A Commercial Clay-Based Material as a Carrier for Targeted Lysozyme Delivery in Animal Feed.

The controlled supply of bioactive molecules is a subject of debate in animal nutrition. The release of bioactive molecules in the target organ, in this case the intestine, results in improved feed, as well as having a lower environmental impact. However, the degradation of bioactive molecules' in transit in the gastrointestinal passage is still an unresolved issue. This paper discusses the feasibility of a simple and cost-effective procedure to bypass the degradation problem. A solid/liquid adsorption procedure was applied, and the operating parameters (pH, reaction time, and LY initial concentration) were studied. Lysozyme is used in this work as a representative bioactive molecule, while Adsorbo®, a commercial mixture of clay minerals and zeolites which meets current feed regulations, is used as the carrier. A maximum LY loading of 32 mgLY/gAD (LY(32)-AD) was obtained, with fixing pH in the range 7.5-8, initial LY content at 37.5 mgLY/gAD, and reaction time at 30 min. A full characterisation of the hybrid organoclay highlighted that LY molecules were homogeneously spread on the carrier's surface, where the LY-carrier interaction was mainly due to charge interaction. Preliminary release tests performed on the LY(32)-AD synthesised sample showed a higher releasing capacity, raising the pH from 3 to 7. In addition, a preliminary Trolox equivalent antioxidant capacity (TEAC) assay showed an antioxidant capacity for the LY of 1.47 ± 0.18 µmol TroloxEq/g with an inhibition percentage of 33.20 ± 3.94%.

Capture and Release Mechanism of Ni and La Ions via Solid/Liquid Process: Use of Polymer-Modified Clay and Activated Carbons.

This study is a starting point for the development of an efficient method for rare earths (REs) and transition metals (TMs) recovery from waste electrical and electronic equipment (WEEE) via a hydrometallurgical process. The capture and release capability of mineral clays (STx) and activated carbons (AC), pristine and modified (STx-L6 and AC-L6) with a linear penta-ethylene-hexamine (L6), towards solutions representative of the process, are assessed in the lab-scale. The solids were contacted with synthetic mono- and bi-ionic solutions containing Ni(II) and La(III) in a liquid/solid adsorption process. Contacting experiments were carried out at room temperature for 90 min by fixing a La concentration at 19 mM and varying the Ni one in the range of 19-100 mM. The four solids were able to capture Ni(II) and La(III), both in single- and bi-ionic solutions; however, the presence of the polyamine always results in a large improvement in the capture capability of the pristine sorbents. For all the four solids, capture behaviour is ascribable to an adsorption or ion-sorbent interaction process, because no formation of aquo- and hydroxy-Ni or La can be formed. The polyamine, able to capture Ni ions via coordination, allowed to differentiate ion capture behaviour, thus bypassing the direct competition between Ni and La ions for the capture sites found in the pristine solids. Release values in the 30-100% range were found upon one-step treatment with concentrated HNO3 solution. However, also, in this case, different metals recovery was found depending on both the sorbent and the ions, suggesting a possible selective recovery.

Influence of the Degradation Medium on Water Uptake, Morphology, and Chemical Structure of Poly(Lactic Acid)-Sisal Bio-Composites.

A series of poly(lactic acid) (PLA) and poly(lactic acid)-based bio-composites (sisal PLA) were prepared and studied by spectroscopic and microscopic techniques as such and after immersion at room temperature in different degradation mediums (i.e., distilled and natural sea water and solutions at pH = 2, 6, and 8). In these conditions, some of their macroscopic and microscopic properties were monitored during a period of 30 days. Water absorption increased with the increasing fiber content regardless of the immersion medium. The maximum water absorption was achieved at pH = 8 (~16%), indicating a more severe action of the alkaline mediums on the samples. The diffusivity, D, of PLA decreased with the addition of fibers and acidic mediums showed higher D, indicating higher diffusivity of water through the specimens with respect to those submerged in moderate or alkaline mediums. Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) analysis evidenced a weak interaction between the PLA matrix and the sisal fibers. Very limited degradation phenomena occur in our conditions: Despite some changes in the microstructure, the PLA backbone seems to be largely resistant to hydrolysis, almost regardless of the pH value and even at the highest sisal content.

Polyamine-Based Organo-Clays for Polluted Water Treatment: Effect of Polyamine Structure and Content.

Hybrid materials based on clays and polyamines are supposed to be efficient heavy metals sorbents due to the well-known adsorption behaviour of the clay matrix and to the coordination properties of un-protonated amino groups. For this purpose, a montmorillonite clay was modified with three different aliphatic polyamines: L6 and L10 have a linear structure with six and ten amino groups, respectively, while B14 is a branched polyamine with fourteen amino groups. Initial amine concentration was the main parameter investigated and data were fitted with Langmuir and Freundlich models. Interaction mechanisms between clay and amines were deeply investigated by different experimental techniques such as X-ray powder diffraction (XRD), thermal analysis measurements (DTG), Fourier Transform Infrared Spectroscopy (FT-IR) and diffuse reflectance (NIR) spectroscopy. Experimental results showed that the amount of amines efficiently immobilized in the solid phase can be increased by increasing the initial concentration of polyamines in the clay modification process. These data were best fitted by Freundlich model, indicating a presence of surface sites of different nature. In the resulting hybrid materials, neither the accessibility of the NH/NH2 groups of the amines, nor the accessibility of the structural OH of the clay was hindered. Several preliminary tests in La ions' uptake and release from aqueous solution were also carried out. In the conditions used for this study, total metal ion removal was achieved at sufficiently low linear amine loadings (i.e., 0.45 mmol/gclay for the small L6 amine), suggesting that these hybrid materials are promising for the proposed application in environmental remediation.

Fabrication of alginate modified brushite cement impregnated with antibiotic: Mechanical, thermal, and biological characterizations.

Treatment of postsurgical infections, associated with orthopedic surgeries, has been a major concern for orthopedics. Several strategies including systematic and local administration of antibiotics have been proposed to this regard. The present work focused on fabricating alginate (Alg) modified brushite (Bru) cements, which could address osteogeneration and local antibiotic demands. To find the proper method of drug incorporation, Gentamicin sulfate (Gen) was loaded into the samples in the form of solution or powder. Several characterization tests including compression test, morphology, cytotoxicity, and cell adhesion assays were carried out to determine the proper concentration of Alg as a modifier of the Bru cement. The results indicated that addition of 1 wt% Alg led to superior mechanical and biological properties of the cement. Moreover, Alg addition changed the morphology of the cement from plate and needle-like structures to petal-like structure. Fourier transform infrared spectroscopy results confirmed the successful loading of Gen on the cements, specifically when Gen solution was used, and X-Ray Diffractometer result indicated that Gen caused a decrease in crystalline size. Furthermore, thermal analysis revealed that Gen-loaded sample had more stable structure as the transformation temperature slightly shifted to a higher one. The stability study confirmed the chemical stability and adequate mechanical performance of the cements within 1 month of soaking time. Finally, the addition of Alg has a positive impact on the release behavior at low concentration of Gen solution so that 20% decrease within 2 weeks of release experiment was remarkably detected.

Surface Characterization of Mesoporous CoOx/SBA-15 Catalyst upon 1,2-Dichloropropane Oxidation.

The active combustion catalyst that is based on 30 wt % cobalt oxide on mesoporous SBA-15 has been tested in 1,2-dichloropropane oxidation and is characterized by means of FT-IR (Fourier transform infrared spectroscopy) and ammonia-TPD (temperature-programmed desorption). In this work, we report the spectroscopic evidence for the role of surface acidity in chloroalkane conversion. Both Lewis acidity and weakly acidic silanol groups from SBA support are involved in the adsorption and initial conversion steps. Moreover, total oxidation reaction results in the formation of new Bronsted acidic sites, which are likely associated with the generation of HCl at high temperature and its adsorption at the catalyst surface. Highly dispersed Co oxide on the mesoporous support and Co-chloride or oxychloride particles, together with the presence of several families of acidic sites originated from the conditioning effect of reaction products may explain the good activity of this catalyst in the oxidation of Chlorinated Volatile Organic Compounds.

Innovative Mesoporous Nanosilicas: SBR Nanocomposite for Low Environmental Impact Tread Tyre.

Silica nanoparticles with different aspect ratios (A.R.) were tested as reinforcing fillers of styrenebutadiene copolymer (s-SBR) for "green tyres," i.e., tires with lower rolling resistance. A commercial nanosilica with A.R. = 1 (Aerosil® 200) was compared with two nanosilica samples with A.R. = 2 and 4, synthesized by means of an innovative process, to ascertain if the filler shape was significant to improve the composite properties. In addition, bis-triethoxysilylpropyltetrasulfide was grafted onto the particles surface, in order to obtain more hydrophobic materials and to enhance their dispersion in the elastomeric composites: pristine and modified silicas were then compared. Grafting extent was evaluated by thermogravimetric analysis. The surface properties of silicas were investigated by Fourier transform infrared spectroscopy and inverse gas chromatography. s-SBR/silica nanocomposites were then prepared and characterized assessing their dynamic-mechanical properties and carrying out morphological observations by transmission electron microscopy.

3D Porous Gelatin/PVA Hydrogel as Meniscus Substitute Using Alginate Micro-Particles as Porogens.

One of the current major challenges in orthopedic surgery is the treatment of meniscal lesions. Some of the main issues include mechanical consistency of meniscal implants, besides their fixation methods and integration with the host tissues. To tackle these aspects we realized a micro-porous, gelatin/polyvinyl alcohol (PVA)-based hydrogel to approach the high percentage of water present in the native meniscal tissue, recapitulating its biomechanical features, and, at the same time, realizing a porous implant, permissive to cell infiltration and tissue integration. In particular, we adopted aerodynamically-assisted jetting technology to realize sodium alginate micro-particles with controlled dimensions to be used as porogens. The porous hydrogels were realized through freezing-thawing cycles, followed by alginate particles leaching. Composite hydrogels showed a high porosity (74%) and an open porous structure, while preserving the elasticity behavior (E = 0.25 MPa) and high water content, typical of PVA-based hydrogels. The ex vivo animal model validation proved that the addition of gelatin, combined with the micro-porosity of the hydrogel, enhanced implant integration with the host tissue, allowing penetration of host cells within the construct boundaries. Altogether, these results show that the combined use of a water-insoluble micro-porogen and gelatin, as a bioactive agent, allowed the realization of a porous composite PVA-based hydrogel to be envisaged as a potential meniscal substitute.

New in-situ synthetized hydrogel composite based on alginate and brushite as a potential pH sensitive drug delivery system.

A Series of in-situ alginate-brushite (Alg-Bru) hydrogel composites were fabricated to optimize release profile of ibuprofen (Ibu) and to avoid burst releases associated with the pure form of the hydrogels. The Bru crystals were synthetized and dispersed during the crosslinking process of Alg matrix. The beads with different formulations were subject to various characterization tests such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), dynamic mechanical analysis (DMA), and swelling. In addition, the entrapment Efficiency (%EE) and drug release profile were obtained to investigate the impacts of initial concentration of Alg and content of Bru on these parameters. FTIR and XRD outcomes confirmed the successful fabricating of Alg-Bru composite as well as the loading of Ibu. Besides, the results showed that the presence of Bru within Alg matrix restricted polymer chain movement, improved mechanical properties, and decreased swelling ratio. Although the presence of Bru crystals did not improve%EE, they optimized the release profile in a more gradual manner.

Molecular level interactions in brushite-aminoacids composites.

The interaction of aminoacids (Glycine, Proline, Lysine) with brushite based bone cements has been investigated by several techniques (FTIR spectroscopy, Thermogravimetry-TG, Scanning Electron Microscopy-SEM, mechanical properties studies), with the aim to elucidate the properties of the resulting composite materials and the interaction occurring at molecular level between the inorganic matrix and the organic moieties. Brushite phase is predominantly obtained also in the presence of aminoacids added during preparation of the bone cement. Focusing on Glycine incorporation, the presence of a fraction of bulk Glycine, weakly interacting with the inorganic matrix, together with Glycine specifically interacting with adsorption sites can be envisaged, as pointed out by FT IR and thermogravimetric data. In detail, FT-IR data evidenced changes in shape and position of bands associated to stretching modes of the carboxylic groups in Glycine structure, which can be explained by the coordination of these functional groups with the Ca ions in the matrix. Heating this composite at controlled temperature results in the detection of a condensation products, either cyclic condensation product, either dipeptide. Diffuse and not specific H-bonding seems to be the main form of interaction of Proline and Lysine with brushite. Due to the coordination with Ca ions here described, Glycine can act as retardant during brushite preparation, allowing good workability of the resulting composite.

Synthesis and characterization of poly-L-leucine initialized and immobilized by rehydrated hydrotalcite: understanding stability and the nature of interaction.

PLLs were synthesized by the ring-opening polycondensation (ROP) method using α-L-leucine N-carboxyanhydride (NCA) and initialized by triethylamine (Et3N), water or rehydrated hydrotalcite (HTrus). The role of temperature, different initiators and water in ROP was further investigated. In general, the initiators used in the polymerization reaction lead to PLL alpha-helical chains containing 5-40 monomers with NCA endgroups via a monomer-activated mechanism. However, the water has a twofold effect on ROP, as both a nucleophile and a base, which involves competition between two different types of initiating mechanisms (nucleophilic attack or deprotonation of the NCA monomer) in the polymerization reaction. This competition provides as a main product NCA endgroups with an alpha-helical structure and leads to the formation of the PLL cyclic-chains and beta-sheet structures which reduce the polymer Mw and the PD of the polypeptide. Furthermore, the water can hydrolyze the NCA endgroups resulting in PLL alpha-helical chains that contain living groups as the main product. On the other hand, the HTrus presents a double role: as both an initiator and a support. The polymers synthesized in the presence of HTrus presented a HT-carboxylate endgroup. The PLLs immobilized in HTrus through an anion-exchange method performed for just 30 minutes presented the PLL immobilized in the interlayer space of the HTrus. The PLL chains of the immobilized counterpart are stabilized by H-bonding with the M-OH of the HT structure. All the polypeptides and biohybrid materials synthesized have been characterized using different techniques (EA, ICP, XRD, Raman, MALDI-TOF, ESI-TOF, FT-IR at increasing temperatures, TG/DT analyses and TEM).

Effects of pH on chromate(VI) adsorption by Spirulina platensis biomass: batch tests and FT-IR studies.

Raw and methylated biomass of Spirulina platensis was employed in chromate batch adsorption tests at pH range 1-7. The acid conditions seemed to favour the removal of chromium (Cr) with a yield of 87.0 and 97.6% by using raw and methylated biomass, respectively. However, the chromate and total chromium determination, carried out in the same sample, evidenced that a fraction of the initial chromate present in solution was reduced to Cr(III). This was ascribed to the presence of reducing groups on the biomass surface, active in the acid medium. The data showed that the methylated biomass was able to operate an effective Cr(VI) removal only. In fact, the biomass treatment allowed a lowering of the amount of negative functional groups, making the biomass surface available to bind the anions. The real best efficiency of Cr(VI) removal (83.5%) was obtained by methylated biomass of S. platensis at pH about 7.0. The nature of the biomass/chromate interactions was investigated by Fourier transform infrared spectroscopy (FT-IR) analysis. The bands ascribing to the adsorbed Cr(VI) species were well evident in the spectra of the biomass after adsorption, confirming this experimental finding.

Metal biosorption onto dry biomass of Arthrospira (Spirulina) platensis and Chlorella vulgaris: multi-metal systems.

Binary and ternary systems of Ni(2+), Zn(2+), and Pb(2+) were investigated at initial metal concentrations of 0.5, 1.0 and 2.0mM as competitive adsorbates using Arthrospira platensis and Chlorella vulgaris as biosorbents. The experimental results were evaluated in terms of equilibrium sorption capacity and metal removal efficiency and fitted to the multi-component Langmuir and Freundlich isotherms. The pseudo second order model of Ho and McKay described well the adsorption kinetics, and the FT-IR spectroscopy confirmed metal binding to both biomasses. Ni(2+) and Zn(2+) interference on Pb(2+) sorption was lower than the contrary, likely due to biosorbent preference to Pb. In general, the higher the total initial metal concentration, the lower the adsorption capacity. The results of this study demonstrated that dry biomass of C. vulgaris behaved as better biosorbent than A. platensis and suggest its use as an effective alternative sorbent for metal removal from wastewater.

Hybrid organo-inorganic clay with nonionic interlayers. mid- and near-IR spectroscopic studies.

The intercalation of organic polymers molecules (i.e., PEGs and BRIJ) into a standard Ca-montmorillonite has been studied by XRD, TG, and IR spectroscopy. The polymer intercalation is confirmed by the increasing of the d(001) in XRD spectra as well as by the complex multisteps thermal decomposition behavior of the organo-clay materials. Mid-IR and diffuse reflectance near-IR spectra of the intercalated materials show the polymer diagnostic bands (CH stretching and deformation mode), shifted or changed in shape by the interaction with the clay matrix. Both PEG 1500 and PEG 4000 based materials are likely intercalated in an extended configuration, similar to the amorphous polymer form. BRIJ intercalated polymer spectra suggest the disordered conformation of the alkilic chain in a prevailing "gauche", poorly packed, conformation. Host montmorillonite IR bands, mainly OH and water stretching and deformation fundamentals, combination, and overtone bands, are reduced in intensity by polymer intercalation, pointing out an interaction, likely through H-bonding and/or a possible substitution of cations hydration water molecules.

Decomposition of hexamethylcyclotrisiloxane over solid oxides.

The decomposition of hexamethylcyclotrisiloxane (HMCTS) has been studied at room temperature and in the range 473-673 K over the surface of basic (CaO, MgO) and acidic oxides (Al(2)O(3), SiO(2)). Alumina allows the complete removal of HMCTS from synthetic biogases at 673 K. A reactive adsorption occurs with surface silication and release of methane. The adsorption capacity of our alumina adsorbent (180 m(2) g(-1)), until saturation, at 673 K, is 0.31 g((HMCTS))g((Al2O3))(-1), which corresponds to one silicon atom per 9 A(2), i.e. the silication monolayer capacity. On the contrary, silica, which is an excellent adsorbent for siloxanes at room temperature, looses its adsorption ability at high temperature as it is typical of a molecular adsorption behavior. Basic oxides such as MgO and CaO have strong reactivity in decomposing siloxanes in the absence of CO(2), but loose reactivity when in contact with carbon dioxide because of surface carbonation.

State of supported rhodium nanoparticles for methane catalytic partial oxidation (CPO): FT-IR studies.

The effect of pretreatments as well as of rhodium precursor and of the support over the morphology of Rh nanoparticles were investigated by Fourier transform infrared (FT-IR) spectroscopy of adsorbed CO. Over a Rh/alumina catalyst, both metallic Rh particles, characterized by IR bands in the range 2070-2060 cm-1 and 1820-1850 cm-1, and highly dispersed rhodium species, characterized by symmetric and asymmetric stretching bands of RhI(CO)2 gem-dicarbonyl species, are present. Their relative amount changes following pretreatments with gaseous mixtures, representative of the catalytic partial oxidation (CPO) reaction process. The Rh metal particle fraction decreases with respect to the Rh highly dispersed fraction in the order CO approximately CO/H2 > CH4/H2O, CH4/O2 > CH4 > H2. The metal particle dimensions decrease in the order CH4/O2 > H2 > CH4/H2O > CO > CO/H2. Grafting from a carbonyl rhodium complex also increases the amount and the dimensions of Rh0 particles at the catalyst surface. Increasing the ratio (extended rhodium metal particles/highly dispersed Rh species) allows a shorter conditioning process. The surface reconstruction phenomena going on during catalytic activity are related to this effect.