Energy equipartition and frequency distribution in complex attachments.

As reported in several recent publications, an undamped simple oscillator with a complex attachment that consists of a set of undamped parallel resonators can exhibit unusual energy sharing properties. The conservative set of oscillators of the attachment can absorb nearly all the impulsive energy applied to the primary oscillator to which it is connected. The key factor in the ability of the attachment to absorb energy with near irreversibility correlates with the natural frequency distribution of the resonators within it. The reported results also show that a family of optimal frequency distributions can be determined on the basis of a variational approach, minimizing a certain functional related to the system response. The present paper establishes a link between these optimal frequency distributions and the energy equipartition principle: optimal frequency distributions are those that spread the injected energy as uniformly as possible over the degrees of freedom or over the modes of the system. Theoretical as well as numerical results presented support this point of view.

Vibration absorption using non-dissipative complex attachments with impacts and parametric stiffness.

Studies on prototypical systems that consist of a set of complex attachments, coupled to a primary structure characterized by a single degree of freedom system, have shown that vibratory energy can be transported away from the primary through use of complex undamped resonators. Properties and use of these subsystems as by energy absorbers have also been proposed, particularly using attachments that consist of a large set of resonators. These ideas have been originally developed for linear systems and they provided insight into energy sharing phenomenon in large structures like ships, airplanes, and cars, where interior substructures interact with a master structure, e.g., the hull, the fuselage, or the car body. This paper examines the effects of nonlinearities that develop in the attachments, making them even more complex. Specifically, two different nonlinearities are considered: (1) Those generated by impacts that develop among the attached resonators, and (2) parametric effects produced by time-varying stiffness of the resonators. Both the impacts and the parametric effects improve the results obtained using linear oscillators in terms of inhibiting transported energy from returning to the primary structure. The results are indeed comparable with those obtained using linear oscillators but with special frequency distributions, as in the findings of some recent papers by the same authors. Numerically obtained results show how energy is confined among the attached oscillators.

The thermal transformation of Man Made Vitreous Fibers (MMVF) and safe recycling as secondary raw materials (SRM).

This work describes the high temperature reaction sequence of commercial Man Made Vitreous Fibers (MMVF) Cerafiber, Superwool, Rock wool and Glass wool which may be used as substitute for asbestos in some industrial applications. Knowledge of the reaction path and transformation sequence is very important to assess whether carcinogenic crystalline phases are formed during devitrification, which may occur when used as insulators. In addition, knowledge about the nature of the phases formed at high temperature is mandatory to assess if thermally transformed MMVF can be safely recycled as secondary raw material (SRM). In this scenario, this study provides useful information for the optimization of the industrial annealing process aimed to attain a safe, recyclable product. The results of this work show that one of the high-temperature products of Cerafiber and Superwool is cristobalite which is classified as a carcinogenic. It was possible to define the temperature interval at which Cerafiber and Superwool fibers can be safely used as thermal insulators (e.g. insulators in tunnel and/or roller kilns, etc.). As cristobalite is formed in both synthetic fiber products at temperatures higher than 1200 degrees C, their use should be limited to devices operating at lower temperatures. Rock and Glass wool melt upon thermal treatment. As far as the industrial process of inertization is concerned, a maximum firing temperature of 1100 and 600 degrees C is required to melt Rock wool and Glass wool, respectively, with the high-temperature products that can be safely recycled as SRM. Recycling of these products in stoneware tile mixtures were subsequently attempted. The addition of 1-2 wt.% of the melts of Rock and Glass wool gave promising results in terms of viscous sintering reactions and resistance to staining with the only weak characteristic being the color properties of the fired bodies which tend to worsen.

Mitochondrial changes induced by natural and synthetic asbestos fibers: studies on isolated mitochondria.

Asbestos fibers, such as chrysotile and crocidolite, are known to have cytotoxic effects on different cell types. In vivo exposure to asbestos fibers can induce both fibrotic and malignant lung diseases , however, the mechanisms linking exposure to the subsequent development of the diseases are unknown. Numerous investigations suggest the involvement of reactive oxygen species (ROS). ROS are known to damage biological macromolecules including proteins, cell membrane lipids and nucleic acids; alterations of these essential cellular components can alter cell function and can drive the cell to neoplastic transformation or to cell death. Because the mitochondrial respiratory chain is an important source of ROS and RNS (reactive nitogen species) in the cells, we have investigated the effects of aqueous extracts of asbestos (natural and synthetic) fibers on some mitochondrial activities. Our data show that crocidolite fibers release substances in solution that may interfere directly with the mitochondrial cytochrome oxidase complex. Moreover, the calcium ions released from these fibers induce opening of the permeability transition pore of the inner membrane leading to a possible cytotoxic effect due to the release of apoptotic factors normally localized in the mitochondrial intermembrane space. In addition, crocidolite extracts enhance the mitochondrial production of ROS. No significant biochemical effects are exerted by chrysotile, either natural or synthetic, on isolated mitochondria. Nevertheless, all asbestos fibers tested induce morphological alterations visualized by transmission electron microscopy and morphometric analysis.

Customized hybrid biomimetic hydroxyapatite scaffold for bone tissue regeneration.

Three-dimension (3D) scaffolds for bone tissue regeneration were produced combining three different phases: nanometric hydroxyapatite (HA) was synthesized by precipitation method and the crystals nucleation took place directly within collagen fibrils following a biologically inspired mineralization process; polycaprolactone was employed to give the material a 3D structure. The chemico-physical analysis carried out to test the material's properties and composition revealed a high similarity in composition and morphology with biologically mineralized collagen fibrils and a scaffold degradation pattern suitable for physiological processes. The micro- computerized tomography (micro-CT) showed 53.53% porosity and a 97.86% mean interconnected pores. Computer-aided design and computer-aided manufacturing (CAD-CAM) technology was used for molding the scaffold's volume (design/shape) and for guiding the surgical procedure (cutting guides). The custom made scaffolds were implanted in sheep mandible using prototyped surgical guides and customized bone plates. After three months healing, scanning electron microscopy (SEM) analysis of the explanted scaffold revealed a massive cell seeding of the scaffold, with cell infiltration within the scaffold's interconnected pores. The micro-CT of the explanted construct showed a good match between the scaffold and the adjacent host's bone, to shield the implant primary stability. Histology confirmed cell penetration and widely documented neoangiogenesis within the entire scaffold's volume. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 723-734, 2017.

X-ray diffraction study of bovine lens capsule collagen.

The wide angle X-ray diffraction pattern of air-dried lens capsule collagen under tension is the same as the tendon collagen diffraction pattern with regard to the main reflections, and indicates that lens capsule collagen has the characteristic three-stranded helical structure with an axial repeat of 0.29 nm as tendon collagen. The low angle X-ray diffraction pattern shows several weak diffraction maxima corresponding to the meridional reflections of capsule collagen which show orders of 63.0 nm periodicity. This is an evidence of quarter staggered molecular assembly typical of tendon collagen even if less ordered. The results are consistent with the existence in lens capsule collagen of clearly defined molecular units, which can be oriented by stress and are packed in a poor-ordered fibrillar assembly.

HA/alginate hybrid composites prepared through bio-inspired nucleation.

Poorly crystalline apatite has been directly nucleated on self-assembling alginate chains by neutralization synthesis to obtain a biomimetic artificial bone-like composite. It has been observed that in preparing HA/alginate composites, Ca2+ ions present on the apatitic surface cross-link the alginate chains to produce a material with different morphology and thermal stability, both functions of the HA/alginate weight ratio. In vitro tests were performed on different samples in terms of both the HA/alginate ratio and synthesis temperature. All the samples were cultured for seven days with MG63 osteoblast-like cells and then underwent morphological and biochemical analyses (MTT and ALP tests). Scaffolds showed a different solubility into the culture media, which was related to the temperature of synthesis and to the HA/alginate ratio. All our data confirm the ability of the tested materials to favour cell growth and to maintain their osteoblastic functionality, at least during the examined period.

Hydroxyapatite-gelatin films: a structural and mechanical characterization.

Composite films of gelatin and hydroxyapatite were prepared and characterized by mechanical tests, scanning electron microscopy and X-ray diffraction investigation. The mechanical properties of the films are greatly affected by the presence of hydroxyapatite and change as a function of inorganic phase content. On stretching, the long axis of the collagen molecular portions align parallel to the direction of deformation and the gelatin coarse layered structure becomes more evident and ordered. Furthermore, under deformation the inorganic crystals, which are embedded in the gelatin layers, seem to squeeze out in the interlayer spaces and assume a preferential orientation parallel to the force trajectories. Thus, as the inorganic phase stiffens the gelatin films, the macromolecular matrix distributes the stress promoting the preferential orientation of the apatitic crystals. The results indicate that this experimental approach can be used to prepare composites with anisotropic properties, which can be modulated through variation in composition and mechanical deformation in order to get biomaterials suitable to fulfill specific mechanical functions.

In vitro calcified tendon collagen: an atomic force and scanning electron microscopy investigation.

Atomic force microscopy (AFM), scanning electron microscopy and X-ray energy dispersive spectroscopy have been performed on decalcified turkey tendons submitted to in vitro calcification in order to investigate the morphology and the surface relationships between the inorganic phase and the collagen fibres during deposition and compare with those found for physiologically calcified samples. 'Tapping mode' AFM was used to reduce the vertical force applied to the samples, which were examined without any preparation. A further characterization has been carried out by means of X-ray diffraction, infrared absorption and chemical analyses. The observations indicate that the inorganic phase deposited on collagen fibres during in vitro calcification is poorly crystalline B carbonated apatite. The composition, structure and dimensions of apatitic crystallites, as well as their orientation with respect to collagen fibrils, are very similar to those characteristic of physiologically calcified tissues. However, the crystallites seem to be nucleated on the fibril surface, without appreciably affecting the molecular packing of collagen.

Stabilization of gelatin films by crosslinking with genipin.

The possibility to stabilize gelatin films by crosslinking with genipin was investigated through a mechanical, chemical and thermal characterization of samples treated with genipin solutions at different concentrations. The extent of crosslinking, evaluated as difference between the number of free epsilon -amino groups before and after crosslinking, increases as a function of genipin concentration up to about 85%. Simultaneously, the deformability of the films decreases whereas the Young's modulus E, increases. Furthermore, crosslinking provokes a significant reduction of the swelling in physiological solution, and enhances the thermal stability of the samples, as indicated by the results of the d.s.c. investigation. The data obtained from the films treated with genipin at concentrations higher than 0.67% are quite similar, and indicative of a good stabilizing effect of genipin. In spite of the small gelatin release (2%) observed after 1 month of storage in buffer solution, the mechanical, thermal and swelling properties of the films are very close to those previously obtained for glutaraldehyde crosslinked gelatin, and suggest that genipin, which is by far less cytotoxic, can be considered a valid alternative for crosslinking gelatin biomaterials.

Drawn gelatin films with improved mechanical properties.

Chain anisotropic distribution in gelatin films has been obtained by uniaxial stretching at constant relative humidity, followed by air drying and successive cross-linking with glutaraldehyde. The drawn samples have been characterized by mechanical tests, differential scanning calorimetry and scanning electron microscopy. The Young's modulus, E, and the stress at break, sigma(b), increase linearly with the draw ratio and reach values which are about five times those characteristic of undrawn samples. Furthermore, on stretching the alignment of the gelatin strands along the direction of deformation increases while the thickness of the layers decreases significantly. The renaturation level, that is the fraction of gelatin in a collagen-like structure, has been calculated as the ratio between the melting enthalpy of gelatin samples and that of tendon collagen. The results indicate that the improvement of mechanical properties achieved by drawn gelatin is closely related to the renaturation level. The experimental approach utilized to induce segmental orientation in gelatin films, allows to obtain anisotropic materials with improved mechanical properties in the direction of deformation, and can be usefully applied in the preparation of biomaterials.

Mechanical and thermal properties of gelatin films at different degrees of glutaraldehyde crosslinking.

The mechanical, thermal, swelling and release properties of glutaraldehyde (GTA) crosslinked gelatin films have been investigated in order to verify the influence of GTA concentration on the stability of the films. Air-dried films were submitted to treatment with GTA solutions at concentrations ranging from 0.05 to 2.5 wt%. At the smallest GTA concentration, the crosslinking degree, determined by trinitrobenzensulfonic acid assay, amounts to about 60% and increases up to values near 100%, obtained with GTA concentrations > or = 1 wt%. Simultaneously, the deformability of the films decreases, whereas the stress at break, sigmab, and the Young's modulus, E, increase. A crosslinking degree of about 85%, obtained using 0.25% GTA, is enough to prevent gelatin release in buffer solution and to provoke a significant reduction of the swelling in physiological solution. Furthermore, crosslinking greatly affects the thermal stability of the samples, as indicated by the results of differential scanning calorimetry (d.s.c.) investigation carried out on wet and air-dried films. The data suggest that the use of GTA at low concentration, which is desiderable to prevent toxicity, allows to modulate the physico-chemical properties of gelatin films, in order to obtain stable materials with a wide range of possible biomedical applications.

X-ray diffraction study of in vitro calcification of tendon collagen.

Decalcified samples of turkey leg tendon were submitted to in vitro calcification in the presence of metastable solutions of calcium phosphate at different concentrations. The structural relationship between apatitic deposits and collagen fibrils was examined by high- and small-angle X-ray diffraction using conventional and synchrotron radiation sources. At high supersaturation the apatitic crystallites were deposited on the collagen fibrils with their crystallographic c-axis preferentially oriented parallel to the fibril axis. At lower supersaturation, a fraction of the apatitic crystallites also grew with the c-axis preferentially oriented parallel to the collagen fibril axis, whereas other exhibited a preferential orientation perpendicular to the fibril axis. The analysis of the small-angle X-ray diffraction data indicates that the deposition of the apatitic phase in the sample stored in solution at lower supersaturation induced modifications of the collagen electron density distribution in the axial direction, which can be attributed to the deposition of the inorganic crystallites inside the gap region of the collagen structure.

Characterization of synthetic apatites for bioceramic implants.

Hydroxyapatite has been studied as a substance suitable for surgical substitution of bones and teeth with emphasis on its biocompatibility. The present work tries to identify the characteristics of this material either from the chemico-physical-structural point of view, or from the technological one, evaluating the best performance. By X-ray, i.r., thermal, chemical and SEM analyses, the relationship of different phenomena involved in the sintering was evaluated. Technological tests demonstrated the stability and the workability characteristics. In particular, the influence of CO2 was studied, in connection with the most suitable technique for hydroxyapatite (HAP) sintering, considering the eventual aims and requirements for industrial production.

Ultrastructural and biochemical modifications of collagen from tissue of Morbus Dupuytren patients.

Small angle X-ray diffraction and biochemical analyses were carried out on normal palmar aponeurosis and on tissue from patients suffering from Dupuytren contractures (MD). Pathological tissue exhibits a higher overall content of collagen III. Type I collagen extracted from pathological tissue has a melting point of 0.8 degrees C higher than that of normal collagen. The only chemical differences compared to normal collagen I are 50% overhydroxylation of lysyl residues and a reduced amount of diglycosylated hydroxylysine residues. Analysis of the electron density distribution inside the collagen repeating period of MD-samples reveals disordered molecular packing in MD samples compared to in normal collagen. The disorder, which is higher in the gap region, is considerably reduced upon stretching.

Structural and morphological characterization of synthetic chrysotile single crystals.

Stoichiometric chrysotile single crystals have been synthesized as a unique phase by hydrothermal reaction under controlled conditions; the synthesized monocrystals show a cylinder-in-cylinder morphology and can be used as a reference sample with definite chemical composition to investigate the factors responsible of the chrysotile cytotoxicities and carcinogenicities.

Relationship between Solid State NMR Parameters and X-ray Structural Data in Tricadmium Phosphates.

31P and (113)Cd MAS NMR spectra of solid beta'-tricadmium phosphate (beta'-TCdP) show a number of highly resolved resonances that agree well with the number of independent crystallographic sites indicated by the results of X-ray diffraction studies. A correlation of the (31)P chemical shifts with the crystallographic sites for the six different PO(4)(3)(-) groups in the unit cell of beta'-TCdP has been obtained by a method based on the computation of bond strength at oxygen atoms in phosphate moieties. The assignment of the (113)Cd resonances has been carried out on the basis of the relationship between the asymmetry of the chemical shift tensor (evaluated by analysis of the spinning side bands intensities in the MAS spectrum) and a geometric parameter related to the distortion from the bipyramidal trigonal coordination at each cadmium center. Samples of tricadmium phosphate with different degrees of magnesium substitution for cadmium were investigated by (31)P MAS NMR, (113)Cd MAS NMR, and X-ray diffraction. The results of these investigations showed that the magnesiums distribute randomly in the cadmium sites, inducing a marked decrease in the order of the structure.

Thermal conversion of octacalcium phosphate into hydroxyapatite.

The thermal conversion of octacalcium phosphate into hydroxyapatite has been investigated by a crystallographic, thermogravimetric, and calorimetric study. The conversion of octacalcium phosphate takes place through the remotion of three of its five water molecules and yields a poor crystalline apatitic phase. The three water molecules are lost in two steps. The first one, which is reversible, corresponds to the remotion of one water molecule and induces a slight contraction of the unit cell of OCP. The successive remotion of two water molecules, which provokes the structural conversion of OCP into apatite, is in irreversible process. The mechanism of the water loss of OCP is explained in terms of its crystal structure.

Thermal behavior of bone and synthetic hydroxyapatites submitted to magnesium interaction in aqueous medium.

The thermal behavior of the products obtained from magnesium interaction with powdered femoral bone and carbonate containing synthetic hydroxyapatite under conditions of pH fluctuation in aqueous medium has been investigated. The products, heat treated at different temperatures from 100 to 1300 degrees C, have been characterized by infrared spectroscopy and X-ray diffraction technique. The results show that the interaction with magnesium ion destabilizes the apatitic structure and favours its thermal conversion into beta-tricalcium phosphate (beta-TCP). The replacement of magnesium with calcium in the beta-TCP crystal lattice hinders its subsequent thermal conversion into the alpha form. The influence of magnesium on the thermal stability is much more evident for carbonate-containing synthetic hydroxyapatite than for bone apatite.

Structural and chemical characterization of gallstones resistant to dissolution therapy.

X-ray diffraction, i.r. spectroscopic, and chemical analyses have been carried out on radiolucent gallstones resistant to dissolution therapy. Cholesterol represents the main component of all the examined stones, while the ratio between the amounts of pigmented material and calcium carbonate is about 1 in the inner and outer layers of the stones and 3 in the medial layer. Calcium carbonate is present in two distinct crystalline forms: vaterite, which is the main inorganic crystalline phase, and calcite. The cell parameters of vaterite and calcite are shorter in the inner and outer layers of the stones than in the medial layer. The observed variation of the cell parameters has been related to the substitution of copper to calcium in the carbonate structures, on the basis of the data obtained on vaterite and calcite synthesized in presence of different copper concentrations in solution. The results indicate that the failure of the dissolution therapy can be related to the inhomogeneous distribution in the stones of calcium carbonate and calcium bilirubinate.