RESUMO
Polymerization-induced crystallization-driven self-assembly (PI-CDSA) is combined, for the first time, with helical, rod-coil block copolymer (BCP) self-assembly to enable scalable and controllable in situ synthesis of chiral nanostructures of variable shape, size, and dimensionality. Herein, we report newly developed asymmetric PI-CDSA (A-PI-CDSA) methodologies in the synthesis and in situ self-assembly of chiral, rod-coil BCPs composed of poly(aryl isocyanide) (PAIC) rigid-rod and poly(ethylene glycol) (PEG) random-coil components. Using PEG-based nickel(II) macroinitiators, the construction of PAIC-BCP nanostructures with variable chiral morphologies is accomplished at solids contents ranging 5.0-10 wt %. At low core-to-corona ratios for PAIC-BCPs, we demonstrate the scalable formation of chiral one-dimensional (1D) nanofibers via "living" A-PI-CDSA whose contour lengths can be tuned through alterations to unimer-to-1D seed particle ratio. At high core-to-corona ratios, A-PI-CDSA was implemented for the rapid fabrication of molecularly thin, uniform hexagonal nanosheets via spontaneous nucleation and growth aided by vortex agitation. Investigations into 2D seeded, living A-PI-CDSA revealed a brand-new paradigm in the context of CDSA where hierarchically chiral, M helical spirangle morphologies (i.e., hexagonal helicoids) are size-tuned in three dimensions (i.e., heights and areas) via alterations to unimer-to-seed ratio. These unique nanostructures are formed in situ at scalable solids contents up to 10 wt % via rapid crystallization about screw dislocation defect sites in an enantioselective fashion. The liquid crystalline nature of PAIC blocks dictates the hierarchical assembly of these BCPs, with chirality translated across length scales and in multiple dimensions affording large amplifications in chiroptical activity with g-factors reaching -0.030 for spirangle nanostructures.
RESUMO
Molecular encoding in abiotic sequence-defined polymers (SDPs) has recently emerged as a versatile platform for information and data storage. However, the storage capacity of these sequence-defined polymers remains underwhelming compared to that of the information storing biopolymer DNA. In an effort to increase their information storage capacity, herein we describe the synthesis and simultaneous sequencing of eight sequence-defined 10-mer oligourethanes. Importantly, we demonstrate the use of different isotope labels, such as halogen tags, as a tool to deconvolute the complex sequence information found within a heterogeneous mixture of at least 96 unique molecules, with as little as four micromoles of total material. In doing so, relatively high-capacity data storage was achieved: 256 bits in this example, the most information stored in a single sample of abiotic SDPs without the use of long strands. Within the sequence information, a 256-bit cipher key was stored and retrieved. The key was used to encrypt and decrypt a plain text document containing The Wonderful Wizard of Oz. To validate this platform as a medium of molecular steganography and cryptography, the cipher key was hidden in the ink of a personal letter, mailed to a third party, extracted, sequenced, and deciphered successfully in the first try, thereby revealing the encrypted document.
