Molecularly imprinted polymer-sol-gel tablet toward micro-solid phase extraction: I. Determination of methadone in human plasma utilizing liquid chromatography–tandem mass spectrometry

In the present work molecularly imprinted sol-gel tablet (MIP-Tablet) was prepared. The MIP-sol-gel was prepared as a thin layer on polyethylene material in a tablet form. Methadone-d₉ was selected as the template and 3-(propylmethacrylate)-trimethoxysilane was used as precursor. MIP-Tablet was applied for micro-solid phase extraction (μ-SPE). The MIP-Tablet was used for the determination of methadone in human plasma samples utilizing liquid chromatography-tandem mass spectrometry; and each tablet could be used twenty times. The extraction time was 10 min while desorption time was 6 min. Factors affecting the extraction efficiency such as desorption solvents, sample pH, salt addition, extraction time, desorption time and adsorption capacity were investigated. The calibration curves were obtained within the range of 5–5000 ng/mL using methadone in human plasma samples. The coefficients of determination (r²) values were ≥0.999 for all runs and the extraction recovery was >80%. The accuracy values for quality control samples varied from +3.6 to +9.7% and the inter-day precision (RSD %) values were ranged from 5.0 to 8.0%. The limit of detection was 1.0 ng/mL and the lower limit of quantification was 5 ng/mL utilizing methadone in human plasma samples.     

A combined experimental and DFT investigation of the adsorption of humic acid by-products on polypyrrole

This study sheds light on the removal of humic acid by-products (trimellitic and pyromellitic acids; TMA and PMA, respectively) from aqueous solution using conducting polypyrrole (PPy) as an effective adsorbent. The effects of experimental factors including contact time, solution pH, initial concentration, adsorbent dose, and temperature were systematically investigated. The pseudo-second-order kinetic model provides the best correlation with adsorption experimental data. The equilibrium adsorption was well described by the Langmuir model with maximum mono-layer adsorption capacities of 47.62 and 71.43?mg?g^?1 for TMA and PMA, respectively. The analysis of thermodynamic parameters indicated that the adsorption process was spontaneous and endothermic in nature. In addition, we investigated the adsorption mechanism using the density functional theory (DFT) calculations. The TMA and PMA were physisorbed on the PPy surface through the formation of hydrogen bonds between carboxylic groups of adsorbate molecules and the amino group of the adsorbent. The calculated theoretical data were in good agreement with experiments.     

Convenient synthesis of substituted benzo[e][1,2,4]- or [d][1,2,6]oxadiazepines,benzo[f][1,3,5]triazocines from N-aryliminoesters

We report herein a short and efficient synthesis of benz[e][1,2,4]- or [d][1,2,6]oxadiazepines and benzo[f][1,3,5]triazocines from easily prepared N-aryl iminoesters. The strategy involves a bis-nucleophile reagent (hydroxylamine or guanidine) that promotes a one-step ring closure from the starting functionalized iminoesters.     

NOUVELLE SYNTHÈSE DE [1,2-A]BENZIMIDAZOLO-1,3,5,2-TRIAZAPHOSPHORINES ET DE [1,2-A]BENZIMIDAZOLO-1,3,5,2- TRIAZAPHOSPHORINE-2-THIONES

The condensation of N₁-benzimidazolyl amidines 1 with tris(dimethy- lamino)phosphine leads to the corresponding [1,2a]Benzimidazolo-1,3,5,2-triazaphosphorines 3 . The N₂-phosphoroamidine intermediates 2′ are isolated and yielded the corresponding cyclic compounds 4 upon heating. The oxidation by sulfur of the compounds 3 gives the thiooxide derivatives 4 .

The structure of these compounds is unambiguously confirmed by IR, ¹H, ³¹P, and ¹³C NMR spectroscopy and by MS for some products.     

Cyclodesulfurization of Substituted Thiosemicarbazides into 1,3,4-Oxadiazoles via Hydrazonoyl Chlorides

Abstract

The reaction of thiosemicarbazides 1a–h with hydrazonoyl chlorides 2a–g at ambient temperature, in the presence of triethylamine yielded, in each case, two products. The structure of these compounds was confirmed as 1,3,4-oxadiazoles 14a–h and hydrazonothioates 15a–g. The structure of 15b was confirmed through single crystal X-ray diffraction. A mechanism was proposed for this cyclodesulfurization reaction.     

SYNTHESIS AND REACTIONS OF SOME NEW HETEROCYCLIC COMPOUNDS CONTAINING THE THIENYLTHIENO[2,3-B]PYRIDINE MOIETY

(4-Aryl-3-cyano-6-(2-thienyl)pyridin-2-ylthio)acethydrazides (5a–c), 3-amino-4-aryl-6-(2-thienyl)thieno[2,3-b]pyridine-2-carbohydrazides (6a–c) and 3-amino-4-phenyl-6-(2-thienyl)thieno[2,3-b]pyridine-2-carboxylic acid (30) were prepared and employed as key intermediates in the synthesis of the title compounds.     

Pyridazine Derivatives and Related Compounds. Part 11: 1Synthesis of Some Pyrimido[4′,5′:4,5]thieno[2,3-c]pyridazines

3-Substituted pyrimido[4′,5′:4,5]thieno[2,3-c]pyridazine-2,4-di-ones and 3-amino-2-methylpyrimido[4′,5′:4,5]thieno[2,3-c]pyridazine-4-ones were synthesized starting from ethyl 5-aminothieno[2,3-c] pyridazine-6-carboxylate 1. Reaction of amino ester 1with phenyl isothiocyanate affords thiourea derivative 10which undergo further transformation to the related fused heterocyclic systems.     

Hydrolysis-Condensation Kinetics of Different Silane Coupling Agents

Abstract

The hydrolysis kinetics of 14 alkoxy silane coupling agents were carried out in an ethanol:water 80:20 (w/w) solution under acidic conditions and were monitored by ¹H, ¹³C, and ²⁹Si NMR spectroscopy. Acidic conditions were selected in order to enhance the silanol formation and to slow down the self-condensation between the resulting hydrolysed silanol groups. In situ ²⁹Si NMR spectroscopy allowed the determination of the intermediate species as a function of the reaction time. Thus, the following silane coupling agents were studied: 3-methacryloxypropyl trimethoxy silane (MPMS), 3-mercaptopropyl trimethoxy silane (MRPMS), 3-cyanopropyl triethoxy silane (CPES), triethoxy vinyl silane (VES), trimethoxy (2-phenylethyl) silane (PEMS), octyl triethoxy silane (OES), trimethoxy (7-octen-1-yl) silane (OEMS), 3-aminopropyl triethoxy silane (APES), 3-aminopropyl trimethoxy silane (APMS), 3-(2-aminoethylamino)propyl trimethoxy silane, (DAMS), 3-[2-(2-aminoethylamino)-ethylamino]propyl trimethoxy silane (TAMS), 4-amino-3,3-dibutyl trimethoxy silane (ADBMS), trimethoxy [3-(phenylamino)propyl] silane (PAPMS), and triethoxy-3-(2-imidazolin-1-yl) propyl silane (IZPES). A parameter quantifying the grafting potentiality of each silane coupling agent towards OH-rich solid substrates (such as cellulose) was established as a function of the nature of the alkoxy groups (methoxy or ethoxy), as well as that of the fourth substituent (vinyl, aminopropyl, etc.) of the silane studied.

GRAPHICAL ABSTRACT