全文获取类型
收费全文 | 3937篇 |
免费 | 129篇 |
国内免费 | 58篇 |
专业分类
化学 | 2480篇 |
晶体学 | 15篇 |
力学 | 133篇 |
数学 | 735篇 |
物理学 | 761篇 |
出版年
2024年 | 4篇 |
2023年 | 28篇 |
2022年 | 104篇 |
2021年 | 116篇 |
2020年 | 102篇 |
2019年 | 117篇 |
2018年 | 112篇 |
2017年 | 92篇 |
2016年 | 159篇 |
2015年 | 124篇 |
2014年 | 144篇 |
2013年 | 264篇 |
2012年 | 292篇 |
2011年 | 296篇 |
2010年 | 194篇 |
2009年 | 162篇 |
2008年 | 259篇 |
2007年 | 219篇 |
2006年 | 259篇 |
2005年 | 235篇 |
2004年 | 182篇 |
2003年 | 137篇 |
2002年 | 122篇 |
2001年 | 60篇 |
2000年 | 43篇 |
1999年 | 47篇 |
1998年 | 28篇 |
1997年 | 24篇 |
1996年 | 25篇 |
1995年 | 22篇 |
1994年 | 27篇 |
1993年 | 10篇 |
1992年 | 16篇 |
1991年 | 17篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1988年 | 6篇 |
1986年 | 3篇 |
1985年 | 7篇 |
1984年 | 6篇 |
1983年 | 8篇 |
1982年 | 5篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1976年 | 4篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1972年 | 2篇 |
1971年 | 2篇 |
排序方式: 共有4124条查询结果,搜索用时 15 毫秒
991.
Biljana Jančić-Stojanović Igor Popović Anđelija Malenović Darko Ivanović Mirjana Medenica 《Chromatographia》2010,71(9-10):799-804
In this paper optimization of chromatographic retention of ramipril and its five impurities employing factorial design is presented. On the basis of preliminary experiments three factors were chosen as inputs (acetonitrile content, pH of the mobile phase and buffer concentration) and retention factor as output. As optimal full factorial design 23 was chosen, factors were examined at two different levels “low” and “high”. Three replications at zero level were added in order to check linearity and complete statistical tests. Relationship between inputs and output is presented in form of second order interaction model. Adequacy of model was explained using analysis of variance. After analysis of results optimal chromatographic conditions were set. Separations were conducted on a C18 column with a mixture of acetonitrile and water phase (TEA in potassium dihydrogen phosphate) in ratio 23:77 v/v. Finally, the LC method was validated and applied for quality control analysis of commercially available tablets. The proposed method is simpler and faster as compared to existing official methods and therefore more adequate for routine control of ramipril during shelf life. Also a general approach which includes factorial design in method optimization offers a possibility for predicting and following the chromatographic behavior of such complex mixtures. 相似文献
992.
The use of semiconductor quantum dots (QDs) in biological sensing and labeling continues to grow with each year. Current and
projected applications include use as fluorescent labels for cellular labeling, intracellular sensors, deep-tissue and tumor
imaging agents, sensitizers for photodynamic therapy, and more recently interest has been sparked in using them as vectors
for studying nanoparticle-mediated drug delivery. Many of these applications will ultimately require the QDs to undergo targeted
intracellular delivery, not only to specific cells, but also to a variety of subcellular compartments and organelles. It is
apparent that this issue will be critical in determining the efficacy of using QDs, and indeed a variety of other nanoparticles,
for these types of applications. In this review, we provide an overview of the current methods for delivering QDs into cells.
Methods that are covered include facilitated techniques such as those that utilize specific peptide sequences or polymer delivery
reagents and active methods such as electroporation and microinjection. We critically examine the benefits and liabilities
of each strategy and illustrate them with selected examples from the literature. Several important related issues such as
QD size and surface coating, methods for QD biofunctionalization, cellular physiology and toxicity are also discussed. Finally,
we conclude by providing a perspective of how this field can be expected to develop in the future. 相似文献
993.
An approach based on cavity compliance contribution tensor is utilized for evaluation of effective stiffness of anisotropic materials with irregularly shaped pores. The shapes considered in the present work were extracted from the X-ray computed microtomography of a carbon/carbon composite sample. The cavity contribution tensors of individual pores were calculated numerically and then employed in the micromechanical modeling procedure. It was shown that presence of pores with total porosity of p = 9.13% results in approximately 20% reduction in the material's Young's moduli. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
994.
Perepichka IF Roquet S Leriche P Raimundo JM Frère P Roncali J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(11):2960-2966
The dimer and trimer of 3,4-phenylenedioxythiophene (PheDOT) have been synthesized. Unlike the parent systems based on 3,4-ethylenedioxythiophene (EDOT), these compounds are quite stable under atmospheric conditions. The electronic absorption spectra of di- and tri-PheDOT exhibit a well-resolved vibronic fine structure indicative of self-rigidification of the conjugated structure by noncovalent intramolecular sulfur-oxygen interactions. Comparison of UV-visible data for the PheDOT oligomers with those of the corresponding EDOT oligomers reveals a faster decrease of the HOMO-LUMO gap with chain length for the former. Cyclic voltammetric data show that whereas PheDOT oxidizes at a lower potential than EDOT, the PheDOT dimer and trimer exhibit much higher oxidation potentials than their EDOT-based analogues. A comparative analysis of the electropolymerization of the three PheDOT-based systems shows that although PheDOT is very difficult to polymerize, its dimer and trimer can be readily electropolymerized. This unexpected increase of reactivity with chain extension is discussed with the aid of theoretical calculations. 相似文献
995.
Lebedev N Trammell SA Spano A Lukashev E Griva I Schnur J 《Journal of the American Chemical Society》2006,128(37):12044-12045
The photosynthetic reaction center (RC) found in photosynthetic bacteria is one of the most advanced photoelectronic devices developed by nature. However, after immobilization on the electrode surface, the efficiency of electron transfer (ET) between the RC and the electrode is relatively low. This inefficiency has limited the possibility of using the RC for technological applications. Here we show that photoinduced electron transfer between the immobilized RC and a gold electrode can be increased by several tens-fold by incorporation of cytochrome c into the RC-self-assembled monolayer (SAM)-electrode complex. The effect does not depend on the initial redox state of the cytochrome and seems to be the result of the formation of a complex between the RC and the cytochrome c serving as an ET wire. This observation opens the possibility for electrochemical analysis of the special pair in the RC protein that is deeply buried inside the protein globe and is barely electrically addressable from the electrode surface. 相似文献
996.
Cotton FA Koshevoy IO Lahuerta P Murillo CA Sanaú M Ubeda MA Zhao Q 《Journal of the American Chemical Society》2006,128(42):13674-13675
A general method for the syntheses of dipalladium compounds having a singly bonded Pd26+ core and the formula R,S-cis-Pd2(C6H4PPh2)2(O2CR)2Cl2 is described. When the alkyl group in the carboxylate ligands is an electron donating group, the compounds are stable and the yields high. The Pd-Pd distances for the diamagnetic compounds with R = CF3 and CMe3 are 2.5434(4) and 2.5241(9) A, respectively. Calculations at the DFT level suggest that the electronic configuration is sigma2pi4delta2delta*2pi*4. These represent rare examples of palladium(III) compounds. 相似文献
997.
Pons T Medintz IL Wang X English DS Mattoussi H 《Journal of the American Chemical Society》2006,128(47):15324-15331
We present a single particle fluorescence resonance energy transfer (spFRET) study of freely diffusing self-assembled quantum dot (QD) bioconjugate sensors, composed of CdSe-ZnS core-shell QD donors surrounded by dye-labeled protein acceptors. We first show that there is direct correlation between single particle and ensemble FRET measurements in terms of derived FRET efficiencies and donor-acceptor separation distances. We also find that, in addition to increased sensitivity, spFRET provides information about FRET efficiency distributions which can be used to resolve distinct sensor subpopulations. We use this capacity to gain information about the distribution in the valence of self-assembled QD-protein conjugates and show that this distribution follows Poisson statistics. We then apply spFRET to characterize heterogeneity in single sensor interactions with the substrate/target and show that such heterogeneity varies with the target concentration. The binding constant derived from spFRET is consistent with ensemble measurements. 相似文献
998.
Larrosa I Da Silva MI Gómez PM Hannen P Ko E Lenger SR Linke SR White AJ Wilton D Barrett AG 《Journal of the American Chemical Society》2006,128(43):14042-14043
The first total synthesis of (+)-clavilactone B, a potent antifungal agent and novel tyrosine kinase inhibitor, is described. The absolute configuration of clavilactones has been unambiguously established by using Sharpless asymmetric epoxidation to generate the enantiomerically pure substrate. The strategy highlights the use of a powerful and convergent three-component benzyne coupling with a methylallyl Grignard and a chiral epoxy-aldehyde to generate two C-C bonds and install the carbon skeleton of clavilactone. Oxidative lactonization, ten-membered ring construction by ring closing metathesis, and oxidation gave clavilactone B. 相似文献
999.
The hydration structures and dynamics of phenol in aqueous solution at infinite dilution are investigated using molecular-dynamics simulation technique. The simulations are performed at several temperatures along the coexistence curve of water up to the critical point, and above the critical point with density fixed at 0.3 g/cm3. The hydration structures of phenol are characterized using the radial, cylindrical, and spatial distribution functions. In particular, full spatial maps of local atomic (solvent) density around a solute molecule are presented. It is demonstrated that in addition to normal H bonds with hydroxyl group of phenol, water forms pi-type complexes with the center of the benzene ring, in which H2O molecules act as H-bond donor. At ambient conditions phenol is solvated by 38 water molecules, which make up a large hydrophobic cavity, and forms on average 2.39 H bonds (1.55 of which are due to the hydroxyl group-water interactions and 0.84 are due to the pi complex) with its hydration shell. As temperature increases, the hydration structure of phenol undergoes significant changes. The disappearance of the pi-type H bonding is observed near the critical point. Self-diffusion coefficients of water and phenol are also calculated. Dramatic increase in the diffusivity of phenol in aqueous solution is observed near the critical point of simple point-charge-extended water and is related to the changes in water structure at these conditions. 相似文献
1000.
Lyudmila F. Sharanda Igor V. Babich Igor V. Plyuto Jerzy Stoch 《Applied Surface Science》2006,252(24):8549-8556
Hybrid carbon-coated alumina supports have been synthesised using 4,4′-methylenebis(phenylisocyanate) as carbon precursor. The adsorption of 4,4′-methylenebis(phenylisocyanate) on the alumina support is irreversible, the resulting organic moiety can undergo pyrolysis under elevated temperature with the formation of carbon coating on the alumina support. Carbon loading in the synthesised materials and thus a degree of coverage of the alumina surface with carbon layer can be increased by repetition of 4,4′-methylenebis(phenylisocyanate) adsorption-pyrolysis cycles. The carbon coating does not substantially influence the pore structure of the initial alumina support. Upon increasing the carbon loading, the carbon coating becomes more uniform with respect to carbon localisation both on the internal and the external surface of the alumina support. The carbon coating on an alumina support can be discriminated from carbonaceous deposits due to a difference in the steady-state surface charging of the samples. Moreover, carbonaceous surface species which associated with CO, CO and OCO groups in carbon coating can also be identified. 相似文献