Study of Linear and Cyclic Graft Polystyrenes with Identical Backbone Contour in Dilute Solutions: Preparation, Characterization, and Conformational Properties

Zhou, Jianing; Yang, Jinxian; Ishaq, Muhammad; Li, Lianwei

doi:10.1021/acs.macromol.1c02029

Cited by 11 publications

(12 citation statements)

References 57 publications

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“…As shown in Figure (dashed lines), after cyclization, the SEC peak is obviously shifted to a higher elution time ( t e ). The ratio of peak molar masses of the cyclic product ( M p, c ) to the linear precursor ( M p, l ), i.e., M p, c / M p, l , is found to be from 0.75 to 0.76, which is consistent with the values reported in the literature. , MALDI-TOF-MS is employed to further confirm the highly efficient cyclization reaction (Figure S1). The interpretation of data in relevant spectra is given in the Supporting Information.…”

Section: Resultssupporting

confidence: 88%

Investigation of the Multimer Cyclization Effect during Click Step-Growth Polymerization of AB-Type Macromonomers

et al. 2022

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In this work, by combining size exclusion chromatography (SEC) and liquid chromatography at the critical condition (LCCC) techniques, we have studied the multimer cyclization effect during click step-growth polymerization of AB-type macromonomers. First, by atom transfer radical polymerization (ATRP), we have synthesized a series of alkynyl and azide functional AB-type polystyrene macromonomers with different molar masses, i.e., PS n . Second, via the click step-growth polymerization of a PS n macromonomer in dimethylformamide (DMF) at varied reaction concentrations (Cs), we have prepared polyaddition products [(PS n ) m ] with large polydispersity indices, where m represents the average degree of polymerization of the macromonomer. Further, narrowly distributed fractions have been obtained by SEC fractionation. Third, we have quantitatively analyzed how the macromonomer molar mass, reaction concentration, and multimer molar mass influence the percentage of a cyclic topoisomer (wtcyclic) for (PS n ) m samples. In particular, we have established the relation between wtcyclic and C for unfractionated (PS n ) m , i.e., wtcyclic = 0.86–0.32 log C, and the relation between wtcyclic and m for fractionated (PS n ) m prepared at a constant C = 100 g/L, i.e., log wtcyclic = −0.46m + 0.16. For the first time, our result has unambiguously pointed out that neither a cyclic topoisomer nor a linear topoisomer can be ignored when considering the structure–property quantitative relationship for polyaddition products.

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Section: Resultssupporting

confidence: 88%

Investigation of the Multimer Cyclization Effect during Click Step-Growth Polymerization of AB-Type Macromonomers

et al. 2022

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“…One can see that the backbones of the linear BBPs become more rigid upon increasing the PEO side-chain length, consistent with many previous studies. , For cyclic BBPs, the backbone also becomes more elongated, but the overall structure remains more compact compared to the linear counterpart. Previous experiments have shown that cyclic BBPs are more compact and assume a smaller hydrodynamics volume than the corresponding linear ones . To quantitatively compare the range of conformations that bottlebrushes explore, we calculated the frequency distribution of the radius of gyration ( R g ) of the cyclic and linear BBPs, shown in Figure .…”

Section: Resultsmentioning

confidence: 99%

“…Experiments have established that the difference in backbone topology results in different molecular properties, e.g., cyclic BBPs exhibit a more compact shape and less interchain association , than their linear analogues. Although experiments ,− and dissipative particle dynamics simulations have elucidated many macroscopic properties of cyclic BBPs such as viscosity and self-assembled structures, the molecular-level details of structure and dynamics are still missing. Obviously, it would be informative to investigate the similarities and differences in the conformational behavior and properties of cyclic and linear BBPs in order to achieve a fundamental understanding of the chain topology effect.…”

Section: Introductionmentioning

confidence: 99%

Cyclic vs Linear Bottlebrush Polymers in Solution: Side-Chain Length Effect

Chen

Dormidontova

2023

Macromolecules

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Bottlebrush polymers (BBPs) of different architecture are of considerable interest for a broad range of applications, including nanomedicine, electronics, and self-healing materials. Using atomistic molecular dynamics simulations, we investigate and compare the structural and hydration properties of cyclic and linear poly(vinyl alcohol)-graft-poly(ethylene oxide) (PVA-g-PEO N sc ) BBPs in aqueous solution as functions of PEO side-chain length, N sc. We find that overall cyclic BBPs are smaller than the corresponding linear BBPs and their shape changes from donutlike to disklike to starlike with increasing side-chain length, while linear BBPs vary in shape from an expanded coil to a rod/cylinder. The radius of gyration of cyclic BBPs increases with an increase of the side-chain length at a somewhat slower rate than the linear BBPs but follows the same scaling R g ∼ N sc 0.58 in the limit of long side chains. For short grafts, we determine that the persistence length, l p, for both cyclic and linear BBPs increases in a similar manner following an l p ∼ N sc 0.54 dependence. In the long side-chain limit, the persistence length (l p) of cyclic BBP saturates, while for linear BBPs l p strongly increases following the expected scaling relation l p ∼ N sc 15/8. We propose a scaling model that shows that the fraction of side-chains located inside the cyclic BBPs depends on the radius of the backbone ring and significantly decreases with an increase of graft length. For both cyclic and linear BBPs, the hydrogen bonding between PEO side chains and water is somewhat reduced near the backbone, where local chain stretching is observed, while reaching full hydration on the periphery. Overall, the hydration shell within 1 nm of the cyclic BBP backbone is found to be more dynamically stable compared to linear BBPs.

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“…The detail of synthesis is summarized in the Supporting Information (pages S2–S5). In fact, the esterification of PAA by the TMG method has been widely proven very efficient even under the condition of stoichiometric ratio. − In our study, the sufficient reaction time and much excess of TMG and benzyl bromide can ensure the complete conversion of AA into the ester group. A set of PBA samples with different molar masses have been prepared (Figure a).…”

Section: Resultsmentioning

confidence: 78%

Regulating the Flow-Driven Translocation of Macromolecules through Nanochannels by Interfacial Physical Adsorption

Zhou

Wang

2023

Macromolecules

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By using a model system composed of an anodic aluminum oxide nanopore (AAO), poly(benzyl acrylate) (PBA N ) adsorbent, and polystyrene (PS N ) probe, where N represents the degree of polymerization, this work has explored how the physical adsorption of PBA onto the surface of the AAO nanopore (r p ≈ 10 nm) influences the flow-driven translocation of PS in toluene. In the low flow rate range (Q = 0.02 mL/h), the translocation of PS chains is purely diffusive, and the partially reversible adsorption behavior of PBA N is observed only when N < ∼360, showing a strong chain length dependence. In the partially reversible regime, the interfacial thickness (δ) of the adsorption layer is estimated to be from ∼1.5 to ∼2.9 nm depending on the chain length. In the mixed solutions, when N increases from 0 to 75 and 150 for PBA N , the cut-off size (COS) of the membrane for broadly distributed PS B-285K (M w /M n ≈ 2.48) is estimated to decrease from ∼10.0 to ∼8.0 and ∼6.0 nm, respectively; in addition, the introduction of PBA 360 can promote the separation of narrowly distributed PS 655 and PS 1200 by regulating r e , whereas in the high flow rate range (Q > 0.02 mL/h), the translocation for PS long chains is based on the mechanism of molecular deformation, and the flow ratedependent translocation shows a strong dependence on the chain length of PBA N . Namely, in mixed solutions, when N increases from 150 to 360, the critical flow rate (Q c ) is found to slightly increase from ∼0.30 to ∼0.45 mL/h for PS 1500 translocation; in addition, the cut-off performance of PS B-285K displays dependence both on flow rate and PBA N chain length. Our result has demonstrated a novel strategy to regulate the cut-off performance during the translocation of (bio)macromolecules through nanopores via partially reversible interfacial physical adsorption.

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Study of Linear and Cyclic Graft Polystyrenes with Identical Backbone Contour in Dilute Solutions: Preparation, Characterization, and Conformational Properties

Cited by 11 publications

References 57 publications

Investigation of the Multimer Cyclization Effect during Click Step-Growth Polymerization of AB-Type Macromonomers

Investigation of the Multimer Cyclization Effect during Click Step-Growth Polymerization of AB-Type Macromonomers

Cyclic vs Linear Bottlebrush Polymers in Solution: Side-Chain Length Effect

Regulating the Flow-Driven Translocation of Macromolecules through Nanochannels by Interfacial Physical Adsorption

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