Controlling and imaging biomimetic self-assembly.

The self-assembly of chemical entities represents a very attractive way to create a large variety of ordered functional structures and complex matter. Although much effort has been devoted to the preparation of supramolecular nanostructures based on different chemical building blocks, an understanding of the mechanisms at play and the ability to monitor assembly processes and, in turn, control them are often elusive, which precludes a deep and comprehensive control of the final structures. Here the complex supramolecular landscape of a platinum(II) compound is characterized fully and controlled successfully through a combination of supramolecular and photochemical approaches. The supramolecular assemblies comprise two kinetic assemblies and their thermodynamic counterpart. The monitoring of the different emission properties of the aggregates, used as a fingerprint for each species, allows the real-time visualization of the evolving self-assemblies. The control of multiple supramolecular pathways will help the design of complex systems in and out of their thermodynamic equilibrium.

[1]  E. W. Meijer,et al.  Pathway selection in peptide amphiphile assembly. , 2014, Journal of the American Chemical Society.

[2]  V. Kisil Properties and Applications , 1994 .

[3]  Jeffrey S. Moore,et al.  Nucleation—Elongation: A Mechanism for Cooperative Supramolecular Polymerization , 2004 .

[4]  R. Finke,et al.  Protein aggregation kinetics, mechanism, and curve-fitting: a review of the literature. , 2009, Biochimica et biophysica acta.

[5]  C. Kübel,et al.  Self-assembly of a neutral platinum(II) complex into highly emitting microcrystalline fibers through metallophilic interactions. , 2014, Chemical communications.

[6]  E. W. Meijer,et al.  Functional Supramolecular Polymers , 2012, Science.

[7]  A. J. Markvoort,et al.  An equilibrium model for chiral amplification in supramolecular polymers. , 2012, The journal of physical chemistry. B.

[8]  Jean-Marie Lehn,et al.  Perspectives in Supramolecular Chemistry—From Molecular Recognition towards Molecular Information Processing and Self‐Organization , 1990 .

[9]  G. Odian,et al.  Principles of polymerization , 1981 .

[10]  F. Hovorka,et al.  The System Dioxane and Water , 1936 .

[11]  G. Whitesides,et al.  Molecular self-assembly and nanochemistry: a chemical strategy for the synthesis of nanostructures. , 1991, Science.

[12]  E. Powers,et al.  Mechanisms of protein fibril formation: nucleated polymerization with competing off-pathway aggregation. , 2008, Biophysical journal.

[13]  R. Mosquera,et al.  A density functional theory study on pelargonidin. , 2007, The journal of physical chemistry. A.

[14]  Sheng Zhong,et al.  Block Copolymer Assembly via Kinetic Control , 2007, Science.

[15]  I. Manners,et al.  Monodisperse cylindrical micelles by crystallization-driven living self-assembly. , 2010, Nature chemistry.

[16]  F. Würthner,et al.  Supramolecular stereomutation in kinetic and thermodynamic self-assembly of helical merocyanine dye nanorods. , 2005, Angewandte Chemie.

[17]  Jeffrey S. Moore,et al.  Nucleation-elongation: a mechanism for cooperative supramolecular polymerization. , 2003, Organic & biomolecular chemistry.

[18]  A. R.,et al.  Review of literature , 1969, American Potato Journal.

[19]  E. W. Meijer,et al.  Pathway complexity in supramolecular polymerization , 2012, Nature.

[20]  V. Yam,et al.  Supramolecular self-assembly of amphiphilic anionic platinum(II) complexes: a correlation between spectroscopic and morphological properties. , 2011, Journal of the American Chemical Society.

[21]  Nicolas Giuseppone,et al.  Dynamic combinatorial evolution within self-replicating supramolecular assemblies. , 2009, Angewandte Chemie.

[22]  Ian Manners,et al.  Tailored hierarchical micelle architectures using living crystallization-driven self-assembly in two dimensions. , 2014, Nature chemistry.

[23]  Jean-Marie Lehn,et al.  Toward complex matter: Supramolecular chemistry and self-organization , 2002, Proceedings of the National Academy of Sciences of the United States of America.

[24]  Suliana Manley,et al.  A near-infrared fluorophore for live-cell super-resolution microscopy of cellular proteins. , 2013, Nature chemistry.

[25]  Yiyong Mai,et al.  Self-assembly of block copolymers. , 2012, Chemical Society reviews.

[26]  Tom F A de Greef,et al.  Controlling chemical self-assembly by solvent-dependent dynamics. , 2012, Journal of the American Chemical Society.

[27]  Jean-Marie Lehn,et al.  Supramolecular chemistry — Scope and perspectives: Molecules — Supermolecules — Molecular devices , 1988 .

[28]  D. Hertel,et al.  Switching on luminescence by the self-assembly of a platinum(II) complex into gelating nanofibers and electroluminescent films. , 2011, Angewandte Chemie.

[29]  P. Hilbers,et al.  Understanding cooperativity in hydrogen-bond-induced supramolecular polymerization: a density functional theory study. , 2010, The journal of physical chemistry. B.

[30]  Pier Luigi Luisi,et al.  Autocatalytic self-replicating micelles as models for prebiotic structures , 1992, Nature.

[31]  Biwu Ma,et al.  Synthetic control of Pt...Pt separation and photophysics of binuclear platinum complexes. , 2005, Journal of the American Chemical Society.

[32]  D. Genovese,et al.  Recent Advances in Phosphorescent Pt(II) Complexes Featuring Metallophilic Interactions: Properties and Applications , 2015 .

[33]  E. W. Meijer,et al.  Probing the Solvent-Assisted Nucleation Pathway in Chemical Self-Assembly , 2006, Science.

[34]  T. Swager,et al.  Columnar liquid crystallinity and mechanochromism in cationic platinum(II) complexes. , 2014, Journal of the American Chemical Society.

[35]  Jean-Marie Lehn,et al.  Supramolecular Chemistry—Scope and Perspectives Molecules, Supermolecules, and Molecular Devices (Nobel Lecture) , 1988 .

[36]  J E A N-M A R I E L E H N,et al.  SUPRAMOLECULAR CHEMISTRY - SCOPE AND PERSPECTIVES MOLECULES - SUPERMOLECULES - MOLECULAR DEVICES , 2022 .

[37]  F. Cohen,et al.  Pathway Complexity of Prion Protein Assembly into Amyloid* , 2002, The Journal of Biological Chemistry.

[38]  George M. Whitesides,et al.  Beyond molecules: Self-assembly of mesoscopic and macroscopic components , 2002, Proceedings of the National Academy of Sciences of the United States of America.

[39]  V. Yam,et al.  Solvent-induced aggregation through metal...metal/pi...pi interactions: large solvatochromism of luminescent organoplatinum(II) terpyridyl complexes. , 2002, Journal of the American Chemical Society.

[40]  Jean-Marie Lehn,et al.  Toward Self-Organization and Complex Matter , 2002, Science.

[41]  Masayuki Takeuchi,et al.  Living supramolecular polymerization realized through a biomimetic approach , 2014, Nature Chemistry.

[42]  I. Manners,et al.  Non-Centrosymmetric Cylindrical Micelles by Unidirectional Growth , 2012, Science.

[43]  Christopher A Waudby,et al.  Mechanosensitive Self-Replication Driven by Self-Organization , 2010, Science.

[44]  Gösta. Åkerlöf,et al.  The Dielectric Constant of Dioxane—Water Mixtures between 0 and 80° , 1936 .