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NEW JOURNAL OF CHEMISTRY · 2020 ·Vol. 44 ·期 23 ·9903-9911 · IF 3.288

Physically and chemically dual-crosslinked hydrogels with superior mechanical properties and self-healing behavior

Xueqin Zhang,Ruqing Zhang,Shu Wu,Ying Sun,Hong Yang,Baoping Lin

An ideal hydrogel for biomedical engineering or flexible devices should have excellent properties, especially high stretchability, strength, resilience and self-healing ability to withstand cyclic loading and damage. The formation of hydrogels by physically and chemically dual-crosslinked structures is a powerful method to improve the strength and resilience. Here, we have designed a physically and chemically dual-crosslinked (PCDC) hydrogel with sodium dodecyl sulfate-stearyl methacrylate (SDS-C18) micelles as physical crosslinkers, amphiphilic polyether modified polysiloxane terminated by isocyanoethyl methacrylate (SiPU) nanoparticles as chemical crosslinkers, and acrylamide (AM) as the monomer. The prepared PCDC hydrogels have a tensile strength of more than 130 kPa and a tensile elongation at break value of over 710%, and can quickly recover their original state in cyclic tensile and cyclic compression tests, exhibiting excellent stretchability, strength and resilience. Based on the hydrophobic interaction mechanism, remarkable self-healing properties of the hydrogels were achieved, allowing re-adhesion of cut surfaces without any external stimulus.

研究领域: 生物医学工程 · 材料科学
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Polymers · 2021 ·Vol. 13 ·期 20 ·3565 · IF 4.329

Ionic and Enzymatic Multiple-Crosslinked Nanogels for Drug Delivery

Qian Tao,Julong Zhong,Rui Wang,Yuzhu Huang

Both ionic and enzymatic crosslink are efficient strategies for constructing network materials of high biocompatibility. Here chitosan was modified firstly and then crosslinked by these two methods for complementary advantages. The preparation methods and ionic crosslinkers can regulate the size and uniformity of the multiple-crosslinked nanogels. The multiple-crosslinked nanogels with the smallest size and the best uniformity was selected for the drug delivery. The drug-loading content and encapsulation efficiency were up to 35.01 and 66.82%, respectively. Their release behaviours are correlated with the pH value and the drug dosage. In general, the lower pH value and the lower drug dosage promoted the drug release. With the assistance of several kinetic models, it is found that drug diffusion plays a preponderant role in drug release, while polymer relaxation has a subtle effect. The multiple-crosslink resulting from ionic compounds and enzymes may provide a new perspective on developing novel biocompatible materials.Keywords:multiple-crosslinked nanogel;ionic crosslink;enzymatic crosslink;drug delivery;natural polymeric materials

研究领域: 生物材料学 · 药物递送系统 · 高分子化学
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JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY · 2017 · IF 1.591

A comparison of rheokinetics on static and shear crosslinking processes of xanthan gum

Hong Zhang,Yongjun Lu,Bo Fang,Xiaohui Qiu,Wen Zhai,Liwei Wang,Hao Jin,Kejing Li

The crosslinking process of xanthan gum was studied under static and shear conditions. Conventional rotational rheometer was adopted to study the shear crosslinking process, and the static crosslinking process was monitored using an optical microrheometer without physical contact between the instrument and the sample. Both experiment and numerical simulation were adopted to compare the two gelation processes at different temperatures. The results showed that the effects of temperature on static and shear crosslinking processes of xanthan gum have the same trend and the rheological curves of the two gelation processes are similar in shape. The same rheokinetics equations were established to describe the two gelation processes and the simulated values are in good agreement with the experimental data. The changes of the model parameters with respect to temperature are quite similar for both the gelation processes, which verifies the feasibility of the microrheology method for measuring the static crosslinking reaction.

研究领域: 生物化学 · 材料科学
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2024 · IF 4.9

Delayed crosslinking gel fracturing fluid with dually crosslinked polymer network for ultra-deep reservoir: Performance and delayed crosslinking mechanism

Zhongzheng Xu,Mingwei Zhao,Ning Sun,Xiangjuan Meng,Ziteng Yang,Yuxin Xie,Fei Ding,Yunbo Dong,Mingwei Gao,Yining Wu,Lin Li,Caili Dai

The gel with dually crosslinked polymer network (DPN) based on supramolecular interaction and chemical crosslinking usually has excellent temperature and shear resistance. The gel fracturing fluid with DPN will provide a new working fluid strategy for the efficient development of deep/ultra-deep oil and gas. Herein, a delayed crosslinking gel fracturing fluid with DPN is reported, which is formed by a supramolecular enhanced polymer containing catechol groups and a multisite organic zirconium delayed crosslinker. The gel breaker and cleanup additive are optimized, and the gel breaking liquid is uniform and had high surface/interface activity. The gel fracturing fluid has excellent delayed crosslinking ability, temperature resistance and shear resistance. It can be crosslinked to the hanging state within 233 s, and the residual viscosity is 71 mPa·s after shearing at 200 °C. The delayed crosslinking behavior and mechanism of gel fracturing fluid are further analyzed by viscoelastic rheological experiment and gelation kinetics calculation. Before reaching the temperature threshold of chemical crosslinking (70 °C), the system is dominated by supramolecular polymer network (SPN). After reaching 70 °C, the addition of chemical crosslinking makes SPN become DPN. The Avrami kinetic calculation results show that the gel growth mode at 70 °C changes from multi-dimensional diffusion growth to one-dimensional linear rapid growth. In addition, the final one-dimensional linear rapid growth stage of gelation is not controlled by temperature. The temperature mainly affected the multidimensional growth stage of gelation.

研究领域: 石油工程 · 材料科学 · 化学工程
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ACS Applied Materials & Interfaces · 2025 · IF 8.2

High-Toughness and Hierarchical Stress-Dissipating Binder Based on Physicochemical Dual-Cross-Linking for High-Performance Silicon Anodes

Yang He,Feng Zhou,Yingxi Zhang,Tuan Lv,Paul K. Chu,Kaifu Huo

Silicon (Si) is a promising anode material for next-generation lithium-ion batteries (LIBs), but the huge volume change of Si particles causes anode fracture and delamination from the current collector, thereby stifling practical implementation. Herein, a high-toughness and hierarchical stress-dissipating binder for Si anodes is prepared by the covalent and hydrogen bonding of poly(acrylic acid) (PAA) and a cross-linked polyurethane (CPU). The physicochemical dual-cross-linked CPU-PAA binder with high toughness, large tensile strength, and hierarchical stress dissipation improves the structural integrity of Si anodes and minimizes thickness swelling. Finite element analysis confirms that the CPU-PAA binder reduces and uniformizes the stress distribution within the Si anodes during cycling. As a result, the Si/CPU-PAA anode shows a high capacity retention of 82.3% after 150 cycles at a high current density of 5 A g–1. Moreover, the Si/CPU-PAA//LiNi0.5Co0.2Mn0.3O2 full cell delivers stable cycling performance, highlighting the great potential of the CPU-PAA binder in high-energy-density LIBs. This work provides insights into the design of high-strength, large-toughness, and efficient stress-dissipating binders for high-performance Si anodes.

研究领域: 材料科学 · 电池技术
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MACROMOLECULES · 2023 · IF 5.5

Structurally Switchable Hydrogels with Multifunctions Enabled by Controlled Catenated Junctions

Xing Liu,Jian Tang,Quan Chen,Lizhu Wang

In the present work, the topological hydrogels are prepared through cross-linking Tetra-PEG chains using catenated junctions of bis(phenanthroline) complexed by metal ions. The catenated junctions are either interlocked through metal–ligand coordination, unlocked through demetalation, or relocked through remetalation. Once unlocked, the cross-links become slidable, thereby leading to a reduction of the elasticity, and the degree of reduction depends on the detailed topological structure, particularly the number of network defects. The mechanical properties of the prepared Tetra-PEG can be tuned by changing either the species of the metal ions or the pH values. In comparison, for the linear PEG precursor, the gel-to-sol transition occurs upon demetalation that leads to the formation of linear chains (i.e., precursor chains connected by the catenated junctions). The paradigm described in this work offers a synthetic approach to the hydrogels with varied cross-links.

研究领域: 材料科学 · 化学
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COMPOSITES SCIENCE AND TECHNOLOGY · 2021 · IF 8.528

Fabrication of a mechanically tough and strong SiO2@EPOSS modified novolac phenolic network by simultaneously improving its crosslinking inhomogeneity and crosslinking density

Zixuan Lei,Jian Wang,Chi Zhang,Qianqiu Wu,Jian Li,Yuhong Liu

Simultaneously improving mechanical strength and toughness of thermosetting polymer nanocomposites remains a great challenge even though massive efforts have been made by controlling the aggregation and interface interaction of nanoparticles . In fact, crosslinking inhomogeneity and crosslinking density of thermosetting polymer nanocomposites can also profoundly affect the competing mechanical properties. Due to their conflicting influence on the toughness and strength of thermosetting polymer nanocomposites, the difficulty lies in how to coordinate the influence effectively. In this work, a mechanically tough and strong novolac phenolic nanocomposites (ESNH) were successfully constructed by introducing a reactive core-shell POSS with nanosilica as core and epoxy-polyhedral oligomeric silsesquioxane as shell (SiO 2 @EPOSS) (ES). Via controlling the quantity and the size of self-polymerized ES phase domain, the crosslinking inhomogeneity and crosslinking density of ESNH can be diversely tuned. Especially for 3%ESNH-3%, remarkably enhanced tensile properties and fracture toughness were realized. The self-polymerized ES phase domain with relatively small quantity and size was homogeneously grafted in phenolic networks, which could pin microstructural interfaces and junct nodular domains of phenolic networks, synergistically improving the crosslinking inhomogeneity and crosslinking density. Therefore, the moderately self-polymerized ES phase domain in the phenolic networks was remarkably contributed to coordinating the performance between the fracture toughness and tensile property. This study provides a novel and efficient envision toward simultaneously improving the toughness and strength of thermosetting polymer nanocomposites via tuning their curing behavior and the corresponding microstructure.

研究领域: 材料科学 · 高分子化学
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INTERNATIONAL JOURNAL OF PHARMACEUTICS · 2022 · IF 6.51

Preparation, characterisation and comparison of glabridin-loaded hydrogel-forming microneedles by chemical and physical cross-linking

Xier Pan,Yushu Li,Weilin Pang,Yaqi Xue,Zhuxian Wang,Cuiping Jiang,Chunyan Shen,Qiang Liu,Li Liu

Poly(vinyl alcohol) (PVA) and carbomer were used as the hydrogel system to fabricate glabridin-loaded hydrogel-forming microneedles (HFMNs) by chemical cross-linking (CCMNs) and physical cross-linking (PCMNs). The properties and drug permeation effects of glabridin-loaded HFMNs with different methods were compared. They both owned excellent shapes, mechanical and insertion properties. PCMNs showed collapsed shapes during swelling due to the low cross-linking rate and high porosity, which probably results in resealing of skin pores during transdermal drug delivery. However, CCMNs could rapidly swell within 2 h with slightly bending. The infrared spectra indicate that CCMNs and PCMNs might form the hydrogel network by generating hydrogen and covalent bonds, respectively. The in vitro release studies showed that cumulative permeation amount within 24 h (1654 μg/cm 2 ) of CCMNs significantly higher than that (372 μg/cm 2 ) achieved by PCMNs and that (118 μg/cm 2 ) achieved by glabridin-loaded gel. The skin barrier recovery test suggests the desirable security of both microneedles (MNs), notwithstanding the presence of mild erythema in the mouse skin applied CCMNs. These results indicate that CCMNs were more desirable for glabridin delivery using PVA and carbomer as a skeleton of the hydrogel network.

CAS / MDL: 9002-89-5 7758-02-3
研究领域: 药剂学 · 生物材料 · 皮肤科学
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JOURNAL OF APPLIED POLYMER SCIENCE · 2024 · IF 2.7

Enhancing the mechanical properties of self-healing polyurethane via chemical crosslinking

Zhang Chenyuan,Liu Zhiqiang,Zhang Zhijia,Zhou Wenjun,Zhang Songsong,Wang Guojun,Wang Qiang,Ma Teng,Wang Lin,Wei Hao

Self-healing research based on commercial polymeric materials (such as polyurethane) is beneficial to sustainable development by prolonging the life of materials. However, developing polymeric materials that integrate robust mechanical properties with self-healing ability at ambient temperature remains a formidable challenge. The formation of polymeric materials by physically and chemically dual crosslinking structures is a powerful method to improve mechanical properties. Herein, a series of dual crosslinking self-healing polyurethane have been designed and successfully synthesized by incorporating 2-ureido-4[1H]-pyrimidinone (UPy) units and triethanolamine (TEOA) into the polymer networks. Relying on the reinforcement of chemical crosslinking which is induced by TEOA, the resulting polyurethane exhibited robust strength of 10.3 MPa and elongation at break of 569.4%, which are quite prominent compared with previous reports. At the same time, the recombination of hydrogen bonds makes the polyurethane with UPy structure achieve rapid self-healing after 24 h at 40°C and the strength recovered to 4.98 MPa. This work provided a novel way to fabricate sustainable polyurethane with robust mechanical properties.

研究领域: 材料科学 · 高分子化学
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EUROPEAN POLYMER JOURNAL · 2018 · IF 3.741

The role of chemical and physical crosslinking in different deformation stages of hybrid hydrogels

Jianyu Xu,Xin Liu,Xiuyan Ren,Guanghui Gao

Hybrid crosslinking hydrogels have exhibited excellent mechanical properties, however, the relationship between chemical and physical crosslinking in the various deformation stages is still indistinct. Here, a hybrid hydrogel was explored by inducing low density of chemical crosslinking into latex particle hydrogels (LP-Gel), in which latex particles act as physical crosslinking centers for inducing efficient aggregation of hydrophobic chains. The resulting hybrid hydrogel exhibited extraordinary mechanical performance. It is found that the role of chemical and physical crosslinking was different during different deformation levels. The synergistic effects of chemical and physical crosslinking allow hydrogels to dissipate a large number of energy, significantly enhancing the mechanical strength of hydrogels. Moreover, the hybrid hydrogel exhibited puncture resistant, excellent ductility and rapid recovery.

研究领域: 材料科学 · 生物材料
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JOURNAL OF POLYMER ENGINEERING · 2020 ·Vol. 41 ·期 1 ·65-71 · IF 1.126

PNIPAAM/SA pH-responsive microcapsules based on chemical and non-covalent crosslinking

Zhengdong Fei,Dong Zheng,Ping Fan,Feng Chen,Mingqiang Zhong

A triple interpenetrating polymer network (IPN) with dual responses to temperature and pH was constructed based on chemical crosslinking and electrostatic interaction. In this IPN, CaCO 3 microspheres were used as the kernel and PNIPAAM/sodium alginate microcapsules were prepared by the inverse emulsion polymerization method. Research results demonstrated that CaCO 3 kernels were decomposed into Ca 2+ and CO 2 at pH 1.2. Such decomposition facilitated the formation of triple IPN of Ca 2+ crosslinking. Moreover, microcapsules were expanded by tension of CO 2 and the volume increased to 3.55 × 10 5 times that of the original microcapsules, with capsules remaining an intact morphology. These microcapsules loading doxorubicin hydrochloride (DOX) stability and responses to environment were investigated. No drug overflow was observed at pH 7.4, indicating the high stability of microcapsules. However, DOX was released gradually in the simulated human stomach acid with a weak solution of hydrochloric acid (pH 1.2, 37 °C). This showed that the prepared microcapsules were feasible for drug-loaded capsules and the controlled drug release behavior could relieve side effects of drugs to human body. Moreover, it will help to increase the drug utilization and realize accurate treatment.

研究领域: 材料科学 · 药学
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JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY · 2025 · IF 1.9

Synthesis of phenyl maleic anhydride polymers and the adsorption of Pb2+: effects of crosslinking agents, equilibrium, kinetics, and adsorption mechanism studies

Mei Tang,Shunxin Liu,Ping Guo,Zhendi Ma,Xiaorong Hu

As a new class of porous materials, hyper-crosslinked polymers can adsorb heavy metal ions from aqueous solutions. This requires them to possess good surface hydrophilicity and active functional groups that can interact with heavy metals. In this research, three polymers, namely MAH-1, MAH-2, and MAH-3, were synthesized via the Friedel–Crafts alkylation reaction using phenyl maleic anhydride (MAH) as the monomer and dimethoxymethane (FDA), 1,4-p-dichloro-benzyl (DCX), and biphenyl dichlorobenzyl (BCMBP) as cross-linkers, respectively. The effect of the molecular size of the cross-linkers on polymer yields, morphology, and Pb2+ adsorption property was investigated. The yield of MAH-1 was low, and the product was soluble in methanol. This implied that when the cross-linker molecule was short, the steric hindrance caused by the substituents on the monomer benzene ring impeded polymer formation. MAH-2 formed nanoparticles that extended into thin sheets, while MAH-3 only formed nanoparticles, exhibiting clearly different morphologies. After alkalization, the maximum Pb2+ adsorption capacities of the two polymers, determined by the Langmuir adsorption isotherm, were 216 mg g−1 and 134 mg g−1, respectively. Both polymers were applied to treat Pb2+ in simulated battery wastewater with a concentration of 32 mg L−1, and both reduced the concentration to below 0.55 mg L−1, meeting the requirements of the Lead and Zinc Industrial Pollutant Discharge Standard GB 25466-2010 (National Standards of the People’s Republic of China). Additionally, the materials demonstrated good reusability and showed potential for treating lead-contaminated water.

研究领域: 环境科学 · 材料科学 · 化学工程
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