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81.
Abbott AP Capper G Davies DL Rasheed RK 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(15):3769-3774
A dark green, viscous liquid can be formed by mixing choline chloride with chromium(III) chloride hexahydrate and the physical properties are characteristic of an ionic liquid. The eutectic composition is found to be 1:2 choline chloride/chromium chloride. The viscosity and conductivity are measured as a function of temperature and composition and explained in terms of the ion size and liquid void volume. The electrochemical response of the ionic liquid is also characterised and it is shown that chromium can be electrodeposited efficiently to yield a crack-free deposit. This approach could circumvent the use of chromic acid for chromium electroplating, which would be a major environmental benefit. This method of using hydrated metal salts to form ionic liquids is shown to be valid for a variety of other salt mixtures with choline chloride. 相似文献
82.
Maria A. Curtin Irwin A. Taub Kenneth Kustin Narith Sao Jeremy R. Duvall Katharine I. Davies Christopher J. Doona Edward W. Ross 《Research on Chemical Intermediates》2004,30(6):647-661
The slow reaction between peroxodisulfate and formate is significantly accelerated by ascorbate at room temperature. The products of this induced oxidation, CO2 and oxalate (C2O2–
4), were analyzed by several methods and the kinetics of this reaction were measured. The overall mechanism involves free radical species. Ascorbate reacts with peroxodisulfate to initiate production of the sulfate radical ion (SO–
4), which reacts with formate to produce carbon dioxide radical ion (CO–
2) and sulfate. The carbon dioxide radical reacts with peroxodisulfate to form CO2 or self-combines to form oxalate. Competition occurring between these two processes determines the overall fate of the carbon dioxide radical species. As pH decreases, protonation of the carbon dioxide radical ion tends to favor production of CO2. 相似文献
83.
Combined Experimental and Computational Investigations of Rhodium‐Catalysed CH Functionalisation of Pyrazoles with Alkenes 下载免费PDF全文
Dr. Andrés G. Algarra Prof. David L. Davies Dr. Qudsia Khamker Prof. Stuart A. Macgregor Dr. Claire L. McMullin Kuldip Singh Dr. Barbara Villa‐Marcos 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(7):3087-3096
Detailed experimental and computational studies have been carried out on the oxidative coupling of the alkenes C2H3Y (Y=CO2Me ( a ), Ph ( b ), C(O)Me ( c )) with 3‐aryl‐5‐R‐pyrazoles (R=Me ( 1 a ), Ph ( 1 b ), CF3 ( 1 c )) using a [Rh(MeCN)3Cp*][PF6]2/Cu(OAc)2 ? H2O catalyst system. In the reaction of methyl acrylate with 1 a , up to five products ( 2 aa – 6 aa ) were formed, including the trans monovinyl product, either complexed within a novel CuI dimer ( 2 aa ) or as the free species ( 3 aa ), and a divinyl species ( 6 aa ); both 3 aa and 6 aa underwent cyclisation by an aza‐Michael reaction to give fused heterocycles 4 aa and 5 aa , respectively. With styrene, only trans mono‐ and divinylation products were observed, whereas with methyl vinyl ketone, a stronger Michael acceptor, only cyclised oxidative coupling products were formed. Density functional theory calculations were performed to characterise the different migratory insertion and β‐H transfer steps implicated in the reactions of 1 a with methyl acrylate and styrene. The calculations showed a clear kinetic preference for 2,1‐insertion and the formation of trans vinyl products, consistent with the experimental results. 相似文献
84.
Nikolai J Loe Ø Dominiak PM Gerlitz OO Autschbach J Davies HM 《Journal of the American Chemical Society》2007,129(35):10763-10772
Quantum chemical DFT calculations at the B3LYP/6-31G(d) level have been used to study the stereochemical course of the photochemical cycloaddition of enone 9 with dienes. The observed products of this photochemically induced cycloaddition showed a stereoselectivity, which is opposite to what would be expected by FMO considerations. The quantum chemical calculations revealed that the unusual stereoselectivity of the reaction can be rationalized by assuming a stereospecific photochemical cis-trans isomerization of enone 9 to trans isomer 9a followed by a thermal Diels-Alder reaction of the diene onto the highly reactive trans enone. The photochemical reaction step involves the selective formation of a twisted triplet intermediate, which accounts for the selectivity of the reaction. 相似文献
85.
FTIR-RAIRS and ATR techniques are shown to provide a powerful means of investigating the molecular behaviour responsible for the pyroelectric properties of organic monolayer assemblies on silicon and aluminised glass. Spectral changes, associated with either proton transfer or head group rearrangement, are well correlated with the level of pyroelectric response for two different devices. The technique promises to be extremely important for the elucidation of the microscopic properties of molecular electronic devices. 相似文献
86.
Bailey S Davies SG Smith AD Withey JM 《Chemical communications (Cambridge, England)》2002,(23):2910-2911
The asymmetric synthesis of (1R,2S,3R)-3-methyl-2-amino-cyclopentane carboxylic acid has been achieved via kinetic resolution of racemic tert-butyl 3-methyl-cyclopentene-1-carboxylate with homochiral lithium (S)-N-benzyl-N-alpha-methylbenzylamide. 相似文献
87.
Isabel V. L. Wilkinson Kelly J. Perkins Hannah Dugdale Lee Moir Aini Vuorinen Maria Chatzopoulou Sarah E. Squire Sebastian Monecke Alexander Lomow Marcus Geese Philip D. Charles Peter Burch Jonathan M. Tinsley Graham M. Wynne Stephen G. Davies Francis X. Wilson Fraydoon Rastinejad Shabaz Mohammed Kay E. Davies Angela J. Russell 《Angewandte Chemie (International ed. in English)》2020,59(6):2420-2428
Duchenne muscular dystrophy (DMD) is a fatal muscle‐wasting disease arising from mutations in the dystrophin gene. Upregulation of utrophin to compensate for the missing dystrophin offers a potential therapy independent of patient genotype. The first‐in‐class utrophin modulator ezutromid/SMT C1100 was developed from a phenotypic screen through to a Phase 2 clinical trial. Promising efficacy and evidence of target engagement was observed in DMD patients after 24 weeks of treatment, however trial endpoints were not met after 48 weeks. The objective of this study was to understand the mechanism of action of ezutromid which could explain the lack of sustained efficacy and help development of new generations of utrophin modulators. Using chemical proteomics and phenotypic profiling we show that the aryl hydrocarbon receptor (AhR) is a target of ezutromid. Several lines of evidence demonstrate that ezutromid binds AhR with an apparent KD of 50 nm and behaves as an AhR antagonist. Furthermore, other reported AhR antagonists also upregulate utrophin, showing that this pathway, which is currently being explored in other clinical applications including oncology and rheumatoid arthritis, could also be exploited in future DMD therapies. 相似文献
88.
Davies IW Marcoux JF Wu J Palucki M Corley EG Robbins MA Tsou N Ball RG Dormer P Larsen RD Reider PJ 《The Journal of organic chemistry》2000,65(15):4571-4574
Substituted acetic acids or acetyl chlorides react with phosphorus oxychloride in DMF to yield the vinamidinium salts 3a-j in moderate to excellent recrystallized yields (28-90%). The cations are conveniently isolated as their hexafluorophosphate salts, which are easily handled nonhygroscopic solids. The nitro compound 3l is prepared in 91% yield by nitration of the parent vinamidinium 3k. The X-ray crystal structure is reported for the 2-phenyl isomer 3e and displays minimal overlap of the two pi-systems. 相似文献
89.
Davies SG Díez D El Hammouni MM Garner AC Garrido NM Long MJ Morrison RM Smith AD Sweet MJ Withey JM 《Chemical communications (Cambridge, England)》2003,(19):2410-2411
Comparison of the kinetic and parallel kinetic resolutions of methyl (RS)-5-tert-butyl-cyclopentene-1-carboxylate allows for the efficient synthesis of both (1R,2S,5S)- and (1S,2R,5R)-enantiomers of methyl 2-amino-5-tert-butyl-cyclopentane-1-carboxylate. 相似文献
90.
Tanil Akyüz Sevim Akyüz J. Eric D. Davies 《Journal of inclusion phenomena and macrocyclic chemistry》1990,9(4):349-354
Three dimensional host lattices have been developed by forming bridges with bidentate pyrazine molecules between adjacent tetracyanonickelate polymeric layers of Ni(II) or Cd(II). The Fourier-transform IR and Raman spectra (4000-200 cm–1) of the compounds with the general formula M(pyz)Ni(CN)4, (where M = Ni or Cd) are reported. These host lattices can include benzene molecules but it is found that aniline molecules cannot be included in these structures. They, however, form complexes with the formula M(an)2Ni(CN)4, by replacing pyrazine ligands. A monodentate pyrazine complex of Cd(II) with the formula Cd(pyz)2Ni(CN)4 has also been prepared. 相似文献