全文获取类型
收费全文 | 46435篇 |
免费 | 1290篇 |
国内免费 | 13篇 |
专业分类
化学 | 28148篇 |
晶体学 | 238篇 |
力学 | 758篇 |
综合类 | 1篇 |
数学 | 8749篇 |
物理学 | 9844篇 |
出版年
2023年 | 332篇 |
2022年 | 283篇 |
2021年 | 457篇 |
2020年 | 665篇 |
2019年 | 607篇 |
2018年 | 950篇 |
2017年 | 869篇 |
2016年 | 1682篇 |
2015年 | 1391篇 |
2014年 | 1346篇 |
2013年 | 3032篇 |
2012年 | 2870篇 |
2011年 | 2686篇 |
2010年 | 1797篇 |
2009年 | 1497篇 |
2008年 | 2365篇 |
2007年 | 2142篇 |
2006年 | 1921篇 |
2005年 | 1972篇 |
2004年 | 1704篇 |
2003年 | 1418篇 |
2002年 | 1230篇 |
2001年 | 949篇 |
2000年 | 951篇 |
1999年 | 660篇 |
1998年 | 510篇 |
1997年 | 431篇 |
1996年 | 574篇 |
1995年 | 409篇 |
1994年 | 483篇 |
1993年 | 440篇 |
1992年 | 468篇 |
1991年 | 394篇 |
1990年 | 443篇 |
1989年 | 360篇 |
1988年 | 367篇 |
1987年 | 332篇 |
1986年 | 321篇 |
1985年 | 447篇 |
1984年 | 411篇 |
1983年 | 324篇 |
1982年 | 325篇 |
1981年 | 341篇 |
1980年 | 279篇 |
1979年 | 272篇 |
1978年 | 270篇 |
1977年 | 260篇 |
1976年 | 277篇 |
1974年 | 252篇 |
1973年 | 263篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
991.
L Fišera U. A. R. Al-Timari P. Ertl N. Prónayová 《Monatshefte für Chemie / Chemical Monthly》1993,124(10):1019-1029
Summary Nitrones2 derived fromD-glucose oxime and benzaldehydes without employing any protection of hydroxyl group were isolated in pure state. The 1,3-dipolar cycloaddition of2 to N-arylmaleimides gave predominantly theanti isoxazolidines3 and was rationalized byZ/E isomerization of N-glycosylnitrones2. The structure and steric configuration of the products have been assigned on the basis of1H- and13C-NMR spectroscopy. AM1 calculations of the nitrones and MM2 calculations of the adducts were performed.
Darstellung und Stereoselektivität der 1,3-dipolaren Cycloaddition vonD-Glucose-abgeleiteten Nitronen an N-Arylmaleimiden
Zusammenfassung Die Nitrone2 wurden ausD-Glucoseoxim und Benzaldehyden ohne Schutz von Hydroxylgruppen in reinem Zustand erhalten. Die 1,3-dipolare Cycloaddition von2 an N-Arylmaleimiden ergab bevorzugt dieanti-Isoxazolidine3; dies wurde über eineZ/E-Isomerisierung der N-Glycosylnitrone2 rationalisiert. Struktur und Stereochemie wurden auf Basis von1H- und13C-NMR-Spektroskopie ermittelt. Außerdem wurden AM1-Berechnungen an den Nitronen und MM2-Rechnungen an den Addukten ausgeführt.相似文献
992.
1,3-Cyclopentanedione bis(4-methylthiosemicarbazone) monohydrochloride produces colored solutions with chlorate ions in strongly acid medium. The yellow color obtained has been used to propose a spectrophotometric method of C103? determination in the concentration range 0.5–6.0 ppm (molar absorptivity 1.26 × 104 liters mol?1 cm?1 at a wavelength of 397 nm). 相似文献
993.
A. Mañanes M. Membrado J. Sañudo A. F. Pacheco L. C. Balbás 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1991,19(4):55-58
An analytic expression for the total energy of metallic clusters composed ofN identical atoms of valencev and with net chargeQ is obtained by means of a variational solution of the Thomas-Fermi-Weizsäcker energy density functional within the spherical jellium model. The minimum energy is given as an expansion in decreasing powers of the cluster radiusR=r s Z 1/3, withZ=vN andr s the radius per electron of the bulk metal. The coefficients are obtained as functions ofr s . Terms of volume (R 3), surface (R 2), curvature (R), constant (R 0), (1/R) and (1/R 2) are clearly separated in the formula, as well as the different contributions (kinetic, coulombic and exchange-correlation) to each of them. The asymptotic values (R→∞) for the work functions,W(r s ), and surface energies σ(r s ), are compared to analogous semiclassical and Kohn-Sham calculations of jellium-like surfaces and to the experimental values. The size dependent behaviour of chemical potentials, μ(R), electron affinities,AF(R), and ionization potentials,IP(R), are easily obtained for any kind of metallic clusters. In particular we discuss the Coulomb and quantum corrections to the coefficients β, δ in the asymptotic formulae:IP?W+β/R andAF?W+δ/R. 相似文献
994.
Summary The retention, selectivity and elution order of fluorescent 1,N6-etheno derivatives of diadenosine polyphosphates and their enzymatic degradation products on octadecyl and phenyl-bonded
silica columns have been studied as a function of mobile phase pH, ionic strength and organic modifier content. Good separations
of the compounds of interest were achieved using mobile phases of around 0.1M potassium phosphate buffers at neutral pH containing
approximately 10% methanol or 4% acetonitrile for C18 columns and 5% methanol or 1.5% acetonitrile for phenyl columns. The data obtained were used to establish isocratic assays
for diadenosine polyphosphate cleaving activities from chromaffin cells using Di(1,N6-ethenoadenosine) polyphosphates as fluorogenic substrate analogues followed by fluorescence detection. 相似文献
995.
A flow cell with a radial distribution of four all-solid-state ion selective electrodes (ISEs), or alternatively three ISEs and one reference electrode, was designed and optimized for mass production. The radial distribution of the electrodes reduces the cell volume and is expected to minimize cross-contamination between different electrodes. Two different cell prototypes were developed and tested for all-solid-state K+-ISEs based on a solvent polymeric ion-selective membrane (ISM) and a conducting polymer, poly(3,4-ethylenedioxythiophene), as solid internal contact. In the first prototype, PEDOT was electropolymerized from an aqueous solution of the monomer and the doping ion salt, sodium polystyrenesulfonate (NaPSS). The second prototype employed an aqueous dispersion of PEDOT(PSS) that is commercially available (Baytron P, Bayer AG). Compared to electrochemical synthesis, solution casting of the polymer dispersion was found to be a more advantageous method to deposit the conducting polymer layer aiming at mass production. The resulting prototypes of the flow cell had a small volume (ca. 17-37 μl), which makes them suitable for application in clinical analysis. 相似文献
996.
We study the nitrogen binding curve with the density matrix renormalization group (DMRG) and single-reference and multireference coupled cluster (CC) theory. Our DMRG calculations use up to 4000 states and our single-reference CC calculations include up to full connected hextuple excitations. Using the DMRG, we compute an all-electron benchmark nitrogen binding curve, at the polarized, valence double-zeta level (28 basis functions), with an estimated accuracy of 0.03 mEh. We also assess the performance of more approximate DMRG and CC theories across the nitrogen curve. We provide an analysis of the relative strengths and merits of the DMRG and CC theory under different correlation conditions. 相似文献
997.
K. Rybáček L. Wilhelmová M. Tomášek 《Journal of Radioanalytical and Nuclear Chemistry》1994,186(3):245-255
Radiocesium in ground layer atmospheric aerosol and fallout in Prague has been examined. After a decline in 1986–1988, controlled by a sum of two negative exponentials,137Cs aerosol concentration reached a constant level based on an equilibrium between its deposition and resuspension. Deposition velocity was compared to that of7Be and226Ra. It confirmed the supposed source of137Cs as resuspension from the ground. Resuspension factor of the order of magnitude of 10–9 was determined, reminding similar values found earlier in Prague as well as those found in Munich. It also agrees well with the USAEC resuspension model. Solubility of137Cs was measured in combined wet and dry fallout. The average undissolved fraction of137Cs was found to be about 70% which can be explained by the conditions of the137Cs aerosol formation in Chernobyl. 相似文献
998.
999.
Vidal JL Vega AB Arrebola FJ González-Rodríguez MJ Sánchez MC Frenich AG 《Rapid communications in mass spectrometry : RCM》2003,17(18):2099-2106
A fast method for the determination of eight organotin compounds (OTs), monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), tetrabutyltin (TeBT), monophenyltin (MPhT), diphenyltin (DPhT), triphenyltin (TPhT) and tetraphenyltin (TePhT), in water, sediments and mussels, was developed using low-pressure gas chromatography/tandem mass spectrometry (LPGC/MS/MS). The method is based on sodium diethyldithiocarbamate (DDTC) complexation of the ionic organotins, followed by extraction of the target matrices and derivatization by a Grignard reagent, as described in a previously published method for water samples. Solid-phase extraction was selected as extraction method from water samples after comparison with liquid-liquid extraction, but extraction of the OTs from sediment and mussel samples was performed using toluene. Matrix-matched calibration standards were used to minimize matrix effects. The analytical process was validated by the analysis of spiked blank samples. Performance characteristics such as linearity, detection limit (LOD), quantitation limit (LOQ), precision, and recovery were determined. Recoveries of OTs in spiked matrices ranged from 86-108% in water and from 78-110% in sediments and mussels, with precision values lower than 18%. Detection limits ranged from 0.1-9.6 ng L(-1) in water, and 0.03-6.10 microg kg(-1) in the other matrices. The present implementation of LPGC rather than conventional capillary GC permitted use of large-volume injection and reduced analysis time by a factor of two. The proposed methodology was applied to the determination of OTs in real samples of water, marine sediments and mussels from the west coast of the Mediterranean Sea (Spain). 相似文献
1000.
M. Šícha J. Glosík J. Pavlík Z. Němeček J. Šafránková M. Tichý 《Czechoslovak Journal of Physics》1983,33(11):1226-1229
Conclusion In the present report an attempt has been made to use the second derivative method for measurements of the electron distribution function in flowing afterglow plasma. It has been shown that using the cross-correlation technique, this method seems to be a useful tool for flowing afterglow plasma investigation. 相似文献