CN111795960A - A molecular platform for spectroscopic and colorimetric detection of different forms of iodine and its preparation method and application - Google Patents
A molecular platform for spectroscopic and colorimetric detection of different forms of iodine and its preparation method and application Download PDFInfo
- Publication number
- CN111795960A CN111795960A CN202010794666.4A CN202010794666A CN111795960A CN 111795960 A CN111795960 A CN 111795960A CN 202010794666 A CN202010794666 A CN 202010794666A CN 111795960 A CN111795960 A CN 111795960A
- Authority
- CN
- China
- Prior art keywords
- platform
- iodine
- solution
- molecular
- different forms
- 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
- 239000011630 iodine Substances 0.000 title claims abstract description 116
- 229910052740 iodine Inorganic materials 0.000 title claims abstract description 116
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000001514 detection method Methods 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000004737 colorimetric analysis Methods 0.000 claims abstract description 57
- 238000004611 spectroscopical analysis Methods 0.000 claims abstract description 53
- -1 iodide ions Chemical class 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 17
- 229940126062 Compound A Drugs 0.000 claims abstract description 16
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 12
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims abstract description 11
- HRJLFSALKDFJBP-UHFFFAOYSA-N 4-amino-2-(1H-naphtho[2,1-e]benzimidazol-2-yl)phenol Chemical compound NC=1C=C(C(=CC=1)O)C=1NC2=C(N=1)C=1C=CC=3C=CC=CC=3C=1C=C2 HRJLFSALKDFJBP-UHFFFAOYSA-N 0.000 claims abstract description 6
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 80
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 38
- 238000012360 testing method Methods 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000003960 organic solvent Substances 0.000 claims description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000012085 test solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000012065 filter cake Substances 0.000 claims description 20
- 239000011550 stock solution Substances 0.000 claims description 20
- 238000002189 fluorescence spectrum Methods 0.000 claims description 18
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 239000007995 HEPES buffer Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 230000005284 excitation Effects 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001506 fluorescence spectroscopy Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000002835 absorbance Methods 0.000 claims description 4
- 239000012491 analyte Substances 0.000 claims description 4
- ORMNPSYMZOGSSV-UHFFFAOYSA-N dinitrooxymercury Chemical compound [Hg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ORMNPSYMZOGSSV-UHFFFAOYSA-N 0.000 claims description 4
- 238000002211 ultraviolet spectrum Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 229910001987 mercury nitrate Inorganic materials 0.000 abstract description 4
- DRXYRSRECMWYAV-UHFFFAOYSA-N nitrooxymercury Chemical compound [Hg+].[O-][N+]([O-])=O DRXYRSRECMWYAV-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007246 mechanism Effects 0.000 abstract description 3
- 230000004044 response Effects 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 17
- 229940006461 iodide ion Drugs 0.000 description 12
- 239000000523 sample Substances 0.000 description 12
- 150000001450 anions Chemical class 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 238000004896 high resolution mass spectrometry Methods 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 206010018498 Goitre Diseases 0.000 description 1
- 206010020850 Hyperthyroidism Diseases 0.000 description 1
- 206010067997 Iodine deficiency Diseases 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- NPOMSUOUAZCMBL-UHFFFAOYSA-N dichloromethane;ethoxyethane Chemical compound ClCCl.CCOCC NPOMSUOUAZCMBL-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 201000003872 goiter Diseases 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 208000003532 hypothyroidism Diseases 0.000 description 1
- 230000002989 hypothyroidism Effects 0.000 description 1
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 description 1
- 238000001566 impedance spectroscopy Methods 0.000 description 1
- 235000006479 iodine deficiency Nutrition 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- 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
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring 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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Optics & Photonics (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
Description
技术领域technical field
本发明涉及碘的检测试剂及其制备方法和应用。The present invention relates to a detection reagent of iodine and a preparation method and application thereof.
背景技术Background technique
碘是地球上的微量元素,因为它分布广泛,并且可以通过碘单质(固态)、碘蒸气(气态)和碘离子(液态)形式存在,所以在环境和生命科学中都发挥着重要作用。碘单质对人体具有毒性和腐蚀性,并且吸入碘蒸气对人体的皮肤、粘膜及呼吸道也有很强的刺激性和腐蚀性。此外,人体中异常的碘离子浓度水平通常会引发一些疾病,碘缺乏或碘过量都会导致诸如甲状腺肿大、甲状腺功能减退和甲状腺机能亢进等疾病,影响人的身体健康,因此碘的监测具有非常重要的意义。Iodine is a trace element on Earth and plays an important role in both the environmental and life sciences because it is widely distributed and can exist in the form of elemental iodine (solid state), iodine vapor (gaseous state) and iodine ion (liquid state). Iodine element is toxic and corrosive to human body, and inhalation of iodine vapor is also highly irritating and corrosive to human skin, mucous membranes and respiratory tract. In addition, abnormal iodine ion concentration levels in the human body usually cause some diseases. Iodine deficiency or iodine excess can lead to diseases such as goiter, hypothyroidism and hyperthyroidism, which affect people's health. Therefore, iodine monitoring is very important. Significance.
2012年,朱颖等人利用富T序列合成了一种DNA荧光探针用于碘离子的检测,并发现该化合物在0.010mmol/LMOPS溶液中对碘离子具有较好的选择识别性,但是其荧光探针检测限较高为30mol/L。2016年,《无机化学通讯》(Inorganic Chemistry Communications)70卷的147-152页的《用于连续识别水性介质中的汞(II)和碘化物比色化学传感器》,报道了一种席夫碱化合物,该探针可通过颜色变化识别Hg2+并对碘离子具有接力识别性能,探针加入Hg2+后溶液颜色由浅黄色变为橙色,当再加入碘离子时溶液颜色又变为浅黄色。此外,碘离子检测限达到2.1×10–7mol/L,具有潜在的应用价值。文献《美国化学学会应用材料与界面》(ACS Applied Materials&Interfaces)在2017年第51卷第9期的44649–44655页发表题目为《对碘蒸气的直接电检测的新型金属有机框架的传感器》的文章,公开了将合成的新型金属有机骨架沸石咪唑酸盐骨架(ZIF-8)暴露于25℃的空气中在720秒内检测到碘单质,并且使用阻抗光谱技术直接检测ZIF-8对于碘离子的实时吸附,但是该仪器价格昂贵、操作复杂,不利于实际应用。近期,《材料化学学报A》第8卷第4期的1966-1974页的《N,N-二乙基丙胺修饰的荧光共轭介孔聚合物对于挥发性碘的实时检测和有效捕获》报道了一种通过碳碳三键连接的三嗪聚合物(CMPN),CMPN通过荧光淬灭现象体现对碘蒸气的检测。当碘蒸气最低浓度为24mg/L时,荧光淬灭率为19.7%。此外,在水蒸气和乙醇蒸气存在的条件下,CMPN仍对碘蒸气显现出较高选择性,但其只能检测碘蒸气一种形式,使这一类材料应用受到限制。In 2012, Zhu Ying et al. synthesized a DNA fluorescent probe for the detection of iodide ions using T-rich sequences, and found that the compound had good selective recognition for iodide ions in 0.010mmol/LMOPS solution, but its The detection limit of the fluorescent probe was as high as 30mol/L. In 2016, Colorimetric Chemical Sensors for Continuous Identification of Mercury(II) and Iodide in Aqueous Media, Inorganic Chemistry Communications, Vol. 70, pp. 147-152, reported a Schiff base Compound, the probe can recognize Hg 2+ through color change and has relay recognition performance for iodide ions. After the probe is added with Hg 2+ , the color of the solution changes from light yellow to orange, and when iodide ions are added, the color of the solution turns light again yellow. In addition, the detection limit of iodide ion reaches 2.1×10 -7 mol/L, which has potential application value. The paper "ACS Applied Materials &Interfaces" (ACS Applied Materials & Interfaces), 2017, Vol. 51, No. 9, pages 44649–44655, published an article titled "A novel metal-organic framework sensor for direct electrical detection of iodine vapor" , disclosed that the synthesized novel metal organic framework zeolite imidazolate framework (ZIF-8) was exposed to the air at 25 °C to detect iodine within 720 seconds, and the impedance spectroscopy technique was used to directly detect the effect of ZIF-8 on iodide ions. Real-time adsorption, but the instrument is expensive and complicated to operate, which is not conducive to practical applications. Recently, "Real-time detection and efficient capture of volatile iodine by N,N-diethylpropylamine-modified fluorescent conjugated mesoporous polymers" reported in "Acta Chemistry A", Vol. 8, No. 4, pages 1966-1974. A triazine polymer (CMPN) linked by carbon-carbon triple bonds has been developed, and CMPN can detect iodine vapor through fluorescence quenching phenomenon. When the lowest concentration of iodine vapor was 24 mg/L, the fluorescence quenching rate was 19.7%. In addition, in the presence of water vapor and ethanol vapor, CMPN still shows high selectivity to iodine vapor, but it can only detect one form of iodine vapor, which limits the application of this type of material.
根据报道文献,目前碘检测主要存在以下缺陷:According to the reported literature, the current iodine detection mainly has the following defects:
1、多数碘检测材料为无机介孔材料,碘检测材料的种类较少;1. Most iodine detection materials are inorganic mesoporous materials, and there are few types of iodine detection materials;
2、多数材料只具备检测一种形式碘的功能;2. Most materials only have the function of detecting one form of iodine;
3、材料对碘的检测机制单一;3. The material has a single detection mechanism for iodine;
4、碘的检出限较高,不适合低浓度碘的检测;4. The detection limit of iodine is high, which is not suitable for the detection of low concentration iodine;
5、多数材料对碘的检测环境要求较高,易受外界环境干扰;5. Most materials have high requirements on the detection environment of iodine and are easily disturbed by the external environment;
发明内容SUMMARY OF THE INVENTION
本发明是要解决现有的碘检测材料种类少、只能检测一种形式碘、检测机制单一、检出限高、易受外界环境干扰等技术问题,而提供一种光谱法和比色法检测不同形式碘的分子平台及制备方法和应用。本发明所提供的光谱法和比色法检测不同形式碘的分子平台,具有制备简单,可检测多种形式碘,检出限底,使用方便、现象直观等优点。The invention provides a spectroscopic method and a colorimetric method to solve technical problems such as few types of existing iodine detection materials, only one form of iodine, single detection mechanism, high detection limit, and easy interference from external environment. Molecular platforms for the detection of different forms of iodine and preparation methods and applications. The molecular platform for detecting different forms of iodine by spectroscopic method and colorimetric method provided by the invention has the advantages of simple preparation, can detect various forms of iodine, detection limit, convenient use, intuitive phenomenon and the like.
本发明的光谱法和比色法检测不同形式碘的分子平台的结构式为:The structural formula of the molecular platform for detecting different forms of iodine by spectrometry and colorimetry of the present invention is:
上述的光谱法和比色法检测不同形式碘的分子平台的制备方法如下:The preparation method of the molecular platform of above-mentioned spectroscopic and colorimetric detection of different forms of iodine is as follows:
一、将2-(3-氨基-6-羟基苯基)菲并咪唑和对苯二甲醛按照物质的量的比为(1~6):1的比例加入到有机溶剂Ⅰ中,在温度为20~80℃的条件下反应1~8h,反应过程中有固体析出;反应结束后,过滤,依次用有机溶剂Ⅱ和蒸馏水洗涤滤饼,滤饼干燥后得到粗产物;将粗产物用有机溶剂Ⅲ重结晶,得到有机化合物A,机化合物A是双[5-(双-1,4-苯亚氨基)-2-(菲并咪唑基-2-)]苯酚;1. 2-(3-amino-6-hydroxyphenyl) phenanthroimidazole and terephthalaldehyde are added to the organic solvent I in a ratio of (1~6):1 according to the amount of the substance, and the temperature is Under the condition of 20~80℃, the reaction is carried out for 1~8h, and there is solid precipitation during the reaction; after the reaction, filter, wash the filter cake with organic solvent II and distilled water in turn, and dry the filter cake to obtain the crude product; use the organic solvent for the crude product III. Recrystallization to obtain organic compound A, which is bis[5-(bis-1,4-phenylimino)-2-(phenanthroimidazolyl-2-)]phenol;
二、有机化合物A和硝酸汞按照物质的量的比为1:(2~10)溶解在有机溶剂IV中,室温搅拌至有固体析出;过滤,滤饼依次采用乙醇和水洗涤,干燥后,得到光谱法和比色法检测不同形式碘的分子平台。Two, the ratio of organic compound A and mercuric nitrate according to the amount of substance is 1: (2~10) be dissolved in organic solvent IV, stir at room temperature until there is solid precipitation; filter, filter cake adopts ethanol and water washing successively, after drying, Molecular platforms for spectroscopic and colorimetric detection of different forms of iodine were obtained.
更进一步地,所述的有机溶剂Ⅰ为冰醋酸、甲醇、乙醇、N,N-二甲基甲酰胺、苯或甲苯。Further, the organic solvent I is glacial acetic acid, methanol, ethanol, N,N-dimethylformamide, benzene or toluene.
更进一步地,所述的洗涤滤饼的有机溶剂Ⅱ为乙酸乙酯、丙酮、乙腈、乙醚、二氯甲烷或氯仿。Further, the organic solvent II for washing the filter cake is ethyl acetate, acetone, acetonitrile, diethyl ether, dichloromethane or chloroform.
更进一步地,所述的粗产物重结晶的有机溶剂Ⅲ为乙酸乙酯,或者是乙酸乙酯和石油醚按体积比为1:(1~2)的混合物,或者是乙酸乙酯和乙醚按体积比为1:(1~3)的混合物,或乙酸乙酯与二氯甲烷按体积比为1:(1~5)的混合物。Further, the organic solvent III of the recrystallization of the crude product is ethyl acetate, or the mixture of ethyl acetate and petroleum ether by volume is 1: (1~2), or the mixture of ethyl acetate and ether by volume. The volume ratio of the mixture is 1: (1-3), or the volume ratio of ethyl acetate and dichloromethane is 1: (1-5).
更进一步地,所述的有机溶剂IV为甲醇、乙醇、N,N-二甲基甲酰胺、苯、甲苯或二甲基亚砜。Further, the organic solvent IV is methanol, ethanol, N,N-dimethylformamide, benzene, toluene or dimethyl sulfoxide.
本发明的光谱法和比色法检测不同形式碘的分子平台的制备过程用下式表示:The preparation process of the molecular platform for detecting different forms of iodine by spectrometry and colorimetry of the present invention is represented by the following formula:
上述的光谱法和比色法检测不同形式碘的分子平台的应用,是将它用于不同介质中碘离子、碘单质或/和碘蒸气的定性或定量检测。The application of the above-mentioned molecular platform for detecting different forms of iodine by spectrometry and colorimetry is to use it for qualitative or quantitative detection of iodide ions, elemental iodine or/and iodine vapor in different media.
利用光谱法和比色法检测不同形式碘的分子平台通过比色法检测碘离子的方法,按照如下步骤进行:A molecular platform for detecting different forms of iodine by spectrometry and colorimetry The method for detecting iodine ions by colorimetry is carried out according to the following steps:
一、将光谱法和比色法检测不同形式碘的分子平台溶解于可与水互溶的有机溶剂中,配置成平台储备液A,浓度为0.50~1.00×10–3mol/L;1. Dissolve the molecular platform for the detection of different forms of iodine by spectrometry and colorimetry in an organic solvent that is miscible with water, and configure the platform stock solution A with a concentration of 0.50-1.00×10 -3 mol/L;
二、将步骤一得到的平台储备液A利用浓度为0.010mol/L、pH=7.40的HEPES溶液稀释成浓度为0.10~0.50×10–4mol/L的平台溶液B;2. Dilute the platform stock solution A obtained in
三、将步骤二得到平台溶液B与待测溶液充分混合,得到测试溶液C;3. Fully mixing the platform solution B obtained in
四、手持紫外灯下照射下,平台溶液B为亮蓝色澄清溶液,若测试溶液C的蓝色变暗,且伴有黑色沉淀生成,说明待测溶液中含有碘离子。4. Under the irradiation of a handheld UV lamp, the platform solution B is a bright blue clear solution. If the blue color of the test solution C becomes dark and accompanied by the formation of black precipitates, it means that the solution to be tested contains iodine ions.
更进一步地,所述的可与水互溶的有机溶剂为冰醋酸、甲醇、乙醇、N,N-二甲基甲酰胺或二甲基亚砜。Further, the water-miscible organic solvent is glacial acetic acid, methanol, ethanol, N,N-dimethylformamide or dimethyl sulfoxide.
利用光谱法和比色法检测不同形式碘的分子平台通过荧光光谱法检测碘离子的方法,按照如下步骤进行:The molecular platform for detecting different forms of iodine by spectrometry and colorimetry The method for detecting iodide ions by fluorescence spectrometry is carried out according to the following steps:
一、将光谱法和比色法检测不同形式碘的分子平台溶解于可与水互溶的有机溶剂中,配置成平台储备液A,浓度为0.50~1.00×10–3mol/L;1. Dissolve the molecular platform for the detection of different forms of iodine by spectrometry and colorimetry in an organic solvent that is miscible with water, and configure the platform stock solution A with a concentration of 0.50-1.00×10 -3 mol/L;
二、将步骤一得到的平台储备液A利用浓度为0.010mol/L、pH=7.40的HEPES溶液稀释成浓度为0.10~0.50×10–4mol/L的平台溶液B;2. Dilute the platform stock solution A obtained in
三、将步骤二得到平台溶液B与待测溶液充分混合,得到测试溶液C;3. Fully mixing the platform solution B obtained in
四、以315nm为激发波长,测定平台溶液B的荧光发射光谱在发射波长为495nm时的发射强度,记为TB;4. Taking 315nm as the excitation wavelength, measure the emission intensity of the fluorescence emission spectrum of the platform solution B when the emission wavelength is 495nm, denoted as T B ;
五、以315nm为激发波长,测定测试溶液C的荧光发射光谱在发射波长为495nm时的发射强度,记为TC;5. Take 315nm as the excitation wavelength, measure the emission intensity of the fluorescence emission spectrum of the test solution C when the emission wavelength is 495nm, and denote it as T C ;
六、比较TB和TC,TB>73TC,则判断待测溶液中含有碘离子。6. Comparing T B and T C , if T B >73 T C , it is judged that the solution to be tested contains iodide ions.
更进一步地,所述的可与水互溶的有机溶剂为冰醋酸、甲醇、乙醇、N,N-二甲基甲酰胺或二甲基亚砜。Further, the water-miscible organic solvent is glacial acetic acid, methanol, ethanol, N,N-dimethylformamide or dimethyl sulfoxide.
利用光谱法和比色法检测不同形式碘的分子平台通过紫外光谱法检测碘单质的方法,按照以下步骤进行:Utilize the molecular platform to detect different forms of iodine by spectrometry and colorimetry. The method of detecting elemental iodine by ultraviolet spectrometry is carried out according to the following steps:
一、将光谱法和比色法检测不同形式碘的分子平台溶解于可与水互溶的有机溶剂中,配置成浓度为0.10~0.50×10–4mmol/L平台溶液A;1. Dissolve the molecular platform for detecting different forms of iodine by spectrometry and colorimetry in an organic solvent that is miscible with water, and configure platform solution A with a concentration of 0.10-0.50×10 -4 mmol/L;
二、将待测物加入到平台溶液A中,静置0.5~10小时,得到测试样品B;2. Add the analyte to the platform solution A, and let it stand for 0.5 to 10 hours to obtain the test sample B;
三、测定平台溶液A的紫外光谱,将吸收波长为530nm处的吸光度记为AA;Three, measure the ultraviolet spectrum of platform solution A, be the absorbance at 530nm place that absorbs wavelength is recorded as A A ;
四、取测试样品B的上清液,测定上清液的紫外光谱,将吸收波长为530nm处的吸光度记为AB;Four, get the supernatant liquid of test sample B, measure the ultraviolet spectrum of supernatant liquid, be the absorbance at 530nm place with absorption wavelength and be recorded as A B ;
五、比较AA和AB,若AA>6AB,则判断待测物中含有碘单质。5. Compare A A and A B , if A A > 6 A B , it is judged that the substance to be tested contains iodine.
更进一步地,所述的可与水互溶的有机溶剂为冰醋酸、甲醇、乙醇、N,N-二甲基甲酰胺或二甲基亚砜。Further, the water-miscible organic solvent is glacial acetic acid, methanol, ethanol, N,N-dimethylformamide or dimethyl sulfoxide.
利用光谱法和比色法检测不同形式碘的分子平台通过荧光光谱法检测碘单质的方法,按照以下步骤进行:A molecular platform for detecting different forms of iodine by spectrometry and colorimetry The method for detecting elemental iodine by fluorescence spectrometry is carried out according to the following steps:
一、将光谱法和比色法检测不同形式碘的分子平台溶解于可与水互溶的有机溶剂中,配置成浓度为0.10~0.50×10–4mmol/L平台溶液A;1. Dissolve the molecular platform for detecting different forms of iodine by spectrometry and colorimetry in an organic solvent that is miscible with water, and configure platform solution A with a concentration of 0.10-0.50×10 -4 mmol/L;
二、将待测物加入到平台溶液A中,静置0.5~10小时,得到测试样品B;2. Add the analyte to the platform solution A, and let it stand for 0.5 to 10 hours to obtain the test sample B;
三、测定平台溶液A的荧光光谱,将发射波长为500nm处的荧光强度分别记为IA;3. Measure the fluorescence spectrum of the platform solution A, and the fluorescence intensity at the emission wavelength at 500 nm is respectively denoted as IA ;
四、取测试样品B的上清液,测定上清液的荧光光谱,将发射波长为500nm处的荧光强度IB;Four, get the supernatant liquid of test sample B, measure the fluorescence spectrum of supernatant liquid, will emission wavelength be the fluorescence intensity I B at 500nm place;
五、比较IA和IB,若IA>18IB,则判断待测物中含有碘单质。5. Compare IA and IB , if IA > 18IB , it is judged that the substance to be tested contains iodine.
更进一步地,所述的可与水互溶的有机溶剂为冰醋酸、甲醇、乙醇、N,N-二甲基甲酰胺或二甲基亚砜。Further, the water-miscible organic solvent is glacial acetic acid, methanol, ethanol, N,N-dimethylformamide or dimethyl sulfoxide.
利用光谱法和比色法检测不同形式碘的分子平台通过比色法检测碘蒸气的方法,按照如下步骤进行:A molecular platform for detecting different forms of iodine by spectrometry and colorimetry The method for detecting iodine vapor by colorimetry is carried out according to the following steps:
一、将光谱法和比色法检测不同形式碘的分子平台溶解于可与水互溶的有机溶剂中,配置成平台储备液A,浓度为0.50~1.00×10–3mol/L;1. Dissolve the molecular platform for the detection of different forms of iodine by spectrometry and colorimetry in an organic solvent that is miscible with water, and configure the platform stock solution A with a concentration of 0.50-1.00×10 -3 mol/L;
二、将步骤一得到的平台储备液A利用浓度为0.010mol/L、pH=7.40的HEPES溶液稀释成浓度为0.10~0.50×10–4mol/L的平台溶液B;2. Dilute the platform stock solution A obtained in
三、将定性滤纸剪成条状,放入平台溶液B中浸泡1~2小时,干燥后,得到利用光谱法和比色法检测不同形式碘的分子平台试纸条;3. Cut the qualitative filter paper into strips, soak them in the platform solution B for 1 to 2 hours, and after drying, obtain molecular platform test strips for detecting different forms of iodine by spectrometry and colorimetry;
四、自然光照射下,平台试纸条为无色;手持紫外灯照射下,平台试纸条为绿色;4. Under natural light irradiation, the platform test strip is colorless; under the irradiation of hand-held UV lamp, the platform test strip is green;
五、将步骤三得到的平台试纸条在测试样品环境中放置30~150分钟后,在自然光下观察,若平台试纸条由无色变为黄色,则说明测试样品中含碘蒸气;在手持紫外灯下观察,若平台试纸条由亮绿色变为暗黄色,则说明测试样品中含碘蒸气。5. After placing the platform test strip obtained in step 3 in the test sample environment for 30 to 150 minutes, observe under natural light. If the platform test strip changes from colorless to yellow, it means that the test sample contains iodine vapor; Observe under the hand-held UV lamp, if the platform test strip changes from bright green to dark yellow, it means that the test sample contains iodine vapor.
更进一步地,所述的可与水互溶的有机溶剂为冰醋酸、甲醇、乙醇、N,N-二甲基甲酰胺或二甲基亚砜。Further, the water-miscible organic solvent is glacial acetic acid, methanol, ethanol, N,N-dimethylformamide or dimethyl sulfoxide.
利用一种光谱法和比色法检测不同形式碘的分子平台荧光法定量检测碘离子的方法为标准曲线法。The method of quantitative detection of iodide ions by a molecular platform fluorescence method that uses a spectroscopic method and a colorimetric method to detect different forms of iodine is the standard curve method.
本发明的提供的一种光谱法和比色法检测不同形式碘的分子平台,制备简单,结构稳定,成本低,已于保存。对碘离子、碘单质和碘蒸气的检测不受其他类似物的干扰,检测效果明显,使用方便,响应迅速、灵敏度高,检测限达到43.1nM,可实现定性和定量检测。可用于碘离子、碘单质和碘蒸气的检测领域。The present invention provides a molecular platform for detecting different forms of iodine by spectroscopic method and colorimetric method, which is simple in preparation, stable in structure, low in cost, and ready for storage. The detection of iodide ion, iodine elemental substance and iodine vapor is not interfered by other analogs, the detection effect is obvious, the use is convenient, the response is rapid, the sensitivity is high, and the detection limit reaches 43.1nM, which can realize qualitative and quantitative detection. It can be used in the field of detection of iodide ion, elemental iodine and iodine vapor.
附图说明Description of drawings
图1是实施例1中平台溶液B(0.10×10–4mol/L,VDMF:VHEPES=1:1,pH=7.40)和测试溶液C的荧光发射光谱图,横坐标为发射波长,纵坐标为荧光强度;图中有机化合物A·2Hg2+为平台溶液B,有机化合物A·2Hg2++碘离子为待测溶液C;Fig. 1 is the fluorescence emission spectrogram of platform solution B (0.10×10 −4 mol/L, V DMF : V HEPES =1:1, pH=7.40) and test solution C in Example 1, the abscissa is the emission wavelength, The ordinate is the fluorescence intensity; the organic compound A 2Hg 2+ in the figure is the platform solution B, and the organic compound A 2Hg 2+ + iodide ion is the solution C to be tested;
图2是实施例1中平台溶液B(0.10×10–4mol/L,VDMF:VHEPES=1:1,pH=7.40)中分别加入不同种阴离子(0.1mol/L)的荧光发射光谱图;横坐标为发射波长,纵坐标为荧光强度;Fig. 2 is the fluorescence emission spectrum of the platform solution B (0.10×10 −4 mol/L, V DMF : V HEPES =1:1, pH=7.40) in Example 1 with different anions (0.1 mol/L) respectively added Figure; the abscissa is the emission wavelength, and the ordinate is the fluorescence intensity;
图3是实施例1中测试溶液C在不同碘离子浓度(0~1.0×10–5mol/L)条件下的荧光发射光谱图,横坐标为发射波长,纵坐标为荧光强度;Fig. 3 is the fluorescence emission spectrum of test solution C under different iodide ion concentrations (0~1.0×10 −5 mol/L) in Example 1, the abscissa is the emission wavelength, and the ordinate is the fluorescence intensity;
图4是实施例1制备的光谱法和比色法检测不同形式碘的分子平台荧光检测碘离子的标准曲线。Figure 4 is the standard curve of fluorescence detection of iodide ions prepared in Example 1 using a molecular platform for spectroscopic and colorimetric detection of different forms of iodine.
图5是实施例1中紫外灯下照射下平台溶液B和测试溶液C的照片;Fig. 5 is the photo of platform solution B and test solution C under irradiation under ultraviolet lamp among the
图6是实施例1中平台试纸条检测碘蒸气时在自然光下和紫外灯下的颜色变化照片。6 is a photo of the color change under natural light and ultraviolet light when the platform test strip detects iodine vapor in Example 1.
具体实施方式Detailed ways
用下面的实施例验证本发明的有益效果:Verify the beneficial effects of the present invention with the following examples:
实施例1:本实施例的光谱法和比色法检测不同形式碘的分子平台的制备方法,按以下方法进行:Embodiment 1: The preparation method of the molecular platform of different forms of iodine detected by spectrometry and colorimetric method of the present embodiment is carried out according to the following method:
一、将0.81克2-(3-氨基-6-羟基苯基)菲并咪唑和0.13克对苯二甲醛加入到15.0mL乙醇中,在温度为60℃的条件下反应5小时,反应过程中有固体析出;反应结束后,过滤,依次用甲醇和蒸馏水各洗涤滤饼3次,滤饼在温度为80℃的条件下干燥8小时,得到粗产物;将粗产物用乙酸乙酯和石油醚按体积比为1:2的混合溶剂重结晶,得到有机化合物A,即双[5-(双-1,4-苯亚氨基)-2-(菲并咪唑基-2-)]苯酚,产率92%,熔点为320℃。1. Add 0.81 g of 2-(3-amino-6-hydroxyphenyl) phenanthroimidazole and 0.13 g of terephthalaldehyde to 15.0 mL of ethanol, and react for 5 hours at a temperature of 60°C. During the reaction There is solid precipitation; after the reaction is completed, filter, wash the filter cake 3 times with methanol and distilled water successively, and dry the filter cake at a temperature of 80 ° C for 8 hours to obtain a crude product; use ethyl acetate and petroleum ether for the crude product. Recrystallization in a mixed solvent with a volume ratio of 1:2 to obtain an organic compound A, namely bis[5-(bis-1,4-phenylimino)-2-(phenanthroimidazolyl-2-)]phenol, yielding The rate is 92%, and the melting point is 320 °C.
二、将0.75克有机化合物A和1.63克硝酸汞溶解在15mL的N,N-二甲基甲酰胺中,室温搅拌至有大量固体析出。过滤,滤饼依次采用乙醇洗涤3次,再用水洗涤3次,滤饼在温度为80℃的条件下干燥8小时,得到光谱法和比色法检测不同形式碘的分子平台,产率65%,熔点>320℃。2. Dissolve 0.75 g of organic compound A and 1.63 g of mercury nitrate in 15 mL of N,N-dimethylformamide, and stir at room temperature until a large amount of solid is precipitated. Filtration, the filter cake was washed 3 times with ethanol and then with water for 3 times, and the filter cake was dried for 8 hours at a temperature of 80 °C to obtain a molecular platform for the detection of different forms of iodine by spectrometry and colorimetry, and the yield was 65%. , melting point> 320 ℃.
本实施例制备有机化合物A的结构表征数据如下:1HNMR(600MHz,DMSO-d6):δ(ppm):13.84(s,2H),13.24(s,2H),8.93~8.97(m,6H),8.64(d,J=8.0Hz,2H),8.54(d,J=7.5Hz,2H),8.38(d,J=8.4Hz,2H),8.20(s,4H),7.81~7.84(m,4H),7.72~7.75(m,4H)7.55(d,J=6.0Hz,2H),7.19(d,J=8.5Hz,2H);13C NMR(600MHz,DMSO):δ(ppm):193.4,158.4,158.0,156.9,149.5,149.4,143.2,141.7,138.9,134.7,130.5,129.6,128.5,128.2,128.1,127.8,126.9,126.5,125.9,124.7,124.4,123.6,122.7,122.4,122.5,120.9,118.5,113.6;IR(KBr,cm–1):3306,3055,1689,1622,1589,1543,1493,1428,1388,1362,1262,1208,1063,967,892,826,794,755,722,673,631,595,565。The structural characterization data of the organic compound A prepared in this example are as follows: 1 HNMR (600MHz, DMSO-d 6 ): δ(ppm): 13.84(s, 2H), 13.24(s, 2H), 8.93~8.97(m, 6H) ),8.64(d,J=8.0Hz,2H),8.54(d,J=7.5Hz,2H),8.38(d,J=8.4Hz,2H),8.20(s,4H),7.81~7.84(m , 4H), 7.72~7.75 (m, 4H) 7.55 (d, J=6.0Hz, 2H), 7.19 (d, J=8.5Hz, 2H); 13 C NMR (600MHz, DMSO): δ (ppm): 193.4,158.4,158.0,156.9,149.5,149.4,143.2,141.7,138.9,134.7,130.5,129.6,128.5,128.2,128.1,127.8,126.9,126.5,125.9,124.7,124.4,123.6,122.7,122.4,122.5, 120.9, 118.5, 113.6; IR(KBr,cm –1 ): 3306, 3055, 1689, 1622, 1589, 1543, 1493, 1428, 1388, 1362, 1262, 1208, 1063, 967, 892, 826, 794, 755, 722, 56, 631, 559
本实施例制备光谱法和比色法检测不同形式碘的分子平台的结构表征数据如下:1HNMR(600MHz,DMSO-d6):δ(ppm):8.90~8.99(m,6H),8.67(d,J=8.01Hz,2H),8.58(d,J=7.5Hz,2H),8.39(d,J=7.4Hz,2H),8.21(d,J=7.4Hz,1H),8.20(s,4H),8.11(d,J=7.4Hz,1H),7.81~7.89(m,4H),7.72~7.75(m,4H),7.55(d,J=6.0Hz,2H),7.19(d,J=8.4Hz,2H);IR(KBr,cm–1):1685,1617,1585,1546,1497,1431,1392,1360,1278,1220,1039,960,887,830,789,746,721,686,621,596。高分辨质谱HR–MS(ESI)得到质合比为1257.4474的峰值,其分子量为[有机化合物A–2H++2Hg2++2Cl–+K+]+再次确定有机化合物A以物质的量为1:2的络合比形成金属络合物A–2Hg。The structural characterization data of the molecular platform for the detection of different forms of iodine by spectrometry and colorimetry in this example are as follows: 1 HNMR (600MHz, DMSO-d 6 ): δ (ppm): 8.90~8.99 (m, 6H), 8.67 ( d, J=8.01Hz, 2H), 8.58(d, J=7.5Hz, 2H), 8.39(d, J=7.4Hz, 2H), 8.21(d, J=7.4Hz, 1H), 8.20(s, 4H), 8.11(d, J=7.4Hz, 1H), 7.81~7.89(m, 4H), 7.72~7.75(m, 4H), 7.55(d, J=6.0Hz, 2H), 7.19(d, J = 8.4 Hz, 2H); IR (KBr, cm −1 ): 1685, 1617, 1585, 1546, 1497, 1431, 1392, 1360, 1278, 1220, 1039, 960, 887, 830, 789, 746, 721, 686, 621, 596. High-resolution mass spectrometry HR-MS (ESI) obtained a peak with a mass-to-mix ratio of 1257.4474, and its molecular weight was [organic compound A–2H + +2Hg 2+ +2Cl – +K + ] + The amount of the organic compound A was determined again to be A complexation ratio of 1:2 forms the metal complex A–2Hg.
从以上的表征结果可知本实施例制备的光谱法和比色法检测不同形式碘的分子平台的结构式为:From the above characterization results, it can be known that the structural formula of the molecular platform for the detection of different forms of iodine by spectrometry and colorimetry prepared in this example is:
对实施例1制备的一种光谱法和比色法检测不同形式碘的分子平台荧光光谱法检测碘离子进行如下的试验:A kind of spectroscopic method prepared in Example 1 and the colorimetric method to detect the molecular platform fluorescence spectrometry of different forms of iodine to detect iodine ions are carried out as follows:
一、将一种光谱法和比色法检测不同形式碘的分子平台溶解于N,N-二甲基甲酰胺中,配置成平台储备液A,浓度为0.50×10–3mol/L;1. Dissolve a molecular platform for the detection of different forms of iodine by spectrometry and colorimetry in N,N-dimethylformamide, and configure the platform stock solution A with a concentration of 0.50×10 -3 mol/L;
二、将步骤一得到的平台储备液A利用浓度为0.01mol/L、pH=7.40的HEPES溶液稀释成浓度为0.10×10–4mol/L的平台溶液B;2. Dilute the platform stock solution A obtained in
三、将步骤二得到平台溶液B与待测溶液充分混合,得到测试溶液C;3. Fully mixing the platform solution B obtained in
四、以315nm为激发波长,测定平台溶液B的荧光发射光谱在发射波长为495nm时的发射强度,记为TB,TB=110a.u.;平台溶液B的荧光发射光谱如图1所示;横坐标为发射波长,纵坐标为荧光强度;4. Taking 315nm as the excitation wavelength, measure the emission intensity of the fluorescence emission spectrum of the platform solution B when the emission wavelength is 495nm, denoted as T B , T B =110a.u.; the fluorescence emission spectrum of the platform solution B is shown in Figure 1 The abscissa is the emission wavelength, and the ordinate is the fluorescence intensity;
五、以315nm为激发波长,测定测试溶液C的荧光发射光谱在发射波长为495nm时的发射强度,记为TC=1.5a.u.;测试溶液C的的荧光发射光谱也绘入图1中;5. Take 315nm as the excitation wavelength, measure the emission intensity of the fluorescence emission spectrum of the test solution C when the emission wavelength is 495nm, denoted as T C =1.5au; the fluorescence emission spectrum of the test solution C is also drawn in Figure 1;
六、比较TB和TC,TB>73TC,则判断待测溶液中含有碘离子。6. Comparing T B and T C , if T B >73 T C , it is judged that the solution to be tested contains iodide ions.
测试实施例1制备的光谱法和比色法检测不同形式碘的分子平台与不同阴离子作用后的荧光发射光谱,具体方法如下:The spectroscopic and colorimetric methods prepared in Test Example 1 were used to detect the fluorescence emission spectra of molecular platforms of different forms of iodine and different anions, and the specific methods were as follows:
将实施例1制备的光谱法和比色法检测不同形式碘的分子平台溶液(浓度为0.10×10–4mol/L)中分别加入不同的阴离子溶液(浓度为0.10mol/L),其中阴离子为F–,Cl–,Br–,I–,S2–,HS–,SO3 2–,HSO3 –,SO4 2–,HPO4 3–,H2PO3 –,NO2 –,NO3 –,AcO–,CO3 2–和SCN–,分别测定加入阴离子前后平台溶液的荧光发射光谱,如图2所示。平台溶液A在激发波长为315nm时,发射波长为495nm处的荧光强度为IA,加入阴离子后的荧光强度为IB,从图2可以看出,除碘离子外,加入其他阴离子的溶液的荧光强度均在80a.u.以上,只有加入碘离子后的样品溶液B在495nm处的荧光强度为IB=1.5a.u.,此时IA>73IB,说明,该分子平台检测碘离子时,不受F–,Cl–,Br–,S2–,HS–,SO3 2–,HSO3 –,SO4 2–,HPO4 3–,H2PO3 –,NO2 –,NO3 –,AcO–,CO3 2–和SCN–离子的影响。The molecular platform solutions (concentration of 0.10×10 -4 mol/L) prepared in Example 1 to detect different forms of iodine by spectrometry and colorimetry were added with different anion solutions (concentration of 0.10mol/L), in which anion For F - , Cl - , Br - , I - , S 2 - , HS - , SO 3 2 - , HSO 3 - , SO 4 2 - , HPO 4 3 - , H 2 PO 3 - , NO 2 - , NO 3 - , AcO - , CO 3 2- and SCN - , the fluorescence emission spectra of the platform solution before and after the addition of anions were measured, respectively, as shown in Figure 2. When the excitation wavelength of the platform solution A is 315nm, the fluorescence intensity at the emission wavelength of 495nm is IA, and the fluorescence intensity after adding anions is IB . It can be seen from Figure 2 that in addition to iodide ions, the solution with other anions is added. The fluorescence intensity is all above 80a.u., only the fluorescence intensity of the sample solution B at 495nm after adding iodide ions is IB = 1.5au, at this time IA> 73IB , indicating that when the molecular platform detects iodide ions, Not affected by F – , Cl – , Br – , S 2 – , HS – , SO 3 2 – , HSO 3 – , SO 4 2 – , HPO 4 3 – , H 2 PO 3 – , NO 2 – , NO 3 – , AcO - , CO 3 2 - and SCN - ions.
利用实施例1制备的光谱法和比色法检测不同形式碘的分子平台检测时碘离子浓度与荧光强度的关系按如下方式测定:The relationship between iodide ion concentration and fluorescence intensity is determined as follows when the molecular platform detection of different forms of iodine is detected by the spectrometry and colorimetric method prepared in Example 1:
一、将光谱法和比色法检测不同形式碘的分子平台溶解于N,N-二甲基甲酰胺中,配置成平台储备液A,浓度为0.50×10–3mol/L;1. Dissolve the molecular platform for the detection of different forms of iodine by spectrometry and colorimetry in N,N-dimethylformamide, and configure the platform stock solution A with a concentration of 0.50×10 -3 mol/L;
二、将步骤一得到的平台储备液A利用浓度为0.01mol/L、pH=7.40的HEPES溶液稀释成浓度为0.10×10–4mol/L的平台溶液B;2. Dilute the platform stock solution A obtained in
三、将步骤二得到平台溶液B与浓度不同的碘离子溶液充分混合,碘离子溶液的浓度从0~2.0×10–6mol/L,得到测试溶液C;3. Fully mix the platform solution B obtained in
四、以315nm为激发波长,测定测试溶液C的荧光发射光谱在发射波长为495nm时的发射强度;测试溶液C的荧光发射光谱如图3所示;横坐标为发射波长,纵坐标为荧光强度;4. Taking 315nm as the excitation wavelength, measure the emission intensity of the fluorescence emission spectrum of the test solution C when the emission wavelength is 495nm; the fluorescence emission spectrum of the test solution C is shown in Figure 3; the abscissa is the emission wavelength, and the ordinate is the fluorescence intensity ;
从图3可以看出,随着碘离子浓度的增加,测试溶液C在495nm处荧光强度逐渐增强,碘离子浓度增加到2.0×10–6mol/L时,荧光强度达到最大值。在碘离子浓度0~0.9×10–6mol/L范围内,测试溶液C在495nm处的荧光强度与碘离子浓度变化的线性关系结果见图4所示。根据检测限的计算公式(CDL=3Sb/m),由空白平行实验,经过拟合得到线性回归方程y=–0.6912x+1.0492,标准偏差R2=0.9940,光谱法和比色法检测不同形式碘的分子平台的检测限达到43.1nM。说明光谱法和比色法检测不同形式碘的分子平台荧光光谱法检测碘离子具有良好的线性关系。It can be seen from Figure 3 that with the increase of iodide ion concentration, the fluorescence intensity of the test solution C at 495 nm gradually increased, and when the iodide ion concentration increased to 2.0×10 -6 mol/L, the fluorescence intensity reached the maximum value. In the range of iodide ion concentration from 0 to 0.9×10 -6 mol/L, the results of the linear relationship between the fluorescence intensity of the test solution C at 495 nm and the change of iodide ion concentration are shown in Figure 4. According to the calculation formula of the detection limit (C DL = 3S b /m), the linear regression equation y=–0.6912x+1.0492 was obtained by the blank parallel experiment, and the standard deviation R 2 = 0.9940. Spectroscopic and colorimetric detection The detection limit of the molecular platform of different forms of iodine reached 43.1 nM. The results indicated that the molecular platform fluorescence spectrometry for the detection of different forms of iodine by spectrometry and colorimetry had a good linear relationship for the detection of iodine ions.
利用实施例1制备的光谱法和比色法检测不同形式碘的分子平台通过比色法检测碘离子的方法,按照如下步骤进行:The molecular platform that utilizes the spectroscopic method and colorimetric method prepared in Example 1 to detect different forms of iodine by colorimetric method detects the method for iodine ion, and is carried out according to the following steps:
一、将光谱法和比色法检测不同形式碘的分子平台溶解于N,N-二甲基甲酰胺中,配置成平台储备液A,浓度为1.00×10–3mol/L;1. Dissolve the molecular platform for the detection of different forms of iodine by spectrometry and colorimetry in N,N-dimethylformamide, and configure the platform stock solution A with a concentration of 1.00×10 –3 mol/L;
二、将步骤一得到的平台储备液A利用浓度为0.010mol/L、pH=7.40的HEPES溶液稀释成浓度为0.10×10–4mol/L的平台溶液B;2. Dilute the platform stock solution A obtained in
三、将步骤二得到平台溶液B与待测溶液充分混合,得到测试溶液C;3. Fully mixing the platform solution B obtained in
四、手持紫外灯下照射下,紫外灯下照射下平台溶液B和测试溶液C的颜色变化如图5所示;平台溶液B为亮蓝色澄清溶液,而测试溶液C的蓝色变暗,且伴有黑色沉淀生成,从而说明待测溶液中含有碘离子。4. The color changes of the platform solution B and the test solution C under the irradiation of the UV lamp are shown in Figure 5; the platform solution B is a bright blue clear solution, while the blue of the test solution C darkens, And accompanied by the formation of black precipitates, indicating that the solution to be tested contains iodine ions.
利用实施例1制备的光谱法和比色法检测不同形式碘的分子平台通过比色法检测碘蒸气的方法,按照如下步骤进行:The molecular platform that utilizes the spectrometry and colorimetric method prepared in Example 1 to detect different forms of iodine by colorimetric method detects the method for iodine vapor, and is carried out according to the following steps:
一、将光谱法和比色法检测不同形式碘的分子平台溶解于可与水互溶的有机溶剂中,配置成平台储备液A,浓度为1.00×10–3mol/L;1. Dissolve the molecular platform for the detection of different forms of iodine by spectrometry and colorimetry in an organic solvent that is miscible with water, and configure the platform stock solution A with a concentration of 1.00×10 -3 mol/L;
二、将步骤一得到的平台储备液A利用浓度为0.010mol/L、pH=7.40的HEPES溶液稀释成浓度为0.10×10–4mol/L的平台溶液B;2. Dilute the platform stock solution A obtained in
三、将定性滤纸剪成条状,放入平台溶液B中浸泡2小时,在温度为25℃的条件下干燥8小时,得到利用光谱法和比色法检测不同形式碘的分子平台试纸条;3. Cut the qualitative filter paper into strips, soak them in platform solution B for 2 hours, and dry them for 8 hours at a temperature of 25 °C to obtain molecular platform test strips for detecting different forms of iodine by spectrometry and colorimetry ;
四、自然光照射下,平台试纸条为无色;手持紫外灯照射下,平台试纸条为绿色;4. Under natural light irradiation, the platform test strip is colorless; under the irradiation of hand-held UV lamp, the platform test strip is green;
五、将步骤三得到的平台试纸条在测试样品环境中放置60分钟后,在自然光下观察,若平台试纸条已经由无色变为黄色,则说明测试样品中含碘蒸气;在手持紫外灯下观察,若平台试纸条也已经由亮绿色变为暗黄色,同样也说明测试样品中含碘蒸气。平台试纸条在自然光下和紫外灯下的颜色变化如图6所示。5. After placing the platform test strip obtained in step 3 in the test sample environment for 60 minutes, observe under natural light. If the platform test strip has changed from colorless to yellow, it means that the test sample contains iodine vapor; Observed under the UV lamp, if the platform test strip has also changed from bright green to dark yellow, it also means that the test sample contains iodine vapor. The color changes of the platform test strips under natural light and UV light are shown in Figure 6.
实施例2:本实施例的光谱法和比色法检测不同形式碘的分子平台的合成方法如下:Embodiment 2: the synthetic method of the molecular platform of different forms of iodine detected by spectrometry and colorimetric method of the present embodiment is as follows:
一、将1.62克2-(3-氨基-6-羟基苯基)菲并咪唑和0.13克对苯二甲醛加入到甲醇中,在温度为40℃的条件下反应8小时,反应过程中有固体析出;反应结束后,过滤,依次用甲醇和蒸馏水洗涤滤饼,滤饼在温度为80℃的条件下干燥8小时后,得到粗产物;将粗产物用乙酸乙酯和二氯甲烷醚按体积比为1:5的混合溶剂重结晶,得到有机化合物A,产率75%,熔点为320℃。1. Add 1.62 grams of 2-(3-amino-6-hydroxyphenyl) phenanthroimidazole and 0.13 grams of terephthalaldehyde to methanol, and react for 8 hours at a temperature of 40°C. There are solids in the reaction process. Precipitation; after the reaction is completed, filter, wash the filter cake with methanol and distilled water in turn, and dry the filter cake at a temperature of 80 ° C for 8 hours to obtain a crude product; use ethyl acetate and dichloromethane ether for the crude product by volume Recrystallization from a mixed solvent with a ratio of 1:5 to obtain organic compound A with a yield of 75% and a melting point of 320°C.
二、将0.75克有机化合物A和0.65克硝酸汞溶解在乙醇中,室温搅拌至有大量固体析出。过滤,滤饼依次采用乙醇洗涤3次,再用水洗涤3次,滤饼在温度为80℃的条件下干燥8小时后,得到光谱法和比色法检测不同形式碘的分子平台,产率57%,熔点>320℃。2. Dissolve 0.75 g of organic compound A and 0.65 g of mercury nitrate in ethanol, and stir at room temperature until a large amount of solid is precipitated. After filtering, the filter cake was washed with ethanol for 3 times, and then with water for 3 times. After drying the filter cake for 8 hours at a temperature of 80 °C, a molecular platform for spectroscopic and colorimetric detection of different forms of iodine was obtained, and the yield was 57 %, melting point>320℃.
实施例3:本实施例的一种光谱法和比色法检测不同形式碘的分子平台的合成方法如下:Embodiment 3: a kind of spectroscopic method and colorimetric method of the present embodiment detect the synthetic method of the molecular platform of different forms of iodine as follows:
一、将1.95克2-(3-氨基-6-羟基苯基)菲并咪唑和0.13克对苯二甲醛加入到苯中,在温度为70℃的条件下反应3小时,反应过程中有固体析出;反应结束后,过滤,依次用甲醇和蒸馏水洗涤滤饼,滤饼在温度为80℃的条件下干燥8小时后,得到粗产物;将粗产物用乙酸乙酯和乙醚醚按体积比为1:3的混合溶剂重结晶,得到有机化合物A,产率40%,熔点为320℃。1. Add 1.95 grams of 2-(3-amino-6-hydroxyphenyl) phenanthroimidazole and 0.13 grams of terephthalaldehyde to benzene, and react for 3 hours at a temperature of 70 ° C. There are solids in the reaction process. Precipitation; after the reaction is completed, filter, wash the filter cake with methanol and distilled water successively, and dry the filter cake at a temperature of 80 ° C for 8 hours to obtain a crude product; use ethyl acetate and diethyl ether to obtain a crude product in a volume ratio of 1:3 mixed solvent was recrystallized to obtain organic compound A with a yield of 40% and a melting point of 320°C.
二、将0.75克有机化合物A和2.93克硝酸汞溶解在二甲基亚砜中,室温搅拌至有大量固体析出。过滤,滤饼依次采用乙醇和水洗涤,滤饼在温度为80℃的条件下干燥8小时后,得到光谱法和比色法检测不同形式碘的分子平台,产率63%,熔点>320℃。。2. Dissolve 0.75 g of organic compound A and 2.93 g of mercury nitrate in dimethyl sulfoxide, and stir at room temperature until a large amount of solid is precipitated. Filtration, the filter cake was washed with ethanol and water in turn, and the filter cake was dried at a temperature of 80 °C for 8 hours to obtain a molecular platform for spectroscopic and colorimetric detection of different forms of iodine, yield 63%, melting point > 320 °C . .
Claims (10)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010794666.4A CN111795960B (en) | 2020-08-10 | 2020-08-10 | Molecular platform for detecting different forms of iodine by spectrometry and colorimetry, and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010794666.4A CN111795960B (en) | 2020-08-10 | 2020-08-10 | Molecular platform for detecting different forms of iodine by spectrometry and colorimetry, and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111795960A true CN111795960A (en) | 2020-10-20 |
CN111795960B CN111795960B (en) | 2022-08-09 |
Family
ID=72833839
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010794666.4A Active CN111795960B (en) | 2020-08-10 | 2020-08-10 | Molecular platform for detecting different forms of iodine by spectrometry and colorimetry, and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111795960B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113004206A (en) * | 2021-03-11 | 2021-06-22 | 齐齐哈尔大学 | Naphthalene derivative fluorescent probe and preparation method and application thereof |
CN113024799A (en) * | 2021-03-01 | 2021-06-25 | 山东大学 | Application of soluble polymer with micropores in iodine vapor detection |
Citations (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0515194A2 (en) * | 1991-05-22 | 1992-11-25 | BEHRINGWERKE Aktiengesellschaft | Assay methods utilizing induced luminescence |
EP0874242A1 (en) * | 1997-04-21 | 1998-10-28 | Randox Laboratories Ltd. | Device and apparatus for the simultaneous detection of multiple analytes |
US20050014197A1 (en) * | 2002-05-03 | 2005-01-20 | Brian Agnew | Compositions and methods for detection and isolation of phosphorylated molecules |
CN1571788A (en) * | 2001-10-17 | 2005-01-26 | 西巴特殊化学品控股有限公司 | Photoactivable nitrogen bases |
JP2005104148A (en) * | 2003-09-11 | 2005-04-21 | Fuji Photo Film Co Ltd | Cellulose acylate film and solution film forming method |
EP1577010A2 (en) * | 1995-12-05 | 2005-09-21 | Tecan Trading AG | Microsystem platform and its use |
US20070004679A1 (en) * | 2004-05-17 | 2007-01-04 | Nathalie Schlienger | Androgen receptor modulators and methods of treating disease using the same |
CN101084235A (en) * | 2002-04-17 | 2007-12-05 | 迪纳米斯治疗公司 | 3-deoxyglucosone and skin |
US20080145869A1 (en) * | 2006-12-15 | 2008-06-19 | Fujifilm Corporation | Immunoassay method |
US20100009381A1 (en) * | 2002-05-03 | 2010-01-14 | Life Technologies Corporation | Compositions and methods for detection and isolation of phosphorylated molecules |
US20120288884A1 (en) * | 2010-07-28 | 2012-11-15 | Nanyang Technological University | Quinazolinone based fluorogenic probes |
AU2013200142A1 (en) * | 2005-08-30 | 2013-03-07 | Takeda Pharmaceutical Company Limited | 1-Heterocyclylsulfonyl, 3-aminomethyl, 5-(hetero-)aryl substituted 1-H-pyrrole derivatives as acid secretion inhibitors |
US20140170735A1 (en) * | 2011-09-25 | 2014-06-19 | Elizabeth A. Holmes | Systems and methods for multi-analysis |
JP2014136675A (en) * | 2013-01-15 | 2014-07-28 | Nara Women's Univ | Metal ion fluorescence probe |
US20140234949A1 (en) * | 2011-09-25 | 2014-08-21 | Theranos, Inc. | Systems and methods for fluid and component handling |
US20140296089A1 (en) * | 2013-02-18 | 2014-10-02 | Theranos, Inc. | Systems and methods for multi-analysis |
CN105255481A (en) * | 2015-11-16 | 2016-01-20 | 齐齐哈尔大学 | Phenanthrene and imidazole-coumarin double-fluorescent group ratio fluorescent molecular probe for iron ion detection and synthesis and use methods thereof |
WO2017014284A1 (en) * | 2015-07-23 | 2017-01-26 | 三菱瓦斯化学株式会社 | Novel compound and method for producing same |
CN106699734A (en) * | 2016-12-19 | 2017-05-24 | 中南大学 | Fluorescent molecular probe and nanoprobe as well as preparation method and application thereof |
US20180024112A1 (en) * | 2016-05-17 | 2018-01-25 | The Regents Of The University Of California | Systems and methods for detecting metal ion concentrations in subjects |
CN108863945A (en) * | 2018-06-12 | 2018-11-23 | 齐齐哈尔大学 | A kind of phenanthro- imidazoles Fe3+Probe and its preparation and application |
CN109470671A (en) * | 2018-11-30 | 2019-03-15 | 齐齐哈尔大学 | A kind of fluorescent test strip for H2S detection and preparation and use method thereof |
TW201930298A (en) * | 2017-11-17 | 2019-08-01 | 美商史基普研究協會 | Bis-benzimidazole compounds and methods of using the same |
CN111777598A (en) * | 2020-08-10 | 2020-10-16 | 齐齐哈尔大学 | A fluorescent probe capable of detecting Cu2+ and using Cu2+ to detect HPO42- and its preparation method and application |
-
2020
- 2020-08-10 CN CN202010794666.4A patent/CN111795960B/en active Active
Patent Citations (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0515194A2 (en) * | 1991-05-22 | 1992-11-25 | BEHRINGWERKE Aktiengesellschaft | Assay methods utilizing induced luminescence |
EP1577010A2 (en) * | 1995-12-05 | 2005-09-21 | Tecan Trading AG | Microsystem platform and its use |
EP0874242A1 (en) * | 1997-04-21 | 1998-10-28 | Randox Laboratories Ltd. | Device and apparatus for the simultaneous detection of multiple analytes |
CN1571788A (en) * | 2001-10-17 | 2005-01-26 | 西巴特殊化学品控股有限公司 | Photoactivable nitrogen bases |
CN101084235A (en) * | 2002-04-17 | 2007-12-05 | 迪纳米斯治疗公司 | 3-deoxyglucosone and skin |
US20050014197A1 (en) * | 2002-05-03 | 2005-01-20 | Brian Agnew | Compositions and methods for detection and isolation of phosphorylated molecules |
US20100009381A1 (en) * | 2002-05-03 | 2010-01-14 | Life Technologies Corporation | Compositions and methods for detection and isolation of phosphorylated molecules |
JP2005104148A (en) * | 2003-09-11 | 2005-04-21 | Fuji Photo Film Co Ltd | Cellulose acylate film and solution film forming method |
US20070004679A1 (en) * | 2004-05-17 | 2007-01-04 | Nathalie Schlienger | Androgen receptor modulators and methods of treating disease using the same |
AU2013200142A1 (en) * | 2005-08-30 | 2013-03-07 | Takeda Pharmaceutical Company Limited | 1-Heterocyclylsulfonyl, 3-aminomethyl, 5-(hetero-)aryl substituted 1-H-pyrrole derivatives as acid secretion inhibitors |
US20080145869A1 (en) * | 2006-12-15 | 2008-06-19 | Fujifilm Corporation | Immunoassay method |
US20120288884A1 (en) * | 2010-07-28 | 2012-11-15 | Nanyang Technological University | Quinazolinone based fluorogenic probes |
US20140170735A1 (en) * | 2011-09-25 | 2014-06-19 | Elizabeth A. Holmes | Systems and methods for multi-analysis |
US20140234949A1 (en) * | 2011-09-25 | 2014-08-21 | Theranos, Inc. | Systems and methods for fluid and component handling |
JP2014136675A (en) * | 2013-01-15 | 2014-07-28 | Nara Women's Univ | Metal ion fluorescence probe |
US20140296089A1 (en) * | 2013-02-18 | 2014-10-02 | Theranos, Inc. | Systems and methods for multi-analysis |
WO2017014284A1 (en) * | 2015-07-23 | 2017-01-26 | 三菱瓦斯化学株式会社 | Novel compound and method for producing same |
CN105255481A (en) * | 2015-11-16 | 2016-01-20 | 齐齐哈尔大学 | Phenanthrene and imidazole-coumarin double-fluorescent group ratio fluorescent molecular probe for iron ion detection and synthesis and use methods thereof |
US20180024112A1 (en) * | 2016-05-17 | 2018-01-25 | The Regents Of The University Of California | Systems and methods for detecting metal ion concentrations in subjects |
CN106699734A (en) * | 2016-12-19 | 2017-05-24 | 中南大学 | Fluorescent molecular probe and nanoprobe as well as preparation method and application thereof |
TW201930298A (en) * | 2017-11-17 | 2019-08-01 | 美商史基普研究協會 | Bis-benzimidazole compounds and methods of using the same |
CN108863945A (en) * | 2018-06-12 | 2018-11-23 | 齐齐哈尔大学 | A kind of phenanthro- imidazoles Fe3+Probe and its preparation and application |
CN109470671A (en) * | 2018-11-30 | 2019-03-15 | 齐齐哈尔大学 | A kind of fluorescent test strip for H2S detection and preparation and use method thereof |
CN111777598A (en) * | 2020-08-10 | 2020-10-16 | 齐齐哈尔大学 | A fluorescent probe capable of detecting Cu2+ and using Cu2+ to detect HPO42- and its preparation method and application |
Non-Patent Citations (5)
Title |
---|
GEOFFREY COOPER.ET: "Photodehydrocyclisation of 1-styrylimidazoles; an HMO study", 《 J. CHEM. SOC., PERKIN TRANS. 1》, 31 December 1976 (1976-12-31), pages 2038 - 2045 * |
MUTHALAGU VETRICHELVAN.ET: "Carbazole-Containing Conjugated Copolymers as Colorimetric/Fluorimetric Sensor for Iodide Anion", 《MACROMOLECULES》, vol. 39, 31 December 2006 (2006-12-31), pages 8303 - 8310, XP055358378, DOI: 10.1021/ma0613537 * |
YULIA A. VLASENKO.ET: "Synthesis of Five-Membered Iodine–Nitrogen Heterocycles from Benzimidazole-Based Iodonium Salts", 《J. ORG. CHEM》, 31 December 2018 (2018-12-31), pages 12056 - 12070 * |
王鑫: "铕—邻菲咯啉衍生物荧光配合物和咔唑卟啉的合成及性能研究", 《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》, 15 September 2009 (2009-09-15), pages 014 - 88 * |
陈冰冰: "菲咪唑、罗丹明和香豆素衍生物的合成及在荧光探针中的应用", 《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》, 15 March 2011 (2011-03-15), pages 014 - 70 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113024799A (en) * | 2021-03-01 | 2021-06-25 | 山东大学 | Application of soluble polymer with micropores in iodine vapor detection |
CN113004206A (en) * | 2021-03-11 | 2021-06-22 | 齐齐哈尔大学 | Naphthalene derivative fluorescent probe and preparation method and application thereof |
CN113004206B (en) * | 2021-03-11 | 2022-06-17 | 齐齐哈尔大学 | Naphthalene derivative fluorescent probe and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN111795960B (en) | 2022-08-09 |
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 | |
Dalapati et al. | Post-synthetic modification of a metal–organic framework with a chemodosimeter for the rapid detection of lethal cyanide via dual emission | |
CN103159682B (en) | 2-aminobenzimidazole Schiff base based cyanide receptor compound and preparation and applications thereof | |
CN106349167B (en) | Benzimidizole derivatives phosphate anion fluorescence probe synthesizes and application method | |
CN106496197A (en) | A kind of Fluorescence Increasing type quick detection sulfurous acid hydrogen radical ion or the synthesis and application of sulfite ion fluorescent molecular probe | |
CN111795960B (en) | Molecular platform for detecting different forms of iodine by spectrometry and colorimetry, and preparation method and application thereof | |
CN106810544A (en) | Iodate-N- ethyls -2-(2-H- aphthopyrans -3- vinyl)Benzothiazole and its preparation method and application | |
CN108675990A (en) | A kind of detection Cu2+Fluorescence probe, preparation method and fluorescent test paper strip preparation and application | |
CN107936953B (en) | A kind of fluorescent probe and its preparation method and application | |
CN101135644A (en) | Mercury ion fluorescent color developer, detection method, test paper and application thereof | |
Qi et al. | Cyanide detection using azo-acylhydrazone in aqueous media with high sensitivity and selectivity | |
CN103387830B (en) | Chromium-ion ratio type fluorescence probe as well as preparation method and application thereof | |
CN107917904B (en) | A method for rapid detection of Fe3+ | |
CN109232558B (en) | For detecting Cu2+Derivatives of (5) | |
CN112945925B (en) | Method for detecting permanganate acid radicals by coumarin-based probe | |
CN106317096A (en) | Phenanthroline imidazole type rare earth coordination molecule-based probe as well as preparation method and application thereof | |
CN106397319A (en) | Fluorescent probe for proportionally detecting hydrazine, method for synthesizing fluorescent probe and application thereof | |
CN108997401A (en) | A kind of fluorescence probe and preparation method thereof for detecting lead ion | |
CN110878100B (en) | Cyanide ion probe capable of being recognized by naked eyes, preparation method thereof and application of cyanide ion probe in detection of cyanide ions in water-containing system | |
CN108484414A (en) | A kind of formaldehyde fluorescence probe and formaldehyde examination piece and preparation method thereof based on tetraphenylethylene, formaldehyde examination piece application method | |
CN1289775A (en) | Ruthenium (II) polypyridine match and its preparing process | |
CN107987018B (en) | Cyanide ion sensor molecule and synthesis and application thereof | |
CN106883159B (en) | A kind of ultraviolet probe of Thiourea and its preparation and application | |
CN108863945A (en) | A kind of phenanthro- imidazoles Fe3+Probe and its preparation and application | |
CN108760707B (en) | Application of probe reagent |
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 |