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Reversibly pH-responsive gold nanoparticles and their applications for photothermal cancer therapy.

ABSTRACT: Microenvironment responsive nanomaterials are attractive for therapeutic applications with regional specificity. Here we report pH responsive gold nanoparticles which are designed to aggregate in acidic condition similar to cancer environment and returned to its original disassembled states in a physiological pH. The pH responsive behavior of the particles is derived by change of electrostatic interaction among the particles where attraction and repulsion play a major role in low and high pH of the environment, respectively. Since different electrostatic interaction behavior of the particles in varied pH is induced not by irreversible chemical change but by simple protonation differences, the pH responsive process of assembly and disassembly is totally reversible. The low pH specific aggregation of gold nanoparticles resulted in red shift of plasmonic absorption peak and showed higher photothermal efficacy in acidic pH than in normal physiological pH. The low pH specific photothermal effect with long wave laser irradiation was directly applied to cancer specific photothermal therapy and resulted higher therapeutic effect for melanoma cancer cells than non-pH responsive gold nanoparticles.

SUBMITTER: Park S

PROVIDER: S-EPMC6934723 | biostudies-literature | 2019 Dec

REPOSITORIES: biostudies-literature

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Reversibly pH-responsive gold nanoparticles and their applications for photothermal cancer therapy.

Park Sanghak S Lee Woo Jin WJ Park Sungmin S Choi Doowon D Kim Sungjee S Park Nokyoung N

Scientific reports 20191227 1

Microenvironment responsive nanomaterials are attractive for therapeutic applications with regional specificity. Here we report pH responsive gold nanoparticles which are designed to aggregate in acidic condition similar to cancer environment and returned to its original disassembled states in a physiological pH. The pH responsive behavior of the particles is derived by change of electrostatic interaction among the particles where attraction and repulsion play a major role in low and high pH of ...[more]

PMID: 31882911

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Project description:Mercaptoundecanoic acid (MUA) functionalized gold nanoparticles (AuNP-MUA) were synthesized and demonstrated to possess pH-triggered aggregation and re-dispersion, as well as the capability of phase transfer between aqueous and organic phases in response to changes in pH. The pH of aggregation for AuNP-MUA is consistent with the pKa of MUA (pH ~4) in solution, while AuNP-MUA phase transition between aqueous and organic phases occurs at pH ~9. The ion pair formation between the amine group in octadecylamine (ODA), the carboxylate group in MUA, and the hydrophobic alkyl chain of ODA facilitates the phase transfer of AuNP-MUA into an organic medium. The AuNP-MUA were investigated as a reusable catalyst in the catalytic reduction of 4-nitrophenol by borohydride-a model reaction for AuNPs. It was determined that 100% MUA surface coverage completely inhibits the catalytic activity of AuNPs. Decreasing the surface coverage was shown to increase catalytic activity, but this decrease also leads to decreased colloidal stability, recoverability, and reusability in subsequent reactions. At 60% MUA surface coverage, colloidal stability and catalytic activity were achieved, but the surface coverage was insufficient to enable redispersion following pH-induced recovery. A balance between AuNP colloidal stability, recoverability, and catalytic activity with reusability was achieved at 90% MUA surface coverage. The AuNP-MUA catalyst can also be recovered at different pH ranges depending on the recovery method employed. At pH ~4, protonation of the MUA results in reduced surface charge and aggregation. At pH ~9, ODA will form an ion-pair with the MUA and induce phase transfer into an immiscible organic phase. Both the pH-triggered aggregation/re-dispersion and aqueous/organic phase transfer methods were employed for catalyst recovery and reuse in subsequent reactions. The ability to recover and reuse the AuNP-MUA catalyst by two different methods and different pH regimes is significant, based on the fact that nanoparticle-catalyzed reactions may occur under different pH conditions.

Project description:Many applications using gold nanoparticles (AuNPs) require (i) their functionalization with a biopolymer to increase their stability and (ii) their transformation into an easy-to-handle material, which provide them with specific properties. In this research, a portable tablet platform is presented based on dextran-encapsulated gold nanoparticles (AuNPs-dTab) by a ligand exchange reaction between citrate-capped gold nanoparticles (AuNPs-Cit) and dextran. These newly fabricated tablets were characterized utilizing ultraviolet-visible spectroscopy (UV-vis), Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR), transmission electron microscopy (TEM), dynamic light scattering (DLS), X-ray diffraction spectroscopy (XRD), differential scanning calorimetry (DSC), and atomic force microscopy (AFM) techniques. The results showed that dextran-capped gold nanoparticles in a tablet platform (AuNPs-dTab) were well-dispersed and highly stable for at least a year at room temperature. In addition to particle and surface characterization of AuNPs-dTab, the tablet morphology in terms of thickness, diameter, density, and opacity was also measured using 6 and 10% dextran with 2, 4 and 8 nM AuNPs-Cit. We further investigated the pH-responsive behavior of AuNPs-dTab in the presence and absence of sodium chloride. Results showed that neutral and alkaline environments were suitable to render AuNPs dispersed in a tablet, while an acidic condition controls the aggregation rate of AuNPs as confirmed by concentration-dependent aggregation phenomena. Besides the easy fabrication, these tablets were portable and low-cost (approx. 1.22 CAD per 100 tablets of a 100 μL solution of dextran-capped gold nanoparticles (AuNPs-dSol)). The biocompatible nature of dextran along with the acidic medium trigger nature of AuNPs makes our proposed tablet a potential candidate for cancer therapy due to the acidic surrounding of tumor tissues as compared to normal cells. Also, our proposed tablet approach paves the way for the fabrication of portable and easy-to-use optical sensors based on the AuNPs embedded in a natural polymeric architecture that would serve as a colorimetric recognition indicator for detecting analytes of interest.

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Reversibly pH-responsive gold nanoparticles and their applications for photothermal cancer therapy.

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Reversibly pH-responsive gold nanoparticles and their applications for photothermal cancer therapy.

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