CN109369527B - 一种含硒纯有机室温磷光化合物的制备及其氧传感应用 - Google Patents
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Abstract
本发明本发明属于发光材料技术领域,公开了一种含硒纯有机室温磷光化合物的制备及其氧传感应用。该化合物由4‑溴‑1,8‑萘酐和正丁胺反应生成萘酰亚胺母体,再由萘酰亚胺母体与二苯基二硒醚反应制得。本发明合成的含硒纯有机室温磷光化合物易于制备,具有良好的氧敏感性,响应速度快,可在氧气浓度为0~100%氧气浓度范围内检测氧气含量,可用来检测有机溶剂中氧气浓度。
Description
技术领域
本发明属于发光材料技术领域,涉及含硒纯有机室温磷光化合物的制备方法及其对氧气浓度的检测。
背景技术
氧传感器在生物医学、食品科学及环境检测等诸多领域有广泛的应用(Opt.Express 2009,17,22341-22350;Bulg.Chem.Commun.2013,45;J.Environ.Eng.2007,133,655-658),因此,开发高效、快速、灵敏的氧检测技术具有重要意义。发光氧传感技术利用氧分子猝灭氧敏感探针的磷光(磷光探针)的原理实现对氧气浓度的检测。处于第一三重激发态(T1)的磷光探针与基态(三重态)氧分子发生动态(扩散控制的)碰撞,磷光探针的T1态能量通过碰撞传递给氧分子,自身的磷光被猝灭,碰撞过程伴随着单重态氧分子的生成。发光氧传感器由于其有着检测过程中不消耗氧、精密度好、准确度高及易于小型化等优点,收到人们的广泛关注
含硒纯有机室温磷光化合物具有激发态寿命长、光稳定性强、不含有金属元素等优点,是一类性能优异的磷光探针。
发明内容
本发明的目的是提供含硒纯有机室温磷光化合物的制备方法及其对氧气浓度的检测。
本发明采用的技术方案是:含硒纯有机室温磷光化合物由4-溴-1,8-萘酐和正丁胺反应生成萘酰亚胺母体,再由萘酰亚胺母体与二苯基二硒醚反应制得,其化学结构式如下:
所述化合物的具体合成步骤如下:
(1)萘酰亚胺母体的合成:将4-溴-1,8-萘二甲酸酐0.8~1.0mmol、正丁胺1.0~1.2mmol和无水乙醇45~60mL加入到圆底烧瓶中,80~100℃加热回流3~5h。反应完后,干燥样品,所得粗产品用层析法分离,制得萘酰亚胺母体。
(2)含硒纯有机室温磷光化合物的合成:向三口烧瓶中加入二苯基二硒醚4~5mmol,真空和惰性气体交替置换,使烧瓶中充满惰性气体,加入无水乙醇20~30mL,冷却烧瓶至0~5℃,然后加入硼氢化钠5~6mmol,加入萘酰亚胺母体4.4~5.5mmol,加入CuI 4.4~5.5mmol,70~90℃加热回流2-3h,薄层色谱法监测反应,反应完后,除去滤液,滤渣用层析法分离,得到含硒纯有机室温磷光化合物。
上述的含硒纯有机室温磷光化合物用做磷光探针,用于检测氧气浓度,包括如下步骤:
步骤1,将该室温磷光化合物溶于有机溶剂中,装入长颈比色皿中,配成浓度为10-100μmol的溶液,鼓入惰性气体,除尽氧气,注入不同体积空气后测试磷光激发光谱,激发波长为吸收光谱的最大吸收波长,将最大发射波长处的磷光强度拟合成标准曲线
步骤2,将该室温磷光化合物溶解到待测溶液中,测试其在最大吸收波长处的磷光光谱,将最大发射波长处的磷光强度,与标准曲线比对后,可知该溶液的氧气含量。
本发明的有益效果是:这种含硒纯有机室温磷光化合物易于制备,由4-溴-1,8-萘酐和正丁胺反应生成萘酰亚胺母体,再由萘酰亚胺母体与二苯基二硒醚反应制得。该化合物有良好的氧敏感性,响应速度快,可在氧气浓度为0~100%氧气浓度范围内检测氧气含量。
附图说明
图1是该化合物在CH3CN中的紫外/可见吸收光谱图。
图2是该化合物在CH3CN中的发射图
图3是该化合物在CH3CN中对不同氧气浓度磷光响应曲线
图4是含硒纯有机室温磷光化合物在CH3CN中不同氧气浓度下的磷光强度曲线。
具体实施方式
实施例1含硒纯有机室温磷光化合物的具体合成步骤如下:
(1)萘酰亚胺母体的合成:将4-溴-1,8-萘二甲酸酐1.0mmol、正丁胺1.2mmol和无水乙醇60mL加入到圆底烧瓶中,100℃加热回流3h。反应完后,用旋转蒸发仪旋干溶剂,所得粗产品用柱层析法分离,制得萘酰亚胺母体。
(2)含硒纯有机室温磷光化合物的合成:向50mL的三口烧瓶中加入二苯基二硒醚2.5mmol,真空和惰性气体交替置换3次后,加入无水乙醇30ml,冷却烧瓶至0-5℃,然后加入硼氢化钠6mmol,加入萘酰亚胺母体5.5mmol,加入CuI5.5mmol,90℃加热回流2h,薄层色谱法监测反应,反应完后,过滤除去滤液,滤渣用柱层析法分离,得到含硒纯有机室温磷光化合物。
实施例2含硒纯有机室温磷光化合物的具体合成步骤如下:
(1)萘酰亚胺母体的合成:将4-溴-1,8-萘二甲酸酐0.8mmol、正丁胺1.0mmol和无水乙醇45mL加入到圆底烧瓶中,80℃加热回流4h。反应完后,用旋转蒸发仪旋干溶剂,所得粗产品用柱层析法分离,制得萘酰亚胺母体。
(2)含硒纯有机室温磷光化合物的合成:向50mL的三口烧瓶中加入二苯基二硒醚2.0mmol,真空和惰性气体交替置换3次后,加入无水乙醇20ml,冷却烧瓶至0-5℃,然后加入硼氢化钠5mmol,加入萘酰亚胺母体4.4mmol,加入CuI 4.4mmol,70℃加热回流3h,薄层色谱法监测反应,反应完后,过滤除去滤液,滤渣用柱层析法分离,得到含硒纯有机室温磷光化合物。
实施例3含硒纯有机室温磷光化合物的光谱性能
图1是该化合物在CH3CN中浓度为10μmol/L得到的归一化紫外/可见吸收光谱图,最大吸收波长是390nm。图2是该化合物在CH3CN中的发射光谱图,其中最大发射波长是600nm。
实施例4含硒纯有机室温磷光化合物对氧气浓度的检测
步骤1,将该化合物溶在CH3CN中,配成浓度为10μmol/L的溶液,取3ml放入长颈比色皿中,比色皿口用胶塞封住,用一根长针头穿过胶塞,鼓氮气30min,除尽氧气,再用针筒通入不同体积的空气,激发波长为390nm,如图3所示测试在不同氧气浓度时该化合物的磷光响应曲线,并将600nm处的磷光强度与氧气体积的关系绘制成图4,拟合的标准曲线为:y=4188.73*exp(-X/0.51)+220.15,R2=0.99。
步骤2,将该化合物溶在CH3CN中,配成浓度为10μmol/L的溶液,取3ml放入长颈比色皿中,比色皿口用胶塞封住,用一根长针头穿过胶塞,鼓氮气5min,测试其磷光强度,将600nm处的磷光强度1787带入标准曲线中,可知,此时溶液中空气含量为0.50ml,即氧气含量为0.05mg/ml。
Claims (2)
1.含硒纯有机室温磷光化合物的制备方法,其特征在于:包括合成步骤如下:
(1)萘酰亚胺母体的合成:将4-溴-1,8-萘二甲酸酐0.8~1.0mmol、正丁胺1.0~1.2mmol和无水乙醇45~60mL加入到圆底烧瓶中,80~100℃加热回流3~4h, 反应完后,干燥样品,所得粗产品用层析法分离,制得萘酰亚胺母体;
(2)含硒纯有机室温磷光化合物的合成:向三口烧瓶中,加入二苯基二硒醚2~2.5mmol,真空和惰性气体交替置换,使烧瓶中充满惰性气体,加入无水乙醇20~30mL,冷却烧瓶至0~5℃,然后加入硼氢化钠5~6mmol,加入萘酰亚胺母体4.4~5.5mmol,加入CuI4.4~5.5mmol,70-90℃加热回流2-3h,薄层色谱法监测反应,反应完后,除去滤液,滤渣用层析法分离,得到用于检测溶液中氧气浓度的含硒纯有机室温磷光化合物;该化合物的化学结构式如下:
2.权利要求1所述方法制备得到的含硒纯有机室温磷光化合物的应用,其特征在于,用于检测氧气浓度,包括如下步骤:
步骤1,将该室温磷光化合物溶于有机溶剂中,装入长颈比色皿中,配成浓度为10-100μmol/L的溶液,鼓入惰性气体,除尽氧气,注入不同体积空气后测试磷光激发光谱,激发波长为吸收光谱的最大吸收波长,将最大发射波长处的磷光强度拟合成标准曲线;
步骤2,将该室温磷光化合物溶解到待测溶液中,测试其在最大吸收波长处的磷光光谱,将最大发射波长处的磷光强度,与标准曲线比对后,可知该溶液的氧气含量。
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