Design of a compressed air modulator to be used in comprehensive multidimensional gas chromatography and its application in the determination of pesticide residues in grapes

In this study, a new modulator that is simple, robust and presents low operation costs, was developed. This modulator uses compressed air to cool two small portions in the first centimeters of the second chromatographic column of a comprehensive multidimensional gas chromatography (GC × GC) system. The results show a variation in the peak area less than 3 and 5% to alkanes and pesticides, respectively. The standard deviations for the retention times in the first and second dimension are around 0.05 min and 0.05 s for all the compounds. The system was optimized with n-alkanes. The GC × GC system proposed was applied in the determination of pyrethroid pesticides (bifenthrin, cypermethrin, deltamethrin, fenvalerate, esfenvalerate, cis- and trans-permethrin) in grape samples. Samples were extracted by the mini-Luke modified method and pesticides were quantified by comprehensive multidimensional gas chromatography with micro electron-capture detection (μECD). The values of method limit of quantification (LOQ) were 0.01–0.02 mg kg⁻¹ for all studied pyrethroid and the values of recovery were between 94.3 and 115.2%, with good precision (RSD < 18.4%), demonstrating that the performance of the total method consisting of a modified Luke extraction method and determination by GC × GC-μECD are satisfactory. This study also showed that the system using a modulator with a double jet of compressed air has the potential for application in the analysis of a wider range of pesticide residues in other commodities since it provides low values of LOQ with acceptable accuracy and precision.     

In vitro photodynamic activity of chloro(5,10,15,20-tetraphenylporphyrinato)indium(III) loaded-poly(lactide-co-glycolide) nanoparticles in LNCaP prostate tumour cells

In(III)-meso-tetraphenylporphyrin (InTPP) was encapsulated into nanoparticles (smaller than 200 nm) of poly(d,l-lactide-co-glycolide) (PLGA) using the emulsification–evaporation technique. The photodynamic efficacy of InTPP-loaded nanoparticles and its cellular uptake was investigated with LNCaP prostate tumour cells, in comparison with the free InTPP. The effects of incubation time (1–3 h), drug concentration (1.8–7.7 μmol/L) and incident light dose (15–45 J/cm²) with both encapsulated and free InTPP were studied. The type of cell death induced by the photochemical process using both encapsulated and free InTPP was also investigated. Cell viability was reduced more significantly with increasing values of these effects for InTPP-loaded nanoparticles than with the free drug. The cellular death induced by both encapsulated and free InTPP was preponderantly apoptotic. Confocal laser scanning microscopy data showed that the InTPP-loaded nanoparticles, as well free InTPP, were localized in the cells, and always in the perinuclear region. Encapsulated InTPP was measured by the intensity of fluorescence intensity of cell extracts and was three times more internalized into the cells than was the free InTPP. Electron paramagnetic resonance experiments corroborated the participation of singlet oxygen in the photocytotoxic effect of nanoparticles loaded with InTPP.     

A variational density matrix approach with nonlocal effective potential

We show that using the Colle–Salvetti correlation-energy functional (Colle and Salvetti in Theoret Chim Acta 37:329, 1975) in the Hartree–Fock-type procedure suggested by Kohn and Sham (Phys Rev 140:A1133PR, 1965), one can calculate quite accurately electronic properties of systems in which the “dynamical” correlation energy is dominant. We compare our results with those obtained by Grabo and Gross (Chem Phys Lett 240:141, 1995) using the optimized effective potential method, and we discuss characteristics and advantages of our procedure.     

A filter-and-fan approach to the job shop scheduling problem

The job shop scheduling problem (JSSP) is a notoriously difficult problem in combinatorial optimization. Extensive investigation has been devoted to developing efficient algorithms to find optimal or near-optimal solutions. This paper proposes a new heuristic algorithm for the JSSP that effectively combines the classical shifting bottleneck procedure (SBP) with a dynamic and adaptive neighborhood search procedure. Our new search method, based on a filter-and-fan (F&F) procedure, uses the SBP as a subroutine to generate a starting solution and to enhance the best schedules produced. The F&F approach is a local search procedure that generates compound moves by a strategically abbreviated form of tree search. Computational results carried out on a standard set of 43 benchmark problems show that our F&F algorithm performs more robustly and effectively than a number of leading metaheuristic algorithms and rivals the best of these algorithms.     

A mass-matrix formulation of unsteady fluctuation splitting schemes consistent with Roe’s parameter vector

A mass-matrix formulation of the fluctuation splitting schemes for solving compressible, unsteady flows is proposed. This formulation is consistent with the conservative linearisation based on parameter vector and allows to extend to unsteady flows the ‘invariance under similarity transformations’ property that had been shown to hold for the steady version of the schemes. Second-order time accuracy is achieved using a Petrov–Galerkin finite element interpretation of the fluctuation splitting schemes. The approach may however be readily applicable to all other time-accurate fluctuation splitting formulations that have been so far proposed in the literature. Applications of the proposed methodology to two- and three-dimensional, inviscid and viscous compressible flows are reported and discussed in the paper.     

Carbon nanotube/dendrimer hybrids as electrodes for supercapacitors

Journal of Solid State Electrochemistry - Carbon nanotubes (CNTs) were surface-modified by a glycodendrimer with four glucose units (4-Gl). Electrodes for supercapacitors based on CNT/4-Gl hybrids...     

Glass/PDMS hybrid microfluidic device integrating vertically aligned SWCNTs to ultrasensitive electrochemical determinations

This communication reports a promising platform for rapid, simple, direct, and ultrasensitive determination of serotonin. The method is related to integration of vertically aligned single-walled carbon nanotubes (SWCNTs) in electrochemical microfluidic devices. The required microfabrication protocol is simple and fast. In addition, the nanomaterial influenced remarkably the obtained limit-of-detection (LOD) values. Our system achieved a LOD of 0.2 nmol L(-1) for serotonin, to the best of our knowledge one of the lowest values reported in the literature.     

Kinetics and thermodynamics of chlorpromazine interaction with lipid bilayers: effect of charge and cholesterol

Passive transport across cell membranes is the major route for the permeation of xenobiotics through tight endothelia such as the blood–brain barrier. The rate of passive permeation through lipid bilayers for a given drug is therefore a critical step in the prediction of its pharmacodynamics. We describe a detailed study on the kinetics and thermodynamics for the interaction of chlorpromazine (CPZ), an antipsychotic drug used in the treatment of schizophrenia, with neutral and negatively charged lipid bilayers. Isothermal titration calorimetry was used to study the partition and translocation of CPZ in lipid membranes composed of pure POPC, POPC:POPS (9:1), and POPC:Chol:POPS (6:3:1). The membrane charge due to the presence of POPS as well as the additional charge resulting from the introduction of CPZ in the membrane were taken into account, allowing the calculation of the intrinsic partition coefficients (K(P)) and the enthalpy change (ΔH) associated with the process. The enthalpy change upon partition to all lipid bilayers studied is negative, but a significant entropy contribution was also observed for partition to the neutral membrane. Because of the positive charge of CPZ, the presence of negatively charged lipids in the bilayer increases both the observed amount of CPZ that partitions to the membrane (KP(obs)) and the magnitude of ΔH. However, when the electrostatic effects are discounted, the intrinsic partition coefficient was smaller, indicating that the hydrophobic contribution was less significant for the negatively charged membrane. The presence of cholesterol strongly decreases the affinity of CPZ for the bilayer in terms of both the amount of CPZ that associates with the membrane and the interaction enthalpy. A quantitative characterization of the rate of CPZ translocation through membranes composed of pure POPC and POPC:POPS (9:1) was also performed using an innovative methodology developed in this work based on the kinetics of the heat evolved due to the interaction of CPZ with the membranes.