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61.
Experimental and Theoretical Studies on Arene‐Bridged Metal–Metal‐Bonded Dimolybdenum Complexes 下载免费PDF全文
Dr. Mario Carrasco Natalia Curado Dr. Eleuterio Álvarez Dr. Celia Maya Dr. Riccardo Peloso Prof. Dr. Manuel L. Poveda Dr. Amor Rodríguez Prof. Dr. Eliseo Ruiz Prof. Dr. Santiago Álvarez Prof. Dr. Ernesto Carmona 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(20):6092-6102
The bis(hydride) dimolybdenum complex, [Mo2(H)2{HC(N‐2,6‐iPr2C6H3)2}2(thf)2], 2 , which possesses a quadruply bonded Mo2II core, undergoes light‐induced (365 nm) reductive elimination of H2 and arene coordination in benzene and toluene solutions, with formation of the MoI2 complexes [Mo2{HC(N‐2,6‐iPr2C6H3)2}2(arene)], 3?C6H6 and 3?C6H5Me , respectively. The analogous C6H5OMe, p‐C6H4Me2, C6H5F, and p‐C6H4F2 derivatives have also been prepared by thermal or photochemical methods, which nevertheless employ different Mo2 complex precursors. X‐ray crystallography and solution NMR studies demonstrate that the molecule of the arene bridges the molybdenum atoms of the MoI2 core, coordinating to each in an η2 fashion. In solution, the arene rotates fast on the NMR timescale around the Mo2‐arene axis. For the substituted aromatic hydrocarbons, the NMR data are consistent with the existence of a major rotamer in which the metal atoms are coordinated to the more electron‐rich C?C bonds. 相似文献
62.
Highly Stable Water‐Soluble Platinum Nanoparticles Stabilized by Hydrophilic N‐Heterocyclic Carbenes 下载免费PDF全文
Edwin A. Baquero Dr. Simon Tricard Dr. Juan Carlos Flores Prof. Dr. Ernesto de Jesús Prof. Dr. Bruno Chaudret 《Angewandte Chemie (International ed. in English)》2014,53(48):13220-13224
Controlling the synthesis of stable metal nanoparticles in water is a current challenge in nanochemistry. The strategy presented herein uses sulfonated N‐heterocyclic carbene (NHC) ligands to stabilize platinum nanoparticles (PtNPs) in water, under air, for an indefinite time period. The particles were prepared by thermal decomposition of a preformed molecular Pt complex containing the NHC ligand and were then purified by dialysis and characterized by TEM, high‐resolution TEM, and spectroscopic techniques. Solid‐state NMR studies showed coordination of the carbene ligands to the nanoparticle surface and allowed the determination of a 13C–195Pt coupling constant for the first time in a nanosystem (940 Hz). Additionally, in one case a novel structure was formed in which platinum(II) NHC complexes form a second coordination sphere around the nanoparticle. 相似文献
63.
Nikolay Djourelov Corine Bas Daniel Sillou Rosario Benavente Ernesto Pérez María L. Cerrada 《Journal of Polymer Science.Polymer Physics》2010,48(18):1994-2002
Copolymers of propylene and 1‐octadecene synthesized by a metallocene catalyst were characterized by PALS, WAXD, DSC, and density measurements. The change in the sizes and the number density of free‐volume holes as a function of the 1‐octadecene content were compared to the master laws published for copolymers of propylene with α‐olefins of shorter lengths. It was found that the samples were separated into two groups. The first set of samples obeyed the master laws while the second group deviated. This behavior was explained by the difference in the copolymer structure. The WAXD analysis confirmed the separation as well. The deviation was explained as due to the mesomorphic crystalline structure of the second group of samples, in contrast to the monoclinic one for the first group, which was a result of the relatively fast cooling from the molten state and from the high comonomer molar content. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1994–2002, 2010 相似文献
64.
María Yolanda Ríos M. Ángeles Ramírez‐Cisneros Ismael León‐Rivera Samuel Estrada‐Soto Gabriel Navarrete‐Vázquez A. Berenice Aguilar‐Guadarrama 《Magnetic resonance in chemistry : MRC》2012,50(4):329-331
Complete 1H and 13C NMR chemical shift assignments for 3,4‐seco‐lup‐20(29)‐en‐3‐oic acid ( 1 ) have been established by means of two‐dimensional COSY, HSQC, HMBC and NOESY spectroscopic experiments as well as by analysis of MS data. Compound 1 was isolated from Decatropis bicolor (Zucc.) Radlk. (Rutaceae) in addition to six coumarins and one alkaloid of known structure. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
65.
66.
Ernesto C. Tuazon Pilar Martin Sara M. Aschmann Janet Arey Roger Atkinson 《国际化学动力学杂志》2011,43(11):631-638
Rate constants for the reactions of 2‐methoxy‐6‐(trifluoromethyl)pyridine, diethylamine, and 1,1,3,3,3‐pentamethyldisiloxan‐1‐ol with OH radicals have been measured at 298 ± 2 K using a relative rate method. The measured rate constants (cm3 molecule?1 s?1) are (1.54 ± 0.21) × 10?12 for 2‐methoxy‐6‐(trifluoromethyl)pyridine, (1.19 ± 0.25) × 10?10 for diethylamine, and (1.76 ± 0.38) × 10?12 for 1,1,3,3,3‐pentamethyldisiloxan‐1‐ol, where the indicated errors are the estimated overall uncertainties including those in the rate constants for the reference compounds. No reaction of 2‐methoxy‐6‐(trifluoromethyl)pyridine with gaseous nitric acid was observed, and an upper limit to the rate constant for the reaction of 1,1,3,3,3‐pentamethyldisiloxan‐1‐ol with O3 of <7 × 10? 20 cm3 molecule?1 s?1 was determined. Using a 12‐h average daytime OH radical concentration of 2 × 106 molecule cm?3, the lifetimes of the volatile organic compounds studied here with respect to reaction with OH radicals are 7.5 days for 2‐methoxy‐6‐(trifluoromethyl)pyridine, 1.2 h for diethylamine, and 6.6 days for 1,1,3,3,3‐pentamethyldisiloxan‐1‐ol. Likely reaction mechanisms are discussed. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 631–638, 2011 相似文献
67.
In this article we show that the order of the point value, in the sense of Łojasiewicz, of a tempered distribution and the
order of summability of the pointwise Fourier inversion formula are closely related. Assuming that the order of the point
values and certain order of growth at infinity are given for a tempered distribution, we estimate the order of summability
of the Fourier inversion formula. For Fourier series, and in other cases, it is shown that if the distribution has a distributional
point value of order k, then its Fourier series is e.v. Cesàro summable to the distributional point value of order k+1. Conversely, we also show that if the pointwise Fourier inversion formula is e.v. Cesàro summable of order k, then the distribution is the (k+1)-th derivative of a locally integrable function, and the distribution has a distributional point value of order k+2. We also establish connections between orders of summability and local behavior for other Fourier inversion problems. 相似文献
68.
A simple transformation of the eight-carbon side chain of a natural spirostan sapogenin into the cephalostatin north 1 spiroketal moiety is described. This methodology, based on an intramolecular hydrogen abstraction reaction promoted by alkoxy radicals, permits the synthesis of C-22 and C-25 stereoisomers of the dioxaspiro[4.4]nonane cephalostatin ring system. The acid-catalyzed isomerization of the spirocenter in the different isomers is studied. [reaction: see text] 相似文献
69.
Carolina Muscoli Daniela Salvemini Donatella Paolino Michelangelo Iannone Ernesto Palma Antonio Cufari Domenicantonio Rotiroti Federico Carlo Perno Stefano Aquaro Vincenzo Mollace 《BMC neuroscience》2002,3(1):13-8
Background
Oxidative stress has shown to contribute in the mechanisms underlying apoptotic cell death occuring in AIDS-dementia complex. Here we investigated the role of peroxynitrite in apoptosis occurring in astroglial cells incubated with supernatants of HIV-infected human primary macrophages (M/M). 相似文献70.