全文获取类型
收费全文 | 2347篇 |
免费 | 113篇 |
国内免费 | 12篇 |
专业分类
化学 | 2025篇 |
晶体学 | 10篇 |
力学 | 16篇 |
数学 | 245篇 |
物理学 | 176篇 |
出版年
2023年 | 17篇 |
2022年 | 43篇 |
2021年 | 61篇 |
2020年 | 62篇 |
2019年 | 56篇 |
2018年 | 29篇 |
2017年 | 43篇 |
2016年 | 89篇 |
2015年 | 75篇 |
2014年 | 84篇 |
2013年 | 126篇 |
2012年 | 163篇 |
2011年 | 179篇 |
2010年 | 100篇 |
2009年 | 102篇 |
2008年 | 143篇 |
2007年 | 136篇 |
2006年 | 149篇 |
2005年 | 120篇 |
2004年 | 104篇 |
2003年 | 95篇 |
2002年 | 86篇 |
2001年 | 31篇 |
2000年 | 20篇 |
1999年 | 21篇 |
1998年 | 19篇 |
1997年 | 12篇 |
1996年 | 23篇 |
1995年 | 21篇 |
1994年 | 13篇 |
1993年 | 9篇 |
1992年 | 11篇 |
1991年 | 13篇 |
1990年 | 9篇 |
1989年 | 8篇 |
1988年 | 8篇 |
1986年 | 3篇 |
1985年 | 4篇 |
1984年 | 6篇 |
1983年 | 13篇 |
1982年 | 7篇 |
1981年 | 7篇 |
1980年 | 7篇 |
1979年 | 9篇 |
1978年 | 3篇 |
1976年 | 5篇 |
1973年 | 3篇 |
1958年 | 55篇 |
1957年 | 20篇 |
1934年 | 4篇 |
排序方式: 共有2472条查询结果,搜索用时 15 毫秒
91.
92.
1,3-Disubstituted pyrroles were prepared by a microwave-assisted reaction of pyrrolidine and aldehydes in toluene as well as in solvent-free conditions. Reactions were completed in a few minutes in the solvent-free condition but a long time (up to 30 min) was necessary to complete reactions in toluene. Yields of products depended considerably on the aldehyde used. 相似文献
93.
This work demonstrates the analytical applicability of single ion-selective membranes (ISMs) and potentiometric sensor array to distinguish and detect cathinone derivatives. Potentiometric data from ISMs based on cation exchanger and varying content of calix[4]arene derivative were processed by principal component analysis (PCA). Such a combination of methods allowed discriminating various individual synthetic cathinones and their recognition from the mixture comprising primary amines (substituted amphetamines+aminoindane). Analytical parameters of ISM containing 1wt % of calix[4]arene derivative were sufficient to detect 1.0×10−4 mol.l−1 1-(4-fluorophenyl)-2-(ethylamino)butan-1-one and 2-(methylamino)-1-phenylbutan-1-one (buphedrone) in both model and saliva samples. 相似文献
94.
Dr. Eva Kirchner Dr. David Bialas Prof. Frank Würthner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(48):11294-11301
Exciton coupling between different types of chromophores has been rarely investigated. Herein, a systematic study on the exciton coupling between merocyanine chromophores of different conjugation length with varying excited state energies is presented. In this work well-defined hetero-dimer stacks were obtained upon folding of bis(merocyanine) dyes in nonpolar solvents. They show distinctly different absorption properties in comparison with the spectra of the single chromophores, revealing a significant coupling between the different chromophores. The simulated absorption spectra obtained from time-dependent density functional theory (TD-DFT) calculations are in good agreement with the experimental spectra. Our theoretical analysis based on an extension of Kasha's exciton theory discloses strong coupling between the dyes’ transition dipole moments despite of an excited-state energy difference of 0.60 eV between the chromophores. 相似文献
95.
Eva Lucaccini Matteo Briganti Dr. Mauro Perfetti Dr. Laure Vendier Dr. Jean‐Pierre Costes Dr. Federico Totti Prof. Dr. Roberta Sessoli Prof. Dr. Lorenzo Sorace 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(16):5552-5562
The magnetic behaviour of a Dy(LH)3 complex (LH? is the anion of 2‐hydroxy‐N′‐[(E)‐(2‐hydroxy‐3‐methoxyphenyl)methylidene]benzhydrazide) was analysed in depth from both theoretical and experimental points of view. Cantilever torque magnetometry indicated that the complex has Ising‐type anisotropy, and provided two possible directions for the easy axis of anisotropy due to the presence of two magnetically non‐equivalent molecules in the crystal. Ab initio calculations confirmed the strong Ising‐type anisotropy and disentangled the two possible orientations. The computed results obtained by using ab initio calculations were then used to rationalise the composite dynamic behaviour observed for both pure DyIII phase and YIII diluted phase, which showed two different relaxation channels in zero and non‐zero static magnetic fields. In particular, we showed that the relaxation behaviour at the higher temperature range can be correctly reproduced by using a master matrix approach, which suggests that Orbach relaxation is occurring through a second excited doublet. 相似文献
96.
Dr. Marzia Dell'Aera Dr. Filippo Maria Perna Dr. Paola Vitale Dr. Angela Altomare Prof. Alessandro Palmieri Dr. Lewis C. H. Maddock Leonie J. Bole Dr. Alan R. Kennedy Prof. Eva Hevia Prof. Vito Capriati 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(40):8742-8748
We report the first transition metal catalyst- and ligand-free conjugate addition of lithium tetraorganozincates (R4ZnLi2) to nitroolefins. Displaying enhanced nucleophilicity combined with unique chemoselectivity and functional group tolerance, homoleptic aliphatic and aromatic R4ZnLi2 provide access to valuable nitroalkanes in up to 98 % yield under mild conditions (0 °C) and short reaction time (30 min). This is particularly remarkable when employing β-nitroacrylates and β-nitroenones, where despite the presence of other electrophilic groups, selective 1,4 addition to the C=C is preferred. Structural and spectroscopic studies confirmed the formation of tetraorganozincate species in solution, the nature of which has been a long debated issue, and allowed to unveil the key role played by donor additives on the aggregation and structure of these reagents. Thus, while chelating N,N,N’,N’-tetramethylethylenediamine (TMEDA) and (R,R)-N,N,N’,N’-tetramethyl-1,2-diaminocyclohexane (TMCDA) favour the formation of contacted-ion pair zincates, macrocyclic Lewis donor 12-crown-4 triggers an immediate disproportionation process of Et4ZnLi2 into equimolar amounts of solvent-separated Et3ZnLi and EtLi. 相似文献
97.
Miroslav Veverka Peter ?imon Ján Lokaj Eva Veverková 《Monatshefte für Chemie / Chemical Monthly》2012,10(4):65-71
Abstract
Crystals of the α-form of imatinib mesylate with various habits (e.g., polyhedral-like and plate-like) were prepared from various organic solvents (e.g., butyl lactate, 4-methyl-2-pentanone, 2-methyl-2-butanol, 2-isopropoxyethanol, propyl ether) by several precipitation methods. The methods provide imatinib mesylate in a non-needle-shaped crystalline α-form. The crystal modification was identified by hot-stage microscopy, scanning electron microscopy, differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and X-ray powder diffraction (XRPD). The analyses by DSC, IR, and XRPD indicate that imatinib mesylate crystals with various habits have the same crystal structure. The plate-like habit has been also observed in the system where the organic solvent acts as a precipitant. 相似文献98.
99.
Nallusamy Venkatachalam Eva Hemmer Tomoyoshi Yamano Hiroshi Hyodo Hidehiro Kishimoto Kohei Soga 《Progress in Crystal Growth and Characterization of Materials》2012,58(2-3):121-134
Yttrium hydroxyl carbonate (Y(OH)CO3) precursors were synthesized by the homogeneous co-precipitation method in the presence of polyacrylic acid (PAAc). Resultant precursor particle size is about 15–20 nm with narrow size distribution whereas the particle size is smaller than those acquired by the conventional homogeneous precipitation method. Effective decrease of Y(OH)CO3 particle size was found to be higher for the presence of weak polyanionic ionomer such as PAAc than the presence of strong polyanionic ionomer such as sodium polystyrene sulfonate (PSS). It was observed that the morphology and size of the precursors are almost unchanged after the calcination process. Er3+ doped Y2O3 nanoparticles were synthesized by PAAc assisted homogeneous co-precipitation method showed bright green (550 nm) and red (660 nm) upconversion (UC) as well as near-infrared (NIR) fluorescence (1550 nm) under 980-nm excitation. UC and NIR fluorescence bioimaging and in-vitro cytotoxicity assay of Er3+ doped Y2O3 nanoparticles were successfully attempted with commercially available macrophages and B-cell hybridomas. Cellular uptake of nanoparticles is evidenced from bright field, UC and NIR fluorescence images of macrophages. 相似文献
100.
José Maria Esbrí Anna Bernaus Marta ávila David Kocman Eva M. García‐Noguero Beatriz Guerrero Xavier Gaona Rodrigo álvarez Gustavo Perez‐Gonzalez Manuel Valiente Pablo Higueras Milena Horvat Jorge Loredo 《Journal of synchrotron radiation》2010,17(2):179-186
The mobility, bioavailability and toxicity of mercury in the environment strongly depend on the chemical species in which it is present in soil, sediments, water or air. In mining districts, differences in mobility and bioavailability of mercury mainly arise from the different type of mineralization and ore processing. In this work, synchrotron‐based X‐ray absorption near‐edge spectroscopy (XANES) has been taken advantage of to study the speciation of mercury in geological samples from three of the largest European mercury mining districts: Almadén (Spain), Idria (Slovenia) and Asturias (Spain). XANES has been complemented with a single extraction protocol for the determination of Hg mobility. Ore, calcines, dump material, soil, sediment and suspended particles from the three sites have been considered in the study. In the three sites, rather insoluble sulfide compounds (cinnabar and metacinnabar) were found to predominate. Minor amounts of more soluble mercury compounds (chlorides and sulfates) were also identified in some samples. Single extraction procedures have put forward a strong dependence of the mobility with the concentration of chlorides and sulfates. Differences in efficiency of roasting furnaces from the three sites have been found. 相似文献