CN115326764A - 氮磷共掺杂红色荧光碳点的制备方法、氮磷共掺杂红色荧光碳点对孔雀石绿的检测方法 - Google Patents
氮磷共掺杂红色荧光碳点的制备方法、氮磷共掺杂红色荧光碳点对孔雀石绿的检测方法 Download PDFInfo
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Abstract
氮磷共掺杂红色荧光碳点的制备方法、氮磷共掺杂红色荧光碳点对孔雀石绿的检测方法,属于食品安全检测技术领域,本发明提供一种pH敏感型氮磷共掺杂红色荧光碳点及其对孔雀石绿的检测方法。本发明提供的氮磷共掺杂红色荧光碳点,制备方法简单易操作,对鱼产品和环境水样中MG的检测方法操作简单、灵敏度高、成本低廉、检测迅速,基于氮磷共掺杂红色荧光碳点水凝胶试剂盒实现了MG的可视化检测、现场的定性鉴别和半定量分析,为进一步深入研究食品安全问题提供可靠的方法依据。
Description
技术领域
本发明属于食品安全检测技术领域,具体涉及一种氮磷共掺杂红色荧光碳点的制备方法、水凝胶试剂盒及氮磷共掺杂红色荧光碳点对孔雀石绿的检测方法。
背景技术
孔雀石绿(MG)分子式为C23H25ClN2,是一种三苯甲烷类碱性染料,也是杀真菌、杀细菌、杀寄生虫的药物,长期超量使用可致癌,无公害水产养殖领域国家明令禁止添加。其虽然称作孔雀石绿,但其实它不含有孔雀石的成分,只是两者颜色相似而已。孔雀石和孔雀石绿是两种完全不同的物质。孔雀石是一种天然的矿石,为碱式碳酸铜[Cu2(OH)2CO3],呈翠绿或草绿色的块石,主要用于铜的提炼和供作颜料,但并不用于水产养殖业。
MG的用途主要有:
(1)针对鱼体水霉病和鱼卵的水霉病有特效,现市面上还暂无针对水霉病能够短时间解决水霉病的特效药物。
(2)可以用于治疗鳃霉病、小瓜虫病、车轮虫病、指环虫病、斜管虫病、三代虫病,和其他一些细菌性疾病。我国农业部已将孔雀石绿列为水产上的禁药,非食用鱼的观赏鱼还可以使用。
(3)染料MG可用作丝绸、皮革和纸张的染料。商品MG染料,是将色素溶于热草酸溶液,冷却后得草酸盐的结晶。或用盐酸中和后,加定量的氯化锌(ZnCl2)结晶出氯化锌复盐,成为绿色碱性染料,用于染羊毛,丝,皮革等,是专职的染料。
(4)MG可用作生物染色剂,把细胞或细胞组织染成蓝绿色,方便在显微镜下研究,可用于植物病毒感染的宿主细胞染色,细菌、芽胞染色,红细胞、蛔虫卵染色。
(5)杀菌剂MG可用作治理鱼类或鱼卵的寄生虫、真菌或细菌感染,对付真菌Saprolegnia 特别有效,渔场的鱼卵会感染这种真菌。MG也常用作处理受寄生虫影响的淡水水产。用作抑菌剂或杀阿米巴原虫剂;对脂鲤和鲶鱼等海产动物来说,有高度毒性、高残留等副作用,故使用时,通常只下一半份量。
(6)其他应用:用作细菌多醣体试剂;用作临床诊断试剂(无机磷酸盐的测定);用作镓、钽、锑的光度测定;钨的催化光度测定;点滴试验亚硫酸盐和铈、钨;用作酸碱指示剂,pH0.0(黄)~2.0(绿),11.6(蓝绿)~14(无色);用作氧化还原指示剂。
另外有一些研究发现,MG进入水生动物体内后,会快速代谢成脂溶性的无色孔雀石绿。 MG具有潜在的致癌、致畸、致突变的作用,其在养殖业中的使用未得到美国食品与药物管理局(FDA)的认可;根据欧盟法案2002/675/EC的规定,动物源性食品中孔雀石绿和无色孔雀石绿残留总量限制为2μg/kg;日本的肯定列表也明确规定在进口水产品中不得检出孔雀石绿残留;我国在农业行业标准《NY5071-2002无公害食品鱼药使用准则》中也将MG列为禁用药物。由于没有低廉有效的替代品,MG在水产养殖中的使用屡禁不止。因此,建立一种简单、快速、灵敏的检测MG的分析方法对于保证环境、食品安全和消费者健康是十分必要的。
目前MG的检测方法主要有高效液相色谱法、液相色谱-质谱联用法、气相色谱-质谱联用法以及酶联免疫法。这几种方法在测定和分析水产品中孔雀石绿的残留都具有结果可靠、灵敏度高、选择性高、重复性好的优点。但是这些方法在样品前处理过程都存在繁琐、复杂、耗时等不足,而且设备昂贵,检测成本高;不仅需要消耗大量的溶剂和大量的时间,还容易造成二次污染,影响检测结果的准确性;酶联免疫法则需要制备抗体,操作复杂,且易受pH 值、温度等环境条件的影响,检测条件苛刻。因此,发展一种简单高效的MG检测方法对控制水产品质量安全具有重要意义。
发明内容
针对现有技术存在的缺陷,本发明提供一种氮磷共掺杂红色荧光碳点及其对鱼产品和/或环境水样中痕量MG的检测方法,该检测方法具有操作简单、灵敏度高、成本低廉、检测迅速的优点;同时还提供基于N,P-CDs荧光碳点的水凝胶,实现了MG的现场定性鉴别和半定量分析。
本发明的技术方案如下:
本发明提供一种氮磷共掺杂红色荧光碳点的制备方法,包括如下步骤:
将邻苯二胺加入超纯水后溶解完全,随后加入磷酸,混匀,反应完全,待反应冷却至室温后,将得到的产物用0.22μm滤膜过滤,再用透析袋(截流分子量为MW:500Da)透析24h后,冷冻干燥得到氮磷共掺杂红色荧光碳点(N,P-CDs)粉末。
上述制备方法,其中:
所述邻苯二胺和磷酸质量体积比为1g/5mL-1g/7.5mL。
所述反应温度及反应时间为180℃反应10h。
本发明还提供所述氮磷共掺杂红色荧光碳点在鱼产品和/或环境水样中检测痕量MG的应用。
所述氮磷共掺杂红色荧光碳点对鱼产品和/或环境水样中痕量的MG的检测方法,包括如下步骤:
取水样和鱼样,首先,将水样离心10-15min后,取上清液用0.22μm滤膜过滤,得到预处理后的水样;鱼样品切碎,取鱼肉组织和有机溶剂至离心管中,超声,离心后,取上清液用0.22μm滤膜过滤,得到预处理后的鱼样品;将预处理的水样和鱼样品分别加入至N,P-CDs溶液中,用超纯水稀释,再用HCl/NaOH溶液调pH至3,剧烈涡旋后,记录611nm激发下的发射光谱强度,每个样品平行制备三份,取平均值。
上述检测方法,其中:
所述水样选自水产养殖水、河水、湖水;所述鱼样选自鲤鱼、草鱼、鲫鱼等常见鱼类。
所述离心为10000rpm离心10-15min。鱼肉组织和有机溶剂的质量体积比为1g/5mL- 1g/10mL;所述有机溶剂选自乙腈、甲醇、乙醇,其主要目的为提取鱼肉组织中的MG。
预处理后的水样和鱼样品与N,P-CDs溶液的混合比例为400μL:50μL;其中N,P-CDs浓度为20μg·mL-1。
采用的HCl/NaOH溶液浓度为0.1mol·L-1。
一种基于N,P-CDs的荧光水凝胶试剂盒的制备方法,包括如下步骤:
将0.2g琼脂糖加入至20mL超纯水中,加热并不断搅拌至琼脂糖完全溶解,随后加入1 mL N,P-CDs(100μg·mL-1)溶液混匀。快速取上述混合液200μL至样品瓶中,待完全凝固后得到基于N,P-CDs的荧光水凝胶试剂盒。
本发明还提供所述基于氮磷共掺杂红色荧光碳点的荧光水凝胶试剂盒在鱼产品和/或环境水样中检测痕量MG的应用。
与现有技术相比,本发明具有以下特点:
1)本发明制得的pH敏感型N,P-CDs原料来源广泛,价廉易得。
2)本发明提供的pH敏感型N,P-CDs制备方法水热法简单,适用性广泛,同时所得产品物相均匀、纯度高、结晶良好、产率高,并且产品形貌与大小可控。
3)本发明制得的pH敏感型N,P-CDs具有较高的灵敏度,可用于鱼产品和/或环境水样中MG的痕量检测。
4)本发明制得的基于N,P-CDs的荧光水凝胶试剂盒,用于MG的可视化检测,具有成本低、操作简单、检测速度快等优点。
5)基于N,P-CDs的荧光水凝胶试剂盒实现了MG的现场定性鉴别和半定量分析,可适用于MG的灵敏检测。
附图说明
图1为N,P-CDs的TEM图像(插图显示了粒度分布和HRTEM图像);
图2为N,P-CDs傅里叶变换红外光谱;
图3(A)为N,P-CDs的全XPS谱图;(B)为C1s的高分辨XPS谱图;(C)为N1s 的高分辨XPS谱图;(D)为O1s的高分辨XPS谱图;(E)为P 2p的高分辨XPS谱图;
图4(A)为N,P-CDs的紫外-可见吸收光谱和荧光光谱(插图:N,P-CDs在自然光和紫外光灯下的图像);(B)为N,P-CDs在不同激发波长下的发射光谱;(C)、(D)及 (E)分别为辐射时间、NaCl浓度及储存时间对N,P-CDs荧光强度的影响;
图5为不同反应条件对MG检测的影响:(A)N,P-CDs的浓度,(B)反应体系的pH 值,(C)反应时间;
图6为MG检测范围测定;(A)不同浓度MG下N,P-CDs的荧光光谱;(B)和(C) MG的线性校准曲线范围为0.08μmol·L-1和1-50μmol·L-1;
图7为N,P-CDs对MG检测的选择性和抗干扰性;
图8(A)为N,P-CDs荧光水凝胶在365nm紫外光灯下荧光颜色随MG浓度增加的变化;(B)为N,P-CDs荧光水凝胶在365nm紫外光灯下对MG的选择性。
具体实施方式
为了使本技术领域的人员更好的理解本发明方案,并使本发明的上述目的,特征和优点能够更加明显易懂,下面结合实施例对本发明做进一步详细的说明。
实施例1
一种氮磷共掺杂红色荧光碳点的制备方法,具体操作步骤如下:
精密称取0.1g邻苯二胺置于反应釜中,加入9.5mL超纯水后超声溶解,随后加入0.5 mL磷酸,混匀,混合液于180℃反应10h。待反应冷却至室温后,将得到的产物用0.22μm滤膜过滤,再用透析袋(MW:500Da)透析24h后,冷冻干燥得到氮磷共掺杂红色荧光碳点 (N,P-CDs)粉末,表征结果见附图:图1-图3。
对制得的N,P-CDs进行的光学特性检测结果如下:
N,P-CDs在234nm和278nm处有两个强吸收峰,350-550nm范围处有宽吸收峰,最佳激发、发射波长分别为611nm和624nm,同时,内插图表明N,P-CDs在紫外灯照射下呈现出明亮的红色荧光表征结果见附图:图4A;
N,P-CDs在570-620nm范围内的不同激发波长下表现出了非激发依赖性,并且N,P-CDs在611nm激发下的绝对量子产率为17.28%,表征结果见附图:图4B;
同时,N,P-CDs的荧光强度在611nm激发波长下连续照射100min、高离子强度(1mol·L-1,NaCl)和40天内的贮存下几乎没有变化,这表明制备的N,P-CDs具有极好的稳定性,表征结果见附图:图4C-4E。
实施例2
氮磷共掺杂红色荧光碳点对MG的检测
(1)MG的测定及其检测限的计算
将400μL不同浓度的MG(0-50μmol·L-1)溶液加入至50μL N,P-CDs(20μg·mL-1)溶液中,用超纯水稀释至1mL,随后用HCl/NaOH(0.1mol·L-1)溶液调pH至3。剧烈涡旋 20s后,记录611nm激发下的发射光谱强度。每个样品平行制备三份。此外,根据3σ/k原则,计算该方法测定MG的检测限。
(2)MG检测的条件优化
为了获得测定MG的最佳分析性能,本实验对N,P-CDs的浓度、pH和反应时间等因素进行优化。当N,P-CDs的浓度为20μg·mL-1、pH为3、反应时间为20s时,F0/F值(F0和 F分别表示N,P-CDs在加入MG之前和之后的荧光强度)达到最大,此时该方法的分析性能达到最优。结果见附图:图5。
(3)MG检测的范围
在上述步骤(2)中得到的最佳检测条件下,研究基于N,P-CDs测定MG的可行性。N,P-CDs的荧光强度随着MG浓度的增加而逐渐降低,在0.08-1μmol·L-1和1-50μmol·L-1范围内,F0/F值与MG的浓度呈良好的线性关系,回归方程分别为y=0.0947x+1.0214(R2=0.9955)和y=0.0424x+1.0257(R2=0.9966)。此外,计算得到的检测限为0.07μmol·L-1和0.74μmol·L-1(检测限是平行制备11份空白样品,计算标准差,再根据步骤(1)中得到的线性斜率计算得到)。结果见附图:图6。
(4)MG的选择性考察
通过考察一些常见的染料、金属离子和阴离子对N,P-CDs荧光强度的影响,评估了本实验测定MG的选择性和抗干扰性。MG(50μmol·L-1)能够显著猝灭N,P-CDs的荧光,而两倍浓度的染料(CV、MO、CR)、五倍浓度的金属离子(Ca2+、Na+、Ba2+、K+、Fe3+、Zn2+、 Mn2+、Pb2+、Cu2 +、Al3+、Ag+、Mg2+)和五倍浓度的阴离子(SO4 2-、HCO3 -、CO3 2-)对N,P- CDs的荧光几乎没有影响,表征结果见附图:图7。
同时,MG对N,P-CDs的荧光猝灭程度也不受这些潜在干扰物质共存的影响。因此,本实验对MG的测定表现出了良好的选择性和抗干扰性。
实施例3
氮磷共掺杂红色荧光碳点对鱼产品和环境水样中痕量的MG的检测方法,包括如下步骤:
测定3种水样(水产养殖水、河水、湖水)和2种鱼样(鲤鱼、草鱼)中MG的含量,首先,将每种水样以10000rpm离心10min后,分别取上清液用0.22μm滤膜过滤,得到预处理后的水样。将每种鱼样切碎的1g鱼组织、5mL乙腈至10mL离心管中,超声10min,再以10000rpm离心10min后,取上清液用0.22μm滤膜过滤,得到预处理后的鱼样品。分别将400μL预处理的水样和鱼样品加入至50μL N,P-CDs(20μg·mL-1)溶液中,用超纯水稀释至1mL,再用HCl/NaOH(0.1mol·L-1)溶液调pH至3。剧烈涡旋20s后,记录611nm 激发下的发射光谱强度。每个样品平行制备三份。水样中MG的平均回收率在95.6-101.5%之间,RSD小于4.5%,鱼样中MG的平均回收率在96.4-102.2%之间,RSD小于4.6%,数据结果见表1;
表1实际样品中孔雀石绿的回收率
实施例4
基于N,P-CDs的荧光水凝胶试剂盒的制备方法,具体操作步骤如下:
将0.2g琼脂糖加入至20mL超纯水中,加热并不断搅拌至琼脂糖完全溶解,随后加入1 mL N,P-CDs(100μg·mL-1)溶液混匀。快速取上述混合液200μL至样品瓶中,待完全凝固后得到基于N,P-CDs的荧光水凝胶试剂盒。
基于N,P-CDs的荧光水凝胶用于MG的可视化检测
在365nm紫外灯照射下,水凝胶的荧光随着MG浓度(0-120μmol·L-1)的不断增加呈现出橙色逐渐变浅的变化,对比结果见附图:图8A。
将染料、金属离子和阴离子加入到水凝胶中观察了荧光颜色的变化。加入MG(100μmol·L-1)的水凝胶表现出明显的荧光猝灭,而其他干扰物质(染料:100μmol·L-1、离子类: 250μmol·L-1)的加入几乎没有影响到水凝胶的荧光,对比结果见附图:图8B
表明该方法对于MG的识别表现出了高度的选择性。因此,基于N,P-CDs的荧光水凝胶可适用于MG的现场检测和视觉上的半定量分析。
以上是结合具体的优选实施方案对本发明所作的进一步详细说明,不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说,在不脱离本发明构思的前提下,做出的若干简单推演或替换,都应当视为属于本发明的保护范围。
Claims (8)
1.一种氮磷共掺杂红色荧光碳点的制备方法,其特征在于,包括如下步骤:
将邻苯二胺加入超纯水后溶解完全,随后加入磷酸,混匀,反应完全,待反应冷却至室温后,将得到的产物用0.22μm滤膜过滤,再用截流分子量为500Da的透析袋透析后,冷冻干燥得到氮磷共掺杂红色荧光碳点粉末。
2.根据权利要求1所述的氮磷共掺杂红色荧光碳点的制备方法,其特征在于,所述邻苯二胺和磷酸质量体积比为1g/5mL-1g/7.5mL;所述反应温度及反应时间为180℃反应10h。
3.根据权利要求1或2所述氮磷共掺杂红色荧光碳点的制备方法,其特征在于,所述制备方法制备得到的氮磷共掺杂红色荧光碳点用于检测鱼产品和/或环境水样中痕量孔雀石绿,所述环境水样选自养殖水、河水、湖水。
4.一种采用权利要求1或2所述制备方法制备得到的氮磷共掺杂红色荧光碳点对鱼产品和/或环境水样中痕量的孔雀石绿的检测方法,其特征在于,包括如下步骤:
取水样和鱼样,首先,将水样离心后,取上清液用0.22μm滤膜过滤,得到预处理后的水样;鱼样品切碎,取鱼肉组织和有机溶剂至离心管中,超声,离心后,取上清液用0.22μm滤膜过滤,得到预处理后的鱼样品;将预处理的水样和鱼样品分别加入至氮磷共掺杂红色荧光碳点溶液中,用超纯水稀释,再用HCl/NaOH溶液调pH至3,剧烈涡旋后,记录611nm激发下的发射光谱强度,每个样品平行制备三份,取平均值。
5.根据权利要求4所述氮磷共掺杂红色荧光碳点对鱼产品和/或环境水样中痕量的孔雀石绿的检测方法,其特征在于,所述水样选自水产养殖水、河水、湖水;所述鱼样选自鲤鱼、草鱼。
6.根据权利要求4所述氮磷共掺杂红色荧光碳点对鱼产品和/或环境水样中痕量的孔雀石绿的检测方法,其特征在于,所述离心为10000rpm离心10-15min;鱼组织和有机溶剂的质量体积比为1g/5mL-1g/10mL;所述有机溶剂选自乙腈、甲醇、乙醇。
7.根据权利要求4所述氮磷共掺杂红色荧光碳点对鱼产品和/或环境水样中痕量的孔雀石绿的检测方法,其特征在于,预处理后的水样和鱼样品与氮磷共掺杂红色荧光碳点溶液的混合比例为400μL:50μL;其中氮磷共掺杂红色荧光碳点溶液浓度为20μg·mL-1;采用的HCl/NaOH溶液浓度为0.1mol·L-1。
8.一种基于权利要求1或2所述氮磷共掺杂红色荧光碳点的荧光水凝胶试剂盒在鱼产品和/或环境水样中检测痕量孔雀石绿的应用。
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