New Polymeric Adsorbents Functionalized with Aminobenzoic Groups for the Removal of Residual Antibiotics.

In this paper, we present the synthesis of new polymeric adsorbents derived from macroporous chloromethylated styrene-divinylbenzene (DVB) copolymers with different cross-linking degrees functionalized with the following aminobenzoic groups: styrene-6.7% DVB (PAB1), styrene-10% DVB (PAB2), and styrene-15% DVB (PAB3). The new polymeric products, PAB1, PAB2, and PAB3, were characterized by FTIR spectroscopy, thermogravimetric analysis, and EDX, SEM, and BET analysis, respectively. The evolution of the functionalization reaction was followed by FTIR spectroscopy, which revealed a decrease in the intensity of the γCH2Cl band at 1260 cm-1, and, simultaneously, the appearance of C=O carboxylic bands from 1685-1695 cm-1 and at 1748 cm-1. The thermal stability increased with the increase in the cross-linking degree. The data obtained from the EDX analysis of the novel cross-linked copolymers confirmed the functionalization with aminobenzoic groups through the presence and content of nitrogen, as follows: PAB1: N% = 0.47; PAB2: N% = 0.85; and PAB3: N% = 1.30. The adsorption performances of the novel polymeric adsorbents, PAB1, PAB2, and PAB3, were tested in the adsorption of three antibiotics, tetracycline, sulfamethoxazole, and amoxicillin, from aqueous solutions, by using extensive kinetic, equilibrium, and thermodynamic studies. The best adsorption capacity was demonstrated by the tetracycline. Amoxicillin adsorption was also attempted, but it did not show positive results.

The Effect of Calcium and Iron (III) Oxides on Lead Spent Plates: Spectroscopic, Voltametric, and EIS Investigations.

In this study, xCaO‧5Fe2O3‧(95-x)Pb glasses and vitroceramics containing various concentrations of calcium ions (from 0 to 50 mol% CaO) were prepared using the spent anodic plate of a car battery. X-ray diffraction analysis revealed changes in the network structure as a function of CaO content. The intensities of the IR bands due to the sulfate and sulfite units were lowered, indicating a decrease in the sulfurization degree within the lead network. In the UV-vis spectra, the presence of electronic transitions of the Fe3+, Pb2+, and Fe2+ ions were identified. The EPR spectra were characterized by resonance signals centered at about g ~ 2 and 4.3, corresponding to the trivalent iron ions. For the samples with 5 ≤ x ≤ 12, the signals decreased abruptly, suggesting a Fe3+→Fe2+ interconversion and the formation of the Fe3O4 crystalline phase. A considerable increase in the intensity of the signal centered around g ~ 2 was observed as the CaO concentration increased to 30% in the host matrix. Our results confirm that the higher CaO levels of 3 mol% are responsible for the increase in the radius of curvature of the semicircle arcs in the EIS plots and the decrease in their conductivity.

Circular causality analysis of corporate performance and accounting quality in M&As.

The past performance and the capital structure of the companies that are involved in mergers and acquisition (M&As) are considered into the analysis of the circular causality relationship between financial performance and market value. Considering two models, one for value relevance and one for accounting conservatism, this paper aims to analyze if the capital market influences the accounting practices of a target company or that the accounting figures influence the capital market. The analyzed sample used in the study is represented by the target companies involved in M&As which took place in the European Union Enlarged in 2017-2018. Financial and market data were considered for eight years (2011-2018). Using the conservatism model, the results show that targets' earnings are significantly influenced by their financial leverage as an indicator for financial structure. Using the value relevance model, the capital market reaction is influenced by prices and return on equity that indicates the capital market influence on accounting figures.

Recycled and Nickel- or Cobalt-Doped Lead Materials from Lead Acid Battery: Voltammetric and Spectroscopic Studies.

The active mass of the plates of aspent car battery with higher wear after an efficient desulfatization can be used as sources of a new electrode. This paper proposes the recycling of spent electrodes from a lead acid battery and the incorporation of NiO or Co3O4 contents by the melt-quenching method in order to enrich the electrochemical properties. The analysis of X-ray diffractograms indicates the gradual decrease in the sulfated crystalline phases, respectively, 4PbO·PbSO4 and PbO·PbSO4 phases, until their disappearance for higher dopant concentrations. Infrared (IR) spectra show a decreasing trend in the intensity of the bands corresponding to the sulfate ions and a conversion of [PbO3] pyramidal units into [PbO4] tetrahedral units by doping with high dopant levels, yielding to the apparition of the PbO2 crystalline phase. The observed electron paramagnetic resonance (EPR) spectra confirm three signals located on the gyromagnetic factor, g~2, 2.2 and 8 assigned to the nickel ions in higher oxidation states as well as the metallic nickel nanoparticles. This compositional evolution can be explained by considering a process of the drastic reduction in nickel ions from the superior oxidation states to metallic nickel. The linewidth and the intensity of the resonance lines situated at about g~2, 2.17, 4.22 and 7.8 are attributed to the Co+2 ions from the EPR data. The best reversibility of the cyclic voltammograms was highlighted for the samples with x = 10 mol% of NiO and 15 mol% of Co3O4, which are recommended as suitable in applications as new electrodes for the lead acid battery.

Structure-Bioactivity Relationship of the Functionalized Polysulfone with Triethylphosphonium Pendant Groups: Perspective for Biomedical Applications.

Development of new biomaterials based on polysulfones tailored to act in various biomedical fields represents a promising strategy which provides an opportunity for enhancing the diagnosis, prevention, and treatment of specific illnesses. To meet these requirements, structural modification of the polysulfones is essential. In this context, for design of new materials with long-term stability, enhanced workability, compatibility with biological materials and good antimicrobial activity, the functionalization of chloromethylated polysulfones with triethylphosphonium pendant groups (PSFEtP+) was adopted. The surface chemistry analysis (Fourier transform infrared spectroscopy (FTIR), Energy-dispersive X-ray spectroscopy (EDX)), rheological properties, morphological aspects (Scanning electron microscopy (SEM), polarized light microscopy (POM)), and antimicrobial activity of the synthetized polysulfone were investigated to establish the relationship between its structure and properties, as an important indicator for targeted applications. Based on the obtained features, evaluated by the relationship between the rheological properties and microstructural aspects, and also the response at the biomaterial-bacteria interface, these qualities have been confirmed in their performance, in terms of thermal stability, antimicrobial activity, and also an increase in lifetime. Consequently, derived results constitute the preliminary basis for future tests concerning their functionality as gel matrices in biomedical devices.

Facile Preparation of PVDF/CoFe2O4-ZnO Hybrid Membranes for Water Depollution.

In this investigation, CoFe2O4-PVDF and CoFe2O4-ZnO-PVDF hybrid membranes were prepared using a modified phase inversion method in which a magnetic field was applied during the casting process to ensure a uniform distribution of nanomaterials on the membrane surface. Thus, better absorption of light and increased participation of nanoparticles in the photodegradation process is ensured. The influence of nanomaterials on the crystalline structure, surface morphology, and hydrophilicity properties of the PVDF membrane was investigated. The obtained results indicated that the hybrid membrane exhibited significant differences in its intrinsic properties due to the nanomaterials addition. The hydrophilicity properties of the PVDF membrane were improved by the presence of nanoparticles. The photocatalytic decomposition of aqueous Rhodamine B solution in the presence of the prepared membrane and under visible light irradiation was tested. The hybrid membrane containing CoFe2O4-ZnO on its surface exhibited a high removal rate.

Impact on the Photocatalytic Dye Degradation of Morphology and Annealing-Induced Defects in Zinc Oxide Nanostructures.

In this study, three different morphologies, nanoflower (NF), nano sponge (NS), and nano urchin (NU), of zinc oxide (ZnO) nanostructures were synthesized successfully via a mild hydrothermal method. After synthesis, the samples were annealed in the atmosphere at 300, 600, and 800 °C. Although annealing provides different degradation kinetics for different morphologies, ZnO NS performed significantly better than other morphologies for all annealing temperatures we used in the study. When the photoluminescence, electron paramagnetic resonance spectroscopy, BET surface, and X-ray diffraction analysis results are examined, it is revealed that the defect structure, pore diameter, and crystallinity cumulatively affect the photocatalytic activity of ZnO nanocatalysts. As a result, to obtain high photocatalytic activity in rhodamine B (RhB) degradation, it is necessary to develop a ZnO catalyst with fewer core defects, more oxygen vacancies, near band emission, large crystallite size, and large pore diameter. The ZnO NS-800 °C nanocatalyst studied here had a 35.6 × 10-3 min-1 rate constant and excellent stability after a 5-cycle photocatalytic degradation of RhB.

Photoluminescence and Photocatalytic Properties of MWNTs Decorated with Fe-Doped ZnO Nanoparticles.

The present work reports the photoluminescence (PL) and photocatalytic properties of multi-walled carbon nanotubes (MWCNTs) decorated with Fe-doped ZnO nanoparticles. MWCNT:ZnO-Fe nanocomposite samples with weight ratios of 1:3, 1:5 and 1:10 were prepared using a facile synthesis method. The obtained crystalline phases were evidenced by X-ray diffraction (XRD). X-ray Photoelectron spectroscopy (XPS) revealed the presence of both 2+ and 3+ valence states of Fe ions in a ratio of approximately 0.5. The electron paramagnetic resonance EPR spectroscopy sustained the presence of Fe3+ ions in the ZnO lattice and evidenced oxygen vacancies. Transmission electron microscopy (TEM) images showed the attachment and distribution of Fe-doped ZnO nanoparticles along the nanotubes with a star-like shape. All of the samples exhibited absorption in the UV region, and the absorption edge was shifted toward a higher wavelength after the addition of MWCNT component. The photoluminescence emission spectra showed peaks in the UV and visible region. Visible emissions are a result of the presence of defects or impurity states in the material. All of the samples showed photocatalytic activity against the Rhodamine B (RhB) synthetic solution under UV irradiation. The best performance was obtained using the MWCNT:ZnO-Fe(1:5) nanocomposite samples, which exhibited a 96% degradation efficiency. The mechanism of photocatalytic activity was explained based on the reactive oxygen species generated by the nanocomposites under UV irradiation in correlation with the structural and optical information obtained in this study.

Recent Advances in Photochargeable Integrated and All-in-One Supercapacitor Devices.

Photoassisted energy storage systems, which enable both the conversion and storage of solar energy, have attracted attention in recent years. These systems, which started about 20 years ago with the individual production of dye-sensitized solar cells and capacitors and their integration, today allow more compact and cost-effective designs using dual-acting electrodes. Solar-assisted batterylike or hybrid supercapacitors have also shown promise with their high energy densities. This review summarizes all of these device designs and conveys the cutting-edge studies in this field. Besides, this review aims to emphasize the effects of point, extrinsic, intrinsic, and 2D-planar defects on the performance of photoassisted energy storage systems since it is known that defect structures, as well as electrical, optical, and surface properties, affect the device performance. Here, it is also targeted to draw attention to how critical the design, material selection, and material properties are for these new-generation energy conversion and storage devices, which have a high potential to see commercial examples quickly and to be recognized by more readers.

Synthesis of new phosphorus-containing (co)polyesters using solid-liquid phase transfer catalysis and product characterization.

This paper is directed towards the development of safe, and thermally stable solid polymer electrolytes. Linear phosphorus-containing (co)polyesters are described, including their synthesis, thermal analysis, conductivity, and non-flammability. Polycondensation of phenylphosphonic dichloride (PPD) with poly(ethylene glycol) (PEG 12000) with and without bisphenol A (BA) was carried out using solid-liquid phase transfer catalysis. Potassium phosphate is used as base. Yields in the range of 85.0-88.0%, and inherent viscosities in the range of 0.32-0.58 dL/g were obtained. The polymers were characterized by gel permeation chromatography, FT-IR, (1)H- and (31)P-NMR spectroscopy and thermal analysis. Their flammability was investigated by measuring limiting oxygen index values. The polymers are flame retardants and begin to lose weight in the 190 °C-231 °C range. Solid phosphorus- containing (co)polyesters were complexed with lithium triflate and the resulting ionic conductivity was determined. Conductivities in the range of 10(-7)-10(-8) S cm(-1) were obtained.

Structural, Optical, and Magnetic Studies of the Metallic Lead Effect on MnO2-Pb-PbO2 Vitroceramics.

MnO2-lead materials have attracted attention in their applications as electrodes. This work reports a detailed spectroscopic study of the compositional variation of MnO2-xLead vitroceramic materials with varied Pb contents. The concentration variation of lead and manganese ions issystematically characterized throughthe analysis of X-ray diffraction (XRD), Fourier transform infrared (FTIR), ultraviolet-visible (UV-Vis), and electron paramagnetic resonance (EPR) spectroscopy.The MnO2-xLead samples consist of a vitroceramic structure with Pb, PbO, PbO2,and Mn3O4 crystalline phases. The introduction of higher Pb content in the host vitroceramic reveals the [PbO6]→[PbOn] conversion, where n = 3, 4, and the formation of distorted [MnO6] octahedral units. The UV-Vis data of the samples possess the intense bands between 300 and 500 nm, which are due to the presence of divalent lead ions (320 nm) and divalent and trivalent manganese ions (420 and 490 nm, respectively) in the structure of glass ceramics. The EPR data show resonance lines located around g ~ 8 and 4.3, and a sextet hyperfine structure at g ~ 2, which isascribed to the Mn+3 and Mn+2 ions.

Chemical Modification of Chitosan for Removal of Pb(II) Ions from Aqueous Solutions.

Biomacromolecule have a significant contribution to the adsorption of metal ions. Moreover, chitosan is one of the most studied biomacromolecule, which has shown a good performance in the field of wastewater treatment. In this context, a new adsorbent of the aminophosphonic modified chitosan-supported Ni(II) ions type was prepared from the naturally biopolymer, chitosan. In the first step, modified chitosan with aminophosphonic acid groups was prepared using the "one-pot" Kabachnik-Fields reaction. It was characterized by different techniques: FTIR, SEM/EDAX, TGA, and 31P-NMR. In the second step, the modified chitosan with aminophosphonic acid was impregnated with Ni(II) ions using the hydrothermal reaction at different values of pH (5, 6 and 7). The physical-chemical characteristics of final products (modified chitosan carrying aminophosphonic groups and Ni(II) ions) were investigated using FTIR, SEM images, EDAX spectra and thermogravimetric analysis. In this work, the most important objective was the investigation of the adsorbent performance of the chitosan modified with aminophosphonic groups and Ni(II) ions in the process of removing Pb(II) ions from aqueous solutions by studying the effect of pH, contact time, and Pb(II) ions concentration. For removal of Pb(II) ions from the aqueous solution, the batch adsorption method was used.

Photocatalytic and Electrocatalytic Properties of NGr-ZnO Hybrid Materials.

N-doped graphene-ZnO hybrid materials with different N-doped graphene:ZnO wt% ratios (1:10; 1:20; 1:30) were prepared by a simple and inexpensive sol-gel method. The materials denoted NGr-ZnO-1 (1:10), NGr-ZnO-2 (1:20), and NGr-ZnO-3 (1:30) were investigated with advanced techniques and their morpho-structural, photocatalytic, and electrocatalytic properties were reported. Hence, pure N-doped graphene sample contains flakes with the size ranging from hundreds of nanometers to micrometers. In the case of all NGr-ZnO hybrid materials, the flakes appear heavily decorated with ZnO nanoparticles, having a cauliflower-like morphology. The X-ray powder diffraction (XRD) investigation of N-doped graphene sample revealed that it was formed by a mixture of graphene oxide, few-and multi-layer graphene. After the ZnO nanoparticles were attached to graphene, major diffraction peaks corresponding to crystalline planes of ZnO were seen. The qualitative and quantitative compositions of the samples were further evidenced by X-ray photoelectron spectroscopy (XPS). In addition, UV photoelectron spectroscopy (UPS) spectra allowed the determination of the ionization energy and valence band maxima. The energy band alignment of the hybrid materials was established by combining UV-Vis with UPS results. A high photocatalytic activity of NGr-ZnO samples against rhodamine B solution was observed. The associated reactive oxygen species (ROS) generation was monitored by electron paramagnetic resonance (EPR)-spin trapping technique. In accordance with bands alignment and identification of radical species, the photocatalytic mechanism was elucidated.

Photocatalytic activity of SnO2-TiO2 composite nanoparticles modified with PVP.

Interface modified SnO2-TiO2 composite nanoparticles were produced in two stages: first SnO2 nanoparticles were prepared by chemical precipitation in the presence of polyvinylpyrrolidone (PVP) and thermally treated at 500 °C then TiO2 was deposited on top of modified SnO2 and followed by a final annealing. As a consequence SnO2-TiO2 composite nanoparticles get crystallized while PVP is decomposed into monomer units and other attached smaller molecular fragments. TGA coupled with FT-IR spectroscopy confirmed the presence of monomers and other moieties as a result of PVP thermal fragmentation. The crystalline phases and composition of the two oxides were evidenced by X-ray diffraction, HRTEM and XPS. It was found that specific surface area of the composites increases with the increase in the initial amount of PVP. Also, the oxidation potential of the TiO2 shell, as determined by UV photoelectron spectroscopy (UPS), significantly decreases as the PVP quantity increase and further modifies the band alignment between SnO2 and TiO2 components. Additionally, both XPS and UPS spectra as well as EPR investigations indicate the presence of many localized states inside the band gap of TiO2. With a moderate PVP content the combined effects of band alignment, gap localized states and porosity make possible an increased number of reactive oxygen species (ROS) generation thus increasing photocatalytic activity against RhB dye solution under visible irradiation. The photocatalytic mechanism was elucidated based on the identification of radical species involved and in accordance with energy bands alignment, gap states, and porosity. Besides water purification by photocatalysis, SnO2-TiO2, as ROS generating heterostructures may be used in applications like antibacterial and antitumoral, deodorizing, air purifying, self-cleaning, gas sensing, as well as in hydrogen production.

Data on the removal of Optilan Blue dye from aqueous media using starch-coated green synthesized magnetite nanoparticles.

In this data article, we present supplementary data related to the research article entitled "Starch-coated green synthesized magnetite nanoparticles for removal of textile dye Optilan Blue from aqueous media" Stan et al., 2019. Data interpretations are included in the related research article Stan et al., 2019. The synthesized starch-coated Fe3O4 nanoparticles (ST-coated Fe3O4 NPs) were analyzed by scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM) to illustrate the shape and surface coating of nanoparticles. Moreover, the Brunauer-Emmett-Teller (BET) technique was used to evidence starch deposition on magnetite nanoparticles. The obtained nanocomposites were used for adsorption of Optilan Blue (OB) in batch conditions and the optimum agitation speed and point of zero charge (pHpzc) were established. After OB adsorption on ST-coated Fe3O4 NPs, the nanocomposites were analyzed by transmission electron microscopy (TEM), X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR). The stability of starch coated Fe3O4 NPs in the acidic as well as alkaline pH was also evidenced by FTIR spectroscopy. In addition, to test the stability of ST-coated Fe3O4 NPs, leaching experiments were carried out. The experimental data were compared with isotherm and kinetic models in order to determine the most suitable for fitting.

New Evidences of Key Factors Involved in "Silent Stones" Etiopathogenesis and Trace Elements: Microscopic, Spectroscopic, and Biochemical Approach.

The knowledge of the key factors involved in etiopathogenesis of the gallstone disease requires chemical, structural, and elemental composition analysis. The application of different complementary analytical techniques, both microscopic and spectroscopic, are aimed to provide a more comprehensive determination of the gallbladder calculi ultrastructure and trace element identification. High sensitivity techniques such as electron microscopy (SEM), Fourier transform infrared (FTIR), electron paramagnetic resonance (EPR) spectroscopy, and X-ray diffraction (XRD) along with biochemical analysis are used in a new attempt to investigate various factors which play a regulatory role in the pathogenesis of gallstones. The microstructure of different types of gallbladder stones has specific characteristics which are related to the elemental composition. The binding of metal ions with bile salts and bilirubin plays important roles in gallstone formation as revealed by FTIR spectrum of calcium bilirubinate complex in pigment gallstones. The EPR results demonstrated the generation of bilirubin free radicals and variation of its electronic structure and conjugation system in the skeleton of bilirubin molecule during complex formation. EPR spectra of pigment gallstones demonstrate the coexistence of four paramagnetic centers including stable bilirubin free radical, Mn2+, Cu2+, and Fe3+ with distinct magnetic parameters and well-resolved hyperfine structure in the case of Mn2+ ions. The result confirms a macromolecular network structure with proteins and the formation of bilirubin-coordinated polymer. Bilirubin and bilirubinate free radical complexes may play an important role in pigment gallstone formation.

Grafted α-hydroxyphosphonic acids onto polymeric supports: preparation, characterization, and antimicrobial effect.

The paper deals with the preparation and characterization of compounds with antimicrobial activity: α-hydroxyphosphonic acids grafted onto styrene-12%-(15%)-divinylbenzene copolymer. These products proved to have antimicrobial effect against two species of gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa) and two species of gram-positive bacteria (Staphylococcus aureus and Bacillus cereus) and a species of yeast (Candida albicans). Tests showed the reduction of bacterial load at different time intervals during the 18 h of contact.

Detection of Lysyl Oxidase-Like 2 (LOXL2), a Biomarker of Metastasis from Breast Cancers Using Human Blood Samples.

Metastasis accounts for 90% of the mortality associated with breast cancer. Upregulated expression of members of the lysyl oxidase (LOX) family of secreted copper amine oxidases catalyzes the crosslinking of collagens and elastin in the extracellular matrix. LOXs are linked to the development and metastatic progression of breast cancers. Accordingly, aberrant expression of LOX-like 2 (LOXL2) is observed in poorly differentiated, high-grade tumors and is predictive of diseases recurrence, and for decreased overall patient survival. Therefore, LOXL2 expression may serve as a biomarker for breast cancer. Mechanistically, hydrogen peroxide is produced as a byproduct of LOXL2 when using an appropriate substrate, lysine. We exploited this chemistry to generate a revolutionary gold-based electrochemical biosensor capable of accurately detecting nanomolar quantities of LOXL2 in mouse blood, and in human blood samples. Two different sources of the blood samples obtained from breast cancer patients were used in this study indicating the applicability of detecting LOXL2 in breast cancers patients. Limited numbers of urine specimens from breast cancer patients were also tested. Collectively, all of these tests show the promise and potential of this biosensor for detecting LOXL2 as a surrogate biomarker of breast cancer. This work is described in WO 052962 A1 (2014).

Effect of metal precursor on the growth and electrochemical sensing properties of Pt-Ag nanoboxes.

Pt-Ag nanoboxes prepared using a Pt(4+) versus Pt(2+) precursor show not only stoichiometric, but also catalytic effects on the nanobox growth, resulting in metal content and surface morphology differences. Electrochemical studies on these nanoboxes reveal the combined importance of composition and hollow, rough-walled nanostructure for improved detection of electroactive molecules.