Effect of amino functional groups on the surface properties and Lewis's acid base parameters of UiO-66(NH2) by inverse gas chromatography.

Amino-functionalized metal organic frameworks (MOFs) have attracted much attention for various applications such as carbon dioxide capture, water remediation and catalysis. The focus of this study is to determine the surface and Lewis's acid-base properties of UiO-66(NH2) crystals by the inverse gas chromatography (IGC) technique at infinite dilution. The latter was applied to evaluate the dispersive component of the surface energy γsd(T) by using thermal model and several molecular models. The obtained results proved that γsd(T) decreases when the temperature increases. The best results were achieved by using the thermal model that takes into account the effect of the temperature on the surface areas of the organic molecules. We also observed a decrease of the Gibbs surface free energy of adsorption by increasing the temperature of the different organic solvents. The polar interactions of UiO-66(NH2) were obtained by using the methods of Saint-Flour Papirer, Donnet et al., Brendlé-Papirer and the different molecular models. The Lewis's acid base constants KA and KD were further calculated by determining the different variables of adsorption of the probes on the solid surface and the obtained values were 1.07 and 0.45 for KA and KD respectively, with an acid-base ratio (KA/KD) of 2.38. These values showed the high acidic surface of the solid substrate; whereas, the values of the entropic acid base parameters, ωA, ωD and ωA/ωD respectively equal to 1.0×10-3, 3.8×10-4 and 2.73, also highlighted the important acidity of UiO-66-(NH2) surface. These important findings suggest that the surface defects (missing linkers and/or clusters) in UiO-66(NH2) are the main determining factor of the acid-base properties of UiO-66 based structures.

Silica Nanoparticles in Xanthan Gum Solutions: Oil Recovery Efficiency in Core Flooding Tests.

Polymer flooding is one of the enhanced oil recovery (EOR) methods that increase the macroscopic efficiency of the flooding process and enhanced crude oil recovery. In this study, the effect of silica nanoparticles (NP-SiO2) in xanthan gum (XG) solutions was investigated through the analysis of efficiency in core flooding tests. First, the viscosity profiles of two polymer solutions, XG biopolymer and synthetic hydrolyzed polyacrylamide (HPAM) polymer, were characterized individually through rheological measurements, with and without salt (NaCl). Both polymer solutions were found suitable for oil recovery at limited temperatures and salinities. Then, nanofluids composed of XG and dispersed NP-SiO2 were studied through rheological tests. The addition of nanoparticles was shown to produce a slight effect on the viscosity of the fluids, which was more remarkable over time. Interfacial tension tests were measured in water-mineral oil systems, without finding an effect on the interfacial properties with the addition of polymer or nanoparticles in the aqueous phase. Finally, three core flooding experiments were conducted using sandstone core plugs and mineral oil. The polymers solutions (XG and HPAM) with 3% NaCl recovered 6.6% and 7.5% of the residual oil from the core, respectively. In contrast, the nanofluid formulation recovered about 13% of the residual oil, which was almost double that of the original XG solution. The nanofluid was therefore more effective at boosting oil recovery in the sandstone core.

Particles' Organization in Direct Oil-in-Water and Reverse Water-in-Oil Pickering Emulsions.

This paper addresses the impact of the particle initial wetting and the viscosity of the oil phase on the structure and rheological properties of direct (Oil/Water) and reverse (Water/Oil) Pickering emulsions. The emulsion structure was investigated via confocal microscopy and static light scattering. The flow and viscoelastic properties were probed by a stress-controlled rheometer. Partially hydrophobic silica particles have been employed at 1 and 4 wt.% to stabilize dodecane or paraffin-based emulsions at 20 vol.% of the dispersed phase. W/O emulsions were obtained when the particles were dispersed in the oily phase while O/W emulsions were prepared when the silica was introduced in the aqueous phase. We demonstrated that, although the particles adsorbed at the droplets interfaces for all the emulsions, their organization, the emulsion structure and their rheological properties depend in which phase they were previously dispersed in. We discuss these features as a function of the particle concentration and the oil viscosity.

Surface thermodynamics and Lewis acid-base properties of metal-organic framework Crystals by Inverse gas chromatography at infinite dilution.

In this study, the surface thermodynamic properties and more particularly, the dispersive component γsd of the surface energy of crystals of a Zr-based MOF, UiO-66 (Zr6O4(OH)4(BDC)6; BDC = benzene 1,4-dicarboxylic acid), the specific interactions, and their acid-base constants were determined by using different molecular models and inverse gas chromatography methods. The determination of γsd of the UiO-66 surface was obtained by using several models such as Dorris-Gray and those based on the Fowkes relation by applying the various molecular models giving the surface areas of n-alkanes and polar organic molecules. Six models were used: Kiselev, spherical, geometric, Van der Waals, Redlich-Kwong, and cylindrical models. The obtained results were corrected by using our model taking into account the thermal effect on the surface areas of molecules. A linear equation was obtained between γsd and the temperature. The specific free energy, enthalpy and entropy of adsorption of polar molecules, as well as the acid and base constants of UiO-66 particles were determined with an excellent precision. It was also proved that the UiO-66 surface exhibited an amphoteric acid-base character with stronger acidity. The linear variations of the specific free energy of interaction as a function of the temperature allowed to obtain the specific surface enthalpy and entropy of adsorption, as well as the acid and base constants of UiO-66 by using ten different models and methods. The best results were obtained by using our model that gave the more precise values of the acid constant KA=0.57, the base constant KD=0.18 of the MOF particles and the ratio KA/KD = 3.14 clearly proving a strong acid character of the UiO-66 surface.

New approach to determine the surface and interface thermodynamic properties of H-ß-zeolite/rhodium catalysts by inverse gas chromatography at infinite dilution.

The thermodynamic surface properties and Lewis acid-base constants of H-ß-zeolite supported rhodium catalysts were determined by using the inverse gas chromatography technique at infinite dilution. The effect of the temperature and the rhodium percentage supported by zeolite on the acid base properties in Lewis terms of the various catalysts were studied. The dispersive component of the surface energy of Rh/H-ß-zeolite was calculated by using both the Dorris and Gray method and the straight-line method. We highlighted the role of the surface areas of n-alkanes on the determination of the surface energy of catalysts. To this aim various molecular models of n-alkanes were tested, namely Kiselev, cylindrical, Van der Waals, Redlich-Kwong, geometric and spherical models. An important deviation in the values of the dispersive component of the surface energy [Formula: see text] determined by the classical and new methods was emphasized. A non-linear dependency of [Formula: see text] with the specific surface area of catalysts was highlighted showing a local maximum at 1%Rh. The study of RTlnVn and the specific free energy ∆Gsp(T) of n-alkanes and polar solvents adsorbed on the various catalysts revealed the important change in the acid properties of catalysts with both the temperature and the rhodium percentage. The results proved strong amphoteric behavior of all catalysts of the rhodium supported by H-ß-zeolite that actively react with the amphoteric solvents (methanol, acetone, tri-CE and tetra-CE), acid (chloroform) and base (ether) molecules. It was shown that the Guttmann method generally used to determine the acid base constants KA and KD revealed some irregularities with a linear regression coefficient not very satisfactory. The accurate determination of the acid-base constants KA, KD and K of the various catalysts was obtained by applying Hamieh's model (linear regression coefficients approaching r2 ≈ 1.000). It was proved that all acid base constants determined by this model strongly depends on the rhodium percentage and the specific surface area of the catalysts.

A Facile Approach for Doxorubicine Delivery in Cancer Cells by Responsive and Fluorescent Core/Shell Quantum Dots.

Biocompatible thermoresponsive copolymers based on 2-(2-methoxyethoxy) ethyl methacrylate (MEO2MA) and oligo (ethylene glycol) methacrylate (OEGMA) were grown from the surface of ZnO quantum dots (QDs) by surface initiated atom transfer radical polymerization with activators regenerated by electron transfer (SI-ARGET ATRP) in order to design smart and fluorescent core/shell nanosystems to be used toward cancer cells. Tunable lower critical solution temperature (LCST) values were obtained and studied in water and in culture medium. The complete efficiency of the process was demonstrated by the combination of spectroscopic and microscopic studies. The colloidal behavior of the ZnO/copolymer core/shell QDs in water and in physiological media with temperature was assessed. Finally, the cytotoxicity toward human colon cancer HT29 cells of the core/shell QDs was tested. The results showed that the polymer-capped QDs exhibited almost no toxicity at concentrations up to 12.5 µg.mL-1, while when loaded with doxorubicin hydrochloride (DOX), a higher cytotoxicity and a decreased HT29 cancer cell viability in a short time were observed.

Titania and silica nanoparticles coupled to Chlorin e6 for anti-cancer photodynamic therapy.

In this study, light-sensitive photosensitizers (Chlorin e6, Ce6) were linked to TiO2 and SiO2 nanoparticles (NPs) in order to develop new kinds of NP-based drug delivery systems for cancer treatment by PDT. TiO2 or SiO2 NPs were modified either by the growth of a polysiloxane layer constituted of two silane reagents ((3-aminopropyl)triethoxysilane (APTES) and tetraethyl orthosilicate (TEOS)) around the core (PEGylated NPs: TiO2@4Si-Ce6-PEG, SiO2@4Si-Ce6-PEG) or simply modified by APTES alone (APTES-modified NPs: TiO2-APTES-Ce6, SiO2-APTES-Ce6). Ce6 was covalently attached onto the modified TiO2 and SiO2 NPs via an amide bond. The absorption profile of the hybridized NPs was extended to the visible region of the light. The physicochemical properties of these NPs were explored by TEM, HR-TEM, XRD, FTIR and zeta potential. The photophysical characteristics including the light absorption, the fluorescence properties and the production reactive oxygen species (1O2 and HO) were also addressed. In vitro experiments on glioblastoma U87 cells were performed to evaluate the photodynamic efficiency of the new hybridized NPs. The cells were exposed to different concentrations of NPs and illuminated (λexc = 652 nm, fluence rate 10 J/cm2). In contrast to the PEGylated NPs, the APTES-modified nanosystems were found to be more efficient for PDT. An interesting photodynamic effect was observed in the case of TiO2-APTES-Ce6 NPs. After illumination, the viability of U87 was decreased by 89% when they were exposed to 200 µg/mL of TiO2-APTES-Ce6 NPs, which corresponds to 0.22 µM of Ce6. The same effect can be obtained with free photosensitizer but using a higher concentration of 10 µM of Ce6.

Iron-impregnated zeolite catalyst for efficient removal of micropollutants at very low concentration from Meurthe river.

In this paper, for the first time, faujasite Y zeolite impregnated with iron (III) was employed as a catalyst to remove a real cocktail of micropollutants inside real water samples from the Meurthe river by the means of the heterogeneous photo-Fenton process. The catalyst was prepared by the wet impregnation method using iron (III) nitrate nonahydrate as iron precursor. First, an optimization of the process parameters was conducted using phenol as model macro-pollutant. The hydrogen peroxide concentration, the light wavelength (UV and visible) and intensity, the iron loading immobilized, as well as the pH of the solution were investigated. Complete photo-Fenton degradation of the contaminant was achieved using faujasite containing 20 wt.% of iron, under UV light, and in the presence of 0.007 mol/L of H2O2 at pH 5.5. In a second step, the optimized process was used with real water samples from the Meurthe river. Twenty-one micropollutants (endocrine disruptors, pharmaceuticals, personal care products, and perfluorinated compounds) including 17 pharmaceutical compounds were specifically targeted, detected, and quantified. All the initial concentrations remained in the range of nanogram per liter (0.8-88 ng/L). The majority of the micropollutants had a large affinity for the surface of the iron-impregnated faujasite. Our results emphasized the very good efficiency of the photo-Fenton process with a cocktail of a minimum of 21 micropollutants. Except for sulfamethoxazole and PFOA, the concentrations of all the other microcontaminants (bisphenol A, carbamazepine, carbamazepine-10,11-epoxide, clarithromycin, diclofenac, estrone, ibuprofen, ketoprofen, lidocaine, naproxen, PFOS, triclosan, etc.) became lower than the limit of quantification of the LC-MS/MS after 30 min or 6 h of photo-Fenton treatment depending on their initial concentrations. The photo-Fenton degradation of PFOA can be neglected. The photo-Fenton degradation of sulfamethoxazole obeys first-order kinetics in the presence of the cocktail of the other micropollutants.

The application of titanium dioxide, zinc oxide, fullerene, and graphene nanoparticles in photodynamic therapy.

Nanoparticles (NPs) have been shown to have good ability to improve the targeting and delivery of therapeutics. In the field of photodynamic therapy (PDT), this targeting advantage of NPs could help ensure drug delivery at specific sites. Among the commonly reported NPs for PDT applications, NPs from zinc oxide, titanium dioxide, and fullerene are commonly reported. In addition, graphene has also been reported to be used as NPs albeit being relatively new to this field. In this context, the present review is organized by these different NPs and contains numerous research works related to PDT applications. The effectiveness of these NPs for PDT is discussed in detail by collecting all essential information described in the literature. The information thus assembled could be useful in designing new NPs specific for PDT and/or PTT applications in the future.

Thermo-responsive magnetic Fe3O4@P(MEO2MAX-OEGMA100-X) NPs and their applications as drug delivery systems.

The unique physical properties of the superparamagnetic nanoparticles (SPIONs) have made them candidates of choice in nanomedicine especially for diagnostic imaging, therapeutic applications and drug delivery based systems. In this study, superparamagnetic Fe3O4 NPs were synthesized and functionalized with a biocompatible thermoresponsive copolymer to obtain temperature responsive core/shell NPs. The ultimate goal of this work is to build a drug delivery system able to release anticancer drugs in the physiological temperatures range. The core/shell NPs were first synthesized and their chemical, physical, magnetic and thermo-responsive properties where fully characterized in a second step. The lower critical solution temperature (LCST) of the core/shell NPs was tuned in physiological media in order to release the cancer drug at a controlled temperature slightly above the body temperature to avoid any premature release of the drug. The core/shell NPs exhibiting the targeted LCST were then loaded with Doxurubicin (DOX) and the drug release properties were then studied with the temperature. Moreover the cytotoxicity tests have shown that the core/shell NPs had a very limited cytotoxicity up to concentration of 25µg/mL. This investigation showed that the significant release occurred at the targeted temperature in the physiological media making those nano-systems very promising for further use in drug delivery platform.