全文获取类型
收费全文 | 1113篇 |
免费 | 51篇 |
国内免费 | 6篇 |
专业分类
化学 | 723篇 |
晶体学 | 2篇 |
力学 | 40篇 |
数学 | 194篇 |
物理学 | 211篇 |
出版年
2023年 | 11篇 |
2022年 | 15篇 |
2021年 | 38篇 |
2020年 | 27篇 |
2019年 | 20篇 |
2018年 | 17篇 |
2017年 | 25篇 |
2016年 | 49篇 |
2015年 | 40篇 |
2014年 | 49篇 |
2013年 | 56篇 |
2012年 | 60篇 |
2011年 | 74篇 |
2010年 | 32篇 |
2009年 | 37篇 |
2008年 | 71篇 |
2007年 | 77篇 |
2006年 | 90篇 |
2005年 | 57篇 |
2004年 | 44篇 |
2003年 | 31篇 |
2002年 | 36篇 |
2001年 | 14篇 |
2000年 | 15篇 |
1999年 | 13篇 |
1998年 | 12篇 |
1997年 | 8篇 |
1996年 | 6篇 |
1995年 | 7篇 |
1994年 | 6篇 |
1993年 | 6篇 |
1992年 | 8篇 |
1991年 | 3篇 |
1990年 | 4篇 |
1989年 | 6篇 |
1988年 | 4篇 |
1986年 | 5篇 |
1985年 | 6篇 |
1984年 | 13篇 |
1983年 | 7篇 |
1982年 | 3篇 |
1981年 | 8篇 |
1980年 | 12篇 |
1979年 | 10篇 |
1978年 | 5篇 |
1977年 | 6篇 |
1976年 | 7篇 |
1975年 | 4篇 |
1974年 | 4篇 |
1972年 | 2篇 |
排序方式: 共有1170条查询结果,搜索用时 15 毫秒
151.
Silvia Colomban Mirko De Rosso Riccardo Flamini Luciano Navarini 《Journal of mass spectrometry : JMS》2023,58(10):e4970
The present study aims to both identify and quantify trans-sinapoylquinic acid (SiQA) regioisomers in green coffee by combined UHPLC-ESI-QqTOF-MS/MS and UHPLC-ESI-QqQ-MS/MS methods. Among the various mono-acyl chlorogenic acids found in green coffee, SiQA regioisomers are the least studied despite having been indicated as unique phytochemical markers of Coffea canephora (known as Robusta). The lack of commercially available authentic standards has been bypassed by resorting to the advantages offered by high-resolution LC–MS as far as the identification is concerned. SiQA regioisomers have been identified in several samples of Robusta and Coffea arabica (known as Arabica) commercial lots from different geographical origin and, for the first time, in different samples of coffee wild species (Coffea liberica and Coffea pseudozanguebariae). Quantification (total SiQA ranging from 3 to 5 mg/100 g) let to reconsider these chlorogenic acids as unique phytochemical markers of Robusta being present in the same quantity and distribution in C. liberica as well. Gardeniae Fructus samples (fruits of Gardenia jasminoides) have additionally been characterized as this matrix is recognized as one of the few naturally occurring SiQA sources. The SiQA regioisomer content (total SiQA about 80 mg/100 mg) fully supports the proposal to use this matrix as a surrogate standard for further studies. 相似文献
152.
Pesavento IC Bertazzo A Flamini R Vedova AD De Rosso M Seraglia R Traldi P 《Journal of mass spectrometry : JMS》2008,43(2):234-241
Until now the study of pathogenic related proteins in grape juice and wine, performed by ESI-MS, LC/ESI-MS, and MALDI/MS, has been proposed for differentiation of varieties. In fact, chitinases and thaumatin-like proteins persist through the vinification process and cause hazes and sediments in bottled wines. An additional instrument, potentially suitable for the grape varieties differentiation, has been developed by MALDI/MS for the grape seed protein analysis. The hydrosoluble protein profiles of seeds extract from three different Vitis vinifera grape (red and white) varieties were analyzed and compared. In order to evaluate the environmental conditions and harvest effects, the seed protein profiles of one grape variety from different locations and harvests were studied. 相似文献
153.
Benzyl ether protected polyhydroxylated alkene compounds containing allylic alcohol, ether or ester functionality undergo a stereospecific cyclisation reaction upon treatment with TFA-acetonitrile-toluene with inversion of configuration at the allylic position and loss of a benzyl ether to give tetrahydrofurans. 相似文献
154.
Riccardo Boero Marco Castellani Flaminio Squazzoni 《Computational & Mathematical Organization Theory》2008,14(2):156-174
The paper aims at presenting an agent-based modeling exercise to illustrate how small differences in the cognitive properties
of agents can generate very different macro social properties. We argue that it is not necessary to assume highly complicated
cognitive architectures to introduce cognitive properties that matter for computational social science purposes. Our model
is based on different simulation settings characterized by a gradual sophistication of behavior of agents, from simple heuristics
to macro-micro feedback and other second-order properties. Agents are localized in a spatial interaction context. They have
an individual task but are influenced by a collective coordination problem. The simulation results show that agents can generate
efficiency at a macro level particularly when socio-cognitive sophistication of their behavior increases.
相似文献
Flaminio Squazzoni (Corresponding author)Email: |
155.
Nanotexturing of polystyrene surface in fluorocarbon plasmas: from sticky to slippery superhydrophobicity 总被引:1,自引:0,他引:1
Mundo RD Palumbo F d'Agostino R 《Langmuir : the ACS journal of surfaces and colloids》2008,24(9):5044-5051
In this work plasma etching processes have been studied to roughen and fluorinate polystyrene surface as an easy method to achieve a superhydrophobic slippery character. Radiofrequency discharges have been fed with CF(4)/O(2) mixtures and the effect of the O(2):CF(4) ratio, the input power, and the treatment duration have been investigated in terms of wettability, with focus on sliding performances. For this purpose, surface morphological variations, evaluated by means of scanning electron microscopy and atomic force microscopy, together with the chemical assessment by X-ray photoelectron spectroscopy, have been correlated with water contact angle hysteresis and volume resolved sliding angle measurements. Results indicate that by increasing the height and decreasing the density of the structures formed by etching, within a tailored range, a transition from sticky to slippery superhydrophobicity occurs. A short treatment time (5 min) is sufficient to obtain such an effect, provided that a high power input is utilized. Optimized surfaces show a unaltered transparency to visible light according to the low roughness produced. 相似文献
156.
Beverina L Crippa M Landenna M Ruffo R Salice P Silvestri F Versari S Villa A Ciaffoni L Collini E Ferrante C Bradamante S Mari CM Bozio R Pagani GA 《Journal of the American Chemical Society》2008,130(6):1894-1902
Singlet oxygen sensitization by organic molecules is a topic of major interest in the development of both efficient photodynamic therapy (PDT) and aerobic oxidations under complete green chemistry conditions. We report on the design, synthesis, biology, and complete spectroscopic characterization (vis-NIR linear and two-photon absorption spectroscopy, singlet oxygen generation efficiencies for both one- and two-photon excitation, electrochemistry, intrinsic dark toxicity, cellular uptake, and subcellular localization) of three classes of innovative singlet oxygen sensitizers pertaining to the family of symmetric squaraine derivatives originating from pi-excessive heterocycles. The main advantage of pi-extended squaraine photosensitizers over the large number of other known photosensitizers is their exceedingly strong two-photon absorption enabling, together with sizable singlet oxygen sensitization capabilities, for their use at the clinical application relevant wavelength of 806 nm. We finally show encouraging results about the dark toxicity and cellular uptake capabilities of water-soluble squaraine photosensitizers, opening the way for clinical small animal PDT trials. 相似文献
157.
Quarta A Di Corato R Manna L Argentiere S Cingolani R Barbarella G Pellegrino T 《Journal of the American Chemical Society》2008,130(32):10545-10555
The combination of materials that possess different properties (such as, for instance, fluorescence and magnetism) into one single object of nanoscale size represents an attractive challenge for biotechnology, especially for their potential relevance in biomedical applications. We report here the preparation of novel bifunctional conjugates based on the linkage of inorganic nanoparticles to organic oligothiophene fluorophores (OTFs). In comparison to the organic dyes commonly used in bioimaging and more similarly to colloidal quantum dots, OTFs have broad optical absorption spectra, and therefore OTF fluorophores emitting at different colors can be excited with a single excitation source, allowing for easier multiplexing analysis. In this work we show the preparation of OTF-nanoparticle conjugates based on gold and iron oxide nanoparticles and their characterization using different techniques such as gel electrophoresis, photoluminescence spectroscopy, dynamic light scattering, and so on. In addition, by performing an in vitro study on human tumor cells we show that OTF-nanoparticle conjugates emitting at different colors can be used for multiplexing detection. Also, in the case of iron oxide-OTF conjugates, once uptaken by the cells, we show that they preserve both their fluorescent and their magnetic properties. 相似文献
158.
Amorati R Catarzi F Menichetti S Pedulli GF Viglianisi C 《Journal of the American Chemical Society》2008,130(1):237-244
Rotation about the Ar-S bond in ortho-(alkylthio)phenols strongly affects the bond dissociation enthalpy (BDE) and the reactivity of the OH group. Newly synthesized sulfur containing heterocycles 3 and 4, where the -SR group is almost coplanar with the phenolic ring, are characterized by unusually low BDE(O-H) values (79.6 and 79.2 kcal/mol, respectively) and by much higher reactivities toward peroxyl radicals than the ortho-methylthio derivative 1 (82.0 kcal/mol). The importance of the intramolecular hydrogen bond (IHB) in determining the BDE(O-H) was demonstrated by FT-IR experiments, which showed that in heterocycles 3 and 4 the IHB between the phenolic OH group and the S atom is much weaker than that present in 1. Since the IHB can be formed only if the -SR group adopts an out-of-plane geometry, this interaction is possible only in the methylthio derivative 1 and not in 3 and 4. The additive contribution to the phenolic BDE(O-H) of the -SR substituent therefore varies from -3.1 to +2.8 kcal/mol for the in-plane and out-of-plane conformations, respectively. These results may be relevant to understanding the role of the tyrosine-cysteine link in the active site of galactose oxidase, an important enzyme that catalyzes the two-electron aerobic oxidation of primary alcohols to aldehydes. The switching of the ortho -SR substituent between perpendicular and planar conformations may account for the catalytic efficiency of this enzyme. 相似文献
159.
Marchetti F Pettinari C Pettinari R Cerquetella A Di Nicola C Macchioni A Zuccaccia D Monari M Piccinelli F 《Inorganic chemistry》2008,47(24):11593-11603
Arene ruthenium(II) complexes containing bis(pyrazolyl)methane ligands have been prepared by reacting the ligands L' (L' in general; specifically L(1) = H(2)C(pz)(2), L(2) = H(2)C(pz(Me2))(2), L(3) = H(2)C(pz(4Me))(2), L(4) = Me(2)C(pz)(2) and L(5) = Et(2)C(pz)(2) where pz = pyrazole) with [(arene)RuCl(mu-Cl)](2) dimers (arene = p-cymene or benzene). When the reaction was carried out in methanol solution, complexes of the type [(arene)Ru(L')Cl]Cl were obtained. When L(1), L(2), L(3), and L(5) ligands reacted with excess [(arene)RuCl(mu-Cl)](2), [(arene)Ru(L')Cl][(arene)RuCl(3)] species have been obtained, whereas by using the L(4) ligand under the same reaction conditions the unexpected [(p-cymene)Ru(pzH)(2)Cl]Cl complex was recovered. The reaction of 1 equiv of [(p-cymene)Ru(L')Cl]Cl and of [(p-cymene)Ru(pzH)(2)Cl]Cl with 1 equiv of AgX (X = O(3)SCF(3) or BF(4)) in methanol afforded the complexes [(p-cymene)Ru(L')Cl](O(3)SCF(3)) (L' = L(1) or L(2)) and [(p-cymene)Ru(pzH)(2)Cl]BF(4), respectively. [(p-cymene)Ru(L(1))(H(2)O)][PF(6)](2) formed when [(p-cymene)Ru(L(1))Cl]Cl reacts with an excess of AgPF(6). The solid-state structures of the three complexes, [(p-cymene)Ru{H(2)C(pz)(2)}Cl]Cl, [(p-cymene)Ru{H(2)Cpz(4Me))(2)}Cl]Cl, and [(p-cymene)Ru{H(2)C(pz)(2)}Cl](O(3)SCF(3)), were determined by X-ray crystallographic studies. The interionic structure of [(p-cymene)Ru(L(1))Cl](O(3)SCF(3)) and [(p-cymene)Ru(L')Cl][(p-cymene)RuCl(3)] (L' = L(1) or L(2)) was investigated through an integrated experimental approach based on NOE and pulsed field gradient spin-echo (PGSE) NMR experiments in CD(2)Cl(2) as a function of the concentration. PGSE NMR measurements indicate the predominance of ion pairs in solution. NOE measurements suggest that (O(3)SCF(3))(-) approaches the cation orienting itself toward the CH(2) moiety of the L(1) (H(2)C(pz)(2)) ligand as found in the solid state. Selected Ru species have been preliminarily investigated as catalysts toward styrene oxidation by dihydrogen peroxide, [(p-cymene)Ru(L(1))(H(2)O)][PF(6)](2) being the most active species. 相似文献
160.
The total charge density distribution rho(r) of the colossal magnetoresistive transition metal sulfide FeCr(2)S(4) was evaluated through a multipole formalism from a set of structure factors obtained both experimentally, by means of single crystal high-quality x-ray diffraction data collected at T=23 K, and theoretically, with an extended-basis unrestricted Hartree-Fock periodic calculation on the experimental geometry. A full topological analysis, followed by the calculation of local energy density values and net atomic charges, was performed using the quantum theory of atoms in molecules. The experimental and theoretical results were compared. Good agreement was found for the topological properties of the system, as well as for the atomic net charges and the nature of the chemical bonds. An analysis of the electron density rho(r), its Laplacian nabla(2)[rho(r)], and the total energy density H(r) at the bond critical points was employed to classify all the interactions that resulted as predominantly closed shell (ionic) in nature. The topological indicators of the bonded interactions for Fe are distinct from those for Cr. The Fe-S bond distances were found to be 0.145 A shorter than the ideal values computed on the basis of Shannon's crystal radii, much shorter than the Cr-S distances with respect to their ideal Shannon lengths. Concomitantly, rho(r) and |H(r)| at the bond critical points are greater for Fe-S interactions, indicating that the local concentration of charge density in the internuclear region is larger for the tetrahedrally coordinated iron than for the octahedrally coordinated chromium. The isosurface in the real space for nabla(2)[rho(r)]=0 was plotted for both iron and chromium, pointing out the local zones of valence shell charge concentration and relating them to the partial d-orbital occupancy of the two transition metal atoms. 相似文献