Order–disorder transition in supramolecular polymer combs/brushes with polymeric side chains

Golkaram, Milad; Portale, Giuseppe; Mulder, P. O. M.; Maniar, Dina; Faraji, Shirin; Loos, Katja

doi:10.1039/c9py01915d

Cited by 5 publications

(5 citation statements)

References 54 publications

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“…Indeed, as mentioned in Section , a lamellar periodicity of around 100 Å implies that the HPB chains located between two lamellae are oriented, especially in the vicinity of the lamellae where the segments are strongly stretched and impenetrable. As discussed in refs and , this also contributes to the sample rigidity.…”

Section: Results and Discussionmentioning

confidence: 79%

“…9,60,61 If the supramolecular junctions organize into well-defined stacks, it has been shown that supramolecular polymer brushes can be obtained, with either lamellar or hexagonal cylinder morphologies, depending on the aggregation strength as well as on the mobility of the pending chains. 10,62 The examples described above support that it is possible to obtain a strong reversible network based on the short linear building blocks bearing directional binding motifs at their extremities. This requires the phase separation, aggregation, glass formation, or crystallization of the supramolecular junctions, 24 which strongly affect the sample properties.…”

Section: Introductionmentioning

confidence: 99%

“…As for telechelic linear building blocks, the supramolecular moieties resulting from the assembly of mono-functional linear chains can also phase-separate into larger objects . Since the chains only have one functionalized extremity, the secondary aggregation of the supramolecular junctions does not allow the formation of a network but rather leads to the formation of micelle-like objects, from star-like polymers to colloidal particles. ,, If the supramolecular junctions organize into well-defined stacks, it has been shown that supramolecular polymer brushes can be obtained, with either lamellar or hexagonal cylinder morphologies, depending on the aggregation strength as well as on the mobility of the pending chains. , …”

Section: Introductionmentioning

confidence: 99%

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Dynamics and Structure of Metallo-supramolecular Polymers Based on Short Telechelic Precursors

et al. 2021

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We study the viscoelastic properties and the structure of a short hydrogenated polybutadiene (HPB) building block end-capped by terpyridine ligands. Adding metal ions in the sample leads to the formation of metallo-supramolecular junctions between the blocks, while the difference in polarity between the HPB chains and the metal complexes leads to the phase separation of the complexes into well-organized structures. By varying the nature and amount of metal ions added to the system, with the temperature, as well as with the sample thermal history, we show that it is possible to modulate these associations and obtain a very rich range of properties. In particular, while increasing the amount of metal ions leads to the sample reinforcement, it also causes a decrease of its melting temperature. This result is linked to the structure of the sample, which is characterized, in specific conditions, by the co-existence of two lamellar structures that we attribute to the existence of mono-complexes. The stability of these two lamellar structures is discussed based on the structural evolution during several heating and cooling ramps. We also show that the usually observed lamellar structure can be changed into a hexagonal structure if excess of metal ions are added to the sample.

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Section: Results and Discussionmentioning

confidence: 79%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Dynamics and Structure of Metallo-supramolecular Polymers Based on Short Telechelic Precursors

et al. 2021

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“…Since there are only a few reports of UPy monomer polymerization with RAFT, ,, we checked the linearity of the polymerization kinetics during the process. UPy-functionalized CTAs have already been shown to maintain the linear growth of RAFT polymers and thus a methacrylated version was expected to perform similarly.…”

Section: Resultsmentioning

confidence: 99%

Complementary Supramolecular Functionalization Enhances Antifouling Surfaces: A Ureidopyrimidinone-Functionalized Phosphorylcholine Polymer

Feliciano

Soares

Bosman

et al. 2023

ACS Biomater. Sci. Eng.

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Fibrosis of implants remains a significant challenge in the use of biomedical devices and tissue engineering materials. Antifouling coatings, including synthetic zwitterionic coatings, have been developed to prevent fouling and cell adhesion to several implantable biomaterials. While many of these coatings need covalent attachment, a conceptually simpler approach is to use a spontaneous self-assembly event to anchor the coating to a surface. This could simplify material processing through highly specific molecular recognition. Herein, we investigate the ability to utilize directional supramolecular interactions to anchor an antifouling coating to a polymer surface containing a complementary supramolecular unit. A library of controlled copolymerization of ureidopyrimidinone methacrylate (UPyMA) and 2-methacryloyloxyethyl phosphorylcholine (MPC) was prepared and their UPy composition was assessed. The MPC-UPy copolymers were characterized by 1 H NMR, Fourier transform infrared (FTIR), and gel permeation chromatography (GPC) and found to exhibit similar mol % of UPy as compared to feed ratios and low dispersities. The copolymers were then coated on an UPy elastomer and the surfaces were assessed for hydrophilicity, protein absorption, and cell adhesion. By challenging the coatings, we found that the antifouling properties of the MPC-UPy copolymers with more UPy mol % lasted longer than the MPC homopolymer or low UPy mol % copolymers. As a result, the bioantifouling nature could be tuned to exhibit spatio-temporal control, namely, the longevity of a coating increased with UPy composition. In addition, these coatings showed nontoxicity and biocompatibility, indicating their potential use in biomaterials as antifouling coatings. Surface modification employing supramolecular interactions provided an approach that merges the simplicity and scalability of nonspecific coating methodology with the specific anchoring capacity found when using conventional covalent grafting with longevity that could be engineered by the supramolecular composition itself.

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“…55 Therefore, ODINs are more likely to make hydrogen bonding with PEG (or PTHF) 41 than with PmA or PnBa in our latest study. 56,57 This leads to an easier dissociation of the dimerized ODIN moieties in the PEG matrix in comparison to PmA, and consequently, PEG-ODINs can flow faster at higher temperatures or longer frequencies. In other words, the brush morphology is easier to be obtained in PmA.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Supramolecular Polymer Brushes: Influence of Molecular Weight and Cross-Linking on Linear Viscoelastic Behavior

et al. 2020

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The origin of unique rheological response in supramolecular brush polymers is investigated using different polymer chemistries (poly(methyl acrylate) (PmA) and poly(ethylene glycol) (PEG)), topologies (linear or star), and molecular weights. A recently developed hydrogen-bonding moiety (1-(6-isocyanatohexyl)-3-(7-oxo-7,8-dihydro-1,8-naphthyridin-2-yl)-urea) (ODIN) was coupled to PmAs and PEGs to form supramolecular brush polymers, the backbone of which is formed by the associated moieties. At low molecular weights of monofunctionalized polymers (both PmA and PEG), the formed brushes are mostly composed of a thick backbone (with very short arms) and are surrounded by other similar brush polymers, which prevent them from diffusing and relaxing. Therefore, the monofunctionalized PmA with a low M n does not show terminal flow even at the highest experimentally studied temperature (or at longest time scales). By increasing the length of the chains, supramolecular brushes with longer arms are obtained. Due to their lower density of thick backbones, these last ones have more space to move and their relaxation is therefore enhanced. In this work, we show that despite similarities between covalent and transient brush polymers, the elastic response in the latter does not originate from the brush entanglements with a large M e (entanglement molecular weight), but it rather stems from the impenetrable rigid backbone and caging effect similar to the one described for hyperstars.

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Order–disorder transition in supramolecular polymer combs/brushes with polymeric side chains

Cited by 5 publications

References 54 publications

Dynamics and Structure of Metallo-supramolecular Polymers Based on Short Telechelic Precursors

Dynamics and Structure of Metallo-supramolecular Polymers Based on Short Telechelic Precursors

Complementary Supramolecular Functionalization Enhances Antifouling Surfaces: A Ureidopyrimidinone-Functionalized Phosphorylcholine Polymer

Supramolecular Polymer Brushes: Influence of Molecular Weight and Cross-Linking on Linear Viscoelastic Behavior

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