Effect of Size and Crystalline Phase of TiO2 Nanoparticles on Photocatalytic Inactivation of Escherichia coli.

We studied the size dependent toxicity of TiO2 nanoparticles (TiO2 NPs; 5-50 nm) of the anatase and rutile crystalline phases (including the mixture of anatase and rutile) against the model organism Escherichia coli. All the TiO2 NPs were characterized and their photocatalytic inactivation of E. coli was studied under the solar simulated light irradiation and dark conditions. In addition, the mechanism of toxicity was studied by measurement of reactive oxygen species (ROS), an indicator of oxidative stress. Rutile TiO2 NPs (TiO2-R-30 nm) of 30 nm showed the highest photocatalytic activity against E. coli (LC50 of 14.11 mg/L), followed by rutile TiO2 NPs (TiO2-R-50 nm) (LC50 of 35.96 mg/L). The anatase and rutile mixture of 20 nm size produced LC50 of 17.12 and 27.26 mg/L for A80%-R20% and A20%-R80% respectively, whereas none of the anatase TiO2 NPs with various sizes (5 nm, 15 nm and 30 nm) showed any toxicity against E. coli. The results indicate that the rutile had higher photocatalytic activity than anatase and the toxicity is size dependent, while the mixture of anatase and rutile had the median toxicity. Hydroxyl radical formation is the major ROS causing oxidative stress in E. coli, the primary mechanism of toxicity.

The current application of nanotechnology in food and agriculture.

The rapid development of nanotechnology has been facilitating the transformations of traditional food and agriculture sectors, particularly the invention of smart and active packaging, nanosensors, nanopesticides and nanofertilizers. Numerous novel nanomaterials have been developed for improving food quality and safety, crop growth, and monitoring environmental conditions. In this review the most recent trends in nanotechnology are discussed and the most challenging tasks and promising opportunities in the food and agriculture sectors from selected recent studies are addressed. The toxicological fundamentals and risk assessment of nanomaterials in these new food and agriculture products are also discussed. We highlighted the potential application of bio-synthesized and bio-inspired nanomaterial for sustainable development. However, fundamental questions with regard to high performance, low toxic nanomaterials need to be addressed to fuel active development and application of nanotechnology. Regulation and legislation are also paramount to regulating the manufacturing, processing, application, as well as disposal of nanomaterials. Efforts are still needed to strengthen public awareness and acceptance of the novel nano-enabled food and agriculture products. We conclude that nanotechnology offers a plethora of opportunities, by providing a novel and sustainable alternative in the food and agriculture sectors.

Toxicity of engineered nanomaterials mediated by nano-bio-eco interactions.

Engineered nanomaterials may adversely impact human health and environmental safety by nano-bio-eco interactions not fully understood. Their interaction with biotic and abiotic environments are varied and complicated, ranging from individual species to entire ecosystems. Their behavior, transport, fate, and toxicological profiles in these interactions, addressed in a pioneering study, are subsequently seldom reported. Biological, chemical, and physical dimension properties, the so-called multidimensional characterization, determine interactions. Intermediate species generated in the dynamic process of nanomaterial transformation increase the complexity of assessing nanotoxicity. We review recent progress in understanding these interactions, discuss the challenges of the study, and suggest future research directions.

Nanostructures: Current uses and future applications in food science.

Recent developments in nanoscience and nanotechnology intend novel and innovative applications in the food sector, which is rather recent compared with their use in biomedical and pharmaceutical applications. Nanostructured materials are having applications in various sectors of the food science comprising nanosensors, new packaging materials, and encapsulated food components. Nanostructured systems in food include polymeric nanoparticles, liposomes, nanoemulsions, and microemulsions. These materials enhance solubility, improve bioavailability, facilitate controlled release, and protect bioactive components during manufacture and storage. This review highlights the applications of nanostructured materials for their antimicrobial activity and possible mechanism of action against bacteria, including reactive oxygen species, membrane damage, and release of metal ions. In addition, an overview of nanostructured materials, and their current applications and future perspectives in food science are also presented.

Assessing the effect of different natural dissolved organic matters on the cytotoxicity of titanium dioxide nanoparticles with bacteria.

Titanium dioxide nanoparticles (TiO2 NPs) are among the most widely manufactured nanomaterials on a global scale. However, prudent and vigilant surveillance, incumbent upon the scientific community with the advent of new technologies, has revealed potentially undesirable effects of TiO2 NPs on biological systems and the natural environment during their application and discharge. Such effects are likely best evaluated by first assessing the fate of the TiO2 NPs in natural environments. In this study, the effects of terrestrial humic acid (HA) and tannic acid (TA), two major members of the collective: dissolved organic matter (DOM), on the cytotoxicity of TiO2 NPs to Escherichia coli were investigated in the presence and absence of natural sunlight. Qualitative (transmission electron microscopy (TEM)) and quantitative (LC50) analyses were employed in this study. In addition, the production of reactive oxygen species (ROS) in the form of OH was further assessed-as HA or TA increased the production of ROS decreased. The inhibition of bacterial viability in the light treatment groups, with respective treatment organics at concentrations of 10 ppm, was less in TA than in terrestrial HA. SAS was used to analyze the treatment effect of individual factors of light irradiation, DOM, and concentration of TiO2 NPs.

Assessing the effects of surface-bound humic acid on the phototoxicity of anatase and rutile TiO2 nanoparticles in vitro.

In this study, the cytotoxicity of two different crystal phases of TiO2 nanoparticles, with surface modification by humic acid (HA), to Escherichia coli, was assessed. The physicochemical properties of TiO2 nanoparticles were thoroughly characterized. Three different initial concentrations, namely 50, 100, and 200 ppm, of HA were used for synthesis of HA coated TiO2 nanoparticles (denoted as A/RHA50, A/RHA100, and A/RHA200, respectively). Results indicate that rutile (LC50 (concentration that causes 50% mortality compared the control group)=6.5) was more toxic than anatase (LC50=278.8) under simulated sunlight (SSL) irradiation, possibly due to an extremely narrow band gap. It is noted that HA coating increased the toxicity of anatase, but decreased that of rutile. Additionally, AHA50 and RHA50 had the biggest differences compared to uncoated anatase and rutile with LC50 of 201.9 and 21.6, respectively. We then investigated the formation of reactive oxygen species (ROS) by TiO2 nanoparticles in terms of hydroxyl radicals (·OH) and superoxide anions (O2(·-)). Data suggested that O2(·-) was the main ROS that accounted for the higher toxicity of rutile upon SSL irradiation. We also observed that HA coating decreased the generation of ·OH and O2(·-) on rutile, but increased O2(·-) formation on anatase. Results from TEM analysis also indicated that HA coated rutile tended to be attached to the surface of E. coli more than anatase.

Nanotechnology in food science: Functionality, applicability, and safety assessment.

Rapid development of nanotechnology is expected to transform many areas of food science and food industry with increasing investment and market share. In this article, current applications of nanotechnology in food systems are briefly reviewed. Functionality and applicability of food-related nanotechnology are highlighted in order to provide a comprehensive view on the development and safety assessment of nanotechnology in the food industry. While food nanotechnology offers great potential benefits, there are emerging concerns arising from its novel physicochemical properties. Therefore, the safety concerns and regulatory policies on its manufacturing, processing, packaging, and consumption are briefly addressed. At the end of this article, the perspectives of nanotechnology in active and intelligent packaging applications are highlighted.

Trends in infant mortality in United States: a brief study of the Southeastern states from 2005-2009.

While overall infant mortality rates have declined over the past several decades, the Southeastern states have remained the leading states in high infant death in the United States. In this study, we studied the differences in infant mortality in the southeastern United States from 2005 through 2009 according to mother's characteristics (age of mother, marital status, maternal race, maternal education), birth characteristics (month when maternal prenatal care began, birth weight), and infant's characteristics (age of infant at death). This paper illustrates the significance level of each characteristic of mothers and infants, as well as socioeconomic factors that contribute to significant infant mortality that impacts subgroups within the US population. Descriptive statistics and analysis of variance studies were performed and presented. Statistical analysis of the contribution of causes of infant death to infant mortality at the national and state level was elaborated. Data suggest that mothers with no prenatal care had a very high overall infant death rate (5281.83 and 4262.16 deaths per 100,000 births in Mississippi and Louisiana, respectively, whereas the US average was 3074.82 deaths (p < 0.01)). It is suggested that better education and living quality should be available and improved for the residents in Alabama, Louisiana, and Mississippi.

Metal Oxide Nanomaterials in Nanomedicine: Applications in Photodynamic Therapy and Potential Toxicity.

Metal oxide nanomaterials have exhibited excellent performance as nanomedicines in photodynamic therapy (PDT) for cancer and infection treatment. Their unique and tunable physicochemical properties advance them as promising alternatives in drug delivery, early diagnosis, imaging, and treatment against various tumors and infectious diseases. Moreover, the implementation of nanophototherapy in deep tissue sites is enhanced by advancements in photosensitization technology. Notwithstanding the progress made in emerging metal oxide nanomaterials-derived PDT, the potential toxicity towards adjunct tissues associated with this approach remains challenging. Regulation and legislation have also been recommended and subsequently enacted in response to public concerns related to large-scale production, transportation, use, and disposal of those nanomaterials. Consequently, a quantitative structure-activity relationship (QSAR) paradigm has been adopted and is widely used in evaluating and predicting the side effects of nanomedicines, thus influencing their design and fabrication. This article briefly reviews the application of metal oxide nanomaterials in PDT and their associated adverse impacts as reported in recent publications. The future trends and implications of this platform in nanomedicine are also highlighted. However, more studies and efforts have to be carried out for developing novel nano-therapeutics with high selectivity, sensitivity, biocompatibility, and minimal side effects in PDT.

An in vivo study on the photo-enhanced toxicities of S-doped TiO2 nanoparticles to zebrafish embryos (Danio rerio) in terms of malformation, mortality, rheotaxis dysfunction, and DNA damage.

The role of light on the acute toxicities of S-doped and Sigma TiO2 nanoparticles in zebrafish was studied. Metrics included mortality for both, and rheotaxis dysfunction and DNA damage for S-doped only. It was found that the acute toxicity of S-TiO2 nanoparticles was enhanced by simulated sunlight (SSL) irradiation (96-h LC50 of 116.56 ppm) and exceeded that of Sigma TiO2, which was essentially non-toxic. Behavioral disorder, in terms of rheotaxis, was significantly increased by treatment with S-TiO2 nanoparticles under SSL irradiation. In order to further understand its toxicity mechanism, we investigated hair cells in neuromasts of the posterior lateral line (PLL) using DASPEI staining. Significant hair cell damage was observed in the treated larvae. The Comet assay was employed to investigate the DNA damage, which might be responsible for the loss of hair cells. Production of the superoxide anion ([Formula: see text]), a major ROS generated by TiO2 nanoparticles, was assayed and used to postulate causative factors to account for these damages. Oxidative effects were most severe in the liver, heart, intestine, pancreatic duct, and pancreatic islet - results consistent with our earlier findings in the investigation of embryonic malformation. TEM micrographs, used to further investigate the fate of S-TiO2 nanoparticles at the cellular level, suggested receptor-mediated autophagy and vacuolization. Our findings validate the benefit of using the transparent zebrafish embryo as an in vivo model for evaluating photo-induced nanotoxicity. These results highlight the importance of conducting a systematic risk assessment in connection with the use of doped TiO2 nanoparticles in aquatic ecosystems.

Mechanisms of nanotoxicity: generation of reactive oxygen species.

Nanotechnology is a rapidly developing field in the 21(st) century, and the commercial use of nanomaterials for novel applications is increasing exponentially. To date, the scientific basis for the cytotoxicity and genotoxicity of most manufactured nanomaterials are not understood. The mechanisms underlying the toxicity of nanomaterials have recently been studied intensively. An important mechanism of nanotoxicity is the generation of reactive oxygen species (ROS). Overproduction of ROS can induce oxidative stress, resulting in cells failing to maintain normal physiological redox-regulated functions. This in turn leads to DNA damage, unregulated cell signaling, change in cell motility, cytotoxicity, apoptosis, and cancer initiation. There are critical determinants that can affect the generation of ROS. These critical determinants, discussed briefly here, include: size, shape, particle surface, surface positive charges, surface-containing groups, particle dissolution, metal ion release from nanometals and nanometal oxides, UV light activation, aggregation, mode of interaction with cells, inflammation, and pH of the medium.

Using a holistic approach to assess the impact of engineered nanomaterials inducing toxicity in aquatic systems.

In this report, we critically reviewed selected intrinsic physicochemical properties of engineered nanomaterials (ENMs) and their role in the interaction of the ENMs with the immediate surroundings in representative aquatic environments. The behavior of ENMs with respect to dynamic microenvironments at the nano-bio-eco interface level, and the resulting impact on their toxicity, fate, and exposure potential are elaborated. Based on this literature review, we conclude that a holistic approach is urgently needed to fulfill our knowledge gap regarding the safety of discharged ENMs. This comparative approach affords the capability to recognize and understand the potential hazards of ENMs and their toxicity mechanisms, and ultimately to establish a quantitative and reliable system to predict such outcomes.

Synergistic combination of marine oligosaccharides and azithromycin against Pseudomonas aeruginosa.

In this paper we describe how utilization of low molecular weight alginate-derived oligosaccharide (ADO) and chito-oligosaccharide (COS) in conjunction with antibiotics, could more effectively inhibit the growth of wild-type and resistant Pseudomonas aeruginosa. Inhibition is effected by modulating the bacteria's quorum sensing (QS) system, thus regulating biofilm formation and reducing resistance to antibiotic treatment. This can be demonstrated by using conventional MIC screening. COS showed synergistic effects with azithromycin, whereas ADO indicated additive effects against wild-type P. aeruginosa. Using electrospray-ionization mass spectroscopy (ESI-MS), matrix-assisted laser desorption/ionization-time of flightmass spectroscopy (MALDI-TOF-MS) and nuclear magnetic resonance (NMR), the chemical structure of ADO and of COS was characterized. The wild-type and resistant strains were identified by 16S rRNA sequence analysis. This report demonstrates the feasibility of attenuating the tolerance of P. aeruginosa to azithromycin by using specific marine oligosaccharides.

Effects of light energy and reducing agents on C60-mediated photosensitizing reactions.

Many biomolecules contain photoactive reducing agents, such as reduced nicotinamide adenine dinucleotide (NADH) and 6-thioguanine (6-TG) incorporated into DNA through drug metabolism. These reducing agents may produce reactive oxygen species under UVA irradiation or act as electron donors in various media. The interactions of C60 fullerenes with biological reductants and light energy, especially via the Type-I electron-transfer mechanism, are not fully understood although these factors are often involved in toxicity assessments. The two reductants employed in this work were NADH for aqueous solutions and 6-TG for organic solvents. Using steady-state photolysis and electrochemical techniques, we showed that under visible light irradiation, the presence of reducing agents enhanced C60 -mediated Type-I reactions that generate superoxide anion (O2(.-)) at the expense of singlet oxygen ((1)O2) production. The quantum yield of O2(.-) production upon visible light irradiation of C60 is estimated below 0.2 in dipolar aprotic media, indicating that the majority of triplet C60 deactivate via Type-II pathway. Upon UVA irradiation, however, both C60 and NADH undergo photochemical reactions to produce O2(.-), which could lead to a possible synergistic toxicity effects. C60 photosensitization via Type-I pathway is not observed in the absence of reducing agents.

Using experimental data of Escherichia coli to develop a QSAR model for predicting the photo-induced cytotoxicity of metal oxide nanoparticles.

A quantitative structure-activity relationship (QSAR) study of seventeen metal oxide nanoparticles (MNPs), in regard to their photo-induced toxicity to bacteria Escherichia coli, was developed by using quantum chemical methods. A simple and statistically significant QSAR model (F=33.83, R(2)=0.87) was successfully developed for the dark group based on two descriptors, absolute electronegativity of the metal and the metal oxide. Similarly, a best correlation (F=20.51, R(2)=0.804) was obtained to predict the photo-induced toxicity of MNPs by using two descriptors, molar heat capacity and average of the alpha and beta LUMO (lowest unoccupied molecular orbital) energies of the metal oxide. Revelation of these influential molecular descriptors may be useful in elucidating the mechanisms of nanotoxicity and for predicting the environmental risk associated with release of the MNPs. In addition, the developed model may have a role in the future design and manufacture of safe nanomaterials.

Determination of the mechanism of photoinduced toxicity of selected metal oxide nanoparticles (ZnO, CuO, Co3O4 and TiO2) to E. coli bacteria.

Cytotoxicity of selected metal oxide nanoparticles (MNPs) (ZnO, CuO, Co3O4 and TiO2) was investigated in Escherichia coli both under light and dark conditions. Cytotoxicity experiments were conducted with spread plate counting and the LC50 values were calculated. We determined the mechanism of toxicity via measurements of oxidative stress, reduced glutathione, lipid peroxidation, and metal ions. The overall ranking of the LC50 values was in the order of ZnO < CuO < Co3O4 < TiO2 under dark condition and ZnO < CuO < TiO2 < Co3O4 under light condition. ZnO MNPs were the most toxic among the tested nanoparticles. Our results indicate depletion of reduced glutathione level and elevation of malondialdehyde level correlated with the increase in oxidative stress. Released metal ions were found to have partial effect on the toxicity of MNPs to E. coli. In summary, the dynamic interactions of multiple mechanisms lead to the toxicity of the tested MNPs to E. coli.

Photoinactivation of Escherichia coli by sulfur-doped and nitrogen-fluorine-codoped TiO2 nanoparticles under solar simulated light and visible light irradiation.

Titanium dioxide (TiO2) is one of the most widely used photocatalysts for the degradation of organic contaminants in water and air. Visible light (VL) activated sulfur-doped TiO2 (S-TiO2) and nitrogen-fluorine-codoped TiO2 (N-F-TiO2) were synthesized by sol-gel methods and characterized. Their photoinactivation performance was tested against Escherichia coli under solar simulated light (SSL) and VL irradiation with comparison to commercially available TiO2. Undoped Degussa-Evonik P-25 (P-25) and Sigma-TiO2 showed the highest photocatalytic activity toward E. coli inactivation under SSL irradiation, while S-TiO2 showed a moderate toxicity. After VL irradiation, Sigma-TiO2 showed higher photoinactivation, whereas S-TiO2 and P-25 showed moderate toxicity. Oxidative stress to E. coli occurred via formation of hydroxyl radicals leading to lipid peroxidation as the primary mechanism of bacterial inactivation. Various other biological models, including human keratinocytes (HaCaT), zebrafish liver cells (ZFL), and zebrafish embryos were also used to study the toxicity of TiO2 NPs. In conclusion, N-F-TiO2 did not show any toxicity based on the assay results from all the biological models used in this study, whereas S-TiO2 was toxic to zebrafish embryos under all the test conditions. These findings also demonstrate that the tested TiO2 nanoparticles do not show any adverse effects in HaCaT and ZFL cells.

In vitro cytotoxicity of CdSe/ZnS quantum dots with different surface coatings to human keratinocytes HaCaT cells.

Quantum dots (QD) nanoparticles have been widely used in biomedical and electronics fields, because of their novel optical properties. Consequently it confers enormous potential for human exposure and environmental release. To increase the biocompatibility of QDs, a variety of surface coatings or functional groups are added to increase their bioactivity and water solubility. Human adult low calcium high temperature (HaCaT) cells are the epithelial cells derived from adult human skin that exhibits normal differentiation capacity and a DNA fingerprint pattern that is unaffected by long-term cultivation, transformation, or the presence of multiple chromosomal alternations. Human keratinocytes, HaCaT cells were used to systematically evaluate the cytotoxicity of biocompatible QD made of CdSe metal core and ZnS shell with three different coatings and at three different wavelengths (530, 580 and 620 nm). In terms of half-maximal inhibitory concentration, QSA-QDs with amine-polyethyleneglycol coating and QSH-QDs with amphiphilic polymer coating were not cytotoxic, while QEI-QDs with polyethylenimine coating were highly toxic to the HaCaT cells in comparison to a reference CuInS2/ZnS. QEI-QDs led to significant increase in reactive oxygen species, decrease in mitochondrial membrane potential and DNA damage in HaCaT cells. The mechanisms of toxicity of QEI-530 and QEI-580 can be attributed to the combination of intracellular reactive oxygen species production and loss of MMP. The QDs toxicity can be attributed to the polyethylemimine surface coating which was highly toxic to cells in comparison with amine-polyethyleneglycol, but not due to the release of cadmium ions.

Effect of humic acids and sunlight on the cytotoxicity of engineered zinc oxide and titanium dioxide nanoparticles to a river bacterial assemblage.

The effect of a terrestrial humic acid (HA) and Suwannee River HA on the cytotoxicity of engineered zinc oxide nanoparticles (ZnONPs) and titanium dioxide nanoparticles (TiO2NPs) to natural aquatic bacterial assemblages was measured with spread plate counting. The effect of HA (10 and 40 ppm) on the cytotoxicity of ZnONPs and TiO2NPs was tested factorially in the presence and absence of natural sunlight (light irradiation (LI)). The experiment was of full factorial, completely randomized design and the results were analyzed using the General Linear Model in SAS analytical software. The method of least squares means was used to separate the means or combinations of means. We determined the mechanism of toxicity via measurements of oxidative stress and metal ions. The toxicity of ZnONPs and TiO2NPs to natural aquatic bacterial assemblages appears to be concentration dependent. Moreover, the cytotoxicity of ZnONPs and TiO2NPs appeared to be affected by HA concentration, the presence of sunlight irradiation, and the dynamic multiple interactions among these factors. With respect to light versus darkness in the control group, the data indicate that bacterial viability was inhibited more in the light exposure than in the darkness exposure. The same was true in the HA treatment groups. With respect to terrestrial versus Suwanee River HA for a given nanoparticle, in light versus darkness, bacterial viability was more inhibited in the light treatment groups containing the terrestrial HA than in those containing Suwanee River HA. Differences in the extent of reactive oxygen species formation, adsorption/binding of ZnONPs/TiO2NPs by HA, and the levels of free metal ions were speculated to account for the observed cytotoxicity. TEM images indicate the attachment and binding of the tested nanoparticles to natural bacterial assemblages. Besides the individual parameter, significant effects on bacterial viability count were also observed in the following combined treatments: HA-ZnONPs, HA-LI, ZnONPs-LI, and HA-ZnONPs-LI. The main effects of all independent variables, plus interaction effects in all cases were significant with TiO2NPs.

A study of the mechanism of in vitro cytotoxicity of metal oxide nanoparticles using catfish primary hepatocytes and human HepG2 cells.

Nanoparticles (NPs), including nanometal oxides, are being used in diverse applications such as medicine, clothing, cosmetics and food. In order to promote the safe development of nanotechnology, it is essential to assess the potential adverse health consequences associated with human exposure. The liver is a target site for NP toxicity, due to NP accumulation within it after ingestion, inhalation or absorption. The toxicity of nano-ZnO, TiO(2), CuO and Co(3)O(4) was investigated using a primary culture of channel catfish hepatocytes and human HepG2 cells as in vitro model systems for assessing the impact of metal oxide NPs on human and environmental health. Some mechanisms of nanotoxicity were determined by using phase contrast inverted microscopy, 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assays, reactive oxygen species (ROS) assays, and flow cytometric assays. Nano-CuO and ZnO showed significant toxicity in both HepG2 cells and catfish primary hepatocytes. The results demonstrate that HepG2 cells are more sensitive than catfish primary hepatocytes to the toxicity of metal oxide NPs. The overall ranking of the toxicity of metal oxides to the test cells is as follows: TiO(2)