全文获取类型
收费全文 | 1304篇 |
免费 | 34篇 |
国内免费 | 5篇 |
专业分类
化学 | 860篇 |
晶体学 | 9篇 |
力学 | 39篇 |
数学 | 184篇 |
物理学 | 251篇 |
出版年
2023年 | 5篇 |
2022年 | 11篇 |
2021年 | 14篇 |
2020年 | 13篇 |
2019年 | 16篇 |
2018年 | 16篇 |
2017年 | 6篇 |
2016年 | 41篇 |
2015年 | 30篇 |
2014年 | 28篇 |
2013年 | 70篇 |
2012年 | 88篇 |
2011年 | 108篇 |
2010年 | 56篇 |
2009年 | 48篇 |
2008年 | 78篇 |
2007年 | 72篇 |
2006年 | 78篇 |
2005年 | 70篇 |
2004年 | 70篇 |
2003年 | 44篇 |
2002年 | 50篇 |
2001年 | 16篇 |
2000年 | 15篇 |
1999年 | 18篇 |
1998年 | 12篇 |
1997年 | 21篇 |
1996年 | 16篇 |
1995年 | 6篇 |
1994年 | 10篇 |
1993年 | 10篇 |
1992年 | 14篇 |
1990年 | 10篇 |
1989年 | 12篇 |
1986年 | 11篇 |
1985年 | 14篇 |
1984年 | 12篇 |
1983年 | 13篇 |
1982年 | 12篇 |
1981年 | 12篇 |
1980年 | 9篇 |
1979年 | 11篇 |
1978年 | 6篇 |
1977年 | 8篇 |
1976年 | 5篇 |
1975年 | 4篇 |
1974年 | 10篇 |
1973年 | 9篇 |
1972年 | 9篇 |
1971年 | 4篇 |
排序方式: 共有1343条查询结果,搜索用时 31 毫秒
71.
Catherine Bourdieu Andre Foucaud 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):365-368
Abstract 1,2-Dihydro 1,2-Δ3? azaphosphorines were prepared by reaction of dichlorophenylphosphine with two equivalents of imines. 2-Oxo 1,2-azaphospholenes were also obtained in some cases. 相似文献
72.
Jean Guillon Jean-Michel Leger Cecilia Dapremont Lou Apollonia Denis Pascal Sonnet Stéphane Massip 《Supramolecular chemistry》2013,25(5):319-329
The synthesis of new 25,27-dialkyloxy-5,17-diarylcalix[4]arenes-crown-6 1a–f in 1,3-alternate conformation by Suzuki cross-coupling reaction is reported. Their conformation was determined using 1H, 13C, 2D NMR and ROESY analysis, and X-ray crystallography. Extraction experiments using a two-phase solvent method involving sodium, potassium or cesium picrate showed good extraction of the cesium cation. The X-ray crystal structures of 1,3-alternate 25,27-dipropoxy-5,17-diphenylcalix[4]arene-crown-6 ether 1a and its cesium picrate complex were established. Solid-state data were used to determine the complexation behavior of these new ligands. The efficiency of calixarenes 1a–f for cesium ion extraction could be ascribed to the rigidity and flatness linkages caused by the aryl groups at the lower rim of the aromatic moieties in the calixarene skeleton. In addition, the introduction of these aromatic moieties in positions 5 and 17 enhanced the solubility of the metal complexes in organic media. 相似文献
73.
74.
Dr. Andre Nicolai Petelski Josefina Marquez Silvana Carina Pamies Prof. Dr. Gladis Laura Sosa Prof. Dr. Nélida María Peruchena 《Chemphyschem》2021,22(7):665-674
Due to their potential binding sites, barbituric acid (BA) and its derivatives have been used in metal coordination chemistry. Yet their abilities to recognize anions remain unexplored. In this work, we were able to identify four structural features of barbiturates that are responsible for a certain anion affinity. The set of coordination interactions can be finely tuned with covalent decorations at the methylene group. DFT-D computations at the BLYP-D3(BJ)/aug-cc-pVDZ level of theory show that the C−H bond is as effective as the N−H bond to coordinate chloride. An analysis of the electron charge density at the C−H⋅⋅⋅Cl− and N−H⋅⋅⋅Cl− bond critical points elucidates their similarities in covalent character. Our results reveal that the special acidity of the C−H bond shows up when the methylene group moves out of the ring plane and it is mainly governed by the orbital interaction energy. The amide and carboxyl groups are the best choices to coordinate the ion when they act together with the C−H bond. We finally show how can we use this information to rationally improve the recognition capability of a small cage-like complex that is able to coordinate NaCl. 相似文献
75.
Melkonian JM Forget N Bretenaker F Drag C Lefebvre M Rosencher E 《Optics letters》2007,32(12):1701-1703
We report on what we believe to be the first active mode locking of near-degenerate, doubly and singly resonant cw-pumped optical parametric oscillators (OPOs). We show experimentally that a steady-state regime of short pulses is reached in a few tens of microseconds under cw pumping. The oscillation buildup dynamics of both OPOs is also explored, evidencing an unusual transient behavior in the mode-locking process. 相似文献
76.
Muchena J. Kailemia Melvin Park Desmond A. Kaplan Andre Venot Geert-Jan Boons Lingyun Li Robert J. Linhardt I. Jonathan Amster 《Journal of the American Society for Mass Spectrometry》2014,25(2):258-268
High-field asymmetric waveform ion mobility spectrometry (FAIMS) is shown to be capable of resolving isomeric and isobaric glycosaminoglycan negative ions and to have great utility for the analysis of this class of molecules when combined with Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and tandem mass spectrometry. Electron detachment dissociation (EDD) and other ion activation methods for tandem mass spectrometry can be used to determine the sites of labile sulfate modifications and for assigning the stereochemistry of hexuronic acid residues of glycosaminoglycans (GAGs). However, mixtures with overlapping mass-to-charge values present a challenge, as their precursor species cannot be resolved by a mass analyzer prior to ion activation. FAIMS is shown to resolve two types of mass-to-charge overlaps. A mixture of chondroitin sulfate A (CSA) oligomers with 4–10 saccharides units produces ions of a single mass-to-charge by electrospray ionization, as the charge state increases in direct proportion to the degree of polymerization for these sulfated carbohydrates. FAIMS is shown to resolve the overlapping charge. A more challenging type of mass-to-charge overlap occurs for mixtures of diastereomers. FAIMS is shown to separate two sets of epimeric GAG tetramers. For the epimer pairs, the complexity of the separation is reduced when the reducing end is alkylated, suggesting that anomers are also resolved by FAIMS. The resolved components were activated by EDD and the fragment ions were analyzed by FTICR-MS. The resulting tandem mass spectra were able to distinguish the two epimers from each other. Figure
? 相似文献
77.
Matthew Wallace Andre Zamith Cardoso Dr. William J. Frith Dr. Jonathan A. Iggo Dr. Dave J. Adams 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(50):16484-16487
The magnetic‐field‐induced alignment of the fibrillar structures present in an aqueous solution of a dipeptide gelator, and the subsequent retention of this alignment upon transformation to a hydrogel upon the addition of CaCl2 or upon a reduction in solution pH is reported. Utilising the switchable nature of the magnetic field coupled with the slow diffusion of CaCl2, it is possible to precisely control the extent of anisotropy across a hydrogel, something that is generally very difficult to do using alternative methods. The approach is readily extended to other compounds that form viscous solutions at high pH. It is expected that this work will greatly expand the utility of such low‐molecular‐weight gelators (LMWG) in areas where alignment is key. 相似文献
78.
Maryam Khaleel Andrew J. Wagner Prof. K. Andre Mkhoyan Prof. Michael Tsapatsis 《Angewandte Chemie (International ed. in English)》2014,53(36):9456-9461
A structural study of a hierarchical zeolite X, which is similar to the one first synthesized by Inayat et al., 12 was performed using transmission electron microscopy imaging and diffraction. Evidence is provided, by comparison to simulations, that this material is an intergrowth of FAU and EMT and a conceptual model is presented for the growth of the FAU material with a small fraction of EMT in an atypical morphology of assembled sheets with well‐defined intersection angles. 相似文献
79.
Macromolecule Loading into Spherical,Elliptical, Star‐Like and Cubic Calcium Carbonate Carriers 下载免费PDF全文
Dr. Bogdan V. Parakhonskiy Dr. Alexey M. Yashchenok Dr. Senem Donatan Dr. Dmitry V. Volodkin Dr. Francesco Tessarolo Prof. Renzo Antolini Prof. Helmuth Möhwald Prof. Andre G. Skirtach 《Chemphyschem》2014,15(13):2817-2822
We fabricated calcium carbonate particles with spherical, elliptical, star‐like and cubical morphologies by varying relative salt concentrations and adding ethylene glycol as a solvent to slow down the rate of particle formation. The loading capacity of particles of different isotropic (spherical and cubical) and anisotropic (elliptical and star‐like) geometries is investigated, and the surface area of such carriers is analysed. Potential applications of such drug delivery carriers are highlighted. 相似文献
80.
Celest Samyn Goedele Claes Marcel van Beylen Anneleen De Wachter Andre Persoons 《Macromolecular Symposia》1996,102(1):145-158
The synthesis and second harmonic coefficients, d3,1 and d3,3 as well as the related susceptibilities χ(2)zzz of five series of (NLO-dye methacrylate)-(methyl methacrylate) copolymers were investigated. The NLO-chromophores bound covalently to the polymer backbone were 5-(2,2-dicyanovinyl)-or 4-(2-cyano-2-methoxycarbonyl)vinyl-1-piperidino-2-thiophene (P1 and P2), 4-nitro-4′-alkoxy-stilbene (P3), 4-nitro-3′-methoxy-4′-alkoxystilbene (P4) and 4-nitro-4′-alkoxy-α-cyano stilbene (P5). The second order nonlinear optical properties of corona-poled aligned thin polymer films, using a needle electrode in order to induce noncentrosymmetry, were evaluated. Nonlinear susceptibilities, χ(2)zzz, of the films were derived from the analysis of full-angle Maker fringe patterns at 1064 nm, χ(2)zzz values as high as 1.98×10−7 esu for P2 copolymers and of 1.19×10−7 esu for P3 copolymers could be achieved. 相似文献