全文获取类型
收费全文 | 1852篇 |
免费 | 27篇 |
国内免费 | 5篇 |
专业分类
化学 | 958篇 |
晶体学 | 18篇 |
力学 | 68篇 |
数学 | 167篇 |
物理学 | 673篇 |
出版年
2023年 | 16篇 |
2022年 | 32篇 |
2021年 | 32篇 |
2020年 | 41篇 |
2019年 | 31篇 |
2018年 | 37篇 |
2017年 | 46篇 |
2016年 | 52篇 |
2015年 | 29篇 |
2014年 | 53篇 |
2013年 | 115篇 |
2012年 | 105篇 |
2011年 | 116篇 |
2010年 | 71篇 |
2009年 | 68篇 |
2008年 | 93篇 |
2007年 | 83篇 |
2006年 | 60篇 |
2005年 | 66篇 |
2004年 | 59篇 |
2003年 | 54篇 |
2002年 | 50篇 |
2001年 | 27篇 |
2000年 | 31篇 |
1999年 | 36篇 |
1998年 | 18篇 |
1997年 | 19篇 |
1996年 | 21篇 |
1995年 | 13篇 |
1994年 | 23篇 |
1993年 | 31篇 |
1992年 | 28篇 |
1991年 | 22篇 |
1990年 | 14篇 |
1989年 | 23篇 |
1988年 | 15篇 |
1987年 | 16篇 |
1986年 | 14篇 |
1985年 | 20篇 |
1984年 | 13篇 |
1983年 | 13篇 |
1982年 | 13篇 |
1981年 | 15篇 |
1979年 | 12篇 |
1978年 | 19篇 |
1977年 | 12篇 |
1976年 | 12篇 |
1975年 | 12篇 |
1974年 | 14篇 |
1973年 | 10篇 |
排序方式: 共有1884条查询结果,搜索用时 0 毫秒
31.
Three-dimensional mesoporous titanosilicates prepared by modified sol-gel method: Ideal gold catalyst supports for enhanced propene epoxidation 总被引:2,自引:0,他引:2
Sinha AK Seelan S Okumura M Akita T Tsubota S Haruta M 《The journal of physical chemistry. B》2005,109(9):3956-3965
Mesoporous titanosilicates with 1-12 mol % Ti content and with three-dimensional wormhole-like mesoporosity are prepared by a modified sol-gel technique. Sorption analysis shows that there is little change in the surface properties with increasing Ti concentration in the samples, implying that Ti atoms either are well-dispersed on the walls of the silica matrix or are present inside the framework with no pore blocking effect. Spectroscopic analysis shows that the Ti atoms are atomically dispersed in the silica matrix even at very high Ti concentration and there is no observable Ti aggregate (anatase) present in the samples. These titanosilicate samples after Au deposition followed by trimethylsilylation (for enhanced hydrophobicity) are highly efficient catalysts for vapor-phase propene epoxidation using O2 and H2. It was possible to achieve commercially desirable performance with about 7% propene conversion, >90% propene oxide selectivity, and about 40% hydrogen efficiency. 相似文献
32.
Michael J. Beam Jeannette Schulz Anvita Sinha Pamela Collins Susan Hallenbeck Michael Kustin 《Journal of heterocyclic chemistry》1989,26(2):521-524
Notwithstanding its tendency toward air oxidation in solution, 2-hydrazinobenzothiazole I reacted with aromatic aldehydes in ethanol to give the corresponding hydrazones III-XV in high yields and analytical purity. In related examples, acylation took place under similar conditions to produce hydrazides XVI-XX . The near-infrared bands of the absorption spectra of the araldehyde hydrazones have been associated with charge transfer and appeared to correlate with structural elements of the compounds in a way suggesting that the charge transfer was intermolecular. 相似文献
33.
Using the Wigner-Kirkwood expansion and bare Lennard-Jones (LJ) (12-6) potential, an effectiveLJ potential is derived, which includes the quantum effects through the expressions of the effective diameter∂(T, λ) and well-depth
(T, λ). We use theWCA perturbation theory to calculate the free energy and pressure for theLJ and effectiveLJ potentials. Simple analytic expressions are given for the reference system and the first order correction calculated. The
results are quite good at high density. The quantum effects on the free energy and pressure are also discussed. 相似文献
34.
Arylazoimidazoles (2) are N,N-chelating ligands. The polymerization trend of the azolate system is restricted via N(1)-benzylation. The parent molecules (2), N(1)-benzylated products (3) and palladium complexes (4) were made by standard methods. The ligands (3) and complexes (4) are new. They have been characterized by elemental analysis, i.r., u.v.-vis. and high resolution 1H-n.m.r. spectral data. Redox studies were carried out by cyclic voltammetry. On complexation, azo reduction is shifted anodically. 相似文献
35.
H. K. Sinha O. K. Abou-Zied M. Ludwiczak A. Maciejewski R. P. Steer 《Chemical physics letters》1994,230(6):547-554
The S2-S0 fluorescence excitation spectra ofxanthione (XT) and azulene (AZ) complexed with 1 or 2 molecules of the C1 to C10 n-alkanes and the C1 to C6 perfluoro-n-alkanes have been measured. The 1:1 complexes exhibit microscopic solvent shifts, Δ
gn, which are larger for the alkanes than the corresponding perfluoroalkanes, despite the larger molecular polarizability of the latter. The values of Δ
gn increase monotonically with carbon number of the adduct to C10 in 1:1 n-alkane complexes with XT and to C5 in 1:1 n-alkane complexes with AZ. However, Δ
gn exhibits no further increase beyond C2 in 1:1 perfluoro-n-alkane complexes with XT and beyond C3 in 1:1 perfluoro-n-alkane complexes with AZ. The results are interpreted in terms of a model in which the n-alkanes stretch out along the long axis of the chromophore and ‘wet’ its surface whereas the perfluoro-n-alkanes with carbon numbers 3 away from the surface of the chromophore and are ‘non-wetting’. 相似文献
36.
The retroaldol-aldol isomerization of the epimeric hydroxyketones and was found to yield predominantly and , respectively, under kinetic conditions in the presence of chelating lithium cations. In hydroxylic medium is the preferred kinetic product. Under equilibration conditions and predominate. 相似文献
37.
The effect of buoyancy force on laminar boundary layer in two dimensional flow and heat transfer along a semi-infinite vertical surface, when the velocity of the on-coming stream oscillates in magnitude about a steady mean, is analysed. Two separate solutions valid for low and high frequency ranges are developed. It is found that for low frequency oscillations the phase angles of oscillatory components of skin friction and the rate of heat transfer increase as the Grashof number increases. For very high frequencies, the velocity field is of shear-wave type unaffected by the mean flow; the phase lead in the skin friction is, then, /4 and the rate of heat transfer fluctuation indicates a phase lag of /2 over that of the free stream oscillations.The authors are thankful to referee for many useful suggestions. 相似文献
38.
The structure of the local anaesthetic benzocaine was solved by direct methods and refined to anR of 0·12 for 531 observed reflections. The packing of the molecule is stabilised by N−H … O hydrogen-bonds (2–97 ?). The alkyl
chain attached to the benzene ring is intrans-trans conformation. The benzoic moiety shows a quinonoid character as found in some other local anaesthetics.
DCB contribution No. 699 相似文献
39.
(E)-4-(2',4',5'-trimethoxyphenyl)but-1,3-diene (4) and (E)-4-(2',4',5'-trimethoxyphenyl)but-1-ene (6), bioactive phenylbutanoids of Zingiber cassumunar, were synthesized exclusively with trans geometry. Treatment of methylmagnesium iodide with (E)-2',4',5'-trimethoxycinnamaldehyde (2), an oxidized product of abundantly available toxic (Z)-phenylpropanoid (1) of Acorus calamus, gave (E)-4-(2',4',5'-trimethoxyphenyl)but-3-en-2-ol (3) which upon dehydration with copper sulphate/silica gel under microwave irradiation for 3 min afforded 4 in 58% yield. Further, catalytic hydrogenation of 4 with 10% Pd/C afforded 4-(2',4',5'-trimethoxyphenyl)butane (5) which upon dehydrogenation with DDQ/SiO2 afforded hypolipidemic 6 in 54% yield. 相似文献
40.
Organoboron derivatives of biologically potent β‐enamino esters of the type [Where R = CH3(1a), C2H5 (1b), C3H7(1c) and C (CH3)3 (1d)] have been prepared by the reactions of β‐enamino esters and Phenyl boronic acid [PhB (OH)2] in 1:2 molar ratio in refluxing tetrahydrofuran (THF). All these derivatives have been characterized by physico‐chemical properties, elemental analyses and molecular weight measurements. The structures of these compounds have been proposed on the basis of IR, 1H, 13C, 11B NMR spectral data and GC‐mass spectrometry. Phenyl boronic acid, β‐enamino esters and their respective phenylboronates derivatives have been screened for the antibmicrobial activities against pathogenic bacteria (B. subtilis and E. coli) and fungi (A. niger and P. peniculosum) to access their growth inhibiting potential. In addition to this, antiandrogenic effect of Ligand, LaH2 and its boron derivative (1a) has also been tested in male albino rats. 相似文献