skip to main content


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
NSF-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. null (Ed.)
    Photoactivatable protecting groups (PPGs) are useful for a broad range of applications ranging from biology to materials science. In chemical biology, induction of biological processes via photoactivation is a powerful strategy for achieving spatiotemporal control. The importance of cysteine, glutathione, and other bioactive thiols in regulating protein structure/activity and cell redox homeostasis makes modulation of thiol activity particularly useful. One major objective for enhancing the utility of photoactivatable protecting groups (PPGs) in living systems is creating PPGs with longer wavelength absorption maxima and efficient two-photon (TP) absorption. Toward these objectives, we developed a carboxyl- and dimethylamine-functionalized nitrodibenzofuran PPG scaffold (cDMA-NDBF) for thiol photoactivation, which has a bathochromic shift in the one-photon absorption maximum from λ max = 315 nm with the unfunctionalized NDBF scaffold to λ max = 445 nm. While cDMA-NDBF-protected thiols are stable in the presence of UV irradiation, they undergo efficient broad-spectrum TP photolysis at wavelengths as long as 900 nm. To demonstrate the wavelength orthogonality of cDMA-NDBF and NDBF photolysis in a biological setting, caged farnesyltransferase enzyme inhibitors (FTI) were prepared and selectively photoactivated in live cells using 850–900 nm TP light for cDMA-NDBF-FTI and 300 nm UV light for NDBF-FTI. These experiments represent the first demonstration of thiol photoactivation at wavelengths above 800 nm. Consequently, cDMA-NDBF-caged thiols should have broad applicability in a wide range of experiments in chemical biology and materials science. 
    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. Iron (Fe) is ubiquitous in nature and found as Fe II or Fe III in minerals or as dissolved ions Fe 2+ or Fe 3+ in aqueous systems. The interactions of soluble Fe have important implications for fresh water and marine biogeochemical cycles, which have impacts on global terrestrial and atmospheric environments. Upon dissolution of Fe III into natural aquatic systems, organic carboxylic acids efficiently chelate Fe III to form [Fe III –carboxylate] 2+ complexes that undergo a wide range of photochemistry-induced radical reactions. The chemical composition and photochemical transformations of these mixtures are largely unknown, making it challenging to estimate their environmental impact. To investigate the photochemical process of Fe III –carboxylates at the molecular level, we conduct a comprehensive experimental study employing UV-visible spectroscopy, liquid chromatography coupled to photodiode array and high-resolution mass spectrometry detection, and oil immersion flow microscopy. In this study, aqueous solutions of Fe III –citrate were photolyzed under 365 nm light in an experimental setup with an apparent quantum yield of ( φ ) ∼0.02, followed by chemical analyses of reacted mixtures withdrawn at increment time intervals of the experiment. The apparent photochemical reaction kinetics of Fe 3+ –citrates (aq) were expressed as two generalized consecutive reactions of with the experimental rate constants of j 1 ∼ 0.12 min −1 and j 2 ∼ 0.05 min −1 , respectively. Molecular characterization results indicate that R and I consist of both water-soluble organic and Fe–organic species, while P compounds are a mixture of water-soluble and colloidal materials. The latter were identified as Fe–carbonaceous colloids formed at long photolysis times. The carbonaceous content of these colloids was identified as unsaturated organic species with low oxygen content and carbon with a reduced oxidation state, indicative of their plausible radical recombination mechanism under oxygen-deprived conditions typical for the extensively photolyzed mixtures. Based on the molecular characterization results, we discuss the comprehensive reaction mechanism of Fe III –citrate photochemistry and report on the formation of previously unexplored colloidal reaction products, which may contribute to atmospheric and terrestrial light-absorbing materials in aquatic environments. 
    more » « less
  4. In the marine sediment record, concentrations and isotope ratios of chromium (Cr) can be used to reconstruct ocean biogeochemical conditions. These reconstructions rely on a detailed understanding of the chemical pathways that Cr undergoes as it is transferred from the water column to the sediment record. We examined Cr concentrations in marine pore fluids and sediments from six continental margin sites, which can be grouped into two basic environments: (1) sites where sediments are oxygenated and rich in solid phase Mn (herein termed oxic), and (2) sites where sediments are organic C (Corg)-rich and oxygen is depleted (anoxic). We found Cr concentrations to be lower (maximum of 12 nM in pore fluids and 124 ppm sediment solid phase) at oxic sites compared with anoxic sites (maximum of 77 nM and 184 ppm). Our findings confirm previously published interpretations of dissolved Cr in pore fluids (Brumsack and Gieskes, 1983; Shaw et al., 1990). In oxic surface sediments, particulate Cr(III) can be oxidised by Mn oxides, which leads to elevated concentrations of dissolved Cr co-occurring at the same depth as elevated Mn concentrations in the sediment. Under these oxidising conditions, down-core sediments contain relatively low solid-phase Cr concentrations. In oxic sediments, Cr speciation reveals that most of the pore fluid Cr is in the Cr(VI) state. At the site where Mn oxide-rich sediments rest below an oxic water column, oxidative loss of Cr from the sediment to the bottom water leads to the lowest estimated Cr burial efficiency of the sites examined here. Under anoxic Corg-rich conditions, both pore fluids and sediment solid phases contain high Cr concentrations, with 40–80% of dissolved pore fluid Cr present as Cr(III). This enrichment of Cr appears to be tightly linked to the presence of high total organic carbon (TOC) content and scavenging of Cr by (organic) particles in the water column. Combined, these data highlight the strong dependence of Cr on both sedimentary redox conditions as well as biological productivity. Based on the data from modern continental margin sediments, we propose that Cr concentrations and isotope compositions of the authigenic sediment fraction may record a combination of redox conditions and biological productivity in the water column. If confirmed by Cr isotope analyses, these findings will add support for the notion that Cr may serve as a proxy for ocean biological and chemical sedimentological conditions. Thus, careful assessment of the impact of organic matter on Cr is required for reconstructions of redox conditions with sedimentary records. 
    more » « less
  5. Acetaldehyde cations (CH 3 CHO + ) were prepared using single-photon vacuum ultraviolet ionization of CH 3 CHO in a molecular beam and the fragmentation dynamics explored over the photolysis wavelength range 390–210 nm using velocity-map ion imaging and photofragment yield (PHOFY) spectroscopy. Four fragmentation channels are characterized: CH 3 CHO + → C 2 H 3 O + + H (I), CH 3 CHO + → HCO + + CH 3 (II), CH 3 CHO + → CH 3 + + HCO (III), CH 3 CHO + → CH 4 + + CO (IV). Channels (I), (II), and (IV) are observed across the full photolysis wavelength range while channel (III) is observed only at λ < 317 nm. Maximum fragment ion yields are obtained at ∼250 nm. Ion images were recorded over the range 316–228 nm, which corresponds to initial excitation to the B̃ 2 A′ and C̃ 2 A′ states of CH 3 CHO + . The speed and angular distributions are distinctly different for each detected ion and show evidence of both statistical and dynamical fragmentation pathways. At longer wavelengths, fragmentation via channel (I) leads to modest translational energies ( E T ), consistent with dissociation over a small barrier and production of highly internally excited CH 3 CO + . Additional components with E INT greater than the CH 3 CO + secondary dissociation threshold appear at shorter wavelengths and are assigned to fragmentation products of vinyl alcohol cation or oxirane cation formed by isomerization of energized CH 3 CHO + . The E T distribution observed for channel (III) products peaks at zero but is notably colder than that predicted by phase space theory, particularly at longer photolysis wavelengths. The colder-than-statistical E T distributions are attributed to contributions from secondary fragmentation of energized CH 3 CO + formed via channel (I), which are attenuated by CH 3 CHO + isomerization at shorter wavelengths. Fragmentation via channels (II) and (IV) results in qualitatively similar outcomes, with evidence of isotropic statistical components at low- E T and anisotropic components due to excited state dynamics at higher E T . 
    more » « less