Self-Assembly Propensity Dictates Lifetimes in Transient Naphthalimide-dipeptide Nanofibers.

We present transient self-assembly of dipeptide nanofibers with lifetimes that are predictably variable through dipeptide sequence design. This is achieved using 1,8-Naphthalimide (NI)- amino acid methyl-esters (Phe, Tyr, Leu) that are biocatalytically coupled to amino acid-amides (Phe, Tyr, Leu, Val, Ala, Ser) to form self-assembling NI-dipeptides. However, competing hydrolysis of the dipeptides results in disassembly. We demonstrate that the kinetic parameters like lifetimes of these nanofibers can be predictably regulated by the thermodynamic parameter, namely the self-assembly propensity of the constituent dipeptide sequence. These lifetimes could vary from minutes, to hours, to permanent gels that do not degrade. Moreover, the in-built NI fluorophore was utilized to image the transient nanostructures in solution with stimulated emission depletion (STED) based on super-resolution fluorescence microscopy.

[1]  D. Adams,et al.  On the Mechanical Properties of N-Functionalised Dipeptide Gels , 2019, Molecules.

[2]  N. Gianneschi,et al.  Self-assembling peptides imaged by correlated liquid cell transmission electron microscopy and MALDI-imaging mass spectrometry , 2019, Nature Communications.

[3]  N. Wagner,et al.  A chemically fueled non-enzymatic bistable network , 2019, Nature Communications.

[4]  M. Webber,et al.  Electrostatic-driven self-sorting and nanostructure speciation in self-assembling tetrapeptides. , 2019, Nanoscale.

[5]  D. Adams,et al.  Gel to gel transitions by dynamic self-assembly. , 2019, Chemical communications.

[6]  Ankit Jain,et al.  Chemical fuel-driven living and transient supramolecular polymerization , 2019, Nature Communications.

[7]  Sahnawaz Ahmed,et al.  Chemically Fueled Dissipative Self-Assembly that Exploits Cooperative Catalysis. , 2018, Angewandte Chemie.

[8]  L. J. Prins,et al.  Energy consumption in chemical fuel-driven self-assembly , 2018, Nature Nanotechnology.

[9]  Stephen Mann,et al.  Enzyme-powered motility in buoyant organoclay/DNA protocells , 2018, Nature Chemistry.

[10]  Andreas Herrmann,et al.  Dissipative adaptation in driven self-assembly leading to self-dividing fibrils , 2018, Nature Nanotechnology.

[11]  Lucas W Antony,et al.  Dynamic actuation of glassy polymersomes through isomerization of a single azobenzene unit at the block copolymer interface , 2018, Nature Chemistry.

[12]  A. Hochbaum,et al.  Amino-acid-encoded biocatalytic self-assembly enables the formation of transient conducting nanostructures , 2018, Nature Chemistry.

[13]  Karteek K. Bejagam,et al.  Biomimetic temporal self-assembly via fuel-driven controlled supramolecular polymerization , 2018, Nature Communications.

[14]  D. Adams,et al.  Low-Molecular-Weight Gels: The State of the Art , 2017 .

[15]  Ankit Jain,et al.  Adenosine-Phosphate-Fueled, Temporally Programmed Supramolecular Polymers with Multiple Transient States. , 2017, Journal of the American Chemical Society.

[16]  S. Maiti,et al.  Temporal Control over Transient Chemical Systems using Structurally Diverse Chemical Fuels. , 2017, Chemistry.

[17]  A. Bausch,et al.  Non-equilibrium dissipative supramolecular materials with a tunable lifetime , 2017, Nature Communications.

[18]  Alessandro Sorrenti,et al.  Non-equilibrium steady states in supramolecular polymerization , 2017, Nature Communications.

[19]  Tom F. A. de Greef,et al.  Non-equilibrium supramolecular polymerization , 2017, Chemical Society reviews.

[20]  Bing Xu,et al.  Enzyme-Instructed Assembly and Disassembly Processes for Targeting Downregulation in Cancer Cells , 2017, Journal of the American Chemical Society.

[21]  Rein V. Ulijn,et al.  Peptide-Based Molecular Hydrogels as Supramolecular Protein Mimics. , 2017, Chemistry.

[22]  Ryou Kubota,et al.  In situ real-time imaging of self-sorted supramolecular nanofibres. , 2016, Nature chemistry.

[23]  E. W. Meijer,et al.  Super-resolution microscopy reveals structural diversity in molecular exchange among peptide amphiphile nanofibres , 2016, Nature Communications.

[24]  Irving R. Epstein,et al.  Reaction-diffusion processes at the nano- and microscales. , 2016, Nature nanotechnology.

[25]  Jie Zhou,et al.  Supramolecular Hydrogelators and Hydrogels: From Soft Matter to Molecular Biomaterials , 2015, Chemical reviews.

[26]  Job Boekhoven,et al.  Transient assembly of active materials fueled by a chemical reaction , 2015, Science.

[27]  Hui Zhao,et al.  Light-controlled self-assembly of non-photoresponsive nanoparticles. , 2015, Nature chemistry.

[28]  Rein V Ulijn,et al.  Biocatalytic Pathway Selection in Transient Tripeptide Nanostructures. , 2015, Angewandte Chemie.

[29]  Andreas Walther,et al.  Generic concept to program the time domain of self-assemblies with a self-regulation mechanism. , 2015, Nano letters.

[30]  Joost Groen,et al.  Rational design of functional and tunable oscillating enzymatic networks. , 2015, Nature chemistry.

[31]  David Beljonne,et al.  A dynamic supramolecular polymer with stimuli-responsive handedness for in situ probing of enzymatic ATP hydrolysis , 2014, Nature Communications.

[32]  R. Ulijn,et al.  Design of nanostructures based on aromatic peptide amphiphiles. , 2014, Chemical Society reviews.

[33]  Rein V. Ulijn,et al.  Peptide nanofibers with dynamic instability through nonequilibrium biocatalytic assembly. , 2013, Journal of the American Chemical Society.

[34]  G. L. Butterfoss,et al.  Enzyme-triggered hydrogelation via self-assembly of alternating peptides. , 2013, Chemical communications.

[35]  Rein V. Ulijn,et al.  Virtual Screening for Dipeptide Aggregation: Toward Predictive Tools for Peptide Self-Assembly , 2011, The journal of physical chemistry letters.

[36]  Job Boekhoven,et al.  Dissipative self-assembly of a molecular gelator by using a chemical fuel. , 2010, Angewandte Chemie.

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

[38]  Rein V Ulijn,et al.  Enzyme-assisted self-assembly under thermodynamic control. , 2009, Nature nanotechnology.

[39]  Rein V Ulijn,et al.  Enzyme-triggered self-assembly of peptide hydrogels via reversed hydrolysis. , 2006, Journal of the American Chemical Society.

[40]  H. Gu,et al.  Enzymatic Formation of Supramolecular Hydrogels , 2004 .

[41]  S. Hell.  Toward fluorescence nanoscopy , 2003, Nature Biotechnology.

[42]  R. Laursen,et al.  Protease substrate specificity mapping using membrane-bound peptides. , 1994, Analytical biochemistry.

[43]  W. Rutter,et al.  Mapping the S' subsites of serine proteases using acyl transfer to mixtures of peptide nucleophiles. , 1993, Biochemistry.

[44]  Jeremy M. Berg,et al.  Thermodynamic β -sheet propensities measured using a zinc-finger host peptide , 1993, Nature.

[45]  P. Adlercreutz,et al.  Nucleophile specificity in alpha-chymotrypsin- and subtilisin-(Bacillus subtilis strain 72) catalyzed reactions. , 1992, Biochimica et biophysica acta.

[46]  Prof. Dr. Borivoj Keil.  Specificity of Proteolysis , 1992, Springer Berlin Heidelberg.