Metal oxide nanoparticles are used in a wide range of commercial products, leading to an increased interest in the behavior of these materials in the aquatic environment. The current study focuses on the stability of some of the smallest ZnO nanomaterials, 4 ± 1 nm in diameter nanoparticles, in aqueous solutions as a function of pH and ionic strength as well as upon the adsorption of humic acid. Measurements of nanoparticle aggregation due to attractive particle-particle interactions show that ionic strength, pH, and adsorption of humic acid affect the aggregation of ZnO nanoparticles in aqueous solutions, which are consistent with the trends expected from Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Measurements of nanoparticle dissolution at both low and high pH show that zinc ions can be released into the aqueous phase and that humic acid under certain, but not all, conditions can increase Zn(2+)(aq) concentrations. Comparison of the dissolution of ZnO nanoparticles of different nanoparticle diameters, including those near 15 and 240 nm, shows that the smallest nanoparticles dissolve more readily. Although qualitatively this enhancement in dissolution can be predicted by classical thermodynamics, quantitatively it does not describe the dissolution behavior very well.
Understanding size-dependent processes, including dissolution, of engineered nanoparticles is essential in addressing the potential environmental and health impacts of these materials as well as their long-term stability. In this study, experimental measurements of size-dependent dissolution of well-characterized zinc oxide (ZnO) nanoparticles with particle diameters in the range of 4 to 130 nm have been measured at circumneutral pH (pH 7.5) and compared. Dissolution was found to be enhanced with smaller ZnO nanoparticles compared to larger-sized particles, even though the nanoparticles were present in solution as aggregates with hydrodynamic diameters on the order of 1-3 μm in size. The presence of citric acid significantly enhanced the extent of ZnO dissolution for all sizes, and the greatest enhancement was observed for the 4 nm particles. Although these results are found to be in qualitative agreement with theoretical predictions, a linearized form of the Kelvin equation to calculate a surface free energy yielded quantities inconsistent with expected values from the literature. Reasons for this inconsistency are discussed and include potential deviations of solubility behavior from classical thermodynamics as a result of a lack of detailed knowledge of surface structure and surface properties, including the presence of different surface crystal facets, and the aggregation state.
We developed an electrospun carbon nanofiber-carbon nanotube (CNF-CNT) composite with optimal sorption capacity and material strength for point-of-use (POU) water treatment. Synthesis variables including integration of multiwalled carbon nanotubes (CNTs) and macroporosity (via sublimation of phthalic acid), relative humidity (20 and 40%), and stabilization temperature (250 and 280 °C) were used to control nanofiber diameter and surface area (from electron microscopy and BET isotherms, respectively), surface composition (from XPS), and strength (from AFM nanoindentation and tensile strength tests). Composites were then evaluated using kinetic, isotherm, and pH-edge sorption experiments with sulfamethoxazole (log Kow = 0.89) and atrazine (log Kow = 2.61), representative micropollutants chosen for their different polarities. Although CNFs alone were poor sorbents, integration of CNTs and macroporosity achieved uptake comparable to granular activated carbon. Through reactivity comparisons with CNT dispersions, we propose that increasing macroporosity exposes the embedded CNTs, thereby enabling their role as the primary sorbent in nanofiber composites. Because the highest capacity sorbents lacked sufficient strength, our optimal formulation (polyacrylonitrile 8 wt %, CNT 2 wt %, phthalic acid 2.4 wt %; 40% relative humidity; 280 °C stabilization) represents a compromise between strength and performance. This optimized sorbent was tested with a mixture of ten organic micropollutants at environmentally relevant concentrations in a gravity-fed, flow-through filtration system, where removal trends suggest that both hydrophobic and specific binding interactions contribute to micropollutant uptake. Collectively, this work highlights the promise of CNF-CNT filters (e.g., mechanical strength, ability to harness CNT sorption capacity), while also prioritizing areas for future research and development (e.g., improved removal of highly polar micropollutants, sensitivity to interfering cosolutes).
Ag(I) is used to form a π-stacked metal-organic solid that exhibits remarkably high electrical conductivity. The solid undergoes a single-crystal-to-single-crystal [2+2] photodimerization to generate a 1D coordination polymer with over 40% higher conductivity. The Ag(I) complex represents the first example of an increase in conductivity resulting from a [2+2] photodimerization. Density of states calculations show a higher contribution from Ag(I) ions to the valence band in the photodimerized solid, supporting the increase in conductivity.
A correlation between Young's modulus, as determined by using nanoindentation atomic force microscopy (AFM), and atomic polarizability is observed for members of a series of cocrystals based on systematic changes to one cocrystal component. Time domain spectroscopy over terahertz frequencies (THz-TDS) is used for the first time to directly measure the polarizability of macro- and nanosized organic solids. Cocrystals of both macro- and nanodimensions with highly polarizable atoms result in softer solids and correspondingly higher polarizabilities.
Nano-dimensional crystals of aspirin generated through sonochemistry exhibit Young's modulus values an order of magnitude softer than macro-dimensional crystals.
Importance of the thermal annealing in solar cell fabrication. Evaluation of the surface morphology with AFM. Measuring the device efficiency and its relation with the surface roughness.
Currently, there is an increased demand for advanced food packages, which can significantly increase the shelf life of food items. In the current context, it is envisaged that nanotechnology has the potential to address stability, toxicity, shelf-life, and low-cost issues of antimicrobials associated with the packaging industry. Antimicrobial nanocomposite systems are believed to be more efficient than their microscale counterparts due to the high surface area to volume ratio and quantum mechanical involvement in deciding their properties. As a result of high surface area, they are able to attach more copies of microbial molecules and cells, thus reducing the quantity of material required while significantly improving their activity. This study focuses on the development of slow-release antimicrobial material based on natural citrate (α-hydroxycitrate) intercalated layered double hydroxide (LDH) nanohybrid. Natural citrate ions available in Citrus aurantifolia (lime) were extracted by a simple chemical method and intercalated into Mg-Al-Layered Double Hydroxide following a one-step co-precipitation method. Successful intercalation of the citrate ion was confirmed by powder X-ray diffraction (PXRD) and Fourier transform infrared (FTIR) spectroscopic analysis. Release kinetics of resulted nanohybrid was studied and compared using different release kinetic models. Antimicrobial properties of this novel nanohybrid were confirmed against two common food pathogens, Colletotrichum gloeosporioides and Saccharomyces cerevisiae, and the results were compared against sodium benzoate, which is the commonly used commercial antimicrobial agent in the food industry. Successful intercalation of natural citrate ions into LDH and its activity against the tested microbes show the potential of using it as a slow-release nanohybrid material in many food-related applications.
Keywords: Layered Double Hydroxide, α-Hydroxycitrate, Natural, Safe, Lime Extract, Slow Release, Antimicrobial
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