将金属纳米簇与天然聚合物结合制备具有特定物理化学性质的复合胶囊成为了近年来的研究热点。通过一种新型、绿色环保的方法,可直接同步制备铜纳米簇及其海藻酸钠复合胶囊,该方法具有操作简便、工艺环保、条件温和等优势。所得铜纳米簇/海藻酸钠复合胶囊呈光滑稳定的球体,具有清晰的核壳结构,并展现出铜纳米簇的鲜明红色荧光。透射电子显微镜观察显示,铜纳米簇在复合胶囊内部均匀分布。紫外光谱及荧光光谱分析结果进一步证实复合胶囊内存在铜纳米簇。释放研究表明,复合胶囊内的铜纳米簇可向周围介质释放,并且铜纳米簇的释放量与释放速率可通过外部pH条件或对应钙离子浓度的制备条件进行调控。因此,所得铜纳米簇/海藻酸钠复合胶囊在荧光成像与控制释放领域具有良好的应用前景。
The preparation of composite capsules with specific physicochemical properties by combining metal nanoclusters with natural polymers has become a hot research topic in recent years.A novel,green and environmentally friendly method was used to prepare copper nanoclusters/sodium alginate composite capsules directly and synchronously.This method had the advantages of easy operation,environmentally friendly process and mild conditions.The resulting copper nanocluster/sodium alginate composite capsules were smooth and stable spheres with a clear core-shell structure and exhibited the distinctive red fluorescence of copper nanoclusters.Transmission electron microscopy observation showed that the copper nanoclusters were uniformly distributed inside the composite capsules.The results of UV spectroscopy and fluorescence spectroscopy further confirmed the presence of copper nanoclusters inside the composite capsules.Release studies showed that the copper nanoclusters inside the composite capsule could be released into the surrounding medium,and the amount and rate of release of copper nanoclusters could be regulated by external pH conditions or preparation conditions corresponding to calcium ion concentration.Therefore,the prepared copper nanocluster/sodium alginate composite capsules exhibited good application prospects in the field of fluorescence imaging and controlled release.
[1] He L,Dong T,Jiang D E,et al.Recent progress in atomically precise metal nanoclusters:from bio-related properties to biological applications[J].Coordination Chemistry Reviews,2025,535:216633.
[2] Gao N,Xu J,Li X,et al.Colorimetric sensing of biomarkers based on the enzyme-mimetic activity of metal nanoclusters[J].Chemical Engineering Journal,2023,465:142817.
[3] Kong Z,Zhao X,Li W C,et al.Cluster engineering in water catalytic reactions:synthesis,structure-activity relationship and mechanism[J].ACS Applied Materials & Interfaces,2024,17(1):67-90.
[4] Xue Y,Cheng Z,Luo M,et al.Synthesis of copper nanocluster and its application in pollutant analysis[J].Biosensors-Basel,2021,11(11):424.
[5] Demirhan B E,Kara H E S,Demirhan B,et al.One-step green aqueous synthesis of blue light emitting copper nanoclusters for quantitative determination of food color Ponceau 4R[J].Journal of Photochemistry and Photobiology A:Chemistry,2021,417:113356.
[6] Ouyang X,Wu Y,Guo L,et al.Self-assembly induced enhanced electrochemiluminescence of copper nanoclusters using DNA nanoribbon templates[J].Angewandte Chemie International Edition Edition,2023,62(21):e202300893.
[7] Zhang J,Pang Y,Shen X.Rapid microwave-assisted synthesis of copper nanoclusters for “on-off-on” fluorescent sensor of tert-butylhydroquinone in edible oil[J].Microchemical Journal,2023,193:109070.
[8] Zhang H,Li B,Ding C,et al.Core-shell structured magnetic beads based on sodium alginate/chitosan for nitrogen removal enhancement[J].Chemical Engineering Journal,2025,512:162203.
[9] Li H,Zhu X,Zhao J,et al.Emerging adsorbents:applications of sodium alginate/graphene oxide composite materials in wastewater treatment[J].Journal of Water Process Engineering,2024,59:105100.
[10] Sun L,Shen Y,Li M,et al.Preparation and modification of collagen/sodium alginate-based biomedical materials and their characteristics[J].Polymers,2024,16(2):171.
[11] Guo H,Zhang A,Fu H,et al.In situ generation of CeCoSx bimetallic sulfide derived from egg-box seaweed biomass on S/N co-doped graphene aerogels for flexible all solid-state supercapacitors[J].Chemical Engineering Journal,2023,453:139633.
[12] 李沁园,谢鑫,贾露凡,等.改性海藻酸钙-壳聚糖微球包膜缓释肥的制备及性能研究[J].化工新型材料,2022,50(7):250-255.
[13] Nakal-Chidiac A,Garcia O,Garcia-Fernandez L,et al.Chitosan-stabilized silver nanoclusters with luminescent,photothermal and antibacterial properties[J].Carbohydrate Polymers,2020,250:116973.
[14] Mosmeri H,Alaie E,Shavandi M,et al.Bioremediation of benzene from groundwater by calcium peroxide (CaO2) nanoparticles encapsulated in sodium alginate[J].Journal of the Taiwan Institute of Chemical Engineers,2017,78:299-306.
[15] Li Z,Chen P,Xu X,et al.Preparation of chitosan-sodium alginate microcapsules containing ZnS nanoparticles and its effect on the drug release[J].Materials Science & Engineering C-Materials for Biological Applications,2009,29(7):2250-2253.
[16] 高静,申静.纳米药物递送系统辅助治疗牙周炎研究进展[J].现代口腔医学杂志,2025,39(4):326-329.
[17] Qu F,Wang B,Li K,et al.Copper nanoclusters@Al3+complexes with strong and stable aggregation-induced emission for application in enzymatic determination of urea[J].Microchimica Acta,2020,187(8):457.
[18] Ye M,Yu Y,Lin B,et al.Copper nanoclusters reversible switches based on ions-triggered for detection of inorganic pyrophosphatase activity[J].Sensors and Actuators B-Chemical,2019,284:36-44.
[19] Dong Q,Song W,Zhang S,et al.Cysteine-assisted synthesis of copper nanoclusters for construction of FRET-based ratiometric sensor for visual detection of alkaline phosphatase[J].Talanta,2025,291:127910.
基金资助
武汉理工大学自主创新研究基金项目(104972025BKS0237)
PDF
