全文获取类型
收费全文 | 2238篇 |
免费 | 91篇 |
国内免费 | 22篇 |
专业分类
化学 | 1456篇 |
晶体学 | 16篇 |
力学 | 80篇 |
数学 | 437篇 |
物理学 | 362篇 |
出版年
2023年 | 19篇 |
2022年 | 31篇 |
2021年 | 46篇 |
2020年 | 55篇 |
2019年 | 58篇 |
2018年 | 57篇 |
2017年 | 40篇 |
2016年 | 78篇 |
2015年 | 76篇 |
2014年 | 93篇 |
2013年 | 143篇 |
2012年 | 175篇 |
2011年 | 240篇 |
2010年 | 114篇 |
2009年 | 104篇 |
2008年 | 157篇 |
2007年 | 128篇 |
2006年 | 138篇 |
2005年 | 107篇 |
2004年 | 97篇 |
2003年 | 80篇 |
2002年 | 58篇 |
2001年 | 31篇 |
2000年 | 21篇 |
1999年 | 12篇 |
1998年 | 14篇 |
1997年 | 15篇 |
1996年 | 19篇 |
1995年 | 10篇 |
1994年 | 7篇 |
1993年 | 12篇 |
1992年 | 9篇 |
1991年 | 3篇 |
1990年 | 5篇 |
1989年 | 6篇 |
1988年 | 4篇 |
1987年 | 5篇 |
1986年 | 3篇 |
1985年 | 8篇 |
1984年 | 4篇 |
1983年 | 5篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1980年 | 4篇 |
1978年 | 7篇 |
1976年 | 5篇 |
1973年 | 4篇 |
1961年 | 3篇 |
1942年 | 6篇 |
1940年 | 3篇 |
排序方式: 共有2351条查询结果,搜索用时 15 毫秒
101.
Ewan Couic Alicia Tribondeau Vanessa Alphonse Alexandre Livet Noureddine Bousserrhine 《Molecules (Basel, Switzerland)》2022,27(6)
Understanding ecological trajectories after mine site rehabilitation is essential to develop relevant protocols adapted for gold mining sites. This study describes the influence of a range of mine site rehabilitation and revegetation protocols on soil physicochemical parameters and microbial activities related to carbon, nitrogen and phosphorus cycles. We sampled soil from six rehabilitated mining sites in French Guiana with different plant cover (herbaceous, Cyperaceous, monoculture of Clitoria racemosa and Acacia mangium and association of C. racemosa and A. mangium). We measured the mineralization potential of organic matter by estimating the mineralization of carbon, nitrogen and phosphorus and the microbial catabolic diversity balance. The results showed an improvement in the quality of organic matter on revegetated sites with tree cover. On restored sites with fabaceous species, the microbial biomass is three times higher than non-restored sites, improving the rates of organic matter mineralization and restoring the catabolic diversity to the level of natural Guyanese soils. These results confirm that the establishment of fabaceous species under controlled conditions significantly improves the restoration of microbial communities in mining soils. 相似文献
102.
Alexandre P. Felgueiras Fbio M. S. Rodrigues Rui M. B. Carrilho Pedro F. Cruz Vitor H. Rodrigues Tams Kgl Lszl Kollr Mariette M. Pereira 《Molecules (Basel, Switzerland)》2022,27(6)
Four stereoisomeric monoether derivatives, based on axially chiral (R)- or (S)-BINOL bearing a chiral (+)- or (−)-neomenthyloxy group were synthesised and fully characterised by NMR spectroscopy and X-ray crystallography. The respective tris-monophosphites were thereof prepared and fully characterised. The coordination ability of the new bulky phosphites with Rh(CO)2(acac), was attested by 31P NMR, which presented a doublet in the range of δ = 120 ppm, with a 1J(103Rh-31P) coupling constant of 290 Hz. The new tris-binaphthyl phosphite ligands were further characterised by DFT computational methods, which allowed us to calculate an electronic (CEP) parameter of 2083.2 cm−1 and an extremely large cone angle of 345°, decreasing to 265° upon coordination with a metal atom. Furthermore, the monophosphites were applied as ligands in rhodium-catalysed hydroformylation of styrene, leading to complete conversions in 4 h, 100% chemoselectivity for aldehydes and up to 98% iso-regioselectivity. The Rh(I)/phosphite catalytic system was also highly active and selective in the hydroformylation of disubstituted olefins, including (E)-prop-1-en-1-ylbenzene and prop-1-en-2-ylbenzene. 相似文献
103.
104.
Peiguang Zhou Alexandre Blumstein 《Journal of polymer science. Part A, Polymer chemistry》1996,34(16):3399-3406
An interpenetrating polymer network (IPN) based on poly(N-butyl 2-ethynylpyridinum bromide) (PB2EPB) and polycarbonate-urethane (PCU) has been prepared and characterized. The simultaneous full IPNs of PCU and PB2EPB have two glass transition temperatures corresponding to those of the linear chain blends measured by DSC. This suggests immiscibility of the two networks in the IPNs. The IPNs display a multiphase morphology which is confirmed by SEM observation. The full IPNs exhibit excellent solvent resistance, good thermal stability and good mechanical properties. High UV absorption of these materials extending to the visible range and beyond indicates that the polyacetylene network is extensively conjugated. The electrical conductivity of the IPNs increases linearly with increasing polyacetylene content reaching 10-4 S/cm. © 1996 John Wiley & Sons, Inc. 相似文献
105.
Rosana V. Pinto Sujing Wang Sergio R. Tavares Joo Pires Fernando Antunes Alexandre Vimont Guillaume Clet Marco Daturi Guillaume Maurin Christian Serre Moiss L. Pinto 《Angewandte Chemie (International ed. in English)》2020,59(13):5135-5143
Materials for the controlled release of nitric oxide (NO) are of interest for therapeutic applications. However, to date, many suffer from toxicity and stability issues, as well as poor performance. Herein, we propose a new NO adsorption/release mechanism through the formation of nitrites on the skeleton of a titanium‐based metal–organic framework (MOF) that we named MIP‐177, featuring a suitable set of properties for such an application: (i) high NO storage capacity (3 μmol mg?1solid), (ii) excellent biocompatibility at therapeutic relevant concentrations (no cytotoxicity at 90 μg mL?1 for wound healing) due to its high stability in biological media (<9 % degradation in 72 hours) and (iii) slow NO release in biological media (≈2 hours for 90 % release). The prospective application of MIP‐177 is demonstrated through NO‐driven control of mitochondrial respiration in cells and stimulation of cell migration, paving the way for the design of new NO delivery systems for wound healing therapy. 相似文献
106.
Dr. Louwanda Lakiss Dr. Aurélie Vicente Prof. Jean-Pierre Gilson Dr. Valentin Valtchev Dr. Svetlana Mintova Dr. Alexandre Vimont Dr. Robert Bedard Dr. Suheil Abdo Dr. Jeffery Bricker 《Chemphyschem》2020,21(16):1873-1881
We outline two methodologies to selectively characterize the Brønsted acidity of the external surface of FAU-type zeolites by IR and NMR spectroscopy of adsorbed basic probe molecules. The challenge and goal are to develop reliable and quantitative IR and NMR methodologies to investigate the accessibility of acidic sites in the large pore FAU-type zeolite Y and its mesoporous derivatives often referred to as ultra-stable Y (USY). The accessibility of their Brønsted acid sites to probe molecules (n-alkylamines, n-alkylpyridines, n-alkylphosphine- and phenylphosphine-oxides) of different molecular sizes is quantitatively monitored either by IR or 31P NMR spectroscopy. It is now possible, for the first time to quantitatively discriminate between the Brønsted acidity located in the microporosity and on the external surface of large pore zeolites. For instance, the number of external acid sites on a Y (LZY-64) zeolite represents 2 % of its total acid sites while that of a USY (CBV760) represents 4 % while the latter has a much lower framework Si/Al ratio. 相似文献
107.
Inside Cover: Supramolecular Complexes of Multivalent Cholesterol‐Containing Polymers to Solubilize Carbon Nanotubes in Apolar Organic Solvents (Chem. Asian J. 5/2014)
下载免费PDF全文
![点击此处可从《化学:亚洲杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
108.
Insights into the Complexity of Weak Intermolecular Interactions Interfering in Host–Guest Systems
下载免费PDF全文
![点击此处可从《Chemphyschem》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dawei Zhang Dr. Bastien Chatelet Eloisa Serrano Dr. Olivier Perraud Dr. Jean‐Pierre Dutasta Prof. Dr. Vincent Robert Prof. Dr. Alexandre Martinez 《Chemphyschem》2015,16(14):2931-2935
The recognition properties of heteroditopic hemicryptophane hosts towards anions, cations, and neutral pairs, combining both cation–π and anion–π interaction sites, were investigated to probe the complexity of interfering weak intermolecular interactions. It is suggested from NMR experiments, and supported by CASSCF/CASPT2 calculations, that the binding constants of anions can be modulated by a factor of up to 100 by varying the fluorination sites on the electron‐poor aromatic rings. Interestingly, this subtle chemical modification can also reverse the sign of cooperativity in ion‐pair recognition. Wavefunction calculations highlight how short‐ and long‐range interactions interfere in this recognition process, suggesting that a disruption of anion–π interactions can occur in the presence of a co‐bound cation. Such molecules can be viewed as prototypes for examining complex processes controlled by the competition of weak interactions. 相似文献
109.
110.