Insight on bacteria communities in outdoor bronze and marble artefacts in a changing environment.

Epilithic bacteria play a fundamental role in the conservation of cultural heritage (CH) materials. On stones, bacterial communities cause both degradation and bioprotection actions. Bronze biocorrosion in non-burial conditions is rarely studied. Only few studies have examined the relationship between bacteria communities and the chemical composition of patinas (surface degradation layers). A better comprehension of bacterial communities growing on our CH is fundamental not only to understand the related decay mechanisms but also to foresee possible shifts in their composition due to climate change. The present study aims at (1) characterizing bacterial communities on bronze and marble statues; (2) evaluating the differences in bacterial communities' composition and abundance occurring between different patina types on different statues; and (3) providing indications about a representative bacterial community which can be used in laboratory tests to better understand their influence on artefact decay. Chemical and biological characterization of different patinas were carried out by sampling bronze and marble statues in Bologna and Ravenna (Italy), using EDS/Raman spectroscopy and MinION-based 16SrRNA sequencing. Significant statistical differences were found in bacterial composition between marble and bronze statues, and among marble patinas in different statues and in the same statue. Marble surfaces showed high microbial diversity and were characterized mainly by Cyanobacteria, Proteobacteria and Deinococcus-Thermus. Bronze patinas showed low taxa diversity and were dominated by copper-resistant Proteobacteria. The copper biocidal effect is evident in greenish marble areas affected by the leaching of copper salts, where the bacterial community is absent. Here, Ca and Cu oxalates are present because of the biological reaction of living organisms to Cu ions, leading to metabolic product secretions, such as oxalic acid. Therefore, a better knowledge on the interaction between bacteria communities and patinas has been achieved.

Insights into the Electrochemical Reduction of 5-Hydroxymethylfurfural at High Current Densities.

The electrocatalytic reduction of 5-hydroxymethylfurfural (HMF) is highly selective to 2,5-bishydroxymethylfuran (BHMF) at pH=9.2, diluted HMF solutions, and low current densities. In this work, the electrochemical reduction of 0.05 m HMF solutions was investigated in the 5-50 mA cm-2 current density range over an AgCu foam electrocatalyst. The selectivity towards the formation of BHMF or the dimerization depended on the current density, likely due to differences in the electrode potential, and on the reaction time. Operating at current densities of 40-50 mA cm-2 allowed to find a trade-off between HMF and H2 O activation, achieving 85 % BHMF selectivity and fostering the productivity (0.567 mmol cm-2 h-1 ), though co-producing H2 . The electrochemical characterization by Tafel slopes and electrochemical impedance spectroscopy indicated that the HMF reduction was kinetically favored in comparison to the hydrogen evolution reaction and that the process was limited by charge transfer.

AgCu Bimetallic Electrocatalysts for the Reduction of Biomass-Derived Compounds.

The electrochemical transformation of biomass-derived compounds (e.g., aldehyde electroreduction to alcohols) is gaining increasing interest due to the sustainability of this process that can be exploited to produce value-added products from biowastes and renewable electricity. In this framework, the electrochemical conversion of 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF) is studied. Nanostructured Ag deposited on Cu is an active and selective electrocatalyst for the formation of BHMF in basic media. However, this catalyst deserves further research to elucidate the role of the morphology and size of the coated particles in its performance as well as the actual catalyst surface composition and its stability. Herein, Ag is coated on Cu open-cell foams by electrodeposition and galvanic displacement to generate different catalyst morphologies, deepening on the particle growth mechanism, and the samples are compared with bare Ag and Cu foams. The chemical-physical and electrochemical properties of the as-prepared and spent catalysts are correlated to the electroactivity in the HMF conversion and its selectivity toward the formation of BHMF during electroreduction. AgCu bimetallic nanoparticles or dendrites are formed on electrodeposited and displaced catalysts, respectively, whose surface is Cu-enriched along with electrochemical tests. Both types of bimetallic AgCu particles evidence a superior electroactive surface area as well as an enhanced charge and mass transfer in comparison with the bare Ag and Cu foams. These features together with a synergistic role between Ag and Cu superficial active sites could be related to the twofold enhanced selectivity of the Ag/Cu catalysts for the selective conversion of HMF to BHMF, that is, >80% selectivity and ∼ 100% conversion, and BHMF productivity values (0.206 and 0.280 mmol cm-2 h-1) ca. 1.5-3 times higher than those previously reported.

Mucoadhesive multiparticulate patch for the intrabuccal controlled delivery of lidocaine.

The aim of the present study was to prepare and evaluate patches for the controlled release of lidocaine in the oral cavity. Mucoadhesive buccal patches, containing 8 mg/cm(2) lidocaine base, were formulated and developed by solvent casting method technique, using a number of different bio-adhesive and film-forming semi-synthetic and synthetic polymers (Carbopol, Poloxamer, different type Methocel) and plasticizers (PEG 400, triethyl citrate); the patches were evaluated for bioadhesion, in vitro drug release and permeation using a modified Franz diffusion cell. A lidocaine/Compritol solid dispersion in the form of microspheres, embedded inside the patch, alone or together with free lidocaine, was also examined to prolong the drug release. The effects of the composition were evaluated considering a number of technological parameters and the release of the drug. All the formulations tested offer a variety of drug release mechanisms, obtaining a quick or delayed or prolonged anesthetic local activity with simple changes of the formulation parameters.

Diclofenac salts, part 7: are the pharmaceutical salts with aliphatic amines stable?

Eight cyclic aliphatic amines, pyrrolidine (Py), piperidine (Pp), morpholine (M), piperazine (Pz), and the N-hydroxyethyl (HE) analogues, were employed to prepare a salt with acidic diclofenac (D). These salts were examined by thermal [differential scanning calorimetry (DSC), thermogravimetric analysis, and hot-stage microscopy (HSM)] and spectroscopic [Fourier transform infrared (FTIR), Raman, (1) H NMR, and ultraviolet] analysis. The results show the thermal instability of these salts: the thermal dissociation leaves the starting acidic D, evidenced by the FTIR and Raman spectra inside the molten mass of the salts with M and HEM. The nature of the salt with Pz (1:1 or 1:2) and HEPy (anhydrous or hydrate polymorph), but not for the salt with HEPz and Py, depends on the polarity of the solvent used for the preparation of the salt. Incomplete dehydration of the hydrate Py and Pz salts progressively modifies the thermogram profiles and originates false information. Melting of the salts with Pp, M, and HEM could be demonstrated by HSM, but not with DSC. The difficulty of providing a description of these salts in a simple way originates doubts on the utility of a wide application of aliphatic amines to prepare pharmaceutical salts with D, whose solubility in water does not significantly differ from that of the common sodium D.

Theophylline-loaded compritol microspheres prepared by ultrasound-assisted atomization.

Nine solid dispersions were prepared by the melting method in the form of particles containing theophylline at 10%, 20%, and 30% (w/w) in three Compritols (Compritol 888 ATO, HD5 ATO, E ATO) to compare their efficiency in controlling theophylline release. After solidification the mass was ground and granules were evaluated by thermal [differential scanning calorimetry, hot stage microscopy (HSM)] and spectroscopic [Fourier transform infrared (FTIR), Raman, X-ray powder diffraction (XRD)] analysis and the solubility parameters. Another nine samples of the same composition were obtained as microspheres by ultrasound-assisted (US) atomization. XRD confirmed the presence of crystalline theophylline inside the solid dispersions. FTIR and Raman microspectroscopy revealed that crystals of the drug were present on the granule surface. On the contrary, the surface of the final microspheres did not present free drug crystals. The granules do not work so efficiently as microspheres in controlling the release of theophylline: 888 ATO ≈ HD5 ATO > E ATO represents the order of the ability of the Compritols to control the theophylline release from microspheres. HSM revealed that, on aging, the dissolved drug crystallizes, considerably modifying the granule formulation and that US vibration, speeding up the crystallization of the drug during the preparation of microspheres, greatly reduces the changes associated with aging.

Diclofenac Salts. V. Examples of Polymorphism among Diclofenac Salts with Alkyl-hydroxy Amines Studied by DSC and HSM.

Nine diclofenac salts prepared with alkyl-hydroxy amines were analyzed for their properties to form polymorphs by DSC and HSM techniques. Thermograms of the forms prepared from water or acetone are different in most cases, suggesting frequent examples of polymorphism among these salts. Polymorph transition can be better highlighted when analysis is carried out by thermo-microscopy, which in most cases made it possible to observe the processes of melting of the metastable form and re-crystallization of the stable one. Solubility values were qualitatively related to the crystal structure of the salts and the molecular structure of the cation.

Green pigments of the Pompeian artists' palette.

Green colored samples on wall paintings and green powder from a pigment pot found in Pompeii area are investigated by micro-Raman, FT-IR and, for one sample, SEM-EDX. To obtain the green color, green earths and malachite were used, together with mixture of Egyptian blue and yellow ochre. The mineralogical identification of the green earths has been attempted through the comparison of the vibrational features, discriminating between celadonite and glauconite spectra. Traces of a modern synthetic pigment containing copper phthalocyanine were found in a fresco fragment.

ATR/Raman and fractal characterization of HPBCD/progesterone complex solid particles.

PURPOSE: Characterization of hydroxypropyl-beta-cyclodextrin/progesterone (HPBCD/P) complex solid particles obtained from an aqueous solution, by three different technological processes, with the aim of preparing ready-to-dissolve powders for injectable as well as solid oral formulations in progestinic therapy. METHODS: HPBCD/P complex in the 2:1 molar ratio was prepared in aqueous solution and obtained as dry solid particles by freeze-drying, by spray-drying and by fluid-bed evaporation of the solvent. The particles were characterized by mu-FT-IR, mu-Raman and X-ray spectroscopy, by thermal analysis (differential scanning calorimetry-DSC and thermogravimetry-TGA), by Karl Fischer (KF) titration, by image and fractal analysis and by BET specific surface area analysis. The structure of the complex was also defined by comparison of FT-IR and Raman spectra of progesterone with those of pregnenolone and testosterone, structurally related. Dissolution tests were also performed. RESULTS: Powders of the complex obtained by the three different methods are different in size and shape. Particles obtained by freeze-drying are flat and angular, irregularly shaped without any relation to known geometrical solid figures. Particles obtained by spray-drying are spherically shaped and display a very small size (5-10 microm), with evident deformations and depression of the external surface, due to the rapid evaporation of the solvent. Particles obtained by fluid bed technique have intermediate sizes, display a tri-dimensional structure and irregular surface, with small and rounded protuberances. Fractal dimension of the particle contour was found close to one unit for the microspheres obtained by spray-drying. FT-IR and Raman spectra confirm the occurrence of the complexation by the shift of representative bands of the two carbonyl groups in positions 3 and 20 of the complexed progesterone. X-ray diffractograms indicate the amorphous nature of all the types of particles, also suggested by the absence of any melting peak of the drug in DSC thermograms. The samples contain different amounts of humidity: particles obtained by fluid-bed method demonstrated non-porous in BET analysis. Dissolution of different types of particles is complete after 3 min and only negligible differences could be appreciated among the three powders. CONCLUSIONS: - mu-FT-IR, mu-Raman and X-ray spectroscopy, and the dissolution test did not reveal defined differences among the three different types of particles, confirming occurrence of the complex in the solid state. The spherical shape, the very small size and the low value of the contour fractal dimension allows better technological performance of the particles obtained by spray-drying: this drying process appears the most promising one to prepare dry particles of the HPBCD/P complex, in view of its formulation in the fast preparation of extemporaneous injectable solutions and solid oral formulations intended for sublingual delivery.

Raman and thermal analysis of indomethacin/PVP solid dispersion enteric microparticles.

Indomethacin (IMC) and three types of poly-(vinylpyrrolidone) (PVP 12PF, PVP K30 and PVP K90) were studied in the form of solid dispersion, prepared with the solvent evaporation method, by spectroscopic (Raman, FT-IR, X-ray diffraction), thermal (differential scanning calorimetry, thermogravimetry, hot-stage microscopy), fractal and image analysis. Raman and FT-IR micro-spectroscopy indicated the occurrence of drug/polymer interaction and the presence of an amorphous form of IMC, as also resulting from X-ray diffractometry. Hot-stage microscopy suggested that the interaction between IMC and the polymer occurring on heating of a physical mixture, is common to other acidic compounds and causes a depression of the temperature of the appearance of a molten phase. Co-evaporated particles were coated by spray-congealing process with molten stearic acid for gastroprotection, but also for stabilization of the amorphous structure of the drug: the final particles were spherically shaped. Dissolution tests carried out on the final microparticles showed that the coating with stearic acid prevents IMC release at acidic pH and also protects against recovery of the IMC crystallinity, at least after 9 months of aging: the extent and mode of the release, before and after aging, overlap perfectly. The test revealed a notable improvement of the drug release rate from the solid dispersion at suitable pH, with respect to pure IMC. The comparison of the present solid dispersion with IMC/PVP (surface) solid dispersion obtained by freeze-drying of an aqueous suspension, where IMC maintained its crystalline state, revealed that there was no difference concerning the release rate, but suggested a superior quality of this last process as a mean of improving IMC availability for the easiness of preparation and stability, due to the absence of the amorphous state of the drug, as a possible instability source of the system. Finally, the coating with stearic acid is discussed as a determining process for the practical application of solid dispersions.

Solid state characterization of progesterone in a freeze dried 1:2 progesterone/HPBCD mixture.

Progesterone rapidly dissolves in an aqueous solution containing hydroxypropyl-beta-cyclodextrin (HPBCD) at 1:2 molar ratio, forming a soluble inclusion complex. After filtration and freeze-drying of the final solution, the final powder was examined by SEM, DSC, TGA, XRD, Raman, and FTIR spectroscopy. Experimental results confirm that an inclusion complex exists in the solid state and possible structure of the complex is briefly discussed.