全文获取类型
收费全文 | 5073篇 |
免费 | 119篇 |
国内免费 | 6篇 |
专业分类
化学 | 4002篇 |
晶体学 | 7篇 |
力学 | 44篇 |
数学 | 646篇 |
物理学 | 499篇 |
出版年
2019年 | 42篇 |
2018年 | 36篇 |
2017年 | 29篇 |
2016年 | 105篇 |
2015年 | 65篇 |
2014年 | 103篇 |
2013年 | 149篇 |
2012年 | 155篇 |
2011年 | 164篇 |
2010年 | 137篇 |
2009年 | 121篇 |
2008年 | 168篇 |
2007年 | 162篇 |
2006年 | 182篇 |
2005年 | 206篇 |
2004年 | 173篇 |
2003年 | 142篇 |
2002年 | 181篇 |
2001年 | 115篇 |
2000年 | 110篇 |
1999年 | 106篇 |
1998年 | 86篇 |
1997年 | 98篇 |
1996年 | 100篇 |
1995年 | 80篇 |
1994年 | 89篇 |
1993年 | 91篇 |
1992年 | 94篇 |
1991年 | 92篇 |
1990年 | 72篇 |
1989年 | 89篇 |
1988年 | 87篇 |
1987年 | 84篇 |
1986年 | 71篇 |
1985年 | 97篇 |
1984年 | 113篇 |
1983年 | 63篇 |
1982年 | 88篇 |
1981年 | 115篇 |
1980年 | 84篇 |
1979年 | 101篇 |
1978年 | 70篇 |
1977年 | 68篇 |
1976年 | 61篇 |
1975年 | 77篇 |
1974年 | 51篇 |
1973年 | 70篇 |
1972年 | 52篇 |
1971年 | 43篇 |
1970年 | 52篇 |
排序方式: 共有5198条查询结果,搜索用时 15 毫秒
101.
Günther Kraft Dieter Lindenberger Heinz Beck 《Fresenius' Journal of Analytical Chemistry》1976,282(2):119-121
Zusammenfassung Die Intensität des flammenabsorptionsspektrometrischen Cr-Signals hängt in einer sehr komplexen Weise von der Wertigkeit des Chroms und der Flammentemperatur ab. Ferner ist ein ausgeprägter Kalium-Einfluß vorhanden. Alle diese Schwierigkeiten können am besten dadurch eliminiert werden, daß in der Lachgasflamme gearbeitet und die Analysenlösung mit einer höheren K-Konzentration gepuffert wird.
Effect of valency on the determination of chromium by flame absorption spectrometry
The intensity of the chromium signal in AAS depends in a very complex manner strongly on the valency of the Cr and the flame temperature. It is furthermore influenced by potassium, if present. The best way to overcome all these interferences is to use the nitrous oxide flame and to buffer the solution with a higher concentration of potassium.相似文献
102.
Ramanan Krishnamoorti William W. Graessley Achim Zirkel Dieter Richter Nikos Hadjichristidis Lewis J. Fetters David J. Lohse 《Journal of Polymer Science.Polymer Physics》2002,40(16):1768-1776
The unperturbed chain dimensions (〈R2〉o/M) of cis/trans‐1,4‐polyisoprene, a near‐atactic poly(methyl methacrylate), and atactic polyolefins were measured as a function of temperature in the melt state via small‐angle neutron scattering (SANS). The polyolefinic materials were derived from polydienes or polystyrene via hydrogenation or deuteration and represent structures not encountered commercially. The parent polymers were prepared via lithium‐based anionic polymerizations in cyclohexane with, in some cases, a polymer microstructure modifier present. The polyolefins retained the near‐monodisperse molecular weight distributions exhibited by the precursor materials. The melt SANS‐based chain dimension data allowed the evaluation of the temperature coefficients [dln 〈R2〉o/dT(κ)] for these polymers. The evaluated polymers obeyed the packing length (p)‐based expressions of the plateau modulus, G = kT/np3 (MPa), and the entanglement molecular weight, Me = ρNanp3 (g mol?1), where nt denotes the number (~21) of entanglement strands in a cube with the dimensions of the reptation tube diameter (dt) and ρ is the chain density. The product np3 is the displaced volume (Ve) of an entanglement that is also expressible as pd or kT/G. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1768–1776, 2002 相似文献
103.
The primary all-trans to 13-cis chromophore isomerization of the light driven chloride pump halorhodopsin has been studied by means of transient absorption spectroscopy in the visible and mid-infrared regime at a time resolution of better than 100 and 220 fs, respectively. The picosecond vibrational dynamics are dominated by two time constants, i.e., 2 and 7.7 ps in accordance with the biphasic decay of the retinal excited electronic state and electronic ground state formation with 1.5 and 6.6 ps. The transient vibrational spectra of the participating electronic states strongly suggest the existence of two distinct S1 populations as a result of an early branching reaction. It is shown that the 13-cis product is formed with the fast time constant, whereas the all-trans educt state is repopulated via both time constants. Concomitant protein dynamics are indicated by spectral changes on a similar time scale in the amide region. 相似文献
104.
105.
Qian-Feng Zhang Richard D. Adams Dieter Fenske 《Journal of inclusion phenomena and macrocyclic chemistry》2005,53(3):275-279
The self-assemblies of two pyrogallol[4]arenes held together by 48 intermolecular hydrogen bonds stably associate in the form of spherical hexameric capsules. The molecular structures of two hexameric capsules with large interior space were analyzed by single crystal X-ray crystallography. 相似文献
106.
Synthesis and Crystal Structure of the Nitrido Complex [Na-15-crown-5]2[MoNF4]2 · 2 CH3CN The title compound is synthesized by the reaction of [MoCl4(NSCl)]2 with excess NaF in boiling acetonitrile in the presence of the crown ether 15-crown-5. [Na-15-crown-5]2[MoNF4]2 · 2 CH3CN forms yellow crystals, which were characterized by an X-ray structure determination. Space group P1 , Z = 1. Lattice dimensions at ?90°C: a = 855.5, b = 1 069.9, C = 1 143.5 pm, α = 105.71°, β = 95.29°, γ = 102.25° (4 096 independent observed reflexions, R = 0.039). Short Na…?F contacts of 234 pm with the four axial fluoro ligands of the dimeric anion [MoNF4]22? allow formulation of a triple ion. The centrosymmetric anion is dimerized by bent fluoro bridges with Mo? F distances of 198 and 245 pm. The long Mo? F distances of the MoF2Mo ring are in transposition to the nitrido ligands, the bond lengths of which (165 pm) correspond to triple bonds. 相似文献
107.
Dieter Sellmann 《Angewandte Chemie (International ed. in English)》1974,13(10):639-649
Compared to the large number of CO complexes, N2 complexes are still rare. In certain cases they may be formed from N2 gas and metal compounds under physiological conditions, and are therefore frequently considered as possible intermediates in N2 assimilation. However, despite numerous attempts it has not yet been possible to reduce the N2 ligand of a fully characterized N2 complex to NH3. This negative evidence recently prompted the discoverers of the first dinitrogen complex, the [Ru(NH3)5N2]2⊕ ion isolated in 1965, to express doubt whether such complexes really do play a part in the enzymatic reduction of N2. The latest findings nevertheless incline toward a somewhat more optimistic view. Thus, the mild partial reduction of the N2 ligand in metal complexes with inert gas configuration, hitherto considered nonreducible, justifies the hope that a suitable system permitting the catalytic reduction of molecular nitrogen under normal conditions will one day be found. Even apart from any technical potential, the N2 complexes constitute an interesting chapter of modern inorganic chemistry. 相似文献
108.
Guo R Liang X Chen J Wu W Zhang Q Martens D Kettrup A 《Journal of chromatography. A》2004,1035(1):31-36
To avoid the limitation of the widely used prediction methods of soil organic carbon partition coefficients (KOC) from hydrophobic parameters, e.g., the n-octanol/water partition coefficients (KOW) and the reversed phase high performance liquid chromatographic (RP-HPLC) retention factors, the soil column liquid chromatographic (SCLC) method was developed for KOC prediction. The real soils were used as the packing materials of RP-HPLC columns, and the correlations between the retention factors of organic compounds on soil columns (ksoil) and KOC measured by batch equilibrium method were studied. Good correlations were achieved between ksoil and KOC for three types of soils with different properties. All the square of the correlation coefficients (R2) of the linear regression between log ksoil and log KOC were higher than 0.89 with standard deviations of less than 0.21. In addition, the prediction of KOC from KOW and the RP-HPLC retention factors on cyanopropyl (CN) stationary phase (kCN) was comparatively evaluated for the three types of soils. The results show that the prediction of KOC from kCN and KOW is only applicable to some specific types of soils. The results obtained in the present study proved that the SCLC method is appropriate for the KOC prediction for different types of soils, however the applicability of using hydrophobic parameters to predict KOC largely depends on the properties of soil concerned. 相似文献
109.
The perfluoroalkyliodine (V) fluorides CF3IF4 and CF3IOF2 react with many alcohols, acids and anhydrids in solution to give fluorine exchange. In all these reactions we observed equilibria, e.g.: These reactions depend strongly on the kind of the reacting compounds and on the conditions, and they can be followed by n.m.r. spectroscopy. When trying to isolate the new derivatives always decomposition takes place.These reactions, the n.m.r. spectra, the properties of the new compounds and the decomposition reactions will be reported. 相似文献
110.
An unconventional SCF method for calculations on large molecules with more than 100 basis functions is described. Storage problems which arise in conventional SCF schemes when storing more than 107 integrals are avoided by repeated calculation of integrals. The resulting increase in computational times is kept at a reasonable level by (a) improving the initial guess, (b) accelerating convergence, (c) employing a recursive construction of the Fock matrix, and (d) eliminating insignificant integrals from the calculation by a density-weighted cutoff criterion. Sample calculations show that, compared with conventional SCF calculations, computational times increase by 25%–75% depending on the basis set and the shape of the molecule. 相似文献