CHINESE JOURNAL OF ENERGETIC MATERIALS
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BPTAP的荧光特性及其稳定性
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1.火箭军工程大学核工程学院, 陕西 西安 710025;2.中国工程物理研究院化工材料研究所, 四川 绵阳 621999;3.湖北三江航天江河化工科技有限公司, 湖北 宜昌 444200

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国家自然科学基金资助(21975235)


Fluorescence Properties and Fluorescence Stability of BPTAP
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1.School of Nuclear Engineering, Rocket Force University of Engineering, Xi′an 710025, China;2.Institute of Chemical Materials, CAEP, Mianyang 621999, China;3.Hubei Sanjiang Aerospace Jianghe Chemical Technology Co.,Ltd.,Yichang 444200,China

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    摘要:

    为了掌握2,4,8,10-四硝基苯并-1,3a,6,6a-四氮杂戊搭烯并吡啶(BPTAP)独特的荧光性能,研究了BPTAP在不同溶剂(乙腈、甲醇、四氢呋喃、丙酮、三氯甲烷、乙酸乙酯、N′,N′-二甲基甲酰胺、二甲基亚砜)、含水量(0~100%)和pH(2.0~12.0)中的光谱性质,考察了光照、温度、pH等对BPTAP溶液荧光稳定性的影响,并结合超高效液相色谱-高分辨质谱联用技术解析了BPTAP的荧光衰退机制。结果表明,尽管BPTAP拥有4个硝基取代基,但其在部分有机溶剂中展现出较强的绿色荧光。BPTAP在乙腈中荧光强度最大,其最大吸收/发射波长为460 nm/508 nm。低含水量(≤10%)会增加BPTAP荧光强度,而高含水量(>10%)会使BPTAP荧光强度急剧下降。BPTAP在酸性、中性及弱碱性中具有较强荧光,当pH大于≥9.0时,BPTAP荧光强度随pH增大急剧下降。BPTAP在室温和自然光下稳定性较好,光照波长越接近其最大吸收波长,荧光稳定性越差。升高温度会使BPTAP荧光稳定性变差。pH增大不仅会降低BPTAP的荧光强度,同时也会加速BPTAP荧光的衰退。BPTAP在碱性条件下的荧光衰退机制涉及基于亲核取代反应的化学变化过程,BPTAP吡啶环对位的硝基在碱性溶液中被羟基所取代,形成新的化合物1([M-H]-的元素组成为C11H3N8O7)。

    Abstract:

    The fluorescence properties and fluorescence stability of 2,4,8,10-tetrabroitro-benzopyrido-1,3a,6,6a-tetraazapentylene (BPTAP) were comprehensively investigated. The spectral properties of BPTAP in different solvents (acetonitrile, methanol, tetrahydrofuran, acetone, trichloromethane, ethyl acetate, N"-N"-dimethylformamide, dimethyl sulfone), content of water (0-100%), pH (2.0-12.0) were studied in detail. The effects of light, temperature and pH value on the fluorescence stability of BPTAP solution were investigated, and the mechanism of fluorescence decay of BPTAP solution was analyzed by ultra performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS). The results show that although BPTAP has four nitro groups, it exhibits strong green fluorescence in some organic solvents. The fluorescence intensity of BPTAP in acetonitrile is the highest, and its maximum absorption/emission wavelength is 460 nm/508 nm. Low content of water (≤10%) can increase fluorescence intensity of BPTAP, while high content of water (>10%) decrease the fluorescence of BPTAP sharply. BPTAP has higher fluorescence in acidic, neutral and weak alkaline conditions. When the pH value is above 9.0, the fluorescence of BPTAP decreases rapidly with the increase of pH value. BPTAP shows good stability in room temperature and natural light. The closer the light wavelength is to the maximum absorption wavelength of BPTAP and the higher the temperature, the worse the fluorescence stability of BPTAP. The increase of pH value not only reduces the fluorescence intensity of BPTAP, but also accelerates the decline of BPTAP fluorescence. The mechanism of fluorescence decay of BPTAP under alkaline condition is based on nucleophilic substitution. The nitro group at para site of pyridine ring is replaced by the hydroxyl group in alkaline solution to form a new compound 1 (the elemental composition [M-H]- is C11H3N8O7).

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引用本文

楼英杰,陈建波,丁欢,等. BPTAP的荧光特性及其稳定性[J].含能材料, 2022, 30(11):1157-1164. DOI:10.11943/CJEM2022166.
LOU Ying-jie, CHEN Jian-bo, DING Huan, et al. Fluorescence Properties and Fluorescence Stability of BPTAP[J]. Chinese Journal of Energetic Materials, 2022, 30(11):1157-1164. DOI:10.11943/CJEM2022166.

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  • 收稿日期: 2022-06-20
  • 最后修改日期: 2022-09-29
  • 录用日期: 2022-09-01
  • 在线发布日期: 2022-09-21
  • 出版日期: 2022-11-25