Functionalized Photocatalytic Nanocoatings for Inactivating COVID-19 Virus Residing on Surfaces of Public and Healthcare Facilities

The current COVID-19 pandemic, caused by the Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2) has affected the large population across the globe by serious respiratory illness and death. Since the medicine for this new disease is yet to discover, the treatment op-tions against pandemic COVID-19 are very limited and unsatisfactory. Further, the hospitals, wherethe COVID-19 patients are admitted for treatment, are the major source of the spread of this virus, as it survives on the surfaces of inanimate objects for days. Therefore, hospitals have become hotspots for SARS-CoV-2 infection. The non-availability of quality personal protective equipment (PPE) and exposure to severe COVID patients have been major factors for the infection in millions of healthcare workers. However, developing an effective medicine has remained challenging due to its unpredictable mutation rate. Here, this article describes functionalized photocatalytic nanocoat-ings to destroy the COVID-19 virus, which can be applied on the surface of inanimate objects, such as paper, cloth, glass, wood, ceramic, metallic, and polymeric surfaces. With the supporting experimental results, various possible ways of killing the virus and its relevant mechanism are dis-cussed. This article provides new insights for developing nano solutions to address this COVID-19 issue.Copyright © 2021 Bentham Science Publishers.

Inactivation of SARS-CoV-2 variants by nitrogen-doped titanium dioxide loaded with metals as visible-light photocatalysts.

PURPOSE: We examined the inactivation of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) by a nitrogen-doped titanium dioxide (N-TiO2) visible-light photocatalyst that was activated via light irradiation in the natural environment and was safe for human use as a coating material. METHODS: The photocatalytic activity of glass slides coated with three types of N-TiO2 without metal or loaded with copper or silver and copper was investigated by measuring acetaldehyde degradation. The titer levels of infectious SARS-CoV-2 were measured using cell culture after exposing photocatalytically active coated glass slides to visible light for up to 60 min. RESULTS: N-TiO2 photoirradiation inactivated the SARS-CoV-2 Wuhan strain and this effect was enhanced by copper loading and further by the addition of silver. Hence, visible-light irradiation using silver and copper-loaded N-TiO2 inactivated the Delta, Omicron, and Wuhan strains. CONCLUSION: N-TiO2 could be used to inactivate SARS-CoV-2 variants, including emerging variants, in the environment.

Synthesis and application of titanium dioxide photocatalysis for energy, decontamination and viral disinfection: a review.

Global pollution is calling for advanced methods to remove contaminants from water and wastewater, such as TiO2-assisted photocatalysis.  The environmental applications of titanium dioxide have started after the initial TiO2 application for water splitting by Fujishima and Honda in 1972. TiO2 is now used for self-cleaning surfaces, air and water purification systems, microbial inactivation and selective organic conversion. The synthesis of titanium dioxide nanomaterials with high photocatalytic activity is actually a major challenge. Here we review titanium dioxide photocatalysis with focus on mechanims, synthesis, and applications. Synthetic methods include sol-gel, sonochemical, microwave, oxidation, deposition, hydro/solvothermal, and biological techniques. Applications comprise the production of energy, petroleum recovery, and the removal of microplastics, pharmaceuticals, metals, dyes, pesticides, and of viruses such as the severe acute respiratory syndrome coronavirus 2.

Development of a high-speed bioaerosol elimination system for treatment of indoor air.

We developed a high-speed filterless airflow multistage photocatalytic elbow aerosol removal system for the treatment of bioaerosols such as severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). Human-generated bioaerosols that diffuse into indoor spaces are 1-10 µm in size, and their selective and rapid treatment can reduce the risk of SARS-CoV-2 infection. A high-speed airflow is necessary to treat large volumes of indoor air over a short period. The proposed system can be used to eliminate viruses in aerosols by forcibly depositing aerosols in a high-speed airflow onto a photocatalyst placed inside the system through inertial force and turbulent diffusion. Because the main component of the deposited bioaerosol is water, it evaporates after colliding with the photocatalyst, and the nonvolatile virus remains on the photocatalytic channel wall. The residual virus on the photocatalytic channel wall is mineralized via photocatalytic oxidation with UVA-LED irradiation in the channel. When this system was operated in a 4.5 m3 aerosol chamber, over 99.8% aerosols in the size range of 1-10 µm were removed within 15 min. The system continued delivering such performance with the continuous introduction of aerosols. Because this system exhibits excellent aerosol removal ability at a flow velocity of 5 m/s or higher, it is more suitable than other reactive air purification systems for treating large-volume spaces.

THE USE OF NANO-SIZED NATURAL SILICA TO VISIBLE LIGHT PHOTOCATALYST AS A MASK COATING FOR INACTIVATION OF SARS-CoV-2: A REVIEW

Research on antiviral agents to inactivate SARS-CoV-2 is still a concern of researchers. Many innovations have been made, one of which is coating the surface of cloth masks using photocatalyst materials. Visible light photocatalysts have been shown to have antimicrobial properties in sunlight. The study of material modification becomes important to select and optimize the supporting materials used. We observed that modifications with nano-silica particles (SiO2) have good transmission capabilities and can be produced from natural sources (biological and non-biological). Therefore, this utilization is carried out to apply the principle of zero waste, namely renewable natural sources as a source/precursor of nano-silica. In this study, we focus on renewable research related to the use of natural nano-silica as supporting material for visible light photocatalysts will be explored to be coated on polyester mask fabrics as an effort to inactivate SARS-CoV-2 on the surface of the mask. © 2022, Rasayan Journal of Chemistry, c/o Dr. Pratima Sharma. All rights reserved.

Rutile-TiO2/PtO2 Glass Coatings Disinfects Aquatic Legionella pneumophila via Morphology Change and Endotoxin Degradation under LED Irradiation

Legionella pneumophila (L. pneumophila) is the causative agent of Legionnaires’ disease and Pontiac fever, collectively known as legionellosis. L. pneumophila infection occurs through inhalation of contaminated aerosols from water systems in workplaces and institutions. The development of disinfectants that can eliminate L. pneumophila in such water systems without evacuating people is needed to prevent the spread of L. pneumophila. Photocatalysts are attractive disinfectants that do not harm human health. In particular, the TiO2 photocatalyst kills L. pneumophila under various conditions, but its mode of action is unknown. Here, we confirmed the high performance of TiO2 photocatalyst containing PtO2 via the degradation of methylene blue (half-value period: 19.2 min) and bactericidal activity against Escherichia coli (half-value period: 15.1 min) in water. Using transmission electron microscopy, we demonstrate that the disinfection of L. pneumophila (half-value period: 6.7 min) by TiO2 photocatalyst in water is accompanied by remarkable cellular membrane and internal damage to L. pneumophila. Assays with limulus amebocyte lysate and silver staining showed the release of endotoxin from L. pneumophila due to membrane damage and photocatalytic degradation of this endotoxin. This is the first study to demonstrate the disinfection mechanisms of TiO2 photocatalyst, namely, via morphological changes and membrane damage of L. pneumophila. Our results suggest that TiO2 photocatalyst might be effective in controlling the spread of L. pneumophila.

Synthesis of Silver Nanoparticles-Modified Graphitic Carbon Nitride Nanosheets for Highly Efficient Photocatalytic Hydrogen Peroxide Evolution.

As a promising metal-free photocatalyst, graphitic carbon nitride (g-C3N4) is still limited by insufficient visible light absorption and rapid recombination of photogenerated carriers, resulting in low photocatalytic activity. Here, we adjusted the microstructure of the pristine bulk-g-C3N4 (PCN) and further loaded silver (Ag) nanoparticles. Abundant Ag nanoparticles were grown on the thin-layer g-C3N4 nanosheets (CNNS), and the Ag nanoparticles decorated g-C3N4 nanosheets (Ag@CNNS) were successfully synthesized. The thin-layer nanosheet-like structure was not only beneficial for the loading of Ag nanoparticles but also for the adsorption and activation of reactants via exposing more active sites. Moreover, the surface plasmon resonance (SPR) effect induced by Ag nanoparticles enhanced the absorption of visible light by narrowing the band gap of the substrate. Meanwhile, the composite band structure effectively promoted the separation and transfer of carriers. Benefiting from these merits, the Ag@CNNS reached a superior hydrogen peroxide (H2O2) yield of 120.53 µmol/g/h under visible light irradiation in pure water (about 8.0 times higher than that of PCN), significantly surpassing most previous reports. The design method of manipulating the microstructure of the catalyst combined with the modification of metal nanoparticles provides a new idea for the rational development and application of efficient photocatalysts.

TiO2/core-shell structured carbon support materials derived from hydrothermal carbonization of waste masks biomass: a green photocatalyst

Surgical masks have become mandatory to protect against the COVID-19 epidemic. For this reason, the amount of waste masks has also reached severe dimensions. Turning these waste masks into functional materials (MC) in a green synthesis method is critical. In this study, carbon material from waste masks was synthesized by the hydrothermal carbonization method (HTC) and was used to increase the photocatalytic activity of TiO2. In addition, TiO2 nanoparticles were successfully synthesized by the solvothermal method. Thermo-gravimetric analysis (TGA), scanning-electron microscope(SEM), x-ray diffraction (XRD), Fourier transform- infrared spectroscopy (FT-IR), energy dispersive x-ray(EDX), transmission-electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS), electrochemical-impedance spectroscopy (EIS) and Brunauer–Emmett–Teller (BET) analyzes were performed to illuminate the photocatalytic properties of the MC-TiO2 photocatalyst. In this sense, the functionality of the shell-core skeleton-based new generation carbon material was also investigated. The photocatalytic activity of the green type of photocatalyst was detected by comparing methylene blue (MB) and phenol photodegradation rates. In photocatalytic degradation experiments, both UV-A effect and visible light effect were examined. New type of photocatalyst an exhibited excellent photocatalytic effect. Superior photodegradation capacity may be referred as to the core-shell composition and functional groups of the effective carbon support material synthesized by the HTC method. In particular, the photocatalytic effect of the novel carbon support material is discussed in-depth with the proposed mechanism. With the present study, we aimed to bring a green perspective to the photocatalytic studies in the literature.

WO3 Photocatalyst Containing Copper Inactivates SARS-CoV-2 Pango Lineage A and Omicron BA.2 Variant in Visible Light and in Darkness.

Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) is the causative agent of coronavirus disease 2019, which has been a global pandemic. Since SARS-CoV-2 is transmitted through contaminated surfaces and aerosols, environmental disinfection is important to block the spread of the virus. Photocatalysts are attractive tools for virus inactivation and are widely used as air purifiers and coating materials. However, photocatalysts are inactive in the dark, and some of them need to be excited with light of a specific wavelength. Therefore, photocatalysts that can effectively inactivate SARS-CoV-2 in indoor environments are needed. Here, we show that a WO3 photocatalyst containing copper inactivated the SARS-CoV-2 WK-521 strain (Pango lineage A) upon irradiation with white light in a time- and concentration-dependent manner. Additionally, this photocatalyst also inactivated SARS-CoV-2 in dark conditions due to the antiviral effect of copper. Furthermore, this photocatalyst inactivated not only the WK-521 strain but also the Omicron variant BA.2. These results indicate that the WO3 photocatalyst containing copper can inactivate indoor SARS-CoV-2 regardless of the variant, in visible light or darkness, making it an effective tool for controlling the spread of SARS-CoV-2.

CHALLENGES OF TIO2-COMPOSITE, AS A VISIBLE ACTIVE PHOTOCATALYST MATERIAL FOR SARS-COV-2 ANTIVIRAL COMPARED WITH THE OTHER VIRUSES

The efforts in dealing with COVID-19 in various aspects are continuously being carried out, such as the photocatalytic process. Interestingly, TiO2 plays an important role as an environmentally friendly photocatalyst with a visible and UV absorption range. The increase in the antiviral performance of this compound is further maximized by formulating TiO2-based composites and doping it to reduce the bandgap. This review aims to determine the challenges of TiO2-based composite as a visible active photocatalyst material for SARS-CoV-2 antiviral. It presents a discussion of the photocatalytic function of TiO2, by comparing the secondary data obtained from viruses that have been successfully degraded by the SARS-CoV-2. The literature search led to the analysis of the photocatalyst quality, structure, composition, and the degraded viruses. This comparison was based on the photocatalyst's general constituents, such as protein and RNA. The virus morphology as observed in the secondary data was successfully destroyed by hydroxyl radicals resulting from the photocatalytic processes. It was observed that TiO2 photocatalyst generated ROS, capable of inactivating various viruses, therefore, it has the potential in fighting against the SARS-CoV-2. Moreover, further research is needed in photocatalyst design, its role, and the overall mechanism of virus inactivation. © 2022 Sociedade Brasileira de Quimica. All rights reserved.

Current perspective in metal oxide based photocatalysts for virus disinfection: A review.

Nanotechnology holds huge potential for the prevention of various viral outbreaks that have increased at a disquieting rate over the past decades. Metal oxide nanomaterials with oxidative capability are the effective materials that provide platforms as well as tools for the well understanding of the mechanism, its detection, and treatment of various viral diseases like measles, influenza, herpes, ebola, current COVID-19 etc. In this inclusive review, we survey various previous research articles on different notable photoactive transition metal oxides that possess enough potential to act as antiviral agents for the deactivation of harmful viruses. We investigated and highlighted the plausible photocatalytic oxidative mechanism of photoactive transition metal oxides in degrading viral coatings, genomic RNA using suitable free radical generation. The key finding of the present review article including the discovery of a vision on the suitable photocatalytic transition metal oxides that have been proven to be excellent against harmful viruses and consequently combatting deadly CoV-2 in the environment. This review intends to provide conclusive remarks and a realistic outlook on other advanced photocatalytic metal oxides as a potential solution in battling other similar upcoming pandemics.

Detoxifying SARS-CoV-2 antiviral drugs from model and real wastewaters by industrial waste-derived multiphase photocatalysts.

The use of antiviral drugs has surged as a result of the COVID-19 pandemic, resulting in higher concentrations of these pharmaceuticals in wastewater. The degradation efficiency of antiviral drugs in wastewater treatment plants has been reported to be too low due to their hydrophilic nature, and an additional procedure is usually necessary to degrade them completely. Photocatalysis is regarded as one of the most effective processes to degrade antiviral drugs. The present study aims at synthesizing multiphase photocatalysts by a simple calcination of industrial waste from ammonium molybdate production (WU photocatalysts) and its combination with WO3 (WW photocatalysts). The X-ray diffraction (XRD) results confirm that the presence of multiple crystalline phases in the synthesized photocatalysts. UV-Vis diffuse reflectance spectra reveal that the synthesized multiphase photocatalysts absorb visible light up to 620 nm. Effects of calcination temperature of industrial waste (550-950 °C) and WO3 content (0-100%) on photocatalytic activity of multiphase photocatalysts (WU and WW) for efficient removal of SARS-CoV-2 antiviral drugs (lopinavir and ritonavir) in model and real wastewaters are studied. The highest k1 value is observed for the photocatalytic removal of ritonavir from model wastewater using WW4 (35.64 ×10-2 min-1). The multiphase photocatalysts exhibit 95% efficiency in the photocatalytic removal of ritonavir within 15 of visible light irradiation. In contrast, 60 min of visible light irradiation is necessary to achieve 95% efficiency in the photocatalytic removal of lopinavir. The ecotoxicity test using zebrafish (Danio rerio) embryos shows no toxicity for photocatalytically treated ritonavir-containing wastewater, and the contrary trend is observed for photocatalytically treated lopinavir-containing wastewater. The synthesized multiphase photocatalysts can be tested and applied for efficient degradation of other SARS-CoV-2 antiviral drugs in wastewater in the future.

Present and Future of Phase-Selectively Disordered Blue TiO2 for Energy and Society Sustainability.

Titanium dioxide (TiO2) has garnered attention for its promising photocatalytic activity, energy storage capability, low cost, high chemical stability, and nontoxicity. However, conventional TiO2 has low energy harvesting efficiency and charge separation ability, though the recently developed black TiO2 formed under high temperature or pressure has achieved elevated performance. The phase-selectively ordered/disordered blue TiO2 (BTO), which has visible-light absorption and efficient exciton disassociation, can be formed under normal pressure and temperature (NPT) conditions. This perspective article first discusses TiO2 materials development milestones and insights of the BTO structure and construction mechanism. Then, current applications of BTO and potential extensions are summarized and suggested, respectively, including hydrogen (H2) production, carbon dioxide (CO2) and nitrogen (N2) reduction, pollutant degradation, microbial disinfection, and energy storage. Last, future research prospects are proposed for BTO to advance energy and environmental sustainability by exploiting different strategies and aspects. The unique NPT-synthesized BTO can offer more societally beneficial applications if its potential is fully explored by the research community.

Are photocatalytic processes effective for removal of airborne viruses from indoor air? A narrative review.

A wide variety of methods have been applied in indoor air to reduce the microbial load and reduce the transmission rate of acute respiratory diseases to personnel in healthcare sittings. In recent months, with the occurrence of COVID-19 pandemic, the role of portable ventilation systems in reducing the load of virus in indoor air has received much attention. The present study delineates a comprehensive up-to-date overview of the available photocatalysis technologies that have been applied for inactivating and removing airborne viruses. The detection methods for identifying viral particles in air and the main mechanisms involving in virus inactivation during photocatalysis are described and discussed. The photocatalytic processes could effectively decrease the load of viruses in indoor air. However, a constant viral model may not be generalizable to other airborne viruses. In photocatalytic processes, temperature and humidity play a distinct role in the inactivation of viruses through changing photocatalytic rate. The main mechanisms for inactivation of airborne viruses in the photocatalytic processes included chemical oxidation by the reactive oxygen species (ROS), the toxicity of metal ions released from metal-containing photocatalysts, and morphological damage of viruses.

SARS-CoV-2 Disinfection of Air and Surface Contamination by TiO2 Photocatalyst-Mediated Damage to Viral Morphology, RNA, and Protein.

SARS-CoV-2 is the causative agent of COVID-19, which is a global pandemic. SARS-CoV-2 is transmitted rapidly via contaminated surfaces and aerosols, emphasizing the importance of environmental disinfection to block the spread of virus. Ultraviolet C radiation and chemical compounds are effective for SARS-CoV-2 disinfection, but can only be applied in the absence of humans due to their toxicities. Therefore, development of disinfectants that can be applied in working spaces without evacuating people is needed. Here we showed that TiO2-mediated photocatalytic reaction inactivates SARS-CoV-2 in a time-dependent manner and decreases its infectivity by 99.9% after 20 min and 120 min of treatment in aerosol and liquid, respectively. The mechanistic effects of TiO2 photocatalyst on SARS-CoV-2 virion included decreased total observed virion count, increased virion size, and reduced particle surface spike structure, as determined by transmission electron microscopy. Damage to viral proteins and genome was further confirmed by western blotting and RT-qPCR, respectively. The multi-antiviral effects of TiO2-mediated photocatalytic reaction implies universal disinfection potential for different infectious agents. Notably, TiO2 has no adverse effects on human health, and therefore, TiO2-induced photocatalytic reaction is suitable for disinfection of SARS-CoV-2 and other emerging infectious disease-causing agents in human habitation.

Antimicrobial TiO2 nanocomposite coatings for surfaces, dental and orthopaedic implants.

Engineering of self-disinfecting surfaces to constrain the spread of SARS-CoV-2 is a challenging task for the scientific community because the human coronavirus spreads through respiratory droplets. Titania (TiO2) nanocomposite antimicrobial coatings is one of the ideal remedies to disinfect pathogens (virus, bacteria, fungi) from common surfaces under light illumination. The photocatalytic disinfection efficiency of recent TiO2 nanocomposite antimicrobial coatings for surfaces, dental and orthopaedic implants are emphasized in this review. Mostly, inorganic metals (e.g. copper (Cu), silver (Ag), manganese (Mn), etc), non-metals (e.g. fluorine (F), calcium (Ca), phosphorus (P)) and two-dimensional materials (e.g. MXenes, MOF, graphdiyne) were incorporated with TiO2 to regulate the charge transfer mechanism, surface porosity, crystallinity, and the microbial disinfection efficiency. The antimicrobial activity of TiO2 coatings was evaluated against the most crucial pathogenic microbes such as Escherichia coli, methicillin-resistant Staphylococcus aureus, Pseudomonas aeruginosa, Bacillus subtilis, Legionella pneumophila, Staphylococcus aureus, Streptococcus mutans, T2 bacteriophage, H1N1, HCoV-NL63, vesicular stomatitis virus, bovine coronavirus. Silane functionalizing agents and polymers were used to coat the titanium (Ti) metal implants to introduce superhydrophobic features to avoid microbial adhesion. TiO2 nanocomposite coatings in dental and orthopaedic metal implants disclosed exceptional bio-corrosion resistance, durability, biocompatibility, bone-formation capability, and long-term antimicrobial efficiency. Moreover, the commercial trend, techno-economics, challenges, and prospects of antimicrobial nanocomposite coatings are also discussed briefly.

Photo-catalyzed TiO2 inactivates pathogenic viruses by attacking viral genome.

Previous observations have been reported that viruses were inactivated using strong irradiation. Here, new evidence was disclosed by studying the effects of nanosized TiO2 on viral pathogens under a low irradiation condition (0.4 mW/cm2 at UVA band) that mimics the field setting. We showed that photo-activated TiO2 efficiently inhibits hepatitis C virus infection, and weak indoor light with intensity of 0.6 mW/cm2 at broad-spectrum wavelength and around 0.15 mW/cm2 of UVA band also lead to partial inhibition. Mechanistic studies demonstrated that hydroxyl radicals produced by photo-activated TiO2 do not destroy virion structure and contents, but attack viral RNA genome, thus inactivating the virus. Furthermore, we showed that photo-activated TiO2 inactivates a broad range of human viral pathogens, including SARS-CoV-2, a novel coronavirus responsible for the ongoing COVID-19 pandemic. In conclusion, we showed that photo-catalyzed nanosized TiO2 inactivates pathogenic viruses, paving a way to its field application in control of viral infectious diseases.

Application of a Photocatalyst as an Inactivator of Bovine Coronavirus.

Bovine coronavirus (BCoV), a major causative pathogen of bovine enteric and respiratory diseases and a zoonotic pathogen transmissible between animals and humans, has led to severe economic losses in numerous countries. BCoV belongs to the genus Betacoronavirus, which is a model of a pathogen that is threatening human health and includes severe acute respiratory syndrome coronavirus (SARS-CoV), SARS-CoV-2, and Middle East respiratory syndrome coronavirus. This study aimed to determine whether photocatalytic material effectively reduces CoVs in the environment. Using the film adhesion method of photocatalytic materials, we assessed its antiviral activity and the effect of visible light irradiation according to methods defined by the International Organization for Standardization. Consequently, photocatalytic material was found to have antiviral activity, reducing the viral loads by 2.7 log TCID50 (tissue culture infective dose 50)/0.1 mL (500 lux), 2.8 log TCID50/0.1 mL (1000 lux), and 2.4 log TCID50/0.1 mL (3000 lux). Hence, this photocatalytic material might be applicable not only to reducing CoVs in the cattle breeding environment but also perhaps in other indoor spaces, such as offices and hospital rooms. To our knowledge, this study is the first to evaluate the antiviral activity of a photocatalytic material against CoV.