Rational controlled morphological transitions in the self-assembled multi-headed giant surfactants in solution

Abstract

A series of multi-headed giant surfactants based on polystyrene (PS)-polyhedral oligomeric silsesquioxane(s) (POSS) conjugates, with a different number and topology of POSS heads, are found to self-assemble into different supramolecular structures including vesicles, cylindrical and spherical micelles in H2O/DMF mixed solvents. The transitions among different morphologies can be rationally controlled by tuning the number and topology of POSS heads, as well as the macromolecular concentration.

Sequence‐Mandated, Distinct Assembly of Giant Molecules

“…However,with the asymmetric number of BPOSS cages on both side of the DPOSS cage, this might generate surface defects at the spherical building blocks of BDB 3 .Inthis case,the supramolecular structure of BDB 3 is identified to be ad odecagonal quasicrystal (DQC), as illustrated by the characteristic SAXS pattern (the 00002, 12100, 10102, and 12101 diffractions in Figure 3D(ii)). More than one representative tiling patterns of 3 2 .4.3.4, 3 3 .4 2 ,4 4 and 3 6 could be observed in the BF TEM image in Figure 3D(v), illustrating that the structure losses the translational symmetry along the a*b*-plane. [9d, 14a] ForB 2 DB 2 (n = 4, x = 2), the sequence change resulted in shorter but symmetric BPOSS tails,a nd it forms an A15 phase again.…”

“…[2] Although the synthesis of sequence-controlled polymers at asimilar level of precision to natural polymers is an enormous endeavor by itself, [3] it remains to be demonstrated how sequence could dictate molecular topology and assembly toward different structures and functions in synthetic polymers. [6] In this case,o ligomers/polymers with nanosized macromonomers [7] is an effective approach to build phase-separated nanostructures with the most significant impact of sequence. [6] In this case,o ligomers/polymers with nanosized macromonomers [7] is an effective approach to build phase-separated nanostructures with the most significant impact of sequence.…”

“…[2c,4] While assembly of most synthetic macromolecules is driven by interaction of monomers, [5] theminute differences between individual monomers are often insufficient to discriminate assembly pathways.T hus,p recisely controlled collective and cooperative interactions have been increasingly recognized as the key process to form hierarchical structures with feature sizes of only af ew nanometers. [6] In this case,o ligomers/polymers with nanosized macromonomers [7] is an effective approach to build phase-separated nanostructures with the most significant impact of sequence.Thei mposing challenge that we are facing is not only to achieve am acromolecule with precisely defined sequences and sizes,b ut also to design and control their self-assembled structures and develop desired properties.Recent advances of click chemistry and other efficient transformations allow scientists to achieve macromolecules with high structural precision and controlled heterogeneity.O nt he other hand, the supramolecular structures are modularly assembled from aset of building blocks and thus the topology and interaction of each building block are critically important to the final assembled structures.T hey,i nt urn, must be accurately determined by the composition and sequence of the macromolecule.A iming at such an enormous task, we begin by rationally designing as eries of model amphiphilic giant molecules (so-called "giant" relative to their small-molecule counterparts) [8] forthe study of sequence-phase relationships and the role of sequences in the formation unconventional phases in soft matters. [9] More specifically,t hese giant molecules here refer to precise macromolecules build-up by molecular nanoparticle building blocks.W eh ave previously investigated the effects of composition and topology on the self-assembly of giant molecules.…”

“…[2c,4] While assembly of most synthetic macromolecules is driven by interaction of monomers, [5] theminute differences between individual monomers are often insufficient to discriminate assembly pathways.T hus,p recisely controlled collective and cooperative interactions have been increasingly recognized as the key process to form hierarchical structures with feature sizes of only af ew nanometers. [6] In this case,o ligomers/polymers with nanosized macromonomers [7] is an effective approach to build phase-separated nanostructures with the most significant impact of sequence.…”

Sequence‐Mandated, Distinct Assembly of Giant Molecules

“…More specifically, these giant molecules here refer to precise macromolecules build‐up by molecular nanoparticle building blocks. We have previously investigated the effects of composition and topology on the self‐assembly of giant molecules . However, the importance of sequence has not been systematically explored in terms of their impact on phase formation.…”