Environmental Hazard Potential of Nano‐Photocatalysts Determined by Nano‐Bio Interactions and Exposure Conditions

Nano‐photocatalysts are known for their ability to degrade pollutants or perform water splitting catalyzed by light. Being the key functional ingredients of current and future products, the potential of nano‐photocatalysts releasing into the environment and causing unintended harm to living organisms warrants investigation. Risk assessment of these materials serves as an important step to allow safe implementation and to avoid irrational fear. Using TiO₂ and g‐C₃N₄ as representative nano‐photocatalysts, this study evaluates their hazard potential in zebrafish. Under simulated solar light, nano‐photocatalysts up to 100 mg L^?1 show no acute toxicity to zebrafish embryos due to the protection of chorions. The short‐lived reactive oxygen species generated by nano‐photocatalysts only exert injury to the hatched larvae at and above 50 mg L^?1. The input of solar energy, determined by the depth of water, irradiation time, and light intensity, greatly influences the toxicity outcome. Increasing concentrations of natural organic matters contribute positively to the hazard potential at 0–10 mg L^?1 while gradually diminishing the hazardous effect above 10 mg L^?1. This study demonstrates the importance of nano‐bio interactions and environmental exposure conditions in determining the safety profile of nano‐photocatalysts.     

The Crucial Role of Environmental Coronas in Determining the Biological Effects of Engineered Nanomaterials

In aquatic environments, a large number of ecological macromolecules (e.g., natural organic matter (NOM), extracellular polymeric substances (EPS), and proteins) can adsorb onto the surface of engineered nanomaterials (ENMs) to form a unique environmental corona. The presence of environmental corona as an eco–nano interface can significantly alter the bioavailability, biocompatibility, and toxicity of pristine ENMs to aquatic organisms. However, as an emerging field, research on the impact of the environmental corona on the fate and behavior of ENMs in aquatic environments is still in its infancy. To promote a deeper understanding of its importance in driving or moderating ENM toxicity, this study systemically recapitulates the literature of representative types of macromolecules that are adsorbed onto ENMs; these constitute the environmental corona, including NOM, EPS, proteins, and surfactants. Next, the ecotoxicological effects of environmental corona‐coated ENMs on representative aquatic organisms at different trophic levels are discussed in comparison to pristine ENMs, based on the reported studies. According to this analysis, molecular mechanisms triggered by pristine and environmental corona‐coated ENMs are compared, including membrane adhesion, membrane damage, cellular internalization, oxidative stress, immunotoxicity, genotoxicity, and reproductive toxicity. Finally, current knowledge gaps and challenges in this field are discussed from the ecotoxicology perspective.     

Epitaxial Growth of Lattice‐Mismatched Core–Shell TiO2@MoS2 for Enhanced Lithium‐Ion Storage

Core–shell structured nanohybrids are currently of significant interest due to their synergetic properties and enhanced performances. However, the restriction of lattice mismatch remains a severe obstacle for heterogrowth of various core–shells with two distinct crystal structures. Herein, a controlled synthesis of lattice‐mismatched core–shell TiO₂@MoS₂ nano‐onion heterostructures is successfully developed, using unilamellar Ti_0.87O₂ nanosheets as the starting material and the subsequent epitaxial growth of MoS₂ on TiO₂. The formation of these core–shell nano‐onions is attributed to an amorphous layer‐induced heterogrowth mechanism. The number of MoS₂ layers can be well tuned from few to over ten layers, enabling layer‐dependent synergistic effects. The core–shell TiO₂@MoS₂ nano‐onion heterostructures exhibit significantly enhanced energy storage performance as lithium‐ion battery anodes. The approach has also been extended to other lattice‐mismatched systems such as TiO₂@MoSe₂, thus suggesting a new strategy for the growth of well‐designed lattice‐mismatched core–shell structures.     

Continued Efforts on Nanomaterial‐Environmental Health and Safety Is Critical to Maintain Sustainable Growth of Nanoindustry

Nanotechnology is enjoying an impressive growth and the global nanotechnology industry is expected to exceed US$ 125 billion by 2024. Based on these successes, there are notions that enough is known and efforts on engineered nanomaterial environmental health and safety (nano‐EHS) research should be put on the back burner. However, there are recent events showing that it is not the case. The US Food and Drug Administration found ferumoxytol (carbohydrate‐coated superparamagnetic iron oxide nanoparticle) for anemia treatment could induce lethal anaphylactic reactions. The European Union will categorize TiO₂ as a category 2 carcinogen due to its inhalation hazard and France banned use of TiO₂ (E171) in food from January 1, 2020 because of its carcinogenic potential. Although nanoindustry is seemingly in a healthy state, growth could be hindered for the lack of certainty and more nano‐EHS research is needed for the sustainable growth of nanoindustry. Herein, the current knowledge gaps and the way forward are elaborated.     

Toxicity of Metal Oxide Nanoparticles: Mechanisms,Characterization, and Avoiding Experimental Artefacts

Metal oxide nanomaterials are widely used in practical applications and represent a class of nanomaterials with the highest global annual production. Many of those, such as TiO₂ and ZnO, are generally considered non‐toxic due to the lack of toxicity of the bulk material. However, these materials typically exhibit toxicity to bacteria and fungi, and there have been emerging concerns about their ecotoxicity effects. The understanding of the toxicity mechanisms is incomplete, with different studies often reporting contradictory results. The relationship between the material properties and toxicity appears to be complex and diifficult to understand, which is partly due to incomplete characterization of the nanomaterial, and possibly due to experimental artefacts in the characterization of the nanomaterial and/or its interactions with living organisms. This review discusses the comprehensive characterization of metal oxide nanomaterials and the mechanisms of their toxicity.     

Effect of heat treatment on structure evolution and properties of nano zinc titanate ceramics

Nano zinc titanate ceramics are prepared using a conventional solid state method. The obtained compacts are sintered at 800, 900, 1000 and 1100 °C for 3 h. The prepared compacts are analyzed using X‐ray diffraction (XRD) and scanning electron microscopy (SEM) for structural and microstructural studies. Based on the X‐ray diffraction (XRD) data, it is observed the coexistence of ZnTiO₃ and α‐Zn₂TiO₄ phases together at low temperature (800 °C) without the presence of TiO₂ (rutile) contradicting the general mechanism stating the transformation of ZnTiO₃ to α‐Zn₂TiO₄ and TiO₂ at higher temperatures. A new mechanism is proposed to explain the formation of nano ZnTiO₃ and α‐Zn₂TiO₄ structures depending on the role of TiO₂ in achieving this mission. According to this mechanism, we propose a partial diffusion of TiO₂ in the ZnO lattice forming the ZnTiO₃ phase. The second part of TiO₂ acts as a catalyst that facilitates the transformation of nano ZnTiO₃ to nano α‐Zn₂TiO₄. The catalytic power of rutile is achieved from its enhanced tensile stress that induces the phase transition from nano ZnTiO₃ to nano α‐Zn₂TiO₄.     

Quantitative Proteomics Study Reveals Changes in the Molecular Landscape of Human Embryonic Stem Cells with Impaired Stem Cell Differentiation upon Exposure to Titanium Dioxide Nanoparticles

The increasing number of nanoparticles (NPs) being used in various industries has led to growing concerns of potential hazards that NP exposure can incur on human health. However, its global effects on humans and the underlying mechanisms are not systemically studied. Human embryonic stem cells (hESCs), with the ability to differentiate to any cell types, provide a unique system to assess cellular, developmental, and functional toxicity in vitro within a single system highly relevant to human physiology. Here, the quantitative proteomics approach is adopted to evaluate the molecular consequences of titanium dioxide NPs (TiO₂ NPs) exposure in hESCs. The study identifies ≈328 unique proteins significantly affected by TiO₂ NPs exposure. Proteomics analysis highlights that TiO₂ NPs can induce DNA damage, elevated oxidative stress, apoptotic responses, and cellular differentiation. Furthermore, in vivo analysis demonstrates remarkable reduction in the ability of hESCs in teratoma formation after TiO₂ NPs exposure, suggesting impaired pluripotency. Subsequently, it is found that TiO₂ NPs can disrupt hESC mesoderm differentiation into cardiomyocytes. The study unveils comprehensive changes in the molecular landscape of hESCs by TiO₂ NPs and identifies the impact which TiO₂ NPs can have on the pluripotency and differentiation properties of human stem cells.     

Intracellular Uptake and Toxicity of Ag and CuO Nanoparticles: A Comparison Between Nanoparticles and their Corresponding Metal Ions

An increased understanding of nanoparticle toxicity and its impact on human health is essential to enable a safe use of nanoparticles in our society. The aim of this study is to investigate the role of a Trojan horse type mechanism for the toxicity of Ag‐nano and CuO‐nano particles and their corresponding metal ionic species (using CuCl₂ and AgNO₃), i.e., the importance of the solid particle to mediate cellular uptake and subsequent release of toxic species inside the cell. The human lung cell lines A549 and BEAS‐2B are used and cell death/membrane integrity and DNA damage are investigated by means of trypan blue staining and the comet assay, respectively. Chemical analysis of the cellular dose of copper and silver is performed using atomic absorption spectroscopy. Furthermore, transmission electron microscopy, laser scanning confocal microscopy, and confocal Raman microscopy are employed to study cellular uptake and particle‐cell interactions. The results confirm a high uptake of CuO‐nano and Ag‐nano compared to no, or low, uptake of the soluble salts. CuO‐nano induces both cell death and DNA damage whereas CuCl₂ induces no toxicity. The opposite is observed for silver, where Ag‐nano does not cause any toxicity, whereas AgNO₃ induces a high level of cell death. In conclusion: CuO‐nano toxicity is predominantly mediated by intracellular uptake and subsequent release of copper ions, whereas no toxicity is observed for Ag‐nano due to low release of silver ions within short time periods.     

Foodborne Titanium Dioxide Nanoparticles Induce Stronger Adverse Effects in Obese Mice than Non‐Obese Mice: Gut Microbiota Dysbiosis,Colonic Inflammation,and Proteome Alterations

The recent ban of titanium dioxide (TiO₂) as a food additive (E171) in France intensified the controversy on safety of foodborne‐TiO₂ nanoparticles (NPs). This study determines the biological effects of TiO₂ NPs and TiO₂ (E171) in obese and non‐obese mice. Oral consumption (0.1 wt% in diet for 8 weeks) of TiO₂ (E171, 112 nm) and TiO₂ NPs (33 nm) does not cause severe toxicity in mice, but significantly alters composition of gut microbiota, for example, increased abundance of Firmicutes phylum and decreased abundance of Bacteroidetes phylum and Bifidobacterium and Lactobacillus genera, which are accompanied by decreased cecal levels of short‐chain fatty acids. Both TiO₂ (E171) and TiO₂ NPs increase abundance of pro‐inflammatory immune cells and cytokines in the colonic mucosa, indicating an inflammatory state. Importantly, TiO₂ NPs cause stronger colonic inflammation than TiO₂ (E171), and obese mice are more susceptible to the effects. A microbiota transplant study demonstrates that altered fecal microbiota by TiO₂ NPs directly mediate inflammatory responses in the mouse colon. Furthermore, proteomic analysis shows that TiO₂ NPs cause more alterations in multiple pathways in the liver and colon of obese mice than non‐obese mice. This study provides important information on the health effects of foodborne inorganic nanoparticles.     

Water absorption behavior,mechanical and thermal properties of nano TiO2 enhanced glass fiber reinforced polymer composites

Nano TiO₂ particle is one of the promising inorganic nano fillers used in polymer matrix composites to enhance the mechanical properties. However, reliability of this type of nano composites is yet to be ensured in hydrothermal environment. The present work investigates the addition of nano TiO₂ filler on water sorption, residual strength and thermal properties of glass fiber reinforced polymer (GFRP) composites. The results revealed that addition of 0.1 wt% TiO₂ has reduced water diffusion coefficient by 9%, improved residual flexural strength by 19% and residual interlaminar shear strength by 18% among all the nano TiO₂ modified composites. The improvement of mechanical properties in hydrothermal environment creates opportunity and reliability to be used in different engineering applications. Weibull design parameters are evaluated and found a good agreement between Weibull stress-strain curves and experimental one. Fractographic analysis confirmed the various failures and strengthening mechanisms of nano composites in dry and hydrothermal environment.     

Multiphoton Microscopy of Nonfluorescent Nanoparticles In Vitro and In Vivo

Nanotechnology holds great promise for a plethora of potential applications. The interaction of engineered nanomaterials with living cells, tissues, and organisms is, however, only partly understood. Microscopic investigations of nano‐bio interactions are mostly performed with a few model nanoparticles (NPs) which are easy to visualize, such as fluorescent quantum dots. Here the possibility to visualize nonfluorescent NPs with multiphoton excitation is investigated. Signals from silver (Ag), titanium dioxide (TiO₂), and silica (SiO₂) NPs in nonbiological environments are characterized to determine signal dependency on excitation wavelength and intensity as well as their signal stability over time. Ag NPs generate plasmon‐induced luminescence decaying over time. TiO₂ NPs induce photoluminescent signals of variable intensities and in addition strong third harmonic generation (THG). Optimal settings for microscopic detection are determined and then applied for visualization of these two particle types in living cells, in murine muscle tissue, and in the murine blood stream. Silica NPs produce a THG signal, but in living cells it cannot be discriminated sufficiently from endogenous cellular structures. It is concluded that multiphoton excitation is a viable option for studies of nano‐bio interactions not only for fluorescent but also for some types of nonfluorescent NPs.     

Toxicological Aspects of Long‐Term Treatment of Keratinocytes with ZnO and TiO2 Nanoparticles

Sunscreens containing ZnO and TiO₂ nanoparticles (NPs) are increasingly applied to skin over long time periods to reduce the risk of skin cancer. However, long‐term toxicological studies of NPs are very sparse. The in vitro toxicity of ZnO and TiO₂ NPs on keratinocytes over short‐ and long‐term applications is reported. The effects studied are intracellular formation of radicals, alterations in cell morphology, mitochondrial activity, and cell‐cycle distribution. Cellular response depends on the type of NP, concentration, and exposure time. ZnO NPs have more pronounced adverse effects on keratinocytes than TiO₂. TiO₂ has no effect on cell viability up to 100 μg mL^?1, whereas ZnO reduces viability above 15 μg mL^?1 after short‐term exposure. Prolonged exposure to ZnO NPs at 10 μg mL^?1 results in decreased mitochondrial activity, loss of normal cell morphology, and disturbances in cell‐cycle distribution. From this point of view TiO₂ has no harmful effect. More nanotubular intercellular structures are observed in keratinocytes exposed to either type of NP than in untreated cells. This observation may indicate cellular transformation from normal to tumor cells due to NP treatment. Transmission electron microscopy images show NPs in vesicles within the cell cytoplasm, particularly in early and late endosomes and amphisomes. Contrary to insoluble TiO₂, partially soluble ZnO stimulates generation of reactive oxygen species to swamp the cell redox defense system thus initiating the death processes, seen also in cell‐cycle distribution and fluorescence imaging. Long‐term exposure to NPs has adverse effects on human keratinocytes in vitro, which indicates a potential health risk.     

Nano‐TiO2 Drives Epithelial–Mesenchymal Transition in Intestinal Epithelial Cancer Cells

The majority of cancer mortality is associated with cancer metastasis. Epithelial‐to‐mesenchymal transition (EMT) is a process by which cells attain migratory and invasive properties, eventually leading to cancer metastasis. Here, it is shown that titanium dioxide nanoparticles (nano‐TiO₂), a common food additive, can induce the EMT process in colorectal cancer cells. Nano‐TiO₂ exposure is observed to activate transforming growth factor‐β (TGF‐β)/mitogen‐activated protein kinase (MAPK) and wingless (Wnt) pathways, and drive the EMT process. Similarly, silica nanoparticles (nano‐SiO₂) and hydroxyapatite nanoparticles (nano‐HA), as food‐based additives, can be ingested and accumulated in the stomach, and are found to be able to induce the EMT progression. The implication of this work can be profound for colorectal cancer patients where these food additives may unknowingly and unnecessarily hasten the progression of their cancers.     

TiO2 Nanorod Array Constructed Nanotopography for Regulation of Mesenchymal Stem Cells Fate and the Realization of Location‐Committed Stem Cell Differentiation

As a physical cue for controlling the fate of stem cells, surface nanotopography has attracted much attention to improve the integration between implants and local host tissues and cells. A biocompatible surface TiO₂ nanorod array is proposed to regulate the fate of bone marrow derived mesenchymal stem cells (MSCs). TiO₂ substrates with different surface nanotopographies: a TiO₂ nanorod array and a polished TiO₂ ceramic are built by hydrothermal and sintering processes, respectively. The assessment of morphology, viability, gene expression, and protein characterization of the MSCs cultured on the different TiO₂ substrates proves that a TiO₂ nanorod array promotes the osteogenic differentiation of MSCs, while a TiO₂ ceramic with a smooth surface suppresses it. Periodically assembled TiO₂ nanorod array stripes on the smooth TiO₂ ceramic are constructed by a combination of microfabrication and a chemical synthesis process, which realizes the location‐committed osteogenic differentiation of MSCs. A route to control the differentiation of MSCs by a nanostructured surface, which can also control the location and direction of MSCs on the surface of biomaterials with micro‐nano scale surface engineering, is demonstrated.     

A Murine Oral‐Exposure Model for Nano‐ and Micro‐Particulates: Demonstrating Human Relevance with Food‐Grade Titanium Dioxide

Human exposure to persistent, nonbiological nanoparticles and microparticles via the oral route is continuous and large scale (10¹²–10¹³ particles per day per adult in Europe). Whether this matters or not is unknown but confirmed health risks with airborne particle exposure warns against complacency. Murine models of oral exposure will help to identify risk but, to date, lack validation or relevance to humans. This work addresses that gap. It reports i) on a murine diet, modified with differing concentrations of the common dietary particle, food grade titanium dioxide (fgTiO₂), an additive of polydisperse form that contains micro‐ and nano‐particles, ii) that these diets deliver particles to basal cells of intestinal lymphoid follicles, exactly as is reported as a “normal occurrence” in humans, iii) that confocal reflectance microscopy is the method of analytical choice to determine this, and iv) that food intake, weight gain, and Peyer's patch immune cell profiles, up to 18 weeks of feeding, do not differ between fgTiO₂‐fed groups or controls. These findings afford a human‐relevant and validated oral dosing protocol for fgTiO₂ risk assessment as well as provide a generalized platform for application to oral exposure studies with nano‐ and micro‐particles.     

Nanofunctionalized Superhydrophobic Antifouling Coatings for Environmental Sensor Applications—Advancing Deployment with Answers from Nature

In this work, a novel preparation for superhydrophobic nanofunctionalized silver and gold, copper‐coated substrates as potential antifouling coatings for environmental monitoring devices are fabricated. The superhydrophobic coating is topographically similar to the design of the Lotus leaf (Nelumbo necifera) and was synthesized by creating an electroless galvanic reaction between copper and the metal salt. In doing so, a nano‐ and micro‐topographical structure was created on the surface of a copper substrate which can be rendered superhydrophobic through the addition of a self‐assembled monolayer (SAM) of CF₃(CF₂)7CH₂CH₂SH. The work investigates whether the hydrophobicity of such materials affects micro‐organism attachment and subsequent biofouling. The materials are deployed in a marine environment in Dublin, Ireland for a 6 week study to determine the overall antifouling capacity. The materials are analyzed for biomass, slime (glycocalyx) production and more specifically protein and carbohydrate adsorption all of which are attributed to the inherent makeup of biofilm and exopolymeric substances (EPS) which are secreted by micro‐organisms during the biofouling process. This work highlights the dominance of combinational antifouling approaches rather than single tactics for such a complex problem and one that plagues multiple research areas. This novel approach in developing a new antifouling material for sensors, and indeed, any aquatic platform has shown excellent results throughout.     

Photoelectric study on a new semiconductor: 6,13-diphenylpentacene and TiO<Subscript>2</Subscript> nano composites film

6,13-Diphenylpentacene(DPP)-TiO₂ nano composites were firstly constructed. A series of characterizations proved that nano TiO₂ was successfully coated by DPP molecules, leading to the generation of some novel properties. The most interesting result is that the forbidden band gaps of composites were much smaller than that of DPP and nano TiO₂. The new composites can overcome the poor conductivity for pentacene at reduction potential, and the poor conductivity for nano TiO₂ at oxidation potential.     

An investigation of super-hydrophilic properties of TiO2/SnO2 nano composite thin films

A sol-gel dip coating technique was used to fabricate TiO₂/SnO₂ nano composite thin films on soda-lime glass. The solutions of SnO₂ and TiO₂ were mixed with different molar ratios of SnO₂:TiO₂ as 0, 3, 4, 6, 8, 9, 10.5, 13, 15, 19.5, 25 and 28 mol.% then the films were prepared by dip coating of the glasses. The effects of SnO₂ concentration, number of coating cycles and annealing temperature on the hydrophilicity of films were studied using contact angle measurement. The films were characterized by means of scanning electron microscopy, X-ray diffraction and atomic force microscopy measurements. The nano composite thin films fabricated with 8 mol.% of SnO₂, four dip coating cycles and annealing temperature of 500 °C showed super-hydrophilicity.     

One‐Step Transfer and Integration of Multifunctionality in CVD Graphene by TiO2/Graphene Oxide Hybrid Layer

We present a straightforward method for simultaneously enhancing the electrical conductivity, environmental stability, and photocatalytic properties of graphene films through one‐step transfer of CVD graphene and integration by introducing TiO₂/graphene oxide layer. A highly durable and flexible TiO₂ layer is successfully used as a supporting layer for graphene transfer instead of the commonly used PMMA. Transferred graphene/TiO₂ film is directly used for measuring the carrier transport and optoelectronic properties without an extra TiO₂ removal and following deposition steps for multifunctional integration into devices because the thin TiO₂ layer is optically transparent and electrically semiconducting. Moreover, the TiO₂ layer induces charge screening by electrostatically interacting with the residual oxygen moieties on graphene, which are charge scattering centers, resulting in a reduced current hysteresis. Adsorption of water and other chemical molecules onto the graphene surface is also prevented by the passivating TiO₂ layer, resulting in the long term environmental stability of the graphene under high temperature and humidity. In addition, the graphene/TiO₂ film shows effectively enhanced photocatalytic properties because of the increase in the transport efficiency of the photogenerated electrons due to the decrease in the injection barrier formed at the interface between the F‐doped tin oxide and TiO₂ layers.     

Dual Cocatalysts in TiO2 Photocatalysis

Semiconductor photocatalysis is recognized as a promising strategy to simultaneously address energy needs and environmental pollution. Titanium dioxide (TiO₂) has been investigated for such applications due to its low cost, nontoxicity, and high chemical stability. However, pristine TiO₂ still suffers from low utilization of visible light and high photogenerated‐charge‐carrier recombination rate. Recently, TiO₂ photocatalysts modified by dual cocatalysts with different functions have attracted much attention due to the extended light absorption, enhanced reactant adsorption, and promoted charge‐carrier‐separation efficiency granted by various cocatalysts. Recent progress on the component and structural design of dual cocatalysts in TiO₂ photocatalysts is summarized. Depending on their components, dual cocatalysts decorated on TiO₂ photocatalysts can be divided into the following categories: bimetallic cocatalysts, metal–metal oxide/sulfide cocatalysts, metal–graphene cocatalysts, and metal oxide/sulfide–graphene cocatalysts. Depending on their architecture, they can be categorized into randomly deposited binary cocatalysts, facet‐dependent selective‐deposition binary cocatalysts, and core–shell structural binary cocatalysts. Concluding perspectives on the challenges and opportunities for the further exploration of dual cocatalyst–modified TiO₂ photocatalysts are presented.