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991.
J. Graham K. Kanov X. I. A. Yang M. Lee N. Malaya C. C. Lalescu 《Journal of Turbulence》2016,17(2):181-215
The output from a direct numerical simulation (DNS) of turbulent channel flow at Reτ ≈ 1000 is used to construct a publicly and Web services accessible, spatio-temporal database for this flow. The simulated channel has a size of 8πh × 2h × 3πh, where h is the channel half-height. Data are stored at 2048 × 512 × 1536 spatial grid points for a total of 4000 time samples every 5 time steps of the DNS. These cover an entire channel flow-through time, i.e. the time it takes to traverse the entire channel length 8πh at the mean velocity of the bulk flow. Users can access the database through an interface that is based on the Web services model and perform numerical experiments on the slightly over 100 terabytes (TB) DNS data on their remote platforms, such as laptops or local desktops. Additional technical details about the pressure calculation, database interpolation, and differentiation tools are provided in several appendices. As a sample application of the channel flow database, we use it to conduct an a-priori test of a recently introduced integral wall model for large eddy simulation of wall-bounded turbulent flow. The results are compared with those of the equilibrium wall model, showing the strengths of the integral wall model as compared to the equilibrium model. 相似文献
992.
Rapid Construction of a Benzo‐Fused Indoxamycin Core Enabled by Site‐Selective C−H Functionalizations 下载免费PDF全文
T. Aaron Bedell Graham A. B. Hone Dr. Damien Valette Prof. Jin‐Quan Yu Prof. Huw M. L. Davies Prof.Prof. Erik J. Sorensen 《Angewandte Chemie (International ed. in English)》2016,55(29):8270-8274
Methods for functionalizing carbon–hydrogen bonds are featured in a new synthesis of the tricyclic core architecture that characterizes the indoxamycin family of secondary metabolites. A unique collaboration between three laboratories has engendered a design for synthesis featuring two sequential C?H functionalization reactions, namely a diastereoselective dirhodium carbene insertion followed by an ester‐directed oxidative Heck cyclization, to rapidly assemble the congested tricyclic core of the indoxamycins. This project exemplifies how multi‐laboratory collaborations can foster conceptually novel approaches to challenging problems in chemical synthesis. 相似文献
993.
Dalton T. Snyder Christopher J. Pulliam Joshua S. Wiley Jason Duncan R. Graham Cooks 《Journal of the American Society for Mass Spectrometry》2016,27(7):1243-1255
Secular frequency scanning is implemented and characterized using both a benchtop linear ion trap and a miniature rectilinear ion trap mass spectrometer. Separation of tetraalkylammonium ions and those from a mass calibration mixture and from a pesticide mixture is demonstrated with peak widths approaching unit resolution for optimized conditions using the benchtop ion trap. The effects on the spectra of ion trap operating parameters, including waveform amplitude, scan direction, scan rate, and pressure are explored, and peaks at black holes corresponding to nonlinear (higher-order field) resonance points are investigated. Reverse frequency sweeps (increasing mass) on the Mini 12 are shown to result in significantly higher ion ejection efficiency and superior resolution than forward frequency sweeps that decrement mass. This result is accounted for by the asymmetry in ion energy absorption profiles as a function of AC frequency and the shift in ion secular frequency at higher amplitudes in the trap due to higher order fields. We also found that use of higher AC amplitudes in forward frequency sweeps biases ions toward ejection at points of higher order parametric resonance, despite using only dipolar excitation. Higher AC amplitudes also increase peak width and decrease sensitivity in both forward and reverse frequency sweeps. Higher sensitivity and resolution were obtained at higher trap pressures in the secular frequency scan, in contrast to conventional resonance ejection scans, which showed the opposite trend in resolution on the Mini 12. Mass range is shown to be naturally extended in secular frequency scanning when ejecting ions by sweeping the AC waveform through low frequencies, a method which is similar, but arguably superior, to the more usual method of mass range extension using low q resonance ejection. 相似文献
994.
The complexes of 3-carboxy-4-hydroxybenzenesulfonic acid (5-sulfosalicylic acid, H3SSA) with rubidium(I), caesium(I) and lead(II) have been synthesized and characterized using single-crystal X-ray methods at 130 K. The rubidium(I) complex 1, [Rb3(H2SSA)(HSSA)(H2O)4]n, is an unstable hydrate variant of a previously described complex [Rb(H2SSA)(H2O)]n, and comprises three independent and different seven-coordinate metal polyhedra interlinked through oxygen donors of the sulfonate, carboxylate and phenolate groups of the 5-sulfosalicylate ligands (one of which is dianionic, the other monoanionic), and one bridging water, giving a three-dimensional hydrogen-bonded framework polymer structure. The anhydrous caesium(I) complex 2 [Cs(H2SSA)]n, which has been previously described in a room-temperature determination, has a three-dimensional framework polymer structure based on an irregular Cs–O9 repeating unit. Complex 3 with lead(II), [Pb(H2SSA)2(H2O)]n, forms helical step-polymer ribbon substructures having an irregular Pb–O7 coordination centre comprising a single monodentate water and six sulfonate-O donors bridging three separate metals. The carboxylic acid and phenol substituent groups of the 5-sulfosalicylate ligand link the ribbons peripherally through hydrogen bonds, giving a three-dimensional layered framework polymer structure. 相似文献
995.
Montague M Ducker RE Chong KS Manning RJ Rutten FJ Davies MC Leggett GJ 《Langmuir : the ACS journal of surfaces and colloids》2007,23(13):7328-7337
The UV photo-oxidation of oligo(ethylene glycol) (OEG)-terminated self-assembled monolayers (SAMs) has been studied using static secondary ion mass spectrometry, X-ray photoelectron spectroscopy, contact angle measurement, and friction force microscopy. OEG-terminated SAMs are oxidized to yield sulfonates, but photodegradation of the OEG chain also occurs on a more rapid time scale, yielding degradation products that remain bound to the surface via gold-sulfur bonds. The oxidation of these degradation products is the rate-limiting step in the process. Photopatterning of OEG-terminated SAMs may be accomplished by using a mask and suitable light source or by using scanning near-field photolithography (SNP) in which the mask is replaced by a scanning near-field optical microscope coupled to a UV laser. Using SNP, it is possible to fabricate patterns in SAMs with a full width at half-maximum height (fwhm) as small as 9 nm, which is approximately 15 times smaller than the conventional diffraction limit. SNP-patterned OEG-terminated SAMs may be used to fabricate protein nanopatterns. By adsorbing carboxylic acid-terminated thiols into oxidized regions and converting these to active ester intermediates, it has been possible to fabricate lines of protein molecules with widths of only a few tens of nanometers. 相似文献
996.
Friction force microscopy measurements have been made for self-assembled monolayers of mercaptoundecanoic acid (C10COOH) and dodecanethiol (C11CH3) in different liquid media. In perfluorodecalin, the friction-load relationship was nonlinear and consistent with adhesion-controlled sliding. The effective range of the attractive force was controlled by using AFM tips functionalized with alkanethiols (chemical force microscopy). Like pairs of interacting molecules yielded data that were characterized by the Johnson-Kendall-Roberts model of contact mechanics, whereas the interaction between dissimilar pairs of molecules fitted the behavior predicted by the Derjaguin-Muller-Toporov model. In ethanol, the adhesive force was much smaller, and sliding was not adhesion-controlled. Under this condition of low adhesion, the friction force varied linearly with the applied load. 相似文献
997.
Synthesis of four trinitrotoluene stilbene derivatives and assessment for SERRS activity is reported. 相似文献
998.
Structural studies of dimethyl sulfoxide (DMSO) reductases were hampered by modification of the active site during purification. We report an X-ray absorption spectroscopic analysis of the molybdenum active site of Escherichia coli DMSO reductase contained within its native membranes. The enzyme in these preparations is expected to be very close to the form found in vivo. The oxidized active site was found to have four Mo-S ligands at 2.43 A, one Mo=O at 1.71 A, and a longer Mo-O at 1.90 A. We conclude that the oxidized enzyme is a monooxomolybdenum(VI) species coordinated by two molybdopterin dithiolenes and a serine. The bond lengths determined for E. coli DMSO reductase are very similar to those determined for the well-characterized Rhodobacter sphaeroides DMSO reductase, suggesting similar active site structures for the two enzymes. Furthermore, our results suggest that the form found in vivo is the monooxobis(molybdopterin) species. 相似文献
999.
A research area of great interest to the flavour industry is the analysis of odour active compounds in essential oils. In this paper, a methodology is presented for the identification of character-impact odorants in essential oil samples using (a) gas chromatography-olfactometry (GC-O); (b) comprehensive two-dimensional gas chromatography (GC x GC) combined to time-of-flight mass spectrometry (TOFMS) and (c) heart-cut multidimensional gas chromatography-olfactometry (MDGC-O). The specific advantages and limitations of each technique are discussed. The advantage of combining these techniques in a strategy to identify character-impact odorants is demonstrated using examples from coriander leaf (Coriandrum sativum) and hop (Humulus lupulus) essential oils. In particular, resolution of co-eluting regions of compounds and evaluation of their individual odour activity is discussed. In coriander leaf, only E-2-dodecenal was found to contribute to a co-eluting odour region, E-2-dodecen-1-ol and 1-dodecanol being present below detection threshold. Using MDGC on a hop essential oil sample, eight significant peaks were resolved from an 18 s heart-cut where a potent odorant was perceived during GC-O. 相似文献
1000.
Jackson AU Talaty N Cooks RG Van Berkel GJ 《Journal of the American Society for Mass Spectrometry》2007,18(12):2218-2225
The salt tolerance of desorption electrospray ionization (DESI) was systematically investigated by examining three different drug mixtures in the presence of 0, 0.2, 2, 5, 10, and 20% NaCl:KCl (1:1) from different surfaces. At physiological salt concentrations, the individual drugs in each mixture were observed in each experiment. Even at salt concentrations significantly above physiological levels, particular surfaces were effective in providing spectra that allowed the ready identification of the compounds of interest in low nanogram amounts. Salt adducts, which are observed even in the absence of added salt, could be eliminated by adding 0.1% 7 M ammonium acetate to the standard methanol:water (1:1) spray solvent. Comparison of the salt tolerance of DESI with that of electrospray ionization (ESI) demonstrated better signal/noise characteristics for DESI. The already high salt tolerance of DESI can be optimized further by appropriate choices of surface and spray solution. 相似文献