Biosynthesis of Zinc Oxide Nanoparticles on l-Carnosine Biofunctionalized Polyacrylonitrile Nanofibers; a Biomimetic Wound Healing Material.

Multifunctional biohybrid nanofibers (NFs) that can simultaneously drive various cellular activities and confer antibacterial properties are considered desirable in producing advanced wound healing materials. In this study, a bionanohybrid formulation was processed as a NF wound dressing to stimulate the adhesion and proliferation of fibroblast and endothelial cells that play a major role in wound healing. Polyacrylonitrile (PAN) electrospun NFs were hydrolyzed using NaOH and biofunctionalized with l-carnosine (CAR), a dipeptide which could later biosynthesize zinc oxide (ZnO) nanoparticles (NPs) on the NFs surface. The morphological study verified that ZnO NPs are uniformly distributed on the surface of CAR/PAN NFs. Through EDX and XRD analysis, it was validated that the NPs are composed of ZnO and/or ZnO/Zn(OH)2. The presence of CAR and ZnO NPs brought about a superhydrophilicity effect and notably raised the elastic modulus and tensile strength of Zn-CAR/PAN NFs. While CAR ligands were shown to improve the viability of fibroblast (L929) and endothelial (HUVEC) cells, ZnO NPs lowered the positive impact of CAR, most likely due to their repulsive negative surface charge. A scratch assay verified that CAR/PAN NFs and Zn-CAR/PAN NFs aided HUVEC migration more than PAN NFs. Also, an antibacterial assay implied that CAR/PAN NFs and Zn-CAR/PAN NFs are significantly more effective in inhibiting Staphylococcus aureus (S. aureus) than neat PAN NFs are (1000 and 500%, respectively). Taken together, compared to the neat PAN NFs, CAR/PAN NFs with and without the biosynthesized ZnO NPs can support the cellular activities of relevance for wound healing and inactivate bacteria.

Antiviral polysaccharide and antiviral peptide delivering nanomaterials for prevention and treatment of SARS-CoV-2 caused COVID-19 and other viral diseases.

Antiviral peptides and antiviral polysaccharides can play a major role in the prevention and treatment of emerging viral health problems. These antiviral compounds are biocompatible, environmentally friendly, non-toxic, and cost-effective, yet are poorly water soluble and vulnerable to enzymatic (protease) degradation within the aggressive intercellular microenvironment. Therefore, they should be properly protected and delivered to viruses and host cells by the well-designed nanocarriers that mimic viruses in terms of size, morphology, and smart function. This literature review is meant to introduce the latest advances (mainly within the past five years) in antiviral nano-assemblies comprising antiviral peptides or antiviral polysaccharides. To the best of our knowledge, there is no similar study in the literature that has solely and sufficiently investigated such antiviral nanomaterials partially or totally derived from nature. The rational classification of microorganism-, plant-, and animal-derived antiviral polysaccharide and antiviral peptide delivering nanomaterials and exploration of their relevant applications will clarify the promising capacity of these state-of-the-art materials for a number of technologies developed to inactivate viruses.

Could Nanotheranostics be the Answer to the Coronavirus Crisis?

The COVID-19 pandemic is expanding worldwide. This pandemic associated with COVID-19 placed the spotlight on how bacterial (e.g., methicillin-resistant Staphylococcus aureus) co-infections may impact responses to coronavirus. In this review the ways in which nanoparticles can contain and rapidly diagnose COVID-19 under the umbrella of nanotheranostics (i.e., smart, single agents combining nanodiagnostics and nanotherapeutics) are elaborated. The present work provides new insights into the promising incorporation of antiviral nanotheranostics into nanostructured materials, including electrospun fibers with tailored pore sizes and hydrophobicity, namely "superhydrophobic self-disinfecting electrospun facemasks/fabrics (SSEF)." SSEFs are proposed as smart alternatives to address the drawbacks of N95 respirators. The challenges of coronavirus containment are underscored, literature is reviewed, and "top-five suggestions" for containing COVID-19 are offered, including: i) preventive appraisals-avoiding needless hospital admission and practicing frequent hand washing (from 20 to 60 s). ii) Diagnostics-highly recommending nanodiagnostics, detecting COVID-19 within 10 min. iii) Therapeutics-expanding nanotherapeutics to treat COVID-19 and bacterial co-infections after safety assessments and clinical trials. iv) Multipronged and multinational, including China, collaborative appraisals. v) Humanitarian compassion to traverse this pandemic in a united way.

COVID-19 Pandemic: What about the Safety of Anti-Coronavirus Nanoparticles?

Every day, new information is presented with respect to how to best combat the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). This manuscript sheds light on such recent findings, including new co-factors (i.e., neuropilin-1) and routes (i.e., olfactory transmucosal) allowing cell entry of SARS-CoV-2 and induction of neurological symptoms, as well as the new SARS-CoV-2 variants. We highlight the SARS-CoV-2 human-animal interfaces and elaborate containment strategies using the same vaccination (i.e., nanoparticle "NP" formulations of the BNT162b2 and mRNA-1273 vaccines) for humans, minks, raccoon dogs, cats, and zoo animals. We investigate the toxicity issues of anti-CoV NPs (i.e., plasmonic NPs and quantum dots) on different levels. Namely, nano-bio interfaces (i.e., protein corona), in vitro (i.e., lung cells) and in vivo (i.e., zebrafish embryos) assessments, and impacts on humans are discussed in a narrative supported by original figures. Ultimately, we express our skeptical opinion on the comprehensive administration of such antiviral nanotheranostics, even when integrated into facemasks, because of their reported toxicities and the different NP parameters (e.g., size, shape, surface charge, and purity and chemical composition of NPs) that govern their end toxicity. We believe that more toxicity studies should be performed and be presented, clarifying the odds of the safe administration of nanotoxocological solutions and the relief of a worried public.

Nanotheranostics: A Possible Solution for Drug-Resistant Staphylococcus aureus and their Biofilms?

Staphylococcus aureus is a notorious pathogen that colonizes implants (orthopedic and breast implants) and wounds with a vicious resistance to antibiotic therapy. Methicillin-resistant S. aureus (MRSA) is a catastrophe mainly restricted to hospitals and emerged to community reservoirs, acquiring resistance and forming biofilms. Treating biofilms is problematic except via implant removal or wound debridement. Nanoparticles (NPs) and nanofibers could combat superbugs and biofilms and rapidly diagnose MRSA. Nanotheranostics combine diagnostics and therapeutics into a single agent. This comprehensive review is interpretative, utilizing mainly recent literature (since 2016) besides the older remarkable studies sourced via Google Scholar and PubMed. We unravel the molecular S. aureus resistance and complex biofilm. The diagnostic properties and detailed antibacterial and antibiofilm NP mechanisms are elucidated in exciting stories. We highlight the challenges of bacterial infections nanotheranostics. Finally, we discuss the literature and provide "three action appraisals". (i) The first appraisal consists of preventive actions (two wings), avoiding unnecessary hospital visits, hand hygiene, and legislations against over-the-counter antibiotics as the general preventive wing. Our second recommended preventive wing includes preventing the adverse side effects of the NPs from resistance and toxicity by establishing standard testing procedures. These standard procedures should provide breakpoints of bacteria's susceptibility to NPs and a thorough toxicological examination of every single batch of synthesized NPs. (ii) The second appraisal includes theranostic actions, using nanotheranostics to diagnose and treat MRSA, such as what we call "multifunctional theranostic nanofibers. (iii) The third action appraisal consists of collaborative actions.

Bovine Serum Albumin (BSA)/polyacrylonitrile (PAN) biohybrid nanofibers coated with a biomineralized calcium deficient hydroxyapatite (HA) shell for wound dressing.

Here, for the first time, a nanofibrous (NF) wound dressing comprising biomineralized polyacrylonitrile (PAN) nanofibers is developed. In contrast to the majority of the currently available nanofibrous wound dressings that are based on natural polymers, PAN is a synthetic, industrial polymer, which has been rarely considered for this purpose. PAN NFs are first hydrolyzed to allow for tethering of biofunctional agents (here Bovine Serum Albumin (BSA)). Later, the biofunctionlized PAN NFs are biomineralized by immersion in simulated body fluid (SBF). As a result, core-shell, calcium deficient hydroxyapatite (HA)/BSA/PAN nanofibers form, that are mechanically stronger (elastic modulus; 8.5 vs. 6 MPa) compared to the untreated PAN NFs. The biomineralized PAN NFs showed promising bioactivity as reflected in the cell biology tests with fibroblast and keratinocyte cells. Hs68 fibroblasts and HaCat keratinocytes were found to be more viable in the presence of the biomineralized NFs than when they were co-cultured with the neat PAN NFs. Such mechanical and biological characteristics of the biomineralized PAN NFs are favorable for wound dressing applications.

Size-Tailored Physicochemical Properties of Monodisperse Polystyrene Nanoparticles and the Nanocomposites Made Thereof.

The latex monodisperse polystyrene (PS) colloids are important for different advanced applications (e.g. in coating, biotechnology etc.). However, the size dependency of their structural properties that impacts the characteristics of the nanocomposites composed thereof is largely unknown. Here, monodisperse PS nanoparticles (MPNPs) are synthesized via emulsion polymerization in five sizes (50, 150, 300, 350, and 450 nm). The size of the PS MPNPs is tailored by controlling the reaction time, temperature, and amount of surfactant and initiator. The correlation between the particle size and structural properties of the PS MPNPs is established by different thermomechanical and optical characterizations. The smaller particles (50 and 150 nm) show a lower glass transition (Tg) and thermal decomposition temperature and a lower Raman peak intensity. Yet, they trigger a higher IR absorption, thanks to a larger surface area. When incorporated in a polyvinyl alcohol (PVA) matrix, the smaller particles impart the resulting nanocomposite a higher tensile strength, and elastic and storage moduli. Whereas, they decline the elongation and loss factor. The very few examples of the MPNPs incorporated polymeric nanocomposites have been unstudied from this perspective. Thus, these tangible knowledge can profit scalable production of this kind of nanocomposite materials for different applications in a cost/energy efficient manner.

Ups and Downs of Water Photodecolorization by Nanocomposite Polymer Nanofibers.

Given the exponentially expanding water pollution causing water scarcity, there is an urgent need for operative nanotechnological systems that can purify water, with insignificant energy consumption, and rapidly. Here, we introduce a nanocomposite system based on TiO2 nanoparticles (NPs) and PES nanofibers (NFs) that can adsorb and then photodecompose organic water pollutants such as dye molecules. We evaluate pros and cons of this system with respect to its purification efficiency and structural properties that can be impacted by the photocatalytic activity of the nanofillers. While the material is superhydrophilic and able to remove 95% methylene blue (MB) from water via adsorption/photodecomposition, its thermomechanical properties decline upon UV irradiation. However, these properties still remain at the level of the neat NFs. The removal behavior is modeled by the first- and second-order kinetic models from the kinetic point of view. The nanocomposite NFs' removal behavior complies much better with the second-order kinetic model. Overall, such feedbacks implied that the nanocomposite can be effectively applied for water treatment and the structural properties are still as reliable as those of the neat counterpart.

A Ni-loaded, metal-organic framework-graphene composite as a precursor for in situ electrochemical deposition of a highly active and durable water oxidation nanocatalyst.

A novel approach to construct a highly active and durable Ni(OH)2 nanoparticle/graphene hybrid electrocatalyst for the oxygen-evolution reaction (OER) is reported. This approach utilized the Ni-loaded, graphene-supported, Zr-carboxylate metal-organic framework (UiO-66-NH2-Ni@G) as a sacrificial pre-catalyst to engender the true catalyst in an electrochemical surface restructuring process. This has resulted in an exceptionally active (η10 = 0.38 V vs. RHE) and highly durable OER catalyst, and can potentially be employed as a viable facile alternative to the commonly utilized pyrolysis of MOFs, to access heterogenous catalysts for demanding electrochemically-promoted reactions.

Plasmonic Metaparticles on a Blackbody Create Vivid Reflective Colors for Naked-Eye Environmental and Clinical Biodetection.

Plasmonic dipoles are famous for their strong absorptivity rather than their reflectivity. Here, the as-yet unknown specular reflection and the Brewster effect of ultrafine plasmonic dipoles, metaparticles, are introduced and exploited as the basis of new design rules for advanced applications. A configuration of "Plasmonic metaparticles on a blackbody" is demonstrated and utilized for the design of a tailored perfect-colored absorber and for visual detection of environmental dielectrics that is not readily done by extinction plasmonics. Moreover, the Plasmonic Brewster Wavelength (PBW) effect is introduced as a new platform for the naked-eye and bulk biodetection of analytes. The technique operates based on slight changes of molecular polarizability which is not detectable via conventional plasmon resonance techniques. As a specific highlight, the clinical applicability of the PBW method is demonstrated while addressing the transduction plasmonic techniques' challenge in detection of bulk refractive index changes of the healthy and diseased human serum exosomes. Finally, the sputtering-based fabrication method used here is simple, inexpensive, and scalable, and does not require the sophisticated patterning approach of lithography or precise alignment of light coupling for the biodetection.

The Electrospun Ceramic Hollow Nanofibers.

Hollow nanofibers are largely gaining interest from the scientific community for diverse applications in the fields of sensing, energy, health, and environment. The main reasons are: their extensive surface area that increases the possibilities of engineering, their larger accessible active area, their porosity, and their sensitivity. In particular, semiconductor ceramic hollow nanofibers show greater space charge modulation depth, higher electronic transport properties, and shorter ion or electron diffusion length (e.g., for an enhanced charging-discharging rate). In this review, we discuss and introduce the latest developments of ceramic hollow nanofiber materials in terms of synthesis approaches. Particularly, electrospinning derivatives will be highlighted. The electrospun ceramic hollow nanofibers will be reviewed with respect to their most widely studied components, i.e., metal oxides. These nanostructures have been mainly suggested for energy and environmental remediation. Despite the various advantages of such one dimensional (1D) nanostructures, their fabrication strategies need to be improved to increase their practical use. The domain of nanofabrication is still advancing, and its predictable shortcomings and bottlenecks must be identified and addressed. Inconsistency of the hollow nanostructure with regard to their composition and dimensions could be one of such challenges. Moreover, their poor scalability hinders their wide applicability for commercialization and industrial use.

Underwater Leidenfrost nanochemistry for creation of size-tailored zinc peroxide cancer nanotherapeutics.

The dynamic underwater chemistry seen in nature is inspiring for the next generation of eco-friendly nanochemistry. In this context, green synthesis of size-tailored nanoparticles in a facile and scalable manner via a dynamic process is an interesting challenge. Simulating the volcano-induced dynamic chemistry of the deep ocean, here we demonstrate the Leidenfrost dynamic chemistry occurring in an underwater overheated confined zone as a new tool for customized creation of nanoclusters of zinc peroxide. The hydrodynamic nature of the phenomenon ensures eruption of the nanoclusters towards a much colder region, giving rise to growth of monodisperse, size-tailored nanoclusters. Such nanoparticles are investigated in terms of their cytotoxicity on suspension and adherent cells to prove their applicability as cancer nanotherapeutics. Our research can pave the way for employment of the dynamic green nanochemistry in facile, scalable fabrication of size-tailored nanoparticles for biomedical applications.

A shape tailored gold-conductive polymer nanocomposite as a transparent electrode with extraordinary insensitivity to volatile organic compounds (VOCs).

In this study, the transparent conducting polymer of poly (3,4-ethylenendioxythiophene): poly(styrene sulphonate) (PEDOT:PSS) was nanohybridized via inclusion of gold nanofillers including nanospheres (NSs) and nanorods (NRs). Such nanocomposite thin films offer not only more optimum conductivity than the pristine polymer but also excellent resistivity against volatile organic compounds (VOCs). Interestingly, such amazing properties are achieved in the diluted regimes of the nanofillers and depend on the characteristics of the interfacial region of the polymer and nanofillers, i.e. the aspect ratio of the latter component. Accordingly, a shape dependent response is made that is more desirable in case of using the Au nanorods with a much larger aspect ratio than their nanosphere counterparts. This transparent nanocomposite thin film with an optimized conductivity and very low sensitivity to organic gases is undoubtedly a promising candidate material for the touch screen panel production industry. Considering PEDOT as a known material for integrated electrodes in energy saving applications, we believe that our strategy might be an important progress in the field.

Antireflective Coatings: Conventional Stacking Layers and Ultrathin Plasmonic Metasurfaces, A Mini-Review.

Reduction of unwanted light reflection from a surface of a substance is very essential for improvement of the performance of optical and photonic devices. Antireflective coatings (ARCs) made of single or stacking layers of dielectrics, nano/microstructures or a mixture of both are the conventional design geometry for suppression of reflection. Recent progress in theoretical nanophotonics and nanofabrication has enabled more flexibility in design and fabrication of miniaturized coatings which has in turn advanced the field of ARCs considerably. In particular, the emergence of plasmonic and metasurfaces allows for the realization of broadband and angular-insensitive ARC coatings at an order of magnitude thinner than the operational wavelengths. In this review, a short overview of the development of ARCs, with particular attention paid to the state-of-the-art plasmonic- and metasurface-based antireflective surfaces, is presented.

Broadband Anti-Reflective Coating Based on Plasmonic Nanocomposite.

We report on the fabrication, the characterization, and the optical simulation of a gold-silica nanocomposite and present its integration into a broadband anti-reflective coating (ARC) for a silicon substrate. The two-layer ARC consists of a nanocomposite (randomly distributed gold cluster in a silica matrix) and a pure silica film. We capitalize on the large refractive index of the composite to impose an abrupt phase change at the interface of the coating to diminish the light reflection from the substrate through the ultrathin nanocoating. The average reflectivity of the silicon can be reduced by such a coating to less than 0.1% in the entire visible spectrum. We experimentally and numerically prove that percolated nanocomposites with an overall thickness of 20 nm can provide anti-reflectivity up to near infrared (NIR). The ARC bandwidth can be shifted more than 500 nm and broadened to cover even the NIR wavelength by changing the volume filling fraction of the gold clusters. The angular sensitivity of thin ultrathin antireflective coating is negligible up to 60°. The present ARC could find applications in thermo-photovoltaics and bolometers.

A Novel Nanohybrid Nanofibrous Adsorbent for Water Purification from Dye Pollutants.

In this study, we devised a novel nanofibrous adsorbent made of polyethersulfone (PES) for removal of methylene blue (MB) dye pollutant from water. The polymer shows a low isoelectric point thus at elevated pHs and, being nanofibrous, can offer a huge highly hydroxylated surface area for adsorption of cationic MB molecules. As an extra challenge, to augment the adsorbent's properties in terms of adsorption capacity in neutral and acidic conditions and thermal stability, vanadium pentoxide (V2O5) nanoparticles were added to the nanofibers. Adsorption data were analyzed according to the Freundlich adsorption model. The thermodynamic parameters verified that only at basic pH is the adsorption spontaneous and in general the process is entropy-driven and endothermic. The kinetics of the adsorption process was evaluated by the pseudo-first- and pseudo-second-order models. The latter model exhibited the highest correlation with data. In sum, the adsorbent showed a promising potential for dye removal from industrial dyeing wastewater systems, especially when envisaging their alkaline and hot conditions.

Light-Controlled Conductance Switching in Azobenzene-Containing MWCNT-Polymer Nanocomposites.

We report on reversible light-controlled conductance switching in devices consisting of multiwalled carbon nanotube (MWCNT)-polymer nanocomposites blended with azobenzene molecules and photoisomerization of the latter. Both the azobenzene molecules and MWCNT, which are functionalized with carboxyl groups (MWCNT-COOH), are embedded independently in a poly(methyl methacrylate) matrix, and thin films are prepared by using a simple spin-coating technique. We demonstrate the feasibility of the present concept with a photocurrent switching amplitude of almost 10%.

Biomimetic transferable surface for a real time control over wettability and photoerasable writing with water drop lens.

We demonstrate a transferable device that can turn wettability of surfaces to sticky or slippy, as per requirement. It is composed of polymeric yarn with a fibrous structure, which can be lifted and placed on any surface to render it the unique wettability properties. We introduce Polyvinylidenefluoride (PVDF) random fiber as biomimetic rose petal surface. When it is decorated with PVDF nanofibers yarns, the random mesh transform from rose petal sticky state into grass leaf slippy state. When it is placed on sticky, hydrophilic metal coin, it converts the surface of the coin to super hydrophobic. Adjustments in the yarn system, like interyarn spacing, can be done in real time to influence its wettability, which is a unique feature. Next, we load the polymer with a photochromic compound for chemical restructuring. It affects the sliding angle of water drop and makes the fibers optically active. We also demonstrate a "water droplets lens" concept that enables erasable writing on photochromic rose petal sticky fibrous surface. The droplet on a highly hydrophobic surface acts as a ball lens to concentrate light onto a hot spot; thereby we demonstrate UV light writing with water lenses and visible light erasing.

Toxicity of functional nano-micro zinc oxide tetrapods: impact of cell culture conditions, cellular age and material properties.

With increasing production and applications of nanostructured zinc oxide, e.g., for biomedical and consumer products, the question of safety is getting more and more important. Different morphologies of zinc oxide structures have been synthesized and accordingly investigated. In this study, we have particularly focused on nano-micro ZnO tetrapods (ZnO-T), because their large scale fabrication has been made possible by a newly introduced flame transport synthesis approach which will probably lead to several new applications. Moreover, ZnO-T provide a completely different morphology then classical spherical ZnO nanoparticles. To get a better understanding of parameters that affect the interactions between ZnO-T and mammalian cells, and thus their biocompatibility, we have examined the impact of cell culture conditions as well as of material properties on cytotoxicity. Our results demonstrate that the cell density of fibroblasts in culture along with their age, i.e., the number of preceding cell divisions, strongly affect the cytotoxic potency of ZnO-T. Concerning the material properties, the toxic potency of ZnO-T is found to be significantly lower than that of spherical ZnO nanoparticles. Furthermore, the morphology of the ZnO-T influenced cellular toxicity in contrast to surface charges modified by UV illumination or O2 treatment and to the material age. Finally, we have observed that direct contact between tetrapods and cells increases their toxicity compared to transwell culture models which allow only an indirect effect via released zinc ions. The results reveal several parameters that can be of importance for the assessment of ZnO-T toxicity in cell cultures and for particle development.

Thermo-Plasmonics for Localized Graphitization and Welding of Polymeric Nanofibers.

There is a growing interest in modulating the temperature under the illumination of light. As a heat source, metal nanoparticles (NPs) have played an important role to pave the way for a new branch of plasmonics, i.e., thermo-plasmonics. While thermo-plasmonics have been well established in photo-thermal therapy, it has received comparatively less attention in materials science and chemistry. Here, we demonstrate the first proof of concept experiment of local chemistry and graphitization of metalized polymeric nanofibers through thermo-plasmonic effect. In particular, by tuning the plasmonic absorption of the nanohybrid through a change in the thickness of the deposited silver film on the fibers, the thermo-plasmonic effect can be adjusted in such a way that high enough temperature is generated enabling local welding and graphitization of the polymeric nanofibers.