CN109053626A - 一种荧光探针及其制备方法和其在二价钯检测中的应用 - Google Patents
一种荧光探针及其制备方法和其在二价钯检测中的应用 Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 53
- 239000000523 sample Substances 0.000 title claims abstract description 45
- 238000001514 detection method Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000000126 substance Substances 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- ZMZSYUSDGRJZNT-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)acetonitrile Chemical compound C1=CC=C2SC(CC#N)=NC2=C1 ZMZSYUSDGRJZNT-UHFFFAOYSA-N 0.000 claims description 8
- 238000001917 fluorescence detection Methods 0.000 claims description 8
- 238000006482 condensation reaction Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 150000003053 piperidines Chemical group 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- QLBGFCHJCWNVIN-UHFFFAOYSA-N 2-(1,3-thiazol-2-yl)acetonitrile Chemical compound N#CCC1=NC=CS1 QLBGFCHJCWNVIN-UHFFFAOYSA-N 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000002953 phosphate buffered saline Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000007853 buffer solution Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000011550 stock solution Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000003480 eluent Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021554 Chromium(II) chloride Inorganic materials 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910003244 Na2PdCl4 Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 229910019032 PtCl2 Inorganic materials 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000033077 cellular process Effects 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- ZTRPYTHOEREHEN-UHFFFAOYSA-N piperazine pyridine Chemical compound N1CCNCC1.N1=CC=CC=C1.N1=CC=CC=C1 ZTRPYTHOEREHEN-UHFFFAOYSA-N 0.000 description 1
- 238000000918 plasma mass spectrometry Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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Abstract
本发明提供一种具有式I所示结构的荧光探针，属于分析化学技术领域，本发明提供的具有式I所示结构的荧光探针可快速检测二价钯物质，且不受其它价态钯物质的干扰，灵敏度高，抗干扰能力强，且实现了二价钯物质的定量检测。
Description
技术领域
本发明涉及分析化学技术领域，特别涉及一种荧光探针及其制备方法和其在二价钯检测中的应用。
背景技术
钯是一种特殊的过渡金属，在合成化学和材料科学中扮演着重要的角色。然而，钯的频繁使用对环境造成污染，对人体健康构成威胁，作为可以结合含硫蛋白质和其他生物分子的过渡金属，钯可能会影响细胞代谢过程并对人类构成健康威胁。因此，有必要开发检测钯的工具。
传统的分析技术，如电感耦合等离子体质谱(ICP-MS)，原子吸收光谱法(AAS)和X射线荧光(XRF)等测试技术均需长时间制备钯或需要昂贵的设备。相比之下，荧光探针提供了一种简便灵敏的检测方法。近年来，基于Pd催化的裂解反应，Pd与配合物配位的几种荧光探针已被开发用于探测钯。但是，这些探针都不能区分二价的钯物质与其他钯物质，而在钯物质中二价钯物质的毒性最大。如T.Gao等人在《A water-soluble ESIPT fluorescentprobe with high quantum yield and red emission for ratiometric detection ofinorganic and organic palladium》(an Asian journal，Chemistry，2015，10：1142～1145)发表的文章公开了结构为
的探针，但是该探针容易受到其它价态的钯物质的干扰，不能将二价钯物质与其他钯物质区分开。
发明内容
有鉴于此，本发明目的在于提供一种二价钯荧光探针及其制备方法和其在二价钯检测中的应用，本发明提供的荧光探针用于二价钯物质荧光检测，特异性地识别二价钯，检测灵敏度高，抗干扰能力强。
本发明提供了一种具有式I所示结构的荧光探针：
本发明还提供了上述荧光探针的制备方法，包括以下步骤：
将具有式II所示结构的化合物、苯并噻唑-2-乙腈、催化剂和有机溶剂混合后在无氧环境下进行缩合反应，得到具有式I所示结构的荧光探针；
优选地，所述具有式II所示结构的化合物与苯并噻唑-2-乙腈的摩尔比为1：0.3～3。
优选地，所述催化剂为哌啶。
优选地，所述催化剂与具有式II所示结构的化合物的物质的量比为1：10～50。
优选地，所述有机溶剂为乙醇。
本发明还提供了上述荧光探针在二价钯物质荧光检测中的应用。
优选地，所述二价钯物质荧光检测包括水环境和生物体系中二价钯物质的传感检测。
有益技术效果：本发明提供的具有式I所示结构的荧光探针。该荧光探针合成方法简单；可快速检测二价钯物质，且不受其它价态钯物质的干扰，灵敏度高，抗干扰能力强，且实现了二价钯物质的定量检测。
附图说明
图1为实施例1中得到的红色固体的氢核磁谱图；
图2为实施例1中得到的红色固体的碳核磁谱图；
图3为实施例1中得到的荧光探针在不同浓度Pd(OAc)2中的荧光发射图谱；
图4为实施例1中得到的荧光探针在不同价态钯物质溶液中的荧光发射图谱；
图5为实施例1中得到的荧光探针在不同金属离子溶液中的荧光发射图谱。
具体实施方式
本发明提供了一种具有式I所示结构的荧光探针：
本发明还提供了上述荧光探针的制备方法，包括以下步骤：
将具有式II所示结构的化合物、苯并噻唑-2-乙腈、催化剂和有机溶剂混合后在无氧环境下进行缩合反应，得到具有式I所示结构的荧光探针；
在本发明中，所述具有式II所示结构的化合物与苯并噻唑-2-乙腈的摩尔比优选为1：0.3～3，更优选为1：1.5～2.5，最优选为1：2。
在本发明中，所述催化剂优选为哌啶。
在本发明中，所述催化剂与具有式II所示结构的化合物的物质的量比优选为1：10～50，更优选为1：20～40，最优选为1：25～30。
在本发明中，所述有机溶剂优选为乙醇。
在本发明中，所述有机溶剂的用量优选为15～30ml，更优选为25ml。
在本发明中，所述缩合反应优选在室温下进行。
在本发明中，所述缩合反应的时间优选为12～24h，更优选为16～20h。
在本发明中，所述无氧环境优选为充入氮气提供无氧环境。
在本发明中，所述缩合反应完成后还优选包括依次对反应液进行减压蒸发、硅胶住色谱法纯化，得到有式I所示结构的荧光探针。
在本发明中，优选使用薄板层析法测缩合反应是否完成。
在本发明中，所述减压蒸发的温度优选为30～50℃，更优选为40～45℃；所述减压蒸发的时间优选为5～25分钟，更优选为15～20分钟。
在本发明中，所述硅胶色谱柱的洗脱剂优选为己烷和二氯甲烷的混合物，所述己烷和二氯甲烷的体积比优选为1：1～5，更优选为1：2～3。
本发明还提供了上述荧光探针在二价钯物质荧光检测中的应用。
在本发明中，所述二价钯物质荧光检测优选包括水环境和生物体系中二价钯物质的传感检测。
在本发明中，所述传感检测优选包括荧光检测、细胞成像检测和组织成像检测。
在本发明中，所述式I结构中含有炔基和氰基，在对钯金属检测过程中，首先，不同价态金属钯可与探针中的炔基和氰基配位，随后三苯基膦加入，不同价态金属钯被原位还原成零价钯，最后，原位产生的零价钯催化消除炔丙基，成环产生荧光响应产物。由于零价钯本身(Pd(PPh3)4)含有四个配体，但是，探针氰基和炔基之间空间有限，导致零价钯同探针配位能力有限，产生弱荧光，此外，虽然四价钯能配位，但是，四价钯被三苯基膦还原成零价钯的效率弱于二价。因此，二价钯能被选择性检测。
为了更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。
实施例1
将0.5mmol具有式II所示结构的化合物和0.5mmol苯并噻唑-2-乙腈在氮气氛围下加入到反应瓶中，然后将25mL乙醇一次性加入至上述反应瓶中，氮气下加入两滴哌啶，于室温下搅拌12小时，点板检测反应完全，减压蒸发溶剂，得到粗产物，然后通过硅胶柱色谱法纯化，洗脱剂配比为己烷：二氯甲烷＝1：1，得到红色固体，对得到的红色固体的核磁表征，其氢谱图和碳谱图分别如图1和图2所示，其具体数据如下所示：
1H-NMR(400MHz,CDCl3)δ(ppm):8.53(s,1H),8.44(d,J＝8.0Hz,1H),8.02(d,J＝8.0Hz,1H),7.83(d,J＝8.0Hz,1H),7.48-7.44(m,1H),7.36-7.32(m,1H),6.42(dd,1H),6.31(s,1H),4.84(d,J＝2Hz,2H),3.49-3.43(q,J＝7.2Hz,4H),2.59(t,J＝2Hz,1H),1.25(t,J＝7.2Hz,6H)；13C-NMR(100MHz,CDCl3)δ(ppm):165.8,159.4,154.0,152.4,141.0,134.6,130.9,126.5125.0,123.0,121.5118.8,110.3,105.9,96.9,94.9,78.3,76.5,56.3,45.2,12.9。
由上述数据可知，实施例1中得到的红色固体为具有式I所示结构的化合物，产率为65％，纯度为100％。
实施例2
将实施例1中得到的探针在磷酸缓冲盐溶液(以下简称为PBS缓冲液)中加入不同浓度Pd(OAc)2的光谱测试
将实施例1中制备的探针分子溶于DMF中，制备成10mM的储备液。从储备液中取出3μL加到5mL的离心管中，用PBS缓冲溶液(PBS,20mM,pH 7.4)稀释至3mL，加入不同浓度Pd(OAc)2在37℃孵育30分钟，然后加入100μM PPh3在37℃保温3h。在激发波长为478nm下测量其荧光性质，结果如图3所示，图3中曲线由下到上，Pd(OAc)2的浓度逐渐升高，荧光探针在522nm处的荧光强度随Pd(OAc)2浓度的增强而增加，其中在Pd(OAc)2的浓度为5μM时探针荧光增加达到平台。由此可说明在检测限范围内，该探针可对Pd(OAc)2定量检测。
实施例3
将实施例1中得到的探针在磷酸缓冲盐溶液(以下简称为PBS缓冲液)中加入不同价态钯的光谱测试
将实施例1中制备的探针分子溶于DMF中，制备成10mM的储备液。从储备液中取出3μL加到5mL的离心管中，用PBS缓冲溶液(PBS,20mM,pH 7.4)稀释至3mL，分别加入不同价态钯包括PdCl2、Pd(OAc)2、PbCl2(CH3CN)2、Na2PdCl4、Pd(PPh3)4和(NH4)2PdCl6在37℃孵育30分钟，然后加入100μM PPh3在37℃保温3h。在激发波长为478nm，最大发射波长522nm下测量其荧光性质，其结果如图4所示。由图4可知探针在不同价态钯物质中选择性和抗干扰性好，对二价钯物质具有很好的选择响应性。
将实施例1中得到的探针在磷酸缓冲盐溶液(以下简称为PBS缓冲液)中加入不同金属种类的光谱测试
将实施例1中制备的探针分子溶于DMF中，制备成10mM的储备液。从储备液中取出3μL加到5mL的离心管中，用PBS缓冲溶液(PBS,20mM,pH 7.4)稀释至3mL，分别加入不同金属种类包括Pb(NO3)2、CrCl2、HgCl2、NiSO4、CuCl2·2H2O、ZnCl2、CdCl2·2.5H2O、CaCl2、CoCl2·6H2O、MgCl2·6H2O、BaCl2·2H2O、MnCl2、FeCl3·6H2O、FeCl2·4H2O、CrCl3·6H2O,PtCl2,AuCl3,RhCl3和RuCl3，在激发波长为478nm，最大发射波长522nm下测量其荧光性质，其结果如图5所示，由图5可知，探针在不同金属离子中对二价钯物质的的选择性非常好，灵敏度高。
实施例4
将0.5mmol具有式II所示结构的化合物和1mmol苯并噻唑-2-乙腈在氮气氛围下加入到反应瓶中，然后将25mL乙醇一次性加入至上述反应瓶中，氮气下加入0.02mmol哌啶，于室温下搅拌16小时，点板检测反应完全，减压蒸发溶剂，得到粗产物，然后通过硅胶柱色谱法纯化，洗脱剂配比为己烷：二氯甲烷＝1：2，得到红色固体，其核磁表征数据如下所示：
1H-NMR(400MHz,CDCl3)δ(ppm):8.53(s,1H),8.44(d,J＝8.0Hz,1H),8.02(d,J＝8.0Hz,1H),7.83(d,J＝8.0Hz,1H),7.48-7.44(m,1H),7.36-7.32(m,1H),6.42(dd,1H),6.31(s,1H),4.84(d,J＝2Hz,2H),3.49-3.43(q,J＝7.2Hz,4H),2.59(t,J＝2Hz,1H),1.25(t,J＝7.2Hz,6H)；13C-NMR(100MHz,CDCl3)δ(ppm):165.8,159.4,154.0,152.4,141.0,134.6,130.9,126.5125.0,123.0,121.5118.8,110.3,105.9,96.9,94.9,78.3,76.5,56.3,45.2,12.9。
由上述数据可知，上述得到的红色固体为具有式I所示结构的荧光探针，产率为70％，纯度为100％。
实施例5
将0.5mmol具有式II所示结构的化合物和1.25mmol苯并噻唑-2-乙腈在氮气氛围下加入到反应瓶中，然后将25mL乙醇一次性加入至上述反应瓶中，氮气下加入0.02mmol哌啶，于室温下搅拌20小时，点板检测反应完全，减压蒸发溶剂，得到粗产物，然后通过硅胶柱色谱法纯化，洗脱剂配比为己烷：二氯甲烷＝1：2.5，得到红色固体，其核磁表征数据如下所示：
1H-NMR(400MHz,CDCl3)δ(ppm):8.53(s,1H),8.44(d,J＝8.0Hz,1H),8.02(d,J＝8.0Hz,1H),7.83(d,J＝8.0Hz,1H),7.48-7.44(m,1H),7.36-7.32(m,1H),6.42(dd,1H),6.31(s,1H),4.84(d,J＝2Hz,2H),3.49-3.43(q,J＝7.2Hz,4H),2.59(t,J＝2Hz,1H),1.25(t,J＝7.2Hz,6H)；13C-NMR(100MHz,CDCl3)δ(ppm):165.8,159.4,154.0,152.4,141.0,134.6,130.9,126.5125.0,123.0,121.5118.8,110.3,105.9,96.9,94.9,78.3,76.5,56.3,45.2,12.9。
由上述数据可知，上述得到的红色固体为具有式I所示结构的荧光探针，产率为75％，纯度为100％。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (8)
1.一种具有式I所示结构的荧光探针：
2.一种权利要求1所述荧光探针的制备方法，包括以下步骤：
将具有式II所示结构的化合物、苯并噻唑-2-乙腈、催化剂和有机溶剂混合后在无氧环境下进行缩合反应，得到具有式I所示结构的荧光探针；
3.根据权利要求2所述的制备方法，其特征在于，所述具有式II所示结构的化合物与苯并噻唑-2-乙腈的摩尔比为1：0.3～3。
4.根据权利要求2所述的制备方法，其特征在于，所述催化剂为哌啶。
5.根据权利要求2或4所述的制备方法，其特征在于，所述催化剂与具有式II所示结构的化合物物质的量比为1：10～50。
6.根据权利要求2所述的制备方法，其特征在于，所述有机溶剂为乙醇。
7.一种权利要求1所述荧光探针在二价钯物质荧光检测中的应用。
8.根据权利要求7所述的应用，其特征在于，所述二价钯物质荧光检测包括水环境或生物体系中二价钯物质的传感检测。
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| CN116425738A (zh) * | 2023-06-12 | 2023-07-14 | 苏州市独墅湖医院(苏州大学附属独墅湖医院) | α-氰基苯撑乙烯衍生物在检测人血清白蛋白中的用途 |
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| CN113912596A (zh) * | 2021-11-25 | 2022-01-11 | 江苏科技大学 | 一种基于苯并噻唑母体的钯离子检测荧光探针及其制备方法与应用 |
| CN113912596B (zh) * | 2021-11-25 | 2022-12-02 | 江苏科技大学 | 一种基于苯并噻唑母体的钯离子检测荧光探针及其制备方法与应用 |
| WO2023093399A1 (zh) * | 2021-11-25 | 2023-06-01 | 江苏科技大学 | 一种基于苯并噻唑母体的钯离子检测荧光探针及其制备方法与应用 |
| CN116425738A (zh) * | 2023-06-12 | 2023-07-14 | 苏州市独墅湖医院(苏州大学附属独墅湖医院) | α-氰基苯撑乙烯衍生物在检测人血清白蛋白中的用途 |
| CN116425738B (zh) * | 2023-06-12 | 2023-09-05 | 苏州市独墅湖医院(苏州大学附属独墅湖医院) | α-氰基苯撑乙烯衍生物在检测人血清白蛋白中的用途 |
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