Colorimetric Detection of Sulfite in Foods by a TMB–O₂–Co₃O₄ Nanoparticles Detection System

Abstract

In this paper, we first discovered that Co3O4 nanoparticles (NPs) possess intrinsic oxidase-like activity and can catalytically oxidize peroxidase substrates, such as 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) and 3,3',5,5'-tetramethylbenzidine (TMB), to form colored products, in the absence of exogenously added H2O2. The presence of sulfite inhibited the TMB-O2-Co3O4 NPs reaction system and caused a change in color of the reaction system. On the basis of this phenomenon, a colormetric approach to detect sulfite was established with a good linear relationship ranging from 0.2×10(-6) to 1.6×10(-5) M and a detection limit of 5.3×10(-8) M. The method was used to detect sulfite in foods. Good recoveries ranging from 93.8% to 100.5% were obtained. Furthermore, the mechanism was studied and results showed that the oxidase-like activity of the Co3O4 NPs was not from •OH or O2•- radical generated. It may probably originate from their ability to transfer an electron between the peroxidase substrate and oxygen absorbed on the surface of the Co3O4 NPs.

Scientific Opinion on the re‐evaluation of sulfur dioxide (E 220), sodium sulfite (E 221), sodium bisulfite (E 222), sodium metabisulfite (E 223), potassium metabisulfite (E 224), calcium sulfite (E 226), calcium bisulfite (E 227) and potassium bisulfite (E 228) as food additives

“…A good correlation was obtained between a cyclic voltammetric measure, based upon the response produced before and after acetaldehyde additions, and the concentration of free sulfur dioxide in eight white wines measured by the Monier-Williams procedure. Qin et al (2014) found out that nanoparticles of cobalt oxides have intrinsic oxidase-like activity and can catalytically oxidise peroxidase substrates, such as 2,2'-azino-bis(3-ethylbenzothiazoline-6sulfonic acid) diammonium salt and 3,3',5,5'-tetramethylbenzidine, to form coloured products (which can be measured via spectrophotometry), a reaction which is inhibited by sulfites. The method was tested in three food matrices and the LOD was 0.053 mol of sulfite anion, calculated by the Panel to be 0.0034 mg/kg when expressed as sulfur dioxide.…”

Recent advances in applications of nanoparticles as enzyme mimetics

“…纳米材料类别 模拟酶类型 应用 四氧化三铁 过氧化物酶 葡萄糖测定 [50,51] ; 葡萄糖、半乳糖、胆碱测定 [52] ; 多巴胺、3,4-二羟苯丙氨酸、 去甲肾上腺素、肾上腺素测定 [53] ; 胆碱测定 [54] ; 还原性谷胱甘肽测定 [55] ; 乙醇测 定 [56] ; 汞离子测定 [57] ; 灭线磷 [58] , 乙酰甲胺磷、甲基对氧磷、沙林测定 [59] ; 纳米 颗粒组织分布 [60] ; 核酸测定 [61] ; 免疫测定 [4,62] ; 肿瘤细胞抑制 [63] ; 病原微生物抑 制 [64] ; 苯酚和苯胺化合物的降解 [65] ; 罗丹明降解 [66] ; 磺胺降解 [67] 四氧化三铁-铂 过氧化物酶 免疫测定 [68] 四氧化三铁-还原性氧化石 墨烯 过氧化物酶 乙酰胆碱测定 [69] 四氧化三铁-金-氧化硅 过氧化物酶, 葡萄糖氧化酶 葡萄糖测定 [11] 四氧化三铁-碳 过氧化物酶 肿瘤细胞抑制 [70] 普鲁士蓝 过氧化物酶 葡萄糖测定 [71] ; 还原性谷胱甘肽测定(GSH) [72] 三氧化二铁 过氧化物酶 葡萄糖测定 [73] 三氧化二铁-普鲁士蓝 过氧化物酶 亚甲基蓝降解 [74] 三氧化钼 亚硫酸氧化酶 亚硫酸氧化酶缺陷治疗 [9] 五氧化二钒 卤素过氧化物酶 病原微生物抑制 [7] 四氧化三钴 过氧化物酶 葡萄糖测定 [75] ; 免疫测定 [22] 过氧化氢酶 钙测定 [76] 氧化酶 亚硫酸盐测定 [77] 四氧化三钴-还原性氧化石 墨烯 过氧化物酶 亚甲基蓝降解 [78] 二氧化锰 过氧化物酶 过氧化氢(H 2 O 2 ), 免疫测定 [79] 氧化镍 过氧化物酶 H 2 O 2 , 葡萄糖测定 [80] 二氧化铈 过氧化物酶 葡萄糖测定 [81] 超氧化物歧化酶 自由基清除 [19] 氧化酶 核酸测定 [82] ; 肿瘤细胞测定 [15,16] 氧化铜 过氧化物酶 乳酸、葡萄糖测定 [83] ; 胆固醇测定 [84] 碲化镍 过氧化物酶 葡萄糖测定 [85] 多金属盐 过氧化物酶 葡萄糖测定 [86] 羧基化富勒烯 过氧化物酶 葡萄糖测定 …”

“…氧 化 酶 催 化 底 物 氧 化 的 同 时 , 还 原 氧 气 为 水 或者 H 2 O 2 . 不同于过氧化物酶样活性, 具有氧化 酶样活性的纳米材料当前报道的还比较少, 主要有 金 [10,11,14,24] 、二氧化铈 [15,16,82] 、四氧化三钴 [77] 、铁酸 钴 [13] 等, 并分别应用于葡萄糖 [11,24] 、核酸 [24,82] 、胰蛋 白酶 [14] 、亚硫酸盐 [13,77] 以及肿瘤细胞 [15,16] 的检测.…”

A Highly Sensitive Colorimetric Method for Copper Ions Detection Based on Controlling the Peroxidase-like Activity of Au@Pt Nanocatalysts

“…3 Recently, many metallic nanoparticles with enzyme-like activity, termed as "enzyme mimics", have attracted considerable interest. 17 These enzyme mimics have demonstrated broad application in detecting various targets, such as metal ions, 18,19 anions, [20][21][22] small molecules [23][24][25] and nucleotide acid, 26 etc. Among various metallic nanoparticles, the (gold core)@ (platinum shell) nanoparticle possessed unique catalytic properties and attracted special attention.…”