全文获取类型
收费全文 | 2359篇 |
免费 | 70篇 |
国内免费 | 28篇 |
专业分类
化学 | 1539篇 |
晶体学 | 27篇 |
力学 | 57篇 |
数学 | 448篇 |
物理学 | 386篇 |
出版年
2023年 | 20篇 |
2022年 | 71篇 |
2021年 | 83篇 |
2020年 | 50篇 |
2019年 | 53篇 |
2018年 | 45篇 |
2017年 | 43篇 |
2016年 | 91篇 |
2015年 | 75篇 |
2014年 | 99篇 |
2013年 | 145篇 |
2012年 | 137篇 |
2011年 | 145篇 |
2010年 | 99篇 |
2009年 | 102篇 |
2008年 | 136篇 |
2007年 | 139篇 |
2006年 | 117篇 |
2005年 | 106篇 |
2004年 | 97篇 |
2003年 | 79篇 |
2002年 | 55篇 |
2001年 | 37篇 |
2000年 | 38篇 |
1999年 | 32篇 |
1998年 | 37篇 |
1997年 | 24篇 |
1996年 | 28篇 |
1995年 | 29篇 |
1994年 | 25篇 |
1993年 | 19篇 |
1992年 | 25篇 |
1991年 | 20篇 |
1990年 | 17篇 |
1989年 | 16篇 |
1988年 | 15篇 |
1987年 | 8篇 |
1986年 | 11篇 |
1985年 | 20篇 |
1984年 | 16篇 |
1983年 | 7篇 |
1982年 | 6篇 |
1981年 | 6篇 |
1980年 | 6篇 |
1979年 | 5篇 |
1978年 | 3篇 |
1977年 | 8篇 |
1976年 | 3篇 |
1974年 | 4篇 |
1966年 | 1篇 |
排序方式: 共有2457条查询结果,搜索用时 15 毫秒
81.
Krzysztof Marynowski 《European Journal of Mechanics - A/Solids》2010,29(5):879-886
In this paper, the viscoelastic theory is applied to the axially moving Levy-type plate with two simply supported and two free edges. On the basis of the elastic – viscoelastic equivalence, a linear mathematical model in the form of the equilibrium state equation of the moving plate is derived in the complex frequency domain. Numerical calculations of dynamic stability were conducted for a steel plate. The effects of transport speed and relaxation times modeled with two-parameter Kelvin–Voigt and three-parameter Zener rheological models on the dynamic behavior of the axially moving viscoelastic plate are analyzed. 相似文献
82.
Sara Janowska Dmytro Khylyuk Anna Bielawska Anna Szymanowska Agnieszka Gornowicz Krzysztof Bielawski Jarosaw Noworl Sawomir Mandziuk Monika Wujec 《Molecules (Basel, Switzerland)》2022,27(6)
We designed and synthesized the 1,3,4-thiadiazole derivatives differing in the structure of the substituents in C2 and C5 positions. The cytotoxic activity of the obtained compounds was then determined in biological studies using MCF-7 and MDA-MB-231 breast cancer cells and normal cell line (fibroblasts). The results showed that in both breast cancer cell lines, the strongest anti-proliferative activity was exerted by 2-(2-trifluorometylophenylamino)-5-(3-methoxyphenyl)-1,3,4-thiadiazole. The IC50 values of this compound against MCF-7 and MDA-MB-231 breast cancer cells were 49.6 µM and 53.4 µM, respectively. Importantly, all new compounds had weaker cytotoxic activity on normal cell line than on breast cancer cell lines. In silico studies demonstrated a possible multitarget mode of action for the synthesized compounds. The most likely mechanism of action for the new compounds is connected with the activities of Caspase 3 and Caspase 8 and activation of BAX proteins. 相似文献
83.
Magorzata Kapelko-eberska Marta Meisel Krzysztof Buksa Artur Gryszkin Antoni Szumny Bogna Latacz Bartosz Raszewski Tomasz Ziba 《Molecules (Basel, Switzerland)》2022,27(8)
The present study aimed to determine changes in the properties of starch triggered by its long-lasting (1, 2, 4, 7, 10, or 14 days) retention with citric acid (5 g/100 g) at a temperature of 40 °C. The starch citrates obtained under laboratory conditions had a low degree of substitution, as confirmed via NMR and HPSEC analyses. The prolonging time of starch retention with citric acid at 40 °C contributed to its increased esterification degree (0.05–0.11 g/100 g), swelling power (30–38 g/g), and solubility in water (19–35%) as well as to decreased viscosity of the starch pastes. Starch heating with citric acid under the applied laboratory conditions did not affect the course of DSC thermal characteristics of starch pasting. The low-substituted starch citrates exhibited approximately 15% resistance to amylolysis. 相似文献
84.
Konrad Skotnicki Ireneusz Janik Klaudia Sadowska Grazyna Leszczynska Krzysztof Bobrowski 《Molecules (Basel, Switzerland)》2022,27(1)
One-electron oxidation of 2-selenouracil (2-SeU) by hydroxyl (●OH) and azide (●N3) radicals leads to various primary reactive intermediates. Their optical absorption spectra and kinetic characteristics were studied by pulse radiolysis with UV-vis spectrophotometric and conductivity detection and by the density functional theory (DFT) method. The transient absorption spectra recorded in the reactions of ●OH with 2-SeU are dominated by an absorption band with an λmax = 440 nm, the intensity of which depends on the concentration of 2-SeU and pH. Based on the combination of conductometric and DFT studies, the transient absorption band observed both at low and high concentrations of 2-SeU was assigned to the dimeric 2c-3e Se-Se-bonded radical in neutral form (2●). The dimeric radical (2●) is formed in the reaction of a selenyl-type radical (6●) with 2-SeU, and both radicals are in equilibrium with Keq = 1.3 × 104 M−1 at pH 4 (below the pKa of 2-SeU). Similar equilibrium with Keq = 4.4 × 103 M−1 was determined for pH 10 (above the pKa of 2-SeU), which admittedly involves the same radical (6●) but with a dimeric 2c-3e Se-Se bonded radical in anionic form (2●−). In turn, at the lowest concentration of 2-SeU (0.05 mM) and pH 10, the transient absorption spectrum is dominated by an absorption band with an λmax = 390 nm, which was assigned to the ●OH adduct to the double bond at C5 carbon atom (3●) based on DFT calculations. Similar spectral and kinetic features were also observed during the ●N3-induced oxidation of 2-SeU. In principle, our results mostly revealed similarities in one-electron oxidation pathways of 2-SeU and 2-thiouracil (2-TU). The major difference concerns the stability of dimeric radicals with a 2c-3e chalcogen-chalcogen bond in favor of 2-SeU. 相似文献
85.
A method for the deposition of BN onto graphite and other substrates is described. Boron trichloride (BCl3) and ammonia (NH3) diluted with Ar were used as reacting gases. The deposition process was carried out at 1300 K as well as lower temperatures in an open system at pressures of 1 atm. The consequences of the introduction of hydrogen to the system were considered. It was demonstrated that the replacement of argon with hydrogen increases the efficiency of the process as well as the theoretical rate of BN deposition. However, the acceleration of the deposition seems to be unprofitable, because the resulting supersaturation leads to the formation of an amorphous phase. The modification of the experimental conditions were proposed.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday 相似文献
86.
Aleksandra Dymek Jarosaw Widelski Krzysztof Kamil Wojtanowski Paulina Poszaj Rostyslav Zhuravchak Tomasz Mroczek 《Molecules (Basel, Switzerland)》2021,26(6)
Alkaloids of the Lycopodiaceae family are of great interest to researchers due to their numerous properties and wide applications in medicine. They play a very important role mainly due to their potent antioxidant, antidepressant effects and a reversible ability to inhibit acetylcholinesterase (AChE) enzyme activity. This property is of immense importance due to the growing problem of an increasing number of patients with neurodegenerative diseases in developed countries and a lack of effective and efficient treatment for them. Numerous studies have shown that Lycopodiaceae alkaloids are a rich source of AChE inhibitors. In the obtaining of new therapeutic phytochemicals from plant material, the extraction process and its efficiency is crucial. Therefore, the aim of this work was to optimize the conditions of modern PLE to obtain bioactive alkaloids from two Lycopodium species: L. clavatum L. and L. annotinum L. Five different solvents of different polarity were used for prepared plant extracts in order to compare the alkaloid content in and thereby effectiveness of the entire extraction. PLE parameters were used based on multiple studies conducted that gave the highest alkaloids recovery. Crude extracts were purified using solid-phase extraction (SPE) on Oasis HLB cartridge and examined by HPLC/ESI-QTOF–MS of the highly abundant alkaloids. To the best of our knowledge, this is the first time such high recoveries have been obtained for known Lycopodiaceae alkaloids. The best extraction results of alkaloid-lycopodine were detected in the dichloromethane extract from L. clavatum, where the yield exceeded 45%. The high recovery of annotinine above 40% presented in L. annotinum was noticed in dichloromethane and ethyl acetate extracts. Moreover, chromatograms were obtained with all isolated alkaloids and the best separation and quality of the bands in methanolic extracts. Interestingly, no alkaloid amounts were detected in cyclohexane extracts belonging to the non-polar solvent. These results could be helpful for understanding and optimizing the best conditions for isolating potent AChE inhibitors. 相似文献
87.
Anna Hanft Dr. Krzysztof Radacki Priv.-Doz. Dr. Crispin Lichtenberg 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(20):6230-6239
The behavior of the redox-active aminotroponiminate (ATI) ligand in the coordination sphere of bismuth has been investigated in neutral and cationic compounds, [Bi(ATI)3] and [Bi(ATI)2Ln][A] (L=neutral ligand; n=0, 1; A=counteranion). Their coordination chemistry in solution and in the solid state has been analyzed through (variable-temperature) NMR spectroscopy, line-shape analysis, and single-crystal X-ray diffraction analyses, and their Lewis acidity has been evaluated by using the Gutmann–Beckett method (and modifications thereof). Cyclic voltammetry, in combination with DFT calculations, indicates that switching between ligand- and metal-centered redox events is possible by altering the charge of the compounds from 0 in neutral species to +1 in cationic compounds. This adds important facets to the rich redox chemistry of ATIs and to the redox chemistry of bismuth compounds, which is, so far, largely unexplored. 相似文献
88.
Annalena Gärtner Matthäus Marek Dr. Merle Arrowsmith Dr. Dominic Auerhammer Krzysztof Radacki Dr. Dominic Prieschl Dr. Rian D. Dewhurst Prof. Dr. Holger Braunschweig 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(37):9694-9699
Cyclic alkyl(amino)carbene-stabilized (cyano)hydroboryl anions were synthesized by deprotonation of (cyano)dihydroborane precursors. While they display boron-centered nucleophilic reactivity towards organohalides, generating fully unsymmetrically substituted cyano(hydro)organoboranes, they show cyano-nitrogen-centered nucleophilic reactivity towards haloboranes, resulting in the formation of hitherto unknown linear 2-aza-1,4-diborabutatrienes. 相似文献
89.
Krzysztof Wolinski Robert Haacke James F. Hinton Peter Pulay 《Journal of computational chemistry》1997,18(6):816-825
We implemented our gauge-including atomic orbital (GIAO) NMR chemical shielding program on a workstation cluster, using the parallel virtual machine (PVM) message-passing system. On a modest number of nodes, we achieved close to linear speedup. This program is characterized by several novel features. It uses the new integral program of Wolinski that calculates integrals in vectorized batches, increases efficiency, and simplifies parallelization. The self-consistent field (SCF) step includes a multi-Fock algorithm, i.e., the simultaneous calculation of several Fock matrices with the same integral set, increasing the efficiency of the direct SCF procedure. The SCF diagonalization step, which is difficult to parallelize, has been replaced by pseudodiagonalization. The latter, widely used in semiempirical programs, becomes important in ab initio type calculations above a certain size, because the ultimate scaling of the diagonalization step is steeper than that of integral computation. Examples of the calculation of the NMR shieldings in large systems at the SCF level are shown. Parallelization of the density functional code is underway. © 1997 by John Wiley & Sons, Inc. J Comput Chem 18: 816–825, 1997 相似文献
90.
Julia Pretula Krzysztof Kaluzynski Jan Libiszowski Ryszard Szymanski Stanislaw Penczek 《Journal of polymer science. Part A, Polymer chemistry》1997,35(9):1733-1742
Copolymers of 7-oxabicyclo[2.2.1] heptane (B) (and of its 2-methyl derivatives) with 1,3-dioxane (D) were obtained by cationic copolymerization initiated with benzoylium hexafluoroantimonate. Structure of copolymers was determined by 1H- and 13C-NMR. The proportion of the acetal bonds in copolymers was additionally confirmed in studies of the products of hydrolysis (only the acetal bonds hydrolyze). D is unable to homopolymerize for the thermodynamic reasons and therefore mostly pseudoperiodic copolymers (-DBx-)y are formed. Nevertheless, the reshuffling reactions are responsible for the appearance of “wrong” units. These are: the separate oxymethylene and oxy-1,3-propylene units (P, subunits of D) located between two B units. Only the acetal bonds are cleaved in the acidic hydrolysis with dilute HCl. This gives the promesogenic telechelic oligomers of mostly HO-P-Bx-OH structure. This article is the first to describe successful cationic copolymerization of a cyclic acetal with a cyclic ether. Moreover, the inability of D to homopolymerize gives the thermodynamic basis of the pseudoperiodic copolymer formation. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 1733–1742, 1997 相似文献