CN107353300A - 一种苯硼酸类次氯酸比色荧光探针的制备与应用 - Google Patents
一种苯硼酸类次氯酸比色荧光探针的制备与应用 Download PDFInfo
- Publication number
- CN107353300A CN107353300A CN201710496515.9A CN201710496515A CN107353300A CN 107353300 A CN107353300 A CN 107353300A CN 201710496515 A CN201710496515 A CN 201710496515A CN 107353300 A CN107353300 A CN 107353300A
- Authority
- CN
- China
- Prior art keywords
- hypochlorous acid
- probe
- hypochlorous
- acid
- preparation
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000523 sample Substances 0.000 title abstract description 68
- KKBQAPCFXBBOEH-UHFFFAOYSA-N ClO.C1(=CC=CC=C1)B(O)O Chemical compound ClO.C1(=CC=CC=C1)B(O)O KKBQAPCFXBBOEH-UHFFFAOYSA-N 0.000 title abstract description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims abstract description 55
- HXITXNWTGFUOAU-UHFFFAOYSA-N dihydroxy-phenylborane Natural products OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 18
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000009182 swimming Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 2
- 150000002148 esters Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 150000007530 organic bases Chemical class 0.000 claims 1
- 150000003053 piperidines Chemical class 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 17
- -1 phenylboronic acid compound Chemical class 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 238000002189 fluorescence spectrum Methods 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000003480 eluent Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tert-butyl alcohol Substances CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 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
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 125000005909 ethyl alcohol group Chemical group 0.000 description 4
- 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 4
- 230000004044 response Effects 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 108010024636 Glutathione Proteins 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 102000003896 Myeloperoxidases Human genes 0.000 description 2
- 108090000235 Myeloperoxidases Proteins 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000012491 analyte Substances 0.000 description 2
- 238000004458 analytical method Methods 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
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 2
- 235000018417 cysteine Nutrition 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 229960003180 glutathione Drugs 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940005654 nitrite ion Drugs 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 201000001320 Atherosclerosis Diseases 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 201000008482 osteoarthritis Diseases 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 206010039073 rheumatoid arthritis Diseases 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- 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"
-
- 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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- 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
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (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)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
本发明涉及一种苯硼酸类次氯酸比色荧光探针的制备与应用。具体地,本发明的探针为一种苯硼酸类化合物,其可作为次氯酸比色荧光探针用于次氯酸的检测。这类探针可实现如下的技术效果中的至少一个:灵敏高选择性地识别次氯酸并进行准确检测;可以快速对次氯酸实现响应;可以实现对次氯酸的即时检测;性质稳定,可以长期保存使用;有利于在实际样本中对(体内/体外)次氯酸进行检测。
Description
技术领域
本发明涉及苯硼酸类化合物作为次氯酸比色荧光探针,其可在水溶液中对次氯酸进行快速灵敏高选择性检测,或者其可测定实际水样中次氯酸的浓度。
背景技术
在人体内,次氯酸可以以髓过氧化物酶(MPO)催化反应的过氧化氢和氯离子的调节方式产生,其与先天宿主防御和对杀死各种病原体非常重要。在体外,由于泳池水次氯酸浓度过高导致的游泳池中毒事件现依旧频频发生。生物体内产生或蓄积过量的次氯酸,会引起多种疾病,包括心血管疾病,动脉粥样硬化,骨关节炎,类风湿性关节炎和肺损伤,严重还会导致癌症。因此,检测实际水体和生物体系中次氯酸的浓度已成为一个重要的课题,现亟待发展快速、灵敏、高选择性检测次氯酸的手段。
当前,常见的次氯酸检测手段主要是碘还原滴定法、分光光度法、化学发光分析法、库伦法等。但这些分析手段在实际应用中既昂贵又繁琐,且常常需要特殊的昂贵实验仪器和高技能专业操作人员。因此,高效、廉价、简捷的次氯酸检测手段成为重要的研究课题。
在各种离子/分子的检测方法中,比色荧光探针检测法由于操作简单,可在现场使用,选择性和灵敏度高,检测范围广,响应时间快速,能够进行原位检测和实时监测,检测过程对样品没有破坏而极为引人注目。但是目前报道的荧光探针仍存在一些问题,包括灵敏度低、选择性差以及合成复杂等。总之,发展具有高灵敏度、高选择性、合成步骤简单的次氯酸比色荧光探针是本领域技术人员急需解决的问题。
发明内容
本领域急需一种制备简单的快速高灵敏高选择性识别次氯酸的比色荧光探针,从而能够有效检测体内或体外次氯酸。为此,本发明合成了一类新颖的次氯酸比色荧光探针,其合成简单、超灵敏、稳定性高、和/或选择性高,和/或能够快速特异性识别次氯酸。
具体而言,本发明提供了一种次氯酸比色荧光探针,其为苯硼酸类化合物,其结构如下:
优选的,本发明的荧光探针是:
在本发明的次氯酸比色荧光探针的制备方法中,反应温度为25℃;反应时间是6h;苯并噻唑-2-乙腈和对醛基苯硼酸的摩尔比为约1:1至1:3,优选为1:1.1或1:1.3;二异丙基乙基胺作为有机碱催化剂。
本发明还提供了用于检测样本(例如游泳池水样本)中次氯酸浓度的检测制剂或试剂盒,其包含本发明的探针。优选地,本发明的检测制剂或试剂盒还包含产品的使用说明书。还优选地,本发明的试剂盒还包含用于测定样本中的次氯酸浓度的缓冲剂。
本发明还提供了检测样本(例如游泳池水样本)中次氯酸浓度的方法,其包括将本发明的探针与待测样本接触的步骤。
本发明还提供了本发明的探针在制备用于检测样本(例如游泳池水样本)中次氯酸浓度的制剂中的用途。
本发明的次氯酸荧光探针可与次氯酸进行特异性作用,产生荧光光谱的增强变化,从而实现对次氯酸的定量检测。
具体而言,本发明的次氯酸比色荧光探针分别与过氧化氢、过氧化叔丁醇、羟基自由基以及其他物质进行作用均不能导致荧光光谱的明显改变,从而实现对次氯酸的特异性识别。
可选择地,本发明的次氯酸荧光探针的稳定性好,进而能够长期保存使用。
进一步的,本发明的次氯酸荧光探针是快速高选择性次氯酸比色荧光探针,且合成简单,成本低廉,有利于商业化的推广应用。
附图说明
图1a是探针溶液随次氯酸浓度变化的吸收光谱,插图为反应前后溶液的颜色变化。
图1b是A446/A332对不同次氯酸浓度的拟合曲线。
图2是探针溶液(5μM)随次氯酸浓度变化(0-20μM)的荧光光谱,插图是515nm的荧光强度对次氯酸浓度的拟合曲线。
图3是探针对次氯酸的响应时间测定。
图4是探针(5μM)对不同分析物(0.1mM)的响应情况。其中a:探针溶液,b:钾离子,c:钙离子,d:钠离子,e:镁离子,f:锌离子,g:硝酸根离子,h:亚硝酸根离子,i:一氧化氮,j:半胱氨酸,k:谷胱甘肽,l:过氧化氢,m:过氧化叔丁醇,n:过氧化叔丁醇自由基,o:羟基自由基,p:单线态氧,q:超氧阴离子,r:抗坏血酸,s:高碘酸钠,t:次氯酸(20μM)。
具体实施方式:
本发明提供了上述快速灵敏高选择性次氯酸比色荧光探针的合成路线、方法及其光谱性能。
本发明的次氯酸比色荧光探针是一种苯硼酸类化合物,其具有以下结构通式:
上式中:R1,R2,R3,R4,R5和R6为氢原子,直链或支链烷基,直链或支链烷氧基,磺酸基,酯基,羧基;R1,R2,R3,R4,R5和R6可以相同或不同。
该类次氯酸比色荧光探针的合成路线和方法如下:
具体地,本发明的比色荧光探针可以通过如下方法制备,将苯并噻唑-2-乙腈(2mmol)、对醛基苯硼酸(2.5mmol)和二异丙基乙基胺(3mmol)溶于20mL乙醇中,25℃下搅拌反应6h,然后用硅胶柱色谱提纯(洗脱剂为二氯甲烷:石油醚=2:1)得到纯品固体(产率91%)。
因此,本发明还提供了对醛基苯硼酸类化合物在制备用于检测次氯酸的比色荧光探针中的用途。
本发明还提供了苯并噻唑-2-乙腈类化合物在制备用于检测次氯酸的试剂盒中的用途。
本发明的快速高灵敏高选择性识别次氯酸比色荧光探针的显著特征是能够快速高选择性特异性地识别次氯酸,能够准确对次氯酸进行定量分析。
下面将通过借助以下实施例来更详细地说明本发明。以下实施例仅是说明性的,应该明白,本发明并不受下述实施例的限制。
实施例1
(方案1)将苯并噻唑-2-乙腈(348mg,2mmol)和对醛基苯硼酸(300mg,2mmol)溶解于20mL无水乙醇中,然后逐滴加入二异丙基乙基胺(646mg,3mmol),反应液在室温下反应6小时。反应完成后,旋蒸除去溶剂得到粗产品,然后用硅胶柱(洗脱剂为二氯甲烷:石油醚=2:1)分离提纯,得到黄色固体508mg,产率为83%。
(方案2)将苯并噻唑-2-乙腈(348mg,2mmol)和对醛基苯硼酸(330mg,2.2mmol)溶解于20mL无水乙醇中,然后逐滴加入二异丙基乙基胺(646mg,3mmol),反应液在室温下反应6小时。反应完成后,旋蒸除去溶剂得到粗产品,然后用硅胶柱(洗脱剂为二氯甲烷:石油醚=2:1)分离提纯,得到黄色固体539mg,产率为88%。
(方案3)将苯并噻唑-2-乙腈(348mg,2mmol)和对醛基苯硼酸(375mg,2.5mmol)溶解于20mL无水乙醇中,然后逐滴加入二异丙基乙基胺(646mg,3mmol),反应液在室温下反应6小时。反应完成后,旋蒸除去溶剂得到粗产品,然后用硅胶柱(洗脱剂为二氯甲烷:石油醚=2:1)分离提纯,得到黄色固体557mg,产率为91%。
(方案4)将苯并噻唑-2-乙腈(348mg,2mmol)和对醛基苯硼酸(450mg,3.0mmol)溶解于20mL无水乙醇中,然后逐滴加入二异丙基乙基胺(646mg,3mmol),反应液在室温下反应6小时。反应完成后,旋蒸除去溶剂得到粗产品,然后用硅胶柱(洗脱剂为二氯甲烷:石油醚=2:1)分离提纯,得到黄色固体569mg,产率为93%。
1H NMR(400MHz,DMSO-d6)δ(×10-6):7.52(t,J=8.0Hz,1H),7.59(t,J=8.0Hz,1H),7.97(d,J=8.0Hz,1H),8.05(d,J=8.0Hz,1H),8.11(t,J=8.0Hz,2H),8.19(d,J=8.0Hz,1H),8.35(s,1H),8.42(s,1H).13C NMR(100MHz,DMSO-d6)δ(×10-6):106.27,116.55,122.97,123.68,126.86,127.63,129.49,134.02,134.83,135.10,148.78,153.35,163.61.ESI-MS计算值:C16H12BN2O2S[M+H]+307.0713,实测值:307.0705。
实施例2
本发明的发明人进行了如下测试:(a)在PBS pH=7.4条件下不同浓度次氯酸对探针溶液吸收光谱的影响;(b)吸收光谱法定量分析次氯酸的线性关系图;上述测定是在10mMPBS的水溶液中进行的,所使用的探针是实施例1中所制备的探针,且所有光谱测试都是在25℃下次氯酸加入作用1min后测得的。结果参见图1。
从图1可以看出,在加入次氯酸之前,探针的吸收峰在320nm;加入次氯酸之后,随着次氯酸浓度的增高,320nm处的吸收峰逐渐消失,并在446nm处产生一个新的吸收峰。吸收峰红移了126nm,并在357nm处有一个完美的等吸收点,反应液由无色逐渐变为了黄色。这说明探针与次氯酸发生了反应,并且生成了一种新的物种,导致了吸收峰的红移。此外,两个吸收峰处吸光度的比值(A446/A332)与次氯酸的浓度之间保持好的线性关系。经计算,探针对次氯酸吸收光谱法的检出限为181nM。
实施例3
在PBS pH=7.4条件下,不同浓度次氯酸对探针溶液荧光光谱的影响,插图是荧光光谱法定量分析次氯酸的线性关系图;上述测定是在10mM PBS的水溶液中进行的,所使用的探针是实施例1中所制备的探针,且所有光谱测试都是在25℃下次氯酸加入作用1min后测得的。结果参见图2。
图2是探针的荧光光谱随不同浓度次氯酸的变化情况图。由图可以看出,在加入次氯酸之前,探针几乎没有荧光;当加入次氯酸之后,随着次氯酸浓度的增加,515nm处的荧光强度逐渐增强。而且515nm处的发射峰荧光强度与次氯酸的浓度之间保持好的线性关系,说明探针可以用荧光光谱法定量检测次氯酸。经计算,探针对次氯酸的检出限为9.5nM。
实施例4
探针(5μM)对次氯酸(5μM)响应时间的测试结果。上述测定是在10mM PBS,pH 7.4的水溶液中进行的,所使用的探针是实施例1中所制备的探针,且所有光谱测试都是在25℃下测得的。结果参见图3。
从图3可以看出,加入等浓度次氯酸后,荧光强度骤然上升,并且在1min内能够响应完成。
实施例5
(a)不同分析物对探针(5μM)荧光光谱的影响。分析物包括:a:探针溶液,b:钾离子,c:钙离子,d:钠离子,e:镁离子,f:锌离子,g:硝酸根离子,h:亚硝酸根离子,i:一氧化氮,j:半胱氨酸,k:谷胱甘肽,l:过氧化氢,m:过氧化叔丁醇,n:过氧化叔丁醇自由基,o:羟基自由基,p:单线态氧,q:超氧阴离子,r:抗坏血酸,s:高碘酸钠,t:次氯酸(20μM)。它们的浓度(除特殊标注)均为100μM。所有测试条件是10mM PBS,pH=7.4的水溶液中进行的,所使用的探针是实施例1中所制备的探针,且所有光谱测试都是在25℃下作用1min后测得的。结果参见图4。具体地,移取50μL的探针储备液(1mM)放进10mL比色管中,然后依次加入2mL乙醇和5mL超纯水,再移取相应体积的上述分析物储备液加入比色管内,然后移取1mL的PBS溶液(pH7.4,100mM),加入比色管内,最后用超纯水定容至10mL。摇匀,静置1min,即可测定。结果如图4所示。
从图4可以看出,探针对次氯酸具有很高的选择性,能够专一性地和次氯酸进行反应,反应前后,荧光光谱有明显变化,而其他分析物与探针作用后荧光强度并不发生明显变化。而且其他物质不会明显干扰探针对次氯酸的定性与定量检测。
虽然用上述实施方式描述了本发明,应当理解的是,在不背离本发明的精神的前提下,本发明可进行进一步的修饰和变动,且这些修饰和变动均属于本发明的保护范围之内。
Claims (10)
1.化合物,其具有以下结构:
上式中:R1,R2,R3,R4,R5和R6为氢原子,直链或支链烷基,直链或支链烷氧基,磺酸基,酯基,或羧基;R1,R2,R3,R4,R5和R6可以相同或不同。
2.根据权利要求1所述的化合物,其为如下结构的化合物:
3.用于检测样本中次氯酸含量的制剂或试剂盒,其包含权利要求1或2中的化合物:
4.根据权利要求3所述的制剂或试剂盒,其中所述的样本是游泳池中的水样本。
5.根据权利要求3或4所述的制剂或试剂盒,其还包括用于检测样本中次氯酸含量的缓冲剂和/或使用说明书。
6.制备权利要求1或2的化合物的方法,其包括使苯并噻唑-2-乙腈和对醛基苯硼酸反应。
7.根据权利要求6的方法,其中苯并噻唑-2-乙腈和对醛基苯硼酸的摩尔比为1:1至1:3。
8.根据权利要求6所述的方法,其中反应温度是20℃~100℃。
9.根据权利要求6所述的方法,其中反应溶剂为乙醇、甲醇、异丙醇、正丁醇等质子溶剂中的一种或混合物;以及,二异丙基乙基胺、三乙胺、哌啶等有机碱作为催化剂。
10.根据权利要求6所述的方法,其中反应时间是2~12h。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710496515.9A CN107353300B (zh) | 2017-06-26 | 2017-06-26 | 一种苯硼酸类次氯酸比色荧光探针的制备与应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710496515.9A CN107353300B (zh) | 2017-06-26 | 2017-06-26 | 一种苯硼酸类次氯酸比色荧光探针的制备与应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107353300A true CN107353300A (zh) | 2017-11-17 |
CN107353300B CN107353300B (zh) | 2018-03-27 |
Family
ID=60272504
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710496515.9A Expired - Fee Related CN107353300B (zh) | 2017-06-26 | 2017-06-26 | 一种苯硼酸类次氯酸比色荧光探针的制备与应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107353300B (zh) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108727362A (zh) * | 2018-08-01 | 2018-11-02 | 中南大学 | 一类固体荧光小分子的合成与应用 |
CN111393462A (zh) * | 2020-04-10 | 2020-07-10 | 山西大学 | 一种基于双机理的用于检测onoo-的荧光探针及其制备方法和应用 |
CN115029132A (zh) * | 2022-05-27 | 2022-09-09 | 重庆师范大学 | 一种新型的多巴胺功能化荧光碳点的制备方法及其产品和应用 |
EP4057900A4 (en) * | 2019-11-13 | 2023-12-06 | Senseonics, Incorporated | IDENTIFICATION OF DEGRADATION SPECIES |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102977130A (zh) * | 2012-12-21 | 2013-03-20 | 天津理工大学 | 一种用于检测次氯酸根的分子荧光探针及其制备和应用 |
CN105001858A (zh) * | 2015-07-30 | 2015-10-28 | 济南大学 | 一种新型检测碱性环境中过氧化氢的荧光探针及其制备方法与生物应用 |
-
2017
- 2017-06-26 CN CN201710496515.9A patent/CN107353300B/zh not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102977130A (zh) * | 2012-12-21 | 2013-03-20 | 天津理工大学 | 一种用于检测次氯酸根的分子荧光探针及其制备和应用 |
CN105001858A (zh) * | 2015-07-30 | 2015-10-28 | 济南大学 | 一种新型检测碱性环境中过氧化氢的荧光探针及其制备方法与生物应用 |
Non-Patent Citations (2)
Title |
---|
LI WU等,: "Photostable Ratiometric Pdot Probe for in Vitro and in Vivo Imaging of Hypochlorous Acid", 《J. AM. CHEM. SOC.》 * |
毋尧,: "苯硼酸类荧光探针的合成及应用研究", 《西北大学硕士学位论文》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108727362A (zh) * | 2018-08-01 | 2018-11-02 | 中南大学 | 一类固体荧光小分子的合成与应用 |
EP4057900A4 (en) * | 2019-11-13 | 2023-12-06 | Senseonics, Incorporated | IDENTIFICATION OF DEGRADATION SPECIES |
US12000784B2 (en) | 2019-11-13 | 2024-06-04 | Senseonics, Incorporated | Identification of degradative species |
CN111393462A (zh) * | 2020-04-10 | 2020-07-10 | 山西大学 | 一种基于双机理的用于检测onoo-的荧光探针及其制备方法和应用 |
CN115029132A (zh) * | 2022-05-27 | 2022-09-09 | 重庆师范大学 | 一种新型的多巴胺功能化荧光碳点的制备方法及其产品和应用 |
Also Published As
Publication number | Publication date |
---|---|
CN107353300B (zh) | 2018-03-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107353300B (zh) | 一种苯硼酸类次氯酸比色荧光探针的制备与应用 | |
CN107266397B (zh) | 一种硫代氨基甲酸酯类次氯酸荧光探针的制备与应用 | |
Chen et al. | A new off–on chemosensor for Al 3+ and Cu 2+ in two different systems based on a rhodamine B derivative | |
CN107033177B (zh) | 一种以硼酸频哪醇酯为识别受体的超灵敏高选择过氧化亚硝酸盐比色比率荧光探针 | |
CN107746406B (zh) | 一种超灵敏高选择性次氯酸荧光探针的制备及应用 | |
CN107033158B (zh) | 一种超灵敏分析汞离子的比色荧光探针及其制备方法 | |
CN110204564A (zh) | 一种检测氰根离子的荧光探针及其制备方法和应用 | |
CN108409697A (zh) | 一种超灵敏高选择性检测次氯酸的探针 | |
CN111205220B (zh) | 一种荧光探针及其制备方法和应用 | |
Shen et al. | A ratiometric and colorimetric fluorescent probe designed based on FRET for detecting SO32−/HSO3− in living cells and mice | |
KR101359508B1 (ko) | 히드라진 선택성을 갖는 화학센서 및 이를 이용한 히드라진 검출방법 | |
CN110204535B (zh) | 一种香豆素类水合肼荧光探针及其制备方法 | |
CN108530459B (zh) | 一种荧光探针的制备方法 | |
CN110452250A (zh) | 一种荧光素母体结构的检测肼用荧光探针 | |
CN108774171A (zh) | 一种实时灵敏检测次氯酸荧光探针的制备与应用 | |
Li et al. | Several fluorescent probes based on hemicyanine for the detection of SO 2 derivatives | |
Chen et al. | A dual functional probe: sensitive fluorescence response to H 2 S and colorimetric detection for SO 3 2− | |
Liu et al. | A simple levulinate-based ratiometric fluorescent probe for sulfite with a large emission shift | |
CN110483542B (zh) | 用于水合肼检测的v型香豆素荧光探针及其制备方法 | |
CN108444962B (zh) | 一种基于苝的甲醛比色探针和甲醛荧光试纸、其制备方法与使用方法 | |
CN109734710A (zh) | 一种检测半胱氨酸的荧光探针及其合成方法与应用 | |
Li et al. | A fluorescent chemosensor for Hg2+ based on a rhodamine derivative in an aqueous solution | |
CN109370573A (zh) | 一种二价汞离子和温度检测的荧光探针、制备方法及其应用 | |
CN107098881A (zh) | 一种超灵敏高选择性次氯酸比色荧光探针 | |
CN113735796A (zh) | 一种基于吩噻嗪可逆荧光探针的设计合成及性质研究 |
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 | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180327 Termination date: 20190626 |