Optimization of Ultrasound-Assisted Extraction of Phenolics from Sideritis raeseri Using Response Surface Methodology

In this study we define the optimal conditions for ultrasound-assisted extraction of bioactive polyphenols from S. raeseri aerial parts using response surface methodology. The influence of ethanol concentration (10–90%), extraction temperature (20–80 °C), extraction time (10–60 min), and solid-to-solvent ratio (1:10–1:50) on total phenolic content as well as on content of individual flavonoids, and hypolaetin and isoscutellarein derivatives was studied. For the experimental design, a central composite design was chosen. In the obtained extracts, the following ranges of targeted compounds were detected: total phenol from 19.32 to 47.23 mg GAE/g dw, HYP from 1.05 to 11.46 mg/g dw, ISC 1 from 0.68 to 10.68 mg/g dw, and ISC 2 from 0.74 to 15.56 mg/g dw. The optimal extraction conditions were set as: ethanol concentration of 65%, extraction time of 50 min, extraction temperature of 63 °C, and solid-to-solvent ratio of 1:40. Contents of TP, HYP, ISC 1, and ISC 2 in optimal extracts were 47.11 mg GAE/g dw, 11.73 mg/g dw, 9.54 mg/g dw, and 15.40 mg/g dw, respectively. Experimentally set values were in good agreement with those predicted by the response surface methodology model, indicating suitability of the used model, as well as the success of response surface methodology in optimizing the conditions of the extraction.     

Helical nuclear spin order in a strip of stripes in the quantum Hall regime

We investigate nuclear spin effects in a two-dimensional electron gas in the quantum Hall regime modeled by a weakly coupled array of interacting quantum wires. We show that the presence of hyperfine interaction between electron and nuclear spins in such wires can induce a phase transition, ordering electrons and nuclear spins into a helix in each wire. Electron-electron interaction effects, pronounced within the one-dimensional stripes, boost the transition temperature up to tens to hundreds of millikelvins in GaAs. We predict specific experimental signatures of the existence of nuclear spin order, for instance for the resistivity of the system at transitions between different quantum Hall plateaus.     

Application of the Solvatic Model for Prediction of Retention in RP-LC for Multi-Step Gradient Profiles

Application of the solvatic retention model of reversed-phase liquid chromatography was studied to predict retention of phenylisothiocyanate derivatives of amino acids from structural formulae and stationary and mobile phase properties. The gradient elution mode with methanol and acetonitrile aqueous mobile phases was used. It was shown that practically acceptable prediction or retention time values can be achieved after the first approximation step when experimental data of one run are used. The zero approximation level predictions—from structural formulae, column and mobile phase properties can be used as a “first guess” method from which further optimization can begin.

     

Parallel Water/Aromatic Interactions of Non‐Coordinated and Coordinated Water

The parallel interactions of non‐coordinated and coordinated water molecules with an aromatic ring were studied by analyzing data in the Cambridge structural database (CSD) and by using quantum chemical calculations. The CSD data show that water/aromatic contacts prefer parallel to OH/π interactions, which indicates the importance of parallel interactions. The results reveal the influence of water coordination to a metal ion; the interactions of aqua complexes are stronger. Coordinated water molecules prefer a parallel‐down orientation in which one O?H bond is parallel to the aromatic ring, whereas the other O?H bond points to the plane of the ring. The interactions of aqua complexes with parallel‐down water/benzene orientation are as strong as the much better known OH/π orientations. The strongest calculated interaction energy is ?14.89 kcal mol^?1. The large number of parallel contacts in crystal structures and the quite strong interactions indicate the importance of parallel orientation in water/benzene interactions.     

Using xanthated Lagenaria vulgaris shell biosorbent for removal of Pb(II) ions from wastewater

Chemically modified Lagenaria vulgaris shell was applied as a new sorbent for the removal of lead (II) ions from aqueous solution in a batch process mode. The influence of contact time, initial concentration of lead (II) ions, initial pH value, biosorbent dosage, particle size and stirring speed on the removal efficiency was evaluated. Biosorbent characterization was performed by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). Four kinetic models (pseudo-first order, pseudo-second order, Elovich model and Intraparticle diffusion model) were used to determine the kinetic parameters. The experimental results were fitted to the Langmuir, Freundlich, Dubinin–Radushkevich and Temkin models of isotherm. Pseudo-second order kinetic model and Langmuir isotherm model best fitted the experimental data. Sorption process is obtained to be fast and equilibrium was attained within 40 min of contact time. The maximum sorption capacity was 33.21 mg g^?1. Biosorption was highly pH-dependent where optimum pH was found to be 5. The results of FTIR and SEM analysis showed the presence of new sulfur functional groups. This study indicated that xanthated Lagenaria vulgaris shell could be used as an effective and low-cost biosorbent for the removal of lead (II) ions from aqueous solution.     

Simultaneous determination of some water-soluble vitamins and preservatives in multivitamin syrup by validated stability-indicating high-performance liquid chromatography method

HPLC stability-indicating method has been developed for the simultaneous determination of some water-soluble vitamins (ascorbic acid, thiamine hydrochloride, riboflavin-5'-phosphate sodium, pyridoxine hydrochloride, nicotinamide, D(+)-panthenol) and two preservatives (methylparaben and sodium benzoate) in multivitamin syrup preparation. Water-soluble vitamins, preservatives and their degradants were separated on Zorbax SB-Aq (C(18)) (250 mm x 4.6 mm, 5 microm) column at an ambient temperature. Combined isocratic and gradient elution was performed with a mobile phase consisting of 0.0125 M hexane-1-sulfonic acid sodium salt in 0.1% (m/v) o-phosphoric acid, pH 2.4-2.5 (solvent A) and acetonitrile (solvent B) at the flow-rate 1 ml min(-1). Starting with solvent A an isocratic elution was performed for 15 min, then the composition was changed to 85% of A and 15% of B during the next 20 min and it was constant for 5 min, then the composition was changed to 70% of A and 30% of B during next 15 min and it was constant for 5 min and finally was changed to 100% of A as at the beginning of the elution. Detection was performed with diode array detector at 210, 230 and 254 nm. Multivitamin syrup preparation was subjected to stress testing (forced degradation) in order to demonstrate that degradants from the vitamins, preservatives and/or product excipients do not interfere with the quantification of vitamins and preservatives. Typical validation characteristics: selectivity, accuracy, precision, linearity, range, limit of quantification and limit of detection were evaluated for vitamins and preservatives.     

Thiamacrocyclic lactones: new Ag(I)-ionophores

The syntheses of novel adamantane thialactones 5-12 are reported, and the results of the heavy- and transition-metal cation extraction experiments are described. The results are compared with those obtained with similar thiamacrocyclic ligands that have flexible chains of methylene groups incorporated into the macrocyclic framework as in 13-20. The results show that most of the hosts studied are very good in complexing the Ag(+) ion. The formation of complexes has also been demonstrated using NMR titration experiments for macrocycles 13 and 14 with AgTFA. Introduction of a single polycyclic molecule into the 15- to 18-membered rings increases the rigidity and preorganizes the ligand for complexation. However, two adamantane molecules embedded in the ring usually diminish the complexing ability of the ligand, primarily due to sterical effects of the bulky adamantane moiety that obstructs formation of an optimal geometry for binding the desired metal ion. The structures of macrocycles 5, 7, 9, 11, and 19 were determined by X-ray structure analysis, and their conformational properties are discussed. In the solid state, 7, 11, and 19 are organized into tubular fashion using C-H...O interactions. Also, two silver complexes with thialactone 13, Ag13 and Ag(13)(2), were prepared and characterized. The structure analysis of Ag13 and Ag(13)(2) reveals the formation of mononuclear and binuclear species with silver in ambivalent, tetrahedral coordination via sulfur and oxygen from trifluoroacetate anion.     

The influence of water molecule coordination to a metal ion on water hydrogen bonds

The geometry of hydrogen bonds in the crystal structures from the Cambridge Structural Database and calculated data show that water coordination to a metal ion has a remarkable influence on hydrogen bonds. The calculated energies of hydrogen bonds of coordinated water are much stronger, even if the aqua complex is neutral.     

Vortex grinding for mechanochemistry: application for automated supramolecular catalysis and preparation of a metal-organic framework

An automated grinding method based on a vortex mixer has been developed. The method enables simultaneous grinding and UV-irradiation, as well as in situ monitoring of solid-state reactivity. The method has been applied to a cocrystallization, supramolecular catalysis, and the preparation of a metal-organic framework.     

Arsenopyrite mineral based electrochemical sensor for acid–base titrations in γ-butyrolactone and propylene carbonate

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.