Optimisation of the ultrasound-assisted extraction of betalains and polyphenols from Amaranthus hypochondriacus var. Nutrisol

The present study optimised the ultrasound-assisted extraction (UAE) of bioactive compounds from Amaranthus hypochondriacus var. Nutrisol. Influence of temperature (25.86–54.14 °C) and ultrasonic power densities (UPD) (76.01–273.99 mW/mL) on total betalains (BT), betacyanins (BC), betaxanthins (BX), total polyphenols (TP), antioxidant activity (AA), colour parameters (L*, a*, and b*), amaranthine (A), and isoamaranthine (IA) were evaluated using response surface methodology. Moreover, betalain extraction kinetics and mass transfer coefficients (K_La) were determined for each experimental condition. BT, BC, BX, TP, AA, b*, K_La, and A were significantly affected (p < 0.05) by temperature extraction and UPD, whereas L*, a*, and IA were only affected (p < 0.05) by temperature. All response models were significantly validated with regression coefficients (R²) ranging from 87.46 to 99.29%. BT, A, IA, and K_La in UAE were 1.38, 1.65, 1.50, and 29.93 times higher than determined using conventional extraction, respectively. Optimal UAE conditions were obtained at 41.80 °C and 188.84 mW/mL using the desired function methodology. Under these conditions, the experimental values for BC, BX, BT, TP, AA, L*, a*, b*, K_La, A, and IA were closely related to the predicted values, indicating the suitability of the developed quadratic models. This study proposes a simple and efficient UAE method to obtain betalains and polyphenols with high antioxidant activity, which can be used in several applications within the food industry.     

Enantioselective C−H Activation with Earth‐Abundant 3d Transition Metals

Molecular syntheses largely rely on time‐ and labour‐intensive prefunctionalization strategies. In contrast, C?H activation represents an increasingly powerful approach that avoids lengthy syntheses of prefunctionalized substrates, with great potential for drug discovery, the pharmaceutical industry, material sciences, and crop protection, among others. The enantioselective functionalization of omnipresent C?H bonds has emerged as a transformative tool for the step‐ and atom‐economical generation of chiral molecular complexity. However, this rapidly growing research area remains dominated by noble transition metals, prominently featuring toxic palladium, iridium and rhodium catalysts. Indeed, despite significant achievements, the use of inexpensive and sustainable 3d metals in asymmetric C?H activations is still clearly in its infancy. Herein, we discuss the remarkable recent progress in enantioselective transformations via organometallic C?H activation by 3d base metals up to April 2019.     

Pd based on 2-Aminopyrimidine and 1H-benzo[d]imidazol-2-amine functionalizedFe3O4 nanoparticles as novel recyclable magnetic nanocatalysts for Ullmann coupling reaction

In this study, Pd based on 2-Aminopyrimidine and 1H-benzo[d]imidazol-2-amine functionalized Fe₃O₄ magnetic nanoparticles [(Pd-APM-PSi-Fe₃O₄) and (Pd-BIA-PSi-Fe₃O₄)] was designed and used for the synthesis of di aryl ether by Ulmann cross-coupling reactions. Ulmann reaction performed with mixing of the arylhalides and phenol derivatives in DMF solvent. The prepared catalysts were characterized with various analytical techniques such as FT-IR, XRD, TGA, SEM, TEM, EDX, ICP and VSM. Pd-APM-PSi-Fe₃O₄ and Pd-BIA-PSi-Fe₃O₄ catalysts demonstrated good to excellent yields catalytic efficiency for Ulmann reactions in comparison with to commercial palladium catalysts. The catalyst is easily recycled and reused without loss of the catalytic activity. The combined merits of reusable catalyst conditions make the condensation with safe operation, no leaching of pd into environment, low pollution, rapid access to products and simple workup. Also, these novel magnetic nanocatalysts are superior to the industry standard Pd in every relevant aspect. They feature a way higher initial activity, a much more convenient separation, better recycling, and less contamination of the products. Last but not least, they can be very easily prepared from commercially available Fe₃O₄ nanoparticles using standard laboratory equipment.     

On actions of Drinfel'd doubles on finite dimensional algebras

Let q be an nth root of unity for $n>2$ and let $T_n(q)$ be the Taft (Hopf) algebra of dimension $n^2$. In 2001, Susan Montgomery and Hans-Jürgen Schneider classified all non-trivial $T_n(q)$-module algebra structures on an n-dimensional associative algebra A. They further showed that each such module structure extends uniquely to make A a module algebra over the Drinfel'd double of $T_n(q)$. We explore what it is about the Taft algebras that leads to this uniqueness, by examining actions of (the Drinfel'd double of) Hopf algebras H “close” to the Taft algebras on finite-dimensional algebras analogous to A above. Such Hopf algebras H include the Sweedler (Hopf) algebra of dimension 4, bosonizations of quantum linear spaces, and the Frobenius–Lusztig kernel $u_q({\mathfrak{sl}}_2)$.     

Mixing time of an unaligned Gibbs sampler on the square

The paper concerns a particular example of the Gibbs sampler and its mixing efficiency. Coordinates of a point are rerandomized in the unit square ${[0,1]}^2$ to approach a stationary distribution with density proportional to $exp(?A^2{(u?v)}^2)$ for $(u,v)\in {[0,1]}^2$ with some large parameter $A$.Diaconis conjectured the mixing time of this process to be $O\left(A^2\right)$ which we confirm in this paper. This improves on the currently known $O(exp\left(A^2\right))$ estimate.     

Determination of terbinafine in human plasma using UPLC–MS/MS: Application to a bioequivalence study in healthy subjects

A high‐throughput and sensitive ultra‐performance liquid chromatography–tandem mass spectrometry (UPLC–MS/MS) method has been developed for the determination of terbinafine in human plasma. The method employed liquid–liquid extraction of terbinafine and terbinafine‐d7 (used as internal standard) from 100 μL human plasma with ethyl acetate–n‐hexane (80:20, v/v) solvent mixture. Chromatography was performed on a BEH C₁₈ (50 × 2.1 mm, 1.7 μm) column using acetonitrile–8.0 mm ammonium formate, pH 3.5 (85:15, v/v) under isocratic elution. For quantitative analysis, MS/MS ion transitions were monitored at m/z 292.2/141.1 and m/z 299.1/148.2 for terbinafine and terbinafine‐d7, respectively, using electrospray ionization in the positive mode. The method was validated according to regulatory guidance for selectivity, sensitivity, linearity, recovery, matrix effect, stability, dilution reliability and ruggedness with acceptable accuracy and precision. The method shows good linearity over the tested concentration range from 1.00 to 2000 ng/mL (r² ≥ 0.9984). The intra‐batch and inter‐batch precision (CV) was 1.8–3.2 and 2.1–4.5%, respectively. The method was successfully applied to a bioequivalence study with 250 mg terbinafine in 32 healthy subjects. The major advantage of this method includes higher sensitivity, small plasma volume for processing and a short analysis time.     

In situ fabrication of paclitaxel‐loaded core‐crosslinked micelles via thiol‐ene “click” chemistry for reduction‐responsive drug release

In this study, a facile method to fabricate reduction‐responsive core‐crosslinked micelles via in situ thiol‐ene “click” reaction was reported. A series of biodegradable poly(ether‐ester)s with multiple pendent mercapto groups were first synthesized by melt polycondensation of diol poly(ethylene glycol), 1,4‐butanediol, and mercaptosuccinic acid using scandium trifluoromethanesulfonate [Sc(OTf)₃] as the catalyst. Then paclitaxel (PTX)‐loaded core‐crosslinked (CCL) micelles were successfully prepared by in situ crosslinking hydrophobic polyester blocks in aqueous media via thiol‐ene “click” chemistry using 2,2′‐dithiodiethanol diacrylate as the crosslinker. These PTX‐loaded CCL micelles with disulfide bonds exhibited reduction‐responsive behaviors in the presence of dithiothreitol (DTT). The drug release profile of the PTX‐loaded CCL micelles revealed that only a small amount of loaded PTX was released slowly in phosphate buffer solution (PBS) without DTT, while quick release was observed in the presence of 10.0 mM DTT. Cell count kit (CCK‐8) assays revealed that the reduction‐sensitive PTX‐loaded CCL micelles showed high antitumor activity toward HeLa cells, which was significantly higher than that of reduction‐insensitive counterparts and free PTX. This kind of biodegradable and biocompatible CCL micelles could serve as a bioreducible nanocarrier for the controlled antitumor drug release. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 99–107     

Desirability functions as response in a d‐optimal design for evaluating the extraction and purification steps of six tranquillizers and an anti‐adrenergic by liquid chromatography‐tandem mass spectrometry

Internal standards can be added at different stages of an analytical procedure. When they are added at the beginning of a multiresidue method and their behavior is not exactly the same as that of the analytes, the intended correction for small variations within the analytical process could not be achieved. Because of this, in the present work, the use of d ‐optimal designs together with desirability functions is proposed to state the experimental response under study. The overall desirability function used relates two analytical criteria: to assess a similar chemical behavior of each analyte in relation to its internal standard and to avoid a significant reduction of the absolute peak area of the internal standards. This strategy has been applied to the analysis of the effect of four factors related to the extraction and purification steps of six tranquillizers and a β‐blocker from pig muscle analyzed by liquid chromatography–tandem mass spectrometry. The effect of those factors has been evaluated by means of an ad hoc d ‐optimal design consisting of only 11 experiments. The resulting levels of the four factors that enable to achieve the greatest overall desirability have also been compared with those obtained when either the standardized or absolute peak area has been considered as response. Differences in both the significant factors and their optimum levels have been observed. It is noticeable that the experimental effort necessary to study the effect of the factors has been reduced by more than 50% thanks to the d ‐optimal design. Copyright © 2015 John Wiley & Sons, Ltd.     

Evaluation of an activated carbon from olive stones used as an adsorbent for heavy metal removal from aqueous phases

The performance of a microporous activated carbon prepared chemically from olive stones for removing Cu(II), Cd(II) and Pb(II) from single and binary aqueous solutions was investigated via the batch technique. The activated carbon sample was characterized using N₂ adsorption–desorption isotherms, SEM, XRD, FTIR, and Boehm titration. The effect of initial pH and contact time were studied. Adsorption kinetic rates were found to be fast and kinetic experimental data fitted very well the pseudo-second-order equation. The adsorption isotherms fit the Redlich–Peterson model very well and maximum adsorption amounts of single metal ions solutions follow the trend Pb(II) > Cd(II) > Cu(II). The adsorption behavior of binary solution systems shows a relatively high affinity to Cu(II) at the activated carbon surface of the mixture with Cd(II) or Pb(II). An antagonistic competitive adsorption phenomenon was observed. Desorption experiments indicated that about 59.5% of Cu(II) and 23% of Cd(II) were desorbed using a diluted sulfuric acid solution.