Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

Energy landscapes and functions of supramolecular systems

Journal Article · · Nature Materials
DOI:https://doi.org/10.1038/nmat4538· OSTI ID:1820613
 [1];  [2];  [3];  [3];  [3];  [4];  [3];  [3];  [5];  [6];  [5];  [3];  [7];  [8];  [9]
  1. Northwestern Univ., Chicago, IL (United States); Northwestern Univ., Evanston, IL (United States); Northwestern CBES
  2. Northwestern Univ., Chicago, IL (United States); Northwestern Univ., Evanston, IL (United States); Technische Univ. München, Munich (Germany); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Northwestern Univ., Evanston, IL (United States)
  4. Dept. of Chemical and Biological Engineering, Evanston, IL (United States)
  5. Northwestern Univ., Chicago, IL (United States); Northwestern Univ., Evanston, IL (United States)
  6. Northwestern Univ., Chicago, IL (United States); Technische Univ. München, Munich (Germany); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  7. Northwestern Univ., Evanston, IL (United States); Dept. of Chemical and Biological Engineering, Evanston, IL (United States); Dept. of Physics & Astronomy, Evanston, IL (United States)
  8. Northwestern Univ., Evanston, IL (United States); Dept. of Chemical and Biological Engineering, Evanston, IL (United States)
  9. Northwestern Univ., Chicago, IL (United States); Northwestern Univ., Evanston, IL (United States); Dept. of Biomedical Engineering, Evanston, IL (United States)
By means of two supramolecular systems—peptide amphiphiles engaged in hydrogen-bonded β-sheets, and chromophore amphiphiles driven to assemble by π-orbital overlaps—we show that the minima in the energy landscapes of supramolecular systems are defined by electrostatic repulsion and the ability of the dominant attractive forces to trap molecules in thermodynamically unfavourable configurations. Furthermore, these competing interactions can be selectively switched on and off, with the order of doing so determining the position of the final product in the energy landscape. Within the same energy landscape, the peptide-amphiphile system forms a thermodynamically favoured product characterized by long bundled fibres that promote biological cell adhesion and survival, and a metastable product characterized by short monodisperse fibres that interfere with adhesion and can lead to cell death. Our findings suggest that, in supramolecular systems, functions and energy landscapes are linked, superseding the more traditional connection between molecular design and function.
Research Organization:
Northwestern Univ., Evanston, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0000989
OSTI ID:
1820613
Alternate ID(s):
OSTI ID: 1387388
Journal Information:
Nature Materials, Journal Name: Nature Materials Journal Issue: 4 Vol. 15; ISSN 1476-1122
Publisher:
Springer Nature - Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

References (38)

25th Anniversary Article: Supramolecular Materials for Regenerative Medicine journal February 2014
Dynamic Display of Bioactivity through Host-Guest Chemistry journal September 2013
Dissipative Self-Assembly of a Molecular Gelator by Using a Chemical Fuel journal May 2010
Electrostatic Control of Bioactivity journal May 2011
How to Distinguish Isodesmic from Cooperative Supramolecular Polymerisation
  • Smulders, Maarten M.  J.; Nieuwenhuizen, Marko M.  L.; de Greef, Tom F.  A.
  • Chemistry - A European Journal, Vol. 16, Issue 1 https://doi.org/10.1002/chem.200902415
journal January 2010
Serum-induced leakage of liposome contents journal April 1980
Atomistic Molecular Dynamics Simulations of Peptide Amphiphile Self-Assembly into Cylindrical Nanofibers journal March 2011
Photodynamic Control of Bioactivity in a Nanofiber Matrix journal November 2012
Cell attachment activity of fibronectin can be duplicated by small synthetic fragments of the molecule journal May 1984
Pathway complexity in supramolecular polymerization journal January 2012
Self-assembling hydrogel scaffolds for photocatalytic hydrogen production journal October 2014
Precise hierarchical self-assembly of multicompartment micelles journal January 2012
Cell death versus cell survival instructed by supramolecular cohesion of nanostructures journal February 2014
A self-assembly pathway to aligned monodomain gels journal June 2010
Analysis of the kinetics of folding of proteins and peptides using circular dichroism journal December 2006
Supramolecular nanostructures that mimic VEGF as a strategy for ischemic tissue repair journal August 2011
Direct three-dimensional visualization of membrane disruption by amyloid fibrils journal November 2012
Self-Assembly and Mineralization of Peptide-Amphiphile Nanofibers journal November 2001
Selective Differentiation of Neural Progenitor Cells by High-Epitope Density Nanofibers journal February 2004
Reversible Optical Transcription of Supramolecular Chirality into Molecular Chirality journal April 2004
Spontaneous and X-ray-Triggered Crystallization at Long Range in Self-Assembling Filament Networks journal December 2009
Functional Supramolecular Polymers journal February 2012
Supramolecular Materials: Self-Organized Nanostructures journal April 1997
Self-Assembling Nanofibers Inhibit Glial Scar Formation and Promote Axon Elongation after Spinal Cord Injury journal April 2008
Dissipative Self-Assembly of a Molecular Gelator by Using a Chemical Fuel journal May 2010
Electrostatic Control of Bioactivity journal May 2011
Dynamic Display of Bioactivity through Host-Guest Chemistry journal September 2013
Pathway Selection in Peptide Amphiphile Assembly journal June 2014
Autocatalytic self-replicating micelles as models for prebiotic structures journal May 1992
Responsive gels formed by the spontaneous self-assembly of peptides into polymeric β-sheet tapes journal March 1997
Fibroblast polarization is a matrix-rigidity-dependent process controlled by focal adhesion mechanosensing journal November 2011
Catalytic control over supramolecular gel formation journal April 2013
Biocatalytic induction of supramolecular order journal October 2010
Nano-Biomechanical Study of Spatio-Temporal Cytoskeleton Rearrangements that Determine Subcellular Mechanical Properties and Endothelial Permeability journal June 2015
Alginate–peptide amphiphile core–shell microparticles as a targeted drug delivery system journal January 2015
Fibril Fragmentation Enhances Amyloid Cytotoxicity journal October 2009
Transient assembly of active materials fueled by a chemical reaction journal September 2015
Self-Assembling Nanofibers Inhibit Glial Scar Formation and Promote Axon Elongation after Spinal Cord Injury journal April 2008

Cited By (86)

Steering the Self‐Assembly Outcome of a Single NDI Monomer into Three Morphologically Distinct Supramolecular Assemblies, with Concomitant Change in Supramolecular Polymerization Mechanism journal June 2019
Opening a Can of Worm(-like Micelle)s: The Effect of Temperature of Solutions of Functionalized Dipeptides journal July 2017
Engineering responsive supramolecular biomaterials: Toward smart therapeutics journal September 2016
The Design of Dissipative Molecular Assemblies Driven by Chemical Reaction Cycles journal March 2020
Supramolecular Assembly of Peptide Amphiphiles journal September 2017
Supramolecular Self-Assembly To Control Structural and Biological Properties of Multicomponent Hydrogels journal September 2019
Nucleation and Growth of Ordered Arrays of Silver Nanoparticles on Peptide Nanofibers: Hybrid Nanostructures with Antimicrobial Properties journal April 2016
Programmable Assembly of Peptide Amphiphile via Noncovalent-to-Covalent Bond Conversion journal June 2017
Supramolecular Packing and Macroscopic Alignment Controls Actuation Speed in Macroscopic Strings of Molecular Motor Amphiphiles journal November 2018
Polymorphism in the Assembly of Phase-Segregated Block Molecules: Pathway Control to 1D and 2D Nanostructures journal September 2019
Super-resolution microscopy reveals structural diversity in molecular exchange among peptide amphiphile nanofibres journal May 2016
A minimal length rigid helical peptide motif allows rational design of modular surfactants journal January 2017
Non-equilibrium dissipative supramolecular materials with a tunable lifetime journal July 2017
Sulfated glycopeptide nanostructures for multipotent protein activation journal June 2017
One-pot universal initiation-growth methods from a liquid crystalline block copolymer journal June 2019
Study of Structural stability and formation mechanisms in DSPC and DPSM liposomes: A coarse-grained molecular dynamics simulation journal February 2020
Non-equilibrium supramolecular polymerization journal January 2017
Diffusion across a gel–gel interface – molecular-scale mobility of self-assembled ‘solid-like’ gel nanofibres in multi-component supramolecular organogels journal January 2018
Atheroma Niche-Responsive Nanocarriers for Immunotherapeutic Delivery journal January 2019
pH‐Triggered Conformational Change of Antp‐Based Drug Delivery Platform for Tumor Treatment with Combined Photothermal Therapy and Chemotherapy journal June 2019
Peptide Tectonics: Encoded Structural Complementarity Dictates Programmable Self‐Assembly journal April 2019
Programmierbare transiente Thermogele vermittelt durch eine pH- und Redox-regulierte supramolekulare Polymerisation journal November 2017
Co-assembly of Polyoxometalates and Zwitterionic Amphiphiles into Supramolecular Hydrogels: From Crystalline Fibrillar to Amorphous Micellar Networks journal March 2018
Secondary Self‐Assembly of Supramolecular Nanotubes into Tubisomes and Their Activity on Cells journal December 2018
Pathway Control in Cooperative vs. Anti‐Cooperative Supramolecular Polymers journal July 2019
Impact of Positional Isomerism on Pathway Complexity in Aqueous Media journal February 2020
Opening a Can of Worm(-like Micelle)s: The Effect of Temperature of Solutions of Functionalized Dipeptides journal July 2017
Tuneable Transient Thermogels Mediated by a pH- and Redox-Regulated Supramolecular Polymerization journal November 2017
Co-assembly of Polyoxometalates and Zwitterionic Amphiphiles into Supramolecular Hydrogels: From Crystalline Fibrillar to Amorphous Micellar Networks journal March 2018
Secondary Self‐Assembly of Supramolecular Nanotubes into Tubisomes and Their Activity on Cells journal December 2018
Pathway Control in Cooperative vs. Anti‐Cooperative Supramolecular Polymers journal August 2019
Impact of Positional Isomerism on Pathway Complexity in Aqueous Media journal February 2020
Energy-Landscape-Independent Kinetic Trap of an Incomplete Cage in the Self-Assembly of a Pd 2 L 4 Cage journal June 2018
Hierarchical Self-Assembly Induced by Dilution-Enhanced Hydrophobic Hydration journal April 2018
Living Supramolecular Polymerisation of Perylene Diimide Amphiphiles by Seeded Growth under Kinetic Control journal September 2018
Functional Control of Peptide Amphiphile Assemblies via Modulation of Internal Cohesion and Surface Chemistry Switch journal August 2018
Tunable Supramolecular Gel Properties by Varying Thermal History journal April 2019
Kinetic Control of a Self‐Assembly Pathway towards Hidden Chiral Microcoils journal May 2019
Seeded Polymerization of an Amide‐Functionalized Diketopyrrolopyrrole Dye in Aqueous Media journal May 2019
Template‐Free Self‐Assembly of Artificial De Novo Viral Coat Proteins into Nanorods: Effects of Sequence, Concentration, and Temperature journal September 2009
Emergent Self‐Assembly Pathways to Multidimensional Hierarchical Assemblies using a Hetero‐Seeding Approach journal September 2019
Template‐Free Self‐Assembly of Artificial De Novo Viral Coat Proteins into Nanorods: Effects of Sequence, Concentration, and Temperature journal September 2009
Applications of Dissipative Supramolecular Materials with a Tunable Lifetime journal June 2018
Dissipative Self‐Assembly of Peptides journal April 2019
Controlling supramolecular polymerization through multicomponent self-assembly journal October 2016
β sheet assembly in amyloidogenic glutamic acid nanostructures: Insights from X‐ray scattering and infrared nanospectroscopy journal April 2019
Template‐Dependent (Ir)reversibility of Noncovalent Synthesis Pathways journal February 2020
Control over differentiation of a metastable supramolecular assembly in one and two dimensions journal December 2016
Covalent-supramolecular hybrid polymers as muscle-inspired anisotropic actuators journal June 2018
Amino-acid-encoded biocatalytic self-assembly enables the formation of transient conducting nanostructures journal April 2018
Supramolecular polymerization through kinetic pathway control and living chain growth journal December 2019
Shaping and structuring supramolecular gels journal May 2019
Hierarchical self-assembly and emergent function of densely glycosylated peptide nanofibers journal May 2019
Supramolecular pathway selection of perylenediimides mediated by chemical fuels journal January 2016
Co-organizing synthesis of heterogeneous nanostructures through the photo-cleavage of pre-stabilized self-assemblies journal January 2017
Supramolecular materials journal January 2017
Dissipative out-of-equilibrium assembly of man-made supramolecular materials journal January 2017
Drug delivery by supramolecular design journal January 2017
Peptide supramolecular materials for therapeutics journal January 2018
Peptide-based nanoprobes for molecular imaging and disease diagnostics journal January 2018
Hydrogels that listen to cells: a review of cell-responsive strategies in biomaterial design for tissue regeneration journal January 2017
The effect of carbohydrate structures on the hydrogelation ability and morphology of self-assembled structures of peptide–carbohydrate conjugates in water journal January 2017
Optimising low molecular weight hydrogels for automated 3D printing journal January 2017
Enzyme-instructed self-assembly of a novel histone deacetylase inhibitor with enhanced selectivity and anticancer efficiency journal January 2019
Narrowing the diversification of supramolecular assemblies by preorganization journal January 2018
Annealing multicomponent supramolecular gels journal January 2019
Using reversible non-covalent and covalent bonds to create assemblies and equilibrating molecular networks that survive 5 molar urea journal January 2019
Structure and luminescence properties of supramolecular polymers of amphiphilic aromatic thioether–peptide conjugates in water journal January 2019
Self-assembly of model short triblock amphiphiles in dilute solution journal January 2018
Dimensional control of supramolecular assemblies of diacetylene-derived peptide gemini amphiphile: from spherical micelles to foamlike networks journal January 2018
Construction of supramolecular hydrogels using photo-generated nitric oxide radicals journal January 2018
Dissipative assemblies that inhibit their deactivation journal January 2018
Polyamine-induced, chiral expression from liquid crystalline peptide nanofilaments to long-range ordered nanohelices journal January 2019
Disulfide crosslinking and helical coiling of peptide micelles facilitate the formation of a printable hydrogel journal January 2019
Deciphering the potentiometric properties of (porphinato)zinc( ii )-derived supramolecular polymers and related superstructures journal January 2018
Supramolecular assembly of functional peptide–polymer conjugates journal January 2019
Secondary structure of end group functionalized oligomeric- l -lysines: investigations of solvent and structure dependent helicity journal January 2019
Designing stable, hierarchical peptide fibers from block co-polypeptide sequences journal January 2019
The pathway and kinetics of hierarchical assembly of ionic oligomers into a lyotropic columnar phase journal January 2019
Chromophore amphiphile–polyelectrolyte hybrid hydrogels for photocatalytic hydrogen production journal January 2020
Assembly effect on the charge carrier mobility in quaterthiophene-based n/p-materials journal January 2019
Injectable biomimetic liquid crystalline scaffolds enhance muscle stem cell transplantation journal September 2017
A combination of bioactive and nonbioactive alkyl-peptides form a more stable nanofiber structure for differentiating neural stem cells: a molecular dynamics simulation survey journal January 2019
Machine learning and molecular design of self-assembling -conjugated oligopeptides journal April 2018
Force and time-dependent self-assembly, disruption and recovery of supramolecular peptide amphiphile nanofibers journal May 2018
Kinetically Controlled Self-Assembly of Phthalocyanine–Peptide Conjugate Nanofibrils Enabling Superlarge Redshifted Absorption journal January 2019

Similar Records

Supramolecular Interactions and Morphology of Self-Assembling Peptide Amphiphile Nanostructures
Journal Article · Tue Jul 13 20:00:00 EDT 2021 · Nano Letters · OSTI ID:1846599