CN113683632B - 一种近红外钯离子荧光探针化合物及其合成方法 - Google Patents
一种近红外钯离子荧光探针化合物及其合成方法 Download PDFInfo
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Abstract
本发明公开了一种式Ⅰ所示的近红外钯离子荧光探针化合物及其合成方法及应用:该探针化合物具有可见‑近红外光区吸收、荧光及良好的生物相容性,在溶液中对钯离子表现出了高灵敏度、高选择性的600‑800nm近红外荧光响应,检测限为0.85ppb,抗干扰性强,有潜力应用于复杂生物体系,特别是活体内钯离子的检测与示踪。
Description
技术领域:
本发明涉及钯离子检测与荧光探针领域,具体涉及一种近红外钯离子荧光探针化合物及其合成方法。
背景技术:
钯(Pd)是第五周期Ⅷ族铂系重要过渡金属元素之一,既可以作为多种化学反应的高效催化剂,也是汽车领域、电子产品、航空航天、医疗器械、燃料电池等行业不可或缺的关键材料。钯的广泛应用使其在生态环境中不断积累,研究表明,Pd2+可与DNA、含硫醇的氨基酸、蛋白质和维生素B6配位,干扰细胞进程,还会引起过敏反应,如刺激眼睛和皮肤等,对生态系统和人类健康构成了严重威胁。目前,人们对钯的毒性还知之甚少,其在生物体内的作用机制有待进一步探究。因此,准确、有效地检测环境和生物体系中的钯离子具有重要意义。
使用仪器检测钯离子的方法灵敏度虽高,但设备大都较为昂贵,样品前处理相对繁琐,需要严格的实验条件和高技能的操作人员。近年来,荧光探针因其灵敏度高、特异性强、响应速度快、技术简单等优点,已发展成为一种有效的金属离子和生物分子检测方法。荧光探针可以作为显像剂来观察和测定金属离子在活细胞、组织和整个生物体中的浓度和分布,并监测其动态和通量,是研究金属离子与生物体系相互作用的有效途径。近年来,文献报道了多例基于小分子有机荧光团(如荧光素、罗丹明B、萘酰亚胺、菁染料等)((a)Garner,A.L.;Koide,K.,J.Am.Chem.Soc.2008,130(49),16472-16473;(b)Li,H.;Fan,J.;Peng,X.,Chem.Soc.Rev.2013,42(19),7943-7962;(c)Balamurugan,R.;Liu,J.-H.;Liu,B.-T.,Coord.Chem.Rev.2018,376,196-224.)和纳米材料(如荧光碳纳米颗粒、共轭聚合物纳米粒子、介孔二氧化硅微球接枝识别单元等)((a)Sharma,V.;Saini,A.K.;Mobin,S.M.,J.Mater.Chem.B 2016,4(14),2466-2476;(b)Zhang,Y.;Zhao,Y.;Shi,L.;Zhang,L.;Du,H.;Huang,H.;Xiao,Y.;Zhang,Y.;He,X.;Wang,K.,Analyst 2020,145(16),5631-5637;(c)Liang,G.;Cai,Q.;Zhu,W.;Xu,Y.;Qian,X.Anal.Methods 2015,7(12),4877-4880.)的配位或反应型钯离子荧光探针。尽管取得了进展,具有高灵敏度、选择性、水溶性和生物相容性,但是适用于生物体系钯离子检测的荧光探针仍较为稀缺。
氟硼二吡咯(BODIPY)是一类优秀的小分子荧光染料,在可见光区具有高摩尔消光系数(ε>70000M-1cm-1)和荧光量子产率(ΦF约0.5-0.8),是理想的荧光探针候选物。但BODIPY本身水溶性较差,较短的激发波长限制了其在生物体系,尤其是组织及活体成像中的应用。理想的生物体系荧光探针需要具备较高的水溶性与近红外的吸收:亲水性有利于探针进入细胞,近红外光具有更好的组织穿透性,并能极大程度得避免生物体系内其他噪音信号的干扰(生物体系内许多物质具有紫外或可见光区的吸收与荧光发射)。发明人于2020年成功研发了基于光诱导电子转移(PET)机制的配位型钯离子荧光探针BDP-Pd,探针在可见光区(500-600nm)对钯离子有高灵敏度、高选择性的荧光“OFF-ON”响应;体外细胞实验表明,探针具有良好的细胞通透性,可应用于A549人非小细胞肺癌细胞内钯离子荧光成像(Chen,X.-F.;Ma,Q.;Wang,Z.;Xie,Z.;Song,Y.;Ma,Y.;Yang,Z.;Zhao,X.Chem.AsianJ.2020,15(23),4104-4112.)。但还有待进一步提高探针的生物相容性。
发明内容:
本发明的目的是提供一种近红外钯离子荧光探针化合物及其合成方法及应用,该探针化合物具有可见-近红外光区吸收、荧光及良好的生物相容性,在溶液中对钯离子表现出了高灵敏度、高选择性的近红外荧光响应(600-800nm),检测限为0.85ppb,抗干扰性强,有潜力应用于复杂生物体系,特别是活体内钯离子的检测与示踪。
本发明是通过以下技术方案予以实现的:
结构式如式Ⅰ所示的近红外钯离子荧光探针化合物,记为dis-BDP-Pd:
本发明还保护上述近红外钯离子荧光探针化合物dis-BDP-Pd的合成方法,该方法合成路线如下:
包括如下步骤:
(1)氮气保护下,向化合物1和化合物2的甲苯溶液中加入哌啶、冰醋酸和高氯酸镁,加热反应后分离纯化制得化合物3;
(2)氮气保护下向化合物3的冰醋酸溶液加入锌粉,搅拌反应,分离纯化制得化合物4;
(3)氮气保护下,向化合物4、化合物5的1,2-二氯乙烷溶液中加入活化分子筛、冰醋酸及氰基硼氢化钠,搅拌反应,分离纯化制得化合物6;
(4)氮气保护下,将化合物6溶于盐酸气饱和的乙酸乙酯中搅拌反应,分离纯化制得化合物7;
(5)氮气保护下,向化合物8、1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐与4-二甲氨基吡啶的二氯甲烷溶液中加入化合物7加热回流,分离纯化制得近红外钯离子荧光探针化合物dis-BDP-Pd。
化合物1为硝基BODIPY,化合物2为对-三乙二醇单甲醚苯甲醛,化合物5为N-Boc-2-氨基乙醛,化合物8为3-氨基-2-萘甲酸。
优选地,步骤(1)具体步骤为:氮气保护下,向化合物1和化合物2的甲苯溶液中加入哌啶、冰醋酸和高氯酸镁,加热回流,使用Dean-Stark分水器装置分水,反应时间为4-6h更优选为5h;化合物1、化合物2、哌啶、冰醋酸的摩尔比为1:3-5:100:50,高氯酸镁为催化量。反应完成后,减压除去溶剂,柱层析纯化后制得化合物3。
优选地,步骤(2)反应温度为室温,化合物3与锌粉的摩尔比为1:64-66,反应时间为10-30min,更优选为20min,反应完毕后,加水稀释,乙酸乙酯萃取,饱和NaHCO3水溶液中和,柱层析纯化后制得化合物4。
优选地,步骤(3)的具体步骤为:氮气保护下,向化合物4与化合物5的1,2-二氯乙烷溶液中加入适量的活化分子筛和冰醋酸,室温搅拌反应1h后,再加入氰基硼氢化钠,继续室温搅拌反应8h,反应完成后分离纯化制得化合物6;化合物4、化合物5与氰基硼氢化钠的摩尔比为1:2-4:6。
优选地,步骤(4)反应温度为室温,反应时间为20-40min,更优选为30min,反应完毕后,蒸干溶剂,加入二氯甲烷,饱和NaHCO3水溶液中和,有机相干燥浓缩后,柱层析纯化后制得化合物7。
优选地,步骤(5)化合物7、化合物8、1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐与4-二甲氨基吡啶的摩尔比为1:1.5:2:3,反应加热回流12h。反应完毕后,柱层析纯化后制得探针化合物dis-BDP-Pd。
本发明的另一个目的是保护上述近红外钯离子荧光探针化合物在钯离子检测中的应用。
本发明的有益效果如下:
(1)本发明的钯离子荧光探针化合物具有可见至近红外光区的吸收与荧光响应,钯离子存在下,探针在600-800nm区间荧光有明显增强,表现为“OFF-ON”的荧光响应,手持紫外灯下肉眼可查。
(2)本发明的钯离子荧光探针化合物检测限低至0.85ppb,灵敏度处于目前文献所报道的钯离子荧光探针前沿;钯离子与探针的络合常数高达3.8×1010M-2。
(3)本发明的钯离子荧光探针化合物抗干扰性强,对其他19种干扰金属阳离子均无明显响应,只对钯离子选择性响应,适用于复杂生物体系内钯离子荧光成像与示踪。
总之,该探针化合物具有可见-近红外光区吸收、荧光及良好的生物相容性,在溶液中对钯离子表现出了高灵敏度、高选择性的600-800nm近红外荧光响应,检测限为0.85ppb,抗干扰性强,有潜力应用于复杂生物体系,特别是活体内钯离子的检测与示踪。
附图说明:
图1为实施例5荧光探针化合物dis-BDP-Pd的1H NMR谱图;
图2为实施例5荧光探针化合物dis-BDP-Pd的13C NMR谱图;
图3a为实施例6荧光探针化合物dis-BDP-Pd的吸收与荧光发射谱图,图3b为不同浓度的dis-BDP-Pd在乙腈中的吸收光谱;
图4为实施例7加入钯离子后荧光探针化合物dis-BDP-Pd在650nm处的荧光强度变化图;
图5为实施例8荧光探针化合物dis-BDP-Pd与钯离子的Job’s plot曲线;
图6a为实施例9荧光探针化合物dis-BDP-Pd在不同浓度钯离子存在下的吸收谱图;图6b为dis-BDP-Pd在不同浓度钯离子存在下的荧光发射谱图;图6c为dis-BDP-Pd在7-15μM钯离子存在下650nm处的荧光变化(ΔI)图;图6d为络合常数计算图;
图7a为实施例10荧光探针化合物dis-BDP-Pd与不同金属阳离子混合后的荧光发射谱图;图7b为dis-BDP-Pd与不同金属阳离子混合后在650nm处的荧光发射强度柱状对比图,内图为365nm紫外线灯照射下溶液的颜色变化图。
具体实施方式:
以下是对本发明的进一步说明,而不是对本发明的限制。
近红外钯离子荧光探针化合物dis-BDP-Pd的合成路径为(所涉及化合物distyrylBODIPY 3、4、6、7及dis-BDP-Pd均为首次报道):
实施例1:化合物3的制备
氮气保护下,向化合物1硝基BODIPY(800mg,2.16mmol)与化合物2对-三乙二醇单甲醚苯甲醛(2.32g,8.64mmol)的甲苯溶液(80mL)中加入冰醋酸(2.4mL)、哌啶(8mL)和催化量的高氯酸镁,加热回流5h,Dean-Stark装置分水。反应完毕后,减压除去溶剂,粗产品以乙酸乙酯为洗脱剂,硅胶柱层析纯化,正己烷/乙酸乙酯重结晶得墨绿色固体化合物3(976mg,52%)。1H NMR(CDCl3):δ8.36(d,J=8.3Hz,2H,ArH),7.51-7.62(m,8H,ArH and CH),7.21(d,J=16.3Hz,2H,CH),6.94(d,J=8.5Hz,4H,ArH),6.61(s,2H,pyrrole-H),4.17(t,J=4.8Hz,4H,CH2),3.87(t,J=4.8Hz,4H,CH2),3.72-3.77(m,4H,CH2),3.64-3.71(m,8H,CH2),3.54-3.56(m,4H,CH2),3.38(s,6H,CH3),1.39(s,6H,CH3).13C{1H}NMR(CDCl3):δ159.8,153.4,148.3,142.4,140.9,136.7,134.4,132.3,130.3,129.4,129.2,124.2,118.1,116.9,115.0,71.9,70.9,70.7,70.6,69.7,67.5,59.1,15.0.HRMS(ESI):m/zC47H54BF2N3O10Na[M+Na]+:892.3771,计算值为892.3970。
实施例2:化合物4的制备
氮气保护下,向化合物3(200mg,0.23mmol)的冰醋酸(9mL)溶液缓慢加入锌粉(960mg,15mmol),室温搅拌20min。反应完毕后,加水稀释(10mL),乙酸乙酯萃取(50mL×3),合并有机相,饱和NaHCO3溶液洗涤,无水NaSO4干燥,过滤,蒸干溶剂,粗产品以乙酸乙酯为洗脱剂,硅胶柱层析纯化,正己烷/乙酸乙酯重结晶得深蓝色固体化合物4(150mg,78%)。HNMR(CDCl3):δ7.55-7.62(m,6H,ArH and CH),7.19(d,J=16.3Hz,2H,CH),7.05(d,J=8.4Hz,2H,ArH),6.94(d,J=8.7Hz,4H,ArH),6.79(d,J=8.4Hz,2H,ArH),6.66(s,2H,pyrrole-H),4.18(t,J=4.9Hz,4H,CH2),3.89(t,J=4.9Hz,4H,CH2),3.85(s,2H,NH2),3.74-3.78(m,4H,CH2),3.65-3.78(m,8H,CH2),3.54-3.59(m,4H,CH2),3.39(s,6H,CH3),1.55(s,6H,CH3).13C{1H}NMR(CDCl3):δ159.5,152.4,147.0,141.9,139.1,135.4,133.8,129.8,129.5,128.9,125.0,117.4,117.3,115.4,114.9,71.9,70.9,70.7,70.6,69.7,67.5,59.1,14.9.HRMS(ESI):m/z C47H57BF2N3O8[M+H]+:840.4211,计算值为840.4209。
实施例3:化合物6的制备
氮气保护下,向化合物4(150mg,0.179mmol)和化合物5(85.2mg,0.536mmol)的1,2-二氯乙烷溶液(10mL)中加入适量的活化分子筛滴加一滴冰醋酸,室温搅拌反应1h后,加入NaBH3CN(67.7mg,1.074mmol),继续室温搅拌反应8h。反应完毕后,向体系加入饱和碳酸氢钠溶液(10mL),二氯甲烷(3×25mL)萃取。合并的有机相依次用水、饱和食盐水洗,无水硫酸钠干燥,过滤,蒸干溶剂后所得的粗产品以二氯甲烷/甲醇(V:V=45:1)为淋洗液硅胶柱层析纯化,重结晶得到蓝黑色固体化合物6(72.1mg,41%)。1H NMR(CDCl3):δ7.54-7.63(m,6H,ArH and CH),7.18(d,J=16.2Hz,2H,CH),7.05(d,J=8.5Hz,2H,ArH),6.94(d,J=8.7Hz,4H,ArH),6.69(d,J=8.5Hz,2H,ArH),6.60(s,2H,pyrrole-H),4.83(s,1H,NH),4.25(s,1H,NH),4.18(t,J=4.8Hz,4H,CH2),3.88(t,J=4.8Hz,4H,CH2),3.75-3.78(m,4H,CH2),3.65-3.71(m,8H,CH2),3.55-3.58(m,4H,CH2),3.39-3.44(m,2H,CH2),3.39(s,6H,CH3),3.28-3.32(m,2H,CH2),1.61(s,6H,CH3),1.47(s,9H,Boc-H).13C{1H}NMR(CDCl3):δ159.6,152.4,142.1,135.4,134.0,129.9,129.6,129.1,117.6,117.3,115.0,112.9,72.1,71.0,70.8,70.7,69.8,67.6,59.2,31.7,28.5,22.8,15.1,14.3.HRMS(ESI):m/zC54H70BF2N4O10[M+H]+:983.5160,计算值为983.5157。
实施例4:化合物7的制备
氮气保护下,将化合物6(72mg,0.073mmol)溶于10mL盐酸气饱和的乙酸乙酯中,室温下搅拌0.5h后,蒸干溶剂,加入二氯甲烷(50mL)萃取,有机相经饱和NaHCO3溶液洗,无水NaSO4干燥,过滤,浓缩得到的粗产品以二氯甲烷/甲醇(V:V=10:1)为淋洗液硅胶柱层析纯化,重结晶得到黑绿色固体化合物7(51.6mg,72%)。1H NMR(DMSO-d6):δ8.10(s,2H,NH2),7.56(d,J=8.7Hz,4H,ArH),7.50(d,J=16.3Hz,2H,CH),7.38(d,J=16.3Hz,2H,CH),7.10(d,J=8.4Hz,2H,ArH),7.04(d,J=8.7Hz,4H,ArH),6.91(s,2H,pyrrole-H),6.79(d,J=8.4Hz,2H,ArH),6.28(s,1H,NH),4.13-4.17(m,4H,CH2),3.74-3.78(m,4H,CH2),3.59(m,4H,CH2),3.54-3.55(m,4H,CH2),3.50-3.52(m,4H,CH2),3.41-3.44(m,6H,CH2),3.23(s,6H,CH3),3.02(t,J=6.3Hz,2H,CH2),1.54(s,6H,CH3).13C{1H}NMR(DMSO-d6):δ160.0,152.1,150.0,142.0,136.5,133.7,130.1,129.4,129.2,118.2,116.6,115.6,114.9,112.6,71.8,70.4,70.3,70.1,69.3,67.8,58.5,40.7,35.6,15.1.HRMS(ESI):m/z C49H62BF2N4O8[M+H]+:883.4620,计算值为883.4632。
实施例5:近红外钯离子荧光探针化合物dis-BDP-Pd的制备
氮气保护下,将3-氨基-2-萘甲酸(化合物8,4.77mg,0.025mmol)、1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐(6.53mg,0.034mmol)与4-二甲氨基吡啶(6.22mg,0.051mmol)溶于4mL二氯甲烷中得到反应液。实施例4得到的化合物7(15mg,0.017mmol)溶于2mL二氯甲烷后加入上述反应液中,加热回流12h。反应完毕后,蒸干溶剂,粗产品以二氯甲烷/甲醇(V:V=60:1)为淋洗液过硅胶层析柱制得深色固体dis-BDP-Pd(6.0mg,33%)。1HNMR(CDCl3):δ7.91(s,1H,ArH),7.58-7.65(m,3H,ArH and CH),7.53(d,J=8.5Hz,4H,ArH),7.38(t,J=7.5Hz,1H,ArH),7.15-7.19(m,3H,ArH and CH),6.94-7.05(m,3H,ArH),6.91(d,J=8.5Hz,4H,ArH),6.75-6.79(m,1H,ArH),6.70(d,J=8.0Hz,2H,ArH),6.56(s,2H,pyrrole-H),5.27(s,2H,NH2),4.47(s,1H,NH),4.15(t,J=4.8Hz,4H,CH2),3.86(t,J=4.8Hz,4H,CH2),3.64-3.76(m,14H,CH2),3.54-3.57(m,4H,CH2),3.42(t,J=5.9Hz,2H,CH2),3.38(s,6H,CH3),1.51(s,6H,CH3).13C{1H}NMR(CDCl3):δ170.1,159.5,152.3,148.5,144.5,142.0,139.4,136.2,135.4,133.9,129.7,129.5,128.9,128.4,128.2,128.1,126.4,125.3,123.7,122.9,121.1,117.3,114.9,112.8,110.6,71.9,70.9,70.7,70.6,69.7,67.5,59.1,44.1,39.6,15.0.HRMS(ESI):m/z C60H69BF2N5O9[M+H]+:1052.5122,计算值为1052.5161。
实施例6:光物理性质测试
配制实施例5得到的荧光探针化合物dis-BDP-Pd的DMSO母液,浓度为2mM。以乙腈稀释至5μM,测试其吸收与荧光发射光谱。
实验结果见图3a,由图3a可以得出,dis-BDP-Pd在紫外-可见及近红外光区(300-700nm)有强吸收,表现为362nm(logε=4.86)和632nm(logε=5.04)两个主吸收峰,分别对应化合物的Soret与Q带吸收。以575nm波长的光激发后,探针仅表现出微弱的荧光发射(ФF=0.02),最大发射波长为650nm。化合物较弱的荧光发射是源于分子内的PET效应。化合物在乙腈中溶解度良好,测试浓度范围内(1-9μM)未表现出明显的聚集现象,其吸光度与浓度呈良好的线性关系(参见图3b)。
实施例7:钯离子响应测试
向dis-BDP-Pd的乙腈溶液中(5μM)加入4倍当量的氯化钯(20μM),充分混匀后,记录荧光探针随时间的荧光发射强度变化。
实验结果见图4,图4为dis-BDP-Pd在650nm处荧光强度随时间变化(ΔI/I0)。加入Pd2+之后,探针的荧光强度立即增强为3倍;随着时间的推移,探针荧光强度不断增长,20min内趋于稳定,荧光增强约11倍(ΦF=0.22)。探针的荧光增强可以归因于荧光探针与Pd2+结合后所引发的PET的禁阻,致使BODIPY荧光团自身荧光恢复。由实验结果可知,探针与钯离子在乙腈中的络合效应显著,响应时间较快,前后荧光变化明显,紫外灯下肉眼即可观察判断。
实施例8:络合比测定
固定dis-BDP-Pd和钯离子的总浓度为10μM,配制溶液,其中,dis-BDP-Pd的浓度(μM)分别为0、1、2、3、4、5、6、7、8、9和10;对应的,钯离子的浓度(μM)分别为10、9、8、7、6、5、4、3、2、1和0,混合均匀,静置,测定溶液的荧光光谱,以650nm处的荧光强度变化(ΔI)对[dis-BDP-Pd]/([dis-BDP-Pd]+[Pd2+])作图。
实验结果见图5,由图5可以得出,经判定,探针dis-BDP-Pd与钯离子的络合比为1:2。
实施例9:滴定测试
探针dis-BDP-Pd浓度为5μM,滴入0-15μM的钯离子(每次0.1当量),充分混匀,静置5min,测定溶液吸收及荧光光谱。
实验结果如下:随着钯离子的加入,探针的吸收光谱基本保持不变(图6a);但585-800nm区间的荧光发射逐渐增强(图6b)。
检测限计算:
根据探针的荧光强度变化,以650nm处的荧光增量ΔI对钯离子浓度(7-14μM)作图。根据公式:检测限=3xσ/K,计算探针对钯离子的检测限。
实验结果参见图6c,由图6c可知,探针在所选浓度范围内荧光强度变化与钯离子浓度呈线性关系,经计算,dis-BDP-Pd对钯离子的检测限为0.85ppb,其灵敏度处于目前文献所报道的钯离子荧光探针前沿。
探针与钯离子的络合常数计算:
基于实施例8所给出的主-客体络合比(1:2),探针与钯离子的络合常数可根据以下公式进行计算:
其中,[H]0和[G]0分别为主客体的初始浓度,ΔI为探针的荧光强度变化,Δεa为主客体络合前后的发射系数变化。主-客体的络合常数可由[H]0[G]0 2/ΔI对[G]0([G]0+4[H]0)作图计算(图6d)。经计算,本发明所述的荧光探针与钯离子的络合常数为3.8×1010M-2。
实施例10:对钯离子的选择性测试
测试乙腈中dis-BDP-Pd(5μM)对其他金属离子(Na+、K+、Cd2+、Ca2+,、Mg2+、Ag+、Mn2+、Cr3+、Cu2+、Fe3+、Fe2+、Zn2+、Ba2+、Cd2+、Co2+、Hg2+、Pb2+、Al3+、Pt2+、Rh3+、Ru3+,浓度均为20μM)的荧光响应,以评价探针的选择性。
实验结果如下:如图7所示,由荧光发射光谱可知,dis-BDP-Pd本身仅有微弱荧光,加入钯离子后,荧光有显著增强,且对其他干扰金属阳离子无明显响应;在手持荧光灯照射下(365nm),肉眼可以观察到探针与钯离子产生明亮的荧光现象。可见,探针对钯离子选择性高,抗干扰性强。适于复杂体系的钯离子检测与示踪。
Claims (8)
1.结构式如式Ⅰ所示的近红外钯离子荧光探针化合物:
2.权利要求1所述近红外钯离子荧光探针化合物的合成方法,其特征在于,该方法合成路线如下:
包括如下步骤:
(1)氮气保护下,向化合物1和化合物2的甲苯溶液中加入哌啶、冰醋酸和高氯酸镁,加热反应后分离纯化制得化合物3;
(2)氮气保护下向化合物3的冰醋酸溶液加入锌粉,搅拌反应,分离纯化制得化合物4;
(3)氮气保护下,向化合物4、化合物5的1,2-二氯乙烷溶液中加入活化分子筛、冰醋酸及氰基硼氢化钠,搅拌反应,分离纯化制得化合物6;
(4)氮气保护下,将化合物6溶于盐酸气饱和的乙酸乙酯中搅拌反应,分离纯化制得化合物7;
(5)氮气保护下,向化合物8、1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐与4-二甲氨基吡啶的二氯甲烷溶液中加入化合物7加热回流,分离纯化制得近红外钯离子荧光探针化合物。
3.根据权利要求2所述近红外钯离子荧光探针化合物的合成方法,其特征在于,步骤(1)使用Dean-Stark分水器装置分水,反应时间为4-6h;化合物1、化合物2、哌啶、冰醋酸的摩尔为1:3-5:100:50。
4.根据权利要求2所述近红外钯离子荧光探针化合物的合成方法,其特征在于,步骤(2)反应温度为室温,化合物3与锌粉的摩尔比为1:64-66,反应时间为10-30min,反应完毕后,加水稀释,乙酸乙酯萃取,饱和NaHCO3水溶液中和,柱层析纯化后制得化合物4。
5.根据权利要求2所述近红外钯离子荧光探针化合物的合成方法,其特征在于,步骤(3)的具体步骤为:氮气保护下,向化合物4与化合物5的1,2-二氯乙烷溶液中加入适量的活化分子筛和冰醋酸,室温搅拌反应1h后,再加入氰基硼氢化钠,继续室温搅拌反应8h,反应完成后分离纯化制得化合物6;化合物4、化合物5与氰基硼氢化钠的摩尔比为1:2-4:6。
6.根据权利要求2所述近红外钯离子荧光探针化合物的合成方法,其特征在于,步骤(4)反应温度为室温,反应时间为20-40min,反应完毕后,蒸干溶剂,加入二氯甲烷,饱和NaHCO3水溶液中和,有机相干燥浓缩后,柱层析纯化后制得化合物7。
7.根据权利要求2所述近红外钯离子荧光探针化合物的合成方法,其特征在于,步骤(5)化合物7、化合物8、1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐与4-二甲氨基吡啶的摩尔比为1:1.5:2:3,反应加热回流12h。
8.权利要求1近红外钯离子荧光探针化合物在钯离子检测中的应用。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005022985A (ja) * | 2003-06-30 | 2005-01-27 | Tetsuo Nagano | 亜鉛蛍光プローブ |
JP2014152243A (ja) * | 2013-02-08 | 2014-08-25 | Hokkaido Univ | ケイ光イオンセンサー色素 |
CN107602600A (zh) * | 2017-08-30 | 2018-01-19 | 平顶山学院 | 氨基取代氮杂氟硼二吡咯近红外pH荧光探针及其制法和用途 |
CN109320536A (zh) * | 2018-11-20 | 2019-02-12 | 南京工业大学 | 一种基于Aza-BODIPY的近红外二窗的荧光探针及其制备与应用 |
CN111393461A (zh) * | 2020-03-17 | 2020-07-10 | 广东省测试分析研究所(中国广州分析测试中心) | 一种基于bodipy的钯离子荧光探针化合物及其合成方法 |
CN112094416A (zh) * | 2020-09-23 | 2020-12-18 | 中国药科大学 | 一种用于血浆中唾液酸荧光检测的镧系配位聚合物荧光探针、制法和检测方法 |
CN112745340A (zh) * | 2020-12-30 | 2021-05-04 | 河南大学 | 基于bodipy染料靶向溶酶体选择性检测h2s的荧光探针、制备及应用 |
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CN103666456B (zh) * | 2013-12-02 | 2015-02-04 | 大连理工大学 | 一类氟化硼络合二吡咯甲川荧光探针,其制备方法及应用 |
-
2021
- 2021-07-22 CN CN202110832161.7A patent/CN113683632B/zh active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005022985A (ja) * | 2003-06-30 | 2005-01-27 | Tetsuo Nagano | 亜鉛蛍光プローブ |
JP2014152243A (ja) * | 2013-02-08 | 2014-08-25 | Hokkaido Univ | ケイ光イオンセンサー色素 |
CN107602600A (zh) * | 2017-08-30 | 2018-01-19 | 平顶山学院 | 氨基取代氮杂氟硼二吡咯近红外pH荧光探针及其制法和用途 |
CN109320536A (zh) * | 2018-11-20 | 2019-02-12 | 南京工业大学 | 一种基于Aza-BODIPY的近红外二窗的荧光探针及其制备与应用 |
CN111393461A (zh) * | 2020-03-17 | 2020-07-10 | 广东省测试分析研究所(中国广州分析测试中心) | 一种基于bodipy的钯离子荧光探针化合物及其合成方法 |
CN112094416A (zh) * | 2020-09-23 | 2020-12-18 | 中国药科大学 | 一种用于血浆中唾液酸荧光检测的镧系配位聚合物荧光探针、制法和检测方法 |
CN112745340A (zh) * | 2020-12-30 | 2021-05-04 | 河南大学 | 基于bodipy染料靶向溶酶体选择性检测h2s的荧光探针、制备及应用 |
Non-Patent Citations (1)
Title |
---|
Xiao-Fei Chen, et al..A Boron Dipyrromethene-Based Fluorescence 'OFF-ON' Probe for Sensitive and Selective Detection of Palladium(II) Ions and Its Application in Live Cell Imaging.Chemistry An Asian Journal.2020,第15卷第4104-4112页. * |
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