全文获取类型
收费全文 | 1438篇 |
免费 | 42篇 |
国内免费 | 10篇 |
专业分类
化学 | 795篇 |
晶体学 | 5篇 |
力学 | 56篇 |
数学 | 219篇 |
物理学 | 415篇 |
出版年
2021年 | 16篇 |
2020年 | 13篇 |
2019年 | 19篇 |
2018年 | 18篇 |
2017年 | 7篇 |
2016年 | 29篇 |
2015年 | 16篇 |
2014年 | 39篇 |
2013年 | 45篇 |
2012年 | 67篇 |
2011年 | 82篇 |
2010年 | 45篇 |
2009年 | 35篇 |
2008年 | 69篇 |
2007年 | 64篇 |
2006年 | 87篇 |
2005年 | 77篇 |
2004年 | 45篇 |
2003年 | 45篇 |
2002年 | 44篇 |
2001年 | 30篇 |
2000年 | 25篇 |
1999年 | 22篇 |
1998年 | 20篇 |
1997年 | 25篇 |
1996年 | 23篇 |
1995年 | 23篇 |
1994年 | 13篇 |
1993年 | 20篇 |
1992年 | 17篇 |
1991年 | 12篇 |
1990年 | 13篇 |
1989年 | 15篇 |
1988年 | 10篇 |
1987年 | 9篇 |
1985年 | 19篇 |
1984年 | 17篇 |
1983年 | 16篇 |
1982年 | 22篇 |
1981年 | 30篇 |
1980年 | 17篇 |
1979年 | 21篇 |
1978年 | 21篇 |
1977年 | 19篇 |
1976年 | 17篇 |
1975年 | 16篇 |
1974年 | 16篇 |
1973年 | 13篇 |
1971年 | 8篇 |
1969年 | 6篇 |
排序方式: 共有1490条查询结果,搜索用时 46 毫秒
41.
J. W. Petersen G. Weyer S. Damgaard H. L. Nielsen 《Zeitschrift für Physik B Condensed Matter》1980,38(4):313-326
Single crystalline and polycrystalline -tin has been implanted at room temperature with 80-keV ions of radioactive119m
Sn,119Sb, and119m
Te. The radioactive nuclei decay to the Mössbauer level of119Sn. Mössbauer spectra of the emitted 24-keV radiation have been measured for different source temperatures by resonance counting techniques. Five individual lines in the spectra are characterized mainly by their isomer shifts and Debye temperatures. From these parameters the radiogenic119Sn atoms are concluded to be located in regular substitutional and interstitial lattice sites and in defect complexes. Simple models for the defects are proposed: A Sn-vacancy pair consists of Sn atoms on (nearly) substitutional sites with a dangling bond into an adjacent vacancy. In a complex oxygen-containing defect the Sn atoms have approximately a 5s
2 configuration withp-bonds to two nearest neighbour atoms. Sn atoms, having an atomic 5s
2 5p
2 configuration and large vibrational amplitudes, are concluded to be in non-bonding regular interstitial sites. For special implantation conditions minor fractions of SnO2 molecules are formed in the bulk. The interstitial119Sn and the119Sn-vacancy pairs are proposed to represent elementary point defects in -tin. Conclusions are also drawn concerning the lattice location and the defects created in the implantation process of the implanted parent isotopes. 相似文献
42.
The influence of a partially filled conduction band on the magnetic properties of ferromagnetic semiconductors is studied within the framework of thes-f model. Allowing for magnon scattering to arbitrary order in the form of virtual electron- holecreation the magnon spectral density is derived, from which one gets magnon energies which are substantially renormalized by the presence of conduction electrons. In particular it is shown how the quasiparticle structure of the electronic excitation energies [4, 5] leads to scattering corrections in the magnon spectrum. These corrections are always negative and reduce the positive mean field part, which is proportional to the electron densityn. The calculated magnon spectrum is then used to determine the strikingn-dependence of the Curie-temperatureT
c
of Gd-doped EuO and EuS. 相似文献
43.
Preben C. Mrk John Ugelstad Jan Ole Aasen 《Journal of polymer science. Part A, Polymer chemistry》1995,33(11):1759-1765
Expressions for calculating the stationary state distribution of radicals in compartmentalized systems with a constant number of reaction loci containing an oil-soluble initiator are given. Besides pairwise formation of radicals in the particles, desorption and reabsorption, water phase termination, solubility of the initiator in the aqueous phase, and the possibility of formation of a single radical species are taken into consideration. The calculation is based on a probabilistic analysis leading to a third-order recurrence relation solved using confluent, hypergeometric Kummer functions. Some calculated curves illustrating the de-pendence of the average number of radicals per particle on various relevant parameters are included. © 1995 John Wiley & Sons, Inc. 相似文献
44.
Elhottová D Tríska J Petersen SO Santrůcková H 《Fresenius' Journal of Analytical Chemistry》2000,367(2):157-164
Application of gas chromatography-mass spectrometry (GC-MS) can significantly improve trace analyses of compounds in complex matrices from natural environments compared to gas chromatography only. A GC-MS/MS technique for determination of poly-beta-hydroxybutyrate (PHB), a bacterial storage compound, has been developed and used for analysis of two soils stored for up to 319 d, fresh samples of sewage sludge, as well as a pure culture of Bacillus megaterium. Specific derivatization of beta-hydroxybutyrate (3-OH C4:0) PHB monomer units by N-tert-butyl-dimethylsilyl-N-methyltrifluoracetamide (MTBSTFA) improved chromatographic and mass spectrometric properties of the analyte. The diagnostic fragmentation scheme of the derivates tert-butyldimethylsilyl ester and ether of beta-hydroxybutyric acid (MTBSTFA-HB) essential for the PHB identification was shown. The ion trap MS was used, therefore the scan gave the best sensitivity and with MS/MS the noise decreased, so the S/N was better and also with second fragmentation the amount of ions increased compared to SIM. The detection limit for MTBSTFA-HB by GC-MS/MS was about 10(-13) g microL(-1) of injected volume, while by GC (FID) and GC-MS (scan) it was around 10(-10) g microL(-1) of injected volume. Sensitivity of GC-MS/MS measurements of PHB in arable soil and activated sludge samples was down to 10 pg of PHB g(-1) dry matter. Comparison of MTBSTFA-HB detection in natural soil sample by GC (FID), GC-MS (scan) and by GC-MS/MS demonstrated potentials and limitations of the individual measurement techniques. 相似文献
45.
Schultz J Gottlieb DM Petersen M Nesic L Jacobsen S Søndergaard I 《Electrophoresis》2004,25(3):502-511
Methods for classification of two-dimensional (2-DE) electrophoresis gels based on multivariate data analysis are demonstrated. Two-dimensional gels of ten wheat varieties are analyzed and it is demonstrated how to classify the wheat varieties in two qualities and a method for initial screening of gels is presented. First, an approach is demonstrated in which no prior knowledge of the separated proteins is used. Alignment of the gels followed by a simple transformation of data makes it possible to analyze the gels in an automated explorative manner by principal component analysis, to determine if the gels should be further analyzed. A more detailed approach is done by analyzing spot volume lists by principal components analysis and partial least square regression. The use of spot volume data offers a mean to investigate the spot pattern and link the classified protein patterns to distinct spots on the gels for further investigation. The explorative approach in analysis of 2-D gels makes it possible, in a fast and convenient way, to screen many gels in order to determine the protein patterns that form clusters and could be selected for further examination. 相似文献
46.
Using Brion, Moser and Yamazaki's SCF LCAO MO the spin orbit splitting of the X
2
state of NO has been calculated using various potentials. Experimentally W (2
3/2) –W (2
1/2) is known to be 122 cm–1. Using an unscreened nuclear field we find a value of 328 cm–1. Inclusion of screening due to electronic repulsions reduces this value to 283 cm–1. Agreement with the experimental value may be obtained by reducing the orbital exponents in the 2 molecular orbital by 30% over the value given by Slater's rules.
Zusammenfassung Die Spin-Bahn-Aufspaltung des X 2 -Zustandes von NO wurde mit verschiedenen Potentialen unter Verwendung der SCF LCAO MOs von Brion, Moser und Yamazaki berechnet. Der experimentelle Wert für W (2 3/2) –W (2 1/2) beträgt 122 cm–1. Die Rechnung mittels eines reinen Kernfeldes liefert den Wert 328 cm–1 und unter Einschluß der Abschirmung durch die Elektronen 283 cm–1. Übereinstimmung mit dem experimentellen Wert läßt sich erzielen, wenn man den Exponenten des 2-Zustandes 30% kleiner als nach den Slater Regeln macht.
Résumé Avec les orbitals moléculaires SCF LCAO de Brion, Moses et Yamazaki, nous avons calculé le dédoublement spin-orbitale de l'état X 2 de NO. La valeur expérimentale W (2 3/2) –W (2 1/2) est 122 cm–1. Dans un champ nucléaire «sans écran» on trouve 328 cm–1. L'inclu-sion de l'effet d'écran dû aux répulsions interélectroniques réduit cette valeur à 283 cm–1. La valeur expérimentale s'obtient, si l'on réduit de 30% les exposants d'après Slater dans l'orbi-tale moléculaire 2.相似文献
47.
Ole J. Nielsen Matthew S. Johnson Timothy J. Wallington Lene K. Christensen Jesper Platz 《国际化学动力学杂志》2002,34(5):283-291
Pulse radiolysis techniques were used to measure the gas phase UV absorption spectra of the title peroxy radicals over the range 215–340 nm. By scaling to σ(CH3O2)240 nm = (4.24 ± 0.27) × 10?18, the following absorption cross sections were determined: σ(HO2)240 nm = 1.29 ± 0.16, σ(C2H5O2)240 nm = 4.71 ± 0.45, σ(CH3C(O)CH2O2)240 nm = 2.03 ± 0.22, σ(CH3C(O)CH2O2)230 nm = 2.94 ± 0.29, and σ(CH3C(O)CH2O2)310 nm = 1.31 ± 0.15 (base e, units of 10?18 cm2 molecule?1). To support the UV measurements, FTIR‐smog chamber techniques were employed to investigate the reaction of F and Cl atoms with acetone. The F atom reaction proceeds via two channels: the major channel (92% ± 3%) gives CH3C(O)CH2 radicals and HF, while the minor channel (8% ± 1%) gives CH3 radicals and CH3C(O)F. The majority (>97%) of the Cl atom reaction proceeds via H atom abstraction to give CH3C(O)CH2 radicals. The results are discussed with respect to the literature data concerning the UV absorption spectra of CH3C(O)CH2O2 and other peroxy radicals. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 283–291, 2002 相似文献
48.
The Ru(II) amido complex (PCP)Ru(CO)(PMe(3))(NHPh) (1) (PCP = 2,6-(CH(2)P(t)Bu(2))(2)C(6)H(3)) reacts with compounds that possess polar C=N, C triple bond N, or C=O bonds (e.g., nitriles, carbodiimides, or isocyanates) to produce four-membered heterometallacycles that result from nucleophilic addition of the amido nitrogen to an unsaturated carbon of the organic substrate. Based on studies of the reaction of complex 1 with acetonitrile, the transformations are suggested to proceed by dissociation of trimethylphosphine, followed by coordination of the organic substrate and then intramolecular N-C bond formation. In the presence of ROH (R = H or Me), the fluorinated amidinate complex (PCP)Ru(CO)(N(Ph)C(C(6)F(5))NH) (6) reacts with excess pentafluorobenzonitrile to produce (PCP)Ru(CO)(F)(N(H)C(C(6)F(5))NHPh) (7). The reaction with MeOH also produces o-MeOC(6)F(4)CN (>90%) and p-MeOC(6)F(4)CN (<10%). Details of the solid-state structures of (PCP)Ru(CO)(F)(N(H)C(C(6)F(5))NHPh) (7), (PCP)Ru(CO)[PhNC{NH(hx)}N(hx)] (8), (PCP)Ru(CO){N(Ph)C(NHPh)O} (9), and (PCP)Ru(CO){OC(Ph)N(Ph)} (10) are reported. 相似文献
49.
Rate constants for the reactions of OH radicals and Cl atoms with CH3ONO, C2H5ONO, n-C3H7ONO, n-C4H9ONO, and n-C5H11ONO have been determined at 298 ± 2 K and a total pressure of approximately 1 atm. The OH rate data were obtained using both the absolute rate technique of pulse radiolysis combined with kinetic spectroscopy and a relative rate method involving simultaneous measurement of the loss of the nitrite and the reference compound. The Cl rate constants were measured using the relative rate method. Values of the rate constants in units of 10?13 cm3 molecule?1 s?1 are:
When compared to rate data for the corresponding alkanes the results show that the -ONO group decreases the rate constant for H atom abstraction by the OH radical from groups bonded to the -ONO group and also decreases that for groups in the β position. Similar results were found for the reaction of Cl atoms with these compounds. The results are discussed in terms of reactivity trends. 相似文献
Relative Cl | Relative OH | Absolute OH | |
---|---|---|---|
CH3ONO | 94.4 ± 7.4 | 3.0 ± 1.0 | 2.6 ± 0.5 |
C2H5ONO | 295 ± 13 | 7.0 ± 1.5 | 7.0 ?1.1 |
n-C3H7ONO | 646 ± 58 | 11.0 ± 1.5 | 12.0 ± 0.5 |
n-C4H9ONO | 1370 ± 58 | 22.7 ± 0.8 | 27.2 ± 6.0 |
n-C5H11ONO | 2464 ± 444 | 37.4 ± 5.0 | 42.5 ± 8.0 |
50.
Analyzing a gliadin extract by matrix assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS) combined with an artificial neural network (ANN) is a suitable method for identification of wheat varieties. However, the ANN can not distinguish between all different wheat varieties. Two-dimensional polyacrylamide gel electrophoresis (2-D PAGE) was applied to three pairs of wheat varieties, which can not be classified correctly by ANN. By 2-D PAGE the varieties in the three pairs can be discriminated and these six wheat varieties can be separated from each other, which could not be separated by MALDI-TOF-MS and NN. 相似文献