CN108844904A - 一种基于多齿氮杂环三氮唑-偶氮生色团比率比色检测痕量Cu2+的方法 - Google Patents
一种基于多齿氮杂环三氮唑-偶氮生色团比率比色检测痕量Cu2+的方法 Download PDFInfo
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Abstract
本发明涉及一种基于多齿氮杂环三氮唑‑偶氮生色团比率比色检测痕量Cu2+的方法，包括：多齿配体显色剂3,5‑二‑2’,4’,6’‑三羟基苯基偶氮三氮唑的制备及其对环境水样中痕量Cu2+的检测；向10mL的容量瓶依次加入浓度为4.0×10–5mol/L目标染料标准溶液1.0mL、无水乙醇2.0mL,pH值值为7.0的混合磷酸盐缓冲溶液1.0mL及待测铜样品1.0mL，定容，摇匀，空白试剂(未加待测样品)作参比，1cm比色皿，测量300～800nm范围内的吸收光谱，根据600nm和396nm处吸光度比值(A600/A396)计算待测样品中痕量Cu2+的含量。本方法具有操作简单，响应速度快，分区间线性范围宽，背景吸收干扰小等，可快速、准确地用于水环境痕量Cu2+的即时检测。
Description
技术领域
本发明属于环境中痕量Cu2+比率比色传感领域，特别涉及一种基于多齿氮杂环三氮唑-偶氮生色团比率比色检测痕量Cu2+的方法。
背景技术
随着现代工业、农业和矿产业的高速发展，大量富含铜(Cu2+)等重金属离子废水的恣意排放，致使水、土壤和食品等资源不同程度污染，对人类健康和生存构成了重大威胁，已成为经济和社会可持续发展的重大障碍。
尽管人们已设计制备了分析检测铜离子不同的有效方法，如X-射线衍射法、荧光光谱法、化学发光法、原子吸收光谱法和电化学方法等，虽然可以对目标待测物进行定性和定量分析，灵敏度高，但也需要昂贵的仪器和较长的分析周期，难以满足对环境重金属污染进行快速、即时检测的需求。比色-分析法，因其过程简单、操作简便、检测效率更高、甚至可以裸眼观察等直接进行现场监测等优点，成为替代昂贵仪器分析的首选，引起了越来越多科学工作者的重视并投入研究；其中，有机生色团因结构易于设计、光学性能可控、加工简单等优点，备受关注。
为了进一步提高水相中Cu2+比色检测的选择性、稳定性和灵敏度，降低分析检测误差，本发明拟构筑一种多齿配体显色剂3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑，旨在通过多齿N、O等配位原子增强对重金属Cu2+的配位能力、利用空间尺寸效应提高配位的选择性以及双波长比率比色响应降低分析检测的背景干扰及系统误差等等，探讨它们在比色传感、富集与分离环境重金属Cu2+离子等方面的应用，实现对水样中的重金属Cu2+快速有效地裸眼检测，操作简单、便捷。
发明内容
本发明所要解决的技术问题是提供一种基于多齿氮杂环三氮唑-偶氮生色团比率比色检测痕量Cu2+的方法，该方法具有操作简单，选择性好，系统误差小等优点，可准确的用于环境水样品中痕量Cu2+的裸眼、即时分析检测。
本发明的一种基于多齿氮杂环三氮唑-偶氮生色团比率比色检测痕量Cu2+的方法，主要内容包括：
(1)多齿显色剂3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑的制备
分别称(量)取0.01g(1.01×10–4mol)3,5-二氨基三氮唑于50mL圆底烧瓶中，加入1.0mL水和0.5mL乙醇混合物使其完全溶解，用浓盐酸调节pH值1～2，在冰水浴恒温0～5℃条件下，缓慢滴加0.3mL含有0.0146g(2.12×10–4mol)的NaNO2水溶液，恒温反应30min后,加入0.006g(0.1mol)尿素除去过量的NaNO2；再向反应体系中缓慢滴加入0.02534g(2.02×10–4mol)间苯三酚，并控制pH值为8.0；室温下继续反应2h，抽滤，得粗产物，再经碱性水溶液溶解、酸性条件下结晶的方法制得橙黄色固体；所述步骤(1)中的水溶性显色剂3-羟基-4-(N-乙基-N-羟乙基苯基偶氮)萘磺酸染料系通过偶氮基团和氢键的双重作用，将生色团苯胺和萘基团偶联起来，不仅具有刚性平面结构，还具有很高的稳定性。
(2)多齿3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑标准溶液的配制
称取上述橙黄色固体0.0015g，溶于100mL N,N-二甲基甲酰胺(DMF)中，配制成浓度为4.0×10–5mol·L–1多齿3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑标准溶液，在4℃下避光保存，使用时稀释到所需浓度；
(3)Cu2+标准溶液的配制
称取CuSO4·5H2O晶体0.025g，溶于100mL双重蒸馏水中，配置成浓度为1.0mmol L–1的Cu2+标准溶液，在4℃下保存，使用时稀释到所需浓度；
(4)环境水样的制备
随机量取三处环境的水各1000.0mL，分别依次用孔径为4μm的微孔过滤膜过滤除去悬浮固体，再经氮吹浓缩法浓缩到10.0mL，制得不同的环境水样，分别标记为水样1，水样2和水样3，室温下保存，备用；
(5)果汁或蔬菜汁的制备
称取100.0g新鲜水果或蔬菜，用自来水洗净、晾干后，切成0.5厘米大小的方块后，用商业榨汁机榨汁后，将所得的汁液用2,000转速的离心机离心20min，收集上清液，在4℃下保存，备用；
(6)样品中Cu2+浓度的测定
向10mL的容量瓶依次加入2.0mL无水乙醇、1.0mL浓度为4.0×10–5mol/L的多齿3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑标准溶液、1.0mL pH值为7.0的混合磷酸盐缓冲溶液和1.0mL待测样品，加双重蒸馏水定容至刻度线，摇匀，空白试剂作参比，测量300～800nm范围内的吸收光谱，根据600nm和396nm处吸光度比值(A600/A396)计算待测样品中痕量Cu2+的含量。
所述步骤(1)中的多齿配体显色剂3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑系通过偶氮双键将多齿功能基团三氮唑及均三苯酚偶联起来，不仅共轭强度大，配位能力也大大提高。
所述步骤(1)中的多齿配体显色剂3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑是在冰水浴(0～5℃)、pH值8.0条件下，以均三苯酚、3,5-二氨基三氮唑和亚硝酸钠为原料，搅拌反应2h制得。
所述步骤(1)中的多齿配体显色剂3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑是通过调控溶剂的酸碱性重结晶提纯的。
本发明从反应原理入手，讨论了体系的溶剂效应、pH值值、离子强度、反应时间及共存物质的干扰等影响因素，确定了最佳测试条件：指示剂浓度为4.0×10-5mol/L，pH值值为7.0条件下即时检测Cu2+的灵敏度最高。
最佳测试条件下，所述步骤(1)中的多齿配体显色剂3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑在600nm和396nm处吸光度比值(A600/A396)对Cu2+的浓度有良好的线性关系。能有效排除其他常见共存离子对Cu2+比色检测的干扰。即：当铜离子浓度为4.0～120×10– 7mol/L时，比率检测Cu2+线性回归方程为A600/A396＝0.1081+0.0024cCu 2+，相关系数(R2)为0.9981，检测限为3.7×10–9mol/L,；当铜离子浓度为120.0～320×10–7mol/L时，比率检测Cu2+线性回归方程为A600/A396＝0.3736+0.000261cCu 2+，相关系数(R2)为0.99787；样品中Cu2+回收率95.6％～106.7％之间，相对误差(RSD)小于4.3％。
有益效果
本发明可在中性pH值条件下对水环境中痕量Cu2+即时比色检测，多齿显色剂不仅水溶解性好、吸光系数大，多齿N、O等配位原子与金属离子五元环配位、稳定性高、选择性好，对痕量Cu2+比色检测的灵敏度高；同时该方法在600nm和396nm处吸光度比值(A600/A396)响应降低分析检测的背景干扰及系统误差，对有机体无伤害，有望用于生物免疫分析、检测等领域。
附图说明
图1为多齿配体显色剂3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑合成路线
图2为多齿配体显色剂3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑与Cu2+作用机理及作用前后电子云和能级的变化；
图3为不同溶剂对比色即时检测痕量Cu2+体系吸收光谱的影响
图4为pH值对比色即时检测痕量Cu2+体系吸收光谱的影响
图5为不同的共存离子对比色即时检测痕量Cu2+的选择性
图6a)为体系紫外光谱随Cu2+浓度变化的滴定曲线(From up to down:0,4,6,12,16,24,32,40,56,72,88,112,136,168,200,240,280,320×10-7mol·L-1)；b)体系的比吸光度(A600/A396)与Cu2+浓度在不同区间内的线性关系曲线。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
(1)多齿显色剂3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑的制备
如附图1所示，分别称(量)取0.01g(1.01×10–4mol)3,5-二氨基三氮唑于50mL圆底烧瓶中，加入1.0mL水和0.5mL乙醇混合物使其完全溶解，用浓盐酸调节pH值1～2，在冰水浴恒温0～5℃条件下，缓慢滴加0.3mL含有0.0146g(2.12×10–4mol)的NaNO2水溶液，恒温反应30min后,加入0.006g(0.1mol)尿素除去过量的NaNO2；再向反应体系中缓慢滴加入0.02534g(2.02×10–4mol)间苯三酚，并控制pH值为8.0；室温下继续反应2h，抽滤，得粗产物，再经碱性水溶液溶解、酸性条件下结晶的方法制得橙黄色固体，产率85.1％。
1H NMR(400MHz,DMSO-d6)δ:12.8(1H,s,N-H),6.72(4H,s,Ar-H),5.04(6H,s,O-H).13C NMR(400MHz,DMSO-d6)δ:94.8,97.5,152.9,160.3,162.4.MS(ESI),m/z:274.3[M+H]+.元素分析理论值(％)：C 45.05,H 2.97,N 26.27,O 25.72；实测值：C 45.39,H 3.15,N26.01,O 25.45。
(2)多齿3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑标准溶液的配制
称取上述橙黄色固体0.0015g，溶于100mL N,N-二甲基甲酰胺(DMF)中，配制成浓度为4.0×10–5mol·L–1多齿3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑标准溶液，在4℃下避光保存，使用时稀释到所需浓度；
(3)Cu2+标准溶液的配制
称取CuSO4·5H2O晶体0.025g，溶于100mL双重蒸馏水中，配置成浓度为1.0mmol L–1的Cu2+标准溶液，在4℃下保存，使用时稀释到所需浓度；
(4)环境水样的制备
随机量取三处环境的水各1000.0mL，分别依次用孔径为4μm的微孔过滤膜过滤除去悬浮固体，再经氮吹浓缩法浓缩到10.0mL，制得不同的环境水样，分别标记为水样1，水样2和水样3，室温下保存，备用；
(5)果汁或蔬菜汁的制备
称取100.0g新鲜水果或蔬菜，用自来水洗净、晾干后，切成0.5-厘米大小的方块后，用商业榨汁机榨汁后，将所得的汁液用2,000转速的离心机离心20min，收集上清液，在4℃下保存，备用；
(6)检测条件的优化
依据多齿比色传感材料对Cu2+作用机理(见附图2)，分别研究了溶剂效应(见附图3)、pH值效应(见附图4)、及常见共存金属离子(见附图5)等对传感性能的影响，确定了最佳测试条件：指示剂浓度为4.0×10–5mol/L，pH值为7.0条件下即时检测Cu2+的灵敏度最高，其它常见共存金属离子对检测的影响均在误差范围内，优化结果见附图6所示。即最佳测试条件下，体系的比吸光度(A600/A396)与Cu2+浓度在分区间内呈现出良好的线性关系，即：当铜离子浓度为4.0～120×10–7mol/L时，比率检测Cu2+线性回归方程为A600/A396＝0.1081+0.0024cCu 2+，相关系数(R2)为0.9981，检测限3.7×10–9mol/L；当铜离子浓度为120.0～320×10–7mol/L时，比率检测Cu2+线性回归方程为A600/A396＝0.3736+0.000261cCu 2+，相关系数(R2)为0.99787；样品中Cu2+回收率95.6％～106.7％之间，相对误差(RSD)小于4.3％。
(7)样品中Cu2+浓度的测定
向10mL的容量瓶依次加入2.0mL无水乙醇、1.0mL浓度为4.0×10–5mol/L的多齿3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑标准溶液、1.0mL pH值为7.0的混合磷酸盐缓冲溶液和1.0mL待测样品，加双重蒸馏水定容至刻度线，摇匀，空白试剂作参比，测量300～800nm范围内的吸收光谱，根据600nm和396nm处吸光度比值(A600/A396)计算待测样品中痕量Cu2+的含量。
该方法成功的用于对上述两类环境水样品及2类蔬菜水果样品中Cu2+含量的检测，结果见表1。样品中Cu2+回收率95.6％～106.7％之间，相对误差(RSD)小于4.3％。
表1体系对环境样品的检测结果(n＝5)a
a.PB,pH值7.0,cPTAT＝4.0×10–6mol/L
b.The real values are the table values×10-2nmol·L-1for the detectedwater samples were concentrated 100times.
Claims (5)
1.一种基于多齿氮杂环三氮唑-偶氮生色团比率比色检测痕量Cu2+的方法，包括：
(1)多齿显色剂3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑的制备
分别称(量)取0.01g(1.01×10–4mol)3,5-二氨基三氮唑于50mL圆底烧瓶中，加入1.0mL水和0.5mL乙醇混合物使其完全溶解，用浓盐酸调节pH值1～2，在冰水浴恒温0～5℃条件下，缓慢滴加0.3mL含有0.0146g(2.12×10–4mol)的NaNO2水溶液，恒温反应30min后,加入0.006g(0.1mol)尿素除去过量的NaNO2；再向反应体系中缓慢滴加入0.02534g(2.02×10– 4mol)间苯三酚，并控制pH值为8.0；室温下继续反应2h，抽滤，得粗产物，再经碱性水溶液溶解、酸性条件下结晶的方法制得橙黄色固体；
(2)多齿3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑标准溶液的配制
称取上述橙黄色固体0.0015g，溶于100mL N,N-二甲基甲酰胺(DMF)中，配制成浓度为4.0×10–5mol·L–1多齿3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑标准溶液，在4℃下避光保存，使用时稀释到所需浓度；
(3)Cu2+标准溶液的配制
称取CuSO4·5H2O晶体0.025g，溶于100mL双重蒸馏水中，配置成浓度为1.0mmol L–1的Cu2+标准溶液，在4℃下保存，使用时稀释到所需浓度；
(4)环境水样的制备
随机量取三处环境的水各1000.0mL，分别依次用孔径为4μm的微孔过滤膜过滤除去悬浮固体，再经氮吹浓缩法浓缩到10.0mL，制得不同的环境水样，分别标记为水样1，水样2和水样3，室温下保存，备用；
(5)果汁或蔬菜汁的制备
称取100.0g新鲜水果或蔬菜，用自来水洗净、晾干后，切成0.5厘米大小的方块后，用商业榨汁机榨汁后，将所得的汁液用2,000转速的离心机离心20min，收集上清液，在4℃下保存，备用；
(6)样品中Cu2+浓度的测定
向10mL的容量瓶依次加入2.0mL无水乙醇、1.0mL浓度为4.0×10–5mol/L的多齿3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑标准溶液、1.0mL pH值为7.0的混合磷酸盐缓冲溶液和1.0mL待测样品，加双重蒸馏水定容至刻度线，摇匀，空白试剂作参比，测量300～800nm范围内的吸收光谱，根据600nm和396nm处吸光度比值(A600/A396)计算待测样品中痕量Cu2+的含量。
2.根据权利要求1所述的一种基于多齿氮杂环三氮唑-偶氮生色团比率比色检测痕量Cu2+的方法，其特征在于：所述步骤(1)中的多齿配体显色剂3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑系通过偶氮双键将多齿功能基团三氮唑及均三苯酚偶联起来。
3.根据权利要求1所述的一种基于多齿氮杂环三氮唑-偶氮生色团比率比色检测痕量Cu2+的方法，其特征在于：所述步骤(1)中的多齿配体显色剂3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑是在冰水浴(0～5℃)、pH值8.0条件下，以均三苯酚、3,5-二氨基三氮唑和亚硝酸钠为原料，搅拌反应2h制得。
4.根据权利要求1所述的一种基于多齿氮杂环三氮唑-偶氮生色团比率比色检测痕量Cu2+的方法，其特征在于：所述步骤(1)中的多齿配体显色剂3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑通过调控溶剂的酸碱性重结晶提纯。
5.根据权利要求1所述的一种基于多齿氮杂环三氮唑-偶氮生色团比率比色检测痕量Cu2+的方法，其特征在于：所述步骤(1)中的多齿配体显色剂3,5-二-2’,4’,6’-三羟基苯基偶氮三氮唑在600nm和396nm处吸光度比值(A600/A396)对Cu2+的浓度分区间线性范围宽。
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