全文获取类型
收费全文 | 9225篇 |
免费 | 1293篇 |
国内免费 | 1944篇 |
专业分类
化学 | 9913篇 |
晶体学 | 117篇 |
力学 | 306篇 |
综合类 | 73篇 |
数学 | 51篇 |
物理学 | 2002篇 |
出版年
2024年 | 62篇 |
2023年 | 152篇 |
2022年 | 424篇 |
2021年 | 493篇 |
2020年 | 698篇 |
2019年 | 526篇 |
2018年 | 358篇 |
2017年 | 372篇 |
2016年 | 416篇 |
2015年 | 428篇 |
2014年 | 480篇 |
2013年 | 784篇 |
2012年 | 639篇 |
2011年 | 494篇 |
2010年 | 377篇 |
2009年 | 454篇 |
2008年 | 464篇 |
2007年 | 477篇 |
2006年 | 497篇 |
2005年 | 438篇 |
2004年 | 458篇 |
2003年 | 392篇 |
2002年 | 400篇 |
2001年 | 254篇 |
2000年 | 255篇 |
1999年 | 192篇 |
1998年 | 187篇 |
1997年 | 168篇 |
1996年 | 163篇 |
1995年 | 170篇 |
1994年 | 136篇 |
1993年 | 126篇 |
1992年 | 112篇 |
1991年 | 69篇 |
1990年 | 55篇 |
1989年 | 42篇 |
1988年 | 41篇 |
1987年 | 44篇 |
1986年 | 21篇 |
1985年 | 24篇 |
1984年 | 18篇 |
1983年 | 11篇 |
1982年 | 16篇 |
1981年 | 15篇 |
1980年 | 17篇 |
1979年 | 12篇 |
1978年 | 6篇 |
1977年 | 4篇 |
1976年 | 8篇 |
1973年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 11 毫秒
71.
In the absence of ligand, copper and amine, a recoverable nanoparticle palladium(0) catalyzed Sonogashira reaction of aryl iodides and bromides with terminal alkynes was developed. The protocol involved the use of an environmental-friendly reaction system with ethanol as the solvent, potassium carbonate as a base, and poly(vinylpyrrolidone) (PVP) supported nanosized palladium metal colloids as the catalyst. The palladium metal was recovered and recycled by a simple decantation of the reaction solution and used for eight consecutive trials without significant loss of its reactivity. 相似文献
72.
Jale Müslehiddino?lu Yusuf Uluda? Hilmi Önder Özbelge Levent Yilmaz 《Journal of membrane science》1998,140(2):396-266
Performance of continuous polymer enhanced ultrafiltration (PEUF) method was investigated for removal of mercury and cadmium from binary mixtures. This method includes the addition of polyethyleneimine (PEI) as a water soluble polymer to bind the metals, which was followed by ultrafiltration operation performed on both laboratory and pilot scale systems. The influence of various operating parameters such as temperature, metal/polymer ratio, presence of calcium ions and pH on retention of metals and permeate flux was investigated. To investigate the possibility of selective separation of mercury and cadmium, experiments were conducted for binary solutions at different pH and loading ratios. It was seen that the retention of mercury decreased and permeate flux increased when the temperature increased. The increased pH and decreased metal/polymer ratio, loading (L), resulted in higher retention of both metals. Shapes of retention vs. pH or L curves were very similar for both metals. Retentions stay almost constant at a value very close to unity until a critical L or pH value was reached, then, R decreases almost linearly with L or pH. However, retention of cadmium was affected more than that of mercury as the pH decreased and L increased. This leads to the selective separation of mercury and cadmium. At low pH values (about 5) and at high L values (about 0.3), mercury was removed by ultrafiltration operation while almost all cadmium passed through the membrane. At pH 5.5 and cadmium/polymer ratio about 0.35 and mercury/polymer ratio about 0.39, the highest separation factor was obtained as 49. 相似文献
73.
《Surface and interface analysis : SIA》2004,36(7):624-631
In this paper Al, Zn and Al–43.4Zn–1.6Si (AlZn) alloy‐coated steel have been treated with the organofunctional silane γ‐mercaptopropyltrimethoxysilane (γ‐MPS). The influence of different metal substrates on the structure and composition of the silane films was investigated with XPS and AES. The films were obtained by dipping the substrates in the silane solution followed by a blow‐dry procedure in nitrogen gas. The results show that the surface concentration of the deposited silane is independent of the metal substrate and that the thickness of the silane film is non‐uniform. The AES measurements indicate that the silane film covers the entire substrate surface and XPS analysis of the silane‐treated substrate surfaces at different take‐off angles indicates that the γ‐MPS molecule is randomly orientated. Also, the results show that the silane is well hydrolysed under the solution conditions used. Finally, in the zinc‐containing silane‐metal systems, i.e. the silane‐treated AlZn and Zn substrates, the results indicate that the γ‐MPS molecules can bond to the substrate surfaces via the thiol group of the molecule. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
74.
Prochiral alkenes, aldehydes, and ketones constitute the most frequently used starting materials for enantioselective organic syntheses. Protocols often involve chiral binding agents or Lewis acids that can give two diastereomeric adducts, the ratios of which are measures of chiral recognition. With π adducts, the diastereomers differ in the enantioface of the C?C or O?C group bound to the Lewis acid. This review provides the first comprehensive analysis of such equilibria and related binding phenomena with chiral transition metal Lewis acids. An extensive body of data from the authors' laboratory for complexes of the pyramidal rhenium fragment [(η5?C5H5)Re(No)(PPh3)]+ ( I ) affords particular insight. Literature data for other complexes are also summarized. A general model for chiral recognition based upon the relative steric properties of four quadrants is presented. This enables binding selectivities to be individually and rationally optimized for different classes of ligands. Electronic effects are also identified and correlated with specific structural properties. Relationships between binding equilibria, reactivity, and product configurations are discussed. 相似文献
75.
Chiral α,ω-diesters react under high-pressure conditions (10 kbar) with α,ω-diamines to give chiral cyclic tetraamides of C2-symmetry. The complexation properties of tetraamides towards alkali metal cations (Li+, Na+, K+, Rb+ and Cs+) were estimated on the basis of ESI-MS spectra. 相似文献
76.
77.
L. F. Kosyanchuk N. V. Kozak O. I. Antonenko G. Ya. Menzheres Yu. S. Lipatov 《Theoretical and Experimental Chemistry》2006,42(6):357-363
For semi-interpenetrating polymer networks (semi-IPNs) based on an incompatible polyurethane network/linear polymethylmethacrylate
pair formed in situ in the presence of 3d metal chelates, we have studied the effect of the system composition on the kinetics
of formation of the components and the nature of complex formation between the metal compound and the polymer matrix. The
ratio of the system components has been shown to have an effect on the selection of the macroligand in formation of complexes
of the metal chelate with the polar groups of the semi-IPN, where the general character of the kinetic behavior for the formation
of the network and the linear polymer is preserved.
__________
Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 6, pp. 351–356, November–December, 2006. 相似文献
78.
A novel chiral Salen ligand with a glucose moiety was synthesized from the condensation of 1,2:5,6-di-O-isopropylidene-3-O-methylene-[5-(3-tert-butyl-2-hydroxy benzaldehyde)]-α-D-glucofuranose with (1R,2R)-1,2-diaminocyclohexane. Several chiral complexes of Mn3+, Fe3+, Co2+ and Cu2+ were prepared from this ligand. Both the ligand and the complexes were characterized by elemental analysis, NMR, IR, MS, and UV-Vis. 相似文献
79.
80.
M~++BrCN─→MCN~++Br气相反应的从头算研究朱荣顺,戴树珊(云南大学化学系,昆明,650091)关键词气相反应,过渡金属阳离子,溴化氰,从头算,相对论赝势对过渡金属离子与一些小分子的气相反应已有大量的实验和理论研究[1~5],MichelS... 相似文献