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JOURNAL OF APPLIED POLYMER SCIENCE · 2022 ·Vol. 139 ·期 20 ·52144 · IF 3.057

Synthesis and self-healing investigation of waterborne polyurethane based on reversible covalent bond

Jingyu Ren,Xiangbin Dong,Yanjie Duan,Lin Lin,Xiaowei Xu,Jichao Shi,Runping Jia,Dandan Wu,Xinyao He

A series of self-healing waterborne polyurethane (WPU) films utilizing reversible covalent bond acylhydrazones diol (PA) as chain extender were successfully synthesized. The self-healing performance of WPU with different content of chain extender PA has been systemically characterized via cut-and-healing tests and mechanical quantitative evaluation. The film can repair cracks through acylhydrazone exchange reactions within 12 h. When the content of PA is 1.5 wt%, the WPU has the highest self-healing efficiency of 90.5%. Meanwhile, the effect of PA mass fraction on the particle size distribution, mechanical ability, crystallization, water resistance properties, and thermal stability of WPU were evaluated. With the introduction of acylhydrazone bonds, the hydrophobicity of the WPU material was enhanced, while achieving self-healing performance, which solves the problem of aging and replacement of materials. These results indicated that the self-healing WPU exhibited great application prospect as a versatile material.

研究领域: 材料科学 · 高分子化学
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EUROPEAN POLYMER JOURNAL · 2024 · IF 5.8

Mechanically strong, reprocessable and chemically recyclable furan-based poly(acylhydrazone)s materials with hydrogen-bonding networks

Xiaowei Li,Chilong Liu,Xiaoru Quan,Yanxin Zhang,Su Wang,Shuangfei Zhao,Jiming Yang,Yirong Feng,Wei He,Kai Guo

Acylhydrazone linkages are attractive in designing reconfigurable and chemically recyclable polymer due to their reversible characteristics and ease of preparation. We fabricate mechanically strong, thermally stable and chemically recyclable poly(acylhydrazone)s (pDFF-IPDH) using biobased 2,5-diformylfuran (DFF) and dihydrazide compounds as monomers. The linear chains are physically cross-linked via hydrogen bonding between the acylhydrazone moieties. The pDFF-IPDH sample exhibits good mechanical properties, offering both high strength and toughness. The linear and reversible acylhydrazone backbones endow polymers with attractive temperature-dependent dynamic natures, which enables the topological network to rearrange, giving the poly(acylhydrazone)s excellent reprocessability. Moreover, the feasibility of formaldehyde-promoted depolymerization presents an effective recycling pathway, offering promising opportunities in addressing the challenge between recyclability and service performance.

研究领域: 材料科学 · 化学工程
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RSC Advances · 2014 ·Vol. 4 ·期 92 ·50301-50311 · IF 3.708

A hydrazone crosslinked zwitterionic polypeptide nanogel as a platform for controlled drug delivery

Caicai Lu,Bingqiang Li,Na Liu,Guolin Wu,Hui Gao,Jianbiao Ma

A pH-responsive polypeptide nanogel was prepared via hydrazone self-crosslinking under mild conditions. Zwitterionic sulfobetaine was introduced to the polypeptide by aminolysis reaction of polysuccinimide with N,N-dimethylaminopropylamine, and the subsequent ring-opening reaction between tertiary amine and 1,3-propanesultone. The hydrazine and aldehyde modified poly(α,β-L-aspartic acid) precursors, poly(aspartamide sulfobetaine-co-aspartylhydrazide) and poly(aspartamide sulfobetaine-co-2-oxoethyl aspartamide) were prepared by the successive aminolysis reaction of polysuccinimide. The obtained zwitterionic poly(aspartamide) nanogel exhibited excellent anti-protein adsorption ability and stability in protein solutions. An anticancer drug, doxorubicin (DOX), was entrapped into the nanogel, and showed accelerated release under acidic conditions. Additionally, the nanogel entrapped DOX could be successfully released into the cancer cells and showed high cytotoxicity. This easily prepared nanogel, with features of biocompatibility, anti-protein adsorption ability, and pH-responsiveness, is a promising controlled drug delivery system.

CAS / MDL: 109-55-7 1120-71-4
研究领域: 生物材料 · 药学 · 生物医学工程
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JOURNAL OF MOLECULAR STRUCTURE · 2015 · IF 1.602

Mono-Schiff-base or di-Schiff-base? Synthesis, spectroscopic, X-ray structural and DFT study of a series of Schiff-bases derived from benzil dihydrazone

Xue-Jie Tan,Xiu-Qi Hao,Qing-Zhe Zhao,Shuang-Shuang Cheng,Wen-Long Xie,Dian-Xiang Xing,Yun Liu,Lai-Zhou Song

A series of mono- and di-Schiff-bases based on Benzil Dihydrazone ( BDH ) were designed and synthesized to be set as the model compounds to explain which one should be the advanced product and which parameters will determine the end-product. As the first step of a series of investigations, this article presents the syntheses and characterization of five new Schiff-bases plus one preliminary reported Schiff-base, all derived from BDH . The compounds were characterized by single crystal (or conventional powder) X-ray diffractometry, elemental analysis , m.p., 1 H NMR, 13 C NMR, IR and UV–Vis. Structural features of the five new Schiff-bases are similar. For instance, all molecules are nonsymmetrical/symmetrical double helix with the torsion angle of two “half-parts” about 72–97°. The Ph-C N–N C-Ph moiety all exists in planar and anti form, indicating significant conjugation. The crystal structures appear to be stabilized by π-stacking between the aromatic rings , as well as by intermolecular hydrogen bonds and C–H … π stacking interactions. DFT calculations have been performed to explain the trend of the experimentally measured reaction yields. In the case of the studied systems by us, the type of Schiff-bases exhibits a clear dependence on the molar ratio of reactants if the products have similar stabilities. Otherwise the importance of reaction conditions will be weakened and the most stable product will be favored.

CAS / MDL: 7664-39-3
研究领域: 有机化学 · 理论化学
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Applied Sciences-Basel · 2015 ·Vol. 5 ·期 4 ·910-925 · IF 1.484

Double Properties of Novel Acylhydrazone Nanomaterials Based on a Conjugated System: Anion Binding Ability and Antibacterial Activity

Xuefang Shang,Wanli Li,Yaqian Feng,Xin Li,Xiufang Xu

A series of new compounds (1–12) containing 1,5-diaza-fluorenone, 1,10-phenanthroline-5,6-dione, ferrocene-1,1ʹ-dione, anthracene-9-carbaldehyde have been synthesized and optimized. The nanomaterials were also developed successfully. The binding properties were evaluated for biologically important anions (F−, Cl−, Br−, I−, AcO−, and H2PO4−) by theoretical investigation, UV-vis, and fluorescence experiments, and compound6displayed the strongest binding ability for AcO−ion among the synthesized compounds. Theoretical investigation analysis revealed that the intramolecular hydrogen bond existed in the structure of compound6and the roles of molecular frontier orbitals in molecular interplay. In addition, compound6showed wide antibacterial activity for colon bacillus, typhoid bacillus, andPseudomonas aeruginosa, and inferior activity for hay bacillus andStaphylococcus aureus. This series of acylhydrazone nanomaterials showed double properties, anion binding ability, and antibacterial activity.Keywords:binding ability;antibacterial activity;acylhydrazone derivative;nanomaterials;synthesis

研究领域: 有机化学 · 材料科学 · 生物学
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ACS Applied Materials & Interfaces · 2020 · IF 8.758

Bioinspired Self-Healing of Kinetically Inert Hydrogels Mediated by Chemical Nutrient Supply

Yuanbo Zhong,Panpan Li,Jingcheng Hao,Xu Wang

Dynamic stability and self-healing ability are two inherently compatible properties for living organisms. By contrast, kinetic stability and intrinsic healability are two desired but mostly incompatible properties for synthetic materials. This is because the healing of these materials heavily relies on the kinetic lability of the chemical bonds or physical interactions in materials. Inspired by the hierarchically and temporally controlled wound healing in biological systems, here, we report the intrinsic healing of kinetically stable hydrogels, regulated by the consumption of chemical nutrients. The acylhydrazone-based polymer hydrogels with preinstalled urease and urea were formed at a low initial pH, followed by in situ enzymatic generation of a base to deactivate the dynamic bonds, allowing efficient fabrication of kinetically stable hydrogels. The healing of damaged hydrogels was effective when fed with proper chemical nutrients (i.e., acidic urea solutions), in which case a transient acidic pH state was temporally programmed by combining a fast acidic activator (for structural healing) with the slow, biocatalytic generation of a base (for property recovery). The ability to regulate both hydrogel fabrication and healing via a single enzymatic reaction could provide a new approach to create kinetically stable materials capable of healing damages on demand.

CAS / MDL: 78-67-1 79-06-1
研究领域: 材料科学 · 生物医学工程
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International Journal of Electrochemical Science · 2023 · IF 1.5

Ultra-sensitive Electrochemical Determination of Mercury Ions Based on the Dithizone Modified Electrode

Wei Zhu,Jiejuan Tang,Ling Huang

Mercury-ion pollution in water is very dangerous to human health and ecological environments. It is necessary to propose a simple, fast and low-cost testing method for mercury-ion detection. Cold atomic spectrophotometers are often used for the detection of mercury ions, but because the instruments are expensive and cumbersome to operate, the method is only suitable for laboratories. In this work, we propose a simple electrochemical method for the determination of mercury ions based on a dithizone-modified glassy carbon electrode. The dithizone modification can significantly enhance the sensing performance of the electrode. Under optimized conditions, the proposed electrochemical sensor can linearly detect Hg(II) between 0.1 and 100 μg/L with a low detection limit of 17 ng/L.

研究领域: 环境科学 · 分析化学
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JOURNAL OF COORDINATION CHEMISTRY · 2014 · IF 2.212

A thiosemicarbazone copper(II) complex as a potential anticancer agent

Zhong-Ying Ma,Jia Shao,Wei-Guo Bao,Zhao-Yan Qiang,Jing-Yuan Xu

The preparation and the structure of a copper(II) complex, [Cu(4ML)Cl] (1) (H4ML = 2-acetylpyridine-4-methylthiosemicarbazone), are described. Complex 1 crystallizes in a monoclinic P21/c space group with a = 7.977(2) Å, b = 15.824(5) Å, c = 9.126(2) Å, α = γ = 90°, β = 91.974(2)°, V = 1151.26(5) Å3, Z = 4, F(0 0 0) = 620. According to X-ray crystallographic studies, each Cu(II) ion lies in a square planar coordination geometry based on the 4ML− and Cl− ligands. The complex displayed excellent inhibitory activity against various tumor cells (HeLa, HepG-2 and SGC-7901), offering lower IC50 value of 3.2 ± 0.7 μM than cisplatin (10 ± 2 μM) on HeLa cells at 48 h. Complex 1 could significantly suppress HeLa cell viability in a dose-dependent manner. Flow cytometric analysis showed that 1 induced HeLa cell apoptosis, which might be associated with cell cycle arrests at S and G2 phases. Consistent with results of DNA cleavage experiments, comet assay indicated that 1 caused severe DNA fragmentation. The production of ROS was elevated with increasing concentration of 1, suggesting that 1 was capable of promoting HeLa cell apoptosis through an oxidative DNA damage pathway.

研究领域: 药物化学 · 肿瘤学 · 生物无机化学
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Materials Research Express · 2018 ·Vol. 5 ·期 5 ·055605 · IF 1.151

Ratiometric fluorescent nanosensor based on carbon dots for the detection of mercury ion

Yusha Ma,Jing Mei,Jianliang Bai,Xu Chen,Lili Ren

A novel ratiometric fluorescent nanosensor based on carbon dots has been synthesized via bonding rhodamine B hydrazide to the carbon dots surface by an amide reaction. The ratiometric fluorescent nanosensor showed only a single blue fluorescence emission around 450 nm. While, as mercury ion was added, due to the open-ring of rhodamine moiety bonded on the CDs surface, the orange emission of the open-ring rhodamine would increase obviously according to the concentration of mercury ion, resulting in the distinguishable dual emissions at 450 nm and 575 nm under a single 360 excitation wavelength. Meanwhile, the ratiometric fluorescent nanosensor based on carbon dots we prepared is more sensitive to qualitative and semi-quantitative detection of mercury ion in the range of 0–100 μM, because fluorescence changes gradually from blue to orange emission under 365 nm lamp with the increasing of mercury ion in the tested solution.

研究领域: 分析化学 · 环境科学 · 材料科学
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JOURNAL OF HAZARDOUS MATERIALS · 2024 · IF 12.2

Modularization of dual recognized CRISPR/Cas12a system for the detection of Staphylococcus aureus assisted by hydrazone chemistry

Jingyi Yang,Yining Zhao,Lelin Qian,Ying Yu,Yuan Zhang,Juan Zhang

In this work, a dual recognized CRISPR/Cas12a system has been proposed, in which the activation chain is cleverly divided into two parts that can serve for precise dual target recognition, and hydrazone chemistry is introduced for the formation of a whole activation chain. It has been further explored to construct a new method for the specific and sensitive detection of Staphylococcus aureus (SA) as one of the most common pathogens in infectious diseases. In virtue of proximity effect contributed by complementary base pairing, hydrazone chemistry accelerates the formation of the whole activation strand and improves the specificity of the CRISPR/Cas12a system, serving for the accurate analysis of SA. Moreover, the temporary aggregation of CRISPR/Cas12a around SA enhances its catalytical efficiency so as to further amplify signal. With high sensitivity, stability, reproducibility and specificity, the established method has been successfully applied to detect SA in complex substrates. Meanwhile, our established method can well evaluate the inhibition effect of chlorogenic acid and congo red in comparison with flow cytometry. Environmental implication Bacterial pathogens exist widely in the environment and seriously threaten the safety of human health. Staphylococcus aureus (SA) is the most common pathogen of human suppurative infection, which can cause local suppurative infection, pneumonia, and even systemic infections such as sepsis. In this work, a dual recognized CRISPR/Cas12a system mediated by hydrazone chemistry has been proposed. With high sensitivity and low detection limit, the established method can specifically detect SA and effectively evaluate the antibacterial effect of inhibitors. This method is expected to be further developed into a detection method in different scenarios such as environmental monitoring and clinical diagnosis.

CAS / MDL: 64987-85-5
研究领域: 分子生物学 · 病原微生物学 · 分析化学
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EUROPEAN POLYMER JOURNAL · 2024 · IF 5.8

Preparation and properties of self-healing SBS modified bitumen with dynamic acylhydrazone bonds

Yanheng He,Sanpeng Mao,Tianwei Zhang,Shangheng Zeng,Hao Duan,Ronghua Zhuang,Jianying Yu

Styrene-butadiene-styrene triblock copolymer (SBS) modified bitumen (SMB) with excellent self-healing performance not only saves resources, but is also important for the sustainable development of pavement and construction industry. In this paper, a self-healing agent (SHA) with acylhydrazone bond was synthesized, and the dynamic acylhydrazone bond was introduced into the SBS molecular chains to prepare the self-healing SMB (SHMB). The structure of SHA was characterized, and the physical properties, chemical structure, microstructure and self-healing performance of the SHMB were investigated. Fourier transform infrared (FTIR) spectra and nuclear magnetic resonance spectra demonstrated that SHA was successfully synthesized. The physical performances of SMB were significantly improved by SHA and its optimal dosage was 0.6 %. FTIR indicated that the dynamic acylhydrazone bond was introduced into the SBS molecular chains, and formed hydrogen bonds in SHMB. The fluorescence microscope showed that SHMB had a denser network structure than SMB. The crack healing observation indicated that the crack healing speed of SHMB was much higher than that of SMB. The break tensile performance recovery showed that the recovery rate of elongation at break (R ε ) of SMB and SHMB were 14.38 % and 58.27 % after self-healing at 25℃ for 32 h, and the R ε of SMB and SHMB was elevated to 50.12 % and 92.58 % after self-healing at 40℃ for 4 h, which indicated that the introduction of dynamic acylhydrazone bonds greatly enhanced the self-healing ability of SHMB.

研究领域: 材料科学 · 土木工程
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ACS Applied Polymer Materials · 2024 · IF 4.4

Thiosemicarbazones-Loaded Injectable Hydrogels with Self-Healing and Antibacterial Activity for Wound Healing

Peifang Wang,Yue Su,Min Ma,Yuqing Wang,Shuang Hou,Changqing Wang,Lin Sun,Jianshe Wei,Mingxue Li

An injectable hydrogel loading α-N-heterocyclic thiosemicarbazones with antibacterial activity was designed to attain therapy against wounds with high efficiency. In the present study, the injectable FPZ-H2L hydrogel was synthesized by loading 2,6-diacetylpyridine bis(N4-methylthiosemicarbazone) (H2L) on transition-metal ions (Zn2+)-cross-linked-folic acid (FA)-co-polydopamine (PDA) hydrogel (FPZ hydrogel). The injectable hydrogel (FPZ-H2L) cross-linked by coordination and hydrogen bonds displayed an excellent self-healing performance and completely covered the irregular wound. Compared with the FPZ hydrogel, the FPZ-H2L hydrogel has stronger antibacterial efficacy on typical Gram-positive/negative bacteria and drug-resistant bacteria. The antibacterial mechanisms of the hydrogel were related to biofilm ablation, the disruption of the cell membrane integrity, leakage of nucleic acids and proteins, and the production of oxidative stress response, thus causing bacterial death. Cell Counting Kit-8 (CCK-8) test shows that FPZ-H2L hydrogel has excellent cell compatibility, and gel drug loading technology greatly overcomes the problem of high cytotoxicity of H2L. The wound healing experiments indicated that the hydrogel enhanced the wound healing efficacy of mice. These results prove that the mixed hydrogel has broadened the field of vision for the design of antibacterial wound dressings.

研究领域: 生物材料学 · 医学 · 药剂学
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