Vesna Vodnik

Nanomaterial with High Antimicrobial Efficacy—Copper/Polyaniline Nanocomposite

This study explores different mechanisms of antimicrobial action by designing hybrid nanomaterials that provide a new approach in the fight against resistant microbes. Here, we present a cheap copper-polyaniline (Cu-PANI) nanocomposite material with enhanced antimicrobial properties, prepared by simple in situ polymerization method, when polymer and metal nanoparticles are produced simultaneously. The copper nanoparticles (CuNPs) are uniformly dispersed in the polymer and have a narrow size distribution (dav = 6 nm). We found that CuNPs and PANI act synergistically against three strains, Escherichia coli, Staphylococcus aureus, and Candida albicans, and resulting nanocomposite exhibits higher antimicrobial activity than any component acting alone. Before using the colony counting method to quantify its time and concentration antimicrobial activity, different techniques (UV-visible spectroscopy, transmission electron microscopy, scanning electron microscope, field emission scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectrophotometry, and inductively coupled plasma optical emission spectrometry) were used to identify the optical, structural, and chemical aspects of the formed Cu-PANI nanocomposite. The antimicrobial activity of this nanocomposite shows that the microbial growth has been fully inhibited; moreover, some of the tested microbes were killed. Atomic force microscopy revealed dramatic changes in morphology of tested cells due to disruption of their cell wall integrity after incubation with Cu-PANI nanocomposite.

Interfacial Synthesis of Gold-Polyaniline Nanocomposite and Its Electrocatalytic Application.

Gold-polyaniline (Au-PANI) nanocomposite was prepared using a simple interfacial polymerization method, performed in an immiscible water/toluene biphasic system using tetrachloroaurate, AuCl4(-) as an oxidant. The formation of Au nanoparticles (AuNPs) or Au-PANI nanocomposite can be controlled to a certain degree by varying the ratio of initial Au(+) and aniline concentrations. Under optimal condition (HAuCl4/aniline ratio is 1:2), green dispersion of Au-PANI nanocomposite is produced in aqueous phase, whose morphology, structure and physicochemical properties are investigated in details. The nanocomposite shows granular morphology with mostly rodlike AuNPs embedded in polymer. It was found that polyaniline in the composite is in the conducting emeraldine salt form, containing high amount of Au (28.85 wt %). Furthermore, the electrical conductivity of the nanocomposite was found to be four-fold higher than that of the polymer itself. In addition, the nanocomposite powder, isolated from the as-prepared aqueous dispersion, can later be easily redispersed in water and further used for various applications. Moreover, the obtained Au-PANI nanocomposite showed excellent electrocatalytic performance toward the electrochemical oxygen reduction reaction (ORR), with high ORR onset potential and good selectivity. This makes it a promising candidate for a new class of Pt-free ORR catalyst.

Sonophotocatalytic degradation of dye C.I. Acid Orange 7 by TiO2 and Ag nanoparticles immobilized on corona pretreated polypropylene non-woven fabric.

This study discusses the possibility of using corona pre-treated polypropylene (PP) non-woven fabric as a support for immobilization of colloidal TiO2 and Ag nanoparticles in order to remove dye C.I. Acid Orange 7 from aqueous solution. Dye removal efficiency by sonocatalysis, photocatalysis and sonophotocatalysis was evaluated on corona pre-treated fabric loaded with TiO2 nanoparticles, corona pre-treated fabric double loaded with TiO2 nanoparticles and corona pre-treated fabrics loaded with TiO2 nanoparticles before and after deposition of Ag nanoparticles. In addition, the stability of PP non-woven fabric during these processes was investigated. The substrates were characterized by SEM, EDX and AAS analyses. The change of the dye concentration was evaluated by UV-VIS spectrophotometry. Unlike sonocatalysis and photocatalysis, complete dye removal from both solution and non-woven fabric was obtained already after 240-270 min of sonophotocatalysis. Corona pre-treated PP non-woven fabric loaded with Ag nanoparticles prior to deposition of TiO2 nanoparticles provided excellent degradation efficiency and superior reusability. Sonophotocatalytic degradation of dye in the presence of all investigated samples was the most prominent in acidic conditions. Although this nanocomposite system ensured fast discoloration of dye solution, TOC values of water measured after sonophotocatalysis were not satisfactory because of PP degradation. Therefore, it is suggested to include TOC evaluation in each case study where different supports for TiO2 nanoparticles are used since these nanoparticles may guarantee the dye removal from solution but the stability of support could be problematic causing even more serious environmental impact.

Optical, structural and thermal characterization of gold nanoparticles – poly(vinylalcohol) composite films

We report synthesis and characterization of gold NPs/PVA composite films. Gold colloidal NPs were introduced into a PVA matrix by simple solution-casting method to obtain homogenous, transparent, and colored films. NPs and NC films with different contents of inorganic phase (0.7, 1.4, and 2.1 wt %) were characterized by UV/Vis and FTIR spectrophotometry. Dimensions of the colloidal NPs were obtained by TEM (d ∼ 15±3 nm) and compared with results obtained by AFM of NC films. Comparison of thermal properties of the pure PVA and NC films showed that thermal stability is slightly reduced. DSC measurements revealed that Tg and melting temperatures of NCs are higher compared to pure PVA films.

Tryptophan-functionalized gold nanoparticles for deep UV imaging of microbial cells

Biocompatible fluorescent nanostructures were prepared by a functionalization of gold nanoparticles with the amino acid tryptophan. The gold-tryptophan bioconjugates were investigated by TEM and HRTEM and various spectroscopy methods (XPS, FTIR, UV-vis and photoluminescence). It was found that the gold nanoparticles, initially 8 nm in diameter, aggregate in the presence of the amino acid. From the XPS and FTIR spectroscopy results, it was concluded that the tryptophan gold interactions mainly take place via indole and carboxyl groups. Although the indole group is involved in the interaction with the gold surfaces, the tryptophan-gold hybrids showed strong fluorescence due to the presence of multilayers of tryptophan. Deep ultra violet (DUV) imaging performed at the SOLEIL synchrotron showed that it is possible to detect these hybrid nanostructures within Escherichia coli cells.

The influence of triangular silver nanoplates on antimicrobial activity and color of cotton fabrics pretreated with chitosan

The effect of cotton fabric pretreatment with biopolymer chitosan (CHT) on deposition of colloidal triangular silver nanoplates was studied. Also, the influence of deposited silver nanoparticles on color and antimicrobial activity of cotton fabrics was evaluated. Characterization of colloidal silver nanoparticles as well as silver nanoparticles deposited on cotton fabrics was performed using electron microscopy (TEM and FESEM), XRD analysis, atomic absorption spectroscopy, UV–Vis absorption, and reflectance spectroscopy. The cotton fabric turned from white to blue color upon deposition of triangular silver nanoplates. Antimicrobial activity of CHT pretreated cotton fabric impregnated with silver nanoparticles was tested against Gram-negative bacteria Escherichia coli, Gram-positive bacteria Staphylococcus aureus, and fungi Candida albicans. Deposited silver nanoparticles imparted excellent antimicrobial properties to cotton fabric. The standard sterilization procedure of cotton fabric for antimicrobial activity testing resulted in color change of the fabric from blue to yellow. This color change is most likely consequence of transformation of triangular silver nanoplates into nanodiscs and/or their agglomeration into spheroids.

Thermal properties of poly(urethane-ester-siloxane)s based on hyperbranched polyester

Novel polyurethanes (PUs) were synthesized using hydroxy-terminated hyperbranched polyester (BH-20) and 4,4′-methylenediphenyl diisocyanate (MDI) as hard segments and hydroxy-terminated ethylene oxide-poly(dimethylsiloxane)-ethylene oxide triblock copolymer (PDMS-EO) as soft segment, with soft segment content ranging from 30 to 60 wt %. The PUs were synthesized by two-step solution polymerization method. The influence of the soft segment content on the structure, swelling behavior and thermal properties of PUs was investigated. According to the results obtained by swelling measurements, the increase of the hard segment content resulted in the increase of the crosslinking density of synthesized samples. DSC results showed that the glass transition temperatures increase from 36 to 65°C with increasing hard segment content. It was demonstrated using thermogravimetric analysis (TGA) that thermal stability of investigated PUs increases with increase of the soft PDMS-EO content. This was concluded from the temperatures corresponding to the 10 wt % loss, which represents the beginning of thermal degradation of samples.

Negative influence of Ag and TiO2 nanoparticles on biodegradation of cotton fabrics

Abstract Recently, many efforts have been made to efficiently impregnate different textile materials with metal and metal oxide nanoparticles in order to provide antimicrobial, UV protective or self-cleaning properties. Evidence of their environmental risks is limited at this point. The aim of this study was to explore the influence of Ag and TiO2 nanoparticles on biodegradation of cotton fabrics. Biodegradation behavior of cotton fabrics impregnated with Ag and TiO2 NPs from colloidal solutions of different concentrations was assessed according to standard test method ASTM 5988-03 and soil burial test. Degradation of cotton fabrics was also evaluated by enzymatic hydrolysis with cellulase. The morphology of fibers affected by biodegradation was analyzed by scanning electron microscopy (SEM). In order to get better insight into biodegradation process, dehydrogenase activity of soil has been determined. Ag and particularly TiO2 nanoparticles suppressed the biodegradation of cotton fabrics. The dehydrogenase activity of soil with cotton fabrics impregnated with TiO2 nanoparticles was the weakest. Severe damage of cotton fibers during the biodegradation process was confirmed by SEM.Graphical Abstract

Spectrophotometric observations of thiacyanine dye J-aggregation on citrate capped silver nanoparticles

Abstract The J-aggregation of anionic cyanine dye, 5,5’ – disulfopropyl-3,3’ – dichloro - thiacyanine sodium salt (TC) in the presence of 2x10-3 M KCl and citrate capped silver nanoparticles (AgNPs, diameter ~10nm) was investigated. The influence of added salt (KCl), as well as AgNPs and TC concentration on the intensity of the absorption bands with the maxima at 464 and 481 nm, characteristic of the J-aggregation of the dye in solution and on AgNPs surface, respectively, was studied. The spectrophotometric and fluorescence spectra confirmed that AgNPs induced the decomposition of J-aggregates formed in solution on the account of their formation on NPs surface. The obtained results enabled the evaluation of number of TC molecules per AgNPs participating in J-aggregate formation. The experimental results yielded about 320 molecules of TC per AgNPs in at least three layers in a slanted orientation.

Spectroscopic and fluorescence properties of silver-dye composite nanoparticles

The aim of this work was to investigate the formation of J-aggregates of thiacyanine dye (TC, 5,5′-disulfopropyl-3,3′-dichlorothiacyanine sodium salt) in the presence of 6 nm spherical silver nanoparticles (Ag NPs) using spectrophotometric and fluorescence methods. The formation of J-aggregates was concentration dependent and characterized by the appearance of the new absorption band with the maximum at 481 nm. Spectrophotometric study of J-aggregate formation and time stability suggested that they were formed on the account of monomer form of TC. Moreover, the stability of J-aggregates increased with the lowering AgNPs concentration. The measurements of fluorescence of the NPs—dye assembly clearly indicated that the fluorescence of TC was quenched by Ag NPs on the concentration dependent manner. The spectrophotometric and fluorescence properties of NPs—dye assembly were found to be quantitatively related to the surface coverage of the dye on the Ag NPs.