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Journal of Materials Chemistry B · 2015 ·Vol. 4 ·期 6 ·1122-1133 · IF 4.726

Polymeric complex micelles based on the double-hydrazone linkage and dual drug-loading strategy for pH-sensitive docetaxel delivery

Zhihui Su,Yanchao Liang,Yao Yao,Tianqi Wang,Na Zhang

Stimuli-triggered drug release and improved drug loading are two key prerequisites in the preparation of nano-drug delivery systems. Herein, we constructed the first pluronic P123-double (d)–hydrazone bond (hyd)–docetaxel (DTX)/DTX complex micelles (P123-d–hyd–DTX/DTX) which integrated the highly pH-sensitive strategy and the dual drug-loading pattern in one platform. We synthesized pluronic P123-double (d)–hydrazone bond (hyd)–docetaxel (DTX) conjugates (P123-d–hyd–DTX) by conjugating DTX to the PEO chains of P123 via two hydrazone linkages in the backbone for the first time. An increase in the number of hydrazone linkages within the unimolecular conjugate was conducive to improve the pH sensitivity of conjugated-based micelles. Besides, aiming at improving drug loading, the dual drug-loading strategy (chemical conjugation and physical encapsulation) was adopted. Namely, pH-sensitive P123-d–hyd–DTX was used as a vehicle to further encapsulate DTX for preparing P123-d–hyd–DTX/DTX complex micelles. The resulting P123-d–hyd–DTX/DTX micelles exhibited intact spherical shape, uniform particle size distribution (110.37 nm) and higher drug loading (12.64%). The release study in vitro confirmed that P123-d–hyd–DTX/DTX micelles and P123-d–hyd–DTX micelles (as a control) showed highly pH-responsive release properties. In particular at pH 6.5, almost 90.9% and 75% of DTX was released within 48 h, respectively. Compared to P123-d–hyd–DTX micelles, P123-d–hyd–DTX/DTX complex micelles exhibited higher proliferation inhibition effects on B16F10 cells (p < 0.01), while the cytotoxicity of P123-d–hyd–DTX/DTX complex micelles was slightly inferior to that of free DTX (p < 0.05). In the xenograft B16F10 melanoma model, P123-d–hyd–DTX/DTX complex micelles suppressed tumor growth more effectively than Duopafei® (p < 0.01) and P123-d–hyd–DTX micelles (p < 0.05), without causing obvious adverse effects. Overall, the novel polymeric complex micelle based on double-hydrazone bond and dual drug-loading strategies was a promising delivery platform to improve therapeutic efficiency and decrease side effects in cancer treatments.

研究领域: 药剂学 · 肿瘤学 · 生物材料学
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JOURNAL OF MOLECULAR STRUCTURE · 2019 · IF 2.12

A facile accessible acylhydrazone as Al3+ sensor with excellent sensitivity and selectivity

Zhenyuan Yang,Daqiang Wu,Ke Dai,Shiquan Cao,Zongchen Li,Heyan Huang,Zhibin Shang,Hua Liang,Minhao Yan,Suyuan Xie

As Al 3+ is detrimental both to human and other organisms, a simple sensor, acylhydrazone AhzF , is synthesized in one step and its structure is confirmed by single crystal X-ray diffraction. AhzF shows specific fluorescence turn-on response for Al 3+ over other metal ions at UV 365 nm, observed by naked-eyes. Its detection limit can reach to 1.11 × 10 −9  M in ethanol. Meanwhile, AhzF at low concentration can detect Al 3+ with excellent interference resistance to typical disturbing metal ions including Cu 2+ and Fe 3+ . For the first time, concentration influence of Fe 3+ during AhzF detecting Al 3+ has been explored and it has been found that the fluorescence of AhzF-Al 3+ is partly quenched by Fe 3+ while with no influence by Cu 2+ at high concentration (above 10 −6  M), indicating its good low concentration advantage during Al 3+ detection. The binding mode exhibits a 1:1 M ratio between AhzF and Al 3+ , which are confirmed by titration test, Job’s plot, 1 H NMR spectra and mass spectrum . It also exhibits good reusability by alternate addition of Al 3+ and EDTA to the AhzF solution. The pH effect tests suggest its good sensitivity from pH 4 to pH 10 and AhzF can recognize labeled Al 3+ in tap water directly by naked eyes, which makes it possible for the application in real environment.

研究领域: 化学传感器 · 环境科学 · 分析化学
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ENVIRONMENTAL SCIENCE & TECHNOLOGY · 2024 · IF 10.8

Highly Sensitive Surface-Enhanced Raman Scattering Detection of Hydroxyl Radicals in Water Microdroplets Using Phthalhydrazide/Ag Nanoparticles Nanosensor

Shengmao Chao,Chiara Valsecchi,Ji Sun,Hong Shao,Xinxia Li,Changyu Tang,Meikun Fan

The spontaneous generation of hydrogen peroxide (H2O2) within atmospheric microdroplets, such as raindrops and aerosols, plays a crucial role in various environmental processes including pollutant degradation and oxidative stress. However, quantifying hydroxyl radicals (•OH), essential for H2O2 formation, remains challenging due to their short lifespan and low concentration. This study addresses this gap by presenting a highly sensitive and selective surface-enhanced Raman scattering (SERS) nanosensor specifically designed for quantifying •OH within water microdroplets. Utilizing a phthalhydrazide (Phth) probe, the SERS technique enables rapid, interference-free detection of •OH at nanomolar concentrations. It achieves a linear detection range from 2 nM to 2 μM and a limit of detection as low as 0.34 nM. Importantly, the SERS sensor demonstrates robustness and accuracy within water microdroplets, paving the way for comprehensive mechanistic studies of H2O2 generation in the atmosphere. This innovative approach not only offers a powerful tool for environmental research but also holds potential for advancing our understanding of atmospheric H2O2 formation and its impact on air quality and pollutant degradation.

研究领域: 环境科学 · 分析化学
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APPLIED ORGANOMETALLIC CHEMISTRY · 2018 ·Vol. 32 ·期 10 ·e4483 · IF 3.581

Copper-catalyzed C-N coupling reaction of tosylhydrazones

Xufeng Wu,Lingyu Li,Wenlong Jiang,Lihong Zhou,Qingle Zeng

Tosylhydrazones are a kind of labile and highly reactive compounds, which are apt to be transformed into reactive diazo compounds and then into extremely reactive carbenes under the basic condition. In order to fulfil the valuable C-N coupling reaction, diaryliodonium salts are evaluated and prove to be a class of efficient electrophiles. The reaction with ligand-free copper salt as catalyst shows a wide range of substrate scope. A plausible mechanism is proposed.

研究领域: 有机化学 · 合成化学
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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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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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