Hydrogen-atom and oxygen-atom transfer reactivities of iron(IV)-oxo complexes of quinoline-substituted pentadentate ligands.

A series of iron(II) complexes with the general formula [FeII(L2-Qn)(L)]n+ (n = 1, L = F-, Cl-; n = 2, L = NCMe, H2O) have been isolated and characterized. The X-ray crystallographic data reveals that metal-ligand bond distances vary with varying ligand field strengths of the sixth ligand. While the complexes with fluoride, chloride and water as axial ligand are high spin, the acetonitrile-coordinated complex is in a mixed spin state. The steric bulk of the quinoline moieties forces the axial ligands to deviate from the Fe-Naxial axis. A higher deviation/tilt is noted for the high spin complexes, while the acetonitrile coordinated complex displays least deviation. This deviation from linearity is slightly less in the analogous low-spin iron(II) complex [FeII(L1-Qn)(NCMe)]2+ of the related asymmetric ligand L1-Qn due to the presence of only one sterically demanding quinoline moiety. The two iron(II)-acetonitrile complexes [FeII(L2-Qn)(NCMe)]2+ and [FeII(L1-Qn)(NCMe)]2+ generate the corresponding iron(IV)-oxo species with higher thermal stability of the species supported by the L1-Qn ligand. The crystallographic and spectroscopic data for [FeIV(O)(L1-Qn)](ClO4)2 bear resemblance to other crystallographically characterized S = 1 iron(IV)-oxo complexes. The hydrogen atom transfer (HAT) and oxygen atom transfer (OAT) reactivities of both the iron(IV)-oxo complexes were investigated, and a Box-Behnken multivariate optimization of the parameters for catalytic oxidation of cyclohexane by [FeII(L2-Qn)(NCMe)]2+ using hydrogen peroxide as the terminal oxidant is presented. An increase in the average Fe-N bond length in [FeII(L1-Qn)(NCMe)]2+ is also manifested in higher HAT and OAT rates relative to the other reported complexes of ligands based on the N4Py framework. The results reported here confirm that the steric influence of the ligand environment is of critical importance for the reactivity of iron(IV)-oxo complexes, but additional electronic factors must influence the reactivity of iron-oxo complexes of N4Py derivatives.

Disposable pipette extraction: A critical review of concepts, applications, and directions.

Analytical chemistry has always been evolving towards techniques that are increasingly simple and effective and that conform to green principles. Disposable pipette extraction (DPX, also known as dispersive pipette tip solid phase extraction) is a recent technique that has become an interesting tool in sample preparation methodologies. The principle is based on a dynamic mixture between the matrix and the sorbent which allows rapid and effective extraction of analytes and provides vigorous clean-up of the samples. In the context of fitting in with green chemistry, DPX has contributed to replacing commercially available materials with natural alternative materials. The production of these materials is also simple, reduces sample/solvent volumes, consequently generates less waste and is less laborious and safer for the laboratory worker. This review is a source of information about the DPX technique, dealing with its basic concepts, procedure, optimizations, materials for the main applications published so far, which are in the food, environmental and biological (forensic) sciences.

High-throughput approach for the in situ generation of magnetic ionic liquids in parallel-dispersive droplet extraction of organic micropollutants in aqueous environmental samples.

In this work, a novel and high-throughput parallel-dispersive droplet extraction (Pa-DDE) based on in situ formation of the hydrophobic MILs ([Co(C4IM)4+2]2[NTf2-], [Ni(C4IM)4+2]2[NTf2-] and [Ni(BeIM)4+2]2[NTf2-]) is demonstrated, for the first time, for the determination of benzophenone, metolachlor, triclocarban, pendimethalin, 4-methylbenzylidene camphor, and 2-ethylhexyl-4-methoxycinnamate from aqueous environmental samples. This experimental setup is comprised of a 96-well plate system containing a set of magnetic pins which were used to collect the MIL droplet after in situ formation. This consolidated system enabled simultaneous extraction of up to 96 samples and MIL production in one step. Using this apparatus, sample preparation times of 0.78 min per sample was achieved. The experimental conditions were carefully optimized using uni and multivariate approaches. The optimal conditions were comprised of sample volume of 1.25 mL, 4 mg of [Co(C4IM)4+2]2[Cl-] and 40 µL of LiNTf2 for the in situ formation, and dilution in 20 µL of acetonitrile. The analytical parameters of merit were successfully determined with LODs ranging from 7.5 to 25 µg L-1 and coefficients of determination higher than 0.989. Intraday and interday precision ranged from 6.4 to 20.6% (n = 3) and 11.6-22.9% (n = 9), respectively, with analyte relative recovery ranging between 53.9 and 129.1%.

Novel strategy for disposable pipette extraction (DPX): Low-cost Parallel-DPX for determination of phthalate migration from common plastic materials to saliva simulant with GC-MS.

In widespread use in commercial products as plasticizers, phthalic acid esters (phthalates) have worried researchers and society in general, given the negative impacts on living organisms, especially human health. Since they are not chemically linked to the polymeric matrix, their migration is evident for samples that come into contact with plastics that contain them, such as water, food and saliva. In this work, a new strategy is described, named parallel-disposable pipette extraction (Pa-DPX), in a fast, efficient and robust analytical method using five simultaneous extractions for the determination of migration of 6 phthalates from common plastic materials (children's toys, school supplies, dog toys and oral contact items) to saliva simulant, using gas chromatography-mass spectrometry (GC-MS). The optimized conditions were 5 extraction cycles with 1600 µL of saliva simulant and desorption with 200 µL of ethyl acetate using 5 cycles with the same aliquot. The calibration curves resulted in determination coefficients higher than 0.9915, limits of detection at 1.5 µg L-1, and the quantification limits were 5.0 µg L-1. Excellent results were obtained for repeatability (relative standard deviation ranging from 8.7% to 20.1% for 5 µg L-1) and intermediate precision, varying the day of analyses (7.9%-16.2%). The analyte recovery ranged from 75% to 114% for two different samples, in four different levels of concentration. The Pa-DPX-GC-MS method was successfully applied to determine the migration of PAE from 21 samples. At least one PAE was detected in 81% of samples, and di-n-octyl phthalate was found in higher concentration, achieving the migration of almost 30 µg per g of sample.

Determination of bisphenol A: Old problem, recent creative solutions based on novel materials.

Bisphenol A is a synthetic compound widely used in industry, in the production of polycarbonate, epoxy resins, and thermal paper, among others. Its annual production is estimated at millions of tons per year, demonstrating its importance. Despite its wide application in various everyday products, once in the environment (due to its disposal or leaching), it has high toxicity to humans and animal life, and this problem has been well known for years. Given this problem, many researchers seek alternatives for its monitoring in matrices such as natural water, waste, food, and biological matrices. For this, new advanced materials have been developed, characterized, and applied in creative ways for the preparation of samples for the determination of bisphenol A. This article aims to present some of these important and recent applications, describing the use of molecularly imprinted polymers, metal and covalent organic frameworks, ionic liquids and magnetic ionic liquids, and deep eutectic solvents as creative solutions in sample preparation for the long-standing problem of bisphenol A determination.