Sequence‐Mandated, Distinct Assembly of Giant Molecules

Abstract

Although controlling the primary structure of synthetic polymers is itself a great challenge, the potential of sequence control for tailoring hierarchical structures remains to be exploited, especially in the creation of new and unconventional phases. A series of model amphiphilic chain-like giant molecules was designed and synthesized by interconnecting both hydrophobic and hydrophilic molecular nanoparticles in precisely defined sequence and composition to investigate their sequence-dependent phase structures. Not only compositional variation changed the self-assembled supramolecular phases, but also specific sequences induce unconventional phase formation, including Frank-Kasper phases. The formation mechanism was attributed to the conformational change driven by the collective hydrogen bonding and the sequence-mandated topology of the molecules. These results show that sequence control in synthetic polymers can have a dramatic impact on polymer properties and self-assembly.

Encoding biological recognition in a bicomponent cell-membrane mimic

“…These complex architectures, which were discovered and elucidated via structural and retrostructural analysis of libraries of self-assembling dendrons and dendrimers, employed diffraction methods analogous to those used to develop the field of structural biology (16). Later these same phases were found by the same methods (17) in block copolymers (18–22), surfactants (23–26), lipids (27–33), glycolipids (34), and in other systems (35–38). Recently, amphiphilic Janus dendrimers (JDs) (39, 40), and their sugar-presenting analogs, Janus glycodendrimers (JGDs) (41), which provide synthetic alternatives to natural lipids and glycolipids that are readily functionalized, have been reported to self-assemble in either water or buffer (42) into vesicles, named dendrimersomes (DSs) and glycodendrimersomes (GDSs) (43), respectively.…”

Investigation of the Locked‐Unlocked Mechanism in Living Anionic Polymerization Realized with 1‐(Tri‐isopropoxymethylsilylphenyl)‐1‐phenylethylene

“…Based on this basic understanding,m olecular switches [2] and motors [3] have been synthesized and have revealed how switching between locked and unlocked states can be accomplished in both inorganic and organic chemistry. [5] Furthermore,the ability to control the locked and unlocked states in chain-growth polymerization has wonderful potential for the synthesis of advanced materials possessing specific structures or functions. [5] Furthermore,the ability to control the locked and unlocked states in chain-growth polymerization has wonderful potential for the synthesis of advanced materials possessing specific structures or functions.…”

“…[4] By controlling the facile transformation between locking and unlocking,e laborate behaviors such as moving, folding, repairing,and sensing have been achieved at the molecular level. [5] Furthermore,the ability to control the locked and unlocked states in chain-growth polymerization has wonderful potential for the synthesis of advanced materials possessing specific structures or functions. Because al arge number of living centers exists during chain propagation, if some portion of them can be controllably switched between the locked and unlocked states,t he chain-propagation reaction can either insert specific monomer units or block structures at specific sites.M ore recently,p hotocontrolled radical polymerization (Photo-CRP) reactions have been explored, and the entire propagation can be locked and unlocked in af acile manner since the ON/OFF state can be controlled with light.…”

Analysis of monodisperse, sequence-defined, and POSS-functionalized polyester copolymers by MALDI tandem mass spectrometry

“…9 An alternative approach to generate sequence-controlled polymers is by introducing differently functionalized side chains in a homopolymeric backbone, as shown by Cheng et al. for polyester oligomers comprised of succinic anhydride and neopentyl triol functionalized with two different polyhedral oligomeric silsesquioxane (POSS) cages 10,11 and by Joy et al. for polyesters synthesized from succinic acid and diols functionalized with bioinspired pendants.…”