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1. Cu nanoparticle geometry as the key to bicolor behavior in Oregon sunstones: An application of LSPR theory in nanomineralogy

   https://doi.org/10.2138/am-2023-9141  

   Wang, Chengsi; Shen, Andy H; Heaney, Peter J; Palke, Aaron; Wang, Ke; Wang, Haiying; Kiefert, Lore (February 2025, American Mineralogist)

   Grew, Edward S (Ed.)

   Abstract The coloration mechanism of Oregon sunstone is a classic and controversial topic in mineralogy because of the unique coexistence of anisotropic (green-red) and isotropic (red) color zones within single feldspar crystals. After nearly 50 years of research, no models proposed to date have satisfactorily accounted for all observed optical phenomena. Here, we present high-resolution transmission electron microscopy analyses of samples prepared by focused ion beam extraction along specific crystal directions. In both the anisotropic and the isotropic color zones, we observed Cu nanoparticles (NPs) included within plagioclase but with different geometries. In the isotropic (red) zone, NPs were randomly distributed nano-spheres or nano-ellipsoids (8.7–12 nm in diameter) with an aspect ratio of 1–1.3. In contrast, in dichroic (green/red) zones, NPs were directionally aligned nano-rods (8.5–21 nm along the long axis) with an aspect ratio of ∼2.5. We applied localized surface plasmon resonance (LSPR) theory to simulate absorption spectra and developed a model to explain the observed optical properties. LA-ICP-MS and polarized UV-Vis spectroscopy were also performed to confirm our conclusions. This study systematically reveals the existence and optical influence of variably shaped metal-NP inclusions in feldspar crystals. Furthermore, it demonstrates the necessity of including LSPR in the canon of mineral coloration mechanisms. Cu-NP-bearing labradorite has been shown to exhibit third-order nonlinear optical properties, and approaches that incorporate NP shapes and sizes will assist in designing NP-embedded optical materials with tailored optical properties. 

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2. Tailoring carrier dynamics in perovskite solar cells via precise dimension and architecture control and interfacial positioning of plasmonic nanoparticles

   https://doi.org/10.1039/c9ee03937f  

   Cui, Xun; Chen, Yihuang; Zhang, Meng; Harn, Yeu Wei; Qi, Jiabin; Gao, Likun; Wang, Zhong Lin; Huang, Jinsong; Yang, Yingkui; Lin, Zhiqun (January 2020, Energy & Environmental Science)

   Placing plasmonic nanoparticles (NPs) in close proximity to semiconductor nanostructures renders effective tuning of the optoelectronic properties of semiconductors through the localized surface plasmon resonance (LSPR)-induced enhancement of light absorption and/or promotion of carrier transport. Herein, we report on, for the first time, the scrutiny of carrier dynamics of perovskite solar cells (PSCs) via sandwiching monodisperse plasmonic/dielectric core/shell NPs with systematically varied dielectric shell thickness yet fixed plasmonic core diameter within an electron transport layer (ETL). Specifically, a set of Au NPs with precisely controlled dimensions ( i.e. , fixed Au core diameter and tunable SiO 2 shell thickness) and architectures (plain Au NPs and plasmonic/dielectric Au/SiO 2 core/shell NPs) are first crafted by capitalizing on the star-like block copolymer nanoreactor strategy. Subsequently, these monodisperse NPs are sandwiched between the two consecutive TiO 2 ETLs. Intriguingly, there exists a critical dielectric SiO 2 shell thickness, below which hot electrons from the Au core are readily injected to TiO 2 ( i.e. , hot electron transfer (HET)); this promotes local electron mobility in the TiO 2 ETL, leading to improved charge transport and increased short-circuit current density ( J sc ). It is also notable that the HET effect moves up the Fermi level of TiO 2 , resulting in an enhanced built-in potential and open-circuit voltage ( V oc ). Taken together, the PSCs constructed by employing a sandwich-like TiO 2 /Au NPs/TiO 2 ETL exhibit both greatly enhanced J sc and V oc , delivering champion PCEs of 18.81% and 19.42% in planar and mesostructured PSCs, respectively. As such, the judicious positioning of rationally designed monodisperse plasmonic NPs in the ETL affords effective tailoring of carrier dynamics, thereby providing a unique platform for developing high-performance PSCs. 

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3. Chemical Detection by Analyte-Induced Change in Electrophoretic Deposition of Gold Nanoparticles

   https://doi.org/10.1149/1945-7111/ac418c  

   Mainali, Badri P; Zamborini, Francis P (January 2022, Journal of The Electrochemical Society)

   The electrophoretic deposition (EPD) of citrate-stabilized Au nanoparticles (cit-Au NPs) occurs on indium tin oxide (ITO)-coated glass electrodes upon electrochemical oxidation of hydroquinone (HQ) due to the release of hydronium ions. Anodic stripping voltammetry (ASV) for Au oxidation allows the determination of the amount of Au NP deposition under a specific EPD potential and time. The binding of Cr 3+ to the cit-Au NPs inhibits the EPD by inducing aggregation and/or reducing the negative charge, which could lower the effective NP concentration of the cit-Au NPs and/or lower the electrophoretic mobility. This lowers the Au oxidation charge in the ASV, which acts as an indirect signal for Cr 3+ . The binding of melamine to cit-Au NPs similarly leads to aggregation and/or lowers the negative charge, also resulting in reduction of the ASV Au oxidation peak. The decrease in Au oxidation charge measured by ASV increases linearly with increasing Cr 3+ and melamine concentration. The limit of detection (LOD) for Cr 3+ is 21.1 ppb and 16.0 ppb for 15.1 and 4.1 nm diameter cit-Au NPs, respectively. Improving the sensing conditions allows for as low as 1 ppb detection of Cr 3+ . The LOD for melamine is 45.7 ppb for 4.1 nm Au NPs. 

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4. Green Synthesis of Gold Nanoparticles Using Upland Cress and Their Biochemical Characterization and Assessment

   https://doi.org/10.3390/nano12010028  

   Hutchinson, Noah; Wu, Yuelin; Wang, Yale; Kanungo, Muskan; DeBruine, Anna; Kroll, Emma; Gilmore, De’Jorra; Eckrose, Zachary; Gaston, Stephanie; Matel, Phoebe; et al (January 2022, Nanomaterials)

   This article belongs to the Special Issue Synthesis and Applications of Gold Nanoparticles) Rodolphe Antoine (Ed.)

   This research focuses on the plant-mediated green synthesis process to produce gold nanoparticles (Au NPs) using upland cress (Barbarea verna), as various biomolecules within the upland cress act as both reducing and capping agents. The synthesized gold nanoparticles were thoroughly characterized using UV-vis spectroscopy, surface charge (zeta potential) analysis, scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDX), atomic force microscopy (AFM), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), and X-ray diffraction (XRD). The results indicated the synthesized Au NPs are spherical and well-dispersed with an average diameter ~11 nm and a characteristic absorbance peak at ~529 nm. EDX results showed an 11.13% gold content. Colloidal Au NP stability was confirmed with a zeta potential (ζ) value of −36.8 mV. X-ray diffraction analysis verified the production of crystalline face-centered cubic gold. Moreover, the antimicrobial activity of the Au NPs was evaluated using Gram-negative Escherichiacoli and Gram-positive Bacillus megaterium. Results demonstrated concentration-dependent antimicrobial properties. Lastly, applications of the Au NPs in catalysis and biomedicine were evaluated. The catalytic activity of Au NPs was demonstrated through the conversion of 4-nitrophenol to 4-aminophenol which followed first-order kinetics. Cellular uptake and cytotoxicity were evaluated using both BMSCs (stem) and HeLa (cancer) cells and the results were cell type dependent. The synthesized Au NPs show great potential for various applications such as catalysis, pharmaceutics, and biomedicine. 

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5. Plasmonic Response of Light-Activated, Nano-Gold Doped Polymers

   https://doi.org/10.1557/adv.2019.286  

   Andriolo, Jessica M.; Joseph, McKenzie L.; Brockway, Molly C.; Skinner, Jack L. (January 2019, MRS Advances)

   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. 

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