Butylated hydroxytoluene enediyne: access to diradical and electrophilic quinone methide intermediates

A theoretical study was carried out on the unimolecular reaction of an enediyne with a fused butylated hydroxytoluene to internally scavenge the p‐benzyne diradical sites formed after the Bergman cyclization. The calculations revealed that the conversion of the p‐benzyne diradical (2‐tert‐butyl‐4‐methyl‐5,8‐didehydro‐1‐naphthalenol) to p‐quinone methide is favored over the conversion to a phenoxy/benzene diradical 4 in an approximate 95:5 ratio. Based on this model, the Bergman cyclization leads in a bifunctional manner to intermediates for competing reactivity with intermolecular H‐atom abstraction. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and characterization of cellulose acetate from cellophane industry residues. Application as acetaminophen controlled-release membranes

Journal of Thermal Analysis and Calorimetry - Cellophane film production generates cellulosic residues from scraps, edges, and low-quality films. In this work, cellophane was used as a raw material...     

Kinetics of dehydration and textural characterizations of selectively leached vermiculites

Acid leaching of aluminosilicates is an interesting procedure for preparing high surface porous silica. Thermal behavior of vermiculite leached with a nitric acid solution at various concentrations was studied by thermogravimetry and differential scanning calorimetry. Activation energies of the dehydration process in selected temperature zones were determined by two different methods: Ozawa–Flynn–Wall and Friedman. The material obtained was characterized through Fourier transform infrared spectroscopy, X-ray diffraction, and nitrogen adsorption at 77 K to relate them to the estimated activation energies.     

Electrochemical characterisation of a Zn/(PEO)4ZnCl2/Nb2O5 solid-state cell

The (PEO)₄ZnCl₂ electrolyte (PEO, polyethylene oxide) was studied in view of its potential application in a solid-state rechargeable zinc cell. The electrochemical stability window was established, and decomposition voltage values between 3.19 (20 °C) and 1.44 V (150 °C) were estimated. Cyclic voltammetry studies using a Pt/(PEO)₄ZnCl₂/Pt cell indicated reversibility of the Zn²⁺/Zn couple at the electrode/electrolyte interface. Laboratory cells Zn(−)/(PEO)₄ZnCl₂/Nb₂O₅(+) were assembled and studied at 55 °C, under various discharge current densities. Results of cell discharge profiles, capacity values, charge–discharge cycles and cell stabilities are reported.     

Assessment of dispersive liquid–liquid microextraction for the simultaneous extraction,preconcentration, and derivatization of Hg2+ and CH3Hg+ for further determination by GC–MS

This work reports the development of a dispersive liquid – liquid microextraction method for the simultaneous extraction, preconcentration, and derivatization of Hg²⁺ and CH₃Hg⁺ species from water samples for further determination by GC – MS. Some parameters of the proposed method, such as volume and type of disperser and extraction solvent, and Na[B(C₆H₅)₄] concentration were investigated using response surface methodology. Suitable recoveries were obtained using 80 μL C₂Cl₄ (as extraction solvent), 1000 μL ethanol (as disperser solvent), and 300 μL 2.1 mmol/L Na[B(C₆H₅)₄] (as derivatizing agent). Accuracy was evaluated in terms of recovery and ranged from 87 to 99% with RSD values <7%. In addition, a certified reference material of water (NIST 1641d) was analyzed and agreed with the certified value about 107% (for Hg²⁺), with RSD values <8.5%. LODs were 0.3 and 0.2 μg/L, with enrichment factors of 112 and 115 for Hg²⁺ and CH₃Hg⁺, respectively. The optimized method was applied for the determination of Hg²⁺ and CH₃Hg⁺ in tap, well, and lake water samples.     

Performance of hydrophobic interaction ligands for human membrane‐bound catechol‐O‐methyltransferase purification

Despite of membrane catechol‐O‐methyltransferase (MBCOMT, EC 2.1.1.6) physiological importance on catecholamines’ O‐methylation, no studies allowed their total isolation. Therefore, for the first time, we compare the performance of three hydrophobic adsorbents (butyl‐, epoxy‐, and octyl‐Sepharose) in purification of recombinant human COMT (hMBCOMT) from crude Brevibacillus choshinensis cell lysates to develop a sustainable chromatographic process. Hydrophobic matrices were evaluated in terms of selectivity and hMBCOMT's binding and elution conditions. Results show that hMBCOMT's adsorption was promoted on octyl and butyl at ≤375 mM NaH₂PO_4, while on epoxy higher concentrations (>850 mM) were required. Additionally, hMBCOMT's elution was promoted on epoxy, butyl, and octyl using respectively 0.1–0.5, 0.25–1, and 1% of Triton X‐100. On butyl media, a stepwise strategy using 375 and 0 mM NaH₂PO₄, followed by three elution steps at 0.25, 0.7 and 1% Triton X‐100, allowed selective hMBCOMT isolation. In conclusion, significant amounts of MBCOMT were purified with high selectivity on a single chromatography procedure, despite its elution occurs on multiple peaks. Although successful applications of hydrophobic interaction chromatography in purification of membrane proteins are uncommon, we proved that traditional hydrophobic matrices can open a promising unexplored field to fulfill specific requirements for kinetic and pharmacological trials.     

Determination of seven selected antipsychotic drugs in human plasma using microextraction in packed sorbent and gas chromatography–tandem mass spectrometry

A method using microextraction by packed sorbent (MEPS) and gas chromatography–tandem mass spectrometry (GC-MS/MS) is described for the determination of seven antipsychotic drugs in human plasma. The studied compounds were chlorpromazine (CPZ), haloperidol (HAL), cyamemazine, quetiapine, clozapine, olanzapine (OLZ), and levomepromazine; promazine, protriptyline, and deuterated CPZ were used as internal standards. The validation parameters included selectivity, linearity and limits of detection and quantitation, intra- and interday precision and trueness, recovery, and stability and were studied according to internationally accepted guidelines. The method was found to be linear between the lower limit of quantitation and 1000 ng/mL, except for OLZ and HAL (200 ng/mL), with determination coefficients higher than 0.99 for all analytes, and extraction efficiencies ranged from 62 to 92 %. Intra- and interday precision ranged from 0.24 to 10.67 %, while trueness was within a ±15 % interval from the nominal concentration for all analytes at all studied levels. MEPS has shown to be a rapid procedure for the determination of the selected antipsychotic drugs in human plasma, allowing reducing the handling time and the costs of analysis. Furthermore, GC-MS/MS has demonstrated to be a powerful tool for the simultaneous quantitation of the studied compounds, enabling obtaining adequate selectivity and sensitivity using a sample volume of as low as 0.25 mL.