Phase transition and dynamics of defects in the molecular piezoelectric TMCM-MnCl3 and the effect of partial substitutions of Mn

We present dielectric and anelastic spectroscopy measurements of the molecular piezoelectric TMCM-MnCl3 and TMCM-Mn0.95M0.05Cl3 (M = Cu, Fe, Ni; TMCM = trimethylchlorometylammonium), whose powders were pressed into discs and bars and deposited as films on Si by Matrix-Assisted Pulsed Laser Evaporation (MAPLE). As in other molecular ferroelectrics, the dielectric permittivity e0 drops at the structural transition temperature TC, below which the number of directions that the polar TMCM molecules visit is reduced, with the formation of ferroelectric domains. Concomitantly, the Young’s modulus E starts increasing and the elastic energy loss has a step-like increase, attributable to the motion of the domain walls. Both the dielectric and elastic anomalies indicate the improper character of the ferroelectric transition, where the ordering of the molecular orientations is not driven by the cooperative interaction of their electric dipoles. Below room temperature, at least two thermally activated relaxation processes appear both in the dielectric and anelastic spectra, whose real and imaginary parts measured at several frequencies can be fit with the Havriliak–Negami formula. The microscopic parameters so-obtained indicate that they are due to point defects, and it is argued that they are Cl vacancies and their complexes with TMCM vacancies. The considerable width of these relaxation maxima is explained by the geometry of the hexagonal perovskite structure. The partial substitution of Mn with 5% Ni has little effect on the anelastic and dielectric spectra, while Cu and, especially, Fe cause a large enhancement of the losses attributed to domain wall relaxation, with substantial contributions also above TC. The condensation of water from the humidity in the powders compacted by cold pressing was observed and discussed. The piezoelectric activity of the films was assessed by PFM

Resveratrol Encapsulation and Release from Pristine and Functionalized Mesoporous Silica Carriers

Resveratrol, a naturally occurring polyphenol, has attracted significant attention due to its antioxidant, cardioprotective and anticancer potential. However, its low aqueous solubility limits resveratrol bioavailability and use. In this work, different mesoporous silica matrices were used to encapsulate the polyphenol and to increase its dissolution rate. Pristine MCM-41, MCM-48, SBA-15, SBA-16, FDU-12 and MCF silica were obtained. The influence of SBA-15 functionalized with aminopropyl, isocyanate, phenyl, mercaptopropyl, and propionic acid moieties on resveratrol loading and release profiles was also assessed. The cytotoxic effects were evaluated for mesoporous carriers and resveratrol-loaded samples against human lung cancer (A549), breast cancer (MDA-MB-231) and human skin fibroblast (HSF) cell lines. The effect on apoptosis and cell cycle were assayed for selected resveratrol-loaded carriers. The polyphenol molecules are encapsulated only inside the mesopores, mostly in amorphous state. All materials containing either pristine or functionalized silica carriers increased polyphenol dissolution rate. The influence of the physico-chemical properties of the mesoporous carriers and resveratrol-loaded supports on the kinetic parameters was identified. Resv@SBA-15-SH and Resv@SBA-15-NCO samples exhibited the highest anticancer effect against A549 cells (IC50 values were 26.06 and 36.5 µg/mL, respectively) and against MDA-MB-231 (IC50 values were 35.56 and 19.30 µg/mL, respectively), which highlights their potential use against cancer

A Review of Composite Phase Change Materials Based on Porous Silica Nanomaterials for Latent Heat Storage Applications

Phase change materials (PCMs) can store thermal energy as latent heat through phase transitions. PCMs using the solid-liquid phase transition offer high 100–300 J g−1 enthalpy at constant temperature. However, pure compounds suffer from leakage, incongruent melting and crystallization, phase separation, and supercooling, which limit their heat storage capacity and reliability during multiple heating-cooling cycles. An appropriate approach to mitigating these drawbacks is the construction of composites as shape-stabilized phase change materials which retain their macroscopic solid shape even at temperatures above the melting point of the active heat storage compound. Shape-stabilized materials can be obtained by PCMs impregnation into porous matrices. Porous silica nanomaterials are promising matrices due to their high porosity and adsorption capacity, chemical and thermal stability and possibility of changing their structure through chemical synthesis. This review offers a first in-depth look at the various methods for obtaining composite PCMs using porous silica nanomaterials, their properties, and applications. The synthesis and properties of porous silica composites are presented based on the main classes of compounds which can act as heat storage materials (paraffins, fatty acids, polymers, small organic molecules, hydrated salts, molten salts and metals). The physico-chemical phenomena arising from the nanoconfinement of phase change materials into the silica pores are discussed from both theoretical and practical standpoints. The lessons learned so far in designing efficient composite PCMs using porous silica matrices are presented, as well as the future perspectives on improving the heat storage materials

Embedding Polyphenols Extract from Grape Marc into Inorganic Supports with Enhanced Stability

Grape marc is a residue from the wine industry that. [...

Mesoporous Silica and Titania-Based Materials for Stability Enhancement of Polyphenols

To improve phytochemical stability, polyphenolic extracts prepared from Salvia officinalis L., which is a valuable source of phytocompounds with health benefits, were embedded into mesopores of silica, titania, or titania-ceria materials. Ethanolic and hydroalcoholic extracts were prepared by conventional, microwave- or ultrasound-assisted extraction. The influence of the extraction conditions on chemical profile, radical scavenger activity (RSA), and antimicrobial potential of the extracts was assessed. The extracts were characterized by spectrophotometric determination of total polyphenols, flavonoids, chlorophyll pigment contents, as well as RSA. A reverse phase HPLC- PDA analysis was performed for the identification and quantification of extract polyphenols. The extract-loaded materials exhibited an enhanced RSA compared to the free extract after several months of storage, resulting in better polyphenol stability over time following embedding into a mesoporous matrix. Selected extracts free and embedded into mesoporous support were tested against Pseudomonas aeruginosa ATCC 27853, Escherichia coli ATCC 25922, and Staphylococcus aureus ATCC 25923; the best antimicrobial activity was obtained for S. aureus. A slight improvement in antimicrobial activity was observed for the ethanolic extract prepared by ultrasound-assisted extraction following embedding into the TiO2 matrix compared to MCM-41 silica due to the support contribution

Resveratrol Encapsulation and Release from Pristine and Functionalized Mesoporous Silica Carriers

Resveratrol, a naturally occurring polyphenol, has attracted significant attention due to its antioxidant, cardioprotective and anticancer potential. However, its low aqueous solubility limits resveratrol bioavailability and use. In this work, different mesoporous silica matrices were used to encapsulate the polyphenol and to increase its dissolution rate. Pristine MCM-41, MCM-48, SBA-15, SBA-16, FDU-12 and MCF silica were obtained. The influence of SBA-15 functionalized with aminopropyl, isocyanate, phenyl, mercaptopropyl, and propionic acid moieties on resveratrol loading and release profiles was also assessed. The cytotoxic effects were evaluated for mesoporous carriers and resveratrol-loaded samples against human lung cancer (A549), breast cancer (MDA-MB-231) and human skin fibroblast (HSF) cell lines. The effect on apoptosis and cell cycle were assayed for selected resveratrol-loaded carriers. The polyphenol molecules are encapsulated only inside the mesopores, mostly in amorphous state. All materials containing either pristine or functionalized silica carriers increased polyphenol dissolution rate. The influence of the physico-chemical properties of the mesoporous carriers and resveratrol–loaded supports on the kinetic parameters was identified. Resv@SBA-15-SH and Resv@SBA-15-NCO samples exhibited the highest anticancer effect against A549 cells (IC50 values were 26.06 and 36.5 µg/mL, respectively) and against MDA-MB-231 (IC50 values were 35.56 and 19.30 µg/mL, respectively), which highlights their potential use against cancer

Nanoplatforms for Irinotecan Delivery Based on Mesoporous Silica Modified with a Natural Polysaccharide

Natural compounds are an important source of beneficial components that could be used in cancer therapy along with well-known cytostatic agents to enhance the therapeutic effect while targeting tumoral tissues. Therefore, nanoplatforms containing mesoporous silica and a natural polysaccharide, ulvan, extracted from Ulva Lactuca seaweed, were developed for irinotecan. Either mesoporous silica-ulvan nanoplatforms or irinotecan-loaded materials were structurally and morphologically characterized. In vitro drug release experiments in phosphate buffer solution with a pH of 7.6 emphasized the complete recovery of irinotecan in 8 h. Slower kinetics were obtained for the nanoplatforms with a higher amount of natural polysaccharide. Ulvan extract proved to be biocompatible up to 2 mg/mL on fibroblasts L929 cell line. The irinotecan-loaded nanoplatforms exhibited better anticancer activity than that of the drug alone on human colorectal adenocarcinoma cells (HT-29), reducing their viability to 60% after 24 h. Moreover, the cell cycle analysis proved that the irinotecan loading onto developed nanoplatforms caused an increase in the cell number trapped at G0/G1 phase and influenced the development of the tumoral cells

Cerium-Containing Mesoporous Bioactive Glasses (MBGs)-Derived Scaffolds with Drug Delivery Capability for Potential Tissue Engineering Applications

Finding innovative solutions to improve the lives of people affected by trauma, bone disease, or aging continues to be a challenge worldwide. Tissue engineering is the most rapidly growing area in the domain of biomaterials. Cerium-containing MBG-derived biomaterials scaffolds were synthesized using polymethyl methacrylate (PMMA) as a sacrificial template. The obtained scaffolds were characterized by X-ray powder diffraction (XRPD), infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The Ce4+/Ce3+ ratio in the scaffolds was estimated. In vitro testing revealed good cytocompatibility of the investigated scaffolds in mouse fibroblast cell line (NCTC clone L929). The results obtained regarding bioactivity, antibacterial activity, and controlled drug delivery functions recommend these scaffolds as potential candidates for bone tissue engineering applications

Mechanochemical Synthesis of Resveratrol–Piperazine Cocrystals

The 1:1 resveratrol–piperazine cocrystal was successfully synthesized and scaled-up to 300 g scale with the mechanochemical method, as a result of investigating key process parameters, namely the solvent and the grinding time. The use of water, ethanol or ethanol–water mixtures and reaction times up to 50 min were evaluated relative to the dry grinding process. Cocrystal formation and purity were monitored through X-ray diffraction and calorimetry measurements. The dry grinding resulted in an incomplete cocrystal formation, while the use of water or water–ethanol mixture yielded a monohydrate solid phase. Pure ethanol was found to be the optimal solvent for large-scale cocrystallization, as it delivered cocrystals with high crystallinity and purity after 10–30 min grinding time at the laboratory scale. Notably, a relatively fast reaction time (30–60 min) was sufficient for the completion of cocrystallization at larger scales, using a planetary ball mill and a plant reactor. Also, the obtained cocrystal increases the aqueous solubility of resveratrol by 6%–16% at pH = 6.8. Overall, this study highlights the potential of solvent-assisted mechanochemical synthesis as a promising new approach for the efficient production of pure resveratrol–piperazine cocrystals

Comparison between Two Different Synthesis Methods of Strontium-Doped Hydroxyapatite Designed for Osteoporotic Bone Restoration

Development of efficient controlled local release of drugs that prevent systemic side effects is a challenge for anti-osteoporotic treatments. Research for new bone-regeneration materials is of high importance. Strontium (Sr) is known as an anti-resorptive and anabolic agent useful in treating osteoporosis. In this study, we compared two different types of synthesis used for obtaining nano hydroxyapatite (HA) and Sr-containing nano hydroxyapatite (SrHA) for bone tissue engineering. Synthesis of HA and SrHA was performed using co-precipitation and hydrothermal methods. Regardless of the synthesis route for the SrHA, the intended content of Sr was 1, 5, 10, 20, and 30 molar %. The chemical, morphological, and biocompatibility properties of HA and SrHA were investigated. Based on our results, it was shown that HA and SrHA exhibited low cytotoxicity and demonstrated toxic behavior only at higher Sr concentrations