Dilute solution structure of bottlebrush polymers

Dutta, Sarit; Wade, Matthew A.; Walsh, Dylan J.; Guironnet, Damien; Rogers, Simon A.; Sing, Charles E.

doi:10.1039/c9sm00033j

Cited by 78 publications

(169 citation statements)

References 117 publications

Supporting

Mentioning

148

Contrasting

Order By: Relevance

“…Bottlebrush and dendronized polymers have elongated conformations in solution due to their large side chain size [60–63] . Compared to linear polymers, bottlebrush and dendronized polymers have enhanced backbone scission rates with US, which we attributed to their elongated conformations [44, 47] .…”

Section: Introductionmentioning

confidence: 87%

Mechanochemical Reactivity of Bottlebrush and Dendronized Polymers: Solid vs. Solution States

2021

View full text Add to dashboard Cite

We explored the mechanochemical degradation of bottlebrush and dendronized polymers in solution (with ultrasonication, US) and solid states (with ball-mill grinding, BMG). Over 50 polymers were prepared with varying backbone length and arm architecture,composition, and size.With US,w ef ound that bottlebrush and dendronized polymers exhibited consistent backbone scission behavior,w hichw as related to their elongated conformations in solution. Considerably different behavior was observed with BMG,a sa rm architecture and composition had as ignificant impact on backbone scission rates.A rm scission was also observed for bottlebrush polymers in both solution and solid states,but only in the solid state for dendronized polymers.Motivated by these results,m ulti-mechanophore polymers with bottlebrush and dendronized polymer architectures were prepared and their reactivity was compared. Although dendronized polymers showed slower arm-scission, the selectivity for mechanophore activation was muchh igher.O verall, these results have important implications to the development of new mechanoresponsive materials.

show abstract

Section: Introductionmentioning

confidence: 87%

Mechanochemical Reactivity of Bottlebrush and Dendronized Polymers: Solid vs. Solution States

2021

View full text Add to dashboard Cite

show abstract

“…Additionally, it would be beneficial to couple either model with complementary measurements or simulations to more fully inform the scattering analysis and either eliminate correlations or constrain model parameters. Dynamic light scattering, for example, can provide information on the hydrodynamic radius, complementing the information gained through neutron or X‐ray scattering . Finally, constraining L c in the flexible cylinder model based on the backbone contour length, estimated from the chemical structure of the monomer and the molar mass, will provide a more consistent basis for comparisons.…”

Section: Introductionmentioning

confidence: 99%

Addressing the challenges of modeling the scattering from bottlebrush polymers in solution

Sunday

Martin

Chang

et al. 2020

Journal of Polymer Science

View full text Add to dashboard Cite

Small-angle scattering measurements of complex macromolecules in solution are used to establish relationships between chemical structure and conformational properties. Interpretation of the scattering data requires an inverse approach where a model is chosen and the simulated scattering intensity from that model is iterated to match the experimental scattering intensity. This raises challenges in the case where the model is an imperfect approximation of the underlying structure, or where there are significant correlations between model parameters. We examine three bottlebrush polymers (consisting of polynorbornene backbone and polystyrene side chains) in a good solvent using a model commonly applied to this class of polymers: the flexible cylinder model. Applying a series of constrained Monte-Carlo Markov Chain analyses demonstrates the severity of the correlations between key parameters and the presence of multiple close minima in the goodness of fit space. We demonstrate that a shape-agnostic model can fit the scattering with significantly reduced parameter correlations and less potential for complex, multimodal parameter spaces. We provide recommendations to improve the analysis of complex macromolecules in solution, highlighting the value of Bayesian methods. This approach provides richer information for understanding parameter sensitivity compared to methods which produce a single, best fit. K E Y W O R D SBayesian analysis, bottlebrush, neutron scattering, small-angle scattering | INTRODUCTIONCharacterization of the solution-state properties of macromolecules is one of the fundamental means of evaluating the relationship between structural parameters and conformation, which in turn controls properties ranging from self-assembly to rheology. Small-angle X-ray scattering and neutron (small-angle neutron scattering [SANS]) scattering are the workhorse methods for performing this characterization. Modern instrumentation allows rapid, routine collection of data from solution samples and, as a result, much of the challenge in utilizing these techniques resides with the proper interpretation and modeling. Small-angle scattering data are typically modeled with an inverse-iterative approach, where simulated data from a real-or Fourier-space model is iteratively fit to a set of experimental data. The parameters of the model are then interpreted to describe the structure and

show abstract

“…However, combs with molar masses lower than 10kD should rather behave as hyper-branched or star-like polymers, thus displaying low α-parameters. 51,52 The latter case corresponds well to the comb-Vin-PE-DMMS sample.…”

Section: Post-condensation Of α-Vinylω-methoxysilyl Pes Into Comb-like and Star-like Vinyl-functional Polyethylenesmentioning

confidence: 56%

One-pot syntheses of heterotelechelic α-vinyl,ω-methoxysilane polyethylenes and condensation into comb-like and star-like polymers with high chain end functionality

et al. 2020

View full text Add to dashboard Cite

show abstract

Dilute solution structure of bottlebrush polymers

Abstract: Simulations of dilute bottlebrush polymers exhibit quantitative agreement with viscometry and light scattering experiments, showing trends in bottlebrush molecular conformations.

Cited by 78 publications

References 117 publications

Mechanochemical Reactivity of Bottlebrush and Dendronized Polymers: Solid vs. Solution States

Mechanochemical Reactivity of Bottlebrush and Dendronized Polymers: Solid vs. Solution States

Addressing the challenges of modeling the scattering from bottlebrush polymers in solution

One-pot syntheses of heterotelechelic α-vinyl,ω-methoxysilane polyethylenes and condensation into comb-like and star-like polymers with high chain end functionality

Contact Info

Product

Resources

About