Jiang, Wenfeng and Qu, Zhi-bei and Kumar, Prashant and Vecchio, Drew and Wang, Yuefei and Ma, Yu and Bahng, Joong Hwan and Bernardino, Kalil and Gomes, Weverson R. and Colombari, Felippe M. and Lozada-Blanco, Asdrubal and Veksler, Michael and Marino, Emanuele and Simon, Alex and Murray, Christopher and Muniz, Sérgio Ricardo and de Moura, André F. and Kotov, Nicholas A. (2020) Emergence of complexity in hierarchically organized chiral particles. Science, 368 (6491). pp. 642-648. ISSN 0036-8075. doi:10.1126/science.aaz7949. https://resolver.caltech.edu/CaltechAUTHORS:20200410-121043032
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Abstract
The structural complexity of composite biomaterials and biomineralized particles arises from the hierarchical ordering of inorganic building blocks over multiple scales. Although empirical observations of complex nanoassemblies are abundant, the physicochemical mechanisms leading to their geometrical complexity are still puzzling, especially for nonuniformly sized components. We report the self-assembly of hierarchically organized particles (HOPs) from polydisperse gold thiolate nanoplatelets with cysteine surface ligands. Graph theory methods indicate that these HOPs, which feature twisted spikes and other morphologies, display higher complexity than their biological counterparts. Their intricate organization emerges from competing chirality-dependent assembly restrictions that render assembly pathways primarily dependent on nanoparticle symmetry rather than size. These findings and HOP phase diagrams open a pathway to a large family of colloids with complex architectures and unusual chiroptical and chemical properties.
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| Additional Information: | © 2020 American Association for the Advancement of Science. Received 9 October 2019; accepted 30 March 2020. Published online 9 April 2020. We thank National Laboratory for Scientific Computing, LNCC/MCTI, Brazil (http://sdumont.lncc.br) for the access to the SDumont supercomputer and the Cloud@UFSCar (http://portalcloud.ufscar.br/) for the HPC resources, and the Michigan Center for Materials Characterization (MC)2 for its assistance with electron microscopy. N.A.K. thanks D. Lioi from Universal Technology Corporation, Wright Patterson Air Force Base, and S. Glotzer of the University of Michigan for insightful discussions. S.R.M. thanks S. Pratavieira and F. Guimarães at IFSC/USP for technical assistance and discussions. Funding: Supported by the Vannevar Bush DoD Fellowship to N.A.K. titled “Engineered Chiral Ceramics” ONR N000141812876, NSF project “Energy- and Cost-Efficient Manufacturing Employing Nanoparticles” (NSF 1463474, ONR N000141812876); NSF 1566460 “Nanospiked Particles for Photocatalysis”; NSF grant 1538180; NSF grant DMR-9871177 for funding the JEOL 2010F analytical electron microscope used in this work; and the Brazilian funding agencies CAPES (finance code 001), CNPq, and FAPESP (process 2009/54035-4, 2012/15147-4, 2013/07276-1, 2013/07296-2, and 2017/12063-8). Support for the Dual Source and Environmental X-ray Scattering Facility at the University of Pennsylvania was provided by the Laboratory for Structure and Matter which is funded in part by NSF MRSEC 1720530. Also supported by Office of Naval Research Multidisciplinary University Research Initiative Award ONR N00014-18-1-2497 (E.M. and C.M.); an MEC/PET fellowship (2014–2020) and a CNPq Fellowship of Research Productivity (2020) (A.F.d.M.); and the China Scholarship Council and Shanghai Jiao Tong University (W.J.). Author contributions: N.A.K. conceived the project. W.J. and N.A.K. designed the experiments. W.J. did the design, synthesis, and characterization of the supraparticles and studied their chemical and chiroptical properties. S.R.M. designed, carried out, and analyzed the experiments combining time and spectrally resolved fluorescence. Z.Q. performed the MD simulations of the Au-Cys nanosheets. Y.W. and P.K. studied the phase diagram of Au-Cys supraparticles. Y.M. helped W.J. with some synthesis and characterizations. J.H.B. did the FDTD simulations of the CD spectra. K.B., W.R.G., F.M.C., A.L.-B., and A.F.d.M. carried out the DFT MD simulations, calculations of CD spectra, and coarse-grained simulations of nanoparticle assemblies. N.A.K. conceived and calculated the GT models for the characterization of the complexity of different structures. E.M. measured and analyzed the SAXS data. W.J. and N.A.K. co-wrote the paper. All authors contributed to data analysis, discussion, and writing. Competing interests: Authors declare no competing interests. Patents: N.A.K. and J.Y., Synthesis of Chiral Nanoparticles Using Circularly Polarized Light, #14/940,845, filed 13 November 2015, granted 29 January 2019. N.A.K., Self-Assembly Methods for Forming Mesoscale Hedgehog-Shaped Particles, application no. 62/563,966, filed 27 September 2017. Data and materials availability: All data are available in the main text or the supplementary materials. | ||||||||||||||||||||||||||||||||||||||
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| Issue or Number: | 6491 | ||||||||||||||||||||||||||||||||||||||
| DOI: | 10.1126/science.aaz7949 | ||||||||||||||||||||||||||||||||||||||
| Record Number: | CaltechAUTHORS:20200410-121043032 | ||||||||||||||||||||||||||||||||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20200410-121043032 | ||||||||||||||||||||||||||||||||||||||
| Official Citation: | Emergence of complexity in hierarchically organized chiral particles. BY WENFENG JIANG, ZHI-BEI QU, PRASHANT KUMAR, DREW VECCHIO, YUEFEI WANG, YU MA, JOONG HWAN BAHNG, KALIL BERNARDINO, WEVERSON R. GOMES, FELIPPE M. COLOMBARI, ASDRUBAL LOZADA-BLANCO, MICHAEL VEKSLER, EMANUELE MARINO, ALEX SIMON, CHRISTOPHER MURRAY, SÉRGIO RICARDO MUNIZ, ANDRÉ F. DE MOURA, NICHOLAS A. KOTOV. SCIENCE 08 MAY 2020: 642-648; doi: 10.1126/science.aaz7949 | ||||||||||||||||||||||||||||||||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||||||||||||||||||||||||||||||||
| ID Code: | 102488 | ||||||||||||||||||||||||||||||||||||||
| Collection: | CaltechAUTHORS | ||||||||||||||||||||||||||||||||||||||
| Deposited By: | Tony Diaz | ||||||||||||||||||||||||||||||||||||||
| Deposited On: | 10 Apr 2020 19:56 | ||||||||||||||||||||||||||||||||||||||
| Last Modified: | 16 Nov 2021 18:12 |
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