Thickness control of 2D nanosheets assembled from precise side-chain giant molecules

Feng, Fengfeng; Guo, Dong Ming; Shao, Yu; Xiang, Yan; Yue, Kan; Pan, Zhipeng; Li, Xiangqian; Xiao, Dongcheng; Jin, Liang; Zhang, Wenbin; Líu, Hao

doi:10.1039/d1sc00021g

Cited by 14 publications

(22 citation statements)

References 54 publications

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“…As size-amplified analogues of canonical polymers at larger length scales, polymeric chains made of “giant” monomers allow direct observation of structural characteristics using optical microscopy or even the naked eye, offering an intriguing alternative for exploration of chain dynamics and phase behaviors. , Giant monomers usually refer to granular or colloidal particles with diameters ranging from millimeters to nanometers, such as Teflon beads, , water droplets, colloidal particles, − peptide bundles, globular proteins, or molecular clusters. − Through elaborately designed supramolecular recognition and/or chemical coupling, the giant monomers can be “polymerized” into particle arrays with a chain-like configuration. Compared with individual monomers, the connection along the main chain endows these giant polymeric chains with appealing properties through cumulative and collective effects .…”

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confidence: 99%

Precise Amphiphilic Giant Polymeric Chain Based on Nanosized Monomers with Exact Regio-Configuration

et al. 2021

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Polymeric chains made of "giant" monomers at a larger length scale provide intriguing insights into the fundamental principles of polymer science. In this study, we modularly prepared a library of discrete amphiphilic polymeric chains using molecular nanoparticles as repeat units, with exact control of composition, chain length, surface property, and regio-configuration. These giant polymeric chains selfassembled into a rich collection of highly ordered phases. The precise chemical structure and uniform chain length eliminate all the inherent molecular "defects", while the nanosized monomer amplifies minute structural differences, providing an ideal platform for a systematic scrutiny of the self-assembly behaviors at a larger length scale. The compositional and regioconfigurational contribution was carefully studied. The regio-regularity is found to have a direct and profound impact on the chain conformation, leading to a distinct molecular packing scheme and therefore shifting the phase boundaries. With increasing the length of the linker, the regio-constraint gradually diminishes, and the neighboring particles would eventually be decoupled.

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Precise Amphiphilic Giant Polymeric Chain Based on Nanosized Monomers with Exact Regio-Configuration

et al. 2021

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“…As shown in Figure 4, Tables S3 and S4, and Figure S11, unimolecular spherical micelles were obtained in DPD simulations after minimizing the total free energy. Additionally, simulation results also showed that the diameters of unimolecular spherical micelles formed by solution self-assembly of poly(APOSS-BPOSS) 12 , poly(APOSS-BPOSS) 17 , poly(APOSS-BPOSS) 22 , and poly-(APOSS-BPOSS) 35 were 3.25, 3.58, 4.44, and 5.02 nm, respectively. Considering the inevitable errors of the coarse-grained (CG) model and experimental errors, the micellar sizes obtained by simulations were consistent with the experimental results measured by DLS (3.4, 3.6, 3.7, and 4.5 nm for n = 12, 17, 22, and 35, respectively).…”

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confidence: 90%

“…Air-dried samples from prepared solution were examined by bright-field transmission electron microscopy (TEM; sample preparation was described in the Supporting Information (SI)), and typical spherical morphologies were observed for all poly(APOSS-BPOSS) n samples with an initial concentration of 2 mg/mL (Figure S7). The diameters of these spherical micelles formed by poly(APOSS-BPOSS) 12 , poly(APOSS-BPOSS) 17 , poly-(APOSS-BPOSS) 22 , and poly(APOSS-BPOSS) 35 were measured by TEM as 3.2 ± 0.5, 3.3 ± 0.5, 3.5 ± 0.5, and 4.2 ± 0.6 nm, respectively. To further confirm the morphologies and diameters of these spherical micelles, we performed DLS characterization of all solutions.…”

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confidence: 99%

“…The synthesis of well-defined nanoscale JPs with molecular precision, high uniformity, and shape and volume persistence is usually challenging. Traditionally, JPs can be constructed by inorganic nanoparticles, colloidal particles, or an amphiphilic flexible polymer chain with special topological structures; however, their large variations in sizes, shapes, or flexible conformation result in limited controllability of their self-assembly to three-dimensional long-range ordered structures. − In this respect, researchers have recently designed and synthesized a set of molecular JPs based on volume and shape-persistent molecular nanoparticles (MNPs), such as fullerene (C60), polyoxometalate (POM), and polyhedral oligomeric silsesquioxanes (POSS) , through efficient chemical transformations like “click” reactions. − The resulting molecular JPs can self-assemble into several unconventional structures in solution and bulk, − attributing to the symmetry breaking in both molecular geometries and chemical interactions. − Besides that, diverse functional groups are able to be efficiently incorporated into MNPs, affording these MNP-based molecular JPs with specific functions. In this regard, constructing molecular JPs using MNPs is not only of scientific importance, but also provides a versatile platform to generate functional materials with nanosized features.…”

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confidence: 99%

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Self-Assembly of Poly(Janus particle)s into Unimolecular and Oligomeric Spherical Micelles

Feng

et al. 2021

ACS Macro Lett.

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Using shape-persistent Janus particles to construct poly-(Janus particle)s and studying their self-assembly behaviors are of great interest, but remain largely unexplored. In this work, we reported a type of amphiphiles constructed by the ring-opening metathesis polymerization of nonspherical molecular Janus particles (APOSS-BPOSS), called poly-(Janus particle)s (poly(APOSS-BPOSS) n , n = 12, 17, 22, and 35, and M n = 35−100 kg/mol). Unlike traditional bottlebrush polymers consisting of flexible side chains, these poly(Janus particles) consist of rigid hydrophilic and hydrophobic polyhedral oligomeric silsesquioxane (POSS) cages as side chains. Interestingly, instead of maintaining an expected extended chain conformation, they could also collapse and then self-assemble to form unconventional unimolecular or oligomeric spherical micelles in solutions with a feature size smaller than 7 nm. More importantly, unlike traditional amphiphilic polymer brushes that could form unimolecular micelles at a relatively high degree of polymerization by self-assembly, these poly(Janus particles)s could accomplish self-assembly at a quite low degree of polymerization because of their unique chemical structure and molecular topology. The formation of unimolecular and oligomeric micelles was also further confirmed by dissipative particle dynamics simulations. This study of introducing the POSS-based poly(Janus particle)s as a class of shape amphiphiles will provide a model system for generating unimolecular and oligomeric micellar nanostructures through solution self-assembly.

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“…Very recently, we modularly synthesized a series of POSS-based precise side-chain giant molecules (SCGMs) in a pre-programmed order. 37 Various numbers of isobutyl-bearing POSS derivatives (BPOSS) and one carboxylbearing POSS derivative (APOSS) were consecutively connected as the pendants. Because BPOSS cages are crystalline and APOSS cages are not, crystallization of SCGMs from dilute solution resulted in 2D rhombic nanosheets resembling the planar single crystals of linear polymers.…”

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confidence: 99%

Crystallization of Precise Side-Chain Giant Molecules with Tunable Sequences and Functionalities

Feng

Shao

et al. 2021

Macromolecules

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Side-chain giant molecules, constructed from giant monomers by precision synthesis, are viewed as a size-amplified analogue of conventional linear polymers. The molecular accuracy in terms of composition, sequence, topology, and functionality makes these precise macromolecules an ideal platform to investigate the interplay of various molecular parameters in their hierarchical assembly processes. In this study, we studied the crystallization of two sets of amphiphilic side-chain giant molecules with elegantly designed chain sequences and functionalities. When crystallizing from dilute solutions, they form well-defined two-dimensional (2D) crystals with a unique sequence-independent feature. In-depth structural characterization suggested a sandwich-like configuration with head-to-head packing of the side-chain components. Interestingly, the chain stem orientation is supposed to be perpendicular to the normal direction of the nanosheet crystals, which was distinct from the classic folded-chain model of conventional linear polymers. Besides, by intentionally altering the functional groups of the non-crystalline moieties to be non-ionic, cationic, or anionic, we proposed that the solvation effect played a key role in inhibiting the crystal stacking along the surface normal direction and thus in stabilizing the 2D crystals. Our findings revealed the unique crystallization behavior of precise side-chain giant molecules and might provide a strategy to engineer 2D nanomaterials with pre-programmed compositions and functions.

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Thickness control of 2D nanosheets assembled from precise side-chain giant molecules

Abstract: The performance of 2D nanomaterials hinges on both the chemical compositions and the morphological structures across different length scales. Among all the three dimensions, thickness is the only one that...

Cited by 14 publications

References 54 publications

Precise Amphiphilic Giant Polymeric Chain Based on Nanosized Monomers with Exact Regio-Configuration

Precise Amphiphilic Giant Polymeric Chain Based on Nanosized Monomers with Exact Regio-Configuration

Self-Assembly of Poly(Janus particle)s into Unimolecular and Oligomeric Spherical Micelles

Crystallization of Precise Side-Chain Giant Molecules with Tunable Sequences and Functionalities

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