Microwave-assisted extraction through an aqueous medium and simultaneous cleanup by partition on hexane for determining pesticides in agricultural soils by gas chromatography: a critical study

A simple microwave-assisted extraction and partitioning method (MAEP) using water-acetonitrile and n-hexane for desorption and simultaneous partitioning, respectively, together with gas chromatography (GC) was studied to determine representative pesticides (trifluralin, metolachlor, chlorpyriphos and triadimefon) with a broad range of physico-chemical properties in agricultural soils. Three points were considered crucial in this study: instrumental and sample-associated factors affecting extraction of the target compounds were studied through experimental design; the spiking procedure at trace levels was carried out to reproduce the solute-soil sorption taking place in the environment as closely as possible; and results were analyzed taking into account the adsorption behaviour of the compounds on different kinds of soils. The complete analytical procedure proposed consisted of the MAEP of pesticides from 1.0 g of soil with 1 mL of 1:1 water/acetonitrile mixture, and 5 mL of hexane for trapping. The microwave heating program applied was 2 min at 250 W and 10 min at 900 W, and 130 °C maximum temperature. After extraction, the hexane layer was evaporated to dryness; the residue was re-dissolved and directly analyzed by gas chromatography electron capture detection (GC-ECD). Clean chromatograms were obtained without any additional cleanup step. Besides the four pesticides used to optimise MAEP, the method was applied to determine an additional group of pesticides (triallate, acetochlor, alachlor, endosulphan I and II, endrin, methoxychlor and tetradifon) in different soils. Most of the compounds studied were recovered in good yields with relative standard deviations (R.S.D.s) below 9% and detection limits ranged from 0.004 to 0.036 μg g⁻¹. The described method is efficient and fast to determine hydrophobic pesticides at ng g⁻¹ level in soil with different clay-to-organic matter ratios.     

Structure and mechanical properties of poly(l-lactide)/layered silicate nanocomposites

Poly(ε-caprolactone) (PCL) masterbatches with the intercalated and the exfoliated morphology were prepared by ring opening polymerization of ε-caprolactone in the presence of organomodified montmorillonite (MMT) Cloisite 30B. Poly(l-lactide) (PLLA) nanocomposites with Cloisite 30B or PCL masterbatches were prepared by melt blending. The effects of the silicate type, MMT content and the nanocomposite morphology on thermal and mechanical properties of PLLA nanocomposites were examined. The montmorillonite particles in PLLA/Cloisite 30B and PLLA/intercalated masterbatch nanocomposites were intercalated. In contrary to expectations, the exfoliated silicate layers of exfoliated masterbatch were not transferred into the PLLA matrix. Due to a low miscibility of PCL and PLLA, MMT remained in the phase-separated masterbatch domains. The stress-strain characteristics of PLLA nanocomposites, Young modulus E, yield stress σ_y and yield strain ε_y, decreased with increasing MMT concentration, which is associated with the increase in PCL content. The expected stiffening effect of MMT was low due to a low aspect ratio of its particles and was obscured by both plastifying effects of PCL and low PLLA crystallinity. Interestingly, in contrast to the neat PLLA, ductility was enhanced in all PLLA/Cloisite 30B materials and in PLLA/masterbatch nanocomposites with low MMT concentrations.     

Synthesis and characterization of oligoproline-based molecular assemblies for light harvesting

Helical oligoproline arrays provide a structurally well-defined environment for building photochemical energy conversion assemblies. The use of solid-phase peptide synthesis (SPPS) to prepare four such arrays, consisting of 16, 17, 18, and 19 amino acid residues, is described here. Each array contains the chromophore [Rub'(2)m](PF(6))(2) (b' = 4,4'-diethylamidocarbonyl-2,2'-bipyridine; m = 4-methyl-2,2'-dipyridine-4'-carboxylic acid) and the electron transfer donor PTZ (phenothiazine). The arrays differ systematically in the distance between the redox-active metal complex and PTZ sites. They have been used in photophysical studies to provide insight into the distance dependence of electron transfer. (J. Am. Chem. Soc. 2004, 126, 14506-14514). This work describes the synthesis, purification, and characterization of the oligoproline arrays, including a general procedure for the synthesis of related arrays.     

Structure and dynamics of tetrakis(thiophosphinato)resorcinarene complexes of silver(I), gold(I), and palladium(II)

The coordination chemistry of the tetrakis(thiophosphinato)resorcinarene sulfur-donor ligands [(C6H2CH{CH2CH2Ph})4{OC(O)R}4{OP(=S)Ph2}4] (L), where R = OCH2Ph, 4-C6H4CH3, C6H11, C4H3S, or OCH2CCH, is reported. Both silver(I) and gold(I) form cationic complexes of the type [LM2]2+, in which the ligand acts as a bis(chelate) in forming complexes with linear S-M-S (M = Ag or Au) stereochemistry. Gold(I) also forms the unusual complex [L(AuCl)2][LAu2]2+, which forms a supramolecular polymer through intermolecular aurophilic attractions. Palladium(II) forms the complex [LPd2Cl2(mu-Cl)2], in which the dipalladium(II) unit extends the natural bowl structure of the resorcinarene. The solid-state and solution conformations of the complexes, as determined by X-ray structure determination and NMR spectroscopy, respectively, are similar, but several complexes were found to exhibit dynamic behavior in solution, involving either conformational mobility of the resorcinarene unit or intermolecular ligand exchange.     

Resolving the composition of protein complexes using a MALDI LTQ orbitrap

Current biological studies have been advanced by the continuous development of robust, accurate, and sensitive mass spectrometric technologies. The MALDI LTQ Orbitrap is a new addition to the Orbitrap configurations, known for their high resolving power and accuracy. This configuration provides features inherent to the MALDI source, such as reduced spectra complexity, forgiveness to contaminants, and sample retention for follow-up analyses with targeted or hypothesis-driven questions. Here we investigate its performance for characterizing the composition of isolated protein complexes. To facilitate the assessment, we selected two well characterized complexes from Saccharomyces cerevisiae, Apl1 and Nup84. Manual and automatic MS and MS/MS analyses readily resolved their compositions, with increased confidence of protein identification compared with our previous reports using MALDI QqTOF and MALDI IT. CID fragmentation of singly-charged peptides provided sufficient information for conclusive identification of the isolated proteins. We then assessed the resolution, accuracy, and sensitivity provided by this instrument in the context of analyzing the isolated protein assemblies. Our analysis of complex mixtures of singly-charged ions up to m/z 4000 showed that (1) the resolving power, inversely proportional to the square root of m/z, had over four orders of magnitude dynamic range; (2) internal calibration led to improved accuracy, with an average absolute mass error of 0. 5 ppm and a distribution centered at 0 ppm; and (3) subfemtomole sensitivity was achieved using both CHCA and DHB matrices. Additionally, our analyses of a synthetic phosphorylated peptide in mixtures showed subfemtomole level of detection using neutral loss scanning.     

Thermal behavior of some vanadyl complexes with flavone derivatives as potential insulin-mimetic agents

Two new complexes having general formula VOL₂·nH₂O [(1) L: 5-hydroxyflavone, n = 1; (2) L: chrysin, n = 4] were synthesized and characterized. Based on IR and electronic data we concluded that studied flavones act as bidentate ligands in complexes with metallic ion coordinated in a square-pyramidal stereochemistry. The thermal analysis (TG, DTA) elucidated the composition and also the number and nature of the water molecules. The thermal behavior also indicated strong interactions between oxovanadium (IV) and these oxygen donor ligands.     

Thermal behaviour of some new complexes with bismacrocyclic ligands as potential biological active species

Novel complexes of type [M₂LCl₄]·nH₂O ((1) M:Ni, n = 5; (2) M:Cu, n = 0 and (3) M:Zn, n = 2; L: ligand resulted from 1,2-phenylenediamine, 3,6-diazaoctane-1,8-diamine and formaldehyde template condensation) were synthesised and characterised. The features of complexes have been assigned from microanalytical, IR and UV–Vis data. The thermal analyses have evidenced the thermal intervals of stability and also the thermodynamic effects that accompany them. Processes as water or hydrochloric acid elimination as well as oxidative degradation of the organic ligand were observed. Complexes display a different thermal behaviour as result of dissimilar chemical interaction of metal ions with chloride anions. The final product of decomposition was metal(II) oxide as powder X-ray diffraction indicated.     

Self-organization of 1-methylnaphthalene on the surface of artificial snow grains: a combined experimental-computational approach

A combined experimental-computational approach was used to study the self-organization and microenvironment of 1-methylnaphthalene (1MN) deposited on the surface of artificial snow grains from vapors at 238 K. The specific surface area of this snow (1.1 × 10(4) cm(2) g(-1)), produced by spraying very fine droplets of pure water from a nebulizer into liquid nitrogen, was determined using valerophenone photochemistry to estimate the surface coverage by 1MN. Fluorescence spectroscopy at 77 K, in combination with molecular dynamics simulations, and density functional theory (DFT) and second-order coupled cluster (CC2) calculations, provided evidence for the occurrence of ground- and excited-state complexes (excimers) and other associates of 1MN on the snow grains' surface. Only weak excimer fluorescence was observed for a loading of 5 × 10(-6) mol kg(-1), which is ～2-3 orders of magnitude below monolayer coverage. However, the results indicate that the formation of excimers is favored at higher surface loadings (>5 × 10(-5) mol kg(-1)), albeit still being below monolayer coverage. The calculations of excited states of monomer and associated moieties suggested that a parallel-displaced arrangement is responsible for the excimer emission observed experimentally, although some other associations, such as T-shape dimer structures, which do not provide excimer emission, can still be relatively abundant at this surface concentration. The hydrophobic 1MN molecules, deposited on the ice surface, which is covered by a relatively flexible quasi-liquid layer at 238 K, are then assumed to be capable of dynamic motion resulting in the formation of energetically preferred associations to some extent. The environmental implications of organic compounds' deposition on snow grains and ice are discussed.     

Thermal degradation behavior of some ruthenium complexes with fluoroquinolone derivatives as potential antitumor agents

Three new complexes with ligands belong to the fluoroquinolone class having the general formula [RuL₂Cl₂]Cl nH₂O ((1) L: norfloxacin (nf), n = 4; (2) L: ciprofloxacin (cp), n = 3; (3) L: enrofloxacin (enro), n = 5) were synthesized and characterized by chemical analysis UV–Vis and IR spectroscopy. In all complexes fluoroquinolone derivative acts as bidentate chelate ligand. The thermal behavior steps were investigated in synthetic air flow. The thermal transformations are complex processes according to TG and DTG curves including dehydration, quinolone derivative degradation, as well as RuCl₃ conversion in RuO₂.     

Azulen-1-yl diazenes substituted at C-3 with phenyl-chalcogene moieties: dye synthesis, product characterization and properties

Abstract  

Two synthesis strategies were used for the generation of azulene-1-yl diazenes substituted at C-3 with a phenyl-chalcogenyl moiety, the synthesis of azulenes substituted at C-3 followed by azo-coupling and azulene substitution at C-3 in azulene-azo dyes. The last synthetic route seems to give more satisfactory results for the synthesis of the desired chalcogenic derivatives. Another target of this study was to investigate the changes induced by the phenyl-chalcogenic substitution on the NMR and UV-vis spectra, and also to compare this effect with the one exerted by halogen atoms and by strongly electron donating groups such as AcNH or PhCOO. Whereas the latter groups exhibit a strong influence on the NMR and UV-vis spectra, PhS, PhSe, or PhTe groups as well as halogen atoms produce only a small effect because of the moderate change in electron distribution over the entire molecule.