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971.
Martin Vlk Milan Urban Tomas Elbert Jan Sarek 《Journal of Radioanalytical and Nuclear Chemistry》2013,298(2):1149-1157
The aim of this work was to synthesize deuterated and tritiated analogues of highly oxidized lupane derivatives known from our group. We selected compounds that previously showed very high cytotoxic activity on multiple cancer cell lines in order to further investigate the mechanism of their action. From starting material (compounds 1–4), we obtained benzyl platanate (5) and its reaction with deuteromethyltriphenylphosphonium iodide gave deuterated compound 6. Following benzyl deprotection gave free acid 7 and oxidation with SeO2 gave 30-oxo-[29-2H2]lup-20(29)-en-28-oic acid (8), which is one of the most active compounds synthesized in our group to date (IC50 6 μmol/L on CEM cell line). The alkylation of benzyl 2-hydroxy-3-oxolupa-1,20(29)-dien-28-oate (9) with methyliodide or deuteromethyliodide followed by a series of deprotection and hydrogenation steps gave compounds 10–14, where 2β-[31-2H3]methoxy-3-oxolupan-20(29)-en-28-oic acid (13) is especially interesting, it showed lower activity on CEM cell line (IC50 10 μmol/L) however, it was very active against Ph1—positive human leukemia BV-173 (IC50 0.91 μmol/L) and against human myelogenous leukemia K562 (IC50 0.52 μmol/L). Selectively labelled [3α-2H] and [3α-3H] methyl 3β-acetoxy-21,22-dioxolup-18-en-28-oates 24, 25 were prepared in three steps by reduction of corresponding 3-oxo derivatives and they showed moderate activity on CEM cell line (IC50 10 μmol/L). In total, 11 labelled compounds (6–8, 11, 14, 18, 19, 21, 22, 24 and 25) have not been reported before. 相似文献
972.
Recycling of ZnCl2 as a catalyst in the cyclocondensation of trimethylhydroquinone and isophytol to all-rac-α-tocopherol was studied. ZnCl2 was recycled at over 98 % efficiency in required purity by repeated extraction of the reaction streams with water, followed by switching of solvent to butyl acetate and then back to water. Recycled ZnCl2 had no negative effect on the yield of all-rac-α-tocopherol (maintaining over 90 %) at nearly total conversion of isophytol and only a 3 % molar excess of trimethylhydroquinone. 相似文献
973.
Mučaji P Záhradníková A Bezáková L Cupáková M Rauová D Nagy M 《Molecules (Basel, Switzerland)》2011,16(10):8198-8208
The aim of the study was a HPLC evaluation of the lipoxygenase activity inhibiting activity of a water infusion of Ligustrum vulgare L. leaves and selected isolates from it. The antiradical activity of the water infusion was determined using DPPH, ABTS and FRAP tests. Oleuropein and echinacoside concentrations in the water infusion were determined by HPLC. Water infusion, echinacoside and oleuropein were used for an antilipoxygenase activity assay using lipoxygenase isolated from rat lung cytosol fraction. Activity of 8-LOX, 12-LOX and 15-LOX were monitored through formation of 8-HETE, 12-HETE and 15-HETE, respectively. The water infusion exhibited the highest activity against all lipoxygenases, followed by oleuropein. Echinacoside was ineffective against LOXs in lower concentrations, while higher concentration showed similar inhibition on 8-LOX and 12-LOX. 15-LOX was affected more and the presence of echinacoside remarkably decreased its activity. 相似文献
974.
The effect of acidic pH on the translocation of single-stranded DNA through the α-hemolysin pore is investigated. Two significantly different types of events, i.e. deep blockades and shallow blockades, are observed at low pH. The residence times of the shallow blockades are not significantly different from those of the DNA translocation events obtained at or near physiological pH, whereas the deep blockades have much larger residence times and blockage amplitudes. With a decrease in the pH of the electrolyte solution, the percentage of the deep blockades in the total events increases. Furthermore, the mean residence time of these long-lived events is dependent on the length of DNA, and also varies with the nucleotide base, suggesting that they are appropriate for use in DNA analysis. In addition to being used as an effective approach to affect DNA translocation in the nanopore, manipulation of the pH of the electrolyte solution provides a potential means to greatly enhance the sensitivity of nanopore stochastic sensing. 相似文献
975.
Eugene Arthur‐Baidoo Joo Ameixa Patrick Ziegler Filipe Ferreira da Silva Milan On
k Stephan Denifl 《Angewandte Chemie (International ed. in English)》2020,59(39):17177-17181
Tirapazamine (TPZ) has been tested in clinical trials on radio‐chemotherapy due to its potential highly selective toxicity towards hypoxic tumor cells. It was suggested that either the hydroxyl radical or benzotriazinyl radical may form as bioactive radical after the initial reduction of TPZ in solution. In the present work, we studied low‐energy electron attachment to TPZ in the gas phase and investigated the decomposition of the formed TPZ? anion by mass spectrometry. We observed the formation of the (TPZ–OH)? anion accompanied by the dissociation of the hydroxyl radical as by far the most abundant reaction pathway upon attachment of a low‐energy electron. Quantum chemical calculations suggest that NH2 pyramidalization is the key reaction coordinate for the reaction dynamics upon electron attachment. We propose an OH roaming mechanism for other reaction channels observed, in competition with the OH dissociation. 相似文献
976.
Marcel Krug Maximilian Wagner Tobias A. Schaub Wen‐Shan Zhang Christoph M. Schüßlbauer Johannes D. R. Ascherl Peter W. Münich Rasmus R. Schrder Franziska Grhn Pavlo O. Dral Mario Barbatti Dirk M. Guldi Milan Kivala 《Angewandte Chemie (International ed. in English)》2020,59(37):16233-16240
We report on the impact of the central heteroatom on structural, electronic, and spectroscopic properties of a series of spirofluorene‐bridged heterotriangulenes and provide a detailed study on their aggregates. The in‐depth analysis of their molecular structure by NMR spectroscopy and X‐ray crystallography was further complemented by density functional theory calculations. With the aid of extensive photophysical analysis the complex fluorescence spectra were deconvoluted showing contributions from the peripheral fluorenes and the heteroaromatic cores. Beyond the molecular scale, we examined the aggregation behavior of these heterotriangulenes in THF/H2O mixtures and analyzed the aggregates by static and dynamic light scattering. The excited‐state interactions within the aggregates were found to be similar to those found in the solid state. A plethora of morphologies and superstructures were observed by scanning electron microscopy of drop‐casted dispersions. 相似文献
977.
Milan Meloun Zuzana Feren?íková Irena Niesnerová Tomá? Pekárek 《Central European Journal of Chemistry》2013,11(2):271-279
pH-spectrophotometric titration data were used to determine protonation constants of vardenafil at different ionic strengths I and temperatures of 25°C and 37°C. The use of two different multiwavelength and the multivariate treatment of spectral data, SPECFIT32 and SQUAD(84) nonlinear regression analyses and INDICES factor analysis is presented. The reliability of the protonation constants of the drug was proven with goodness-of-fit tests of the pH-spectra. The thermodynamic protonation constants log K T i were estimated by a nonlinear regression of (log K, I) data using the Debye-Hückel equation, yielding log K 4 T = 3.59(1) and 3.26(1), log K 3 T = 5.64(1) and 5.81(1), log K 2 T = 9.41(1) and 8.59(2), log K 1 T = 10.92(2) and 10.05(1) at 25°C and 37°C, where the figure in brackets is the standard deviation in last significant digit. Concurrently, the experimental determination of four thermodynamic protonation constants was combined with the computational prediction of the MARVIN program based on knowledge of the chemical structures of the drug and was in good agreement with its experimental value. The factor analysis of spectra in the INDICES program predicts the correct number of light-absorbing components when the instrument error is known and when the signal-to-error ratio SER is higher than 10. 相似文献
978.
We give numerical evidence that the two-dimensional nonequilibrium zero-temperature random field Ising model exhibits critical behavior. Our findings are based on the results of scaling analysis and collapsing of data, obtained in extensive simulations of systems with sizes sufficiently large to clearly display the critical behavior. 相似文献
979.
Slobodan Nickovic Vladimir Djurdjevic Mirjam Vujadinovic Zavisa I. Janjic Milan Curcic Borivoj Rajkovic 《Journal of computational physics》2011,230(5):1865-1875
Generation of short gravity wave noise often occurs on semi-staggered rectangular grids as a result of sub-grid decoupling when there is a strong forcing in the mass field. In this study a numerical scheme has been proposed to prevent the generation of the gravity wave decoupling. The proposed numerical method provides efficient communication between decoupled gravity wave finite-difference solutions by a simple averaging of a term in the height tendency in the continuity equation. The proposed method is tested using a shallow water sink model developed for the purpose of this study. It has been demonstrated that this method outperforms other existing approaches. The new scheme is time efficient, based on explicit time integration and can be easily implemented. The proposed method is applicable in hydrodynamic models specified on semi-staggered B or E grids. 相似文献
980.
Lenka Findoráková Katarína Győryová Marian Koman Jan Moncol Milan Melník 《Journal of chemical crystallography》2010,40(2):145-150