, especially for those with an extra Cotton band in the ECD spectrum, where a wrong helical sense is assigned based on ECD, while ROA alerts of this misassignment. 相似文献
68.
Emilio Celotti Georgios Lazaridis Jakob Figelj Yuri Scutaru Andrea Natolino 《Molecules (Basel, Switzerland)》2022,27(1)
The oxidation processes of white wines can occur during storage and commercialization due to several factors, and these can negatively affect the color, aroma, and quality of the wine. Wineries should have faster and simpler methods that provide valuable information on oxidation stability of wines and allow fast decision-making procedures, able to trigger suitable technological interventions. Using a portable prototype instrument for light irradiations at different wavelengths and times was considered and evaluated on sensorial, spectrophotometric, and colorimetric parameters of white wines. The sensorial analysis revealed that white and light blue were the most significant, after only 1 h of irradiation. The experimental results showed that hydrogen peroxide could enhance the effect of light treatment, allowing a contemporary evaluation of the oxidation stability of wine against light and chemical stresses. As expected, a good correlation (R2 > 0.89) between optical density at 420 nm and b* parameter was highlighted. The synergic effect of light and H2O2 was also studied on the hydrolyzable and condensed tannins’ additions to white wine. The proposed methodology could be used to evaluate the oxidative stability of white wines, but also to evaluate the effect of some oenological adjuvants on wine stability. 相似文献
69.
70.