Structurally Induced Chirality of an Achiral Chromophore on Self-Assembled Nanofibers: A Twist Makes It Chiral

Abstract

The surface domains of self-assembled amphiphiles are well-organized and can perform many physical, chemical, and biological functions. Here, we present the significance of chiral surface domains of these self-assemblies in transferring chirality to achiral chromophores. These aspects are probed using l- and d-isomers of alkyl alanine amphiphiles which self-assemble in water as nanofibers, possessing a negative surface charge. When bound on these nanofibers, positively charged cyanine dyes (CY524 and CY600), each having two quinoline rings bridged by conjugated double bonds, show contrasting chiroptical features. Interestingly, CY600 displays a bisignated circular dichroic (CD) signal with mirror-image symmetry, while CY524 is CD silent. Molecular dynamics simulations reveal that the model cylindrical micelles (CM) derived from the two isomers exhibit surface chirality and the chromophores are buried as monomers in mirror-imaged pockets on their surfaces. The monomeric nature of template-bound chromophores and their binding reversibility are established by concentration- and temperature-dependent spectroscopies and calorimetry. On the CM, CY524 displays two equally populated conformers with opposite sense, whereas CY600 is present as two pairs of twisted conformers in each of which one is in excess, due to differences in weak dye–amphiphile hydrogen bonding interactions. Infrared and NMR spectroscopies support these findings. Reduction of electronic conjugation caused by the twist establishes the two quinoline rings as independent entities. On-resonance coupling between the transition dipoles of these units generates bisignated CD signals with mirror-image symmetry. The results presented herein provide insight on the little-known structurally induced chirality of achiral chromophores through transfer of chiral surface information.

Development of Polymethine Dyes for NIR‐II Fluorescence Imaging and Therapy

“…The aggregation of self‐assembled dyes often leads to enhanced fluorescence signals, thereby boosting detection sensitivity and aiding in detecting low concentrations of biomolecules. [ 100–102 ]…”

Red Circularly Polarized Luminescence from Dimeric H-Aggregates of Acridine Orange by Chiral Induction

“…The thickness of the CMs, which corresponds to twice the molecular length, matches the height observed in the AFM images (Figures F and S1E). Although the relative positioning of chiral valine groups in either CM does not immediately reveal any handedness, analyzing the distributions of θ, φ, and ψ torsions (Figure I,J) discloses that the CMs possess surface chirality . More specifically, the θ distribution (Figure J) indicates that, in the CM, the headgroup has a preferred orientation with respect to its tail.…”

“…More recently, chiral scaffolds (template) have been used for generating chiroptical signals through chiral induction to achiral molecules on their surface. − Other approaches include: (i) suppression of nonradiative decay induced by the aggregation of achiral molecules − and (ii) energy transfer to coassembled achiral chromophores. − Coupling between the transition dipoles of template-bound molecules contributes to the emergent chiroptical properties. The nature of exciton coupling (on- or off-resonance) is reflected as mono- or bisignation in the CD/CPL spectrum.…”

“…Besides, for each of the three torsions, the distribution for the CM of C 16 - l -Val is mirror-imaged to that for the CM of C 16 - d -Val (Figure J). Consequently, when the tail atoms of C 16 - l -Val and C 16 - d -Val are overlaid, their most favored headgroup conformations in the respective CMs are mirror-imaged (Figure K), a clear evidence of surface chirality …”