CN114957309A - 砜基修饰硅芴及二噻吩砜并硅芴衍生物及其制备方法和应用 - Google Patents
砜基修饰硅芴及二噻吩砜并硅芴衍生物及其制备方法和应用 Download PDFInfo
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Abstract
本发明采用原位化学氧化合成策略,提供了一类同时具有长波长发射、发射光颜色可调、高颜色纯度、高量子产率、高亮度、高光热稳定性和可用于活细胞成像特性的砜基修饰硅芴及二噻吩砜并硅芴衍生物,该类砜基修饰硅芴及二噻吩砜并硅芴衍生物的制备方法简单、高效,且该类砜基修饰硅芴及二噻吩砜并硅芴衍生物可作为传统荧光染料的替代品,用作荧光可视化材料应用于酸碱蒸汽传感器、生物成像和潜在指纹检测与识别。
Description
技术领域
本发明属于化学技术、光电材料领域,涉及硅芴化合物,具体涉及一类砜基修饰硅芴及二噻吩砜并硅芴衍生物、该类硅芴衍生物的制备方法及其在荧光可视化中的应用。
背景技术
近年来,芴类结构9-位为硅桥联的硅芴类化合物以其独特的电子结构和光电性能受到研究者们越来越多的关注,这类化合物在有机发光二极管(OLED)、有机太阳能电池(OSC)、有机场效应管(OFET)等光电功能材料领域有广泛的应用前景。此外,硅芴类化合物作为有机光电功能材料因其独特的电子结构和性能,在有机电致发光、有机固体激光、光电传感器、生物成像以及光动力治疗等许多高科技领域展现出极大的应用前景,已经成为一个新兴的多学科交叉前沿研究领域。随着研究工作的深入,硅芴衍生物已被证明在生物成像和荧光成像技术方面可能优于传统荧光染料,因此,最近几年已经开发了许多简便、高效和创新的硅芴化合物合成技术,以便得到具有新的结构和功能的硅芴衍生物。
荧光染料用于荧光可视化传感、生物成像等方面的应用,须具备长波长发射、色纯度高、足够的亮度和良好的光热稳定性等优点。因此,硅芴衍生物作为传统荧光染料的替代品,也需要具有长波长发射、高颜色纯度、高量子产率、足够亮度、高光热稳定性和可用于活细胞成像的特点,这些特点也是硅芴衍生物能广泛应用所必需的关键特性。目前,开发同时具有上述关键特性的硅芴衍生物仍然是本领域具有挑战性的研究。
发明内容
通过简单的合成策略,设计合成具有长波长发射、高颜色纯度、高量子产率、足够亮度、高光热稳定性和可用于活细胞成像的硅芴衍生物,作为传统荧光染料的替代品,具有重要价值和意义。其中通过简单的原位化学氧化,改变硅芴化合物的电子结构,利用负诱导效应以增加电子亲和力和电子注入能力,增大荧光发射波长,提高量子产率和光亮度便是一种简单的策略。
为解决现有技术的问题,本发明采用原位化学氧化合成策略,提供了一类同时具有长波长发射、高颜色纯度、高量子产率、足够亮度、高光热稳定性和可用于活细胞成像特性的砜基修饰硅芴及二噻吩砜并硅芴衍生物。
本发明的具体技术方案如下:
本发明提供的砜基修饰硅芴衍生物,其特征在于,结构如下式Ⅰ所示:
式Ⅰ中:R1选自4-甲氧基苯基、2,4-二甲氧基苯基、4-二甲氨基苯基或三苯胺基。
本发明还提供了一种上述砜基修饰硅芴衍生物的制备方法,其特征在于,包括如下步骤:步骤S1-1,将结构如下式Ⅱ所示的化合物放入配有搅拌棒的双颈烧瓶中,加入无水二氯甲烷和间氯过氧苯甲酸,在氮气、氩气或空气氛围中搅拌进行反应,
式Ⅱ中:R1选自4-甲氧基苯基、2,4-二甲氧基苯基、4-二甲氨基苯基或三苯胺基;步骤S1-2,待反应结束后,用亚硫酸钠溶液、碳酸氢钠溶液、食盐水洗涤反应产物,制得预处理产物;步骤S1-3,用无水硫酸钠干燥并浓缩预处理产物,制得粗产物;步骤S1-4,通过柱色谱纯化粗产物,即可获得砜基修饰硅芴衍生物。
本发明提供的砜基修饰硅芴衍生物的制备方法,还可以具有这样的技术特征,其中,步骤S1-1中结构如式Ⅱ所示的化合物与间氯过氧苯甲酸的摩尔比为1:4。
本发明提供的砜基修饰硅芴衍生物的制备方法,还可以具有这样的技术特征,其中,步骤S1-4中柱色谱的纯化溶剂为二氯甲烷或石油醚。
本发明还提供了上述砜基修饰硅芴衍生物在酸碱蒸汽传感器、生物成像和潜在指纹检测与识别中作为荧光可视化材料的应用。
本发明提供的二噻吩砜并硅芴衍生物,其特征在于,结构如下式Ⅲ所示:
式Ⅲ中:R1选自4-甲氧基苯基、2,4-二甲氧基苯基或三苯胺基;R2选自氢原子、4-甲氧基苯基或4-甲氧基苯乙炔基。
本发明还提供了一种上述二噻吩砜并硅芴衍生物的制备方法,其特征在于,包括如下步骤:步骤S2-1,将结构如下式Ⅳ所示的化合物放入配有搅拌棒的双颈烧瓶中,加入无水二氯甲烷和间氯过氧苯甲酸,在氮气、氩气或空气氛围中搅拌进行反应,
式Ⅳ中:R1选自4-甲氧基苯基、2,4-二甲氧基苯基或三苯胺基,R2选自氢原子、4-甲氧基苯基或4-甲氧基苯乙炔基;步骤S2-2,待反应结束后,用亚硫酸钠溶液、碳酸氢钠溶液、食盐水洗涤反应产物,制得预处理产物;步骤S2-3,用无水硫酸钠干燥并浓缩预处理产物,制得粗产物;步骤S2-4,通过柱色谱纯化粗产物,即可获得所述二噻吩砜并硅芴衍生物。
本发明提供的二噻吩砜并硅芴衍生物的制备方法,还可以具有这样的技术特征,其中,步骤S2-1中结构如式Ⅳ所示的化合物与间氯过氧苯甲酸的摩尔比为1:8。
本发明提供的二噻吩砜并硅芴衍生物的制备方法,还可以具有这样的技术特征,其中,步骤S2-4中柱色谱的纯化溶剂为二氯甲烷或石油醚。
本发明还提供了上述二噻吩砜并硅芴衍生物在酸碱蒸汽传感器、生物成像和潜在指纹检测与识别中作为荧光可视化材料的应用。
发明的作用与效果
由于本发明提供的一类砜基修饰硅芴及二噻吩砜并硅芴衍生物是采用简单的原位化学氧化合成策略,通过改变硅芴化合物的电子结构,利用负诱导效应以增加电子亲和力和电子注入能力,以增大荧光发射波长、提高量子产率和光亮度,实现获得同时具有长波长发射、高颜色纯度、高量子产率、足够亮度、高光热稳定性和可用于活细胞成像特性的硅芴衍生物。
因此本发明提供的一类砜基修饰硅芴及二噻吩砜并硅芴衍生物具备作为传统荧光染料的替代品应该具备的特性,而且该类硅芴衍生物的发射光颜色可调。该类硅芴衍生物的制备方法简单、高效,且该类硅芴衍生物可作为荧光可视化材料用于酸碱蒸汽传感器、生物成像和潜在指纹检测与识别。
附图说明
图1是本发明实施例的砜基修饰硅芴及二噻吩砜并硅芴衍生物的合成路径示意图;
图2是本发明实施例中砜基修饰硅芴衍生物1的核磁氢谱;
图3是本发明实施例中砜基修饰硅芴衍生物1的核磁碳谱;
图4是本发明实施例中二噻吩砜并硅芴衍生物6的核磁氢谱;
图5是本发明实施例中二噻吩砜并硅芴衍生物6的核磁碳谱;
图6是本发明实施例中硅芴衍生物2、3、6、9的晶体结构;
图7是本发明实施例中硅芴衍生物1~9在二氯甲烷中的紫外可见吸收光谱、荧光发射光谱和荧光照片;
图8是本发明实施例中硅芴衍生物1~9的固体荧光光谱和荧光照片;
图9是本发明实施例中砜基修饰硅芴衍生物3用作酸碱蒸汽传感器的照片;
图10是本发明实施例中硅芴衍生物4、7、9用于海拉细胞的细胞成像照片;
图11是本发明实施例中二噻吩砜并硅芴衍生物6、9用作潜在指纹检测与识别的照片。
具体实施方式
以下通过实施例说明本发明的具体步骤,但不受实施例限制。
在本发明中使用的术语,除非另有说明,一般具有本领域普通技术人员通常理解的含义。
在以下实施例中,未详细描述的各种过程和方法是本领域中公知的常规方法。
下述实施例中所采用的试剂为普通商业途径购得,未注明的实验操作及实验条件参考本领域的常规操作及常规条件。
以下结合附图来说明本发明的具体实施方式。
<实施例>
本实施例提供了一种砜基修饰硅芴衍生物,其结构如下式Ⅰ所示:
式Ⅰ中:
R1选自4-甲氧基苯基、2,4-二甲氧基苯基、4-二甲氨基苯基或三苯胺基。
本实施例还提供了上述砜基修饰硅芴衍生物的制备方法,具体包括如下步骤:
步骤S1-1,将0.18mmol结构如下式Ⅱ所示的化合物放入配有搅拌棒的50mL双颈烧瓶中,加入20mL无水二氯甲烷和间氯过氧苯甲酸(4.0当量,146mg,质量分数为85%),45℃,在氩气氛围中搅拌反应12小时,
式Ⅱ中:
R1选自4-甲氧基苯基、2,4-二甲氧基苯基、4-二甲氨基苯基或三苯胺基;
步骤S1-2,待反应结束,用亚硫酸钠溶液、碳酸氢钠溶液、食盐水洗涤反应产物,得到预处理产物;
步骤S1-3,用无水硫酸钠干燥并浓缩预处理产物,得到粗产物;
步骤S1-4,通过200~300目柱层析硅胶分离纯化粗产物,纯化溶剂为二氯甲烷和石油醚的混合物(二氯甲烷和石油醚的体积比为2:1),即可获得黄绿色粉末状的砜基修饰硅芴衍生物。
本实施例制得的4个砜基修饰硅芴衍生物,其结构如下式1~4所示:
4个砜基修饰硅芴衍生物的产率分别为:72.7%、69.1%、78.6%和75.3%。
本实施例还提供了一种二噻吩砜并硅芴衍生物,其结构如下式Ⅲ所示:
式Ⅲ中:
R1选自4-甲氧基苯基、2,4-二甲氧基苯基或三苯胺基;
R2选自氢原子、4-甲氧基苯基或4-甲氧基苯乙炔基。
本实施例还提供了上述二噻吩砜并硅芴衍生物的制备方法,具体包括如下步骤:
步骤S2-1,将0.18mmol结构如下式Ⅳ所示的化合物放入配有搅拌棒的50mL双颈烧瓶中,加入20mL无水二氯甲烷和间氯过氧苯甲酸(8.0当量,292mg,质量分数为85%),45℃,在氩气氛围中搅拌反应12小时,
式Ⅳ中:
R1选自4-甲氧基苯基、2,4-二甲氧基苯基或三苯胺基,
R2选自氢原子、4-甲氧基苯基或4-甲氧基苯乙炔基;
步骤S2-2,待反应结束,用亚硫酸钠溶液、碳酸氢钠溶液、食盐水洗涤反应产物,得到预处理产物;
步骤S2-3,用无水硫酸钠干燥并浓缩预处理产物,得到粗产物;
步骤S2-4,通过200~300目柱层析硅胶分离纯化粗产物,纯化溶剂为二氯甲烷和石油醚的混合物(二氯甲烷和石油醚的体积比为3:1),即可获得黄绿色粉末状的二噻吩砜并硅芴衍生物。
本实施例制得的5个二噻吩砜并硅芴衍生物,其结构如下式5~9所示:
5个二噻吩砜并硅芴衍生物的产率分别为:80.4%、78.8%、71.9%、75.6%和79.3%。
图1是本实施例的砜基修饰硅芴及二噻吩砜并硅芴衍生物的合成路径示意图。其中,图1(a)是本实施例的砜基修饰硅芴衍生物的合成路径示意图,图1(b)是本实施例的二噻吩砜并硅芴衍生物的合成路径示意图。
对本实施例制得的硅芴衍生物1~9进行核磁共振氢谱(1H NMR)、核磁共振碳谱(13C NMR)、傅里叶变换红外光谱(IR)、高分辨质谱(HRMS)测试表征,结果如下所示:
砜基修饰硅芴衍生物1:
1H NMR(400MHz,CDCl3):δ8.58(s,2H),7.98(s,2H),7.57(d,J=8.8Hz,4H),6.93(d,J=8.8Hz,4H),3.85(s,6H),3.35(s,6H)ppm;
13C NMR(101MHz,CDCl3):δ159.74,144.80,144.06,142.32,137.48,132.52,120.98,120.68,113.45,113.37,99.19,84.29,54.55,41.51,–4.71ppm;
IR(KBr,cm–1):2931,2205,1603,1506,1449,1308,1245,1137,1024,828,775,535,511;
HRMS(ESI,m/z):[M+H]+calculated for C34H30O6S2Si,627.1325;found627.1324。砜基修饰硅芴衍生物2:
1H NMR(400MHz,CDCl3):δ8.57(s,2H),7.98(s,2H),7.51(d,J=8.4Hz,2H),6.52(d,J=8.4Hz,2H),6.48(s,2H),3.91(s,6H),3.85(s,6H),3.44(s,6H),0.52(s,6H)ppm;
13C NMR(101MHz,CDCl3):δ162.38,161.84,145.68,144.85,143.14,138.62,134.82,122.16,121.43,105.43,104.31,98.67,97.01,89.09,55.94,55.71,42.18,–3.69ppm;
IR(KBr,cm–1):2922,2195,1700,1605,1566,1449,1300,1205,1137,1020,832,772,733,525;
HRMS(ESI,m/z):[M+H]+calculated for C36H34O8S2Si,687.1537;found687.1533。砜基修饰硅芴衍生物3:
1H NMR(600MHz,CDCl3):δ8.55(s,2H),7.94(s,2H),7.50(d,J=8.7Hz,4H),6.68(d,J=8.8Hz,4H),3.36(s,6H),3.03(s,12H),0.52(s,6H)ppm;
13C NMR(101MHz,CDCl3):δ150.96,145.29,144.83,142.80,138.13,133.23,122.45,121.47,111.91,108.77,102.03,85.10,42.39,40.28,–3.66ppm;
IR(KBr,cm–1):2925,2178,1696,1605,1531,1444,1360,1302,1238,1193,1135,944,808,783,760,667,511;
HRMS(ESI,m/z):[M+H]+calculated for C36H36N2O4S2Si,653.1958;found653.1952。
砜基修饰硅芴衍生物4:
1H NMR(600MHz,CDCl3):δ8.57(s,2H),7.97(s,2H),7.45(d,J=8.5Hz,4H),7.30(t,J=7.8Hz,8H),7.14(d,J=7.8Hz,8H),7.10(t,J=7.4Hz,4H),7.02(d,J=8.6Hz,4H),3.35(s,6H),0.53(s,6H)ppm;
13C NMR(101MHz,CDCl3):δ149.15,147.00,145.71,145.01,143.25,138.43,132.89,129.65,125.52,124.19,122.00,121.74,121.66,114.47,100.66,85.75,42.50,–3.70ppm;
IR(KBr,cm–1):2916,2199,1583,1486,1313,1271,1139,1082,1016,785,752,692,614,509;
HRMS(ESI,m/z):[M+H]+calculated for C56H44N2O4S2Si,901.2584;found901.2588。
二噻吩砜并硅芴衍生物5:
1H NMR(600MHz,CDCl3):δ8.17(s,2H),7.80(d,J=7.5Hz,4H),7.62(s,2H),7.18(s,2H),7.00(d,J=3.2Hz,4H),3.87(s,6H),0.52(s,6H)ppm;
13C NMR:由于硅芴衍生物5的溶解性较差,无法获得具有满意分辨率的核磁共振碳谱;
IR(KBr,cm–1):2918,1605,1508,1440,1389,1296,1261,1181,1139,1028,826,785,671,589,517;
HRMS(ESI,m/z):[M+H]+calculated for C32H26O6S2Si,621.0832;found621.0848。二噻吩砜并硅芴衍生物6:
1H NMR(600MHz,CDCl3):δ8.11(s,2H),8.07(d,J=8.6Hz,2H),7.68(s,2H),7.62(s,2H),6.62(d,J=7.9Hz,2H),6.54(s,2H),3.89(s,6H),3.86(s,6H),0.50(s,6H)ppm;
13C NMR(101MHz,CDCl3):δ162.23,160.21,147.46,145.95,139.32,138.73,132.25,129.59,128.97,124.32,113.97,109.65,105.13,99.62,55.74,55.70,–3.66ppm;
IR(KBr,cm–1):2922,1727,1607,1568,1504,1449,1300,1282,1214,1139,1043,915,826,772,603,577;
HRMS(ESI,m/z):[M+H]+calculated for C34H30O8S2Si,659.1224;found659.1221。二噻吩砜并硅芴衍生物7:
1H NMR(600MHz,CDCl3):δ8.12(s,2H),7.67(d,J=8.8Hz,4H),7.60(s,2H),7.31(t,J=7.9Hz,8H),7.15(d,J=7.6Hz,10H),7.11(t,J=7.4Hz,4H),7.08(d,J=8.8Hz,4H),0.51(s,6H)ppm;
13C NMR(151MHz,CDCl3):δ149.94,147.55,146.84,146.12,142.96,139.82,131.38,129.68,128.78,127.63,125.64,124.37,122.04,120.39,119.85,114.32,–3.69ppm;
IR(KBr,cm–1):2920,1717,1583,1488,1284,1193,1141,1073,822,785,750,694,583;
HRMS(ESI,m/z):[M+H]+calculated for C54H40N2O4S2Si,873.2271;found873.2271。
二噻吩砜并硅芴衍生物8:
1H NMR(600MHz,CDCl3):δ8.21(s,2H),7.59–7.53(m,4H),7.21(d,J=8.7Hz,4H),6.86(d,J=8.7Hz,4H),6.48(dd,J=8.5,2.3Hz,2H),6.27(d,J=2.3Hz,2H),3.76(s,6H),3.74(s,6H),3.33(s,6H),0.35(s,6H)ppm;
13C NMR(151MHz,CDCl3):δ162.59,160.20,159.05,147.71,145.71,140.06,139.30,134.35,133.01,131.94,130.03,127.69,124.63,114.68,114.12,108.53,105.13,99.44,55.66–55.22,–3.65ppm;
IR(KBr,cm–1):2927,1733,1603,1572,1498,1457,1296,1247,1207,1144,1026,942,832,785,614,573;
HRMS(ESI,m/z):[M+H]+calculated for C48H42O10S2Si,871.2061;found871.2048。二噻吩砜并硅芴衍生物9:
1H NMR(600MHz,CDCl3):δ8.20(s,2H),7.92(s,2H),7.86(d,J=8.5Hz,2H),7.45(d,J=8.7Hz,4H),6.92(d,J=8.7Hz,4H),6.62(dd,J=8.6,2.2Hz,2H),6.58(d,J=2.2Hz,2H),3.88(s,6H),3.85(d,J=1.4Hz,12H),0.59(s,6H)ppm;
13C NMR(151MHz,CDCl3):δ163.16,160.86,160.00,148.04,146.14,139.73,138.77,133.82,131.35,131.24,127.49,122.11,114.43,114.14,114.07,109.02,105.07,104.24,99.28,80.73,55.69,55.56,–3.60ppm;
IR(KBr,cm–1):2925,2191,1733,1601,1568,1508,1459,1292,1251,1209,1146,1024,828,787,690,624,579;
HRMS(ESI,m/z):[M+H]+calculated for C52H42O10S2Si,919.2061;found919.2055。
图2是本发明实施例中砜基修饰硅芴衍生物1的核磁氢谱;图3是本发明实施例中砜基修饰硅芴衍生物1的核磁碳谱。由图2、3所示,核磁结果所得的结构式和本实施例中砜基修饰硅芴衍生物1的理论结构式一致。
图4是本发明实施例中二噻吩砜并硅芴衍生物6的核磁氢谱。图5是本发明实施例中二噻吩砜并硅芴衍生物6的核磁碳谱。由图4、5所示,核磁结果所得的结构式和本实施例中二噻吩砜并硅芴衍生物6的理论结构式一致。
图6是本发明实施例中硅芴衍生物2、3、6、9的晶体结构。对本实施例制得的硅芴衍生物2、3、6、9进行单晶X-射线衍射测试表征,结果如图6所示,单晶X-射线衍射测试表征所得晶体结构和本实施例中硅芴衍生物2、3、6、9的理论晶体结构一致。
分别在二氯甲烷和四氢呋喃中对本实施例制得的硅芴衍生物1~9进行紫外可见吸收光谱和荧光发射光谱测试(测试温度298K,测试浓度为5×10-6mol/L),并对硅芴衍生物进行固体荧光光谱测试,测试结果如下表所示:
由表可知,二噻吩砜并硅芴衍生物5在四氢呋喃中具有最高溶液量子产率,为99%,二噻吩砜并硅芴衍生物7在四氢呋喃中最大溶液发射波长,为558nm。
图7是本发明实施例中硅芴衍生物1~9在二氯甲烷中的紫外可见吸收光谱、荧光发射光谱和荧光照片。如上述表和图7所示,在二氯甲烷中,砜基修饰硅芴衍生物2具有最高的溶液量子产率,为96%,二噻吩砜并硅芴衍生物7具有最大的溶液发射波长,为568nm。
图8是本发明实施例中硅对本实施例制得的硅芴衍生物1~9进行紫外可见吸收光谱和荧光发射光谱测试1~9的固体荧光光谱和荧光照片。如上述表和图8所示,二噻吩砜并硅芴衍生物8具有最高固体量子产率,为11%;二噻吩砜并硅芴衍生物7具有最大固体发射波长,为577nm。
本实施例还将上述制备得到的砜基修饰硅芴衍生物3作为荧光可视化材料用于酸碱蒸汽传感器,具体实施方式如下:
将砜基修饰硅芴衍生物3制备成二氯甲烷溶液(浓度1×10-3mol/L),用点样毛细管在薄层层析硅胶板上写上“TJU”字样,室温干燥5min,分别对其在自然光和紫外光条件下的颜色及荧光进行拍照,随后放入含有氯化氢蒸汽的广口瓶中熏5s并取出,并重复以上拍照工作,最后再放入含有氨气的广口瓶中熏5s并取出,重复以上拍照工作。
图9是本发明实施例中砜基修饰硅芴衍生物3用作酸碱蒸汽传感器的照片。如图9所示,在紫外灯照射下,在薄层层析硅胶板上用砜基修饰硅芴衍生物3写上“TJU”字样,该“TJU”字样发橙光,经氯化氢蒸汽熏后该字样发蓝光,再经氨气熏后又恢复到橙光。该酸碱蒸汽传感器的响应时间短,仅为5秒,且具有高度可恢复性。
本实施例还将上述制备得到的砜基修饰硅芴衍生物4和二噻吩砜并硅芴衍生物7、9作为荧光可视化材料用于海拉细胞的细胞成像,具体实施方式如下:
生长对数期的人宫颈癌Hela细胞,胰酶消化后,加入培养基终止消化,离心,弃去培养基及胰酶,细胞计数后,于6孔板中加入20mm的爬片,接种300~400万个细胞,分别加入硅芴衍生物4、7、9(10μM),用含10%胎牛血清(FBS)和1%青霉素-链霉素溶液双抗的DMEM培养基于37℃、5%CO2条件下培养24h,最后,将细胞用4%多聚甲醛固定0.5h,并用磷酸盐缓冲液(PBS)洗涤。采用荧光显微镜(Nikon ECLIPSE Ti2,Nikon Corporation,Tokyo,Japan)进行拍照获得荧光成像,绿色通道在494nm处激发并在500~530nm范围内收集。
图10是本发明实施例中硅芴衍生物4、7、9用于海拉细胞的细胞成像照片,其中,空白照片为未加入硅芴衍生物的海拉细胞通过荧光显微镜拍得的照片,荧光照片为加入硅芴衍生物的海拉细胞照片通过荧光显微镜拍得的照片,合并照片为将空白照片和荧光照片合并得到。如图10所示,将硅芴衍生物4、7、9加入到培养基中并培养海拉细胞,通过荧光显微镜可在细胞质中观测到明亮的绿光并和细胞重叠。
本实施例还将上述制备得到的二噻吩砜并硅芴衍生物6、9作为荧光可视化材料用于潜在指纹检测与识别,具体实施方式如下:
分别将上述制备得到的二噻吩砜并硅芴衍生物6、二噻吩砜并硅芴衍生物9和经过盐酸和高温处理过的硅藻土进行复合并干燥,二噻吩砜并硅芴衍生物的质量为硅藻土质量的0.1‰,形成荧光粉6@硅藻土和荧光粉9@硅藻土;分别将荧光粉6@硅藻土和荧光粉9@硅藻土用于载玻片、锌板、铜板、白色瓷砖、透明塑料袋、木板和皮革物体表面潜在指纹检测与识别;紫外灯照射、相机拍照,即可获得潜在指纹照片。
图11是本发明实施例中二噻吩砜并硅芴衍生物6、9用作潜在指纹检测与识别的照片。如图11所示,荧光粉6@硅藻土和荧光粉9@硅藻土在7种物体表面均可获得较清晰的潜在指纹照片,且无需荧光显微镜,仅需紫外灯照射、相机拍照,便可获得。其中,这两种荧光粉用于锌板表面潜在指纹检测与识别所获得的指纹照片最清晰。
以上是对实施例的详细描述,方便本领域的技术人员能正确理解和使用本发明。凡本领域的技术人员依据本发明在现有技术基础上,不经过创新性的劳动,仅通过分析、类推或有限列举等方法得到的改进或修改技术方案,都应该在由权利要求书所确定的保护范围内。
Claims (10)
3.根据权利要求2所述的砜基修饰硅芴衍生物的制备方法,其特征在于:
其中,步骤S1-1中所述结构如式Ⅱ所示的化合物与所述间氯过氧苯甲酸的摩尔比为1:4。
4.根据权利要求2所述的砜基修饰硅芴衍生物的制备方法,其特征在于:
其中,步骤S1-4中所述柱色谱的纯化溶剂为二氯甲烷或石油醚。
5.如权利要求1所述的砜基修饰硅芴衍生物在酸碱蒸汽传感器、生物成像和潜在指纹检测与识别中作为荧光可视化材料的应用。
8.根据权利要求7所述的二噻吩砜并硅芴衍生物的制备方法,其特征在于:
其中,步骤S2-1中所述结构如式Ⅳ所示的化合物与所述间氯过氧苯甲酸的摩尔比为1:8。
9.根据权利要求7所述的二噻吩砜并硅芴衍生物的制备方法,其特征在于:
其中,步骤S2-4中所述柱色谱的纯化溶剂为二氯甲烷或石油醚。
10.如权利要求6所述的二噻吩砜并硅芴衍生物在酸碱蒸汽传感器、生物成像和潜在指纹检测与识别中作为荧光可视化材料的应用。
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