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11.
Pavol Ondrisek Dr. Margaux Elie Marion Pupier Dr. Adiran de Aguirre Dr. Amalia I. Poblador-Bahamonde Dr. Céline Besnard Prof. Jérôme Lacour 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(15):e202104405
Cationic triangulenes, and related helicenes, constitute a rich class of dyes and fluorophores, usually absorbing and emitting light at low energy, in the orange to red domains. Recently, to broaden the scope of applications, regioselective late-stage functionalizations on these core moieties have been developed. For instance, with the introduction of electron-donating groups (EDGs), important bathochromic shifts are observed pushing absorptions towards or in the near-infrared (NIR) spectral domain while emissive properties disappear essentially completely. Herein, to upset this drawback, acetylene derivatives of cationic diazaoxa triangulenes (DAOTA) and [4]helicenes are prepared (16 examples). Contrary to other EDG-functionalized derivatives, C≡C− functionalized products remain broadly fluorescent, with red-shifted absorptions (Δλabs up to 25 nm) and emissions (Δλem up to 73 nm, ΦPL up to 51 %). Quite interestingly, a general dynamic stereoisomerism phenomenon is evidenced for the compounds derived from achiral DAOTA cores. At low temperature in 1H NMR spectroscopy (218 K), N−CH2 protons become diastereotopic with chemical shifts differences (Δδ) as high as +1.64 ppm. The signal coalescence occurs around 273 K with a barrier of ∼12 kcal mol−1. This phenomenon is due to planar chiral conformations (Sp and Rp configurations), induced by the geometry of the alkyl (n-propyl) side-chains next to the acetylenic substituents. Ion pairing studies with Δ-TRISPHAT anion not only confirm the occurrence of the chiral conformations but evidence a moderate but definite asymmetric induction from the chiral anion onto the cations. Finally, DFT calculations offer a valuable insight on the geometries, the corresponding stereodynamics and also on the very large difference in NMR for some of the diastereotopic protons. 相似文献
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This work evaluated the efficacy of pomegranate byproducts, specifically peel powder, as valid preservatives for food quality. Ready-to-cook cod sticks breaded with pomegranate peel powder were prepared. Shelf-life tests were conducted on breaded cod sticks during refrigerated storage (17 days) at 4 °C, monitoring the pH, microbiological and sensory quality. In addition, the nutritional quality of both the breaded and control samples was assessed. The results highlighted that active samples showed higher phenol and flavonoid content and higher antioxidant activity compared to the control fish, suggesting that pomegranate peel powder was responsible for a significant increase in cod stick nutritional quality. Furthermore, the cod stick active breading led to a delay in microbial growth without affecting the sensory properties; rather, it helped slow down the sensory attribute decline during the refrigerated storage. The data suggest that using pomegranate byproducts in breaded cod stick was effective in prolonging its shelf life, as well as improving its nutritional quality. Therefore, pomegranate peel powder can be considered as a potential resource as natural food preservative. 相似文献
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Uncatalyzed Hydroamination of Electrophilic Organometallic Alkynes: Fundamental,Theoretical, and Applied Aspects 下载免费PDF全文
Dr. Yanlan Wang Camille Latouche Dr. Amalia Rapakousiou Colin Lopez Prof Isabelle Ledoux‐Rak Dr. Jaime Ruiz Prof. Jean‐Yves Saillard Prof. Didier Astruc 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(26):8076-8088
Simple reactions of the most used functional groups allowing two molecular fragments to link under mild, sustainable conditions are among the crucial tools of molecular chemistry with multiple applications in materials science, nanomedicine, and organic synthesis as already exemplified by peptide synthesis and “click” chemistry. We are concerned with redox organometallic compounds that can potentially be used as biosensors and redox catalysts and report an uncatalyzed reaction between primary and secondary amines with organometallic electrophilic alkynes that is free of side products and fully “green”. A strategy is first proposed to synthesize alkynyl organometallic precursors upon addition of electrophilic aromatic ligands of cationic complexes followed by endo hydride abstraction. Electrophilic alkynylated cyclopentadienyl or arene ligands of Fe, Ru, and Co complexes subsequently react with amines to yield trans‐enamines that are conjugated with the organometallic group. The difference in reactivities of the various complexes is rationalized from the two‐step reaction mechanism that was elucidated through DFT calculations. Applications are illustrated by the facile reaction of ethynylcobalticenium hexafluorophosphate with aminated silica nanoparticles. Spectroscopic, nonlinear‐optical and electrochemical data, as well as DFT and TDDFT calculations, indicate a strong push–pull conjugation in these cobalticenium– and Fe– and Ru–arene–enamine complexes due to planarity or near‐planarity between the organometallic and trans‐enamine groups involving fulvalene iminium and cyclohexadienylidene iminium mesomeric forms. 相似文献
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The reaction Fe(CN)4(bpy)2? + S2O82? has been studied in aqueous micellar solutions of N‐tetradecyl‐N,N‐dimethyl‐3‐ammonio‐1‐propanesulfonate, SB3‐14. The influence of changes in the surfactant concentration as well as in the peroxodisulfate ions concentration on kobs was investigated. Spectroscopic and conductivity measurements have given information about the distribution of both anionic reagents between the aqueous and micellar pseudophases of the SB3‐14 micellar solutions. A discussion about the adequacy of various equations based on the pseudophase model to rationalize kinetic micellar effects for anion‐anion reactions in sulfobetaine micellar solutions has been done. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 225–231, 2001 相似文献
17.
Davies DL Macgregor SA Poblador-Bahamonde AI 《Dalton transactions (Cambridge, England : 2003)》2010,39(43):10520-10527
Density functional theory calculations have been employed to model ethene hydroarylation using an [Ir(κ(2)-OAc)(PMe(3))Cp](+) catalyst, 1. The reaction proceeds via: (i) an acetate-assisted C-H activation of benzene via an AMLA-6 transition state; (ii) rate-limiting insertion of ethene into the Ir-Ph bond; and (iii) protonolysis of the β-phenylethyl species by HOAc. A range of competing processes are assessed, the most important of which are the C-H activation of ethene at 1 and trapping of the β-phenylethyl intermediate with ethene. The former process gives rise to Ir-vinyl species which can then access further ethene insertion to give stable allyl by-products. A comparison with other ethene hydroarylation catalysts reported in the literature is presented. 相似文献
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Reverdito Ana María García Mariano Hernán Salerno Alejandra Locani Oscar Alberto Perillo Isabel Amalia 《平面色谱法杂志一现代薄层色谱法》2007,20(3):227-230
JPC – Journal of Planar Chromatography – Modern TLC - When the components of a reaction mixture cannot be quantified by UV-visible spectrophotometry, because the λmax values of... 相似文献
20.
A Highly Effective Ruthenium System for the Catalyzed Dehydrogenative Cyclization of Amine–Boranes to Cyclic Boranes under Mild Conditions 下载免费PDF全文
Dr. Christopher J. Wallis Dr. Gilles Alcaraz Dr. Alban S. Petit Dr. Amalia I. Poblador‐Bahamonde Dr. Eric Clot Dr. Christian Bijani Dr. Laure Vendier Dr. Sylviane Sabo‐Etienne 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(37):13080-13090
We recently disclosed a new ruthenium‐catalyzed dehydrogenative cyclization process (CDC) of diamine–monoboranes leading to cyclic diaminoboranes. In the present study, the CDC reaction has been successfully extended to a larger number of diamine–monoboranes ( 4 – 7 ) and to one amine–borane alcohol precursor ( 8 ). The corresponding NB(H)N‐ and NB(H)O‐containing cyclic diaminoboranes ( 12 – 15 ) and oxazaborolidine ( 16 ) were obtained in good to high yields. Multiple substitution patterns on the starting amine–borane substrates were evaluated and the reaction was also performed with chiral substrates. Efforts have been spent to understand the mechanism of the ruthenium CDC process. In addition to a computational approach, a strategy enabling the kinetic discrimination on successive events of the catalytic process leading to the formation of the NB(H)N linkage was performed on the six‐carbon chain diamine–monoborane 21 and completed with a 15N NMR study. The long‐life bis‐σ‐borane ruthenium intermediate 23 possessing a reactive NHMe ending was characterized in situ and proved to catalyze the dehydrogenative cyclization of 1 , ascertaining that bis σ‐borane ruthenium complexes are key intermediates in the CDC process. 相似文献