CN105924410B - 一种聚集诱导发光的配体及配合物 - Google Patents
一种聚集诱导发光的配体及配合物 Download PDFInfo
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- CN105924410B CN105924410B CN201610257331.2A CN201610257331A CN105924410B CN 105924410 B CN105924410 B CN 105924410B CN 201610257331 A CN201610257331 A CN 201610257331A CN 105924410 B CN105924410 B CN 105924410B
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- BWRRWBIBNBVHQF-UHFFFAOYSA-N 4-(3-pyridin-2-yl-1,2,4-oxadiazol-5-yl)butanoic acid Chemical compound O1C(CCCC(=O)O)=NC(C=2N=CC=CC=2)=N1 BWRRWBIBNBVHQF-UHFFFAOYSA-N 0.000 description 1
- RRRCKIRSVQAAAS-UHFFFAOYSA-N 4-[3-(3,4-dihydroxyphenyl)-1,1-dioxo-2,1$l^{6}-benzoxathiol-3-yl]benzene-1,2-diol Chemical compound C1=C(O)C(O)=CC=C1C1(C=2C=C(O)C(O)=CC=2)C2=CC=CC=C2S(=O)(=O)O1 RRRCKIRSVQAAAS-UHFFFAOYSA-N 0.000 description 1
- ANOXEUSGZWSCQL-LOYHVIPDSA-N Cycleanine Chemical compound C([C@H]1N(C)CCC=2C=C(C(=C(OC3=CC=C(C=C3)C[C@H]3N(C)CCC=4C=C(OC)C(OC)=C(C3=4)O3)C=21)OC)OC)C1=CC=C3C=C1 ANOXEUSGZWSCQL-LOYHVIPDSA-N 0.000 description 1
- PEVPVMCJEMVCAS-UHFFFAOYSA-N Cycleanine Natural products COc1cc2CCN(C)C3Cc4ccc(Oc5cccc6CCN(C)C(Cc7ccc(Oc(c1OC)c23)cc7)c56)cc4 PEVPVMCJEMVCAS-UHFFFAOYSA-N 0.000 description 1
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- ANOXEUSGZWSCQL-UHFFFAOYSA-N O-Methyl-isochondodendrin Natural products O1C(C2=3)=C(OC)C(OC)=CC=3CCN(C)C2CC(C=C2)=CC=C2OC(C=23)=C(OC)C(OC)=CC=2CCN(C)C3CC2=CC=C1C=C2 ANOXEUSGZWSCQL-UHFFFAOYSA-N 0.000 description 1
- BELBBZDIHDAJOR-UHFFFAOYSA-N Phenolsulfonephthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2S(=O)(=O)O1 BELBBZDIHDAJOR-UHFFFAOYSA-N 0.000 description 1
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- 230000003466 anti-cipated effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- SYWDWCWQXBUCOP-UHFFFAOYSA-N benzene;ethene Chemical group C=C.C1=CC=CC=C1 SYWDWCWQXBUCOP-UHFFFAOYSA-N 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
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- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
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- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/06—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations
- A61K49/08—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by the carrier
- A61K49/085—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by the carrier conjugated systems
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/06—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations
- A61K49/08—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by the carrier
- A61K49/10—Organic compounds
- A61K49/101—Organic compounds the carrier being a complex-forming compound able to form MRI-active complexes with paramagnetic metals
- A61K49/106—Organic compounds the carrier being a complex-forming compound able to form MRI-active complexes with paramagnetic metals the complex-forming compound being cyclic, e.g. DOTA
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/06—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations
- A61K49/08—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by the carrier
- A61K49/10—Organic compounds
- A61K49/101—Organic compounds the carrier being a complex-forming compound able to form MRI-active complexes with paramagnetic metals
- A61K49/106—Organic compounds the carrier being a complex-forming compound able to form MRI-active complexes with paramagnetic metals the complex-forming compound being cyclic, e.g. DOTA
- A61K49/108—Organic compounds the carrier being a complex-forming compound able to form MRI-active complexes with paramagnetic metals the complex-forming compound being cyclic, e.g. DOTA the metal complex being Gd-DOTA
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/14—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D295/145—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/15—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6524—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having four or more nitrogen atoms as the only ring hetero atoms
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Radiology & Medical Imaging (AREA)
- Medicinal Chemistry (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Biomedical Technology (AREA)
- Materials Engineering (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
本发明涉及一种聚集诱导发光的配体及其金属配合物,属于生物检测领域。配体中同时含有大环胺类基团和聚集诱导发光(AIE)的基团,二者共价连接或者通过常见的有机单元桥连。根据配合物中螯合的金属离子不同,配合物会表现出各自不同的功能。其中锌、镉等配合物可以作为阴离子荧光探针,用于核酸、蛋白质等分子的检测;镧系金属配合物可用于时间分辨的荧光磷光检测及成像;顺磁性的金属配合物可以用于磁共振成像。
Description
技术领域
本发明涉及一种聚集诱导发光的配体及其金属配合物,可以作为探针分子用于荧光检测、细胞或组织的荧光成像、磁共振成像等,属于生物检测领域。
背景技术
聚集诱导发光(AIE)是指一类荧光生色团在溶液状态下微弱发光甚至不发光,而在固态或聚集状态下荧光显著增强的一种光物理现象。由于荧光物质在溶液中,分子聚集度小,分子内部基团可以自由旋转,分子吸收的光大多以热能的形式放出去,所以,AIE荧光物质在溶液中不发荧光。近年来,一大批的AIE特性的有机分子被合成出来,不仅用于制作有机光电材料,还运用到无机离子和生物分子的检测中。具有AIE特性的分子作为荧光探针在无机离子和生物检测领域有着传统荧光探针分子不能比拟的优点:AIE探针分子更多的结合到生物大分子上获得高亮度的荧光,而不必担心像传统的荧光分子那样发生聚集导致的荧光猝灭,这为荧光检测提供了便利。
金属配合物在分子探针领域有较多的应用。一方面,配位作用与氢键和静电作用相比,具有更高的键能,这就使得配位作用可以在水等质子化溶剂中稳定存在,因而以配位作用结合的探针可以更有效的在于水溶液中发挥检测作用。另外一方面,一些过渡金属离子可以用于构建磷光金属配合物,相对于一般的有机小分子探针,具有较长的激发态寿命,可以用于时间分辨的检测和成像,以去除散射光和短寿命荧光的干扰。
近年来,时间分辨荧光技术已成为生物化学与生物物理领域的主要研究工具之一。时间分辨的荧光成像技术可以同时获得分子状态以及空间分布的信息,在生物学和医学领域也得到了越来越广泛的应用。当体系中含有多种荧光物质时,由于各物质的荧光发射光谱可能会出现重叠和干扰的情况,单独依靠通常的荧光发射光谱手段可能无法得到体系准确的信息。而利用时间分辨的荧光技术,可以通过荧光寿命的差异,解析出体系中荧光物质的组成情况,从而提供有价值的信息。另外一方面,小分子荧光的寿命一般在纳秒的范围,相对于寿命长达毫秒的稀土配合物的磷光,对仪器有更高的要求,因此,发展长寿命、长波长发射的成像探针,不仅可降低仪器的依懒性,并区分短寿命的荧光,而且可以从光谱上避免生物体内短波长自荧光的影响,意义重大。
发明内容
本发明提供一类聚集诱导发光的配体化合物及相应的金属配合物。根据不同的配体和金属原子,这些配体和配合物可以分别用于荧光检测、时间分辨的检测以及磁共振造影剂等领域。
这些配体的结构特点为:分子中同时含有大环胺类基团和聚集诱导发光的基团,二者共价连接或者通过常见的有机单元桥连。这些配体与特定的金属配位即可得到相应的配合物。
本发明所提供的配体的结构通式如下所示:
其中,a、b、c、d、e、f、g、h、i各自独立,a、b、c、d选自1-3的整数,e、i选自0-5的整数,f、g选自1-20的整数,h选自0-10的整数。
L选自(CH2)p、 其中p为0-10的整数;R选自:H、烷基、不饱和烃基、含取代基的烷基或含取代基的不饱和烃基,所述取代基选自卤素、羟基、羧基、氨基、酰胺基、芳香环或杂环基。
AIE为具有聚集诱导发光性质的荧光基团,具体结构可以参考聚集诱导发光领域已知的文献,其中优选结构为四苯乙烯、含有取代基的四苯乙烯、以及四苯乙烯基取代的芳环基。
R1、R2、R3各自独立,选自:
其中p为1-5的整数;Ra、Rb、Rc各自独立,选自H、烷基、不饱和烃基、含取代基的烷基、含取代基的不饱和烃基,取代基选自卤素、羟基、羧基、氨基、酰胺基、芳香环或杂环基。
上述配体的制备方法如下:以大环胺类化合物为原料,将聚集诱导发光的小分子共价修饰到大环胺类化合物上,再根据具体分子结构进行进一步的功能化。具体的方法可以参考有机合成领域中大环胺类化合物的合成文献。
例如,当R1、R2、R3选自可以参考如下文献制备:
Chem.Commun.,2002,890–891;Chem.Commun.,2006,4084–4086;
Org.Biomol.Chem.,2006,4,1572–1579;Chem.Commun.,2007,129–131;
Chem.Commun.,2007,3389–3391;Dalton Trans.,2009,4712–4721;
Dalton Trans.,2011,40,484–488;Chem.Commun.,2011,47,206–208;
J.Am.Chem.Soc.2009,131,17542–17543;
J.Am.Chem.Soc.2011,133,11847–11849;
J.Am.Chem.Soc.2012,134,10725-10728;
J.Am.Chem.Soc.2012,134,16099-16102。
当R1、R2、R3选自时,可以参考如下文献制备:
European Journal of Inorganic Chemistry,(1),119-136;2009;
Inorganic Chemistry,31(21),4422-4;1992;
European Journal of Inorganic Chemistry,(1),119-136;2009;
European Journal of Inorganic Chemistry,2012(15),2533-2547;2012;
Journal of Inorganic Biochemistry,102(7),1531-1540;2008;
Inorganic Chemistry,40(26),6572-6579;2001;
Chemistry-A European Journal,19(24),7748-7757;2013。
根据上述结构通式,一些优选的配体结构如下:
其中,m选自0-10的整数,n选自0-3的整数,
X选自:(CH2)p、 其中p为0-10的整数。
R4选自H、Rd、Re选自H、烷基、不饱和烃基、含杂环取代基的烷基等。
根据本发明的结构通式,可以列举一些优选的配体结构如下(这些结构不作为本发明的限制):
配体1:配体2:配体3:配体4:配体5:配体6:配体7:配体8:配体9:配体10:配体11:配体12:配体13:
上述配体与不同的金属盐反应,可以形成相应的配合物。具体制备方法可参考相关的金属配合物领域已知的文献制备。
现列举一些优选的配合物结构如下(这些结构不作为本发明的限制):
根据不同配位的金属离子,配合物会表现出相应的功能。
如果选择主族金属元素、IIB和IIIB族元素的金属离子,则所获得的配合物可以通过中心金属离子配位结合阴离子,可以作为阴离子荧光探针。可以用于核酸、蛋白质等分子的检测。在核酸的检测应用中,这类化合物无论对单链还是双链核酸都有高灵敏度。除了用于溶液中检测核酸,还可以用作凝胶电泳中单链DNA的显色剂,对比同位素标记或荧光标记的单链DNA电泳,这种显色方法降低了成本并简化了操作。将此类探针应用于凝胶电泳、细胞内核酸成像或生物样品中核酸的检测和显色具有较好的应用前景。
如果选择以镧系金属离子配位,则聚集诱导发光基团在检测过程中分子内旋转受到限制后,可以实现配体到金属离子的能量转移,获得长寿命的磷光的聚集诱导发光配合物,可以用于时间分辨的荧光磷光检测及成像。
如果选择Gd3+、Fe3+、Mn2+等顺磁性金属离子进行配位,所获得的配合物可以用于磁共振造影成像。
此外,上述一些胺基配体,可以与核酸结合,从而限制分子的旋转,抑制非辐射的激发态弛豫,荧光显著增强,即实现对核酸的检测。
上述所有化合物的检测原理为:金属离子与目标分子通过配位结合,从而使四苯乙烯聚集在目标分子周围,进而通过聚集诱导荧光增强现象判断目标分子的存在。根据这一原理,只要大环胺类化合物与聚集诱导发光基团是共价连接,不论该共价键的长短如何,都可以达到类似的检测效果;此外,根据相同的原理,其他具有聚集诱导发光性质的分子也可以用于这类探针的分子设计,并可以预料具有类似的检测效果。这些改进均没有超出本发明的实质内涵。
附图说明
图1为配合物Zn1检测DNA的荧光图谱。
图2为配合物Zn1溶液的荧光强度随DNA浓度的变化图。
图3为配合物Zn2溶液的荧光强度随DNA浓度的变化图。
图4为配合物Zn3溶液的荧光强度随DNA浓度的变化图。
图5为配合物Zn4溶液的荧光强度随DNA浓度的变化图。
图6为配合物Cd1检测DNA的荧光图。
图7为配合物Eu1检测牛血清蛋白的稳态荧光图。
图8为配合物Eu1检测牛血清蛋白的时间分辨的光谱图。
具体实施方式
下面通过具体实施例对本发明作进一步的说明,其目的在于帮助更好的理解本发明的内容,但这些具体实施方案不以任何方式限制本发明的保护范围。本实施方案所用的原料为已知化合物,可在市场上购得,或可用本领域已知的方法合成。
实施例1,锌、镉配合物用于核酸的检测
配合物Zn1的合成:
配体5的合成:将原料A1(0.46g,1mmol)和轮环藤宁(0.69g,4mmol),放入单口圆底烧瓶中,加40mL无水乙腈,回流反应1天后,减压蒸馏,柱层析分离,得目标产物0.39g,产率为71%。ESI-MS:m/z[M+H]+:547.Anal.Calcd for C36H42N4O:C,79.08;H,7.74;N,10.25;Found:C,78.94;H,7.58;N,10.07。
配合物Zn1的制备:取107mg(0.2mmol)的配体5溶解在0.5mL的甲醇溶液中,同时称取Zn(NO3)2·6H2O 84mg(0.3mmoL)溶解在0.5mL的甲醇溶液中。将硝酸锌的甲醇溶液缓慢滴加到配体5的甲醇溶液中,期间会有白色的固体产生并沉淀下来,放置一段时间,抽滤,烘干,得到白色固体92mg,产率为63%。ESI-MS:m/z[M-NO3]+:672.2.Anal.Calcd forC36H42N6O7Zn:C,58.74;H,5.75;N,11.42;Found:C,58.88;H,5.30;N,11.85。
根据类似的方法,使用不同的大环胺类化合物,通过亲核取代反应可以制备配体1至7。
根据类似的方法,选用相应的配体和金属盐,可以制备出以下配合物:
这些配合物可以用于核酸的荧光检测,原理是配合物的中心离子可以与核酸的碱基配位结合,并诱导疏水的四苯乙烯基团聚集,从而使得荧光增强。
将配合物Zn1用于检测DNA,所用序列为TTTTT,结果如附图1所示,溶液荧光随着DNA浓度的增加显著提高。在相同条件下,加入其它三条序列(GGGGG、AAAAA、CCCCC),荧光增强不明显(附图2),说明该配合物具有一定的碱基选择性。检测条件为:配合物浓度:10μM,[HEPES]=10mM,[NaCl]=50mM,pH=7.0,λex=330nm,λem=470nm。
配合物Zn2和Zn3检测不同DNA的结果如附图3和4所示,检测条件为:配合物浓度:10μM,[Phenol red]=10μM,[NaCl]=100mM,pH=8.0,λex=330nm,λem=470nm。
配合物Zn4检测不同DNA的结果如附图5所示,检测条件为:配合物浓度:10μM,[Catechol violet]=10μM,[NaCl]=100mM,pH=8.0,λex=330nm,λem=470nm。
配合物Cd1用于检测DNA,结果如附图6所示,溶液荧光随着DNA浓度的增加显著提高。检测条件为:配合物浓度:10μM,[HEPES]=10mM,[NaCl]=50mM,pH=7.0,λex=330nm。
相对于一般的核酸探针,这些基于配位结合的探针可以与核酸中特异的碱基配位结合,因而在单链核酸的检测中具有较高的灵敏度,并且对不同的核酸序列表现出一定的选择性。
按相同的原理和思路,配体1-7,以及具有类似结构的配体都可以用来设计金属配合物,并可以达到类似于本实例中配合物的检测效果。
按相同的原理和思路,其它金属离子也可以用来设计这类配合物探针,并可以达到类似于本实例中配合物的检测效果。
实施例2,稀土配合物的制备及时间分辨的检测
配合物Eu1的合成路线如下:
配体8的制备:向圆底烧瓶加入配体5(0.08g,0.146mmol)、2-氯-N,N-二乙基乙酰胺(0.11g,0.74mmol)、碘化钾(0.20g,1.2mmol)、碳酸钾(0.22g,1.6mmol)和10mL乙腈,在氩气保护下回流反应48h后,减压浓缩,以氯仿-甲醇(v:v=20:1)为淋洗剂,经硅胶柱层析纯化得无色油状液体0.12g,产率93%。ESI-MS:m/z[M+H]+:886,[M+Na]+:908。
配合物Eu1的制备:向单口瓶中加配体8(0.048g,0.053mmol),六水和三氯化铕(0.022g,0.06mmol)和2.5mL甲醇,回流反应15h后,过滤收集滤液,减压蒸馏得黄色透明固体。用1mL甲醇溶解,加乙醚析出固体,过滤收集固体,再如此溶解、析出、过滤,然后干燥得黄色固体0.053g,产率85%。ESI-MS:m/z[M+H3O]+:1164,[M-Cl]+:1108。
根据类似的方法,将配体8与相应的金属盐反应,可以制备出以下配合物:
这些配合物在水溶液中具有非常低的量子产率,可以用于蛋白质的检测,具有高的荧光增强倍数。此外这些配合物可以用于时间分辨的检测,用于去除背景荧光和散射光的干扰,显著提高检测的信噪比。
配合物Eu1检测牛血清蛋白的稳态荧光图如附图7所示,相应的时间分辨的检测光谱如附图8所示,随着牛血清蛋白(BSA)浓度的增强,分子的荧光和磷光都显著增加,通过时间分辨的检测(延迟0.05ms,积分1ms),短寿命的荧光被去除,显示出铕离子的红光特征发射。检测条件为:配合物浓度:50μM,[HEPES]=10mM,pH=7.0,λex=330nm。
按相同的原理和思路,配体8-13,以及具有类似结构的配体都可以用来设计金属配合物,并可以达到类似于本实例中配合物的检测效果。
按相同的原理和思路,其它镧系金属离子也可以用来设计这类配合物探针,并可以达到类似于本实例中配合物的检测效果。此外一些镧系金属配合物如Yb1和Nd1等金属磷光的发射在近红外区,可以作为近红外的探针用于相关的检测。
实施例3,磁造影剂的合成
配体9和配体10的合成路线如下:
配体9的合成:向圆底烧瓶加入配体5(0.11g,0.2mmol)、溴乙酸叔丁酯(0.4g,4mmol)和10mL乙腈,回流反应48h后,减压浓缩,以氯仿-甲醇(v:v=20:1)为淋洗剂,经硅胶柱层析纯化得无色油状液体0.15g,产率84%。ESI-MS:m/z[M+H]+:889。
配体10的合成:向圆底烧瓶加入配体9(0.09g,0.1mmol)和浓盐酸5mL,搅拌反应4h后,70℃减压浓缩,得白色固体产物约0.06g,产率83%。ESI-MS:m/z[M-H]-:719。
按实施实例2中的方法,将配体10分别与EuCl3、GdCl3、MnCl2反应,可以得到相应的配合物,结构如下:
这些配合物由于含有顺磁性的金属离子,可以作为磁共振造影剂。类似的,其它顺磁性的金属离子也可以与配体10反应,所得配合物也可以用于磁共振造影。按类似的原理,其它大环胺类配体(如配体8-13)也可以用来合成顺磁性金属配合物,并用于磁共振造影。
Claims (6)
1.一种配体,其特征在于:分子中同时含有大环胺类基团和聚集诱导发光的基团,二者共价连接或者通过有机单元桥连;配体的结构通式如下:
其中,a、b、c、d、e为1,f为1或2,g为1-20的整数,h为1;
AIE为四苯乙烯基;
L为
R1、R2、R3各自独立,为H或N,N-二乙基乙酰胺基。
2.一种金属配合物,其特征在于:由权利要求1所述的配体与金属离子螯合构成。
3.如权利要求2所述的配合物,其特征在于,配合物结构为:
4.权利要求2所述的配合物在制备检测核酸或蛋白质的荧光探针上的用途,其特征在于,构成配合物的金属离子选自主族金属元素、IIB和IIIB族元素的金属离子。
5.权利要求2所述的配合物在制备用于时间分辨的荧光检测的探针上的用途,其特征在于,构成配合物的金属离子选自镧系金属离子。
6.权利要求2所述的配合物在制备磁造影剂上的用途,其特征在于,构成配合物的金属离子选自顺磁性的金属离子。
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