KR20140098436A - Ratiometric fluorescent chemosensor including boronic acid binding to mercury ion selectively, preparation method thereof and detection method of mercury ion using the same - Google Patents
Ratiometric 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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- KR20140098436A KR20140098436A KR1020130011080A KR20130011080A KR20140098436A KR 20140098436 A KR20140098436 A KR 20140098436A KR 1020130011080 A KR1020130011080 A KR 1020130011080A KR 20130011080 A KR20130011080 A KR 20130011080A KR 20140098436 A KR20140098436 A KR 20140098436A
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- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000001514 detection method Methods 0.000 title claims abstract description 20
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title description 2
- -1 mercury ions Chemical class 0.000 claims abstract description 94
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 89
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
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- 238000000034 method Methods 0.000 claims description 19
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- 238000005859 coupling reaction Methods 0.000 claims description 15
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 12
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical group OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 12
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- 229910001430 chromium ion Inorganic materials 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
- 239000002131 composite material Substances 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 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
- 238000011156 evaluation Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 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
- 238000005259 measurement Methods 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
- ULWOJODHECIZAU-UHFFFAOYSA-N n,n-diethylpropan-2-amine Chemical compound CCN(CC)C(C)C ULWOJODHECIZAU-UHFFFAOYSA-N 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
- 239000010452 phosphate Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 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
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- 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
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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
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Abstract
The present invention relates to mercury ions (Hg + 2) and proportional (ratiometric) sensitive fluorescent chemical sensor, a production method thereof, and mercury ions (Hg 2+) detection method using the same, optionally comprising an acid that binds. The mercury ion fluorescence detection sensor according to the present invention selectively quantitatively analyzes mercury ions (Hg 2 + ) by selectively ratiometric fluorescence emission in a mixed solution of an aqueous solution of 100% and an aqueous solution and an organic solution in the presence of other metal ions This is easy. 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.
Description
The present invention relates to mercury ions (Hg + 2) and proportional (ratiometric) sensitive fluorescent chemical sensor, a production method thereof, and mercury ions (Hg + 2) detection method using the same, optionally comprising an acid that binds.
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, Minamata City, Japan, a group of people who ate fish and shellfish containing methylmercury, such as Itaiitai, methylmercury has a serious neurotoxicity, which makes it easy to pass through membranes in living organisms due to its lipophilic nature. It is not only easily absorbed but also accumulates for a long time and acts as a source of mercury contamination related to 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.
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).
Thus, the inventors of metal ions in the mercury ion (Hg 2 +) a while trying to Kane for selectively detecting the study modosi m, mercury ions (Hg 2 +) and the anthracene derivative, optionally including acid that binds or pyrene In addition to being selectively sensitive to mercury ions (Hg 2 + ) even in the presence of other ions, the boronic acid and mercury ions (Hg 2 + ) contained in the fluorescent chemical sensor irreversibly form covalent bonds, (Hg < 2 + & gt ; ), the present invention has been completed.
It is an object of the present invention to provide a mercury ion (Hg 2 + ) selective, ratiometric fluorescent sensitized chemical sensor.
It is another object of the present invention to provide a method for manufacturing the ratiometric fluorescent sensitized chemical sensor.
It is still another object of the present invention to provide a mercury ion (Hg 2 + ) detection method using the ratiometric fluorescent sensitized chemical sensor.
In order to achieve the above object,
The present invention provides a ratiometric fluorescent sensitized chemical sensor comprising a boronic acid which selectively binds to a mercury ion (Hg < 2 + & gt ; ) represented by the following formula (1)
[Chemical Formula 1]
(Wherein R, Q, W, Z 1 , Z 2 , l, m and n are as defined in the present invention).
The present invention also relates to a process for producing a compound represented by the formula (1)
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 + ) < / RTI > selective, fluorescent fluorinated chemical sensor comprising the step of removing the solid phase of the compound of
[Reaction Scheme 1]
(Wherein R, Q, W, X, Y, Z 1 , Z 2 , D, l, m, n and
Further, the present invention relates to a method for detecting mercury ions (Hg 2 + ), comprising the steps of: (1) injecting a proportional fluorescent chemical sensor represented by Chemical Formula 1 into a sample to be detected; And
By measuring the fluorescence signal for the presence of mercury ions (Hg 2 +) and the reaction product obtained through a covalent bond between the compound of formula (I) to within the target sample in the first step occurs by selective mercury ions (Hg 2 +), mercury (Hg < 2 + & gt ; ) detection method comprising a step (step 2) of sensitively detecting the concentration of ions (Hg < 2 + & gt ; ).
The mercury ion fluorescence detection sensor according to the present invention selectively quantitatively analyzes mercury ions (Hg 2 + ) by selectively ratiometric fluorescence emission in a mixed solution of an aqueous solution of 100% and an aqueous solution and an organic solution in the presence of other metal ions This is easy. 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.
FIG. 3 is a fluorescence spectrum showing fluorescence change of the compound-mercury ion (Hg 2 + ) complex prepared in Example 1 in the presence of other transition metal ions.
4 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.
FIG. 5 is a fluorescence spectrum showing fluorescence change of the compound-mercury ion (Hg 2 + ) complex prepared in Example 2 in the presence of other transition metal ions.
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 1 according to mercury ion (Hg 2 + ) concentration.
FIG. 8 is a fluorescence spectrum showing the fluorescence change of the compound-mercury ion (Hg 2 + ) complex prepared in Example 2 according to mercury ion (Hg 2 + ) concentration.
Figure 9 is a plot graph of Job's mercury ions (Hg + 2) and a compound of mercury ions (Hg + 2) prepared in Example 1 with a molar fraction of the.
Figure 10 is a plot graph of Job's mercury ions (Hg + 2) and a compound of mercury ions (Hg + 2) prepared in Example 2 using the mole fraction of the.
11 is an absorption spectrum of the compound-mercury ion (Hg 2 + ) complex prepared in Example 1 according to the present invention.
12 is an absorption spectrum of the compound-mercury ion (Hg 2 + ) complex prepared in Example 2 according to the present invention.
Hereinafter, the present invention will be described in detail.
The present invention provides a ratiometric fluorescent sensitized chemical sensor comprising a boronic acid which selectively binds to a mercury ion (Hg 2 + ) represented by the following formula (1).
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 arylboronic acid substituted with a nitro group, or a second group consisting of pyrene and anthracene, and Q and W are selected from different groups Being;
Z 1 and Z 2 are independently of each other
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 hydrogen, methyl, ethyl, propyl or butyl;
Q and W are unsubstituted or substituted by one or more fluoro; Trifluoromethyl; Hydroxy; Methoxy; Amine; Or phenyl-boronic acid substituted with a nitro group, or a second group consisting of pyrene and anthracene, wherein Q and W are each selected from different groups;
Z 1 and Z 2 are independently of each other
L and m are integers from 0 to 1; And
n is an integer of 1 to 4;
Most preferably, mercury ion (Hg < 2 + & gt ; ) selective, ratiometric fluorescent sensitized chemical sensors represented by the above formula (1)
(1) 4- (1-amino-1-oxo-5- (2- (pyrene-4-yl) acetamido) pentan-2-ylcarbamoyl) phenylboronic acid; or
(2) 4- (1-Amino-5- (anthracene-9-carboxamido) -1-oxopentan-2-ylcarbamoyl) phenylboronic acid.
The present invention also relates to a process for producing a compound represented by the formula (1)
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
(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 + ) < / RTI > selective, fluorescent fluorinated chemical sensor comprising the step of removing the solid phase of the compound of
[Reaction Scheme 1]
(Wherein R, Q, W, Z 1 , Z 2 , l, m and n are as defined in
Hereinafter, the method of preparing the mercury ion (Hg 2 + ) selective, proportional 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 in the coupling reaction of
The organic solvent that can be used in
Next, the
At this time, deprotonation conditions of
Next, the
When the reductive amination reaction is carried out in the coupling reaction of
Examples of the solvent usable in the reductive amination reaction include dichloroethane (DCE), tetrahydrofuran (THF), methanol, isopropanol, dimethylformamide (DMF) and the like.
When the sulfonylation reaction of the amine is carried out by the coupling reaction of
Examples of the organic solvent which can be used for the sulfonylation reaction of the amine include dichloromethane, chloroform, tetrahydrofuran, diethyl ether, toluene, xylene, xylene, benzene, chlorobenzene and dimethylformamide .
In the coupling reaction of
Next, the
At this time, the deprotonation condition of
Next,
At this time, the coupling reaction of
Next,
At this time, the organic solvent which can be used for the reaction for removing the solid phase in the
Further, the present invention provides a method for detecting mercury ions (Hg 2 + ), comprising the steps of: (1) injecting a proportional fluorescent sensitized chemical sensor represented by the following
By measuring the fluorescence signal for the presence of mercury ions (Hg 2 +) and the reaction product obtained through a covalent bond between the compound of formula (I) to within the target sample in the first step occurs by selective mercury ions (Hg 2 +), mercury (Hg < 2 + & gt ; ) detection method comprising a step (step 2) of sensitively detecting the concentration of ions (Hg < 2 + & gt ; ).
[Chemical Formula 1]
(Wherein R, Q, W, Z 1 , Z 2 , l, m and n are as defined in 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 experiments in which 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) according to the present invention and mercury ion (Hg 2+ ) in an aqueous solution or an aqueous solution containing an organic solution Therefore, it is easy to detect mercury ions (Hg 2+ ) in an aqueous solution containing an aqueous solution or an organic solution.
The organic solution contained in the aqueous solution according to the present invention is preferably, but not limited to, dimethylformamide, acetonitrile, methanol or ethanol.
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 +) selectively, in proportion (ratiometric) of mercury ions present in the target sample with respect to the (Hg 2 +) and mercury through a covalent bond between the compound of formula (I) Ion (Hg 2 + ) is detected irreversibly.
When mercury ions in the compound represented by
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-1-oxo-5- (2- ( Pyrene Yl) Acetamido ) Pentan-2-ylcarbamoyl) Phenylboronic acid Produce
Step 1: Allyl 4 - ((9H- Fluorene -9-yl) Methyl carbamate ) -5-Amino-5- Oxopentyl Carbamate Methylbenzohydrile amine Manufacture of 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 before the reaction was added to a solution of resin in dimethylformamide (1.5 ml) and 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-1-oxo-5- (2- ( Pyrene Yl) Acetamido ) Pentan-2- Ika Baroyl) Phenylboronic acid Methylbenzohydrile amine Manufacture of resin
Tetrakis (triphenylphosphine) of 1.1 equivalent to a resin prepared in
Step 4: 4- (1-Amino-1-oxo-5- (2- ( Pyrene Yl) Acetamido ) Pentan-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
m.p.:183-184 DEG C;
1 H NMR (400 MHz, DMSO 6): δ 8.35 (d, J = 9.2 Hz, 1H), 8.30 (d, J = 8.0 Hz, 1H), 8.26 (d, J = 7.6 Hz, 1H), 8.23 ( (d, J = 7.6 Hz, 1H), 8.19 (d, J = 7.2 Hz, 1H), 8.16 1H), 7.97 (d, J = 7.6 Hz, 1H), 7.84 (m, 4H), 7.37 (brs, 3.15 (m, 2H), 1.82-1.73 (m, 2H), 1.42-1.50 (m, 2H) ppm;
13 C NMR (100 MHz, DMSO 6 ):? 173.77, 169.93,166.36,135.42,133.83,131.04,131.79,130.33,129.66,128.95,128.59,127.36,127.17,126.77,126.35,126.31,125.03,124.88,124.72, 124.07, 123.98, 123.90, 93.96, 52.93, 29.28, 26.13 ppm;
ESI-Mass ( m / z ): [M + Na < + >] 544.11 (calc. 544.21).
< Example 2 > 4- (1-Amino-5- (anthracene-9- Carboxamido )-One- Oxopentane -2- Ika Baroyl) Phenylboronic acid Produce
The target compound (yield: 76%) was obtained in the same manner as in Example 1, except that anthracene-9-carboxylic acid was used instead of pyreneacetic acid in the
m.p .: 181-182 DEG C;
1 H NMR (400MHz, DMSO 6 ): δ 8.80 (t, J = 8.0 Hz, 1H), 8.63 (brs, 1H), 8.36 (d, J = 8.4 Hz, 1H), 8.10 (d, J = 8.8 Hz 2H), 7.93 (d, J = 8.8 Hz, 2H), 7.85 (m, 4H), 7.52 (d, J = 8.4 Hz, 4H), 7.43 (brs, m, 1 H), 3.45-3.51 (m, 2 H), 1.83-1.92 (m, 2 H) 1.70-1.78 (m, 2 H) ppm;
ESI-Mass ( m / z ): [M + Na < + >] 484.09 (calc. 484.20).
< 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
As shown in FIG. 1, in the ESI-MS spectrum of the compound prepared in Example 1 according to the present invention, values of 678.08 m / e, 775.17 m / e and 1355.32 m / e were observed. In this case, 678.08 m / e Example the compound prepared in the first mercury ions (Hg 2 +) and a value of the combined state, 775.17 m / e are the compounds methanol and mercury ions produced in Example 1 (Hg 2 + ). ≪ / RTI > Of the combined and and the proton (H +) form-addition, 1355.32 m / e will As shown in following general formula (11), in Example 1 the Compound (2) molecules produced in the mercury ion (Hg 2 +), perchlorate (ClO 4) Value. From this, the compound represented by the formula (I) according to the invention it can be seen that it is possible to form a stable complex is excellent in binding property of the mercury ion (Hg 2 +), about the mercury ions (
Next, as shown in FIG. 2, the ESI-MS spectrum of the compound prepared in Example 2 according to the present invention showed values of 675.14 m / e and 676.09 m / e. At this time, 675.14 m / e is a value in the state where the compound prepared in Example 2 is combined with mercuric chloride ion ((HgCl) + ), and 676.09 m / e is a value in the case where the compound prepared in Example 2 is mercuric chloride HgCl) + ) and a proton. From this, it can be seen that the compound represented by formula (I) according to the present invention is excellent in the binding property with mercury ion (Hg 2 + ) and can form a stable complex.
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
(DMSO, 2: 98 (v / v), pH 7.4, 1 ml) was added to the test tube, and then 1 mM of the fluorescent sensitized chemical sensor reagent prepared in Experimental Example 1 Solution was added and 2 μl each of the Group I and Group II metal and transition metal based solutions prepared above, or transition metal ion-mercury (Hg 2 + ) standard solutions of Groups I and II were added, respectively. Then, distilled water was added to make the total amount of the solution to 2 ml, and the concentration of the sensor was 10 μM, the concentration of the metal was 10 μM, and the concentration of the HEPES buffer solution-dimethylsulfoxide (DMSO) was 10 mM in the test solution . The solution was mixed to prepare a test solution. The fluorescence spectrum was measured by controlling the excitation wavelength to 330 nm and the widths of the excitation slit and the emission slit to 10 nm and 5 nm, respectively. The results are shown in FIGS. 3 to 6 Respectively.
As shown in FIG. 3 and FIG. 4, the compound prepared in Example 1 according to the present invention had fluorescence spectra of a test solution in which each of Group I and Group II transition metal ions were mixed. As a result, mercury ions Hg < 2 + & gt ; ). Further, the compound prepared in Example 1 binds to mercury ion (Hg 2 + ), whereby fluorescence in the range of 350-400 nm is reduced by about 70 times, and excimer band of pyrene in the range of 475 nm is reduced (See Fig. 3). 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). Thus, the compound of Example 1 according to the present invention selectively detects a complex with mercury ions (Hg 2 + ) even when other Group I and Group II transition metal ions are present in the sample when mercury ions (Hg 2 + ) are detected And the fluorescence change occurs.
Next, as shown in FIG. 5 and FIG. 6, the test solutions prepared by mixing the respective 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, the compound prepared in Example 2 binds to mercury ion (Hg 2 + ), whereby fluorescence in the 420 nm range is reduced, and the excimer band of the anthracene in the 485 nm range is increased about 2 times (See FIG. 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. 6). From this, it can be seen that the compound of Example 2 according to the present invention selectively detects a complex with mercury ion (Hg 2 + ) even when other Group I and Group II transition metal ions are present in the sample when mercury ion (Hg 2 + ) is detected And the fluorescence change occurs.
Therefore, the compound represented by
Experimental Example 3: Mercury ions (Hg 2+ ) Detection ability according to concentration
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.
First, a 1 mM reference solution was prepared by dissolving perchlorate (ClO 4 - ) salt of mercury ion (Hg 2 + ) in distilled water. After adding 10 mM HEPES buffer solution-dimethyl sulfoxide (DMSO, 2:98 (v / v), pH 7.4, 1 ml) to the test tube, the cells of Example 1 and Example 2 prepared in Experimental Example 1 Was added to a test tube such that the concentration of the fluorescence sensitized chemical sensor reagent was 10 μM, and then 0 equivalent, 0.2 equivalent, 0.4 equivalent, 0.6 equivalent, 0.8 equivalent of the compound of
7 to 8, 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, It can be confirmed that the intensity and the wavelength of the fluorescence change gradually with the change from the equivalent to 2 equivalents. It was also found that the fluorescence spectral changes of the compounds prepared in Example 1 and Example 2 were saturated at a mercury ion (Hg 2 + ) concentration of about 1 equivalent or less.
Next, as shown in FIG. 9 to FIG. 10, the fluorescence of the mercury ions (Hg 2 + ) was found to be highest at about 0.34 mole fraction through Job's plot of the compounds of Example 1 and Example 2. This means that the mercury ion (Hg < 2 + & gt ; ) and the compounds of Example 1 and Example 2 according to the present invention form a one to two bond to form a complex.
Next, as shown in FIG. 11 and FIG. 12, it was confirmed that the compound prepared in Example 1 according to the present invention had a reduced light intensity at a wavelength of 342 nm, and in the case of the compound prepared in Example 2, 363 nm wavelength was decreased. This is due to the specific absorption intensity reduction of pyrene and anthracene, which are the fluorescent moieties of each compound. When the mercury ion (Hg 2 + ) is present around the compound according to the present invention, the fluorescent moiety is bonded to the mercury ion (Hg 2+ ) becomes superimposed with, the structure compound and mercury ion represented by the general formula (1) according to the invention (Hg 2 +) is reversible (reversible) interaction (interaction) metal exchange reaction is not acid there mercury ions (Hg 2 +) it can be seen that it forms an irreversible covalent bond through transmetallation.
From this, it can be indirectly known that the mercury ion (Hg 2 + ) and the compound represented by the formula (1) according to the present invention form a one-to-two bond as in the analyzes of FIGS. 9 to 10, It can be seen that the mercury ion (Hg < 2 + & gt ; ) and the compound represented by the formula (1) form an irreversible covalent bond as in the analysis of Fig.
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 straight or branched chain alkyl of C1 to C6;
Q and W are unsubstituted or substituted by halogen; C1-C4 alkyl substituted with halogen; Hydroxy; C1-C4 alkyloxy; Amine; Or a C6-C12 arylboronic acid substituted with a nitro group, or a second group consisting of pyrene and anthracene, and Q and W are selected from different groups Being;
Z 1 and Z 2 are independently of each other
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 hydrogen, methyl, ethyl, propyl or butyl;
Q and W are unsubstituted or substituted by one or more fluoro; Trifluoromethyl; Hydroxy; Methoxy; Amine; Or phenyl-boronic acid substituted with a nitro group, or a second group consisting of pyrene and anthracene, wherein Q and W are each selected from different groups;
Z 1 and Z 2 are independently of each other
L and m are integers from 0 to 1; And
and n is an integer of 1 to 4.
The ratiometric fluorescent sensitized chemical sensor represented by the above formula (1) comprises:
(1) 4- (1-amino-1-oxo-5- (2- (pyrene-4-yl) acetamido) pentan-2-ylcarbamoyl) phenylboronic acid; or
(2) A proportional fluorescent sensitized chemical sensor characterized by being 4- (1-amino-5- (anthracene-9-carboxamido) -1-oxopentane-2-ylcarbamoyl) phenylboronic acid.
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 + ) < / RTI > selective, fluorescent fluorinated chemical sensor comprising the step of removing the solid phase of the compound of formula 10 prepared in step 5 to remove the compound of formula 1 Way:
[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 an aldehyde, carboxylic acid or sulfonyl chloride;
X and Y are amine protecting groups, wherein X and Y are different from each other; And
Amino acids represented by the formula (2) in step 1 is a process for producing a mercury ion (Hg + 2) optionally, a proportional-sensitive fluorescent chemical sensors, characterized in that the terminal amine group-protected an ornithine (Orn).
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, proportional fluorescent sensitized chemical sensor characterized in that it is one selected from the group consisting of nanoparticles and chitosan.
By measuring the fluorescence signal for the presence of mercury ions (Hg 2 +) and the reaction product obtained through a covalent bond between the compound of formula (I) to within the target sample in the first step occurs by selective mercury ions (Hg 2 +), mercury (Hg < 2 + & gt ; ) detection step (step 2) of detecting the concentration of the ion (Hg < 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, characterized in that mercury ion species, one is selected from dimethyl formamide, acetonitrile, and the group consisting of methanol and ethanol (Hg + 2) detection method.
Claim 1 mercury ions (Hg 2 +) selectively, proportional fluorescent sensitive chemical sensors mercury ions (Hg 2 +) through a covalent bond between the presence of mercury ions (Hg 2 +) and the compound of formula (I) to within the target sample the ratio (Hg < 2 + & gt ; ) detection method according to claim 1, wherein the detection is performed irreversibly.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106442665A (en) * | 2016-12-22 | 2017-02-22 | 山东理工大学 | Preparation method of ratio-dependent adapter sensor for detecting antibiotic residues based on screen-printed electrodes |
| KR20210041246A (en) * | 2019-10-07 | 2021-04-15 | 대구대학교 산학협력단 | Fluorescence sensor having selectivity for mercury ion and method for detecting mercury ion using the same |
| WO2021096263A1 (en) * | 2019-11-12 | 2021-05-20 | 이화여자대학교 산학협력단 | Cell imaging composition and cellular material imaging method using same |
| KR20210069288A (en) | 2019-12-03 | 2021-06-11 | 한국과학기술연구원 | Tetraphenylene-based mercury ion detection sensor and mercury ion detection method using the same |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002054067A2 (en) | 2001-01-05 | 2002-07-11 | Sensors For Medicine And Science, Inc. | Detection of analytes |
| KR20090097704A (en) * | 2008-03-12 | 2009-09-16 | 인하대학교 산학협력단 | Flourescent peptide probe for selective detection copper or zinc ion, and preparation method thereof |
| KR20090129105A (en) * | 2008-06-12 | 2009-12-16 | 이화여자대학교 산학협력단 | Rhodamine derivative, fluorescein derivative and probes theirof |
| KR20120062223A (en) | 2010-12-06 | 2012-06-14 | 고려대학교 산학협력단 | Pyrene derivatives having mercury ion selectivity, and fluorescent chemodosimeter using the same |
| 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 |
-
2013
- 2013-01-31 KR KR1020130011080A patent/KR101665046B1/en active IP Right Grant
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002054067A2 (en) | 2001-01-05 | 2002-07-11 | Sensors For Medicine And Science, Inc. | Detection of analytes |
| KR20090097704A (en) * | 2008-03-12 | 2009-09-16 | 인하대학교 산학협력단 | Flourescent peptide probe for selective detection copper or zinc ion, and preparation method thereof |
| KR20090129105A (en) * | 2008-06-12 | 2009-12-16 | 이화여자대학교 산학협력단 | Rhodamine derivative, fluorescein derivative and probes theirof |
| KR20120062223A (en) | 2010-12-06 | 2012-06-14 | 고려대학교 산학협력단 | Pyrene derivatives having mercury ion selectivity, and fluorescent chemodosimeter using the same |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| Org. Lett. 7, (2005), 4943. |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106442665A (en) * | 2016-12-22 | 2017-02-22 | 山东理工大学 | Preparation method of ratio-dependent adapter sensor for detecting antibiotic residues based on screen-printed electrodes |
| CN106442665B (en) * | 2016-12-22 | 2018-12-25 | 山东理工大学 | A kind of preparation method of the Ratio-type aptamer sensor based on screen printing electrode detection antibiotic residue |
| US11780857B2 (en) | 2019-04-17 | 2023-10-10 | EWHA University—Industry Collaboration Foundation | Probe compounds for amino alcohols, and simultaneous fluorescence and circular dichroism analysis method |
| KR20210041246A (en) * | 2019-10-07 | 2021-04-15 | 대구대학교 산학협력단 | Fluorescence sensor having selectivity for mercury ion and method for detecting mercury ion using the same |
| WO2021096263A1 (en) * | 2019-11-12 | 2021-05-20 | 이화여자대학교 산학협력단 | Cell imaging composition and cellular material imaging method using same |
| KR20210057700A (en) * | 2019-11-12 | 2021-05-21 | 이화여자대학교 산학협력단 | Composition for cell imaging, and cell-material imaging method using the same |
| KR20210069288A (en) | 2019-12-03 | 2021-06-11 | 한국과학기술연구원 | Tetraphenylene-based mercury ion detection sensor and mercury ion detection method using the same |
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