CN105085581A - 一类羧酸根桥联双核铁硫簇荧光探针、制备方法及应用 - Google Patents
一类羧酸根桥联双核铁硫簇荧光探针、制备方法及应用 Download PDFInfo
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 34
- BKWBIMSGEOYWCJ-UHFFFAOYSA-L iron;iron(2+);sulfanide Chemical compound [SH-].[SH-].[Fe].[Fe+2] BKWBIMSGEOYWCJ-UHFFFAOYSA-L 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000012692 Fe precursor Substances 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000007259 addition reaction Methods 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 25
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000000413 hydrolysate Substances 0.000 claims description 8
- ATFKBWNEVZUSKC-UHFFFAOYSA-N methyl 2-isocyanatobenzoate Chemical compound COC(=O)C1=CC=CC=C1N=C=O ATFKBWNEVZUSKC-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- WQIQNKQYEUMPBM-UHFFFAOYSA-N pentamethylcyclopentadiene Chemical compound CC1C(C)=C(C)C(C)=C1C WQIQNKQYEUMPBM-UHFFFAOYSA-N 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 5
- 150000004696 coordination complex Chemical class 0.000 abstract description 3
- 238000004448 titration Methods 0.000 abstract description 2
- 150000007942 carboxylates Chemical class 0.000 abstract 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical class COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 abstract 2
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- NPHKOGXZHXSAKP-UHFFFAOYSA-N anthracene;methanamine Chemical compound NC.C1=CC=CC2=CC3=CC=CC=C3C=C21 NPHKOGXZHXSAKP-UHFFFAOYSA-N 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 abstract 1
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- FQDDBYGPHUUTRN-UHFFFAOYSA-N methyl 4-isocyanatobenzoate Chemical compound COC(=O)C1=CC=C(N=C=O)C=C1 FQDDBYGPHUUTRN-UHFFFAOYSA-N 0.000 abstract 1
- 229940095102 methyl benzoate Drugs 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 4
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 102000000505 Ribonucleotide Reductases Human genes 0.000 description 2
- 108010041388 Ribonucleotide Reductases Proteins 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- -1 carboxylate salt Chemical class 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000005558 fluorometry Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 206010007027 Calculus urinary Diseases 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 206010016818 Fluorosis Diseases 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 208000009911 Urinary Calculi Diseases 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 208000004042 dental fluorosis Diseases 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000007421 fluorometric assay Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 108010009977 methane monooxygenase Proteins 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
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- 238000010792 warming Methods 0.000 description 1
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Abstract
本发明提供一类具有通式I的结构的羧酸根桥联的双核铁硫簇荧光探针。制备方法为由蒽甲胺和对甲氧羰基苯基异氰酸酯经过加成反应得到取代的苯甲酸甲酯；然后经过水解得到相应的羧酸；得到的羧酸和碱反应得到羧酸盐；再与双核铁前体配位得到荧光探针。与现有技术相比，本发明首次提供了金属配合物与生物酶的核心结构相近的羧酸根桥联双核铁硫簇；所述的金属配合物作为荧光探针，对氟离子检测选择性好，荧光滴定实验操作简单，荧光变化敏锐。
Description
技术领域
本发明涉及一类羧酸根桥联双核铁硫簇荧光探针配合物及其制备方法和用途，属于精细化工领域中离子的检测。
背景技术
生物体中含有很多种类的酶，其中有若干种中心结构为羧酸根桥联的双核铁的生物酶，比如核糖核苷酸还原酶(RNR)和可溶性甲烷单加氧酶(sMMO)，它们可以催化转化生物体中一些重要的底物，在生物体内起到了非常重要的作用。所以模拟这些生物酶的结构和功能是一项具有挑战性的工作，同时也具有重要意义。(Acc.Chem.Res.2011,44,280-288；Coord.Chem.Rev.2013,257,3-26.)。
阴离子普遍存在于生命体中，具有很重要的作用，其中氟离子是人体不可缺少的微量元素之一。氟是牙齿和骨骼的组分中必不可少的部分。适量的氟离子可以有效地预防龋齿疾病的发生，所以牙膏含有微量的氟离子。如果摄入大量的氟离子可能导致氟中毒，产生骨质疏松和尿石症等疾病；严重者可能会影响儿童的智力发育及生理系统。日常生活用水均含有微量的氟离子。由于其重要性，所以检测氟离子就尤为重要和关键(Chem.Rev.2014,114,5511-5571；Chem.Soc.Rev.2010,39,3746-3771；Chem.Commun.2009,2809-2829.)。
检测氟离子的方法有电化学法、19F-NMR分析法、紫外分析法以及荧光分析法。前三种方法都有一定的局限性，比如：设备昂贵、无法实时检测等。而利用荧光分析法具有高灵敏度、实时检测、超低浓度检测以及细胞内检测等优势，所以近年来利用荧光法检测氟离子受到研究者的青睐。
目前，利用金属配合物荧光探针实现氟离子的检测鲜有报道。它们的中心金属多为钌(Ru)、钴(Co)、铕(Eu)以及铁(Fe)等，荧光团或者发色团多为邻菲罗啉和萘等(DaltonTrans.2009,12,2096-2102；DaltonTrans.2012,41,4484-4496；Appl.Organometal.Chem.,2008,22,258-261；Analyst,2013,138,278-283；Polym.Chem.,2012,3,2640-2648.)，而羧酸根桥联的双核铁硫簇的氟离子荧光探针还未见报道。所以开展此类氟荧光探针的研究具有一定的创新和价值。
发明内容
本发明目的在于提供一类新颖的具有优良性能的羧酸根桥联的双核铁硫簇氟离子荧光探针。所述羧酸根桥联的双核铁硫簇氟离子荧光探针具有通式I的结构：
其中，R为甲基或者乙基。
本发明另一方面提供所述的羧酸根桥联的双核铁硫簇荧光探针的制备方法，包括以下步骤：(1)加成反应：将9-蒽甲胺与对甲氧羰基苯基异氰酸酯进行加成反应，反应温度为0～40℃，反应时间为1～48小时，得加成产物；
(2)水解反应：将步骤(1)所得加成产物与碱性水溶液混合，进行水解反应，反应温度为0～100℃，反应时间为1～24小时；然后用酸性水溶液调解pH至6～7，得水解产物；
(3)中和反应：将步骤(2)所得水解产物与碱反应，反应温度为0～80℃，反应时间为1～24小时，得配体；
(4)配位反应：将步骤(3)所得配体与双核铁前体进行配位反应，反应温度为0～80℃，反应时间为1～48小时；
所述双核铁前体为[Cp*Fe(μ-SR)2(MeCN)2FeCp*][PF6]2；其中，Cp*＝五甲基环戊二烯基；R＝Me(4a)或Et(4b)。
双核铁前体4a和4b的制备方法参考J.Am.Chem.Soc.2011,133,1147-1149。
作为优选的技术方案，所述步骤(1)中，9-蒽甲胺与甲氧羰基苯基异氰酸酯的物质的量之比为1:1～2:1，反应溶剂为二氯甲烷、甲苯、四氢呋喃、乙腈、乙酸乙酯、丙酮、乙醚中的至少一种。
作为优选的技术方案，所述步骤(2)中，所用碱性水溶液的体积与甲氧羰基苯基异氰酸酯的质量比为5:1～50:1mL/g。
作为优选的技术方案，所述步骤(3)中，碱为叔丁醇钾、叔丁醇钠、三乙胺、氢化钠、氢氧化钠、氢氧化钾、甲醇钠、乙醇钠中的至少一种；所述碱的加入量与水解产物的物质的量之比为1:1～2:1。
作为优选的技术方案，所述步骤(4)中，双核铁前体的加入量与配体的物质的量之比为1:1～1:2；，配位反应溶剂为二氯甲烷、四氢呋喃、乙腈、丙酮中的至少一种。
再一方面，本发明还提供上述的羧酸根桥联的双核铁硫簇荧光探针在氟离子检测中的应用。
本发明提供的荧光探针可以快速、高选择性地实现对氟离子荧光增强检测。
与现有技术相比，本发明的优点在于：
(1)本发明首次提供了金属配合物与生物酶的核心结构相近的羧酸根桥联双核铁硫簇；
(2)本发明制备的金属配合物作为荧光探针，对氟离子检测选择性好，荧光滴定实验操作简单，荧光变化敏锐。
附图说明
图1荧光探针5a与不同量的F-作用荧光光谱谱图；
图2荧光探针5b与不同量的F-作用荧光光谱谱图；
图3荧光探针5a与不同阴离子作用荧光光谱谱图；
图4荧光探针5b与不同阴离子作用荧光光谱谱图；
具体实施方式
下面结合实施例详细说明本发明，但下面的实施例仅为本发明较佳的实施方式，本发明的保护范围并不局限于此，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，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。
羧酸根桥联的双核铁硫簇荧光探针的制备方法，反应机理如下：
(1)加成反应
将9-蒽甲胺与对甲氧羰基苯基异氰酸酯进行加成反应，得到相应的羧酸酯；
(2)水解反应
将步骤(1)所得产物溶液与水混合，进行水解反应，得到中间体3；
(3)中和反应
将步骤(2)所得中间体3与碱反应，得到羧酸盐；
(4)配位反应
将步骤(3)所得羧酸盐与双核铁前体4a或者4b进行配位反应，得到荧光探针5a和5b。
实施例1羧酸根桥联的双核铁硫簇荧光探针5a的合成
将0.86g对甲氧羰基苯基异氰酸酯加入含有9-蒽甲胺(1g)的180mL二氯甲烷溶液中，室温搅拌24小时，过滤，10mL氯仿洗涤滤饼，随后将此滤饼溶解在乙醇(10mL)中，向其中加入2M氢氧化钠溶液(10mL)，升温至75℃反应12小时。然后向反应液中加入3M盐酸调节pH＝6，抽滤，分别用5mL水和乙醇洗涤滤饼，最后用二甲基亚砜-丙酮的混合溶剂重结晶得到水解产物3(0.92g，52％)。
1HNMR(400MHz,DMSO-d6):δ11.24(br,1H),8.99(s,1H),8.61(br,1H),8.54(d,JH-H＝8Hz,2H),8.11(br,2H),7.72(br,2H),7.54-7.61(m,4H),7.35(br,3H),5.31(br,2H).13CNMR(100MHz,DMSO-D6):δ155.08,141.50,131.08,130.97,129.78,128.83,127.11,126.22,125.17,124.60,115.93,35.17。
ESI-HRMS(m/z):[M-H]-369.1317；calcd.valueforC23H18N2O3:369.1326。
将叔丁醇钾(22mg)加入含有水解产物3(72mg)的30mL四氢呋喃溶液中，50℃反应2小时，减压除去溶剂。氩气保护下，加入30mL乙腈和双核铁前体4a(150mg)，室温反应48小时。过滤，减压除去乙腈；3mL二氯甲烷溶解残留物，过滤，减压除去二氯甲烷；3mL四氢呋喃溶解残留物，过滤，减压除去四氢呋喃；最后用乙醚(2×2mL)洗涤残留物后得到浅绿色固体5a(108mg,60％)。
1HNMR(400MHz,CD2Cl2):δ8.43(s,1H),8.32(br,2H),7.99(br,2H),7.44-7.50(m,4H),7.13(br,2H),6.95(br,2H),6.72(s,1H),5.25(br,2H),1.79(s,6H),1.43(s,30H).IR(KBr,cm-1):3419(m),2921(s),1695(m),1597(m),1550(m),1516(s),1397(s),1375(m),1318(w),1216(w),1178(m),1018(m),955(w),842(s),778(m),735(m)。
ESI-HRMS(m/z):[M-PF6]+845.2170；calcd.valueforC45H53Fe2N2O3S2:845.2196。
实施例2羧酸根桥联的双核铁硫簇荧光探针5b的合成
双核铁前体采用4b，其余操作步骤与实施例1相同，得到5b(105mg,58％)。
1HNMR(400MHz,CD2Cl2):δ8.44(s,1H),8.33(d,JH-H＝8Hz,2H),8.01(d,JH-H＝8Hz,2H),7.46-7.51(m,4H),7.14(d,JH-H＝8Hz,2H),6.93(d,JH-H＝8Hz,2H),6.73(s,1H),5.33(br,2H),5.26(br,1H),1.93(t,JH-H＝8Hz,6H),1.63(q,JH-H＝8Hz,4H),1.46(s,30H).IR(KBr,cm-1):3421(m),3056(w),2981(m),2925(s),1698(s),1597(s),1519(s),1448(w)1403(s),1375(m),1319(m),1231(m),1178(m),1073(w),1018(s),845(s),778(m),736(m)。
ESI-HRMS(m/z):[M-PF6]+873.2506；calcd.valueforC47H57Fe2N2O3S2:873.2509。
实施例3氟离子的量对荧光探针5a荧光发射的影响
每次取3mL浓度为10-5mol/L的5a(实施例1制备)四氢呋喃溶液于比色皿中，然后依次加入0.2当量、0.4当量、0.6当量、0.8当量、1.0当量、1.2当量、1.4当量、1.6当量、1.8当量、2.0当量、2.2当量、2.4当量、2.6当量、2.8当量以及3.0当量的四丁基氟化铵的水溶液，测试其荧光发射光谱，得到图1所示的结果。从图中可以看出，随着氟离子量的增加，体系的荧光明显的增强。
同样的方法可以得到氟离子的量对荧光探针5b的荧光发射的影响结果，如图2所示。
实施例4不同阴离子对荧光探针5a的荧光发射的影响
每次取3mL浓度为10-5mol/L的5a(实施例1制备)四氢呋喃溶液于比色皿中，然后依次加入3当量的F-、Br-、Cl-、H2PO4 -、HSO4 -、Ac-、NO3 -和I-，在370nm激发光作用下，测试其荧光发射光谱，得到图3所示的结果。从图中可以看出，体系可以选择性识别氟离子。
同样的方法可以得到不同阴离子对荧光探针5b的荧光发射的影响结果，如图4所示。
Claims (7)
1.一类羧酸根桥联的双核铁硫簇荧光探针，其特征在于：具有通式I的结构：
其中，R为甲基或者乙基。
2.权利要求1所述的羧酸根桥联的双核铁硫簇荧光探针的制备方法，其特征在于包括以下步骤：
(1)加成反应：将9-蒽甲胺与对甲氧羰基苯基异氰酸酯进行加成反应，反应温度为0～40℃，反应时间为1～48小时，得加成产物；
(2)水解反应：将步骤(1)所得加成产物与碱性水溶液混合，进行水解反应，反应温度为0～100℃，反应时间为1～24小时；然后用酸性水溶液调解pH至6～7，得水解产物；
(3)中和反应：将步骤(2)所得水解产物与碱反应，反应温度为0～80℃，反应时间为1～24小时，得配体；
(4)配位反应：将步骤(3)所得配体与双核铁前体进行配位反应，反应温度为0～80℃，反应时间为1～48小时；
所述双核铁前体为[Cp*Fe(μ-SR)2(MeCN)2FeCp*][PF6]2；其中，Cp*＝五甲基环戊二烯基；R＝Me或Et。
3.根据权利要求2所述的羧酸根桥联的双核铁硫簇荧光探针的制备方法，其特征在于：所述步骤(1)中，9-蒽甲胺与甲氧羰基苯基异氰酸酯的物质的量之比为1:1～2:1，反应溶剂为二氯甲烷、甲苯、四氢呋喃、乙腈、乙酸乙酯、丙酮、乙醚中的至少一种。
4.根据权利要求2所述的羧酸根桥联的双核铁硫簇荧光探针的制备方法，其特征在于：所述步骤(2)中，所述碱性水溶液的浓度为1mol/L～5mol/L，所用碱性水溶液的体积与甲氧羰基苯基异氰酸酯的质量比为5:1～50:1mL/g。
5.根据权利要求2所述的羧酸根桥联的双核铁硫簇荧光探针的制备方法，其特征在于：所述步骤(3)中，碱为叔丁醇钾、叔丁醇钠、三乙胺、氢化钠、氢氧化钠、氢氧化钾、甲醇钠、乙醇钠中的至少一种；所述碱的加入量与水解产物重量之比为1:3～2:3。
6.根据权利要求2所述的羧酸根桥联的双核铁硫簇荧光探针的制备方法，其特征在于：所述步骤(4)中，双核铁前体的加入量与配体的物质的量之比为1:1～1:2；，配位反应溶剂为二氯甲烷、四氢呋喃、乙腈、丙酮中的至少一种。
7.权利要求1所述的羧酸根桥联的双核铁硫簇荧光探针在氟离子检测中的应用。
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