全文获取类型
收费全文 | 10019篇 |
免费 | 187篇 |
国内免费 | 31篇 |
专业分类
化学 | 5706篇 |
晶体学 | 199篇 |
力学 | 209篇 |
数学 | 1695篇 |
物理学 | 2428篇 |
出版年
2022年 | 203篇 |
2021年 | 214篇 |
2020年 | 127篇 |
2019年 | 181篇 |
2018年 | 188篇 |
2017年 | 177篇 |
2016年 | 312篇 |
2015年 | 245篇 |
2014年 | 337篇 |
2013年 | 754篇 |
2012年 | 516篇 |
2011年 | 582篇 |
2010年 | 454篇 |
2009年 | 414篇 |
2008年 | 477篇 |
2007年 | 480篇 |
2006年 | 427篇 |
2005年 | 387篇 |
2004年 | 341篇 |
2003年 | 313篇 |
2002年 | 235篇 |
2001年 | 181篇 |
2000年 | 159篇 |
1999年 | 129篇 |
1998年 | 134篇 |
1997年 | 113篇 |
1996年 | 104篇 |
1995年 | 138篇 |
1994年 | 84篇 |
1993年 | 76篇 |
1992年 | 89篇 |
1991年 | 66篇 |
1990年 | 79篇 |
1989年 | 72篇 |
1988年 | 72篇 |
1987年 | 63篇 |
1986年 | 75篇 |
1985年 | 121篇 |
1984年 | 129篇 |
1983年 | 80篇 |
1982年 | 82篇 |
1981年 | 84篇 |
1980年 | 91篇 |
1979年 | 63篇 |
1978年 | 71篇 |
1977年 | 77篇 |
1976年 | 67篇 |
1975年 | 61篇 |
1974年 | 51篇 |
1973年 | 44篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
131.
The complexation of L ‐ and D ‐enantiomers of phenylglycine, phenylalanine, and tryptophan with D ‐mannonaphto‐crown‐6‐ether in methanol solution was studied by NMR and isothermal titration calorimetry (ITC) at 298.15 K. The total heat effects attributed to the binding phenomena were measured in the range of 1.8 to 7.7 mJ, and the complexation was found stereo‐specific. The binding topologies were estimated basing on 1H 2D‐ROESY experiments. The analysis of Job plots obtained from 1H NMR‐monitored titrations proved the coexistence of 1:1 and 1:2 (crown ether:amino acids) complexes, which thermodynamic parameters, Ks, ΔG, ΔH°, and TΔS were determined with the aid of ITC. The 1:1 complexes were found enthalpically stabilized, generally by electrostatic interactions between the charged NH group of amino acid and crown ether macrocyclic moiety, while the binding of the second amino acid molecule was driven entropically due to solvatophobic effect. Strong enthalpy–entropy compensation points towards the uniform binding mode of all complexes studied. The mode of complex formation was found solvent dependent. For phenylalanine guest studied in various solvent systems, in contrast to the aqueous media, the noticeable chiral recognition is observed in methanol solution, and the complex stoichiometry (1:2 ether:Phe) differs from the 2:1 one, determined previously for the same host‐guest system in water (J. Thermal. Anal. Cal. 2006; 83: 575–578). Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
132.
Chromatographia - The possibility of rare earth elements (REE) separation by ion interaction chromatography (IIC) employing their complexes with diglycolic acid (ODA) in anion exchange mode has... 相似文献
133.
Alina T. Dubis Piotr Stasiewicz Katarzyna Pogorzelec‐Glaser Andrzej Łapiński 《Journal of Physical Organic Chemistry》2015,28(10):652-662
The formation of intramolecular hydrogen bonding by certain N‐substituted 2‐acylpyrroles has been demonstrated by B3LYP/aug‐cc‐pVDZ calculations, the quantum theory of atoms in molecules, and the natural bond orbital method. Total electron energy densities HBCP at the bond critical point of the H?O bond were applied to analyze the strength of these interactions. The relations between quantum theory of atoms in molecules, carbonyl stretching vibrational modes νC = O, and natural bond orbital parameters associated with the formation of the C–H?O interaction have been established. The short contacts were found experimentally in the crystal structure of a new 2‐acylpyrrole derivative 5‐chloro‐2‐oxopentyl‐1‐(5‐chloro‐2‐oxopentyl)pyrrolo‐2‐carboxylate. The influence of 2‐ and N‐substitution of 2‐acylpyrroles on C‐H?O interaction energy is discussed. It was found that the methylene group may act as a proton donor leading to a red‐shift or blue‐shift phenomenon of the νC–H stretching mode. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
134.
135.
136.
Polyurethane cationomer coats were synthesised on the basis of typical diisocyanates, properly selected polyether polyols, HO-tertiary amines and HCOOH as quaternisation reagents. The values of their surface free energy (SFE) parameters were obtained by the van Oss-Good method, with the use of the contact angle values which had been found by the goniometric method. Based on the obtained findings, empirical models were developed which made it possible to anticipate the effects of the raw material types on the SFE values of the produced coats. The possibility was noted to adjust the SFE values within 25–50 mJ/m2 by selecting carefully suitable parent substances. The principal consequences for the formation of improved hydrophobicity coats, applicable inter alia specialised protective coatings, were found to come not only from diisocyanate and polyol types but also from the alkylammonium cation structure which results from the use of different tertiary amines. The fundamental SFE lowering effect was noted when tertiary amines with 0–15 % of the 2,2,3,3-tetrafluoro-1,4-butanediol as a fluorinated chain extender was incorporated into polymer chains. 相似文献
137.
Ewa Wagner-Wysiecka Natalia ukasik Andrzej Okuniewski Baej Galiski 《Monatshefte für Chemie / Chemical Monthly》2020,151(3):331-343
The synthesis and ion binding properties of new amide derived from propeller-like tris(2-pyridyl)amine and 2,6-pyridinedicarboxylic acid chloride were described. Amide binds divalent metal cations: copper(II), nickel(II), zinc(II), and lead(II) in acetonitrile. In acetonitrile:water mixture (9:1 v/v) amide interacts only with copper(II) and nickel(II) cations forming complexes of 1:1 stoichiometry. It was found that the introduction of bulky, nitrogen donor atom bearing pendant groups can influence coordination mode of pyridine-2,6-dicarboxamides. The probable model of ligand-ion interactions is proposed on the basis of 1H NMR and FT-IR spectroscopy. 相似文献
138.
The stereochemical course of the epoxide-induced oxidative rearrangement of ribonucleoside cyclic 3′,5′-phosphorothioates into the corresponding 2′,3′-phosphates has been determined using styrene [18O] oxide and (Sp)-uridine cyclic 3′,5′-phosphorothioate. The evidence of full stereoselectivity of this reaction is presented and mechanistic implications of the presence of the nucleoside 2′-hydroxyl group are discussed in terms of a classical Hamer Mechanism. 相似文献
139.
Waldemar Wolczyski 《Crystal Research and Technology》1989,24(11):1113-1120
In order to find a generalized entropy production for steady-state eutectic growth the entropy production per unit time and volume is to be determined. A relationship which expresses the entropy production per unit time and volume as a function of KRUPKOWSKI 's equations is shown. It is in a qualitative accuracy with LESOULT -TURPIN 's theory. The above quantity is to be integrated over a distinguished volume of the unidirectionally solidified eutectic structure. A correlation between this volume and entropy production is discussed. 相似文献
140.
Piotr Kurcok Andrzej Matuszowicz Zbigniew Jedliski Hans R. Kricheldorf Philippe Dubois Robert Jrme 《Macromolecular rapid communications》1995,16(7):513-519
The influence of methyl substituent on the mechanism of the ring-opening polymerization of β-lactones initiated by alkali metal alkoxides is discussed. Attention has been paid to the effect of the substituent position in the monomer molecule on the ring-opening mechanism, the 3,3-dimethyl-2-oxetanone (pivalolactone), 4-methyl-2-oxetanone (β-butyrolactone) and 2-oxetanone (β-propiolactone) being chosen as model monomers. Moreover, it was found unexpectedly that in the case of pivalolactone polymerization, besides open-chain polymers, cyclic oligomers are produced. 相似文献