摘要
快速选择性检测苦味酸(PA)、三硝基芴酮(TNF)等硝基芳环爆炸物已成为当前研究的热点之一.基于B3LYP/6-311+g(d,p)理论水平,对氮杂苯并菲基元取代的α-氰基二苯乙烯(TPN-Ar-DPA:a)、氮、氧杂苯并菲基元取代的α-氰基二苯乙烯(TPNO-Ar-DPA:b)探针分子及八个被检硝基芳环分子进行结构优化与频率计算;对a、b分子稳定结构分别计算气态和四氢呋喃(C_(4)H_(8)O)溶剂中的电子吸收光谱及荧光光谱;对a、b探针分子与硝基芳环所形成二聚体分子的结合能分别计算;最后对二聚体分子进行了简约化密度梯度(RDG)分析.研究结果表明,分子b的平面性优于a,分子b的能隙值小于a.气相与C_(4)H_(8)O溶剂中,分子b吸收光谱与荧光光谱比分子a均明显红移,但在C_(4)H_(8)O溶剂中,两个分子的荧光光谱均有不同程度的蓝移;与分子a相比,分子b与八个被检物所形成二聚体的结合能绝对值相对较大,对硝基芳香环检测物的选择性和灵敏度更好,可设计为对硝基酚(PNP)、TNF、PA、3,4-二硝基苯甲酸(DNBA)的探针分子.探针分子对硝基芳环具有较好地选择性和灵敏度,主要源于二聚体分子间存在较强的氢键作用.
The rapid and selective detection of nitroaromatic explosives such as trinitrophenol(PA)and trinitrofluorenone(TNF)has become one of the current research hotspots.Based on the B3LYP/6-311+g(d,p)theoretical level,The structural optimization and frequency calculation were performed on these molecules,which are α-cyanostilbene(TPN-Ar-DPA:a)substituted by azabenzophene and α-cyanostilbene(TPNO-Ar-DPA:b)substituted by nitrogen and oxobenzophene,eight detected nitro-aromatic ring molecules.The electron absorption spectra and fluorescence spectra in gaseous and tetrahydrofuran(C_(4)H_(8)O)solvents for stable structures of molecules a and b were calculated,respectively.The binding energies of dimer molecules formed by probe molecules a and b with nitroaromatic rings were separately calculated.Finally,reduced density gradient(RDG)analysis was performed on the dimer molecules.The research results indicate that the planarity of molecule b is better than that of a,and the energy gap value of molecule b is less than that of a.In gas phase and C_(4)H_(8)O solvent,the absorption and fluorescence spectra of molecule b show a significant red shift compared to molecule a,but in C_(4)H_(8)O solvent,the fluorescence spectra of both molecules show varying degrees of blue shift;Compared with a,probe molecule b has a relatively higher absolute value of binding energy to the dimer formed by the eight analytes.b has the best selectivity and sensitivity for the detection of nitroaromatic ring and can be designed as the probe molecule of p-nitrophenol(PNP),TNF,PA,and 3,4-dinitrobenzoic acid(DNBA).The probe molecules have good selectivity and sensitivity to nitroaromatic rings,mainly due to the strong hydrogen bonding between dimer molecules.
作者
张宇金
陈自然
李博
张宇红
何旭东
张莉萍
ZHANG Yu-Jin;CHEN Zi-Ran;LI Bo;ZHANG Yu-Hong;HE Xu-Dong;ZHANG Li-Ping(School of Civil Engineeringand Architecture,Sichuan Vocational and Technical College,Suining 629000,China;School of Energy,Chemical Engineering and Environment,Sichuan Vocational and Technical College,Suining 629000,China)
出处
《原子与分子物理学报》
CAS
北大核心
2025年第5期27-34,共8页
Journal of Atomic and Molecular Physics
基金
四川省科技计划项目(2019YFG0252)
四川职业技术学院自然科学重点项目(2022YZA003)。
关键词
苯并菲基元
硝基芳环
爆炸物
探针性能
密度泛函理论
简化密度梯度分析
Benzofield Primitive
Nitro-aromatic ring
Explosive
Probe performance
Density functional theory
Simplified density gradient analysis
