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81.
Christian Grugel Manfred Lehnig Wilhelm P. Neumann Josef Sauer 《Tetrahedron letters》1980,21(3):273-276
Tristannanes used as photochemical precursors for the synthesis of organic compounds react via triplet states followed by homolytic CSn and SnSn bond scission. 相似文献
82.
α-Diazo phosphonates with a conjugated 1,3-diene unit are synthesised by the Bamford-Stevens reaction ( →→). They undergo [4+2]-cycloadditions with the dienophile to form the tetrahydrotriazolopyridazines , which possess an unchanged diazo group. In contrast, dimethyl acetylenedicarboxylate () reacts exclusively with the diazo dipole of to yield the 3H-pyrazoles , which rearrange to by sigmatropic PO-shifts and hydrolyse to form . The diazo compound isomerises to the pyrazole when heated in benzene. 相似文献
83.
Loss of vinyl alcohol from 1-amino-3-aryloxy-2-propanols under electron impact Under electron impact compounds of type 1 (see Scheme 1) split off 44 mass units from the molecular ion. This unusual reaction was studied using derivatives and deuterium labelled compounds. It could be demonstrated that for this fragmentation reaction 16 is the important structural feature from which H2(C3)?C(2)HOH (44 mass units) is lost. The preferred reaction mechanism involves a transition state in which four members of the side chain are involved (Scheme 2, mechanism 2). 相似文献
84.
Contribution to the mass spectrometry of substituted α,ω-alkane diamines The main mass spectral fragmentation pattern of compounds of types 1 to 4 is discussed. After loss of C6H5 · CH2 · from the molecular ion the acid correspondin to the N,N-disubstituted residue is splitted off. The mechanism of this fragmentation reaction depends on the member of CH2-groups between the two nitrogen atoms (Schemes 1 and 3) and on the substitution pattern of both nitrogens (Scheme 2). 相似文献
85.
Monwar M Oh SJ Rinaldi PL McCord EF Hutchinson RA Buback MM Latz H 《Analytical and bioanalytical chemistry》2004,378(6):1414-1427
Poly(n-butylacrylate-co-carbon monoxide-co-ethylene) (polyEBC) samples prepared from 13C-labeled monomer, n-butyl acrylate, were characterized using two dimensional (2D) pulsed field gradient (PFG) 750 MHz NMR spectroscopy. To elucidate the complex structure of the terpolymer, 2D-1H/13C-heteronuclear single quantum coherence (HSQC) and heteronuclear multiple bond correlation (HMBC) experiments were conducted by selectively exciting the enhanced resonances in the spectra of two polymer samples, one polymer resulting from synthesis with 1-13C-n-butylacrylate monomer and a second polymer obtained from a synthesis with 2-13C-n-butylacrylate monomer. High-resolution 2D-NMR combined with 13C-labeling of the polymer greatly simplifies the 2D-NMR spectra, selectively enhances the weak peaks from low occurrence B-centered triad structures, and aids in their resonance assignments. In all experiments, the sample temperature was 120 degrees C, to ensure a homogeneous solution and sufficient molecular mobility. Electronic Supplementary Material: Supplementary material (1D 13C NMR spectra of the 13C-labeled and unlabeled polymers) is available in the online version of this article at http://dx.doi.org/100.1007/s00216-003-2402-3. 相似文献
86.
Winter B Weber R Hertel IV Faubel M Jungwirth P Brown EC Bradforth SE 《Journal of the American Chemical Society》2005,127(19):7203-7214
Photoelectron spectroscopy combined with the liquid microjet technique enables the direct probing of the electronic structure of aqueous solutions. We report measured and calculated lowest vertical electron binding energies of aqueous alkali cations and halide anions. In some cases, ejection from deeper electronic levels of the solute could be observed. Electron binding energies of a given aqueous ion are found to be independent of the counterion and the salt concentration. The experimental results are complemented by ab initio calculations, at the MP2 and CCSD(T) level, of the ionization energies of these prototype ions in the aqueous phase. The solvent effect was accounted for in the electronic structure calculations in two ways. An explicit inclusion of discrete water molecules using a set of snapshots from an equilibrium classical molecular dynamics simulations and a fractional charge representation of solvent molecules give good results for halide ions. The electron binding energies of alkali cations computed with this approach tend to be overestimated. On the other hand, the polarizable continuum model, which strictly provides adiabatic binding energies, performs well for the alkali cations but fails for the halides. Photon energies in the experiment were in the EUV region (typically 100 eV) for which the technique is probing the top layers of the liquid sample. Hence, the reported energies of aqueous ions are closely connected with both structures and chemical reactivity at the liquid interface, for example, in atmospheric aerosol particles, as well as fundamental bulk solvation properties. 相似文献
87.
Meinhard Wlaschek Gudrun Heinen Arndt Poswig Agatha Schwarz Thomas Krieg Karin Scharffetter-Kochanek 《Photochemistry and photobiology》1994,59(5):550-556
Abstract— Previous work has shown that fibroblast-derived collagenase/matrix-metalloproteinase-1(MMP–1), responsible for the breakdown of dermal interstitial collagen, was dose-dependently induced in vitro and in vivo by UVA irradiation and this induction was at least partly mediated byinterleukin–6(IL–6). We here provide evidence that UVA-inducedIL–1α andIL–1β play a central role in the induction of the synthesis both ofIL–6 and collagenase/MMP–1. In contrast to the late increase ofIL–1α andIL–1β mRNA levels at 6 h postirradiation, bioactivity ofIL–1 is already detectable at 1 h postirradiation. This early peak ofIL–1 bioactivity appears to be responsible for the induction ofIL–6 synthesis and together withIL–6 lead to an increase of the steady-state mRNA level of collagenase/MMP–1 as deduced from studies usingIL–1α andIL–1β antisense oligonucleotides or neutralizing antibodies againstIL–1α andIL–1β Besides the early posttranslationally controlled release of intracellularIL–1, a latter pretranslationally controlled synthesis and release ofIL–1 perpetuates the UV response. From these data we suggest a UV-induced cytokine network consisting ofIL–1α,IL–1β andIL–6, which via interrelated autocrine loops induce collagenase/MMP–1 and thus may contribute to the loss of interstitial collagen in cutaneous photoaging. 相似文献
88.
89.
Guy Guelachvili K. Narahari Rao Richard H. Tipping Brenda P. Winnewisser Manfred Winnewisser 《Mikrochimica acta》1988,95(1-6):339-343
This paper reports the observation of the far infrared absorption spectrum of a single crystal of N2, measured over absorption paths of 4 cm (lengthwise) and 2 cm (across the crystal). The crystal chamber, with quartz windows, was immersed in a flow of cold helium gas. The spectrum from 20 to 120 cm–1 was recorded in the liquid phase, the-phase, and over the full temperature range of the-phase (35.6–2.0 K) with a Fourier transform spectrometer. The spectral resolution, which was not instrument-limited, and the large path allowed the observation of more detailed multiphonon-transition structure in the spectrum of the-phase than has previously been observed. 相似文献
90.
Manfred Herrmann 《Fresenius' Journal of Analytical Chemistry》1961,181(1):122-125
Zusammenfassung Durch Anwendung der Röntgenfluorescenzanalyse an Stelle der bisher üblichen Methoden bei der quantitativen Bestimmung von Brom in organischen Substanzen läßt sich eine beträchtliche Zeitersparnis erzielen. Dies gilt besonders bei Anwesenheit anderer Halogenide wie Chlor oder Jod. Die Bestimmung wird unter Zugabe von Selen nach der Methode des inneren Standards durchgeführt, die Analysengenauigkeit deckt sich mit den Ergebnissen der bisher naßchemisch durchgeführten Bestimmungen.Herrn Dr. F. Ehrenberger und Dr. S. Gorbach danke ich für Anregungen und für ihre wertvolle Mitarbeit. 相似文献