Supramolecular Self-Assembly Bioinspired Synthesis of Luminescent Gold Nanocluster-Embedded Peptide Nanofibers for Temperature Sensing and Cellular Imaging.

Metal nanoclusters (NCs) hold great potential as novel luminescent nanomaterials in many applications, while the synthesis of highly luminescent metal NCs still remains challenging. In this work, we report self-assembling peptides as a novel bioinspired scaffold capable of significantly enhancing the luminescence efficiency of gold nanoclusters (AuNCs). The resulting AuNCs capped with motif-designed peptides can self-assemble to form nanofiber structures, in which the luminescence of AuNCs is enhanced nearly 70-fold, with 21.3% quantum yield. The underlying mechanism responsible for the luminescence enhancement has been thoroughly investigated by the combined use of different spectroscopic and microscopic techniques. The resultant highly luminescent AuNC-decorated peptide nanofibers exhibit physicochemical properties that are advantageous for biological applications. As a proof of concept, we demonstrate the use of these nanostructure as fluorescent thermometers and for imaging living cells, both showing very promising results.

[1]  Zhiqiang Su,et al.  Self-assembling peptide and protein amyloids: from structure to tailored function in nanotechnology. , 2017, Chemical Society reviews.

[2]  Ruirui Xing,et al.  Peptide self-assembly: thermodynamics and kinetics. , 2016, Chemical Society reviews.

[3]  Ning Gu,et al.  Micro/Nanoscale Thermometry for Cellular Thermal Sensing. , 2016, Small.

[4]  Y. Tan,et al.  Rational Design of Biomolecular Templates for Synthesizing Multifunctional Noble Metal Nanoclusters toward Personalized Theranostic Applications , 2016, Advanced healthcare materials.

[5]  Lina Zhao,et al.  Peptide protected gold clusters: chemical synthesis and biomedical applications. , 2016, Nanoscale.

[6]  C. Ong,et al.  Gold nanocluster sensitized TiO2 nanotube arrays for visible-light driven photoelectrocatalytic removal of antibiotic tetracycline. , 2016, Nanoscale.

[7]  Dongpeng Yan,et al.  Surface-confined fluorescence enhancement of Au nanoclusters anchoring to a two-dimensional ultrathin nanosheet toward bioimaging. , 2016, Nanoscale.

[8]  G. Nienhaus,et al.  In Situ Monitoring of the Intracellular Stability of Nanoparticles by Using Fluorescence Lifetime Imaging. , 2016, Small.

[9]  Li Zhang,et al.  Chiral Nanoarchitectonics: Towards the Design, Self‐Assembly, and Function of Nanoscale Chiral Twists and Helices , 2016, Advanced materials.

[10]  Christopher M. Andolina,et al.  Ligand-Mediated "Turn On," High Quantum Yield Near-Infrared Emission in Small Gold Nanoparticles. , 2015, Journal of the American Chemical Society.

[11]  G. Nienhaus,et al.  Motif‐Designed Peptide Nanofibers Decorated with Graphene Quantum Dots for Simultaneous Targeting and Imaging of Tumor Cells , 2015 .

[12]  J. G. Solé,et al.  Hybrid Nanostructures for High‐Sensitivity Luminescence Nanothermometry in the Second Biological Window , 2015, Advanced materials.

[13]  Chao Li,et al.  Gold Nanoclusters‐Based Nanoprobes for Simultaneous Fluorescence Imaging and Targeted Photodynamic Therapy with Superior Penetration and Retention Behavior in Tumors , 2015 .

[14]  R. Jin,et al.  Atomically precise metal nanoclusters: stable sizes and optical properties. , 2015, Nanoscale.

[15]  Chia-Wei Wang,et al.  Fluorescent gold nanoclusters: recent advances in sensing and imaging. , 2015, Analytical chemistry.

[16]  Yongdong Jin,et al.  Fluorescent Au nanoclusters: recent progress and sensing applications , 2014 .

[17]  Xiaopeng Zheng,et al.  WS2 nanosheet as a new photosensitizer carrier for combined photodynamic and photothermal therapy of cancer cells. , 2014, Nanoscale.

[18]  G. Baker,et al.  Exploring luminescence-based temperature sensing using protein-passivated gold nanoclusters. , 2014, Nanoscale.

[19]  Jenny J. Yang,et al.  Enhancing near IR luminescence of thiolate Au nanoclusters by thermo treatments and heterogeneous subcellular distributions. , 2014, Nanoscale.

[20]  Barry P Rand,et al.  Thin Film Metal Nanocluster Light‐Emitting Devices , 2014, Advanced materials.

[21]  Nikolai G Khlebtsov,et al.  Uptake of engineered gold nanoparticles into mammalian cells. , 2014, Chemical reviews.

[22]  N. Jana,et al.  Gold nanoclusters with enhanced tunable fluorescence as bioimaging probes. , 2014, Wiley interdisciplinary reviews. Nanomedicine and nanobiotechnology.

[23]  Li Shang,et al.  Intracellular thermometry by using fluorescent gold nanoclusters. , 2013, Angewandte Chemie.

[24]  A. Demchenko Nanoparticles and nanocomposites for fluorescence sensing and imaging , 2013, Methods and applications in fluorescence.

[25]  P. Maurer,et al.  Nanometre-scale thermometry in a living cell , 2013, Nature.

[26]  Dejian Zhou,et al.  Near-infrared fluorescent ribonuclease-A-encapsulated gold nanoclusters: preparation, characterization, cancer targeting and imaging. , 2013, Nanoscale.

[27]  Hans H. Gorris,et al.  Photon upconverting nanoparticles for luminescent sensing of temperature. , 2012, Nanoscale.

[28]  Jianping Xie,et al.  From aggregation-induced emission of Au(I)-thiolate complexes to ultrabright Au(0)@Au(I)-thiolate core-shell nanoclusters. , 2012, Journal of the American Chemical Society.

[29]  Chih-Ching Huang,et al.  Fluorescent gold and silver nanoclusters for the analysis of biopolymers and cell imaging , 2012 .

[30]  G. Nienhaus,et al.  Effect of protein adsorption on the fluorescence of ultrasmall gold nanoclusters. , 2012, Small.

[31]  Y. Harada,et al.  Intracellular temperature mapping with a fluorescent polymeric thermometer and fluorescence lifetime imaging microscopy , 2012, Nature Communications.

[32]  B. Nilsson,et al.  Review self‐assembly of amphipathic β‐sheet peptides: Insights and applications , 2012, Biopolymers.

[33]  Jijin Gu,et al.  Self-aggregated pegylated poly (trimethylene carbonate) nanoparticles decorated with c(RGDyK) peptide for targeted paclitaxel delivery to integrin-rich tumors. , 2011, Biomaterials.

[34]  G. Nienhaus,et al.  Ultra-small fluorescent metal nanoclusters: Synthesis and biological applications , 2011 .

[35]  G. Nienhaus,et al.  Facile preparation of water-soluble fluorescent gold nanoclusters for cellular imaging applications. , 2011, Nanoscale.

[36]  R. Jin,et al.  On the ligand's role in the fluorescence of gold nanoclusters. , 2010, Nano letters.

[37]  S. Achilefu,et al.  Fluorescence lifetime measurements and biological imaging. , 2010, Chemical reviews.

[38]  Moon J. Kim,et al.  Luminescent Gold Nanoparticles with Mixed Valence States Generated from Dissociation of Polymeric Au (I) Thiolates. , 2010, The journal of physical chemistry. C, Nanomaterials and interfaces.

[39]  Zhenghua Tang,et al.  Synthesis and structural determination of multidentate 2,3-dithiol-stabilized Au clusters. , 2010, Journal of the American Chemical Society.

[40]  Honggang Cui,et al.  Self‐assembly of peptide amphiphiles: From molecules to nanostructures to biomaterials , 2010, Biopolymers.

[41]  Rajesh R Naik,et al.  Protein- and peptide-directed syntheses of inorganic materials. , 2008, Chemical reviews.

[42]  G. Gavrila,et al.  High-resolution photoelectron spectroscopy of self-assembled mercaptohexanol monolayers on gold surfaces , 2008 .

[43]  Robert M Dickson,et al.  Highly fluorescent noble-metal quantum dots. , 2007, Annual review of physical chemistry.

[44]  Hoi Sing Kwok,et al.  Aggregation-induced emission , 2006, SPIE Optics + Photonics.

[45]  Katsuyuki Nobusada,et al.  Glutathione-protected gold clusters revisited: bridging the gap between gold(I)-thiolate complexes and thiolate-protected gold nanocrystals. , 2005, Journal of the American Chemical Society.

[46]  R. Dickson,et al.  Highly fluorescent, water-soluble, size-tunable gold quantum dots. , 2004, Physical review letters.

[47]  Hiroshi Yao,et al.  Magic-Numbered Aun Clusters Protected by Glutathione Monolayers (n = 18, 21, 25, 28, 32, 39): Isolation and Spectroscopic Characterization , 2004 .

[48]  Shuguang Zhang Fabrication of novel biomaterials through molecular self-assembly , 2003, Nature Biotechnology.

[49]  A. Rich,et al.  Spontaneous assembly of a self-complementary oligopeptide to form a stable macroscopic membrane. , 1993, Proceedings of the National Academy of Sciences of the United States of America.

[50]  E Ruoslahti,et al.  New perspectives in cell adhesion: RGD and integrins. , 1987, Science.