Physicochemical Characterization of Hydroxyapatite Hybrids with Meloxicam for Dissolution Rate Improvement.

Organic-inorganic hybrids represent a good solution to improve the solubility and dissolution rates of poorly soluble drugs whose number has been increasing in the last few years. One of the most diffused inorganic matrices is hydroxyapatite (HAP), which is a biocompatible and osteoconductive material. However, the understanding of the hybrids' functioning mechanisms is in many cases limited; thus, thorough physicochemical characterizations are needed. In the present paper, we prepared hybrids of pure and Mg-doped hydroxyapatite with meloxicam, a drug pertaining to the Biopharmaceutical Classification System (BCS) class II, i.e., drugs with low solubility and high permeability. The hybrids' formation was demonstrated by FT-IR, which suggested electrostatic interactions between HAP and drug. The substitution of Mg in the HAP structure mainly produced a structural disorder and a reduction in crystallite sizes. The surface area of HAP increased after Mg doping from 82 to 103 m2g-1 as well as the pore volume, justifying the slightly high drug amount adsorbed by the Mg hybrid. Notwithstanding the low drug loading on the hybrids, the solubility, dissolution profiles and wettability markedly improved with respect to the drug alone, particularly for the Mg doped one, which was probably due to the main distribution of the drug on the HAP surface.

Hybrid Nanocomposites of Tenoxicam: Layered Double Hydroxides (LDHs) vs. Hydroxyapatite (HAP) Inorganic Carriers.

The search for effective systems to facilitate the release of poorly bioavailable drugs is a forefront topic for the pharmaceutical market. Materials constituted by inorganic matrices and drugs represent one of the latest research strategies in the development of new drug alternatives. Our aim was to obtain hybrid nanocomposites of Tenoxicam, an insoluble nonsteroidal anti-inflammatory drug, with both layered double hydroxides (LDHs) and hydroxyapatite (HAP). The physicochemical characterization on the base of X-ray powder diffraction, SEM/EDS, DSC and FT-IR measurements was useful to verify the possible hybrids formation. In both cases, the hybrids formed, but it seemed that the drug intercalation in LDH was low and, in fact, the hybrid was not effective in improving the pharmacokinetic properties of the drug alone. On the contrary, the HAP-Tenoxicam hybrid, compared to the drug alone and to a simple physical mixture, showed an excellent improvement in wettability and solubility and a very significant increase in the release rate in all the tested biorelevant fluids. It delivers the entire daily dose of 20 mg in about 10 min.

The Renewed Interest on Brunogeierite, GeFe2O4, a Rare Mineral of Germanium: A Review.

GeFe2O4, also known as brunogeierite, is a rare mineral of germanium. It has a normal spinel structure and, as with many other spinels, amazing functional properties thanks to its peculiar structural features. In the past, its spectroscopic, optical, magnetic and electronic properties were determined; then, for many years, this compound was left behind. Only recently, a renewed interest in this oxide has arisen, particularly for its application in the electrochemical field. In this review paper, the crystal structure of GeFe2O4 will be described, as well as the synthesis methods required to obtain single crystals or polycrystalline powders. Its spectroscopic, magnetic, optical and electrical properties will be reported in detail. Then, successful applications known so far will be described: its use as anode in Lithium Ion and Sodium Ion Batteries and as electrocatalyst for urea oxidation reaction.

Electrochemistry of orthosilicate-based lithium battery cathodes: a perspective.

Lithium metal orthosilicates are attracting a lot of attention owing to their promising prospects as potential high capacity cathode materials for Li-ion batteries. Currently, great efforts are being made in order to achieve the full theoretical specific capacity of 330 mA h g(-1), but many issues remain unsolved (e.g., poor structural and cycling stability), which limit their practical application. The present perspective highlights the importance of assessing the electrochemical behaviour of Li2(Fe,Mn)SiO4 by combining an arsenal of characterization techniques both spectroscopic and structural, in and ex situ. Here, we review the most recent achievements in the investigation of the electrochemical performance of lithium metal orthosilicate cathodes and, through some of our recent results, we attempt to clarify the relationship between the structure and electrochemistry of these compounds.

Hydroxyapatite Nanorods Based Drug Delivery Systems for Bumetanide and Meloxicam, Poorly Water Soluble Active Principles.

Poorly water-soluble drugs represent a challenge for the pharmaceutical industry because it is necessary to find properly tuned and efficient systems for their release. In this framework, organic-inorganic hybrid systems could represent a promising strategy. A largely diffused inorganic host is hydroxyapatite (HAP, Ca10(PO4)6(OH)2), which is easily synthesized with different external forms and can adsorb different kinds of molecules, thereby allowing rapid drug release. Hybrid nanocomposites of HAP nanorods, obtained through hydrothermal synthesis, were prepared with two model pharmaceutical molecules characterized by low and pH-dependent solubility: meloxicam, a non-steroidal anti-inflammatory drug, and bumetanide, a diuretic drug. Both hybrids were physically and chemically characterized through the combined use of X-ray powder diffraction, scanning electron microscopy with energy-dispersive spectroscopy, differential scanning calorimetry, and infrared spectroscopy measurements. Then, their dissolution profiles and hydrophilicity (contact angles) in different media as well as their solubility were determined and compared to the pure drugs. This hybrid system seems particularly suitable as a drug carrier for bumetanide, as it shows higher drug loading and good dissolution profiles, while is less suitable for meloxicam, an acid molecule.

Self-Supported Fibrous Sn/SnO2@C Nanocomposite as Superior Anode Material for Lithium-Ion Batteries.

Low-cost and simple methods are constantly chased in order to produce less expensive lithium-ion batteries (LIBs) while possibly increasing the energy and power density as well as the volumetric capacity in order to boost a rapid decarbonization of the transport sector. Li alloys and tin-carbon composites are promising candidates as anode materials for LIBs both in terms of capacity and cycle life. In the present paper, electrospinning was employed in the preparation of Sn/SnOx@C composites, where tin and tin oxides were homogeneously dispersed in a carbonaceous matrix of carbon nanofibers. The resulting self-standing and light electrode showed a greatly enhanced performance compared to a conventional electrode based on the same starting materials that are simply mixed to obtain a slurry then deposited on a Cu foil. Fast kinetics were achieved with more than 90% of the reaction that resulted being surface-controlled, and stable capacities of about 300 mAh/g over 500 cycles were obtained at a current density of 0.5 A/g.

Silver Doped Magnesium Ferrite Nanoparticles: Physico-Chemical Characterization and Antibacterial Activity.

Spinel phases, with unique and outstanding physical properties, are attracting a great deal of interest in many fields. In particular, MgFe2O4, a partially inverted spinel phase, could find applications in medicine thanks to the remarkable antibacterial properties attributed to the generation of reactive oxygen species. In this paper, undoped and Ag-doped MgFe2-xAgxO4 (x = 0.1 and 0.3) nanoparticles were prepared using microwave-assisted combustion and sol-gel methods. X-ray powder diffraction, with Rietveld structural refinements combined with micro-Raman spectroscopy, allowed to determine sample purity and the inversion degree of the spinel, passing from about 0.4 to 0.7 when Ag was introduced as dopant. The results are discussed in view of the antibacterial activity towards Escherichia coli and Staphylococcus aureus, representative strains of Gram-negative and Gram-positive bacteria. The sol-gel particles were more efficient towards the chosen bacteria, possibly thanks to the nanometric sizes of metallic silver, which were well distributed in the powders and in the spinel phase, with respect to microwave ones, that, however, acquired antibacterial activity after thermal treatment, probably due to the nucleation of hematite, itself displaying well-known antibacterial properties and which could synergistically act with silver and spinel.

To Which Extent Is Paramagnetic Solid-State NMR Able To Address Polymorphism in Complex Transition-Metal Oxides?

A detailed characterization of the polymorphs constituting cathode materials, both before and after cell cycling, is mandatory to develop more stable and powerful lithium batteries. In many cases, e.g., for transition metal lithium silicates, standard diffraction techniques cannot give a clear-cut response. Here we show that broadband adiabatic fast MAS NMR can give unique information in the case of model Li2(Mn,Fe)SiO4 high-capacity cathode materials. By coupling 7Li and 29Si 1D and 2D spectra, we are able to address polymorphs speciation also in the mixed Mn/Fe compositions, which is a nearly impossible task for X-rays and neutrons diffraction. We finally discuss the conditions under which this approach is useful when applied to rare nuclei such as 29Si.

Improving the Carprofen Solubility: Synthesis of the Zn2Al-LDH Hybrid Compound.

The development of efficient strategies for drug delivery is considerably desired. Indeed, often several issues such as the drug solubility, the control of the drug release rate, the targeted delivery of drugs, the drug bioavailability, and the minimization of secondary effects still present great obstacles. Different methodologies have been proposed, but the use of nano-hybrids compounds that combine organic and inorganic substances seems particularly promising. An interesting inorganic host is the layered double hydroxide (LDH) with a sheets structure and formula [M2+1-x M3+x (OH)2](An-)x/n yH2O (M2+ = Zn, Mg; M3+ = Al; An- = nitrates, carbonates, chlorides). The possibility to exchange these counterions with drug molecules makes these systems ideal candidates for the drug delivery. In this article, we synthesize by co-precipitation method the hybrid compound Carprofen-Zn2Al-LDH. Carprofen, a poorly soluble anti-inflammatory drug, could also benefit of the association with a natural antacid such as LDH, to reduce the gastric irritation after its administration. Through X-ray diffraction and Fourier-transformed infrared spectroscopy (FT-IR), we could verify the effective drug intercalation into LDH. The dissolution tests clearly demonstrate a significant improvement of the drug release rate when carprofen is in the form of hybrid compound.

Deepening the shear structure FeNb11O29: influence of polymorphism and doping on structural, spectroscopic and magnetic properties.

FeNb11O29 is an intriguing and promising material that has been emerging in the last few years. It is isostructural with Nb12O29, one of the rare compounds in which Nb displays a local magnetic moment and shows both antiferromagnetic ordering and metallic conductivity at low temperatures. Both the two polymorphic monoclinic and orthorhombic forms have a mono-dimensional magnetic arrangement, but the different disposition of the structural building blocks leads to a strong frustration phenomenon of the magnetic order in the high-temperature orthorhombic form. Whereas Nb12O29 has been widely studied, barely few magnetic data can be found on its analogous FeNb11O29, for which a role of the Fe3+ localized d electrons in affecting the original magnetic behaviour can be foreseen. In this paper, we report how we synthesized undoped and, for the first time, Mn- and V-doped FeNb11O29. Both the monoclinic and orthorhombic polymorphs, stable in different temperature ranges, were then thoroughly structurally characterized. With the help of micro-Raman spectroscopy, we investigated the differences introduced into the vibrational levels by doping, while EPR data allowed us to obtain information on the transition metal ions and to point out the related peculiar structural features. Static magnetization measurements evidenced the paramagnetic character of the compounds and the high-spin configuration of Fe3+ ions.

A new tetrahydrated form of sodium naproxen.

The anhydrous sodium naproxen (ASN) can form several hydrated phases if maintained at different relative humidities (RH). The water uptake can promote crystallographic modifications, according to the amount of water. In a previous work, the authors showed that a dihydrated form could be obtained either by crystallization in water or by exposure of the anhydrous form to a RH of 55%. In the present work, the authors report about the formation and characterization of a new tetrahydrated form, obtained by exposing the ASN to RH >or= 75%. All the hydrated compounds were characterized by the combined use of several spectroscopic, thermal, and crystallographic techniques. The thermal stability of both the dihydrated and tetrahydrated compounds was also tested.

Bulk Surfaces Coated with Triangular Silver Nanoplates: Antibacterial Action Based on Silver Release and Photo-Thermal Effect.

A layer of silver nanoplates, specifically synthesized with the desired localized surface plasmon resonance (LSPR) features, was grafted on amino-functionalized bulk glass surfaces to impart a double antibacterial action: (i) the well-known, long-term antibacterial effect based on the release of Ag⁺; (ii) an "on demand" action which can be switched on by the use of photo-thermal properties of silver nano-objects. Irradiation of these samples with a laser having a wavelength falling into the so called "therapeutic window" of the near infrared region allows the reinforcement, in the timescale of minutes, of the classical antibacterial effect of silver nanoparticles. We demonstrate how using the two actions allows for almost complete elimination of the population of two bacterial strains of representative Gram-positive and Gram-negative bacteria.

New materials for Li-ion batteries: synthesis and spectroscopic characterization of Li2(FeMnCo)SiO4 cathode materials.

Improving cathode materials is mandatory for next-generation Li-ion batteries. Exploring polyanion compounds with high theoretical capacity such as the lithium metal orthosilicates, Li2MSiO4 is of great importance. In particular, mixed silicates represent an advancement with practical applications. Here we present results on a rapid solid state synthesis of mixed Li2(FeMnCo)SiO4 samples in a wide compositional range. The solid solution in the P21/n space group was found to be stable for high iron concentration or for a cobalt content up to about 0.3 atom per formula unit. Other compositions led to a mixture of polymorphs, namely Pmn21 and Pbn21. All the samples contained a variable amount of Fe(3+) ions that was quantified by Mössbauer spectroscopy and confirmed by the TN values of the paramagnetic to antiferromagnetic transition. Preliminary characterization by cyclic voltammetry revealed the effect of Fe(3+) on the electrochemical response. Further work is required to determine the impact of these electrode materials on lithium batteries.

Polymorphism and magnetic properties of Li2MSiO4 (M = Fe, Mn) cathode materials.

Transition metal-based lithium orthosilicates (Li2MSiO4, M = Fe, Ni, Co, Mn) are gaining a wide interest as cathode materials for lithium-ion batteries. These materials present a very complex polymorphism that could affect their physical properties. In this work, we synthesized the Li2FeSiO4 and Li2MnSiO4 compounds by a sol-gel method at different temperatures. The samples were investigated by XRPD, TEM, (7)Li MAS NMR, and magnetization measurements, in order to characterize the relationships between crystal structure and magnetic properties. High-quality (7)Li MAS NMR spectra were used to determine the silicate structure, which can otherwise be hard to study due to possible mixtures of different polymorphs. The magnetization study revealed that the Néel temperature does not depend on the polymorph structure for both iron and manganese lithium orthosilicates.

Structure and properties of domperidone and its succinate salt.

This paper describes the structure and properties of the drug domperidone and a novel 1:1 domperidone succinate salt. The new salt is characterized by means of thermal, spectroscopic, microscopic and powder diffraction measurements. The crystal structures of the salt and, for the first time, of pure domperidone have been determined by means of single-crystal X-ray diffraction. In both structures, the piperidine ring of domperidone adopts the expected chair conformation, and supramolecular centrosymmetric R2(2)(8) motifs are formed by N-H...O hydrogen bonds between chlorine-substituted oxobenzimidazolyl groups. Further N-H...O hydrogen bonds occur between non-substituted oxobenzimidazolyl groups and the resulting C(4) motifs originates hydrogen-bonded chains, extending along the crystallographic b axis. In the salt, a single N-H...O hydrogen bond forms between the protonated nitrogen of the piperidine ring and the carboxylic O atom of the succinate ion. Two alternative and mutually exclusive positions for the nonsubstituted oxobenzimidazolyl group have also been observed; this disorder makes the hydrogen-bonded chains originating from the bicyclic group polar. The dissolution behaviour of the salt in dosage form is compared with two reference commercial products. The salt shows an increased solubility, a characteristic that could be of great advantage from a pharmaceutical view point.

Bone reconstruction: Au nanocomposite bioglasses with antibacterial properties.

Bioglasses are of wide interest since they spontaneously bond and integrate with living bone in the body. By varying the glass chemistry and/or by adding some dopants, it is possible to improve their clinical applications. Gold nanoparticles (Au NPs) are a well-known antibacterial agent, as well as a unique probe for sensing and imaging applications. We report on the synthesis of a 58S bioglass doped with Au NPs at two doping levels: 0.1% wt. and 1% wt. Antibacterial properties were observed on the Gram-positive Staphylococcus aureus, whereas no significant effects were found on the Gram-negative Escherichia coli. A possible mechanism of action of Au NPs towards bacteria has been described.

Characterization of nicergoline polymorphs crystallized in several organic solvents.

Nicergoline (NIC), a poorly water-soluble semisynthetic ergot derivative, was crystallized from several organic solvents, obtaining two different polymorphic forms, the triclinic form I and the orthorhombic form II. NIC samples were then characterized by several techniques such as (13)C cross-polarization magic angle spinning solid-state spectroscopy, room-temperature and high-temperature X-ray powder diffraction, differential scanning calorimetry, and by analysis of weight loss, solvent content, powder density, morphology, and particle size. Solubility and intrinsic dissolution rates determined for the two polymorphic forms in water and hydrochloride solutions (HCl 0.1 N) were always higher for form II than for form I, which is actually the form used for the industrial preparation of NIC medicinal products. Preformulation studies might encourage industry for the evaluation of polymorph II, as it is more suitable for pharmaceutical applications. Results in drug delivery, as well as those obtained by the above-mentioned techniques, and the application of Burger-Ramberger's rules make it possible to conclude that there is a thermodynamic relation of monotropy between the two polymorphs. This last assumption may help formulators in predicting the relative stability of the two forms.

Thermal, spectroscopic, and ab initio structural characterization of carprofen polymorphs.

Commercial and recrystallized polycrystalline samples of carprofen, a nonsteroidal anti-inflammatory drug, were studied by thermal, spectroscopic, and structural techniques. Our investigations demonstrated that recrystallized sample, stable at room temperature (RT), is a single polymorphic form of carprofen (polymorph I) that undergoes an isostructural polymorphic transformation by heating (polymorph II). Polymorph II remains then metastable at ambient conditions. Commercial sample is instead a mixture of polymorphs I and II. The thermodynamic relationships between the two polymorphs were determined through the construction of an energy/temperature diagram. The ab initio structural determination performed on synchrotron X-Ray powder diffraction patterns recorded at RT on both polymorphs allowed us to elucidate, for the first time, their crystal structure. Both crystallize in the monoclinic space group type P2(1) /c, and the unit cell similarity index and the volumetric isostructurality index indicate that the temperature-induced polymorphic transformation I → II is isostructural. Polymorphs I and II are conformational polymorphs, sharing a very similar hydrogen bond network, but with different conformation of the propanoic skeleton, which produces two different packing. The small conformational change agrees with the low value of transition enthalpy obtained by differential scanning calorimetry measurements and the small internal energy computed with density functional methods.