pH-Induced Association and Dissociation of Intermolecular Complexes Formed by Hydrogen Bonding between Diblock Copolymers

Mizusaki, Masanobu; Endo, Tatsuya; Nakahata, Rina; Morishima, Yotaro; Yusa, Shin‐ichi

doi:10.3390/polym9080367

Cited by 10 publications

(4 citation statements)

References 27 publications

(28 reference statements)

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“…Interestingly, the radius of gyration ( R g = 12 nm) at 10 mM is about twice as large as the hydrodynamic radius ( R h = 5.5 nm) seen from DLS (Figure a). The ratio of the two, R g / R h ∼ 2, suggests that the supramolecular polymer chain tends to be in an extended conformation on average (Figure c), , which is consistent with the solid-state packing (Figure d). For comparison, the contour length of a fully extended 1D supramolecular polymer chain with nine repeat units is about 13.6 nm (Figure S44) consistent with R g and R h .…”

Section: Resultssupporting

confidence: 74%

Linear Supramolecular Polymers Driven by Anion–Anion Dimerization of Difunctional Phosphonate Monomers Inside Cyanostar Macrocycles

et al. 2019

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Supramolecular polymers have enabled far-reaching fundamental science and the development of diverse macromolecular technologies owing to the reversible and noncovalent chemical connectivities that define their properties. Despite the unabated development of these materials using highly tailorable recognition elements, anion-based polymers remain rare as a result of the weak interactions they mediate. Here, we use design rules inspired by cation-driven polymers to demonstrate a new noncovalent link based on receptor-stabilized anion−anion interactions that enables the efficient linear polymerization of simple difunctional phosphonates. The linear main chain connectivity and molecular topology were confirmed by single crystal X-ray diffraction, which demonstrates the rare 2:2 stoichiometry between the anionic phosphonate end groups and a pair of π-stacked cyanostar macrocycles. The stability of these links enables rapid polymerization of difunctional phosphonates employing different aliphatic linkers (C 6 H 12 , C 8 H 16 , C 10 H 20 , C 12 H 24 ). Diphosphonates with greater chain flexibility (C 12 H 24 ) enable greater polymerization with an average degree of polymerization of nine emerging at 10 mM. Viscosity measurements show a transition from oligomers to polymers at the critical polymerization concentration of 5 mM. In a rare correlation, NMR spectroscopy shows a coincident molecular signature of the polymerization at 5 mM. These polymers are highly concentration dependent, reversibly polymerize with acid and base, and respond to competitive anions. They display the design simplicity of metallo-supramolecular polymers with transfer of the strong 2:2 recognition chemistry to macromolecules. The simplicity and understanding of this new class of supramolecular polymer is anticipated to open opportunities in tailoring anion-based functional materials.

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Section: Resultssupporting

confidence: 74%

Linear Supramolecular Polymers Driven by Anion–Anion Dimerization of Difunctional Phosphonate Monomers Inside Cyanostar Macrocycles

et al. 2019

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“…Triethylammonium hypophosphite was prepared from triethylamine and hypophosphinic acid in toluene. The diblock copolymer NS was prepared as previously reported [ 45 , 55 , 56 , 57 , 58 , 59 , 60 , 61 ]. Dialysis was performed using Spectra/Por ® RC tubing (MWCO: 3.5kD).…”

Section: Methodsmentioning

confidence: 99%

Palladium-Catalyzed Mizoroki–Heck and Copper-Free Sonogashira Coupling Reactions in Water Using Thermoresponsive Polymer Micelles

et al. 2021

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A few kinds of thermoresponsive diblock copolymers have been synthesized and utilized for palladium-catalyzed coupling reactions in water. Poly(N-isopropylacrylamide) (PNIPAAm) and poly(N,N-diethylacrylamide) (PDEAAm) are employed for thermoresponsive segments and poly(sodium 4-styrenesulfonate) (PSSNa) and poly(sodium 2-acrylamido-methylpropanesulfonate) (PAMPSNa) are employed for hydrophilic segments. Palladium-catalyzed Mizoroki–Heck reactions are performed in water and the efficiency of the extraction process is studied. More efficient extraction was observed for the PDEAAm copolymers when compared with the PNIPAAm copolymers and conventional surfactants. In the study of the Sonogashira coupling reactions in water, aggregative precipitation of the products was observed. Washing the precipitate with water gave the product with satisfactory purity with a good yield.

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“…In the last decades, a great progress has been made in developing analysis schemes for DLS data [13,18,19,20,21,22,23,24,25]. As a result, DLS characterization has become a popular tool, mostly due to the easy measurement and automatized data analysis outputs which are provided by commercial DLS instruments produced in compact size and reasonable price [25,26,27,28,29,30,31]. Specifically, their measurement and data analysis software packages have been developed for spherical particles [25].…”

Section: Introductionmentioning

confidence: 99%

A Comparative Study of Dynamic Light and X-ray Scatterings on Micelles of Topological Polymer Amphiphiles

et al. 2018

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Micelles were prepared in organic solvents by using three topological polymer amphiphiles: (i) cyclic poly(n-decyl glycidyl ether-block-2-(2-(2-methoxyethoxy)ethoxy)ethyl glycidyl ether) (c-PDGE-b-PTEGGE) and (ii) its linear analogue (l-PDGE-b-PTEGGE); (iii) linear poly(6-phosphorylcholinehexylthiopropyl glycidyl ether-block-n-dodecanoyl glycidyl ether) (l-PPCGE-b-PDDGE). For the individual micelle solutions, the size and distribution were determined by dynamic light scattering (DLS) and synchrotron X-ray scattering analyses. The synchrotron X-ray scattering analysis further found that c-PDGE-b-PTEGGE forms oblate ellipsoidal micelle in an ethanol/water mixture, l-PDGE-b-PTEGGE makes prolate ellipsoidal micelle in an ethanol/water mixture, and l-PPCGE-b-PDDGE forms cylindrical micelle in chloroform. This comparative study found that there are large differences in the size and distribution results extracted by DLS and X-ray scattering analyses. All possible factors to cause such large differences are discussed. Moreover, a better use of the DLS instrument with keeping its merits is proposed.

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pH-Induced Association and Dissociation of Intermolecular Complexes Formed by Hydrogen Bonding between Diblock Copolymers

Cited by 10 publications

References 27 publications

Linear Supramolecular Polymers Driven by Anion–Anion Dimerization of Difunctional Phosphonate Monomers Inside Cyanostar Macrocycles

Linear Supramolecular Polymers Driven by Anion–Anion Dimerization of Difunctional Phosphonate Monomers Inside Cyanostar Macrocycles

Palladium-Catalyzed Mizoroki–Heck and Copper-Free Sonogashira Coupling Reactions in Water Using Thermoresponsive Polymer Micelles

A Comparative Study of Dynamic Light and X-ray Scatterings on Micelles of Topological Polymer Amphiphiles

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