Development and validation of an analytical methodology for the determination of p,p′-DDT, p,p′-DDE and p,p′-DDD in fish oil pills

An analytical methodology was proposed and validated to be applied to the determination of p,p′-DDT and its metabolites p,p′-DDE and p,p′-DDD in fish oil. The analytical procedure presented in this paper involves a single-step clean up process prior to the analysis. A solution of 1,2,3,4-tetrachloronaphtalene was used as internal standard.The analytical technique used was gas chromatography coupled to an electron capture detector. Details on the validation process are provided.The limits of detection ranged from 2.6 to 4.7 pg μL^− 1. The BCR 598 standard reference material (cod liver oil) was used to evaluate the performance of the methodology with satisfactory recoveries for all the compounds.The analytes were determined in three different fish oil pills sold in Spain as a supplementary vitamin support. The sum of p,p′-DDT and metabolites was from 13.2 to 51.3 ng g^− 1, the dominant compound being p,p′-DDE.     

Solid-phase synthesis of the cyclic lipononadepsipeptide [N-Mst(Ser1), d-Ser4, L-Thr6, L-Asp8, L-Thr9]syringotoxin

An optimized solid-phase strategy for the preparation of the cyclic lipononadepsipeptide [N-Mst(L-Ser1), D-Ser4, L-Thr6, L-Asp8, L-Thr9]syringotoxin is reported. The strategy is based on the use of a mild orthogonal protection scheme and the incorporation of the nonproteinogenic amino acid (Z)-Dhb into the peptide chain as the dipeptide Fmoc-Thr(tBu)-(Z)-Dhb-OH. The didehydrodipeptide was synthesized by a water-soluble carbodiimide-induced beta-elimination of a protected dipeptide containing a residue of Thr with its free hydroxy side chain unprotected.     

Stereoselective synthesis of trans-2,3-disubstituted pyrrolidines via addition to N-acyliminium ions

An efficient and stereoselective synthesis of trans-2,3-disubstituted pyrrolidines is described. The intermolecular alkylation of racemic N-acyliminium ions generated in situ from the corresponding 3-substituted lactams proceeds stereoselectively and in high yield.     

Design and synthesis of push-pull chromophores for second-order nonlinear optics derived from rigidified thiophene-based pi-conjugating spacers.

Two series of push-pull chromophores built around thiophene-based pi-conjugating spacers rigidified either by covalent bonds or by noncovalent intramolecular interactions have been synthesized and characterized by UV-vis spectroscopy, electric field induced second harmonic generation (EFISH) and differential scanning calorimetry. Comparison of the linear and second-order nonlinear optical properties of chromophores based on a covalently bridged dithienylethylene (DTE) spacer with those of their analogues based on open chain DTE shows that the rigidification of the spacer produces a considerable bathochromic shift of the absorption maximum together with a dramatic enhancement of the molecular quadratic hyperpolarizability (mu beta) which reaches values among the highest reported so far. A second series of NLO-phores has been derived from a 2,2'-bi(3,4-ethylenedioxythiophene) (BEDOT) pi-conjugating spacer. As indicated by X-ray and UV-vis data, rigidification of the spacer originates in that case, from noncovalent intramolecular interactions between sulfur and oxygen atoms. Again, comparison with the parent compounds based on an unsubstituted bithiophene spacer reveals a marked red shift of the absorption maximum and a large enhancement of mu beta. In an attempt to distinguish the contribution of the electronic and geometrical effects of the ethylenedioxy group, a third series of NLO-phores based on 3,4-ethylenedioxythiophene (EDOT) and 3,4-dihexyloxythiophene spacers has been synthesized. Comparison with compounds based on unsubstituted thiophene shows that, despite a red shift of lambda(max), introduction of alkoxy groups leads to a decrease of mu beta. Theoretical calculations indicate that this effect results from a decrease of the dipole moment (mu) caused by the auxiliary electron-donor alkoxy groups on the thiophene ring. In contrast, replacement of BT by BEDOT produces an increase of mu, which associated with the noncovalent rigidification of the BT system accounts for the observed enhancement of mu beta.     

Why copper is intrinsically more selective than silver in alkene epoxidation: ethylene oxidation on Cu(111) versus Ag(111)

The heterogeneously catalyzed epoxidation of alkenes is experimentally challenging, theoretically interesting, and technologically important. Although large-scale ethylene epoxidation is universally carried out with Ag catalysts, recent laboratory studies on single crystal surfaces show that Cu is intrinsically much more selective than Ag in the epoxidation of a variety of terminal alkenes. The reasons for this striking difference between Ag and Cu have been investigated by means of density functional theory. It is found that the fundamental cause is the inversion in the ordering of activation barriers for the competing pathways to epoxide formation versus acetaldehyde formation (the latter being the first step on the route to combustion). On Cu, epoxide formation is less activated than aldehyde formation; the opposite is true on Ag. This behavior is associated with a late transition state to epoxidation on Cu (i.e., product-like) compared to an early (reactant-like) transition state to epoxidation on Ag.     

Thermal analysis of CuMg alloys deformed by equal channel angular pressing

Journal of Thermal Analysis and Calorimetry - The thermal behavior of two copper alloys, with 0.2 and 0.5 mass % of Mg, was analyzed after severe plastic deformation processing by Equal Channel...     

Isotope dilution GC-MS routine method for the determination of butyltin compounds in water

A standard GC-MS instrument with electron impact ionisation has been used to develop a fast, simple and reliable method for the simultaneous determination of monobutyltin (MBT), dibutyltin (DBT) and tributyltin (TBT) in water samples. Isotope dilution analysis (IDA) is used for the determination of species, taking advantage of a commercially available spike solution containing a mixture of MBT, DBT and TBT enriched in ¹¹⁹Sn. Method detection limits for 100-mL samples were between 0.18 and 0.25 ng L⁻¹ for the three butyltin compounds with typical RSD between 2 and 4% at levels between 100 and 10 ng L⁻¹, respectively. Recovery of tin species in spiked samples (natural water, wastewater and seawater) was quantitative. The stability of butyltin compounds in collected seawater samples was also studied. The addition of a 1% (v/v) glacial acetic acid preserved tin species in the samples for at least 5 days at room temperature. The IDA method was finally implemented in a routine testing laboratory and it was subsequently accredited by the Spanish National Accreditation Body according to the requirements of UNE-EN ISO/IEC 17025.     

Practical Study into Enhancing IgG Immobilisation on Screen-Printed Electrodes for Environmental Applications

This work is focused on the influence of pH and applied potential for the immobilisation of rabbit IgG on a carbon screen-printed electrode. The orientation of IgG molecule at the surface is fundamental for activity and reproducibility of the immunosensor. As the electrode potential is increased a particular order may be brought to the immobilised antibodies, i.e. the antibodies adapt a more favourable arrangement on the surface to facilitate better binding. The response increased when changing the pH from basic to acidic medium and the reverse trend was observed for the limit of detection (LOD). When a potential was applied to the electrode, the response generally decreased and the LOD increased in the order acidic > basic > neutral pH. The LODs obtained from antibodies immobilised at acidic pH and + 100 mV were better than the LODs obtained at other conditions.