Donor–acceptor interaction-driven self-assembly of amphiphilic rod–coil molecules into supramolecular nanoassemblies

Yu, Shengsheng; Yang, Yuntian; Chen, Tie; Xu, Jingli; Jin, Long

doi:10.1039/c7nr05329k

Cited by 30 publications

(18 citation statements)

References 70 publications

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Section: Development Of Static 2d Materialsmentioning

confidence: 99%

“…constructed supramolecular 2D sheets based on donor–acceptor interactions, in which the pyrene functional group could interact with 2,4,5,7‐tetranitrofluorenone (TNF) (Figure 2b). [ 40 ] They synthesized the rod–coil amphiphilic molecule 2, which consists of one pyrene unit, two biphenyl groups, and heptaethylene glycol as the coil segment. The molecule 2 self‐assembles into nanofibers by hydrophobic interactions and π–π stacking.…”

Section: Development Of Static 2d Materialsmentioning

confidence: 99%

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Supramolecular Two‐Dimensional Systems and Their Biological Applications

et al. 2020

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the construction of functional 2D materials by the self-assembly of synthetic building blocks such as amphiphilic block copolymers, [10] lipid molecules, [11] deoxyribonucleic acids (DNAs), [12] rod-coil amphiphiles, [13] and oligopeptides. [14] Among diverse self-assembling modules, aromatic amphiphiles can serve as remarkable candidates for the creation of well-defined supramolecular 2D structures owing to their rigidity and the π-π stacking of aromatic groups. [15-17] In self-assembled 2D structures composed of aromatic amphiphiles, the rigid aromatic segments surrounded by hydrophilic flexible chains can form relatively stable noncovalent interactions in a preferred direction. [18] Besides, the packing arrangements of aromatic segments can reversibly transform into a different equilibrium state when subjected to subtle environmental changes, demonstrating a distinct adaptive capability of dynamic shape alterations. [19] Therefore, the supramolecular 2D materials formed by aromatic amphiphiles hold promise in biological applications because the physical and chemical properties of the supramolecular 2D structure, which are attributed to the large surface area of these materials, can enhance the detection sensitivity of target molecules and increase the molecular loading and bio-conjugation efficiency. Furthermore, the flexibility, low toxicity, dispersibility, and permeability offered by 2D materials can contribute to the development of the next generation of functional materials in biological systems. [20-25] In this regard, several types of studies have been conducted on supramolecular 2D materials with biological applicability because supramolecular systems are more convenient for the fabrication of materials with multiple functionalities for biology applications. [26-34] Herein, we summarize supramolecular 2D materials based on the corresponding aromatic amphiphiles and discuss several of their biological applications (Figure 1). We classified the strategies of self-assembly of the 2D structure as follows: direct assembly of monomers and assembly in a stepwise manner via primary structures. In the direct assembly strategy, the aromatic amphiphilic blocks are assembled into 2D structures without transition into an intermediate state, in which the monomers are directly arranged in parallel, zigzag, or hexagonal conformations through hydrophobic, hostguest, and electrostatic interactions. However, in the stepwise assembly strategy, the monomers are assembled into primary structures such as dimeric micelles and fibers in the initial state, which is followed by lateral interactions to 2D structures. Various biological systems rely on the supramolecular assembly of biomolecules through noncovalent bonds for performing sophisticated functions. In particular, cell membranes, which are 2D structures in biological systems, have various characteristics such as a large surface, flexibility, and molecule-recognition ability. Supramolecular 2D materials based on biological systems provide a novel perspective for the deve...

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Section: Development Of Static 2d Materialsmentioning

confidence: 99%

Section: Development Of Static 2d Materialsmentioning

confidence: 99%

Supramolecular Two‐Dimensional Systems and Their Biological Applications

et al. 2020

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“…Rod−coil block copolymers can form unique assembly structures and found a range of applications in composites, [ 40 ] biomaterials, [ 41,42 ] and organic electronics. [ 43 ] The rod (rigid) segment studied so far includes aromatic polymers, [ 44,45 ] π‐conjugated polymers, [ 46,47 ] polypeptides, [ 48,49 ] and polyisocyanates. [ 50,51 ] Because itaconate monomers have two alkyl esters at the α‐position, itaconate polymers are rigid and can be used as rod segments in rod−coil copolymers.…”

Section: Figurementioning

confidence: 99%

Organocatalyzed Living Radical Polymerization of Itaconates and Self‐Assemblies of Rod−Coil Block Copolymers

Sarkar

Zheng

et al. 2020

Macromol. Rapid Commun.

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lengths and tend to behave as rod-like polymers. The rod-like conformation is of interest in fundamental and practical perspectives.Living radical polymerization, [22−25] also termed reversible−deactivation radical polymerization, was used for itaconates to synthesize well-defined polymers with predicted molar masses and narrow molar mass distributions. For example, atom transfer radical polymerization (ATRP) and reversible addition−fragmentation chain transfer (RAFT) polymerization of DMI, DBI, and dicyclohexyl itaconate successfully yielded polymers with low dispersity (Đ = M w /M n = 1.3−1.5), [26−28] where M n and M w are the number-and weight-average molar masses, respectively. Because the chain transfer to monomer is generally significant for itaconates at high temperatures, the Đ value tended to increase as the polymerization proceeded. [29,30] The polymerization was also slow because of their small propagation rate constants (due to the large steric hindrance) and typically ceased at moderate monomer conversions (up to 55%). [28] Nevertheless, these results elegantly opened up the use of the biorenewable itaconate monomers to yield structurally controlled polymers.Our research group developed an organocatalyzed living radical polymerization exploiting alkyl iodides (R-I) as initiating dormant species and organic molecules such as tetrabutylammonium iodide (BNI (A + Isalt)) as catalysts. [31−35] The polymer−iodide (polymer−I) dormant species and the catalyst (iodide anion I − in A + I − ) form a complex (polymer−I⋅⋅⋅I -), and the complex subsequently reversibly generates the propagating radical (polymer•) and A + I 2 • − (Scheme 1a). Because A + I 2 •− is not a stable radical, two A + I 2 •− species can undergo disproportionation to produce A + I − and A + I 3 − anions, which are stable species (Scheme 1b). A + I − acts as an activator, whereas A + I 3 acts as a deactivator (Scheme 1c). Polymer• can thus be deactivated by either A + I 2 •-(Scheme 1a) or A + I 3 -(Scheme 1c). This polymerization is termed as reversible complexation mediated polymerization (RCMP). RCMP is attractive for no use of special capping agents or metal catalysts, ease of operation, and applicability to a broad scope of monomers (i.e., methacrylates, acrylates, styrene, and acrylonitrile) and polymer designs. [36−39] The present work aimed to further expand the monomer scope of RCMP to itaconates, i.e., DMI, DEI, and DBI. The use of RCMP may enable the synthesis of those biorenewable polymers with controlled structures in a metal-free and sulfur-free condition. Organocatalyzed living radical polymerizations of itaconates are studied, yielding low-dispersity linear and star polymers (Đ = M w /M n = 1.28−1.46) up to M n = 20 000 and monomer conversion = 62%, where M n and M w are the number-and weight-average molar masses, respectively. The block polymerization with functional methacrylates, an acrylate, and styrene yields various rod−coil block copolymers. Linear A−B diblock, linear B−A−B triblock, and 3-arm star A−B diblock copol...

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“…Tuning the molecular structures and accurate assembly of these molecules is one approach for forming supramolecular advanced materials 17–22 . Rod–coil molecular systems have been proven to be able to produce supramolecular nanostructures in bulk as well as in selective solution states 23–28 . Rod–coil molecules further have strong self‐organizing capacities to produce well‐defined supramolecular nanostructures.…”

Section: Introductionmentioning

confidence: 99%

Construction of nanoaggregates from amphiphilic supramolecules containing barbiturate and Hamilton wedge units

Lü

Deng

Zhong

et al. 2021

Polymer International

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The study of supramolecular morphology is gaining significant attention. This may be attributed to the fact that nanostructures of aggregates have been found to significantly influence the photoelectronic properties of supramolecular materials. In this study, the self‐assembling behaviour of rod–coil molecules with barbiturate (Ba) or Hamilton wedge (Hw) units and the supramolecule Ba‐Hw was investigated. In chloroform solution, molecule Hw consisted of an oligo‐ethylene chain with degree of polymerization of 17 as well as biphenyl, phenyl and Hw units. Ba molecules incorporated octyloxy, biphenyl, phenyl and Ba groups that self‐organized into nanofibres with different diameters. Supramolecular amphiphile Hw‐Ba self‐aggregated into different sizes of nanosheet‐like aggregates. In a dimethylsulfoxide/H2O (1:19 v/v) mixed polar solvent, molecules Hw and Ba aggregated into twist‐shaped and nanosheet aggregates, while the supramolecular Hw‐Ba aggregated into larger‐size microtubes. Experimental results obtained for these molecular assemblies suggest that combining Ba and Hw units by employing hydrogen bonds is an effective strategy for forming amphiphilic supramolecules. Compared with the individual rod–coil molecules Ba and Hw, supramolecule Hw‐Ba has stronger π–π intermolecular forces due to the presence of more planar Hw‐Ba building blocks, which form various supramolecular assemblies with less curvature than the rigid and flexible surfaces of the original molecules. © 2021 Society of Industrial Chemistry.

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Donor–acceptor interaction-driven self-assembly of amphiphilic rod–coil molecules into supramolecular nanoassemblies

Cited by 30 publications

References 70 publications

Supramolecular Two‐Dimensional Systems and Their Biological Applications

Supramolecular Two‐Dimensional Systems and Their Biological Applications

Organocatalyzed Living Radical Polymerization of Itaconates and Self‐Assemblies of Rod−Coil Block Copolymers

Construction of nanoaggregates from amphiphilic supramolecules containing barbiturate and Hamilton wedge units

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