Structural and surface studies of luminescent Ca/Eu phosphate nanomaterials: From the bulk to surface features.

Three luminescent Eu-containing phosphate materials (Ca-doped europium phosphate monohydrate, Eu-doped carbonated-apatite, and europium phosphate monohydrate) were prepared and analyzed on the level of bulk structure and surface properties and compared to the biomimetic non-luminescent counterpart hydroxyapatite. Europium-containing phosphate materials exhibited nanosized dimensions but different luminescence emissions and luminescence lifetimes depending on their crystalline structures (i.e., lanthanide phosphate or apatites) and chemical composition. The introduction of Eu in the crystal lattice leads to a notable decrease in the overall Lewis acidity of the surface cationic sites detected by CO probing. Further, the mixed Eu/Ca-containing materials surfaces were found to be very similar to the reference hydroxyapatite in terms of water adsorption energy, while the pure europium phosphate resulted to have the notably higher energy values of direct interaction of water molecules with the surface cations with no detected propagation of this effect towards water overlayers.

Improved Performance of Solid Polymer Electrolyte for Lithium-Metal Batteries via Hot Press Rolling.

Solid-state batteries (SSBs) are gaining attention as they promise to provide better safety and a higher energy density than conventional liquid electrolyte batteries. Solid polymer electrolytes (SPEs) are promising candidates due to their flexibility providing better interfacial contact between electrodes and the electrolyte. However, SPEs exhibit very low ionic conductivity at ambient temperatures, which prevents their practical use in batteries. Herein, a simple and effective technique of hot press rolling is demonstrated to improve ionic conductivity and, hence, the performance of polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP)-based solid polymer electrolyte. Applying hot press rolling to the electrolyte membrane induced structural changes in the grain boundaries, which resulted in a reduction in the crystallinity of the material and, hence, an increase in the amorphous phase of the material, which eased the movement of the lithium ions within the material. This technique also improved the surface of the membrane, making it homogeneous and smoother, which resulted in better interfacial contact between the electrodes and electrolyte. Electrochemical tests were carried out on electrolyte membranes treated with and without hot press rolling to evaluate the effect of the treatment. The hot pressed electrolyte membrane showed significant improvements in its ionic conductivity and transference number. The cycling performance of the LFP/Li batteries using a hot press rolled electrolyte was also evaluated, which gave a specific discharge capacity of 134 mAh/g at 0.1 C. These results demonstrate that hot press rolling can have a significant effect on the electrochemical performance of solid polymer electrolytes.

Microbial Volatile Organic Compound (VOC)-Driven Dissolution and Surface Modification of Phosphorus-Containing Soil Minerals for Plant Nutrition: An Indirect Route for VOC-Based Plant-Microbe Communications.

We investigated the ability of microbial volatile organic compounds (MVOCs) emitted by Bacillus megaterium (a well-known MVOC producer) to modify the dissolution kinetics and surface of hydroxyapatite, a natural soil mineral. Facilitated phosphate release was induced by the airborne MVOCs in a time-dependent manner. Use of each standard chemical of the MVOCs then revealed that acetic and oxalic acids are crucial for the phenomenon. In addition, the ability of such MVOCs to engineer the apatite surfaces was evidenced by FT-IR spectra showing the COO- band variation with incubation time and the prolonged acceleration of phosphate release during the negligible acidification of the hydroxyapatite-containing solutions. The formation of calcium oxalate was revealed through SEM-EDS and XRD analyses, suggesting that MVOC oxalic acid interacts with calcium ions, leading to the precipitation of calcium oxalate, thus preventing the recrystallization of calcium phosphates. Gel- and soil-based plant cultivation tests employing Arabidopsis thaliana and solid calcium phosphates (i.e., nano- and microsized hydroxyapatites and calcium phosphate dibasic) demonstrated that these MVOC mechanisms facilitate plant growth by ensuring the prolonged supply of plant-available phosphate. The relationship between the growth enhancement and the particle size of the calcium phosphates also substantiated the MVOC sorption onto soil minerals related to plant growth. Given that most previous studies have assumed that MVOCs are a molecular lexicon directly detected by the dedicated sensing machinery of plants, our approach provides a new mechanistic view of the presence of abiotic mediators in the interaction between plants and microbes via MVOCs.

Assessment of In-Situ Gelling Microemulsion Systems upon Temperature and Dilution Condition for Corneal Delivery of Bevacizumab.

Bevacizumab (BVZ), a recombinant humanized monoclonal antibody, has recently been proposed as a topical application in the treatment of anterior segment neovascularization; however, as there are some disadvantages in the administration of common eye-drops, ophthalmic topical drug delivery systems are under study to improve the precorneal residence time, reducing the frequency of administration. In this work, oil-in-water and water-in-oil BVZ-loaded microemulsions are developed, able to increase their viscosity, either by the formation of a liquid-crystalline structure upon aqueous dilution, thanks to the presence of Epikuron® 200 and polysorbate 80, or by body-temperature-induced jellification for the presence of Pluronic® F127 aqueous solution as an external phase. In oil-in-water microemulsion, hydrophobic ion pairs of BVZ were also prepared, and their incorporation was determined by release studies. Microemulsions were characterized for rheological behavior, corneal opacity, in vitro corneal permeation, and adhesion properties. The studied microemulsions were able to incorporate BVZ (from 1.25 to 1.6 mg/mL), which maintained dose-dependent activity on retinal pigment epithelial ARPE-19 cell lines. BVZ loaded in microemulsions permeated the excised cornea easier (0.76-1.56% BVZ diffused, 4-20% BVZ accumulated) than BVZ commercial solution (0.4% BVZ diffused, 5% accumulated) and only a mild irritation effect on the excised cornea was observed. The good adhesion properties as well the increased viscosity after application, under conditions that mimic the corneal environment (from 1 × 103 to more than 100 × 103 mPa·s), might prolong precorneal residence time, proving these systems could be excellent topical BVZ release systems.

Selenium-doped hydroxyapatite nanoparticles for potential application in bone tumor therapy.

In the present study we have studied the incorporation and release of selenite ions (SeO32-) in hydroxyapatite nanoparticles for the treatment of bone tumors. Two types of selenium-doped hydroxyapatite (HASe) nanoparticles (NPs) with a nominal Se/(P + Se) molar ratio ranging from 0.01 up to 0.40 have been synthesized by a new and mild wet method. The two series of samples were thoroughly characterized and resulted to be slightly different in chemical composition, but they had similar properties in terms of morphology and degree of crystallinity. Selenium release from HASe was investigated under neutral and acidic conditions to simulate both healthy tissues and the low-pH environment surrounding a tumor mass, respectively. The comparison of the release profiles at two pH values clearly showed the possibility of modulating the Se release by simply changing the amount of Se in the HASe particles. The correlation between the physicochemical properties of HASe and their dissolution as a function of pH has been also investigated to facilitate future application of the NPs as chemotherapeutic adjuvant agents. Finally, the cytotoxic activity of HASe was evaluated using prostate (PC3) and breast (MDA-MB-231) cancer cells as well as healthy human bone marrow stem cells (hBMSc). HASe NPs exerted a good cytocompatibility at low concentration of Se but, with high Se doping concentration, they displayed strong cytotoxicity.

Phospholipid distribution in the cytoplasmic membrane of Gram-negative bacteria is highly asymmetric, dynamic, and cell shape-dependent.

The distribution of phospholipids across the inner membrane (IM) of Gram-negative bacteria is unknown. We demonstrate that the IMs of Escherichia coli and Yersinia pseudotuberculosis are asymmetric, with a 75%/25% (cytoplasmic/periplasmic leaflet) distribution of phosphatidylethanolamine (PE) in rod-shaped cells and an opposite distribution in E. coli filamentous cells. In initially filamentous PE-lacking E. coli cells, nascent PE appears first in the periplasmic leaflet. As the total PE content increases from nearly zero to 75%, cells progressively adopt a rod shape and PE appears in the cytoplasmic leaflet of the IM. The redistribution of PE influences the distribution of the other lipids between the leaflets. This correlates with the tendency of PE and cardiolipin to regulate antagonistically lipid order of the bilayer. The results suggest that PE asymmetry is metabolically controlled to balance temporally the net rates of synthesis and translocation, satisfy envelope growth capacity, and adjust bilayer chemical and physical properties.

Towards the control of the biological identity of nanobiomaterials: Impact of the structure of 011¯0 surface terminations of nanohydroxyapatite on the conformation of adsorbed proteins.

High-resolution transmission electron microscopy, ζ-potential and in-situ IR spectroscopy of adsorbed CO were combined for elucidating the ratio between {011¯0}_ Ca-rich: {011¯0}_ P-rich terminations of {011¯0} facets, i.e. the surfaces with the highest morphological importance, in two nanohydroxyapatite samples. Bovine serum albumin was found to form at least a monolayer on the surface left accessible to protein molecules by the agglomeration of nanoparticles when suspended in the buffered incubation medium. Noticeably, the conformation of adsorbed proteins appeared sensitive to the ratio between the two types of {011¯0} terminations, also resulting in a difference in the surface exposed toward the exterior by the adsorbed protein layer(s).

Enzyme activation by alternating magnetic field: Importance of the bioconjugation methodology.

Iron oxide nanoparticles (NPs) are attractive materials for enzyme immobilization and, thanks to their superparamagnetism, can be accessed by remote stimuli. This can be exploited to activate molecules that are not remotely actuable. Here, we demonstrate that thermophilic enzymes chemically linked to NPs can be activated in a "wireless" fashion by an external alternate magnetic field (AMF). To this aim, we have conjugated, with different binding strategies, the thermophilic enzymes α-amylase and l-aspartate oxidase to iron oxide NPs obtaining NP-enzyme systems with activities depending on the different orientations and stretching of the enzymes. Since enzyme activation occurs without a significant rise of the "overall" temperature of the systems, we have speculated a local NP-enzyme heating that does not immediately interest the rest of the solution that remains at relatively low temperature, low enough to allow non-thermophilic enzymes to work together with the NP-conjugated thermophilic enzymes. Nanoactuation of thermophilic enzymes by AMF has potential applications in different fields. Indeed, multi-enzymatic processes with enzymes with different temperature optima could be carried out in the same reaction pot and thermolabile products could be efficiently produced by thermophilic enzymes without suffering for the high temperatures. Moreover, our findings represent a proof of concept of the possibility to achieve a fine-tuning of the enzyme-NP system with the aim to intervene in cell metabolism.

On the surface effects of citrates on nano-apatites: evidence of a decreased hydrophilicity.

The surface structure and hydrophilicity of synthetic nanocrystalline apatite with strongly bound citrates on their surface are here investigated at the molecular level, by combining advanced IR spectroscopy, microgravimetry and adsorption microcalorimetry. Citrate are found to form unidentate-like and ionic-like complexes with surface Ca2+ ions, with a surface coverage closely resembling that present in bone apatite platelets (i.e., 1 molecule/(n nm)2, with n ranging between 1.4 and 1.6). These surface complexes are part of a hydrated non-apatitic surface layer with a sub-nanometre thickness. Noticeably, it is found that the hydrophilicity of the nanoparticles, measured in terms of adsorption of water molecules in the form of multilayers, decreases in a significant extent in relation to the presence of citrates, most likely because of the exposure toward the exterior of -CH2 groups. Our findings provide new insights on the surface properties of bio-inspired nano-apatites, which can be of great relevance for better understanding the role of citrate in determining important interfacial properties, such as hydrophobicity, of bone apatite platelets. The evaluation and comprehension of surface composition and structure is also of paramount interest to strictly control the functions of synthetic biomaterials, since their surface chemistry strongly affects the hosting tissue response.