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71.
Lipiao Bao Baolin Zhao Vicent Lloret Marcus Halik Frank Hauke Andreas Hirsch 《Angewandte Chemie (International ed. in English)》2020,59(17):6700-6705
Patterned functionalization can, on the one hand, open the band gap of graphene and, on the other hand, program demanding designs on graphene. The functionalization technique is essential for graphene‐based nanoarchitectures. A new and highly efficient method was applied to obtain patterned functionalization on graphene by mild fluorination with spatially arranged AgF arrays on the structured substrate. Scanning Raman spectroscopy (SRS) and scanning electron microscopy coupled with energy‐dispersive X‐ray spectroscopy (SEM‐EDS) were used to characterize the functionalized materials. For the first time, chemical patterning on the bottom side of graphene was realized. The chemical nature of the patterned functionalization was determined to be the ditopic scenario with fluorine atoms occupying the bottom side and moieties, such as oxygen‐containing groups or hydrogen atoms, binding on the top side, which provides information about the mechanism of the fluorination process. Our strategy can be conceptually extended to pattern other functionalities by using other reactants. Bottom‐side patterned functionalization enables utilization of the top side of a material, thereby opening up the possibilities for applications in graphene‐based devices. 相似文献
72.
报道了N-烷基5-甲酰胺基-1,2,4-氧杂二唑基-3-β-D-吡喃木糖用二乙胺基三氟化硫选择性氟化,得到相应的N-烷基-5-甲酰胺基-1,2,4-氧杂二唑基-3-(4'-脱氧-4'-氟-β-L-吡喃型阿拉伯糖);并用光谱分析确证了它们的构型及在溶液中的构象。 相似文献
73.
Nitrogen adsorption isotherms for fluorinated activated carbon fiber (F-ACF) and fluorinated carbon black (F-CB) were measured at 77 K. Surface structures of F-ACF and F-CB were examined by
s
-plot analysis using the adsorption data on the nonporous carbon black (CB) and F-CB. The surface energy of F-ACF was lower than that of ACF. The micropore structure of ACF was preserved even after fluorination, although the limiting adsorption amount and the micropore width decreased with fluorination. 相似文献
74.
Richard D. Chambers Takashi Okazoe Emmanuelle Thomas 《Journal of fluorine chemistry》2010,131(9):933-936
Reactions of dialkyl ethers with either fluorine or Selectfluor™ led to the formation of unusual difluorinated polyether products in modest yields. A mechanism involving initial fluorination of the site adjacent to ether oxygen followed by elimination of hydrogen fluoride, reaction of the generated enol system with a further equivalent of fluorinating agent giving an oxonium system which reacts with water during aqueous work-up to lead eventually to the products observed, is suggested. 相似文献
75.
Clément Cazorla 《Tetrahedron letters》2009,50(27):3936-1491
Secondary alkyl trifluoroborates undergo facile electrophilic fluorination under mild conditions to afford the corresponding benzylic fluorinated adducts in excellent yield. 相似文献
76.
Richard D Chambers Darren HollingGraham Sandford Horst PuschmannJudith A.K Howard 《Journal of fluorine chemistry》2002,117(2):99-101
Direct fluorination of various quinoline derivatives in acidic reaction media gives fluorinated quinoline products arising from selective, efficient electrophilic substitution processes. 相似文献
77.
Yurii A. Serguchev Maxim V. Ponomarenko Lyudmila F. Lourie Andrey A. Fokin 《Journal of Physical Organic Chemistry》2011,24(5):407-413
The addition of 1‐chloromethyl‐4‐fluoro‐1,4‐diazoniabicyclo[2.2.2]octane bis‐tetrafluoroborate (F‐TEDA) to unsaturated systems was modelled computationally at the ab initio levels and studied experimentally. The reaction of olefins with F‐TEDA is driven exclusively by charge transfer and displays the antibonding orbital picture in the transition structure for F‐transfer, similarly to that for the reactions of olefins with F‐radical. In contrast, the electrophilic and concerted fluorinations, respectively with H2O???F+ complex and with F2, show strong bonding interactions between the fluorine and olefin moieties in the transition structures. The reaction with F‐TEDA involves an initial formation of highly delocalized charge‐transfer complexes in the first step with further low‐barrier (ca 4 kcal) migration of fluorine and is best described as an inner‐sphere electron transfer. This nonelectrophilic mechanism is operative for the transannular addition of F‐TEDA to 3‐methylene‐7‐ethylidenebicyclo[3.3.1]nonane studied experimentally. The addition mode is determined by the formation of a more stable complex via the ethylidene fragment and demonstrates selectivities that differ from conventional electrophilic additions. This mechanistic scenario may be extended to the fluorination with xenon difluoride where similar products are formed in high yields. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
78.
79.
80.
Nguyen Quang VuDanielle Grée René GréeEric Brown Gilles Dujardin 《Tetrahedron letters》2003,44(34):6425-6428
Reaction of polysubstituted 2-hydroxyalkyldihydropyrans with DAST led regiospecifically to fluorination at the exocyclic position, except for primary alcohols. Difluorination of carbonylated analogues with deoxo-fluor™ occurred also regioselectively. The unexpected stability and synthetic potential of these new allylic fluorides are discussed. 相似文献