CN111205335B - 一种铱配合物其制备方法及应用 - Google Patents
一种铱配合物其制备方法及应用 Download PDFInfo
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- CN111205335B CN111205335B CN202010144564.8A CN202010144564A CN111205335B CN 111205335 B CN111205335 B CN 111205335B CN 202010144564 A CN202010144564 A CN 202010144564A CN 111205335 B CN111205335 B CN 111205335B
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- phenylpyridine
- phenanthroline
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 57
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000010668 complexation reaction Methods 0.000 title description 2
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims abstract description 8
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 59
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 238000004440 column chromatography Methods 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- DKPSSMOJHLISJI-UHFFFAOYSA-N 1,10-phenanthrolin-5-amine Chemical compound C1=CC=C2C(N)=CC3=CC=CN=C3C2=N1 DKPSSMOJHLISJI-UHFFFAOYSA-N 0.000 claims description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000003480 eluent Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N CHCl3 Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical group ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 claims description 3
- XKVHLSQTMMYMQQ-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].[Ir].C1=CC=CC=C1C1=CC=CC=N1 XKVHLSQTMMYMQQ-UHFFFAOYSA-N 0.000 claims description 3
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- -1 peroxynitrite ions Chemical class 0.000 abstract description 27
- 239000000523 sample Substances 0.000 abstract description 23
- 238000001514 detection method Methods 0.000 abstract description 12
- 201000010099 disease Diseases 0.000 abstract description 6
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 abstract description 6
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- 239000008346 aqueous phase Substances 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 13
- CMFNMSMUKZHDEY-UHFFFAOYSA-M peroxynitrite Chemical compound [O-]ON=O CMFNMSMUKZHDEY-UHFFFAOYSA-M 0.000 description 12
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 10
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 description 8
- 239000012086 standard solution Substances 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- FFFHZYDWPBMWHY-VKHMYHEASA-N L-homocysteine Chemical compound OC(=O)[C@@H](N)CCS FFFHZYDWPBMWHY-VKHMYHEASA-N 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229960003180 glutathione Drugs 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003642 reactive oxygen metabolite Substances 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007850 fluorescent dye Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 150000004799 α-ketoamides Chemical group 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000008366 buffered solution Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000001296 phosphorescence spectrum Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- RREPYIWLDJQENS-UHFFFAOYSA-N 4-nitrophenylglyoxylic acid Chemical compound OC(=O)C(=O)C1=CC=C([N+]([O-])=O)C=C1 RREPYIWLDJQENS-UHFFFAOYSA-N 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- 208000023275 Autoimmune disease Diseases 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical group CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 108010024636 Glutathione Proteins 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 208000027866 inflammatory disease Diseases 0.000 description 1
- HTFVGARYENKRHF-UHFFFAOYSA-N iridium 2-phenylpyridine Chemical compound [Ir].[Ir].c1ccc(cc1)-c1ccccn1.c1ccc(cc1)-c1ccccn1.c1ccc(cc1)-c1ccccn1.c1ccc(cc1)-c1ccccn1 HTFVGARYENKRHF-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
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- 150000007523 nucleic acids Chemical class 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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Abstract
本发明公开了一种铱配合物其制备方法及应用,所述铱配合物是以三氯化铱为原料,经与2‑苯基吡啶和1,10‑邻菲啰啉共轭衍生物复合配位得到,标记为Ir‑ONOO。本发明提供了一种用于检测水溶液中过氧亚硝酸根离子的探针。本发明还提供了上述铱配合物在检测水溶液中过氧亚硝酸根离子的应用。本发明设计合成的铱配合物探针Ir‑ONOO能够单一选择性、高灵敏度的识别水相中的过氧亚硝酸根离子。本发明的铱配合物探针Ir‑ONOO具有较长的磷光发射寿命,利用时间分辨技术屏蔽背景荧光的干扰,成功应用于生物活细胞成像,有效检测和跟踪细胞内内源性过氧亚硝酸根离子的含量变化,在临床疾病标志物的检测中具有良好的应用前景。
Description
技术领域
本发明属于化学分析检测技术领域,涉及一种铱配合物其制备方法及应用。
背景技术
过氧亚硝酸根离子(ONOO-)是内源性活性氧物质(ROS)之一,具有强氧化性和亲核性,由一氧化氮(NO)和超氧阴离子自由基(O2 ·-)在非酶催化作用下扩散反应而产生(J.Biol.Chem.2013,288(37),26464-26472)。因为过氧亚硝酸根离子具有强氧化性,可以和多种生物分子包括蛋白质,脂质,核酸和含过渡金属的酶发生反应,如果其在体内过量存在,就会对细胞中包括DNA和蛋白质在内的多种分子组分产生损伤,导致自身免疫性疾病,炎性疾病,阿尔茨海默氏病,癌症和其他等疾病(Physiol.Rev.2007,87(1),315-424;Nat.Rev.Drug Discov.2007,6(8),662-680)。因此,过氧亚硝酸根离子可用作检测各种临床疾病的生物标志物。然而,由于该物质在体内具有寿命短、反应活性高、浓度低和难以俘获等性质,导致对其直接检测和跟踪困难,对其在生物系统中致病机理的理解也有待更深入的探究(ACS Chem.Biol.2009,4(3),161-177)。所以,开发在线检测过氧亚硝酸根离子的有效方法对于探索包括药物引起的某些疾病的生理和病理机制具有重要意义。
目前,结合生物成像的荧光探针技术因其操作简单、响应快速,对生物组织没有损伤等特点越来越受到研究者的关注(Acc.Chem.Res.2016,49(10),2115-2126)。虽然基于有机小分子荧光探针用于检测过氧亚硝酸根的研究已有报道(Coord.Chem.Rev.2018,374(1),36–54),但是大多数小分子荧光探针是以荧光染料为发光单元,其发光寿命短,难以屏蔽生物组织背景荧光的干扰;再加上次氯酸和过氧化氢等活性氧物质与过氧亚硝酸根离子性质相似,其区分检测也面临着一定的挑战。因此,利用铱配合物发光寿命长的特点开发铱配合物磷光探针来检测过氧亚硝酸根离子具有重要意义。
发明内容
为了克服现有技术中存在的缺陷,本发明提供铱配合物及其制备方法及应用,主要目的提供一种可准确、灵敏的检测出水溶液中过氧亚硝酸根离子的新型方法。
其技术方案如下:
一种铱配合物,其化学结构式为:
一种本发明所述的铱配合物的制备方法,包括以下步骤:以三氯化铱为原料,经与2-苯基吡啶和1,10-邻菲啰啉共轭衍生物复合配位得到,标记为Ir-ONOO;所述铱配合物命名为:六氟磷酸化2-苯基吡啶·2-(4-硝基苯基)-N-(1,10-邻菲啰啉-5-基)乙醛酰胺合铱(III)。
进一步,具体步骤为:步骤1、合成中间体二氯·四(2-苯基吡啶)合二铱(III):将乙二醇乙醚与水的混合物加入三氯化铱与2-苯基吡啶中,形成一次混合物;所述一次混合物在氩气保护下于130℃下搅拌,将搅拌后的所述一次混合物冷却至室温,过滤出黄色固体沉淀,用水和乙醇洗涤所述黄色固体沉淀后得到所述中间体二氯·四(2-苯基吡啶)合二铱(III);
步骤2、合成中间体2-(4-硝基苯基)-N-(1,10-邻菲啰啉-5-基)乙醛酰胺:向对硝基苯乙醛酸的无水CH2Cl2溶液中依次逐滴加入草酰氯和干燥的N,N-二甲基甲酰胺形成二次混合物;将所述二次混合物在室温下搅拌,再进行旋转蒸发除去溶剂,得到三次混合物;向所述三次混合物中加入无水CH2Cl2溶液形成四次混合物;向5-氨基-1,10-邻菲啰啉的无水CH2Cl2溶液中滴加三乙胺形成五次混合物;将所述五次混合物在室温下搅拌;将所述四次混合物逐滴加入到所述五次混合物中,得到六次混合物;将所述六次混合物在室温下搅拌,得到褐色沉淀,抽滤后的固体用CHCl3溶液洗涤并用柱色谱分离纯化即得到所述中间体2-(4-硝基苯基)-N-(1,10-邻菲啰啉-5-基)乙醛酰胺。
步骤3、合成六氟磷酸化2-苯基吡啶·2-(4-硝基苯基)-N-(1,10-邻菲啰啉-5-基)乙醛酰胺合铱(III):将CH3OH和CH2Cl2的混合溶液加入到所述中间体二氯·四(2-苯基吡啶)合二铱(III)和2-(4-硝基苯基)-N-(1,10-邻菲啰啉-5-基)乙醛酰胺中,形成七次混合物;所述七次混合物在氩气保护下于55℃下搅拌,将搅拌后的所述七次混合物冷却至室温,向所述七次混合物中加入NH4PF6水溶液形成八次混合物;将所述八次混合物在室温下搅拌,搅拌结束后再进行旋转蒸发除去溶剂;所得固体用柱层析色谱分离纯化,再进行重结晶纯化即得到所述铱配合物。
作为优选,所述步骤(1)中所述乙二醇乙醚与水的体积比为3:1;所述三氯化铱与2-苯基吡啶混合时的摩尔比为1:2.2;所述一次混合物在氩气保护下于130℃下搅拌的时间为24h。
作为优选,所述步骤(2)中所述中间体对硝基苯乙醛酸和草酰氯混合时摩尔比为1:3,干燥的N,N-二甲基甲酰胺用量为100μL。所述二次混合物搅拌时间为2h;所述5-氨基-1,10-邻菲啰啉和三乙胺混合时的摩尔比为0.8:1.5;所述五次混合物搅拌时间为30min;所述六次混合物搅拌时间为2h;柱色谱分离纯化洗脱剂为CH2Cl2和CH3OH,CH2Cl2和CH3OH的体积比为15:1。
作为优选,所述步骤(3)中所述中间体二氯·四(2-苯基吡啶)合二铱(III)和2-(4-硝基苯基)-N-(1,10-邻菲啰啉-5-基)乙醛酰胺混合时的摩尔比为1:2;混合溶液中CH3OH和CH2Cl2的体积比为1:1;所述七次混合物搅拌的时间为24h;所述八次混合物搅拌的时间为30min;柱色谱分离纯化洗脱剂为CH2Cl2和CH3OH,CH2Cl2和CH3OH的体积比为4:1,重结晶溶剂选择为CH2Cl2和正己烷,CH2Cl2和正己烷的体积比为1:15。
又一方面,本发明实施例提供了一种用于检测水溶液中过氧亚硝酸根离子的探针,所述探针包括所述的一种铱配合物。
再一方面,本发明实施例提供了一种铱配合物在检测水溶液中过氧亚硝酸根离子过程中的应用。
进一步,所述铱配合物对于过氧亚酸根离子的检测具有单一选择性,使用383nm可见光激发,产生570nm左右的发光,识别检测产生信号增强效果,检测所使用溶剂为磷酸缓冲溶液(50mM,pH=7.4)和无水乙醇体积比为3:1的混合溶液。所述铱配合物具有较长的磷光发射寿命,可以利用时间分辨技术屏蔽背景生物荧光的干扰,成功应用于生物活细胞成像。
与现有技术相比,本发明的有益效果:
本发明制备出的铱配合物探针具有α-酮酰胺结构,能与过氧亚硝酸根离子发生亲核反应。该探针在溶液中分散呈淡黄色,紫外灯下几乎没有磷光发射,当环境中存在过氧亚硝酸根离子时,过氧亚硝酸根离子与α-酮酰胺结构发生亲核加成反应,形成二环氧乙烷结构,随后迅速发生重排形成酸酐,而酸酐易于水解,最终形成氨基结构,呈现黄色磷光发射。
本发明设计合成的铱配合物探针Ir-ONOO能够单一选择性、高灵敏度的识别水相中的过氧亚硝酸根离子。另外,本发明设计合成的铱配合物探针Ir-ONOO具有较长的磷光发射寿命,可以利用时间分辨技术屏蔽生物组织背景荧光的干扰,成功应用于生物活细胞成像,有效检测和跟踪细胞内内源性过氧亚硝酸根离子的含量变化,在临床疾病标志物的检测中具有良好的应用前景。
本发明铱配合物制备方法简单,制备条件温和,反应快速,没有多余副产物,易于纯化。
附图说明
图1是本发明提供的铱配合物探针Ir-ONOO的ESI质谱图;
图2是本发明提供的铱配合物探针Ir-ONOO的1H NMR图;
图3是本发明提供的铱配合物探针Ir-ONOO溶液中加入10倍的过氧亚硝酸根时的紫外吸收光谱图;
图4是本发明提供的铱配合物探针Ir-ONOO对水溶液中ONOO-,H2O2,NaClO,NO,O2·-,t-BuOOH,·OH和1O2等活性氧物质,Ca2+,Cu2+,Fe2+,Fe3+,K+,Mg2+,Na+,Zn2+等阳离子,CH3COO-,CO3 2-,HCO3 -,H2PO4 -,HPO4 2-,NO2 -,NO3 -,SO4 2-,SO3 2-,HSO3 -等阴离子,硫化氢(H2S),半胱氨酸(Cys),谷胱甘肽(GSH),高半胱氨酸(Hcy),抗坏血酸(Vc)等生物小分子的磷光光谱响应图。
具体实施方式
下面结合附图和具体实施方式对本发明的技术方案作进一步详细地说明。
实施例1(制备Ir-ONOO)
步骤1、合成中间体二氯·四(2-苯基吡啶)合二铱(III):将乙二醇乙醚和水(40mL,体积比3:1)的混合物置于含有IrCl3·3H2O(0.353g,1mmol)和2-苯基吡啶(0.314g,2.2mmol)的烧瓶中;在氩气保护下,将混合物在130℃下搅拌24小时;将混合物冷却至室温后,过滤黄色固体沉淀,用水和乙醇洗涤;产率:89%,产量:0.954g;
步骤2、合成中间体2-(4-硝基苯基)-N-(1,10-邻菲啰啉-5-基)乙醛酰胺:将草酰氯(252μL,3mmol)和干燥的N,N-二甲基甲酰胺(100μL)依次逐滴加入到对硝基苯乙醛酸(195mg,1mmol)的无水CH2Cl2溶液(10mL)中,在室温下搅拌2h后,进行旋转蒸发除去溶剂,得到黄色固体。将上述黄色固体用10mL无水CH2Cl2溶解,逐滴加入到5-氨基-1,10-邻菲啰啉(156mg,0.8mmol)和三乙胺(210μL,1.5mmol)的无水CH2Cl2溶液中,在室温下搅拌2h后,得到褐色沉淀。将固体沉淀抽滤并用CHCl3(3mL)分三次洗涤,最后用体积比为15:1的CH2Cl2和CH3OH混合溶液洗脱剂进行柱色谱分离纯化,即得到中间体2-(4-硝基苯基)-N-(1,10-邻菲啰啉-5-基)乙醛酰胺。产率:72%,产量:0.215g;
步骤3、合成六氟磷酸化2-苯基吡啶·2-(4-硝基苯基)-N-(1,10-邻菲啰啉-5-基)乙醛酰胺合铱(III):将体积比为1:1的CH3OH和CH2Cl2的混合溶液(20mL)加入到置有二氯·四(2-苯基吡啶)合二铱(III)(90.3mg,0.084mmol)和2-(4-硝基苯基)-N-(1,10-邻菲啰啉-5-基)乙醛酰胺(62.7mg,0.168mmol)的烧瓶中,在氩气保护下,将混合物在55℃下搅拌24小时;将混合物冷却至室温,向其中加入饱和NH4PF6(136.5mg,0.84mmol)水溶液,在室温下搅拌30min;随后进行旋转蒸发除去溶剂,所得固体用体积比为4:1的CH2Cl2和CH3OH混合溶液洗脱剂进行柱色谱分离纯化;最后用10mL CH2Cl2溶解上述所得黄色固体并逐滴加入到搅拌的正己烷(150mL)中,将析出的黄色固体进行抽滤,干燥即得到所述铱配合物;产量:0.07g,产率:54%。
对实施例1制备的产物结构进行核磁共振检测分析,其数据如下:
ESI质谱质荷比(m/z):873.1539(图1)。
1H NMR(400MHz,DMSO-d6)δ11.60(s,1H),9.01(dd,1H),8.94(d,1H),8.72(s,1H),8.44(d,2H),8.40(d,2H),8.28-8.25(m,3H),8.18(dd,1H),8.10(dd,1H),8.05(dd,1H),7.96(d,2H),7.89(ddd,2H),7.51(dd,2H),7.07(td,2H),7.05–6.99(m,2H),6.99–6.94(m,2H),6.31(t,2H)(图2)。
实施例1制备的铱配合物的化学结构式经上述分析确定为:
实施例2(以实施例1的铱配合物作为探针检测水溶液中过氧亚硝酸根离子)
1、铱配合物探针紫外吸收实验:
测试中使用的铱配合物Ir-ONOO标准溶液均为浓度1×10-2mol·L-1的DMSO溶液;
测试中使用的所有物质均由水配置,所有活性氧物质(ONOO-、H2O2、NaClO、NO、O2·-、t-BuOOH、·OH和1O2)的标准溶液均按照相关文献进行配置,其中过氧亚硝酸根离子(ONOO-)的配置方法为:将亚硝酸钠(0.6M)与用盐酸(0.6M)酸化后的过氧化氢(0.7M)溶液混合,快速(1-2s)加入氢氧化钠(1.5M)溶液稳定,加入适量二氧化锰除去多余的过氧化氢,由于过氧亚硝酸根离子在302nm处的摩尔吸光系数为1670M-1cm-1,所以,过氧亚硝酸根的浓度为CONOO -=Abs302 nm/1.67(mM);所有阳离子(Ca2+、Cu2+、Fe2+、Fe3+、K+、Mg2+、Na+和Zn2+)标准溶液均使用其相应的氯化盐配置,所有阴离子(CH3COO-、CO3 2-、HCO3 -、H2PO4 -、HPO4 2-、NO2 -、NO3 -、SO4 2-、SO3 2-和HSO3 -)的标准溶液均使用其相应的钠盐配置,所有生物小分子(H2S、Cys、GSH、Hcy和Vc)的标准溶液均由商业化试剂稀释配置,除过氧亚硝酸根离子外,其余待测物质浓度均为1×10-2mol·L-1;
测试中使用的水均为去离子水;
测试使用的溶剂条件如无特殊说明均为用去离子水配置的磷酸缓冲溶液(50mM,pH=7.4)和无水乙醇按体积比为3:1配置。
所有测试均在室温下进行;实际测试时,在10mm规格的石英比色皿中加入2mL的测试溶液,使用微量进样器取2μL配置好的Ir-ONOO溶液加入比色皿中,然后以同样方式取10倍当量待测物质加入比色皿中;搅拌均匀后进行紫外吸收测试;扫描范围为220–500nm。
结果显示,只有加入过氧亚硝酸根离子后,铱配合物探针溶液在300-350nm左右的吸收有峰有明显增强(图3),该变化应归属于金属-配体电荷转移(1MLCT)、配体-配体电荷转移(1LLCT)和配体内电荷转移(1ILCT)过程。
2、铱配合物探针发光增强实验:
测试中使用的铱配合物Ir-ONOO标准溶液均为浓度1×10-2mol·L-1的DMSO溶液;
测试中使用的所有物质均由水配置,所有活性氧物质(ONOO-、H2O2、NaClO、NO、O2·-、t-BuOOH、·OH和1O2)的标准溶液均按照相关文献进行配置,其中过氧亚硝酸根离子(ONOO-)的配置方法为:将亚硝酸钠(0.6M)与用盐酸(0.6M)酸化后的过氧化氢(0.7M)溶液混合,快速(1-2s)加入氢氧化钠(1.5M)溶液稳定,加入适量二氧化锰除去多余的过氧化氢,由于过氧亚硝酸根离子在302nm处的摩尔吸光系数为1670M-1cm-1,所以,过氧亚硝酸根的浓度为CONOO -=Abs302 nm/1.67(mM);所有阳离子(Ca2+、Cu2+、Fe2+、Fe3+、K+、Mg2+、Na+和Zn2+)标准溶液均使用其相应的氯化盐配置,所有阴离子(CH3COO-、CO3 2-、HCO3 -、H2PO4 -、HPO4 2-、NO2 -、NO3 -、SO4 2-、SO3 2-和HSO3 -)的标准溶液均使用其相应的钠盐配置,所有生物小分子(H2S、Cys、GSH、Hcy和Vc)的标准溶液均由商业化试剂稀释配置,除过氧亚硝酸根离子外,其余待测物质浓度均为1×10-2mol·L-1;
测试中使用的水均为去离子水;
测试使用的溶剂条件如无特殊说明均为用去离子水配置的磷酸缓冲溶液(50mM,pH=7.4)和无水乙醇按体积比为3:1配置。
所有测试均在室温下进行;实际测试时,在10mm规格的石英比色皿中加入2mL的测试溶液,使用微量进样器取2μL配置好的Ir-ONOO溶液加入比色皿中,然后以同样方式取10倍当量待测物质加入比色皿中;搅拌均匀后进行磷光光谱测试;磷光发射测试扫描范围为500–700nm,激发波长Ex=383nm,狭缝宽度5.0nm/5.0nm。
结果显示,只有加入过氧亚硝酸根离子后,铱配合物探针溶液磷光发射显著增强,在570nm处出现明显的发射峰(图4),溶液在紫外灯下呈现黄色发光。
由实施例2检测结果可知,本发明实施例1制备的铱配合物探针Ir-ONOO能够单一选择性、高灵敏度的识别水相中的过氧亚硝酸根离子。
本发明制备出具有α-酮酰胺结构的铱配合物探针,能与过氧亚硝酸根发生亲核加成反应,形成二环氧乙烷结构,随后迅速发生重排形成酸酐,而酸酐易于水解,最终形成氨基结构,从而导致铱配合物的磷光发射具有较大不同。同时,本发明设计合成的铱配合物探针Ir-ONOO具有较长的磷光发射寿命,可以利用时间分辨技术屏蔽背景荧光的干扰,成功应用于生物活细胞成像,有效检测和跟踪细胞内内源性过氧亚硝酸根的含量变化,在临床疾病标志物的检测中具有良好的应用前景。
以上所述,仅为本发明较佳的具体实施方式,本发明的保护范围不限于此,任何熟悉本技术领域的技术人员在本发明披露的技术范围内,可显而易见地得到的技术方案的简单变化或等效替换均落入本发明的保护范围内。
Claims (1)
1.一种铱配合物的制备方法,其特征在于,所述铱配合物的化学结构式为:
包括以下步骤:
步骤1、合成中间体二氯·四(2-苯基吡啶)合二铱(III):将乙二醇乙醚与水的混合物加入三氯化铱与2-苯基吡啶中,形成一次混合物;所述一次混合物在氩气保护下于130℃下搅拌,将搅拌后的所述一次混合物冷却至室温,过滤出黄色固体沉淀,用水和乙醇洗涤所述黄色固体沉淀后得到所述中间体二氯·四(2-苯基吡啶)合二铱(III);
步骤2、合成中间体2-(4-硝基苯基)-N-(1,10-邻菲啰啉-5-基)乙醛酰胺:向对硝基苯乙醛酸的无水CH2Cl2溶液中依次逐滴加入草酰氯和干燥的N,N-二甲基甲酰胺形成二次混合物;将所述二次混合物在室温下搅拌,再进行旋转蒸发除去溶剂,得到三次混合物;向所述三次混合物中加入无水CH2Cl2溶液形成四次混合物;向5-氨基-1,10-邻菲啰啉的无水CH2Cl2溶液中滴加三乙胺形成五次混合物;将所述五次混合物在室温下搅拌;将所述四次混合物逐滴加入到所述五次混合物中,得到六次混合物;将所述六次混合物在室温下搅拌,得到褐色沉淀,抽滤后的固体用CHCl3溶液洗涤并用柱色谱分离纯化即得到所述中间体2-(4-硝基苯基)-N-(1,10-邻菲啰啉-5-基)乙醛酰胺;
步骤3、合成六氟磷酸化2-苯基吡啶·2-(4-硝基苯基)-N-(1,10-邻菲啰啉-5-基)乙醛酰胺合铱(III):将CH3OH和CH2Cl2的混合溶液加入到所述中间体二氯·四(2-苯基吡啶)合二铱(III)和2-(4-硝基苯基)-N-(1,10-邻菲啰啉-5-基)乙醛酰胺中,形成七次混合物;所述七次混合物在氩气保护下于55℃下搅拌,将搅拌后的所述七次混合物冷却至室温,向所述七次混合物中加入NH4PF6水溶液形成八次混合物;将所述八次混合物在室温下搅拌,搅拌结束后再进行旋转蒸发除去溶剂;所得固体用柱层析色谱分离纯化,再进行重结晶纯化即得到所述铱配合物;
所述步骤(1)中所述乙二醇乙醚与水的体积比为3:1;所述三氯化铱与2-苯基吡啶混合时的摩尔比为1:2.2;所述一次混合物在氩气保护下于130℃下搅拌的时间为24h;
所述步骤(2)中所述中间体对硝基苯乙醛酸用量为1mmol,草酰氯用量为3mmol,干燥的N,N-二甲基甲酰胺用量为100μL;所述二次混合物搅拌时间为2h;所述5-氨基-1,10-邻菲啰啉和三乙胺混合时的摩尔比为0.8:1.5;所述五次混合物搅拌时间为30min;所述六次混合物搅拌时间为2h;柱色谱分离纯化洗脱剂为CH2Cl2和CH3OH,CH2Cl2和CH3OH的体积比为15:1;
所述步骤(3)中所述中间体二氯·四(2-苯基吡啶)合二铱(III)和2-(4-硝基苯基)-N-(1,10-邻菲啰啉-5-基)乙醛酰胺混合时的摩尔比为1:2;混合溶液中CH3OH和CH2Cl2的体积比为1:1;所述七次混合物搅拌的时间为24h;所述八次混合物搅拌的时间为30min;柱色谱分离纯化洗脱剂为CH2Cl2和CH3OH,CH2Cl2和CH3OH的体积比为4:1,重结晶溶剂选择为CH2Cl2和正己烷,CH2Cl2和正己烷的体积比为1:15。
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