He Ye, Li Mengxue, Jiang Wenjing, Yang WeiJuan, Lin Ling, Xu LiangJun, Fu FengFu
Key Lab of Analysis and Detection for Food Safety of Ministry of Education, Fujian Provincial Key Lab of Analysis and Detection for Food Safety, Department of Chemistry, Fuzhou University, Fuzhou, Fujian 350116, China.
J Mater Chem B. 2016 Jan 28;4(4):752-759. doi: 10.1039/c5tb01926e. Epub 2016 Jan 4.
We herein reported on novel phosphatidylserine-functionalized FeO@SiO NPs (nanoparticles) and enzyme-encapsulated liposomes for the visual detection of Cu by employing phosphatidylserine for Cu recognition and the enzymatic catalysis/oxidation of 3,3',5,5'-tetramethylbenzidine sulfate (TMB) as a signal generator. Phosphatidylserine (1,2-dioleoyl-sn-glycero-3-phospho-l-serine, DOPS) was covalently assembled on the FeO@SiO NP surface to obtain DOPS-functionalized FeO@SiO NPs, and was used to encapsulate horseradish peroxidase (HRP) to form HRP-encapsulated DOPS liposomes. It was demonstrated that DOPS-functionalized FeO@SiO NPs can specifically bind HRP-encapsulated DOPS liposomes in the presence of Cu at basic pH. The HRP-encapsulated DOPS liposome bound on the DOPS-functionalized FeO@SiO NPs was then separated from solution with a magnet. Upon the addition of TMB-HO solution, the HRP-encapsulated DOPS liposome bound on the DOPS-functionalized FeO@SiO NPs was broken to release HRP, and the released HRP catalyzes the HO-mediated oxidation of TMB, which gives rise to a change from colourless to blue in solution colour and a new absorption peak at 652 nm. This provided a sensing platform for the sensitive, specific and field-portable colorimetric detection of Cu. By using the sensing platform, a selective and sensitive visual sensor for the detection of Cu was developed. The proposed method has outstanding advantages including adequate sensitivity (the sensitivity can be improved by using a greater volume of the water sample), shorter analysis time, relatively low cost, operation at room temperature and stronger resistibility to the matrix. It can be used to detect as little as 0.1-0.5 μM of Cu in river water using naked-eye observation and 0.05 μM of Cu in river water using UV-visible spectrophotometry when 2 mL of the water sample was used for detection, within 15 min and with a recovery of 95-101% and a RSD < 5% (n = 5). A visual detection limit of 0.1-0.5 μM is much lower than the maximum allowable level of Cu (∼20 μM) in drinking water defined by the USA EPA. The above features make our sensor a promising approach for the rapid and on-site detection of trace free copper ions in aqueous environments by only naked-eye observation.
我们在此报道了新型磷脂酰丝氨酸功能化的FeO@SiO纳米颗粒(NPs)和酶包封脂质体,用于通过利用磷脂酰丝氨酸识别铜以及将3,3',5,5'-四甲基联苯胺硫酸盐(TMB)的酶催化/氧化作为信号发生器来可视化检测铜。磷脂酰丝氨酸(1,2-二油酰基-sn-甘油-3-磷酸-L-丝氨酸,DOPS)共价组装在FeO@SiO NP表面以获得DOPS功能化的FeO@SiO NPs,并用于包封辣根过氧化物酶(HRP)以形成HRP包封的DOPS脂质体。结果表明,在碱性pH条件下,DOPS功能化的FeO@SiO NPs在铜存在时能特异性结合HRP包封的DOPS脂质体。然后用磁铁将结合在DOPS功能化的FeO@SiO NPs上的HRP包封的DOPS脂质体从溶液中分离出来。加入TMB-H₂O₂溶液后,结合在DOPS功能化的FeO@SiO NPs上的HRP包封的DOPS脂质体破裂释放出HRP,释放出的HRP催化H₂O₂介导的TMB氧化,导致溶液颜色从无色变为蓝色,并在652 nm处出现新的吸收峰。这为铜的灵敏、特异和现场便携式比色检测提供了一个传感平台。通过使用该传感平台,开发了一种用于检测铜的选择性和灵敏可视化传感器。所提出的方法具有显著优点,包括足够的灵敏度(通过使用更大体积的水样可提高灵敏度)、更短的分析时间、相对较低的成本、室温操作以及对基质更强的耐受性。当使用2 mL水样进行检测时,在15分钟内,通过肉眼观察可检测河水中低至0.1 - 0.5 μM的铜,通过紫外可见分光光度法可检测河水中0.05 μM的铜,回收率为95 - 101%,相对标准偏差<5%(n = 5)。0.1 - 0.5 μM的可视化检测限远低于美国环境保护局(EPA)规定的饮用水中铜的最大允许水平(约20 μM)。上述特点使我们的传感器成为一种仅通过肉眼观察就能在水性环境中快速现场检测痕量游离铜离子的有前景的方法。