Search

A serious risk that harms the safe use of water and affects aquatic ecosystems is water pollution. This occurs when the water’s natural equilibrium is disrupted by an excessive amount of substances, both naturally occurring and as a byproduct of human activities, that have varied degrees of toxicity. Radiation from Cs isotopes, which are common components of radioactive waste and are known for their long half-lives (30 years), which are longer than the natural decay processes, is a major source of contamination. Adsorption is a commonly used technique for reducing this kind of contamination, and zeolite chabazite has been chosen as the best adsorbent for cesium in this particular situation. The purpose of this research is to investigate a composite material based on magnesium phosphate cement (MPC). Magnesium oxide (MgO), potassium dihydrogen phosphate (KH2PO4), and properly selected retarders are used to create the MPC. The optimal conditions for this composite material are investigated through the utilization of X-ray diffraction, scanning electron microscopy, BET surface area analysis, and atomic absorption spectroscopy. The principal aim is to enable innovations in the elimination of radioactive waste-contaminated water using effective cesium removal. The most promising results were obtained by using KH2PO4 as an acid, and MgO as a base, and aiming for an M/P ratio of two or four. Furthermore, we chose zeolite chabazite as a crucial component. The best adsorption abilities for Cs were found at Qads = 106.997 mg/g for S2 and Qads = 122.108 mg/g for S1. As a result, zeolite is an eco-friendly material that is a potential usage option, with many benefits, such as low prices, stability, and ease of regeneration and use.

The synthesis of core–shell magnetic mesoporous nanoparticles (MMSNs) through a phase transfer process is usually performed at the 100–250 mg scale. At the gram scale, nanoparticles without cores or with multicore systems are observed. Iron oxide core nanoparticles (IO) were synthesized through a thermal decomposition procedure of α-FeO(OH) in oleic acid. A phase transfer from chloroform to water was then performed in order to wrap the IO nanoparticles with a mesoporous silica shell through the sol–gel procedure. MMSNs were then functionalized with DTPA (diethylenetriaminepentacetic acid) and used for the separation of metal ions. Their toxicity was evaluated. The phase transfer procedure was crucial to obtaining MMSNs on a large scale. Three synthesis parameters were rigorously controlled: temperature, time and glassware. The homogeneous dispersion of MMSNs on the gram scale was successfully obtained. After functionalization with DTPA, the MMSN-DTPAs were shown to have a strong affinity for Ni ions. Furthermore, toxicity was evaluated in cells, zebrafish and seahorse cell metabolic assays, and the nanoparticles were found to be nontoxic. We developed a method of preparing MMSNs at the gram scale. After functionalization with DTPA, the nanoparticles were efficient in metal ion removal and separation; furthermore, no toxicity was noticed up to 125 µg mL−1 in zebrafish.

In this study, we used a novel composite material based on magnesium phosphate cement (MPC) to explore the retention of fluoride from used water. Dead-burned magnesium oxide (MgO), ammonium dihydrogen phosphate (NH4H2PO4), and a few retarders were used to create this particular substance. Several studies have corroborated the performance of using aluminum in the capture of fluoride. From this perspective, we attempted to reinforce our matrix with different quantities of aluminum, which increased the resistance of the composite in water. The optimal conditions that were obtained were evaluated and scrutinized using a range of techniques, including scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), Fourier transforms infrared spectroscopy (FTIR), and Brunauer–Emmett–Teller (BET). The adsorbents demonstrated a powerful ability to remove fluoride from contaminated water and the defluoridation capacity was evaluated at 4.84 mg/g. Equilibrium modeling was carried out, and the experimental data were expressed in accordance with the Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich isotherms.

Dendritic mesoporous organosilica nanoparticles (DMON) are a new class of biodegradable nanoparticles suitable for biomolecule delivery. We studied the photochemical internalization (PCI) and photodynamic therapy (PDT) of DMON to investigate new ways for DMON to escape from the endosomes-lysosomes and deliver biomolecules into the cytoplasm of cells. We added photosensitizers in the framework of DMON and found that DMON were loaded with siRNA or FVIII factor protein. We made four formulations with four different photosensitizers. The photosensitizers allowed us to perform imaging of DMON in cancer cells, but the presence of the tetrasulfide bond in the framework of DMON quenched the formation of singlet oxygen. Fortunately, one formulation allowed us to efficiently deliver proapoptotic siRNA in MCF-7 cancer cells leading to 31% of cancer cell death, without irradiation. As for FVIII protein, it was loaded in two formulations with drug-loading capacities (DLC) up to 25%. In conclusion, DMON are versatile nanoparticles capable of loading siRNA and delivering it into cancer cells, and also loading FVIII protein with good DLC. Due to the presence of tetrasulfide, it was not possible to perform PDT or PCI.

L-ascorbic acid (LAA), commonly known as vitamin C, is an excellent and recognized antioxidant molecule used in pharmaceutical and cosmetic formulations. Several strategies have been developed in order to preserve its chemical stability, connected with its antioxidant power, but there is little research regarding the employment of natural clays as LAA host. A safe bentonite (Bent)—which was verified by in vivo ophthalmic irritability and acute dermal toxicity assays—was used as carrier of LAA. The supramolecular complex between LAA and clay may constitute an excellent alternative, since the molecule integrity does not seem to be affected, at least from the point of view of its antioxidant capacity. The Bent/LAA hybrid was prepared and characterized through ultraviolet (UV) spectroscopy, X-ray diffraction (XRD), infrared (IR) spectroscopy, thermogravimetric analysis (TG/DTG) and zeta potential measurements. Photostability and antioxidant capacity tests were also performed. The LAA incorporation into Bent clay was demonstrated, as well as the drug stability due to the Bent photoprotective effect onto the LAA molecule. Moreover, the antioxidant capacity of the drug in the Bent/LAA composite was confirmed.

In this research work, new composite materials based on magnesium phosphate cement (MPC) were developed to evaluate the retention of fluorine from wastewater. This material was prepared with dead burned magnesia oxide (MgO), ammonium dihydrogen phosphate (NH4H2PO4), and some retarding agents. We chose to synthesize with hydrogen peroxide instead of water; alumina and zeolite were also added to the cement. The obtained optimal conditions were studied and analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), BET, and thermogravimetric analysis (TGA). The adsorbents showed a strong ability to remove fluoride from contaminated water, and the best defluoridation capacity was evaluated as 2.21 mg/g for the H2O2 cement. Equilibrium modeling was performed, and the experimental data were presented according to the isotherms of Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich.

Background: In addition to their great optical properties, nanodiamonds (NDs) have recently proved useful for two-photon-excited photodynamic therapy (TPE-PDT) applications. Indeed, they are able to produce reactive oxygen species (ROS) directly upon two-photon excitation but not with one-photon excitation; Methods: Fluorescent NDs (FNDs) with a 100 nm diameter and detonation NDs (DNDs) of 30 nm were compared. In order to use the gems for cancer-cell theranostics, they were encapsulated in a bis(triethoxysilyl)ethylene-based (ENE) periodic mesoporous organosilica (PMO) shell, and the surface of the formed nanoparticles (NPs) was modified by the direct grafting of polyethylene glycol (PEG) and amino groups using PEG-hexyltriethoxysilane and aminoundecyltriethoxysilane during the sol–gel process. The NPs’ phototoxicity and interaction with MDA-MB-231 breast cancer cells were evaluated afterwards; Results: Transmission electronic microscopy images showed the formation of core–shell NPs. Infrared spectra and zeta-potential measurements confirmed the grafting of PEG and NH2 groups. The encapsulation of the NDs allowed for the imaging of cancer cells with NDs and for the performance of TPE-PDT of MDA-MB-231 cancer cells with significant mortality. Conclusions: Multifunctional ND@PMO core–shell nanosystems were successfully prepared. The NPs demonstrated high biocompatibility and TPE-PDT efficiency in vitro in the cancer cell model. Such systems hold good potential for two-photon-excited PDT applications.

(1) Background: Due to human activities, greenhouse gas (GHG) concentrations in the atmosphere are constantly rising, causing the greenhouse effect. Among GHGs, carbon dioxide (CO2) is responsible for about two-thirds of the total energy imbalance which is the origin of the increase in the Earth’s temperature. (2) Methods: In this field, we describe the development of periodic mesoporous organosilica nanoparticles (PMO NPs) used to capture and store CO2 present in the atmosphere. Several types of PMO NP (bis(triethoxysilyl)ethane (BTEE) as matrix, co-condensed with trialkoxysilylated aminopyridine (py) and trialkoxysilylated bipyridine (Etbipy and iPrbipy)) were synthesized by means of the sol-gel procedure, then characterized with different techniques (DLS, TEM, FTIR, BET). A systematic evaluation of CO2 adsorption was carried out at 298 K and 273 K, at low pressure. (3) Results: The best values of CO2 adsorption were obtained with 6% bipyridine: 1.045 mmol·g−1 at 298 K and 2.26 mmol·g−1 at 273 K. (4) Conclusions: The synthetized BTEE/aminopyridine or bipyridine PMO NPs showed significant results and could be promising for carbon capture and storage (CCS) application.

This paper reports on the comparison of three zirconium-based metal organic frameworks (MOFs) for the capture of carbon dioxide and ethanol vapour at ambient conditions. In terms of efficiency, two parameters were evaluated by experimental and modeling means, namely the nature of the ligands and the size of the cavities. We demonstrated that amongst three Zr-based MOFs, MIP-202 has the highest affinity for CO2 (−50 kJ·mol−1 at low coverage against around −20 kJ·mol−1 for MOF-801 and Muc Zr MOF), which could be related to the presence of amino functions borne by its aspartic acid ligands as well as the presence of extra-framework anions. On the other side, regardless of the ligand size, these three materials were able to adsorb similar amounts of carbon dioxide at 1 atm (between 2 and 2.5 µmol·m−2 at 298 K). These experimental findings were consistent with modeling studies, despite chemisorption effects, which could not be taken into consideration by classical Monte Carlo simulations. Ethanol adsorption confirmed these results, higher enthalpies being found at low coverage for the three materials because of stronger van der Waals interactions. Two distinct sorption processes were proposed in the case of MIP-202 to explain the shape of the enthalpic profiles.

The present paper examines the impact that the nanotube morphology and organic or inorganic intercalated species may have on the cesium sorption by layered vanadium oxides prepared with the use of hexadecylamine as a structure-directing agent. The hybrid material represented by a chemical formula of (V2O5)(VO2)1.03(C16H36N)1.46(H2O)x was achieved through accelerated microwave-assisted synthesis carefully optimized to ensure the best compromise between the scroll-like morphology and the hydrophobic character. To enhance its dispersibility in water, this sample was subsequently modified by progressive replacement of the C16H36N+ units by NH4+ cations. The final materials represented a stacking of lamellar sheets with a worse scroll-like morphology. Both the optimization procedure and the template removal were monitored on the basis of scanning and transmission electronic microscopy, X-ray diffraction, infra-red spectroscopy, inductively coupled plasma-optical emission spectrometry, X-ray photoelectron spectroscopy, and elemental analysis, supplemented by adequate simulations methods providing the reference IR spectra and XRD patterns for comparison or the textural parameters of the samples. The comparison of the cesium sorption from either a 4:1 ethanol–water mixture or aqueous solutions pointed toward the solubility of intercalated cations in the bulk solution as the main factor limiting their displacement from the interlayer space by the oncoming cesium ones. The sample obtained after 70% exchange with NH4+ exhibited a maximum sorption capacity of 1.4 mmol g−1 from CsNO3 aqueous solutions and its retention efficiency remained significant from low-concentration Cs solutions in river or sea water.

We report herein the preparation of mixed periodic mesoporous organosilica nanoparticles (E-Pn 75/25 and 90/10 PMO NPs) by sol-gel co-condensation of E-1,2-bis(triethoxysilyl)ethylene ((E)-BTSE or E) with previously synthesized disilylated tert-butyl 3,5-dialkoxybenzoates bearing either sulfide (precursor P1) or carbamate (precursor P2) functionalities in the linker. The syntheses were performed with cetyltrimethylammonium bromide (CTAB) as template in the presence of sodium hydroxide in water at 80 °C. The nanomaterials have been characterized by Transmission Electron Microscopy (TEM), nitrogen-sorption measurements (BET), Dynamic Light Scattering (DLS), zeta-potential, Thermogravimetric Analysis (TGA), FTIR, 13C CP MAS NMR and small angle X-ray diffraction (p-XRD). All the nanomaterials were obtained as mesoporous rodlike-shape nanoparticles. Remarkably, E-Pn 90/10 PMO NPs presented high specific surface areas ranging from 700 to 970 m2g−1, comparable or even higher than pure E PMO nanorods. Moreover, XRD analyses showed an organized porosity for E-P1 90/10 PMO NPs typical for a hexagonal 2D symmetry. The other materials showed a worm-like mesoporosity.

Periodic Mesoporous Organosilica Nanoparticles (PMONPs) are nanoparticles of high interest for nanomedicine applications. These nanoparticles are not composed of silica (SiO2). They belong to hybrid organic−inorganic systems. We considered using these nanoparticles for CO2 release as a contrast agent for High Intensity Focused Ultrasounds (HIFU). Three molecules (P1−P3) possessing two to four triethoxysilyl groups were synthesized through click chemistry. These molecules possess a tert-butoxycarbonyl (BOC) group whose cleavage in water at 90−100 °C releases CO2. Bis(triethoxysilyl)ethylene E was mixed with the molecules Pn (or not for P3) at a proportion of 90/10 to 75/25, and the polymerization triggered by the sol-gel procedure led to PMONPs. PMONPs were characterized by different techniques, and nanorods of 200−300 nm were obtained. These nanorods were porous at a proportion of 90/10, but non-porous at 75/25. Alternatively, molecules P3 alone led to mesoporous nanoparticles of 100 nm diameter. The BOC group was stable, but it was cleaved at pH 1 in boiling water. Molecules possessing a BOC group were successfully used for the preparation of nanoparticles for CO2 release. The BOC group was stable and we did not observe release of CO2 under HIFU at lysosomal pH of 5.5. The pH needed to be adjusted to 1 in boiling water to cleave the BOC group. Nevertheless, the concept is interesting for HIFU theranostic agents.

(1) Background: Nanomedicine has recently emerged as a promising field, particularly for cancer theranostics. In this context, nanoparticles designed for imaging and therapeutic applications are of interest. We, therefore, studied the encapsulation of upconverting nanoparticles in mesoporous organosilica nanoparticles. Indeed, mesoporous organosilica nanoparticles have been shown to be very efficient for drug delivery, and upconverting nanoparticles are interesting for near-infrared and X-ray computed tomography imaging, depending on the matrix used. (2) Methods: Two different upconverting-based nanoparticles were synthesized with Yb3+-Er3+ as the upconverting system and NaYF4 or BaLuF5 as the matrix. The encapsulation of these nanoparticles was studied through the sol-gel procedure with bis(triethoxysilyl)ethylene and bis(triethoxysilyl)ethane in the presence of CTAB. (3) Results: with bis(triethoxysilyl)ethylene, BaLuF5: Yb3+-Er3+, nanoparticles were not encapsulated, but anchored on the surface of the obtained mesoporous nanorods BaLuF5: Yb3+-Er3+@Ethylene. With bis(triethoxysilyl)ethane, BaLuF5: Yb3+-Er3+ and NaYF4: Yb3+-Er3+nanoparticles were encapsulated in the mesoporous cubic structure leading to BaLuF5: Yb3+-Er3+@Ethane and NaYF4: Yb3+-Er3+@Ethane, respectively. (4) Conclusions: upconversion nanoparticles were located on the surface of mesoporous nanorods obtained by hydrolysis polycondensation of bis(triethoxysilyl)ethylene, whereas encapsulation occurred with bis(triethoxysilyl)ethane. The later nanoparticles NaYF4: Yb3+-Er3+@Ethane or BaLuF5: Yb3+-Er3+@Ethane were promising for applications with cancer cell imaging or X-ray-computed tomography respectively.

(1) Background: Nanomedicine has recently emerged as a new area of research, particularly to fight cancer. In this field, we were interested in the vectorization of pepstatin A, a peptide which does not cross cell membranes, but which is a potent inhibitor of cathepsin D, an aspartic protease particularly overexpressed in breast cancer. (2) Methods: We studied two kinds of nanoparticles. For pepstatin A delivery, mesoporous silica nanoparticles with large pores (LPMSNs) and hollow organosilica nanoparticles (HOSNPs) obtained through the sol–gel procedure were used. The nanoparticles were loaded with pepstatin A, and then the nanoparticles were incubated with cancer cells. (3) Results: LPMSNs were monodisperse with 100 nm diameter. HOSNPs were more polydisperse with diameters below 100 nm. Good loading capacities were obtained for both types of nanoparticles. The nanoparticles were endocytosed in cancer cells, and HOSNPs led to the best results for cancer cell killing. (4) Conclusions: Mesoporous silica-based nanoparticles with large pores or cavities are promising for nanomedicine applications with peptides.

Careful analysis of any new nanomedicine device or disposal should be undertaken to comprehensively characterize the new product before application, so that any unintended side effect is minimized. Because of the increasing number of nanotechnology-based drugs, we can anticipate that regulatory authorities might adapt the approval process for nanomedicine products due to safety concerns, e.g., request a more rigorous testing of the potential toxicity of nanoparticles (NPs). Currently, the use of mesoporous silica nanoparticles (MSN) as drug delivery systems is challenged by a lack of data on the toxicological profile of coated or non-coated MSN. In this context, we have carried out an extensive study documenting the influence of different functionalized MSN on the cellular internalization and in vivo behaviour. In this article, a synthesis of these works is reviewed and the perspectives are drawn. The use of magnetic MSN (Fe3O4@MSN) allows an efficient separation of coated NPs from cell cultures with a simple magnet, leading to results regarding corona formation without experimental bias. Our interest is focused on the mechanism of interaction with model membranes, the adsorption of proteins in biological fluids, the quantification of uptake, and the effect of such NPs on the transcriptomic profile of hepatic cells that are known to be readily concerned by NPs’ uptake in vivo, especially in the case of an intravenous injection.