Pickering emulsions stabilized by nanoparticle surfactants

Amphiphilic gold nanoparticles are demonstrated to effectively stabilize emulsions of hexadecane in water. Nanoparticle surfactants are synthesized using a simple and scalable one-pot method that involves the sequential functionalization of particle surfaces with thiol-terminated polyethylene glycol (PEG) chains and short alkane-thiol molecules. The resulting nanoparticles are shown to be highly effective emulsifying agents due to their strong adsorption at oil-water and air-water interfaces. The original nonfunctionalized gold nanoparticles are unable to effectively stabilize oil-water emulsions due to their small size and low adsorption energy. Small-angle X-ray scattering and electron microscopy are used to demonstrate the formation of nanoparticle-stabilized colloidosomes that are stable against coalescence and show significant shifts in plasmon resonance enhancing the near-infrared optical absorption.     

Is Quantum Tunneling Relevant in Free‐Radical Polymerization?

Quantum tunneling in hydrogen transfer reactions active in FRP is investigated theoretically. Three systems are examined: polyethylene, polystyrene, and poly(vinyl chloride). Kinetic parameters of backbiting reactions are evaluated adopting quantum chemistry. Tunneling corrections are estimated adopting the one‐dimensional Eckart model, which provides a reasonable accuracy along with a limited computational effort. The relevance of quantum tunneling in the investigated systems is highlighted, with focus on the temperature dependence of the tunneling correction in the typical polymerization conditions of the investigated monomers. Obtained results clearly show that tunneling plays an important role in the kinetics estimation of hydrogen abstractions in FRP.

     

Structure and dynamics of dodecaborate clusters in water

We have studied using molecular dynamics simulations the interaction of the dodecaborate anion, B(12)H(12)(2-), and its amino, trimethyl, and triethyl derivatives with water molecules. We found peculiar organization of the water molecules in the first solvation shell with the formation of a dihydrogen bond between the hydrogen atoms of the anions and the hydrogen atoms of the water molecules. The simulations also show that the organization of the hydration shell is strongly influenced by the substituents in the anions. These differences are likely to play an important role in understanding the interaction of the anions with biological systems like membranes and proteins in aqueous environments.     

Thermal,Mechanical and Morphological Properties of Composites Developed from Glycerol and Dicarboxylic Acids Reinforced with Piassava Fiber

Summary: Vegetable fibers are being widely used as reinforcement in polymer composites. These composites can be applied in several fields, such as automotive, packaging and even construction. The polymer matrix used was synthesized from glycerol with phthalic and terephthalic acids in order to open future perspectives in the use of glycerin generated from the production of purified biodiesel. Composites with 2, 5, 10 wt% untreated and treated piassava fiber were obtained. Thermal, morphological and mechanical properties were evaluated. The tensile stress-strain curve of the polyester synthesized and composites was typical of a ductile material. SEM of the surface of fracture showed that the adhesion between fiber and matrix was enhanced after chemical treatment. However, the fiber content was more efficient than the superficial treatment when incorporated into the matrix. Therefore, the material under study is promising for the industrial marketplace, due to its good compatibility with natural fibers.     

Determination of inorganic anions, carboxylic acids and amino acids in plant matrices by capillary zone electrophoresis

Summary Physiological investigations of solute transport in plants affords knowledge of solute distribution between different tissues. Capillary electrophoresis using indirect UV and laser induced fluorescence (LIF) detection is demonstrated as a useful technique for the simultaneous determination of inorganic anions, amino acids and carboxylic acids in plant samples. Cell sap obtained from plant tissues as well as simple ethanolic or aqueous plant extracts can be analysed directly without any pretreatment. This matrix stability and the very small volumes required allow fast determinations of various compounds in small plant tissue sections. In the case of carboxylic acids, resolution can be optimized using calcium for selective complexation of some of the compounds. Selective and sensitive determination of amino acids is possible using precolumn derivatisation with orthophthaldialdehyde (OPA) and laser induced fluorescence detection. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996     

Conformational and electronic properties of a microperoxidase in aqueous solution: a computational study.

A theoretical study of the conformational properties of a small heme peptide in aqueous solution is carried out by classical, long-timescale molecular dynamics simulations. The electronic properties of this species, that is, the relative energies of its excited electronic states and the redox potential, are reproduced and related to the conformational behavior using the perturbed matrix method and basic statistical mechanics. Our results show an interesting coupling between the conformational transitions and the electronic properties. These investigations, beyond the biophysically relevant results addressing the long-standing question of the actual role of the enzyme structure on the enzyme activity, are also of some methodological interest since they offer a further computational perspective for including the electronic degrees of freedom into the modeling of rather complex molecular systems.     

Molecular dynamics simulation of water near nanostructured hydrophobic surfaces: interfacial energies.

We present results from molecular dynamics simulations of water near structured hydrophobic surfaces. The surface structures reported herein are a planar alkane crystal as a reference and crystals with a hole and a protrusion of approximately 2.5 nm diameter and 0.5 nm depth or height. All indicators show that surface structuring increases the hydrophobicity: The water density is reduced near the structure elements, and the number of residual contacts between water and the surface decreases by about 40 % with respect to the planar surface. Thermodynamic integration shows that the interfacial energy of the structured surfaces is about 7 mJ m(-2) higher for structured surfaces than for the planar surface. The hydrophobicity increases by a similar amount for the hole and the protrusion geometries compared to the planar surface.     

Pilot study of capillary electrophoresis coupled to mass spectrometry as a tool to define potential prostate cancer biomarkers in urine

We describe the use of capillary electrophoresis (CE) coupled with mass spectrometry (MS) to identify single polypeptides and patterns of polypeptides specific for prostate cancer (CaP) in human urine. Using improved sample preparation methods that enable enhanced comparability between different samples, we examined samples from 47 patients who underwent prostate biopsy. Of this group, 21 patients had benign pathology and 26 with CaP, and these were used to define potential biomarkers, which allow discrimination between these two states. In addition, CE-MS data from these 47 urine samples were compared to that of 41 young men (control) without known or suspected clinical CaP to further confirm the polypeptides indicative for CaP. Upon crossvalidation of the same samples, several polypeptides were selected that enabled correct classification of the CaP patients with 92% sensitivity and 96% specificity. We then examined an additional 474 samples from patients with renal disease enrolled in other studies and found that 14 (3%) had polypeptides suggestive of CaP possibly indicating that they harbor clinical CaP. In conclusion, this early pilot study suggests that CE-MS of urine warrants further investigation as a tool that can identify putative biomarkers for CaP.     

Raman microspectrometric investigation of wall paintings in S. Giovanni Evangelista Abbey in Parma: a comparison between two artists of the 16th century

Micro-Raman spectroscopy, combined with gas chromatography and ultra-violet fluorescence photography, was used to study some wall paintings in the S. Giovanni Evangelista Abbey in Parma, Italy. The restoration of some painted chapels enabled a comparison between two painters of the 16th century: Parmigianino (Girolamo Francesco Maria Mazzola, 1503-1540) and Michelangelo Anselmi (1492?-1556?). Micro-Raman spectroscopy determined the palette used by the artists, leading to the identification of different white, yellow, red, brown, green, blue and black pigments. Some pigments are evidence of later restorations. Gas chromatography combined with mass spectroscopy revealed the presence of organic binding media and enabled to distinguish between fresco and secco paintings.     

Sulla determinazione polarografica delle impurezze metalliche nello zinco iperpuro

Résumé (W) On précise les conditions expérimentales les plus favorables pour l'exécution d'analyses polarographiques de zine extrêmement pur, en vue d'endéceler les impuretés, soit les éléments Cu, Bi, Pb, Cd, Tl et Fe. La méthode, très sensible, permet le dosage de ces divers métaux quand la concentration, dans le zinc, est de 0,0001% pour Pb, Bi et Tl, et de 0,00005% pour Cd, Cu et Fe.

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Zusammenfassung Es wurden die günstigsten experimentellen Bedingungen für die polarographische Bestimmung der in äußerst reinem Zink als Verunreinigungen vorkommenden Elemente Cu, Bi, Pb, Cd, Tl und Fe ermittelt.Das sehr empfindliche Verfahren gestattet die Bestimmung dieser Metalle, selbst wenn die betreffenden Konzentrationen im Zink bloß 0,0001% Pb, Bi oder Tl und 0,00005% Cd, Cu oder Fe betragen.

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Riassuno Vengono precisate le condizioni sperimentali più favorevoli per l'esecuzione dell'analisi polarografica dello zinco iperpuro per la determinazione delle impurezze di Cu, Bi, Pb, Cd, Tl, Fe.Il metodo, molto sensibile, permette il dosaggio dei varii metalli anche quando la concentrazione nello zinco è di 0,0001% per Pb, Bi, Tl e di 0,00005% per Cd, Cu, Fe.

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A 3 figure