Controlling thermal expansion and phase transitions in Ca1-xSrxMnO3-δ by Sr-content.

Perovskite oxides of the general formula ABO3-δ, with A and B being metal cations, present themselves in various crystal structures that originate from a distorted ideal cubic perovskite. Understanding how composition, temperature, atmosphere and reduction extent of these non-stoichiometric redox materials induce structural changes on an atomic, as well as macroscopic, level is crucial to transfer newly developed materials to industrial scale applications in the redox-based energy conversion sector. Herein, Ca1-xSrxMnO3-δ (x ∈ [0,0.2]) and its micro- and macroscopic structural changes at elevated temperatures and varying oxygen partial pressure are analyzed by means of in situ high temperature XRD, DSC and dilatometry. Results are expanded by room temperature XRD of compositions with higher Sr-content up to x = 0.4. By adjusting the Sr-content, the formed crystal structure can be governed and thermal expansion can be impacted beneficially in the context of future applications utilizing monolithic structures. Phase transitions from orthorhombic to cubic were found to shift from 900 °C to 830 °C under air and to even lower temperatures under 1% O2 atmosphere. Small amounts of Sr-content (5-10%) stabilize the macroscopic structural integrity by improving the reversibility of the cyclic thermal expansion and contraction in a 1% O2 atmosphere. However, at Sr-contents of 20% an increased irreversible residual expansion within each thermal cycle becomes apparent and shows that such improvements do not follow a linear dependency with Sr-content, but most benefits in this context can be found at Sr-contents below 20%. The results demonstrate the sensitivity of such materials micro- and macroscopic characteristics to composition. In the context of utilization of monolithic structures, fabricated entirely from Ca1-xSrxMnO3-δ, in thermochemical or thermoelectric applications, the results have considerable significance as minor A-site Sr-substitution can substantially improve macroscopic stability of monolithic structures over multiple thermal cycles. Besides the often solely regarded thermodynamic characteristic, this work demonstrates the importance to consider the impact of composition on structural behavior in materials design processes including perovskites for thermochemical applications.

Oral Drug Delivery Systems Based on Ordered Mesoporous Silica Nanoparticles for Modulating the Release of Aprepitant.

Two different types of ordered mesoporous nanoparticles, namely MCM-41 and MCM-48, with similar pore sizes but different pore connectivity, were loaded with aprepitant via a passive diffusion method. The percentage of the loaded active agent, along with the encapsulation efficiency, was evaluated using High-performance Liquid Chromatography (HPLC) analysis complemented by Thermogravimetric Analysis (TGA). The determination of the pore properties of the mesoporous particles before and after the drug loading revealed the presence of confined aprepitant in the pore structure of the particles, while Powder X-ray Diffractometry(pXRD), Differential Scanning Calorimetry (DSC), and FTIR experiments indicated that the drug is in an amorphous state. The release profiles of the drug from the two different mesoporous materials were studied in various release media and revealed an aprepitant release up to 45% when sink conditions are applied. The cytocompatibility of the silica nanoparticles was assessed in Caco-2 cell monolayers, in the presence and absence of the active agent, suggesting that they can be used as carriers of aprepitant without presenting any toxicity in vitro.

One-Pot Synthesis of Functionalised rGO/AgNPs Hybrids as Pigments for Highly Conductive Printing Inks.

This work provides a method for the development of conductive water-based printing inks for gravure, flexography and screen-printing incorporating commercial resins that are already used in the printing industry. The development of the respective conductive materials/pigments is based on the simultaneous (in one step) reduction of silver salts and graphene oxide in the presence of 2,5-diaminobenzenesulfonic acid that is used for the first time as the common in-situ reducing agent for these two reactions. The presence of aminophenylsulfonic derivatives is essential for the reduction procedure and in parallel leads to the enrichment of the graphene surface with aminophenylsulfonic groups that provide a high hydrophilicity to the final materials/pigments.

Graphene-Based Composites with Silver Nanowires for Electronic Applications.

Graphene/metal nanocomposites have shown a strong potential for use in electronic applications. In particular, the combination of silver nanowires (AgNWs) with graphene derivatives leads to the formation of an efficient conductive network, thus improving the electrical properties of a composite. This work focused on developing highly conductive hydrophilic hybrids of simultaneously functionalized and reduced graphene oxide (f-rGO) and AgNWs in different weight ratios by following two different synthetic routes: (a) the physical mixture of f-rGO and AgNWs, and (b) the in situ reduction of GO in the presence of AgNWs. In addition, the role of AgNWs in improving the electrical properties of graphene derivatives was further examined by mixing AgNWs with a hybrid of few-layered graphene with functionalized multiwalled carbon nanotubes (FLG/MWNT-f-OH). The studied materials showed a remarkable improvement in the overall electrical conductivity due to the synergistic effect of their components, which was proportional to the percentage of Ag and dependent on the procedure of the hybrid formation. One of the f-rGO/AgNWs composites was also selected for the preparation of gravure printing inks that were tested to determine their rheological and printing properties. All of the f-rGO/AgNWs composites were shown to be very promising materials for use as conductive inks for flexible electronics.

Biodistribution of Mesoporous Carbon Nanoparticles via Technetium-99m Radiolabelling after Oral Administration to Mice.

The use of ordered mesoporous matrices, and in particular carbon-based mesoporous nanoparticles has shown great potential towards enhancing the bioavailability of orally administered drugs. Nevertheless, elucidation of the in vivo absorption, distribution, and excretion of such carriers is essential for understanding their behaviour, and radiolabelling provides a very useful way to track their occurrence inside the body. In this work, uniform spherical CMK-1-type ordered mesoporous carbon nanoparticles have been radiolabelled with Technetium-99m (99mTc) and traced after oral administration to mice. Ex vivo biodistribution studies showed that the radiolabelled nanoparticles accumulated almost exclusively in the gastrointestinal tract; complete elimination of the radiotracer was observed within 24 h after administration, with practically no uptake into other main organs. These findings along with the results from in vitro stability studies indicate that the spherical carbon nanoparticles examined could be safely used as drug carriers with minimal side effects, but also support the great value of radiolabelling methods for monitoring the particles' behaviour in vivo.

Embedding Ordered Mesoporous Carbons into Thermosensitive Hydrogels: A Cutting-Edge Strategy to Vehiculate a Cargo and Control Its Release Profile.

The high drug loading capacity, cytocompatibility and easy functionalization of ordered mesoporous carbons (OMCs) make them attractive nanocarriers to treat several pathologies. OMCs' efficiency could be further increased by embedding them into a hydrogel phase for an in loco prolonged drug release. In this work, OMCs were embedded into injectable thermosensitive hydrogels. In detail, rod-like (diameter ca. 250 nm, length ca. 700 nm) and spherical (diameter approximately 120 nm) OMCs were synthesized by nanocasting selected templates and loaded with ibuprofen through a melt infiltration method to achieve complete filling of their pores (100% loading yield). In parallel, an amphiphilic Poloxamer® 407-based poly(ether urethane) was synthesized (Mn¯ 72 kDa) and solubilized at 15 and 20% w/v concentration in saline solution to design thermosensitive hydrogels. OMC incorporation into the hydrogels (10 mg/mL concentration) did not negatively affect their gelation potential. Hybrid systems successfully released ibuprofen at a slower rate compared to control gels (gels embedding ibuprofen as such), but with no significant differences between rod-like and spherical OMC-loaded gels. OMCs can thus work as effective drug reservoirs that progressively release their payload over time and also upon encapsulation in a hydrogel phase, thus opening the way to their application to treat many different pathological states (e.g., as topical medications).

Engineered pH-Responsive Mesoporous Carbon Nanoparticles for Drug Delivery.

In this work, two types of mesoporous carbon particles with different morphology, size, and pore structure have been functionalized with a self-immolative polymer sensitive to changes in pH and tested as drug nanocarriers. It is shown that their textural properties allow significantly higher loading capacity compared to typical mesoporous silica nanoparticles. In vial release experiments of a model Ru dye at pH 7.4 and 5 confirm the pH-responsiveness of the hybrid systems, showing that only small amounts of the cargo are released at physiological pH, whereas at slightly acidic pH (e.g., that of lysosomes), self-immolation takes place and a significant amount of the cargo is released. Cytotoxicity studies using human osteosarcoma cells show that the hybrid nanocarriers are not cytotoxic by themselves but induce significant cell growth inhibition when loaded with a chemotherapeutic drug such as doxorubicin. In preparation of an in vivo application, in vial responsiveness of the hybrid system to short-term pH-triggering is confirmed. The consecutive in vivo study shows no substantial cargo release over a period of 96 h under physiological pH conditions. Short-term exposure to acidic pH releases an experimental fluorescent cargo during and continuously after the triggering period over 72 h.

Silver Decorated Mesoporous Carbons for the Treatment of Acute and Chronic Wounds, in a Tissue Regeneration Context.

INTRODUCTION: Silver decorated mesoporous carbons are interesting systems that may offer effective solutions for advanced wound care products by combining the well-known anti-microbial activity of silver nanoparticles with the versatile properties of ordered mesoporous carbons. Silver is being used as a topical antimicrobial agent, especially in wound repair. However, while silver shows bactericidal properties, it is also cytotoxic at high concentrations. Therefore, the incorporation of silver into ordered mesoporous carbons allows to exploit both silver's biological effects and mesoporous carbons' biocompatibility and versatility with the purpose of conceiving silver-doped materials in light of the growing health concern in wound care. METHODS: The wound healing potential of an ordered mesoporous carbon also doped with two different loadings of silver nanoparticles (2 wt% and 10 wt%), was investigated through a biological assessment study based on different assays (cell viability, inflammation, antibacterial tests, macrophage-conditioned fibroblast and human keratinocyte cell cultures). RESULTS: The results show silver-doped ordered mesoporous carbons to positively condition cell viability, with a cell viability percentage >70% even for 10 wt% Ag, to modulate the expression of inflammatory cytokines and of genes involved in tissue repair (KRT6a, VEGFA, IVN) and remodeling (MMP9, TIMP3) in different cell systems. Furthermore, along with the biocompatibility and the bioactivity, the silver-doped ordered mesoporous carbons still retain an antibacterial effect, as shown by a maximum of 13.1% of inhibited area in the Halo test. The obtained results clearly showed that the silver-doped ordered mesoporous carbons exhibit both good biocompatibility and antibacterial effect with enhanced re-epithelialization, angiogenesis promotion and tissue regeneration. DISCUSSION: These findings suggest that the exceptional properties of silver-doped ordered mesoporous carbons could be exploited in the treatment of acute and chronic wounds and that such carbon materials could be potential candidates for use in medical devices for wound healing purposes, in particular, the 10 wt% loading, as the results showed to be the most effective.

Electrosprayed mesoporous particles for improved aqueous solubility of a poorly water soluble anticancer agent: in vitro and ex vivo evaluation.

Encapsulation of poorly water-soluble drugs into mesoporous materials (e.g. silica) has evolved as a favorable strategy to improve drug solubility and bioavailability. Several techniques (e.g. spray drying, solvent evaporation, microwave irradiation) have been utilized for the encapsulation of active pharmaceutical ingredients (APIs) into inorganic porous matrices. In the present work, a novel chalcone (KAZ3) with anticancer properties was successfully synthesized by Claisen-Schmidt condensation. KAZ3 was loaded into mesoporous (SBA-15 and MCM-41) and non-porous (fumed silica, FS) materials via two techniques; electrohydrodynamic atomization (EHDA) and solvent impregnation. The effect of both loading methods on the physicochemical properties of the particles (e.g. size, charge, entrapment efficiency, crystallinity, dissolution and permeability) was investigated. Results indicated that EHDA technique can load the active in a complete amorphous form within the pores of the silica particles. In contrast, reduced crystallinity (~79%) was obtained for the solvent impregnated formulations. EHDA engineered formulations significantly improved drug dissolution up to 30-fold, compared to the crystalline drug. Ex vivo studies showed EHDA formulations to exhibit higher permeability across rat intestine than their solvent impregnated counterparts. Cytocompatibility studies on Caco-2 cells demonstrated moderate toxicity at high concentrations of the anticancer agent. The findings of the present study clearly show the immense potential of EHDA as a loading technique for mesoporous materials to produce poorly water-soluble API carriers of high payload at ambient conditions. Furthermore, the scale up potential in EHDA technologies indicate a viable route to enhance drug encapsulation and dissolution rate of loaded porous inorganic materials.

Development of new drug delivery system based on ordered mesoporous carbons: characterisation and cytocompatibility studies.

Ordered mesoporous carbons that encapsulate the poorly soluble compounds ibuprofen and indomethacin were systematically studied by means of X-ray diffraction (XRD), differential scanning calorimetry (DSC) and X-ray photon electron spectroscopy (XPS). The results showed marked differences in the release profiles of the two drug molecules in simulated gastric fluids. In vitro toxicity profiles appear to be compatible with potential therapeutic applications bringing them to the forefront as carriers of poorly water soluble drugs.