"Shake 'n Bake" Route to Functionalized Zr-UiO-66 Metal-Organic Frameworks.

We report a novel synthetic procedure for the high-yield synthesis of metal-organic frameworks (MOFs) with fcu topology with a UiO-66-like structure starting from a range of commercial ZrIV precursors and various substituted dicarboxylic linkers. The syntheses are carried out by grinding in a ball mill the starting reagents, namely, Zr salts and the dicarboxylic linkers, in the presence of a small amount of acetic acid and water (1 mL total volume for 1 mmol of each reagent), followed by incubation at either room temperature or 120 °C. Such a simple "shake 'n bake" procedure, inspired by the solid-state reaction of inorganic materials, such as oxides, avoids the use of large amounts of solvents generally used for the syntheses of Zr-MOF. Acidity of the linkers and the amount of water are found to be crucial factors in affording materials of quality comparable to that of products obtained under solvo- or hydrothermal conditions.

Development of sodium carboxymethyl cellulose based polymeric microparticles for in situ hydrogel wound dressing formation.

18ß-glycyrrhetinic acid (Gly), a natural compound obtained from licorice, is known both for the anti-inflammatory and antioxidant activities and for this reason useful for wound treatment. Due to its poor solubility, Gly is not suitable for formulations used in conventional topical products such as gels, foams and creams. Polymeric bioadhesive microparticles (MP), loaded with Gly, were developed to be introduced in the wound bed and swell, once in contact with the exudate, to form a hydrogel in situ able to close the wound. The MP were prepared by spray drying method from the polymeric solution of polysaccharide sodium carboxymethyl cellulose (CMC) and copolymer Soluplus® (SL). Soluplus® introduction in MP composition, using a 3:1 ratio (CMC/SL wt./wt.), allowed to stabilize Gly in non-crystalline form, favoring the improvement of water solubility, and to obtain a spherical with rugged surface MP morphology. Ex vivo studies showed these MP maintain high swelling capability and are able to form in situ a hydrogel for wound repair. The controlled release of Gly from the hydrogel stimulates keratinocyte growth, potentially supporting the physiological healing processes.

Iridium-Doped Nanosized Zn-Al Layered Double Hydroxides as Efficient Water Oxidation Catalysts.

Layered double hydroxides (LDHs) are an ideal platform to host catalytic metal centers for water oxidation (WO) owing to the high accessibility of water to the interlayer region, which makes all centers potentially reachable and activated. Herein, we report the syntheses of three iridium-doped zinc-aluminum LDHs (Ir-LDHs) nanomaterials (1-3, with about 80 nm of planar size and a thickness of 8 nm as derived by field emission scanning electron microscopy and powder X-ray diffraction studies, respectively), carried out in the confined aqueous environment of reverse micelles, through a very simple and versatile procedure. These materials exhibit excellent catalytic performances in WO driven by NaIO4 at neutral pH and 25 °C, with an iridium content as low as 0.5 mol % (∼0.8 wt %), leading to quantitative oxygen yields (based on utilized NaIO4, turnover number up to ∼10,000). Nanomaterials 1-3 display the highest ever reported turnover frequency values (up to 402 min-1) for any heterogeneous and heterogenized catalyst, comparable only to those of the most efficient molecular iridium catalysts, tested under similar reaction conditions. The boost in activity can be traced to the increased surface area and pore volume (>5 times and 1 order of magnitude, respectively, higher than those of micrometric materials of size 0.3-1 µm) estimated for the nanosized particles, which guarantee higher noble metal accessibility. X-ray absorption spectroscopy (XAS) studies suggest that 1-3 nanomaterials, as-prepared and after catalysis, contain a mixture of isolated, single octahedral Ir(III) sites, with no evidence of Ir-Ir scattering from second-nearest neighbors, excluding the presence of IrO2 nanoparticles. The combination of the results obtained from XAS, elemental analysis, and ionic chromatography strongly suggests that iridium is embedded in the brucite-like structure of LDHs, having four hydroxyls and two chlorides as first neighbors. These results demonstrate that nanometric LDHs can be successfully exploited to engineer efficient WOCs, minimizing the amount of iridium used, consistent with the principle of the noble-metal atom economy.

Solvent-Free Synthetic Route for Cerium(IV) Metal-Organic Frameworks with UiO-66 Architecture and Their Photocatalytic Applications.

A near solvent-free synthetic route for Ce-UiO-66 metal-organic frameworks (MOFs) is presented. The MOFs are obtained by energetically grinding the reagents, cerium ammonium nitrate (CAN) and the carboxylic linkers, in a mortar for a few minutes with the addition of a small amount of acetic acid (AcOH) as a modulator (8.75 equiv, 0.5 mL). The slurry is then transferred into a 2 mL vial and heated at 120 °C for 1 day. The MOFs have been characterized for their composition, crystallinity, and porosity and employed as heterogeneous catalysts for the photo-oxidation reaction of substituted benzylic alcohols to benzaldaldehydes under near-ultraviolet light irradiation. The catalytic performances, such as selectivity, conversion, and kinetics, exceed those of similar systems studied by chemical oxidation using similar Ce-MOFs as a catalyst. Moreover, the MOFs were found to be reusable up to three cycles without loss of activity. Density functional theory (DFT) calculations were used to fully describe the electronic structure of the best performing MOFs and to provide useful information on the catalytic activity experimentally observed.

Dentifrice Based on Fluoride-Hydrotalcite Compounds: Characterization and Release Capacity Evaluation by Novel In Vitro Methods.

Anti-caries activity of fluoride ions is due to the protection against demineralization and the enhancement of remineralization of tooth enamel. Dentifrices available on the market contain sodium fluoride, sodium monofluorophosphate, stannous fluoride, and amine fluoride as source of these ions. A new compound working both as fluoride ion source and as abrasive was projected. Hybrids based on F- ions intercalated between the lamellae of hydrotalcite-like compounds (HTlc-F), namely MgAl-HTlc-F and ZnAl-HTlc-F, were prepared and characterized. Then, three different percentages (2, 3, and 4%) of both HTlc-F compounds were assayed. After the rheological characterization, the dentifrices containing 3 and 4% of MgAl-HTlc-F and ZnAl-HTlc-F, respectively, resulted to be the most suitable ones. Two novel in vitro methods, "rotary toothbrush method" and "manual brushing method," were developed and used in order to study the F- ions release from the prepared dentifrices. The obtained results showed that the dentifrice containing ZnAl-HTlc-F (4%) was the most effective in releasing fluoride ions. The "rotary toothbrush method" resulted to be the most suitable as the simulation of the brushing movements is standardizable and reproducible.

Resin-Based Materials with Chlorhexidine-Loaded MCM-41: Surface Characteristics, Drug Release, and Antibiofilm Activity.

Poly(methyl methacrylate) resins containing chlorhexidine diacetate (CHX)-loaded mesoporous silicate MCM-41 have the ability to prevent Candida biofilm adhesion and growth over time. With the aim of increasing knowledge of the drug release and surface properties of these materials and their relationship with antibiofilm activity, in this paper an acrylic-based resin containing CHX-loaded spherical and narrow size silanized MCM-41 was prepared. Resins containing CHX but no filler were prepared as well and compared. Samples were characterized for polymerization degree, water sorption, and drug release. The sample capacity of inhibiting Candida biofilm adhesion and formation over time was evaluated. All samples were able to reduce the Candida biofilm mass over time. The resin containing CHX loaded into silanized MCM-41 mesopores resulted in less activity during the first 4 h but was able to maintain antibiofilm activity for a longer time. This effect was correlated to the prolonged CHX release and to the sample surface modifications observed after treatment with water and artificial saliva, evaluated by X-ray photoemission spectroscopy, scanning electron, and atomic force microscopies.

Mixed Membrane Matrices Based on Nafion/UiO-66/SO3H-UiO-66 Nano-MOFs: Revealing the Effect of Crystal Size, Sulfonation, and Filler Loading on the Mechanical and Conductivity Properties.

Mixed membrane matrices (MMMs) made up with Nafion and nanocrystals of zirconium metal-organic framework (MOF) UiO-66 or the analogous sulfonated SO3H-UiO-66 were prepared by varying the filler loading and the size of the crystals. The combined effects of size and loading, together with the presence of sulfonic groups covalently linked to the MOFs, were studied with regard to the conductivity and mechanical properties of the obtained composite matrices. A large screening of membranes was preliminarily made and, on the most promising samples, an accurate conductivity study at different relative humidities and temperatures was also carried out. The results showed that membranes containing large crystals (200 nm average size) in low amounts (around 2%) displayed the best results in terms of proton conductivity values, reaching values by 30% higher than those of pure Nafion, while leaving the mechanical properties substantially unchanged. On the contrary, MMMs containing MOFs of small size (20 nm average size) did not show any conductivity improvements if compared to pure Nafion membranes. The effect of MOF sulfonation was negligible at low filler loading whereas it became important at loading values around 10%. Finally, membranes with a high filler loading (up to 60 wt %) of sulfonated UiO-66 showed a slight reduction of conductivity in comparison with membranes loaded at 20% of nonsulfonated ones.

The first route to highly stable crystalline microporous zirconium phosphonate metal-organic frameworks.

The first crystalline microporous zirconium phosphonate metal-organic framework (UPG-1) was synthesized using the novel tritopic ligand 2,4,6-tris(4-(phosphonomethyl)phenyl)-1,3,5-triazine. Its crystal structure was solved ab initio from laboratory powder X-ray diffraction data. UPG-1 displays remarkable thermal stability and hydrolysis resistance and has a good absorption affinity towards n-butane and CO2.

Chitosan films containing mesoporous SBA-15 supported silver nanoparticles for wound dressing.

Chitosan films containing mesoporous SBA-15 supported silver nanoparticles (AgNPs) were prepared to be applied as a potential wound dressing material. First SBA-15-silver nanoparticle (SBA-15-Ag) composite materials were prepared by a controlled annealing process without the use of organic solvents and reagents. The SBA-15-AgNPs were characterized in detail by X-ray powder diffraction, field emission scanning electron microscopy and transmission electron microscopy which evidenced the presence of uniformly distributed silver nanostructures inside the silicate pores. UV-vis spectra of the sample showed a band at 430 nm characteristic of the surface plasmon resonance of silver nanoparticles with a diameter below 10 nm and X-ray photoemission spectra confirmed the formation of metal-nanoparticles on the silicate template. Then SBA-15-Ag was used to prepare chitosan films which were characterized in detail. In particular, they showed good hydration properties, water vapor transmission rate and mechanical properties. After hydration films exhibited good antimicrobial activity against both Gram-negative (Pseudomonas aeruginosa) and Gram-positive (Staphylococcus epidermidis and S. aureus) bacteria.

Solventless supramolecular chemistry via vapor diffusion of volatile small molecules upon a new trinuclear silver(I)-nitrated pyrazolate macrometallocyclic solid: an experimental/theoretical investigation of the dipole/quadrupole chemisorption phenomena.

A comparative study on the tendency of a new trinuclear silver(I) pyrazolate, namely, [N,N-(3,5-dinitropyrazolate)Ag]3 (1), and a similar compound known previously, [N,N-[3,5-bis(trifluoromethyl)pyrazolate]Ag]3 (2), to adsorb small volatile molecules was performed. It was found that 1 has a remarkable tendency to form adducts, at room temperature and atmospheric pressure, with acetone, acetylacetone, ammonia, pyridine, acetonitrile, triethylamine, dimethyl sulfide, and tetrahydrothiophene, while carbon monoxide, tetrahydrofuran, alcohols, and diethyl ether were not adsorbed. On the contrary, 2 did not undergo adsorption of any of the aforementioned volatile molecules. Adducts of 1 were characterized by elemental analysis, IR, thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET) surface area, and diffusion NMR measurements. The crystal structures of 1·2CH3CN and compound 3, derived from an attempt to crystallize the adduct of 1 with ammonia, were determined by single-crystal X-ray diffractometric studies. The former shows a sandwich structure with a 1:2 stoichiometric [Ag3]/[CH3CN] ratio in which one acetonitrile molecule points above and the other below the centroid of the Ag3N6 metallocycle. Compound 3 formed via rearrangement of the ammonia adduct to yield an anionic trinuclear silver(I) derivative with an additional bridging 3,5-dinitropyrazolate and having [Ag(NH3)2](+) as the counterion, [Ag(NH3)2][N,N-(3,5-dinitropyrazolate)4Ag3]. Irreversible sorption and/or decomposition upon vapor exposure are desirable advantages toward toxic gas filtration applications, including ammonia inhalation. TGA confirms the analytical data for all of the samples, showing weight loss for each adsorbed molecule at temperatures significantly higher than the corresponding boiling temperature, which suggests a chemical-bonding nature for adsorption as opposed to physisorption. BET surface measurements of the "naked" compound 1 excluded physical adsorption in its porous cavities. Density functional theory simulation results are also consistent with the chemisorption model, explain the experimental adsorption selectivity for 1, and attribute the lack of similar adsorption by 2 to significantly less polarizable electrostatic potential and also to strong argentophilic bonding whose energy is even higher than the quadrupole-dipole adduct bond energy upon proper selection of the density functional.

Mesoporous silicate MCM-41 as a particulate carrier for octyl methoxycinnamate: Sunscreen release and photostability.

Octyl methoxycinnamate (OMC) is a widely used UV filter characterized by good absorbing properties; however, it shows light susceptibility (photoinstability) and potential skin permeation. This paper describes the application of a new particulate carrier to improve OMC safety and photostability. The UV filter was included into the pores of the mesoporous silicate MCM-41 and then entrapped there by plugging the pore openings. The last step was performed treating the MCM-41 inclusion product with a lipid cosmetic ingredient by the hot-melt method. The loaded samples were characterized by X-ray powder diffraction, Fourier transform infrared spectroscopy, and N2 adsorption isotherms. Photochemical studies demonstrated that the coated samples allow a broader photoprotection range and remarkable improvement of sunscreen photostability. Finally, they were properly formulated in an emulgel, and the sunscreen release was studied in vitro by Franz diffusion cell and compared with those obtained from the same formulation containing the free filter. Sunscreen release from the studied formulations resulted negligible, meaning that the proposed approach represents a valuable strategy for UV filters stabilization toward light and safety improvement.

Production of nitric oxide by human salivary peroxidase and by bovine lactoperoxidase.

Peroxidases catalyze the oxidation of nitrite to nitrate in the presence of hydrogen peroxide. Two pathways may occur: one entailing the intermediate formation of NO(2) and the other implying the generation of peroxynitrite. The products of nitrite (NO(2) (-) ) oxidation by salivary peroxidase (SPO) and commercial bovine lactoperoxidase (LPO) are studied by utilizing an electrochemical assay that allows the direct, continuous monitoring of NO and/or NO(2) and by HPLC to assess nitrates at the end of the reaction. Dialyzed saliva and LPO, in the presence of H(2) O(2) , convert nitrite into nitrate and form some NO, with a molar ratio of 10(3) . In our experimental conditions, no NO(2) was detectable among the products of nitrite oxidation. SCN(-) inhibits NO formation and so does I(-) , although at higher concentrations. No effects are observed with Cl(-) or Br(-) . We conclude that SPO and LPO transform NO(2) (-) into nitrate-forming small amounts of NO in the presence of H(2) O(2) as an intermediate or a by-product, synthesized through the peroxynitrite pathway.

Use of SBA-15 for furosemide oral delivery enhancement.

The objective of this research was to realize a new oral solid dosage form in order to improve the release of furosemide (FURO) in its preferential absorption region. In fact FURO is a drug labeled in class IV of the Biopharmaceutical Classification System (BCS) characterized by low and variable bioavailability due to both low solubility and low permeability and because of its weakly acid nature is preferentially absorbed in the stomach whereas its solubility is hampered. FURO was included in the mesoporous silica material SBA-15 obtaining an inorganic-organic compound fully characterized by: thermogravimetric analysis (TGA), X-ray Powder Diffraction (XRPD), Differential Scanning Calorimetry (DSC), Fourier Transform Infrared Spectroscopy (FT-IR) and nitrogen adsorption-desorption analysis and then submitted to in vitro dissolution. The results showed a remarkable dissolution rate improvement in comparison to the crystalline drug and to the marketed product Lasix®. The inclusion product was also submitted to physical stability studies that revealed the matrix ability to prevent re-organization in crystal nucleus of the drug molecules.

Econazole nitrate-loaded MCM-41 for an antifungal topical powder formulation.

The aim of this article was to prepare a topical powder for the treatment of fungal infections, such as Candida intertrigo and tinea pedis. Thus, an econazole nitrate (ECO) formulation with improved drug dissolution and proper moisture adsorption was designed. ECO was melt with the mesoporous silicate MCM-41 (drug/MCM-41 1/3) and the resulting inclusion compound was characterized by X-ray powder diffraction (XRPD) and differential scanning calorimetry (DSC). The drug loading was confirmed by the decrease of specific surface area and pore volume between MCM-41 and the inclusion compound. Formulations containing the inclusion compound were prepared and submitted to in vitro dissolution test and in vitro antifungal activity. A remarkable dissolution rate improvement as well as a higher antifungal activity was observed for the inclusion compound if compared to a commercial product. Moisture sorption properties for MCM-41 and formulations were evaluated as well.

A snapshot of a coordination polymer self-assembly process: the crystallization of a metastable 3D network followed by the spontaneous transformation in water to a 2D pseudopolymorphic phase.

A metastable copper(II) 3D hybrid with 4,4'-bipyridine (4,4'-bipy) and P,P'-diphenylethylenediphosphinate (pc2p(2-)) undergoes a spontaneous, quantitative, transformation to a stable 2D polymorphic species either spontaneously in water, or after thermal dehydration followed by hydration.

Use of calcined Mg-Al-hydrotalcite to enhance the stability of celecoxib in the amorphous form.

The use of compound in amorphous forms is a promising approach to improve solubility of poorly water-soluble drugs. However, during storage, amorphous state can spontaneously transform to the lower energy crystalline form and this is a limiting factor for a large commercial use of drugs. In this paper, calcined hydrotalcite was employed to support amorphous celecoxib and several preparations at different weight drug/carrier ratio were prepared. Solubility of celecoxib from the prepared systems was evaluated and its physical stability during storage at different conditions was examined as well. The results show that HTlc-calc can be used as a support of amorphous celecoxib with consequent improvement of drug solubility and physical stability.

Adsorption of myoglobin onto porous zirconium phosphate and zirconium benzenephosphonate obtained with template synthesis.

Porous zirconium phosphate (P-ZrP) and zirconium benzenephosphonate (P-ZrBP) were prepared in the presence of an anionic surfactant acting as a template. Poorly crystalline materials with a P/Zr molar ratio equal to 2 and having a relatively high surface area and micro/mesoporosity have been obtained. The interaction of myoglobin with the two types of surfaces, the hydrophobic P-ZrBP and the hydrophilic P-ZrP, was investigated, and the adsorption isotherms were determined at different pH and temperature values. A model was proposed for the mechanism of the interaction of the protein with the surface based on the shape of the adsorption isotherm and the physical-chemical properties of myoglobin. The pH has been found to be an important parameter for determining the maximum adsorption capacity of P-ZrBP and P-ZrP for myoglobin molecules because of the changes that occur in the type and net charge of the protein surface as the pH of the medium changes. Protein binding affinity and capacity increase when the temperature is increased. This phenomenon occurs because myoglobin varies its conformation at high temperature with an increase in the exposed hydrophobic region. This process causes a stronger hydrophobic interaction between the protein and the adsorbent and reduces the repulsion between the adsorbed molecules. Studies on the activities of the obtained biocomposites are in progress.

Selective liberation of NO from S-nitrosocysteine with potassium thiocyanate, as monitored by an amperometric sensor.

S-Nitrosocysteine (CysNO) releases either NO (in the presence of divalent cations) or NO+ (in the presence of chelating agents). NO+ is then transferred to peptides or protein SH groups to form high-mass nitrosothiols. The aim of this work was the development of a specific reaction between thiocyanate (SCN-) and CysNO. This reaction selectively liberates NO from CysNO in the presence of high-mass nitrosothiols. Free NO is measured with an amperometric sensor. We examine with this system the transnitrosylation reaction between CysNO and BSA at low molecular ratios and could assay nitrites, SNO-BSA, and CysNO in the incubation mixture without any preliminary purification steps.