Influence of crystal structure and oxygen vacancies on optical properties of nanostructured multi-stoichiometric tungsten suboxides.

Four distinct tungsten suboxide (WO3-x) nanomaterials were synthesized via chemical vapour transport reaction and the role of their crystal structures on the optical properties was studied. These materials grow either as thin, quasi-2D crystals with the WnO3n-1formula (in shape of platelets or nanotiles), or as nanowires (W5O14, W18O49). For the quasi-2D materials, the appearance of defect states gives rise to two indirect absorption edges. One is assigned to the regular bandgap occurring between the valence and the conduction band, while the second is a defect-induced band. While the bandgap values of platelets and nanotiles are in the upper range of the reported values for the suboxides, the nanowires' bandgaps are lower due to the higher number of free charge carriers. Both types of nanowires sustain localized surface plasmon resonances, as evidenced from the extinction measurements, whereas the quasi-2D materials exhibit excitonic transitions. All four materials have photoluminescence emission peaks in the UV region. The interplay of the crystal structure, oxygen vacancies and shape can result in changes in optical behaviour, and the understanding of these effects could enable intentional tuning of selected properties.

Sterilization of polypropylene membranes of facepiece respirators by ionizing radiation.

Ionizing radiation has been identified as an option for sterilization of disposable filtering facepiece respirators in situations where the production of the respirators cannot keep up with demand. Gamma radiation and high energy electrons penetrate deeply into the material and can be used to sterilize large batches of masks within a short time period. In relation to reports that sterilization by ionizing radiation reduces filtration efficiency of polypropylene membrane filters on account of static charge loss, we have demonstrated that both gamma and electron beam irradiation can be used for sterilization, provided that the respirators are recharged afterwards.

Size- and Time-Dependent Particle Removal Efficiency of Face Masks and Improvised Respiratory Protection Equipment Used during the COVID-19 Pandemic.

Size- and time-dependent particle removal efficiency (PRE) of different protective respiratory masks were determined using a standard aerosol powder with the size of particles in the range of an uncoated SARS-CoV-2 virus and small respiratory droplets. Number concentration of particles was measured by a scanning mobility particle sizer. Respiratory protective half-masks, surgical masks, and cotton washable masks were tested. The results show high filtration efficiency of FFP2, FFP3, and certified surgical masks for all sizes of tested particles, while protection efficiency of washable masks depends on their constituent fabrics. Measurements showed decreasing PRE of all masks over time due to transmission of nanoparticles through the mask-face interface. On the other hand, the PRE of the fabric is governed by deposition of the aerosols, consequently increasing the PRE.

Heterologous expression of the atypical tetracycline chelocardin reveals the full set of genes required for its biosynthesis.

BACKGROUND: Chelocardin (CHD) exhibits a broad-spectrum antibiotic activity and showed promising results in a small phase II clinical study conducted on patients with urinary tract infections. Importantly, CHD was shown to be active also against tetracycline-resistant Gram-negative pathogens, which is gaining even more importance in today's antibiotic crisis. We have demonstrated that modifications of CHD through genetic engineering of its producer, the actinomycete Amycolatopsis sulphurea, are not only possible but yielded even more potent antibiotics than CHD itself, like 2-carboxamido-2-deacetyl-chelocardin (CD-CHD), which is currently in preclinical evaluation. A. sulphurea is difficult to genetically manipulate and therefore manipulation of the chd biosynthetic gene cluster in a genetically amenable heterologous host would be of high importance for further drug-discovery efforts. RESULTS: We report heterologous expression of the CHD biosynthetic gene cluster in the model organism Streptomyces albus del14 strain. Unexpectedly, we found that the originally defined CHD gene cluster fails to provide all genes required for CHD formation, including an additional cyclase and two regulatory genes. Overexpression of the putative pathway-specific streptomyces antibiotic regulatory protein chdB in A. sulphurea resulted in an increase of both, CHD and CD-CHD production. Applying a metabolic-engineering approach, it was also possible to generate the potent CHD analogue, CD-CHD in S. albus. Finally, an additional yield increase was achieved in S. albus del14 by in-trans overexpression of the chdR exporter gene, which provides resistance to CHD and CDCHD. CONCLUSIONS: We identified previously unknown genes in the CHD cluster, which were shown to be essential for chelocardin biosynthesis by expression of the full biosynthetic gene cluster in S. albus as heterologous host. When comparing to oxytetracycline biosynthesis, we observed that the CHD gene cluster contains additional enzymes not found in gene clusters encoding the biosynthesis of typical tetracyclines (such as oxytetracycline). This finding probably explains the different chemistries and modes of action, which make CHD/CD-CHD valuable lead structures for clinical candidates. Even though the CHD genes are derived from a rare actinomycete A. sulphurea, the yield of CHD in the heterologous host was very good. The corrected nucleotide sequence of the CHD gene cluster now contains all gene products required for the production of CHD in a genetically amenable heterologous host, thus opening new possibilities towards production of novel and potent tetracycline analogues with a new mode of action.

Nanoparticle concentrations and composition in a dental office and dental laboratory: A pilot study on the influence of working procedures.

During material treatment in dentistry particles of different size are released in the air. To examine the degree of particle exposure, air scanning to dental employees was performed by the Scanning Mobility Particle Sizer. The size, shape and chemical composition of particles collected with a low-pressure impactor were determined by scanning electronic microscopy and X-ray dispersive analysis. The average concentrations of nanoparticles during working periods in a clean dental laboratory (45,000-56,000 particles/cm3), in an unclean dental laboratory (28,000-74,000 particles/cm3), and in a dental office (21,000-50,000 particles/cm3), were significantly higher compared to average concentrations during nonworking periods in the clean dental laboratory (11,000-24,000 particles/cm3), unclean laboratory (14,000-40,000 particles/cm3), and dental office (13,000-26,000 particles/cm3). Peak concentration of nanoparticles in work-intensive periods were found significantly higher (up to 773,000 particles/cm3), compared to the non-working periods (147,000 particles/cm3) and work-less intensive periods (365,000 particles/cm3). The highest mass concentration value ranged from 0.055-0.166 mg/m3. X-ray dispersive analysis confirmed the presence of carbon, potassium, oxygen, iron, aluminum, zinc, silicon, and phosphorus as integral elements of dental restorative materials in form of nanoparticle clusters, all smaller than 100 nm. We concluded that dental employees are exposed to nanoparticles in their working environment and are therefore potentially at risk for certain respiratory and systematic diseases.

Effect of ingested tungsten oxide (WOx) nanofibers on digestive gland tissue of Porcellio scaber (Isopoda, Crustacea): fourier transform infrared (FTIR) imaging.

Tungsten nanofibers are recognized as biologically potent. We study deviations in molecular composition between normal and digestive gland tissue of WOx nanofibers (nano-WOx) fed invertebrate Porcellio scaber (Iosopda, Crustacea) and revealed mechanisms of nano-WOx effect in vivo. Fourier Transform Infrared (FTIR) imaging performed on digestive gland epithelium was supplemented by toxicity and cytotoxicity analyses as well as scanning electron microscopy (SEM) of the surface of the epithelium. The difference in the spectra of the Nano-WOx treated and control cells showed up in the central region of the cells and were related to lipid peroxidation, and structural changes of nucleic acids. The conventional toxicity parameters failed to show toxic effects of nano-WOx, whereas the cytotoxicity biomarkers and SEM investigation of digestive gland epithelium indicated sporadic effects of nanofibers. Since toxicological and cytological measurements did not highlight severe effects, the biochemical alterations evidenced by FTIR imaging have been explained as the result of cell protection (acclimation) mechanisms to unfavorable conditions and indication of a nonhomeostatic state, which can lead to toxic effects.

Populus seed fibers as a natural source for production of oil super absorbents.

The genus Populus, which includes poplars, cottonwoods and aspen trees, represents a huge natural source of fibers with exceptional physical properties. In this study, the oil absorption properties of poplar seed hair fibers obtained from Populus nigra italica when tested with high-density motor oil and diesel fuel are reported. Poplar seed hair fibers are hollow hydrophobic microtubes with an external diameter between 3 and 12 µm, an average length of 4±1 mm and average tube wall thickness of 400±100 nm. The solid skeleton of the hollow fibers consists of lignocellulosic material coated by a hydrophobic waxy coating. The exceptional chemical, physical and microstructural properties of poplar seed hair fibers enable super-absorbent behavior with high absorption capacity for heavy motor oil and diesel fuel. The absorption values of 182-211 g heavy oil/g fiber and 55-60 g heavy oil/g fiber for packing densities of 0.005 g/cm(3) and 0.02 g/cm(3), respectively, surpass all known natural absorbents. Thus, poplar seed hair fibers obtained from Populus nigra italica and other trees of the genus Populus are an extremely promising natural source for the production of oil super absorbents.

Application and characterization of a novel PVDF-HFP/PVP polymer composite with MoO3 nanowires as a protective coating for wood.

The coatings on wood must sometimes give aesthetic and basic protection to wooden elements and prevent the development and transmission of microorganisms. Several polymers containing different nanoparticles have already been offered to day for this purpose. The research presents a novel poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)/polyvinylpyrrolidone (PVP) polymer composite with MoO3 nanowires with the ability to form coating films on wood. The films of the developed coating exhibit elastic behaviour, which depends on the coating film thickness [tested wet film thicknesses (90, 180 and 360) µm]. The coating showed the ability to interact well with the surface of common beech (Fagus sylvatica L.) wood, in terms of wetting (contact angles of 15.6°), fast spilling on the surface, good penetration of the coating in wood structure and formation of up to 40 µm-thick films with excellent pull-off adhesion strength (6 MPa). An increased roughness of wood coated with C + MoO3 was a consequence of wood etching by the dimethylformamide solvent present in the coating. Moreover, the presence of C + MoO3 on wood made it considerably more hydrophobic, with contact angle of water raising to 123° from initially 46° measured on uncoated wood. The irradiation of wood surfaces with ultra-violet light resulted in visible colour changes on both uncoated and coated wood. The wood coated with C + MoO3 has a good resistance to water, alcohol and dry heat (grade 3 to 4). The antimicrobial testing showed that the presence of MoO3 in the coating plays an important role in the resistance of the coated wood to blue-stain fungi and mould development. The developed PVDF-HFP/PVP/MoO3 coating has an excellent ability to interact with the wood surface and has the potential to be used as a protection for wood in sensitive environments.

Tribological Evaluation of Vegetable Oil/MoS2 Nanotube-Based Lubrication of Laser-Textured Stainless Steel.

In the present work, the functionalisation of austenitic stainless steel, AISI 316L surfaces via nanosecond Nd:YAG laser texturing in order to modify the surface morphology with crosshatch and dimple patterns is presented. A tribological analysis under lubrication with sunflower and jojoba oil with and without the addition of a solid lubricant, MoS2 nanotubes, was performed. In conjunction with friction/wear response laser-textured surface wettability, oil spreadability and oil retention capacity were also analysed. It was shown that the crosshatch pattern generally exhibited lower friction than the dimple pattern, with the addition of MoS2 nanotubes not having any significant effect on the coefficient of friction under the investigated contact conditions. This was found in addition to the better oil spreadability and oil retention capacity results of the crosshatch-textured surface. Furthermore, texturing reduced the wear of the stainless-steel surfaces but led to an approximately one order of magnitude larger wear rate of the steel counter-body, primarily due to the presence of hard bulges around the textured patterns. Overall, the crosshatch pattern showed better oil retention capacity and lower friction in combination with different vegetable oils, thus making it a promising choice for improving tribological performance in various environmentally friendly applications.

Pseudomonas fragi biofilm on stainless steel (at low temperatures) affects the survival of Campylobacter jejuni and Listeria monocytogenes and their control by a polymer molybdenum oxide nanocomposite coating.

Pseudomonas spp. are widely distributed bacteria on surfaces in the food production and processing environment, where they form extracellular polymeric substance rich biofilms that interact with other bacteria. In this study, the influence of biofilm of Pseudomonas fragi ATCC 4973 on Listeria monocytogenes ATCC 19115 and Campylobacter jejuni NCTC 11168 was investigated at 5 °C and 15 °C on stainless steel in broth and food homogenates (fish or chicken meat). Stainless steel was then coated with PVDF-HFP/PVP/MoO3 nanocomposite and examined for surface changes (scanning electron microscope, static contact angle, Vickers hardness and elastic modulus). The effect of the prepared nanocomposite coating on P. fragi and on L. monocytogenes and C. jejuni was evaluated in mono- and co-culture. P. fragi produced more biofilm at 15 °C than at 5 °C, especially when food homogenates were used as growth media. Co-cultivation with pathogens did not affect biofilm production by P. fragi, but significant changes were observed in L. monocytogenes and C. jejuni, resulting in a decrease and increase, respectively, in the determined number of culturable biofilm cells. The first change was probably due to competition for the surface, and the second to the oxygen gradient. Stainless steel was then coated with a PVDF-HFP/PVP/MoO3 nanocomposite, which was characterised by lower roughness and higher wettability, but lower hardness compared to uncoated stainless steel. The prepared nanocoating showed bactericidal activity when tested in phosphate buffered saline. When used in food homogenates, a reduction of over 95 % in bacterial counts was observed. An abundant biofilm of P. fragi proved protective to L. monocytogenes and C. jejuni against the functionalised nanocomposite surface when tested in food homogenates. The control of spoilage Pseudomonas spp., which are common in the food production and processing environment, is important for reducing the contamination of food with spoilage bacteria and with pathogens such as L. monocytogenes and C. jejuni, which may be present in the same environment. The PVDF-HFP/PVP/MoO3 nanocomposite showed good potential for use as a coating for food contact surfaces, but possible migration of nanoparticles from the nanocomposite coating to food should be evaluated before its commercial use.

Enhanced Filtration Efficiency of Natural Materials with the Addition of Electrospun Poly(vinylidene fluoride-co-hexafluoropropylene) Fibres.

Pollutants and infectious diseases can spread through air with airborne droplets and aerosols. A respiratory mask can decrease the amount of pollutants we inhale and it can protect us from airborne diseases. With the onset of the COVID-19 pandemic, masks became an everyday item used by a lot of people around the world. As most of them are for a single use, the amount of non-recyclable waste increased dramatically. The plastic from which the masks are made pollutes the environment with various chemicals and microplastic. Here, we investigated the time- and size-dependent filtration efficiency (FE) of aerosols in the range of 25.9 to 685.4 nm of five different natural materials whose FE was enhanced using electrospun poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF) fibres. A scanning electron microscope (SEM) was used to determine the morphology and structure of the natural materials as well as the thickness of the PVDF fibres, while the phase of the electrospun fibres was determined by Raman spectroscopy. A thin layer of the electrospun PVDF fibres with the same grammage was sandwiched between two sheets of natural materials, and their FE increased up to 80%. By varying the grammature of the electrospun polymer, we tuned the FE of cotton from 82.6 to 99.9%. Thus, through the optimization of the grammage of the electrospun polymer, the amount of plastic used in the process can be minimized, while achieving sufficiently high FE.

Single-Layer and Double-Layer Filtration Materials Based on Polyvinylidene Fluoride-Co-hexafluoropropylene Nanofibers Coated on Melamine Microfibers.

In this work, we demonstrate selected optimization changes in the simple design of filtration masks to increase particle removal efficiency (PRE) and filter quality factor by combining experiments and numerical modeling. In particular, we focus on single-layer filters fabricated from uniform thickness fibers and double-layer filters consisting of a layer of highly permeable thick fibers as a support and a thin layer of filtering electrospun nanofibers. For single-layer filters, we demonstrate performance improvement in terms of the quality factor by optimizing the geometry of the composition. We show significantly better PRE performance for filters composed of micrometer-sized fibers covered by a thin layer of electrospun nanofibers. This work is motivated and carried out in collaboration with a targeted industrial development of selected melamine-based filter nano- and micromaterials.

Non-Destructive Low-Temperature Contacts to MoS2 Nanoribbon and Nanotube Quantum Dots.

Molybdenum disulfide nanoribbons and nanotubes are quasi-1D semiconductors with strong spin-orbit interaction, a nanomaterial highly promising for quantum electronic applications. Here, it is demonstrated that a bismuth semimetal layer between the contact metal and this nanomaterial strongly improves the properties of the contacts. Two-point resistances on the order of 100 kΩ are observed at room temperature. At cryogenic temperature, Coulomb blockade is visible. The resulting stability diagrams indicate a marked absence of trap states at the contacts and the corresponding disorder, compared to previous devices that use low-work-function metals as contacts. Single-level quantum transport is observed at temperatures below 100 mK.

Water versus Oil Lubrication of Laser-Textured Ti6Al4V Alloy upon Addition of MoS2 Nanotubes for Green Tribology.

A Nd-YAG laser was used for texturing the Ti6Al4V surface with dimples of diameter 50 and 100 µm and centre-to-centre distance 100, 200 and 400 µm, defining the surface texture density. The tribological evaluation was conducted to analyse and compare the behaviour of un-textured and laser-textured samples under water in comparison to oil (PAO6) lubrication without and with the addition of MoS2 nanotubes into the lubricant. MoS2 nanotubes had a positive effect on friction in both media for laser-textured Ti6Al4V. Evaluation of friction and wear in water and PAO6 showed a comparable tribological response in water to oil for specific laser-textured configurations, proving the novel concept of green tribology for laser texturing in combination with MoS2 nanotubes/water lubrication.

Synthesis and Characterization of Tungsten Suboxide WnO3n-1 Nanotiles.

WnO3n-1 nanotiles, with multiple stoichiometries within one nanotile, were synthesized via the chemical vapour transport method. They grow along the [010] crystallographic axis, with the thickness ranging from a few tens to a few hundreds of nm, with the lateral size up to several µm. Distinct surface corrugations, up to a few 10 nm deep appear during growth. The {102}r crystallographic shear planes indicate the WnO3n-1 stoichiometries. Within a single nanotile, six stoichiometries were detected, namely W16O47 (WO2.938), W15O44 (WO2.933), W14O41 (WO2.928), W13O38 (WO2.923), W12O35 (WO2.917), and W11O32 (WO2.909), with the last three never being reported before. The existence of oxygen vacancies within the crystallographic shear planes resulted in the observed non-zero density of states at the Fermi energy.

Multi-stoichiometric quasi-two-dimensional WnO3n-1 tungsten oxides.

Quasi-two-dimensional tungsten oxide structures, which nucleate by epitaxial growth on W19O55 nanowires (NW) and grow as thin platelets, were identified. Both the nanowires and the platelets accommodate oxygen deficiency by the formation of crystallographic shear planes. Stoichiometric phases, W18O53 (WO2.944), W17O50 (WO2.941), W16O47 (WO2.938), W15O44 (WO2.933), W14O41 (WO2.929), W10O29 (WO2.9), and W9O26 (WO2.889), syntactically grow inside a single platelet. These layered crystals show a new kind of polycrystallinity, where crystallographic shear planes accommodate oxygen deficiency and at the same time stabilize this multi-stoichiometric structure.

In-vitro toxicity of molybdenum trioxide nanoparticles on human keratinocytes.

Molybdenum trioxide (MoO3) nanoparticles (NPs) embedded in polymer films have been proposed as a cheap way of producing antibacterial coatings on external surfaces. Recently, we synthesized MoO3 nanowires in a unique shape and degree of anisotropy, which enables their fast water dissolution and quick antimicrobial reaction. Potential human health risks following the exposure to MoO3 NPs however need to be assessed prior their wide use. We therefore, investigated the biological effect of these newly synthesized MoO3 NPs on the human keratinocyte cell line HaCaT, used here as a model for the human skin. Exposure of HaCaT cells to 1 mg/mL MoO3 NPs concentration for 1 h showed no effect on cell survival, had no influence on reactive oxygen species production, expression of proteins involved in antioxidant defense, secretion of pro-inflammatory cytokines, nor induced DNA damage. Interestingly however, ERK and p38 MAP kinases were activated, and upon longer time exposure, induced a moderate release of the pro-inflammatory cytokine interleukin 6, increased DNA damage and increased the level of caspase independent cell death. Our study indicates that exposing HaCaT cells to antibacterial MoO3 NPs water-based solution in durations less than 1 h exhibits no cytotoxicity, but rather triggers cell signalling involved in cell survival and inflammation; which should be taken into consideration when evaluating MoO3 NPs for medical applications.

RF plasma-enhanced conducting Polymer/W5O14 based self-propelled micromotors for miRNA detection.

Functionalized micro/nanomotors having immobilized biological molecules provide excellent and powerful tools for the detection of target molecules. Based on surface modifications and mobilities of micromotors, we report herein a new experimental design of high-speed, self-propelled and plasma modified micromotors for biomedical applications. Within this scope, in the first step, poly (3,4-ethylenedioxythiophene) (PEDOT) was in-situ synthesized onto W5O14 (tungsten trioxide) wires by using radio frequency (RF) rotating plasma reactor. Then, W5O14/PEDOT-Platinum (Pt) hybrid micromotors were fabricated by using magnetron sputtering technique. The detection of miRNA-21 was performed using both single-stranded DNA (ssDNA) (probe DNA) immobilized W5O14-Pt and W5O14/PEDOT-Pt micromotors. The fluorescence signals were determined after hybridization of probe DNA immobilized these novel W5O14-Pt and W5O14/PEDOT-Pt micromotors with different molar concentrations of the synthetic target (6-carboxyfluorescein dye (FAM)-labeled miRNA-21). The changes in the micromotor speeds after the hybridization process were also evaluated. W5O14/PEDOT-Pt micromotors presented better sensor properties compared to the W5O14-Pt micromotors. A good linearity for miRNA-21 concentration between 0.1 nM and 100 nM was obtained for these micromotors based on their fluorescence intensities. The detection limit was found as 0.028 nM for W5O14/PEDOT-Pt micromotors (n = 3). Thus, sensor and motor characteristics of the W5O14-Pt micromotors were improved by RF plasma enhanced PEDOT coatings. The new catalytic W5O14 based micromotors demonstrated here had great potential for the development of sensitive and simple sensing platforms for detection of miRNA-21.

Quantitative measurement of charge accumulation along a quasi-one-dimensional W5O14 nanowire during electron field emission.

We use an electron holographic method to determine the charge distribution along a quasi-one-dimensional W5O14 nanowire during in situ field emission in a transmission electron microscope. The results show that the continuous charge distribution along the nanowire is not linear, but that there is an additional accumulation of charge at its apex. An analytical expression for this additional contribution to the charge distribution is proposed and its effect on the field enhancement factor and emission current is discussed.

Enhanced carrier transport by transition metal doping in WS2 field effect transistors.

High contact resistance is one of the primary concerns for electronic device applications of two-dimensional (2D) layered semiconductors. Here, we explore the enhanced carrier transport through metal-semiconductor interfaces in WS2 field effect transistors (FETs) by introducing a typical transition metal, Cu, with two different doping strategies: (i) a "generalized" Cu doping by using randomly distributed Cu atoms along the channel and (ii) a "localized" Cu doping by adapting an ultrathin Cu layer at the metal-semiconductor interface. Compared to the pristine WS2 FETs, both the generalized Cu atomic dopant and localized Cu contact decoration can provide a Schottky-to-Ohmic contact transition owing to the reduced contact resistances by 1-3 orders of magnitude, and consequently elevate electron mobilities by 5-7 times. Our work demonstrates that the introduction of transition metal can be an efficient and reliable technique to enhance the carrier transport and device performance in 2D TMD FETs.