CN114409641A - 一种特异性识别高氯酸铝的化合物及其制备方法与应用 - Google Patents
一种特异性识别高氯酸铝的化合物及其制备方法与应用 Download PDFInfo
- Publication number
- CN114409641A CN114409641A CN202111495896.1A CN202111495896A CN114409641A CN 114409641 A CN114409641 A CN 114409641A CN 202111495896 A CN202111495896 A CN 202111495896A CN 114409641 A CN114409641 A CN 114409641A
- Authority
- CN
- China
- Prior art keywords
- compound
- aluminum perchlorate
- probe
- fluorescence
- detected
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- ZRGUXTGDSGGHLR-UHFFFAOYSA-K aluminum;triperchlorate Chemical compound [Al+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZRGUXTGDSGGHLR-UHFFFAOYSA-K 0.000 title claims abstract description 38
- 150000001875 compounds Chemical class 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000523 sample Substances 0.000 claims abstract description 35
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 21
- 238000002189 fluorescence spectrum Methods 0.000 claims abstract description 13
- 239000007850 fluorescent dye Substances 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 17
- 239000011550 stock solution Substances 0.000 claims description 14
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- WLKXPQFZTSRGHP-UHFFFAOYSA-N diazonio(pyren-1-ylmethyl)azanide Chemical compound C1=C2C(CN=[N+]=[N-])=CC=C(C=C3)C2=C2C3=CC=CC2=C1 WLKXPQFZTSRGHP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 6
- 230000005284 excitation Effects 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 125000001725 pyrenyl group Chemical group 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000012491 analyte Substances 0.000 description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000027455 binding Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- -1 mono-substituted pyrenyl Chemical group 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 3
- 238000000954 titration curve Methods 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000000427 antigen Substances 0.000 description 1
- 102000036639 antigens Human genes 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910001411 inorganic cation Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 230000009834 selective interaction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000009870 specific binding Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- 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
- 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
- G01N21/6428—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
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
-
- 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"
- G01N2021/6443—Fluorimetric titration
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
本发明属于荧光探针材料技术领域,公开了一种特异性识别高氯酸铝的化合物及其制备方法与应用。本发明的特异性识别高氯酸铝的化合物,具体为单取代芘基‑硫杂杯[4]芳烃荧光探针。本发明还提供其制备方法及在特异性识别高氯酸铝中的应用。本发明化合物在硫杂杯[4]芳烃的一个酚羟基上引入一个芘基作为荧光信号发射单元,将该探针的识别行为以荧光的形式表现出来,可特异性识别整个高氯酸铝无机分子。当待测物体系中仅含有Al3+离子或者仅有ClO4 ‑根时,其荧光光谱均不产生excimer发射峰;且仅仅在待测物体系中Al(ClO4)3存在的情况下才会出现excimer发射峰。因此,本发明化合物可识别整个高氯酸铝无机分子。
Description
技术领域
本发明属于荧光探针材料技术领域,具体涉及一种特异性识别高氯酸铝的化合物及其制备方法与应用。
背景技术
分子识别,是两个或以上的分子之间通过非共价键结合相互作用。除了氢键,金属耦合,疏水性,范德华力等直接相互接触的作用以外,在溶液中,水常常可以起到很重要的介导作用。也指分子选择性相互作用,例如抗体与抗原之间,酶与底物之间,激素与受体之间的专一结合。分子识别是通过两个分子各自的结合部位来实现的。要实现分子识别,一要求两个分子的结合部位是结构互补的,二要求两个结合部位有相应的基团,相互之间能够产生足够的作用力,使两个分子能够结合在一起。分子识别,作为超分子化学中重要的研究范畴,受到科学家的广泛关注。
通常情况下,分子识别一般分为,阳离子识别、阴离子识别,或者有机中性分子识别。分子,通常分为有机分子、无机分子,有机分子通常以完整分子整体形式而存在,而无机分子通常以阴、阳离子形式共存。因此分子识别过程中,也往往是要么识别整个有机分子,或者无机阳离子,或者无机阴离子。而同时识别整个无机分子却鲜有报道。
发明内容
为了克服上述现有技术的缺陷,本发明通过设计、合成,提出了一种特异性识别高氯酸铝的化合物,具体为单取代芘基-硫杂杯[4]芳烃荧光探针(TCA-Py)。本发明化合物可特异性识别整个高氯酸铝无机分子。
本发明还提供一种上述特异性识别高氯酸铝的化合物的制备方法。
本发明还提供上述化合物在特异性识别高氯酸铝中的应用。
具体通过以下技术方案实现:
一种特异性识别高氯酸铝的化合物,具体为单取代芘基-硫杂杯[4]芳烃荧光探针(TCA-Py),化学结构式如下所示:
本发明化合物在硫杂杯[4]芳烃的一个酚羟基上引入一个芘基作为荧光信号发射单元,将该探针的识别行为以荧光的形式表现出来,可特异性识别整个高氯酸铝无机分子。
本发明还提供一种上述特异性识别高氯酸铝的化合物的制备方法,由单取代炔基-硫杂杯[4]芳烃(TCA-CCH)与1-(叠氮甲基)芘经点击化学反应得到。
所用单取代炔基-硫杂杯[4]芳烃(TCA-CCH)与1-(叠氮甲基)芘的摩尔比为1:1-1:2.5;更优选为1:1.5。
所述反应的时间优选为18-36h,更优选为24h。
所述反应在催化剂的催化下进行,如可在碘化亚铜和N,N-二异丙基乙胺(DIPEA)、硫酸铜与抗坏血酸等催化体系催化下进行。所用催化剂的用量为催化量即可。
所述反应可在四氢呋喃/水混合溶剂中进行。所述四氢呋喃/水混合溶剂中,四氢呋喃/水体积比优选为4:1。
所述反应完成后,可通过冷却至室温,减压蒸馏除去溶剂,用二氯甲烷萃取,无水硫酸钠干燥,柱层析分离,得到纯化的目标产物单取代芘基硫杂杯[4]芳烃(TCA-Py)。上述分离纯化的操作为常规操作即可。
具体的,制备方法的反应方程式如下所示:
本发明还提供上述化合物在特异性识别高氯酸铝中的应用。具体可包括以下步骤:
(1)将本发明化合物溶于溶剂中得到探针储备溶液;
(2)将探针储备溶液与待测物混合,检测所得溶液的荧光光谱;
(3)当荧光光谱中出现了芘的excimer荧光发射峰,说明待测物中含有高氯酸铝。
步骤(1)中所述探针储备溶液中,化合物的浓度优选为1mmol/L。本发明制备的探针储备溶液为高浓度溶液。
步骤(1)中,所述溶剂优选为二氯甲烷。
步骤(2)中,待检测溶液中,探针的浓度优选为10μmol/L;待测物的浓度优选为10-200μmol/L,更优选为100μmol/L。
步骤(2)中,检测荧光光谱的激发波长为344nm。
步骤(3)中,所述excimer荧光发射峰的波长为474nm左右。
本发明对检测光谱的设备优选为荧光光谱仪。
本发明特异性识别高氯酸铝的化合物可特异性识别整个高氯酸铝无机分子,当待测物体系中仅含有Al3+离子(如AlCl3)或者仅有ClO4 -根(如NaClO4)时,其荧光光谱均不产生excimer发射峰;且仅仅在待测物体系中Al(ClO4)3存在的情况下才会出现excimer发射峰。因此,本发明化合物可识别整个高氯酸铝无机分子。
本发明与现有技术相比具有如下优点:
1.本发明首次设计出了一种能识别整个高氯酸铝无机分子的化合物,丰富了分子识别的模式。
2.本发明化合物对高氯酸铝分子具有特异性的识别能力,为高氯酸铝分子的高效识别提供了重要的方法。
附图说明
为了更清楚地说明本申请实施例中的技术方案,下面将对实施例描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本申请的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为本发明提供的特异性识别高氯酸铝的化合物的化学结构示意图;
图2为本发明单取代芘基-硫杂杯[4]芳烃的1H NMR谱图;
图3为本发明探针TCA-Py(10μM)识别检测金属离子的荧光光谱图;
图4为本发明探针TCA-Py(10μM,EtOH/CH2Cl2/H2O=94/1/5)与Al(ClO4)3的荧光滴定曲线图(0-50倍);
图5为本发明探针TCA-Py(10μM)分别与10倍量的Al(ClO4)3或NaClO4或AlCl3的荧光响应曲线图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅是本发明的一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。下列实施例中,各组分用量以质量份、体积份计,mg、mL。
一实施方式,一种特异性识别高氯酸铝的化合物,具体为单取代芘基-硫杂杯[4]芳烃荧光探针(TCA-Py),化学结构式如图1所示。
本发明化合物在硫杂杯[4]芳烃的一个酚羟基上引入一个芘基作为荧光信号发射单元,将该探针的识别行为以荧光的形式表现出来,可特异性识别整个高氯酸铝无机分子。
一实施方式,一种上述特异性识别高氯酸铝的化合物的制备方法,由单取代炔基-硫杂杯[4]芳烃(TCA-CCH)与1-(叠氮甲基)芘经点击化学反应得到。
一实施例中,所用单取代炔基-硫杂杯[4]芳烃(TCA-CCH)与1-(叠氮甲基)芘的摩尔比例为1:1;另一实施例中,所用单取代炔基-硫杂杯[4]芳烃(TCA-CCH)与1-(叠氮甲基)芘的摩尔比例为1:1.5;再一实施例中,所用单取代炔基-硫杂杯[4]芳烃(TCA-CCH)与1-(叠氮甲基)芘的摩尔比例为1:2.5。
所述反应在催化剂的催化下进行。一实施例中,所用催化剂为碘化亚铜和N,N-二异丙基乙胺(DIPEA)催化体系;另一实施例中,所用催化剂为硫酸铜与抗坏血酸的催化体系。所用催化剂的用量为催化量即可。
一实施例中,所述反应在四氢呋喃/水混合溶剂中进行。所述四氢呋喃/水混合溶剂中,四氢呋喃/水体积比为4:1。
一实施例中,所述反应的时间为24h;另一实施例中,所述反应的时间为18h;再一实施例中,所述反应的时间为36h。
一实施例中,所述反应完成后,通过冷却至室温,减压蒸馏除去溶剂,用二氯甲烷萃取,无水硫酸钠干燥,柱层析分离,得到纯化的目标产物单取代芘基硫杂杯[4]芳烃(TCA-Py)。
一实施方式,上述化合物在特异性识别高氯酸铝中的应用。具体包括以下步骤:
(1)将本发明化合物溶于溶剂中得到探针储备溶液;
(2)将探针储备溶液与待测物混合,检测所得溶液的荧光光谱;
(3)当荧光光谱中出现了芘的excimer荧光发射峰,说明待测物中含有高氯酸铝。
一实施例中,步骤(1)中所述探针溶液中,化合物的浓度为1mmol/L。
一实施例中,步骤(1)中,所述溶剂为二氯甲烷。
一实施例中,步骤(2)中,待检测溶液中,探针的浓度为10μmol/L。
一实施例中,步骤(2)中,待检测溶液中,待测物的浓度为10μmol/L;另一实施例中,待测物的浓度为200μmol/L;再一实施例中,待测物的浓度为100μmol/L。
一实施例中,步骤(2)中,检测荧光光谱的激发波长为344nm。
一实施例中,步骤(3)中,所述excimer荧光发射峰的波长为474nm左右。
具体实施例
实施例1
TCA-Py的合成:加入单取代炔基-硫杂杯[4]芳烃(TCA-CCH)200质量份,2.0摩尔倍1-(叠氮甲基)芘135质量份,溶于35体积份四氢呋喃/水混合溶剂(4:1),然后加入催化剂量的碘化亚铜和N,N-二异丙基乙胺(DIPEA),回流反应24小时。冷却至室温,减压蒸馏除去溶剂,用二氯甲烷萃取,无水硫酸钠干燥,柱层析分离,得到单取代芘基硫杂杯[4]芳烃(TCA-Py,123mg,46%)。1H NMR谱图见图2。
1H NMR(400MHz,CDCl3)δ:8.49(s,2H),8.38(d,J=9.2Hz,1H),8.33–8.14(m,5H),8.07(d,J=7.5Hz,1H),7.97(dd,J=12.4,8.2Hz,2H),7.90(d,J=8.9Hz,1H),7.82(t,J=7.6Hz,1H),7.55(s,2H),7.48(d,J=2.5Hz,2H),7.34(d,J=2.5Hz,2H),7.29(s,2H),6.41(s,2H),5.49(s,2H),1.21(s,9H),1.13(s,18H),1.12(s,9H)ppm。
实施例2
(1)探针储备溶液的配制:称取实施例1制备得到的探针,用二氯甲烷溶解,配制成浓度为1mmol/L的溶液。
(2)待测溶液的制备:金属离子Li+,Na+,K+,Mg2+,Ca2+,Ba2+,Hg2+,Sr2+,Zn2+,Al3+,Fe3 +,Co2+,Ni2+,Cu2+,Zn2+,Pb2+,Cd2+,Mn2+储备液的配制:分别取相应金属离子的高氯酸盐,Cr3+离子用对应的硝酸盐分别用超纯水溶解并配制成10mmol/L的金属离子储备液。
实施例3:探针TCA-Py对Al(ClO4)3的识别检测
(1)样品配制:在一系列10mL容量瓶中分别加入100μL实施例2步骤(1)制备的探针TCA-Py储备液后,再分别加入100μL实施例2步骤(2)制备的金属离子储备液或者100μL超纯水做空白,用乙醇稀释至刻度。
(2)样品测试:设置344nm激发波长,取3mL样品溶液于1cm的比色皿中进行荧光光谱测定。本发明探针TCA-Py(10μM)在376/396nm处有微弱的荧光发射峰,此为探针的芘基monomer特征荧光发射峰(即单体芘的荧光发射峰)。分别加入100μM金属离子的样品,其探针在376/396nm处的荧光发射峰均有不同程度的增强或者减弱。但是仅有Al(ClO4)3的加入,出现了芘的excimer荧光发射峰(474nm,芘的π-π相互作用荧光发射峰),如图3所示。因此,可以很明确的依靠这个excimer发射峰,来鉴别出Al3+,即在此条件下探针对Al3+有识别检测作用。
(3)在浓度为10μM的探针溶液中,加入不同浓度的Al(ClO4)3,控制最终溶液为(体积比EtOH/CH2Cl2/H2O=94/1/5)的混合溶液,以344nm为荧光激发波长,测定荧光光谱滴定曲线,结果见图4。由图4的滴定曲线可见,本发明探针的荧光变化过程分为两段,首先随着Al(ClO4)3浓度的增加,探针monomer发射峰剧烈荧光增强,但是增强到一定阶段后就不再变化,随后探针的excimer峰开始逐渐荧光增强。这说明,本发明的探针识别Al(ClO4)3的过程是分两步走的。进一步的,检测本发明探针TCA-Py(10μM)分别与10倍量的Al(ClO4)3或NaClO4或AlCl3的荧光光谱,其荧光响应曲线图见图5。由图5可见,单纯的含有Al3+离子(如AlCl3)或者仅有ClO4 -根(如NaClO4)均不产生excimer发射峰,该现象是在且仅仅在Al(ClO4)3存在的情况下才能出现。本发明探针TCA-Py可高选择性的识别Al(ClO4)3分子。这种识别整个无机分子的现象,还未见报道。
本发明与现有技术相比具有如下优点:
1.本发明首次设计出了一种能识别整个高氯酸铝无机分子的化合物,丰富了分子识别的模式。
2.本发明化合物对高氯酸铝分子具有特异性的识别能力,为高氯酸铝分子的高效识别提供了重要的方法。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
2.一种特异性识别高氯酸铝的化合物的制备方法,其特征在于由单取代炔基-硫杂杯[4]芳烃与1-(叠氮甲基)芘经点击化学反应得到。
3.根据权利要求2所述的制备方法,其特征在于:所用单取代炔基-硫杂杯[4]芳烃与1-(叠氮甲基)芘的摩尔比为1:1-1:2.5。
4.根据权利要求2所述的制备方法,其特征在于:所述反应的时间为18-36h。
5.权利要求1所述的特异性识别高氯酸铝的化合物在特异性识别高氯酸铝中的应用。
6.根据权利要求5所述的应用,其特征在于具体包括以下步骤:
(1)将权利要求1所述的特异性识别高氯酸铝的化合物溶于溶剂中得到探针储备溶液;
(2)将探针储备溶液与待测物混合,检测所得溶液的荧光光谱;
(3)当荧光光谱中出现了芘的excimer荧光发射峰,说明待测物中含有高氯酸铝。
7.根据权利要求6所述的应用,其特征在于:步骤(1)中所述探针储备溶液中,化合物的浓度为1mmol/L;所述溶剂为二氯甲烷。
8.根据权利要求6所述的应用,其特征在于:步骤(2)中,待检测溶液中,探针的浓度为10μmol/L。
9.根据权利要求6所述的应用,其特征在于:步骤(2)中,待检测溶液中,待测物的浓度为10-200μmol/L。
10.根据权利要求6所述的应用,其特征在于:步骤(2)中,检测荧光光谱的激发波长为344nm。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111495896.1A CN114409641B (zh) | 2021-12-08 | 2021-12-08 | 一种特异性识别高氯酸铝的化合物及其制备方法与应用 |
PCT/CN2022/136887 WO2023104023A1 (zh) | 2021-12-08 | 2022-12-06 | 一种特异性识别高氯酸铝的化合物及其制备方法与应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111495896.1A CN114409641B (zh) | 2021-12-08 | 2021-12-08 | 一种特异性识别高氯酸铝的化合物及其制备方法与应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114409641A true CN114409641A (zh) | 2022-04-29 |
CN114409641B CN114409641B (zh) | 2023-11-03 |
Family
ID=81265552
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111495896.1A Active CN114409641B (zh) | 2021-12-08 | 2021-12-08 | 一种特异性识别高氯酸铝的化合物及其制备方法与应用 |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN114409641B (zh) |
WO (1) | WO2023104023A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023104023A1 (zh) * | 2021-12-08 | 2023-06-15 | 深圳先进技术研究院 | 一种特异性识别高氯酸铝的化合物及其制备方法与应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20100044497A (ko) * | 2008-10-22 | 2010-04-30 | 고려대학교 산학협력단 | 카드뮴 또는 아연 이온 선택성을 갖는 칼릭스[4]아렌 유도체, 이의 제조 방법, 이를 이용한 카드뮴 또는 아연 이온 검출 방법 및 형광화학센서 |
CN103342699A (zh) * | 2013-07-16 | 2013-10-09 | 贵州大学 | 一种香豆素-硫杂杯[4]芳烃荧光试剂及其制备方法和应用 |
CN107936953A (zh) * | 2017-11-23 | 2018-04-20 | 深圳先进技术研究院 | 一种荧光探针及其制备方法和应用 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114409641B (zh) * | 2021-12-08 | 2023-11-03 | 深圳先进技术研究院 | 一种特异性识别高氯酸铝的化合物及其制备方法与应用 |
-
2021
- 2021-12-08 CN CN202111495896.1A patent/CN114409641B/zh active Active
-
2022
- 2022-12-06 WO PCT/CN2022/136887 patent/WO2023104023A1/zh unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20100044497A (ko) * | 2008-10-22 | 2010-04-30 | 고려대학교 산학협력단 | 카드뮴 또는 아연 이온 선택성을 갖는 칼릭스[4]아렌 유도체, 이의 제조 방법, 이를 이용한 카드뮴 또는 아연 이온 검출 방법 및 형광화학센서 |
CN103342699A (zh) * | 2013-07-16 | 2013-10-09 | 贵州大学 | 一种香豆素-硫杂杯[4]芳烃荧光试剂及其制备方法和应用 |
CN107936953A (zh) * | 2017-11-23 | 2018-04-20 | 深圳先进技术研究院 | 一种荧光探针及其制备方法和应用 |
Non-Patent Citations (2)
Title |
---|
XIN-LONG NI等: "Synthesis and evaluation of a novel pyrenyl-appended triazole-based thiacalix[4]arene as a fluorescent sensor for Agþ ion", TETRAHEDRON, vol. 67, pages 3248 - 3253, XP093069245, DOI: 10.1016/j.tet.2011.03.008 * |
李园义等: "硫杂杯[4]芳烃基胶束自组装荧光探针的结构性质及检测性能的研究", 光谱学与光谱分析, vol. 39, no. 4, pages 1092 - 1096 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023104023A1 (zh) * | 2021-12-08 | 2023-06-15 | 深圳先进技术研究院 | 一种特异性识别高氯酸铝的化合物及其制备方法与应用 |
Also Published As
Publication number | Publication date |
---|---|
WO2023104023A1 (zh) | 2023-06-15 |
CN114409641B (zh) | 2023-11-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Wang et al. | Fabrication and characterization of a fluorescent sensor based on Rh 6G-functionlized silica nanoparticles for nitrite ion detection | |
Tavallali et al. | A new application of bromopyrogallol red as a selective and sensitive competition assay for recognition and determination of acetate anion in DMSO/water media | |
Jain et al. | Selective extraction, preconcentration and transport studies of thorium (IV) using octa-functionalized calix [4] resorcinarene-hydroxamic acid | |
CN114409641B (zh) | 一种特异性识别高氯酸铝的化合物及其制备方法与应用 | |
Zhang et al. | A photo-stable fluorescent chiral thiourea probe for enantioselective discrimination of chiral guests | |
CN109799197B (zh) | 菁染料在检测铅离子中的用途、铅离子检测试剂盒及方法 | |
CN113264893B (zh) | 一种镨离子荧光探针化合物、其制备方法及应用 | |
Xu et al. | The detection of uranium (VI) with a synthesized ditopic bidentate ligand as probe by resonance light scattering | |
CN108623616B (zh) | 一种咪唑类环蕃受体及其合成方法和对铁离子及磷酸二氢根离子的识别应用 | |
CN115073338B (zh) | 一种高选择性识别汞离子荧光探针、制备方法与应用 | |
KR20180010403A (ko) | 영가철의 반응성 판단 시스템 및 방법 | |
CN110423609A (zh) | 一种识别硫氰酸根的荧光探针及其制备和识别方法 | |
Marken et al. | Electrochemical Oxidation and Reduction of Cationic Carbonyl Hydride Complexes of Group VI Transition Metals | |
CN113736091B (zh) | 一种荧光微米探针检测槲皮素的方法和应用 | |
CN111187289B (zh) | 一种过氧化氢荧光探针及其制备方法和应用 | |
Liu et al. | Ferrocene Macrocyclic Schiff Base Complex: Synthesis, Structure and Recognition Properties for Dual Hg 2+ and Cu 2+ | |
CN109111384B (zh) | 基于识别汞离子的1,2位对称的方酸菁探针及其制备方法和应用 | |
CN113248443A (zh) | 三齿苯并咪唑盐化合物及其制备方法与应用 | |
Hosseini et al. | Speciation determination of chromium using 1, 4-diaminoanthraquinone with spectrophotometric and spectrofluorometric methods | |
Fukumoto et al. | Simultaneous determination of titanium, zirconium, and hafnium in aqueous solution by phosphorus-31 nuclear magnetic resonance spectrometry | |
CN113004311B (zh) | 一种氟硼二吡咯类荧光探针、其制备方法及在金离子检测中的应用 | |
Serih et al. | Determination of tetraethyl lead in gasoline fuel | |
US9447008B2 (en) | Acetone production using silicon nanoparticles and catalyst compositions | |
Liu et al. | A Schiff base chemical sensor for selective detection of hexavalent chromium ions: Real sample application | |
CN113292490B (zh) | 一种识别氯离子的荧光探针及其制备方法和用途 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |