skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Photochemistry of ferritin decorated with plasmonic gold nanoparticles
The photochemistry of a plasmonic biomaterial that consisted of gold nanoparticles (AuNP) on the exterior of the iron sequestration protein, ferritin (Ftn), was investigated. The light driven photochemistry of the hybrid system was studied mechanistically and for the reduction of the high priority pollutant, chromate, Cr( vi ) as CrO 4 2− . In the absence of aqueous Cr( vi ), but in the presence of a sacrificial electron donor, the Fe( iii ) oxyhydroxide semiconducting core of Ftn underwent a photoreaction to release Fe( ii ) when exposed to light having wavelengths, λ < 475 nm. AuNP grown on the exterior of the Ftn produced plasmonic heterostructures (Au/Ftn) that allowed similar photochemistry to occur at longer wavelengths of light ( i.e. , λ > 475 nm). Au/Ftn also facilitated the reduction of Cr( vi ) to Cr( iii ) in the presence of visible light ( λ > 475 nm), a reaction that was not observed if AuNP were not attached to the Ftn cage. Results also indicated that AuNP need to be intimately bound to Ftn to extend the photochemistry of Au/Ftn to longer light wavelengths, relative to Au-free Ftn.  more » « less
Award ID(s):
1708793
PAR ID:
10111969
Author(s) / Creator(s):
; ; ; ; ;
Date Published:
Journal Name:
Environmental Science: Nano
Volume:
6
Issue:
1
ISSN:
2051-8153
Page Range / eLocation ID:
85 to 93
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Hexavalent chromium, Cr(VI), is a highly toxic carcinogen occurring in natural and industrial environments. Pathways to economical reduction to the more benign trivalent form, Cr(III), are necessary for treatment of contaminated groundwater. Magnetite’s (Fe3O4) mixture of Fe(II) and Fe(III) make it a promising material for remediation. This study investigated the mechanisms for reduction of Cr(VI) catalyzed by Fe3O4as a redox mediator in the presence of oxalic acid in HClO4and SO42−solutions, a system where the interactions among these species are not fully understood. The reduction of Cr(VI) in different anion environments is first measured on an Au rotating disk electrode. SO42−inhibits the formation of a passivation layer and Cl-partially inhibits passivation. The reduction of Cr(VI) on Fe3O4is limited by the availability of Fe(II) surface sites. Addition of oxalic acid works synergistically through liberation of Fe(II)-oxalate and soluble Cr(III)-oxalate products. A combination of Fe3O4activated by exposure to oxalic acid and use of an oxalic acid solution as a medium for reduction of Cr(VI) produces over 97% removal of Cr(VI). These results provide relevant insights regarding interactions of Fe3O4with organic acids and the anion environment which lead to the effective reduction of Cr(VI). 
    more » « less
  2. Abstract Incorporation of metallic nanoparticles (NPs) in polymer matrix has been used to enhance and control dissolution and release of drugs, for targeted drug delivery, as antimicrobial agents, localized heat sources, and for unique optoelectronic applications. Gold NPs in particular exhibit a plasmonic response that has been utilized for photothermal energy conversion. Because plasmonic nanoparticles typically exhibit a plasmon resonance frequency similar to the visible light spectrum, they present as good candidates for direct photothermal conversion with enhanced solar thermal efficiency in these wavelengths. In our work, we have incorporated ∼3-nm-diameter colloidal gold (Au c ) NPs into electrospun polyethylene glycol (PEG) fibers to utilize the nanoparticle plasmonic response for localized heating and melting of the polymer to release medical treatment. Au c and Au c in PEG (PEG+Au c ) both exhibited a minimum reflectivity at 522 nm or approximately green wavelengths of light under ultraviolet-visible (UV-Vis) spectroscopy. PEG+Au c ES fibers revealed a blue shift in minimum reflectivity at 504 nm. UV-Vis spectra were used to calculate the theoretical efficiency enhancement of PEG+Au c versus PEG alone, finding an approximate increase of 10 % under broad spectrum white light interrogation, and ∼14 % when illuminated with green light. Au c enhanced polymers were ES directly onto resistance temperature detectors and interrogated with green laser light so that temperature change could be recorded. Results showed a maximum increase of 8.9 °C. To further understand how gold nanomaterials effect the complex optical properties of our materials, spectroscopic ellipsometry was used. Using spectroscopic ellipsometry and modeling with CompleteEASE® software, the complex optical constants of our materials were determined. The complex optical constant n (index of refraction) provided us with optical density properties related to light wavelength divided by velocity, and k (extinction coefficient) was used to show the absorptive properties of the materials. 
    more » « less
  3. Ultrathin and two-dimensional (2D) metals can support strong plasmons, with concomitant tight field confinement and large field enhancement. Accordingly, 2D-metal nanostructures exhibiting plasmonic resonances are highly sensitive to the environment and intrinsically suitable for optical sensing. Here, based on a proof-of-concept numerical study, nano-engineered ultrathin 2D-metal films that support infrared plasmons are demonstrated to enable highly responsive refractive index (RI) sensing. For 3 nm-Au nanoribbons exhibiting plasmonic resonances at wavelengths around 1600 nm, a RI sensitivity of SRI > 650 nm per refractive index unit (RIU) is observed for a 100 nm-thick analyte layer. A parametric study of the 2D-Au system indicates the strong dependence of the RI sensitivity on the 2D-metal thickness. Furthermore, for an analyte layer as thin as 1 nm, a RI sensitivity up to 110 (90 nm/RIU) is observed in atomically thin 2D-In (2D-Ga) nanoribbons exhibiting highly localized plasmonic resonances at mid-infrared wavelengths. Our results not only reveal the extraordinary sensing characteristics of 2D-metal systems but also provide insight into the development of 2D-metal-based plasmonic devices for enhanced IR detection. 
    more » « less
  4. Municipalities in central Oklahoma, U.S.A. increasingly rely on water drawn from the Central Oklahoma Aquifer (COA) as surface water resources have not grown in proportion to population and current water demands. However, water drawn from certain regions of the COA frequently contains elevated levels of naturally occurring hexavalent chromium. Rock samples from the Norman Arsenic Test Hole Core (NATHC) were investigated to identify the mineralogic host(s) of Cr and mechanisms of Cr( vi ) release via bulk mineralogy and chemistry measurements, selective chemical extractions, and microscale elemental analyses. Results demonstrate most COA Cr is contained in Fe oxides and clays as isomorphic substitutions for Fe( iii ). Analyses of regional groundwater data, including hierarchical clustering methods and GIS, demonstrate the most intense Cr( vi ) occurrence is linked to cation exchange with Na-clays at depth. Cation exchange allows dissolution of Mn-bearing dolomite, which in turn produces Mn oxides in otherwise dolomite-saturated groundwaters. Mn oxides in turn are known to oxidize Cr( iii ) to Cr( vi ). In general, co-occurrence of Mn-bearing carbonates and exchangeable clays in any aquifer, particularly those with Cr( iii ) present in iron oxide cements, serve as ingredients for groundwater occurrences of oxidizable trace metals. 
    more » « less
  5. Abstract Dissolved organic matter (DOM) impacts the structure and function of aquatic ecosystems. DOM absorbs light in the UV and visible (UV–Vis) wavelengths, thus impacting light attenuation. Because absorption by DOM depends on its composition, UV–Vis absorbance is used to constrain DOM composition, source, and amount. Ferric iron, Fe(III), also absorbs in the UV–Vis; when Fe(III) is present, DOM-attributed absorbance is overestimated. Here, we explore how differing behavior of DOM and Fe(III) at the catchment scale impacts UV–Vis absorbance and evaluate how system-specific variability impacts the effectiveness of existing Fe(III) correction factors in a temperate watershed. We sampled five sites in the Connecticut River mainstem bi-weekly for ~ 1.5 years, and seven sites in the Connecticut River watershed once during the summer 2019. We utilized size fractionation to isolate the impact of DOM and Fe(III) on absorbance and show that variable contributions of Fe(III) to absorbance at 254 nm (a 254 ) and 412 nm (a 412 ) by size fraction complicates correction for Fe(III). We demonstrate that the overestimation of DOM-attributed absorbance by Fe(III) is correlated to the Fe(III):dissolved organic carbon concentration ratio; thus, overestimation can be high even when Fe(III) is low. a 254 overestimation is highly variable even within a single system, but can be as high as 53%. Finally, we illustrate that UV-Vis overestimation might impart bias to seasonal, discharge, and land-use trends in DOM quality. Together, these findings argue that Fe(III) should be measured in tandem with UV–Vis absorbance for estimates of CDOM composition or amount. 
    more » « less