Oil-in-water emulsions stabilized by highly charged polyelectrolyte-grafted silica nanoparticles

Fully sulfonated poly(styrenesulfonate) brushes were grown from the surface of colloidal silica particles and used to prepare stable trichloroethylene-in-water and heptane-in-water Pickering emulsions. These particles were highly charged and colloidally stable in water but could not be dispersed in trichloroethylene or heptane. Both two-phase (emulsion plus neat water) and three-phase (emulsion separating neat oil and water phases) systems were observed, with water-continuous emulsion phases in all cases. Emulsion phases containing as much as 83% (v/v) oil were stable for over six months. Poly(styrenesulfonate)-grafted particles were very efficient emulsifiers; stable emulsion phases were prepared when using as little as 0.04 wt% particles. The emulsifying effectiveness of the poly(styrenesulfonate)-grafted silica particles can be attributed to the hydrophobicity of the vinylic polymer backbone that makes this highly charged polyelectrolyte unusually surface active at the oil/water interface.     

Capillary zone electrophoresis of alpha-helical diastereomeric peptide pairs with anionic ion-pairing reagents

The present study uses an unique capillary electrophoresis (CE) approach, that we have termed ion-interaction capillary zone electrophoresis (II-CZE), for the separation of diastereomeric peptide pairs where a single site in the centre of the non-polar face of an 18-residue amphipathic alpha-helical peptide is substituted by the 19 L- or D-amino acids. Through the addition of perfluorinated acids at very high concentrations (up to 400 mM), such concentration levels not having been used previously in chromatography or CE, to the background electrolyte (pH 2.0), we have been able to achieve baseline resolution of all 19 diastereomeric peptide pairs with an uncoated capillary. Since each diastereomeric peptide pair has the same sequence, identical mass-to-charge ratio and identical intrinsic hydrophobicity, such a separation by CZE has previously been considered theoretically impossible. Excellent resolution was achieved due to maximum advantage being taken of even subtle disruption of peptide structure/conformation (due to the presence of D-amino acids) of the non-polar face of the amphipathic alpha-helix and its interaction with the hydrophobic anionic ion-pairing reagents. In addition, due to the excellent resolution of diastereomeric peptide pairs by this novel CZE approach, we have also been able to separate a mixture of these closely-related alpha-helical peptides.     

Capillary electrophoresis of cationic random coil peptide standards: effect of anionic ion-pairing reagents and comparison with reversed-phase chromatography

The present study compares a charge/hydrophobicity capillary electrophoresis (CE) approach to reversed-phase high-performance liquid chromatography (RP-HPLC) for the separation of three series of four synthetic, random coil peptide standards. Each series has peptides of the same positive charge (+1, +2 and +3 series) and length but differing in hydrophobicity. Complete resolution of the 12 peptides was achieved via a novel CE approach: a capillary zone electrophoresis (CZE) mode effected a separation of identically charged peptides; within each charged group of peptides, the addition of perfluorinated acid anionic ion-pairing reagents allowed resolution of the peptides through a mechanism based on peptide hydrophobicity which we have termed ioninteraction (II)-CZE. The peak capacity and peptide resolution of this CE approach was superior to that of RP-HPLC and stresses an important role for CE for peptide/proteomic applications.     

金纳米粒子在TiO2气凝胶基质上的行为: 光催化活性评价和结构研究

TiO2 -Au aerogels containing different amounts of gold nanoparticles of different sizes (5 and 16 nm) were successfully synthesized using a sol-gel procedure, and were tested for salicylic acid photodegradation under UV irradiation. The structure and morphology of the obtained materials were investigated using X-ray diffraction, transmission electron microscopy, and N2 adsorption-desorption measurements. UV-Vis spectroscopy was used to study the optical properties. The effects of the gold nanoparticles on the TiO2 crystallization process were twofold, as follows: (i) the number of crystallized zones was strongly related to the concentration of the gold nanoparticles, and (ii) the smaller gold particles increased the time taken for the crystallization of the samples. It was found that the noble metal-doped samples exhibited higher degradation rates compared with bare titania. It was found that the most active photocatalyst in each studied system was the sample with the highest concentration of gold nanoparticles. Additionally, the highest degradation rate value was obtained with the smallest Au nanoparticles (46.4 10-3 μmol/(L·s).     

Involvement of cyan and ester groups in surface interactions of aerosil–cyanophenyl alkyl benzoate systems with high silica density: Infrared investigations

Composites prepared from aerosil A380 and liquid crystals (LCs) of 4-n-alkyl-4′-cyanophenyl benzoate type, with four to six carbon atoms in the alkyl chain were investigated by infrared spectroscopy. Their high silica content (of 2–7 g aerosil/1 g of LC) was given by thermogravimetric investigations and allows the observation of a rather thin LC layer on the silica particles. Several surface species onto the external surface of the grains were demonstrated. Arguments are given that monomer and dimer species are present in the bulk cyanophenyl benzoate materials while bulk-like species along with hydrogen-bonded ones coexist in the so-called surface layer of the composites. The main interaction of LC molecules with the aerosil surface is by hydrogen bonding taking place with the involvement of the cyan group. There is a contribution of ester carbonyl group to these surface interactions but this cannot be well quantified.     

On the dynamics of interaction between a moving mass and an infinite one-dimensional elastic structure at the stability limit

The paper herein deals with the study of the dynamic behaviour generated by the instability of the vibration of a loaded mass, uniformly moving along an Euler-Bernoulli beam on a viscoelastic foundation, induced by the anomalous Doppler waves excited in the beam. This issue is relevant for the case of modern trains travelling along a track with soft soil when the trains speed exceeds the phase velocity of the waves induced in the track. The model corresponds to a railway vehicle reduced to a loaded wheel running along a (half) track. The beam takes account of the bending stiffness of the rail and the mass of the track, including the mass of the rail, semi-sleepers and half of the ballast layer, where the viscoelastic foundation represents the subgrade. The model includes the wheel/rail Hertzian contact and it allows the simulation of the possibility of contact loss. The nonlinear equations of motion are integrated using a numerical approach based on the Green’s function method. When the vibration becomes unstable, the system evolution is a limit cycle characterised by a succession of shocks, due to the action of two opposite factors: the anomalous Doppler waves that pump energy at the interface between the moving mass and the beam, thus forcing the mass to take off, and the static load that push the mass downwards. The frequency of the shocks increases at higher velocity and the magnitude of the impact force decreases; the most dangerous velocity is the critical one, which represents the stability limit of the linear approximation of the motion equations. The transient behaviour that precedes the limit cycle appearance is being analysed. The Hertzian contact influences the time history of the limit cycle and the magnitude of the impact force and, therefore, it is essential to be included in the model. To the authors’ knowledge, this problem has never been dealt with.     

Antioxidant activity of rosemary extracts in solution and embedded in polymeric systems

The rosemary extract was encapsulated in polyethylene or in covalently-based network gels. The covalent gels were obtained by the reaction of isocyanate end-capped polyethylene glycol (PEG) with β-cyclodextrin or glycerol. The 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay was used to evaluate the antioxidant activity (AA) of rosemary extract entrapped in polymeric structures and in ethanol or water solutions. The AA of the rosemary extract was determined using a DPPH radical for samples prepared in ethanol, and a water-soluble derivative, the sulphonated DPPH radical (DPPH-SO₃Na), for the rosemary extract in water. Formulation of the rosemary extract in polymeric gels ensures a rapid release which determines the AA values similar to those in solution.     

Chemiluminescence kinetic analysis on the oxidative degradation of poly(lactic acid)

The oxidation of polymers is characterized by the generation of free radicals, and the kinetic parameters depicting the progress of oxidation are specific for each material structure and formulation. The durability of materials depends intrinsically on the molecular structure, and degradation mechanism influences the long-term stability of products. The intimate transformations of macromolecules can be reliably characterized by chemiluminescence (CL), which depicts the evolution of oxidation state by the reaction of free radicals with molecular oxygen. The isothermal and nonisothermal CL spectra are complementary proofs for the interpretation of oxidation behavior involving hydroperoxide as the initiators of oxidation. The degradation of PLA takes place by decomposition and fragmentation to lactide. The values of five kinetic parameters (initial CL intensity, CL intensity at the first peak, temperature corresponding to the first peak, oxidation induction time and oxidation rate) obtained for oxidative degradation of PLA lead to the activation energies ranged between 49 and 99 kJ mol^?1. The evolution of thermal degradation for poly(lactic acid) is an excellent example for the explanation of the decay fate of radical intermediates.     

Novel Supramolecular Hydrogels as Artificial Vitreous Substitutes

The possibility of employing self-healing gels as potential artificial vitreous substitutes is being explored. Advancement of traditional synthetic hydrogels as vitreous substitutes is hindered by their fragmentation upon injection into the vitreous cavity leading ultimately to inflammation. Preliminary work involved developing first generation self-healing gels, using amphiphilic tri-block copolymers of poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) (PPG-PEG-PPG) as the building block. Eight linear self-healing gels are synthesized by tethering an ureidopyrimidinone system to synthetically modified PPG-PEG-PPG via the formation of a bis-urea as a linker. The reversible nature of the hydrogen bonds permits alteration of their physical properties by changing the environment, yet retaining desirable characteristics. Despite low solubility in water, these polymers demonstrated associating behaviour under the investigated conditions, which is encouraging. Future generations of self-healing gels should involve the selection of a more hydrophilic core and/or star-like polymers to facilitate gel formation and strengthen the network.