KR20140098434A - Turn-on type fluorescent chemosensor including boronic acid binding to mercury ion selectively, preparation method thereof and detection method of mercury ion using the same - Google Patents
Turn-on type fluorescent chemosensor including boronic acid binding to mercury ion selectively, preparation method thereof and detection method of mercury ion using the same Download PDFInfo
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- KR20140098434A KR20140098434A KR1020130011077A KR20130011077A KR20140098434A KR 20140098434 A KR20140098434 A KR 20140098434A KR 1020130011077 A KR1020130011077 A KR 1020130011077A KR 20130011077 A KR20130011077 A KR 20130011077A KR 20140098434 A KR20140098434 A KR 20140098434A
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- mercury
- mercury ion
- compound
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- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000001514 detection method Methods 0.000 title claims abstract description 26
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title description 4
- 239000000126 substance Substances 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
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- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims description 126
- -1 5- (dimethylamino) naphthalene-1- Sulfonyl Chemical group 0.000 claims description 103
- 229910052753 mercury Inorganic materials 0.000 claims description 80
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 57
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000011347 resin Substances 0.000 claims description 20
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 17
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- 125000006242 amine protecting group Chemical group 0.000 claims description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 10
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000001584 benzyloxycarbonyl group Chemical group C(=O)(OCC1=CC=CC=C1)* 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005048 flame photometry Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000000926 neurological effect Effects 0.000 description 1
- 230000007135 neurotoxicity Effects 0.000 description 1
- 231100000228 neurotoxicity Toxicity 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- UYWQUFXKFGHYNT-UHFFFAOYSA-N phenylmethyl ester of formic acid Natural products O=COCC1=CC=CC=C1 UYWQUFXKFGHYNT-UHFFFAOYSA-N 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- 239000003440 toxic substance Substances 0.000 description 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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Abstract
Description
The ON (turn-on) type fluorescent sensitive chemical sensors, their preparation and mercury ions (Hg 2 +) detection method using the same - the invention is mercury ions (Hg 2 +) and turn optionally containing a boronic acid to be coupled .
Mercury (Hg 2 + ) is the third most commonly found list of the Agency for Toxic Substances and Disease Registry (ATSDR) and is the second most common toxic heavy metal. Mercury contamination is widespread and arises from a variety of natural causes. Once introduced into the marine environment, bacteria convert inorganic mercury ions (Hg 2 + ) to methylmercury. In 1956 in Minamata City, Japan, methylmercury occurred collectively in residents who ate seafood containing methylmercury. Methylmercury, due to its neurotoxicity, can easily pass through membranes in living organisms due to its lipophilic nature. Not only absorbed but also accumulate for a long time and act as a source of mercury associated with irreversible neurological damage. Accordingly, there is a growing interest in methods for selectively detecting mercury ions (Hg 2 + ) in the fields of chemistry, biotechnology, and environmental engineering.
Conventionally, analytical methods such as atomic absorption spectrometry (AAS), ion selective electrodes (ISE) and flame photometry have been used for quantitative analysis of such metal cations. However, these methods have a disadvantage in that they are expensive, require a large number of samples, and can not be continuously monitored. On the other hand, fluorescence sensors are simple to measure, have high selectivity, high sensitivity, and fast response time, so that many fluorescence sensors have been developed that detect the photophysical changes occurring in metal-cation complexes.
Recently, the use of chemidosimeters as a chemical sensor that utilizes a specific irreversible chemical reaction between target molecules and dosimetric molecules that induce fluorescence changes in the receptor has received much attention have. The use of simple, high-sensitivity and irreversible and selective reactions induced by the desired analytes is also receiving attention, and the accumulated effect is directly related to the concentration of the analyte.
Conventionally, detection techniques using chemomotimeters have been used to detect the desulfurization reaction of thioamidic derivatives or thioacetyl groups induced by mercury ions (Hg 2 + ) by chemical sensitization sensors, desulfurization with mercury ions A mercury-based chemometric meter using a reaction has been developed (Patent Document 1).
However, since the developed chemomotometer has a low water-solubility, poor response time and sensitivity, it is not suitable for industrial application. Therefore, in order to be applicable to biological and environmental engineering processes, Development of a chemometric meter capable of selectively detecting mercury ions (Hg < 2 + & gt ; ) even when other metal cations are mixed is desired.
On the other hand, boronic acid is known to have high affinity for substances containing adjacent diol groups and has been used as a fluorescent chemical sensor for carbohydrates (Patent Document 2). In addition, stilbene boronic acid has been utilized as a cofactor in antibody-based sensors for monitoring mercury ions (Hg 2+ ) (Non-Patent Document 1).
Accordingly, the inventors of the present invention have been studying a chemometric meter that selectively detects mercury ions (Hg 2 + ) among metal ions, and found that a compound containing a boronic acid that selectively binds to mercury ions (Hg 2 + ), under Fig mercury ions (Hg 2 +) Alternatively, as well as sensitive, acid there mercury ions contained in the fluorescent chemical sensor (Hg 2 +) is ion mercury to form a covalent bond irreversibly (Hg 2 +) only for The present inventors confirmed that they were removed at the same time as the detection and completed the present invention.
It is an object of the present invention to provide a turn-on type fluorescent sensitized chemical sensor for selectively detecting mercury ions (Hg 2 + ).
Another object of the present invention is to provide a method of manufacturing a turn-on type fluorescent sensitized chemical sensor.
It is still another object of the present invention to provide a mercury ion (Hg 2 + ) detection method using the turn-on type fluorescent chemical sensor.
In order to achieve the above object,
The present invention provides a turn-on type fluorescent sensitized chemical sensor comprising a boronic acid selectively bonded to a mercury ion (Hg 2 + ) represented by the following formula (1).
[Chemical Formula 1]
(Wherein R, Q, W, Z 1 , Z 2 , l, m And n are as defined herein.
Also, as shown in the following
Introducing an amino acid represented by the general formula (2) wherein the terminal amine group is protected with a protecting group into the solid compound represented by the general formula (3) (step 1);
The step (2) of preparing a compound represented by the formula (5) wherein the terminal amine protecting group represented by X is deprotected by performing a deprotection reaction of the compound represented by the formula (4) prepared in the
Performing coupling reaction between the compound of Formula 5 and the compound of Formula 6 prepared in
(Step 4) of preparing a compound represented by the formula (8) wherein the terminal amine protecting group represented by Y is deprotected by performing the deprotection reaction of the compound represented by the formula (7) prepared in the
(Step 5); coupling the compound of Formula 8 and the compound of Formula 9 to the compound of Formula 10; And
(Hg < 2 + & gt ; ) selective turn-on type fluorescent sensitized chemical sensor comprising a step of removing the solid phase of the compound represented by the formula (10) prepared in the step 5 and removing the compound represented by the formula Lt; RTI ID = 0.0 > of:
[Reaction Scheme 1]
(Wherein R, Q, W, Z 1 , Z 2 , D, X, Y,
Furthermore, the present invention mercury ions (Hg 2 +) selectively turns for detecting the of the formula 1-step (step of input on the target sample to determine the turn-on fluorescent light-sensitive chemical sensor with a mercury ion (Hg 2 +) or without One); And
The mercury ion (Hg 2 + ) is selectively detected by measuring the fluorescence signal generated by the reaction product obtained through the covalent bond between the mercury ion (Hg 2 + ) present in the target sample of the
The mercury ion fluorescence detection sensor according to the present invention selectively emits fluorescence by binding to a mercury ion (Hg 2 + ) in a mixed solution of an aqueous solution of 100% aqueous solution and an organic solution in the presence of other metal ions, (Hg 2 + ) is easily detected by the turn-on effect in which the intensity of fluorescence increases as the concentration of H 2 + is increased. In addition, since an irreversible covalent bond is formed through a metal exchange reaction between a boronic acid and a mercury ion of a chemical sensor, and there is an environment-friendly effect of separating a chemical sensor from an analyte and simultaneously removing mercury ions, , Aquatic environments such as rivers, and biological samples.
1 is an ESI-MS spectrum of the compound-mercury ion (Hg 2 + ) complex prepared in Example 1 according to the present invention.
2 is an ESI-MS spectrum of the compound-mercury ion (Hg 2 + ) complex prepared in Example 2 according to the present invention.
3 is a fluorescence spectrum showing fluorescence change of the compound-metal ion complex prepared in Example 1 according to the type of transition metal ion.
4 is a fluorescence spectrum showing the change in fluorescence of the compound-mercury ion (Hg 2 + ) complex prepared in Example 1 in the presence of other transition metal ions.
FIG. 5 is a photograph of the fluorescence change of the compound-metal ion complex prepared in Example 1 according to the type of transition metal ion under an ultraviolet lamp.
6 is a fluorescence spectrum showing fluorescence change of the compound-metal ion complex prepared in Example 2 according to the type of transition metal ion.
FIG. 7 is a fluorescence spectrum showing the change in fluorescence of the compound-mercury ion (Hg 2 + ) complex prepared in Example 2 in the presence of other transition metal ions.
FIG. 8 is a photograph of the fluorescence change of the compound-metal ion complex prepared in Example 2 according to the type of transition metal ion under an ultraviolet lamp. FIG.
FIG. 9 is a fluorescence spectrum showing the change in fluorescence of the compound-mercury ion (Hg 2 + ) complex prepared in Example 1 according to mercury ion (Hg 2 + ) concentration.
10 is a fluorescence spectrum showing the change in fluorescence of the compound-mercury ion (Hg 2 + ) complex prepared in Example 2 according to mercury ion (Hg 2 + ) concentration.
FIG. 11 is a fluorescence spectrum showing the fluorescence change of the compound-mercury ion (Hg 2 + ) complex prepared in Example 3 according to mercury ion (Hg 2 + ) concentration.
FIG. 12 is a fluorescence spectrum showing the fluorescence change over time of the compound-mercury ion (Hg 2 + ) complex prepared in Example 1 according to mercury ion (Hg 2 + ) concentration.
Hereinafter, the present invention will be described in detail.
The present invention provides a turn-on type fluorescent sensitized chemical sensor comprising a boronic acid that selectively binds to a mercury ion (Hg 2 + ) represented by the following formula (1): < EMI ID =
In Formula 1,
R is -NR 1 R 2 or -OR 1 ;
R 1 and R 2 are independently hydrogen or
Q and W are unsubstituted or substituted by halogen; C1-C4 alkyl substituted with halogen; Hydroxy; C1-C4 alkyloxy; Amine; Or a C6-C12 aryl boronic acid substituted with a nitro group; (Dimethylamino) naphthalene-1-sulfonyl (dansyl), 5- (dimethylamino) naphthalene-1-sulfonyl, , Fluorescein, boron-dipyramethenyl (BODIPY), boron-dipyrromethenyl, tetramethylrhodamine, Alexa, cyanine,
Z 1 and Z 2 are hydrogen or oxygen (O);
L and m are integers from 0 to 3; And
n is an integer of 1 to 6;
Preferably,
Wherein R is -NR 1 R 2 or -OR 1 ;
R 1 and R 2 are independently hydrogen, methyl, ethyl, propyl or butyl;
Q and W are unsubstituted or substituted by halogen; C1-C4 alkyl substituted with halogen; Hydroxy; C1-C4 alkyloxy; Amine; Or C6-C12 aryl boronic acid substituted with a nitro group, or any one selected from the group consisting of 7-hydroxycoumarin-methyl, 7-hydroxycoumarin-ethyl, 5- (dimethylamino) naphthalene- Sulfonyl (dansyl, 5- (dimethylamino) naphthalene-1-sulfonyl), fluorescein, boron-dipyramethane (BODIPY, boron-dipyrromethene), tetramethylrhodamine Tetramethylrhodamine, Alexa, Cyanine, allopicocyanine, rhodamine, 4 ', 6-diamidino-2-phenylindole (DAPI), 4', 6 -diamidino-2-phenylindole, Texas Red, and Texas blue, wherein Q and W are each selected from a different group;
Z 1 and Z 2 are hydrogen or oxygen (O);
L and m are integers from 0 to 1; And
n is an integer of 1 to 4;
Most preferably, the turn-on type fluorescent sensitized chemical sensor represented by
(1) 4- (1-amino-3- (5-dimethylamino) naphthylene-1-sulfonamido) -1-oxopropane-2-ylcarbamoyl) phenylboronic acid;
(2) 4- (1-Amino-5- (5- (dimethylamino) naphthylene-1-sulfonamido) -1-oxopentan-2-ylcarbamoyl) phenylboronic acid;
(3) 4- (1-Amino-6- (5-dimethylamino) naphthalene-1-sulfonamido) -1-oxohexan-2-ylcarbamoyl) phenylboronic acid;
(4) Synthesis of 4- (1-amino-5- (2- (7-hydroxy-2-oxo-2H- Phenylboronic acid;
(5) 4 - ((1-Amino-3- (5- (dimethylamino) naphthalene-1-sulfonamido) -1-oxopropan-2-ylamino) methyl) phenylboronic acid;
(6) 4- (1-Amino-4- (5- (dimethylamino) naphthalene-1-sulfonamido) -1-oxobutan-2-ylcarbamoyl) phenylboronic acid;
(7) 4 - ((3-Amino-2- (5- (dimethylamino) naphthalene-1-sulfonamido) -3-oxopropylamino) methyl) phenylboronic acid; And
(8) 4 - ((4-Amino-3- (5- (dimethylamino) naphthalene-1-sulfonamido) -4-oxobutylamino) methyl) phenylboronic acid.
Also, as shown in the following
Introducing an amino acid represented by the general formula (2) wherein the terminal amine group is protected with a protecting group into the solid compound represented by the general formula (3) (step 1);
The step (2) of preparing a compound represented by the formula (5) wherein the terminal amine protecting group represented by X is deprotected by performing a deprotection reaction of the compound represented by the formula (4) prepared in the
Performing coupling reaction between the compound of Formula 5 and the compound of
(Step 4) of preparing a compound represented by the formula (8) wherein the terminal amine protecting group represented by Y is deprotected by performing the deprotection reaction of the compound represented by the formula (7) prepared in the
(Step 5); coupling the compound of
(Hg < 2 + & gt ; ) selective turn-on type fluorescent sensitized chemical sensor comprising a step of removing the solid phase of the compound represented by the formula (10) prepared in the step 5 and removing the compound represented by the formula : ≪
[Reaction Scheme 1]
(In the
Wherein R, Q, W, Z 1 , Z 2 , l, m And n is as defined in
D is hydrogen or hydroxy;
X and Y are amine protecting groups, wherein X and Y are different from each other; And
Hereinafter, a method for manufacturing the mercury-ion (Hg 2 + ) selective, turn-on type fluorescent sensitized chemical sensor will be described in detail.
At this time, the amino acid represented by the general formula (2) of the
The protecting groups X and Y for protecting the terminal amine group of the amino acid represented by the
Examples of the protecting group that can be used for protecting the terminal amine group in the above formula (2) include t-butoxycarbonyl (Boc), 9H-fluoren-9-ylmethoxycarbonyl (Fmoc), trityl, benzyl, Benzyloxycarbonyl, p-methoxybenzyloxycarbonyl, formyl, trifluoroacetyl, p-toluenesulfonyl, benzenesulfonyl, methanesulfonyl, p-nitrobenzyloxycarbonyl, 2,2,2- Trichloroethoxycarbonyl, allyloxycarbonyl (Alloc), and the like can be used. Preferably, 9H-fluoren-9-ylmethoxycarbonyl (Fmoc) and allyloxycarbonyl (Alloc) can be used, but are not limited thereto.
Further, in the
Coupling agents usable for the coupling reaction of
The organic solvent usable in
Next, the
At this time, deprotonation conditions of
Next, the
When the reductive amination reaction is carried out in the coupling reaction of
As the solvent usable in the reductive amination reaction, dichloroethane (DCE), tetrahydrofuran (THF), methanol, isopropanol or dimethylformamide (DMF) which does not adversely affect the reaction can be used.
In the coupling reaction of
Next, the
At this time, the deprotonation condition of
Next, step 5 according to the present invention is a step of performing a coupling reaction between the compound of formula (8) and the compound of formula (9) to prepare the compound of formula (10). More specifically, when D of the compound represented by the formula (9) is hydrogen, the compound of the formula (8) prepared in the
At this time, the coupling reaction of Step 5 according to the present invention can be carried out under the same conditions as in
Next,
At this time, the organic solvent which can be used for the reaction to remove the solid phase in the
Further, the present invention relates to a method of detecting the presence or absence of mercury ions (Hg 2 + ) in a turn-on type fluorescent sensitized chemical sensor for selectively detecting mercury ions (Hg 2 + ) represented by the following formula Into a target sample (step 1); And
The mercury ion (Hg 2 + ) is selectively detected by measuring the fluorescence signal generated by the reaction product obtained through the covalent bond between the mercury ion (Hg 2 + ) present in the target sample of the
[Chemical Formula 1]
Wherein R 1 , R 2 , R 3 and n are the same as defined in the above formula (1).
Hereinafter, the mercury ion (Hg 2 + ) detection method will be described in detail for each step.
First, the
At this time, the target sample in
Referring to the results of the experiment for confirming the formation of a complex between the compound of
Therefore, the fluorescent-sensitive chemical sensor according to the present invention has a high solubility in water and is excellent in the binding property between the compound of formula (I) and mercury ion (Hg 2 + ) according to the present invention in an aqueous solution containing an aqueous solution or an organic solution Therefore, it is easy to detect mercury ions (Hg 2 + ) in an aqueous solution or an aqueous solution containing an organic solution.
The organic solution contained in the aqueous solution is preferably dimethylformamide, acetonitrile, methanol, ethanol or the like, but is not limited thereto.
By yirum mercury ions (Hg 2 +) a case of mixing the organic solvent in an aqueous solution merchant target sample to be measured, methanol, ethanol, dimethylformamide, or an organic solvent such as acetonitrile, are daily single high solubility in water, The mercury ion (Hg 2 + ) can be detected accurately without changing the fluorescence detection sensitivity.
Next, in the
The mercury detection method according to the invention are mercury ions (Hg 2 +) optional, mercury ions present in the target sample with respect to the (Hg 2 +) and the fluorescence increase (turn-on via a covalent bond between the compound of formula (I) ) To detect mercury ions (Hg < 2 + & gt ; ) irreversibly.
Referring to the results of confirming the detection of fluorescence increase through complex formation with mercury ion (Hg 2 + ) selectivity and mercury ion (Hg 2 + ) of the compound represented by formula (1) according to the present invention, (Hg < 2 + & gt ; ) with a transition metal ion of group I and group II other than mercury ion (Hg < 2 + & gt ; (Experimental Example 2, Figs. 3 to 8). In addition, the compound represented by the formula (1) according to the present invention is fluorescently emitted by boron acid which is quenching the phosphor contained in the compound and is removed by metal exchange with mercury ion (Hg 2 + ). As a result, There is a turn-on effect (see Experimental Example 3 and Figs. 9 to 11) in which the intensity of the fluorescence is increased. In addition, an irreversible (irreversible) of the present invention the formula compounds represented by one of the mercury ion (Hg 2 +) and mercury ions by the metal exchange reaction of a boronic acid in the compound (Hg 2 +) and fluorescence-sensitive chemical sensor The covalent bond is formed, whereby mercury ions (Hg 2 + ) are removed from the analyte simultaneously with detection (see Experimental Example 1, FIGS. 1 and 2). Accordingly, the compound of formula (I) according to the present invention has high selectivity to react with mercury ions (Hg 2 + ) in the presence of other transition metal ions to form a complex with a high binding force. When mercury ions (Hg 2 + ) are detected, The fluorescence detection problem due to the fluorescence interferences of the mercury ions (Hg < 2 + & gt ; ) can be minimized.
Hereinafter, the present invention will be described in detail with reference to Examples and Experimental Examples.
However, the following Examples and Experimental Examples are merely illustrative of the present invention, and the present invention is not limited to the following Examples and Experimental Examples.
< Example 1> 4- (1-Amino-5- (5- ( Dimethylamino ) Naphthylene -One- Sulfonamido )-One- Oxopentane -2- Il carbamoyl ) Phenylboronic acid Produce
Step 1: Preparation of allyl 4 - ((9H-fluoren-9-yl) methylcarbamate) -5-amino-5-oxopentylcarbamate methylbenzohydrate amine resin
First, the link amide methylbenzohydriramine (MBHA) resin (200 mg, 0.1 mmol) was added to a solution of dimethylformamide (3 ml) and then swelled for about 10 minutes. To the swollen resin, 20% piperidine / dimethylformamide mixed solution (3 ml) was added and the mixture was stirred for 15 minutes. After removing the Fmoc protecting group at the terminal of the amino group, the remaining piperidine solution was dissolved in dimethyl The resin was washed three times with formamide solution and methanol solution, respectively. Then, Fmoc-L-ornithine (Alloc) -OH (105.9 mg, 0.3 mmol), diisopropylcarbodiimide (DIC, 47 μl, 0.1 mmol) and hydroxybenzoate Triazole (HOBt, 40 mg, 0.3 mmol) was added and the reaction was preactivated for 15 minutes and then added to a solution of resin in dimethylformamide (1.5 ml) and the reaction was stirred for about 4 hours. After the reaction, the reaction solution was filtered, and the filtered resin was washed several times with dimethylformamide and methanol to obtain the target compound.
Step 2: 4- (5- Allyloxycarbonylamino ) -1-amino-1- Oxopentane -2- Il carbamoyl ) Phenylboronic acid Methylbenzohydrile amine Manufacture of resin
To the dimethylformamide solution in which 4- (4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl) benzoic acid (74.5 mg, (DIC, 47 [mu] l, 0.1 mmol) and hydroxybenzotriazole (HOBt, 40 mg, 0.3 mmol) were added and allowed to react for 15 min. Then, 20% piperidine / dimethylformamide mixed solution (3 ml) was added to the resin prepared in
Step 3: 4- (1-Amino-5- (5- ( Dimethylamino ) Naphthylene -One- Sulfonamido )-One- Oxopentane -2 days Carbamo Work) Phenylboronic acid Methylbenzohydrile amine Manufacture of resin
Tetrakis (triphenylphosphine) of 1.1 equivalent to a resin prepared in
Step 4: 4- (1-Amino-5- (5- ( Dimethylamino ) Naphthylene -One- Sulfonamido )-One- Oxopentane -2- Il carbamoyl ) Phenylboronic acid Produce
About 10 mL of trifluoroacetic acid containing water at a volume ratio of 5% was added to the resin prepared in
1 H NMR (400 MHz, DMSO -d 6: δ 8.42 (d, J = 8.4 Hz, 1H), 8.30 (d, J = 8.4 Hz, 1H), 8.22 (d, J = 7.3 Hz, 1H), 7.88 J = 8.0 Hz, 1H), 7.31 (br s, 1H), 7.27 (d, J = 2H), 1.74-1.66 (m, 1H), 1.62 (m, 2H), 2.83 (s, 1.59 (m, 1 H), 1.44 - 1.42 (m, 2 H);
13 C NMR (100 MHz, DMSO -d 6): [delta] 173.6, 166.3, 136.0, 135.3, 133.7, 128.9, 128.8, 128.1, 127.7, 126.3, 119.5, 115.3, 52.6, 45.1, 42.1, 28.8, 26.2.
< Example 2 > 4- (1-Amino-3- (5- Dimethylamino ) Naphthylene -One- Sulfonamido ) -1-oxopropane-2- Il carbamoyl ) Phenylboronic acid Produce
L-Dap (Alloc) -OH (Fmoc-L-Diaminopropanoic acid (Alloc) -OH) was used instead of Fmoc-L-ornithine (Alloc) -OH in
1 H NMR (400 MHz, DMSO -d 6): δ 8.43 (d, J = 8.8 Hz, 1H), 8.27 (d, J = 8.8 Hz, 1H), 8.21 (d, J = 8.0 Hz, 1H), (D, J = 7.6 Hz, 2H), 7.83 (d, J = 7.6 Hz, 2H), 7.74 (d, J = 7.2 Hz, 1H), 7.14 (brs, 1H), 4.44-4.42 (m, 1H), 3.21-3.20 , ≪ / RTI > 2H), 2.8 (s, 6H);
13 C NMR (50 MHz, DMSO -d 6): δ 171.33, 166.36, 158.15, 150.77, 135.86, 135.16, 133.78, 128.36, 128.99, 128.93, 128.22, 127.87, 126.35, 123.70, 119.36, 115.33, 53.51, 45.13, 43.89.
< Example 3> 4- (1-Amino-6- (5- Dimethylamino ) Naphthalene-1- Sulfonamido ) -1-oxohexane-2- Il carbamoyl ) Phenylboronic acid Produce
L-lys (Alloc) -OH (Fmoc-L-Diaminobutanoic acid (Alloc) -OH) was used instead of Fmoc-L-ornithine (Alloc) -OH in the
1 H NMR (400 MHz, DMSO -d 6): δ 8.41 (d, J = 8.4 Hz, 1H), 8.28 (d, J = 8.4 Hz, 1H), 8.22 (d, J = 7.6 Hz, 1H), (D, J = 8.0 Hz, 2H), 7.88-7.83 (m, 4H), 7.78 2H), 7.30 (d, J = 7.6 Hz, 1H), 6.97 (br s, 1H), 3.31-3.24 (m, , 1.36-1.32 (m, 2H), 1.21 (s, 12H), 0.98-0.91 (m, 3H).
< Example 4> 4- (1-Amino-5- (2- (7- Hydroxy -2-oxo-2H- Kromen -4- Acetate Amido) -1- Oxopentane -2- Il carbamoyl ) Phenylboronic acid Produce
L-lys (Alloc) -OH (Fmoc-L-Diaminobutanoic acid (Alloc) -OH) was used instead of Fmoc-L-ornithine (Alloc) -OH in
1 H NMR (400 MHz, DMSO -d 6): δ 8.21 (d, J = 8.4 Hz, 1H), 7.98 (d, 2H), 7.74 (d, 1H), 7.14 (d, 1H), 6.88 (s 2H), 1.43-1. 51 (m, 2H), 1.43-1.41 (m, 2H), 2.82 (s, ).
< Experimental Example 1> Fluorescence Sensitive Chemical Sensor - Mercury Ion ( Hg 2 + ) Preparation of complex
In order to analyze the binding state and the state of mercury ions (Hg 2 + ) in the aqueous solution of the compound represented by the formula (1) according to the present invention, the following experiment was conducted.
The compound of
First, as shown in FIG. 1, the high performance liquid chromatography of the compound prepared in Example 1 according to the present invention shows that the
Next, as shown in FIG. 2, a value of 677.02 m / e was observed in the ESI-MS spectrum of the compound prepared in Example 2 according to the present invention. At this time, 677.02 m / e is a value in a state where the compound prepared in Example 2 is combined with a mercuric chloride ion ((HgCl) + ) derived from a perchlorate (ClO 4 - ) salt. From this, it can be seen that the compound represented by the formula (1) according to the present invention is excellent in the binding property with mercury ions (Hg 2 + ) in an aqueous solution and can form a stable complex. Further, FIG compound and mercury ion represented by the general formula (1) according to the present invention, as in 1 (Hg 2 +) metal exchange of the reversible (reversible) interaction (interaction) the acid there mercury ions (Hg 2 +) and not And forms an irreversible covalent bond through transmetallation.
Thus, the mercury ions (Hg 2 +) compound represented by the formula (1) fluorescent-sensitive chemical sensor according to the invention the binding of the mercury ion (Hg 2 +) in an aqueous solution excellent, and mercury ions (Hg 2 +) and (Hg 2 + ) can be removed simultaneously with the detection of mercury ions (Hg 2 + ) by forming an irreversible covalent bond. Therefore, in a general industrial field requiring detection of mercury ions (Hg 2 + ) such as groundwater and aquatic environments Can be usefully used.
< Experimental Example 2> Evaluation of Metal Ion Selectivity of Fluorescence Sensitive Chemical Sensor
The following experiment was conducted to evaluate the mercury ion (Hg 2 + ) selectivity of the compound represented by
In order to evaluate the mercury ion (Hg 2 + ) selectivity of the compound represented by the formula (1) according to the present invention, the transition metal ions of group I and group II were tested. Transition metal ions of the Ⅰ group and Ⅱ group used in the experiment, the ion (Ag +), aluminum ion (Al 3 +), calcium ions (Ca 2 +), cadmium ion (Cd 2 +), cobalt ion (Co 3 +), chromium ion (Cr 3 +), copper ion (Cu 2 +), potassium ion (K +), mercury ions (Hg 2 +), magnesium ions (Mg 2 +), manganese ion (Mn 2 +), Sodium ion (Na + ), nickel ion (Ni 2 + ), zinc ion (Zn 2 + ) and lead ion (Pb 2 + ). Perchlorate (ClO 4 - ) salts of the transition metal ions of Group I and Group II were dissolved in distilled water to prepare 10 mM solutions of Group I and Group II transition metal ions, respectively, and each of Groups I and II 10 mM Group I and II transition metal ion - mercury (Hg 2 + ) reference solutions containing both transition metal ions and mercury ions (Hg 2 + ) were also prepared.
1 mM HEPES buffer solution - Acetonitrile (AcCN) (2:98 (v / v), pH 7.4, 1 ml) was added to the test tube, and then 1 mM solution of the fluorescent sensitized chemical sensor reagent prepared in Experimental Example 1 Was added and 2 μl each of the Group I and Group II metals and transition metal based solutions prepared above, or the transition metal ion-mercury ion (Hg 2 + ) standard solutions of Group I and Group II were added. Then, distilled water was added so that the total amount of the solution became 2 ml, so that the concentration of the sensor was 10 μM, the concentration of the metal was 10 μM, and the concentration of the HEPES buffer-acetonitrile (AcCN) was 10 mM in the test solution. The test solution was prepared by mixing the above solutions. A part of the prepared test solution (1 ml) had an excitation wavelength of 330 nm and a fluorescence spectrum was measured by controlling the widths of the excitation slit and the emission slit to 10 nm and 5 nm, respectively , And the remaining part (1 ml) was observed for fluorescence under ultraviolet lamp. The results are shown in Figs. 3 to 8. Fig.
As shown in FIG. 3 to FIG. 5, the compound prepared in Example 1 according to the present invention was measured for fluorescence spectrum of a test solution containing a transition metal ion of Group I and Group II, Hg < 2 + & gt ; ). Further, the fluorescence of the compound prepared in Example 1 shifted to about 35 nm in short wavelength region by binding with mercury ion (Hg 2 + ), and the intensity thereof was also 480 nm compared with that before binding with mercury ion (Hg 2 + ) Which is about 9 times as high as the standard. It was also confirmed that the change in fluorescence under an ultraviolet lamp also caused fluorescence only to mercury ions (Hg 2 + ) (see FIGS. 3 and 5). Furthermore, Ⅰ group and Ⅱ group of transition metal ions and mercury ions (Hg 2 +) a transition metal of Ⅰ group and Ⅱ group comprising with the ion - For test solution using a mercury ion (Hg 2 +) reference solution, mix is done in other ⅰ group and ⅱ group optionally ionic mercury (Hg + 2) and the complex without the influence of transition metal ions (Hg + 2) has been confirmed to cause the change in fluorescence (see FIG. 4). From this, it can be seen that the compound of Example 1 according to the present invention forms a complex with mercury ions (Hg 2 + ) even when other Group I and Group II transition metal ions are present in the sample, thereby causing fluorescence change .
Next, as shown in FIG. 6 to FIG. 8, the test solutions prepared by mixing the Group I and Group II transition metal ions of the compound prepared in Example 2 according to the present invention were subjected to fluorescence spectroscopy. As a result, (Hg < 2 + & gt ; ). In addition, carried out by combination with fluorescence mercury ions (Hg 2 +) of the compound from Example 2, a short-wavelength region has moved from about 40 nm, the intensity also, approximately 12, compared before combining and mercury ions (Hg 2 +) Times higher than that of the previous study. It was also confirmed that the change in fluorescence under an ultraviolet lamp also caused fluorescence only to mercury ions (Hg 2 + ) (see FIGS. 6 and 8). Furthermore, Ⅰ group and Ⅱ group of transition metal ions and mercury ions (Hg 2 +) a transition metal of Ⅰ group and Ⅱ group comprising with the ion - For test solution using a mercury ion (Hg 2 +) reference solution, mix is done in other ⅰ group and ⅱ group optionally ionic mercury (Hg + 2) and the complex without the influence of transition metal ions (Hg + 2) has been confirmed to cause the change in fluorescence (see Fig. 7). From this, it can be seen that the compound of Example 2 according to the present invention forms a complex with mercury ions (Hg 2 + ) even when other Group I and Group II transition metal ions are present in the sample, .
Therefore, the compound represented by
< Experimental Example 3> mercury ion of fluorescent sensitive chemical sensor ( Hg 2 + ) Depending on concentration Detection power evaluation
In order to evaluate the detection ability of the compound represented by the formula (1) according to the present invention according to the mercury ion (Hg 2 + ) concentration, the following experiment was conducted.
Perchlorate (ClO 4 - ) salt of mercury ion (Hg 2 + ) was dissolved in distilled water to prepare a 1 mM reference solution. After adding 10 mM HEPES buffer solution - Acetonitrile (AcCN) (0.5: 99.5 (v / v), pH 7.4, 1 ml) to the test tube, the fluorescence of Example 1 and Example 2 0.2 equivalents, 0.4 equivalents, 0.6 equivalents, 0.8 equivalents, and 0.1 equivalents, respectively, of the compound of Chemical Formula (1), which is a fluorescent sensitized chemical sensor present in the mixed solution, A test solution was prepared by adding a mercury ion (Hg < 2 + & gt ; ) standard solution to each reaction solution so as to have 1.0 equivalents, 1.2 equivalents, 1.6 equivalents and 2.0 equivalents. Also, the fluorescent sensitized chemical sensor reagent prepared in Example 3 was prepared in the same manner as in Experimental Example 1, and a test solution was prepared in the same manner as described above. The fluorescence spectra of the test solutions were measured under the same conditions as in Experimental Example 2, and the fluorescence intensities of the fluorescent sensitometric sensors prepared in Example 1 were observed with time. The results are shown in FIG. 9 to FIG.
9 to 11, the fluorescence spectrum according to the mercury ion (Hg 2 + ) concentration indicates that the mercury ion (Hg 2 + ) is 0 for the compound of the formula (1), which is a fluorescent sensitized chemical sensor present in the test solution, The fluorescence wavelength is shifted to a short wavelength as the equivalent to 2 equivalents, and the intensity of fluorescence gradually increases. In addition, the fluorescence spectral changes of the compounds prepared in Examples 1 to 3 were found to be saturated at mercury ion (Hg 2 + ) concentration of at least 1 equivalent. From this, the compound represented by the formula (I) according to the invention and emit fluorescence by being acid boron to quenching (quenching) to the phosphor contained in the compound removed by metal exchange with mercury ions (Hg 2 +), which due to the mercury concentration (Hg 2 + ) is higher than that of mercury ions (Hg 2 + ) and that of boron ions (Hg 2 + ) is higher than that of
Next, as shown in FIG. 12, the compound prepared in Example 1 according to the present invention showed an increase in fluorescence intensity over time, and in particular, the concentration of mercury ions (Hg 2 + ) was increased The increase rate of the fluorescence intensity was found to be fast. When the mercury ion (Hg 2 + ) was not added to the compound prepared in Example 1 according to the present invention, the change in fluorescence intensity was not observed even after 2 hours. In addition, when 1 equivalent of mercury ion (Hg 2 + ) was used, it took about 100 minutes to complete the increase of fluorescence intensity, and it took about 30 minutes to use 1.5 equivalents. From this, the compound of formula (I) according to the invention are mercury ions (Hg 2 +) selective, as well as can be seen, the mercury ions (Hg 2 +), if more than 1.5 equivalents of use compared to the reaction rate remarkably improved to only the The detection time can be shortened.
Therefore, the compound represented by
Claims (10)
[Chemical Formula 1]
(In the formula 1,
R is -NR 1 R 2 or -OR 1 ;
R 1 and R 2 are independently hydrogen or C 1 to C 6 straight or branched chain alkyl;
Q and W are unsubstituted or substituted by halogen; C1-C4 alkyl substituted with halogen; Hydroxy; C1-C4 alkyloxy; Amine; Or a C6-C12 aryl boronic acid substituted with a nitro group, or a group selected from the group consisting of a C1-C6 alkyl substituted with hydroxy, a 5- (dimethylamino) naphthalene-1- Sulfonyl (dansyl, 5- (dimethylamino) naphthalene-1-sulfonyl), fluorescein, boron-dipyramethenyl (BODIPY), boron-dipyrromethenyl, tetramethylrhodamine Tetramethylrhodamine, Alexa, Cyanine, allopicocyanine, rhodamine, 4 ', 6-diamidino-2-phenylindole (DAPI), 4', 6 -diamidino-2-phenylindole, Texas Red, and Texas blue, wherein Q and W are each selected from a different group;
Z 1 and Z 2 are hydrogen or oxygen (O);
L and m are integers from 0 to 3; And
and n is an integer of 1 to 6).
R is -NR 1 R 2 or -OR 1 ;
R 1 and R 2 are independently hydrogen, methyl, ethyl, propyl or butyl;
Q and W are unsubstituted or substituted by halogen; C1-C4 alkyl substituted with halogen; Hydroxy; C1-C4 alkyloxy; Amine; Or C6-C12 aryl boronic acid substituted with a nitro group, or any one selected from the group consisting of 7-hydroxycoumarin-methyl, 7-hydroxycoumarin-ethyl, 5- (dimethylamino) naphthalene- Sulfonyl (dansyl, 5- (dimethylamino) naphthalene-1-sulfonyl), fluorescein, boron-dipyramethane (BODIPY, boron-dipyrromethene), tetramethylrhodamine Tetramethylrhodamine, Alexa, Cyanine, allopicocyanine, rhodamine, 4 ', 6-diamidino-2-phenylindole (DAPI), 4', 6 -diamidino-2-phenylindole, Texas Red, and Texas blue, wherein Q and W are each selected from a different group;
Z 1 and Z 2 are hydrogen or oxygen (O);
L and m are integers from 0 to 1; And
and n is an integer of from 1 to 4. < RTI ID = 0.0 > 8. < / RTI >
The turn-on type fluorescent sensitized chemical sensor represented by Formula 1 may include:
(1) 4- (1-amino-3- (5-dimethylamino) naphthylene-1-sulfonamido) -1-oxopropane-2-ylcarbamoyl) phenylboronic acid;
(2) 4- (1-Amino-5- (5- (dimethylamino) naphthylene-1-sulfonamido) -1-oxopentan-2-ylcarbamoyl) phenylboronic acid;
(3) 4- (1-Amino-6- (5-dimethylamino) naphthalene-1-sulfonamido) -1-oxohexan-2-ylcarbamoyl) phenylboronic acid;
(4) Synthesis of 4- (1-amino-5- (2- (7-hydroxy-2-oxo-2H- Phenylboronic acid;
(5) 4 - ((1-Amino-3- (5- (dimethylamino) naphthalene-1-sulfonamido) -1-oxopropan-2-ylamino) methyl) phenylboronic acid;
(6) 4- (1-Amino-4- (5- (dimethylamino) naphthalene-1-sulfonamido) -1-oxobutan-2-ylcarbamoyl) phenylboronic acid;
(7) 4 - ((3-Amino-2- (5- (dimethylamino) naphthalene-1-sulfonamido) -3-oxopropylamino) methyl) phenylboronic acid; And
(8) a compound selected from the group consisting of 4 - ((4-amino-3- (5- (dimethylamino) naphthalene-1-sulfonamido) -4-oxobutylamino) methyl) Features a turn-on type fluorescent chemical sensor.
Introducing an amino acid represented by the general formula (2) wherein the terminal amine group is protected with a protecting group into the solid compound represented by the general formula (3) (step 1);
The step (2) of preparing a compound represented by the formula (5) wherein the terminal amine protecting group represented by X is deprotected by performing a deprotection reaction of the compound represented by the formula (4) prepared in the step 1;
Performing coupling reaction between the compound of Formula 5 and the compound of Formula 6 prepared in Step 2 to prepare a compound represented by Formula 7 (Step 3);
(Step 4) of preparing a compound represented by the formula (8) wherein the terminal amine protecting group represented by Y is deprotected by performing the deprotection reaction of the compound represented by the formula (7) prepared in the step 3;
(Step 5); coupling the compound of Formula 8 and the compound of Formula 9 to the compound of Formula 10; And
(Hg < 2 + & gt ; ) selective turn-on type fluorescent sensitized chemical sensor comprising a step of removing the solid phase of the compound represented by the formula (10) prepared in the step 5 and removing the compound represented by the formula : ≪
[Reaction Scheme 1]
(In the above Reaction Scheme 1,
Wherein R, Q, W, Z 1 , Z 2 , l, m And n are as defined in claim 1;
D is hydrogen or hydroxy;
X and Y are amine protecting groups, wherein X and Y are different from each other; And
5. The method of claim 4,
The amino acid represented by the general formula (2) in the step 1 may be selected from the group consisting of Ornith, Lys, Dap., Diaminopropionic acid or Dab. Diaminobutanoic acid, (Hg < 2 + & gt ; ) selective, turn-on type fluorescent sensitized chemical sensor.
The solid phase of the solid phase compound represented by the general formula (3) in the step (1) can be prepared by reacting amide-linked methylbenzohydrillamine (MBHA) resin, Wang resin, polyethylene glycol-polystyrene (PEG-PS) resin, silica nanoparticles, titanium oxide (Hg < 2 + & gt ; ) selective nanoparticle and chitosan.
The mercury ion (Hg 2 + ) is selectively detected by measuring the fluorescence signal generated by the reaction product obtained through the covalent bond between the mercury ion (Hg 2 + ) present in the target sample of the step 1 and the compound of the formula (Hg < 2 + & gt ; ) detection step comprising a step (step 2).
The sample ions mercury (Hg + 2) detecting method, characterized in that the aqueous solution containing the merchant aqueous or organic solution.
The organic solution is dimethylformamide, mercury ions (Hg + 2) detecting method, characterized in that one species selected from the acetonitrile, the group consisting of methanol and ethanol.
The mercury-ion (Hg 2 + ) selective, turn-on type fluorescent-sensitized chemical sensor of claim 1 is characterized in that the mercury ion (Hg 2 + ) through the covalent bond between the mercury ion (Hg 2 + (Hg < 2 + & gt ; ) detection method according to claim 1 or 2 , wherein the mercury ions are detected irreversibly.
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| CN115010733A (en) * | 2022-05-23 | 2022-09-06 | 首都医科大学 | Coumarin modified phenylboronic acid derivative and preparation method thereof, curcumin dynamic covalent compound and preparation method and application thereof |
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| KR101179513B1 (en) | 2011-05-24 | 2012-09-07 | 인하대학교 산학협력단 | Methionine amino acid based chemical sensor for selective detecting mercury ion, and preparation method thereof |
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| CN115010733A (en) * | 2022-05-23 | 2022-09-06 | 首都医科大学 | Coumarin modified phenylboronic acid derivative and preparation method thereof, curcumin dynamic covalent compound and preparation method and application thereof |
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