Anhydrous Superprotonic Conductivity in the Zirconium Acid Triphosphate ZrH5 (PO4 )3.

The development of solid-state proton conductors with high proton conductivity at low temperatures is crucial for the implementation of hydrogen-based technologies for portable and automotive applications. Here, we report on the discovery of a new crystalline metal acid triphosphate, ZrH5 (PO4 )3 (ZP3), which exhibits record-high proton conductivity of 0.5-3.1×10-2  S cm-1 in the range 25-110 °C in anhydrous conditions. This is the highest anhydrous proton conductivity ever reported in a crystalline solid proton conductor in the range 25-110 °C. Superprotonic conductivity in ZP3 is enabled by extended defective frustrated hydrogen bond chains, where the protons are dynamically disordered over two oxygen centers. The high proton conductivity and stability in anhydrous conditions make ZP3 an excellent candidate for innovative applications in fuel cells without the need for complex water management systems, and in other energy technologies requiring fast proton transfer.

Immobilization of Alendronate on Zirconium Phosphate Nanoplatelets.

Different amounts of sodium-alendronate (ALN) were loaded into layered zirconium phosphates of alpha and gamma type (αZP and γZP) by means of topotactic exchange reactions of phosphate with ALN. In order to extend the exchange process to the less accessible interlayer regions, ALN solutions were contacted with colloidal dispersions of the layered solids previously exfoliated in single sheets by means of intercalation reaction of propylamine (for αZP) or acetone (for γZP). The ALN loading degree was determined by liquid P-nuclear magnetic resonance (NMR) and inductively coupled plasma (ICP), and it was reported as ALN/Zr molar ratios (Rs). The maximum R obtained for γZP was 0.34, while αZP was able to load a higher amount of ALN, reaching Rs equal to 1. The synthesized compounds were characterized by X-ray powder diffractometry, scanning electron microscopy (SEM), solid-state NMR, and infrared spectroscopy. The way the grafted organo-phosphonate groups were bonded to the layers of the host structure was suggested. The effect of ZP derivatives was assessed on cell proliferation, and the results showed that after 7 days of incubation, none of the samples showed a decrease in cell proliferation.

Alginate Ag/AgCl Nanoparticles Composite Films for Wound Dressings with Antibiofilm and Antimicrobial Activities.

Recently, silver-based nanoparticles have been proposed as components of wound dressings due to their antimicrobial activity. Unfortunately, they are cytotoxic for keratinocytes and fibroblasts, and this limits their use. Less consideration has been given to the use of AgCl nanoparticles in wound dressings. In this paper, a sustainable preparation of alginate AgCl nanoparticles composite films by simultaneous alginate gelation and AgCl nanoparticle formation in the presence of CaCl2 solution is proposed with the aim of obtaining films with antimicrobial and antibiofilm activities and low cytotoxicity. First, AgNO3 alginate films were prepared, and then, gelation and nanoparticle formation were induced by film immersion in CaCl2 solution. Films characterization revealed the presence of both AgCl and metallic silver nanoparticles, which resulted as quite homogeneously distributed, and good hydration properties. Finally, films were tested for their antimicrobial and antibiofilm activities against Staphylococcus epidermidis (ATCC 12228), Staphylococcus aureus (ATCC 29213), Pseudomonas aeruginosa (ATCC 15692), and the yeast Candida albicans. Composite films showed antibacterial and antibiofilm activities against the tested bacteria and resulted as less active towards Candida albicans. Film cytotoxicity was investigated towards human dermis fibroblasts (HuDe) and human skin keratinocytes (NCTC2544). Composite films showed low cytotoxicity, especially towards fibroblasts. Thus, the proposed sustainable approach allows to obtain composite films of Ag/AgCl alginate nanoparticles capable of preventing the onset of infections without showing high cytotoxicity for tissue cells.

Eco-Sustainable Silk Fibroin/Pomegranate Peel Extract Film as an Innovative Green Material for Skin Repair.

Skin disorders are widespread around the world, affecting people of all ages, and oxidative stress represents one of the main causes of alteration in the normal physiological parameters of skin cells. In this work, we combined a natural protein, fibroin, with antioxidant compounds extracted in water from pomegranate waste. We demonstrate the effective and facile fabrication of bioactive and eco-sustainable films of potential interest for skin repair. The blended films are visually transparent (around 90%); flexible; stable in physiological conditions and in the presence of trypsin for 12 days; able to release the bioactive compounds in a controlled manner; based on Fickian diffusion; and biocompatible towards the main skin cells, keratinocytes and fibroblasts. Furthermore, reactive oxygen species (ROS) production tests demonstrated the high capacity of our films to reduce the oxidative stress induced in cells, which is responsible for various skin diseases.

Synthesis, Crystal Structure, and Antibacterial Properties of Silver-Functionalized Low-Dimensional Layered Zirconium Phosphonates.

New insoluble layered zirconium phosphate carboxyaminophosphonates (ZPs), with the general formula Zr2(PO4)H5[(O3PCH2)2N(CH2)nCOO]2·mH2O (n = 3, 4, and 5), have been prepared and characterized. The crystal structure for n = 3 and 4 samples was determined ab initio from X-ray powder diffraction data. The structure for n = 3 was monoclinic in space group C2/c with the following unit cell parameters: a = 34.346(1) Å, b = 8.4930(2) Å, c = 9.0401(2) Å, and ß = 97.15(1)°. The structure for n = 4 was triclinic in space group P1̅ with the following unit cell parameters: a = 17.9803(9) Å, b = 8.6066(4) Å, c = 9.0478(3) Å, α = 90.466(3)°, ß = 94.910(4)°, and γ = 99.552(4)°. The two structures had the same connectivity as Zr phosphate glycine diphosphonate (n = 1), as previously reported. By intercalation of short amines, these layered compounds were exfoliated in single lamella or packets of a few lamellae, which formed colloidal dispersions in water. After a thorough characterization, the dispersed lamellae were functionalized with Ag nanoparticles, which were grown in situ on the surface of exfoliated lamellae. Finally, their antimicrobial activity was tested on several Gram-positive and Gram-negative bacteria. All of these systems were found to be active against the four pathogens most frequently isolated from orthopedic prosthetic infections and often causative of nosocomial infections. Interestingly, they were found to express powerful inhibitory activity even against bacterial strains exhibiting a relevant profile of antibiotic resistance such as Staphylococcus aureus ATCC 700699.

Polydopamine Coated CeO2 as Radical Scavenger Filler for Aquivion Membranes with High Proton Conductivity.

CeO2 nanoparticles were coated with polydopamine (PDA) by dopamine polymerization in water dispersions of CeO2 and characterized by Infrared and Near Edge X-ray Absorption Fine Structure spectroscopy, Transmission Electron Microscopy, Thermogravimetric analysis and X-ray diffraction. The resulting materials (PDAx@CeO2, with x = PDA wt% = 10, 25, 50) were employed as fillers of composite proton exchange membranes with Aquivion 830 as ionomer, to reduce the ionomer chemical degradation due to hydroxyl and hydroperoxyl radicals. Membranes, loaded with 3 and 5 wt% PDAx@CeO2, were prepared by solution casting and characterized by conductivity measurements at 80 and 110 °C, with relative humidity ranging from 50 to 90%, by accelerated ex situ degradation tests with the Fenton reagent, as well as by in situ open circuit voltage stress tests. In comparison with bare CeO2, the PDA coated filler mitigates the conductivity drop occurring at increasing CeO2 loading especially at 110 °C and 50% relative humidity but does not alter the radical scavenger efficiency of bare CeO2 for loadings up to 4 wt%. Fluoride emission rate data arising from the composite membrane degradation are in agreement with the corresponding changes in membrane mass and conductivity.

PVC grafted zinc oxide nanoparticles as an inhospitable surface to microbes.

Antimicrobial Polyvinyl chloride (PVC) was obtained by covalent bonding of zinc oxide nanoparticles, which have gained important achievements in antimicrobial fields because of their auspicious properties. This was achieved by grafting mercaptopropyltrimethoxysilane onto PVC, followed by the growth of zinc oxide nanoparticles covalently bonded on the polymer surface. In this study, the relationship between the physicochemical features of modified-surface PVC and antimicrobial activity on Staphylococcus aureus and Candida albicans was investigated. Zinc oxide with controllable morphologies (rods, rod flowers, and petal flowers) was synthesized on the polymer surface by tuning merely base-type and concentration using a hydrothermal process. The antimicrobial activity was more pronounced for rod flower morphology, because of their differences in microscopic parameters such as specific Zn-polar planes. This work provides an important hint for the safe use of PVC for biomedical devices by the structure surface tuning without injuring polymer bulk properties and a reduced risk of the covalently bonded nanoparticle dispersion in the host and the environment.

Bioinspired Reactive Interfaces Based on Layered Double Hydroxides-Zn Rich Hydroxyapatite with Antibacterial Activity.

This work is focused on the preparation and multi-technique characterization of potentially biocompatible reactive interfaces obtained by combining layered double hydroxides (LDHs) and hydroxyapatite (HA). Antimicrobial and osteoinductive metallic ions as Zn2+ and Ga3+ were chosen as intralayer constituents of LDH to obtain ZnAl and ZnAlGa systems. These LDHs, exchanged with dihydrogenphosphate anions, promoted the precipitation of HA on the LDH surface yielding HA@LDH composites. X-ray diffraction quantitative analysis, through the Rietveld refinement method, coupled with elemental analysis and micro-Raman spectroscopy showed the formation of a mixed Ca-Zn HA phase. Scanning electron microscopy revealed that HA, in the presence of LDH, grew preferentially along its a-axis, thus crystallizing mainly in the form of flake crystals. LDH and HA@LDH composites showed antibacterial activity against Staphylococcus aureus and Pseudomonas aeruginosa at not cytotoxic concentrations for human osteoblasts (hFob 1.19), especially when Ga cations were present in the LDH structure. The effect of the presence of HA in the composites on the bone-bonding ability and on human osteoblast proliferation was also investigated. The HA seemed to reduce the toxicity of the LDH toward human osteoblast while did not affect the bone-bonding ability. This multidisciplinary study provides the bio-chemical, structural characterization of new LDH and HA@LDH composites, evaluating also their bioactivity to be potentially applicable to titanium-based prostheses.

Synthesis and characterization of 1,2,4-triazolo[1,5-a]pyrimidine-2-carboxamide-based compounds targeting the PA-PB1 interface of influenza A virus polymerase.

Influenza viruses (Flu) are responsible for seasonal epidemics causing high rates of morbidity, which can dramatically increase during severe pandemic outbreaks. Antiviral drugs are an indispensable weapon to treat infected people and reduce the impact on human health, nevertheless anti-Flu armamentarium still remains inadequate. In search for new anti-Flu drugs, our group has focused on viral RNA-dependent RNA polymerase (RdRP) developing disruptors of PA-PB1 subunits interface with the best compounds characterized by cycloheptathiophene-3-carboxamide and 1,2,4-triazolo[1,5-a]pyrimidine-2-carboxamide scaffolds. By merging these moieties, two very interesting hybrid compounds were recently identified, starting from which, in this paper, a series of analogues were designed and synthesized. In particular, a thorough exploration of the cycloheptathiophene-3-carboxamide moiety led to acquire important SAR insight and identify new active compounds showing both the ability to inhibit PA-PB1 interaction and viral replication in the micromolar range and at non-toxic concentrations. For few compounds, the ability to efficiently inhibit PA-PB1 subunits interaction did not translate into anti-Flu activity. Chemical/physical properties were investigated for a couple of compounds suggesting that the low solubility of compound 14, due to a strong crystal lattice, may have impaired its antiviral activity. Finally, computational studies performed on compound 23, in which the phenyl ring suitably replaced the cycloheptathiophene, suggested that, in addition to hydrophobic interactions, H-bonds enhanced its binding within the PAC cavity.

Ionic and covalent crosslinking in chitosan-succinic acid membranes: Effect on physicochemical properties.

In this work, chitosan-succinic acid membranes were prepared by casting method and the physicochemical and mechanical properties of non-neutralized and neutralized with NaOH films were compared. Mechanical strength, flexibility, thermal stability and water-vapor permeability of chitosan membranes are significantly improved after neutralization. These improvements could be partly ascribed to the use of a dicarboxylic acid, which decreases the spacing between chitosan chains as a consequence of ionic crosslinking. Moreover, the addition of the strong base to the hydrogel promotes the formation of amide bonds, as suggested by FTIR analysis and demonstrated by acid-base titration. The favorable features of chitosan-succinic acid films as well as the possibility to easily incorporate drugs, enzymes, essential oils or other additives in the hydrogel, make such membranes suitable for many applications.

Whole genome integrity and enhanced developmental potential in ram freeze-dried spermatozoa at mild sub-zero temperature.

Freeze-dried spermatozoa typically shows a reduction in fertility primarily due to the DNA damage resulting from the sublimation process. In order to minimize the physical/mechanical damage resulting from lyophilization, here we focused on the freezing phase, comparing two cooling protocols: (i) rapid-freezing, where ram sperm sample is directly plunged into liquid nitrogen (LN-group), as currently done; (ii) slow-freezing, where the sample is progressively cooled to - 50 °C (SF-group). The spermatozoa dried in both conditions were analysed to assess residual water content by Thermal Gravimetric Analysis (TGA) and DNA integrity using Sperm Chromatin Structure Assay (SCSA). TGA revealed more than 90% of water subtraction in both groups. A minor DNA damage, Double-Strand Break (DSB) in particular, characterized by a lower degree of abnormal chromatin structure (Alpha-T), was detected in the SF-group, comparing to the LN-one. In accordance with the structural and DNA integrity data, spermatozoa from SF-group had the best embryonic development rates, comparing to LN-group: cleaved embryos [42/100 (42%) versus 19/75 (25.3%), P < 0.05, SL and LN respectively] and blastocyst formation [7/100 (7%) versus 2/75 (2.7%), P < 0.05, SF and LN respectively]. This data represents a significant technological advancement for the development of lyophilization as a valuable and cheaper alternative to deep-freezing in LN for ram semen.

Use of calcium carbonate as an excipient for release of poorly water soluble drugs: The case of carbamazepine.

Carbamazepine (CBZ) is a poorly water soluble drug owing to the Biopharmaceutic Classification System (BCS) class II. It is characterized by a variable bioavailability and by the presence of different polymorphs. In this paper the effects of CaCO3 on the physicochemical properties of CBZ and its solubility and release were evaluated. CaCO3 is a naturally non-toxic biomineral and was chosen because it is a safe, cheap and eco-friendly excipient able to dissolve in an acidic environment. Composites with different CBZ loadings were prepared by ball milling and antisolvent method. The composites were characterized by X-ray powder diffraction, differential scanning calorimetry analysis and attenuated total reflectance FT-IR which revealed that both the presence of CaCO3 and the preparation procedure affect the polymorphic form crystallinity and intermolecular interactions among the drug molecules. Scanning electron microscopy showed that small drug crystals with different crystalline forms were deposited on the surface of the CaCO3 particles. Solubility and dissolution tests showed an increase in the apparent solubility of CBZ and improved drug release. These results demonstrated that CaCO3 affected the drug release properties likely due to its pH-sensitive characteristics.

Biocompatible alginate silica supported silver nanoparticles composite films for wound dressing with antibiofilm activity.

Alginate films containing pyrogenic silica supported silver nanoparticles were prepared as potential wound dressings. First silica supported silver nanoparticles (CAB-O-SIL-Ag) were prepared via solid state sintering route without the use of any solvent and reducing agent. The obtained composite was characterized by X-ray powder diffraction, transmission electron microscopy and UV-vis spectroscopy which evidenced the presence of 8-20 nm spherical silver nanoparticles uniformly distributed and grown on the silica surface. Then the CAB-O-SIL-Ag was used as filler to prepare alginate films by casting method and successive gelation. Films with two different silver concentrations were prepared. They showed good hydration properties and a very slow silver release. Films exhibited antimicrobial and antibiofilm activities against Staphylococcus aureus and Pseudomonas aeruginosa and showed no cytotoxicity towards human skin keratinocytes and human fibroblasts HuDe.

Effect of Chemically Engineered Au/Ag Nanorods on the Optical and Mechanical Properties of Keratin Based Films.

In this work we report the preparation and characterization of free-standing keratin-based films containing Au/Ag nanorods. The effect of nanorods surface chemistry on the optical and mechanical properties of keratin composite films is fully investigated. Colloid nanorods confer to the keratin films interesting color effects due to plasmonic absorptions of the metal nanostructures. The presence of metal NRs induces also substantial change in the protein fluorescence emission. In particular, the relative contribution of the ordered-protein aggregates emission is enhanced by the presence of cysteine and thus strictly related to the surface chemistry of nanorods. The presence of more packed supramolecular structures in the films containing metal nanorods (in particular cysteine modified ones) is confirmed by ATR measurements. In addition, the films containing nanorods show a higher Young's modulus compared to keratin alone and again the effect is more pronounced for cysteine modified nanorods. Collectively, the reported results indicate the optical and mechanical properties of keratin composites films are related to a common property and can be tuned simultaneously, paving the way to the optimization and improvement of their performances and enhancing the exploitation of keratin composites in highly technological optoelectronic applications.

Investigating the effect of positional isomerism on the assembly of zirconium phosphonates based on tritopic linkers.

We report on the use of a novel tritopic phosphonic linker, 2,4,6-tris[3-(phosphonomethyl)phenyl]-1,3,5-triazine, for the synthesis of a layered zirconium phosphonate, named UPG-2. Comparison with the structure of the permanently porous UPG-1, based on the related linker 2,4,6-tris[4-(phosphonomethyl)phenyl]-1,3,5-triazine, reveals that positional isomerism disrupts the porous architecture in UPG-2 by preventing the formation of infinitely extended chains connected through Zr-O-P-O-Zr bonds. The presence of free, acidic P-OH groups and an extended network of hydrogen bonds makes UPG-2 a good proton conductor, reaching values as high as 5.7 × 10-4 S cm-1.

A new challenge for nanocrystalline α-zirconium phosphate: reaction with a diepoxyalkane.

New organic derivatives of α-zirconium phosphate (ZrP) were prepared by reaction of a gel of nanocrystalline ZrP with 1,2,7,8-diepoxyoctane (diepoxide), leading to the formation of P-O-C bonds. A series of compounds having composition Zr(O3POH)2-2x(O3POCH2CH(OH)(CH2)4CH(OH)CH2OPO3)x (hereafter indicated as ZrP(dep)x) were obtained by varying the diepoxide/Zr molar ratio in the range 0.25-1. The samples were characterized by elemental, thermal and X-ray powder diffraction analysis. The reaction turned out to be nearly quantitative, the x values of ZrP(dep)x being in the range 0.16 to 1.0. The interlayer distance slightly increased with increasing x, going from 12.7 to 13.2 Å. Interestingly, the materials easily intercalated alkanols at room temperature, both from liquid and vapor phases; it is noteworthy that ZrP(dep)0.30 was able to reversibly take up 42 wt% ethanol from the vapor phase, in agreement with the presence of available free space both in the interlayer and in the intercrystal region. Geometrical structural models in which the α-ZrP layers are connected by the dep chains were proposed to support the obtained results.

Antibacterial Properties of a Novel Zirconium Phosphate-Glycinediphosphonate Loaded with Either Zinc or Silver.

A novel compound consisting of a zirconium phosphate-glycinediphosphonate (ZPGly) has recently been introduced. This 2D-structured material forming nanosheets was exfoliated under appropriate conditions, producing colloidal aqueous dispersions (ZPGly-e) which were then loaded with zinc (Zn/ZPGly) or silver ions. Silver ions were subsequently reduced to produce metallic silver nanoparticles on exfoliated ZPGly nanosheets (Ag@ZPGly). In the search for new anti-infective materials, the present study investigated the properties of colloidal dispersions of ZPGly-e, Zn/ZPGly, and Ag@ZPGly. Ag@ZPGly was found to be a bactericidal material and was assayed to define its minimal inhibitory concentration (MIC) and minimal bactericidal concentration (MBC) on the five most prevalent pathogens of orthopaedic implant infections, namely: Staphylococcus aureus ATCC25923, Staphylococcus epidermidis RP62A, Enterococcus faecalis ATCC29212, Escherichia coli ATCC51739, and Pseudomonas aeruginosa ATCC27853. MIC and MBC were in the range of 125-250 µg/mL and 125-1000 µg/mL, respectively, with E. coli being the most sensitive species. Even colloidal suspensions of exfoliated ZPGly nanosheets and Zn/ZPGly exhibited some intrinsic antibacterial properties, but only at greater concentrations. Unexpectedly, Zn/ZPGly was less active than ZPGly-e.

Zirconium Carboxyaminophosphonate Nanosheets as Support for Ag Nanoparticles.

A layered insoluble inorganic-organic solid, namely zirconium phosphate glycine-N,N-bismethylphosphonate, was used to prepare dispersions of nanosheets to support active metals such as metallic silver nanoparticles and zinc ions. Zr phosphate-phosphonate microcrystals were first exfoliated with methylamine to produce a stable colloidal dispersion and then the methylamine was removed by treatment with hydrochloric acid. The obtained colloidal dispersion of Zr phosphate-phosphonate nanosheets was used to immobilize silver or zinc cations, via ion exchange, with the acidic protons of the sheets. The layered matrix showed a great affinity for the metal cations up taking all the added cations. The treatment of the dispersions containing silver ions with ethanol yielded metal silver nanoparticles grafted on the surface of the layered host. The samples were characterized by X-ray powder diffraction, elemental analysis transmission electron microscopy, and selected samples were submitted to antimicrobial tests. The nanocomposites based on Ag nanoparticles showed good bactericidal properties against the bacterial reference strain Staphylococcus epidermidis (S. epidermidis).

Nanostructured zinc oxide on silica surface: Preparation, physicochemical characterization and antimicrobial activity.

Zinc oxide nanoparticles were synthesized using two silica supports largely used in pharmaceutical field as excipients, Cab-O-Sil-H5 and Syloid 244 FP characterized by high surface area and different porosity. In order to evaluate the effects of different silica on nanoparticle chemical physical properties, composites (ZnO-SiO2) containing different amounts of ZnO nanoparticles were obtained and characterized by X-ray Powder Diffraction (XRPD), Transmission Electron Microscopy (TEM), Attenuated Transmission Reflectance (ATR), UV-vis spectroscopy and finally Photoluminescence (PL). Composites showed the presence of quite uniformly distributed zinc nanostructures on the silica surface with size in the range of 30-50 nm with an estimated specific surface area ranged from ca. 20 to 70 m2/g. The formation of a Zn-O-Si interface in ZnO-SiO2 was observed as well. Photoluminescence studies revealed that ZnO-SiO2 samples based on Cab-O-Sil present a higher contribution of oxygen vacancies per unit volume. Finally, the resulting composites were tested for antibacterial and antifungal activities. Whereas silica supports did not show any antibacterial and antifungal activities, most of the prepared composites, both with Cab-O-Sil-5H and Syloid 244 FP supports, resulted active against both bacteria and fungi. In particular the contingency analysis showed that the amount of zinc oxide in the composites was partly related to MIC results in bacteria (p = 0.059), whereas it showed an interesting p = 0.022 in yeast in the case of low amount of ZnO (10%). Thus, the described ZnO-SiO2 composites can be proposed for the preparation of both pharmaceutical formulations and medical disposals with antibacterial and antifungal activities.

Polydopamine Nanoparticle-Coated Polysulfone Porous Granules as Adsorbents for Water Remediation.

Water purification technologies possibly based on eco-sustainable, low cost, and multifunctional materials are being intensively pursued to resolve the current water scarcity and pollution. In this scenario, polysulfone hollow porous granules (PS-HPGs) prepared from scraps of the industrial production of polysulfone hollow fiber membranes were recently introduced as adsorbents and filtration materials for water and air treatment. Here, we report the functionalization of PS-HPGs with polydopamine (PD) nanoparticles for the preparation of a new versatile and efficient adsorbent material, namely, PSPD-HPGs. The in situ growth of PD under mild alkaline oxidative polymerization allowed us to stably graft PD on polysulfone granules. Enhanced removal efficiency of ofloxacin, an antibiotic drug, with an improvement up to 70% with respect to the pristine PS-HPGs, and removal of Zn(II) and Ni(II) were also observed after PD modification. Remarkably, removal of Cu(II) ions with an efficiency up to 80% was observed for PSPD-HPGs, whereas no adsorption was found for the PD-free precursor. Collectively, these data show that modification with a biocompatible polymer such as PD provides a simple and valuable tool to enlarge the field of application of polysulfone hollow granules for water remediation from both organic and metal cation contaminants.