CN106749362B - 一种锰和铜双离子响应的荧光探针及其制备方法 - Google Patents
一种锰和铜双离子响应的荧光探针及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种新的近红光氟硼二吡咯甲川衍生物及其制备方法,属于荧光探针方面的内容,本发明以8‑(4‑(氯甲基)苯基)‑4,4‑二氟‑1,3,5,7‑四甲基‑4‑硼‑3a,4a‑二吡咯(标记为BODIPY‑C)、二吡啶甲基胺、对二甲胺基苯甲醛为原料合成了一种新的近红光氟硼二吡咯甲川化合物:1,7‑二甲基‑3,5‑(二(4‑(二甲氨基苯基)‑2‑烯基))‑8‑((二(2‑吡啶甲基)胺‑4‑苯甲基)‑4,4‑二氟‑4‑硼‑3a,4a‑二吡咯,简称为BODIPY‑NPDA)。发现BODIPY‑NPDA的最大紫外‑可见光吸收波长在704nm,能够作为荧光探针检测Cu2+和Mn2+。
Description
技术领域
本发明涉及一种新的近红光氟硼二吡咯甲川衍生物及其制备方法,属于荧光探针方面的内容,能够作为锰和铜双离子响应的荧光探针。
背景技术
近年来,在现代生物技术和生命科学研究的诸多检测识别方法中,荧光分析方法由于其灵敏度高,选择性好,检出限低等优点,在生物化学分析领域有着不可替代的作用。因此,使用人工设计合成的荧光探针选择性的检测和识别生态环境及生物系统中的重要离子,尤其是重金属离子受到诸多科学研究者的广泛关注。铜离子和锰离子在工业上有着广泛的应用,同时,铜离子和锰离子又是维持人体健康的必需微量元素。尽管铜离子和锰离子在人体和其他生物系统中扮演着重要角色,但是铜离子和锰离子的代谢异常同样会引起一系列的疾病。例如,铜离子代谢异常,会导致阿尔茨海默氏病、帕金森病、心血管疾病等病症;而锰离子代谢异常,会导致延迟凝血、高胆固醇血症、神经损伤等病症。因此,在生态环境和生物体系中快速简单且具有选择性的检测铜离子和锰离子显得尤为重要。
最近BODIPY类荧光探针BPDA被报道用于小鼠体内的铜离子含量的检测(Xue X,Fang H,Chen H,et al.In vivo fluorescence imaging for Cu 2+in live mice by anew NIR fluorescent sensor[J].Dyes&Pigments,2016,130:116-121.),同样的,荧光素系列和罗丹明系列探针被报道用于生物体内的锰离子含量的检测(Adhikari S,Ghosh A,Sahana A,et al.Tailoring Ligand Environment toward Development ofColorimetric and Fluorescence Indicator for Biological Mn(II)Imaging[J].Analytical Chemistry,2015,88(2).)。但是这些荧光探针具有较小的斯托克斯位移,光稳定性较差和NIR荧光团的低量子产率,荧光受环境影响较大,具有一定的低毒性,难以准确的检测细胞中铜离子和锰离子。我们前期报道过一种铜离子荧光探针(陈秋云,李赞,一种铜离子荧光探针及其合成方法,中国发明专利申请号,201210539628.X),其最大吸收仅为499nm。为降低细胞等生物环境背景荧光的干扰,我们进一步通过对其结构进行修饰,制备了一种新的近红光荧光探针,其最大吸收达到700nm,能够在近红光区对铜离子和锰离子进行双响应,有望用于生物体内铜离子和锰离子的检测。
发明内容
本发明以8-(4-(氯甲基)苯基)-4,4-二氟-1,3,5,7-四甲基-4-硼-3a,4a-二吡咯(标记为BODIPY-C)、二吡啶甲基胺、对二甲胺基苯甲醛为原料合成了一种新的近红光氟硼二吡咯甲川化合物:1,7-二甲基-3,5-(二(4-(二甲氨基苯基)-2-烯基))-8-((二(2-吡啶甲基)胺-4-苯甲基)-4,4-二氟-4-硼-3a,4a-二吡咯,简称为BODIPY-NPDA)。发现BODIPY-NPDA的最大紫外-可见光吸收波长在704nm,能够作为荧光探针检测Cu2+和Mn2+。
本发明的一种铜锰双离子响应荧光探针(BODIPY-NPDA),其结构如下:
上述化合物的制备方法如下:
1,7-二甲基-3,5-(二(4-(二甲氨基苯基)-2-烯基))-8-((二(2-吡啶甲基)胺-4-苯甲基)-4,4-二氟-4-硼-3a,4a-二吡咯(简称BODIPY-NPDA)是由8-(4-(氯甲基)苯基)-4,4-二氟-1,3,5,7-四甲基-4-硼-3a,4a-二吡咯(BODIPY-C)与二甲基吡啶胺、对二甲氨基苯甲醛反应制得。
BODIPY-NDPA经典反应步骤如下:
A.将BODIPY-C与二吡啶甲基胺按1:2~2:1摩尔比例混合后(最佳摩尔比例为1:1.2),加入乙腈作为溶剂,接着加入三乙胺、KI和18-冠醚-6;其中BODIPY-C与三乙胺的摩尔比例为1:2~2:1(最佳摩尔比例为1:1.5),BODIPY-C 与KI的摩尔比例为1:1~1:2(最佳摩尔比例为1:1.2),KI与18-冠醚-6的质量比为300:1,混合后,体系在氮气保护下,40℃-80℃下(最佳70℃)油浴回流反应,反应7小时,反应结束后,浓缩反应液并用二氯甲烷溶解后过滤除去不溶物,将溶液除去,得混合固体。
B.在步骤A制备的混合固体反应瓶上搭建分水器回流,接着在混合溶液中加入对二甲胺基苯甲醛,其中二甲胺基苯甲醛与BODIPY-C的摩尔比例为3:1~1:1(最佳摩尔比例2.5:1),加入甲苯为反应溶剂,甲苯与BODIPY-C的体积摩尔比为30-100mL:1.34mmol,最佳量为50mL:1.34mmol),再加入4-甲基苯磺酸和哌啶,其中4-甲基苯磺酸与BODIPY-C摩尔比例为0.1:1~0.5:1(最佳摩尔比例为0.2:1),哌啶与BODIPY-C摩尔比例为0.3:1~1:1(最佳摩尔比例为0.5:1),混合后加热至100℃~130℃(最佳125℃),反应9小时,反应结束后,浓缩反应液并用二氯甲烷溶解,使用饱和NaCl溶液萃取,水相用二氯甲烷反萃取,收集有机相,无水硫酸钠干燥,浓缩溶剂,用乙酸乙酯重结晶,抽滤,乙酸乙酯洗涤,得深褐色固体BODIPY-NPDA。1HNMR(400MHz CDCl3).δ=8.57-8.56(d,J=4Hz,2H),7.74-7.72(t,J=8Hz,2H),7.60-7.54(m,10H),7.32-7.30(d,J=8Hz,2H),7.22-7.18(m,4H),6.74-6.72(d,J=8Hz,4H),6.59(s,2H),3.86(s,4H),3.79(s,2H),3.05(s,12H),1.39(s,6H).ES-MS(ESI+,MeOH):calcd.for[C50H51BF2N7]+:798.81,found:799.00.
BODIPY-NPDA在乙腈溶液中呈现红色,在近红光区域704nm有较强的吸收,以704nm激发,在760nm处有强荧光发射。该化合物能够进入MCF-7细胞,以红光激发获得红色细胞荧光成像。BODIPY-NPDA能够在溶液中分别与铜离子和锰离子1:1络合形成BODIPY-NPDA-Mn和BODIPY-NPDA-Cu。发现Mn2+使BODIPY-NPDA在760nm荧光发射增强,而Cu2+使BODIPY-NPDA在760nm荧光发射淬灭,其他金属离子对其荧光发射影响较小。因此,BODIPY-NPDA可作为Mn2+和Cu2+响应的荧光探针,也可用于检测活体细胞中的Cu2+和Mn2+含量。
化合物BODIPY-NPDA用于溶液中Cu2+和Mn2+的定量检测见附图1,附图2。实验结果显示,随着CuCl2溶液的加入,BODIPY-NDPA乙腈溶液处于760nm的荧光随着CuCl2的增加而减弱,当BODIPY-NPDA与Cu2+的摩尔浓度为1:1.6 时,荧光几乎淬灭,溶液中Cu2+检测限度的检测限度达到0.1μM,同时伴随着760nm处荧光淬灭。
另一方面,随着MnCl2溶液的加入,BODIPY-NPDA乙腈溶液处于760nm的荧光随着MnCl2的增加而增强,当BODIPY-NPDA与Mn2+的摩尔浓度比为1:1时,荧光强度较大,溶液中Mn2+的检测限度达到0.1μM,同时伴随760nm处荧光增强。
此外,活体细胞荧光成像也进一步证实了探针BODIPY-NPDA能够进入细胞对Cu2+和Mn2+进行检测。
附图说明:
图1 BODIPY-NPDA(1μM)的乙腈溶液随着氯化铜加入的荧光变化图谱(λex=704nm);其中CuCl2的浓度(a-j=0,0.2,0.4,0.6,0.8,1.0,1.2,1.4,1.6,1.8μM)
图2 BODIPY-NPDA(1μM)的乙腈溶液随着氯化锰的加入的荧光变化图谱(λex=704nm);其中MnCl2的浓度(a-j=0,0.2,0.4,0.6,0.8,1.0,1.2μM)
具体实施方式
试剂与仪器:反应中所用的溶剂皆为分析纯,用分子筛进行除水处理,所用试剂未加特殊说明直接应用而未经任何特殊处理。二氯甲烷、哌啶、4-甲基苯磺酸、四氢呋喃、甲苯(分析纯,国家集团化学试剂有限公司);乙酸乙酯、石油醚(分析纯,上海中试化工总公司);三乙胺、碘化钾、氯化钠(分析纯,上海化学试剂有限公司);对二甲胺基苯甲醛(分析纯,三氟化硼乙醚、18-冠醚-6均购自安耐吉公司);8-(4-(氯甲基)苯基)-4,4-二氟-1,3,5,7-四甲基-4-硼-3a,4a-二吡咯(BODIPY-C)参考文献报道的方法合成(陈秋云,李赞,一种铜离子荧光探针及其合成方法,中国发明专利申请号,201210539628.X)。美国Nicolet 20DXBFR-IR型傅立叶红外光谱仪,KBr压片,400~4000cm-1;日本岛津UV-2450型紫外可见分光光度仪,800-190nm。
1,7-二甲基-3,5-(二(4-(二甲氨基苯基)-2-烯基))-8-((二(2-吡啶甲基)胺-4-苯甲基)-4,4-二氟-4-硼-3a,4a-二吡咯(简称BODIPY-NPDA)见实例1.
实例1(最佳合成案例)
BODIPY-C(1.34mmol)与二吡啶甲基胺(1.608mmol)以摩尔比1:1.2混合后加入30mL乙腈作为溶剂,接着加入三乙胺(2.01mmol),KI(1.608mmol)和18-冠醚-6(0.88mg);混合后,体系在氮气保护下,70℃油浴回反应7小时,反应结束后,浓缩反应液并用二氯甲烷溶解后过滤除去不溶物,将混合溶液除去溶剂,得混合固体;混合固体搭建分水器回流,接着加入对二甲胺基苯甲醛(3.35mmol)与BODIPY-C比例为2.5:1;加入50mL甲苯溶解后,在加入4-甲基苯磺酸(0.268mmol)和哌啶(0.67mmol),混合后,125℃分水器回流反应9小时。反应结束后,浓缩反应液并用二氯甲烷溶解,使用饱和NaCl溶液(3×15mL)萃取三次,水相用二氯甲烷(3×10mL)反萃取三次,收集有机相,无水硫酸钠干燥,浓缩溶剂,用乙酸乙酯重结晶,抽滤,乙酸乙酯洗涤,得深褐色固体BODIPY-NPDA,767mg,产率71.70%。
实例2
BODIPY-C(1.34mmol)与二吡啶甲基胺(0.67mmol)以摩尔比1:0.5混合后加入30mL乙腈作为溶剂,接着加入三乙胺(2.01mmol)、KI(1.608mmol)和18-冠醚-6(0.88mg);混合后,体系在氮气保护下,70℃油浴回反应7小时,反应结束后,浓缩反应液并用二氯甲烷溶解后过滤除去不溶物,将混合溶液除去溶剂,得混合固体;混合固体搭分水器回流,接着加入对二甲胺基苯甲醛(3.35mmol)与BODIPY-C比例为2.5:1;加入50mL甲苯溶解后,在加入4-甲基苯磺酸(0.268mmol)和哌啶(0.67mmol),混合后,125℃分水器回流反应9小时。反应结束后,浓缩反应液并用二氯甲烷溶解,使用饱和NaCl溶液(3×15mL)萃取三次,水相用二氯甲烷(3×10mL)反萃取三次,收集有机相,无水硫酸钠干燥,浓缩溶剂,用乙酸乙酯重结晶,抽滤,乙酸乙酯洗涤,得深褐色固体BODIPY-NPDA,234mg,产率21.86%。
实例3
BODIPY-C(1.34mmol)与二吡啶甲基胺(1.34mmol)以摩尔比1:1混合后加入30mL乙腈作为溶剂,接着加入三乙胺(2.01mmol)、KI(1.608mmol)和18-冠醚-6(0.88mg);混合后,体系在氮气保护下,70℃油浴回流反应7小时,反应结束后,浓缩反应液并用二氯甲烷溶解后过滤除去不溶物,将混合溶液除去溶剂,得混合固体;混合固体搭建分水器回流,接着加入对二甲胺基苯甲醛(3.35mmol)与BODIPY-C比例为2.5:1;加入50mL甲苯溶解后,在加入4-甲基苯磺酸(0.268mmol)和哌啶(0.67mmol),混合后,125℃分水器回流反应9小时。反应结束后,浓缩反应液并用二氯甲烷溶解,使用饱和NaCl溶液(3×15mL)萃取三次,水相用二氯甲烷(3×10mL)反萃取三次,收集有机相,无水硫酸钠干燥,浓缩溶剂,用乙酸乙酯重结晶,抽滤,乙酸乙酯洗涤,得深褐色固体BODIPY-NPDA 548mg,产率52.21%。
实例4
BODIPY-C(1.34mmol)与二吡啶甲基胺(2.68mmol)以摩尔比1:2混合后加入30mL乙腈作为溶剂,接着加入三乙胺(2.01mmol)、KI(1.608mmol)和18-冠醚-6(0.88mg);混合后,体系在氮气保护下,70℃油浴回流反应7小时,反应结束后,浓缩反应液并用二氯甲烷溶解后过滤除去不溶物,将混合溶液除去溶剂,得混合固体;混合固体搭建分水器回流,接着加入对二甲胺基苯甲醛(3.35mmol)与BODIPY-C比例为2.5:1;加入50mL甲苯溶解后,在加入4-甲基苯磺酸(0.268mmol)和哌啶(0.67mmol),混合后,125℃分水器回流反应9小时。反应结束后,浓缩反应液并用二氯甲烷溶解,使用饱和NaCl溶液(3×15mL)萃取三次,水相用二氯甲烷(3×10mL)反萃取三次,收集有机相,无水硫酸钠干燥,浓缩溶剂,用乙酸乙酯重结晶,抽滤,乙酸乙酯洗涤,得深褐色固体BODIPY-NPDA 498mg,产率46.54%。
实例5
BODIPY-C(1.34mmol)与二吡啶甲基胺(1.608mmol)以摩尔比1:1.2混合后加入30mL乙腈作为溶剂,接着加入三乙胺(2.01mmol)、KI(1.608mmol)和18-冠醚-6(0.88mg);混合后,70℃油浴回流反应7小时,反应结束后,浓缩反应液并用二氯甲烷溶解后过滤除去不溶物,将混合溶液除去溶剂,得混合固体;混合固体搭建分水器回流,接着加入对二甲胺基苯甲醛(3.35mmol)与BODIPY-C比例为2.5:1;加入50mL甲苯溶解后,在加入4-甲基苯磺酸(0.268mmol)和哌啶(0.67mmol),混合后,125℃分水器回流反应9小时。反应结束后,浓缩反应液并用二氯甲烷溶解,使用饱和NaCl溶液(3×15mL)萃取三次,水相用二氯甲烷(3×10mL)反萃取三次,收集有机相,无水硫酸钠干燥,浓缩溶剂,用乙酸乙酯重结晶,抽滤,乙酸乙酯洗涤,得深褐色固体BODIPY-NPDA368mg,产率34.39%。
实例6
BODIPY-C(1.34mmol)与二吡啶甲基胺(1.608mmol)以摩尔比1:1.2混合后加入30mL乙腈作为溶剂,接着加入三乙胺(2.01mmol)、KI(1.608mmol)和18-冠醚-6(0.88mg);混合后,体系在氮气保护下,55℃油浴回反应7小时,反应结束后,浓缩反应液并用二氯甲烷溶解后过滤除去不溶物,将混合溶液除去溶剂,得混合固体;混合固体搭建分水器回流,接着加入对二甲胺基苯甲醛(3.35mmol)与BODIPY-C比例为2.5:1;加入50mL甲苯溶解后,在加入4-甲基苯磺酸(0.268mmol)和哌啶(0.67mmol),混合后,125℃分水器回流反应9小时。反应结束后,浓缩反应液并用二氯甲烷溶解,使用饱和NaCl溶液(3×15mL)萃取三次,水相用二氯甲烷(3×10mL)反萃取三次,收集有机相,无水硫酸钠干燥,浓缩溶剂,用乙酸乙酯重结晶,抽滤,乙酸乙酯洗涤,得深褐色固体BODIPY-NPDA324mg,产率30.28%。
实例7
BODIPY-C(1.34mmol)与二吡啶甲基胺(1.608mmol)以摩尔比1:1.2混合后加入30mL乙腈作为溶剂,接着加入三乙胺(2.01mmol)、KI(1.608mmol)和18-冠醚-6(0.88mg);混合后,体系在氮气保护下,70℃油浴回流反应7小时,反应结束后,浓缩反应液并用二氯甲烷溶解后过滤除去不溶物,将混合溶液除去溶剂,得混合固体;混合固体搭建分水器回流,接着加入对二甲胺基苯甲醛(2.01mmol)与BODIPY-C比例为1.5:1;加入50mL甲苯溶解后,在加入4-甲基苯磺酸(0.268mmol)和哌啶(0.67mmol),混合后,125℃分水器回流反应9小时。反应结束后,浓缩反应液并用二氯甲烷溶解,使用饱和NaCl溶液(3×15mL)萃取三次,水相用二氯甲烷(3×10mL)反萃取三次,收集有机相,无水硫酸钠干燥,浓缩溶剂,用乙酸乙酯重结晶,抽滤,乙酸乙酯洗涤,得深褐色固体BODIPY-NPDA356mg,产率33.27%。
实例8
BODIPY-C(1.34mmol)与二吡啶甲基胺(1.608mmol)以摩尔比1:1.2混合后加入30mL乙腈作为溶剂,接着加入三乙胺(2.01mmol)、KI(1.608mmol)和18-冠醚-6(0.88mg);混合后,体系在氮气保护下,70℃油浴回流反应7小时,反应结束后,浓缩反应液并用二氯甲烷溶解后过滤除去不溶物,将混合溶液除去溶剂,得混合固体;混合固体搭建分水器回流,接着加入对二甲胺基苯甲醛(4.02mmol)与BODIPY-C比例为3:1;加入50mL甲苯溶解后,在加入4-甲基苯磺酸(0.268mmol)和哌啶(0.67mmol),混合后,125℃分水器回流反应9小时。反应结束后,浓缩反应液并用二氯甲烷溶解,使用饱和NaCl溶液(3×15mL)萃取三次,水相用二氯甲烷(3×10mL)反萃取三次,收集有机相,无水硫酸钠干燥,浓缩溶剂,用乙酸乙酯重结晶,抽滤,乙酸乙酯洗涤,得深褐色固体BODIPY-NPDA,650mg,产率60.74%。
实例9
BODIPY-C(1.34mmol)与二吡啶甲基胺(1.608mmol)以摩尔比1:1.2混合后加入30mL乙腈作为溶剂,接着加入三乙胺(2.01mmol)、KI(1.608mmol)和18-冠醚-6(0.88mg);混合后,体系在氮气保护下,70℃油浴回流反应7小时,反应结束后,浓缩反应液并用二氯甲烷溶解后过滤除去不溶物,将混合溶液除去溶剂,得混合固体;混合固体搭建分水器回流,接着加入对二甲胺基苯甲醛(3.35mmol)与BODIPY-C比例为2.5:1;加入50mL甲苯溶解后,在加入4-甲基苯磺酸(0.268mmol)和哌啶(0.67mmol),混合后,100℃分水器回流反应9小时。反应结束后,浓缩反应液并用二氯甲烷溶解,使用饱和NaCl溶液(3×15mL)萃取三次,水相用二氯甲烷(3×10mL)反萃取三次,收集有机相,无水硫酸钠干燥,浓缩溶剂,用乙酸乙酯重结晶,抽滤,乙酸乙酯洗涤,得深褐色固体BODIPY-NPDA,450mg,产率42.06%。
实例10
BODIPY-C(1.34mmol)与二吡啶甲基胺(1.608mmol)以摩尔比1:1.2混合后加入30mL乙腈作为溶剂,接着加入三乙胺(2.01mmol)、KI(1.608mmol)和18-冠醚-6(0.88mg);混合后,体系在氮气保护下,70℃油浴回流反应7小时,反应结束后,浓缩反应液并用二氯甲烷溶解后过滤除去不溶物,将混合溶液除去溶剂,得混合固体;混合固体搭建分水器回流,接着加入对二甲胺基苯甲醛(3.35mmol)与BODIPY-C比例为2.5:1;加入50mL甲苯溶解后,在加入4-甲基苯磺酸(0.268mmol)和哌啶(0.67mmol),混合后,140℃分水器回流反应9小时。反应结束后,浓缩反应液并用二氯甲烷溶解,使用饱和NaCl溶液(3×15mL)萃取三次,水相用二氯甲烷(3×10mL)反萃取三次,收集有机相,无水硫酸钠干燥,浓缩溶剂,用乙酸乙酯重结晶,抽滤,乙酸乙酯洗涤,得深褐色固体BODIPY-NPDA,543mg,产率50.74%。
实例11
BODIPY-C(1.34mmol)与二吡啶甲基胺(1.608mmol)以摩尔比1:1.2混合后加入30mL乙腈作为溶剂,接着加入三乙胺(2.01mmol),KI(1.608mmol)和18-冠醚-6(0.88mg);混合后,体系在氮气保护下,70℃油浴回反应7小时,反应结束后,浓缩反应液并用二氯甲烷溶解后过滤除去不溶物,将混合溶液除去溶剂,得混合固体;混合固体搭建分水器回流,接着加入对二甲胺基苯甲醛(3.35mmol)与BODIPY-C比例为2.5:1;加入30mL甲苯溶解后,在加入4-甲基苯磺酸(0.268mmol)和哌啶(0.67mmol),混合后,125℃分水器回流反应9小时。反应结束后,浓缩反应液并用二氯甲烷溶解,使用饱和NaCl溶液(3×15mL)萃取三次,水相用二氯甲烷(3×10mL)反萃取三次,收集有机相,无水硫酸钠干燥,浓缩溶剂,用乙酸乙酯重结晶,抽滤,乙酸乙酯洗涤,得深褐色固体BODIPY-NPDA,695.5mg,产率65.00%
实例12
BODIPY-C(1.34mmol)与二吡啶甲基胺(1.608mmol)以摩尔比1:1.2混合后加入30mL乙腈作为溶剂,接着加入三乙胺(2.01mmol),KI(1.608mmol)和18-冠醚-6(0.88mg);混合后,体系在氮气保护下,70℃油浴回反应7小时,反应结束后,浓缩反应液并用二氯甲烷溶解后过滤除去不溶物,将混合溶液除去溶剂,得混合固体;混合固体搭建分水器回流,接着加入对二甲胺基苯甲醛(3.35mmol)与BODIPY-C比例为2.5:1;加入100mL甲苯溶解后,在加入4-甲基苯磺酸(0.268mmol)和哌啶(0.67mmol),混合后,125℃分水器回流反应9小时。反应结束后,浓缩反应液并用二氯甲烷溶解,使用饱和NaCl溶液(3×15mL)萃取三次,水相用二氯甲烷(3×10mL)反萃取三次,收集有机相,无水硫酸钠干燥,浓缩溶剂,用乙酸乙酯重结晶,抽滤,乙酸乙酯洗涤,得深褐色固体BODIPY-NPDA,713mg,产率66.64%。
Claims (5)
1.一种锰和铜双离子响应的荧光探针,其特征在于:其结构如下:
简称BODIPY-NPDA;
荧光探针的最大紫外-可见光吸收波长在700nm,能够作为荧光探针检测Cu2+和Mn2+,也可用于检测活体细胞中的Cu2+和Mn2+含量。
2.如权利要求1所述的一种锰和铜双离子响应的荧光探针的制备方法,其特征在于:1,7-二甲基-3,5-(二(4-(二甲氨基苯基)-2-烯基))-8-((二(2-吡啶甲基)胺-4-苯甲基)-4,4-二氟-4-硼-3a,4a-二吡咯(简称BODIPY-NPDA)是由8-(4-(氯甲基)苯基)-4,4-二氟-1,3,5,7-四甲基-4-硼-3a,4a-二吡咯(BODIPY-C)与二甲基吡啶胺、对二甲氨基苯甲醛反应制得。
3.如权利要求2所述的一种锰和铜双离子响应的荧光探针的制备方法,其特征在于:
A.将BODIPY-C与二吡啶甲基胺按1:2~2:1摩尔比例混合后,加入乙腈作为溶剂,接着加入三乙胺、KI和18-冠醚-6;其中BODIPY-C与三乙胺的摩尔比例为1:2~2:1,BODIPY-C与KI的摩尔比例为1:1~1:2,KI与18-冠醚-6的质量比为300:1,混合后,体系在氮气保护下,40℃-80℃下油浴回流反应,反应7小时,反应结束后,浓缩反应液并用二氯甲烷溶解后过滤除去不溶物,将溶液除去,得混合固体;
B.在步骤A制备的混合固体反应瓶上搭建分水器回流,接着在混合溶液中加入对二甲胺基苯甲醛,其中二甲胺基苯甲醛与BODIPY-C的摩尔比例为3:1~1:1,加入甲苯为反应溶剂,甲苯与BODIPY-C的体积摩尔比为30-100mL:1.34mmol,再加入4-甲基苯磺酸和哌啶,其中4-甲基苯磺酸与BODIPY-C摩尔比例为0.1:1~0.5:1,哌啶与BODIPY-C摩尔比例为0.3:1~1:1,混合后加热至100℃~130℃,反应9小时,反应结束后,浓缩反应液并用二氯甲烷溶解,使用饱和NaCl溶液萃取,水相用二氯甲烷反萃取,收集有机相,无水硫酸钠干燥,浓缩溶剂,用乙酸乙酯重结晶,抽滤,乙酸乙酯洗涤,得深褐色固体BODIPY-NPDA。
4.如权利要求3所述的一种锰和铜双离子响应的荧光探针的制备方法,其特征在于:
步骤A中,将BODIPY-C与二吡啶甲基胺的摩尔比例为1:1.2,BODIPY-C与三乙胺的摩尔比例为1:1.5,BODIPY-C与KI的摩尔比例为1:1.2,体系在氮气保护下,70℃油浴回流反应。
5.如权利要求3所述的一种锰和铜双离子响应的荧光探针的制备方法,其特征在于:步骤B中,二甲胺基苯甲醛与BODIPY-C的摩尔比例为2.5:1,加入甲苯为反应溶剂,甲苯与BODIPY-C的体积摩尔比为50mL:1.34mmol,4-甲基苯磺酸与BODIPY-C摩尔比例0.2:1,哌啶与BODIPY-C摩尔比例为0.5:1,混合后加热至125℃。
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