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JOURNAL OF CONTROLLED RELEASE · 2025 · IF 11.5

Comparative study on the redox-responsive properties and antitumor efficacy of polyurethane nanocarriers with mono-, Di-, and trisulfide bonds

Jiaxin Wu,Shuai Yang,Yuyue Xiong,Jiacheng Liu,Zhongkui Wu,Ruogu Qi,Lesan Yan

Polyurethane (PU) is considered an ideal nanocarrier for drug delivery due to its excellent biocompatibility and efficient drug-loading capacity. Sulfur bonds (such as monosulfide, disulfide, and trisulfide bonds), have attracted considerable attention in drug delivery systems due to their redox-responsive properties. However, current research primarily focuses on the application of sulfur bonds in prodrug nanoassemblies, where designs rely on specific chemical conjugation groups, limiting their applicability to a narrow range of drug molecules and thus restricting broader utility. Integrating sulfur bonds into polyurethane structures offers a promising approach to enhance carrier biocompatibility while significantly expanding their versatility for delivering various hydrophobic small-molecule drugs. Nevertheless, whether sulfur bonds retain their inherent redox-responsive behavior within a polyurethane requires systematic validation. To address this, we designed and synthesized three amphiphilic polyurethane materials incorporating monosulfide, disulfide, and trisulfide bonds as core components. These polymers self-assembled into nanomicelles, enabling a systematic comparison of their redox-responsive properties. Furthermore, the hydrophobic anticancer drug doxorubicin (DOX) was encapsulated as a model payload to evaluate the in vivo antitumor efficacy of the resulting drug-loaded nanomicelles. Our findings demonstrate that the incorporation of sulfur bonds markedly enhances the redox responsiveness of polyurethane nanocarriers, with the trisulfide bonds exhibiting the most pronounced reduction-sensitive behavior. This study provides deep insights into the influence of sulfur bonds type on the redox-responsive behavior of polyurethane nanomicelles and underscores the exceptional potential of trisulfide bonds in developing redox-responsive polyurethane-based nanocarriers for drug delivery. These results offer critical theoretical and experimental foundations for the design and optimization of smart polyurethane-based drug delivery systems.

研究领域: 材料科学 · 药学 · 纳米技术 · 生物医学工程 · 高分子化学
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2023 · IF 8.2

Enhancing the activity of disulfide-bond-containing proteins via promoting disulfide bond formation in Bacillus licheniformis

Shiyi Wang,Yiwen Zhao,Shufen Mao,Jiang Zhu,Yangyang Zhan,Dongbo Cai,Xin Ma,Dong Wang,Shouwen Chen

Disulfide bonds in proteins have strongly influence on the folding efficiency by constraining the conformational space. The inefficient disulfide bond formation of proteins is the main limiting factor of enzyme activity and stability. This study aimed to increase the activity of disulfide-bond-containing proteins via promoting disulfide bonds formation in Bacillus licheniformis . Initially, the glutamate decarboxylase GAD from Escherichia coli was selected as the model protein and introduced into the B. licheniformis . Then, the disulfide isomerase and oxidoreductase from different sources were excavated and overexpressed successively to improve the catalytic efficiency of GAD. The final engineered B. licheniformis showed significantly improved GAD specific activity (from 10.4 U/mg to 80.0 U/mg), which also presented perfect adaptability for other disulfide-bond-containing proteins, for instance, UDP-glucosyltransferase from Arabidopsis thaliana . Taken together, our work demonstrated that the activity of GAD in B. licheniformis was regulated by the disulfide bonds formation status and provided a promising platform for the expression of disulfide-bond-containing proteins.

CAS / MDL: 54-47-7
研究领域: 微生物学 · 蛋白质工程 · 酶学
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CARBOHYDRATE POLYMERS · 2018 · IF 5.158

Disulfide bond reconstruction: A novel approach for grafting of thiolated chitosan onto wool

Pan Zhang,Nan Zhang,Qiang Wang,Ping Wang,Jiugang Yuan,Jinsong Shen,Xuerong Fan

Chitosan, a natural biopolymer, is used as a multifunctional agent for modification of wool either through chemical crosslinking or physical coating. For the first time, wool fabric has been modified with chitosan through disulfide bond breaking and reforming reactions. The chitosan was thiolated and then grafted onto the reduced wool fibers through disulfide bonds. In order to understand the mechanism of the grafting of thiolated chitosan onto wool, glutathione was used as a model compound for wool in the research. The structures of thiolated chitosan reacted with glutathione and wool fabrics grafted with thiolated chitosan were investigated by FTIR, 13 CNMR, XPS, XRD, SEM. The dyeability, shrink-resistance and biocompatibility were also tested. The results suggested that glutathione reacted with thiolated chitosan and formed disulfide bond. The thiolated chitosan-grafted wool fabric had good shrink-resistance and dyeability. Hydrophilicity and antibacterial properties were also improved compared with untreated wool fabric. The results provide a novel approach for modification of wool through fiber-intrinsic groups like disulfide bonds.

CAS / MDL: 616-91-1 70-18-8
研究领域: 材料科学 · 纺织工程 · 生物化学
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ACS Applied Materials & Interfaces · 2021 · IF 9.229

Highly Efficient Self-Repairing Slippery Liquid-Infused Surface with Promising Anti-Icing and Anti-Fouling Performance

Qingqing Rao,Yulin Lu,Lina Song,Yang Hou,Xiaoli Zhan,Qinghua Zhang

Smart slippery liquid-infused porous surfaces (SLIPSs) have aroused remarkable attention owing to tremendous application foreground in biomedical instruments and industry. However, challenges still remain in fabricating durable SLIPSs. In this work, a fast and highly efficient self-repairing slippery surface (SPU-60M) was fabricated based on a polyurethane membrane and silicone oil. By introducing a great quantity of reversible disulfide bonds into the polymer backbone and hydrogen bonds in the polymer interchain, this SLIPS material could be quickly repaired in 15 min with 97.8% healing efficiency. Moreover, the self-healing efficiency could be maintained at 42.75% after the 10th cutting–healing cycle. Notably, SPU-60M showed excellent self-repairing ability not only in an ambient environment but also in an underwater environment and at ultralow temperatures. Besides, the icing delay time (DT) of SPU-60M could be prolonged to 1182 s at −15 °C, and the ice adhesion strength was only 10.33 kPa at −30 °C. In addition, SPU-60M had excellent anti-fouling performance with BSA adsorption of 2.41 μg/cm2 and Escherichia coli CFU counts of 41 × 104. These findings provide a facile way to design highly efficient self-repairing SLIPSs with multifunctionality.

研究领域: 材料科学 · 生物医学工程 · 表面科学
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EUROPEAN POLYMER JOURNAL · 2018 · IF 3.741

Design of a self-healing cross-linked polyurea with dynamic cross-links based on disulfide bonds and hydrogen bonding

Ting Li,Zhining Xie,Jun Xu,Yunxuan Weng,Bao-Hua Guo

In this work, diamine chain extenders containing disulfide bonds are reacted with triisocyanates to yield dynamic chemical cross-links based on exchangeable disulfide bonds. The polyurea system with dynamic bonding shows drastic decline of storage modulus and very short relaxation times above 150 °C so that this polymer exhibits typical dynamic properties, e.g. self-healing, recycling and hysteresis loop recovery. The introduction of disulfide bonds dominates the thermal stimulated dynamic properties, since the control samples without disulfide bonds have longer relaxation times even at high temperatures. Interestingly, presence of disulfide bonds leads to the decline of hydrogen bonding strength which can result in their easier dissociation and subsequently easier topological network rearrangement. In addition, almost complete reversibility of the hydrogen bonding is observed from temperature-dependent Fourier Transform Infrared Spectroscopy, which reveals the important influence of hydrogen bonding on dynamic properties. Thus, Hydrogen bonding dissociation is an indirect reason of dynamic properties, while exchange reaction of disulfide bonds is the primary cause. The results may deepen our understanding of the role of hydrogen bonding in the dynamic materials. In addition, the available commercial raw component, operational feasibility and simplicity constitute a great advantage of the so-prepared dynamic polyurea system, i.e. an effective step to implementation of industrial applications and recycle the nonbiodegradable crosslinked polyureas.

CAS / MDL: 822-06-0
研究领域: 材料科学 · 化学
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REACTIVE & FUNCTIONAL POLYMERS · 2025 · IF 5.1

Enhancement of thermo-oxidative stability in natural rubber via strain-induced network reorganization

Gui-Xiang Liu,Yu-Ting Huang,Shuangquan Liao,Yan-Chan Wei

Rubber materials are frequently degraded by environmental factors such as light, heat and oxygen during service. Conventional protective approaches, however, often involve adding antioxidants during processing, which not only causes significant environmental pollution but also limits the applicability of rubber products in the biomedical field. Therefore, developing robust aging mitigation strategies constitutes a critical imperative to ensure material longevity. This study proposes a feasible and effective strategy: inducing network rearrangement in rubber through pre-stretching to achieve a more stable crosslinked structure, thereby enhancing its thermo-oxidative stability. During vulcanization, polysulfide and disulfide bonds are formed in the crosslinking network of rubber. Pre-stretching preferentially broke weaker bonds, inducing the conversion of polysulfide bonds to disulfide bonds during the stretching process. This strain-induced network rearrangement enhanced the rigidity and stability of rubber. At elevated temperatures, this mechanism became more pronounced. Pre-stretching triggered rapid conversion of polysulfide to disulfide bonds during the initial stages of thermo-oxidative aging. Given the higher bond energy and stability of disulfide bonds under thermal-oxidative conditions, the aging resistance of rubber is significantly improved. Both atomic force microscopy tests and mechanical tests demonstrated that stretching induced dynamic transformation of sulfur bonds in the crosslinking network, leading to significant changes in spatial heterogeneity under thermo-oxidative conditions. As a result, the thermo-oxidative resistance of natural rubber was enhanced, with the retention of tensile strength increasing from 58.6 % to 81.1 % after 24 h of thermo-oxidative aging. This study not only provided important guidance for the general design of thermo-oxidation-resistant elastomers but also advanced the understanding of rubber network evolution mechanisms under thermo-mechanical coupling conditions.

CAS / MDL: 57-11-4
研究领域: 材料科学 · 高分子科学 · 机械工程 · 化学工程
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POLYMER · 2017 · IF 3.684

Rapid degradation of disulfide-based thermosets through thiol-disulfide exchange reaction

Lin Zhou,Mao Chen,Xiuli Zhao

Development of a methodology to achieve the rapid degradation of thermosets under mild conditions is an important challenge. In this paper, we present a new method for rapid disassembly of thermosetting polyurethanes (PUs), using synergism of multiple stimuli. The PUs were prepared using multi-sensitivity dynamic disulfide bonds as the cross-linker. When soaked in DMF, the fabricated PUs only swell but undissolve. While reducing agent was added, the polymer completely dissolved after 12 h immersion at 25 °C, owing to the thiol-disulfide exchange mechanism. Moreover, as the temperature increases from 25 °C to 60 °C, the time required for complete dissolution of the PUs decreases from 12 h to 50 min, indicating that the synergistic effect of reducing agent and temperature can accelerate the degradation. In addition, other combined multi-stimuli, including reducing agent and ultrasound, can also be used to adjust the dissolution rate of the disulfide bonds cross-linked thermosets. When used as adhesives, the rapidly detachable PUs have potential applications in recycling the valuable adhesive components conveniently.

研究领域: 材料科学 · 聚合物化学 · 可持续材料
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Polymers · 2018 ·Vol. 10 ·期 12 ·1392 · IF 2.935

Self-Healing Cellulose Nanocrystals-Containing Gels via Reshuffling of Thiuram Disulfide Bonds

Wenyan Li,Shengchang Lu,Mengchan Zhao,Xinxing Lin,Min Zhang,He Xiao,Kai Liu,Liulian Huang,Lihui Chen,Xinhua Ouyang,Yonghao Ni,Hui Wu

Self-healing gels based on reshuffling disulfide bonds have attracted great attention due to their ability to restore structure and mechanical properties after damage. In this work, self-healing gels with different cellulose nanocrystals (CNC) contents were prepared by embedding the thiuram disulfide bonds into gels via polyaddition. By the reshuffling of thiuram disulfide bonds, the CNC-containing gels repair the crack and recover mechanical properties rapidly under visible light in air. The thiuram disulfide-functionalized gels with a CNC content of 2.2% are highly stretchable and can be stretched approximately 42.6 times of their original length. Our results provide useful approaches for the preparation of dynamic CNC-containing gels with implications in many related engineering applications.Keywords:cellulose;disulfide;gel;self-healing

研究领域: 材料科学 · 化学工程
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EUROPEAN POLYMER JOURNAL · 2020 · IF 3.862

A high stiffness and self-healable polyurethane based on disulfide bonds and hydrogen bonding

Maochen Liu,Jiang Zhong,Zijian Li,Jinchuang Rong,Kun Yang,Jiyong Zhou,Liang Shen,Fei Gao,Xuelong Huang,Haifeng He

Despite lots of strategies involving extrinsic and intrinsic solutions to self-healing materials, it remains a challenge to achieve a self-healable material with excellent mechanical properties. Here, we describe the use of poly(vinyl alcohol)-graft-(ε-caprolactone) cured isocyanate-terminated disulfide-containing polyurethane to tune the strength and self-healing efficiencies. The results of solvent swelling experiments and Fourier transform infrared spectrometer indicate crosslinking structure and numerous hydrogen bonds in our synthetic polymers. The strong hydrogen bonding interactions and appropriate crosslinked networks provide good tensile mechanical performance. Meanwhile, the dynamic disulfide bonds and hydrogen bonds in this system also enjoyably contribute to the self-healable behavior at a moderate temperature. The self-healing polyurethane displays a maximum Young’s moduli of 112 MPa, a toughness value of 81 MJ/m 3 , which are quite remarkable compared to the previous reports. The self-repairing efficiency is impressively as high as 94%. Moreover, this material also exhibits an attractive reprocessing ability.

研究领域: 材料科学 · 化学
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ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH · 2017 ·Vol. 24 ·期 21 ·17711-17718 · IF 2.741

Degradation and regeneration of feather keratin in NMMO solution

Ma Bomou,Sun Qisong,Yang Jing,Wizi Jakpa,Hou Xiuliang,Yang Yiqi

Chicken feather, a potential source of keratin, is often disposed as waste material. Although some methods, i.e., hydrolysis, reduction, and oxidation, have been developed to isolate keratin for composites, it has been limited due to the rising environmental concerns. In this work, a green solvent N -methylmorpholine N -oxide (NMMO) was used to extract keratin from chicken feather waste. Eighty-nine percent of keratin was extracted using 75% NMMO solution. However, the result from size exclusion HPLC showed that most of the keratin degraded into polypeptide with molecular weight of 2189 and only 25.3% regenerated keratin was obtained with molecular weight of 14,485. Analysis of amino acid composition showed a severe damage to the disulfide bonds in keratin during the extraction procedure. Oxidization had an important effect on the reconstitution of the disulfide bonds, which formed a stable three-dimensional net structure in the regenerated keratins. Besides, Raman spectra, NMR, FT-IR, XRD, and TGA were used to characterize the properties of regenerated keratin and raw chicken feather. In the end, a possible mechanism was proposed based on the results.

CAS / MDL: 872-50-4
研究领域: 生物化学 · 材料科学
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COLLOID AND POLYMER SCIENCE · 2014 ·Vol. 292 ·期 9 ·2157-2172 · IF 2.41

Investigation of removal of Pb(II) and Hg(II) by a novel cross-linked chitosan-poly(aspartic acid) chelating resin containing disulfide bond

Chen Xing Juan,Cai Jian Chong,Zhang Zheng Han,Liu Li Jia,Yang Guang Lei

A novel cross-linked chitosan-poly(aspartic acid) chelating resin was synthesized by combining chitosan and poly(aspartic acid) derivative with crosslinker. The structure and morphology of the resin containing disulfide bonds were characterized by 1 H NMR, FT-IR, Raman spectra, and SEM. Adsorption of Pb(II) and Hg(II) from aqueous solution by the resulted chelating resin was investigated in batch techniques. The result of the Raman spectra suggests that the disulfide bonds in the resin also play an important role in the adsorption of Pb(II) and Hg(II). The kinetic data were fitted to pseudo-first-order, pseudo-second-order, and intraparticle diffusion models, which is suggestive of following closely the pseudo-second-order kinetic model. Equilibrium data were fitted to Langmuir, Freundlich, and D–R isotherm models. The results of equilibrium isotherm reveal that the empirical Langmuir equation provides an accurate description of the experimental data under the studied concentration range. In addition, thermodynamic and regeneration properties of the adsorbent were also studied.

研究领域: 环境科学 · 材料科学
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JOURNAL OF POLYMER RESEARCH · 2025 ·Vol. 32 ·期 4 ·1-11 · IF 2.8

Castor oil-based self-healing polyurethane based on multiple hydrogen bonding and disulfide bonds

Liang Miaoqing,Guan Fanglan,Zhang Mei,Nie Jinmei,Bao Lihong

Self-healing materials have gained significant attention due to their ability to autonomously repair damage, extending material lifespan. In this study, bio-based self-healing polyurethanes were synthesized using modified castor oil (MCO) as the soft segment and 5-(2-hydroxyethyl)- 6-methyl- 2-aminouracil (UPY) and 2,2'-diaminodiphenyldisulfide (DTDA) as dynamic components. The synergistic effect of quadruple hydrogen bonding and disulfide bonds was investigated by varying the n(UPY)/n(DTDA) ratio. Structural and mechanical properties were characterized using IR, DSC, TGA, XRD, and tensile testing. The results revealed that the castor oil-based polyurethanes exhibited transparency and amorphous structures, making them promising bio-based self-healing materials. When the DTDA content was 9.54% and the UPY content was 1.62%, the material achieved a self-healing efficiency of 96.38% under 80 °C for 12 h. Additionally, at a DTDA content of 6.65% and a UPY content of 2.43%, the tensile strength reached 17.76 MPa. Mechanistic analysis revealed that disulfide bonds played a dominant role in self-healing, while hydrogen bonds provided additional reinforcement. This work presents a novel bio-based polyurethane system with tunable mechanical and self-healing properties, contributing to the development of sustainable smart materials.

研究领域: 材料科学 · 生物化学
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