Photoelectric and magnetic properties of chemically synthesized Cd-Ni Ferrite nanomagnetic particles

Cadmium nickel (Cd-Ni) ferrite samples have been successfully synthesized via chemical co-precipitation technique. The structural analysis revealed the formation of FCC framework and Fe-phase in a trivalent state. The crystallite size is decreased with increasing Cd2+ ion composition whereas the lattice constant is increased. SEM was used to obtain the surface morphology and average grain size of the microstructure. The FTIR shows the formation of metal oxide, hydroxyl and carboxylic groups. EDX revealed the formation of Ni2+, Cd2+, Fe3+, and O2- ions in proper stoichiometric composition. Large optical losses were revealed by Cd2+ poor-NiFe2O4 samples whereas Cd2+ rich-CdxNi1-xFe2O4 samples revealed low optical losses and showed enhanced photoconductivity and photoelectric effect. Result from optical analysis showed that Cd2+ rich-CdxNi1-xFe2O4 nanoparticles can be used as infrared (IR) detector, ultraviolet (UV) filter and in optoelectronics device applications. VSM measurement showed an increase in saturation magnetization and decrease in coercivity as Cd2+ ion content is increased. The remanance magnetization and magnetic anisotropy were also examined. Photoluminescence (PL) spectroscopy examined the nature of the light emission of the samples at the excitation wavelength 380 nm and emission of series of colours such as red, green, yellow, orange and violet light at different wavelengths were found.

Mineral-associated soil organic matter: characteristics and behavior under diagenesis

The main part of soil organic matter (OM) is mineral-associated: 88 ± 11% of С and even more – 93 ± 9% of N. The aims of the given study were: 1 – to demonstrate experimentally the adsorption selectivity of organic compounds towards minerals with different physico-chemical properties (palygorskite vs montmorillonite); 2 – to characterize mineral-associated OM of buried Late Holocene palaeosols and estimate its diagenetic transformations; 3 – to investigate the OM of humin from modern soils of different genesis and Pleistocene and Holocene palaeosols and estimate its diagenetic transformations. The basic soil properties were determined using standard methods. Clay fractions (<2 um) – natural organo-mineral complexes (OMC) were obtained by sedimentation, their mineralogy was studied by XRD. The elemental composition of OM was studied with CNS-analyzer. The structural characteristics of organic matter were determined with the solid-state 13C-NMR-spectroscopy and FTIR-spectroscopy, isotopic composition of C and N – by mass-spectrometry. The obtained results show that the characteristics of mineral-associated OM depends on the properties of mineral “filter” as well as the fate of OM under diagenesis: how long, in what quantity and quality it will persist. It was shown that palygorskite adsorbed predominantly O-alkyls, which are chemically strongly bound. As a result, the age of fulvic type humus in palygoskite palaeosols can reach 300 My. From other side humus of smectitic paleosols of the same age is present by deeply transformed aromatic structures (“coal”). Mineral-associated OM of buried under kurgans Holocene palaeosols contains more alkyls and carboxylic groups, is less aromatic in a comparison with OM of the respective soils. The specific feature of mineral-associated OM is its enrichment in N-compounds. The later are present by both vegetal and microbial compounds, and demonstrate the large affinity towards the mineral surfaces. The formation of chemical bounds between them provides the persistence of OM in OMC. E.g. H2O2 treatment results in preferential destruction of C-rich compounds and oxidized OM demonstrates larger C/N values. Mineral-associated OM of buried Holocene soils keeps the decreased values of C/N (7–14 vs 14–21 for OM of whole soils). Additionally they are characterized by heavier isotopic composition of δ15N in a comparison with the respective soils (5–11‰ vs 6–9‰). It could be explained either by the accumulation of microbial N, or increasing of the humification degree – the loss of aliphatic C and increasing of aromaticity. Humin is the considerable part of soil humus. Experimentally shown that OM of humins both of soils and OMC is enriched in O-alkyls and C of acetal groups. OM of humins are not homogeneous, and consists from at least two groups: mineral-associated OM and partly mineralized plant fragments. As a consequence, the content of humin in OMC is smaller in a comparison with respective soils. It is concluded that mineral-associated OM and humin as well as soil humus represent dynamic soil systems.

Water-Activated Semiquinone Formation and Carboxylic Acid Dissociation in Melanin Revealed by Infrared Spectroscopy

Eumelanin is a widespread biomacromolecule pigment in the biosphere and has been widely investigated for numerous bioelectronics and energetic applications. Many of these applications depend on eumelanin’s ability to conduct proton current at various levels of hydration. The origin of this behavior is connected to a comproportionation reaction between oxidized and reduced monomer moieties and water. A hydration-dependent FTIR spectroscopic study on eumelanin is presented herein, which allows for the first time tracking the comproportionation reaction via the gradual increase of the overall aromaticity of melanin monomers in the course of hydration. We identified spectral features associated with the presence of specific “one and a half” C𝌁O bonds, typical for o-semiquinones. Signatures of semiquinone monomers with internal hydrogen bonds and that carboxylic groups, in contrast to semiquinones, begin to dissociate at the very beginning of melanin hydration were indicated. As such, we suggest a modification to the common hydration-dependent conductivity mechanism and propose that the conductivity at low hydration is dominated by carboxylic acid protons, whereas higher hydration levels manifest semiquinone protons.

ISOLATION AND PHYSICOCHEMICAL CHARACTERIZATION OF PECTIN FROM NONCONVENTIONAL NATU-RAL RAW MATERIALS

Obtaining and studying the functional properties and determining the subsequent purpose in the practical use of pectin substances requires a thorough study of physical and chemical characteristics of the polysaccharide. By using the acidic hydrolysis method, pectic polysaccharides were isolated from nonconventional raw materials of natural origins - basidial fungus mushrooms Fomes fomentarius, Ganoderma lucidum, Inonotus hispidus, Polýporus squamosus. The polysaccharides isolated were characterized: such as content of free and etherifying carboxyl groups, total -СООН groups, -ОСН3 groups, degree of etherification and by data of the IR-spectroscopy. The pectic polysaccharides isolated in identical conditions from the basidial mushrooms were powders with colors from light yellow to is light-brown by the appearance, possess sub-acidic taste, have no extraneous smack and a smell. The pectin from Inonotus hispidus was much lighter than other pectins (Fomes fomentarius, Ganoderma lucidum, Polýporus squamosus). The pectin’s isolated were similar to the apple pectin by the organoleptic properties. They can classified as averagely etherified pectins regarding the degree etherification. Etherification degree of the studied pectins was in the range of 50.00–66.67%. The methoxyl groups were ranged between 8.47–11.43%. Content of free carboxylic groups in the range of 2.25–5.40%.

Nonylphenol Ethoxylate Surfactants Modified by Carboxyl Groups for Foam EOR at High-Salinity Conditions

High mineralization of water complicates the use of foam in reservoir conditions. Anionic–nonionic surfactants are one of the best candidates for these conditions since they have both high surface activity and salt tolerance. One of the ways to obtain anionic–nonionic surfactants is to modify nonionic surfactants by an anionic group. The type of the group and its chemical structure can strongly affect the properties of the surfactant. In this work, widely-produced nonionic surfactant nonylphenol (12) ethoxylate (NP12EO) was modified by new types of carboxylic groups through the implementation of maleic (NP12EO-MA) and succinic (NP12EO-SA) anhydrides with different saturation levels. The main objectives of this work were to compare synthesized surfactants with nonionic precursor and to reveal the influence of unsaturated bonds in the carboxyl group on the properties of the foam. NaCl concentration up to 20 wt% was used to simulate high mineralization conditions, as well as to assess the effect of unsaturated bonds on foam properties. Synthesized anionic–nonionic surfactants retained surfactant solubility and long-term stability in high-salinity water, but have better foaming ability, as well as higher apparent viscosity, in porous media. The presence of an unsaturated bond in NP12EO-MA surfactant lowers foaming ability at high mineralization.

Wrinkling on Stimuli-Responsive Functional Polymer Surfaces as a Promising Strategy for the Preparation of Effective Antibacterial/Antibiofouling Surfaces

Biocompatible smart interfaces play a crucial role in biomedical or tissue engineering applications, where their ability to actively change their conformation or physico-chemical properties permits finely tuning their surface attributes. Polyelectrolytes, such as acrylic acid, are a particular type of smart polymers that present pH responsiveness. This work aims to fabricate stable hydrogel films with reversible pH responsiveness that could spontaneously form wrinkled surface patterns. For this purpose, the photosensitive reaction mixtures were deposited via spin-coating over functionalized glasses. Following vacuum, UV, or either plasma treatments, it is possible to spontaneously form wrinkles, which could increase cell adherence. The pH responsiveness of the material was evaluated, observing an abrupt variation in the film thickness as a function of the environmental pH. Moreover, the presence of the carboxylic acid functional groups at the interface was evidenced by analyzing the adsorption/desorption capacity using methylene blue as a cationic dye model. The results demonstrated that increasing the acrylic acid in the microwrinkled hydrogel effectively improved the adsorption and release capacity and the ability of the carboxylic groups to establish ionic interactions with methylene blue. Finally, the role of the acrylic acid groups and the surface topography (smooth or wrinkled) on the final antibacterial properties were investigated, demonstrating their efficacy against both gram-positive and gram-negative bacteria model strains (E. coli and S. Aureus). According to our findings, microwrinkled hydrogels presented excellent antibacterial properties improving the results obtained for planar (smooth) hydrogels.

Synthesis, Characterization, and Antifungal Activity of Silver Nanoparticles Embedded in Pullulan Matrices

Steady developments made in nanotechnology-based products have facilitated new perspectives for combating drug-resistant fungi. Silver nanoparticles represent one of the most attractive nanomaterials in biomedicine due to their exclusive optical, electromagnetic, and catalytic properties and antifungal potency compared with other metal nanoparticles. Most studies show that the physicochemical parameters affecting the antifungal potential of AgNPs include the shape, size, surface charge, and concentration and colloidal state. For the present study, pullulan (P) and its oxidized counterpart (PO) have been selected as matrices for the silver nanoparticles’ generation and stabilization (AgNPs). The TEMPO (2,2,6,6-tetramethylpiperidin-1-yl radical)–sodium hypochlorite–sodium bromide system was used for the C6 selective oxidation of pullulan in order to introduce negatively charged carboxylic groups in its structure. The structure and morphology of the synthesized AgNPs were analyzed using FTIR and EDX. The main objective of this study was to elucidate the antifungal activity of AgNPs on the clinical yeasts isolates and compare the performance of AgNPs with the conventional antifungals. In this study, different concentrations of AgNPs were tested to examine antifungal activity on various clinical isolates.

Solid-State Structures and Photoluminescence of Lamellar Architectures of Cu(I) and Ag(I) Paddlewheel Clusters with Hydrogen-Bonded Polar Guests

Two hexanuclear paddlewheel-like clusters appending six carboxylic-acid pendants have been isolated with the inclusion of polar solvent guests: [Cu6(Hmna)6]·7DMF (1·7DMF) and [Ag6(Hmna)6]·8DMSO (2·8DMSO), where H2mna = 2-mercaptonicotininc acid, DMF = N,N’-dimethylformamide, and DMSO = dimethyl sulfoxide. The solvated clusters, together with their fully desolvated forms 1 and 2, have been characterized by FTIR, UV–Vis diffuse reflectance spectroscopy, TG-DTA analysis, and DFT calculations. Crystal structures of two solvated clusters 1·7DMF and 2·8DMSO have been unambiguously determined by single-crystal X-ray diffraction analysis. Six carboxylic groups appended on the clusters trap solvent guests, DMF or DMSO, through H-bonds. As a result, alternately stacked lamellar architectures comprising of a paddlewheel cluster layer and H-bonded solvent layer are formed. Upon UV illumination (λex = 365 nm), the solvated hexasilver(I) cluster 2·8DMSO gives intense greenish-yellow photoluminescence in the solid state (λPL = 545 nm, ΦPL = 0.17 at 298 K), whereas the solvated hexacopper(I) cluster 1·7DMF displays PL in the near-IR region (λPL = 765 nm, ΦPL = 0.38 at 298 K). Upon complete desolvation, a substantial bleach in the PL intensity (ΦPL < 0.01) is observed. The desorption–sorption response was studied by the solid-state PL spectroscopy. Non-covalent interactions in the crystal including intermolecular H-bonds, CH···π interactions, and π···π stack were found to play decisive roles in the creation of the lamellar architectures, small-molecule trap-and-release behavior, and guest-induced luminescence enhancement.

A Simple Graphene Functionalized Electrochemical Aptasensor for the Sensitive and Selective Detection of Glycated Albumin

Glycated albumin (GA) has been previously introduced as a promising biomarker for glycemic monitoring in diabetes patients with thalassemia. In this study, a label-free graphene oxide (GO)-modified aptasensor was developed for the rapid detection of GA. The fabrication of the aptasensor was dependent on the covalent interaction of the amine-functionalized GA-specific aptamer with the carboxylic groups of GO. Square wave voltammetry (SWV) analysis was carried out for the measurement of GA-aptamer binding to their specific proteins. The peak current changes before and after incubation with GA protein were directly proportional to the concentration. The developed aptasensor exhibited a broad linearity (1–10,000 µg mL−1), a low detection limit (LOD) of 0.031 µg mL−1, and high selectivity for GA detection. In addition, the aptasensor was successfully applied to detect GA in both spiked and clinical serum samples. The comparison of the developed method with a commercial assay validated the reliability of the aptasensor for clinical application. Therefore, the newly developed aptasensor is a promising tool for GA measurements in diabetic patients with underlying thalassemia.