Phosphatidylcholine‐Coated Iron Oxide Nanomicelles for In Vivo Prolonged Circulation Time with an Antibiofouling Protein Corona

We report the synthesis of micellar phosphatidylcholine‐coated superparamagnetic iron oxide nanoparticles as a new long circulation contrast agents for magnetic resonance imaging. Oleic acid‐coated Fe₃O₄ nanoparticles were first prepared through thermal degradation and then encapsulated into small clusters with a phosphatidylcholine coating to obtain hydrophilic nanomicelles. A thorough characterization confirmed the chemical nature of the coating and the excellent colloidal stability of these nanomicelles in aqueous media. Magnetization and relaxivity properties proved their suitability as magnetic resonance imaging (MRI) contrast agent and in vitro cell viability data showed low toxicity. Vascular lifetime and elimination kinetics in the liver were assessed by blood relaxometry and by in vivo MRI in rats and compared with “control” particles prepared with a polyethylene glycol derivative. These micellar particles had a lifetime in blood of more than 10 h, much longer than the control nanoparticles (≈2 h), which is remarkable considering that the coating molecule is a small biocompatible zwitterionic phospholipid. The protein corona was characterized after incubation with rat serum at different times by high‐throughput proteomics, showing a higher proportion of bound apolipoproteins and other dysopsonins for the phosphatidylcholine particles. The antibiofouling properties of this corona and its resistance to the adsorption of proteins corroborate the observed enhanced stability and prolonged systemic circulation.     

Electronic and Structural Properties of Highly Aluminum Ion Doped TiO2 Nanoparticles: A Combined Experimental and Theoretical Study

This study presents the experimental and theoretical study of highly internally Al‐doped TiO₂ nanoparticles. Two synthesis methods were used and detailed characterization was performed. There were differences in the doping and the crystallinity, but the nanoparticles synthesized with the different methods share common features. Anatase to rutile transformation occurred at higher temperatures with Al doping. X‐ray photoelectron spectroscopy showed the generation of oxygen vacancies, which is an interesting feature in photocatalysis. In turn, the band‐gap energy and the valence band did not change appreciably. Periodic density functional calculations were performed to model the experimentally doped structures, the formation of the oxygen vacancies, and the band gap. Calculation of the density of states confirmed the experimental band‐gap energies. The theoretical results confirmed the presence of Ti⁴⁺ and Al³⁺. The charge density study and electron localization function analysis indicated that the inclusion of Al in the anatase structure resulted in a strengthening of the Ti?O bonds around the vacancy.     

Production of a Bioemulsifier with Potential Application in the Food Industry

Biosurfactants are of considerable interest due to their biodegradability, low degree of toxicity, and diverse applications. However, the high production costs involved in the acquisition of biosurfactants underscore the need for optimization of the production process to enable viable application on an industrial scale. The aims of the present study were to select a species of Candida that produces a biosurfactant with the greatest emulsifying potential and to investigate the influence of components of the production medium and cultivation conditions. Candida utilis achieved the lowest surface tension (35.53 mN/m), best emulsification index (73 %), and highest yield (12.52 g/l) in a medium containing waste canola frying oil as the carbon source and ammonium nitrate as the nitrogen source. The best combination of medium components and cultivation conditions was 6 % (w/v) glucose, 6 % (w/v) waste canola frying oil, 0.2 % (w/v) ammonium nitrate, 0.3 % (w/v) yeast extract, 150 rpm, 1 % inoculum (w/v), and 88 h of fermentation. The greatest biosurfactant production and the lowest surface tension were achieved in the first 24 h of production, and the maximum biomass production was recorded at 72 h. The biosurfactant produced from C. utilis under the conditions investigated in the present study has a potential to be a bioemulsifier for application in the food industry.     

Study of the inhibiting effect of a quaternary ammonium surfactants mixture synthesized from petroleum fraction (reformate) against the carbon steel corrosion in HCl 1 M

Quaternary ammonium cationic surfactants were synthesized from reformate, a liquid mixture of hydrocarbons (aromatics, naphthenes and paraffins), via chloromethylation/quaternization sequences. The petroleum surfactants thus obtained were evaluated as corrosion inhibitors for carbon steel in 1 M HCl, by gravimetry, potentiodynamic polarization and electrochemical impedance spectroscopy. The corrosion inhibiting efficiency was assessed as functions of surfactant concentration. The results showed that the inhibiting efficiency increased with surfactant concentration; its optimal value of 70 % was for a surfactant concentration of 320 mg/L at 25 °C. Potentiodynamic polarization measurements showed that the mixture acts as a mixed type inhibitor. The corrosion inhibiting mechanism is thought to proceed via an adsorption of the surfactant molecules on the steel surface, generating a film and hindering the active sites. Our experimental adsorption data were found to obey the Langmuir adsorption isotherm. SEM images of the treated specimens, revealing the likely formation of a protective film, demonstrated the inhibiting capacity of the petroleum quaternary ammonium surfactants against the carbon steel corrosion.     

Enantioselective reduction and deracemisation using the non-conventional yeast Pichia glucozyma in water/organic solvent biphasic systems: preparation of (S)-1,2-diaryl-2-hydroxyethanones (benzoins)

Water/organic solvent two-liquid-phase systems have been successfully applied in the synthesis of enantiomerically pure (S)-benzoin through two different methodologies catalysed by whole cells from the non-conventional yeast Pichia glucozyma: the stereoselective monoreduction of benzil and the deracemisation of benzoin. The presence of the organic solvent influences the redox systems implied in the reactions, avoiding the formation of the corresponding diols, increasing the enantioselectivity and allowing the easy isolation of the products in high yields and excellent enantiomeric excesses. The use of both strategies has been extended to the preparation of different chiral benzoin derivatives.     

From superhydrophobic‐ to superhydrophilic‐patterned poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) architectures as a novel platform for biotechnological applications

The manufacture of three‐dimensional patterned electroactive poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) microstructures with tailored architecture, morphology, and wettability is presented. The patterned microstructures are fabricated using a simple, effective, low cost, and reproducible technique based on microfluidic technology. These novel structures can represent innovative platforms for advanced strategies in a wide range of biotechnological applications, including tissue engineering, drug delivery, microfluidic, and sensors and actuators devices. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1802–1810     

Potentiality of reflectometry for the study of the adsorption on dielectric and metal substrates: application to the adsorption of polyvinylimidazole on silica and gold

Optical fixed-angle reflectometry was examined as a technique to study the adsorption of organics (polymers, surfactants) on metallic substrates. Calculations were made to evaluate the sensitivity of the method with regard to the refractive index and the thickness of the metal and the incidence angle. Theoretical results show that Ti, Cr, V, Zr, and gold have an appropriate sensitivity for detecting the adsorption accurately. Parallel experiments using gold and silica substrates and polyvinylimidazole (PVI) as an organic material were carried out. Adsorption measurements as a function of polymer concentration, pH, and ionic strength were in accordance with expected trends.     

Robust fuzzy principal component analysis (FPCA). A comparative study concerning interaction of carbon-hydrogen bonds with molybdenum-oxo bonds

Principal component analysis (PCA) is a favorite tool in chemometrics for data compression and information extraction. PCA finds linear combinations of the original measurement variables that describe the significant variations in the data. However, it is well-known that PCA, as with any other multivariate statistical method, is sensitive to outliers, missing data, and poor linear correlation between variables due to poorly distributed variables. As a result data transformations have a large impact upon PCA. In this regard one of the most powerful approaches to improve PCA appears to be the fuzzification of the matrix data, thus diminishing the influence of outliers. In this paper we discuss a robust fuzzy PCA algorithm (FPCA). The new algorithm is illustrated on a data set concerning interaction of carbon-hydrogen bonds with transition metal-oxo bonds in molybdenum complexes. Considering, for example, a two component model, FPCA accounts for 97.20% of the total variance and PCA accounts only for 69.75%.     

A site-specific low-enrichment (15)N,(13)C isotope-labeling approach to unambiguous NMR spectral assignments in nucleic acids

We demonstrate that base and sugar protons within a DNA oligomer can be assigned unambiguously following site-specific 15N,13C isotope incorporation at levels as low as 1% enrichment. This simple and cost-effective methodology is demonstrated on the d(GGGTTCAGG) DNA sequence, which forms a dimeric G-quadruplex containing G.G.G.G tetrads sandwiched between G.(C-A) triads.     

Orbital picture of ionization and its breakdown in nanoarrays of quantum dots

We present exact numerical results indicating that ionization could be a useful tool to study electron correlations in artificial molecules and nanoarrays of metallic quantum dots. For nanorings consisting of Ag quantum dots of the type already fabricated, we demonstrate that the molecular orbital picture breaks down even for lowest energy ionization processes, in contrast to ordinary molecules. Our ionization results yield a transition point between localization and delocalization regimes in good agreement with various experimental data.