Efficiency of sepiolite in broilers diet as uranium adsorbent.

The use of phosphate mineral products in animal nutrition, as a major source of phosphor and calcium, can lead to uranium entering the food chain. The aim of the present study was to determine the protective effect of natural sepiolite and sepiolite treated with acid for broilers after oral intake of uranium. The broilers were contaminated for 7 days with 25 mg/uranyl nitrate per day. Two different adsorbents (natural sepiolite and sepiolite treated with acid) were given via gastric tube immediately after the oral administration of uranium. Natural sepiolite reduced uranium distribution by 57% in kidney, 80% in liver, 42% in brain, and 56% in muscle. A lower protective effect was observed after the administration of sepiolite treated with acid, resulting in significant damage of intestinal villi in the form of shortening, fragmentation, and necrosis, and histopathological lesions on kidney in the form of edema and abruption of epithelial cells in tubules. When broilers received only sepiolite treated with acid (no uranyl nitrate), shortening of intestinal villi occurred. Kidney injuries were evident when uranium concentrations in kidney were 0.88 and 1.25 µg/g dry weight. It is concluded that adding of natural sepiolite to the diets of broilers can reduce uranium distribution in organs by significant amount without adverse side effects.

Real-time application and modelling of the NOx-sorption reaction on a particulate calcium carbonate surface-flow filter exposed to combustion exhaust.

Of major interest, especially in city environments, and increasingly inside vehicles or industrial plants, is the drive to reduce human exposure to nitrogen oxides (NOx). This trend has drawn increasing attention to filtration, which has developed remarkably owing to the capabilities of recently developed mathematical models and novel filter concepts. This paper reports on the study of the kinetic modelling of adsorption of nitrogen dioxide (NO2), collected from the tailpipe of a diesel engine, reacting to calcium nitrate salt (Ca(NO3)2) on a surface flow filter consisting of a coating of fine ground limestone or marble (CaCO3) in combination with micro-nanofibrillated cellulose (MNFC) acting as binder and humectant applied onto a multiply recycled newsprint substrate. The coating and substrate are both porous, but on different pore size scales, with the coating having significantly lower permeability. To maximise gas-coating contact, therefore, the coating deposition is pixelated, achieved by pin coating. An axially dispersed gaseous plug flow model (dispersion model) was used to simulate the transport within the coating pore network structure, following earlier flow modelling studies, and a kinetic reaction model was used to examine NO2 to NO3- conversion in correlation with experimental results. Modelling results indicate a 60.38% conversion of exposed NO2 gas to Ca(NO3)2 under the specific conditions applied, with an absolute relative error between the predicted and experimentally estimated value being 0.81%. The model additionally enabled a prediction of effects of changing parameters over a limited perturbation range, thus assisting in predicting filter element consumption, with attention given to the active component CaCO3 surface as a function of particle size in relation to the gas contact exchange, promoting the reaction over time. It is intended that the Ca(NO3)2 formed from the reaction can go on to be used as a value-added fertiliser, thus contributing to circular economy.

Micro Nanofibrillated Cellulose as Functional Additive Supporting Processability of Surface-Active Mineral Suspensions: Exemplified by Pixel Coating of an NOx-Sorbent Layer.

Unlike established coating formulations, functional particulate coatings often demand the omission of polymer dispersant so as to retain surface functionality. This results in heterogeneous complex rheology. We take an example from a novel development for an NOx mitigation surface flow filter system, in which ground calcium carbonate (GCC), applied in a coating, reacts with NO2 releasing CO2. Inclusion of mesoporous ancillary mineral acts to capture the CO2. The coating is applied as droplets to maximize gas-contact dynamic by forming a pixelated 2D array using a coating device consisting of protruding pins, which are loaded by submersion in the aqueous coating color such that the adhering droplets are transferred onto the substrate. The flow is driven by surface meniscus wetting causing lateral spread and bulk pore permeation. Filamentation occurs during the retraction of the pins. Stress-related viscoelastic and induced dilatancy in the suspension containing the ancillary mesoporous mineral disrupts processability. Adopting shear, oscillation and extensional rheometric methods, we show that the inclusion of an ancillary mineral that alone absorbs water, e.g., perlite (a naturally occurring porous volcanic glass), is rheologically preferable to one that in addition to absorbing water also immobilizes it on the mineral surface, e.g., sepiolite. When including micro-nanofibrillated cellulose (MNFC), critical for maintaining moisture to support NO2 sorption, it is observed that it acts also as a flow modifier, enabling uniform coating transfer to be achieved, thus eliminating any possible detrimental effect on mineral surface activity by avoiding the use of soluble polymeric dispersant.

Biodegradable Cellulose/Polycaprolactone/Keratin/Calcium Carbonate Mulch Films Prepared in Imidazolium-Based Ionic Liquid.

Ionic liquid 1-butyl-3-methylimidazolium chloride [BMIM][Cl] was used to prepare cellulose (CELL), cellulose/polycaprolactone (CELL/PCL), cellulose/polycaprolactone/keratin (CELL/PCL/KER), and cellulose/polycaprolactone/keratin/ground calcium carbonate (CELL/PCL/KER/GCC) biodegradable mulch films. Attenuated Total Reflectance Fourier-Transform Infrared (ATR-FTIR) spectroscopy, optical microscopy, and Field-Emission Scanning Electron Microscopy (FE-SEM) were used to verify the films' surface chemistry and morphology. Mulch film made of only cellulose regenerated from ionic liquid solution exhibited the highest tensile strength (75.3 ± 2.1 MPa) and modulus of elasticity of 944.4 ± 2.0 MPa. Among samples containing PCL, CELL/PCL/KER/GCC is characterized by the highest tensile strength (15.8 ± 0.4 MPa) and modulus of elasticity (687.5 ± 16.6 MPa). The film's breaking strain decreased for all samples containing PCL upon the addition of KER and KER/GCC. The melting temperature of pure PCL is 62.3 °C, whereas that of CELL/PCL film has a slight tendency for melting point depression (61.0 °C), which is a characteristic of partially miscible polymer blends. Furthermore, Differential Scanning Calorimetry (DSC) analysis revealed that the addition of KER or KER/GCC to CELL/PCL films resulted in an increment in melting temperature from 61.0 to 62.6 and 68.9 °C and an improvement in sample crystallinity by 2.2 and 3.0 times, respectively. The light transmittance of all studied samples was greater than 60%. The reported method for mulch film preparation is green and recyclable ([BMIM][Cl] can be recovered), and the inclusion of KER derived by extraction from waste chicken feathers enables conversion to organic biofertilizer. The findings of this study contribute to sustainable agriculture by providing nutrients that enhance the growth rate of plants, and hence food production, while reducing environmental pressure. The addition of GCC furthermore provides a source of Ca2+ for plant micronutrition and a supplementary control of soil pH.

Enhanced antimicrobial properties and bioactivity of 3D-printed titanium scaffolds by multilayer bioceramic coating for large bone defects.

The restoration of large bone defects caused by trauma, tumor resection, or infection is a major clinical problem in orthopedics and dentistry because postoperative infections, corrosion, and limited osteointegration of metal implants can lead to loosening of the implant. The aim of this study was to improve the surface properties of a 3D-printed (electron beam melting) Ti6Al4V-based macroporous scaffold by multilayer coating with bioactive silicate glasses (BAGs) and hydroxyapatite doped with a silver (AgHAP) or AgHAP additionally sonochemically modified with ZnO (ZnO-AgHAP). The coated scaffolds AgHAP_BAGs_Ti and ZnO-AgHAP_BAGs_Ti enhanced cytocompatibility in L929 and MRC5 cell lines and expressed bioactivity in simulated body fluid. A lower release of vanadium ions in coated samples compared to bare Ti scaffold indicates decreased dissolution of Ti alloy in coated samples. The coated samples reduced growth ofEscherichia coliandStaphylococcus aureusfor 4-6 orders of magnitude. Therefore, the 3D-printed Ti-based scaffolds coated with BAGs and (ZnO-)AgHAP have great potential for application as a multifunctional implant with antibacterial properties for the restoration of defects in load-bearing bones.

Modification of CaCO3 and CaCO3 pin-coated cellulose paper under supercritical carbon dioxide-ethanol mixture for enhanced NO2 capture.

In this work, we examine two modifications of fine-ground calcium carbonate material (GCC) in order to enhanced sorption of NO2 and subsequent reaction properties toward NO2-/NO3- formation by firstly exposing the GCC to supercritical (sc) CO2 in order to increase particle surface area, a choice specifically made to avoid altering the surface chemistry, and secondly considering the potential advantage of using a surface coupling agent toward NO2. The modification by the coupling agent amino silane (AMEO silane) was applied in a supercritical CO2-ethanol mixture. The samples were characterised before and after modification by field emission scanning electron microscopy (FESEM), specific surface area determination (BET nitrogen adsorption), ATR-FTIR spectroscopy and ion chromatography to reveal the effects of the surface modification(s) on the morphology, surface textural properties and sorption versus reaction properties with NO2. The performance of the treated sorbents for NO2 capture was evaluated at room temperature. Results show that reactivity of NO2 with GCC was observed to increase as a function of increased surface area resulting from scCO2 exposure, but that the presence of AMEO silane on the surface, while enhancing initial adsorption of NO2 was seen subsequently to act to block reactivity. Thus, judicious use of coupling agent can provide desired rapid initial adsorption of the gas, but the goal of long-term CaCO3-consuming reactivity, so as to prolong the uptake of NO2 beyond surface saturation alone, is achieved by increasing surface area while retaining chemical-free exposed CaCO3 surface.

Novel composite scaffolds based on alginate and Mg-doped calcium phosphate fillers: Enhanced hydroxyapatite formation under biomimetic conditions.

In the present study, we synthesized hydroxyapatite (HAP) powders followed by the production of alginate based macroporous scaffolds with the aim to imitate the natural bone structure. HAP powders were synthesized by using a hydrothermal method, and after calcination, dominant phases in the powders, undoped and doped with Mg2+ were HAP and ß-tricalcium phosphate, respectively. Upon mixing with Na-alginate, followed by gelation and freeze-dying, highly macroporous composite scaffolds were obtained with open and connected pores and uniformly dispersed mineral phase as determined by scanning electron microscopy. Mechanical properties of the scaffolds were influenced by the composition of calcium phosphate fillers being improved as Ca2+ concentration increased while Mg2+ concentration decreased. HAP formation within all scaffolds was investigated in simulated body fluid (SBF) during 28 days under static conditions while the best candidate (Mg substituted HAP filler, precursor solution with [Ca + Mg]/P molar ratio of 1.52) was investigated under more physiological conditions in a biomimetic perfusion bioreactor. The continuous SBF flow (superficial velocity of 400 µm/s) induced the formation of abundant HAP crystals throughout the scaffolds leading to improved mechanical properties to some extent as compared to the initial scaffolds. These findings indicated potentials of novel biomimetic scaffolds for use in bone tissue engineering.

Dissimilar sintered calcium phosphate dental inserts as dentine substitutes: Shear bond strength to restorative materials.

The application of sintered calcium phosphate dental inserts in the central part of tooth cavities can reduce amount of embedded dental composite and polymerization shrinkage of final dental fillings. The aim of this study was to analyze comparatively physico-chemical and mechanical properties of dental inserts and shear bond strength (SBS) between three dissimilar hydroxyapatite-based dental inserts and different restorative materials, after application of different clinical protocols. Starting from two different hydroxyapatite nano powders and nanostructured stabilized zirconia (YSZ), monophasic two-step sintered dense HAp inserts (TSSHAp), biphasic single-step sintered controlled porous inserts (HAp/TCp), and single-step sintered reinforced HAp/YSZ inserts were processed and characterized. Obvious differences in the microstructure of inserts surface were visualized after etching with 37% phosphoric acid. Fracture toughness of sintered inserts was ranged between 1.01 and 1.85 MPam1/2 (maximum value in the case of HAp/YSZ), while hardness values were in the range of 3.71-5.22 GPa (maximum value in the case of TSSHAp). Acid etching before application improved SBS between inserts and Maxcem compared to direct cement application. TSSHAp and HAP/TCp inserts showed comparable and relatively high SBS values, certainly higher compared to HAp/YSZ inserts. Slightly higher SBS values were measured in the case of TSSHAp insert group, and the highest mean SBS value of 18.51 MPa was determined between TSSHAp inserts and Filtek Z250_SBU following the "self-etch" protocol.

Highly Active Rutile TiO2 Nanocrystalline Photocatalysts.

The controllable synthesis of rutile TiO2 single crystal particles with the preferential orientation of {111} facets still remains a scientific and technological challenge. Here, we developed a facile route for fabrication of rutile TiO2 nanorod crystals (RTiO2NRs) having high ratios of oxidative {111} to reductive {110} surfaces. RTiO2NRs were synthesized using a peroxo-titanium complex (PTC) approach, which was controlled by changing the Ti/H2O2 ratio. The thus obtained RTiO2NRs revealed a high tendency to agglomerate through orientation-dependent attachment along the {110} facets. This resulted in an increased {111}/{110} surface ratio and led to a markedly improved photocatalytic activity of RTiO2NR aggregates. The reported findings illustrate the rich potential of the herein proposed facile and energy-efficient synthesis of nanostructured rutile TiO2-based photocatalysts.

The irritative property of alpha-tricalcium phosphate to the rabbit skin.

The aim of this study was to assess the irritant properties of a new developed calcium phosphate ceramic, alpha-tricalcium phosphate (alpha-TCP) after single application to intact skin of the rabbit. The test substance, alpha-TCP was produced by modified hydrothermal method and prepared in two different forms, as a solid material (disc 5 x 2 mm) and paste. Both, solid material and paste of alpha-TCP were evaluated for primary skin irritation to the ISO 10993-10:2002/Amd 1:2006 Biological Evaluation of Medical Devices - Part 10. At the end of the study macroscopic examination of the skin was performed. In this model, general and local tolerances were good. Score of primary irritation (SPI) and primary irritation index (PII) of alpha-TCP for both, solid material and paste, revealed that there was no significant toxicity/irritability (PII = 0.0) as compared to the negative control (PII = 0.0). Positive control did cause significant skin irritation in acute irritation test using Draize technique in rabbit model (PII = 2.11). Based on present results, it can be concluded that the the irritation potential of the tested material is negligible. However, other procedures for preclinical safety assessments of the alpha-TCP material are needed in order to completely elucidate its toxic potential.

Enhanced absorption of TiO2 nanotubes by N-doping and CdS quantum dots sensitization: insight into the structure.

Anodization of titanium film sputtered on fluorine doped tin oxide (FTO) glass was performed to obtain highly ordered ∼2 µm long and ∼60 nm wide TiO2 nanotubes. The titania films were annealed in ammonia atmosphere to enable the doping with N. The annealing did not affect the nanotubular morphology and the porosity remained open which is a very important requirement for further deposition of CdS quantum dots. The analysis done by transmission electron microscopy (TEM) has shown that the N-doped nanotubes have a smaller interplanar distance as compared to the undoped ones, whose interplanar distance corresponded to anatase phase. This difference was attributed to the N doping and the Sn migration from the substrate, as demonstrated by energy dispersive spectroscopy (EDS) combined with electron energy loss spectroscopy (EELS). The near edge X-ray absorption fine structure (NEXAFS) analysis clearly demonstrated that also the doped TiO2 film has anatase phase. Regarding the chemical composition of the studied samples, the X-ray photoelectron spectroscopy (XPS) and synchrotron radiation photoelectron spectroscopy (SRPES) analyses have shown that N is incorporated both interstitially and substitutionally in the TiO2 lattice, with a decreased contribution of the interstitial after ionic sputtering. The shift of the valence band maximum (VBM) position for the doped TiO2 vs. the undoped TiO2 proved the narrowing of the band gap. The CdS/TiO2 films show bigger VBM shifting that can be attributed to CdS deposit. Comparing the absorption spectra of the bare undoped and doped TiO2 samples, it was noticed that the doping causes a red shift from 397 to 465 nm. Furthermore, the CdS deposition additionally enhances the absorption in the visible range (575 nm for undoped TiO2/CdS and 560 nm for doped TiO2/CdS films).

Bond strength of restorative materials to hydroxyapatite inserts and dimensional changes of insert-containing restorations during polymerization.

OBJECTIVE: To determine the shear bond strength (SBS) between synthetic controlled porous hydroxyapatite (HAP) inserts and restorative materials and dimensional changes of insert-containing restorations during curing. METHODS: Cylinder-shaped HAP inserts (4mm in diameter, 1.6mm thick) were cemented in dentin discs (5mm×1.6mm), cut mid-coronally from human third molars, using one of the following materials: universal microhybrid composite Filtek Z250, flowable composite Filtek Ultimate or glass-ionomer Vitrebond (all 3M ESPE). SBS of the same materials to HAP inserts was tested in a universal testing machine. Three-dimensional digital image correlation system Aramis (GOM) was used to measure strains and displacements. Data were statistically analyzed using one-way ANOVA with Tukey's post-test (α=0.05). RESULTS: SBS of restorative materials to HAP inserts ranged between 12.2±2.1MPa (Filtek Z250) and 0.7±0.4MPa (Filtek Z250 without an adhesive). The 'total-etch' approach of adhesive application significantly increased SBS of both Filtek Z250 (12.2±2.1MPa) and Filtek Ultimate flowable (9.5±2.5MPa) compared to the 'self-etch' approach (8.2±1.6MPa and 4.4±0.9MPa, respectively) (p<0.05). HAP inserts reduced polymerization shrinkage to below 0.5% as well as displacements in the central region of the restorations. Peripheral shrinkage of restorative materials was similar with and without HAP inserts as were displacements of Filtek Z250 and Vitrebond. SIGNIFICANCE: Replacing major part of dentin clinically, especially in large cavities, HAP inserts may shorten clinical working time, improve dimensional stability of the restoration by reducing central shrinkage and displacements and provide adhesive bonding to universal composites following a 'total-etch' approach.

In vitro cell response to Co-containing 1,393 bioactive glass.

Cobalt ions are known to stimulate angiogenesis via inducing hypoxic conditions and hence are interesting agents to be used in conjunction with bioactive glasses (BGs) in bone tissue engineering approaches. In this work we investigated in vitro cell biocompatibility of Co releasing 1393 BG composition (in wt.%: 53SiO2, 6Na2O, 12K2O, 5MgO, 20CaO, and 4P2O5) derived scaffolds with osteoblast-like cells (MG-63) and human dermal microvascular endothelial cells (hDMECs). Cell viability, cell number and cell morphology of osteoblast-like cells in contact with particulate glass and 3D scaffolds were assessed showing good biocompatibility of 1393 reference material and with 1 wt.% CoO addition whereby 5 wt.% of CoO in the glass showed cytotoxicity. Furthermore for 1393 with 1 wt.% of CoO increased mitochondrial activity was measured. Similar observations were made with hDMECs: while 1393 and 1393 with 1 wt.% CoO were biocompatible and the endothelial phenotype was retained, 5 wt.% CoO containing BG showed cytotoxic effects after 1 week of cell culture. In conclusion, 1 wt.% Co containing BG was biocompatible with osteoblast like cells and endothelial cells and showed slightly stimulating effects on osteoblast-like cells whereas the addition of 5 wt.% CoO seems to exceed the vital therapeutic ranges of Co ions being released in physiological fluids.

Cobalt-releasing 1393 bioactive glass-derived scaffolds for bone tissue engineering applications.

Loading biomaterials with angiogenic therapeutics has emerged as a promising approach for developing superior biomaterials for engineering bone constructs. In this context, cobalt-releasing materials are of interest as Co is a known angiogenic agent. In this study, we report on cobalt-releasing three-dimensional (3D) scaffolds based on a silicate bioactive glass. Novel melt-derived "1393" glass (53 wt % SiO2, 6 wt % Na2O, 12 wt % K2O, 5 wt % MgO, 20 wt % CaO, and 4 wt % P2O5) with CoO substituted for CaO was fabricated and was used to produce a 3D porous scaffold by the foam replica technique. Glass structural and thermal properties as well as scaffold macrostructure, compressive strength, acellular bioactivity, and Co release in simulated body fluid (SBF) were investigated. In particular, detailed insights into the physicochemical reactions occurring at the scaffold-fluid interface were derived from advanced micro-particle-induced X-ray emission/Rutherford backscattering spectrometry analysis. CoO is shown to act in a concentration-dependent manner as both a network former and a network modifier. At a concentration of 5 wt % CoO, the glass transition point (Tg) of the glass was reduced because of the replacement of stronger Si-O bonds with Co-O bonds in the glass network. Compressive strengths of >2 MPa were measured for Co-containing 1393-derived scaffolds, which are comparable to values of human spongy bone. SBF studies showed that all glass scaffolds form a calcium phosphate (CaP) layer, and for 1393-1Co and 1393-5Co, CaP layers with incorporated traces of Co were observed. The highest Co concentrations of ∼12 ppm were released in SBF after reaction for 21 days, which are known to be within therapeutic ranges reported for Co(2+) ions.

Corrosion stability and bioactivity in simulated body fluid of silver/hydroxyapatite and silver/hydroxyapatite/lignin coatings on titanium obtained by electrophoretic deposition.

Hydroxyapatite is the most suitable biocompatible material for bone implant coatings. However, its brittleness is a major obstacle, and that is why, recently, research focused on creating composites with various biopolymers. In this study, hydroxyapatite coatings were modified with lignin in order to attain corrosion stability and surface porosity that enables osteogenesis. Incorporating silver, well known for its antimicrobial properties, seemed the best strategy for avoiding possible infections. The silver/hydroxyapatite (Ag/HAP) and silver/hydroxyapatite/lignin (Ag/HAP/Lig) coatings were cathaphoretically deposited on titanium from ethanol suspensions, sintered at 900 °C in Ar, and characterized by X-ray diffraction, scanning electron microscopy, field emission scanning electron microscopy, attenuated total reflection Fourier transform infrared, and X-ray photoelectron spectroscopy. The corrosion stability of electrodeposited coatings was evaluated in vitro in Kokubo's simulated body fluid (SBF) at 37 °C using electrochemical impedance spectroscopy. Bioactivity was estimated by immersion in SBF to evaluate the formation of hydroxyapatite on the coating surface. A microcrystalline structure of newly formed plate-shaped carbonate-hydroxyapatite was detected after only 7 days, indicating enhanced bioactive behavior. Both coatings had good corrosion stability during a prolonged immersion time. Among the two, the Ag/HAP/Lig coating had a homogeneous surface, less roughness, and low values of contact angle.

The effect of grain size on the biocompatibility, cell-materials interface, and mechanical properties of microwave-sintered bioceramics.

The effect of decreasing the grain size on the biocompatibility, cell-material interface, and mechanical properties of microwave-sintered monophase hydroxyapatite bioceramics was investigated in this study. A nanosized stoichiometric hydroxyapatite powder was isostatically pressed at high pressure and sintered in a microwave furnace in order to obtain fine grained dense bioceramics. The samples sintered at 1200°C, with a density near the theoretical one, were composed of micron-sized grains, while the grain size decreased to 130 nm on decreasing the sintering temperature to 900°C. This decrease in the grain size certainly led to increases in the fracture toughness by much as 54%. An in vitro investigation of biocompatibility with L929 and human MRC-5 fibroblast cells showed noncytotoxic effects for both types of bioceramics, while the relative cell proliferation rate, cell attachment and metabolic activity of the fibroblasts were improved with decreasing of grain size. An initial in vivo investigation of biocompatibility by the primary cutaneous irritation test showed that both materials exhibited no irritation properties.