Magnetic Polypyrrole-Gelatin-Barium Ferrite Cryogel as an Adsorbent for Chromium (VI) Removal.

Polypyrrole-gelatin aerogels, containing magnetic barium ferrite (BaFe) particles, (PPy-G-BaFe) were synthesized by oxidative cryopolymerization and used as adsorbents for the removal of Cr(VI) from aqueous media. The removal was performed at pH 4, which was shown to be the optimal value, due to HCrO4- being the dominant species in these conditions and its more favorable adsorption and reduction compared to CrO42-, present at pH > 4. It was found that the presence of magnetic BaFe particles had no effect on the adsorption performance of PPy aerogels in terms of capacity and kinetics, which was attributed to its relatively low content in the composite. After the adsorption, the presence of chromium in the composites was confirmed by EDX and its electrostatic interaction with the adsorbent was pointed at by vibrational spectroscopy, corresponding to the accepted adsorption mechanism. The adsorption kinetics followed the pseudo-second-order model pointing at chemisorption being the rate-limiting step. The adsorption isotherm data was best fitting with the Temkin model. The maximum adsorption capacity, calculated using the Langmuir model, was 255.8 mg g-1 (the maximum experimental value was 161.6 mg g-1). Additionally, the possibility of Cr(VI) adsorption in the presence of Cl-, Br-, NO3- and SO42- as interfering ions was shown.

Amphiphilic (di-)gradient copoly(2-oxazoline)s are potent amyloid fibril formation inhibitors.

MOTIVATION: Amyloidoses are diseases caused by the accumulation of normally soluble proteins in the form of insoluble amyloids, leading to the gradual dysfunction and failure of various organs and tissues. Inhibiting amyloid formation is therefore an important therapeutic target. HYPOTHESIS: We hypothesized that mono- and di-gradient amphiphilic copolymers of hydrophilic 2-(m)ethyl-2-oxazoline and hydrophobic 2-aryl-2-oxazolines may inhibit amyloid fibril formation. EXPERIMENTS: In the model system with hen egg white lysozyme (HEWL) as amyloidogenic protein we determined the effect of these polymers on the amyloid formation by making use of the thioflavin T fluorescence, transmission electron microscopy, isothermal titration calorimetry, and dynamic light scattering. FINDINGS: We found that some gradient copolymers possess very potent concentration-dependent inhibitory effects on HEWL amyloid formation. Structure-activity relationship revealed that copolymers with higher ratios of aromatic monomeric units had stronger amyloid suppression effects, most plausibly due to the combination of hydrophobic and π-π interactions. The measurements also revealed that the polymers that inhibit amyloid formation most plausibly do so in the form of micelles that interact with the growing amyloid fibril ends, not with isolated HEWL molecules in solution. These findings suggest the potential use of these gradient copolymers as therapeutic agents for amyloidoses.

Hydrophilic Copolymers with Hydroxamic Acid Groups as a Protective Biocompatible Coating of Maghemite Nanoparticles: Synthesis, Physico-Chemical Characterization and MRI Biodistribution Study.

Superparamagnetic iron oxide nanoparticles (SPION) with a "non-fouling" surface represent a versatile group of biocompatible nanomaterials valuable for medical diagnostics, including oncology. In our study we present a synthesis of novel maghemite (γ-Fe2O3) nanoparticles with positive and negative overall surface charge and their coating by copolymer P(HPMA-co-HAO) prepared by RAFT (reversible addition-fragmentation chain-transfer) copolymerization of N-(2-hydroxypropyl)methacrylamide (HPMA) with N-[2-(hydroxyamino)-2-oxo-ethyl]-2-methyl-prop-2-enamide (HAO). Coating was realized via hydroxamic acid groups of the HAO comonomer units with a strong affinity to maghemite. Dynamic light scattering (DLS) demonstrated high colloidal stability of the coated particles in a wide pH range, high ionic strength, and the presence of phosphate buffer (PBS) and serum albumin (BSE). Transmission electron microscopy (TEM) images show a narrow size distribution and spheroid shape. Alternative coatings were prepared by copolymerization of HPMA with methyl 2-(2-methylprop-2-enoylamino)acetate (MMA) and further post-polymerization modification with hydroxamic acid groups, carboxylic acid and primary-amino functionalities. Nevertheless, their colloidal stability was worse in comparison with P(HPMA-co-HAO). Additionally, P(HPMA-co-HAO)-coated nanoparticles were subjected to a bio-distribution study in mice. They were cleared from the blood stream by the liver relatively slowly, and their half-life in the liver depended on their charge; nevertheless, both cationic and anionic particles revealed a much shorter metabolic clearance rate than that of commercially available ferucarbotran.

Tuning of Morphological and Antibacterial Properties of Poly(3,4-ethylenedioxythiophene):Peroxodisulfate by Methyl Violet.

This study demonstrates a one-step synthesis of poly(3,4-ethylenedioxythiophene) (PEDOT) in the presence of the methyl violet (MV) dye. The structural properties of PEDOT:peroxodisulfate were studied using Raman and MALDI-TOF spectroscopies. The use of the MV dye in the polymerization process resulted in a change in the typical irregular morphology of PEDOT:peroxodisulfate, leading to the formation of spherical patterns. SEM and TEM analyses revealed that increasing the dye concentration can produce larger spherical aggregates probably due to the hydrophobic and π-π interactions. These larger aggregates hindered the charge transport and reduced the electrical conductivity. Interestingly, at higher dye concentrations (0.05 and 0.075 M), the PEDOT:peroxodisulfate/MV films exhibited significantly improved antibacterial activity against Staphylococcus aureus and Escherichia coli. Furthermore, the PEDOT:peroxodisulfate films with the incorporated MV dye exhibited a well-defined and repeatable redox behavior. The remarkable amalgamation of their optical, electrochemical and antibacterial properties provides the PEDOT:peroxodisulfate/MV materials with an immensely diverse spectrum of applications, including in optical sensors and medical devices.

Polypyrrole Aerogels: Efficient Adsorbents of Cr(VI) Ions from Aqueous Solutions.

Three-dimensional and porous polypyrrole (PPy) aerogels were prepared using a facile two-step procedure in which cryogels were synthesized via the cryopolymerization of pyrrole with iron (III) chloride in the presence of supporting water-soluble polymers (poly(N-vinylpyrrolidone), poly(vinyl alcohol), gelatin, methylcellulose or hydroxypropylcellulose), followed by freeze-drying to obtain aerogels. The choice of supporting polymers was found to affect the morphology, porosity, electrical conductivity, and mechanical properties of PPy aerogels. PPy aerogels were successfully used as adsorbents to remove toxic Cr(VI) ions from aqueous solutions.

One-Step Accelerated Synthesis of Conducting Polymer/Silver Composites and Their Catalytic Reduction of Cr(VI) Ions and p-Nitrophenol.

In this paper, silver nitrate was used as an oxidant to prepare polyaniline, polypyrrole, and poly(3,4-ethylene dioxythiophene)/silver composites through a simultaneous oxidation/reduction process. In addition, p-phenylenediamine was added with 1 mole% relative to the concentrations of the monomers to accelerate the polymerization reaction. The prepared conducting polymer/silver composites were characterized by scanning and transmission electron microscopies to study their morphologies; Fourier-transform infrared and Raman spectroscopies to confirm their molecular structures; and thermogravimetric analysis (TGA) to study their thermal stabilities. The silver content in the composites was estimated by energy-dispersive X-ray spectroscopy, ash analysis, and TGA. The conducting polymer/silver composites were utilized for the remediation of water pollutants through catalytic reduction. Hexavalent chromium ions (Cr(VI)) were photocatalytically reduced to trivalent chromium ions, and p-nitrophenol was catalytically reduced to p-aminophenol. The catalytic reduction reactions were found to follow the first-order kinetic model. Among the prepared composites, polyaniline/silver composite has shown the highest activity for the photocatalytic reduction of Cr(VI) ions with an apparent rate constant of 0.226 min-1 and efficiency of 100% within 20 min. Additionally, poly(3,4-ethylene dioxythiophene)/silver composite showed the highest catalytic activity towards the reduction of p-nitrophenol with an apparent rate constant of 0.445 min-1 and efficiency of 99.8% within 12 min.

Polypyrrole-Barium Ferrite Magnetic Cryogels for Water Purification.

Magnetic polypyrrole-gelatin-barium ferrite (PPy-G-BaFe) cryogels/aerogels were synthesized by one-step oxidative cryopolymerization of pyrrole in the presence of various fractions of barium ferrite (BaFe) nanoparticles, dispersed in aqueous gelatin solution. The successful incorporation of BaFe into the composites was confirmed by elemental analysis and scanning electron microscopy paired with an energy-dispersive X-ray detector. The maximum achieved content of BaFe in the resulting material was 3.9 wt%. The aerogels with incorporated BaFe had significantly higher specific surface area and conductivity, reaching 19.3 m2 g-1 and 4 × 10-4 S cm-1, respectively, compared to PPy-G aerogel, prepared in the absence of BaFe (7.3 m2 g-1 and 1 × 10-5 S cm-1). The model adsorption experiment using an anionic dye, Reactive Black 5, showed that magnetic PPy-G-BaFe aerogel, prepared at 10 wt% BaFe fraction, had significantly higher adsorption rate and higher adsorption capacity, compared to PPy-G (dye removal fraction 99.6% and 89.1%, respectively, after 23 h). Therefore, the prepared PPy-G-BaFe aerogels are attractive adsorbents for water purification due to their enhanced adsorption performance and the possibility of facilitated separation from solution by a magnetic field.

Preparation of Smart Surfaces Based on PNaSS@PEDOT Microspheres: Testing of E. coli Detection.

The main task of the research is to acquire fundamental knowledge about the effect of polymer structure on the physicochemical properties of films. A novel meta-material that can be used in manufacturing sensor layers was developed as a model. At the first stage, poly(sodium 4-styrenesulfonate) (PNaSS) cross-linked microspheres are synthesized (which are based on strong polyelectrolytes containing sulfo groups in each monomer unit), and at the second stage, PNaSS@PEDOT microspheres are formed. The poly(3,4-ethylenedioxythiophene) (PEDOT) shell was obtained by the acid-assisted self-polymerization of the monomer; this process is biologically safe and thus suitable for biomedical applications. The suitability of electrochemical impedance spectroscopy for E. coli detection was tested; it was revealed that the attached bacterial wall was destroyed upon application of constant oxidation potential (higher than 0.5 V), which makes the PNaSS@PEDOT microsphere particles promising materials for the development of antifouling coatings. Furthermore, under open-circuit conditions, the walls of E. coli bacteria were not destroyed, which opens up the possibility of employing such meta-materials as sensor films. Scanning electron microscopy, X-ray photoelectron spectroscopy, water contact angle, and wide-angle X-ray diffraction methods were applied in order to characterize the PNaSS@PEDOT films.

Cationic Polymer-Coated Magnetic Nanoparticles with Antibacterial Properties: Synthesis and In Vitro Characterization.

Uniformly sized magnetite nanoparticles (Dn = 16 nm) were prepared by a thermal decomposition of Fe(III) oleate in octadec-1-ene and stabilized by oleic acid. The particles were coated with Sipomer PAM-200 containing both phosphate and methacrylic groups available for the attachment to the iron oxide and at the same time enabling (co)polymerization of 2-(dimethylamino)ethyl methacrylate and/or 2-tert-butylaminoethyl methacrylate at two molar ratios. The poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) and poly[2-(dimethylamino)ethyl methacrylate-co-2-tert-butylaminoethyl methacrylate] [P(DMAEMA-TBAEMA)] polymers and the particles were characterized by 1H NMR spectroscopy, size-exclusion chromatography, transmission electron microscopy, dynamic light scattering, thermogravimetric analysis, magnetometry, and ATR FTIR and atomic absorption spectroscopy. The antimicrobial effect of cationic polymer-coated magnetite nanoparticles tested on both Escherichia coli and Staphylococcus aureus bacteria was found to be time- and dose-responsive. The P(DMAEMA-TBAEMA)-coated magnetite particles possessed superior biocidal properties compared to those of P(DMAEMA)-coated one.

Poly[2-(dimethylamino)ethyl methacrylate-co-ethylene dimethacrylate]nanogel by dispersion polymerization for inhibition of pathogenic bacteria.

Bacterial infections and antimicrobial resistance are one of the major public health problems and various strategies to prevent potential threats have been developed. Protonated polymers were proven as efficient agents against several microbial pathogens. Poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) linear polymer and its copolymers represent one example of functional materials which inhibit the growth of both harmful Gram-negative and Gram-positive bacteria. However, the antimicrobial effect of positively charged PDMAEMA particles has been never tested. In this report, we deeply studied several parameters of free-radical polymerization, including the effect of crosslinking monomer, medium composition, solvency and polarity, and type and concentration of initiator and stabilizer, to fabricate high-quality poly[2-(dimethylamino)ethyl methacrylate-co-ethylene dimethacrylate] (PDMAEMA-EDMA) nanogel. We successfully found that dispersion polymerization in water/2-methoxyethanol medium (80/20 w/w), initiated with 0.2 wt% potassium persulfate (KPS) and stabilized with 0.5 wt% poly(vinyl alcohol) (PVA), produced a well-defined and sub-micron 167 nm PDMAEMA-EDMA nanogel. Bactericidal activity of the quaternized PDMAEMA-EDMA nanogel was assessed via time-kill curve assay against two Gram-positive and Gram-negative pathogenic bacteria, namely Staphylococcus aureus (S. aureus) and Acinetobacter baumannii (A. baumannii). The results illustrated that the quaternized PDMAEMA-EDMA nanogel acted as an effective bactericidal agent against both tested bacteria.

Does polysaccharide glycogen behave as a promoter of amyloid fibril formation at physiologically relevant concentrations?

We investigated the influence of glycogen (GG), phytoglycogen (PG), mannan (MAN) and cinnamoyl-modified GG (GG-CIN) on amyloid fibril formation. We used hen egg-white lysozyme (HEWL) as a model system and amyloid beta peptide (1-42) (Aß1-42) as an Alzheimer's disease-relevant system. For brief detection of fibrils was used thioflavin T (ThT) fluorescence assay and the results were confirmed by transmission electron microscopy (TEM). We also deal with the interaction of polysaccharides and HEWL with isothermal titration calorimetry (ITC) and dynamic light scattering (DLS). We found that all polysaccharides accelerated the formation of amyloid fibrils from both HEWL and Aß1-42. At high but physiologically relevant concentrations of GG, amyloid fibril formation was extremely accelerated for HEWL. Therefore, on the basis of the herein presented in vitro data, we hypothesize, that dietary d-glucose intake may influence amyloid fibril formation not only by influencing regulatory pathways, but also by direct glycogen-amyloid precursor protein molecular interaction, as glycogen levels in tissues are highly dependent on d-glucose intake.

Chemically modified glycogens: how they influence formation of amyloid fibrils?

The formation of amyloid fibrils from certain proteins stays behind a number of pathologies, so-called amyloidoses. Glycosaminoglycans are polysaccharides and are known natural constituents of amyloids in vivo. However, little is known about the effect of other naturally abundant polysaccharides, and even less is known about the effect of chemically modified polysaccharides on the formation of amyloid fibrils. In the case of low-molecular weight compounds, aromatic substances are known to often influence amyloid formation significantly. We investigated the influence of glycogen (GG) and several modifications of GG with cinnamoyl groups, benzoyl groups and phenylacetyl groups. As model systems, hen egg-white lysozyme (HEWL) and amyloid beta peptide (1-42) (Aß1-42), which is an Alzheimer disease-relevant system, were used. The fluorescence of thioflavin-T (ThT) was used for the rapid detection of fibrils, and the fluorescence results were confirmed by transmission electron microscopy (TEM). Other techniques, such as isothermal titration calorimetry (ITC) and dynamic light scattering (DLS), were employed to determine the interactions between HEWL and the modifications. We achieved similar results with both model systems (HEWL and Aß1-42). We showed that π-π interactions played an important role in the process of amyloid fibril formation because fundamental changes were observed in this process even with a very small number of groups containing an aromatic ring. It was found that almost all GG modifications accelerated the formation of amyloid fibrils in both model systems, HEWL and Aß1-42, except for GG-Ph1 (1.6 mol% phenylacetyl groups), which had a retarding effect compared to all other modifications.

Multimodal PSSMA-Functionalized GdF3 : Eu3+ (Tb3+ ) Nanoparticles for Luminescence Imaging, MRI, and X-Ray Computed Tomography.

Biocompatible poly(4-styrenesulfonic acid-co-maleic acid)-stabilized GdF3 : Eu3+ (Tb3+ ) nanoparticles were obtained by a one-step coprecipitation method in ethylene glycol or water. The particles are very small (3 nm), have a narrow size distribution, and were detectable by fluorescence, magnetic resonance, and X-ray contrast imaging. These properties allow multimodal imaging, which has prospective applications in the simultaneous and detailed detection of diseased tissues.

The use of hydrophilic poly(N,N-dimethylacrylamide) for promoting engulfment of magnetic gamma-Fe2O3 nanoparticles by mammalian cells.

gamma-Fe2O3 nanoparticles obtained by coprecipitation of Fe(II) and Fe(III) chlorides with a base and subsequent oxidation were coated with a shell of hydrophilic biocompatible poly(N,N-dimethylacrylamide) (PDMAAm). Various initiators were attached to the iron oxide surface to enable the use of the "grafting-from" approach for immobilization of PDMAAm. They included 2,2'-azobis(2-methylpropanimidamide) dihydrochloride (AMPA), 2,2'-azobis(N-hydroxy-2-methylpropanimidamide) dihydrochloride (ABHA) and 4-cyano-4-{[1-cyano-3-(N-hydroxycarbamoyl)-1-methylpropyl]azo}pentanoic acid (CCHPA). Engulfment of PDMAAm-coated y-Fe2O3 nanoparticles by murine J774.2 macrophages was investigated. Only some nanoparticles were engulfed by the macrophages. PDMAAm-AMPA-gamma-Fe2O3 and PDMAAm-ABHA-y-Fe2O3 nanoparticles were rapidly engulfed by the cells. In contrast, neat y-Fe2O3 and PDMAAm-CCHPA-gamma-Fe2O3 particles induced formation of transparent vacuoles indicating toxicity of the particles. Thus, PDMAAm-coated AMPA- and ABHA-gamma-Fe2O3 nanoparticles can be recommended as non-toxic labels for mammalian cells.