CN115181061B - 一种镍化合物及其合成方法和在检测农残草甘膦中的应用 - Google Patents
一种镍化合物及其合成方法和在检测农残草甘膦中的应用 Download PDFInfo
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
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- C07—ORGANIC CHEMISTRY
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
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Abstract
本发明涉及有机合成技术领域，特别涉及一种镍化合物及其合成方法和在检测农残草甘膦中的应用，所述合成方法包括向反应容器中加入2,2':6',2"‑三联吡啶‑4,4',4"‑三甲酸、六水合乙酸镍和溶剂，将所得混合液进行水热反应，待反应结束后，降温析出晶体，分离并收集晶体，干燥，得到镍化合物；结合实践可知，基于本发明提供的方法合成得到的镍化合物与纳米金相结合来修饰玻碳电极，修饰后的AuNPs/镍化合物/GCE传感器对农药草甘膦的检测表现出较好的选择性、高的稳定性和灵敏性以及宽的检测范围。
Description
技术领域
本发明涉及有机合成技术领域，特别涉及一种镍化合物及其合成方法和在检测农残草甘膦中的应用。
背景技术
农药残留向来是一个很严重的环境问题，由于农药大都具有显著和生物毒性，一旦进入环境，其毒性、高残留特性便会发生效应，以各种形态相互转化、分散以及富集过程(即迁移)，它们可以通过大气、水、食品等进入人体，在人体某些器官中积累，造成中毒，危害人体健康。
草甘膦(GLY,Glyphosate)是一种有机膦类除草剂，具有非选择性和广谱特性，作为世界上生产和使用最多的除草剂之一。草甘膦的大量使用带来了环境问题，在许多国家的地表水中有所检出。同时，有研究表明土壤和饮用水中存在的草甘膦残留会对人体健康造成影响，可使乙酰胆碱酯酶不可逆失活，产生各种健康风险，如呼吸、心肌和神经肌肉功能障碍。但由于实际样品中的农残草甘膦含量往往很少，共存物质复杂，因此建立快速、高灵敏、高选择性的农残检测方法具有重要的现实意义。
配位聚合物(CPs,Coordination Polymers)是指在晶体工程自组装原理指导下，有机配体与金属原子通过配位键而形成的不同维数的金属-有机化合物。特别是具有活性位点的配位聚合物。如在结构上具有开放的金属位点或具有活性官能团等特点的化合物。具有活性位点的配位聚合物能与目标物快速产生作用，这主要是因为活性位点可以与目标物产生弱作用或发生交换使检测物与化合物的框架发生作用。因此，将具有活性位点的配位聚合物与电化学传感技术相结合，发展高选择性、高灵敏度、微型化和实用性强的新型化学/纳米传感分析技术具有重要的理论和实际意义。同时，在衡量农残检测、监控及治理方面具有十分重要的应用前景。
发明内容
本发明的目的在于提供一种镍化合物的合成方法，并将合成得到的镍化合物应用于农残草甘膦的电化学检测中，对农残草甘膦的检测表现出较好的选择性、高的稳定性和灵敏性以及宽的检测范围。
为了实现上述目的，本发明采用以下技术方案予以实现：
一种镍化合物的合成方法，包括向反应容器中加入2,2':6',2"-三联吡啶-4,4',4"-三甲酸、六水合乙酸镍和溶剂，将所得混合液进行水热反应，待反应结束后，降温析出晶体，分离并收集晶体，干燥，得到镍化合物。
在进一步的技术方案中，所述溶剂是由N,N'-二甲基乙酰胺、去离子水和乙腈混配而成。
在进一步的技术方案中，所述混合液的pH值为6.0。
在进一步的技术方案中，所述2,2':6',2"-三联吡啶-4,4',4"-三甲酸与六水合乙酸镍的摩尔比为2:3。
在进一步的技术方案中，所述水热反应的条件包括，反应温度为110-120℃，反应时间为5-7天。
在进一步的技术方案中，降温速率为5℃/h。
本发明还提供了一种基于上述方法合成得到的镍化合物。
在进一步的技术方案中，所述镍化合物的结构式为Ni(HTTC)(H2O)2。
本发明还提供了一种基于上述镍化合物在检测农残草甘膦中的应用。
与现有技术相比，本发明具有以下技术效果：
1、本发明提供的是一种水热合成法合成镍化合物的方案，具有合成方法简单，容易实现的优点；
2、结合实践可知，基于本发明提供的方法合成得到的镍化合物具有较高的热稳定性，框架能稳定到310℃左右；
3、结合实践可知，基于本发明提供的方法合成得到的镍化合物与纳米金相结合来修饰玻碳电极，修饰后的AuNPs/镍化合物/GCE传感器对农药草甘膦的检测表现出较好的选择性、高的稳定性和灵敏性以及宽的检测范围。
本发明的其他特征和优点将在随后的具体实施方式中予以详细说明。
附图说明
图1示出为本发明实施例1合成得到的化合物1中镍原子的配位模式；
图2示出为一个HTTC配体连接着二个中心镍原子，在空间形成的链状结构；
图3示出为化合物1通过氢键将链状结构形成三维的孔状结构；
图4示出为本发明实施例1合成得到的化合物1的热重曲线；
图5示出为循环伏安法探针各个电极的传导性；
图6示出为修饰电极AuNPs/化合物1/GCE对草甘膦的浓度在5×10-12mol/l-5×10- 7mol/l的范围内展现出很好的线性关系和低检测限(参数：频率40Hz,振幅20mV,电压增量4mV)；
图7示出为修饰电极对草甘膦具有很好的选择性(频率40Hz,振幅20mV,电压增量4mV)；
图8示出为共存物质存在的情况下修饰电极对草甘膦检测的影响(频率40Hz,振幅20mV,电压增量4mV)；
图9示出为修饰电极对草甘膦检测的重复性(频率40Hz,振幅20mV,电压增量4mV)。
具体实施方式
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解，下面结合具体实施例，进一步阐明本发明。
实施例1
本实施例提供了一种镍化合物的合成方法，包括将0.1mmol(36.5mg)的2,2':6',2"-三联吡啶-4,4',4"-三甲酸(H3TTC)和0.15mmol(34.2mg)的六水合乙酸镍((CH3COO)2Ni·6H2O)混合后加入到小玻璃瓶中，然后加入5.0ml N,N'-二甲基乙酰胺(DMA)、2.0ml去离子水和3.0ml乙腈，滴加2滴硝酸溶液，使混合液pH值为6.0；此时混合液为澄清状态，将小玻璃瓶密封，加热到115℃并保温6天，然后以5℃/h的速率降到室温，此时小玻璃瓶内有草绿色的块状晶体析出，分离并收集晶体，干燥，得到所述镍化合物。
为方便描述，将实施例1制得镍化合物定义为化合物1，化合物1的结构测定：
选取形状规则光亮的合适尺寸的晶体在室温下置于Bruker Smart-APEXII CCD单晶X-射线衍射仪上，用经石墨单色器单色纯化的Mo-Kα射线(λ＝0.071073nm)，以ω扫描方式扫描，收集衍射数据，全部强度数据经Lp校正和吸收校正。晶体结构通过SHELXTL软件由直接法解得。全部非氢原子坐标、各向异性温度因子和氢原子坐标及各向同性温度因子经全矩阵最小二乘法F2精修修正至收敛。所有计算均用SHELXL-97程序包完成。化合物1的相关晶体学数据列于表1中。
表1化合物1的晶体数据
化合物1的结构描述：
本实施例中，化合物1是由水热合成法合成的一例具有活性位点的镍化合物[Ni(HTTC)(H2O)2](1)；
化合物1为六配位的八面体结构，其中三个配位的氮原子来自一个HTTC配体上的三个氮原子，三个氧原子分别来自一个部分质子化的HTTC配体和配位的水分子，如图1所示。在化合物1中，羧酸配体部分质子化，其中一个羧酸没有脱去氢原子，这为化合物1留下了活性位点，一个HTTC配体连接着二个中心镍原子，在空间形成链状结构，如图2所示。化合物1可以通过氢键将这些链状结构形成三维的孔状结构，如图3所示。
化合物1的稳定性试验：
将化合物1在室温下烘干以备用，实验研究了化合物1的热稳定性，如图4所示。化合物1的热重曲线有两个失重阶段。第一步失重为7.52％，对应于失去配位的二个水分子(理论值：7.86％)，然后框架保持稳定。当温度为310℃时，化合物1中的有机物开始分解，框架发生坍塌。最终，样品残余量为17.55％。
利用化合物1电化学检测草甘膦试验：
将化合物1协同纳米金覆盖在玻碳电极(GCE)表面，发展新型电化学修饰电极AuNPs/化合物1/GCE。修饰后的玻碳电极对草甘膦的检测表现出很好的选择性、高的稳定性和灵敏性以及宽的检测范围。
用循环伏安法(CVS)去探针各个电极的传导性。图5为不同电极下获得的CVs曲线(扫描速度为100mV·s-1)。曲线a为裸GCE电极；b为1/GCE电极，即化合物1/GCE电极；c为AuNPs/1/GCE电极，即AuNPs/化合物1/GCE电极。实验结果显示，AuNPs/化合物1/GCE电极有较好的传导性。
为了进一步优化检测效果，优化了最佳实验条件。沉积金段数为6段，电解质为氯化钾溶液；电解质浓度为0.05M的氯化钾，最佳的静止时间为100秒。
在最佳优化的条件下，修饰电极AuNPs/化合物1/GCE对草甘膦的浓度在5×10- 12mol/l-5×10-7mol/l的浓度范围内展现出很好的线性关系(R2＝0.9915)，见图6所示。这远低于美国环境署(EPA)及世界卫生组织(WHO)制定的限度浓度。尤其是修饰电极AuNPs/化合物1/GCE对草甘膦展现出的宽的线性范围及低的检测限，这与汞电极及其检测方法相比有较大优势。对草甘膦的高敏感性及低检测限应归因于化合物1和纳米金增大了电极表面比表面积以及化合物1具有活性位点，使得放大了草甘膦的浓度，降低了检测极限。
高的特异性是化学修饰电极最主要的优势。值得一提的是，修饰电极AuNPs/化合物1/GCE对其他农药[毒死蜱(CHL)、草铵膦(GLA)、吡蚜酮(PYM)、苯醚甲环唑(DIF)、啶虫脒(ACE)、莠去津(ATR)、苦参碱(MAT)、吡唑醚菌酯(PYR)]检测的电化学信号强度较弱。这说明了修饰电极AuNPs/化合物1/GCE对草甘膦具有很好的选择性，见图7。此外，卓越的电化学传感器在检测时，不会被其他共存物质所干扰。因此，实验研究了共存农药存在的情况下修饰电极AuNPs/化合物1/GCE对草甘膦检测的影响。在加入干扰物质前后，AuNPs/化合物1/GCE对草甘膦的检测几乎没有影响，如图8所示。此外，实验研究了AuNPs/化合物1/GCE传感器每隔两天对草甘膦进行检测实验，结果发现峰的强度减小很少，这说明修饰电极AuNPs/化合物1/GCE对草甘膦检测有较高的重复性，如图9所示。因此，修饰电极AuNPs/化合物1/GCE传感器对草甘膦的检测具有很高的选择性，好的抗干扰性、高的灵敏性和宽的检测极限。
基于上述，将具有活性位点的化合物1与纳米金相结合来修饰玻碳电极。修饰后的玻碳电极对农药草甘膦的检测表现出很好的选择性、高的稳定性和灵敏性以及宽的检测范围。这项工作为寻找新的传感器以及电化学材料提供了新的思路和方法。
以上显示和描述了本发明的基本原理、主要特征和本发明的特点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明的范围内。本发明要求保护的范围由所附的权利要求书及其等效物界定。
Claims (5)
1.一种镍化合物在检测农残草甘膦中的应用，所述镍化合物的合成方法包括：向反应容器中加入2,2':6',2"-三联吡啶-4,4',4"-三甲酸、六水合乙酸镍和溶剂，将所得混合液进行水热反应，待反应结束后，降温析出晶体，分离并收集晶体，干燥，得到镍化合物；
所述溶剂是由N,N'-二甲基乙酰胺、去离子水和乙腈混配而成；
所述镍化合物中镍原子的配位模式如下：
所述镍化合物的晶体数据如下：
分子式 C18H13NiN3O8
分子量 458
空间群 C2/c
a [Å] 19.659
b [Å] 13.943
c [Å] 17.066
α/(°) 90
β/(°) 115.377
γ/(°) 90
V [Å3] 4226.28
Z 2
μ [mm-1] 0.702
Final R [a] indices R 1 = 0.068
[I>2σ(I)] wR 2 = 0.042。
2.根据权利要求1所述的应用，其特征在于，所述混合液的pH值为6.0。
3.根据权利要求1所述的应用，其特征在于，所述2,2':6',2"-三联吡啶-4,4',4"-三甲酸与六水合乙酸镍的摩尔比为2:3。
4.根据权利要求1所述的应用，其特征在于，所述水热反应的条件包括，反应温度为110-120℃，反应时间为5-7天。
5.根据权利要求1所述的应用，其特征在于，降温速率为5℃/h。
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