CN115536673B - 一种检测高效氟吡甲禾灵的双离子型环状鎓盐探针及其合成方法 - Google Patents
一种检测高效氟吡甲禾灵的双离子型环状鎓盐探针及其合成方法 Download PDFInfo
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Abstract
本发明公开一种检测高效氟吡甲禾灵的双离子型环状鎓盐探针及其合成方法,该荧光探针分子式为C52H60Cl2N8O4,该荧光探针使用时通过颜色变化和荧光增强可以快速灵敏地检测高效氟吡甲禾灵,应用前景广阔。
Description
技术领域
本发明具体涉及一种检测高效氟吡甲禾灵的双离子型环状鎓盐探针及其合成方法,属于有机合成与分析化学技术领域。
背景技术
随着农业产业化的发展,农药、抗生素和激素等外源物质的使用越来越泛滥。不合理的使用这些物质必将导致农产品中的农药残留超标,影响着人以及动物的健康安全,造成疾病,导致发育畸形,甚至直接导致中毒死亡。农药残留问题逐渐显现在人们的面前,控制农药使用量或者去农药是一项亟待解决的问题。高效氟吡甲禾灵,属于苯氧羧酸类除草剂,是脂肪酸合成抑制剂。该药剂是内吸传导型除草剂,由叶片、茎秆和根系吸收,在植物体内抑制脂肪酸的生物合成,使细胞生长、分裂停止,细胞膜等含脂结构破坏而导致杂草死亡。该除草剂茎叶处理后能很快被禾本科类杂草的叶子吸收,传导至整个植株,抑制植物分生组织而杀死杂草。
目前,农药残留检测方法包括样本的制备、提取、净化、浓缩、检测等方面内容。其中,检测分析方法主要采用气相色谱法、气质联用色谱法、液相色谱法以及液质联用技术等。对于高效氟吡甲禾灵有效的简便检测方法尚未有报道。因此,开发出一种能快速简便、高灵敏度原位检测高效氟吡甲禾灵的荧光探针是具有十分重要的现实意义和应用价值。
发明内容
本发明提供一种检测高效氟吡甲禾灵的双离子型环状鎓盐探针及其合成方法,合成的探针在使用时通过颜色变化和荧光增强可以快速灵敏地检测高效氟吡甲禾灵,应用前景广阔。
本发明的技术方案如下:
本发明的目的之一在于提供一种检测高效氟吡甲禾灵的双离子型环状鎓盐探针,其分子式为C52H60Cl2N8O4,化学结构式,即化合物1如下所示:
本发明目的之二在于提供一种检测高效氟吡甲禾灵的双离子型环状鎓盐探针的合成方法,其合成路线为:
其中,化合物1为双离子型环状鎓盐探针,化合物2为1,4-(二-(2-(N-咪唑基己氧基苯基)-2-氰基-乙烯基))苯,化合物3为R,R-1,2-二(氯乙酰氨基)环己烷;
所述合成方法具体包括如下步骤:
在氮气保护下,将化合物2和环己二胺衍生物混合,加入甲苯做溶剂,在120℃下搅拌反应12~24h;
反应结束后,趁热过滤出沉淀,沉淀再利用有机溶剂进行洗涤,即得到所述的双离子型环状鎓盐探针,即化合物1。
进一步的,所述化合物2和环己二胺衍生物的摩尔比为1:0.5~1.5。
进一步的,所述甲苯溶剂的加入量为30~60mL。
进一步的,所述沉淀依次利用二氯甲烷、甲醇、丙酮进行洗涤,且二氯甲烷、甲醇、丙酮各取10mL。
相较于现有技术,本发明的有益效果在于:
1、本发明合成的双离子型环状鎓盐探针在高效氟吡甲禾灵存在下发生明显的荧光增强和颜色变化,其他常见分子和离子的存在对高效氟吡甲禾灵的检测干扰很小,检测限为1.41×10-7M,可用于选择性灵敏检测高效氟吡甲禾灵,这对食品安全中高效氟吡甲禾灵的检测具有重要的现实应用价值。
2、本发明提供的的双离子型环状鎓盐探针,即化合物1,在二甲基亚砜中显亮青绿色,在494nm处有较强的荧光发射;在二甲基亚砜与水(体积比为5:95)溶液中,该探针在514nm处有较弱的荧光发射;该荧光探针在此溶液中与高效氟吡甲禾灵溶液形成1:1配合物,并发生明显的荧光增强和最大发射波长蓝移的现象,可用于农药高效氟吡甲禾灵的灵敏检测,其他常见分子和离子干扰小,是一种理想的农药高效氟吡甲禾灵快速检测的荧光探针。
附图说明
图1为本发明提供的双离子型环状鎓盐探针(浓度为1×10-5M)和不同分子或离子(浓度为1×10-4M)在二甲基亚砜-水(体积比为5:95)溶液中的荧光光谱图;
图2为本发明提供的双离子型环状鎓盐探针(浓度为1×10-5M)和不同浓度的高效氟吡甲禾灵在二甲基亚砜-水(体积比为5:95)溶液中的荧光光谱图;
图3为依据图2建立的高效氟吡甲禾灵浓度梯度变化与荧光强度变化标准曲线;
图4为在二甲基亚砜-水(体积比为5:95)溶液中,本发明提供的双离子型环状鎓盐探针与高效氟吡甲禾灵和其他干扰分子混合的荧光强度(I)与双离子型环状鎓盐探针加入高效氟吡甲禾灵的荧光强度(I0)比值;
图5为本发明提供的双离子型环状鎓盐探针官能团结构的红外光谱图;
图6为本发明提供的双离子型环状鎓盐探针的核磁共振氢谱图;
图7为本发明提供的双离子型环状鎓盐探针的核磁共振碳谱图;
图8为本发明提供的双离子型环状鎓盐探针的质谱图。
具体实施方式
下面结合附图和较佳实施例对本发明做进一步的说明,给出的实施例仅为了阐明本发明,而不是为了限制本发明的范围。
下述实施例中所用的材料、试剂等,如无特殊说明,均可从商业途径得到;
以下实施例中的定量试验,均设置三次重复实验,结果取平均值。
下述实施例中的实验方法,如无特殊说明,均为常规方法。
实施例1
一种检测高效氟吡甲禾灵的双离子型环状鎓盐探针,该荧光探针分子式为C52H60Cl2N8O4,化学结构式如下所示:
实施例2
一种检测高效氟吡甲禾灵的双离子型环状鎓盐探针的合成方法,其合成路线为:
所述合成方法具体包括如下步骤:
在氮气保护下,往三颈烧瓶依次加入化合物2(0.1g,0.15mmol)和化合物3(0.04g,0.15mmol)进行混合,在加入30mL甲苯做溶剂,在120℃下搅拌反应12h;期间不断通过TCL检测反应的进行程度,直至化合物3(R,R-1,2-二(氯乙酰氨基)环己烷)检测无明显变化;反应结束后,趁热过滤出沉淀,沉淀再依次利用10mL二氯甲烷、10mL甲醇、10mL丙酮进行洗涤,即可得黄色固体,为双离子型环状鎓盐探针,即化合物1,产率为60%;
化合物2的制备方法如下:在三颈烧瓶中加入双氰基二苯乙烯衍生物,即化合物4和咪唑(摩尔比1:2~4)于30~60mL甲苯中,加热120℃下搅拌反应12~24小时,反应结束后,用甲苯和二氯甲烷(体积比为1:1)重结晶,所得固体为化合物2;化合物4的制备以对苯二甲醛和对氰基苯甲醇为原料,具体制备方法参见文献“Yunmei Wu,Hui Tan,LiangbinLin,Hongyu Guo,and Fafu Yang,First Gemini-type fluorescence ionic liquids:Synthesis,fluorescence emission and self-assembly in liquid crystals andgels,Dyes and Pigments,2022,206,110667”;
化合物3为环己二胺衍生物,其制备方法参见“范天文,基于氰基二苯乙烯新型手性发光衍生物的合成与性能研究,福建师范大学硕士论文,2022年”;
实施例3
与实施例2不同之处在于,本实施例中双离子型环状鎓盐探针的合成方法如下:
在氮气保护下,往三颈烧瓶依次加入化合物2(0.1g,0.15mmol)和化合物3(0.04g,0.15mmol),再加入50mL甲苯做溶剂,在120℃下搅拌反应18h,期间不断通过TCL检测反应的进行程度,直至中间产物3检测无明显变化;趁热过滤出沉淀,沉淀再依次用10mL二氯甲烷、10mL甲醇、10mL丙酮洗涤,即可得黄色固体,为双离子型环状鎓盐,即化合物1,产率为43%。
实施例4
与实施例2不同之处在于,本实施例中双离子型环状鎓盐探针的合成方法如下:
在氮气保护下,往三颈烧瓶依次加入化合物2(0.1g,0.15mmol)和化合物3(0.06g,0.225mmol),再加入60mL甲苯做溶剂,在120℃下搅拌反应24h,期间不断通过TCL检测反应的进行程度,直至中间产物3检测无明显变化;趁热过滤出沉淀,沉淀再依次用,在120℃下搅拌反应,即可得黄色固体,为双离子型环状鎓盐,产率为36%。
性能测试
图1为本发明中双离子型环状鎓盐探针(浓度为1×10-5M)和不同分子或离子(浓度为1×10-4M)在二甲基亚砜-水(体积比为5:95)溶液中的荧光光谱图,横坐标为波长,纵坐标为荧光强度,从图1中可以看出双离子型环状鎓盐探针在常见生物分子和离子中只对除草剂高效氟吡甲禾灵有明显的荧光增强和颜色变化,说明双离子型环状鎓盐探针对高效氟吡甲禾灵能选择性识别,其中,1=探针,2=1+高效氟吡甲禾灵,3=1+Na+,4=1+K+,5=1+NO3 -,6=1+Fe3 +,7=1+ClO-,8=1+HCO3 -,9=CO3 2-,10=1+胞嘧啶,11=1+甘氨酸,12=1+半胱氨酸,13=1+精氨酸,14=1+抗坏血酸,15=1+赖氨酸,16=1+酪氨酸,17=1+亮氨酸,18=1+鸟嘌呤,19=1+脯氨酸,20=1+葡萄糖,21=1+色氨酸,22=1+苏氨酸,23=1+天冬氨酸,24=1+组氨酸。
图2为本发明中双离子型环状鎓盐探针(浓度为1×10-5M)和不同浓度的高效氟吡甲禾灵在二甲基亚砜-水(体积比为5:95)溶液中的荧光光谱图,横坐标为波长,纵坐标为荧光强度,高效氟吡甲禾灵浓度依次为双离子型环状鎓盐探针的0、0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1.0、1.2、1.4、1.6、1.8、3.0、5.0、6.0、7.0、9.0、10.0、20.0、30.0倍,从图2中可以看出,双离子型环状鎓盐探针的荧光强度随着高效氟吡甲禾灵溶液浓度的升高,呈现明显的上升趋势并蓝移,达到饱和后缓慢下降。
将本发明制备的双离子型环状鎓盐探针配制成一定浓度的溶液,同时按双离子型环状鎓盐探针浓度的0、0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1.0、1.2、1.4、1.6、1.8、3.0、5.0、6.0、7.0、9.0、10.0、20.0、30.0倍数配制出浓度呈梯度变化的高效氟吡甲禾灵系列溶液,双离子型环状鎓盐探针分别与高效氟吡甲禾灵系列溶液一一混合,测定它们的荧光强度,建立荧光强度为纵坐标、高效氟吡甲禾灵溶液为横坐标的高效氟吡甲禾灵溶液梯度变化标准曲线,如图3所示;将双离子型环状鎓盐探针与未知浓度的高效氟吡甲禾灵溶液混合,测定混合溶液的荧光强度,将获得的荧光强度值与前述建立的高效氟吡甲禾灵浓度变化标准曲线进行比较,即可从曲线图中读出未知浓度的含高效氟吡甲禾灵溶液中高效氟吡甲禾灵的含量。
在二甲基亚砜/水溶液中二甲基亚砜与水的体积比为5:95,横坐标为常见分子和离子的种类,纵坐标为双离子型环状鎓盐探针与高效氟吡甲禾灵和其他干扰分子或离子混合的荧光强度(I)与化合物1加入高效氟吡甲禾灵的荧光强度(I0)比值,这个比值趋近于1,说明其他分子和离子对高效氟吡甲禾灵检测的干扰小,从图4中看出,其他常见的分子和离子基本不干扰对高效氟吡甲禾灵的高灵敏检测,其中,a=探针,b=1+高效氟吡甲禾灵,c=1+Na+,d=1+K+,e=1+NO3 -,f=1+Fe3 +,g=1+ClO-,h=1+HCO3 -,i=CO3 2-,j=1+胞嘧啶,k=1+甘氨酸,l=1+半胱氨酸,m=1+精氨酸,n=1+抗坏血酸,o=1+赖氨酸,p=1+酪氨酸,q=1+亮氨酸,r=1+鸟嘌呤,s=1+脯氨酸,t=1+葡萄糖,u=1+色氨酸,v=1+苏氨酸,w=1+天冬氨酸,x=1+组氨酸。
如图5所示,为本发明合成的双离子型环状鎓盐探针的各官能团结构的红外光谱图;从图中可知,在3387cm-1处出现了(N-H),在3100cm-1处出现了(Ar-H),在2368cm-1处出现了(N-C=O),在1681cm-1处出现了(C=O),在1248cm-1处出现了(C-O-C)。
如图6所示,本发明合成的双离子型环状鎓盐探针,如图6所示,其分子式为C52H60Cl2N8O4,1H NMR(400MHz,DMSO)δ9.51(bs,2H,N-CH-N),8.49(bs,2H,NH),8.03(d,J=8.0Hz,4H,ArH),7.97(s,2H,CH=CCN),7.82(bs,4H,ArH),7.74(d,J=8.0Hz,4H,ArH),7.07(bs,4H,ArH),5.24-4.91(m,6H,NCH2 and NCH),4.25(bs,4H,OCH2),4.02(bs,4H,NCH2),1.66-1.82(m,12H,CH2),1.23-1.45(m,12H,CH2);如图7所示,核磁共振碳谱13C NMR(101MHz,DMSO)δ165.10,160.18,145.41,139.44,137.85,133.94,130.48,129.76,129.03,127.83,124.41,122.10,115.56,68.08,52.49,51.06,49.25,31.68,29.79,28.81,25.67,25.31;如图8所示,质谱MALDI-TOF-MS(C52H60Cl2N8O4)Calcd.For m/z(-2Cl-)=860.473,found:860.260。
以上所述仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书内容所作的等效结构或等效流程变换,或直接或间接运用在其他相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (5)
1.一种检测高效氟吡甲禾灵的双离子型环状鎓盐探针,其特征在于:分子式为C52H60Cl2N8O4,化学结构式如下所示:
2.一种如权利要求1所述的检测高效氟吡甲禾灵的双离子型环状鎓盐探针的合成方法,其特征在于,合成路线为:
其中,化合物1为双离子型环状鎓盐探针,化合物2为1,4-(二-(2-(N-咪唑基己氧基苯基)-2-氰基-乙烯基))苯,化合物3为R,R-1,2-二(氯乙酰氨基)环己烷;
所述合成方法具体包括如下步骤:
在氮气保护下,将化合物2和化合物3混合,加入甲苯做溶剂,在120℃下搅拌反应12~24h;
反应结束后,趁热过滤出沉淀,沉淀再利用有机溶剂进行洗涤,即得到所述的双离子型环状鎓盐探针,即化合物1。
3.如权利要求2所述的一种检测高效氟吡甲禾灵的双离子型环状鎓盐探针的合成方法,其特征在于:所述化合物2和化合物3的摩尔比为1:0.5~1.5。
4.如权利要求2所述的一种检测高效氟吡甲禾灵的双离子型环状鎓盐探针的合成方法,其特征在于:所述甲苯溶剂的加入量为30~60mL。
5.如权利要求2所述的一种检测高效氟吡甲禾灵的双离子型环状鎓盐探针的合成方法,其特征在于:所述沉淀依次利用二氯甲烷、甲醇、丙酮进行洗涤,且二氯甲烷、甲醇、丙酮各取10mL。
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