The determination of the standard potential of alkyl primary amines is reported for the first time using the nanosecond equilibrium method. The versatility and accuracy of the method demonstrates that it is not only an alternative to the classical and modern electrochemical methods, but also a powerful tool for quantifying inductive and/or solvation effects in a related family of compounds. Two different trends were observed depending on alkyl chain length. For "short-chain" alkyl primary amines, where the solvation around the amino group is expected to be the same, the standard potential value appears to follow a linear relationship with the number of carbon atoms, which indicates that the methylene group (-CH2-) causes an inductive effect that is responsible for the stabilization of the amine cation radical. Meanwhile, the E(o) rises slightly to a constant potential value 1.500 V for "long-chain" unbranched alkyl primary amines. This interesting result can be explained by a steric inhibition of solvation around the amino group due to a fold of the long alkyl chain following a solvent exclusion mechanism. 相似文献
A broad range of substituted 2-cyclopentenone derivatives 3-6 are synthesized by the nickel(0)-mediated [3 + 2] cyclization reaction of chromium alkenyl(methoxy)carbene complexes 1 and internal alkynes 2. The reaction takes place with complete regioselectivity with both unactivated alkynes and activated alkynes (electron-withdrawing and electron-donating substituted alkynes). Representative cycloadducts containing boron and tin substituents are further demonstrated to be active partners in classical Pd-catalyzed C-C coupling processes to allow the production of 2-aryl- and 2-alkynyl-substituted cyclopentenones 9-13. 相似文献
The use of a copper solid amalgam electrode (CuSAE) for the analytical determination of triazine herbicides (atrazine and
ametryne) instead of the conventional hanging mercury drop electrode (HMDE) is reported. The results obtained using electroanalytical
methods utilizing each of these electrodes were also compared with those provided by the HPLC technique. The results indicated
that the CuSAE electrode can be used to detect the herbicides studied, since the detection limits reached using the electrode
(3.06 μg L−1 and 3.78 μg L−1 for atrazine and ametryne, respectively) are lower than the maximum values permitted by CONAMA (Brazilian National Council
for the Environment) for wastewaters (50 μg L−1) and by the US EPA (Environmental Protection Agency of the United States) in natural water samples (10.00 μg L−1). An electroanalytical methodology employing CuSAE and square wave voltammetry (SWV) was successfully applied to the determination
of atrazine and ametryne in natural water samples, yielding good recoveries (70.30%–79.40%). This indicates that the CuSAE
provides a convenient substitute for the HMDE, particularly since the CuSAE minimizes the toxic waste residues produced by
the use of mercury in HDME-based analyses. 相似文献
This work investigates the industrial production of styrene‐butadiene rubber in a continuous reactor train, and proposes a soft sensor for online monitoring of several processes and polymer quality variables in each reactor. The soft sensor includes two independent artificial neural networks (ANN). The first ANN estimates monomer conversion, solid content, polymer production, average particle diameter, and average copolymer composition; the second ANN estimates average molecular weights and average branching degrees. The required ANN inputs are: (i) the reagent feed rates into the first reactor and (ii) the reaction heat rate in each reactor. The proposed ANN‐based soft sensor proved robust to several measurement errors, and is suitable for online estimation and closed‐loop control strategies.
A multiresidue method has been developed for determining pesticide residues in the tropical fruits kiwi, custard apple, and mango. The intended purpose of the method is for regulatory analyses of commodities for pesticides that have established maximum residue limits. A fast and simple extraction method with cyclohexane-ethyl acetate (1 + 1, v/v) and a high-speed homogenizer was optimized. Pressurized liquid extraction was evaluated as an alternative automated extraction technique. The pesticide residues were determined by using low-pressure gas chromatography coupled to tandem mass spectrometry. The proposed methodology was validated for each matrix. Pesticide recoveries ranged from 70 to 110%, with repeatability relative standard deviations of < or = 18% at spiking levels of 12 and 50 microg/kg. The limits of quantitation were in the range of 0.03-6.17 microg/kg, and the limits of detection were between 0.01 and 3.75 microg/kg. Mango can be selected as a representative matrix for calibration on the basis of the results of a potential matrix effect study. The method was successfully applied to the determination of pesticide residues in real samples in Spain. 相似文献
The fluorescence of pyrene has been used for the first time to measure the static dielectric constant of a series of supported ionic liquids phases (SILPs) based on polymeric polystyrene networks. 相似文献
Mixtures of an appropriate carboxylic acid and n-butylstannoic acid constitute modular gelation systems, in which the formation of a well-defined 'tin-drum' nanocluster subsequently underpins the hierarchical assembly of nanostructured fibres, which form self-supporting gel-phase networks in organic solvents. 相似文献
Recent developments concerning metal-catalyzed reactions have led to the implementation of new, rapid, and practical routes to eight- and nine-membered carbocycles based on an oxygen-bridge templated cyclization. 相似文献