Preparation of Sterile Raw Material - Chicken Eggshells in the Process of their Transformation into Selected Calcium Salts.

BACKGROUND: The chicken eggshells and their subcrustal membranes are a valuable source of calcium, but they are not further processed but disposed of as waste from the food industry. Chicken eggshells have high content (>95%) of calcium carbonate. Some properties suggest that eggshells may be a promising alternative to the present calcium sources used in the pharmaceutical industry. METHODS: The effect of roasting chicken eggshells with a selected organic acid (citric or fumaric or lactic acid) on microbiological purity, including the presence of fungi and bacteria Salmonella spp., Staphylococcus aureus, Escherichia coli of obtained calcium salts, was investigated. In this study, chicken eggshells were subjected to chemical reactions with organic acids (citric, fumaric or lactic acid) at two different calcium-acid molar ratios (1:1 or 1:3) and the mixture was heat-treated for 1 or 3 hours at a temperature of 100°C or 120°C. RESULTS AND DISCUSSION: It was found that lactic acid was 100% effective against fungi, and the remaining citric and fumaric acids were -50% (regardless of the other examined conditions). The type of acid used has a significant effect on fungal growth inhibition (p<0.05). Fumaric acid and lactic acid will be nearly 100% effective against bacteria (100% fumaric acid and 97% lactic acid effectiveness), regardless of other factors. CONCLUSION: Lactic acid is the most effective against pathogenic flora - fungi and bacteria. The transformation of chicken eggshells into calcium lactate can provide us with sterile calcium salt, free of 100% fungi and 97% of all bacteria.

In vitro effects of CaO nanoparticles on Triticale callus exposed to short and long-term salt stress.

KEY MESSAGE: Ca2+ NPs enhanced tolerance of Triticale callus under salt stress by improving biochemical activity and confocal laser scanning analysis, conferring salt tolerance on callus cells. CaO NPs (Ca2+) are significant components that act as transducers in many adaptive and developmental processes in plants. In this study, effect of Ca2+ NPs on the response and regulation of the protective system in Triticale callus under short and long-salt treatments was investigated. The activation of Ca2+ NPs was induced by salt stress in callus of Triticale cultivars. MDA, H2O2, POD, and protein activities were determined in callus tissues. Concerning MDA, H2O2, protein activities, it was found that the Ca2+ NPs treatment was significant, and it demonstrated a high correlation with the tolerance levels of cultivars. Tatlicak cultivar was detected for better MDA activities in the short time with 1.5 ppm Ca2+ NPs concentration of 50 g and 100 g NaCl. Similarly, the same cultivar responded with better H2O2 activity at 1.5 ppm Ca2+ NPs 100 g NaCl in the short time. POD activities exhibited a decreasing trend in response to the increasing concentrations of Ca2+ NPs. The best result was observed at 1.5 ppm Ca2+ NPs 100 g NaCl in the short term. Based on the protein content, treatment of short-term cultured callus cells with 1.5 ppm Ca2+ NPs inhibited stress response and it significantly promoted Ca2+ NPs signals as compared to control callus. Confocal laser scanning analysis proved that the application of Ca2+ NPs could alleviate the adverse effects of salt stress by the inhibition of stress severity in callus cells. This study demonstrated, under in vitro conditions, that the application of Ca2+ NPs can significantly suppress the adverse effects of salt stress on Triticale callus; it was also verified that the concentration of Ca2+ NPs could be important parameter to be considered in adjusting the micronutrient content in the media for this plant.

Nanocrystalline Antiferromagnetic High-κ Dielectric Sr2NiMO6 (M = Te, W) with Double Perovskite Structure Type.

Double perovskites have been extensively studied in materials chemistry due to their excellent properties and novel features attributed to the coexistence of ferro/ferri/antiferro-magnetic ground state and semiconductor band gap within the same material. Double perovskites with Sr2NiMO6 (M = Te, W) structure type have been synthesized using simple, non-toxic and costless aqueous citrate sol-gel route. The reaction yielded phase-pure nanocrystalline powders of two compounds: Sr2NiWO6 (SNWO) and Sr2NiTeO6 (SNTO). According to the Rietveld refinement of powder X-ray diffraction data at room temperature, Sr2NiWO6 is tetragonal (I4/m) and Sr2NiTeO6 is monoclinic (C12/m1), with average crystallite sizes of 49 and 77 nm, respectively. Structural studies have been additionally performed by Raman spectroscopy revealing optical phonons typical for vibrations of Te6+/W6+O6 octahedra. Both SNTO and SNWO possess high values of dielectric constants (341 and 308, respectively) with low dielectric loss (0.06 for SNWO) at a frequency of 1 kHz. These values decrease exponentially with the increase of frequency to 1000 kHz, with the dielectric constant being around 260 for both compounds and dielectric loss being 0.01 for SNWO and 0.04 for SNTO. The Nyquist plot for both samples confirms the non-Debye type of relaxation behavior and the dominance of shorter-range movement of charge carriers. Magnetic studies of both compounds revealed antiferromagnetic behavior, with Néel temperature (TN) being 57 K for SNWO and 35 K for SNTO.

Synthesis of La-Sr-Mn-O and La-Sr-Ca-Mn-O Perovskites Through Solution Combustion Using Urea at Fuel Deficient Conditions.

La0.7 Sr0.3 MnO3 (LSMO) nanoparticles have been obtained via solution combustion synthesis (SCS) using urea and glycine as fuels. Also, La0.7 Sr0.27 Ca0.03 MnO3 (LSCMO) nanoparticles have been synthesized through solution combustion using urea as fuel. In this paper, the combustion process was carried out with a fuel to oxidant ratio giving fuel deficient conditions ( ). The thermal analysis (TGA) indicate that the organic residues from the urea-nitrates gel mixture are eliminated above 600 °C and the post-synthesis heat treatment yields the formation of the desired phase without impurities. The obtained phases were analyzed using X-ray diffraction. The infrared analysis confirms the purity of the samples obtained using urea. However, the sample obtained using glycine confirms the formation of SrCO3. The morphology was analyzed using a FE-SEM microscope, and it was found that the particles present a spherical shape with a mean size of around 45 nm in the selected samples. The samples' energy dispersive X-ray spectra show that the desired elements (La, Sr, Ca, Mn and O) are present in the nanoparticles. The measured zero field cooled (ZFC) and field cooled (FC) magnetizations were recorded from 4.5 to 380 K at 105 A/m to obtain their blocking and Curie temperatures. Moreover, the hysteresis loops measured at room temperature confirm the superparamagnetic behavior of the elaborated samples. According to the results obtained, these nanoparticles have interesting properties that make them candidates to explore not only for their potential in biomedical applications but also in refrigeration and magnetic storage devices.

Study on strontium doped tricalcium silicate synthesized through sol-gel process.

We successfully synthesized a strontium-doped tricalcium silicate (SrxCa3-xSiO5, Sr = 0 to 2 mol%) bone cement using the sol-gel process. The material properties including crystallinity, setting time, mechanical strength, and hydration products were characterized. Release of ions and pH values of simulated body fluid soaked with the bone cement were measured. In vitro biocompatibility of different concentrations of the material was evaluated by the viability of L929 cells. The setting times of as-prepared slurries were all <70 min. Doping with 0.5 mol% Sr reduced the final setting time by 20 min. After 14 days curing, 0.25 mol% Sr-doped SrxCa3-xSiO5 possessed the highest compressive strength of 45 MPa among all the Sr-doped groups with no statistical difference to Ca3SiO5. The bioactivity of the materials was confirmed with the formation of an apatite layer on the surface of the materials after immersion in simulated body fluid. In addition, the proliferation of L929 cells exposed to 1 mol% Sr was significantly promoted as compared to no Sr doping. SrxCa3-xSiO5 is a novel and advanced material that has the potential to serve as a bone cement in bone restoration with appropriate mechanical strength and favorable biocompatibility.

Rapid Characterization and Parameter Space Exploration of Perovskites Using an Automated Routine.

Hybrid, e.g., organic inorganic, perovskites from the type methylammonium lead iodide CH3NH3PbI3 are promising solar cell materials. However, due to the large parameter space spanned by the manifold combinations of divalent metals with organic cations and anions, an efficient approach is needed to rapidly test and categorize new promising materials. Herein, we developed a high throughput approach for the automated synthesis of perovskite layers with different precursor ratios at varying annealing temperatures. The layers were analyzed by optical absorption and photoluminescence (PL) spectroscopy as well as X-ray diffraction (XRD) and evaluated using two different procedures. The first one is a stepwise exclusion of nonperforming reactant ratios and synthesis conditions by using both spectroscopic techniques, followed by a final validation of the procedure by XRD. In the second procedure, only PL results were consulted in combination with high throughput screening using design of experiments (DoE) to reduce the total number of experiments needed and compared to the manual cascade approach. Noteworthy, by simple PL screening, it was possible to identify the best ratio of perovskite to byproducts and annealing temperature. Thus, only with PL, more detailed results as with the manual protocol were reached, while at the same time the effort for characterization was significantly reduced (by 60% of the experimental time). In conclusion, our approach opens a way toward fast and efficient identification of new promising materials under different reaction and process conditions.

Facile Synthesis of Colloidal Lead Halide Perovskite Nanoplatelets via Ligand-Assisted Reprecipitation.

In this work, we demonstrate a facile method for colloidal lead halide perovskite nanoplatelet synthesis (Chemical formula: L2[ABX3]n-1BX4, L: butylammonium and octylammonium, A: methylammonium or formamidinium, B: lead, X: bromide and iodide, n: number of [BX6]4- octahedral layers in the direction of nanoplatelet thickness) via ligand-assisted reprecipitation. Individual perovskite precursor solutions are prepared by dissolving each nanoplatelet constituent salt in N,N-dimethylformamide (DMF), which is a polar organic solvent, and then mixing in specific ratios for targeted nanoplatelet thickness and composition. Once the mixed precursor solution is dropped into nonpolar toluene, the abrupt change in the solubility induces the instantaneous crystallization of nanoplatelets with surface-bound alkylammonium halide ligands providing colloidal stability. Photoluminescence and absorption spectra reveal emissive and strongly quantum-confined features. X-ray diffraction and transmission electron microscopy confirm the two-dimensional structure of the nanoplatelets. Furthermore, we demonstrate that the band gap of perovskite nanoplatelets can be continuously tuned in the visible range by varying the stoichiometry of the halide ion(s). Lastly, we demonstrate the flexibility of the ligand-assisted reprecipitation method by introducing multiple species as surface-capping ligands. This methodology represents a simple procedure for preparing dispersions of emissive 2D colloidal semiconductors.

Simultaneous regeneration of calcium lactate and cellulose into PCL nanofiber for biomedical application.

Synthetic polymers are easy to process and have excellent mechanical properties but low wettability and poor cell compatibility limit their applications in tissue scaffolding. In this study, a facile procedure was established to regenerate cellulose and calcium lactate (CaL) into a polycaprolactone (PCL) nanofibrous scaffold for tissue engineering applications. Briefly, varying amounts of lactic acid (LA) was mixed with the blend of PCL and cellulose acetate (CA) solutions and electrospun to fabricate an optimal composite PCL/CA/LA fibrous membrane. Later on, as-prepared membranes were treated with calcium hydroxide solution. This process simultaneously converted CA and LA contents into Cellulose and CaL, respectively. In situ regeneration of Cellulose and CaL into the composite fiber remarkably enhanced the biological and physicochemical properties of the composite fiber. This work provides a novel dual-channel strategy for simultaneous regeneration of biopolymer and bioactive molecule into the PCL nanofiber for regenerative medicine and tissue engineering applications.

Synthesis of fibrous LaFeO3 perovskite oxide for adsorption of Rhodamine B.

The LaFeO3 perovskite oxide decorated active carbon fibers (LFO-ACFs) based on cotton fabric waste were successfully synthesized through sol-gel loading and thermal treatment. LaFeO3 perovskite and cotton fabric waste were combined to an eco-friendly and cheap adsorbent, which could reuse the leftover materials of textile industry and realize their functional modification. The structural, morphology/microstructure and functional groups were investigated through X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray (EDX), Fourier Transform Infrared spectroscopy (FTIR), respectively. The XRD pattern suggested the cotton fabric matrix didn't influence the structure of LaFeO3 perovskite oxide. In SEM studies, LFO-ACFs still maintained fibrous shape of the raw cotton fibers, and the EDX analysis showed that the main elements of the prepared LFO-ACFs were La, Fe, O and C. The synthesized LFO-ACF was employed for adsorption of cational dye of Rhodamine B (RhB), and the effects of adsorption parameters, i.e. pH, contact time, solution temperature and initial concentration of dye, on adsorption behavior were investigated. Results suggested the adsorption performance of LFO-ACF for RhB was nearly not affected by solution pH and its maximum adsorption capacity fitted by the Langmuir isothermal model could attain 182.6 mg/g at 293 K. The adsorption kinetics followed the pseudo-second-order equation and the regeneration of LFO-ACF could be well realized through an easy pyrolysis method.

Biocompatible silk/calcium silicate/sodium alginate composite scaffolds for bone tissue engineering.

Scaffolds are crucial for bone tissue engineering since their compositions and properties could significantly affect the seeded cells' behavior. In this study, we developed an interpenetrating network hydrogel by utilizing Ca2+ from calcium silicate (CS) to simultaneously crosslink silk fibroin (SF) and sodium alginate (SA). Afterwards, the hydrogels were lyophilized to obtain scaffolds and systematically evaluated by physical characterizations, in vitro cytocompatibility and alkaline phosphatase (ALP) assay. We found that CS inside the porous structure of SF/CS/SA scaffolds could remarkably enhance hydrophilicity, degradation, compression resistance, bioactivity and pH of SF/CS/SA scaffolds. Scaffolds with CS concentrations of 25% and 12% (25/CS and 12/CS) could dominantly stimulate proliferation of bone marrow stromal cells (BMSCs). Besides, BMSCs cultured with 25/CS and 12/CS scaffolds showed high ALP activity, respectively. Consequently, this study suggested SF/CS/SA scaffolds possess potential in non-loading bone tissue engineering application.

Synthesis of silver-containing calcium aluminate particles and their effects on a MTA-based endodontic sealer.

OBJECTIVE: To synthetize calcium aluminate (C3A) and silver-containing C3A particles (C3A+Ag) testing their effects on the properties of a MTA-based endodontic sealer in comparison to an epoxy resin- and a calcium silicate-based sealer. METHODS: Pure C3A and C3A+Ag particles were synthesized by a chemical method and characterized using XRD to identify crystalline phases. SEM/EDS analysis investigated morphology, particle size, and elemental composition of particles. Setting time, flow, radiopacity, water sorption and solubility of commercial and modified sealers were evaluated according to ISO 6876/2012. The pH and ions release were measured using a pHmeter and a microwave induced plasma optical emission spectrometer. The inhibition of biofilm growth was evaluated by confocal laser scanning microscopy (CLSM). Data were rank transformed and analyzed by ANOVA and Tukey test (P<0.05). RESULTS: The C3A particles showed an irregular grain agglomerated structure with voids and pores. In C3A+Ag particles, Ag modified the material morphology, confirming the deposition of Ag. The physicochemical properties of the modified MTA-based sealer were similar to the commercial material, except for the significant increase in Ca+2 release. However, there was no Ag release. Setting time, flow, radiopacity, water sorption and solubility were adequate for all materials. All the materials showed alkaline pH. Antibiofilm effect was improved in the presence of C3A particles, while the biofilm inhibition was lower in the presence of Ag. SIGNIFICANCE: The modified sealer presented improved antibiofilm properties and calcium release, without dramatic effects on the other characteristics. It is expected a positive effect in its antimicrobial behavior.

Biocompatibility Investigation of New Endodontic Materials Based on Nanosynthesized Calcium Silicates Combined with Different Radiopacifiers.

INTRODUCTION: The aim of this article was to analyze biocompatibility and bioactivity of new endodontic materials on the basis of nanosynthesized calcium silicates (ALBO-MPCA1 and ALBO-MPCA2) combined with different radiopacifiers in comparison with MTA+. METHODS: Morphology of the samples was studied by scanning electron microscopy, and the pH and ion release analysis were also assessed. Biocompatibility of materials' eluates (24-hour, 7-day, and 21-day) was conducted by using MTT test. Twelve New Zealand white rabbits were used for intraosseous implantation. Four calvarial defects per animal were created and filled with freshly prepared investigated materials. RESULTS: Samples mostly consisted of agglomerates built up from nanoparticles, preferably spherical and rod-like. There was no significant difference among pH values of materials' eluates after 24 hours (P > .05). The amount of calcium and aluminum ion release decreased, whereas the amount of magnesium and bismuth (ALBO-MPCA1, MTA+) and barium (ALBO-MPCA2) increased during 21-day period. The metabolic activity of cells increased after the extraction time, except in case of undiluted elutes of ALBO-MPCA2 and ALBO-MPCA1 (21-day). Histologic analysis of the samples revealed newly formed bone tissue with moderate inflammation for all investigated materials, which subsided during 90-day period to mild. Both MTA+ and ALBO-MPCA1 were in direct contact with the newly formed bone tissue. After 90 days, statistically significant difference in hard tissue formation was observed in comparison of MTA+ and ALBO-MPCA1 with control group (P < .05). CONCLUSIONS: Experimental materials ALBO-MPCA1 and ALBO-MPCA2 possess both biocompatibility and bioactivity. Because ALBO-MPCA1 provokes favorable biological response, it is especially good candidate for further clinical investigations.

Synthesis of Photoactive Materials by Sonication: Application in Photocatalysis and Solar Cells.

In recent years, a good number of methods have become available for the preparation of an important group of photoactive materials for applications in photocatalysis and solar cells. Nevertheless, the benefits derived from preparing those materials through unconventional approaches are very attractive from the green chemistry point of view. This critical review work is focused on sonication as one of these promising new synthetic procedures that allow control over size, morphology, nanostructure and tuning of catalytic properties. Ultrasound-based procedures offer a facile, versatile synthetic tool for the preparation of light-activated materials often inaccessible through conventional methods.

Stability of Fe,Al-bearing bridgmanite in the lower mantle and synthesis of pure Fe-bridgmanite.

The physical and chemical properties of Earth's mantle, as well as its dynamics and evolution, heavily depend on the phase composition of the region. On the basis of experiments in laser-heated diamond anvil cells, we demonstrate that Fe,Al-bearing bridgmanite (magnesium silicate perovskite) is stable to pressures over 120 GPa and temperatures above 3000 K. Ferric iron stabilizes Fe-rich bridgmanite such that we were able to synthesize pure iron bridgmanite at pressures between ~45 and 110 GPa. The compressibility of ferric iron-bearing bridgmanite is significantly different from any known bridgmanite, which has direct implications for the interpretation of seismic tomography data.

Synthesis and Photoluminescence Characteristics of CaIn2O4:Dy3+ Phosphors Co-Doped with Gd3+, Zn2+ or AI3+ Ions.

Novel warm-white emitting phosphors CaIn2O4:Dy3+ co-doped with Gd3+, Zn2+, or Al3+ ions were prepared by solid state reaction. In this paper, a strategy of co-doping with different ions was used with the aim of affecting the luminescence properties of CaIn204:0.6%Dy3+ under NUV excitation. The luminescence intensities of CaIn2O4:0.6%Dy3+ were enhanced by 0.2% Gd3+ or 0.2% Zn2+ ions co-doping under 367 nm excitation, but lowered by co-doping with 0.2% Al3+ ions. Furthermore, the chromaticity coordinates of CaIn2O4:0.6%Dy3+ can be tuned from the cold-white region to warm-white region with Gd3+ or Zn2+ ions co-doping. These findings show that CaIn2O4:0.6%Dy3+,0.2% Gd3+, and CaIn2O4:0.6%Dy3+,0.2% Zn2+ have potential application value as new warm-white LED phosphors.

Effects of Fuel to Synthesis of CaTiO3 by Solution Combustion Synthesis for High-Level Nuclear Waste Ceramics.

A solution combustion process for the synthesis of perovskite (CaTiO3) powders is described. Perovskite is one of the crystalline host matrics for the disposal of high-level radioactive wastes (HLW) because it immobilizes Sr and Lns elements by forming solid solutions. Solution combustion synthesis, which is a self-sustaining oxi-reduction reaction between nitrate and organic fuel, the exothermic reaction, and the heat evolved convert the precursors into their corresponding oxide products above 1100 degrees C in air. To investigate the effects of amino acid on the combustion reaction, various types of fuels were used; a glycine, amine and carboxylic ligand mixture. Sr, La and Gd-nitrate with equivalent amounts of up to 20% of CaTiO3 were mixed with Ca and Ti nitrate and amino acid. X-ray diffraction analysis, SEM and TEM were conducted to confirm the formed phases and morphologies. While powders with an uncontrolled shape are obtained through a general oxide-route process, Ca(Sr, Lns)TiO3 powders with micro-sized soft agglomerates consisting of nano-sized primary particles can be prepared using this method.

Solvent-Assisted Preparation of High-Performance Mesoporous CH3NH3Pbl3 Perovskite Solar Cells.

Organometal trihalide perovskite based solar cells have attracted great attention worldwide since their power conversion efficiency (PCE) have risen to over 15% within only 3 years of development. Comparing with other types of perovskite solar cells, mesostructured perovskite solar cells based on CH3NH3Pbl3 as light harvesting material have already demonstrated remarkable advance in performance and reproducibility. Here, we reported a mesoscopic TiO2/CH3NH3Pbl3 heterojunction solar cell with uniform perovskite thin film prepared via solvent-assisted solution processing method. The best performing device delivered photocurrent density of 20.11 mA cm⁻², open-circuit voltage of 1.02 V, and fill factor of 0.70, leading to a PCE of 14.41%. A small anomalous hysteresis in the J-V curves was observed, where the PCE at forward scan was measured to be 84% of the PCE at reverse scan. Based on a statistical analysis, the perovskite solar cells prepared by the reported method exhibited reproducible and high PCE, indicating its promising application in the fabrication of low-cost and high-efficiency perovskite solar cells.

Highly Efficient Reproducible Perovskite Solar Cells Prepared by Low-Temperature Processing.

In this work, we describe the role of the different layers in perovskite solar cells to achieve reproducible, ~16% efficient perovskite solar cells. We used a planar device architecture with PEDOT: PSS on the bottom, followed by the perovskite layer and an evaporated C60 layer before deposition of the top electrode. No high temperature annealing step is needed, which also allows processing on flexible plastic substrates. Only the optimization of all of these layers leads to highly efficient and reproducible results. In this work, we describe the effects of different processing conditions, especially the influence of the C60 top layer on the device performance.

Calcium Uncaging with Visible Light.

We have designed a nitroaromatic photochemical protecting group that absorbs visible light in the violet-blue range. The chromophore is a dinitro derivative of bisstyrylthiophene (or BIST) that absorbs light very effectively (ε440 = 66,000 M(-1) cm(-1) and two-photon cross section of 350 GM at 775 nm). We developed a "caged calcium" molecule by conjugation of BIST to a Ca(2+) chelator that upon laser flash photolysis rapidly releases Ca(2+) in <0.2 ms. Using the patch-clamp method the optical probe, loaded with Ca(2+), was delivered into acutely isolated mouse cardiac myocytes, where either one- and two-photon uncaging of Ca(2+) induced highly local or cell-wide physiological Ca(2+) signaling events.