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71.
Haruhiko Fuwa Prof. Dr. Asami Saito Shinya Naito Keiichi Konoki Prof. Dr. Mari Yotsu‐Yamashita Prof. Dr. Makoto Sasaki Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(46):12807-12818
The stereocontrolled total synthesis of the originally proposed ( 1 ) and correct ( 2 ) structures of (+)‐neopeltolide, a novel marine macrolide natural product with highly potent antiproliferative activity against several cancer cell lines as well as potent antifungal activity, has been achieved by exploiting a newly developed Suzuki–Miyaura coupling/ring‐closing metathesis strategy. Alkylborate 44 , which was generated in situ from iodide 34 , was coupled with enol phosphate 8 by a Suzuki–Miyaura coupling. Ring‐closing metathesis of the derived diene 45 followed by stereoselective hydrogenation afforded tetrahydropyran 47 as a single stereoisomer in high overall yield from 34 . Our convergent strategy enabled us to construct the 14‐membered macrolactone core structure of 2 in a rapid and efficient manner. Total synthesis and biological evaluation of synthetic intermediates and designed synthetic analogues, performed to establish the structure–activity relationships of 2 , led to the discovery of a structurally simple yet potent cytotoxic analogue, 9‐demethylneopeltolide ( 54 ). 相似文献
72.
73.
Beverina L Crippa M Landenna M Ruffo R Salice P Silvestri F Versari S Villa A Ciaffoni L Collini E Ferrante C Bradamante S Mari CM Bozio R Pagani GA 《Journal of the American Chemical Society》2008,130(6):1894-1902
Singlet oxygen sensitization by organic molecules is a topic of major interest in the development of both efficient photodynamic therapy (PDT) and aerobic oxidations under complete green chemistry conditions. We report on the design, synthesis, biology, and complete spectroscopic characterization (vis-NIR linear and two-photon absorption spectroscopy, singlet oxygen generation efficiencies for both one- and two-photon excitation, electrochemistry, intrinsic dark toxicity, cellular uptake, and subcellular localization) of three classes of innovative singlet oxygen sensitizers pertaining to the family of symmetric squaraine derivatives originating from pi-excessive heterocycles. The main advantage of pi-extended squaraine photosensitizers over the large number of other known photosensitizers is their exceedingly strong two-photon absorption enabling, together with sizable singlet oxygen sensitization capabilities, for their use at the clinical application relevant wavelength of 806 nm. We finally show encouraging results about the dark toxicity and cellular uptake capabilities of water-soluble squaraine photosensitizers, opening the way for clinical small animal PDT trials. 相似文献
74.
C. M. Mari 《Ionics》2003,9(5-6):365-369
Aim of the lecture is to present the operating principles of non-Nernstian electrochemical devices, the state of the art as
well as the weight of the electrode materials electrocatalytic properties in the design of planar sensors.
Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15–21, 2002. 相似文献
75.
Laura L. Tomasevich Stephen M. Zitelli Chelsey R. Gillen Neal J. Baker Jason M. Conley Mari Lynne Starr Patrick J. Carroll 《Tetrahedron letters》2007,48(4):599-602
Condensation of ninhydrin with tryptamide or tryptamine followed by Lewis acid-induced rearrangement provided yohimbanones that were readily converted to β-carbolines via oxidative ring cleavage. The analogous condensation-rearrangement with 3,4-dimethoxyphenethylamine and ninhydrin afforded an oxyprotoberberine, which was further oxygenated at the 13a position. 相似文献
76.
The contamination of subsurface due to the chlorinated solvents such as tetrachlorethylene (PCE) and trichlorethylene (TCE)
is one of the most difficult environmental problems to treat. Bioremediation has been shown by many researchers to be a remedial
alternative for this type of contamination. Chlorinated solvents are not directly mineralized but rather are transformed by
microorganisms into one or more intermediate compounds before converting into a final compound. These sequential reactions,
termed “reductive dehalogenation”, consist of replacing a chlorine atom by a hydrogen atom. The pathway of degradation of
PCE can be expressed by the following scheme
PCE → TCE → DCE → VC → ETH,
where dichloroethene (DCE), vinyl chloride (VC) and finally ETH is ethylene.
Since the biotransformation rate coefficients of each intermediate compound are different, they have to be determined very
precisely to establish an effective treatment operation. The sequential decay can be described by Michaelis–Menten’s kinetics,
which constitutes a highly nonlinear system of ordinary differential equations (ODEs). This is very sensitive to the changes
of biotransformation rate coefficients.
In this study we introduce a methodology how to numerically estimate the rate coefficients for Michaelis–Menten’s equations
from the knowledge of the concentrations of PCE, TCE, DCE, VC and ETH. The efficiency of the proposed method is demonstrated
on some examples. Estimated biotransformation coefficients are employed to predict the concentrations of chlorinated solvents.
Computations and measurements show a very good agreement. 相似文献
77.
Michinori Karikomi Mari Yamada Hirohiko Houjou Kazuhisa Hiratani Tadao Uyehara 《Tetrahedron letters》2005,46(35):5867-5869
Oxidative coupling reaction of both 3-hydroxychrysene and 2-hydroxybenzo[c]phenanthrene by using Cu(NO3)2-3H2O under atmospheric air is described. The former gave the aimed coupled biaryl derivative. However, the latter gave a further oxidized helical quinone derivative. The unique helical structure was characterized by X-ray and NMR analysis. 相似文献
78.
Ab initio calculations are performed to understand the geometry, electronic structure, and vibrational frequencies of nickel
porphyrin (NiP). Hartree-Fock (HF) and second-order perturbation (MP2) theories are applied with polarized basis sets. The
calculated geometrical parameters are in very good agreement with the crystal structure determination. The electronic structure
and bonding are analyzed in terms of complexation and correlation effects. Not unexpectedly, the HF depiction of the metal-porphyrin
interaction is rather ionic while ligand σ donation is dominant at the MP2 level. Scaled HF frequencies of NiP and its isotopomers
are in very good agreement with observed infrared and resonance Raman data.
Received: 7 January 1997 / Accepted: 6 May 1997 相似文献
79.
A compatible statistical interpretation of a wave packet is proposed. De Broglian probabilities which unite wave and particle features of quantons are evaluated for free wave packets and Jor a superposition of wave packets. The obtained expressions provide a very plausible and physically appealing explanation of coherence in apparently incoherent beams and of the characteristic modulation of the momentum distribution, found recently in neutron interferometry combined with spectral filtering. Certain conclusions about dualism and objectivity in quantum domain are also derived. 相似文献
80.
Nigel Ribeiro Denis Heissler Anne Marie Albrecht-Gary Mari Gotoh Yoichi Nakatani Guy Ourisson 《Tetrahedron》2007,63(16):3395-3407
Cholesterol plays the role of membrane reinforcer in eukaryotes, whereas hopanoids play the same role in bacteria. Which components could have reinforced ‘primitive’ membranes? We describe here an efficient biomimetic synthesis of bi- and tri-cyclopolyprenols and demonstrate that these compounds reinforce the membranes of polyprenyl phosphate, which we speculated as ‘primitive’ membranes. 相似文献