全文获取类型
收费全文 | 9121篇 |
免费 | 1419篇 |
国内免费 | 1413篇 |
专业分类
化学 | 10139篇 |
晶体学 | 341篇 |
力学 | 35篇 |
综合类 | 43篇 |
数学 | 12篇 |
物理学 | 1383篇 |
出版年
2024年 | 25篇 |
2023年 | 135篇 |
2022年 | 298篇 |
2021年 | 365篇 |
2020年 | 531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 15 毫秒
171.
Single crystals of potassium iron hydrogen phosphate, KFe3(HPO4)2(H2PO4)6 · 4 H2O, were prepared hydrothermally by heating a mixture of Fe2O3, H3PO4 and K2CO3 with a small amount of water. It crystallizes monoclinic, space group C2/c (N° 15 Int. Tab.) with Z = 4 and a = 1701(2), b = 960.4(5), c = 1750(1) pm, β = 90.88(7)°. The crystal structure was solved by using 1716 unique reflections F0 > 4σ(F0) with a final wR2 value of 0.126 (SHELXL-93). The main feature of the crystal structure are layers formed by PO4-tetrahedra around the FeO6-octahedra parallel to (001). K+ and H2O molecules connect these layers. Effective Coordination Numbers (ECoN), Mean Fictive Ionic Radii (MEFIR), Charge Distribution (CHARDI) and the Madelung Part of Lattice Energy (MAPLE) are calculated for the title compound. The existence of hydrogen bonds is confirmed by these calculations. 相似文献
172.
Conformational stability of G-quartets found in telomeric DNA quadruplex structures requires the coordination of monovalent ions. Here, an extensive Hartree-Fock and density functional theory analysis of the energetically favored position of Li+, Na+, and K+ ions is presented. The calculations show that at quartet-quartet distances observed in DNA quadruplex structures (3.3 A), the Li+ and Na+ ions favor positions of 0.55 and 0.95 A outside the plane of the G-quartet, respectively. The larger K+ ion prefers a central position between successive G-quartets. The energy barrier separating the minima in the quartet-ion-quartet model are much smaller for the Li+ and Na+ ions compared with the K+ ion; this suggests that K+ ions will not move as freely through the central channel of the DNA quadruplex. Spin-spin coupling constants and isotropic chemical shifts in G-quartets extracted from crystal structures of K+- and Na+-coordinated DNA quadruplexes were calculated with B3LYP/6-311G(d). The results show that the sizes of the trans-hydrogen-bond couplings are influenced primarily by the hydrogen bond geometry and only slightly by the presence of the ion. The calculations show that the R(N2N7) distance of the N2-H2...N7 hydrogen bond is characterized by strong correlations to both the chemical shifts of the donor group atoms and the (h2)J(N2N7) couplings. In contrast, weaker correlations between the (h3)J(N1C6') couplings and single geometric factors related to the N1-H1...O6=C6 hydrogen bond are observed. As such, deriving geometric information on the hydrogen bond through the use of trans-hydrogen-bond couplings and chemical shifts is more complex for the N1-H1...O6=C6 hydrogen bond than for the N2-H2...N7 moiety. The computed trans-hydrogen-bond couplings are shown to correlate with the experimentally determined couplings. However, the experimental values do not show such strong geometric dependencies. 相似文献
173.
McDowell SA 《Journal of computational chemistry》2003,24(10):1201-1207
A theoretical study of the properties of the linear LiH dimer was undertaken. In this dimer, an unusual type of hydrogen bonding (termed "inverse" hydrogen bonding by some authors), which involves the hydrogen bonded molecule acting as an electron donor (rather than as a proton donor), is exhibited. The optimized geometry, dipole moment, interaction energy, atomic charges, harmonic vibrational frequencies, and frequency shifts for the dimer are computed at the SCF, MP2, and QCISD levels of theory using mainly a 6-31++G(d,p) basis set. We also examined the relative stability of the mono-deuterated isotopomers of linear (LiH)(2), i.e., Li-H...Li-D and Li-D...Li-H. Analysis of the normal vibrational modes, changes in the partial atomic charges, and changes in the vibrational frequencies of LiH on complexation were used to gain insight into the bonding and properties of the linear LiH dimer and its isotopomers. 相似文献
174.
运用量子化学从头算方法, 在MP2/6-311++G(d,p), MP2/6-311++G(2df,2p), MP2/6-311++G(3df,3pd)和QCISD/6-311++G(d,p)水平上, 研究了CH3F, CH3Cl和CH3Br作为质子给体与Cl-, Br-作为质子接受体形成的氢键CH3…Y. 计算结果表明: 6种复合物中C—H键收缩, 伸缩振动频率增大, 形成蓝移氢键. 分子中原子(Atoms in Molecules, AIM)分析表明, 这些复合物的电子密度拓扑性质与普通氢键有着本质的不同, 在Y…H之间不存在键临界点, 而在Y与C之间存在键临界点, 因此这些相互作用严格地不能称为氢键. 自然键轨道(Natural bond orbital, NBO)分析表明, 在这些复合物中弯曲的CH…Y的特殊结构使得分子间超共轭n(Y)®σ*(C—H)减小到可以忽略; 质子接受体的电子密度没有转移到σ*(C—H)上, 而是转移到了σ*(C—X) (X=F, Cl, Br)上; 存在一定程度的重杂化; 分子内超共轭相互作用减小使得σ*(C—H)的电子密度减少. 这些因素共同导致C—H伸缩振动频率的蓝移. 相似文献
175.
Studies of the Methane Steam Reforming Reaction at High Pressure in a Ceramic Membrane Reactor
下载免费PDF全文
![点击此处可从《天然气化学杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
The effects of temperature and pressure on the steam reforming of methane 3H2+CO) were investigated in a membrane reactor (MR) with a hydrogen permeable membrane. The studies used a novel silica-based membrane prepared by using the chemical vapor deposition (CVD) technique with a permeance for H2 of 6.0×l0-8 mol·m-2·s-1·Pa-1 at 923 K. The results in a packed-bed reactor (PBR) were compared to those of the membrane reactor at various temperatures (773-923 K) and pressures (1-20 atm, 101.3-2026.5 kPa) using a commercial Ni/MgAl2O4 catalyst. The conversion of methane was improved significantly in the MR by the countercurrent removal of hydrogen at all temperatures and allowed product yields higher than the equilibrium to be obtained. Pressure had a positive effect on the hydrogen yield because of the increase in driving force for the permeance of hydrogen. The yield of hydrogen increased with pressure and reached a value of 73×10-6 mol·g-1·s-1 at 2026.5 kPa and 923 K which was higher by 108% than the value of 35×10-6 mol·g-1·s-1 obtained for the equilibrium yield. The results obtained with the silica-based membrane were similar to those obtained with various other membranes as reported in the literature. 相似文献
176.
Mostafa M. Amini Amirreza Azadmher Hamid Reza Bijanzadeh Nasser Hadipour 《Journal of inclusion phenomena and macrocyclic chemistry》2006,54(1-2):77-80
Behavior of {[(CH3)2SnCl2·H2O]2·18-crown-6}n in solution have been investigated by HMBC NMR. The results show that coordination of water to tin containing species and
its hydrogen bonding to crown ether remains intact in non-coordinating solvent in contrast to coordinating solvent. H-NMR
reveals that the chemical shift of water in complex varies by solvent of crystallization. 相似文献
177.
本文提出了一个硫酸中间盐子循环用以代替分解水制氢的KNO_3-I_2混合循环中的电解反应,从而使原混合循环变为一个纯热化学循环。 相似文献
178.
The complexation of tetramethylresorc[4]arene with primary and secondary amines in acetonitrile was investigated spectrophotometrically. The stoichiometry of the complexes formed was shown to depend on the amine concentration. Based on the proposed complexation models, the formation constants of the complexes as well as their thermodynamical parameters were determined and discussed. Depending on the amine concentration, two types of solid complexes of tetramethylresorc[4]arene with amines were obtained. The composition of these complexes was confirmed by 1H NMR. 相似文献
179.
Yu. A. Zolotarev E. V. Laskatelev V. S. Kozik E. M. Dorokhova S. G. Rozenberg Yu. A. Borisov N. F. Myasoedov 《Russian Chemical Bulletin》1997,46(10):1726-1729
The solid-phase catalytic hydrogenation of (R-4tert-butoxy-Δ1-pyrroline-2-carboxylic) acid under the action of hydrogen spillover was studied. The reaction proceeds stereoselectively
with the predominant formation of thel-amino acid. The configuration of the asymmetric center formed is determined by that of the asymmetric C(4) atom. The major
portion of the isotope label is incorporated into the allylic C(3) and C(5) positions, and the β-H atoms are more mobile.
Using quantum-chemical calculations, the geometric structure of thel-hydroxyproline molecule was calculated, and the spin-spin coupling constants for this tritium-labeled amino acid were determined.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1820–1823, October, 1997. 相似文献
180.
V.?I.?VigdorovichEmail author L.?E.?Tsygankova O.?V.?Alekhina T.?P.?D'yachkova 《Russian Journal of Electrochemistry》2005,41(10):1046-1052
The effect of thiourea (0.5–10 mM) on the kinetics of the hydrogen evolution reaction (HER) at iron and the hydrogen transport through a steel membrane out of ethylene glycol (containing 2 and 10 wt % H2O) and aqueous solutions containing HCl (0.1–0.99 M) with a constant ionic strength equal to unity is studied in parallel experiments. The presence of 0.5 mM of thiourea in the solutions raises the overvoltage of hydrogen evolution, while a subsequent increase in its concentration does not effect the HER kinetics. The dependence of the flux of hydrogen diffusion through the membrane on the thiourea content passes through a maximum. 相似文献