Mechanistic investigation on cellular internalization triggering structure-induced conformational modulation of...

Exploring the effects of electron donor (D) and acceptor (A) functional groups in tuning the condensed state properties has been a challenging yet efficient approach to reveal promising materials for cutting-edge applications. Herein, a series of boron-nitrogen (BN) incorporated organic congeners (NBNMe2, NBOMe, NBF, NBCl, NBBr, NBCN, NBPy) appended with functional groups having various degrees of D/A characteristics were developed and their potential in controlling supramolecular assembly and condensed state luminescence features (>90 nm redshift in λ _em,max) was explored. Despite the minor structural engineering in BN-based small molecules, they effectively modulated conformational orientation and molecular packing, leading to the directed growth of distinct and highly ordered self-assembly patterns, i.e., nanosheets, nanospheres, nanowires, and nanorods. The structure-property correlation investigation also highlighted the time-dependent fluorescence enhancement for NBPy owing to morphological growth via the fusion of nanospheres into nanowire conformation. Further, these nano-architectures with distinct conformations were employed to examine the mechanistic aspects as well as the influence of morphologies in cellular uptake and imaging, where all the nano-aggregates exhibited lysosomal localization following multiple endocytosis pathways and the nanorods possessed the highest uptakes (CTCF_4h/0.5h = 3.11) with respect to other conformations. The in-depth inspection of the structural impact in single crystal X-ray diffraction (SCXRD) analysis disclosed the decisive role of boron atoms and functional group tuning that built a conceptual correlation between the molecular architecture and their photophysical characteristics, supramolecular assembly, and cellular internalization process, offering key insights on the development of rapid and effective drug delivery techniques.