Mild chemistry synthesis of ultrathin Bi2O2S nanosheets exhibiting 2D-ferroelectricity at room temperature.

Modern technology demands miniaturization of electronic components to build small, light, and portable devices. Hence, discovery and synthesis of new non-toxic, low cost, ultra-thin ferroelectric materials having potential applications in various electronic and optoelectronic devices are of paramount importance. However, achieving room-temperature ferroelectricity in two dimensional (2D) ultra-thin systems remains a major challenge as conventional three-dimensional ferroelectric materials lose their ferroelectricity when the thickness is brought down below a critical value owing to the depolarization field. Herein, we report room-temperature ferroelectricity in ultra-thin single-crystalline 2D nanosheets of Bi2O2S synthesized by a simple, rapid, and scalable solution-based soft chemistry method. The ferroelectric ground state of Bi2O2S nanosheets is confirmed by temperature-dependent dielectric measurements as well as piezoelectric force microscopy and spectroscopy. High resolution transmission electron microscopy analysis and density functional theory-based calculations suggest that the ferroelectricity in Bi2O2S nanosheets arises due to the local distortion of Bi2O2 layers, which destroys the local inversion symmetry of Bi2O2S.

Hg Doping Induced Reduction in Structural Disorder Enhances the Thermoelectric Performance in AgSbTe2.

Defect engineering, achieved by precise tuning of the atomic disorder within crystalline solids, forms a cornerstone of structural chemistry. This nuanced approach holds the potential to significantly augment thermoelectric performance by synergistically manipulating the interplay between the charge carrier and lattice dynamics. Here, the current study presents a distinctive investigation wherein the introduction of Hg doping into AgSbTe2 serves to partially curtail structural disorder. This strategic maneuver mitigates potential fluctuations originating from pronounced charge and size disparities between Ag+ and Sb3+, positioned in octahedral sites within the rock salt structure. Hg doping significantly improves the phase stability of AgSbTe2 by restricting the congenital emergence of the Ag2Te minor secondary phase and promotes partial atomic ordering in the cation sublattice. Reduction in atomic disorder coalesced with a complementary modification of electronic structure by Hg doping results in increased carrier mobility. The formation of nanoscale superstructure with sizes (2-5 nm) of the order of phonon mean free path in AgSbTe2 is further promoted by reduced partial disorder, causes enhanced scattering of heat-carrying phonons, and results in a glass-like ultralow lattice thermal conductivity (∼0.32 W m-1 K-1 at 297 K). Cumulatively, the multifaceted influence of Hg doping, in conjunction with the consequential reduction in disorder, allows achieving a high thermoelectric figure-of-merit, zT, of ∼2.4 at ∼570 K. This result defies conventional paradigms that prioritize increased disorder for optimizing zT.

Mitigation of SARS-CoV-2 by Using Transition Metal Nanozeolites and Quaternary Ammonium Compounds as Antiviral Agents in Suspensions and Soft Fabric Materials.

Introduction: The coronavirus disease 2019 (COVID-19) pandemic has demonstrated the need for novel, affordable, and efficient reagents to help reduce viral transmission, especially in high-risk environments including medical treatment facilities, close quarters, and austere settings. We examined transition-metal nanozeolite suspensions and quaternary ammonium compounds as an antiviral surface coating for various textile materials. Methods: Zeolites are crystalline porous aluminosilicate materials, with the ability of ion-exchanging different cations. Nanozeolites (30 nm) were synthesized and then ion-exchanged with silver, zinc and copper ions. Benzalkonium nitrate (BZN) was examined as the quaternary ammonium ion (quat). Suspensions of these materials were tested for antiviral activity towards SARS-CoV-2 using plaque assay and immunostaining. Suspensions of the nanozeolite and quat were deposited on polyester and cotton fabrics and the ability of these textiles towards neutralizing SARS-CoV-2 was examined. Results: We hypothesized that transition metal ion containing zeolites, particularly silver and zinc (AM30) and silver and copper (AV30), would be effective in reducing the infectivity of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). Additionally, AM30 and AV30 antiviral potency was tested when combined with a quaternary ammonium carrier, BZN. Our results indicate that exposure of SARS-CoV-2 to AM30 and/or AV30 suspensions reduced viral loads with time and exhibited dose-dependence. Antiviral activities of the combination of zeolite and BZN compositions were significantly enhanced. When used in textiles, AM30 and AV30-coated cotton and polyester fabrics alone or in combination with BZN exhibited significant antiviral properties, which were maintained even after various stress tests, including washes, SARS-CoV-2-repeated exposures, or treatments with soil-like materials. Conclusion: This study shows the efficacy of transition metal nanozeolite formulations as novel antiviral agents and establishes that nanozeolite with silver and zinc ions (AM30) and nanozeolite with silver and copper ions (AV30) when combined with benzalkonium nitrate (BZN) quickly and continuously inactivate SARS-CoV-2 in suspension and on fabric materials.

Self-organized criticality of magnetic avalanches in disordered ferrimagnetic material.

We observe multiple steplike jumps in a Dy-Fe-Ga-based ferrimagnetic alloy in its magnetic hysteresis curve at 2 K. The observed jumps are found to have a stochastic character with respect to their magnitude and the field position, and the jumps do not correlate with the duration of the field. The distribution of jump size follows a power law variation indicating the scale invariance nature of the jumps. We have invoked a simple two-dimensional random bond Ising-type spin system to model the dynamics. Our computational model can qualitatively reproduce the jumps and their scale-invariant character. It also elucidates that the flipping of antiferromagnetically coupled Dy and Fe clusters is responsible for the observed jumps in the hysteresis loop. These features are described in terms of the self-organized criticality.

Modular Nanostructures Facilitate Low Thermal Conductivity and Ultra-High Thermoelectric Performance in n-Type SnSe.

Single crystals of SnSe have gained considerable attention in thermoelectrics due to their unprecedented thermoelectric performance. However, polycrystalline SnSe is more favorable for practical applications due to its facile chemical synthesis procedure, processability, and scalability. Though the thermoelectric figure of merit (zT) of p-type bulk SnSe polycrystals has reached >2.5, zT of n-type counterpart is still lower and lies around ≈1.5. Herein, record high zT of 2.0 in n-type polycrystalline SnSe0.92  + x mol% MoCl5 (x = 0-3) samples is reported, when measured parallel to the spark plasma sintering pressing direction due to the simultaneous optimization of n-type carrier concentration and enhanced phonon scattering by incorporating modular nano-heterostructures in SnSe matrix. Modular nanostructures of layered intergrowth [(SnSe)1.05 ]m (MoSe2 )n like compounds embedded in SnSe matrix scatters the phonons significantly leading to an ultra-low lattice thermal conductivity (κlat ) of ≈0.26 W m-1 K-1 at 798 K in SnSe0.92  + 3 mol% MoCl5 . The 2D layered modular intergrowth compound resembles the nano-heterostructure and their periodicity of 1.2-2.6 nm in the SnSe matrix matches the phonon mean free path of SnSe, thereby blocking the heat carrying phonons, which result in low κlat and ultra-high thermoelectric performance in n-type SnSe.

Strong Anharmonicity-Induced Low Thermal Conductivity and High n-type Mobility in the Topological Insulator Bi1.1 Sb0.9 Te2 S.

Intrinsically low lattice thermal conductivity (κlat ) while maintaining the high carrier mobility (µ) is of the utmost importance for thermoelectrics. Topological insulators (TI) can possess high µ due to the metallic surface states. TIs with heavy constituents and layered structure can give rise to high anharmonicity and are expected to show low κlat . Here, we demonstrate that Bi1.1 Sb0.9 Te2 S (BSTS), which is a 3D bulk TI, exhibits ultra-low κlat of 0.46 Wm-1 K-1 along with high µ of ≈401 cm2  V-1 s-1 . Sound velocity measurements and theoretical calculations suggest that chemical bonding hierarchy and high anharmonicity play a crucial role behind such ultra-low κlat . BSTS possesses low energy optical phonons which strongly couple with the heat carrying acoustic phonons leading to ultra-low κlat . Further, Cl has been doped at the S site of BSTS which increases the electron concentration and reduces the κlat resulting in a promising n-type thermoelectric figure of merit (zT) of ≈0.6 at 573 K.

Observation of Griffiths-like phase in the quaternary Heusler compound NiFeTiSn.

The quaternary Heusler compound NiFeTiSn can be considered to be derived from the exotic pseudogap-compound Fe2TiSn by the replacement of one Fe atom by Ni. In contrast to Fe2TiSn, which shows a disorder induced ferromagnetic phase, the ground state of NiFeTiSn is antiferromagnetic with the signature of spin canting. Interestingly, NiFeTiSn shows a Griffiths-like phase characterized by isolated ferromagnetic clusters before attaining the antiferromagnetic state. The Griffiths-like phase is possibly associated with the antisite disorder between Fe and Ti sites as evident from our powder x-ray diffraction study. The compound also shows rather unusual temperature dependence of resistivity, which can be accounted by the prevailing structural disorder in the system. NiFeTiSn turned out to be a rare example where Griffiths-like phase is observed in a semiconducting 3dtransition metal based intermetallic compound with antiferromagnetic ground state.

High-Performance Thermoelectrics Based on Solution-Grown SnSe Nanostructures.

Two-dimensional layered tin selenide (SnSe) has attracted immense interest in thermoelectrics due to its ultralow lattice thermal conductivity and high thermoelectric performance. To date, the majority of thermoelectric studies of SnSe have been based on single crystals. However, because synthesizing SnSe single crystals is an expensive, time-consuming process that requires high temperatures and because SnSe single crystals have relatively weaker mechanical stability, they are not favorable for scaling up synthesis, commercialization, or practical applications. As a result, research on nanocrystalline SnSe that can be produced in large quantities by simple and low-temperature solution-phase synthesis is needed. In this Perspective, we discuss the progress in thermoelectric properties of SnSe with a particular emphasis on nanocrystalline SnSe, which is grown in solution. We first describe the state-of-the-art high-performance single crystal and polycrystals of SnSe and their importance and drawbacks and discuss how nanocrystalline SnSe can solve some of these challenges. We illustrate different solution-phase synthesis procedures to produce various SnSe nanostructures and discuss their thermoelectric properties. We also highlight a unique solution-phase synthesis technique to prepare CdSe-coated SnSe nanocomposites and its unprecedented thermoelectric figure of merit (ZT) of 2.2 at 786 K, as reported in this issue of ACS Nano. In general, solution synthesis showed excellent control over nanoscale grain growth, and nanocrystalline SnSe shows ultralow thermal conductivity due to strong phonon scattering by the nanoscale grain boundaries. Finally, we offer insight into the opportunities and challenges associated with nanocrystalline SnSe synthesized by the solution route and its future in thermoelectric energy conversion.

Competing magnetic interactions and magnetocaloric effect in Ho5Sn3.

The rare-earth intermetallic compound Ho5Sn3demonstrates fascinating magnetic properties, which include temperature-driven multiple magnetic transitions and field-driven metamagnetism. We address the magnetic character of this exciting compound through a combined experimental and theoretical studies. Ho5Sn3orders antiferromagnetically below 28 K, and shows further spin reorientation transitions at 16 K and 12 K. We observe a sizable amount of low-temperature magnetocaloric effect (MEC) in Ho5Sn3with a maximum value of entropy change ΔS= -9.5 J Kg-1 K-1for an applied field ofH= 50 kOe at around 30 K. The field hysteresis is almost zero above 15 K where the MEC is important. Interestingly, ΔSis found to change its sign from positive to negative as the temperature is increased above about 8 K, which can be linked to the multiple spin reorientation transitions. The signature of the metamagnetism is visible in the ΔSversusHplot. The magnetic ground state, obtained from the density functional theory based calculation, is susceptible to the effective Coulomb interaction (Ueff) between electrons. Depending upon the value ofUeff, the ground state can be ferromagnetic or antiferromagnetic. The compound shows large relaxation (14% change in magnetisation in 60 min) in the field cooled state with a logarithmic time variation, which may be connected to the competing magnetic correlations observed in our theoretical calculations. The competing magnetic ground states are equally evident from the small value of the paramagnetic Curie-Weiss temperature.

Nanoparticle processing: Understanding and controlling aggregation.

Nanoparticles (NPs) are commonly defined as particles with size <100 nm and are currently of considerable technological and academic interest, since they are often the starting materials for nanotechnology. Novel properties develop as a bulk material is reduced to nanodimensions and is reflected in new chemistry, physics and biology. With reduction in size, a greater function of the atoms is at the surface, and promote different interaction with its environment, as compared to the bulk material. In addition, the reduction in size alters the electronic structure of the material, resulting in novel quantum effects. Size also influences mobility, primarily controlled by Brownian motion for NPs, and relevant in biological and environmental processes. However, the small size also leads to high surface energy, and NPs tend to aggregate, thereby lowering the surface energy. In all applications, the uncontrolled aggregation of NPs can have negative effects and needs to be avoided. There are however examples of controlled aggregation of NPs which give rise to novel effects. This review article is focused on the NP features that influences aggregation. Common strategies for synthesis of NPs from the gas and liquid phases are discussed with emphasis on aggregation during and after synthesis. The theory involving Van der Waals attractive force and electrical repulsive force as the controlling features of the stability of NPs is discussed, followed by examples of how repulsive and attractive forces can be manipulated experimentally to control NP aggregation. In some applications, NPs prepared by liquid methods need to be isolated for further applications. The process of solvent removal introduces new forces such as capillary forces that promote aggregation, in many cases, irreversibly. Strategies for controlling aggregation upon drying are discussed. There are also many methods for redispersing aggregated NPs, which involve mechanical forces, as well as manipulating capillary forces and surface characteristics. We conclude this review with a discussion of aggregation relevant real-world applications of NPs. This review should be relevant for scientists and technologists interested in NPs, since emphasis has been on the practical aspects of NP-based technology, and especially, strategies relevant to controlling NP aggregation.

Octahedral tilting and emergence of ferrimagnetism in cobalt-ruthenium based double perovskites.

Rare earth based cobalt-ruthenium double perovskites A2CoRuO6 (A = La, Pr, Nd and Sm) were synthesized and investigated for their structural and magnetic properties. All the compounds crystallize in the monoclinic P21/n structure with the indication of antisite disorder between Co and Ru sites. While La compound is already reported to have an antiferromagnetic state below 27 K, the Pr, Nd and Sm systems are found to be ferrimagnetic below [Formula: see text], 55 and 78 K respectively. Field-dependent magnetization data indicate prominent hysteresis loop below [Formula: see text] in the samples containing magnetic rare-earth ions, however, magnetization does not saturate even at the highest applied fields. Our structural analysis indicates strong distortion in the Co-O-Ru bond angle, as La3+ is replaced by smaller rare-earth ions such as Pr3+ , Nd3+ , and Sm3+ . The observed ferrimagnetism is possibly associated with the enhanced antiferromagnetic superexchange interaction in the Co-O-Ru pathway due to bond bending. The Pr, Nd and Sm samples also show the small magnetocaloric effect with the Nd sample showing the highest value of magnitude ∼3 J kg-1K-1 at 50 kOe. The change in entropy below 20 K is found to be positive in the Sm sample as compared to the negative value in the Nd counterpart.

Photochemical Water Oxidation in a Buffered Tris(2,2'-bipyridyl)ruthenium-Persulfate System Using Iron(III)-Modified Potassium Manganese Oxides as Catalysts.

Study of manganese oxides for electrocatalytic and photocatalytic oxidation of water is an active area of research. The starting material in this study is a high-surface-area disordered birnessite-like material with K+ in the interlayers (KMnOx). Upon ion-exchange with Fe3+, the disordered layer structure collapses (Fe(IE)MnOx), and the surface area is slightly increased. Structural analysis of the Fe(IE)MnOx included examination of its morphology, crystal structure, vibrational spectra, and manganese oxidation states. Using the Ru(bpy)3 2+-persulfate system, the dissolved and headspace oxygen upon visible light photolysis with highly dispersed Fe(IE)MnOx was measured. The photocatalytic activity for O2 evolution of the Fe(IE)MnOx was three times better than KMnOx, with the highest rate being 9.3 mmolO2 molMn -1 s-1. The improvement of the photocatalytic activity was proposed to arise from the increased disorder and interaction of Fe3+ with the MnO6 octahedra. As a benchmark, colloidal IrO2 was a better photocatalyst by a factor of ∼75 over Fe(IE)MnOx.

Biocompatibility and antibacterial activity of nitrogen-doped titanium dioxide nanoparticles for use in dental resin formulations.

The addition of antibacterial functionality to dental resins presents an opportunity to extend their useful lifetime by reducing secondary caries caused by bacterial recolonization. In this study, the potential efficacy of nitrogen-doped titanium dioxide nanoparticles for this purpose was determined. Nitrogen doping was carried out to extend the ultraviolet absorbance into longer wavelength blue light for increased biocompatibility. Titanium dioxide nanoparticles (approximately 20-30 nm) were synthesized with and without nitrogen doping using a sol-gel method. Ultraviolet-Visible spectroscopy indicated a band of trap states, with increasing blue light absorbance as the concentration of the nitrogen dopant increased. Electron paramagnetic resonance measurements indicated the formation of superoxide and hydroxyl radicals upon particle exposure to visible light and oxygen. The particles were significantly toxic to Escherichia coli in a dose-dependent manner after a 1-hour exposure to a blue light source (480 nm). Intracellular reactive oxygen species assay demonstrated that the particles caused a stress response in human gingival epithelial cells when exposed to 1 hour of blue light, though this did not result in detectable release of cytokines. No decrease in cell viability was observed by water-soluble tetrazolium dye assay. The results show that nitrogen-doped titanium dioxide nanoparticles have antibacterial activity when exposed to blue light, and are biocompatible at these concentrations.

Oxidative stress-mediated inhibition of intestinal epithelial cell proliferation by silver nanoparticles.

Given the increasing use of silver nanoparticles (Ag NP) by the food and food packaging industries, this study investigated potential consequences of Ag NP ingestion in intestinal epithelial C2BBe1 cells. Treatment of proliferating cells (<10,000 cells/cm(2)) with 0.25 µg/cm(2) (1.25 µg/mL) of 23 nm Ag NP for 24 h induced 15% necrotic cell death and an 80% reduction in metabolic activity and decreased the GSH/GSSG ratio, indicating oxidative stress. G2/M phase cell cycle arrest and complete inhibition of cell proliferation was also induced by Ag NP treatment. Simulated in vitro digestion of Ag NP prior to cell exposure required the use of slightly higher doses to induce the same toxicity, likely due to slower Ag dissolution. Treatment of cells with silica, titania, and ZnO NP partially inhibited cell proliferation, but inhibition at low doses was unique to Ag NP. These data suggest that Ag NP induces oxidative stress, cell cycle arrest, and the inhibition of cell proliferation. However, toxicity and induction of oxidative stress were not observed in confluent cells (>100,000 cells/cm(2)) treated with 10 µg/cm(2) (40-50 µg/mL) Ag NP, indicating that these cells are less sensitive to Ag NP.

Bendable Zeolite Membranes: Synthesis and Improved Gas Separation Performance.

Separation and sequestration of CO2 emitted from fossil energy fueled electric generating units and industrial facilities will help in reducing anthropogenic CO2, thereby mitigating its adverse climate change effects. Membrane-based gas separation has the potential to meet the technical challenges of CO2 separation if high selectivity and permeance with low costs for large-scale manufacture are realized. Inorganic zeolite membranes in principle can have selectivity and permeance considerably higher than polymers. This paper presents a strategy for zeolite growth within the pores of a polymer support, with crystallization time of an hour. With a thin coating of 200-300 nm polydimethylsiloxane (PDMS) on the zeolite-polymer composite, transport data for CO2/N2 separation indicate separation factors of 35-45, with CO2 permeance between 1600 and 2200 GPU (1 GPU = 3.35 × 10(-10) mol/(m(2) s Pa)) using dry synthetic mixtures of CO2 and N2 at 25 °C. The synthesis process results in membranes that are highly reproducible toward transport measurements and exhibit long-term stability (3 days). Most importantly, these membranes because of the zeolite growth within the polymer support, as contrasted to conventional zeolite growth on top of a support, are mechanically flexible.

Fabrication of zeolite/polymer multilayer composite membranes for carbon dioxide capture: Deposition of zeolite particles on polymer supports.

Membranes, due to their smaller footprint and potentially lower energy consumption than the amine process, offer a promising route for post-combustion CO2 capture. Zeolite Y based inorganic selective layers offer a favorable combination of CO2 permeance and CO2/N2 selectivity, membrane properties crucial to the economics. For economic viability on large scale, we propose to use flexible and scalable polymer supports for inorganic selective layers. The work described in this paper developed a detailed protocol for depositing thin zeolite Y seed layers on polymer supports, the first step in the synthesis of a polycrystalline zeolite Y membrane. We also studied the effects of support surface morphology (pore size and surface porosity) on the quality of deposition and identified favorable supports for the deposition. Two different zeolite Y particles with nominal sizes of 200 nm and 40 nm were investigated. To obtain a complete coverage of zeolite particles on the support surface with minimum defects and in a reproducible manner, a vacuum-assisted dip-coating technique was developed. Images obtained using both digital camera and optical microscope showed the presence of color patterns on the deposited surface which suggested that the coverage was complete. Electron microscopy revealed that the particle packing was dense with some drying cracks. Layer thickness with the larger zeolite Y particles was close to 1 µm while that with the smaller particles was reduced to less than 0.5 µm. In order to reduce drying cracks for layers with smaller zeolite Y particles, thickness was reduced by lowering the dispersion concentration. Transport measurement was used as an additional technique to characterize these layers.

Uptake of bright fluorophore core-silica shell nanoparticles by biological systems.

Nanoparticles are used in a variety of consumer applications. Silica nanoparticles in particular are common, including as a component of foods. There are concerns that ingested nano-silica particles can cross the intestinal epithelium, enter the circulation, and accumulate in tissues and organs. Thus, tracking these particles is of interest, and fluorescence spectroscopic methods are well-suited for this purpose. However, nanosilica is not fluorescent. In this article, we focus on core-silica shell nanoparticles, using fluorescent Rhodamine 6G, Rhodamine 800, or CdSe/CdS/ZnS quantum dots as the core. These stable fluorophore/silica nanoparticles had surface characteristics similar to those of commercial silica particles. Thus, they were used as model particles to examine internalization by cultured cells, including an epithelial cell line relevant to the gastrointestinal tract. Finally, these particles were administered to mice by gavage, and their presence in various organs, including stomach, small intestine, cecum, colon, kidney, lung, brain, and spleen, was examined. By combining confocal fluorescence microscopy with inductively coupled plasma mass spectrometry, the presence of nanoparticles, rather than their dissolved form, was established in liver tissues.

Rapid crystallization of faujasitic zeolites: mechanism and application to zeolite membrane growth on polymer supports.

Zeolites are microporous, crystalline aluminosilicates with the framework made up of T-O-T (T = Si, Al) bonds and enclosed cages and channels of molecular dimensions. Influencing and manipulating the nucleation and growth characteristics of zeolites can lead to novel frameworks and morphologies, as well as decreased crystallization time. In this study, we show that manipulating the supersaturation during synthesis of zeolite X/Y (FAU) via dehydration led to extensive nucleation. Controlled addition of water to this nucleated state promotes the transport of nutrients, with a 4-fold increase in the rate of crystal growth, as compared to conventional hydrothermal process. Structural signature of the nucleated state was obtained by electron microscopy, NMR, and Raman spectroscopy. This extensively intermediate nucleated state was isolated and used as the starting material for zeolite membrane synthesis on porous polymer supports, with membrane formation occurring within an hour. With this time frame for growth, it becomes practical to fabricate zeolite/polymer membranes using roll-to-roll technology, thus making possible new commercial applications.

Tuning the activities and structures of enzymes bound to graphene oxide with a protein glue.

Graphene oxide (GO) is being investigated extensively for enzyme and protein binding, but many enzymes bound to GO denature considerably and lose most of their activities. A simple, novel, and efficient approach is described here for improving the structures and activities of enzymes bound to GO such that bound enzymes are nearly as active as those of the corresponding unbound enzymes. Our strategy is to preadsorb highly cationized bovine serum albumin (cBSA) to passivate GO, and cBSA/GO (bGO) served as an excellent platform for enzyme binding. The binding of met-hemoglobin, glucose oxidase, horseradish peroxidase, BSA, catalase, lysozyme, and cytochrome c indicated improved binding, structure retention, and activities. Nearly 100% of native-like structures of all the seven proteins/enzymes were noted at near monolayer formation of cBSA on GO (400% w/w), and all bound enzymes indicated 100% retention of their activities. A facile, benign, simple, and general method has been developed for the biofunctionalization of GO, and this approach of coating with suitable protein glues expands the utility of GO as an advanced biophilic nanomaterial for applications in catalysis, sensing, and biomedicine.

Minimal intestinal epithelial cell toxicity in response to short- and long-term food-relevant inorganic nanoparticle exposure.

Toxicity of commercial nanoparticles of titania, silica, and zinc oxides is being investigated in this in vitro study. Particles of these compositions are found in many food items, and thus this study is directed toward particle behavior in simulated digestion media and their interaction with intestinal epithelial cell line C2BBe1, a clone of Caco-2 cells, originally isolated from a human colon cancer. Even though the primary particle size of all three particles was below 50 nm, the particles appeared as aggregates in culture media with a negatively charged surface. In the presence of pepsin (pH 2), the charge on the titania became positive, and silica was almost neutral and aggregated extensively, whereas ZnO dissolved. For silica and titania, treatment with simulated intestinal digestive solution led to a strongly negatively charged surface and particle sizes approaching values similar to those in media. On the basis of infrared spectroscopy, we concluded that the surface of silica and titania was covered with bile salts/proteins after this treatment. Transmission electron microscopy indicated that the C2BBe1 cells internalized all three particles. Toxicity assays included investigation of necrosis, apoptosis, membrane damage, and mitochondrial activity. Titania and SiO2 particles suspended in media at loading levels of 10 µg/cm² exhibited no toxicity. With ZnO at the same loading level, mild toxicity was observed based only on the LDH assay and decrease of mitochondrial activity and not necrosis or apoptosis. Titania particles exposed to the simulated digestion media exhibited mild toxicity based on decrease of mitochondrial activity, likely due to transport of toxic bile salts via adsorption on the particle surface.