Main-chain scission of individual macromolecules induced by solvent swelling

Messmer, Daniel; Bertrán, Oscar; Kissner, Reinhard; Alemán, Carlos; Schlüter, A. Dieter

doi:10.1039/c9sc01639b

Cited by 16 publications

(14 citation statements)

References 62 publications

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“…They find that solvent-induced scission is due to sterically induced degradation, that is internal mechanical stress caused by swelling in the dendritic periphery, as opposed to external stressors (e.g., reactants, temperature instability, etc.). 158 These findings provide further evidence that dendronized polymers can be thought of as colloidal particles, rather than classical linear polymers, in solution. 159 Controlled polymer swelling can favorably alter the morphology and functionality of polymer films, for example altering the surface roughness or adhesive properties.…”

Section: Solvation and Swellingmentioning

confidence: 68%

Correlating polymer structure, dynamics, and function with atomic force microscopy

Murphy

Raybin

Sibener

2021

Journal of Polymer Science

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Since its development, atomic force microscopy (AFM) has become an indispensable tool for investigating fundamental and technological applications of polymer materials. The versatility of AFM imaging modes and operating conditions allows for nanoscale characterization of a range of dynamic processes, such as crystallization, phase separation, self assembly, and electronic transport. Advances in AFM technology, particularly high-speed and highresolution imaging, enable investigation of polymer structure, function, and dynamics in real world conditions and across a range of relevant spatial and temporal scales. In this perspective, we highlight a collection of recent polymer studies that utilize AFM to correlate the function and structure of polymer films, with focus on its multiparametric imaging capabilities. As the complexity of polymer materials and morphologies continues to increase, AFM is well poised to meet the accompanying demand for nanoscale imaging and characterization.

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Section: Solvation and Swellingmentioning

confidence: 68%

Correlating polymer structure, dynamics, and function with atomic force microscopy

Murphy

Raybin

Sibener

2021

Journal of Polymer Science

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“…This is because xylene is a poor solvent for PVDF but a good solvent for polystyrene. The thermal treatment induced the degradation of grafted film, and the opposite swelling behavior of the long PVDF and polystyrene chains enhanced the cleavage of graft bonds [47]. Similar phenomena regarding C–C scission induced by adsorption have been reported, where the steric repulsion between short graft chains promotes the breaking of the backbones [48,49].…”

Section: Resultsmentioning

confidence: 82%

Cleavage of the Graft Bonds in PVDF–g–St Films by Boiling Xylene Extraction and the Determination of the Molecular Weight of the Graft Chains

Chen

Seko

2019

Polymers

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To determine the molecular weight of graft chains in grafted films, the polystyrene graft chains of PVDF–g–St films synthesized by a pre-irradiation graft method are cleaved and separated by boiling xylene extraction. The analysis of the extracted material and the residual films by FTIR, nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC) analyses indicates that most graft chains are removed from the PVDF–g–St films within 72 h of extraction time. Furthermore, the molecular weight of the residual films decreases quickly within 8 h of extraction and then remains virtually unchanged up to 72 h after extraction time. The degradation is due to the cleavage of graft bonds, which is mainly driven by the thermal degradation and the swelling of graft chains in solution. This allows determination of the molecular weight of graft chains by GPC analysis of the extracted material. The results indicate that the PVDF–g–St prepared in this study has the structure where one or two graft chains hang from each PVDF backbone.

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“…To verify that the degradation of the networks was not caused by the main-chain scission induced by osmotic pressure due to solvent swelling, 24 thin films with different gel fractions were immersed in dry DCM. DCM was chosen because it does not induce hydrolysis of ester linkages and swells the polyester gel very well (with a swelling ratio of 5.20).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Dynamic Surfaces—Degradable Polyester Networks that Resist Protein Adsorption

Pandiyarajan

et al. 2021

Langmuir

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We synthesized a series of novel degradable alternating copolyesters composed of diglycolic anhydride (DGA) and two epoxides, epoxymethoxytriethylene glycol (ETEG) and a photoactive crosslinking agent epoxy benzophenone (EBP). After UV crosslinking, soaking the films in a good solvent (tetrahydrofuran) removed uncrosslinked material, and the resulting film gel fractions were calculated. These network films were then degraded in buffer solutions of varying pH values. The degradation of networks with lower gel fraction (fewer crosslinks) was faster and followed first-order kinetics. In contrast, the denser network degraded slower and followed zeroth-order kinetics. The lower gel fraction networks possess a higher swelling ratio and resist bovine serum albumin (BSA) adsorption better by entropic shielding and faster degradation. In comparison, higher gel fraction networks with higher EBP mole fractions adsorb more BSA due to hydrophobic interactions and slower degradation.

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Main-chain scission of individual macromolecules induced by solvent swelling

Abstract: We present a comprehensive investigation of main-chain scission processes affecting peripherally charged and neutral members of a class of dendronized polymers (DPs) studied in our laboratory.

Cited by 16 publications

References 62 publications

Correlating polymer structure, dynamics, and function with atomic force microscopy

Correlating polymer structure, dynamics, and function with atomic force microscopy

Cleavage of the Graft Bonds in PVDF–g–St Films by Boiling Xylene Extraction and the Determination of the Molecular Weight of the Graft Chains

Dynamic Surfaces—Degradable Polyester Networks that Resist Protein Adsorption

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