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RSC Advances · 2018 ·Vol. 8 ·期 35 ·19642-19650 · IF 2.936

Synthesis of polyurethanes with pendant azide groups attached on the soft segments and the surface modification with mPEG by click chemistry for antifouling applications

Fancui Meng,Zhuangzhuang Qiao,Yan Yao,Jianbin Luo

Polyurethane with pendant azide groups on the soft segment (PU-GAP) was prepared in this study to further increase the content of reactive azide groups and improve their surfaces enrichment for further functionalization. Polymer diols with pendant azide groups (GAP) were prepared by transforming the pendant chlorine groups at polyepichlorohydrin (PECH) into azide groups with sodium azide. The prepared PECH, GAP and PU-GAP was characterized by GPC, 1H NMR and FTIR. Propargylic mPEG (mPEG-alkyne) was used as model surface modification reagents which was grafted on the prepared azido containing polyurethane films via click chemistry. The surface morphology, chemical composition and wettabilities were studied by SEM, XPS and water contact angle (WCA) analysis, respectively. SEM results demonstrated different surface topologies between mPEG modified PU surface and original PU surface. XPS and WCA analysis proved the successful grafting of mPEG on the pendant azide groups of PUs. The mPEG modified PU surfaces demonstrated good antifouling activities against model bacteria and mPEG with larger molecular weights modified surfaces showed better resistance efficiency to attachment of bacteria. Therefore, the surface reactive polyurethane we prepared can be a universal platform for further functionalization according actual applications.

研究领域: 材料科学 · 生物医学工程
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JOURNAL OF POLYMER RESEARCH · 2020 ·Vol. 27 ·期 6 ·1-11 · IF 2.426

Copolymerization of azide-containing carbonate with lactide and post functionalization

Qiu Xibo,Zhai Hong,Li Longfei,Dong Peng,Bai Ying,Peng Ai-Yun,Quan Daping

The intention of this work was to study the polymerization of a cyclic carbonate monomer bearing one azido group, i.e. 2-(azidemethyl)-2-methyltrimethylene carbonate (AMTC), to disclose the characteristics of the resulted polymers and to explore the feasibility of their post-functionalization with alkynyl compounds via Click reaction. Homopolymerization of AMTC was first studied using stannous octoate (Sn(Oct) 2 ) as the catalyst and dodecanol as the initiator, which had the characteristic of active polymerization. Copolymerization of AMTC with L -lactide ( L -LA) was then investigated under the same reaction condition, in which L- LA exhibited higher reactivity than AMTC. The reactivity of AMTC was low not only in its homopolymerization but also in its copolymerization with L -LA, while the conversion of AMTC increased by extending the reaction time. The copolymer P(AMTC-co- L LA) (PLAC) had the semicrystalline characteristic due to the relative long block-like segments of P L LA ( \( {\overline{L}}_{\mathrm{L}}=35.5 \) ). Based on these results, copolymerization of AMTC with L -LA using PEG 4K as macroinitiator was further studied to afford PLAC-PEG-PLAC copolymers. The copolymerization could be well controlled at low ratio of [M] 0 /[I] 0 (from 10 to 50) and molar fraction of AMTC in feed ( f AMTC  = 0.1, 0.2). The pendent azido groups of PLAC-PEG-PLAC could undergo post-functionalization through azide-alkyne click reaction easily and efficiently.

研究领域: 高分子化学 · 材料科学
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NEW JOURNAL OF CHEMISTRY · 2021 ·Vol. 45 ·期 25 ·11380-11389 · IF 3.591

3-R-4-(5-Methyleneazide-1,2,4-oxadiazol-3-yl)furazan and its ionic salts as low-sensitivity and high-detonation energetic materials

Rui Yang,Yifei Liu,Zhen Dong,Haiyan Li,Zhiwen Ye

As an environmentally friendly energetic group, the azide group can not only control the melting point but also increase the energy of the compound. Therefore, the design and synthesis of energetic compounds with azido groups have long been a focus of research in the field of energetic materials. 3-R-4-(5-methyleneazide-1,2,4-oxadiazol-3-yl)furazan energetic materials were synthesized and fully characterized. Using computational chemistry methods, the interactions of some compounds were studied, and the physical and chemical properties of all of compounds were examined. The results show that 3-amino-4-(5-methyleneazide-1,2,4-oxadiazol-3-yl)furazan (2) has a melting point similar to that of TNT and can be a potential carrier for molten-cast explosives. Hydroxylamine salt (4) has an excellent detonation velocity and detonation pressure of 9090 m s−1 and 35.76 GPa, respectively, and its energy is significantly higher than that of RDX, enabling replacement of RDX as a high-energy explosive. Although the detonation performance of compound 4 is slightly lower than that of HMX, its sensitivity is better than that of HMX, which shows that compound 4 still has a high application value. Non-covalent interactions (NCIs) and Hirshfeld surface models indicate that hydrogen bonding and π–π interactions are the key factors that reduce the sensitivity of compounds. Therefore, our results for 3-R-4-(5-methyleneazide-1,2,4-oxadiazol-3-yl)furazan energetic materials suggest that it may be competitive for application in both molten-cast explosives and high-energy explosives.

研究领域: 化学 · 材料科学 · 爆炸物研究
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BIOMACROMOLECULES · 2024 · IF 5.5

Amphiphilic Block Copolymers Containing Benzenesulfonyl Azide Groups as Visible Light-Responsive Drug Carriers for Image-Guided Delivery

Lei Luo,Fei Liu,Zhiying Li,Siyuan Yue,Liang Wang,Shiling Zhang,Shanmeng Lin,Jinyan Luo,Meng Wang,Yichuan Zhang,Mohamed Abdelrahim,Qi Xing,Jin Geng

Nanoparticles (NPs) containing light-responsive polymers and imaging agents show great promise for controlled drug delivery. However, most light-responsive NPs rely on short-wavelength excitation, resulting in poor tissue penetration and potential cytotoxicity. Moreover, excessively sensitive NPs may prematurely release drugs during storage and circulation, diminishing their efficacy and causing off-target toxicity. Herein, we report visible-light-responsive NPs composed of an amphiphilic block copolymer containing responsive 4-acrylamide benzenesulfonyl azide (ABSA) and hydrophilic N,N′-dimethylacrylamide (DMA) units. The polymer pDMA-ABSA was loaded with the chemotherapy drug dasatinib and zinc tetraphenylporphyrin (ZnTPP). ZnTPP acted as an imaging reagent and a photosensitizer to reduce ABSA upon visible light irradiation, converting hydrophobic units to hydrophilic units and disrupting NPs to trigger drug release. These NPs enabled real-time fluorescence imaging in cells and exhibited synergistic chemophotodynamic therapy against multiple cancer cell lines. Our light-responsive NP platform holds great promise for controlled drug delivery and cancer theranostics, circumventing the limitations of traditional photosensitive nanosystems.

研究领域: 材料科学 · 药学 · 生物医学工程 · 纳米技术 · 癌症研究
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Biomaterials Advances · 2022 · IF 0

Strategy based on multiplexed brush architectures for regulating the spatiotemporal immobilization of biomolecules

Haili Zhao,Tao Chen,Tong Wu,Linsheng Xie,Yulu Ma,Jin Sha

Functional surfaces that enable both spatial and temporal control of biomolecules immobilization have attracted enormous attention for various fields including smart biointerface materials, high-throughput bioarrays, and fundamental research in the biosciences. Here, a flexible and promising method was presented for regulating the spatiotemporal arrangement of multiple biomolecules by constructing the topographically and chemically diverse polymer brushes patterned surfaces. A series of polymer brushes patterned surfaces, including antifouling brushes patterned surface, epoxy-presenting brushes patterned surface without and with antifouling background layer, were fabricated to control the spatial distribution of protein and cell adhesion through specific and nonspecific means. The fluorescence measurements demonstrated the effectiveness of spatially regulating the density of surface-immobilized protein through controlling the areal thickness of the poly (glycidyl methacrylate) (PGMA) brush patterns, leading to various complex patterns featuring well-defined biomolecule concentration gradients. Furthermore, a multiplexed surface bearing epoxy groups and azido groups with various areal densities was fabricated for regulating the spatiotemporal arrangement of different proteins, enabling binary biomolecules patterns with higher degrees of functionality and complexity. The presented strategy for the spatiotemporal control of biomolecules immobilization would boost the development of dynamic and multifunctional biosystems.

研究领域: 智能生物界面材料 · 高通量生物芯片 · 生物科学
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TALANTA · 2021 · IF 6.057

A novel fluorescent strategy based on double modifications of metal organic framework material CAU-10-NH2 for low background and high sensitivity determination of H2S

Wenpeng Gong,Li Zhang,Ying Yu,Bixia Lin,Yumin Wang,Manli Guo,Yujuan Cao

Hydrogen sulfide is typical metabolic marker and environmental pollutant which is worthwhile to determine. Herein, a low background and high sensitivity fluorescent strategy based on double modifications of metal organic framework material CAU-10-NH 2 is proposed for the determination of hydrogen sulfide. Firstly, a functional monomer 3,5-diaminobenzoic acid is employed to modify on the CAU-10-NH 2 , the product CAU-10-NH-dAba has strong fluorescent performance at 412 nm under an excitation wavelength of 320 nm. Subsequently, it is further modified by the azide group to form CAU-10-NH-dAba-N 3 . This azidation inhibits the fluorescent signal. However, in the presence of hydrogen sulfide, the azide group is specifically reduced to amidogen, and results in the recovery of the fluorescence. The CAU-10-NH-DABA-N 3 was characterized by solid state NMR , XPS, fluorescence, IR, XRD, SEM and specific surface area. After the optimization of pH value, temperature and interaction time, the detection results of hydrogen sulfide demonstrate the linear range of this strategy is from 20 to 140 nM with a detection limit of 1.51 nM, which is significantly better than that of the CAU-10-NH 2 merely modified by 3,5-dinitrobenzoic acid. Meanwhile, the satisfactory assay results of hydrogen sulfide in serum sample and Pearl river water suggest a potential application prospect of this strategy in clinical diagnosis and environment monitoring.

研究领域: 分析化学 · 环境科学 · 材料科学 · 生物化学
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