Reversible carrier-type transition in gas-sensing oxides and nanostructures

Despite many important applications of a-Fe2O3 and Fe doped SnO2 in semiconductors, catalysis, sensors, clinical diagnosis and treatments, one fundamental issue that is crucial to these applications remains theoretically equivocal- the reversible carrier-type transition between n- and p-type conductivities during gas-sensing operations. Here, we give unambiguous and rigorous theoretical analysis in order to explain why and how the oxygen vacancies affect the n-type semiconductors, a-Fe2O3 and Fe doped SnO2 in which they are both electronically and chemically transformed into a p-type semiconductor. Furthermore, this reversible transition also occurs on the oxide surfaces during gas-sensing operation due to physisorbed gas molecules (without any chemical reaction). We make use of the ionization energy theory and its renormalized ionic displacement polarizability functional to reclassify, generalize and to explain the concept of carrier-type transition in solids, and during gas-sensing operation. The origin of such a transition is associated to the change in ionic polarizability and the valence states of cations in the presence of (a) oxygen vacancies and (b) physisorped gas molecules.Comment: To be published in ChemPhysChe

Regulating the antibiotic drug release from ß-tricalcium phosphate ceramics by atmospheric plasma surface engineering

Calcium phosphate (CaP) ceramics are of interest in bone substitution due to their good biocompatibility and bioresorbability. Currently certain CaPs in the market are loaded with antibiotics in order to prevent infections but further control is needed over antibiotic release patterns. Cold plasmas have emerged as a useful means of modifying the interactions with drugs through surface modification of polymer materials. In this work we explore the possibility of using atmospheric pressure plasmas as a tool for the surface modification of these CaP materials with newly populated bonds and charges, with views on enabling higher loading and controlled drug release. Herein the surface modification of ß-tricalcium phosphate ceramics is investigated using an atmospheric pressure helium plasma jet as a tool for tuning the controlled release of the antibiotic doxycycline hyclate, employed as a drug model. The surface chemistry is tailored mainly by plasma jet surface interaction with an increasing O/C ratio without changes in the topography as well as by build-up of surface charges. With this surface tailoring it is demonstrated that the atmospheric plasma jet is a new promising tool that leads to the design of a control for drug release from bioceramic matrices.Peer ReviewedPostprint (author's final draft

Radio-frequency plasma in combination with aerosol injection for biomedical applications

Radiofrequency plasma for biomedical applications generated in coaxial geometry at atmospheric pressure was investigated. The plasma was characterized by key parameters, including gas temperature and electron density. It was shown that OH rotational temperature is in agreement with the temperature estimated by Rayleigh and Raman scattering techniques. RF plasma was combined with an aerosol injection for better control of the treated skin temperature and topical drugs delivery

On diagnostics of an annular-shape radio-frequency plasma jet operating in argon at atmospheric conditions

One of the driving forces behind the development of cold plasma sources at atmospheric pressure is their application in the biomedical field. In this respect, radio-frequency (RF) plasma jets are of particular importance due to their possible safe operation on humans and the generation of the high amount of reactive species. For this reason, we designed an RF plasma jet in co-axial geometry with the possibility of aerosol introduction, where its characteristics were evaluated by electrical diagnostics, optical emission and laser scattering spectroscopy. The RF plasma jet operation and stability of diffuse mode were analysed based on energy balance. It was observed that alpha-mode diffuse discharge characterised by an effluent length up to 5 mm was sustained at a power density below 30 W cm(-3). The gas and rotational temperature were determined by means of spectroscopy methods and compared with the results of direct laser scattering. It was established that the gas temperature obtained from N-2 emission of transition C(3)n(u) -> B(3)n(g) (0, 2) is highly overestimated whereas the gas temperature estimated from OH transition A(2)sigma+ -> X(2)n(i) (0, 0) gave a reasonable agreement with both Rayleigh and Raman spectroscopy. Based on the Rayleigh scattering method, uniform gas temperature distribution in the discharge effluent was found at a power below 15 W with the average temperature below 340 15 K. The low gas temperature of argon plasma jets would allow use of this source in temperature-sensitive material applications including skin treatments

Plasma deposition of antibacterial nano-coatings on polymeric materials

Non-woven textile materials with antimicrobial properties are of high demands for applications ranging from medical dressing to everyday cleaning products. A plasma assisted route to engineer antimicrobial nano-composite coatings is proposed. Nano-particles of Ag, Cu and ZnO are tested as antimicrobial agents with average nano-particle size of 20-50 nm. Nanoparticles are incorporated in between two layers of an organosilicon film. The effect of the barrier coating on nano-particles release is determined by XPS. Antibacterial efficiency of the samples against P. aeruginosa ATCC 9027 and S. aureus M u50 bacteria shows that all treated samples exhibit higher antibacterial efficiency against S. aureus. The antibacterial efficiency of AgNPs and CuNPs is above 90% which is practically interesting for medical application while ZnONPs shows lower antibacterial efficiency.This work is supported by the M.Era-Net project IWT 140812 “PlasmaTex”.info:eu-repo/semantics/publishedVersio

Plasma-Induced Interfacial Processes in Metal Halides FTIR Gas Cell Windows

Fourier transform infrared spectroscopy (FTIR) is one of the most widely used vibrational diagnostic techniques to investigate gas-phase reactive oxygen and nitrogen species (RONS). However, the technique carries intrinsic challenges, particularly in relation to interfering peaks in the spectral data. This study explores the interfacial processes that occur when reactive oxygen and nitrogen species generated by a non-equilibrium air plasma interact with the metal halide windows of an FTIR gas cell, leading to the appearance and evolution of spurious absorption peaks which complicate spectral interpretation. Raman spectroscopy, X-ray photoelectron spectroscopy, time of flight secondary ion mass spectrometry and attenuated total reflectance-FTIR spectroscopy were used to elucidate the origin of spurious absorption peaks spanning the 1400–1300 cm−1 spectral range as a result of KBr exposure to plasma generated species. It was found that plasma exposed KBr contained a lower atomic fraction of Br which was replaced by the NO3 nitrate group, the main absorbance peak of which progressively evolved with plasma exposure and affected the window transparency over the corresponding FTIR region. A correlation was revealed between KNO3 formation, plasma power and exposure time to a growth and change in molecular vibrational energies corresponding to asymmetric NO3 stretching vibrations in the KNO3 structure

Dissecting Out the Molecular Mechanism of Insecticidal Activity of Ostreolysin A6/Pleurotolysin B Complexes on Western Corn Rootworm

Ostreolysin A6 (OlyA6) is a protein produced by the oyster mushroom (Pleurotus ostreatus). It binds to membrane sphingomyelin/cholesterol domains, and together with its protein partner, pleurotolysin B (PlyB), it forms 13-meric transmembrane pore complexes. Further, OlyA6 binds 1000 times more strongly to the insect-specific membrane sphingolipid, ceramide phosphoethanolamine (CPE). In concert with PlyB, OlyA6 has potent and selective insecticidal activity against the western corn rootworm. We analysed the histological alterations of the midgut wall columnar epithelium of western corn rootworm larvae fed with OlyA6/PlyB, which showed vacuolisation of the cell cytoplasm, swelling of the apical cell surface into the gut lumen, and delamination of the basal lamina underlying the epithelium. Additionally, cryo-electron microscopy was used to explore the membrane interactions of the OlyA6/PlyB complex using lipid vesicles composed of artificial lipids containing CPE, and western corn rootworm brush border membrane vesicles. Multimeric transmembrane pores were formed in both vesicle preparations, similar to those described for sphingomyelin/cholesterol membranes. These results strongly suggest that the molecular mechanism of insecticidal action of OlyA6/PlyB arises from specific interactions of OlyA6 with CPE, and the consequent formation of transmembrane pores in the insect midgut

Effect of dispersion solvent on the deposition of PVP-Silver nanoparticles onto DBD plasma-treated polyamide 6,6 fabric and Its antimicrobial efficiency

Supplementary Material: https://www.mdpi.com/2079-4991/10/4/607/s1Polyvinylpyrrolidone-coated silver nanoparticles (PVP-AgNPs) dispersed in ethanol, water and water/alginate were used to functionalize untreated and dielectric barrier discharge (DBD) plasma-treated polyamide 6,6 fabric (PA66). The PVP-AgNPs dispersions were deposited onto PA66 by spray and exhaustion methods. The exhaustion method showed a higher amount of deposited AgNPs. Water and water-alginate dispersions presented similar results. Ethanol amphiphilic character showed more affinity to AgNPs and PA66 fabric, allowing better uniform surface distribution of nanoparticles. Antimicrobial effect in E. coli showed good results in all the samples obtained by exhaustion method but using spray method only the DBD plasma treated samples displayed antimicrobial activity (log reduction of 5). Despite the better distribution achieved using ethanol as a solvent, water dispersion samples with DBD plasma treatment displayed better antimicrobial activity against S. aureus bacteria in both exhaustion (log reduction of 1.9) and spray (methods log reduction of 1.6) due to the different oxidation states of PA66 surface interacting with PVP-AgNPs, as demonstrated by X-Ray Photoelectron Spectroscopy (XPS) analysis. Spray method using the water-suspended PVP-AgNPs onto DBD plasma-treated samples is much faster, less agglomerating and uses 10 times less PVP-AgNPs dispersion than the exhaustion method to obtain an antimicrobial effect in both S. aureus and E. coli.This research was funded by FEDER funds through the Operational Competitiveness Program – COMPETE and by National Funds through Fundação para a Ciênciae Tecnologia (FCT) under the project POCI01-0145-FEDER-007136 and UID/CTM/00264/2019. A. Zille also acknowledges financial support of the FCT project PTDC/CTM-TEX/28295/2017 financed by FCT, FEDER and POCI.Isabel Ribeiro (SFRH/BD/137668/2018) acknowledges FCT, Portugal, for its doctoral grant financial support. A. Zille also acknowledges financial support of the FCT project PTDC/CTM-TEX/28295/2017 financed by FCT, FEDER and POCI