title: A dynamic supramolecular polymer with stimuli-responsive handedness for in situ probing of enzymatic ATP hydrolysis.
abstract: Design of artificial systems, which can respond to fluctuations in concentration of adenosine phosphates (APs), can be useful in understanding various biological processes. Helical assemblies of chromophores, which dynamically respond to such changes, can provide real-time chiroptical readout of various chemical transformations. Towards this concept, here we present a supramolecular helix of achiral chromophores, which shows chiral APs responsive tunable handedness along with dynamically switchable helicity. This system, composing of naphthalenediimides with phosphate recognition unit, shows opposite handedness on binding with ATP compared with ADP or AMP, which is comprehensively analysed with molecular dynamic simulations. Such differential signalling along with stimuli-dependent fast stereomutations have been capitalized to probe the reaction kinetics of enzymatic ATP hydrolysis. Detailed chiroptical analyses provide mechanistic insights into the enzymatic hydrolysis and various intermediate steps. Thus, a unique dynamic helical assembly to monitor the real-time reaction processes via its stimuli-responsive chiroptical signalling is conceptualized.
authors.affiliation: New Chemistry Unit, Supramolecular Chemistry Laboratory, Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Bangalore 560064, India.
authors.forename: Mohit
authors.initials: M
authors.lastname: Kumar
authors.affiliation: Laboratory for Chemistry of Novel Materials, Center for Innovation and Research in Materials and Polymers, University of Mons-UMONS, 20, Place du Parc, Mons B-7000, Belgium.
authors.forename: Patrick
authors.initials: P
authors.lastname: Brocorens
authors.affiliation: Laboratory for Chemistry of Novel Materials, Center for Innovation and Research in Materials and Polymers, University of Mons-UMONS, 20, Place du Parc, Mons B-7000, Belgium.
authors.forename: Claire
authors.initials: C
authors.lastname: Tonnelé
authors.affiliation: Laboratory for Chemistry of Novel Materials, Center for Innovation and Research in Materials and Polymers, University of Mons-UMONS, 20, Place du Parc, Mons B-7000, Belgium.
authors.forename: David
authors.initials: D
authors.lastname: Beljonne
authors.affiliation: Laboratory for Chemistry of Novel Materials, Center for Innovation and Research in Materials and Polymers, University of Mons-UMONS, 20, Place du Parc, Mons B-7000, Belgium.
authors.forename: Mathieu
authors.initials: M
authors.lastname: Surin
authors.affiliation: New Chemistry Unit, Supramolecular Chemistry Laboratory, Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Bangalore 560064, India.
authors.forename: Subi J
authors.initials: SJ
authors.lastname: George
mesh_terms: D000244:Adenosine Diphosphate / Q000737:chemistry; D000249:Adenosine Monophosphate / Q000737:chemistry; D000255:Adenosine Triphosphate / Q000032:analysis* / Q000737:chemistry; D006868:Hydrolysis; D007094:Imides / Q000737:chemistry*; D007700:Kinetics; D008968:Molecular Conformation; D056004:Molecular Dynamics Simulation; D015335:Molecular Probes / Q000737:chemistry*; D009281:Naphthalenes / Q000737:chemistry*; D010710:Phosphates / Q000032:analysis / Q000737:chemistry; D011108:Polymers / Q000737:chemistry*; D013057:Spectrum Analysis; D013237:Stereoisomerism
chemical_list: D007094:Imides; D015335:Molecular Probes; D009281:Naphthalenes; D010710:Phosphates; D011108:Polymers; D000249:Adenosine Monophosphate; D000244:Adenosine Diphosphate; D000255:Adenosine Triphosphate