Publications

Abstract The fate and behaviour of 2-hydroxy-4-methoxyphenyl)-(2-hydroxyphenyl)-methanone, ordinarily known as benzophenone-8 (BP8), in aqueous solution, is thoroughly addressed in this study. The reactions were followed by means of high-performance liquid chromatography coupled with ultraviolet, diode-array detection (HPLC-UV-DAD). Potential by-products of degradation were analysed and determined by liquid chromatography coupled with diode-array detection and mass spectrometry (LC-DAD-MS). BP8 displayed very significant reactivity towards free available chlorine, following a pseudo-first order kinetic profile with rate constant k(obs) = 0.0036 +/- 0.0002 s(-1) and a half-life period of t(1/2) = 194.12 +/- 7.90 s. Disinfection-induced degradation yielded only monochlorinated and dichlorinated disinfection by-products (DBPs). With or without dissolved organic matter (DOM) in solution, the pH and chlorine concentration were the only influential variables on degradation. Photo-induced degradation was assessed by means of exposure to artificial solar radiation. The compound proved to be extremely photo-stable, with a kinetic rate constant of k = 0.00083 +/- 0.00002 min(-1) and a half-life period of t(1/2) = 835.12 +/- 20.12 min. Exposure to artificial solar radiation did not generate any meaningful alterations in the UV spectrum of BP8. There are indications of the possible formation of a photo-isomer, but its extremely low significance and intensity, even after pre-concentration, deemed it negligible.

Abstract This paper reports thermodynamic properties of phase transitions of 2,4,6-trichloro and 2,4,6-tribromo anisoles and of 2,4,6-tribromophenol. The vapor pressures of both crystalline and liquid phases (including supercooled liquid) of the three compounds were measured, respectively, in the temperature ranges T = (297.1 to 368.3) K, T = (330.7 to 391.7) K, and T = (336.5 to 401.7) K, using a static method based on capacitance diaphragm manometers. Moreover, the sublimation vapor pressures of 2,4,6-tribromophenol were also measured in the temperature interval (307.2 to 329.2) K, using a Knudsen mass-loss effusion technique. The standard molar enthalpies, entropies, and Gibbs energies of sublimation and of vaporization, at reference temperatures, were derived from the experimental results as well as the (p,T) values of the triple point of each compound. The temperatures and molar enthalpies of fusion of the three benzene derivatives were determined using differential scanning calorimetry and were compared with the values derived indirectly from the vapor pressure measurements. The thermodynamic results were discussed together with the available literature data for 2,4,6-trichlorophenol. To help rationalize the phase behavior of these substances, the crystallographic structure of 2,4,6-tribromophenol was determined by single crystal X-ray diffraction.

Abstract The Ho3+/Yb3+ doped Gd2O3 phosphor was synthesized via the hydrothermal process. Co-doping of Ca2+ and Zn2+ ions caused a change in the particle morphology and aggregation of the Ho3+/Yb3+: Gd2O3 phosphor. The structural characterization of these particles was performed using X-ray diffraction analysis, Fourier transforms infrared spectroscopy and scanning electron microscopy. The 980 nm excitation assisted upconversion luminescence and 449 run excitation assisted downshifting luminescence of these phosphor particles were compared through the incorporation of Ca2+ and Zn2+ co-dopants. The co-dopants concentration was varied at 0, 5, 10, 15 and 20 mol %. The change in upconversion/downshifting luminescence under the influence of the optimized molar concentration of these co-dopants was studied and explained based on structural variations in the present phosphor material. The paramagnetic behavior of these particles was characterized and compared to search possible applications of these particles in the biomedical field. The samples were studied comparatively for temperature sensing.

Abstract This work aims to provide reliable heat capacities for ethylene glycol and selected oligo(ethylene glycol)s (diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, and hexaethylene glycol), which are industrially important chemicals produced on a large scale. Besides, new data extend the database needed for a better understanding of complex behavior of compounds capable of forming hydrogen bonds. Isobaric heat capacities of ethylene glycols were measured with a Tian-Calvet-type calorimeter in the temperature range of 260 to 358 K. The phase behavior was investigated with a heat-flux differential scanning calorimeter. A simple additive estimation method for liquid heat capacity of oligo(ethylene glycol)s was developed and tested through comparison with newly measured liquid heat capacities of polyethylene glycols 400 and 600.

Abstract The selective fluorescence sensing of fructose was achieved by fluorescence quenching of the emission of hydrothermal-synthesized carbon quantum dots prepared by 3-hydroxyphenylboronic acid. Quantification of fructose was possible in aqueous solutions with pH of 9 (Limit of Detection L-OD and Limit of Quantification L-OQ of 2.04 and 6.12mM), by quenching of the emission at 376nm and excitation similar to 380nm with a linearity range of 0-150mM. A Stern-Volmer constant (K-SV) of 2.11x10(-2)mM(-1) was obtained, while a fluorescent quantum yield of 31% was calculated. The sensitivity of this assay towards fructose was confirmed by comparison with other sugars (such as glucose, sucrose and lactose). Finally, the validity of the proposed assays was further demonstrated by performing recovery assays in different matrixes.

Abstract Oxidative treatment of Multi-Walled Carbon Nanotubes (MWCNT's) was done by chemical functionalization by using the mixture acid, which is a mixture of sulfuric acid (H2SO4) and nitric acid (HNO3). Functionalization was governed by four parameters namely mixture acid concentration, temperature(T), time of heating(t) and the amount of MWCNTs used. After functionalization, functionalized MWCNT's were then diluted in dimethylformamide (DMF) to analyse the percentage of soluble MWCNT's. Also, by increasing the time of functionalization, it was observed that overall yield decreases but the percentage of functionalized product inside the yield quantity remains the same. Material characterization was also carried out at several steps to validate this theory. Chemical functionalization of MWCNT's is generally significant for the manufacturing of polymerbased nanocomposites. Oxidative treatment enhances the dispersion and interfacial bonding within the epoxy matrix. In this research work, a bio-based epoxy resin was selected for the manufacturing of nanocomposite samples with various concentrations of pristine and functionalized MWCNTs. Mechanical and electrical characterization was finally carried out to increase the knowledge on the interaction of MWCNT's with the selected green epoxy matrix system and their influence on the original properties of the resin. (C) 2019 The Authors. Published by Elsevier B.V.

Abstract Diabetes mellitus is a chronic disease and leading cause of death worldwide, affecting more than 420 million people. High blood glucose levels are a common effect of uncontrolled diabetes, which can cause serious health damage. Diabetic individuals must measure their blood glucose levels regularly in order to control glycemic levels and minimize the effects of the disease. Glucose sensors have been used in the management of diabetes for more than 50 years, when Clark and Ann Lyons developed the first glucose enzyme electrode in 1962. Electrochemical sensors have become the leading technology for glucose concentration measuring with most of the commercially available devices being based on amperometric detection. However, the detection of glucose in the blood is still an object of intense research. The development of new fluorescent nanomaterials begins to constitute an alternative for glucose blood quantification. These sensors include carbon dots, quantum dots, graphene quantum dots, gold, silver and upconversion nanoparticles. This paper reviews the last 10 year fluorescent nanoparticles based technologies proposed for glucose monitoring and provide an insight into emerging optical fluorescence glucose biosensors.

Abstract Alzheimer's disease is an irreversible, complex and progressive neurodegenerative disorder associated with oxidative stress and mitochondrial dysfunction. Exogenous antioxidants can be beneficial for decreasing oxidative stress, as they are able to reward the lack of efficacy of the endogenous defense systems and raise the overall antioxidant response in a pathological condition. Along our overarching project related with the design and development of potent and safe multi-target mitochondriotropic antioxidants, based on dietary antioxidants, novel derivatives were obtained. Overall, mitochondriotropic antioxidants showed remarkable antioxidant and chelating properties, presenting low cytotoxic effects on human differentiated neuronal (SH-SY5Y) and hepatocarcinoma (HepG2) cells and exhibited neuroprotective properties on SH-SY5Y cells against 6-hydroxydopamine (6-OHDA) or hydrogen peroxide (H2O2) oxidative insults. Moreover, compounds 58, 59, 62, 63, 66 and 67 were able to permeate a layer of hCMEC/D3 cells in a time-dependent manner. Mitochondriotropic antioxidant 67 stands out by its remarkable iron chelating and neuroprotective properties toward both H2O2 and 6-OHDA-induced oxidative damage, drug-like properties and BBB permeability.

Abstract This paper offers a critical review from classical to new perspectives of advanced oxidation processes (AOPs) coupled to two- and multi-way calibration strategies based on multivariate curve resolution alternating least-squares (MCR-ALS) and parallel factory analysis (PARAFAC) with various analytical techniques to monitor the degradation of contaminants in environmental samples. It focuses on the generation of highly reactive hydroxyl (HO center dot) radicals (classical AOPs with emphasis on Fenton, photo-Fenton and ozonation processes) and emerging reactive sulphate (SO4 center dot) radicals (new perspectives of AOPs) for effective degradation of recalcitrant compounds. Other new perspectives of AOPs were also addressed, namely semiconductor photocatalysis (TiO2/UV), combination of processes involving at least one AOP (hybrid or single-step processes and sequential or two-step processes), novel advanced electrochemical oxidation technologies (electro-Fenton and electro-photo-Fenton) and nanocatalytic heterogeneous Fenton technology with high specific surface area. Literature reports since 2008 for real applications in the environmental remediation based on AOPs (from classical to new perspectives) coupled to PARAFAC and MCR-ALS with first-, second- and third-order data were reviewed and the improvements obtained were briefly discussed. The two- and multi-way calibration strategies allow one the successful decomposition of first-, second- and third-order data collected from different analytical techniques. Therefore, the respective profiles obtained allowed qualitative (spectral profiles) and quantitative (concentration profiles) analysis of complex samples during the degradation of contaminants through the second-order advantage. Finally, trends of future research directions for AOPs coupled to various analytical techniques and advanced chemometric models were provided.

Abstract Polyphenols like caffeic acid and its phenethyl ester have been associated with potent anti-aggregating activity. Accordingly, we screened a library of polyphenols and synthetic derivatives thereof for their capacity to inhibit tau-aggregation using a thioflavin T-based fluorescence method. Our results show that the nitrocatechol scaffold is required for a significant anti-aggregating activity, which is enhanced by introducing bulky substituents at the side chain. A remarkable increase in activity was observed for alpha-cyanocarboxamide derivatives 26-27. Molecular docking studies showed that the amide bond provides superior conformational stability in the steric zipper assembly of tau, which drives the increase in activity. We also found that derivatives 24-27 were potent chelators of copper(II) - a property of pharmacological significance in abnormal protein aggregation. These small molecules can provide promising leads to develop new drugs for tauopathies and AD. These findings open a new window on the repurposing of nitrocatechols beyond their established role as catechol-O-methyltransferase inhibitors. (C) 2019 Published by Elsevier Masson SAS.