CN108409719A - It is a kind of to be used to detect the organic compound of metal ion content and application in water environment - Google Patents
It is a kind of to be used to detect the organic compound of metal ion content and application in water environment Download PDFInfo
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- CN108409719A CN108409719A CN201810276090.5A CN201810276090A CN108409719A CN 108409719 A CN108409719 A CN 108409719A CN 201810276090 A CN201810276090 A CN 201810276090A CN 108409719 A CN108409719 A CN 108409719A
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- metal ion
- ion
- organic compound
- compound
- cadmium
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- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000000536 complexating effect Effects 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- -1 compound Ion Chemical class 0.000 claims description 11
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- 238000010668 complexation reaction Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 abstract description 30
- 238000001514 detection method Methods 0.000 abstract description 26
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- 150000002500 ions Chemical class 0.000 description 22
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
-
- 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
- C07F5/022—Boron compounds without C-boron linkages
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Abstract
The invention discloses a kind of organic compounds for metal ion content detection, the compound is with N, N picolines aniline is as complexing of metal ion body, chromophore or fluorophor are introduced in the molecule thereof, generate the colored indicator or fluorescence indicator of metal ion especially cadmium ion and zinc ion.The compound of the present invention can also be fixed on hydrophilic high polymers, being made using the characteristic of chromophore or fluorophor can be with nonexpondable reversible metal ion fluorescence probe, it can be suitable for the continuous detection of the concentration of metal ions various environment, especially to the METHOD FOR CONTINUOUS DETERMINATION of cadmium ion and zinc ion concentration in water environment.
Description
Technical field
The invention belongs to organic compound field more particularly to a kind of can be used for detecting metal ion content in water environment
Organic compound and its related application.
Background technology
Cadmium is human body non-essential element, is often existed with compound state in nature, general content is very low, normal environment
Under state, health is not interfered with.Cadmium and zinc are congeners, in nature cadmium often with zinc, lead symbiosis.When environment by
After cadmium pollution, cadmium can be enriched in vivo, and entering human body by food chain causes slow poisoning.After cadmium is absorbed by the body,
Cadmium sulfoprotein is formed in vivo, is selectively accumulated in liver, kidney.Wherein, kidney can absorb the cadmium into vivo nearly 1/3, is in cadmium
" target organ " of poison.Other internal organs such as spleen, pancreas, thyroid gland and hair etc. also have a certain amount of accumulation.Since cadmium damages renal tubule,
There is glycosuria, albuminuria and acidaminuria in patient.Especially tool makes the metabolism of bone be obstructed, and causes osteoporosis, atrophy, deformation etc.
A series of symptoms.
Zinc is one of the essential trace elements of the human body, important in growth in humans's development, reproduction heredity, immune, endocrine etc.
It plays an important role in physiology course [1].Zinc is present in numerous enzyme systems, as carbonic anhydrase, respiratory enzyme, lactic acid are de-
It is nucleic acid, protein, carbohydrate during hydracid, superoxide dismutase, alkaline phosphatase, DNA and RNA are poly- in enzyme etc.
The necessary material that synthesis and vitamin A utilize.With enhancing development, improve the effect of the sense of taste.Easily occurs the sense of taste when zinc-deficiency
Smell is poor, apocleisis, it is slow-growing with intellectual development less than the performances such as normal.Zinc is also the trace element that content is most in brain, is
Necessary to the normal function for maintaining brain, the content of zinc is excessive or very few can all cause disease in certain normal range (NR)
Disease.Drinking water can cause excessive zinc to enter human body by after zinc pollution.Zinacalism mainly with nausea, have a stomach upset based on
Symptom is wanted, immunologic hypofunction can be also caused, reduces high density or low density lipoprotein cholesterol, reduces ceruloplasmin ferrous iron oxygen
Change enzymatic activity, eventually leads to atherosclerosis, hypertension, coronary heart disease etc..When Zn content is 1mgL in water-1When, to water body
Biological oxidation process has slight inhibiting effect；Zinc content is in 3mgL-1~5mgL-1When, water will present milky white after boiling
There is one layer of grease-like film after placing a period of time in color；Zinc content is more than 5mgL-1When, there is bitter taste in water.
Therefore, the metal ion content research detected in water environment becomes an important scientific research in field of scientific study
Project.In the method for detecting metal ion in water environment at present, most widely used method has inductively coupled plasma to emit light
Spectrometry, Flow Injection Analysis and electrochemical process etc. [2].
Due to some disadvantages (instrument is valuable, takes, and step is complicated, strongly professional) of above-mentioned test method, fluorescence sense
The method of device detection metal ion causes people's extensive concern and great interest with its unique advantage, and obtains in recent years
Larger development.Fluorescent optical sensor ion detection possesses numerous advantages, is expected to substitute previously described conventional method.Than
Such as, test process is efficient and convenient, cheap, " bore hole " Visual retrieval, and selectivity is good, and high sensitivity, molecular structure is easy to
Modification optimization.
Although currently, many heavy metal ion identification carriers of document report, presently used heavy metal ion is known
Other carrier is only used for unitary determination, can not be used continuously and also just cannot achieve automatic detection.
Invention content
For the above-mentioned and other defect of the prior art, present inventor by a large amount of creative research work,
Invented that a kind of efficient, sensitivity is good and favorable reproducibility for detecting the metal ion especially cadmium zinc ion in water environment
The organic compound of content, the compound can be fixed on hydrophilic high polymer, and it is glimmering to can be made into nonexpondable reversible ion
Light probe, the continuous detection of the ion concentration suitable for various environment.
To realize that above-mentioned and other purposes, the present invention provide the following technical solutions.
In first aspect present invention, a kind of organic compound detected for metal ion content in water environment, institute are provided
It includes substituted or unsubstituted N to state compound, and N- picolines aniline is as complexing of metal ion body, and in N, N- picolines
The contraposition of aniline introduces chromophore or fluorophor.In a kind of preferred embodiment, the compound has the following structure
Formula：
Wherein n is independently selected from 1 to 4；R1~R4It independently is arbitrary group, as long as these groups do not influence the chemical combination
The ion complexation of object and colour developing or fluorescence property；Y is chromophore or fluorophor.
In preferred embodiment, R1Independently selected from methoxyl group, R2~R4Independently selected from hydrogen, n independently selected from 1
To 4.In a kind of preferred embodiment, R1Independently selected from methoxyl group, R2~R4Independently selected from hydrogen, n independently selected from 1.
In another preferred embodiment, the chromophore is selected from following structures：
Still in another preferred embodiment, the fluorophor is selected from following structures：
In a kind of preferred embodiment, the metal ion that can be detected with the compounds of this invention is selected from cadmium ion and zinc ion.
In second aspect of the present invention, the product for detecting metal ion content in water environment is provided, the product includes
The above-mentioned organic compound of the present invention and the hydrophilic high polymers as carrier.The product can be the form of detection kit.Often
The hydrophilic high polymers seen are used equally for the present invention, and preferably high polymer is aminocellulose or hydrogel.A kind of preferred embodiment
In, the compounds of this invention addition hydrogel is coated into film as fluorescence probe.
In another preferred embodiment, the metal ion is selected from cadmium ion and zinc ion.
In third aspect present invention, application of the compounds of this invention in water environment in metal ion content detection is provided.
In a kind of preferred embodiment, the metal ion is selected from cadmium ion and zinc ion.In another preferred embodiment, the inspection
It is fluoroscopic examination to survey, continuous to detect.
The organic compound of the present invention has following technical advantage outstanding as metal ion probe：
1, the present invention introduces chromophore in N, N- picoline aniline, and it is (outstanding can to prepare a series of metal ions
It is cadmium ion and zinc ion) colored indicator.Reaction condition is mild, safe, and product purity can reach 99.0% or more.
2, by introducing fluorophor in N, N- picoline aniline, a series of metal ions can be prepared (especially
It is cadmium ion and zinc ion) fluorescence indicator.When metal ion content changes, fluorescence intensity, can be from its fluorescence with change
Intensitometer calculates the content of metal ion in solution.
3, also using the complexing group of the molecule other end, the probe of the present invention is fixed on Polymer Surface, is realized micro-
The analysis for measuring metal ion content greatly improves the efficiency, sensitivity and reproducibility.
Description of the drawings
Fig. 1 is the reaction route that the present invention prepares fluorescent type metal ion dyestuff.
Fig. 2 is fluorescence spectra of the metal ion detection fluorescence probe of the present invention to different ions.
Fig. 3 is fluorescence intensity column diagram of the metal ion detection fluorescence probe of the present invention to different ions.
Fig. 4 is the fluorescence emission spectrogram of compound that cadmium ion of the present invention detects that various concentration cadmium ion is complexed in fluorescence probe.
Fig. 5 is the fluorescence spectra that cadmium ion of the present invention detects that cadmium ion is complexed in fluorescence probe, and the fluorescence of 540 nanometers is strong
Angle value corresponds to concentration of cadmium ions by 0 μM to 25 μM respectively from low to high.
Specific implementation mode
By the present invention in that with N, various metals ion can be complexed in N- picoline aniline structures, so as to for realizing
The analysis of micro ion content.The metal ion that applicant can be complexed the compounds of this invention structure in long-term R＆D process
Extensive detection has been carried out, it is found that it has preferable complexing power to zinc, cadmium ion, and to Ca2+、Co2+、Cr3+、Cu2+、Fe2+、
Fe3+、K+、Hg2+、Mg2+、Mn2+、Na+、Ni2+、 Pb2+And lanthanide metal ion etc. is without binding ability.Among this, especially
There is best complexing power to cadmium ion, there is the complexing power of significant specific binding, it can having as cadmium ion
Imitate carrier.Added lustre to or fluorophor by the contraposition introducing in above-mentioned aniline structure, is based on photic photoinduced electron principle of transfer, when
When ion concentration changes, colour developing or fluorescence intensity change correspondingly, and thus can be calculated from ultraviolet absorption value or fluorescence intensity molten
The content of liquid intermediate ion.
It may include substituted or unsubstituted N, N- picoline aniline structures in the compounds of this invention.Those skilled in the art
Be not difficult determination can carry out which substitution without influence the compounds of this invention complexation of metal ions and develop the color or display fluorescence ability.
In preferred embodiment, " substituted " refers to being replaced by substituent group selected from the following：The alkyl of 1 to 4 carbon atom；1 to 4 carbon
The alkoxy of atom；Halogen, including fluorine, chlorine, bromine, iodine；Halogenated alkyl；Cyano；Nitro；Amino；And phenyl.
In the present context, " alkyl " refers to the linear or branched alkyl group of 1 to 4 carbon atom, for example, methyl, ethyl,
N-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl or tertiary butyl." alkoxy " refers to the alcoxyl with 1 to 4 carbon atom
Base, such as methoxyl group, ethyoxyl, propoxyl group, butoxy.
The continuous detection to ion concentration can be achieved using colour developing principle or fluorescence, especially to the inspection of concentration of cadmium ions
It surveys.Chromophore or fluorophor commonly used in the art is used equally for the present invention.
On the one hand, it is introduced after chromophore in ionophore, that is, aniline structure of the present invention, a series of points generated
Son can generate color response to metal ion especially cadmium ion.Such molecule can generate not in the sample of different ions concentration
Same color can be detected with photometer or naked eyes.Applicant confirms said effect in an experiment.Data show that the molecule can
Using as cadmium ion colored indicator.
On the other hand, it is introduced after fluorophor in the ionophore of the present invention, a series of molecules generated can be right
Metal ion especially cadmium ion and zinc ion generate fluorescence response.Such molecule can produce in the sample of different ion concentrations
The fluorescence of raw varying strength, can be detected with sepectrophotofluorometer.Applicant confirms said effect, fluorescence intensity in an experiment
Increase with the increase of sample intermediate ion concentration, increasing degree can be up to more than ten times.
Since chelation structure is variant for the binding ability of different metal ions, it is contemplated that actual detection application needs
It wants, the most suitable detection object of organic compound of the invention is cadmium ion and zinc ion.
For ease of commercial Application, also the ion detection compound of the present invention can be incorporated into hydrophilic high polymers carrier and use is made
In the product for detecting metal ion content in water quality, the product is, for example, the form of kit.Common hydrophilic high polymers are equal
It can be used for the present invention, preferably high polymer is aminocellulose or hydrogel.In a kind of preferred embodiment, by the compounds of this invention
Hydrogel is added and is coated into film as fluorescence probe.
Attached drawing 1 shows the synthesis road of ion carrier compound and fluorescence indicator of the present invention by taking particular compound as an example
Line.It should be noted that being used herein as particular compound only for the purpose for facilitating understanding, those skilled in the art can basis
The synthetic route of these particular compounds carries out necessary change to prepare other ion carrier compounds for use in the present invention
And indicator.
Shown in refer to the attached drawing 1, it is shown that (also referred to as cadmium ion and zinc ion carries a kind of preferred molecular structure of the invention
Body) i.e. N, the synthetic route of N- picolines aniline and ion fluorescence indicator.
This specification illustrates the present invention above in conjunction with specific implementation mode, it should be appreciated that these description and
Explaination is intended merely to more fully understand the present invention, without constituting any restriction to the present invention.Those skilled in the art are reading
Spirit of the necessary change without departing from the present invention can be carried out after present specification to the specific implementation mode of the present invention
And range.Protection scope of the present invention is limited by the accompanying claims, and covers the equivalents of claim.
The present invention is further detailed with reference to embodiment.In the following embodiments, specificization is provided
Object structure is closed to illustrate the structure type of the compounds of this invention, preparation method and its detection as ion concentration detection probe
Performance.The embodiment provided is merely to illustrate how the present invention can be implemented, and does not constitute and is particularly limited to.With this field profession
The those skilled in the art of knowledge can be drawn inferences about other cases from one instance by following lifted specific example, prepare metal ion especially cadmium from
A series of color developing agents and fluorescence indicator of son and zinc ion.
Unless separately there is other explanations in the application context, otherwise technical term use herein and abbreviation all has this
Conventional sense known to field technology personnel；Unless otherwise stated, raw materials used compound is quotient in following embodiments
Purchase obtains.
The various compounds that the present invention is previously mentioned are prepared according to reaction process described in Fig. 1, the reaction of each step
It is as follows：
The synthesis of compound 1
4- chloro- 1,8 naphthalic anhydrides (10g, 42.99mmol), ethyl glutamate hydrochloride (20.68g, 85.98mmol)
And DIEA (28mL, 171.95mmol) is slowly added in 100mLDMF, 90 DEG C of heating stirring 18h.TLC detections have been reacted
Quan Hou, it is cooling, solvent is screwed out, column chromatography (PE: EA=30: 1) obtains yellow powder product 16g, yield 89.1%.1H NMR
(300MHz, CDCl3)：δ 8.65 (2H, d, J=24Hz), 8.49 (1H, d, J=17Hz), 7.83 (2H, d), 5.71 (1H, m),
4.18 (2H, m), 4.00 (2H, m), 2.71 (1H, m), 2.37 (3H, m), 1.60 (3H, s), 1.13 (6H, m) .13C NMR
(300MHz, CDCl3)：δ 173.076,169.889,163.897,163.637,140.011,132.998,132.208,
132.100,131.555,129.852,129.730,128.451,127.980,123.145,121.633,62.053,
61.025,53.392,31.702,24.632,14.635.
The synthesis of compound 2
Compound 2, o-aminoanisole (4.5g, 36.54mmol), pyridine -2- first are synthesized using the method for reduction amination
Aldehyde (13.97mL, 146.16 mmol) is dissolved in 20mL dichloromethane, is stirred at room temperature down and is slowly added into triacetoxy boron hydride
Reaction 12 hours is stirred at room temperature in sodium (30.98g, 146.16mmol), and the reaction was complete for TLC (PE: EA=7: 3) detections, and 40mL is added
Deionized water is dissolved in condition pH 8~9, dichloromethane extraction with saturated sodium carbonate, and anhydrous sodium sulfate drying is filtered, is spin-dried for, column
Chromatographic purifying obtains compound 9.23g, yield 82.7%.1H NMR(CDCl3) δ 8.49 (ddd, J=4.9,1.6,0.9Hz),
7.60-7.54 (m), 7.49 (d, J=7.8Hz), 7.12-7.06 (m), 6.92-6.85 (m), 6.74 (ddd, J=7.9,6.4,
2.4Hz), 4.52 (s), 3.85 (s)
The synthesis of compound 3
Under ice bath, 10mL phosphorus oxychloride is slowly added drop-wise to 10mLN, in dinethylformamide DMF, keeps 0 DEG C of stirring half
Hour, 1.0g (2.8mmol) compound 2 is dissolved in 5mL DMF, which is slowly titrated to the Vilsmeier reagents of above-mentioned preparation
In, be added dropwise be warming up to 60 DEG C react 18 hours.The reaction was complete for nuclear-magnetism detection.Quickly reaction solution is added drop-wise under stirring
In 150mL ice water, pH~7.0 are adjusted with saturated sodium carbonate solution, are extracted with ethyl acetate, anhydrous sodium sulfate drying is spin-dried for, column
Chromatographic purifying obtains compound 0.69g, yield 69%.1H NMR (CDCl3) δ 9.75 (s), 8.53 (d, J=4.7Hz), 7.62
(td, J=7.7,1.4Hz), 7.39 (dd, J=8.0,4.6Hz), 7.28-7.22 (m), 7.18-7.12 (m), 6.89 (d, J=
8.2Hz), 4.72 (s), 3.81 (s)13C NMR(CDCl3) δ 191.362,159.289,151.944,149.874,
146.198,137.189,130.243,127.325,122.636,122.320,118.458,110.166,78.090,
77.667,77.243,58.786,56.254.
The synthesis of compound 4
Compound 3 (0.4g, 1.20mmol), hydroxylamine hydrochloride (0.17g, 2.40mmol), potassium acetate (0.35g,
It 3.60mmol) is dissolved in 20mL ethyl alcohol: the in the mixed solvent of water 1: 1, is gradually warming up to 40 DEG C, is reacted 18 hours.TLC detections are anti-
Should be complete, etoh solvent is screwed out, is extracted with ethyl acetate twice, ethyl acetate phase is then combined with and is dried with anhydrous sodium sulfate,
It is spin-dried for, it is product, yield 95% to obtain white solid without purification.1H NMR(CDCl3) δ 8.51 (dd, J=2.9,
2.0Hz), 8.01 (s), 7.58 (dd, J=7.6,1.7Hz), 7.46 (d, J=7.8Hz), 7.17 (d, J=1.3Hz), 7.15-
7.09 (m), 6.87-6.80 (m), 4.59 (s), 3.83 (s)13CNMR(CDCl3) δ 159.603,152.549,149.897,
149.129,141.071,137.026,126.595,122.453,122.256,121.287,119.979,108.912,
77.810,77.386,76.963,58.635,55.814.
The synthesis of compound 5
Under ice bath, compound 4 (200mg, 0.574mmol) is dissolved in 2mL acetic acid, and 180mg zinc powders are slowly added to above-mentioned
In solution, being heated with stirring to 65 DEG C of reactions .TLC detections in 18 hours, the reaction was complete, restores to room temperature after reaction solution, filters out not
The zinc powder of dissolving, solvent acetic acid is screwed out, and 10mL dissolvings are added, and is adjusted pH~12 with sodium hydroxide solution, is extracted with ethyl acetate
It takes, is then combined with ethyl acetate phase and is dried with anhydrous sodium sulfate, is spin-dried for, obtain product 120mg, yield 62.5%.
The synthesis of compound 6
Weigh 100mg (0.299mmol) compound 5,125mg (0.299mmol) compound 1,0.05ml (0.299mmol)
N,N-diisopropylethylamine DIEA and 0.2mLN- methyl pyrrolidone NMP is put into 50mL single port eggplant-shape bottles, and 95 DEG C were reacted
At night, the reaction was complete for TLC (PE: EA=1: 1) detections, and during cooling is fallen back, solid is precipitated, filters, and is revolved after dichloromethane dissolving
Dry, crude product column chromatography purifies to obtain 25mg.1H NMR(CDCl3) δ 9.21 (d, J=4.8Hz), 8.40 (d, J=7.3Hz), 8.12
(d, J=8.4Hz), 7.67 (td, J=7.6,1.5Hz), 7.52-7.38 (m), 7.34-7.27 (m), 7.07 (d, J=
7.7Hz), 6.79-6.69 (m), 6.33 (d, J=8.5Hz), 6.20 (s), 5.70 (dd, J=8.8,5.2Hz), 4.89 (s),
4.40 (d, J=5.1Hz), 4.18 (q, J=7.1Hz), 4.01 (qd, J=7.1,2.3Hz), 3.85 (s), 2.75-2.62 (m),
2.50-2.24 (m), 1.30-1.10 (m)
The synthesis of Sensor
25mg above compounds 6 (75 μm of ol) are taken to be dissolved in 2mL methanol, addition sodium hydroxide solution (0.18g,
4.53mmol sodium hydroxides are dissolved in I grades of water of 3mL), 40 DEG C of reactions to complete hydrolysis, TLC (DCM: MeOH=10: 1 detection reactions
Completely).
The present invention passes through to N, and N- picoline aniline introduces chromophore or fluorophor so that the molecule with metal
The variation that color change or fluorescence intensity are generated when ion complexation, to realize trace metal ion Visual retrieval or automatic
Change detection.Color change or the variation of fluorescence intensity after the molecule and complexing of metal ion and the concentration of metal ion in solution
It is directly related, thus the content of metal ion in solution can be calculated according to the color change or fluorescence intensity of the molecule, it is real
Now to the quick and precisely detection of metal ion content.
Fig. 2 and Fig. 3 shows cadmium ion and zinc ionophoric fluorescence emission spectrum and its block diagram to different ions.
Fig. 4 shows that the cadmium-ion solution that various concentration is added, the concentration titrations fluorescence intensity response variation of Sensor are bent
Line is gradually increased with concentration of cadmium ions is added, and the fluorescence of Sensor gradually increases, until when concentration of cadmium ions increases to 25 μM
Fluorescence intensity reaches maximum value and no longer changes, and takes the corresponding fluorescence intensity response variation in the places maximum emission wavelength 540nm opposite
It is as shown in Figure 5 that value does concentration titrations curve to concentration of cadmium ions.
Those skilled in the art can prepare according to the thinking and synthetic method that this specification is provided with complexing energy
The cadmium ion and zinc ion indicator of power, it will not go into details herein.
In summary experimental result is it is found that the organic compound of the present invention has the increase of cadmium ion and zinc ion concentration
Good response, in the very low sample of no cadmium ion, zinc ion or cadmium ion, zinc ion content, fluorescence is very weak, or almost
There is no fluorescence.
Bibliography：
[1] Hou Zhenjiang, Zhang Zongying, Li Yueqiu, trace elements and health research, 2002,19 (4), 65.
[2] it is old just, Wang Binbin, scientific and technical innovation with application, 2016,5,155.
Claims (10)
1. a kind of organic compound for detecting metal ion content in water environment, the compound includes substitution or unsubstituted
N, N- picolines aniline introduces chromophore or fluorophor as complexing of metal ion body, and in the contraposition of its molecule.
2. organic compound according to claim 1, it is characterised in that the compound has the following structure formula：
Wherein n is independently selected from 1 to 4；R1~R4It independently is arbitrary group, as long as these groups do not influence the compound
Ion complexation and colour developing or fluorescence property；Y is chromophore or fluorophor.
3. organic compound according to claim 2, it is characterised in that R1Independently selected from methoxyl group, R2~R4Independently
Selected from hydrogen, n independently selected from 1 to 4.
4. organic compound according to any one of claim 1 to 3, it is characterised in that the chromophore is selected from：
The fluorophor is selected from：
5. a kind of product for detecting metal ion content in water environment, which includes any one of claims 1 to 4 institute
The organic compound stated and the hydrophilic high polymers as carrier.
6. product according to claim 5, it is characterised in that the hydrophilic high polymers are selected from aminocellulose or hydrogel.
7. product according to claim 5, it is characterised in that the product is kit.
8. organic compound any one of Claims 1-4 detects the application in metal ion content in water environment.
9. application according to claim 8, it is characterised in that the metal ion selects zinc ion.
10. application according to claim 8, it is characterised in that it is described to be detected as fluoroscopic examination, it is continuous to detect.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810276090.5A CN108409719A (en) | 2018-03-29 | 2018-03-29 | It is a kind of to be used to detect the organic compound of metal ion content and application in water environment |
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|---|---|---|---|
| CN201810276090.5A CN108409719A (en) | 2018-03-29 | 2018-03-29 | It is a kind of to be used to detect the organic compound of metal ion content and application in water environment |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110003175A (en) * | 2019-03-25 | 2019-07-12 | 天津农学院 | A kind of compound and its application for detecting underwater gold category ion concentration |
| CN110128395A (en) * | 2019-03-25 | 2019-08-16 | 天津农学院 | A kind of fluorescence probe and its application for the detection of underwater gold category ion concentration |
| CN110483468A (en) * | 2019-03-25 | 2019-11-22 | 天津农学院 | A kind of fluorescence probe and its application for detecting underwater gold category ion concentration |
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Cited By (3)
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| CN110003175A (en) * | 2019-03-25 | 2019-07-12 | 天津农学院 | A kind of compound and its application for detecting underwater gold category ion concentration |
| CN110128395A (en) * | 2019-03-25 | 2019-08-16 | 天津农学院 | A kind of fluorescence probe and its application for the detection of underwater gold category ion concentration |
| CN110483468A (en) * | 2019-03-25 | 2019-11-22 | 天津农学院 | A kind of fluorescence probe and its application for detecting underwater gold category ion concentration |
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