Rapid method for the determination of 16 organochlorine pesticides in sesame seeds by microwave-assisted extraction and analysis of extracts by gas chromatography-mass spectrometry

A method for the multiresidue analysis of 16 organochlorine insecticides in sesame seeds has been developed. The method is based on the microwave-assisted extraction (MAE) of the sesame seeds by the use of a water-acetonitrile mixture followed by Florisil clean-up of the extracts and subsequent analysis by gas chromatography-mass spectrometry (GC/MS) in the selected ion monitoring (SIM) mode. MAE operational parameters (extraction solvent, temperature and time, extractant volume) were optimized with respect to extraction efficiency of the target compounds from sesame seeds with 46% oil content. Recoveries >80% with relative standard deviations (RSD) <12% were obtained for all compounds under the selected parameters. The Florisil clean-up step proved sufficient for the removal of co-extracted substances so that no adverse effect on the chromatographic system was observed. Limit of quantification (LOQ) values were in the range of 5-10 microg/kg. The proposed method was applied in the analysis of sesame seed samples imported to Greece.     

Phase separation in semidilute aqueous poly(N-isopropylacrylamide) solutions

The phase separation mechanism in semidilute aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions is investigated with small-angle neutron scattering (SANS). The nature of the phase transition is probed in static SANS measurements and with time-dependent SANS measurements after a temperature jump. The observed critical exponents of the phase transition describing the temperature dependence of the Ornstein-Zernike amplitude and correlation length are smaller than values from mean-field theory. Time-dependent SANS measurements show that the specific surface decreases with increasing time after a temperature jump above the phase transition. Thus, the formation of additional hydrogen bonds in the collapsed state is a kinetic effect: A certain fraction of water remains as bound water in the system. Moreover, H-D exchange reactions observed in PNIPAM have to be taken into account.     

Thermoresponsive hydrogels from symmetrical triblock copolymers poly(styrene-block-(methoxy diethylene glycol acrylate)-block-styrene)

A series of symmetrical, thermo-responsive triblock copolymers was prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization, and studied in aqueous solution with respect to their ability to form hydrogels. Triblock copolymers were composed of two identical, permanently hydrophobic outer blocks, made of low molar mass polystyrene, and of a hydrophilic inner block of variable length, consisting of poly(methoxy diethylene glycol acrylate) PMDEGA. The polymers exhibited a LCST-type phase transition in the range of 20-40 °C, which markedly depended on molar mass and concentration. Accordingly, the triblock copolymers behaved as amphiphiles at low temperatures, but became water-insoluble at high temperatures. The temperature dependent self-assembly of the amphiphilic block copolymers in aqueous solution was studied by turbidimetry and rheology at concentrations up to 30 wt %, to elucidate the impact of the inner thermoresponsive block on the gel properties. Additionally, small-angle X-ray scattering (SAXS) was performed to access the structural changes in the gel with temperature. For all polymers a gel phase was obtained at low temperatures, which underwent a gel-sol transition at intermediate temperatures, well below the cloud point where phase separation occurred. With increasing length of the PMDEGA inner block, the gel-sol transition shifts to markedly lower concentrations, as well as to higher transition temperatures. For the longest PMDEGA block studied (DP(n) about 450), gels had already formed at 3.5 wt % at low temperatures. The gel-sol transition of the hydrogels and the LCST-type phase transition of the hydrophilic inner block were found to be independent of each other.     

Metrological value of participating in interlaboratory comparisons

Quality of chemical measurement is a central issue nowadays with social, political and economic implications. This paper aims to describe how interlaboratory comparisons (ILCs) can contribute towards better quality of chemical measurements. The importance of ILCs as well as the different types and the requirements for proper organization of ILCs are explained. The international structure and organization of metrology is given, highlighting the activities related to chemical measurements. Particularly the use of ILCs in the service of metrology in chemistry is highlighted. A very important discussion concerning ILCs is how they can (or cannot) establish traceability. The view of the authors is that traceability cannot, as such, be established through ILCs. On the other hand, participation in ILCs can clearly support the claims for quality measurements, as ILCs are experimental and objective demonstrations of measurement capability.     

Complex Macrophase‐Separated Nanostructure Induced by Microphase Separation in Binary Blends of Lamellar Diblock Copolymer Thin Films

The nanostructures of thin films spin‐coated from binary blends of compositionally symmetric polystyrene‐b‐polybutadiene (PS‐b‐PB) diblock copolymer having different molar masses are investigated by means of atomic force microscopy (AFM) and grazing‐incidence small‐angle X‐ray scattering (GISAXS) after spin‐coating and after subsequent solvent vapor annealing (SVA). In thin films of the pure diblock copolymers having high or low molar mass, the lamellae are perpendicular or parallel to the substrate, respectively. The as‐prepared binary blend thin films feature mainly perpendicular lamellae in a one‐phase state, indicating that the higher molar mass diblock copolymer dominates the lamellar orientation. The lamellar thickness decreases linearly with increasing volume fraction of the low molar mass diblock copolymer. After SVA, well‐defined macrophase‐separated nanostructures appear, which feature parallel lamellae near the film surface and perpendicular ones in the bulk.

     

Narrow band quantitative and multivariate electroencephalogram analysis of peri-adolescent period

ABSTRACT: BACKGROUND: The peri-adolescent period is a crucial developmental moment of transition from childhood to emergent adulthood. The present report analyses the differences in Power Spectrum (PS) of the Electroencephalogram (EEG) between late childhood (24 children between 8 and 13 years old) and young adulthood (24 young adults between 18 and 23 years old). RESULTS: The narrow band analysis of the Electroencephalogram was computed in the frequency range of 0--20 Hz. The analysis of mean and variance suggested that six frequency ranges presented a different rate of maturation at these ages, namely: low delta, delta-theta, low alpha, high alpha, low beta and high beta. For most of these bands the maturation seems to occur later in anterior sites than posterior sites. Correlational analysis showed a lower pattern of correlation between different frequencies in children than in young adults, suggesting a certain asynchrony in the maturation of different rhythms. The topographical analysis revealed similar topographies of the different rhythms in children and young adults. Principal Component Analysis (PCA) demonstrated the same internal structure for the Electroencephalogram of both age groups. Principal Component Analysis allowed to separate four subcomponents in the alpha range. All these subcomponents peaked at a lower frequency in children than in young adults. CONCLUSIONS: The present approaches complement and solve some of the incertitudes when the classical brain broad rhythm analysis is applied. Children have a higher absolute power than young adults for frequency ranges between 0-20 Hz, the correlation of Power Spectrum (PS) with age and the variance age comparison showed that there are six ranges of frequencies that can distinguish the level of EEG maturation in children and adults. The establishment of maturational order of different frequencies and its possible maturational interdependence would require a complete series including all the different ages.     

Graphene-Oxide-Based Fluoro- and Chromo-Genic Materials and Their Applications

Composite materials and their applications constitute a hot field of research nowadays due to the fact that they comprise a combination of the unique properties of each component of which they consist. Very often, they exhibit better performance and properties compared to their combined building blocks. Graphene oxide (GO), as the most widely used derivative of graphene, has attracted widespread attention because of its excellent properties. Abundant oxygen-containing functional groups on GO can provide various reactive sites for chemical modification or functionalization of GO, which in turn can be used to develop novel GO-based composites. This review outlines the most recent advances in the field of novel dyes and pigments encompassing GO as a key ingredient or as an important cofactor. The interactions of graphene with other materials/compounds are highlighted. The special structure and unique properties of GO have a great effect on the performance of fabricated hybrid dyes and pigments by enhancing the color performance of dyes, the anticorrosion properties of pigments, the viscosity and rheology of inks, etc., which further expands the applications of dyes and pigments in dyeing, optical elements, solar-thermal energy storage, sensing, coatings, and microelectronics devices. Finally, challenges in the current development as well as the future prospects of GO-based dyes and pigments are also discussed. This review provides a reference for the further exploration of novel dyes and pigments.     

A comparative study of acquisition schemes for diffusion tensor imaging using MRI

This study has investigated the effects of the selection of the diffusion-weighted (DW) gradient directions on the precision of a diffusion tensor imaging (DTI) experiment. The theoretical analysis provided a quantitative framework in which the noise performance of DTI schemes could be assessed objectively and for the development of novel DTI schemes, which employ multiple DW gradient directions. This generic framework was first applied to the examination of two commonly used DTI schemes, which employed 6 DW gradient directions and hitherto were used indiscriminately under the sole condition of noncollinearity. It was then used to design and assess a novel 12-DW-gradient-direction DTI protocol, which employed the same total number of DW acquisitions as the two conventional schemes (12). This theoretical investigation was then corroborated using rigorous simulation and DTI experiments on both an isotropic phantom and a healthy human brain. Both the theoretical and the experimental analysis demonstrated that the two conventional schemes showed a significantly different noise performance and that use of the new multiple-DW-gradient-direction scheme clearly improved the precision of the DTI measurements.