Selective and Simultaneous Determination of Dihydroxybenzene Isomers Based on Green Synthesized Gold Nanoparticles Decorated Reduced Graphene Oxide

In the present study, we report the simultaneous electrochemical determination of hydroquinone (HQ), catechol (CC) and resorcinol (RC) at gold nanoparticles (Au‐NPs) decorated reduced graphene oxide (RGO) modified electrode. An enhanced and well defined peak current response with a better peak separation of HQ, CC and RC is observed at RGO/Au‐NPs composite than that of RGO and Au‐NPs modified electrodes. The fabricated modified electrode shows a wide linear response in the concentration range of 3–90 µM, 3–300 µM and 15–150 µM for HQ, CC and RC, respectively. The detection limit of HQ, CC and RC is found as 0.15 µM, 0.12 µM and 0.78 µM, respectively.     

Highly Regio- and Stereoselective Synthesis of β-Halohydrins from Epoxides Catalyzed with Ceric Ammonium Nitrate

Ce(IV) as ceric ammonium nitrate can effectively catalyze ring opening of epoxides with halides under very mild conditions and easy procedure to give the corresponding β-chloro-and β-bromohydrins in excellent yields. The reactions occur with both substituted and unsubstituted quaternary ammonium halides and with high regio- and stereoselectivity. The reaction of optically active styrene oxide with chloride ion was found to be highly stereospecific and afforded the corresponding β-halohydrin in 96% ee.     

Toward the natural didemnaketal A: total synthesis of the isomer of didemnaketal A

The total synthesis of isomer of didemnaketal A was achieved in 26 steps. The position of esters is switched at C7 and C8 with respect to their proposed position in natural didemnaketal A, which shows potent anti-HIV activity but so far has not been synthesized in the laboratory. Structural analysis of synthetic isomer of didemnaketal A indicates that the esters at C7 and C8 are correctly assigned, suggesting that the problems for the structural reassignment of natural didemnaketal A lie elsewhere.     

Remarkable stereoselectivity switch in synthesis of carbonyl substituted N-arylamidrazones with low lipophilicity

Reaction of carbonyl substituted hydrazonoyl chlorides with amines usually leads to Z-configured amidrazone derivatives via nucleophilic substitution of the chlorine atom. Surprisingly, N,N-dimethylcarboxamide substituted hydrazonoyl chlorides yielded E-amidrazones when dialkylamines were used as nucleophilic reagent. The lipophilicities of the obtained amidrazones were found to be drastically reduced compared to their corresponding carboxanilides.     

Simultaneous determination of dihydroxybenzene isomers utilizing a thiadiazole film electrode

The present study reports a sensitive electro-analytical method for the simultaneous determination of dihydroxybenzene isomers by using a thiadiazole film electrode, which was readily prepared by electropolymerization of 2,5-dimercapto-1,3,4-thiadiazole on a glassy carbon electrode with cyclic voltammetry. The functionalized electrode has a distinguishable and sensitive response to dihydroxybenzene isomers. Under the optimized conditions, the linear stripping peak currents showed good linear relationships with hydroquinone, catechol and resorcinol at concentration ranges 0.50-120, 0.50-110 and 1.00-110 μmol/L, and the detection limits are 0.1, 0.1 and 0.3 μmol/L, respectively. The proposed method is applicable to the simultaneous determination of dihydroxybenzene isomers in real samples with the relative standard deviations of less than 5.7% and the recovery rates of 95.6%-106%. The constructed electrode is characterized by simple preparation, good selectivity, and high sensitivity advantages.     

Molecular Chirality Recognized by Achiral Compounds

Abstract

Three cases are described where chirality is recognized by achiral molecules, where chirality is induced into achiral compounds through interactions with chiral compounds, and lastly where induced chirality in the solid-state is utilized for an enantio-selective photoreaction. In the first instance, the thermodynamically and kinetically preferred diastereoisomer of an optically labile chromium complex depended on the nature of the achiral solvent. In the second case, for the first time 1,2-chloroethane was trapped and observed in a chiral near-eclipsed form and 1-chloropropane in the truly eclipsed form at room temperature in a 1:1 inclusion complex with an optically active host molecule. Finally, induced chirality in a prochiral compound in the solid-state was successfully employed in an enantio-selective photoreaction. In the two cases, solid-state CD provided valuable information.     

Simultaneous Voltammetry Determination of Dihydroxybenzene Isomers by Nanogold Modified Electrode

A convenient electrochemical deposition method to prepare nanogold/glassy carbon modified electrode (nano‐Au/GCE) is adopted. In 0.1 mol/L HAc‐NaAc buffer solution (pH 4.61), the nano‐Au/GCE shows an excellent electrocatalytical behavior for the redox of dihydroxybenzene. A simple, rapid and highly selective voltammetry for simultaneous determination of dihydroxybenzene isomers, hydroquinone, catechol, and resorcinol, is developed using the nano‐Au/GCE. This method has been applied to the direct determination of the three dihydroxybenzene isomers in artificial wastewater.     

Synthesis of isomerically pure carboxylate- and sulfonate-substituted xanthene fluorophores

Xanthene-based fluorophores such as fluorescein and rhodamine are typically prepared by acid-catalyzed condensation of the appropriate resorcinol or 3-aminophenol with phthalic anhydride. Condensation of substituted phthalic anhydride species results in functionalized fluorophores that are formed as mixed isomers. Crystallization approaches to isomer separation have been reported elsewhere for symmetric fluorescein carboxylates. We describe crystallization-based separation of protected fluorescein sulfonates and coupling conditions to form sulfonamides, precursors for carboxylate-substituted rhodamines, and precursors for asymmetrically substituted fluoresceins and rhodafluors.     

二苯并-18-冠-6-硝化产物异构体的分离及顺式化合物的结构测定

在改进的条件下,二苯并-18-冠-6硝化反应的产率达90％以上。提出一种分离二硝基二苯并-18-冠-6的顺、反异构体的方法。反应产物经元素分析和红外光谱鉴定,异角X射线衍射法测定了顺式二硝基二苯并-18-冠-6的晶体结构。晶体空间群为P2_1/n,α=15.95i(7),b=20.411(9),c=8.173(4),β=101.09(4)°,Z=4。结构用直接法解出,R=0.067。