Thermally healable and reprocessable polymethacrylate networks based on diol-mediated metathesis of 6-membered boronic esters

2020 ◽  
Vol 11 (11) ◽  
pp. 1860-1870 ◽  
Author(s):  
Yue Yang ◽  
Fu-Sheng Du ◽  
Zi-Chen Li
Keyword(s):  
Mechanical Properties ◽  
Dynamic Behaviors ◽  
Boronic Ester ◽  
Boronic Esters ◽  
Ester Linkage

We demonstrate the thermally repairable and reprocessable poly(methacrylate) networks crosslinked by boronic ester linkage, the dynamic behaviors and mechanical properties of which could be finely tuned by the pendent diols.

Specific cell capture and noninvasive release via moderate electrochemical oxidation of boronic ester linkage

2019 ◽  
Vol 138 ◽  
pp. 111316 ◽  
Author(s):  
Qian-Wen Zhang ◽  
Jun Ouyang ◽  
Yang Wang ◽  
Ting-Ting Zhai ◽  
Chen Wang ◽  
...  
Keyword(s):  
Electrochemical Oxidation ◽  
Specific Cell ◽  
Cell Capture ◽  
Boronic Ester ◽  
Ester Linkage

scholarly journals Internal and external catalysis in boronic ester networks

2021 ◽  
Author(s):  
Boyeong Kang ◽  
Julia Kalow
Keyword(s):  
Mechanical Properties ◽  
Binding Affinity ◽  
Polymer Networks ◽  
Model Systems ◽  
Self Healing ◽  
Dynamic Materials ◽  
Boronic Ester ◽  
Rate Acceleration ◽  
Exchange Spectroscopy ◽  
Kinetics Of

In dynamic materials, the reversible condensation between boronic acids and diols provides adaptability, self-healing ability, and responsiveness to small molecules and pH. Recent work has shown that the thermodynamics and kinetics of bond exchange determine the mechanical properties of dynamic polymer networks. However, prior studies have focused on how structural and environmental factors influence boronic acid–diol binding affinity, and design rules for tuning the kinetics of this dynamic bond are lacking. In this work, we investigate the effects of diol (or polyol) structure and salt additives on the rate of bond exchange, binding affinity, and the mechanical properties of the corresponding polymer networks. To better mimic the environment of polymer networks in our small-molecule model systems, we incorporated proximal amide groups, which are used to conjugate diols to polymers, and included salts commonly found in buffers. Using one-dimensional selective exchange spectroscopy (1D EXSY), we find that both proximal amides and buffering anions induce significant rate acceleration consistent with internal and external catalysis, respectively. This rate acceleration is reflected in the stress relaxation of gels formed using PEG modified with different alcohols, and in the presence of salts containing acetate or phosphate. These findings contribute to the fundamental understanding of the boronic ester dynamic bond and offer new molecular strategies to tune the macromolecular properties of dynamic materials.

Diethanolamine Boronic Esters: Development of a Simple and Standard Process for Boronic Ester Synthesis

2020 ◽  
Vol 24 (9) ◽  
pp. 1683-1689
Author(s):  
Phillip A. Inglesby ◽  
Lauren R. Agnew ◽  
Holly L. Carter ◽  
Oliver T. Ring
Keyword(s):  
Ester Synthesis ◽  
Standard Process ◽  
Boronic Ester ◽  
Boronic Esters

scholarly journals Guest Inclusion Crystal structures of Macrocyclic Boronic Esters

2014 ◽  
Vol 70 (a1) ◽  
pp. C677-C677
Author(s):  
Ryosuke Toyoshima ◽  
Kotaro Fujii ◽  
Kohei Johmoto ◽  
Hidehiro Uekusa ◽  
Yuji Kikuchi ◽  
...  
Keyword(s):  
Crystal Structures ◽  
Boronic Acid ◽  
Guest Molecule ◽  
Covalent Bond ◽  
Macrocyclic Compound ◽  
Channel Structure ◽  
Monoclinic System ◽  
One Dimensional ◽  
Boronic Ester ◽  
Boronic Esters

Macrocyclic compound has been attracting increasing attention because of their application for guest absorption and storage, guest selectivity, and reaction environment, which would utilize void space in the compound. Recently, such macrocyclic compound, boronic esters, has found to be formed as dynamic self-assembly of organic molecules through solvent dependent dynamic covalent bond formation between racemic polyol and planar 1,4-benzen(boronic acid)[1]. Thus, it is important to determine the crystal structure of the macrocyclic boronic esters with incorporated guest molecule to reveal the features of the compounds. In this study, structures of boronic ester of 1,4- naphthalene(boronic acid) (1) are presented and compared. The boronic ester with toluene guest molecule crystalized in monoclinic system, C2/c, Z=4, V=5099.7(6) Å3. As expected, toluene molecule was accommodated within a ring sandwiched by two naphthalene rings suggesting π-π interaction (ca. 3.6 Å separations). It is interesting that other structures of 1 with 1,4-dicyanobenzene, chloroform, and THF also have isomorphic structures to 1 with toluene. It clearly shows the guest inclusion ability of this boronic ester by weak intermolecular interactions. In the crystal structures, the boronic ester aligned along b-axis forming one-dimensional stacking with channel structure filled with guest molecules. Also, 1 with chloroform has a pseudo-polymorph phase (P21/c, V=5780.8(13) Å3) that has two additional chloroform molecules inside and outside of the ring; however, it also shows similar one-dimensional stacking structure with channel, implying this boronic ester has an easily stacking molecular shape. Although, the molecules have similar [2+2] ring structure, dihedral angle between two facing naphthalene rings is different in 1 with toluene, which is smaller as 14.10than 22 to 240in other structures. It may indicate a flexibility of the macrocyclic ring.

scholarly journals The Synthesis of Biarylmonophosphonates via Palladium-Catalyzed Phosphonation, Iridium-Catalyzed C-H Borylation, Palladium-Catalyzed Suzuki–Miyaura Cross-Coupling

2021 ◽  
Author(s):  
Simon Doherty ◽  
Julian G. Knight ◽  
Tina S. T. Tran ◽  
Hussam Y. Alharbi ◽  
Daniel O. Perry
Keyword(s):  
Cross Coupling ◽  
Statistical Mixture ◽  
Boronic Ester ◽  
Synthetic Procedure ◽  
Boronic Esters ◽  
Palladium Catalyzed ◽  
Nucleophilic Reagents ◽  
Sole Product

Abstract The iridium-catalyzed C-H borylation of diethyl phenylphosphonate results in nonselective mono and bisborylation to afford a near statistical mixture of 3-, 3,5- and 4-boryl substituted aryl phosphonates whereas 3-substituted aryl phosphonates undergo highly regioselective C-H borylation to afford the corresponding meta-phosphonate substituted arylboronic esters as the sole product; the resulting boronic esters were used as nucleophilic reagents in a subsequent palladium-catalyzed Suzuki–Miyaura cross-coupling to generate a range of biarylmonophosphonates. Gratifyingly, the Suzuki–Miyaura cross-coupling can be conducted without purifying the boronic ester which greatly simplifies the synthetic procedure. Graphical Abstract

Room-temperature fully recyclable carbon fibre reinforced phenolic composites through dynamic covalent boronic ester bonds

2018 ◽  
Vol 6 (23) ◽  
pp. 10868-10878 ◽  
Author(s):  
Shujuan Wang ◽  
Xiaolong Xing ◽  
Xiaoting Zhang ◽  
Xiao Wang ◽  
Xinli Jing
Keyword(s):  
Mechanical Properties ◽  
Carbon Fibre ◽  
Room Temperature ◽  
Boronic Ester

By utilizing the alcoholysis nature of boronate bonds, the CF/PBNR composites can be fully recycled at room temperature in ethanol solvent without sacrificing the mechanical properties.

scholarly journals Assembly of synthetic Aβ miniamyloids on polyol templates

2015 ◽  
Vol 11 ◽  
pp. 2646-2653 ◽  
Author(s):  
Sebastian Nils Fischer ◽  
Armin Geyer
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Solid Phase ◽  
Solid Phase Peptide Synthesis ◽  
Boronic Acids ◽  
Relative Orientation ◽  
Aβ Peptide ◽  
Aβ Peptides ◽  
Boronic Ester ◽  
Boronic Esters

Covalent dynamic chemistry is used to mimic the first steps of the highly cooperative fibril formation of Aβ peptides. For that purpose, Aβ peptide pentapeptide boronic acids 1 and 2 were synthesized by solid-phase peptide synthesis and studied in esterification experiments with polyhydroxylated templates. The bis-hydroxylated dipeptide Hot=Tap serves as a template of adjustable degree of oligomerization which spontaneously forms boronic esters with peptides of type 1 and 2. Nuclear magnetic resonance can differentiate between regioisomeric boronic esters and identifies preferred sites of esterification on the dimeric template 9. 2-Formylphenylboronic acid (14) is used to link the parent pentapeptide Leu-Val-Phe-Phe-Ala to the template 16 to obtain threefold boronic ester 17. The miniamyloid 17 assembles from seven components by imine and boronic ester bonds between the peptides and the template. The relative orientation and spacing of the peptides mimic the assembly of peptides in Alzheimer β-amyloids.

Sign in / Sign up

Export Citation Format

Share Document