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Electrochemical characterization of palladium electrode has been reported. The investigated electrode showed a linear dynamic response for p-toluensulfonic acid and iodide ions in the concentrations range between 5?×?10?1 and 1?×?10?5 mol L?1 with a Nernstian slope of 55 mV for p-toluensulfonic acid and 63 mV per decade for iodide ions in water, as well as 53 mV for p-toluensulfonic acid and 51 mV per decade for iodide ions in dioxane. The response time of the electrodes was less than 10 s in the used solvents. Some potential analytical applications of the sensors have been pointed. Palladium electrode for the potentiometric titrations of acids (citric, barbituric, and p-toluensulfonic acid), bases (N,N’-diphenylguanidine, tributylamine, and 2,2'–bipyridine), halides, and some real samples in aqueous and non-aqueous solutions were studied. Тetrabutylammonium hydroxide, perchloric acid, and silver nitrate proved to be very suitable titrating agents for these titrations. The standard deviation of the determination of the investigated compounds was less than 0.9 % from those obtained with a glass electrode, i.e., silver electrode. 相似文献
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Cornelis D Franz E Asselberghs I Clays K Verbiest T Koeckelberghs G 《Journal of the American Chemical Society》2011,133(5):1317-1327
A concept of chiral, X-type organized π-conjugated oligomers, linked by means of a binaphthalene pincer, is presented. NMR spectroscopy and cyclic and differential pulse voltammetry indicate that these oligomers are in close proximity and influence each other in a through-space manner in their neutral as well as in their oxidized states. The interaction between the oligomers was also confirmed by UV-vis, CD, and emission spectroscopy. The synthetic versatility of this design also enables the development of heterocoupled binaphthalene derivatives BN1-2 and BN1-3, consisting of an electron-neutral oligothiophene or electron-rich oligomer and an electron-poor oligothiazole. Hyper-Rayleigh scattering data show a significant enhancement of the second-order nonlinear hyperpolarizability β for BN1-3 and BN1-2, in contrast with the homocoupled binaphthalene derivatives (BN1-1, BN2-2, and BN3-3). This enhancement provides direct proof for the through-space charge-transfer interaction between the p-type and the n-type oligomers within BN1-3 and BN1-2. 相似文献
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Ast S Müller H Flehr R Klamroth T Walz B Holdt HJ 《Chemical communications (Cambridge, England)》2011,47(16):4685-4687
The new π-conjugated 1,2,3-triazol-1,4-diyl fluoroionophore 1 generated via Cu(I) catalyzed [3 + 2] cycloaddition shows high fluorescence enhancement factors (FEF) in the presence of Na(+) (FEF=58) and K(+) (FEF=27) in MeCN and high selectivity towards K(+) under simulated physiological conditions (160 mM K(+) or Na(+), respectively) with a FEF of 2.5 for K(+). 相似文献
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Divya KP Sreejith S Suresh CH Ajayaghosh A 《Chemical communications (Cambridge, England)》2010,46(44):8392-8394
A chiral π-conjugated oligomer having alternate bipyridine and carbazole moieties connected through acetylinic bonds undergoes helical folding in chloroform-acetonitrile (40/60, v/v) as evident by fluorescence and circular dichroism changes. In the presence of transition metal cations such as Zn(2+) defolding of the helical conformation occurs. Upon decomplexation of the cation with EDTA, the helical conformation is regained. 相似文献
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Massimiliano Aschi Maira D’Alessandro Monica Pellegrino Alfredo Di Nola Marco D’Abramo Andrea Amadei 《Theoretical chemistry accounts》2008,119(5-6):469-476
Intramolecular charge transfer (ICT) of gaseous π-conjugated oligo-phenyleneethynylenes (OPE) induced by a homogeneous applied electric field has been theoretically investigated
using a combined approach integrating molecular dynamics (MD) simulations and Perturbed Matrix Method calculations. In line
with recent investigations, our results indicate the peculiar role of conformational transitions on OPE electronic properties
which reflects on a strong temperature effect on ICT. Electron transfer reactions inducing chemical alteration on OPE, also
taken into account in this study, revealed extremely important for explaining non-linear ICT effects and probably plays a
central role in the mechanisms underlying molecular transport junctions. Our study further points out the necessity of using
MD-based approach for modelling molecular electronics, even when relatively rigid molecular systems are concerned. 相似文献
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《Tetrahedron letters》1998,39(32):5799-5802
A novel polymer was synthesized by copolymerization of styrene monomer bearing dicyanoketene acetal functionality and ethylene glycol dimethacrylate, and used successfully as a recyclable π-acid catalyst in monothioacetalization of aromatic, aliphatic, acyclic, and cyclic acetals with thiophenol and phenylthiotrimethylsilane. 相似文献
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Xiaopei Miao Lu Liu Shukuan Wang Hong Lin Baoyun Sun Jingbo Hu Meixian Li 《Electrochemistry communications》2010,12(1):90-93
A new ferrocenecarboxylic acid–C60 composite (Fc–C60) has been synthesized by controlled potential electrolysis. A composite modified glassy carbon electrode has been prepared based on its good electrochemical activity. The modified electrode in 0.1 M NaClO4 solution shows a reversible oxidation wave at E1/2 = 0.32 V (vs. SCE) attributed to the oxidation of the ferrocene entity and a quasi-reversible reduction wave of C60 entity at E1/2 = ?0.54 V (vs. SCE). Electrocatalytic studies show that Fc–C60 at the modified electrode can mediate the reduction of hydrogen peroxide (H2O2), and a broad linear range from 1.2 μM to 21.9 mM for H2O2 were obtained with a determination limit of 2.5 × 10?7 M by amperometry. 相似文献
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A ruthenium carbene bearing a uracil (Ur) substituent has been prepared and has a dimeric structure in the solid state-the dimer being held together by hydrogen bonds between two uracil groups on neighbouring molecules: evidence for the persistence of this interaction in solution has been obtained. 相似文献
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Long before the phrases “climate change” and “butterfly effect” were incorporated into the mainstream literature, these phrases appeared in an appropriate context almost verbatim in the first Chapter of a book entitled “The Emigrant” published in the mid-nineteenth century (in 1846) by Sir Francis Bond Head (1793–1875). Head was Upper Canada’s sixth Lieutenant Governor under King George IV and Queen Victoria. Head claimed that forest wildfires were “changing the climate” of North America as manifested in a warming effect “on the thermometer”. In that author’s account, these fires were provoked by First Nations to create fly-free zones meant to attract game that they could then hunt more readily. Head used language such as “swarms of little flies, strange as it may sound, are, and for many years have been, most materially altering the climate…” which is remarkably reminiscent of E. N. Lorenz’s (1917–2008) “butterfly effect” of the theory of chaotic dynamical systems. The historical context and the rationales that may have led Head to use this contemporary environmental language in a proper context are briefly discussed. 相似文献
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Li Liang Wang Hui Jin Yongjiu Shuang Yazhou Li Laisheng 《Analytical and bioanalytical chemistry》2019,411(21):5465-5479
Analytical and Bioanalytical Chemistry - A benzylureido-β-cyclodextrin was synthesized by the reaction of 6-amino-β-cyclodextrin with an active benzyl isocyanate. Then, it was bonded to... 相似文献
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Javad Kalbasi Roozbeh Rahmati Fatemeh Mazaheri Omid 《Research on Chemical Intermediates》2020,46(7):3413-3430
Research on Chemical Intermediates - Acid–base copolymer materials are of considerable interest because of their fundamental implications for acid–base bifunctional catalysis... 相似文献
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Highly enantioselective Michael addition of malonates to enones was achieved using a mixed catalyst consisting of a primary β-amino acid, O-TBDPS (S)-β-homoserine, and its lithium salt. Various cyclic and acyclic enones were converted into 1,5-ketoesters in high yields (up to 92%) with high enantioselectivity (up to 97% ee) under mild reaction conditions. Details of synthesis of the catalyst, optimization of the reaction conditions for the Michael addition reaction, and a plausible reaction mechanism are described. 相似文献
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Determination of rosamultin in rat plasma by LC–MS/MS and its application to a pharmacokinetic study
A specific and reliable LC–MS/MS method for the determination of rosamultin in rat plasma was validated. Plasma samples were prepared with protein precipitation method, and chromatographic separation was performed on a Thermo C18 analytical column (4.6 mm × 50 mm, 3.0 μm). The mass spectrometry (MS) analysis was conducted in positive SRM mode for the transitions of m/z 673.2 → 511.1 for rosamultin and m/z 601.1 → 330.9 for IS. The method validation was conducted over the calibration range of 1.0–500 ng/mL with the precision ≤11.03% and accuracy within ±14.64%. The assay was applied to the pharmacokinetic study after oral administration of rosamultin at a dose of 20 mg/kg in rats. 相似文献
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Kansuinine A is a macrocyclic jatrophane diterpene isolated from the plant Euphorbia kansui Liou. It exhibits many pharmacological activities including cytoxic, antitumor, antiallergic and proinflammatory effects. In the present study, a simple and sensitive LC–MS/MS method was established and validated for the determination of kansuinine A in rat plasma. After methanol-mediated protein precipitation, chromatographic separation was achieved on an Acquity BEH C18 column (2.1 × 100 mm, 1.7 μm) using acetonitrile and 0.1% formic acid in water as mobile phase by gradient elution. Kansuinine A and IS were quantified in negative multiple reaction monitoring mode with ion transitions at m/z 731.1–693.2 for kansuinine A and m/z 723.2–623.1 for IS. The method showed excellent linearity over the range 1–500 ng/ml. The intra- and inter-day precisions (relative standard deviation) were 2.13–4.28 and 3.83–7.67%, respectively, whereas accuracy (relative error) ranged from −4.17 to 3.73%. The extraction recovery, stability and matrix effect met the requirement of the regulations issued by the US Food and Drug Administration. The validated method was successfully applied to the pre-clinical pharmacokinetic study of kansuinine A in rats after oral administration (20 mg/kg) and intravenous administration (2 mg/kg). This study provides valuable reference for the further study of E. kansui liou, especially for the drug development and clinical application of kansuinine A. 相似文献
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Zorka Stani? Jelena Stepanovi? Zoran Simi? 《Monatshefte für Chemie / Chemical Monthly》2012,13(6):1-6
Abstract
A novel acid–base sensor based on the natural mineral arsenopyrite for titrations in γ-butyrolactone and propylene carbonate is validated and studied. This sensor, which requires only small sample volumes, was employed for the titrations of some important organic acids (benzoic, anthranilic, and salicylic acid) with potassium hydroxide. A stable stationary potential was attained at the arsenopyrite electrode in γ-butyrolactone and propylene carbonate in less than 5 min. The change in the electrode potential from the acidic to basic region was 379 to −160 mV in γ-butyrolactone and 434 to −67 mV in propylene carbonate. The arsenopyrite electrode showed a relatively fast response time in the investigated solvents (11 s in γ-butyrolactone and 14 s in propylene carbonate). It can be used without any time limit or without considerable divergence in the potential. The investigated electrode showed a linear dynamic response for p-toluenesulfonic acid concentrations in the range 0.1–0.001 M, and a sub-Nernst dependence in γ-butyrolactone as well as in propylene carbonate. Unlike traditional pH titration, an end-point color indicator is unnecessary in this method, and real-time monitoring can be realized. The relative standard deviations for measurements of benzoic, anthranilic, and salicylic acids were 0.10–0.31%, which show that the repeatability and accuracy of measurements taken with the sensor are satisfactory. 相似文献18.
Structural Chemistry - Hydroboration of CO2 has been recognized as a desirable reaction for value-added chemical production. The main aims of this report are to introduce and study the mechanism of... 相似文献
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Although bilobetin, a biflavone isolated from the leaves of Ginkgo biloba, represents a variety of pharmacological activities, to date there have been no validated determination methods for bilobetin in biological samples. Thus, we developed a liquid chromatographic method using a tandem mass spectrometry for the determination of bilobetin in rat plasma. After protein precipitation with acetonitrile including diclofenac (internal standard), the analytes were chromatographed on a reversed-phased column with a mobile phase of purified water and acetonitrile (3:7, v/v, including 0.1% formic acid). The ion transitions of the precursor to the product ion were principally deprotonated ions [M − H]− at m/z 551.2 → 519.2 for bilobetin and 296.1 → 251.7 for the IS. The accuracy and precision of the assay were in accordance with US Food and Drug Administration regulations for the validation of bioanalytical methods. This analytical method was successfully applied to monitor plasma concentrations of bilobetin over time following intravenous administration in rats. 相似文献
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A highly reactive and acidic chiral Br?nsted acid catalyst, chiral N-triflyl phosphoramide, was developed. Highly enantioselective Diels-Alder reaction of alpha,beta-unsaturated ketone with silyloxydiene was demonstrated using this chiral Br?nsted acid catalyst. 相似文献