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991.
Dennis CA Macneil MA Rosati JY Pitcher TE Fisk AT 《Rapid communications in mass spectrometry : RCM》2010,24(24):3515-3520
A recent literature review reported negative relationships between diet discrimination factors (DDFs = Xfish – Xfood; X = δ15N or δ13C) and the values of δ15N and δ13C in the food of wild organisms but there has been no laboratory‐based confirmation of these relationships to date. Laboratory reared guppies (Poecilia reticulata) fed a series of diets with a range of δ13C (?22.9 to ?6.6‰) and δ15N (6.5 to 1586‰) values were used to magnify diet‐tissue dynamics in order to calculate DDFs once the fish had achieved equilibrium with each of the diets. Values of DDFs range widely for δ15N (7.1 to ?849‰) and δ13C (1.1 to ?7.0‰) and showed a strong negative correlation with the stable isotope value in the food for δ15N (slope = ?0.59 ± 0.02, r2 = 0.95) and δ13C (slope = ?0.56 ± 0.02, r2 = 0.94). Based on these relationships, the magnitude of DDF change over environmentally relevant values of δ15N or δ13C would be significant and could confound the interpretation of stable isotopes in the environment. Using highly enriched experimental diets, our study adds to a growing number of studies that undermine the consistent trophic enrichment paradigm with results that demonstrate the currently poor mechanistic understanding of how DDFs arise. The results of our study highlight that the magnitude of the stable isotope values in prey must be considered when choosing DDF values. Future laboratory studies should therefore be directed at uncovering the mechanistic basis of DDFs and, like others before, we recommend the determination of diet‐dependent DDFs under laboratory conditions before modeling dietary proportions or calculating trophic positions. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
992.
993.
The ν1 and ν2 bands of DOBr centered near 2668.8 and respectively have been observed at resolution. The ν1 band is perturbed by a quintic anharmonic resonance (ΔKa=0) with 3ν3+ν2. In addition, the millimeter wave spectra arising from the v2=1 and v3=1 states have been observed. All rotational and vibrational spectra from both bromine isotopologs have been fitted with a single calculation. The perturbation in the ν1 band has been well described. Equilibrium rotational and centrifugal distortion constants and changes in quadrupole coupling with the BrO stretch and DOBr bend have been determined. The equilibrium structure has been derived from the DOBr and HOBr rotational constants. The harmonic force field has been calculated and compared with those of related molecules as well as with those derived from ab initio calculations. 相似文献
994.
Naela Assadi Sergey Pogodin Shmuel Cohen Amalia Levy Israel Agranat 《Structural chemistry》2009,20(4):541-556
The naphthalogous mono-bridged tetraarylethylenes 9,9′-di-(1-naphthylmethylene)-9H-fluorene (5) and 9,9′-di-(1-naphthylmethylene)-9H-xanthene (6), analogs of bifluorenylidene (1) and bixanthenylidene (2), have been synthesized and their molecular and crystal structures have been determined. Ene 5 has been prepared by two alternative synthetic routes. The molecular structures of 5 and 6 show that each of these enes has very small twist around the central double bond, but the two naphthalene rings in both 5 and 6 are highly twisted. According to the NMR study, 5 and 6 in solution adopt conformations which are similar to those found by X-ray crystal structure analysis. The notable upfield
shifts of H1 and H8 (6.11 and 6.83 ppm, respectively) and H2 and H7 (6.70 and 6.44 ppm, respectively) in 5 and 6 are due to the shielding caused by the nearly orthogonally twisted naphthalene rings. The B3LYP/6-31G(d) calculations of
5, 6, and their 2-naphthyl and phenyl analogs have been performed. In the 1-naphthyl series, the more efficient conjugation between
the naphthyl substituents and the central C=C and the overcrowding due to the peri-hydrogen atoms lead to higher twists of the naphthyl groups and to lower twists of the central C=C. In the 2-naphthyl series,
the opposite effects are noted.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.
相似文献
Israel AgranatEmail: |
995.
Aaron R. Van Dyke Timothy F. Jamison Prof. 《Angewandte Chemie (International ed. in English)》2009,48(24):4430-4432
Extension ladder : The successful application of epoxide‐opening strategies towards the synthesis of ladder‐type polyethers is contingent upon further elaboration of the product. By employing two different functionalized templates, a fragment of gymnocin A that bears four sites for subsequent fragment coupling has been prepared (see scheme; Bn=benzyl).
996.
S. Trajkovska M. Mbaye M. D. Gaye Seye J. J. Aaron M. Chevreuil H. Blanchoud 《Analytical and bioanalytical chemistry》2009,394(4):1099-1106
A detailed toxicological study on several pesticides, including chlorothalonil, cyprodynil, dichlobénil, pendimethaline, trifluraline, and α-endosulfan, present at trace levels in air and total atmospheric precipitations of Paris is presented. The pesticides contained in the atmospheric samples, collected during sampling campaigns in February–March 2007, are identified and quantified by a high-performance liquid chromatographic (HPLC)-UV detection method. The toxicity measurements are performed by means of the Microtox® bioluminescence method, based on the evaluation of the bioluminescence inhibition of the Vibrio fischeri marine bacteria at two exposure times to the pesticide solutions. The specific toxicity, corresponding to the particular toxicity of the compound under study and represented by the EC50 parameter, is determined for these pesticides. Also, the global toxicity, which is the toxicity of all micro-pollutants present in the sample under study, is estimated for the extracts of air and atmospheric precipitation (rainwater) samples. The specific toxicities strongly vary with the nature of the pesticide, the EC50 parameter values being comprised between 0.17 and 0.83 mg/mL and 0.15 and 0.66 mg/mL, respectively, for exposure times of 5 and 15 min. The importance of the atmospheric samples’ global toxicity and the respective contribution of the toxic potency of the various pesticides contained in these samples are discussed. Figure
Passive sampling device for rainwater, located on the roof of Paris 6-Paris 7 universities (Jussieu campus, Paris 5th district) 相似文献
997.
Joshua D. Hansen Bradley J. Newhouse Aaron Anderson Justin Schiro Ellen Laird David Chantry Laurence E. Burgess 《Tetrahedron letters》2006,47(1):69-72
The synthesis of racemic and non-racemic spirocyclic lactams that display high binding affinity toward CCR4 is described. Two distinct series of spirocycles were prepared from the common intermediate 9. 相似文献
998.
We describe the implementation of a general and flexible Monte Carlo (MC) module for the program CHARMM, which is used widely for modeling biomolecular systems with empirical energy functions. Construction and use of an almost arbitrary move set with only a few commands is made possible by providing several predefined types of moves that can be combined. Sampling can be enhanced by noncanonical acceptance criteria, automatic optimization of step sizes, and energy minimization. A systematic procedure for improving MC move sets is introduced and applied to simulations of two peptides. The resulting move sets allow MC to sample the configuration spaces of these systems much more rapidly than Langevin dynamics. The rate of convergence of the difference in free energy between ethane and methanol in explicit solvent is also examined, and comparable performances are observed for MC and the Nosé-Hoover algorithm. Its ease of use combined with its sampling efficiency make the MC module in CHARMM an attractive alternative for exploring the behavior of biomolecular systems. 相似文献
999.
O'Mullane AP Neufeld AK Harris AR Bond AM 《Langmuir : the ACS journal of surfaces and colloids》2006,22(25):10499-10505
The electrochemical reduction of TCNQ to TCNQ*- in acetonitrile in the presence of [Cu(MeCN)4]+ has been undertaken at boron-doped diamond (BDD) and indium tin oxide (ITO) electrodes. The nucleation and growth process at BDD is similar to that reported previously at metal electrodes. At an ITO electrode, the electrocrystallization of more strongly adhered, larger, branched, needle-shaped phase I CuTCNQ crystals is detected under potential step conditions and also when the potential is cycled over the potential range of 0.7 to -0.1 V versus Ag/AgCl (3 M KCl). Video imaging can be used at optically transparent ITO electrodes to monitor the growth stage of the very large branched crystals formed during the course of electrochemical experiments. Both in situ video imaging and ex situ X-ray diffraction and scanning electron microscopy (SEM) data are consistent with the nucleation of CuTCNQ taking place at a discrete number of preferred sites on the ITO surface. At BDD electrodes, ex situ optical images show that the preferential growth of CuTCNQ occurs at the more highly conducting boron-rich areas of the electrode, within which there are preferred sites for CuTCNQ formation. 相似文献
1000.
Li Z Lee D Sheng X Cohen RE Rubner MF 《Langmuir : the ACS journal of surfaces and colloids》2006,22(24):9820-9823
Using a combination of an aqueous layer-by-layer deposition technique, nanoparticle surface modification chemistry, and nanoreactor chemistry, we constructed thin film coatings with two distinct layered functional regions: a reservoir for the loading and release of bactericidal chemicals and a nanoparticle surface cap with immobilized bactericides. This results in dual-functional bactericidal coatings bearing both chemical-releasing bacteria-killing capacity and contact bacteria-killing capacity. These dual-functional coatings showed very high initial bacteria-killing efficiency due to the release of Ag ions and retained significant antibacterial activity after the depletion of embedded Ag because of the immobilized quaternary ammonium salts. 相似文献