全文获取类型
收费全文 | 9048篇 |
免费 | 1410篇 |
国内免费 | 1421篇 |
专业分类
化学 | 10068篇 |
晶体学 | 341篇 |
力学 | 35篇 |
综合类 | 43篇 |
数学 | 11篇 |
物理学 | 1381篇 |
出版年
2024年 | 24篇 |
2023年 | 135篇 |
2022年 | 226篇 |
2021年 | 365篇 |
2020年 | 530篇 |
2019年 | 410篇 |
2018年 | 357篇 |
2017年 | 333篇 |
2016年 | 522篇 |
2015年 | 546篇 |
2014年 | 559篇 |
2013年 | 942篇 |
2012年 | 576篇 |
2011年 | 487篇 |
2010年 | 464篇 |
2009年 | 518篇 |
2008年 | 551篇 |
2007年 | 613篇 |
2006年 | 548篇 |
2005年 | 539篇 |
2004年 | 477篇 |
2003年 | 397篇 |
2002年 | 255篇 |
2001年 | 189篇 |
2000年 | 194篇 |
1999年 | 160篇 |
1998年 | 147篇 |
1997年 | 136篇 |
1996年 | 137篇 |
1995年 | 126篇 |
1994年 | 71篇 |
1993年 | 61篇 |
1992年 | 53篇 |
1991年 | 25篇 |
1990年 | 25篇 |
1989年 | 20篇 |
1988年 | 24篇 |
1987年 | 24篇 |
1986年 | 19篇 |
1985年 | 21篇 |
1984年 | 10篇 |
1983年 | 5篇 |
1982年 | 7篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1977年 | 7篇 |
1976年 | 6篇 |
1975年 | 7篇 |
1974年 | 6篇 |
1973年 | 11篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
131.
In this work, the complexes formed between formamide and water were studied by means of the SAPT and AIM methods. Complexation leads to significant alterations in the geometries and electronic structure of formamide. Intermolecular interactions in the complexes are intense, especially in the cases where the solvent interacts with the carbonyl and amide groups simultaneously. In the transition states, the interaction between the water molecule and the lone pair on the amide nitrogen is also important. In all the complexes studied herein, the electrostatic interactions between formamide and water are the main attractive force, and their contribution may be five times as large as the corresponding contribution from dispersion, and twice as large as the contribution from induction. However, an increase in the resonance of planar formamide with the successive addition of water molecules may suggest that the hydrogen bonds taking place between formamide and water have some covalent character. 相似文献
132.
Koichi Tanaka Hideyuki Takano Zofia Urbanczyk-lipkowska 《Journal of inclusion phenomena and macrocyclic chemistry》2006,56(3-4):281-285
The host compounds 1,1’-binaphthyl-2,2′-dihydroxy-5,5′-dicarboxylic acid (1) and 1,1′-binaphthyl-2,2′-dihydroxy-6,6′-dicarboxylic acid (2) have been synthesized, and their inclusion properties have been studied. Inclusion complexes formed by 1 and 2 with volatile guests such as acetone and methanol release the guests only at much higher temperatures than their boiling
points. The crystal structures of the inclusion complexes have been determined from single crystal X-ray diffraction data
and show different host lattices. 相似文献
133.
Alkanes (cyclohexane, hexane, heptane isomers) are effectively oxidized in CH3CN at 20–70°C by hydrogen peroxide when catalyzed by a Bu4NVO3-pyrazine-2-carboxylic acid system. Alkyl hydroperoxide is the main product; an alcohol and a ketone or an aldehyde are also formed. Under these conditions benzene is oxidized to give phenol, while alkyl benzenes yield oxygenation products both of the ring and the side chain. It has been assumed that the interaction of H2O2 with VO3
– gives rise to generation of HO radicals and other radical-like vanadium containing species that abstract a hydrogen atom from an alkane, RH. The radical R. formed reacts with O2 to produce ROO. which is then transformed to alkyl hydroperoxide.Presented at the VIII International Symposium on Homogeneous Catalysis (Amsterdam, 1992).Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 64–68, January, 1993. 相似文献
134.
Hamada Fumio Kondo Yoshihiko Ito Riko Suzuki Iwao Osa Tetsuo Ueno Akihiko 《Journal of inclusion phenomena and macrocyclic chemistry》1993,16(3):273-281
The crystal structure of thiamine iodide sesquihydrate has been determined by X-ray diffraction methods as a host-guest model for coenzyme-substrate interactions. The asymmetric unit contains two chemical units. Both the thiamine molecules A and B, which are crystallographically independent, assume the usualF conformation and have a disordered hydroxyethyl side chain. An iodide anion (or a water molecule) bridges the pyrimidine and thiazolium rings of molecule A (or B) by forming a hydrogen bond with the amino group and an electrostatic contact with the thiazolium ring to stabilize the molecular conformation. In the crystal the thiamine molecules self-associate to form a pipe-like polymeric structure, in which four thiamine hosts surround an iodide guest and hold it through C(2)-H...I hydrogen bonds and thiazolium...I electrostatic interactions. Crystal data: C12H17N4OS+·I– · 1.5 H2O, monoclinic,P21/c, a=12.585(2), b=25.303(5), c=12.030(2) Å, =115.15(1)°,V=3468(1) Å3,Z=8,D
c=1.606 g cm–3,R=0.045 for 3328 observed reflections.
Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP. 82156 (13 pages). 相似文献
135.
Vladislav?Tomi?i?Email author Vjekoslav?Butorac Jadranka?Viher Vladimir?Simeon 《Journal of solution chemistry》2005,34(6):613-616
The effect of temperature on the π∗←π transition band in the UV absorption spectrum of NO3−(aq) centered at ≈200 nm was studied in the temperature range 10–70 ∘C. The observed temperature independence of this band was in contrast to the significant influence of temperature on the nitrate π∗←n transition reported recently by us. However, taking into account the electronic states involved in both the transitions, it was concluded that this finding was in accordance with our previous assumption that interconversion between spectrally distinct (with respect to π∗←n band) nitrate species included the rupture/formation of hydrogen bond(s) in the hydration shell of the nitrate ion. 相似文献
136.
Syed A. Ali Mohammed A. Siddiqui and Mohammed A. Ali 《Reaction Kinetics and Catalysis Letters》2005,87(1):199-206
Summary A parametric study of catalytic reforming process in a pilot plant was carried out by varying the pressure, H2/HC ratio, and space velocity. The results show that lower aromatics and higher hydrogen yields can be accomplished by increasing
the space velocity in existing reformers, which will also result in better C5+yield. 相似文献
137.
A new crystal-engineering motif has been developed where a ditopic receptor 1 shows a novel syn-syn hydrogen-bonded polymeric supramolecular complex (Fig. 4b) (instead of a 1:1 dimeric syn-syn or polymeric syn-anti complex) giving rise to a hydrogen-bonded stair-like polymeric ribbon structure between the binding groups of the receptor pyridine amide and the carboxyl groups of the guest substrate. 相似文献
138.
139.
ABSTRACTCo-crystallization frequently employs forces such as hydrogen bonds, halogen bonds, and π-π stacking to assemble molecules in a multi-component crystal. In an effort to increase the strength of the intermolecular interaction between the anti-cholesterol drug bezafibrate (BEZA), a wastewater contaminant, and hydrogen-bond-acceptor molecules, we modified the pKa values of the acceptors. Here, we describe the first series of salts incorporating BEZA and achieve a variety of supramolecular architectures including discrete assemblies, 1D chains, tapes, and 2D sheets. We discuss exceptions to the pKa rule, and demonstrate that the presence of hydrogen-bond-donor atoms on the acceptor molecule supports salt formation. 相似文献
140.
M. V. Kirov 《Journal of Structural Chemistry》2003,44(3):420-428
A nanostructural approach to analysis of proton ordering in gas hydrate cages has been worked out within the framework of the topological model of strong and weak H-bonds. The approach involves rejection of the periodic boundary conditions, decomposition of the H-bond net into spherical layers, and two-dimensional drawing of the structure of spherical (spheroidal) fragments in the form of conjugate Schlegel diagrams. To analyze proton ordering in the spherical fragments composed of gas hydrate voids, we used the simulated annealing procedure and the correlation extension method proposed earlier. 相似文献