The synthesis of carbon nanoparticles obtained by direct laser ablation [UV pulsed laser irradiation (248 nm, KrF)] of carbon targets immersed in water is described. Laser ablation features were optimized to produce carbon nanoparticles with dimensions up to about 100 nm. After functionalization with NH 2-polyethylene-glycol (PEG 200) and N-acetyl-l-cysteine (NAC) the carbon nanoparticles become fluorescent with excitation and emission wavelengths at 340 and 450 nm, respectively. The fluorescence decay time was complex and a three-component decay time model originated a good fit (= 1.09) with the following lifetimes: 1 = 0.35 ns; 2 = 1.8 ns; and 3 = 4.39 ns. The fluorescence of the carbon dots is sensitive to pH with an apparent pK a = 4.2. The carbon dots were characterized by 1 H NMR and HSQC and the results show an interaction between PEG 200 and the carbon surface as well as a dependence of the chemical shift with the reaction time. The fluorescence intensity of the nanoparticles is quenched by the presence of Hg(II) and Cu(II) ions with a Stern-Volmer constant (pH = 6.8) of 1.3 × 10 5 and 5.6 × 10 4 M −1 , respectively. As such the synthesis and application of a novel biocompatible nanosensor for measuring Hg(II) is presented.
Wine authenticity methods are in increasing demand mainly in Denomination of Origin designations. The DNA-based methodologies are a reliable means of tracking food/wine varietal composition. The main aim of this work was the study of High Resolution Melting (HRM) application as a screening method for must and wine authenticity. Three sample types (leaf, must and wine) were used to validate the three developed HRM assays (Vv1-705bp; Vv2-375bp; and Vv3-119bp). The Vv1 HRM assay was only successful when applied to leaf and must samples. The Vv2 HRM assay successfully amplified all sample types, allowing genotype discrimination based on melting temperature values. The smallest amplicon, Vv3, produced a coincident melting curve shape in all sample types (leaf and wine) with corresponding genotypes. This study presents sensitive, rapid and efficient HRM assays applied for the first time to wine samples suitable for wine authenticity purposes.
Using a one-step thermal reduction and non-covalent chemical functionalization process, PEGylated reduced nanographene oxide (rGOn-PEG) was produced from nanographene oxide (GOn) and characterized in terms of particle size, dispersion stability, chemistry, and photothermal properties, in view of its use for photothermal therapy (PTT) of non-melanoma skin cancer. GOn infrared spectrum presented more intense bands assigned to oxygen containing functional groups than observed for rGOn-PEG. GOn C/O ratio decreased more than 50% comparing with rGOn-PEG and nitrogen was present in the latter (N at % = 20.6) due to introduction of PEG-NH2. Thermogravimetric analysis allowed estimating the amount of PEG in rGOn-PEG to be of about 56.1%. Simultaneous reduction and PEGylation increased the lateral dimensions from 287 ± 139 nm to 521 ± 397 nm, as observed by transmission electron microscopy and dynamic light scattering. rGOn-PEG exhibited ≈13-fold higher absorbance in the near-infrared radiation (NIR) region, as compared to unmodified GOn. Low power (150 mW cm−2) NIR irradiation using LEDs resulted in rGOn-PEG heating up to 47 °C, which is within the mild PTT temperature range. PEGylation strongly enhanced the dispersibility of rGOn in physiological media (phosphate buffered saline, fetal bovine serum, and cell culture medium) and also improved the biocompatibility of rGOn-PEG, in comparison to GOn (25–250 μg mL−1). After a single NIR LED irradiation treatment of 30 min, a decrease of ≈38% in A-431 cells viability was observed for rGOn-PEG (250 μg mL−1). Together, our results demonstrate the potential of irradiating rGOn-PEG using lower energy, cheaper, smaller, and safer LEDs, as alternative to high power lasers, for NIR mild hyperthermia therapy of cancer, namely non-melanoma skin cancer.
New unsymmetrical aminosquarylium cyanine dyes were synthesized and their potential as photosensitizers evaluated. New dyes, derived from benzothiazole and quinoline, were prepared by nucleophilic substitution of the corresponding O-methylated, the key intermediate that was obtained by methylation with CFSOCH of the related zwitterionic unsymmetrical dye, with ammonia and methylamine, respectively. All three news dyes herein described displayed intense and narrow bands in the Vis/NIR region (693-714nm) and their singlet oxygen formation quantum yields ranged from 0.03 to 0.05. In vitro toxicity, in Caco-2 and HepG2 cells, indicated that dark toxicity was absent for concentrations up to 5µM (for the less active dye) or up to 1µM (for the two more active dyes). The three dyes present potential as photosensitizers, differing in irradiation conditions and period of incubation in the presence of irradiated dye. The less active dye needs a longer irradiation period to exhibit phototoxicity which is only evident after longer period of contact with cells (24h). However, the remaining two more active dyes produce higher phototoxicity, even at shorter incubation periods (1h), with shorter irradiation time (7min). Although in different extents, these dyes show promising in vitro results as photosensitizers.
Single phase Bi 0.7 La 0.3 FeO 3 ceramic samples were successfully synthesized by sol-gel combustion and co-precipitation methods, performing a final sintering at 820-870°C from 10 up to 180 min. Rietveld refinements of the XRD data detected small satellite peaks that were successfully indexed by an incommensurated modulated structure model. Lanthanum doping improves magnetic response, reduces the leakage current and dielectric losses. The piezoelectric coefficient was reported for the first time in the Bi 0.7 La 0.3 FeO 3 composition.
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