Plant-Assisted Green Synthesis of MgO Nanoparticles as a Sustainable Material for Bone Regeneration: Spectroscopic Properties.

This work is devoted to magnesium oxide (MgO) nanoparticles (NPs) for their use as additives for bone implants. Extracts from four different widely used plants, including Aloe vera, Echeveria elegans, Sansevieria trifasciata, and Sedum morganianum, were evaluated for their ability to facilitate the "green synthesis" of MgO nanoparticles. The thermal stability and decomposition behavior of the MgONPs were analyzed by thermogravimetric analysis (TGA). Structure characterization was performed by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), ultraviolet-visible spectroscopy (UV-Vis), dynamic light scattering (DLS), and Raman scattering spectroscopy (RS). Morphology was studied by scanning electron microscopy (SEM). The photocatalytic activity of MgO nanoparticles was investigated based on the degradation of methyl orange (MeO) using UV-Vis spectroscopy. Surface-enhanced Raman scattering spectroscopy (SERS) was used to monitor the adsorption of L-phenylalanine (L-Phe) on the surface of MgONPs. The calculated enhancement factor (EF) is up to 102 orders of magnitude for MgO. This is the first work showing the SERS spectra of a chemical compound immobilized on the surface of MgO nanoparticles.

Nitrogen-Doped Carbon Aerogels Derived from Starch Biomass with Improved Electrochemical Properties for Li-Ion Batteries.

Among all advanced anode materials, graphite is regarded as leading and still-unrivaled. However, in the modern world, graphite-based anodes cannot fully satisfy the customers because of its insufficient value of specific capacity. Other limitations are being nonrenewable, restricted natural graphite resources, or harsh conditions required for artificial graphite production. All things considered, many efforts have been made in the investigation of novel carbonaceous materials with desired properties produced from natural, renewable resources via facile, low-cost, and environmentally friendly methods. In this work, we obtained N-doped, starch-based carbon aerogels using melamine and N2 pyrolysis as the source of nitrogen. The materials were characterized by X-ray powder diffraction, elemental analysis, X-ray photoelectron spectroscopy, galvanostatic charge-discharge tests, cyclic voltammetry, and electrochemical impedance spectroscopy. Depending on the doping method and the nitrogen amount, synthesized samples achieved different electrochemical behavior. N-doped, bioderived carbons exhibit far better electrochemical properties in comparison with pristine ones. Materials with the optimal amount of nitrogen (such as MCAGPS-N8.0%-carbon aerogel made from potato starch modified with melamine and CAGPS-N1.2%-carbon aerogel made from potato starch modified by N2 pyrolysis) are also competitive to graphite, especially for high-performance battery applications. N-doping can enhance the efficiency of Li-ion cells mostly by inducing more defects in the carbon matrix, improving the binding ability of Li+ and charge-transfer process.

SERS activity and spectroscopic properties of Zn and ZnO nanostructures obtained by electrochemical and green chemistry methods for applications in biology and medicine.

This work for the first time evaluates the ability of homogeneous, stable, and pure zinc oxide nanoparticles (ZnONPs-GS) synthesized by "green chemistry" - an environmentally friendly, cheap, and easy method that allows efficient use of plant waste, such as banana peels, for the selective detection of four neurotransmitters present in body fluids and promotion of the SERS effect. Selective adsorption on ZnONPs-GS was compared with adsorption on the surface of (1) ZnONPs, which were obtained by electrochemical dissolution of zinc in a solution free of surfactants and (2) mechanically polished surface of bare Zn. The study showed that SERS spectroscopy using unique marker bands allows distinguishing whether the adsorbate is deposited on the surface of zinc or zinc oxide. Thus, the combination of the SERS technique with an optical probe can allow an in vivo determination of the condition of galvanized implants. The use of SERS has been extended to monitor the photocatalytic properties of surface-functionalized ZnO nanoparticles. It has been shown that despite the same structure, purity, and adsorption properties, ZnONPs-GS obtained using "green chemistry" are more bio-friendly for biological material than those obtained by the electrochemical method. This is because the surface of ZnONPs-GS is free of hydroxyl groups, which can easily form reactive oxygen species when the surface is exposed to visible radiation. Thus, surface-functionalized ZnONPS-GS can protect the biological material from the damage caused by the production and attack of an excess of ROS. Also, for an exemplary neurotransmitter, structural changes when it is not-covalently bound to Zn/ZnO were compared with the structural changes of this neurotransmitter deposited on the surface of various metals (Cu, α-Ti, and α-Fe) and metal oxides (leaf-like CuO, rutile-TiO2, and γ-Fe2O3). It has been shown that adsorption only slightly depends on the type of metallic surface and the development of this surface for roughness up to 1 micron. Metal substrates were characterized before and after the neurotransmitters' adsorption. UV-Vis, Raman, and ATR-FTIR confirmed the formation of ZnO nanoparticles. XRD showed a high crystalline structure of wurtzite. TEM and DLS showed that nanoparticles are spherical, well dispersed, and have a uniform size.

A Strategy to Optimize the Performance of Bio-Derived Carbon Aerogels by a Structuring Additive.

In this work, we investigated the influence of gum arabic (GA) as a structuring additive, on the electrochemical behavior of bio-derived carbon aerogels (CAGs). Modified carbonaceous materials were prepared by the gelatinization process of potato starch (PS) with the addition of GA in various quantities, followed by the thermal treatment of the obtained gels in an inert gas atmosphere. The obtained anode materials were examined by X-ray diffraction (XRD), elemental analysis (EA), galvanostatic charge/discharge tests (GCDT), extensive cycling (LT-GCDT) and cyclic voltammetry (CV) methods. The highest electrochemical performance was achieved for carbon aerogel material, in which 1% w/w GA was added. The results showed that the proper composition of carbon precursor with a structuring promoter improves the rheological properties of starch gel and stabilizes the final aerogel structure affecting CAG functional properties.

The Temperature Effect on the Electrochemical Performance of Sulfur-Doped LiMn2O4 in Li-Ion Cells.

The application of modified spinel materials in commercial systems relates to the verification of their parameters under different conditions. Hence, in this study, the influence of temperature on the electrochemical behavior of sulfur-doped spinel (LiMn2O3.97S0.03), with reference to stoichiometric spinel (LiMn2O4), was investigated. The electrochemical characteristics of Li-ion cells based on the fabricated spinels were investigated using galvanostatic charge-discharge tests (GCDT), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The results show that introducing sulfur into the spinel structure improves the electrochemical properties at each of the studied temperatures (3, 22 and 61 °C). LiMn2O3.97S0.03 exhibits higher specific capacities, enhanced diffusivity and charge-discharge rates (particularly at low temperatures), and much better cycling stability, regardless of the testing conditions. Our research proves that an S-doping system is a better alternative to LiMn2O4 in the context of working parameters, while maintaining environmental friendliness and low manufacturing costs.

Electrochemical Properties and Structure Evolution of Starch-Based Carbon Nanomaterials as Li-Ion Anodes with Regard to Thermal Treatment.

The influence of the pyrolysis temperature on the structural, textural, and electrochemical properties of carbon aerogels obtained from potato, maize, and rice starches was analyzed. The carbonization of organic precursors, followed by gelatinization, exchange of solvent, and drying process, was carried out in an argon atmosphere at temperatures ranging from 600 °C to 1600 °C. The nanostructured carbons were characterized by X-ray powder diffraction (XRD) as well as N2-adsorption/desorption (N2-BET) methods. The electrochemical behavior of Li-ion cells based on the fabricated carbon anodes was investigated using the galvanostatic charge/discharge tests (GCDT) and electrochemical impedance spectroscopy (EIS). The results show that the thermal treatment stage has a crucial impact on the proper formation of the aerogel material's porous structures and also on their working parameters as anode materials. The highest relative development of the external surface was obtained for the samples pyrolysed at 700 °C, which exhibited the best electrochemical characteristics (the highest specific capacities as well as the lowest charge transfer resistances).

Ions-free electrochemically synthetized in aqueous media flake-like CuO nanostructures as SERS reproducible substrates for the detection of neurotransmitters.

The process of catalytic destruction of tumor cells can be strengthened by introducing copper(II) oxide nanostructures (CuONSs) with receptor's agonists/antagonists immobilized on their surface. Here we show a simple and reliable electrochemical method for the fabrication ions-free flake-like CuO nanostructures in a surfactant/ions free aqueous environment. For the determination of the metal surface plasmon, size, rheology, and structure of the fabricated nanostructures ultraviolet-visible (UV-Vis), Fourier-transform infrared (FT-IR), Raman, and X-ray photoelectron (XPS) spectroscopies as well as scanning electron microscope (SEM), high-resolution transmission electron microscopy with energy dispersive X-ray (HDTEM-EDS), X-ray powder diffraction (XRD), and dynamic light scattering (DLS) analysis were used. The fabricated nanostructures were used as highly sensitive, uniform, and reproducible sensors of a natural ligand (bombesin) of some types of metabotropic seven transmembrane G protein-coupled superfamily receptors (GPCRs), which are over-express on the surface of many malignant tumors. Surface-enhanced Raman scattering (SERS) was used to monitor the geometry of adsorbate, separate, enrich, and detect various bombesin C-terminal fragments. It has been shown that the type of used substrate, surface development, and ions present in the solution have little effect on the mode of adsorption.

Multifunctional Carbon Aerogels Derived by Sol-Gel Process of Natural Polysaccharides of Different Botanical Origin.

In this manuscript, we describe the results of our recent studies on carbon aerogels derived from natural starches. A facile method for the fabrication of carbon aerogels is presented. Moreover, the complete analysis of the carbonization process of different starch aerogels (potato, maize, and rice) was performed using thermogravimetric studies combined with a detailed analysis of evolved decomposition products. The prepared carbon aerogels were studied in terms of their morphology and electrical properties to relate the origin of starch precursor with final properties of carbon materials. The obtained results confirmed the differences in carbon aerogels' morphology, especially in materials' specific surface areas, depending on the botanical origin of precursors. The electrical conductivity measurements suggest that carbon aerogels with the best electrical properties can be obtained from potato starch.

Enhancement of Electrochemical Performance of LiMn2O4 Spinel Cathode Material by Synergetic Substitution with Ni and S.

Nickel and sulfur doped lithium manganese spinels with a nominal composition of LiMn2-xNixO4-ySy (0.1 ≤ x ≤ 0.5 and y = 0.01) were synthesized by a xerogel-type sol-gel method followed by subsequent calcinations at 300 and 650 °C in air. The samples were investigated in terms of physicochemical properties using X-ray powder diffraction (XRD), transmission electron microscopy (EDS-TEM), N2 adsorption-desorption measurements (N2-BET), differential scanning calorimetry (DSC), and electrical conductivity studies (EC). Electrochemical characteristics of Li/Li⁺/LiMn2-xNixO4-ySy cells were examined by galvanostatic charge/discharge tests (CELL TEST), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV). The XRD showed that for samples calcined at 650 °C containing 0.1 and 0.2 mole of Ni single phase materials of Fd-3m group symmetry and nanoparticles size of around 50 nm were obtained. The energy dispersive X-ray spectroscopy (EDS) mapping confirmed homogenous distribution of nickel and sulfur in the obtained spinel materials. Moreover, it was revealed that the adverse phase transition at around room temperature typical for the stoichiometric spinel was successfully suppressed by Ni and S substitution. Electrochemical results indicated that slight substitution of nickel (x = 0.1) and sulfur (y = 0.01) in the LiMn2O4 enhances the electrochemical performance along with the rate capability and capacity retention.

Nature of the Electrochemical Properties of Sulphur Substituted LiMn2O4 Spinel Cathode Material Studied by Electrochemical Impedance Spectroscopy.

In this work, nanostructured LiMn2O4 (LMO) and LiMn2O3.99S0.01 (LMOS1) spinel cathode materials were comprehensively investigated in terms of electrochemical properties. For this purpose, electrochemical impedance spectroscopy (EIS) measurements as a function of state of charge (SOC) were conducted on a representative charge and discharge cycle. The changes in the electrochemical performance of the stoichiometric and sulphur-substituted lithium manganese oxide spinels were examined, and suggested explanations for the observed dependencies were given. A strong influence of sulphur introduction into the spinel structure on the chemical stability and electrochemical characteristic was observed. It was demonstrated that the significant improvement in coulombic efficiency and capacity retention of lithium cell with LMOS1 active material arises from a more stable solid electrolyte interphase (SEI) layer. Based on EIS studies, the Li ion diffusion coefficients in the cathodes were estimated, and the influence of sulphur on Li⁺ diffusivity in the spinel structure was established. The obtained results support the assumption that sulphur substitution is an effective way to promote chemical stability and the electrochemical performance of LiMn2O4 cathode material.

Study of quantitative interactions of potato and corn starch granules with ions in diluted solutions of heavy metal salts.

Interactions of potato and corn starch granules with ions in diluted solutions of silver, lead, copper or iron salts were investigated. It was shown experimentally that granules accumulated the cations in amounts depending on the granule structure and water content as well as a type of both metal and counter-ions present in solution. Potato starch retained almost three times more cations compared to corn starch what was proportional to the total phosphorous content in these starches. Quantity of milligrams of cations bound by 1g of starch was inversely correlated with the cation hydration. Ag(+), Pb(2+) and Cu(2+) were connected in stoichiometric amounts of moles to semicrystalline and amorphous parts of the granules. Fe(3+) ions were accumulated in higher than stoichiometric quantities mainly in granule amorphous regions. Metal ions penetrated into granules together with anions except nitrates which remained on surface of potato starch granules. Cations facilitated the starch thermal decomposition in accordance with values of their standard redox potentials. Nitrates supported this process only in the presence of base metal cations.

Ground to conduct: mechanochemical synthesis of a metal-organic framework with high proton conductivity.

We report a high proton-conducting material prepared for the first time by economical and environmentally-friendly mechanochemistry. Structural elucidation of the material from powder X-ray diffraction data reveals the details of the solid-state reaction. The reaction represents a new synthetic strategy towards materials related to fuel cell technology.

Anomaly in the electronic structure of the Na(x)CoO(2-y) cathode as a source of its step-like discharge curve.

In this paper we would like to show a new approach to an explanation of the nature of the discharge-charge curve of Na/Na(+)/NaxCoO2-y batteries, which can justify the existence of the step-like characteristics. This is still an open problem, which until now had no proper description in the literature. On the basis of comprehensive experimental studies of physicochemical properties of NaxCoO2-y cathode material (XRD, electrical conductivity, thermoelectric power, electronic specific heat) supported by calculations performed using the DFT method with accounting for chemical disorder, it has been shown that the observed step-like character of the discharge curve reflects the variation of the chemical potential of electrons (Fermi level) in the density of states of NaxCoO2-y, which is anomalously perturbed by the presence of the oxygen vacancy defects and sodium ordering. Our studies of structural, electronic and thermal properties of NaxCoO2-y cathode material as a function of concentration of electrochemically intercalated sodium document strong and step-like shift of the position of the Fermi level during introduction of electrons in this process. This effect is coherently supported by the shape of calculated density of states (DOS) of NaxCoO2-y having included oxygen defects and sodium ordering.