Ag-Decorated Iron Oxides-Silica Magnetic Nanocomposites with Antimicrobial and Photocatalytic Activity.

Nanotechnology offers unlimited possibilities for creating effective hybrid materials, which combine functional performance in environment depollution and antimicrobial defense with a lack of toxicity, biocompatibility, biodegradability, and natural availability. This paper presents the silver effect on photocatalytic and antibacterial activities of double-coated iron oxide nanoparticles (NPs), Fe3O4@SiO2/ZnO-Ag. The structural, morphological, and textural information of the, core-shell iron oxides-based superparamagnetic nanoparticles (IOMNPs) decorated with 5% Ag by ultrasound-assisted synthesis were evaluated by scanning electron microscopy with energy dispersive spectroscopy (SEM-EDX), X-ray diffraction, Raman spectroscopy, and Brunauer-Emmett-Teller physisorption measurements. Although two synthesis temperatures of 95 and 80 °C were used for the co-precipitated iron oxide cores, the XRD patterns revealed the formation of a single magnetite, Fe3O4, phase. The sorption-photocatalytic activities under dark and UV irradiation encountered a maximum removal efficiency of the MB (90.47%) for the Fe3O4@SiO2/ZnO-Ag sample with iron oxide core obtained at 80 °C. The rate constant for the second-order kinetics was 0.0711 min-1 for 2 h, and the correlation coefficient R2 closed to unity. Two samples with Ag-decorated hybrid SiO2/ZnO shell and hierarchically interconnected porous structure with large surface area (328.8 and 342.5 m2g-1) exhibited the best disk diffusion antimicrobial activity against four microorganisms, especially gram-positive Staphylococcus aureus.

Novel Magnetic Nanocomposites Based on Carboxyl-Functionalized SBA-15 Silica for Effective Dye Adsorption from Aqueous Solutions.

In this study, three novel magnetic nanocomposites based on carboxyl-functionalized SBA-15 silica and magnetite nanoparticles were prepared through an effective and simple procedure and applied for methylene blue (MB) and malachite green G (MG) adsorption from single and binary solutions. Structure, composition, morphology, magnetic, and textural properties of the composites were thoroughly investigated. The influence of the amount of carboxyl functional groups on the physicochemical and adsorptive properties of the final materials was investigated. The capacity of the synthesized composites to adsorb MB and MG from single and binary solutions and the factors affecting the adsorption process, such as contact time, solution pH, and dye concentration, were assessed. Kinetic modelling showed that the dye adsorption mechanism followed the pseudo-second-order kinetic model, indicating that adsorption was a chemically controlled multilayer process. The adsorption rate was simultaneously controlled by external film diffusion and intraparticle diffusion. It was evidenced that the molecular geometry of the dye molecule plays a major role in the adsorption process, with the planar geometry of the MB molecule favoring adsorption. The analysis of equilibrium data revealed the best description of MB adsorption behavior by the Langmuir isotherm model, whereas the Freundlich model described better the MG adsorption.

Magnetic Core-Shell Iron Oxides-Based Nanophotocatalysts and Nanoadsorbents for Multifunctional Thin Films.

In recent years, iron oxides-based nanostructured composite materials are of particular interest for the preparation of multifunctional thin films and membranes to be used in sustainable magnetic field adsorption and photocatalysis processes, intelligent coatings, and packing or bio-medical applications. In this paper, superparamagnetic iron oxide (core)-silica (shell) nanoparticles suitable for thin films and membrane functionalization were obtained by co-precipitation and ultrasonic-assisted sol-gel methods. The comparative/combined effect of the magnetic core co-precipitation temperature (80 and 95 °C) and ZnO-doping of the silica shell on the photocatalytic and nano-sorption properties of the resulted composite nanoparticles were investigated by ultraviolet-visible (UV-VIS) spectroscopy monitoring the discoloration of methylene blue (MB) solution under ultraviolet (UV) irradiation and darkness, respectively. The morphology, structure, textural, and magnetic parameters of the investigated powders were evidenced by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, Brunauer-Emmett-Teller (BET) measurements, and saturation magnetization (vibrating sample magnetometry, VSM). The intraparticle diffusion model controlled the MB adsorption. The pseudo- and second-order kinetics described the MB photodegradation. When using SiO2-shell functionalized nanoparticles, the adsorption and photodegradation constant rates are three-four times higher than for using starting core iron oxide nanoparticles. The obtained magnetic nanoparticles (MNPs) were tested for films deposition.

Facile Synthesis of Cobalt Ferrite (CoFe2O4) Nanoparticles in the Presence of Sodium Bis (2-ethyl-hexyl) Sulfosuccinate and Their Application in Dyes Removal from Single and Binary Aqueous Solutions.

A research study was conducted to establish the effect of the presence of sodium bis-2-ethyl-hexyl-sulfosuccinate (DOSS) surfactant on the size, shape, and magnetic properties of cobalt ferrite nanoparticles, and also on their ability to remove anionic dyes from synthetic aqueous solutions. The effect of the molar ratio cobalt ferrite to surfactant (1:0.1; 1:0.25 and 1:0.5) on the physicochemical properties of the prepared cobalt ferrite particles was evaluated using different characterization techniques, such as FT-IR spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 adsorption-desorption analysis, and magnetic measurements. The results revealed that the surfactant has a significant impact on the textural and magnetic properties of CoFe2O4. The capacity of the synthesized CoFe2O4 samples to remove two anionic dyes, Congo Red (CR) and Methyl Orange (MO), by adsorption from aqueous solutions and the factors affecting the adsorption process, such as contact time, concentration of dyes in the initial solution, pH of the media, and the presence of a competing agent were investigated in batch experiments. Desorption experiments were performed to demonstrate the reusability of the adsorbents.

Comparative Study of CoFe2O4 Nanoparticles and CoFe2O4-Chitosan Composite for Congo Red and Methyl Orange Removal by Adsorption.

(1) Background: A comparative research study to remove Congo Red (CR) and Methyl Orange (MO) from single and binary solutions by adsorption onto cobalt ferrite (CoFe2O4) and cobalt ferrite-chitosan composite (CoFe2O4-Chit) prepared by a simple coprecipitation method has been performed. (2) Methods: Structural, textural, morphology, and magnetic properties of the obtained magnetic materials were examined by X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, N2 adsorption-desorption analysis, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), and magnetic measurements. The optimal operating conditions of the CR and MO removal processes were established in batch experiments. The mathematical models used to describe the processes at equilibrium were Freundlich and Langmuir adsorption isotherms. (3) Results: Cobalt ferrite-chitosan composite has a lower specific surface area (SBET) and consequently a lower adsorption capacity than cobalt ferrite. CoFe2O4 and CoFe2O4-Chit particles exhibited a superparamagnetic behavior which enabled their efficient magnetic separation after the adsorption process. The research indicates that CR and MO adsorption onto prepared magnetic materials takes place as monolayer onto a homogeneous surface. According to Langmuir isotherm model that best fits the experimental data, the maximum CR/MO adsorption capacity is 162.68/94.46 mg/g for CoFe2O4 and 15.60/66.18 mg/g for CoFe2O4-Chit in single solutions. The results of the kinetics study revealed that in single-component solutions, both pseudo-first-order and pseudo-second-order kinetics models represent well the adsorption process of CR/MO on both magnetic adsorbents. In binary solutions, adsorption of CR/MO on CoFe2O4 better follows the pseudo-second-order kinetics model, while the kinetic of CR/MO adsorption on CoFe2O4-Chit is similar to that of the dyes in single-component solutions. Acetone and ethanol were successfully used as desorbing agents. (4) Conclusions: Our study revealed that CoFe2O4 and CoFe2O4-Chit particles are good candidates for dye-contaminated wastewater remediation.

Chitosan-polyglycidol complexes to coating iron oxide particles for dye adsorption.

The study sheds light on the interaction between chitosan (Ch) and polyglycidol (PGL) and uses their interpolymer complex in hydrophilic coating of iron oxide particles (M). Preliminary investigations were performed by modeling chitosan and polyglycidol chains interactions using coarse grained beads approximation and molecular dynamics simulations. The results revealed that Ch and PGL chains associate together forming weak strength complexes, which was experimentally confirmed by surface tension, fluorescence and FTIR. The Ch-PGL mixture (C) and sodium dodecylsulfate (S) were used for layer-by-layer preparation of hydrophilic multilayer coatings of M. The successful covering, demonstrated by DLS, Zeta potential, FTIR, EDAX, preserved the particles super-paramagnetic properties. The most stable multilayer nanocomposite (MSCS) efficiently adsorbed methylene blue from water. The Freundlich model fitted well the equilibrium isotherm data, indicating a heterogeneous, multilayer adsorption. Benefiting from both nano-size and magnetic properties, this adsorbent could be an effectively, cheaply and eco-friendly wastewater treatment means.

Monte Carlo Simulations of the Magnetic Behavior, Ordering Temperature and Magnetocaloric Effects in 1D, 2D and 3D Ferrimagnetic Systems.

As for the systematic investigations of magnetic behaviors and its related properties, computer simulations in extended quantum spin networks have been performed in good conditions via the generalized Ising model using the Monte Carlo-Metropolis algorithm with proven efficiencies. The present work, starting from a real magnetic system, provides detailed insights into the finite size effects and the ferrimagnetic properties in various 1 D, 2D and 3D geometries such as the magnetic moment, ordering temperature, and magnetocaloric effects with the different values of spins localized on the different coordinated sites.

Synthesis, characterization antibacterial and antiproliferative activity of novel Cu(II) and Pd(II) complexes with 2-hydroxy-8-R-tricyclo[7.3.1.0.(2,7)]tridecane-13-one thiosemicarbazone.

Synthesis and biological activity investigation of complex compounds of Cu(II) are challenging issues because of the metal is not a xenobiotic one and the activity of ligands could be modulated by complexation. Complex combinations of Cu(II) and Pd(II) with thiosemicarbazone derivatives of 2-hydroxy-8-R-tricyclo[7.3.1.0.(2,7)]tridecane-13-one (where R=C(3)H(7), C(4)H(3)O) were synthesized. The characterization of the ligands and the newly formed compounds was done by (1)H NMR, (13)C NMR, UV-vis, IR, ESR spectroscopy, elemental analysis, molar electric conductibility and thermal studies. Experiments performed to identify the structures proved that the ligands coordinate to metal ions in different ways - neutral bidentate or mononegative bidentate. Also, if copper(II) acetate, copper(II) nitrate, copper(II) chloride and copper(II) thiocyanate were used, the ligands coordinated in a mononegative bidentate fashion. If copper(II) sulfate was used, the ligands coordinated in a neutral bidentate fashion. The biological activity for the copper(II) synthesized compounds was assessed in terms of antibacterial or antiproliferative activity. The antibacterial activity of the complexes against Staphylococcus aureus var. Oxford 6538, Escherichia coli ATCC 10536, Klebsielle pneumoniae ATCC 100131 and Candida albicans ATCC 10231 strains was studied and compared with that of free ligands. The effect of complex compounds on the proliferation of HeLa cells was tested. For all tested complexes an antiproliferative activity was noted at concentrations higher than 1 microM, but lower than 10 microM. Therefore, complex compounds of copper(II) were synthesized, structurally characterized and tested for biological activity, proving both antibacterial and antiproliferative activity.

Alkoxo-bridged copperII complexes as nodes in designing solid-state architectures. The interplay of coordinative and d10-d10 metal-metal interactions in sustaining supramolecular solid-state architectures.

Four novel polymeric coordination networks have been obtained through self-assembly processes involving alkoxo-bridged copperII species as nodes, and anionic cyano-complexes as linkers: infinity2[{Cu2(pa)2}{M(CN)2}2](M=Ag, 1; Au, 2), (infinity)3[{Cu4(mea)4}{Au(CN)2}4.H2O]3, and (infinity)3[{Cu2(pa)2}{Ni(CN)4}](pa = deprotonated propanolamine; mea = deprotonated monoethanolamine). The supramolecular architectures of compounds 1, and 2 are sustained by argentophilic or strong aurophilic interactions. The solid-state architectures of 1 and 2, which are isomorphous, consist of infinite layers, constructed from binuclear alkoxo-bridged nodes and [M(CN)2]- spacers. The layers are stacked in an offset parallel mode, and are further interconnected through Ag...Ag or Au...Au contacts (1: Ag...Ag 3.015 A; 2: Au....Au 3.069 A). Compound 3 consists of unique fourfold interpenetrating diamondoid nets. The diamondoid topology is built of heterocubane {Cu4O4} nodes, which are connected by [Au(CN)2]- rods. The Cu-O distances within the {Cu4O4} node vary between 1.927(2) and 2.679(1) A, showing unsymmetric bridging of the copper atoms. Aurophilic interactions are established between the bridging and terminal [Au(CN)2]- metalloligands, and connect the interpenetrating nets, resulting in infinite chains of gold atoms (the Au...Au distances vary between 3.253 and 3.305 [Angstrom]). Compound 4 exhibits a 3-D network constructed from {Cu2(pa)2]2+ nodes connected by square-planar [Ni(CN)4]2- ions. Compounds 1, 2 and 4 are weakly paramagnetic. The cryomagnetic investigation of reveals a gradual increase, followed by a decrease of the chiMT product, as the temperature is lowered. A superposition of ferro- (J1=+20.8 cm(-1)) and antiferromagnetic (J2=-6.4) interactions within the tetranuclear node was found. Antiferromagnetic interactions are established between the tetranuclear nodes (theta=-2.99 K).

Hetero di- and trinuclear Cu-Gd complexes with trifluoroacetate bridges: synthesis, structural and magnetic studies.

The synthesis, structural determinations and magnetic properties of an original dinuclear Cu-Gd and two trinuclear Cu-Ln-Cu complexes (Ln = Gd or Dy) made with a Schiff base ligand and carboxylate ligands are reported. In each complex, the copper and gadolinium or dysprosium ions are linked by a double phenoxo bridge and a eta1:eta1:mu trifluoroacetato bridge. The dinuclear Cu-Gd complex exhibits the usual ferromagnetic interaction while the trinuclear (Cu-Gd-Cu) complexes can not be fitted with a simple Hamiltonian that only takes into account the Cu-Gd interaction. Introduction into the Hamiltonian of a Cu-Cu interaction between the terminal copper ions gives a nice fit in the case of a ferromagnetic Cu-Cu interaction (J'(Cu-Cu) = 8.3 and 9.8 cm(-1)). For the first time, the occurrence of a ferromagnetic interaction between the copper ions of the trinuclear entities is evidenced and supported by the field dependence of the magnetization. As there is no direct proof for the existence of an interaction between two centers through a third magnetic center located in between them, we can conclude that the existence of pi-pi stacking interactions through the phenyl rings of the ligands are responsible for the presence of these interactions.

The first coordination compound containing three different types of spin carriers: 2p-3d-4f (TCNQ.-, Cu2+ and Gd3+).

A novel heterospin system, [(CuL)2Gd(TCNQ)2].TCNQ-.CH3OH.2CH3CN, is obtained by reacting the mononuclear complex, [CuL], with gadolinium(III) nitrate, followed by the substitution of the nitrato ions with anionic organic radicals.