基于纳米功能材料的乳品安全和品质快速检测方法与仪器研究
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摘要
乳品,含有丰富的蛋白质、脂肪、乳糖、矿物质以及人体所需的各种维生素和氨基酸,被誉为“最为接近人类理想膳食的食物”。人均乳品消费量是衡量一个国家人民生活水平的主要指标之一,乳品产业已成为世界各国发展现代农业的重要组成部分。自改革开放以来,我国乳品产业呈现快速发展之势,现已成为世界上乳业生产增长最快的国家之一。然而其产品安全状况却不容乐观,尤其是近几年,国内乳品行业频繁爆发质量安全事件,使得乳品的安全问题日益严重。除了安全问题,乳品的品质也存在许多问题,如质量不过关、掺假、虚报营养成分等。乳品的安全与品质需要检测方法的评价。传统的乳品检测方法存在着较多不足,如操作复杂、检测对象有限、仪器昂贵等。
电化学传感技术由于其所需仪器简单、检测成本低、易于实现现场和在线检测等优点,在生物医学、环境监测、农产品和医药等领域具有广泛的应用前景。如何利用电化学传感技术快速、灵敏、准确检测农产品的有害有毒物质,是当前农产品安全领域中既新颖又极具吸引力的热门研究课题之一。但是传统电化学传感器存在着灵敏度低,响应速度慢以及稳定性差等缺点。近年来,纳米功能材料的出现为解决这些问题提供了新的思路。将纳米功能材料应用到电化学传感器件中,由于其独特的性质可提高传感器件的响应性能,已成为当前研究的热点。
本文将纳米技术与电化学传感技术相结合,探索用于乳品安全和品质的快速检测方法。以乳品中常见的有毒有害物质过氧化氢和重金属离子及营养成分抗坏血酸和钙离子作为研究对象,构建了基于纳米功能材料的新型电化学传感器件实现对上述几种对象的快速、灵敏、准确、方便检测。并在此基础上,搭建了基于纳米功能材料的便携式乳品快速检测仪。
主要研究内容、结果和结论如下：
(1)基于氧化铜纳米颗粒的电化学传感技术用于乳品中过氧化氢残留的快速检测
建立了一种基于纳米功能材料的过氧化氢快速检测方法。首先利用化学水相沉淀法制备了氧化铜纳米颗粒,然后将其用于修饰电化学传感器件。为了获得较好的稳定性和抗干扰能力,采用了碳离子液体电极作为基底工作电极,同时为了提高传感器件的重复可用性,本文首次采用了本体修饰法将氧化铜纳米颗粒掺杂在基底工作电极中。实验中,利用电流-时间曲线法测得的响应电流与溶液中过氧化氢浓度之间的线性正比关系,来检测过氧化氢含量。在最优检测条件下,该新型传感器件的分析性能如下：线性响应范围为1.0×10-6～2.5×10-3mol/L,线性回归方程为I(μA)=-0.0667+11.3333C(mM),线性相关系数为0.9990,灵敏度为392.99μA mM-1cm-2,检测下限为0.5×10-6mol/L。同时,该传感器件还具有较高的选择性、一致性、重现性和稳定性。灭菌乳和酸乳中过氧化氢的分析与检测：定性分析采用本文中所研究的新型电化学传感技术与酶催化方法联用,单个乳品样品的定性分析时间约为2min；定量检测采用标准加入法,单个乳品样品的定量检测时间约为20min,分析结果与国标方法(GB23499-2009)相一致,两者之间误差小于5.0%。结果表明,基于氧化铜纳米功能材料的新型电化学传感技术可以实现乳品中过氧化氢残留的快速定性识别和定量检测。
(2)基于氧化铋纳米颗粒的电化学传感技术用于乳品中重金属离子的快速检测
建立了一种基于纳米功能材料的重金属离子快速检测方法。本文首次制备了基于氧化铋纳米颗粒的电化学传感器件。该传感器件利用碳离子液体电极为基底工作电极,通过本体修饰法将氧化铋纳米颗粒掺杂在基底工作电极中。该电极可以在电极表面钝化或受到损伤时,通过简单的打磨处理后,即可继续使用,且重现性高。实验中,采用方波阳极溶出伏安法同时检测铅离子和镉离子。研究了实验参数对分析结果的影响,得出了重金属铅离子和镉离子检测的最佳参数：电极中氧化铋纳米颗粒的掺杂量为2%、醋酸缓冲液的pH值为4.5,沉积时间为180s,沉积电位为-1.2V。在最优条件下,该新型传感器件的分析性能如下：铅离子的线性响应范围为1.0～100.0μg/L,线性回归方程为I(μA)=-0.0083+0.3346C(μg/L),线性相关系数为0.9924,灵敏度为5.23μA(μg/L)-1cm-2,检测下限为0.21μg/L；镉离子的线性响应范围为1.0～100.0μg/L,线性回归方程为I(μA)=-0.0211+0.4037C(μg/L),线性相关系数为0.9927,灵敏度为5.92μA(μg/L)-1cm-2,检测下限为0.1μg/L。干扰实验表明当溶液中常见金属离子浓度200倍于铅离子和镉离子时,两种重金属离子的响应电流变化小于5%。同时该传感器件还具有较好的一致性、重现性和稳定性。全脂奶粉和婴幼儿奶粉中铅离子与镉离子的检测：利用方波阳极溶出伏安法中铅离子和镉离子的溶出峰电位对乳品样品进行定性分析,单个乳品样品的定性分析时间约为5min；定量检测采用标准加入法,单个乳品样品的定量检测时间约为30min,分析结果与国标方法(GB5009.12-2010和GB/T5009.15-2003)相一致。样品中铅离子加标平均回收率为100.8%,镉离子加标平均回收率为100.5%。结果表明,基于氧化铋纳米功能材料的新型电化学传感技术可以实现乳品中痕量重金属铅离子和镉离子的快速定性识别和定量检测。
(3)基于单壁碳纳米管的电化学传感技术用于乳品中抗坏血酸的快速检测
建立了一种基于纳米功能材料的抗坏血酸快速检测方法。本文首次制备了基于单壁碳纳米管和离子液体的电化学传感器件。该新型传感器件对抗坏血酸的氧化表现出较高的电催化活性,能在零电位处催化抗坏血酸的氧化。实验中发现利用差分脉冲伏安法检测抗坏血酸时,其氧化峰的电流值与抗坏血酸的浓度成线性正比关系。在最优条件下,该传感器件的分析性能如下：线性响应范围为3.0×10-6～4.2×10-3mol/L,线性回归方程为I(μA)=0.1603+20.1214C(mM),线性相关系数为0.9990,灵敏度为301.92μA mM-1cm-2,检测下限为1.0×10-6mol/L。同时该传感器件还具有较好的选择性、一致性、重现性和稳定性。采用标准加入法对婴幼儿奶粉和果奶中抗坏血酸的含量进行定量检测,分析结果与AOAC推荐的2,6-Dichloroindophenol商定法相一致,两者之间误差小于4.0%,单个样品的定量检测时间为20min。样品中抗坏血酸加标平均回收率为101.1%。结果表明,基于碳纳米管的新型电化学传感技术可以实现乳品中抗坏血酸的快速定量检测。
(4)基于石墨烯纳米材料的电化学传感技术用于乳品中矿物质元素钙的快速检测
建立了一种基于纳米功能材料的钙离子快速检测方法。本文首次制备了基于石墨烯纳米材料为固态接触层的固态接触型钙离子选择性电极。研究发现采用石墨烯纳米材料作为固态接触型离子选择性电极的固态接触层时,可以显著改进离子选择性电极的稳定性并缩短响应时间。该新型传感器件的分析性能如下：整个线性范围内响应时间(t95%)小于8s,线性响应范围为10-5.8～10-1.8mol/L,线性相关系数为0.9993,响应斜率为29.2mV/decade (±0.3mV/decade),检测下限为10-6mol/L；对五种金属离子(Mg2+、K+、Na+、Li+、NH4+)的选择性系数分别为-4.6,-2.2,-2.8,-2.5,-3.6。水层测试表明石墨烯层与钙离子敏感膜之间无水膜形成。同时研究了溶液中的溶解氧、二氧化碳、氧化还原物质等对传感器件的影响,结果表明上述干扰物质均不会对传感器件的检测带来影响。另外,该传感器件还表现出较高的电位稳定性,持续监测钙离子24h其电位偏移值约为13.7μV/h；较好的电位重现性,连续多次交替测量不同浓度的钙离子溶液时,其电位误差小于1.2%；室温保存三个月后其分析性能无明显变化。在检测灭菌乳和高钙奶中钙离子时,采用了两种方法即一点标定法和标准加入法,两者检测结果基本一致。同时与国标方法(GB5413.21-2010)相比,误差均在5.0%以内。样品中钙离子加标平均回收率为100.6%。结果表明,基于石墨烯纳米功能材料为固态接触层的新型固态接触型钙离子选择性电极可以实现乳品中矿物质元素钙的快速定量检测。
(5)搭建基于纳米功能材料的便携式乳品快速检测仪
探索了搭建基于纳米功能材料的便携式乳品快速检测仪的可行性。采用丝网印刷工艺研制了四种低成本、灵敏度高、一致性好的可抛弃传感器件,分别是基于电化学还原石墨烯纳米材料修饰的过氧化氢传感器件,基于氧化铋纳米颗粒掺杂的重金属离子传感器件,基于化学还原石墨烯纳米材料掺杂的抗坏血酸传感器件及基于电化学还原石墨烯纳米材料和钙离子选择性膜修饰的钙离子传感器件。研制的小型化检测仪可以实现十种电化学分析技术且能完成三种电极体系的电化学分析与检测。便携式乳品快速检测仪由可抛弃传感器件和小型化检测仪组成。该分析仪可以实现多通道同时检测多种分析物或分析多个样品,同时具有体积小便于携带,测量结果准确,精度高,检测速度快,可连续检测等特点。研究结果表明,基于纳米功能材料的便携式乳品快速检测仪可以实现乳品中有毒有害物质和营养成分的快速检测。
Dairy products have been known as the ideal diet food for human due to their rich proteins, fat, lactose, minerals, vitamins and amino acids, etc. The per capita consumption of dairy is one of the key indexes of people's living standards and the dairy industry has become an important part of the development of modern agriculture in the world. The development of dairy industry in China has followed a rapid increasing trend since the year1978. At present, China has become one of the countries with the fastest growth rate in dairy industry in the world. However, the quality of the dairy product is disappointing. The frequent outbreaks of safety incidents in the domestic dairy industry have intensified the dairy safety problems in recent years. In addition to the safety problems, there are also many problems about the quality of dairy products, like the poor quality, counterfeiting, false information about nutrients, and so on. The evaluation of the dairy safety and quality requires the detection methods. The traditional detection methods for the dairy products have some disadvantages including complex operating, limited detection objects, expensive and bulky instrument, and so on.
The electrochemical sensing technique has been widely used in the field of biomedicine, environmental monitoring, food and medicine due to the simple equipment, low cost, easy to realize on-site and capable of online testing. The study on electrochemical sensing technique for rapid, sensitive, and accurate detection of toxic and harmful substances in agricultural products is one of the novel and highly attractive research topics in the field of agricultural safety. However, the traditional electrochemical sensors have some drawbacks including low sensitivity, slow response and poor stability. In recent years, the emergence of nanofunctional materials provides a new approach to solve these problems. The research on using nanofunctional materials to improve the performance of the electrochemical sensors has been attracted extensive attention.
In this study, a novel and rapid detection method based on the combination of nanotechnology and electrochemical sensing technique for the safety and quality of dairy products was explored. The main detection objects are divided into two types, including toxic and harzerdous substances (hydrogen peroxide and heavy metal ions) and nutritional components (ascorbic acid and calcium ion). Several electrochemical sensors based on nanofunctional materials were constructed to detect the above species with high sensitivity and accuracy. Furthermore, a portable dairy rapid analyser based on nanofunctional material was constructed.
Main research contents, results and conclusions are as follows:
(1) Electrochemical sensing technique using copper oxide nanoparticle for the rapid detection of hydrogen peroxide residues in dairy products
A novel and rapid method using nanofunctional material for the detection of hydrogen peroxide was established. The copper oxide nanoparticle was synthesized using the chemical aqueous phase precipitation method and was further employed to modify the electrochemical sensor. In this study, in order to improve the stability and anti-interference ability, carbon ionic liquid electrode was employed as the substrate working electrode. Furthermore, we firstly incorporated the copper oxide nanoparticle into the substrate electrode in order to make the developed sensor be renewable. Results showed that there is a linear relationship between the response current obtained from the amperometric i-t curve and the concentration of hydrogen peroxide. Under the optimal detection conditions, the analytical performance of the electrochemical sensor are as follows:the linear response range is1.0×10-6-2.5×10-3mol/L, the linear regression equation is I(μA)=-0.0667+11.3333C (mM) with the linear correlation coefficient of0.9990, the sensitivity is392.99μA mM-1cm-2and the detection limit is0.5×10-6mol/L. Meanwhile, the developed sensor exhibited good selectivity, consistency, reproducibility and stability. Analysis and detection of hydrogen peroxide residues in sterilized milk and yoghurt:using the developed electrochemical analysis method with the enzymatic method for qualitative analysis and the assay time is about2min per milk sample; using standard addition method for quantitative detection and the detection time is about20min per milk sample. Results are consistent with the national standard method (GB23499-2009). The error between these two methods is less than5.0%. These results demonstrate that the novel electrochemical sensing technique using copper oxide nanofunctional material could be used for rapid qualitative analysis and quantitative detection of hydrogen peroxide residues in dairy products.
(2) Electrochemical sensing technique using bismuth oxide nanoparticle for the rapid detection of trace heavy metal ions in dairy products
A novel and rapid method using nanofunctional material for the detection of heavy metal ions was established. In this study, we firstly reported an electrochemical sensor based on bismuth oxide nanoparticle. The carbon ionic liquid electrode was used as the substrate electrode and the nanoparticle was doped in the electrode body using the bulk modification method. The electrode can be reused with high repeatability by a simple grinding treatment when the electrode surface is passivated or damaged. In this study, the determination of lead ion and cadmium ion was perfomed using the square-wave anodic stripping voltammetry. The optimal parameters for the detection of lead ion and cadmium ion are obtained as followed:the amount of bismuth oxide nanoparticle in the electrode body is2%, the pH of acetate buffer solution is4.5, deposition time is180s, and deposition potential is-1.2V. Under these optimal conditions, the analytical performance of the electrochemical sensor are as follows:the linear response range for lead ions is1.0～100.0μg/L, the linear regression equation is I(μA)=-0.0211+0.4037C (μg/L) with the linear correlation coefficient of0.9924, the sensitivity is5.92μA (μg/L)-1cm-2and the detection limit is0.21μg/L; the linear response range for cadmium ion is1.0～100.0μg/L, the linear regression equation is I(uA)=-0.0211+0.4037C (μg/L) with the linear correlation coefficient of0.9927, the sensitivity is5.92μA (μg/L)-1cm-2and the detection limit is0.15μg/L. Interference experiments showed that the other metal ions in the solution (concentration200times) exhibit no influence on the detection of lead ion and cadmium ion. Meanwhile, the electrochemical sensor exhibited good consistency, reproducibility and stability. Analysis and detection of lead ion and cadmium ion in whole milk powder and infant formula:using the peak potential of lead ion and cadmium ion obtained by square-wave anodic stripping voltammetry to qualitative analysis and the assay time is about5min per milk sample; quantitative detection using standard addition method and the detection time is about30min per milk sample, the results are consistent with the results obtained by the national strandard methods (GB5009.12-2010and GB/T5009.15-2003). Revovery test showed that the average recoveries are100.8%for lead ion and100.5%for cadmium ion. The above results indicate that the quick qualitative identification and quantitative determination of trace concentration of lead ion and cadmium ion in the dairy could be achieved in the developed electrochemical sensing technique based on bismuth oxide nanofunctional material.
(3) Electrochemical sensing technique using single-walled carbon nanotube for the rapid detection of ascorbic acid in dairy products
A novel and rapid method using nanofunctional material for the detection of ascorbic acid was established. In this study, we firstly reported a novel electrochemical sensor consisted of single-walled carbon nanotube and ionic liquid. This sensor showed a high electrocatalytic activity for the oxidation of ascorbic acid which could be used to detect ascorbic acid at the potential of0V. A linear relationship between the oxidation peak current obtained by the differential pulse voltammetry and ascorbic acid concentration could be founded. The analytical performance of the electrochemical sensor are as follows: the linear response range is3.0×10-6～4.2×10-3mol/L, the linear regression equation is I(uA)=0.1603+20.1214C (mM) with the linear correlation coefficient of0.9990, the sensitivity is301.92μA mM-1cm-2and the detection limit is1.0×10-6mol/L. Meanwhile, the developed sensor displayed good selectivity, consistency, reproducibility and stability. Standard addition method was employed for quantitative detection of ascorbic acid in infant formula and fruit milk. Sample test time is about15min per milk sample. The results are consistent with the results obtained by2,6-Dichloroindophenol as recommended by AOAC. These results suggest that the novel electrochemical sensing technique based on carbon nanotube could be used for rapid quantitative detection of ascorbic acid in dairy products.
(4) Electrochemical sensing technique using grapheme nanofunctional material for the rapid detection of mineral element calcium ion in dairy products
A novel and rapid method using nanofunctional material for the detection of calcium ion was explored. In this study, we firstly fabricated a solid-contact calcium ion-selective electrode using graphene nanomaterial as the solid-contact layer. Results showed that the graphene-based solid-contact layer in ion-selective electrode could remarkably improve the stability and shorten the response time. The analytical performance of the developed sensor are as follows:the response time (t95%) is less than8s in the whole linear range, the linear response range is10-58～10-1.8mol/L with the linear correlation coefficient of0.9993, the response slope is29.2mV/decade (±0.3mV/decade) and the detection limit is10-6mol/L. The selectivity coefficients are-4.6,-2.2,-2.8,-2.5, and-3.6for Mg2+, K+, Na+, Li+, and NH4+, respectively. Water layer test showed that no water film is formed between the graphene layer and the sensing membrane. The experiments about the interference from oxygen, carbon dioxide, and redox species demonstrated that the developed sensor is no sensitive to these species. The potential drift is about13.7μV/h in the24h continuous monitoring, indicating the excellent potential stability of the developed sensor. The potential error is less than1.2%when using the sensor to successively measure the solutions containing different concentrations of calcium ion. The storage stability of the sensor is three months. Two detection methods including one point calibration procedure and standard addition method were employed to determine calcium ion in sterilized milk and yogurt. Results obtained by these two methods are consistent. Furthermore, compared to the results obtained by the national standard method (GB5413.21-2010), the errors are less than5.0%. Recovery test showed that an average recovery is100.6%for eight additions. The above results demonstrate that the novel solid-contact calcium ion-selective electrode using graphene nanofunctional material as the solid-contact layer could be used to detect calcium ion in dairy products.
(5) Construction of portable dairy rapid analyser based on nanofunctional materials
The feasibility of the construction of portable dairy rapid analyser based on nanofunctional materials was investigated. Four types of disposable electrochemical sensors with low cost, high sensitivity and good consistency were developed using screen-printing technique, including hydrogen peroxide sensor using electrochemically reduced graphene nanomaterial, heavy metal ions sensor using bismuth oxide nanoparticle, ascorbic acid sensor using chemically reduced graphene nanomaterial, and calcium ion sensor using electrochemically reduced graphene nanomaterial and calcium ion-selective membrane. Ten types of electrochemical analytical techniques and three types of electrode system could be achieved on the developed miniaturizied analyser. The protable dairy rapid analyser was constructed by the disposable sensors and the miniaturizied analyser. This analyzer can achieve multi-channel simulataneous detection of various analytes or analysis of several samples. Futhermore, it is protable and possesses high accuracy, high precision, fast speed and continuous detection. Results show that the developed portable analyser could be used for the rapid detection of the toxic-harzerdous substances and nutritional components in dairy.
电化学传感技术由于其所需仪器简单、检测成本低、易于实现现场和在线检测等优点,在生物医学、环境监测、农产品和医药等领域具有广泛的应用前景。如何利用电化学传感技术快速、灵敏、准确检测农产品的有害有毒物质,是当前农产品安全领域中既新颖又极具吸引力的热门研究课题之一。但是传统电化学传感器存在着灵敏度低,响应速度慢以及稳定性差等缺点。近年来,纳米功能材料的出现为解决这些问题提供了新的思路。将纳米功能材料应用到电化学传感器件中,由于其独特的性质可提高传感器件的响应性能,已成为当前研究的热点。
本文将纳米技术与电化学传感技术相结合,探索用于乳品安全和品质的快速检测方法。以乳品中常见的有毒有害物质过氧化氢和重金属离子及营养成分抗坏血酸和钙离子作为研究对象,构建了基于纳米功能材料的新型电化学传感器件实现对上述几种对象的快速、灵敏、准确、方便检测。并在此基础上,搭建了基于纳米功能材料的便携式乳品快速检测仪。
主要研究内容、结果和结论如下：
(1)基于氧化铜纳米颗粒的电化学传感技术用于乳品中过氧化氢残留的快速检测
建立了一种基于纳米功能材料的过氧化氢快速检测方法。首先利用化学水相沉淀法制备了氧化铜纳米颗粒,然后将其用于修饰电化学传感器件。为了获得较好的稳定性和抗干扰能力,采用了碳离子液体电极作为基底工作电极,同时为了提高传感器件的重复可用性,本文首次采用了本体修饰法将氧化铜纳米颗粒掺杂在基底工作电极中。实验中,利用电流-时间曲线法测得的响应电流与溶液中过氧化氢浓度之间的线性正比关系,来检测过氧化氢含量。在最优检测条件下,该新型传感器件的分析性能如下：线性响应范围为1.0×10-6～2.5×10-3mol/L,线性回归方程为I(μA)=-0.0667+11.3333C(mM),线性相关系数为0.9990,灵敏度为392.99μA mM-1cm-2,检测下限为0.5×10-6mol/L。同时,该传感器件还具有较高的选择性、一致性、重现性和稳定性。灭菌乳和酸乳中过氧化氢的分析与检测：定性分析采用本文中所研究的新型电化学传感技术与酶催化方法联用,单个乳品样品的定性分析时间约为2min；定量检测采用标准加入法,单个乳品样品的定量检测时间约为20min,分析结果与国标方法(GB23499-2009)相一致,两者之间误差小于5.0%。结果表明,基于氧化铜纳米功能材料的新型电化学传感技术可以实现乳品中过氧化氢残留的快速定性识别和定量检测。
(2)基于氧化铋纳米颗粒的电化学传感技术用于乳品中重金属离子的快速检测
建立了一种基于纳米功能材料的重金属离子快速检测方法。本文首次制备了基于氧化铋纳米颗粒的电化学传感器件。该传感器件利用碳离子液体电极为基底工作电极,通过本体修饰法将氧化铋纳米颗粒掺杂在基底工作电极中。该电极可以在电极表面钝化或受到损伤时,通过简单的打磨处理后,即可继续使用,且重现性高。实验中,采用方波阳极溶出伏安法同时检测铅离子和镉离子。研究了实验参数对分析结果的影响,得出了重金属铅离子和镉离子检测的最佳参数：电极中氧化铋纳米颗粒的掺杂量为2%、醋酸缓冲液的pH值为4.5,沉积时间为180s,沉积电位为-1.2V。在最优条件下,该新型传感器件的分析性能如下：铅离子的线性响应范围为1.0～100.0μg/L,线性回归方程为I(μA)=-0.0083+0.3346C(μg/L),线性相关系数为0.9924,灵敏度为5.23μA(μg/L)-1cm-2,检测下限为0.21μg/L；镉离子的线性响应范围为1.0～100.0μg/L,线性回归方程为I(μA)=-0.0211+0.4037C(μg/L),线性相关系数为0.9927,灵敏度为5.92μA(μg/L)-1cm-2,检测下限为0.1μg/L。干扰实验表明当溶液中常见金属离子浓度200倍于铅离子和镉离子时,两种重金属离子的响应电流变化小于5%。同时该传感器件还具有较好的一致性、重现性和稳定性。全脂奶粉和婴幼儿奶粉中铅离子与镉离子的检测：利用方波阳极溶出伏安法中铅离子和镉离子的溶出峰电位对乳品样品进行定性分析,单个乳品样品的定性分析时间约为5min；定量检测采用标准加入法,单个乳品样品的定量检测时间约为30min,分析结果与国标方法(GB5009.12-2010和GB/T5009.15-2003)相一致。样品中铅离子加标平均回收率为100.8%,镉离子加标平均回收率为100.5%。结果表明,基于氧化铋纳米功能材料的新型电化学传感技术可以实现乳品中痕量重金属铅离子和镉离子的快速定性识别和定量检测。
(3)基于单壁碳纳米管的电化学传感技术用于乳品中抗坏血酸的快速检测
建立了一种基于纳米功能材料的抗坏血酸快速检测方法。本文首次制备了基于单壁碳纳米管和离子液体的电化学传感器件。该新型传感器件对抗坏血酸的氧化表现出较高的电催化活性,能在零电位处催化抗坏血酸的氧化。实验中发现利用差分脉冲伏安法检测抗坏血酸时,其氧化峰的电流值与抗坏血酸的浓度成线性正比关系。在最优条件下,该传感器件的分析性能如下：线性响应范围为3.0×10-6～4.2×10-3mol/L,线性回归方程为I(μA)=0.1603+20.1214C(mM),线性相关系数为0.9990,灵敏度为301.92μA mM-1cm-2,检测下限为1.0×10-6mol/L。同时该传感器件还具有较好的选择性、一致性、重现性和稳定性。采用标准加入法对婴幼儿奶粉和果奶中抗坏血酸的含量进行定量检测,分析结果与AOAC推荐的2,6-Dichloroindophenol商定法相一致,两者之间误差小于4.0%,单个样品的定量检测时间为20min。样品中抗坏血酸加标平均回收率为101.1%。结果表明,基于碳纳米管的新型电化学传感技术可以实现乳品中抗坏血酸的快速定量检测。
(4)基于石墨烯纳米材料的电化学传感技术用于乳品中矿物质元素钙的快速检测
建立了一种基于纳米功能材料的钙离子快速检测方法。本文首次制备了基于石墨烯纳米材料为固态接触层的固态接触型钙离子选择性电极。研究发现采用石墨烯纳米材料作为固态接触型离子选择性电极的固态接触层时,可以显著改进离子选择性电极的稳定性并缩短响应时间。该新型传感器件的分析性能如下：整个线性范围内响应时间(t95%)小于8s,线性响应范围为10-5.8～10-1.8mol/L,线性相关系数为0.9993,响应斜率为29.2mV/decade (±0.3mV/decade),检测下限为10-6mol/L；对五种金属离子(Mg2+、K+、Na+、Li+、NH4+)的选择性系数分别为-4.6,-2.2,-2.8,-2.5,-3.6。水层测试表明石墨烯层与钙离子敏感膜之间无水膜形成。同时研究了溶液中的溶解氧、二氧化碳、氧化还原物质等对传感器件的影响,结果表明上述干扰物质均不会对传感器件的检测带来影响。另外,该传感器件还表现出较高的电位稳定性,持续监测钙离子24h其电位偏移值约为13.7μV/h；较好的电位重现性,连续多次交替测量不同浓度的钙离子溶液时,其电位误差小于1.2%；室温保存三个月后其分析性能无明显变化。在检测灭菌乳和高钙奶中钙离子时,采用了两种方法即一点标定法和标准加入法,两者检测结果基本一致。同时与国标方法(GB5413.21-2010)相比,误差均在5.0%以内。样品中钙离子加标平均回收率为100.6%。结果表明,基于石墨烯纳米功能材料为固态接触层的新型固态接触型钙离子选择性电极可以实现乳品中矿物质元素钙的快速定量检测。
(5)搭建基于纳米功能材料的便携式乳品快速检测仪
探索了搭建基于纳米功能材料的便携式乳品快速检测仪的可行性。采用丝网印刷工艺研制了四种低成本、灵敏度高、一致性好的可抛弃传感器件,分别是基于电化学还原石墨烯纳米材料修饰的过氧化氢传感器件,基于氧化铋纳米颗粒掺杂的重金属离子传感器件,基于化学还原石墨烯纳米材料掺杂的抗坏血酸传感器件及基于电化学还原石墨烯纳米材料和钙离子选择性膜修饰的钙离子传感器件。研制的小型化检测仪可以实现十种电化学分析技术且能完成三种电极体系的电化学分析与检测。便携式乳品快速检测仪由可抛弃传感器件和小型化检测仪组成。该分析仪可以实现多通道同时检测多种分析物或分析多个样品,同时具有体积小便于携带,测量结果准确,精度高,检测速度快,可连续检测等特点。研究结果表明,基于纳米功能材料的便携式乳品快速检测仪可以实现乳品中有毒有害物质和营养成分的快速检测。
Dairy products have been known as the ideal diet food for human due to their rich proteins, fat, lactose, minerals, vitamins and amino acids, etc. The per capita consumption of dairy is one of the key indexes of people's living standards and the dairy industry has become an important part of the development of modern agriculture in the world. The development of dairy industry in China has followed a rapid increasing trend since the year1978. At present, China has become one of the countries with the fastest growth rate in dairy industry in the world. However, the quality of the dairy product is disappointing. The frequent outbreaks of safety incidents in the domestic dairy industry have intensified the dairy safety problems in recent years. In addition to the safety problems, there are also many problems about the quality of dairy products, like the poor quality, counterfeiting, false information about nutrients, and so on. The evaluation of the dairy safety and quality requires the detection methods. The traditional detection methods for the dairy products have some disadvantages including complex operating, limited detection objects, expensive and bulky instrument, and so on.
The electrochemical sensing technique has been widely used in the field of biomedicine, environmental monitoring, food and medicine due to the simple equipment, low cost, easy to realize on-site and capable of online testing. The study on electrochemical sensing technique for rapid, sensitive, and accurate detection of toxic and harmful substances in agricultural products is one of the novel and highly attractive research topics in the field of agricultural safety. However, the traditional electrochemical sensors have some drawbacks including low sensitivity, slow response and poor stability. In recent years, the emergence of nanofunctional materials provides a new approach to solve these problems. The research on using nanofunctional materials to improve the performance of the electrochemical sensors has been attracted extensive attention.
In this study, a novel and rapid detection method based on the combination of nanotechnology and electrochemical sensing technique for the safety and quality of dairy products was explored. The main detection objects are divided into two types, including toxic and harzerdous substances (hydrogen peroxide and heavy metal ions) and nutritional components (ascorbic acid and calcium ion). Several electrochemical sensors based on nanofunctional materials were constructed to detect the above species with high sensitivity and accuracy. Furthermore, a portable dairy rapid analyser based on nanofunctional material was constructed.
Main research contents, results and conclusions are as follows:
(1) Electrochemical sensing technique using copper oxide nanoparticle for the rapid detection of hydrogen peroxide residues in dairy products
A novel and rapid method using nanofunctional material for the detection of hydrogen peroxide was established. The copper oxide nanoparticle was synthesized using the chemical aqueous phase precipitation method and was further employed to modify the electrochemical sensor. In this study, in order to improve the stability and anti-interference ability, carbon ionic liquid electrode was employed as the substrate working electrode. Furthermore, we firstly incorporated the copper oxide nanoparticle into the substrate electrode in order to make the developed sensor be renewable. Results showed that there is a linear relationship between the response current obtained from the amperometric i-t curve and the concentration of hydrogen peroxide. Under the optimal detection conditions, the analytical performance of the electrochemical sensor are as follows:the linear response range is1.0×10-6-2.5×10-3mol/L, the linear regression equation is I(μA)=-0.0667+11.3333C (mM) with the linear correlation coefficient of0.9990, the sensitivity is392.99μA mM-1cm-2and the detection limit is0.5×10-6mol/L. Meanwhile, the developed sensor exhibited good selectivity, consistency, reproducibility and stability. Analysis and detection of hydrogen peroxide residues in sterilized milk and yoghurt:using the developed electrochemical analysis method with the enzymatic method for qualitative analysis and the assay time is about2min per milk sample; using standard addition method for quantitative detection and the detection time is about20min per milk sample. Results are consistent with the national standard method (GB23499-2009). The error between these two methods is less than5.0%. These results demonstrate that the novel electrochemical sensing technique using copper oxide nanofunctional material could be used for rapid qualitative analysis and quantitative detection of hydrogen peroxide residues in dairy products.
(2) Electrochemical sensing technique using bismuth oxide nanoparticle for the rapid detection of trace heavy metal ions in dairy products
A novel and rapid method using nanofunctional material for the detection of heavy metal ions was established. In this study, we firstly reported an electrochemical sensor based on bismuth oxide nanoparticle. The carbon ionic liquid electrode was used as the substrate electrode and the nanoparticle was doped in the electrode body using the bulk modification method. The electrode can be reused with high repeatability by a simple grinding treatment when the electrode surface is passivated or damaged. In this study, the determination of lead ion and cadmium ion was perfomed using the square-wave anodic stripping voltammetry. The optimal parameters for the detection of lead ion and cadmium ion are obtained as followed:the amount of bismuth oxide nanoparticle in the electrode body is2%, the pH of acetate buffer solution is4.5, deposition time is180s, and deposition potential is-1.2V. Under these optimal conditions, the analytical performance of the electrochemical sensor are as follows:the linear response range for lead ions is1.0～100.0μg/L, the linear regression equation is I(μA)=-0.0211+0.4037C (μg/L) with the linear correlation coefficient of0.9924, the sensitivity is5.92μA (μg/L)-1cm-2and the detection limit is0.21μg/L; the linear response range for cadmium ion is1.0～100.0μg/L, the linear regression equation is I(uA)=-0.0211+0.4037C (μg/L) with the linear correlation coefficient of0.9927, the sensitivity is5.92μA (μg/L)-1cm-2and the detection limit is0.15μg/L. Interference experiments showed that the other metal ions in the solution (concentration200times) exhibit no influence on the detection of lead ion and cadmium ion. Meanwhile, the electrochemical sensor exhibited good consistency, reproducibility and stability. Analysis and detection of lead ion and cadmium ion in whole milk powder and infant formula:using the peak potential of lead ion and cadmium ion obtained by square-wave anodic stripping voltammetry to qualitative analysis and the assay time is about5min per milk sample; quantitative detection using standard addition method and the detection time is about30min per milk sample, the results are consistent with the results obtained by the national strandard methods (GB5009.12-2010and GB/T5009.15-2003). Revovery test showed that the average recoveries are100.8%for lead ion and100.5%for cadmium ion. The above results indicate that the quick qualitative identification and quantitative determination of trace concentration of lead ion and cadmium ion in the dairy could be achieved in the developed electrochemical sensing technique based on bismuth oxide nanofunctional material.
(3) Electrochemical sensing technique using single-walled carbon nanotube for the rapid detection of ascorbic acid in dairy products
A novel and rapid method using nanofunctional material for the detection of ascorbic acid was established. In this study, we firstly reported a novel electrochemical sensor consisted of single-walled carbon nanotube and ionic liquid. This sensor showed a high electrocatalytic activity for the oxidation of ascorbic acid which could be used to detect ascorbic acid at the potential of0V. A linear relationship between the oxidation peak current obtained by the differential pulse voltammetry and ascorbic acid concentration could be founded. The analytical performance of the electrochemical sensor are as follows: the linear response range is3.0×10-6～4.2×10-3mol/L, the linear regression equation is I(uA)=0.1603+20.1214C (mM) with the linear correlation coefficient of0.9990, the sensitivity is301.92μA mM-1cm-2and the detection limit is1.0×10-6mol/L. Meanwhile, the developed sensor displayed good selectivity, consistency, reproducibility and stability. Standard addition method was employed for quantitative detection of ascorbic acid in infant formula and fruit milk. Sample test time is about15min per milk sample. The results are consistent with the results obtained by2,6-Dichloroindophenol as recommended by AOAC. These results suggest that the novel electrochemical sensing technique based on carbon nanotube could be used for rapid quantitative detection of ascorbic acid in dairy products.
(4) Electrochemical sensing technique using grapheme nanofunctional material for the rapid detection of mineral element calcium ion in dairy products
A novel and rapid method using nanofunctional material for the detection of calcium ion was explored. In this study, we firstly fabricated a solid-contact calcium ion-selective electrode using graphene nanomaterial as the solid-contact layer. Results showed that the graphene-based solid-contact layer in ion-selective electrode could remarkably improve the stability and shorten the response time. The analytical performance of the developed sensor are as follows:the response time (t95%) is less than8s in the whole linear range, the linear response range is10-58～10-1.8mol/L with the linear correlation coefficient of0.9993, the response slope is29.2mV/decade (±0.3mV/decade) and the detection limit is10-6mol/L. The selectivity coefficients are-4.6,-2.2,-2.8,-2.5, and-3.6for Mg2+, K+, Na+, Li+, and NH4+, respectively. Water layer test showed that no water film is formed between the graphene layer and the sensing membrane. The experiments about the interference from oxygen, carbon dioxide, and redox species demonstrated that the developed sensor is no sensitive to these species. The potential drift is about13.7μV/h in the24h continuous monitoring, indicating the excellent potential stability of the developed sensor. The potential error is less than1.2%when using the sensor to successively measure the solutions containing different concentrations of calcium ion. The storage stability of the sensor is three months. Two detection methods including one point calibration procedure and standard addition method were employed to determine calcium ion in sterilized milk and yogurt. Results obtained by these two methods are consistent. Furthermore, compared to the results obtained by the national standard method (GB5413.21-2010), the errors are less than5.0%. Recovery test showed that an average recovery is100.6%for eight additions. The above results demonstrate that the novel solid-contact calcium ion-selective electrode using graphene nanofunctional material as the solid-contact layer could be used to detect calcium ion in dairy products.
(5) Construction of portable dairy rapid analyser based on nanofunctional materials
The feasibility of the construction of portable dairy rapid analyser based on nanofunctional materials was investigated. Four types of disposable electrochemical sensors with low cost, high sensitivity and good consistency were developed using screen-printing technique, including hydrogen peroxide sensor using electrochemically reduced graphene nanomaterial, heavy metal ions sensor using bismuth oxide nanoparticle, ascorbic acid sensor using chemically reduced graphene nanomaterial, and calcium ion sensor using electrochemically reduced graphene nanomaterial and calcium ion-selective membrane. Ten types of electrochemical analytical techniques and three types of electrode system could be achieved on the developed miniaturizied analyser. The protable dairy rapid analyser was constructed by the disposable sensors and the miniaturizied analyser. This analyzer can achieve multi-channel simulataneous detection of various analytes or analysis of several samples. Futhermore, it is protable and possesses high accuracy, high precision, fast speed and continuous detection. Results show that the developed portable analyser could be used for the rapid detection of the toxic-harzerdous substances and nutritional components in dairy.
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