CN111423462B - Tetraphenyl ethylene borate pyridine salt, preparation method and application thereof, and reagent and method for detecting fructose - Google Patents

Tetraphenyl ethylene borate pyridine salt, preparation method and application thereof, and reagent and method for detecting fructose Download PDF

Info

Publication number
CN111423462B
CN111423462B CN202010342626.6A CN202010342626A CN111423462B CN 111423462 B CN111423462 B CN 111423462B CN 202010342626 A CN202010342626 A CN 202010342626A CN 111423462 B CN111423462 B CN 111423462B
Authority
CN
China
Prior art keywords
tetraphenyl
borate
fructose
compound
tetraphenyl ethylene
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.)
Active
Application number
CN202010342626.6A
Other languages
Chinese (zh)
Other versions
CN111423462A (en
Inventor
魏超
解畅
张平竹
李小六
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hebei University
Original Assignee
Hebei University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hebei University filed Critical Hebei University
Priority to CN202010342626.6A priority Critical patent/CN111423462B/en
Publication of CN111423462A publication Critical patent/CN111423462A/en
Application granted granted Critical
Publication of CN111423462B publication Critical patent/CN111423462B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • 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
    • 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"
    • G01N2021/6432—Quenching
    • 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"
    • G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Immunology (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Molecular Biology (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 Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)

Abstract

The invention provides tetraphenyl ethylene borate pyridine salt, a preparation method and application thereof, a reagent for detecting fructose and a method thereof, wherein the structural formula of the tetraphenyl ethylene borate pyridine salt is shown as a formula (I) or (II). The invention prepares a series of tetraphenyl ethylene borate pyridinium compounds by adopting specific raw materials and methods, the compounds can be used as fructose detection reagents, have high selectivity and high sensitivity detection capability on fructose, can detect fructose-containing samples including honey, seminal plasma and other samples, and have wide application prospects.

Description

Tetraphenyl ethylene borate pyridine salt, preparation method and application thereof, and reagent and method for detecting fructose
Technical Field
The invention relates to a fluorescent probe, in particular to tetraphenyl vinyl borate pyridinium, a preparation method and application thereof, and a reagent and a method for detecting fructose.
Background
Fructose is a monosaccharide naturally present in foods such as fruits and honey, has the advantages of good taste, high sweetness, low glycemic index, difficulty in causing dental caries and the like, and is widely used as a general sweetener in foods, beverages and nutritional wines. Also, in the medical field, crystalline fructose is used for preparing a series of fructose-containing electrolyte injections because it has a reduced glycemic index. Fructose is also closely related to human health, e.g., in seminal fluid, fructose supplies energy to sperm, and its concentration serves as an indicator of an indirect measure of testosterone activity. If the patients with hereditary fructose intolerance continuously take fructose for a long time, growth retardation and liver pathological changes can occur, and further liver and kidney function failure can be induced, and finally death can be caused. Therefore, the development of a visualization method for detecting fructose with high selectivity is of great significance to human health.
Currently, methods for detecting fructose in the market, such as colorimetry, high performance liquid chromatography, gas chromatography and the like, are not suitable for detecting fructose in complex samples. In recent years, fluorescent probes have attracted much attention for use in the recognition of saccharides, but the fluorescence enhancement factor of probes bound to fructose is low, generally 60 or less, and the sensitivity is poor. Therefore, it is very necessary to develop a fluorescent probe for detecting fructose with high selectivity and high sensitivity in a systematic manner.
Disclosure of Invention
It is an object of the present invention to provide tetraphenyl vinyl borate pyridinium salts.
The invention also aims to provide a preparation method of the tetraphenyl ethylene borate pyridine salt.
The invention also aims to provide the application of tetraphenyl ethylene borate pyridine salt in the aspect of detecting fructose.
The fourth purpose of the invention is to provide a reagent for detecting fructose.
The fifth purpose of the invention is to provide a method for detecting fructose.
One of the objects of the invention is achieved by:
the chemical structural formula of the tetraphenyl ethylene borate pyridine salt is as follows:
Figure BDA0002469031480000021
wherein R' is H, OH or OCH 3 、
Figure BDA0002469031480000022
Figure BDA0002469031480000023
R is
Figure BDA0002469031480000024
Figure BDA0002469031480000025
X is Br, I, BF 4 Or PF 6 。
Preferably, R' in the tetraphenyl ethylene borate pyridinium is H, OH or OCH 3 、
Figure BDA0002469031480000026
Figure BDA0002469031480000027
R is
Figure BDA0002469031480000028
Figure BDA0002469031480000029
X is Br, I, BF 4 Or PF 6 。
More preferably, R' in the tetraphenyl vinyl borate pyridinium salt is H or
Figure BDA00024690314800000210
R is->
Figure BDA00024690314800000211
Figure BDA0002469031480000031
X is Br, I or BF 6 。
More preferably, R' in the tetraphenyl vinyl borate pyridinium salt is
Figure BDA0002469031480000032
R is->
Figure BDA0002469031480000033
And X is Br.
The second purpose of the invention is realized by the following steps:
alternatively, the preparation method of the tetraphenyl ethylene borate pyridine salt comprises the following steps:
(a) Carrying out wittig reaction on benzophenone, triphenylphosphine and carbon tetrabromide to obtain dibromo stilbene;
(b) Carrying out metal coupling reaction on dibrominated stilbene and pyridine boric acid to obtain stilbene bipyridine;
(c) Carrying out nucleophilic substitution reaction on diphenylethylene bipyridine and bromomethyl phenylboronic acid to obtain tetraphenyl ethylene borate pyridinium;
the tetraphenyl ethylene borate pyridine salt is
Figure BDA0002469031480000034
Preferably, benzophenone is dissolved in a solvent, carbon tetrabromide and triphenylphosphine are sequentially added for reaction, and a compound 1-1 is obtained through filtration, filtrate concentration and separation; dissolving the compound 1-1 in a solvent, adding 4-pyridine borate, reacting, extracting, washing, drying and separating to obtain a compound 1-2; dissolving the compound 1-2 in an organic solvent, adding 2-bromomethyl phenylboronic acid into the organic solvent, reacting, extracting, washing, drying and separating to obtain a target compound; the synthetic route is as follows:
Figure BDA0002469031480000035
specifically, benzophenone is dissolved in anhydrous toluene, carbon tetrabromide and triphenylphosphine are sequentially added, reflux and filtration are carried out, filtrate is concentrated, and a white solid compound 1-1 is obtained through column chromatography separation; dissolving the compound 1-1 in anhydrous toluene, and sequentially adding 4-pyridine borate and K 2 CO 3 Refluxing the water solution overnight, extracting with ethyl acetate, washing with water, drying, and separating by column chromatography to obtain compound 1-2; dissolving the compound 1-2 in anhydrous DMF, adding 2-bromomethyl phenylboronic acid, reacting, extracting with ethyl acetate, washing with water, drying, and performing column chromatography separation to obtain a light yellow solid compound.
Alternatively, a method for preparing tetraphenyl vinyl borate pyridinium salt comprises the following steps:
(a) Taking benzophenone substituted by substituent groups as a raw material, and carrying out Michaelis reaction under the action of titanium chloride and a reducing agent to obtain substituent group modified tetraphenylethylene; the substituent is hydroxyl, methoxy or bromine;
(b) Tetraphenyl ethylene modified by substituent groups and pyridine boric acid are subjected to metal coupling reaction to obtain tetraphenyl ethylene pyridine compounds;
(c) Carrying out nucleophilic substitution reaction on a tetraphenyl vinylpyridine compound and bromomethyl phenylboronic acid to obtain tetraphenyl vinylphosphonic acid bromopyridinium;
the tetraphenyl ethylene borate pyridine salt is
Figure BDA0002469031480000041
Wherein R' is H, OH or OCH 3 、
Figure BDA0002469031480000042
Figure BDA0002469031480000043
R is
Figure BDA0002469031480000044
Figure BDA0002469031480000045
X is Br.
Further, the preparation method of the tetraphenyl ethylene borate pyridine salt comprises the following steps:
(a) Taking substituted benzophenone (hydroxyl benzophenone, methoxy benzophenone and bromo benzophenone) as a raw material, and carrying out a Michamerry Reaction (McMurry Reaction) under the action of titanium chloride and a reducing agent to obtain substituent-modified tetraphenyl ethylene; the substituent is hydroxyl, methoxy or bromine;
(b) Tetraphenyl ethylene modified by substituent groups and pyridine boric acid are subjected to metal coupling reaction to obtain tetraphenyl ethylene pyridine compounds;
(c) Carrying out nucleophilic substitution reaction on a tetraphenyl vinylpyridine compound and bromomethyl phenylboronic acid to obtain tetraphenyl vinylphosphonic acid bromopyridinium;
(d) Performing ion exchange reaction on tetraphenyl ethylene borate bromopyridinium and potassium iodide, potassium fluoborate or potassium hexafluorophosphate to obtain tetraphenyl ethylene borate iodopyridinium, tetraphenyl ethylene borate borofluoride pyridinium or tetraphenyl ethylene borate hexafluorophosphate pyridinium;
the tetraphenyl ethylene borate pyridine salt is
Figure BDA0002469031480000046
Wherein R' is H, OH or OCH 3 、
Figure BDA0002469031480000047
Figure BDA0002469031480000051
R is
Figure BDA0002469031480000052
Figure BDA0002469031480000053
X is I, BF 4 Or PF 6 。
When R' is H, R is
Figure BDA0002469031480000054
When X is Br, (a) 4-bromobenzophenone is dissolved in an organic solvent, and a Michamerry Reaction (McMurry Reaction) is carried out under the action of zinc powder and titanium tetrachloride to obtain dibromotetraphenylethylene; (b) Dissolving dibromo tetraphenylethylene in an organic solvent, and adding 3-pyridine borate or 4-pyridine borate to obtain tetraphenylethylene bipyridine; (c) Dissolving tetraphenyl ethylene dipyridine in an organic solvent, and adding 2-bromomethyl phenylboronic acid, 3-bromomethyl phenylboronic acid or 4-bromomethyl phenylboronic acid to obtain tetraphenyl ethylene borate bromopyridinium salt.
Specifically, dissolving 4-bromobenzophenone in anhydrous tetrahydrofuran, adding zinc powder, adding titanium tetrachloride at-20 ℃, stirring and heating to room temperature, refluxing, filtering, concentrating the filtrate, and separating to obtain a compound 2-1; dissolving compound 2-1 in anhydrous tetrahydrofuran, sequentially adding 3-or 4-pyridine borate and 2N K 2 CO 3 Refluxing, extracting, washing, drying and separating the aqueous solution to obtain a compound 2-2; dissolving the compound 2-2 in an organic solvent, adding 2-bromomethylbenzeneboronic acid, 3-bromomethylbenzeneboronic acid or 4-bromomethylbenzeneboronic acid, reacting, cooling reaction liquid, dropwise adding acetone, and filtering to obtain a white solid compound Q2.
The synthetic route is as follows:
Figure BDA0002469031480000061
when R is
Figure BDA0002469031480000062
R is->
Figure BDA0002469031480000063
In the preparation method, (a) 4,4' -dibromobenzophenone is dissolved inCarrying out McMurry Reaction (McMurry Reaction) in an organic solvent under the action of zinc powder and titanium tetrachloride to obtain tetrabromo tetraphenylethylene; (b) Dissolving tetrabromo tetraphenylethylene in an organic solvent, and adding 4-pyridine borate to obtain tetraphenylethylene bipyridine; (c) Dissolving tetraphenyl ethylene dipyridine in an organic solvent, and adding 2-bromomethyl phenylboronic acid to obtain tetraphenyl ethylene borate pyridinium salt.
Specifically, dissolving 4,4' -dibromo benzophenone in anhydrous tetrahydrofuran, adding zinc powder, adding titanium tetrachloride at-20 ℃, stirring and heating to room temperature, refluxing, filtering, concentrating the filtrate, and separating to obtain a white solid compound 3; dissolving the compound 3 in anhydrous tetrahydrofuran, and sequentially adding 4-pyridine borate and 2N K 2 CO 3 Refluxing the aqueous solution, extracting, washing, drying and separating to obtain a light yellow solid compound 3-1; dissolving the compound 3-1 in an organic solvent, adding 2-bromomethyl phenylboronic acid, reacting, cooling the reaction liquid, dropwise adding acetone, and filtering to obtain yellow solid compounds Q3 and Q4.
The synthetic route is as follows:
Figure BDA0002469031480000071
the third purpose of the invention is realized by the following steps:
the application of the tetraphenyl ethylene borate pyridine salt in detecting fructose.
Preferably, the tetraphenyl vinyl borate pyridinium salt is
Figure BDA0002469031480000072
Wherein R' is H or->
Figure BDA0002469031480000073
R is->
Figure BDA0002469031480000074
X is Br.
The fourth purpose of the invention is realized by the following steps:
the chemical structural formula of the reagent for detecting fructose is as follows:
Figure BDA0002469031480000081
wherein R' is H, OH or OCH 3 、
Figure BDA0002469031480000082
Figure BDA0002469031480000083
R is
Figure BDA0002469031480000084
Figure BDA0002469031480000085
X is Br, I, BF 4 Or PF 6 。
Preferably, the chemical formula of the reagent is as follows:
Figure BDA0002469031480000086
wherein R' is H or
Figure BDA0002469031480000087
R is->
Figure BDA0002469031480000088
And X is Br.
Preferably, R' is H and R is
Figure BDA0002469031480000089
X is Br.
The fifth purpose of the invention is realized by the following steps:
a method for detecting fructose comprises the steps of mixing a sample with 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt (HPTS) solution and the detection reagent, measuring the fluorescence emission intensity of the sample at a specific wavelength by taking 400nm as an excitation light wavelength, and comparing the fluorescence emission intensity with a standard curve to obtain the concentration of the fructose in the sample.
The specific wavelength is 520nm.
The 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt (HPTS) solution is prepared by the following method: dissolving HPTS in Phosphate Buffer Solution (PBS) to prepare mother solution with specific concentration; preferably, the concentration of the PBS solution is 10mM and the pH is 7.4.
The detection reagent is preferably in the form of a solution, which is prepared by the following method: the detection reagent is dissolved in dimethyl sulfoxide (DMSO), and a mother solution with the concentration of 20mM is accurately prepared.
Uniformly mixing a standard D-fructose sample, 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt (HPTS) solution and the detection reagent, incubating at room temperature for 30min, and performing fluorescence emission spectrum test by taking 400nm as an excitation wavelength; the fluorescence intensity at 520nm was plotted against the sample concentration, resulting in the standard curve equation Y = aX + b. Alternatively, the final concentration of HPTS is 4. Mu.M, Q2-4 is 20. Mu.M, and D-fructose is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10mM.
Mixing a sample with a solution of 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt (HPTS) and the detection reagent, and testing the fluorescence emission spectrum at 400 nm; substituting the fluorescence intensity Y at 520nm into a standard curve equation, and calculating to obtain an X value, namely the concentration of the D-fructose in the sample. Preferably, the concentration of fructose in the sample is 1 to 7mM.
The sample can be honey, seminal plasma and other fructose-containing samples.
The invention prepares a series of tetraphenyl ethylene borate pyridine salt compounds by adopting specific raw materials and a method, the compounds can be used as fructose detection reagents, have high selectivity and high sensitivity detection capability on fructose, can detect samples containing fructose, such as honey, seminal plasma and the like, and have wide application prospect.
Drawings
FIG. 1 is a graph showing the fluorescence quenching effect of compounds Q1 to Q4 as quenchers on the fluorescent dye HPTS.
FIG. 2 is a graph showing the fluorescence quenching effect of compound Q2 as a quencher on the fluorescent dye HPTS.
FIG. 3 is a graph showing the results of selectivity of compounds Q1 to Q4 for four monosaccharides (sialic acid, D-galactose, D-fructose, D-glucose).
FIGS. 4 to 5 are graphs showing the results of the selectivity of compound Q2-2 for various carbohydrates, endogenous active small molecules, and metal ions.
FIG. 6 is a graph of the fluorescence titration of compound Q2-2 against D-fructose.
Detailed Description
The invention is further illustrated by the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention in any way.
Procedures and methods not described in detail in the following examples are conventional methods well known in the art, and the reagents used in the examples are either analytically or chemically pure and are either commercially available or prepared by methods well known to those of ordinary skill in the art. The following examples all achieve the objects of the present invention.
Example 1
The synthetic route for compound Q1 is as follows:
Figure BDA0002469031480000101
synthesis of Compound 1-1
N 2 Benzophenone (100mg, 0.55mmol) was dissolved in 10mL of anhydrous toluene under protection, and carbon tetrabromide (364mg, 1.10mmol) and triphenylphosphine (577mg, 2.20mmol) were added in this order, and the mixture was refluxed for 4 days. Cooling to room temperature, suction-filtering the reaction solution, and separating by liquid column chromatography (petroleum ether) to obtain compound 1-1, white needle-like solid 126mg, yield 72%.
Compound 1-1: 1 H NMR(400MHz,CDCl 3 )δ(ppm):7.36-7.29(m,10H).
synthesis of Compound 1-2
N 2 Under protection, compound 1-1 (100mg, 0.30mmol) was dissolved in 4mL of anhydrous toluene, and 4-pyridineboronic acid (109mg, 0.89mmol), tetrakis (triphenylphosphine) palladium (104mg, 0.09mmol) and 0.5mL of 2N K were added in this order 2 CO 3 The solution was refluxed for 24 hours. Cooling to room temperature, extracting with ethyl acetate, washing the organic phase with water and saturated brine respectively, and removing anhydrous MgSO 4 Drying, filtering, concentrating, and separating by column chromatography [ V (petroleum ether)/V (ethyl acetate) =1/2]Compound 1-2 was obtained as a white solid at 29mg, 30% yield.
Compounds 1-2: 1 H NMR(400MHz,CDCl 3 )δ(ppm):8.38(d,J＝4.0Hz,4H),7.21-7.13(m,6H),7.01(d,J＝8.0Hz,4H),6.89(d,J＝8.0Hz,4H).
synthesis of Compound Q1
N 2 Compound 2-bromomethylbenzeneboronic acid (67mg, 0.31mmol) was dissolved in 1.5mL of anhydrous DMF under protection, and compound 1-2 (42mg, 0.13mmol) was added and stirred at 100 ℃ for 72h. Cooling to room temperature, extracting with ethyl acetate, washing the organic phase with water and saturated brine, respectively, anhydrous MgSO 4 Drying, vacuum filtering, concentrating, and separating by column chromatography [ V (methanol)/V (ammonia) = 1/1%]Compound Q1 was obtained as a pale yellow solid 43mg in 56% yield.
Compound Q1: 1 H NMR(400MHz,CD 3 OD)δ(ppm):8.68(s,3H),7.65(d,J＝4.0Hz,3H),7.45-7.32(m,10H),7.26(t,J＝8.0Hz,5H),7.12(d,J＝8.0Hz,5H),5.90(s,4H)； 13 C NMR(100MHz,CD 3 OD)δ(ppm):63.98,128.53,129.24,129.58,129.65,130.60,131.09,135.46,139.81,144.41.
example 2
The synthetic route for compound Q2 is as follows:
Figure BDA0002469031480000111
synthesis of Compound 2-1
N 2 Under protection, 4-bromobenzophenone (10.00g, 38.30mmol) was dissolved in 200mL of anhydrous THF, zinc powder (22.53g, 344.70mmol) was added, and TiCl was added dropwise at-20 deg.C 4 (18.94mL, 172.33mmol), refluxed overnight, and cooled to room temperature. Adjusting pH to 7 with 1N HCl, evaporating THF under reduced pressure, extracting with dichloromethane, washing organic phase with water and saturated saline solution, respectively, and anhydrous MgSO 4 DryingVacuum filtering, concentrating, and column chromatography (petroleum ether) to obtain compound 2-1, white solid 6.80g, and yield 72%.
Compound 2-1; 1 H NMR(400MHz,CDCl 3 )δ(ppm):7.32-7.28(m,4H),7.20-7.15(m,6H),7.06-7.02(m,4H),6.96-6.91(m,4H).
synthesis of Compound 2-2a
N 2 Under protection, compound 2-1 (100mg, 0.20mmol) was dissolved in 2mL of THF, and 3-pyridineboronic acid (75mg, 0.60mmol), tetrakis (triphenylphosphine) palladium (69mg, 0.06mmol), and 1mL of 2N K were added in this order 2 CO 3 The solution was refluxed overnight and cooled to room temperature. THF was distilled off under reduced pressure, methylene chloride was extracted, and the organic phase was washed with water and saturated brine, respectively, and anhydrous MgSO 4 Drying, filtering, concentrating, and separating by column chromatography [ V (petroleum ether)/V (ethyl acetate) =2/1]Compound 2-2a was obtained as a pale yellow solid 41mg with a yield of 40%.
Compound 2-2a, m.p.216-218 ℃; 1 H NMR(400MHz,CDCl 3 )δ(ppm):8.81(s,1H),8.55(d,J＝4.0Hz,1H),7.83(d,J＝8.0Hz,1H),7.66(dd,J＝8.0Hz,J＝12.0Hz,5H),7.55-7.45(m,7H),7.36-7.31(m,3H),7.15-7.10(m,8H).
synthesis of Compound 2-2b
Referring to the synthesis method of compound 2-2a, compound 2-2b was synthesized as a pale yellow solid of 760mg in 38% yield from 4-pyridineboronic acid and compound 2-1.
Compound 2-2b; 1 H NMR(400MHz,CDCl 3 )δ(ppm):8.63(s,4H),7.47(s,4H),7.41(d,J＝8.0Hz,4H),7.16-7.14(m,10H),7.09(dd,J＝4.0Hz,J＝8.0Hz,4H).
synthesis of Compound Q2-1
N 2 Under protection, the compound 2-bromomethylbenzeneboronic acid (110mg, 0.51mmol) was dissolved in 2.5mL of anhydrous DMF, and the compound 2-2a (100mg, 0.20mmol) was added thereto, followed by stirring at 85 ℃ for 72 hours. And cooling to room temperature, dropwise adding acetone into the reaction solution, performing suction filtration, washing a filter cake with acetone, and performing vacuum drying to obtain a compound Q2-1, wherein the white solid is 162mg, and the yield is 85%.
Compound Q2-1:m.p.271-273℃； 1 H NMR(400MHz,CD 3 OD)δ(ppm):9.31(s,2H),8.79(d,J＝8.0Hz,4H),8.08(s,2H),7.61(d,J＝8.0Hz,5H),7.53-7.50(m,6H),7.27(d,J＝8.0Hz,4H),7.17-7.16(m,6H),7.11-7.09(m,4H),6.04(s,2H),5.91(s,2H)； 13 C NMR(100MHz,CD 3 OD)δ(ppm):64.60,126.51,126.92,127.84,128.96,130.96,131.42,132.29,142.62,142.71.
Synthesis of Compounds Q2-2 and Q2-3
Referring to the synthesis method of the compound Q2-1, the compounds Q2-2 and Q2-3 were synthesized with 3-bromomethylbenzeneboronic acid and 4-bromomethylbenzeneboronic acid and the compound 2-2a, respectively, in yields of 97% and 94%, respectively.
Compound Q2-2 m.p.308-310 ℃; 1 H NMR(400MHz,CD 3 OD)δ(ppm):9.43(s,2H),8.91(d,J＝4.0Hz,2H),8.81(d,J＝8.0Hz,2H),8.11(t,J＝8.0Hz,2H),7.85(t,J＝8.0Hz,3H),7.65(d,J＝8.0Hz,4H),7.59(d,J＝8.0Hz,2H),7.47-7.44(m,2H),7.28(d,J＝8.0Hz,4H),7.17-7.16(m,6H),7.11(t,J＝4.0Hz,4H),5.89(s,4H)； 13 C NMR(100MHz,CD 3 OD)δ(ppm):63.77,125.77,128.66,129.05,131.57,132.00,132.71,133.11,134.84,135.44,136.09,142.25,143.40,145.99,148.27,155.36,163.58.
compound Q2-3; 1 H NMR(400MHz,CD 3 OD)δ(ppm):9.42(s,2H),8.93(d,J＝8.0Hz,2H),8.81(d,J＝8.0Hz,2H),8.11(t,J＝8.0Hz,2H),7.80(s,4H),7.64(d,J＝8.0Hz,4H),7.49(d,J＝8.0Hz,4H),7.27(d,J＝8.0Hz,4H),7.16-7.15(m,6H),7.10(t,J＝4.0Hz,4H),5.89(s,4H)； 13 C NMR(100MHz,CD 3 OD)δ(ppm):64.48,126.66,126.93,127.58,128.23,130.96,131.31,132.26,134.58,141.07,141.19,142.30,142.49,142.73,142.98,145.84.
synthesis of Compounds Q2-4, Q2-5 and Q2-6
Referring to the synthesis method of the compound Q2-1, the compound 2-2b was reacted with 2-bromomethylbenzeneboronic acid, 3-bromomethylbenzeneboronic acid, 4-bromomethylbenzeneboronic acid, respectively, to obtain yellow solid compounds Q2-4, Q2-5 and Q2-6 in yields of 49%, 70% and 78%, respectively.
Compound Q2-4； 1 H NMR(400MHz,CD 3 OD)δ(ppm):8.83(d,J＝4.0Hz,4H),8.31(d,J＝4.0Hz,4H),7.80(d,J＝8.0Hz,5H),7.51-7.48(m,6H),7.28(d,J＝12.0Hz,4H),7.17(s,7H),7.10(t,J＝4.0Hz,4H),5.93(s,2H),5.85(s,2H)； 13 C NMR(100MHz,CD 3 OD)δ(ppm):63.46,123.94,127.15,127.28,127.95,128.83,130.97,131.87,132.33,141.56,142.41,144.29,147.73,155.65.
Compound Q2-5 m.p.305-307 ℃; 1 H NMR(400MHz,DMSO-d 6 )δ(ppm):9.20(d,J＝4.0Hz,4H),8.50(d,J＝4.0Hz,4H),8.15(s,4H),7.93(d,J＝8.0Hz,4H),7.88(s,2H),7.83(d,J＝8.0Hz,2H),7.59(d,J＝8.0Hz,2H),7.43-7.40(m,2H),7.21(dd,J＝8.0Hz,J＝16.0Hz,11H),7.08(d,J＝8.0Hz,4H),5.86(s,4H)； 13 C NMR(100MHz,DMSO-d6)δ(ppm):63.79,125.70,126.11,127.03,128.15,130.15,130.61,131.48,140.42,141.81,141.90,144.97.
compound Q2-6, m.p.319-321 ℃; 1 H NMR(400MHz,DMSO-d 6 )δ(ppm):8.49(d,J＝4.0Hz,4H),8.14(s,4H),7.93(d,J＝8.0Hz,4H),7.84(d,J＝8.0Hz,4H),7.48(d,J＝8.0Hz,2H),7.21(dd,J＝8.0Hz,J＝16.0Hz,11H),7.08(d,J＝8.0Hz,4H),5.85(s,4H)； 13 C NMR(100MHz,DMSO-d6)δ(ppm):62.66,123.14,126.35,126.48,127.15,128.03,130.16,131.07,131.53,140.76,141.61,143.49,146.93,154.85.
example 3
The synthetic route for compounds Q3 and Q4 is as follows:
Figure BDA0002469031480000141
synthesis of Compound 3
N 2 Under protection, 4' -dibromobenzophenone (3.50g, 10.29mmol) is dissolved in 40mL anhydrous THF, zinc powder (3.36g, 25.73mmol) is added, tiCl is added dropwise at-20 deg.C 4 (3.00mL, 25.73mmol), refluxed overnight and cooled to room temperature. Adjusting pH to 7 with 1N HCl, evaporating THF under reduced pressure, extracting with dichloromethane, washing organic phase with water and saturated saline solution, respectively, and anhydrous MgSO 4 Drying, suction filtering, concentrating, column chromatography separation (petroleum ether)) Compound 3 was obtained as a white solid 3.04g with a yield of 90%.
Synthesis of Compound 3-1
N 2 Compound 3 (300mg, 0.46mmol) was dissolved in 6mL of THF under protection, and 4-pyridineboronic acid (342mg, 2.78mmol), tetrakis (triphenylphosphine) palladium (924mg, 0.8mmol) and 3mL of 2N K were added in that order 2 CO 3 The solution was refluxed for 24 hours. Cooling to room temperature, evaporating THF under reduced pressure, extracting with dichloromethane, washing organic phase with water and saturated brine, respectively, anhydrous MgSO 4 Drying, filtering, concentrating, and separating by column chromatography [ V (dichloromethane)/V (methanol) = 30/1%]Compound 3-1 was obtained as a yellow solid, 136mg, 46% yield.
Compound 3-1: 1 H NMR(400MHz,CDCl 3 )δ(ppm):8.63(d,J＝4.0Hz,8H),7.49-7.47(m,16H),7.22(d,J＝8.0Hz,8H).
synthesis of Compound Q3
N 2 Under protection, the compound 2-bromomethylbenzeneboronic acid (42mg, 0.20mmol) was dissolved in 2mL of anhydrous DMF, and the compound 3-1 50mg, 0.08mmol) was added thereto, followed by stirring at 85 ℃ for 72 hours. And cooling to room temperature, dropwise adding acetone into the reaction solution, performing suction filtration, washing a filter cake with acetone, and performing vacuum drying to obtain a compound Q3, wherein 79mg of yellow solid is obtained, and the yield is 94%.
Compound Q3: 1 H NMR(400MHz,CD 3 OD)δ(ppm):8.85-8.82(m,4H),8.54(s,4H),8.32(d,J＝4.0Hz,4H),7.87(dd,J＝8.0Hz,J＝4.0Hz,4H),7.67-7.63(m,8H),7.50-7.47(m,8H),7.39(d,J＝8.0Hz,4H),7.29(d,J＝8.0Hz,4H),5.92(s,4H)； 13 C NMR(100MHz,CD 3 OD)δ(ppm):63.52,121.44,124.05,126.49,127.68,128.84,130.81,131.95,132.43,136.13,136.34,143.67,144.37,147.15,148.31,149.18,155.47.
synthesis of Compound Q4
N 2 Compound 2-bromomethylbenzeneboronic acid (118mg, 0.54mmol) was dissolved in 2mL of anhydrous DMF under protection, and compound 3-1 (70mg, 0.11mmol) was added and stirred at 85 ℃ for 72h. And cooling to room temperature, dropwise adding acetone into the reaction solution, performing suction filtration, washing a filter cake with acetone, and performing vacuum drying to obtain a compound Q4, wherein 125mg of a yellow solid is obtained, and the yield is 76%.
Compound Q4: 1 H NMR(400MHz,CD 3 OD)δ(ppm):9.01(d,J＝4.0Hz,8H),8.55(s,8H),8.45(d,J＝8.0Hz,8H),7.97(d,J＝8.0Hz,8H),7.80(d,J＝8.0Hz,4H),7.45-7.42(m,9H),7.34(d,J＝8.0Hz,8H),7.23(d,J＝4.0Hz,4H),5.99(s,8H).
example 4
8-hydroxypyrene-1, 3, 6-trisodium sulfonate (HPTS) is used as a fluorescent group, pyridine phenylboronate is used as a quencher, and a sugar recognition receptor form a two-component phenylboronic acid fluorescent probe system. Test subjects included D-Glucose (D-Glucose), D-galactose (D-galactose), D-fructose (D-fructose), D-mannose (D-mannose), D-xylose (D-xylose), D-ribose (D-ribose), D-arabinose (D-arabinosine), sucrose (sucrose), lactose (lactose), maltotriose (maltotriose), sialic acid (sialic acid).
(1) Preparing stock solution
Preparation of 8-hydroxypyrene-1, 3, 6-sodium trisulfonate (HPTS) stock solution: HPTS is accurately weighed and dissolved in distilled water to prepare mother liquor with the concentration of 2 x 10 < -3 > M, and the mother liquor is placed in a refrigerator at the temperature of minus 20 ℃ for standby.
Preparation of compound Q1-Q4 stock solutions: accurately weighing compounds Q1-Q4, respectively, dissolving in DMSO or methanol to obtain solutions with concentration of 20 × 10 -3 And (4) placing the mother liquor of M in a refrigerator at the temperature of-20 ℃ for later use.
Preparing sugar molecule stock solution: respectively weighing monosaccharide (D-glucose, D-galactose, D-fructose, D-mannose, D-xylose, D-ribose, and D-arabinose), and oligosaccharide (sucrose, lactose, and maltotriose), dissolving in purified water, making into 1M mother liquor, and placing in refrigerator at 4 deg.C for use.
Preparation of sialic acid stock solution: accurately weighing sialic acid, dissolving in purified water to obtain mother liquor with concentration of 0.2M, and placing in a refrigerator at 4 deg.C.
(2) Compound quenching ability test on HPTS
A1X 3 standard cuvette was used, the volume of the solution was 2mL, the excitation wavelength was 400nm, and the excitation and emission slit widths were 2.5 and 5.0nm, respectively. The test water was distilled water, the test solution was phosphate buffer solution (PBS, 10mM, pH 7.4), and compound Q1-Q4 solutions at concentrations of 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, and 100. Mu.M were added to HPTS solution at 20. Mu.M, and after incubation at room temperature for 30 seconds, fluorescence emission spectroscopy was performed with 400nm as an excitation wavelength.
The results of the fluorescence quenching effect of the compounds Q1 to Q4 as quenchers on the fluorescent dye HPTS are shown in FIGS. 1 to 2. As can be seen from the figure, compounds Q1-Q4 all partially or almost completely quench the fluorescence of HPTS. Because the compound has the property of aggregation-induced luminescence, after the addition amount of the compound reaches the quenching HPTS fluorescence, the compound is continuously added to generate the fluorescence induced by aggregation of the compound, wherein the quenching effect of the compound Q1 on the HPTS is weaker, and the HPTS fluorescence can not be completely quenched when the concentration of the compound Q1 is increased to 100 mM; as shown in FIG. 2, the best quenching effect was achieved by the compound Q2 series at a concentration of 20. Mu.M; the optimal quenching concentrations for compounds Q3 and Q4 were 15. Mu.M and 10. Mu.M, respectively.
(3) Test of sugar recognition ability by two-component phenylboronic acid fluorescent probe
A1X 3 standard cuvette was used, the volume of the solution was 2mL, the excitation wavelength was 400nm, and the excitation and emission slit widths were 2.5 and 5.0nm, respectively. The test water was distilled water, the test solution was phosphate buffer solution (PBS, 10mM, pH 7.4), various saccharide compound solutions (10 mM in concentration) were added to different solutions containing HPTS (4. Mu.M in concentration) and the compound Q2-4 (20. Mu.M in concentration), and after incubation at room temperature for 30 minutes, fluorescence emission spectroscopy was performed with 400nm as an excitation wavelength.
The selectivity results of two-component fluorescent probes with different phenylboronic acids for four monosaccharides (sialic acid, D-galactose, D-fructose, and D-glucose) are shown in FIG. 3. The phenylboronic acid pyridinium structure contains two phenylboronic acid two-component fluorescent probes (Q2 series and Q3) which have high selectivity on fructose, wherein the fluorescence enhancement multiples of Q2-1, Q2-2 and Q2-3 systems are respectively about 200 times, 600 times and 400 times, and the Q2-2 system is the phenylboronic acid two-component fluorescent probe system with the largest reported fluorescence enhancement multiple at present.
The selectivity results of the Q2-2 phenylboronic acid two-component fluorescent probe on various carbohydrate compounds, endogenous active small molecules and metal ions are shown in figures 4-5. As can be seen from FIG. 4, the probe Q2-2 has high selectivity to fructose, and FIG. 5 shows that other monosaccharides do not affect the selectivity of the Q2-2 two-component probe to fructose.
Example 5
Measurement of fructose concentration in sample
To a 5mL volumetric flask, 5. Mu.L of HPTS mother liquor and Q2-2 mother liquor were added, and 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50. Mu.L of D-fructose mother liquor was added, respectively, to achieve a constant volume with PBS (4. Mu.M final HPTS concentration, 20. Mu.M final Q2-2 concentration, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10mM final D-fructose concentration). And (3) uniformly mixing the solutions, incubating at room temperature for 30min, and performing fluorescence emission spectrum test by taking 400nm as an excitation wavelength. The fluorescence intensity at 520nm was plotted against the D-fructose concentration, and a standard curve equation Y = aX + b was obtained after fitting.
FIG. 6 is a fluorescence titration curve, from which it can be seen that the Q2-2 two-component probe system has a good linear relationship in the concentration range of fructose 1-7 mM, and can qualitatively and quantitatively detect the fructose concentration.
Adding a solution to be tested with unknown concentration into a mixed solution of the HPTS mother liquor and the Q2-2 mother liquor, carrying out constant volume, uniformly mixing, incubating at room temperature for 30min, and testing the fluorescence emission spectrum by taking 400nm as an excitation wavelength. Substituting the fluorescence intensity at 520nm as Y into the equation, and calculating to obtain the value X, namely the concentration of the D-fructose in the solution to be detected.

Claims (8)

1. A tetraphenyl ethylene borate pyridinium salt characterized by the following chemical structural formula:
Figure FDA0003868407500000011
wherein R' is H, OH or OCH 3 、
Figure FDA0003868407500000012
Figure FDA0003868407500000013
R is
Figure FDA0003868407500000014
Figure FDA0003868407500000015
X is Br, I, BF 4 Or PF 6 ；
The tetraphenyl vinyl borate pyridinium salt can be used as a fructose detection reagent.
2. The tetraphenyl ethylene borate pyridinium salt of claim 1 wherein R' is H and R is
Figure FDA0003868407500000016
X is Br.
3. The method of preparing tetraphenyl ethylene borate pyridinium salt of claim 1 comprising the steps of:
(a) Taking benzophenone substituted by substituent groups as a raw material, and carrying out Michaelis reaction under the action of titanium chloride and a reducing agent to obtain substituent group modified tetraphenylethylene; the substituent is hydroxyl, methoxy or bromine;
(b) Tetraphenyl ethylene modified by substituent groups and pyridine boric acid are subjected to metal coupling reaction to obtain tetraphenyl ethylene pyridine compounds;
(c) Carrying out nucleophilic substitution reaction on a tetraphenyl vinyl pyridine compound and bromomethyl phenylboronic acid to obtain tetraphenyl vinyl borate pyridinium;
the tetraphenyl ethylene borate pyridine salt is
Figure FDA0003868407500000021
Wherein R' is H, OH or OCH 3 、
Figure FDA0003868407500000022
Figure FDA0003868407500000023
Figure FDA0003868407500000024
R is
Figure FDA0003868407500000025
Figure FDA0003868407500000026
X is Br.
4. The method of producing a tetraphenyl vinyl borate pyridinium salt of claim 1 comprising the steps of:
(a) Taking benzophenone substituted by substituent groups as a raw material, and carrying out Michaelis reaction under the action of titanium chloride and a reducing agent to obtain substituent group modified tetraphenylethylene; the substituent is hydroxyl, methoxy or bromine;
(b) The tetraphenylethylene modified by the substituent group and pyridine boric acid are subjected to metal coupling reaction to obtain a tetraphenylethylene pyridine compound;
(c) Carrying out nucleophilic substitution reaction on a tetraphenyl vinyl pyridine compound and bromomethyl phenylboronic acid to obtain tetraphenyl vinyl borate bromopyridinium;
(d) Carrying out ion exchange reaction on tetraphenyl ethylene borate bromopyridinium and potassium iodide, potassium fluoborate or potassium hexafluorophosphate to obtain tetraphenyl ethylene borate iodopyridinium, tetraphenyl ethylene borate borofluoridate or tetraphenyl ethylene borate hexafluorophosphate pyridinium;
the tetraphenyl ethylene borate pyridine salt is
Figure FDA0003868407500000027
Wherein R' is H, OH or OCH 3 、
Figure FDA0003868407500000028
Figure FDA0003868407500000029
R is->
Figure FDA00038684075000000210
Figure FDA0003868407500000031
X is I, BF 4 Or PF 6 。
5. Use of the tetraphenyl vinyl borate pyridinium salt of claim 1 for the detection of fructose.
6. A method for detecting fructose is characterized in that a sample is mixed with a solution of 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt and the tetraphenyl vinyl borate pyridinium salt of claim 1, the fluorescence emission intensity of the sample is measured at a specific wavelength by taking 400nm as the wavelength of excitation light, and the fluorescence emission intensity is compared with a standard curve to obtain the concentration of the fructose in the sample.
7. The method for detecting fructose according to claim 6, wherein the specific wavelength is 520nm.
8. The method for detecting fructose according to claim 6, wherein the concentration of fructose in the sample is 1 to 7mM.
CN202010342626.6A 2020-04-27 2020-04-27 Tetraphenyl ethylene borate pyridine salt, preparation method and application thereof, and reagent and method for detecting fructose Active CN111423462B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010342626.6A CN111423462B (en) 2020-04-27 2020-04-27 Tetraphenyl ethylene borate pyridine salt, preparation method and application thereof, and reagent and method for detecting fructose

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010342626.6A CN111423462B (en) 2020-04-27 2020-04-27 Tetraphenyl ethylene borate pyridine salt, preparation method and application thereof, and reagent and method for detecting fructose

Publications (2)

Publication Number Publication Date
CN111423462A CN111423462A (en) 2020-07-17
CN111423462B true CN111423462B (en) 2023-03-31

Family

ID=71556947

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010342626.6A Active CN111423462B (en) 2020-04-27 2020-04-27 Tetraphenyl ethylene borate pyridine salt, preparation method and application thereof, and reagent and method for detecting fructose

Country Status (1)

Country Link
CN (1) CN111423462B (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6081152B2 (en) * 2012-06-08 2017-02-15 株式会社同仁化学研究所 Fluorescent compounds comprising tetraphenylethene derivatives
CN102887914B (en) * 2012-10-17 2015-04-08 华东理工大学 Coumarins compound containing aryl boric acid and application thereof in detection of sugar
CN108822084B (en) * 2018-08-14 2020-11-10 天津师范大学 Tetraphenyl ethylene bridged tetraphenylimidazole salt and preparation method and application thereof
CN110642882B (en) * 2019-10-21 2021-12-24 内蒙古大学 Fluorescent probe with hydrogen peroxide detection and photodynamic cancer cell killing activity as well as preparation method and application thereof

Also Published As

Publication number Publication date
CN111423462A (en) 2020-07-17

Similar Documents

Publication Publication Date Title
CN109678763B (en) Near-infrared biological thiol fluorescent probe and preparation method and application thereof
CN112939956B (en) Fluorescent probe for detecting mercury ions and hypochlorite ions as well as preparation method and application of fluorescent probe
CN106814057B (en) A kind of fluorescence probe, synthetic method and its application being used for Selective recognition ATP based on aggregation inducing fluorescence enhancement characteristic
CN106749364A (en) A kind of preparation and application of the fluorescent molecular probe for detecting hypochlorite ion
Tharmaraj et al. D-Glucose sensing by (E)-(4-((pyren-1-ylmethylene) amino) phenyl) boronic acid via a photoinduced electron transfer (PET) mechanism
Liu et al. Naphthalimide-based fluorescent photoinduced electron transfer sensors for saccharides
Wang et al. A diboronic acid fluorescent sensor for selective recognition of d-ribose via fluorescence quenching
US6534316B2 (en) Colorimetric and fluorimetric analysis of carbohydrates
CN111423462B (en) Tetraphenyl ethylene borate pyridine salt, preparation method and application thereof, and reagent and method for detecting fructose
CN107843578B (en) Fluorescent probe based on coumarin copper ion complex, preparation method and application of fluorescent probe in selective identification of pyrophosphate
CN111521593A (en) Rapid visual detection method based on water-soluble perylene bisimide derivative
CN109912512B (en) New telmisartan impurity compound and preparation method and application thereof
EP0561160A1 (en) Colorimetric methods and reagents for the assay of calcium in a test sample
CN108997401A (en) A kind of fluorescence probe and preparation method thereof for detecting lead ion
CN109608469B (en) Compound, preparation method thereof and method for detecting Ti3+In (1)
CN109320438B (en) Fluorescent probe for detecting cyanide and synthetic method and application thereof
US4711853A (en) Method of detecting potassium ions using trifluoromethyl-substituted chromogenic crown ethers
CN109942607B (en) Application of diboronic acid fluorescence sensor in ribose recognition
CN113666937A (en) Near-infrared fluorescent probe for detecting zinc ions and preparation method and application thereof
Li et al. A highly selective colorimetric fluorescence probe for Cu 2+ in aqueous media: the synthesis, DFT investigation and its application in living cells
US20070259444A1 (en) Chromoionophore and method of determining sodium ions
Tang et al. A turn-off xanthene-based fluorescent probe for detection of cysteine and its practical application in bioimaging and food samples
CN109721592A (en) A kind of fluorescence probe and its preparation method and application of the Aminopyrazine acyl hydrazone derivative containing cumarin
CN106699660B (en) A kind of Ho3+Detection reagent and its preparation method and application
Ma et al. A novel selective chemosensor for Mg 2+ detection based on quinoline-hydrazone-crown ether

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