全文获取类型
收费全文 | 19088篇 |
免费 | 743篇 |
国内免费 | 99篇 |
专业分类
化学 | 13091篇 |
晶体学 | 120篇 |
力学 | 420篇 |
数学 | 2894篇 |
物理学 | 3405篇 |
出版年
2023年 | 122篇 |
2022年 | 172篇 |
2021年 | 269篇 |
2020年 | 377篇 |
2019年 | 397篇 |
2018年 | 234篇 |
2017年 | 236篇 |
2016年 | 600篇 |
2015年 | 556篇 |
2014年 | 644篇 |
2013年 | 1024篇 |
2012年 | 1115篇 |
2011年 | 1248篇 |
2010年 | 744篇 |
2009年 | 659篇 |
2008年 | 1035篇 |
2007年 | 1020篇 |
2006年 | 949篇 |
2005年 | 880篇 |
2004年 | 772篇 |
2003年 | 637篇 |
2002年 | 605篇 |
2001年 | 308篇 |
2000年 | 290篇 |
1999年 | 273篇 |
1998年 | 241篇 |
1997年 | 232篇 |
1996年 | 264篇 |
1995年 | 247篇 |
1994年 | 218篇 |
1993年 | 211篇 |
1992年 | 199篇 |
1991年 | 176篇 |
1990年 | 174篇 |
1989年 | 174篇 |
1988年 | 149篇 |
1987年 | 125篇 |
1986年 | 114篇 |
1985年 | 166篇 |
1984年 | 161篇 |
1983年 | 126篇 |
1982年 | 153篇 |
1981年 | 157篇 |
1980年 | 133篇 |
1979年 | 140篇 |
1978年 | 158篇 |
1977年 | 116篇 |
1976年 | 100篇 |
1975年 | 118篇 |
1974年 | 91篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
Elaref S. Ratemi Nivedita Namdev Martin S. Gibson 《Journal of heterocyclic chemistry》1993,30(6):1513-1516
3-Substituted 2(1H)-pyridones are produced from reaction of 4-(4-morpholino)-3-pentenone 1 with each of the following carbon acids: cyanoacetamide, malononitrile, cyanothioacetamide, acetylacetamide, benzoyl-acetonitrile. Reaction of ethyl 3-(4-morpholino)-2-butenoate 2 with cyanoacetamide gives the corresponding hydroxypyridone. Pyrimidines are formed by reaction of 1 and of 2 with benzamidine and with S-benzylthio-urea; in the last case, the eliminated morpholine displaces the benzylthio group to give the final product. 相似文献
72.
Dynamics of self-assembled chaining in magnetorheological fluids 总被引:1,自引:0,他引:1
Climent E Maxey MR Karniadakis GE 《Langmuir : the ACS journal of surfaces and colloids》2004,20(2):507-513
The aggregation dynamics of paramagnetic spherical particles embedded in a viscous fluid is investigated via numerical simulations using a fully coupled three-dimensional model. Particles experience simultaneously Brownian motion, dipolar magnetic attraction, and multibody hydrodynamic interactions. When the dipole strength characterizing the ratio of magnetic attraction to random diffusion exceeds a critical value, particles join together forming supraparticle structures. As time evolves, particle/chain and chain/ chain interactions lead to a continuous increase of the cluster size. The mean length of particle chains has a power-law dependence with respect to time, as predicted by the theory of diffusion-limited aggregation. Both the exponent and the characteristic time scale agree very well with the experimental results of Promislow et al. 相似文献
73.
A structural minimization procedure which converges rapidly and restricts the atomic shifts is outlined. It is implemented by adding a harmonic penalty term for the displacements of atomic positions and resetting the reference coordinates with respect to which the constraints are computed during the minimization. The resetting serves to reduce the constraint energy of the minimized structure to negligible levels. 相似文献
74.
In an extension of recently reported syntheses of the I-azaphenoxathiin nucleus as well as several 7-substituted analogs, the synthesis of several 9-substituted members of this series is now reported. In addition, the first 13C-nmr spectral evidence of an interaction between a sulfur atom and the oxygen of an ortho-nilro group which has been previously observed only in X-ray erystallographic studies is also described. The possible consequences of this interaction on the reaction pathway leading to the cyclization of the 9-substituted J-azaphenoxathiin nucleus is also presented. 相似文献
75.
Igumenova TI McDermott AE Zilm KW Martin RW Paulson EK Wand AJ 《Journal of the American Chemical Society》2004,126(21):6720-6727
Solid-state NMR 2D spectroscopy was used to correlate carbon backbone and side-chain chemical shifts for uniformly (13)C,(15)N-enriched microcrystalline ubiquitin. High applied field strengths, 800 MHz for protons, moderate proton decoupling fields, 80-100 kHz, and high magic angle sample spinning frequencies, 20 kHz, were used to narrow the most of the carbon line widths to 0.5-0.8 ppm. Homonuclear magnetization transfer was effected by matching the proton RF field to the spinning frequency, the so-called dipolar-assisted rotational resonance (DARR) (Takegoshi, K.; Nakamura, S.; Terao, T. Chem. Phys. Lett. 2001, 344, 631-637), and a mixing time of 20 ms was used to maximize the intensity of one-bond transfers between carbon atoms. This polarization transfer sequence resulted in roughly 14% transfer efficiencies for directly bonded carbon pairs and 4% transfer efficiencies for carbons separated by a third carbon. With this simple procedure, the majority of the one-bond correlations was observed with moderate transfer efficiencies, and many two-bond correlations were also observed with weaker intensities. Spin systems could be identified for more than half of the amino acid side chains, and site-specific assignments were readily possible via comparison with 400 MHz (15)N-(13)C-(13)C correlation spectroscopy (described separately). 相似文献
76.
We demonstrate that the selectivity of microchip electrophoresis separations is greatly improved by the presence of organically modified silica (Ormosil) sols in the run buffer. A negatively-charged N-(trimethoxysilylpropyl)ethylenediamine triacetic-acid (TETT)-based sol is used for improving the selectivity between nitroaromatic explosives and a methyltrimethoxysilane (MTMOS)-based sol is employed for enhancing the microchip separation of environmental pollutants, aminophenols. These sols are added to the run buffer and act as pseudostationary phases. Their presence in the run buffer changes the apparent mobility of studied solutes, and leads to a higher resolution. The observed mobilities changes reflect the interactions between the Ormosil sols and the solutes. Relevant experimental variables have been characterized and optimized. The diverse chemistry of Ormosil sols should be extremely useful for tailoring the selectivity of a wide range of electrophoresis microchip separations. 相似文献
77.
Synthesis of 2,3-dihydropyrazolo[5,1-b]thiazoles via a tandem condensation sulfur-extrusion reaction
2,3-Dihydropyrazolo[5,1-b]thiazoles 3 are the first representatives of a heterocyclic system, which are conveniently prepared by heating 3-aminorhodanines 1 with ethyl 2-bromo-3,3-diethoxypropionate ( 2 ), via a tandem condensation-sulfur extrusion reaction. 相似文献
78.
R. Sanduja G. E. Martin A. J. Weinheimer M. Alam M. B. Hossain Dick van der Helm 《Journal of heterocyclic chemistry》1984,21(3):845-848
The marine coelenterate Echinopora lamellosa (class Anthozoa, family Scleractinidae) was found to contain a number of unprecedented secondary metabolites which were isolated and identified as smilagenin (I), neodunol methyl ether (II), glycyrrhetic acid (III), 3β-acetoxyglycyrrhetic acid (IV), and 3β-acetoxy-11-deoxoglycyrrhetic acid (V). The structure of neodunol methyl ether was confirmed and its absolute configuration determined by the x-ray diffraction method. 相似文献
79.
Marie-Lise Bourguet-Kondracki Marie-Th r se Martin Mich le Guyot 《Tetrahedron letters》1992,33(52):8079-8080
Smenoqualone, a novel quinonic terpenoid with a rearranged drimane skeleton was isolated from a marine sponge Smenospongia sp. The stereostructure was determined by detailed analyses of 1H and 13C NMR spectra, 1H-1H COSY, 1H-13C correlations via HMQC, HMBC and NOE difference NMR experiments. 相似文献
80.
Summary Thermal field-flow fractionation separates polymers with high selectivity according to their Soret coefficient,S
τ, hence, according to their molar mass, and therefore consitutes an efficeint physicochemical tool for the determination of
the Soret coefficient of a given polymer in the carrier liquid from its retention time. However, the polymer concentration
in the sample influences the retention time and, hence, the value ofS
τ derived from it. An experimental study of the influence of sample concentration on retention,S
τ, and peak shape was performed for the polystyrene-decalin system over a relatively large temperature domain and for various
molar masses.
It is found that the retention time and the value ofS
τ increase with increasing sample concentration, the more so as the cold wall temperature is lower. This appears to be in contradiction
with the general non-equilibrium thermodynamic expression derived for polymer-solvent systems with positive second virial
coefficients, such as the present system over the temperature range investigated. There seems to be a temperature for which
the dependence ofS
τ on sample concentration vanishes. This temperature is about 375 K for the polystyrene-decalin system. As the sample concentration
increases, the peak barycentre and the standard deviation increases. As the peaks are fronting, the skewness is negative and
becomes more negative as the sample concentration increases. The peak skewness appears to be a good indicator of the onset
of sample concentration effects. The threshold concentration, for which these effects begin to become significant, decreases
with increasing molar mass. 相似文献