新型稀土时间分辨荧光探针的合成与应用
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摘要
基于稀土荧光探针长寿命荧光特性而发展起来的高灵敏度时间分辨荧光生化分析技术已经在临床检测和生物技术领域得到了广泛的应用。在本博士学位论文的研究中,分别设计、合成和表征了一种新型的羟基自由基特异性响应铽配合物荧光探针和一种新型的汞离子特异性响应铽配合物荧光探针,建立了基于所合成的稀土配合物探针在时间分辨荧光分析与时间分辨荧光成像分析中的应用方法。另外,设计并探索合成了一种以多羧酸联三吡啶铕配合物为发光基团的锌离子特异性荧光探针。
设计合成了一种可用于羟基自由基特异性识别与时间分辨荧光测定的新型Tb3+配合物荧光探针N,N,N',N'-[2,6-二(3’-氨甲基-1’-吡唑基)-4-(4’-氨基苯氧基)甲基吡啶]四乙酸-Tb3+(BMPTA-Tb3+)。BMPTA-Tb3+几乎不发荧光,与羟基自由基特异性反应以后荧光量子产率增加49倍,且具有超长的荧光寿命(2.76ms)。该探针具有在生理条件下稳定性好、用于羟基自由基测定选择性和灵敏度高等优点,利用该探针成功实现了活体细胞中羟基自由基的时间分辨荧光成像测定。
设计合成了一种可用于汞(Ⅱ)离子特异性识别与时间分辨荧光测定的新型Tb3+配合物荧光探针N,N,N',N'-{2,6-二(3’-氨甲基-1’-吡唑基)-4-[N,N-二(3’,6’-二硫代辛基)-氨甲基]-吡啶}四乙酸-Tb3+(BBAPTA-Tb3+)。该探针本身的荧光非常弱,与Hg2+离子反应形成双核配合物Hg2+-BBAPTA-Tb3+后荧光量子产率增加5倍。利用该探针实现了水溶液中汞(Ⅱ)离子的高灵敏度时间分辨荧光测定。
设计了以N,N-二(2-皮考啉基)胺及4'-溴甲基-2,2':6',2”-联三吡啶-6,6"-二甲胺四乙酸四乙酯为偶联反应原料的Zn2+离子响应铕配合物荧光探针的合成路线。合成出了新化合物4’-溴甲基-2,2':6',2''-联三吡啶-6,6”-二甲胺四乙酸四乙酯,并通过核磁等方法对合成的中间产物和目标产物进行了表征,为进一步研制以联三吡啶多羧酸铕配合物为发光基团的功能性荧光探针提供了一种有用试剂。
Time-resolved luminescence bioassay technique based on long-lived luminescence of lanthanide probes is an ultrasenstive bioanalytical method, and has been widely used in clinical diagnostics and biotechnology. In this doctoral dissertation, two novel Tb3+complex-based luminescent probes specific for hydroxyl radical (·OH) and mercury(II) ions (Hg2+) were designed, synthesized and characterized, respectively, and their application methods for highly sensitive time-resolved luminescence assay and bioimaging were established. In addition, a luminescent probe for zinc(II) ions (Zn2+) using2,2':6',2"-terpyridine polyacid-Eu3+complex as the luminescence moiety were designed and primarily synthesized.
A unique Tb3+complex-based luminescent probe, N,N,N',N'-[2,6-bis(3'-aminomethyl-1'-pyrazolyl)-4-(p-aminophenoxy)methylene-pyridine] tetrakis(acetate)-Tb3+(BMPTA-Tb3+), was designed and synthesized for highly selective and sensitive time-resolved luminescence detection of·OH. The probe itself is almost non-luminescent, but can selectively react with·OH to cause a49-fold increase in luminescence quantum yield with a long luminescence lifetime (2.76ms). The luminescence response of the probe to·OH is highly selective and sensitive in the physiological pH range. Based on this probe, a time-resolved luminescence imaging method for detecting·OH in living cells was successfully established.
A unique Tb3+complex-based luminescent probe, N,N',N',N'-{[2,6-bis(3'-aminomethyl-1'-pyrazolyl)-4-[N,N-bis(3",6"-dithiaoctyl)-aminomethyl]-pyridine]} tetrakis(acetic acid)-Tb3+(BBAPTA-Tb3+), was designed and synthesized for highly selective and sensitive time-resolved luminescence detection of Hg2+. The luminescence of the probe is weak, but can be effectively enhanced upon reaction with Hg2+by the formation of heterobimetallic complex Hg2+-BBAPTA-Tb3+, with a5-fold increase in luminescence quantum yield. Based on this probe, a highly sensitive time-resolved luminescence detection method of Hg2+in aqueous solutions was developed.
A synthesis procedure of a Eu3+complex-based luminescent probe for Zn2+using N,N-bis(2-picolyl)amine and tetraethyl (4-bromomethyl-2,2':6',2"-terpyridine-6,6"-diyl) bis(methylenenitrilo) tetrakis(acetate) as the coupling reaction materials was designed, and the new compound tetraethyl (4-bromomethyl-2,2':6',2"-terpyridine-6,"-diyl) bis(methylenenitrilo) tetrakis(acetate) was synthesized. All the synthesis intermediates and final compound were characterized. The synthesis of this compound provides an essential reagent for the further development of functional probes using2,2':6',2"-terpyridine polyacid-Eu3+complex as the luminescence moiety.
设计合成了一种可用于羟基自由基特异性识别与时间分辨荧光测定的新型Tb3+配合物荧光探针N,N,N',N'-[2,6-二(3’-氨甲基-1’-吡唑基)-4-(4’-氨基苯氧基)甲基吡啶]四乙酸-Tb3+(BMPTA-Tb3+)。BMPTA-Tb3+几乎不发荧光,与羟基自由基特异性反应以后荧光量子产率增加49倍,且具有超长的荧光寿命(2.76ms)。该探针具有在生理条件下稳定性好、用于羟基自由基测定选择性和灵敏度高等优点,利用该探针成功实现了活体细胞中羟基自由基的时间分辨荧光成像测定。
设计合成了一种可用于汞(Ⅱ)离子特异性识别与时间分辨荧光测定的新型Tb3+配合物荧光探针N,N,N',N'-{2,6-二(3’-氨甲基-1’-吡唑基)-4-[N,N-二(3’,6’-二硫代辛基)-氨甲基]-吡啶}四乙酸-Tb3+(BBAPTA-Tb3+)。该探针本身的荧光非常弱,与Hg2+离子反应形成双核配合物Hg2+-BBAPTA-Tb3+后荧光量子产率增加5倍。利用该探针实现了水溶液中汞(Ⅱ)离子的高灵敏度时间分辨荧光测定。
设计了以N,N-二(2-皮考啉基)胺及4'-溴甲基-2,2':6',2”-联三吡啶-6,6"-二甲胺四乙酸四乙酯为偶联反应原料的Zn2+离子响应铕配合物荧光探针的合成路线。合成出了新化合物4’-溴甲基-2,2':6',2''-联三吡啶-6,6”-二甲胺四乙酸四乙酯,并通过核磁等方法对合成的中间产物和目标产物进行了表征,为进一步研制以联三吡啶多羧酸铕配合物为发光基团的功能性荧光探针提供了一种有用试剂。
Time-resolved luminescence bioassay technique based on long-lived luminescence of lanthanide probes is an ultrasenstive bioanalytical method, and has been widely used in clinical diagnostics and biotechnology. In this doctoral dissertation, two novel Tb3+complex-based luminescent probes specific for hydroxyl radical (·OH) and mercury(II) ions (Hg2+) were designed, synthesized and characterized, respectively, and their application methods for highly sensitive time-resolved luminescence assay and bioimaging were established. In addition, a luminescent probe for zinc(II) ions (Zn2+) using2,2':6',2"-terpyridine polyacid-Eu3+complex as the luminescence moiety were designed and primarily synthesized.
A unique Tb3+complex-based luminescent probe, N,N,N',N'-[2,6-bis(3'-aminomethyl-1'-pyrazolyl)-4-(p-aminophenoxy)methylene-pyridine] tetrakis(acetate)-Tb3+(BMPTA-Tb3+), was designed and synthesized for highly selective and sensitive time-resolved luminescence detection of·OH. The probe itself is almost non-luminescent, but can selectively react with·OH to cause a49-fold increase in luminescence quantum yield with a long luminescence lifetime (2.76ms). The luminescence response of the probe to·OH is highly selective and sensitive in the physiological pH range. Based on this probe, a time-resolved luminescence imaging method for detecting·OH in living cells was successfully established.
A unique Tb3+complex-based luminescent probe, N,N',N',N'-{[2,6-bis(3'-aminomethyl-1'-pyrazolyl)-4-[N,N-bis(3",6"-dithiaoctyl)-aminomethyl]-pyridine]} tetrakis(acetic acid)-Tb3+(BBAPTA-Tb3+), was designed and synthesized for highly selective and sensitive time-resolved luminescence detection of Hg2+. The luminescence of the probe is weak, but can be effectively enhanced upon reaction with Hg2+by the formation of heterobimetallic complex Hg2+-BBAPTA-Tb3+, with a5-fold increase in luminescence quantum yield. Based on this probe, a highly sensitive time-resolved luminescence detection method of Hg2+in aqueous solutions was developed.
A synthesis procedure of a Eu3+complex-based luminescent probe for Zn2+using N,N-bis(2-picolyl)amine and tetraethyl (4-bromomethyl-2,2':6',2"-terpyridine-6,6"-diyl) bis(methylenenitrilo) tetrakis(acetate) as the coupling reaction materials was designed, and the new compound tetraethyl (4-bromomethyl-2,2':6',2"-terpyridine-6,"-diyl) bis(methylenenitrilo) tetrakis(acetate) was synthesized. All the synthesis intermediates and final compound were characterized. The synthesis of this compound provides an essential reagent for the further development of functional probes using2,2':6',2"-terpyridine polyacid-Eu3+complex as the luminescence moiety.
引文
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