CN106885779A - 一种含偶氮生色团多齿配体的合成及其比色法同时检测痕量Ag+和Fe3+的方法 - Google Patents
一种含偶氮生色团多齿配体的合成及其比色法同时检测痕量Ag+和Fe3+的方法 Download PDFInfo
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Abstract
本发明公开了一种含偶氮生色团多齿配体的合成及其比色法同时检测痕量Ag+和Fe3+的方法，包括：多齿配体显色剂3,6‑二氨基‑(N‑乙基‑N‑羟乙基苯基偶氮)吖啶染料的制备及其对水样中Ag+和Fe3+的同时比色检测；向10mL的容量瓶依次加入浓度为8.0×10–5mol/L多齿比色染料标准溶液1.0mL、pH值为6.0的混合磷酸盐缓冲溶液1.0mL和待测样品1.0mL，定容，摇匀，以未加待测样品的空白试样为参比，1cm比色皿，测量对应溶液的吸收光谱，计算得待测样品中Fe3+的含量；本发明具有操作简单，可快速、准确地用于水环境样品中痕量Ag+和Fe3+的同时定量测定。
Description
技术领域
本发明涉及水环境中痕量Ag+和Fe3+的同时比色检测领域，具体是一种含偶氮生色团多齿配体的合成及其比色法同时检测痕量Ag+和Fe3+方法。
背景技术
银是一种重要的过渡金属化学元素，在自然界中很少量以游离态单质存在，主要以含银化合物矿石存在。银的化学性质稳定，活跃性低，价格贵，导热、导电性能很好，主要应用于：电子电器是用银量最大的行业，其使用分为电接触材料、复合材料和焊接材料；卤化银感光材料，如摄影胶卷、相纸、X-光胶片、荧光信息记录片、电子显微镜照相软片和印刷胶片等；化工原料，如广泛用于氧化还原和聚合反应，用于处理含硫化物的工业废气等及电子电镀工业制剂，如银浆、氰化银钾等。但过量的银的离子以及化合物对某些细菌、病毒、藻类以及真菌显现出毒性，银的这种杀菌效应使得它在活体外就能够将生物杀死。铁是地壳含量最丰富的金属元素之一，也是生物体主要的组成元素。Fe3+与免疫的关系也比较密切，在提高机体的免疫力、增加中性白细胞和吞噬细胞的吞噬功能、和增强机体的抗感染能力的同时，铁离子缺少常会导致营养性贫血，表现为睡中惊醒、睡中腿抽筋而醒、精神萎靡、厌食、挑食、生长发育迟缓、经常头晕、膝盖疼、抽筋、失眠、感冒、发烧、咳嗽、腹泻、注意力不集中、理解力、记忆力差、学习成绩差，都是缺铁的常见表现。因此，Fe3+和Ag+含量的检测具有重要理论和实践意义。尽管近年来Fe3+和Ag+的分析手段取得了较大进展，人们已设计并提出了不同的分析检测方法，如原子吸收光谱法、高效液相色谱分析法，电分析方法和光谱分析法等。其中，比色检测的方法，以其实验成本低，操作过程简单，尤其是可以通过裸眼代替复杂昂贵的分析仪器进行检测，已引起国内外越来越多的学者的关注。但基于比色法同时检测Fe3+和Ag+含量未见文献报道。
为了提高比色检测水相中Fe3+和Ag+含量的选择性和灵敏度，进一步增强分析检测的效率，节约资源，减少因多次检测对环境可能造成的二次污染等，本发明即，以苯胺衍生物和吖啶生色团为原料，通过偶氮基团基团偶联作用，设计制备了一种多齿配体显色剂3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶染料。目标染料集N-杂吖啶环,–OH and–N＝N–键等多种活性基团于一体，不仅稳定性大大提高，由于共轭刚性平面的增强，多齿配位能力，对金属离子的配位能力大大加强。对其光谱性能、尤其是对金属离子选择性比色传感性能优化探讨的基础上，将所设计的一种多齿配体显色剂3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶染料有效地应用到环境水样中痕量Fe3+和Ag+离子同时比色检测上，其他常见的共存离子对Fe3+和Ag+离子同时比色检测无干扰。最佳测试条件下，Fe3+检测的线性范围3.5～110×10–7mol/L，相关系数(R)0.9786，检测限69nmol/L，相对误差(RSD)小于5.6％；Ag+检测的线性范围2.0～130×10–8mol/L，相关系数(R)0.9961，检测限1.6nmol/L，相对误差(RSD)小于4.5％。
发明内容
本发明的目的在于提供一种含偶氮生色团多齿配体的合成及其比色法同时检测痕量Ag+和Fe3+的方法，该方法具有操作简单，选择性好，灵敏度高等优点，可在中性或弱酸碱性条件下，准确的用于环境水样品中痕量Ag+和Fe3+的比色测定，以解决上述背景技术中提出的问题。
为实现上述目的，本发明提供如下技术方案：
本发明的一种含偶氮生色团多齿配体的合成及其比色法同时检测痕量Ag+和Fe3+的方法，包括：
(1)多齿配体显色剂3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶染料的制备
称取0.06143g(0.25mmol)3,6-二氨基吖啶盐酸盐于50mL圆底烧瓶中，加入2mLDMF和1mL H2O溶解，用浓盐酸调节pH 1～2，再滴加0.5mL含有0.03623g(0.525mmol)的NaNO2水溶液。恒温0～5℃反应30min，加入0.006g(0.1mmol)除去过量的NaNO2。向反应体系中缓慢滴加78.9μL(0.5mmol)N- 乙基-N-羟乙基苯胺，继续反应2h。减压抽滤，得粗产物，再经乙醇重结晶3次，得紫红色晶体，产率89.2％。
所述步骤(1)中的多齿配体显色剂3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶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)多齿配体显色剂标准溶液的配制
称取上述深蓝色晶体0.0449g，溶于100mL双重蒸馏水中，配制成浓度为8.0×10– 5mol·L–1的多齿配体显色剂3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶染料的标准溶液，在4℃下避光保存备用；
(3)Fe3+标准溶液的配制
称取FeCl3晶体0.0162g，溶于100mL双重蒸馏水中，配置成浓度为1.0mmol L–1的Fe3+标准溶液，在4℃下保存；
(4)Ag+标准溶液的配制
称取AgNO3晶体0.017g，溶于100mL双重蒸馏水中，配置成浓度为1.0mmol L–1的Ag+标准溶液，在4℃下保存；
(5)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，再通过减压蒸馏浓缩到10.0mL，得环境水样(分别标记为水样1、水样2和水样3)，室温下保存，备用；
(6)待测样品中Fe3+浓度的测定
向10mL的容量瓶依次加入浓度为8.0×10–5mol/L的多齿配体显色剂3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶染料标准溶液1.0mL、pH值为9.0的混合磷酸盐缓冲溶液1.0mL和待测样品1.0mL，最后加双重蒸馏水定容至刻度线，摇匀，试剂空白作参比，1cm比色皿，记录600nm和505nm波长处体系吸光度的比值A600/A505，计算得待测样品中Fe3+的含量。
(7)待测样品中Ag+浓度的测定
向10mL的容量瓶依次加入浓度为8.0×10–5mol/L的多齿配体显色剂3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶染料标准溶液1.0mL、pH值为9.0的混合磷酸盐缓冲溶液1.0mL和待测样品1.0mL，最后加双重蒸馏水定容至刻度线，摇匀，试剂空白作参比，1cm比色皿，记录505nm波长处体系的吸光度，计算得待测样品中Ag+浓度。
所述步骤(1)中的齿配体显色剂3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶染料在505nm处有强吸收，吸光系数3.83×104L·mol-1·cm-1。
所述步骤(1)中的齿配体显色剂3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶染料是在冰水浴(0～5℃)条件下，以3,6-二氨基吖啶盐酸盐、N-乙基-N-羟乙基苯胺和亚硝酸钠为原料，搅拌反应2小时制得。
本发明从反应原理入手，讨论了体系的溶剂效应、pH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8.0×10-6mol/L，pH值为6.0的混合磷酸盐缓冲溶液测试的灵敏度最高。
本方法能排除其他常见共存离子对Fe3+和Ag+同时比色检测的干扰，采用UV分析仪，甚至裸眼即可同时对Fe3+和Ag+进行分析检测。最佳测试条件下，Fe3+检测的线性回归方程为A600/A505＝1.93+1.84×10–6c(10–7mol/L)，检测的线性范围3.5～110×10–7mol/L，相关系数(R)0.9786，检测限69nmol/L，样品中Fe3+回收率96.2％～109.5％之间，相对误差(RSD)小于5.6％。Ag+检测的线性回归方程为ΔA＝2.33×10–3+8.65×10–4c(10–8mol/L)，检测的线性范围2.0～130×10–8mol/L，相关系数(R)0.9961，检测限1.6nmol/L，样品中Ag+回收率98.2％～107.8％％之间，相对误差(RSD)小于4.5％。
与现有技术相比，本发明的有益效果是：本发明可在中性或弱酸碱pH条件下对水环境中痕量Ag+和Fe3+同时比色分析检测，显色剂的水溶解性好、稳定性高，吸光系数大，因此对痕量Ag+和Fe3+检测灵敏度高，重现性好，同时该方法使用的波长为505nm或600nm波长的可见光，可有效减少背景干扰吸收的同时，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3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶染料合成路线；
图2为不同溶剂对多齿配体显色剂3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶染料吸收光谱的影响；
图3为pH对体系同时比色检测a)Fe2+和b)Ag+吸收光谱的影响；
图4为不同的共存离子对体系同时比色检测Fe2+/Ag+的影响；
图5为多齿配体显色剂3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶染料对痕量检测Fe3+和Ag+的选择性比色响应；
图6为a为吸光度随Fe3+浓度的变化(From up to down:0,3.5,5.0,10.0,15.0,20.0,30.0,40.0,50.0,60.0,70.0,80.0,90.0,100.0,110×10-7mol·L-1)及b)线性关系曲线；
图7为a为吸光度随Ag+浓度的变化(From up to down:0,2.0,4.0,8.0,10.0,15.0,20.0,25.0,30.0,35.0,45.0,55.0,60.0,70.0,80.0,90.0,100.0,110.0,120.0,130×10-8mol·L-1)及b)线性关系曲线。
具体实施方式
除非另有定义，本文所使用的所有学术和科学术语具有本发明所属技术领域普通技术人员所理解的相同含义。
在相抵触的情况下，以本说明书中的定义为准。
除非另有说明，所有的百分数、份数、比例等都是以重量计。
当给出数值或数值范围、优选范围或一系列下限优选值和上限优选值时，应当理解其具体公开了由任何较小的范围限值或优选值和任何较大的范围限值或优选值的任何一对数值所形成的任何范围，而无论范围是否分别被公开。除非另有说明，在本说明书描述数值范围之处，所述的范围意图包括范围端值和范围内的所有整数和分数。
当术语“约”或“左右”用于描述数值或范围的端值时，所公开的内容应当是包括该具体数值或所涉及的端值。
采用“一”和“一个/种”的用法描述本发明的要素和组分，这只是出于便利和为了给出本发明一般情况。除非另有明显表述，应将该说明理解为包括一个/种或至少一个/种。
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1，本发明实施例中，1)多齿配体显色剂3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶染料的制备
称取0.06143g(0.25mmol)3,6-二氨基吖啶盐酸盐于50mL圆底烧瓶中，加入2mLDMF和1mL H2O溶解，用浓盐酸调节pH 1～2，再滴加0.5mL含有0.03623g(0.525mmol)的NaNO2水溶液。恒温0～5℃反应30min，加入0.006g(0.1mmol)除去过量的NaNO2。向反应体系中缓慢滴加78.9μL(0.5mmol)N-乙基-N-羟乙基苯胺，继续反应2h。减压抽滤，得粗产物，再经乙醇重结晶3次，得紫红色晶体，产率89.2％。
IR(KBr),υ(cm-1):3312(-OH),3022(Ar-H),1608,1593,1555(Ar ring),1343(Ar-N(R1R)),1197cm-1(C-O).1H NMR(400MHz,DMSO-d6,δ):8.82(d,J＝7.5Hz,2H,Ar-H),8.40(d,J＝7.7Hz,2H,Ar-H),8.22(d,J＝7.9Hz,4H,Ar-H),7.91(s,1H,Ar-H),7.65(s,2H,Ar-H),6.92(d,J＝7.9Hz,4H,Ar-H),4.82(t,J＝4.8Hz,4H,CH2),3.61(s,2H,-OH),3.32(t,J＝4.7Hz,4H,CH2),2.60(m,J＝3.6Hz,4H,CH2),1.15(t,J＝3.6Hz,6H,CH3).元素分析理论值(％)：C 62.8,H 5.27,N 10.99,O 20.92；实测值：C 62.2,H 5.36,N 10.85,O 21.14。
(2)多齿配体显色剂标准溶液的配制
称取上述紫红色晶体0.0449g，溶于100mLN,N-二甲基甲酰胺(DMF)中，配制成浓度为8.0×10–5mol·L–1的3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶染料的标准溶液，在4℃下避光保存备用；
(3)Fe3+标准溶液的配制
称取FeCl3晶体0.0162g，溶于100mL双重蒸馏水中，配置成浓度为1.0mmol L–1的Fe3+标准溶液，在4℃下保存；
(4)Ag+标准溶液的配制
称取AgNO3晶体0.017g，溶于100mL双重蒸馏水中，配置成浓度为1.0mmol L–1的Ag+标准溶液，在4℃下保存；
(5)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，再通过减压蒸馏浓缩到10.0mL，得环境水样(分别标记为水样1、水样2和水样3)，室温下保存，备用；
(6)Ag+和Fe3+同时检测条件的优化
从反应原理入手(见附图2)，讨论了溶剂效应(见附图3)体系的pH值(见附图4)、及共存物质的干扰(见附图5)等影响因素，确定了最佳测试条件：指示剂浓度为8.0×10–5mol/L，pH值为6.0的混合磷酸盐缓冲溶液测试的灵敏度最高，环境中常见的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7所示。即最佳测试条件下，Fe3+检测的线性回归方程为A600/A505＝1.93+1.84×10–6c(10–7mol/L)，检测的线性范围3.5～110×10–7mol/L，相关系数(R)0.9786，检测限69nmol/L。Ag+检测的线性回归方程为ΔA＝2.33×10–3+8.65×10–4c(10–7mol/L)，检测的线性范围2.0～130×10–8mol/L，相关系数(R)0.9961，检测限1.6nmol/L。
(7)待测样品中Ag+和Fe3+浓度的同时测定
向10mL的容量瓶依次加入经稀释浓度为8.0×10–5mol/L多齿配体显色剂3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶染料的标准溶液1.0mL、pH值为6.0的混合磷酸盐缓冲溶液1.0mL和待测样品1.0mL，最后加水定容至刻度线，摇匀，试剂空白作参比，1cm比色皿，记录505nm波长处体系吸光度的差值ΔA＝A0-A505，其中A0为标准溶液吸光度值，通过回归方程为ΔA＝2.33×10–3+8.65×10–4c(10–8mol/L)，计算得待测样品中Ag+的含量；记录600nm和505nm波长处体系吸光度的比值A600/A505，其中A600和A505分别为体系在600nm和505nm波长处的吸光度，通过回归方程为A600/A505＝1.93+1.84×10–6c(10–7mol/L)，计算得待测样品中Fe3+浓度。
该方法成功的用于对上述三类环境样品中Ag+和Fe3+含量的同时测定，结果见表1。样品中Fe3+回收率96.2％～109.5％之间，相对误差(RSD)小于5.6％；样品中Ag+回收率98.2％～107.8％％之间，相对误差(RSD)小于4.5％。
表1体系对环境样品中Fe3+的检测结果(n＝5)
表2体系对环境样品中Ag+的检测结果(n＝5)
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明的范围由所附权利要求而不是上述说明限定，因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。不应将权利要求中的任何附图标记视为限制所涉及的权利要求。
此外，应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施例中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。
Claims (5)
1.一种含偶氮生色团多齿配体的合成及其比色法同时检测痕量Ag+和Fe3+的方法，包括：
(1)多齿配体显色剂3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶染料的制备
称取0.06143g(0.25mmol)3,6-二氨基吖啶盐酸盐于50mL圆底烧瓶中，加入2mL DMF和1mL H2O溶解，用浓盐酸调节pH 1～2，再滴加0.5mL含有0.03623g(0.525mmol)的NaNO2水溶液；恒温0～5℃反应30min，加入0.006g(0.1mmol)除去过量的NaNO2；向反应体系中缓慢滴加78.9μL(0.5mmol)N-乙基-N-羟乙基苯胺，继续反应2h；减压抽滤，得粗产物，再经乙醇重结晶3次，得紫红色晶体；
(2)多齿配体显色剂标准溶液的配制
称取上述深蓝色晶体0.0449g，溶于100mL双重蒸馏水中，配制成浓度为8.0×10–5mol·L–1的多齿配体显色剂3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶染料的标准溶液，在4℃下避光保存备用；
(3)Fe3+标准溶液的配制
称取FeCl3晶体0.0162g，溶于100mL双重蒸馏水中，配置成浓度为1.0mmol L–1的Fe3+标准溶液，在4℃下保存；
(4)Ag+标准溶液的配制
称取AgNO3晶体0.017g，溶于100mL双重蒸馏水中，配置成浓度为1.0mmol L–1的Ag+标准溶液，在4℃下保存；
(5)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，再通过减压蒸馏浓缩到10.0mL，得环境水样(分别标记为水样1、水样2和水样3)，室温下保存，备用；
(6)待测样品中Fe3+浓度的测定
向10mL的容量瓶依次加入浓度为8.0×10–5mol/L的多齿配体显色剂3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶染料标准溶液1.0mL、pH值为9.0的混合磷酸盐缓冲溶液1.0mL和待测样品1.0mL，最后加双重蒸馏水定容至刻度线，摇匀，试剂空白作参比，1cm比色皿，记录600nm和505nm波长处体系吸光度的比值A600/A505，计算得待测样品中Fe3+的含量。
(7)待测样品中Ag+浓度的测定
向10mL的容量瓶依次加入浓度为8.0×10–5mol/L的多齿配体显色剂3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶染料标准溶液1.0mL、pH值为9.0的混合磷酸盐缓冲溶液1.0mL和待测样品1.0mL，最后加双重蒸馏水定容至刻度线，摇匀，试剂空白作参比，1cm比色皿，记录505nm波长处体系的吸光度，计算得待测样品中Ag+浓度。
2.根据权利要求1所述的一种含偶氮生色团多齿配体的合成及其比色法同时检测痕量Ag+和Fe3+的方法，其特征在于：所述步骤(1)中的多齿配体显色剂3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶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，共轭强度大，还具有很高的稳定性。
3.根据权利要求1所述的一种含偶氮生色团多齿配体的合成及其比色法同时检测痕量Ag+和Fe3+的方法，其特征在于：述步骤(1)中的齿配体显色剂3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶染料在505nm处有强吸收，吸光系数3.83×104L·mol-1·cm-1。
4.根据权利要求1所述的一种含偶氮生色团多齿配体的合成及其比色法同时检测痕量Ag+和Fe3+的方法，其特征在于：所述步骤(1)中的齿配体显色剂3,6-二氨基-(N-乙基-N-羟乙基苯基偶氮)吖啶染料是在冰水浴(0～5℃)条件下，以3,6-二氨基吖啶盐酸盐、N-乙基-N-羟乙基苯胺和亚硝酸钠为原料，搅拌反应2小时制得。
5.根据权利要求1所述的一种含偶氮生色团多齿配体的合成及其比色法同时检测痕量Ag+和Fe3+的方法，其特征在于：指示剂浓度为8.0×10-6mol/L，pH值为6.0的混合磷酸盐缓冲溶液测试的灵敏度最高。
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| CN107748161A (zh) * | 2017-08-23 | 2018-03-02 | 曲阜师范大学 | 一种基于吡啶‑希夫碱衍生物多波长比色区分痕量Fe2+和Fe3+的方法 |
| CN108844904A (zh) * | 2018-05-03 | 2018-11-20 | 曲阜师范大学 | 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 |
| CN108844904B (zh) * | 2018-05-03 | 2020-11-13 | 曲阜师范大学 | 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 |
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