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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Dynamic borate ester bond-based 3D printing fluorescence polysiloxane with self-healing, antimicrobial, and shape memory

Ruilu Guo,Wenning Qi,Hongye Liu,Dongxu Li,Guangxin Chen,Qifang Li,Zheng Zhou

Developing a shape memory polysiloxanes possessing superior mechanical properties, antibacterial qualities, and exceptional self-healing capabilities has become a significant obstacle for the development of smart materials. We tackled this challenge by modifying polysiloxanes using N-acetylcysteine (NACL) and photosensitive molding with a dynamic borate ester crosslinker (S-BDB). The resultant photosensitive polysiloxane exhibited remarkable mechanical properties, with a stress up to 4.7 MPa. By utilizing the hydrogen bonds of grafted NACL and dynamic borate ester bonds of S-BDB to heal the damaged polymer network, the efficient self-healing performance (99.2 %) of photosensitive polysiloxane was obtained. Additionally, the material exhibited typical shape memory properties due to the rapid exchange of hydrogen bonds at elevated temperatures and the fixation of borate esters, enabling shape editing of the material. The material obtained a phosphorescent effect due to the introduction of B-O bonding, making it possible to have application value in the field of complex pattern fluorescent anti-counterfeiting marking manufacturing. Simultaneously, due to the amphiphilic ionic nature of NACL, the resin material obtained exhibited excellent antimicrobial properties.

CAS / MDL: 616-91-1 96-27-5
研究领域: 材料科学 · 生物医学工程
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MACROMOLECULES · 2024 · IF 5.1

Structural Design Strategy of a Biobased Allyl Compound with Dynamic Boronic Ester Bonds to Form Rigid-Soft Self-Healing Polymer Networks via Thiol–Ene “Click” Photopolymerization for Integrated Preparation of a Flexible Device

Meiying Ge,Yonggui Li,Lixin Wu,Ren Liu,Jia-Tao Miao

Fabricating biobased flexible polymers with high toughness and self-healing ability will promote sustainable development of the fast-growing flexible electronic industry. Herein, a biobased allyl compound (BAMDB) with boronic ester bonds was synthesized from renewable eugenol and then combined with multifunctional thiol via thiol–ene “click” photopolymerization to form a series of flexible networks (BAMDB-SH). Their integrated performance, including thermal, optical, and mechanical properties as well as self-healing behavior, was studied. Their glass transition temperature ranged from 42 to 55 °C and showed high transparency (88.2–89.3% at 550 nm). At the same time, BAMDB-SH3 has the most excellent comprehensive mechanical properties with a tensile strength, an elongation at break, and a toughness of 29.8 MPa, 194.3%, and 35.3 MJ m–3, respectively, owing to its rigid-soft network structure with appropriate cross-linking density. Depending on the dynamic exchange of boronic ester bonds, BAMDB-SH3 networks could be healed in 30 min at 80 °C with a high self-healing efficiency of 98%. In addition, based on the excellent comprehensive performance and self-healing properties of BAMDB-SH3, it was used to prepare a sandwich sensor by integrated encapsulation of silver nanowires for wrist activity detection, demonstrating the potential applications of BAMDB-SH in flexible devices.

研究领域: 材料科学 · 可持续化学
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CARBOHYDRATE POLYMERS · 2022 · IF 10.723

Single-component hyaluronic acid hydrogel adhesive based on phenylboronic ester bonds for hemostasis and wound closure

Ming Li,Xinglei Shi,Bo Yang,Jiajun Qin,Xiaobao Han,Wanjia Peng,Yiyan He,Hongli Mao,Deling Kong,Zhongwei Gu

Hydrogel tissue adhesives that currently available are often fabricated by mixing two or more polymeric components. Single-component hydrogels afford injectability, strong and reversible adhesion remain a formidable challenge. This research describes the creation of the first single-component hyaluronic acid hydrogel adhesive-based on phenylboronic acid-diol ester linkages. Phenylboronic acid can not only serve as a cross-linker to form hydrogel, but also act as an adhesion site for glycosyl compounds found in biological cell membranes. The rheological and compressive tests for the hydrogel show that it has excellent self-healing properties, good injectability and strong compressive strength . Adhesion tests demonstrated that the hydrogel has significantly greater adhesion strength than commercial fibrin glue. These findings suggest that the rational design of hydrogel precursors facilitates the formation of single-component networks and multiple functionalities. In vivo studies further proved the hydrogel was an ideal bio-adhesive with biocompatibility, absorbed wound exudate and hemostasis , and accelerated wound closure.

研究领域: 生物材料学 · 医学工程 · 组织修复与再生
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ACS Applied Polymer Materials · 2024 · IF 4.4

A Facile Strategy to Bond Chemically Different Materials Based on Interfacial Interlocked Polymer Networks

Zheng Yue Wang,Yang You,Min Zhi Rong,Ming Qiu Zhang

The present study reports a facile method for gluing chemically different materials without pretreatment of their surfaces by in situ simultaneous formation of multiple interfacial adhesions and cohesion based on the concept of reversibly interlocked polymer networks (RILNs). As a demonstration of the design, the cross-linked polyacrylate containing reversible boronic ester bonds (SN-PA) and cross-linked polyurethane containing reversible disulfide bonds (SN-PU) are stacked and then sandwiched between the target adherends, glass, and fluoropolymer encapsulated polyethylene terephthalate (TPT). Besides, zirconium ions are incorporated into SN-PU in advance. Under hot compression, the two types of reversible covalent bonds are triggered and the temporarily de-cross-linked hydrophilic SN-PA and hydrophobic SN-PU are able to well wet glass and TPT, respectively, and interdiffuse across the SN-PA/SN-PU boundary. During the subsequent cooling, hydrogen bonds and coordination bonds are built up at the polymer/adherend interfaces, while RILNs are produced between SN-PA and SN-PU so that the peeling strength of the bonded glass/TPT assembly achieves 38.94 N/cm, which is higher than the values reported so far.

研究领域: 材料科学 · 化学工程
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Acta Biomaterialia · 2014 · IF 5.684

A pH-responsive drug nanovehicle constructed by reversible attachment of cholesterol to PEGylated poly(l-lysine) via catechol–boronic acid ester formation

Bin Yang,Yin Lv,Jing-yi Zhu,Yun-tao Han,Hui-zhen Jia,Wei-hai Chen,Jun Feng,Xian-zheng Zhang,Ren-xi Zhuo

The present work reports the construction of a drug delivery nanovehicle via a pH-sensitive assembly strategy for improved cellular internalization and intracellular drug liberation. Through spontaneous formation of boronate linkage in physiological conditions, phenylboronic acid-modified cholesterol was able to attach onto catechol-pending methoxypoly(ethylene glycol)- block -poly( l -lysine). This comb-type polymer can self-organize into a micellar nanoconstruction that is able to effectively encapsulate poorly water-soluble agents. The blank micelles exhibited negligible in vitro cytotoxicity, yet doxorubicin (DOX)-loaded micelles could effectively induce cell death at a level comparable to free DOX. Owing to the acid-labile feature of the boronate linkage, a reduction in environmental pH from pH 7.4 to 5.0 could trigger the dissociation of the nanoconstruction, which in turn could accelerate the liberation of entrapped drugs. Importantly, the blockage of endosomal acidification in HeLa cells by NH 4 Cl treatment significantly decreased the nuclear uptake efficiency and cell-killing effect mediated by the DOX-loaded nanoassembly, suggesting that acid-triggered destruction of the nanoconstruction is of significant importance in enhanced drug efficacy. Moreover, confocal fluorescence microscopy and flow cytometry assay revealed the effective internalization of the nanoassemblies, and their cellular uptake exhibited a cholesterol dose-dependent profile, indicating the contribution of introduced cholesterol functionality to the transmembrane process of the nanoassembly.

研究领域: 药剂学 · 生物医学工程 · 分子生物学
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COLLOID AND POLYMER SCIENCE · 2020 ·Vol. 298 ·期 3 ·285-291 · IF 1.536

Self-healing quadruple-shape memory hydrogel based on imine, coordination, and borate bonds with tunable mechanical properties

Wang Minying,Mo Baohang,Chen Birong,Jiang Linbin,Yang Hua

PAM/OSA/PVA hydrogel was prepared by simple copolymerization using acrylamide (PAM), oxidized sodium alginate (OSA), and poly (vinyl alcohol) as monomers. The hydrogel exhibited a quadruple-shape memory effect based on imine, coordination, and borate bonds. Self-healing properties of the quadruple-shape memory hydrogel were observed to evolve due to the imine and borate bonds. The hydrogel demonstrated tunable mechanical properties because of supramolecular interactions including OSA –Ca 2+ , PVA –borax, and OSA –PAM in different conditions. The new hydrogel is envisaged to increase the variety as well as broaden the design and manufacturing of shape memory hydrogels. Dual multi-shape memory images of PAM/OSA/PVA hydrogel and its shape memory mechanism.

CAS / MDL: 9002-89-5 9005-38-3
研究领域: 材料科学 · 生物医学工程
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ACS Omega · 2021 · IF 3.512

Construction of a Phenylboronic Acid-Functionalized Nano-Prodrug for pH-Responsive Emodin Delivery and Antibacterial Activity

Guodong Zheng,Jiahui Zheng,Le Xiao,Tongyi Shang,Yanjun Cai,Yuwei Li,Yiming Xu,Xiaoming Chen,Yun Liu,Bin Yang

In this study, a pH-responsive nano-prodrug was fabricated by conjugating emodin to the PEGylated polyethyleneimine (mPEG-PEI) with acid-sensitive boronate ester bonds. 1H NMR spectra results showed that emodin was effectively bonded to mPEG-PEI, and acid-sensitive assay further confirmed the formation of boronate ester bonds. The size and morphology of the nano-prodrug were ascertained through transmission electron microscopy (TEM) and dynamic light scattering (DLS), which showed that the prodrug has a sphere-like shape with hydrodynamic size around 102 nm at pH 7.4. Subsequently, a drug-release behavior assay was carried out to carefully investigate the acid-sensitive drug-delivery property of the prodrug. Moreover, in vitro cell viability assay confirmed the superior cytotoxic effect of the nano-prodrug against HeLa cells compared to free emodin. Furthermore, the antibacterial study showed that the nano-prodrug could inhibit the bacterial (both Gram-positive and Gram-negative) growth more effectively than free emodin. Overall, this study provides a promising paradigm of the multifunctional nano-prodrug for pH-responsive tumor therapy and antibacterial activity.

研究领域: 药剂学 · 肿瘤学 · 微生物学
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MACROMOLECULAR CHEMISTRY AND PHYSICS · 2023 ·Vol. 224 ·期 14 ·2300042 · IF 2.5

Hot-Pressing/Salt-Leaching Method Assisted by Boronic Ester Dynamic Bond to Prepare Vitrimer Foams with Ultra-Low Relative Permittivity and Superhydrophobic Performance

Yang Xiong,Lili Liu,Chengyao Hu,Junxiao Yang,Yawen Huang

Ultra-low dielectric foams (ULDFs) have found important use in antennas and wave transparent devices. However, the controlled preparation of ULDFs is still a big challenge. In this work, a boronic ester bond-assisted hot-pressing/salt-leaching (BHS) method is proposed to generate interconnected pore structure with tunable porosity and performance. In detail, styrene resin vitrimer is prepared with boronic ester cross-linked network (BESR) which possessed low dielectric constant of 2.70, high modulus of 385 MPa, and reprocessability. BESR vitrimer exhibited drastically enhanced processability at the temperature > T v (160 °C). Thanks to this unique feature, BESR vitrimer foams can be fabricated by hot-pressing with salt particles followed by salt leaching. Such vitrimer foams exhibited advantageous pore-forming processability, fabrication efficiency, and pore stability over conventional polymeric foams. The low extreme of dielectric constant can reach 1.60. Furthermore, owing to interconnected pore structure, superhydrophobic foam (water contact angel (CA) ≈ 154°) is facilely fabricated on the basis of BESR to afford anti-icing performance. The BESR foam can maintain its superhydrophobicity underwater flow impacting at 10 kPa pressure, showing advantageous high durability. BESR foams also have good recyclability and would be potentially applied in recyclable antennas.

研究领域: 材料科学 · 化学工程
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2024 · IF 7.7

Building covalent crosslinks of carboxymethyl konjac glucomannan with boronic ester bonds for fabricating multimodal hydrogel sensor

Xuexue Ding,Lunbo Zhang,Chenguang Jiang,Siyuan Liu,Huajun Li,Juqun Xi,Defeng Wu

As the derivative of konjac glucomannan (KGM), carboxymethyl konjac glucomannan (CMK) has attracted increasing attention in the polysaccharide hydrogel fields with the aim of improving the performance related to drug delivery and release. In this study, we prepared a CMK-based hydrogel with dual characteristic crosslinks, and unlocked new applications of this type of hydrogel in soft sensor fields. CMK and poly (vinyl alcohol) were used as substrates, and physical crosslinks were constructed via the freeze-thawing treatments and covalent crosslinks were built via the boronic ester bonding. As-prepared hydrogel possessed significantly improved mechanical performance because the boronic ester bonding, on the one hand, well associated the two kinds of polymer chains, and on the other hand, played the role of ‘sacrificial crosslinks’. Furthermore, the occurrence of dynamic boronic ester bonding gave the hydrogel strain- and temperature-sensitive ionic conductivity, and therefore, the hydrogels could be used to identify human motions and as-resulted environmental temperature alterations, and worked well in various scenarios. This work activates new application of CMK in the multimodal sensing field, and also proposes an intriguing way of building multiple crosslinks in the KGM derivative-based hydrogels.

CAS / MDL: 9002-89-5 1303-96-4
研究领域: 材料科学 · 生物医学工程
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MACROMOLECULES · 2021 · IF 5.985

Controllable Depolymerization and Recovery of Interlocked Covalent Adaptable Networks via Cascading Reactions of the Built-In Reversible Bonds

Zhi Rong Ou,Wei Li Peng,Min Zhi Rong,Ming Qiu Zhang

A novel strategy for controllable depolymerization and recovery of polymer blends is proposed. The core advance lies in the application of reversible boronic ester bonds and imine bonds, which possess the abilities of correlative scission and rebuilding. Accordingly, reversibly interlocked polymer networks (RILNs) are prepared from two preformed crosslinked polymers, which respectively carry the two reversible bonds. By taking advantage of the intimate packing of the macromolecules from the two networks in the RILNs, the cascading effect between boronic ester bonds and imine bonds is enabled. When the dimethylformamide swollen RILNs are triggered by a little water, the boronic ester bonds in one component network are decomposed, affording boronic acid, which subsequently catalyzes the cleavage of the adjacent imine bonds in the other component network. Meanwhile, scission of the imine bonds also promotes decomposition of the boronic ester bonds as well. The cascading processes can be reversed via dehydration-induced reformation of boronic ester bonds. Hence, RILNs are allowed to be depolymerized in a controlled manner and then recovered by removing the solvent and water.

研究领域: 材料科学 · 化学
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Soft Matter · 2022 ·Vol. 18 ·期 44 ·8436-8445 · IF 4.046

Malleable and self-healing rubbers covalently crosslinked by reversible boronic ester bonds

Jiahao Zhang,Liming Cao,Yukun Chen

Covalent cross-linking of rubbers is essential to obtain high elasticity, which plays a significant role in practical applications. Integrating dynamic covalent bonds into rubbers is a reliable way to endow them with self-healing capacity to repair damage and extend their service life. Herein, we propose a facile and effective method to introduce a crosslinking network composed of dynamic boronic ester bonds into epoxidized natural rubber (ENR). The reaction between dopamine-modified ENR and the hydrolysate of boric acid in weak alkaline solution formed a cross-linking network with reversible boronic ester bonds. Owing to the rearrangement of the crosslinked network initiated by the boronic ester exchange reaction, covalently crosslinked rubbers exhibit relatively better malleability and excellent self-healing ability under moderate conditions (60 °C/24 h).

CAS / MDL: 10043-35-3 62-31-7
研究领域: 材料科学 · 化学
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JOURNAL OF APPLIED POLYMER SCIENCE · 2023 ·Vol. 140 ·期 42 ·e54539 · IF 3

Self-healable, weldable, and reprocessable castor oil-based poly(thiourethane-urethane) networks

Xianjie Pan,Jiawei Li,Fanqi Liu,Chaoying Hu,Yanning Zeng

Vegetable oil-based polyurethane (PU) vitrimer is of significance for sustainable industrial development; however, development of vegetable oil-based PU vitrimers with high mechanical properties and excellent malleability by a facile synthetic process remains a challenge. Herein, a series of versatile, self-healable, weldable, and recyclable castor oil-based poly(thiourethane-urethane) networks are constructed by one-pot reactions. Double bonds and hydroxy groups in castor oil can react with thiol in 2,2′-(1,4-phenylene)-bis[4-mercaptan-1,3,2-dioxaborolane] (BDB) and isocyanate in 4,4′-diphenylmethane diisocyanate (MDI), respectively, as well as a reaction between the thiol of BDB and the isocyanate of MDI, which gives the castor oil-based poly(thiourethane-urethane) vitrimers. The obtained bio-based networks are characterized by Fourier transform infrared (FTIR) and dynamic mechanical analysis (DMA) measurements. The castor oil-based vitrimers show high thermostability ( T 5d > 312°C) due to the incorporation of rigid BDB and MDI with benzene group in the networks. Meanwhile, the castor oil-based networks have been proved to possess more excellent functions in self-healing, welding, shape memory, and reprocessing capabilities at moderate temperatures due to the dynamic boronic ester bonds. This work would be beneficial to developing of versatile vegetable oil-based poly(thiourethane-urethane) materials through a facile approach.

研究领域: 材料科学 · 可持续化学
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