Project description:The use of diverse metal nanoparticles (MNPs) in a wide range of commercial products has led to their co-existence in the aqueous environment. The current study explores the dispersion and aggregation fate of five prominent MNPs (silver, copper, iron, nickel, and titanium), in both their individual and co-existing forms. We address a knowledge gap regarding their environmental fate under turbulent condition akin to flowing rivers. We present tandem analytical techniques based on dynamic light scattering, ultraviolet-visible spectroscopy, and inductively coupled plasma atomic emission spectroscopy for discerning their dispersion behavior under residence times of turbulence, ranging from 0.25 to 4 h. The MNPs displayed a multimodal trend for dispersion and aggregation behavior with suspension time in aqueous samples. The extent of dispersion was variable and depended upon intrinsic properties of MNPs. However, the co-existing MNPs displayed a dominant hetero-aggregation effect, independent of the residence times. Further research with use of real-world environmental samples can provide additional insights on the effects of sample chemistry on MNPs fate.
Project description:Organic capping agents are a ubiquitous and crucial part of preparing reproducible and homogeneous batches of nanomaterials, particularly nanocrystals with well-defined facets. Despite studies reporting surface ligands (e.g., capping agents) having a non-negligible role in catalytic behavior, their impact is less understood in contaminant adsorption, an important consideration given their potential to obfuscate facet-dependent trends in performance. To ascribe observed behaviors to the facet or the ligand, this report evaluates the impact of poly(N-vinyl-2-pyrrolidone) (PVP), a commonly utilized capping agent, on the adsorption performance of nanohematite particles of varying prevailing facet in the removal of selenite (Se(IV)) as a model system. The PVP capping agent reduces the available surface area for contaminant binding, thus resulting in a reduction in overall Se(IV) adsorbed. However, accounting for the effects of surface area, {012}-faceted nanohematite demonstrates a significantly higher sorption capacity for Se(IV) compared with that of {001}-faceted nanohematite. Notably, chemical treatment is minimally effective in removing strongly bound PVP, indicating that complete removal of surface ligands remains challenging.
Project description:Highlights • Hematite with {012} facets exhibited the optical performance of PS photoaging.• •OH played an important role in PS photoaging.• The reaction path of PS photoaging was elucidated by 2D correlation spectroscopy.• The lower activation energy of {012} facets enhanced the water oxidation to •OH. Hematite, as an extensive natural mineral with multiple crystal facets, profoundly affects the migration and transformation of pollutants in the natural environment. However, little is known about the photochemical behavior of microplastics on different facets of hematite in the aquatic environment. In this work, the photoaging of polystyrene microplastics (PS-MPs) on different crystal planes ({001}, {100}, and {012} facets) and related mechanisms were studied. Two-dimensional correlation spectroscopy analysis illustrated that the reaction pathways of PS-MPs photoaging on hematite tended to preferential chemical oxidization. The stronger performance of PS-MPs photoaging, expressed by particle size reduction and surface oxidation, was observed on the {012} crystal facet. Under irradiation, {012} facet-dominated hematite with a narrower bandgap (1.93 eV) reinforced the photogenerated charge carrier separation, and the lower activation energy barrier (1.41 eV calculated from density functional theory) led to effective •OH formation from water oxidation. These findings elucidate the underlying photoaging mechanism of MPs on hematite with different mineralogical phases. Graphical abstract Image, graphical abstract
Project description:Controlling the structure of graphene oxide (GO) phases and their smaller analogues, graphene (oxide) quantum dots (GOQDs), is vitally important for any of their widespread intended applications: highly ordered arrangements of nanoparticles for thin-film or membrane applications of GO, dispersed nanoparticles for composite materials and three-dimensional porous arrangements for hydrogels. In aqueous environments, it is not only the chemical composition of the GO flakes that determines their morphologies; external factors such as pH and the coexisting cations also influence the structures formed. By using accurate models of GO that capture the heterogeneity of surface oxidation and very large-scale coarse-grained molecular dynamics that can simulate the behaviour of GO at realistic sizes of GOQDs, the driving forces that lead to the various morphologies in aqueous solution are resolved. We find the morphologies are determined by a complex interplay between electrostatic, [Formula: see text]-[Formula: see text] and hydrogen bonding interactions. Assembled morphologies can be controlled by changing the degree of oxidation and the pH. In acidic aqueous solution, the GO flakes vary from fully aggregated over graphitic domains to partial aggregation via hydrogen bonding between hydroxylated domains, leading to the formation of planar extended flakes at high oxidation ratios and stacks at low oxidation ratios. At high pH, where the edge carboxylic acid groups are deprotonated, electrostatic repulsion leads to more dispersion, but a variety of aggregation behaviour is surprisingly still observed: over graphitic regions, via hydrogen bonding and "face-edge" interactions. Calcium ions cause additional aggregation, with a greater number of "face-face" and "edge-edge" aggregation mechanisms, leading to irregular aggregated structures. "Face-face" aggregation mechanisms are enhanced by the GO flakes possessing distinct domains of hydroxylated and graphitic regions, with [Formula: see text]-[Formula: see text] and hydrogen bonding interactions prevalent between these regions on aggregated flakes respectively. These findings furnish explanations for the aggregation characteristics of GO and GOQDs, and provide computational methods to design directed synthesis routes for self-assembled and associated applications.
Project description:This article presents the synthesis and characterization of biocompatible superparamagnetic iron oxide nanoparticles (SPIONs) coated with ultrathin layer of anionic derivative of chitosan. The water-based fabrication involved a two-step procedure. In the first step, the nanoparticles were obtained by co-precipitation of ferrous and ferric aqueous salt solutions with ammonia in the presence of cationic derivative of chitosan. In the second step, such prepared materials were subjected to adsorption of oppositely charged chitosan derivative which resulted in the preparation of negatively charged SPIONs. They were found to develop highly stable dispersion in water. The core size of the nanocoated SPIONs, determined using transmission electron microscopy, was measured to be slightly above 10 nm. The coated nanoparticles form aggregates with majority of them having hydrodynamic diameter below 100 nm, as measured by dynamic light scattering. Their composition and properties were studied using FTIR and thermogravimetric analyses. They exhibit magnetic properties typical for superparamagnetic material with a high saturation magnetization value of 123 ± 12 emu g(-1) Fe. Very high value of the measured r(2) relaxivity, 369 ± 3 mM(-1) s(-1), is conducive for the potential application of the obtained SPIONs as promising contrast agents in magnetic resonance imaging. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s11051-012-1372-9) contains supplementary material, which is available to authorized users.
Project description:In the framework of a protein-ligand-fishing strategy to identify proteins that bind to trans-resveratrol, a natural phenolic compound with pharmacological benefits, we have developed magnetic nanoparticles covalently linked to trans-resveratrol through three different derivatives and examined their aggregation behavior in aqueous solution. The monodispersed magnetic core (18 nm diameter) with its mesoporous silica shell (93 nm diameter) exhibited a notable superparamagnetic behavior useful for magnetic bioseparation. The hydrodynamic diameter, deduced from dynamic light scattering analysis, of the nanoparticle increased from 100 to 800 nm when the aqueous buffer changed from pH 10.0-3.0. A size polydispersion occurred from pH 7.0-3.0. In parallel, the value of the extinction cross section increased according to a negative power law of the UV wavelength. This was mainly due to light scattering by mesoporous silica, whereas the absorbance cross section remained very low in the 230-400 nm domain. The three types of resveratrol-grafted magnetic nanoparticles exhibited similar scattering properties, but their absorbance spectrum was consistent with the presence of trans-resveratrol. Their functionalization increased their negative zeta potential when pH increased from 3.0 to 10.0. The mesoporous nanoparticles were monodispersed in alkaline conditions, where their anionic surface strongly repulsed each other but aggregated progressively under van der Waals forces and hydrogen bonding when negative zeta potential decreased. The characterized results of nanoparticle behavior in aqueous solution provide critical insight for further study of nanoparticles with proteins in biological environment.
Project description:Understanding structure and function of solid-liquid interfaces is essential for the development of nanomaterials for various applications including heterogeneous catalysis in liquid phase processes and water splitting for storage of renewable electricity. The characteristic anisotropy of crystalline nanoparticles is believed to be essential for their performance but remains poorly understood and difficult to characterize. Dual scale atomic force microscopy is used to measure electrostatic and hydration forces of faceted semiconducting SrTiO3 nanoparticles in aqueous electrolyte at variable pH. The following are demonstrated: the ability to quantify strongly facet-dependent surface charges yielding isoelectric points of the dominant {100} and {110} facets that differ by as much as 2 pH units; facet-dependent accumulation of oppositely charged (SiO2 ) particles; and that atomic scale defects can be resolved but are in fact rare for the samples investigated. Atomically resolved images and facet-dependent oscillatory hydration forces suggest a microscopic charge generation mechanism that explains colloidal scale electrostatic forces.
Project description:Phthalate esters (PAEs) have been extensively used as additives in plastics and wallcovering, causing severe environmental contamination and increasing public health concerns. Here, we find that hematite nanoparticles with specific facet-control can efficiently catalyze PAEs hydrolysis under ambient humidity conditions, with the hydrolysis rates 2 orders of magnitude higher than that in water saturated condition. The catalytic performance of hematite shows a significant facet-dependence with the reactivity in the order {012} > {104} ≫ {001}, related to the atomic array of surface undercoordinated Fe. The {012} and {104} facets with the proper neighboring Fe-Fe distance of 0.34-0.39 nm can bidentately coordinate with PAEs, and thus induce much stronger Lewis-acid catalysis. Our study may inspire the development of nanomaterials with appropriate surface atomic arrays, improves our understanding for the natural transformation of PAEs under low humidity environment, and provides a promising approach to remediate/purify the ambient air contaminated by PAEs. With a combined experimental and computational study, Jin et al. demonstrate that hematite nanoparticles can efficiently degrade phthalates under ambient humidity conditions, with a rate strongly dependent on the exposed facet via bidentate coordination involving neighbor Fe atoms, suggesting their possible use for indoor air purification
Project description:Biomimetic synthetic functional materials are valuable for a large number of practical applications with improved or tunable performance. In this paper, we present a series of mussel-inspired biomimetic catechol-containing copolymers synthesized from dopamine methacrylamide (DMA) and 2-(2-ethoxyethoxy)ethyl acrylate (EEA) and abbreviated as poly(PDMA-PEEA). The successfully synthesized adhesive polymers allow adhering polytetrafluoroethylene (PTFE) and were used for coating PTFE particles in organic solvent and re-dispersion in an aqueous medium. Adhesive polymer coated PTFE particles were efficiently used as a nanoreactor for generating silver (Ag) metal nanoparticles (NPs).
Project description:The aggregation and colloidal stability of three, commercially-available, gamma-aluminum oxide nanoparticles (γ-Al₂O₃ NPs) (nominally 5, 10, and 20-30 nm) were systematically examined as a function of pH, ionic strength, humic acid (HA) or clay minerals (e.g., montmorillonite) concentration using dynamic light scattering and transmission electron microscopy techniques. NPs possess pH-dependent surface charges, with a point of zero charge (PZC) of pH 7.5 to 8. When pH < PZC, γ-Al₂O₃ NPs are colloidally stable up to 100 mM NaCl and 30 mM CaCl₂. However, significant aggregation of NPs is pronounced in both electrolytes at high ionic strength. In mixed systems, both HA and montmorillonite enhance NP colloidal stability through electrostatic interactions and steric hindrance when pH ≤ PZC, whereas their surface interactions are quite limited when pH > PZC. Even when pH approximates PZC, NPs became stable at a HA concentration of 1 mg·L-1. The magnitude of interactions and dominant sites of interaction (basal planes versus edge sites) are significantly dependent on pH because both NPs and montmorillonite have pH-dependent (conditional) surface charges. Thus, solution pH, ionic strength, and the presence of natural colloids greatly modify the surface conditions of commercial γ-Al₂O₃ NPs, affecting aggregation and colloidal stability significantly in the aqueous environment.