Phase Engineering via Aluminum Doping Enhances the Electrochemical Stability of Lithium-Rich Cobalt-Free Layered Oxides for Lithium-Ion Batteries.

Lithium-rich, cobalt-free oxides are promising potential positive electrode materials for lithium-ion batteries because of their high energy density, lower cost, and reduced environmental and ethical concerns. However, their commercial breakthrough is hindered because of their subpar electrochemical stability. This work studies the effect of aluminum doping on Li1.26 Ni0.15 Mn0.61 O2 as a lithium-rich, cobalt-free layered oxide. Al doping suppresses voltage fade and improves the capacity retention from 46% for Li1.26 Ni0.15 Mn0.61 O2 to 67% for Li1.26 Ni0.15 Mn0.56 Al0.05 O2 after 250 cycles at 0.2 C. The undoped material has a monoclinic Li2 MnO3 -type structure with spinel on the particle edges. In contrast, Al-doped materials (Li1.26 Ni0.15 Mn0.61-x Alx O2 ) consist of a more stable rhombohedral phase at the particle edges, with a monoclinic phase core. For this core-shell structure, the formation of Mn3+ is suppressed along with the material's decomposition to a disordered spinel, and the amount of the rhombohedral phase content increases during galvanostatic cycling. Whereas previous studies generally provided qualitative insight into the degradation mechanisms during electrochemical cycling, this work provides quantitative information on the stabilizing effect of the rhombohedral shell in the doped sample. As such, this study provides fundamental insight into the mechanisms through which Al doping increases the electrochemical stability of lithium-rich cobalt-free layered oxides.

Experimental and DFT Study of Monensinate and Salinomycinate Complexes Containing {Fe3(µ3-O)}7+ Core.

Two trinuclear oxo-centred iron(III) coordination compounds of monensic and salinomycinic acids (HL) were synthesized and their spectral properties were studied using physicochemical/thermal methods (FT-IR, TG-DTA, TG-MS, EPR, Mössbauer spectroscopy, powder XRD) and elemental analysis. The data suggested the formation of [Fe3(µ3-O)L3(OH)4] and the probable complex structures were modelled using the DFT method. The computed spectral parameters of the optimized constructs were compared to the experimentally measured ones. In each complex, three metal centres were joined together at the axial position by a µ3-O unit to form a {Fe3O}7+ core. The antibiotics monoanions served as bidentate ligands through the carboxylate and hydroxyl groups located at the termini. The carboxylate moieties played a dual role bridging each two metal centres. Hydroxide anions secured the overall neutral character of the coordination species. Mössbauer spectra displayed asymmetric quadrupole doublets that were consistent with the existence of two types of high-spin iron(III) sites with different environments-two Fe[O5] and one Fe[O6] centres. The solid-state EPR studies confirmed the +3 oxidation state of iron with a total spin St = 5/2 per trinuclear cluster. The studied complexes are the first iron(III) coordination compounds of monensin and salinomycin reported so far.

Graphene-Based Composites for Thermoelectric Applications at Room Temperature.

The thermoelectric materials that operate at room temperature represent a scientific challenge in finding chemical compositions with three optimized, independent parameters, namely electrical and thermal conductivity and the Seebeck coefficient. Here, we explore the concept of the formation of hybrid composites between carbon-based materials and oxides, with the aim of modifying their thermoelectric performance at room temperature. Two types of commercially available graphene-based materials are selected: N-containing reduced graphene oxide (NrGO) and expanded graphite (ExGr). Although the NrGO displays the lowest thermal conductivity at room temperature, the ExGr is characterized by the lowest electrical resistivity and a negative Seebeck coefficient. As oxides, we choose two perspective thermoelectric materials: p-type Ca3Co4O9 and n-type Zn0.995Al0.005O. The hybrid composites were prepared by mechanical milling, followed by a pelleting. The thermoelectric efficiency was evaluated on the basis of its measured electrical resistivity, Seebeck coefficient and thermal conductivity at room temperature. It was found that that 2 wt.% of ExGr or NrGO leads to an enhancement of the thermoelectric activity of Ca3Co4O9, while, for Zn0.995Al0.005O, the amount of ExGr varies between 5 and 20 wt.%. The effect of the composites' morphology on the thermoelectric properties is discussed on the basis of SEM/EDS experiments.

Review and New Perspectives on Non-Layered Manganese Compounds as Electrode Material for Sodium-Ion Batteries.

After more than 30 years of delay compared to lithium-ion batteries, sodium analogs are now emerging in the market. This is a result of the concerns regarding sustainability and production costs of the former, as well as issues related to safety and toxicity. Electrode materials for the new sodium-ion batteries may contain available and sustainable elements such as sodium itself, as well as iron or manganese, while eliminating the common cobalt cathode compounds and copper anode current collectors for lithium-ion batteries. The multiple oxidation states, abundance, and availability of manganese favor its use, as it was shown early on for primary batteries. Regarding structural considerations, an extraordinarily successful group of cathode materials are layered oxides of sodium, and transition metals, with manganese being the major component. However, other technologies point towards Prussian blue analogs, NASICON-related phosphates, and fluorophosphates. The role of manganese in these structural families and other oxide or halide compounds has until now not been fully explored. In this direction, the present review paper deals with the different Mn-containing solids with a non-layered structure already evaluated. The study aims to systematize the current knowledge on this topic and highlight new possibilities for further study, such as the concept of entatic state applied to electrodes.

Carbon-Based Composites with Mixed Phosphate-Pyrophosphates with Improved Electrochemical Performance at Elevated Temperature.

Sodium iron phosphate-pyrophosphate, Na4Fe3(PO4)2P2O7 (NFPP) emerges as an excellent cathode material for sodium-ion batteries. Because of lower electronic conductivity, its electrochemical performance depends drastically on the synthesis method. Herein, we provide a simple and unified method for synthesis of composites between NFPP and reduced graphene oxide (rGO) and standard carbon black, designed as electrode materials for both sodium- and lithium-ion batteries. The carbon additives affect only the morphology and textural properties of the composites. The performance of composites in sodium and lithium cells is evaluated at elevated temperatures. It is found that NFPP/rGO outperforms NFPP/C in both Na and Li storage due to its hybrid mechanism of energy storage. In sodium half-cells, NFPP/rGO delivers a reversible capacity of 95 mAh/g at 20 °C and 115 mAh/g at 40 °C with a cycling stability of 95% and 88% at a rate of C/2. In lithium half-cells, the capacity reaches a value of 120 mAh/g at 20 and 40 °C, but the cycling stability becomes worse, especially at 40 °C. The electrochemical performance is discussed on the basis of ex situ XRD and microscopic studies. The good Na storage performance of NFPP/rGO at an elevated temperature represents a first step towards its commercialization.

Machine Learning Prediction of the Redox Activity of Quinones.

The redox properties of quinones underlie their unique characteristics as organic battery components that outperform the conventional inorganic ones. Furthermore, these redox properties could be precisely tuned by using different substituent groups. Machine learning and statistics, on the other hand, have proven to be very powerful approaches for the efficient in silico design of novel materials. Herein, we demonstrated the machine learning approach for the prediction of the redox activity of quinones that potentially can serve as organic battery components. For the needs of the present study, a database of small quinone-derived molecules was created. A large number of quantum chemical and chemometric descriptors were generated for each molecule and, subsequently, different statistical approaches were applied to select the descriptors that most prominently characterized the relationship between the structure and the redox potential. Various machine learning methods for the screening of prospective organic battery electrode materials were deployed to select the most trustworthy strategy for the machine learning-aided design of organic redox materials. It was found that Ridge regression models perform better than Regression decision trees and Decision tree-based ensemble algorithms.

In Situ Electron Paramagnetic Resonance Monitoring of Predegradation Radical Generation in a Lithium Electrolyte.

Herein we present an innovative in situ EPR spectroscopy approach complemented with computational modeling as a methodology for assessing a nonaqueous electrolyte behavior just before its massive degradation. As a proof of concept, we use the conventional lithium electrolyte (1 M LiPF6 in EC/DMC), which is utilized in current lithium-ion batteries. Through in situ EPR, long-lived EC•- associates in amounts of 10-250 ppm were detected in a broad potential window (>2.0 V) prior to the electrolyte oxidation or reduction. The pathways of radical formation are discussed in terms of the imperfection in the electron flow across the electrolyte-electrode interface and of the strong affinity of EC to electron trapping. The radical amount could be amplified markedly (above 1000 ppm) by addition of vinylene carbonate (VC) to the electrolyte, while the added CeO2 has a moderate effect. The proposed in situ EPR methodology could be transferred to other electrolyte solutions to become a universal approach.

Lithium Manganese Sulfates as a New Class of Supercapattery Materials at Elevated Temperatures.

To make supercapattery devices feasible, there is an urgent need to find electrode materials that exhibit a hybrid mechanism of energy storage. Herein, we provide a first report on the capability of lithium manganese sulfates to be used as supercapattery materials at elevated temperatures. Two compositions are studied: monoclinic Li2Mn(SO4)2 and orthorhombic Li2Mn2(SO4)3, which are prepared by a freeze-drying method followed by heat treatment at 500 °C. The electrochemical performance of sulfate electrodes is evaluated in lithium-ion cells using two types of electrolytes: conventional carbonate-based electrolytes and ionic liquid IL ones. The electrochemical measurements are carried out in the temperature range of 20-60 °C. The stability of sulfate electrodes after cycling is monitored by in-situ Raman spectroscopy and ex-situ XRD and TEM analysis. It is found that sulfate salts store Li+ by a hybrid mechanism that depends on the kind of electrolyte used and the recording temperature. Li2Mn(SO4)2 outperforms Li2Mn2(SO4)3 and displays excellent electrochemical properties at elevated temperatures: at 60 °C, the energy density reaches 280 Wh/kg at a power density of 11,000 W/kg. During cell cycling, there is a transformation of the Li-rich salt, Li2Mn(SO4)2, into a defective Li-poor one, Li2Mn2(SO4)3, which appears to be responsible for the improved storage properties. The data reveals that Li2Mn(SO4)2 is a prospective candidate for supercapacitor electrode materials at elevated temperatures.

Novel Cerium(IV) Coordination Compounds of Monensin and Salinomycin.

The largely uncharted complexation chemistry of the veterinary polyether ionophores, monensic and salinomycinic acids (HL) with metal ions of type M4+ and the known antiproliferative potential of antibiotics has provoked our interest in exploring the coordination processes between MonH/SalH and ions of Ce4+. (1) Methods: Novel monensinate and salinomycinate cerium(IV)-based complexes were synthesized and structurally characterized by elemental analysis, a plethora of physicochemical methods, density functional theory, molecular dynamics, and biological assays. (2) Results: The formation of coordination species of a general composition [CeL2(OH)2] and [CeL(NO3)2(OH)], depending on reaction conditions, was proven both experimentally and theoretically. The metal(IV) complexes [CeL(NO3)2(OH)] possess promising cytotoxic activity against the human tumor uterine cervix (HeLa) cell line, being highly selective (non-tumor embryo Lep-3 vs. HeLa) compared to cisplatin, oxaliplatin, and epirubicin.

Dual-Ion Intercalation Chemistry Enabling Hybrid Metal-Ion Batteries.

To outline the role of dual-ion intercalation chemistry to reach sustainable energy storage, the present Review aimed to compare two types of batteries: widely accepted dual-ion batteries based on cationic and anionic co-intercalation versus newly emerged hybrid metal-ion batteries using the co-intercalation of cations only. Among different charge carrier cations, the focus was on the materials able to co-intercalate monovalent ions (such Li+ and Na+ , Li+ and K+ , Na+ and K+ , etc.) or couples of mono- and multivalent ions (Li+ and Mg2+ , Na+ and Mg2+ , Na+ and Zn2+ , H+ and Zn2+ , etc.). Furthermore, the Review was directed on co-intercalation materials composed of environmentally benign and low-cost transition metals (e. g., Mn, Fe, etc.). The effect of the electrolyte on the co-intercalation properties was also discussed. The summarized knowledge on dual-ion energy storage could stimulate further research so that the hybrid metal-ion batteries become feasible in near future.

Bio-Based Electrospun Fibers from Chitosan Schiff Base and Polylactide and Their Cu2+ and Fe3+ Complexes: Preparation and Antibacterial and Anticancer Activities.

The Schiff base derivative (Ch-8Q) of chitosan (Ch) and 8-hydroxyquinoline-2-carboxaldehyde (8QCHO) was prepared and fibrous mats were obtained by the electrospinning of Ch-8Q/polylactide (PLA) blend solutions in trifluoroacetic acid (TFA). Complexes of the mats were prepared by immersing them in a solution of CuCl2 or FeCl3. Electron paramagnetic resonance (EPR) analysis was performed to examine the complexation of Cu2+(Fe3+) in the Ch-8Q/PLA mats complexes. The morphology of the novel materials and their surface chemical composition were studied by scanning electron microscopy (SEM), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). The performed microbiological screening demonstrated that in contrast to the neat PLA mats, the Ch-8Q-containing mats and their complexes were able to kill all S. aureus bacteria within 3 h of contact. These fibrous materials had efficiency in suppressing the adhesion of pathogenic bacteria S. aureus. In addition, Ch-8Q/PLA mats and their complexes exerted good anticancer efficacy in vitro against human cervical HeLa cells and human breast MCF-7 cells. The Ch-8Q-containing fibrous materials had no cytotoxicity against non-cancer BALB/c 3T3 mouse fibroblast cells. These properties render the prepared materials promising as wound dressings as well as for application in local cancer treatment.

Novel Salinomycin-Based Paramagnetic Complexes-First Evaluation of Their Potential Theranostic Properties.

Combining therapeutic with diagnostic agents (theranostics) can revolutionize the course of malignant diseases. Chemotherapy, hyperthermia, or radiation are used together with diagnostic methods such as magnetic resonance imaging (MRI). In contrast to conventional contrast agents (CAs), which only enable non-specific visualization of tissues and organs, the theranostic probe offers targeted diagnostic imaging and therapy simultaneously. METHODS: Novel salinomycin (Sal)-based theranostic probes comprising two different paramagnetic metal ions, gadolinium(III) (Gd(III)) or manganese(II) (Mn(II)), as signal emitting motifs for MRI were synthesized and characterized by elemental analysis, infrared spectral analysis (IR), electroparamagnetic resonance (EPR), thermogravimetry (TG) differential scanning calorimetry (DSC) and electrospray ionization mass spectrometry (ESI-MS). To overcome the water insolubility of the two Sal-complexes, they were loaded into empty bacterial ghosts (BGs) cells as transport devices. The potential of the free and BGs-loaded metal complexes as theranostics was evaluated by in vitro relaxivity measurements in a high-field MR scanner and in cell culture studies. RESULTS: Both the free Sal-complexes (Gd(III) salinomycinate (Sal-Gd(III) and Mn(II) salinomycinate (Sal-Mn(II)) and loaded into BGs demonstrated enhanced cytotoxic efficacy against three human tumor cell lines (A549, SW480, CH1/PA-1) relative to the free salinomycinic acid (Sal-H) and its sodium complex (Sal-Na) applied as controls with IC50 in a submicromolar concentration range. Moreover, Sal-H, Sal-Gd(III), and Sal-Mn(II) were able to induce perturbations in the cell cycle of treated colorectal and breast human cancer cell lines (SW480 and MCF-7, respectively). The relaxivity (r1) values of both complexes as well as of the loaded BGs, were higher or comparable to the relaxivity values of the clinically applied contrast agents gadopentetate dimeglumine and gadoteridol. CONCLUSION: This research is the first assessment that demonstrates the potential of Gd(III) and Mn(II) complexes of Sal as theranostic agents for MRI. Due to the remarkable selectivity and mode of action of Sal as part of the compounds, they could revolutionize cancer therapy and allow for early diagnosis and monitoring of therapeutic follow-up.

Molecular Engineering of Quinone-Based Nickel Complexes and Polymers for All-Organic Li-Ion Batteries.

All-organic Li-ion batteries appear to be a sustainable and safer alternative to the currently-used Li-ion batteries but their application is still limited due to the lack of organic compounds with high redox potentials toward Li+/Li0. Herein, we report a computational design of nickel complexes and coordination polymers that have redox potentials spanning the full voltage range: from the highest, 4.7 V, to the lowest, 0.4 V. The complexes and polymers are modeled by binding low- and high-oxidized Ni ions (i.e., Ni(II) and Ni(IV)) to redox-active para-benzoquinone molecules substituted with carboxyl- and cyano-groups. It is found that both the nickel ions and the quinone-derived ligands are redox-active upon lithiation. The type of Ni coordination also has a bearing on the redox potentials. By combining the complex of Ni(IV) with 2-carboxylato-5-cyano-1,4-benzoquinones as a cathode and Ni(II)-2,5-dicarboxylato-3,6-dicyano-1,4-benzoquinone coordination polymer as an anode, all-organic Li-ion batteries could be assembled, operating at an average voltage exceeding 3.0 V and delivering a capacity of more than 300 mAh/g.

Dinuclear vs. Mononuclear Copper(II) Coordination Species of Tylosin and Tilmicosin in Non-Aqueous Solutions.

The veterinary 16-membered macrolide antibiotics tylosin (HTyl, 1a) and tilmicosin (HTilm, 1b) react with copper(II) ions in acetone at metal-to-ligand molar ratio of 1:2 to form blue (2) or green (3) metal(II) coordination species, containing nitrate or chloride anions, respectively. The complexation processes and the properties of 2-3 were studied by an assortment of physicochemical techniques (UV-Vis, EPR, NMR, FTIR, elemental analysis). The experimental data revealed that the main portion of copper(II) ions are bound as neutral EPR-silent dinuclear complexes of composition [Cu2(µ-NO3)2L2] (2a-b) and [Cu2(µ-Cl)2Cl2(HL)2] (3a-b), containing impurities of EPR-active mono-species [Cu(NO3)L] (2a'-b') and [CuCl2(HL)] (3a'-b'). The possible structural variants of the dinuclear- and mono-complexes were modeled by the DFT method, and the computed spectroscopic parameters of the optimized constructs were compared to those measured experimentally. Using such a combined approach, the main coordination unit of the macrolides, involved in the complex formation, was defined to be their mycaminosyl substituent, which acts as a terminal ligand in a bidentate mode through the tertiary nitrogen atom and the oxygen from a deprotonated (2) or non-dissociated (3) hydroxyl group, respectively.

Redox Hyperactive MOF for Li+, Na+ and Mg2+ Storage.

To create both greener and high-power metal-ion batteries, it is of prime importance to invent an unprecedented electrode material that will be able to store a colossal amount of charge carriers by a redox mechanism. Employing periodic DFT calculations, we modeled a new metal-organic framework, which displays energy density exceeding that of conventional inorganic and organic electrodes, such as Li- and Na-rich oxides and anthraquinones. The designed MOF has a rhombohedral unit cell in which an Ni(II) node is coordinated by 2,5-dicyano-p-benzoquinone linkers in such a way that all components participate in the redox reaction upon lithiation, sodiation and magnesiation. The spatial and electronic changes occurring in the MOF after the interaction with Li, Na and Mg are discussed on the basis of calculated electrode potentials versus Li0/Li+, Na0/Na+ and Mg0/Mg2+, respectively. In addition, the specific capacities and energy densities are calculated and used as a measure for the electrode applicability of the designed material. Although the highest capacity and energy density are predicted for Li storage, the greater structural robustness toward Na and Mg uptake suggests a higher cycling stability in addition to lower cost. The theoretical results indicate that the MOF is a promising choice for a green electrode material (with <10% heavy metal content) and is well worth experimental testing.

Rivalry at the Interface: Ion Desolvation and Electrolyte Degradation in Model Ethylene Carbonate Complexes of Li+, Na+, and Mg2+ with PF6 - on the Li4Ti5O12 (111) Surface.

Spinel lithium titanate, Li4Ti5O12 (LTO), emerges as a "universal" electrode material for Li-ion batteries and hybrid Li/Na-, Li/Mg-, and Na/Mg-ion batteries functioning on the basis of intercalation. Given that LTO operates in a variety of electrolyte solutions, the main challenge is to understand the reactivity of the LTO surface toward single- and dual-cation electrolytes at the molecular level. This study first reports results on ion desolvation and electrolyte solvent/salt degradation on an LTO surface by means of periodic DFT calculations. The desolvation stages are modeled by the adsorption of mono- and binuclear complexes of Li+, Na+, and Mg2+ with a limited number of ethylene carbonate (EC) solvent molecules on the oxygen-terminated LTO (111) surface, taking into account the presence of a PF6 - counterion. Alongside cation adsorption, several degradation reactions are discussed: surface-catalyzed dehydrogenation of EC molecules, simultaneous dehydrogenation and fluorination of EC, and Mg2+-induced decay of PF6 - to PF5 and F-. Data analysis allows the rationalization of existing experimentally established phenomena such as gassing and fluoride deposition. Among the three investigated cations, Mg2+ is adsorbed most tightly and is predicted to form a thicker fluoride-containing film on the LTO surface. Gassing, characteristic for carbonate-based electrolytes with LTO electrodes, is foreseen to be suppressed in dual-cation batteries. The latter bears promise to outperform the single-ion ones in terms of durability and safety.

Composites between Perovskite and Layered Co-Based Oxides for Modification of the Thermoelectric Efficiency.

The common approach to modify the thermoelectric activity of oxides is based on the concept of selective metal substitution. Herein, we demonstrate an alternative approach based on the formation of multiphase composites, at which the individual components have distinctions in the electric and thermal conductivities. The proof-of-concept includes the formation of multiphase composites between well-defined thermoelectric Co-based oxides: Ni, Fe co-substituted perovskite, LaCo0.8Ni0.1Fe0.1O3 (LCO), and misfit layered Ca3Co4O9. The interfacial chemical and electrical properties of composites are probed with the means of SEM, PEEM/XAS, and XPS tools, as well as the magnetic susceptibility measurements. The thermoelectric power of the multiphase composites is evaluated by the dimensionless figure of merit, ZT, calculated from the independently measured electrical resistivity (ρ), Seebeck coefficient (S), and thermal conductivity (λ). It has been demonstrated that the magnitude's electric and thermal conductivities depend more significantly on the composite interfaces than the Seebeck coefficient values. As a result, the highest thermoelectric activity is observed at the composite richer on the perovskite (i.e., ZT = 0.34 at 298 K).

Iron oxidation to amplify the Na and Li storage capacities of nano-sized maricite NaFePO4.

This study reports an effective approach to improve dramatically the electrochemical performance of nanosized NaFePO4 with a maricite structure, which is commonly considered as electrochemically inactive due to the absence of structural channels for alkaline ion mobility. The approach is based on the complete oxidation under mild conditions (i.e. at low temperatures around 280 °C and traces of oxygen) of the nanosized maricite phase. It is prepared by the phosphate-formate precursor method and is additionally ball-milled with a carbon additive. The oxidation of Fe2+ proceeds at the nanoscale level within the maricite nanoparticles and causes a massive structural transformation of the maricite phase into a monoclinic NASICON phase Na3Fe2(PO4)3 with the preservation of the crystallinity. The oxidized maricite phase exhibits high specific capacities, cycling stability and rate capability when it is used as an electrode in both Na and Li half-cells. The effect of different sodium and lithium electrolytes on the storage performance is investigated as well. It is found that the highest specific capacity (of about 150 mA h g-1) is achieved in Li half-cells using the LiPF6 electrolyte, while in Na half-cells the electrolyte NaFSI/EC:DMC achieves a specific capacity of around 100 mA h g-1. The rate capability is better in Na half-cells than that in Li half-cells. The mechanism of the reversible intercalation/deintercalation of Na+ and Li+ ions is studied by ex situ XRD and TEM analyses. The results show that the maricite is an electrochemically inactive phase, but through manipulation including oxidation or amorphization it becomes an active electrode material.

Oxygen-Storage Materials to Stabilize the Oxygen Redox Activity of Three-Layered Sodium Transition Metal Oxides.

To double the energy density of lithium- and sodium-ion batteries there is a need to activate simultaneously cationic and anionic redox reactions at the intercalation-type electrodes. In contrast to the cationic redox activity, the oxygen redox activity enforces an enhancement in the surface reactivity of the oxides leading to their poor reversibility and cycling stability. Herein, we propose a new concept to stabilize oxygen redox activity by using oxygen-storage materials as an efficient buffer supplying and receiving oxygen during alkali ion intercalation. As a proof-of-concept, the study is focused on CeO2 as a modifier of sodium nickel-manganese oxide with a three-layer sequence, P3-Na2/3Ni1/2Mn1/2O2. The CeO2-modified P3-Na2/3Ni1/2Mn1/2O2 displays a drastic increase in the reversible capacity following the order Na+ intercalation < Li+ intercalation < Li+,Na+ cointercalation.

8-Hydroxyquinoline-5-Sulfonic Acid-Containing Poly(Vinyl Alcohol)/Chitosan Electrospun Materials and Their Cu2+ and Fe3+ Complexes: Preparation, Antibacterial, Antifungal and Antitumor Activities.

Novel poly(vinyl alcohol) (PVA)/chitosan (Ch)-based fibrous materials containing an ionizable model drug, 8-hydroxyquinoline-5-sulfonic acid (SQ), were successfully fabricated by electrospinning. Complexes between the components of the crosslinked PVA/Ch/SQ mats and Cu2+ and Fe3+ ions were formed. The coordination of these ions in the mats was examined by electron paramagnetic resonance spectroscopy (EPR). The microbiological screening against S. aureus and C. albicans revealed that both the incorporation of SQ in the mats and the complexation with Cu2+ and Fe3+ imparted to these materials antibacterial and antifungal activities. Moreover, the SQ-containing mats and their complexes displayed good cytotoxicity against human cervical HeLa tumor cells. The most prominent was the cytotoxicity of the Cu2+ complex of the mats. The combined antibacterial, antifungal and in vitro antitumor activities render these novel materials promising candidates for wound dressing applications and for application in the local treatment of cervical tumors.