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991.
The conjugated hydrocarbon, cyclo[1,2,3,4-def]benzo[3,4]cyclobuta[6,7]biphenylene, crystallizes in the space group P212121 with a = 15.136(4), b = 16.453(4), c = 5.584(1) Å, Z = 4, ?cal = 1.32, ?obs = 1.31 g cm?3. The structure was solved by application of direct methods after reducing the dominance of hk0 reflections in starting set selection. Full-matrix, least-squares refinement of 1910 independent data collected with MoKα radiation on a four-circle diffractometer yielded a final conventional R = 0.068. Bond lengths in this unusual conjugated hydrocarbon range from 1.34 to 1.53 Å. Calculated iterated-Hückel bond lengths that include effects of σ strain reasonably correspond to the observed bond distances, with the largest differences (0.03 Å) occurring in the four membered rings. The molecule is essentially planar, but exhibits an overall bowing that is probably due to crystal packing forces. 相似文献
992.
Alexander Cumberworth Jennifer M. Bui Jörg Gsponer 《Journal of computational chemistry》2016,37(7):629-640
Implicit solvent models for biomolecular simulations have been developed to use in place of more expensive explicit models; however, these models make many assumptions and approximations that are likely to affect accuracy. Here, the changes in free energies of solvation upon folding of several fast folding proteins are calculated from previously run μs–ms simulations with a number of implicit solvent models and compared to the values needed to be consistent with the explicit solvent model used in the simulations. In the majority of cases, there is a significant and substantial difference between the values calculated from the two approaches that is robust to the details of the calculations. These differences could only be remedied by selecting values for the model parameters—the internal dielectric constant for the polar term and the surface tension coefficient for the nonpolar term—that were system‐specific or physically unrealistic. We discuss the potential implications of our findings for both implicit and explicit solvent simulations. © 2015 Wiley Periodicals, Inc. 相似文献
993.
994.
Jennifer M. Gaskins 《Contemporary Physics》2016,57(4):496-525
The indirect detection of dark matter annihilation and decay using observations of photons, charged cosmic rays and neutrinos offers a promising means of identifying the particle nature of this elusive component of the universe. The last decade has seen substantial advances in observational data-sets, complemented by new insights from numerical simulations, which together have enabled for the first time strong constraints on dark matter particle models, and have revealed several intriguing hints of possible signals. This review provides an introduction to indirect detection methods and an overview of recent results in the field. 相似文献
995.
Gottardo R Polettini A Sorio D Pascali JP Bortolotti F Liotta E Tagliaro F 《Electrophoresis》2008,29(19):4078-4087
A new method for the determination of illicit and abused drugs in blood by capillary zone electrophoresis-electrospray ionization-time-of-flight mass spectrometry is proposed, in view of its application in clinical and forensic toxicology. The analytes (methamphetamine, methylenedioxyamphetamine, methylenedioxyethylamphetamine, methylenedioxymethamphetamine, methadone, cocaine, morphine, codeine, 6-acethylmorphine, benzoylecgonine) were separated with capillary zone electrophoresis by applying 15 kV within 25 min, in an uncoated fused-silica capillary (75 microm x 100 cm) using a 25 mM ammonium formate electrolyte solution (pH 9.5). The capillary electropherograph was coupled to time-of-flight mass spectrometry through an orthogonal electrospray ionization source, with a coaxial sheath liquid interface. The sheath liquid was composed of isopropanol-water (1:1 v/v) containing 0.5% formic acid delivered at 4 microL/min. Forensic drugs were identified by exact mass determination (mass accuracy typically < or =5 ppm) and by matching of the isotopic pattern. Under optimized conditions, linearity was assessed in the range 10-2000 ng/mL, with correlation coefficients between 0.9744 and 0.9982 for all the analytes. LODs were in the range of 2-10 ng/mL (S/N > or =3) and LOQs of 10-30 ng/mL. The CVs (tested at 40 and 800 ng/mL in biological matrix) were below 2.97% for migration times and below 14.61% for peak area ratios (analyte/internal standard). Blood samples were extracted by using a liquid-liquid extraction procedure and injected under field-amplified sample stacking conditions. The method was successfully applied to real cases. 相似文献
996.
Byrne JC Downes MR O'Donoghue N Fitzpatrick JM Dunn MJ Watson RW 《Electrophoresis》2008,29(14):3055-3059
The use of comparative serum proteomic analysis has the potential to reveal protein expression changes present at different stages of disease progression. Depletion strategies allow for the enrichment of low-abundance proteins, which are more likely to be clinically significant biomarkers. We have observed that patient serum samples filtered through 0.22 microm cellulose acetate spin filters prior to depletion showed a variable level of retention of patient material on the upper part of the filter. This could potentially be related to the fasting status of the patient as a reduction in the lipid content of samples through the incorporation of a centrifugation step prior to filtration was found to reduce this effect. In order to determine if proteins were being selectively retained during filtration, a 2-D difference gel electrophoresis (2-D DIGE) experiment was performed. This demonstrated no significant selective retention of protein within crude serum samples. However, as this analysis was carried out on crude serum, it must be emphasised that protein loss could be manifest in the low-abundance proteins which would be masked in our analysis. Depletion of the retentate was not possible due to technical limitations, however based on our results a centrifugation step might act as an alternative to filtration in serum processing prior to depletion. 相似文献
997.
Isci A Himmelsbach JN Pometto AL Raman DR Anex RP 《Applied biochemistry and biotechnology》2008,144(1):69-77
Simultaneous saccharification and fermentation (SSF) of switchgrass was performed following aqueous ammonia pretreatment.
Switchgrass was soaked in aqueous ammonium hydroxide (30%) with different liquid–solid ratios (5 and 10 ml/g) for either 5
or 10 days. The pretreatment was carried out at atmospheric conditions without agitation. A 40–50% delignification (Klason
lignin basis) was achieved, whereas cellulose content remained unchanged and hemicellulose content decreased by approximately
50%. The Sacccharomyces cerevisiae (D5A)-mediated SSF of ammonia-treated switchgrass was investigated at two glucan loadings (3 and 6%) and three enzyme loadings
(26, 38.5, and 77 FPU/g cellulose), using Spezyme CP. The percentage of maximum theoretical ethanol yield achieved was 72.
Liquid–solid ratio and steeping time affected lignin removal slightly, but did not cause a significant change in overall ethanol
conversion yields at sufficiently high enzyme loadings. These results suggest that ammonia steeping may be an effective method
of pretreatment for lignocellulosic feedstocks. 相似文献
998.
Masahiko Isaka Panida Chinthanom Sukitaya Veeranondha Sumalee Supothina J. Jennifer Luangsa-ard 《Tetrahedron》2008,64(49):11028-11033
Two novel cyclopropyl diketones, hamavellone A (1) and B (2), and two new 14-membered nonaketide macrolactones, hamigeromycin A (3) and B (4), together with six known compounds, 89-250904-F1 (radicicol analogue A, 5), pseurotin A (6), emodin (7), ω-hydroxyemodin (8), and emodin bianthrones (9 and 10) were isolated from the soil fungus Hamigera avellanea BCC 17816. The structures of the new compounds were defined by analysis of NMR and MS data. The absolute stereochemistry of 3 was addressed by chemical correlation to 5. Hamavellone B (2) exhibited antimalarial activity with an IC50 of 5.2 μg/mL, whereas it also showed comparable cytotoxicity. 相似文献
999.
Two phosphonated hexaaza-macrocycles with 24- and 26-membered rings have been synthesized via a Mannich reaction and characterized. The novel crystal structures of the macrocyclic ligands show the extended 3-D hydrogen bonded structure in their solid states. These ligands have unusual ring conformations with two or four pendent arms wrapping around the macrocycle with alternating up and down orders. Strong hydrogen bonding between the protonated phosphonate groups and the deprotonated phosphonated groups was observed in those structures together with the complicated solvent hydrogen bonding networks. 相似文献
1000.
Conditional glycosylation in eukaryotic cells using a biocompatible chemical inducer of dimerization
Czlapinski JL Schelle MW Miller LW Laughlin ST Kohler JJ Cornish VW Bertozzi CR 《Journal of the American Chemical Society》2008,130(40):13186-13187
Chemical inducers of dimerization (CIDs) are cell-permeable small molecules capable of dimerizing two protein targets. The most widely used CID, the natural product rapamycin and its relatives, is immunosuppressive due to interactions with endogenous targets and thus has limited utility in vivo. Here we report a new biocompatible CID, Tmp-SLF, which dimerizes E. coli DHFR and FKBP and has no endogenous mammalian targets that would lead to unwanted in vivo side effects. We employed Tmp-SLF to modulate gene expression in a yeast three-hybrid assay. Finally, we engineered the Golgi-resident glycosyltransferase FucT7 for tunable control by Tmp-SLF in mammalian cells. 相似文献