全文获取类型
收费全文 | 62969篇 |
免费 | 5638篇 |
国内免费 | 10740篇 |
专业分类
化学 | 46806篇 |
晶体学 | 1969篇 |
力学 | 2067篇 |
综合类 | 477篇 |
数学 | 10059篇 |
物理学 | 17969篇 |
出版年
2024年 | 120篇 |
2023年 | 984篇 |
2022年 | 1204篇 |
2021年 | 1920篇 |
2020年 | 2038篇 |
2019年 | 1942篇 |
2018年 | 1644篇 |
2017年 | 2008篇 |
2016年 | 2092篇 |
2015年 | 1860篇 |
2014年 | 2711篇 |
2013年 | 5364篇 |
2012年 | 3599篇 |
2011年 | 4673篇 |
2010年 | 3742篇 |
2009年 | 4447篇 |
2008年 | 4433篇 |
2007年 | 4390篇 |
2006年 | 3986篇 |
2005年 | 3532篇 |
2004年 | 3261篇 |
2003年 | 2704篇 |
2002年 | 2364篇 |
2001年 | 1812篇 |
2000年 | 1724篇 |
1999年 | 1443篇 |
1998年 | 1214篇 |
1997年 | 1064篇 |
1996年 | 953篇 |
1995年 | 941篇 |
1994年 | 860篇 |
1993年 | 738篇 |
1992年 | 644篇 |
1991年 | 501篇 |
1990年 | 350篇 |
1989年 | 322篇 |
1988年 | 251篇 |
1987年 | 194篇 |
1986年 | 155篇 |
1985年 | 195篇 |
1984年 | 153篇 |
1983年 | 76篇 |
1982年 | 126篇 |
1981年 | 133篇 |
1980年 | 105篇 |
1979年 | 88篇 |
1978年 | 74篇 |
1977年 | 67篇 |
1976年 | 50篇 |
1973年 | 35篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
11.
In this work, a vanillin complex is immobilized onto MCM-41 and characterized by FT-IR, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and BET techniques. This supported Schiff base complex was found to be an efficient and recoverable catalyst for the chemoselective oxidation of sulfides into sulfoxides and thiols into their corresponding disulfides (using hydrogen peroxide as a green oxidant) and also a suitable catalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in water at 90°C. Using this protocol, we show that a variety of disulfides, sulfoxides, and 2,3-dihydroquinazolin-4(1H)-one derivatives can be synthesized in green conditions. The catalyst can be recovered and recycled for further reactions without appreciable loss of catalytic performance. 相似文献
12.
Weiyi Li Geng Leng Caiqin Li Yajing Lyu 《International journal of quantum chemistry》2020,120(8):e26150
The mechanisms of CO2 coupling with the propargylic alcohol using alkali carbonates M2CO3 (M = Li, Na, K, Cs) have been investigated by means of density functional theory calculations. The calculations reveal that the target product tetronic acid (TA) is yielded through two stages: (a) the formation of the α-alkylidene cyclic carbonate (αACC) intermediate via Cs2CO3-mediated carboxylative cyclization of the propargylic alcohol with CO2, and (b) the conversion of the αACC intermediate with Cs2CO3 to produce the cesium salt of the TA. Since the overall kinetic barriers for the two stages are comparable and affordable, the excellent chemoselectivity to the TA should be primarily originated from the high thermodynamic stability of the cesium salt of the TA. Moreover, relative to the TA, the possibility to yield the by-product acyclic carbonate can be excluded due to the both kinetics and thermodynamic inferiority. This result is different from the organic base-mediated reaction. Alternatively, our calculations predict that CsHCO3 together generated with the cesium salt of the TA might also be an available mediating reagent for the incorporation of CO2 with the propargylic alcohol. Compared to other alkali carbonates M2CO3 (M = Li, Na, K), the stronger basicity of Cs2CO3 and the lower ionic potential of cesium ion can raise the effective concentration of the αACC intermediate, and thus the conversion of the αACC intermediate into the cesium salt of the TA can be achieved with high yield. 相似文献
13.
《Wave Motion》2018
The evolution of surface gravity waves is driven by nonlinear interactions that trigger an energy cascade similarly to the one observed in hydrodynamic turbulence. This process, known as wave turbulence, has been found to display anomalous scaling with deviation from classical turbulent predictions due to the emergence of coherent and intermittent structures on the water surface. In the ocean, waves are spread over a wide range of directions, with a consequent attenuation of the nonlinear properties. A laboratory experiment in a large wave facility is presented to discuss the sensitivity of wave turbulence on the directional properties of model wave spectra. Results show that the occurrence of coherent and intermittent structures become less likely with the broadening of the wave directional spreading. There is no evidence, however, that intermittency completely vanishes. 相似文献
14.
The growth-fragmentation equation describes a system of growing and dividing particles, and arises in models of cell division, protein polymerisation and even telecommunications protocols. Several important questions about the equation concern the asymptotic behaviour of solutions at large times: at what rate do they converge to zero or infinity, and what does the asymptotic profile of the solutions look like? Does the rescaled solution converge to its asymptotic profile at an exponential speed? These questions have traditionally been studied using analytic techniques such as entropy methods or splitting of operators. In this work, we present a probabilistic approach: we use a Feynman–Kac formula to relate the solution of the growth-fragmentation equation to the semigroup of a Markov process, and characterise the rate of decay or growth in terms of this process. We then identify the Malthus exponent and the asymptotic profile in terms of a related Markov process, and give a spectral interpretation in terms of the growth-fragmentation operator and its dual. 相似文献
15.
Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis 下载免费PDF全文
Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
16.
Caesium carbonate supported on hydroxyapatite‐encapsulated Ni0.5Zn0.5Fe2O4 nanocrystallites as a novel magnetically basic catalyst for the one‐pot synthesis of pyrazolo[1,2‐b]phthalazine‐5,10‐diones 下载免费PDF全文
Behrooz Maleki Samaneh Barat Nam Chalaki Samaneh Sedigh Ashrafi Esmail Rezaee Seresht Farid Moeinpour Amir Khojastehnezhad Reza Tayebee 《应用有机金属化学》2015,29(5):290-295
A novel nanomagnetic basic catalyst of caesium carbonate supported on hydroxyapatite‐coated Ni0.5Zn0.5Fe2O4 magnetic nanoparticles (Ni0.5Zn0.5Fe2O4@HAP‐Cs2CO3) was prepared. This new catalyst was fully characterized using Fourier transform infrared spectroscopy, transmission and scanning electron microscopy, X‐ray diffraction and vibrating sample magnetometry techniques, and then the catalytic activity of this catalyst was investigated in the synthesis of 1H‐pyrazolo[1,2‐b]phthalazine‐5,10‐dione derivatives. Also, Ni0.5Zn0.5Fe2O4@HAP‐Cs2CO3 could be reused at least five times without significant loss of activity and could be recovered easily by applying an external magnet. Thus, the developed nanomagnetic catalyst is potentially useful for the green and economic production of organic compounds. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
17.
Given an ‐vertex pseudorandom graph and an ‐vertex graph with maximum degree at most two, we wish to find a copy of in , that is, an embedding so that for all . Particular instances of this problem include finding a triangle‐factor and finding a Hamilton cycle in . Here, we provide a deterministic polynomial time algorithm that finds a given in any suitably pseudorandom graph . The pseudorandom graphs we consider are ‐bijumbled graphs of minimum degree which is a constant proportion of the average degree, that is, . A ‐bijumbled graph is characterised through the discrepancy property: for any two sets of vertices and . Our condition on bijumbledness is within a log factor from being tight and provides a positive answer to a recent question of Nenadov. We combine novel variants of the absorption‐reservoir method, a powerful tool from extremal graph theory and random graphs. Our approach builds on our previous work, incorporating the work of Nenadov, together with additional ideas and simplifications. 相似文献
18.
Theoretical study of (e,2e) triple differential cross sections of pyrimidine and tetrahydrofurfuryl alcohol molecules using multi-center distorted-wave method 下载免费PDF全文
We report theoretical studies of electron impact triple differential cross sections of two bio-molecules,pyrimidine and tetrahydrofurfuryl alcohol,in the coplanar asymmetric kinematic conditions with the impact energy of 250 eV and ejected electron energy of 20 eV at three scattering angles of-5°,-10°,and-15°.Present multi-center distorted-wave method well describes the experimental data,which was obtained by performing(e,2e)experiment.The calculations show that the secondary electron produced by the primary impact electron is strongly influenced by the molecular ionic multi-center potential,which must be considered when the low energy electron interacts with DNA analogues. 相似文献
19.
20.