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Controlled synthesis of highly-branched plasmonic gold nanoparticles through peptoid engineering.

ABSTRACT: In nature, specific biomolecules interacting with mineral precursors are responsible for the precise production of nanostructured inorganic materials that exhibit complex morphologies and superior performance. Despite advances in developing biomimetic approaches, the design rules for creating sequence-defined molecules that lead to the synthesis of inorganic nanomaterials with predictable complex morphologies are unknown. Herein we report the design of sequence-defined peptoids for controlled synthesis of highly branched plasmonic gold particles. By engineering peptoid sequences and investigating the resulting particle formation mechanisms, we develop a rule of thumb for designing peptoids that predictively enabled the morphological evolution from spherical to coral-shaped nanoparticles. Through a combination of hyperspectral UV-Vis extinction microscopy and three-photon photoemission electron microscopy, we demonstrate that the individual coral-shaped gold nanoparticles exhibit a plasmonic enhancement as high as 105-fold. This research significantly advances our ultimate vision of predictive bio-inspired materials synthesis using sequence-defined synthetic molecules that mimic proteins and peptides.

SUBMITTER: Yan F

PROVIDER: S-EPMC5998043 | biostudies-literature | 2018 Jun

REPOSITORIES: biostudies-literature

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Controlled synthesis of highly-branched plasmonic gold nanoparticles through peptoid engineering.

Yan Feng F Liu Lili L Walsh Tiffany R TR Gong Yu Y El-Khoury Patrick Z PZ Zhang Yanyan Y Zhu Zihua Z De Yoreo James J JJ Engelhard Mark H MH Zhang Xin X Chen Chun-Long CL

Nature communications 20180613 1

In nature, specific biomolecules interacting with mineral precursors are responsible for the precise production of nanostructured inorganic materials that exhibit complex morphologies and superior performance. Despite advances in developing biomimetic approaches, the design rules for creating sequence-defined molecules that lead to the synthesis of inorganic nanomaterials with predictable complex morphologies are unknown. Herein we report the design of sequence-defined peptoids for controlled sy ...[more]

PMID: 29899378

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Project description:Octahedral anatase particles (OAPs), prepared by ultrasonication-hydrothermal reaction (US-HT), were modified with 2 wt% of gold by photodeposition. Conditions of US-HT process such as durations of US and durations of HT were varied to obtain OAPs products different by physicochemical and morphological properties. Au/OAPs samples were characterized by X-ray diffraction (XRD), scanning transmission electron microscopy (STEM), X-ray photoelectron spectroscopy (XPS) and diffuse reflectance spectroscopy (DRS). The photocatalytic activity was tested under UV irradiation for decomposition of acetic acid (CO2 system) and dehydrogenation of methanol (H2 system) under aerobic and anaerobic conditions, respectively, and for oxidation of 2-propanol under visible light irradiation. Photodeposition of gold was very fast for all OAPs samples (0.5-10 min) under Ar atmosphere, and the clear correlation between the content of electron traps (ETs) and the induction period, during which nanoparticles (NPs) of gold are formed, indicates that ETs in titania samples are a key-factor for rapidity of gold photodeposition on titania surface. It was found that better morphology of titania (larger content of faceted particles) resulted in formation of larger gold NPs, while small gold NPs were deposited on structural defects. Modification of OAPs with gold NPs resulted in significant enhancement of photocatalytic activity, being e.g., 1.5 (CO2 system), 7.7 (H2 system), and even more than 40 under vis irradiation. It was found that both the properties of titania and gold are crucial for resultant photocatalytic activity, but a direct correlation between one structural/physical property and photocatalytic activity could not be obtained since all structural properties changed simultaneously when conditions of photocatalyst preparation (US-HT) were changed. Therefore, gold NPs of controlled sizes were deposited on OAPs product with the best morphology by modified photodeposition method. Clear correlation between photocatalytic activity under visible light and the size of gold NPs indicates that gold properties are decisive for visible light activity rather than titania properties. 3D-FDTD simulations confirm that an increase in the size of gold NPs results in extended surface areas with field enhancement.

Project description:The leaves and flowering stem of Origanum vulgare contain essential oils, flavonoids, phenolic acids and anthocyanins. We propose a new, simple, one-pot, O. vulgare extract (OVE) mediated green synthesis method of biocompatible gold nanoparticles (AuNPs) possessing improved antioxidant, antimicrobial and plasmonic properties.Different concentrations of OVEs were used to reduce gold ions and to synthetize biocompatible spherical AuNPs. Their morphology and physical properties have been investigated by means of transmission electron microscopy, ultraviolet-visible absorption spectroscopy, photon correlation spectroscopy and Fourier transform infrared spectroscopy, whereas their plasmonic properties have been tested using surface-enhanced Raman spectroscopy (SERS). The antioxidant properties of nanoparticles (NPs) have been evaluated by 2,2-diphenyl-1-picrylhydrazyl radical scavenging assay, and the antimicrobial tests were performed using the disk diffusion assay. Their cytotoxicity has been assessed by means of 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay.The experimental results confirmed the successful synthesis of biocompatible, spherical, plasmonic NPs having a mean diameter of ~40 nm and an outstanding aqueous stability. This new class of NPs exhibits a very good antioxidant activity and presents interesting inhibitory effects against Staphylococcus aureus and Candida albicans. Due to their plasmonic properties, AuNPs are used as SERS substrates for the detection of a test molecule (methylene blue) up to a concentration of 10-7 M and a pharmaceutical compound (propranolol) in solution. Cytotoxicity assays revealed that AuNPs are better tolerated by normal human dermal fibroblast cells, while the melanoma cancer cells are more sensitive.The biocompatible AuNPs synthetized using OVEs showed significant bactericidal and antimycotic activities, the most sensitive microorganisms being S. aureus and C. albicans, both commonly involved in various dermatological infections. Moreover, the significant antioxidant effect might recommend their use for protective and/or preventive effect in various skin inflammatory conditions, including the reduction in side effects in dermatological infections. Meanwhile, the as-synthesized biocompatible AuNPs can be successfully used as SERS substrates for the detection of pharmaceutical compounds in aqueous solutions.

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Controlled synthesis of highly-branched plasmonic gold nanoparticles through peptoid engineering.

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Controlled synthesis of highly-branched plasmonic gold nanoparticles through peptoid engineering.

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