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131.
A heterogeneous magnetic copper catalyst was prepared via anchoring of copper sulfate onto multi‐layered poly(2‐dimethylaminoethyl acrylamide)‐coated magnetic nanoparticles and was characterized using various techniques. The catalyst was found to be active, effective and selective for one‐pot three‐component reaction of alkyl halide, sodium azide and alkyne, known as copper‐catalyzed click synthesis of 1,2,3‐triazoles. As little as 0.3 mol% of catalyst was found to be effective under the optimum conditions. The catalyst could also be recycled and reused up to seven times without significant loss of activity. Thermal stability, high loading level of copper on catalyst, broad diversity of alkyl/benzyl/allyl bromide/chloride and alkyl/aryl terminal alkynes without isolation of azide intermediate, and good to excellent yields of products make this procedure highly economical. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
132.
David J. Lunn Emre H. Discekici Javier Read de Alaniz Will R. Gutekunst Craig J. Hawker 《Journal of polymer science. Part A, Polymer chemistry》2017,55(18):2903-2914
The development of “controlled” and “living” polymerization processes with high end-group fidelity has enabled an unprecedented range of polymeric materials with specific chain-end functionality to be prepared. This highlight provides an overview of available strategies and evaluation of recent approaches for the chain-end functionalization of polymers prepared through controlled chain-growth polymerizations. As a tribute to Professor Robert B. Grubbs on the occasion of his 75th birthday, we also take this opportunity to highlight methods for the chain-end modification of polymers prepared by ring-opening metathesis polymerization within the broader context of functional group tolerant, living polymerizations. Finally, we focus attention toward new directions in polymer chain-end modifications, describing existing gaps in current strategies, and detailing recently reported protocols that show significant improvements over traditional methods. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2903–2914 相似文献
133.
Dr. Jeanette E. Stok Dr. Sharon Chow Dr. Elizabeth H. Krenske Clementina Farfan Soto Csongor Matyas Prof. Raymond A. Poirier Prof. Craig M. Williams Prof. James J. De Voss 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(13):4408-4412
The cytochromes P450 are hemoproteins that catalyze a range of oxidative C?H functionalization reactions, including aliphatic and aromatic hydroxylation. These transformations are important in a range of biological contexts, including biosynthesis and xenobiotic biodegradation. Much work has been carried out on the mechanism of aliphatic hydroxylation, implicating hydrogen atom abstraction, but aromatic hydroxylation is postulated to proceed differently. One mechanism invokes as the key intermediate an arene oxide (and/or its oxepin tautomer). Conclusive isolation of this intermediate has remained elusive and, currently, direct formation of phenols from a Meisenheimer intermediate is believed to be favored. We report here the identification of a P450 [P450cam (CYP101A1) and P450cin (CYP176A1)]‐generated arene oxide as a product of in vitro oxidation of tert‐butylbenzene. Computations (CBS‐QB3) predict that the arene oxide and oxepin have similar stabilities to other arene oxides/oxepins implicated (but not detected) in P450‐mediated transformations, suggesting that arene oxides can be unstable terminal products of P450‐catalyzed aromatic oxidation that can explain the origin of some observed metabolites. 相似文献
134.
135.
Craig M. Davis Megan F. Klein Kenneth T. Nicholson 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3):659-664
Attempts were made to synthesize dinuclear Group 6 metal complexes of the arachno -octahydrotriborate anion. Specifically, the dimer [CpW(CO) 3 ] 2 (Cp = m 5 -C 5 H 5 ) was employed as the metal reagent. However, the formation of dinuclear metallaborane complexes did not ensue. Rather, clean, rapid, systematic borane-cage expansion was observed. The [B 3 H 8 ] m cluster was quantitatively converted to B 5 H 9 ,[B 9 H 14 ] m , or [B 11 H 14 ] m , or both, depending on reaction conditions. Refluxing a 1:1 mixture of [B 3 H 8 ] m and [CpW(CO) 3 ] 2 in toluene or dioxane lead to the rapid, quantitative conversion of [B 3 H 8 ] m to B 5 H 9 . However, refluxing a 2:1 mixture of [B 3 H 8 ] m and [CpW(CO) 3 ] 2 in the same solvents yielded [B 9 H 14 ] m and [B 11 H 14 ] m as the primary products; when glyme was the solvent, only [B 9 H 14 ] m was observed, even after prolonged heating. 相似文献
136.
STUDIES IN THE HETEROCYCLIC COMPOUNDS V1. SOME REACTIONS OF 5-CHLORO-2-THIOPHENESULFONYL DERIVATIVES
Craig A. Obafemi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):119-131
Abstract The reactions of 5-chloro-2-thiophenesulfonyl chloride are described. Treatment of the sulfonyl chloride with ammonia, hydrazine hydrate, sodium azide, indole and imidazole gave the sulfonamides (5), sulfonohydrazide (4), sulfonyl azide (3), 1-(5-chloro-2-thiophenesulfonyl)indole (27) and 1-(5-chloro-2-thiophenesulfonyl)-imidazole (26), respectively. The sulfonyl chloride was reacted further with 20 aryl-and cycloalkyl-amines to give the corresponding sulfonamides (6)-(25). Attempted chlorination of the sulfonyl chloride (2) with sulfuryl chloride or bromination of the sulfonyl azide (3) with pyridinium bromide perbromide failed. However, nitration of the sulfonyl chloride (2) with fuming nitric acid gave the 4-nitro-sulfonyl chloride (28), which with sodium azide afforded the 5-chloro-4-nitro-sulfonyl azide (29). The sulfonyl azides, (3) and (29), have been reacted with triphenylphosphine, triethylphosphite, norbornene and cyclohexene. The azides reacted further with indole and 1-methylindole to give the 2-sulfonyl-iminoindolines (34)-(36). The infra-red spectra and mass spectra of some of the substituted thiophenesulfonyl derivatives are discussed. 相似文献
137.
Abstract The mass spectra of some 2-thiophenemercuric derivatives are determined and the fragmentation interpretations are based on mechanistic analogy and supported in some cases by metastable peaks and low energy mass spectra. They all fragment ultimately to the 2-thienyl cation formed either through a two-step process, by cleavage of Hg[sbnd]X bond to give the 2-thienylmercuric cation, followed by extrusion of mercury, or by a one-step process through cleavage of carbon-mercury bond. Their base peaks being the C3H3 +ion (m/e 39). 相似文献
138.
M. Amélia Santos Adelino Afonso M. Matilde Marques Craig Wilcox 《Supramolecular chemistry》2013,25(3):201-215
Abstract New receptors based upon a carboxamidonaphthyridine unit derivatized with the polyaromatic segments [4-(1-pyrenyl)butyroylamino] and [3-(9-anthracenyl)propanoylamino] have been synthesized and studied by 1H NMR titration in their binding interaction to the guanosine-C8 adducts from the carcinogens 2-acetylaminofluorene and 2-aminofluorene. The high binding energy, in comparison with that of the non-derivatized analogues, is rationalized in terms of a bi-site interaction (hydrogen bonding and aromatic stacking). Although many factors may contribute to the strength of the host-guest complexes described herein, it appears that in some cases π-π interaction may induce a concomitant bending in the hydrogen bond system. 相似文献
139.
Paul D. Sylvester Helen E. Ryan Craig D. Smith Aaron S. Micallef Carl H. Schiesser Uta Wille 《Polymer Degradation and Stability》2013
A profluorescent nitroxide possessing an isoindoline nitroxide moiety linked to a perylene fluorophore was developed to monitor radical mediated degradation of melamine-formaldehyde crosslinked polyester coil coatings in an industry standard accelerated weathering tester. Trapping of polyester-derived radicals (most likely C-radicals) that are generated during polymer degradation leads to fluorescent closed-shell alkoxy amines, which was used to obtain time-dependent degradation profiles to assess the relative stability of different polyesters towards weathering. The nitroxide probe couples excellent thermal stability and satisfactory photostability with high sensitivity and enables detection of free radical damage in polyesters under conditions that mimic exposure to the environment on a time scale of hours rather than months or years required by other testing methods. There are indications that the profluorescent nitroxide undergoes partial photo-degradation in the absence of polymer-derived radicals. Unexpectedly, it was also found that UV-induced fragmentation of the NO–C bond in closed-shell alkoxy amines leads to regeneration of the profluorescent nitroxide and the respective C-radical. The maximum fluorescence intensity that could be achieved with a given probe concentration is therefore not only determined by the amount of polyester radicals formed during accelerated weathering, but also by the light-driven side reactions of the profluorescent nitroxide and the corresponding alkoxy amine radical trapping products. Studies to determine the optimum probe concentration in the polymer matrix revealed that aggregation and re-absorption effects lowered the fluorescence intensity at higher concentrations of the profluorescent nitroxide, but too low probe concentrations, where these effects would be avoided, were not sufficient to trap the amount of polyester radicals formed upon weathering. The optimized experimental conditions were used to assess the impact of temperature and UV irradiance on polymer degradation during accelerated weathering. 相似文献