CN105385439B - Detect response type rhodamine fluorescence probe and its preparation and application of mercury ion - Google Patents
Detect response type rhodamine fluorescence probe and its preparation and application of mercury ion Download PDFInfo
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- CN105385439B CN105385439B CN201510869087.0A CN201510869087A CN105385439B CN 105385439 B CN105385439 B CN 105385439B CN 201510869087 A CN201510869087 A CN 201510869087A CN 105385439 B CN105385439 B CN 105385439B
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- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
Abstract
The invention provides a kind of response type rhodamine fluorescence probe for detecting mercury ion, it is characterised in that its structural formula is：
Description
Technical field
The invention belongs to fluorescence probe material and its preparation field, more particularly to a kind of response type Luo Dan for detecting mercury ion
Bright class fluorescence probe and preparation method and application.
Background technology
Mercury is typical poisonous transition metal ions, can cause the permanent damage of biological nervous system.Due to mercury height
Toxicity and widely paid close attention to, the generation of mercury is mainly derived from the reason for natural and artificial, such as the eruption in ocean and volcano,
The burning and mining of house refuse, the use of particularly power saving fluorescent lamp cause being further exacerbated by for mercury pollution, especially environment
In mercury be oxidized to water miscible dimercurion in atmosphere, as current enter in rivers,lakes and seas, by water-bed micro- life
Thing and become methyl mercury, be present among various algae, by food chain in biological tissue it is highly enriched, to nature and people
Class has larger harm.
Mercury atom has the ability of very strong associativity (usually containing N, S, O elements) with organism, is formed with biomolecule
Complex, sulfydryl, protein caking of enzyme etc. can be caused, destroy organism molecule structure.Mercury is also that one kind can not give birth to simultaneously
The heavy metal element of thing degraded, mercury element and its compound by cutaneous respiration and food chain be deposited on liver, brain and other
In organ, in human body can not eubolism discharge, produce slow poisoning, infringement enteron aisle, kidney and nervous system, cause various diseases
Disease.Nineteen fifty-three is typical mercury nuisance disease in " minamata disease " that Kumamoto County, Japan Minamata town occurs.Heavy metal pollution has turned into
One of major source of pollutant in environment pollution detection at present, thus development can be detected in aqueous environment mercury ion it is quick,
Simply, sensitive detection method, the detection to heavy metal in water body environment are significant.
The main method of mercury element is surveyed in visual inspection：Atomic absorption spectrography (AAS), Neutron activation analysiss, atomic emission spectrometry, X
Ray fluorescence spectrometry, stripping voltammetry, dithizone colorimetric method, coated piezoelectric sensor hair and plasma sensing spectroscopic methodology
Deng.Due to the inferior position (strongly professional, step is complicated, takes, instrument is valuable) of the above method, fluorescence chemical sensor ion detection
Possess the advantages of numerous, it is expected to substitute traditional method, and as test speed is fast, equipment is simple, " bore hole " visual detection, price
Cheap, molecular structure is easy to modification optimization, the advantages that high sensitivity.Have in recent years many on the detection of small-molecule fluorescent probe method
Report (the Sensors and Actuators B of mercury ion：Chemical, 2015,210,519-532), but due to a huge sum of money
Belong to the intrinsic fluorescent quenching property of ion so that developing highly sensitive fluorescence probe has certain challenge.It is additionally useful for
The fluorescence probe of water body environment, not only to ensure that water solubility is good, be applied especially to bioenvironmental fluorescence probe, it is not only water-soluble
Property it is good, but also require can be worked under the conditions of normal physiological environment, be advantageous to excited by visible light and prevent ultraviolet light pair
Loss caused by cell.Rhodamine B fluorescent dye is a kind of bioluminescence material well, has good optical physics
Matter, it absorbs and launched all at long wave (＞ 550nm), and fluorescence quantum yield is high, and molar extinction coefficient is big, and ambient interferences are small etc.
Advantage, therefore there is important application prospect in terms of fluorescence probe is developed.
Chinese patent 201410058568.9 " a kind of response type Rhodamine fluorescent probe for detecting mercury ion and its preparation side
Method ", using rhodamine B and hydrazine hydrate as Material synthesis rhodamine acid amides, water-soluble good production is then obtained with glyoxalic acid reaction
Thing, has the selectivity of height to mercury ion, and other conventional ions without obvious interference, can all answer in pH=5-10 environment
Detection for bioluminescence imaging and water sample；Chinese patent 201310163699.9 " mercury ion fluorescent sensor and its synthesis
Methods and applications ", generation rhodamine acid amides is reacted as raw material using rhodamine B and hydrazine hydrate, then adds isocyanates reaction
Synthesize the Fluorescence Fluorescence sensor of mercury ion；Chinese patent 201410029789.3 " one kind be used to detecting in water environment metal from
The organic compound of sub- content and its application ", with N- [2- ((alkyl mercapto ethyl) the aminobenzene oxygen of N ' N '-two ethyl]-N- alkyl mercaptos
Ethyl -2- alkoxyl anilines are especially right suitable for the continuous detection of various Metals in Environments ion concentrations as ion complexation body
The detection of mercury ion.
The content of the invention
The technical problems to be solved by the invention be to provide a kind of fluorescence probe and preparation method thereof for detecting mercury ion with
Using the fluorescence probe has good selectivity to mercury ion, has preferable using effect in terms of environment measuring.
In order to solve the above-mentioned technical problem, the invention provides a kind of response type rhodamine fluorescence spy for detecting mercury ion
Pin, it is characterised in that its structural formula is：
The preparation method of the response type rhodamine fluorescence probe of above-mentioned detection mercury ion includes：
Step 1：2- bromo methyl cycloheptapyridines hydrobromate and sodium azide are dissolved in solvent, stirring reaction 3-4h, extract, wash
Wash, dry, revolving, produce product 4- (2- alkynyls propoxyl group) benzaldehyde；
Step 2：Parahydroxyben-zaldehyde and propargyl bromide and catalyst are dissolved in solvent, are heated to reflux 3-4h, is cooled down, extraction
Take, dry, rotate, vacuum drying, produce 2- azido-methyl pyridines；
Step 3：By 4- (2- alkynyls propoxyl group) benzaldehydes and 2- azido-methyl pyridines, under the protection of nitrogen, it is dissolved in mixed
In bonding solvent, catalyst is added, stirring reaction 20-24h, is extracted, is dried, revolving, column chromatography is carried out, produces product R；
Step 4：Rhodamine B is dissolved in solvent, hydrazine hydrate is added, is heated to reflux 1-3h, is cooled to room temperature, rotates, adds
Enter hydrochloric acid, adjust pH, filter, drying, produce rhodamine acid amides；
Step 5：Product R and rhodamine acid amides are dissolved in solvent, add acetic acid, heating reflux reaction 5-6h, reaction knot
Shu Hou, revolving, produce the response type rhodamine fluorescence probe (RHPT) for detecting mercury ion.
Preferably, the solvent in described step 1-4 is respectively DMF, acetone, the tert-butyl alcohol and water
Mixture, ethanol, the solvent in step 5 is ethanol.
Preferably, the mol ratio of the 2- bromo methyl cycloheptapyridines hydrobromate in described step 1 and sodium azide be 1: 2.5~
3。
Preferably, the extraction in described step 1 is：Water is added in reaction system, is extracted with dichloromethane, step 1
In solvent, the volume ratio of water and dichloromethane be 1: 0.2~0.5: 5~10.
Preferably, catalyst is potassium carbonate in described step 2, and parahydroxyben-zaldehyde, propargyl bromide and catalyst rub
You are than being 1: 0.4~0.45: 0.4~0.45.
Preferably, the extraction in described step 2 is：Water is added in reaction system, is extracted with dichloromethane, step 2
In solvent, the volume ratio of water and dichloromethane be 1: 0.2~0.3: 0.5~1.
Preferably, the catalyst in described step 3 is CuSO4·5H2O and sodium ascorbate, described 4- (2- alkynyls
Propoxyl group) benzaldehyde, 2- azido-methyls pyridine, CuSO4·5H2The mol ratio of O and sodium ascorbate be 1: 0.5~1: 0.5~
0.8: 0.8~1.
Preferably, the mol ratio of described rhodamine B, hydrazine hydrate and hydrochloric acid is 1: 0.02~0.05: 0.03~0.05.
Preferably, the regulation pH in described step 4 is to adjust pH=9.0-10.0 using sodium hydroxide.
Preferably, in described step 5 product R, rhodamine acid amides and acetic acid mol ratio for 1: 0.8~1: 0.02~
0.03。
Present invention also offers the application process of the response type rhodamine fluorescence probe of above-mentioned detection mercury ion, it is special
Sign is, including：The aqueous solution of the mercury ion of various concentrations is separately added into response type sieve containing above-mentioned detection mercury ion
The pH=4.0-12.0 of red bright class fluorescence probe H3PO4/H2PO4 -Buffer system in, determine fluorescence intensity, excitation wavelength is
560nm, launch wavelength 577-580nm, using the concentration of mercury ion as abscissa, the change of fluorescence intensity turns to ordinate mapping,
Obtain linear work curve；It is glimmering that sewage containing mercury ion is added into the response type rhodamine containing above-mentioned detection mercury ion
The pH=4.0-12.0 of light probe H3PO4/H2PO4 -Buffer system in, by the fluorescence intensity for determining the mercury ion in sewage
It can obtain the content of mercury ion in solution.
Preferably, described H3PO4/H2PO4 -Buffer system pH=7.0.
Amide group of the invention containing rhodamine B base, the middle introducing containing carbon-to-nitrogen double bon and triazole pyridine are therein
Some groups have recognition reaction to mercury ion.Its mechanism is：Due to the isomerization of C=N double bonds, after adding ion, molecule
Rigidity change and conjugation sexually revises color red shift while Fluorescence Increasing for mercury, color change is advantageous to improve probe
Sensitivity.Its syntheti c route is as shown in Figure 7.Novel fluorescence probe RHPT autofluorescences of the present invention are very weak, in mercury ion
Under conditions of, by 560nm excited by visible light, the fluorescence signal at 580nm significantly increases, and can be examined by recording fluorescence intensity
Survey the concentration of mercury ion.Fluorescence probe RHPT can carry out high selectivity detection in pH=7.0 cushioning liquid to mercury ion.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) fluorescence probe of the invention has good selectivity and sensitivity to mercury ion, has in terms of environment measuring
Preferable using effect.
(2) although synthesis step of the invention is relatively more, reaction condition is fairly simple, and equipment requirement is simply easily operated,
The fluorescence probe of synthesis has preferable selectivity and sensitivity to mercury ion.Colouring discrimination before and after addition mercury ion in the solution
Greatly, the optical colorimetry detection of live real-time qualitative and sxemiquantitative can be carried out.
Brief description of the drawings
Fig. 1 is the ultraviolet change collection of illustrative plates that fluorescence probe is added before and after mercury ion；In Fig. 1, abscissa is UV absorption ripple
Long (nm), ordinate is absorbance.
Fig. 2 a and 2b are respectively the change in fluorescence collection of illustrative plates that fluorescence probe is added before and after mercury ion；In fig. 2, abscissa is glimmering
Light launch wavelength (nm), ordinate are fluorescence intensity.
Fig. 3 be (concentration is 10 μM) in acetonitrile solution to the fluorescence spectrum response diagram of mercury ion.In figure 3, abscissa
For fluorescence emission wavelengths (nm), ordinate is fluorescence intensity；Illustration is Hg in figure2+Concentration increases the tendency chart with fluorescence intensity
(excitation wavelength is in 560nm).
Fig. 4 be (concentration is 10 μM) in acetonitrile solution to different metal ion (Cu, Co, Mn, Mg, Fe, Ba, Ca, K,
Na, Ni, Pb, Cd) selection interference detection fluorescence response figure；In Fig. 4, abscissa is different metal ion, ordinate
For fluorescence intensity.
Fig. 5 is the Job-Plot curves that (concentration is 50 μM) is complexed ratio with mercury ion；Abscissa is c [Hg2+]/c[Hg2++
Probe], ordinate is fluorescence F-F0, wherein F, F0It is the fluorescent emission intensity in 560nm.
Fig. 6 is configured with a series of for the probe solution of (concentration is 50 μM) using dihydric phosphate/phosphate buffer solution
Different pH cushioning liquid, then adds a certain amount of mercury ion into probe solution, and fluorescence intensity abscissa is fluorescence
Launch wavelength (nm), ordinate are fluorescence intensity.
Fig. 7 is the syntheti c route figure of the response type rhodamine fluorescence probe of the detection mercury ion of the present invention.
Fig. 8 is the linear work curve that embodiment 2 obtains.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
The purity of 2- bromo methyl cycloheptapyridine hydrobromates used is 95~99% in embodiment.The purity of sodium azide is 95
~99%.The purity of solvent DMF is 95~98%.The purity of extractant dichloromethane is 95~98%.It is dry
The purity of drying prescription anhydrous magnesium sulfate is 95~99%.The purity of parahydroxyben-zaldehyde is 95~99%.2- azido-methyl pyridines
Purity is 95~99%.The purity of extractant dichloromethane is 95~98%.The purity of catalyst potassium carbonate is 95~99%.It is molten
The purity of agent acetone is 95~98%.The purity of drier anhydrous magnesium sulfate is 95~99%.The purity of the tert-butyl alcohol be 95~
98%.Extractant ethyl acetate purity is 95~98%.The purity of catalyst cupric sulfate pentahydrate is 95~99%.Catalyst is anti-bad
The purity of hematic acid sodium is 95~99%.The purity of drier anhydrous sodium bicarbonate is 95~99%.The purity of rhodamine B be 95~
99%.The purity of hydrazine hydrate is 95~98%.The purity of etoh solvent is 95~98%.The purity of sodium hydroxide be 95~
99%.The purity of etoh solvent is 95~98%, and the purity of solvent acetic acid is 95~98%.Above percentage is quality percentage
Number.
Embodiment 1
A kind of response type rhodamine fluorescence probe for detecting mercury ion, its structural formula are：
The preparation method of the response type rhodamine fluorescence probe of above-mentioned detection mercury ion is：
(1) synthesis of intermediate 1：
By 0.50g (1.9mmol) 2- bromo methyl cycloheptapyridines hydrobromate and 0.39g (5.9mmol) in 50mL three-necked bottles
Sodium azide be dissolved in 10mL DMF solvent, stirring reaction 4h at room temperature, after reaction terminates, after adding 5.0mL water, then
With 50.0mL CH2Cl2Extraction, upper strata is yellow clear solution, and lower floor is rose pink muddy shape liquid, and lower floor is organic layer,
Collect and merge organic layer, (excessive NaN is washed away with massive laundering3), with anhydrous MgSO4Dry half an hour, organic solvent rotation
Turn evaporimeter to boil off, obtain the grease (4- (2- alkynyls propoxyl group) benzaldehyde) of yellow.Yield：60-80%.1H NMR
(300MHz, CDCl3)：8.61 (d, J=4.2Hz, 1H), 7.73 (td, J=1.8,7.8Hz, 1H), 7.35 (d, J=7.8Hz,
1H), 7.26 (m, 1H), 4.50 (s, 2H).
(2) synthesis of intermediate 2：
In 500mL three-necked bottles by 0.30g (0.25mol) parahydroxyben-zaldehydes and 7.7mL (0.98mol) propargyl bromides and
14.00g (0.98mol) K2CO3Catalyst is made to be dissolved in 150mL acetone solvent, be heated to reflux at 80 DEG C (with TCL point plates with
Track) take around 4h.Room temperature is cooled to, after adding 37.0mL water, with 100.0mL CH2Cl2Extraction, merges organic layer, and use is anhydrous
MgSO4Half an hour is dried, solvent is boiled off with Rotary Evaporators, is put into 20 DEG C of vacuum drying chambers and is dried to constant weight, obtain yellowish
Color product (2- azido-methyls pyridine).mp：85-86 DEG C, yield 96%.FTIR(KBr)：V=3210cm-1(C ≡ CH),
2122cm-1(C ≡ C), 1668cm-1(C=O), 1603cm-1, 1577cm-1, 1508cm-1, 1453cm-1(C=C), 3070cm-1
(Ar-H), 2836cm-1(CH), 1250cm-1(C-O).1HNMR (400MHz, CDCl3)：9.87 (s, 1H ,-CHO), 7.70 (d, J
=8.8Hz, 2H, Ar-H), 6.96 (d, J=9.0Hz, 2H, Ar-H), 4.68 (s, 2H, O-CH2), 2.51 (s, 1H, C ≡ CH).
(3) synthesis of intermediate 3：
0.32g (2.0mmol) 4- (2 alkynyl propoxyl group) benzaldehydes and 0.26g is added in 250mL three-necked bottles
The 2- azido-methyl pyridines of (2.0mmol), in N2Protection under, be dissolved in volume ratio be 1: 1 the tert-butyl alcohol and water mixed solution
In 30.0mL, 5mol% CuSO is added4·5H2O and 10mol% sodium ascorbate is stirred at room temperature anti-as catalyst
Answer 24h.Should after obtain the product of yellow, extracted with 30.0mL ethyl acetate, merge organic layer, use anhydrous Na2SO4Dry
Half an hour, it is spin-dried for obtaining the grease of brown.White solid (product R) is obtained carrying out column chromatography.Yield 70%.mp：106-
107℃.FTIR：V=3139cm-1(C=CH), 3075cm-1(Ar-H), 2847cm-1, 2864cm-1(C-H), 1681cm-1(C=
O), 1603cm-1, 1577cm-1, 1508cm-1, 1476cm-1(C=C), 1577cm-1, 1422cm-1(Py-H), 1392cm-1(C-H
In-plane bending), 1254cm-1(C-O), 870cm-1, 835cm-1(C=H frequency multiplication peak in Ar).1HNMR (400MHz, CDCl3)：
9.88 (s, 1H ,-CHO), 8.55 (d, J=3.2Hz, 1H), 8.3 (s, 1H), 7.90 (d, J=6.0Hz, 2H), 7.26 (d, J=
8.6Hz, 2H), 7.84 (t, J=8.60Hz, 1H), 7.37 (t, J=5.8Hz, 1H), 7.32 (d, J=8.0Hz, 1H), 5.76
(s, 2H), 5.30 (s, 2H).
(4) synthesis of intermediate 4：
In 250mL three-necked bottles, 1.2g rhodamine B is weighed, is dissolved in 30mL ethanol, is added dropwise at room temperature
3.0mL mass concentrations are 85% hydrazine hydrate solution, and after dropwise addition is over, 80 DEG C are heated to reflux 2h, and solution is slowly changed into from purple
Yellow clear solution, after reaction terminates, room temperature is cooled to, solvent adds 1M HCl 50.0mL after being spin-dried for, 1M is slowly being added dropwise
NaOH about 70.0mL, pH are about 9.0-10.0, and solution is changed into pink from red, and precipitation is filtered under diminished pressure and with 15.0mL water
Wash three times, obtain product drying, obtain pink powder (rhodamine acid amides).Yield：90%.mp：171-172℃.FTIR：v
=3424cm-1(- OH), 3415cm-1(-NH2)2969cm-1, 2928cm-1(C-H), 1696cm-1(C=O, 1615cm-1,
1547cm-1, 1514cm-1, 1374cm-1(C=C), 1357cm-1(CH in-plane bending vibration), 1219cm-1, 1118cm-1(C-
C), 819cm-1, 787cm-1, 699cm-1(the frequency multiplication peak of CH stretching vibrations on phenyl ring).1HNMR (400MHz, CDCl3)：1.16 (t,
12H, NCH2CH3), 3.34 (q, 8H, NCH2CH3), 3.61 (bs, 2H, NH2), 6.29 (dd, 2H, xanthene-H), 6.42 (d,
2H, xanthene-H), 6.48 (d, 2H, xanthene-H), 7.11 (m, 1H, Ar-H), 7.45 (m, 2H, Ar-H), 7.94 (m,
1H, Ar-H).
(5) preparation of fluorescence probe
In 250mL three-necked bottles, BPT (product R) the addition 10.0mL ethanol heating for weighing 0.15g (0.50mmol) is molten
Solution, then 0.23g (0.50mmol) rhodamine acid amides (RHD) is weighed, it is dissolved in 5.0mL ethanol (being in pale pink), be slowly added dropwise
Into three-necked bottle, 3~4 drop acetic acid are added, 80 DEG C, back flow reaction 5-6h is heated to, is tracked with TCL points plate, after reaction terminates, are used
Rotary Evaporators are evaporated, and obtain the solid (the response type rhodamine fluorescence probe of detection mercury ion) of aubergine.Yield：
89%.Mp：199-200℃.FTIR：V=2970cm-1(C-H), 1716cm-1(C=O), 1613cm-1, 1547cm-1, 1514cm-1, 1466cm-1(C=C), 1264cm-1(C-O), 1235cm-1, 1219cm-1(C-C)1118cm-1, 1005cm-1, 758cm-1(benzene
The frequency multiplication peak of H CH stretching vibrations on ring).1HNMR (400MHz, CDCl3)：1.20 (t, 12H, NCH2CH3), 3.75 (q, 8H,
NCH2CH3), 5.20 (s, 2H, OCH2), 5.76 (s2H, CH2), 5.65 (s, 1H), 5.71 (s, 1H), 6.88 (s, 1H, CH=N),
6.90 (s, 1H, Ar-H), 7.12 (s, 1H, triazole-H), 7.15 (s, 2H, xanthene-H), 7.19 (d, 2H,
Xanthene-H), 7.28 (d, 1H, Pyridine-H), 7.45 (d, 2H, Ar-H), 7.50 (t, 1H, Ar-H), 7.69 (t, 1H,
Ar-H), 7.77 (d, 2H, xanthene-H), 7.87 (t, 1H, Pyridine-H), 8.01 (d, 1H, Ar-H), 8.60 (d, 1H,
Xanthene-H), 8.63 (d, 1H, Pyridine-H).
It is 10 μM to prepare probe solution concentration, and concentration and probe concentration and ion concentration are respectively the solution of 10 μM and 100 μM,
Detected under ultra-violet absorption spectrum, as a result as shown in Figure 1.
It is 10 μM to prepare probe solution concentration, and concentration and probe concentration and ion concentration are respectively 10 μM of solution, excitation peak
To be excited at 560nm, excitation peak and emission peak are measured, as a result as shown in figures 2 a and 2b.
The concentration of fixed probe solution is 10 μM, adds different ion concentration of mercury, the mercury ion μ from 0 to 1000 respectively
M, detects its fluorescence intensity respectively, and structure is as shown in Figure 3.
It is 10 μM to prepare probe solution concentration, and the concentration of various ions is also 10 μM.Added respectively with fluorescent detection probe
The fluorescence intensity of different ions total solution, knot are added after the fluorescence intensity of different ions, and fluorescence probe addition mercury ion
Fruit is as shown in Figure 4.
Fixed RHPT and Sn2+Concentration and for 50 μM.Then RHPT and Sn is allowed respectively2+Concentration ratio according to 0: 10；1∶9；
2∶8；3∶7；4∶6；5∶5；6∶4；7∶3；8∶2；9∶1；10: 0. respectively under same slit, detects its fluorescence intensity.Then prepare
The a series of concentration of solution is respectively that its is glimmering with fluoroscopic examination for 0,5,10,15,20,25,30,35,40,45,50 μM of solution
Luminous intensity, data processing is carried out, as a result as shown in Figure 5.
The response type rhodamine fluorescence probe of the detection mercury ion of gained is dissolved in 10 μM of spy is made into acetonitrile solvent
Pin solution, add dihydric phosphate/phosphate buffer solution be configured with it is a series of it is different (pH=1.0,2.0,3.0,4.0,5.0,
6.0th, 7.0,8.0,9.0,10.0,11.0,12.0) pH cushioning liquid, then adds 1.0x10 into probe solution-4M mercury
Ion, detect the change (Fig. 6) of probe solution fluorescence intensity under condition of different pH.It was found that fluorescence when pH=1.0-3.0
Intensity is decreased obviously, and pH=4.0-12.0 fluorescence intensity change unobvious, probe solution is more stable, therefore the fluorescence probe exists
Below pH=1.0-3.0 is influenceed bigger by acid condition in acetonitrile solvent, and probe is solution-stabilized under pH=4.0-12.0
Be advantageous to detect.
Embodiment 2
Mercury ion contains in the response type rhodamine fluorescence probe detection sewage of detection mercury ion in Application Example 1
Amount concretely comprises the following steps：
It is 1.5x10 by 1.0mL concentration-4M、3.0x10-4M、6.0x10-4The aqueous solution of M mercury ion is separately added into 1.0mL
It is 1.0x10 containing weight concentration-5The pH=7.0's of the response type rhodamine fluorescence probe of M above-mentioned detection mercury ion
H3PO4/H2PO4 -Buffer system in, determine fluorescence intensity, excitation wavelength 560nm, launch wavelength 580nm, with mercury ion
Concentration be abscissa, the change of fluorescence intensity turns to ordinate mapping, obtains shown in linear work curve map 8；
It is 1.0x10 that the sewage that 1.0mL contains mercury ion, which is added 1.0mL to contain weight concentration,-5M above-mentioned detection mercury
The pH=7.0 of the response type rhodamine fluorescence probe of ion H3PO4/H2PO4 -Buffer system in, by determining in sewage
The fluorescence intensity of mercury ion be that to can obtain the content of mercury ion in solution be 1.0x10-6M。
Claims (8)
1. a kind of preparation method for the response type rhodamine fluorescence probe for detecting mercury ion, the reaction of described detection mercury ion
The structural formula of type rhodamine fluorescence probe is：
,
Characterized in that, described preparation method includes：
Step 1：2- bromo methyl cycloheptapyridines hydrobromate and sodium azide are dissolved in solvent, stirring reaction 3-4 h, extracted, washing,
Dry, revolving, produce product 2- azido-methyl pyridines；
Step 2：Parahydroxyben-zaldehyde and propargyl bromide and catalyst are dissolved in solvent, are heated to reflux 3-4 h, is cooled down, extraction,
Dry, rotate, vacuum drying, produce 4- (2- alkynyls propoxyl group) benzaldehyde；
Step 3：By 4- (2- alkynyls propoxyl group) benzaldehydes and 2- azido-methyl pyridines, under the protection of nitrogen, it is molten to be dissolved in mixing
In agent, catalyst is added, stirring reaction 20-24h, is extracted, is dried, revolving, column chromatography is carried out, produces product R；
Step 4：Rhodamine B is dissolved in solvent, hydrazine hydrate is added, is heated to reflux 1-3h, is cooled to room temperature, is rotated, adds salt
Acid, pH is adjusted, filtered, drying, produce rhodamine acid amides；
Step 5：Product R and rhodamine acid amides are dissolved in solvent, add acetic acid, heating reflux reaction 5-6 h, reaction terminates
Afterwards, rotate, produce the response type rhodamine fluorescence probe of detection mercury ion.
2. the preparation method of the response type rhodamine fluorescence probe of detection mercury ion, its feature exist as claimed in claim 1
In the mol ratio of 2- bromo methyl cycloheptapyridines hydrobromate and sodium azide in described step 1 is 1：2.5~3.
3. the preparation method of the response type rhodamine fluorescence probe of detection mercury ion, its feature exist as claimed in claim 1
In catalyst is potassium carbonate in described step 2, and the mol ratio of parahydroxyben-zaldehyde, propargyl bromide and catalyst is 1：0.4~
0.45：0.4~0.45.
4. the preparation method of the response type rhodamine fluorescence probe of detection mercury ion, its feature exist as claimed in claim 1
In the extraction in described step 2 is：Water is added in reaction system, is extracted with dichloromethane, solvent, water in step 2 and
The volume ratio of dichloromethane is 1：0.2~0.3：0.5~1.
5. the preparation method of the response type rhodamine fluorescence probe of detection mercury ion, its feature exist as claimed in claim 1
In the catalyst in described step 3 is CuSO4·5H2O and sodium ascorbate, described 4- (2- alkynyls propoxyl group) benzene first
Aldehyde, 2- azido-methyls pyridine, CuSO4·5H2The mol ratio of O and sodium ascorbate is 1：0.5~1：0.5~0.8：0.8~1.
6. the preparation method of the response type rhodamine fluorescence probe of detection mercury ion, its feature exist as claimed in claim 1
In the mol ratio of described rhodamine B, hydrazine hydrate and hydrochloric acid is 1：0.02~0.05：0.03~0.05.
7. the preparation method of the response type rhodamine fluorescence probe of detection mercury ion, its feature exist as claimed in claim 1
In the regulation pH in described step 4 is to adjust pH=9.0-10.0 using sodium hydroxide.
8. the preparation method of the response type rhodamine fluorescence probe of detection mercury ion, its feature exist as claimed in claim 1
In product R, rhodamine acid amides and acetic acid mol ratio are 1 in described step 5：0.8~1：0.02~0.03.
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| CN105911039B (en) * | 2016-04-22 | 2019-06-21 | 东华大学 | A method of trivalent chromic ion is detected using rhodamine fluorescence probe |
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| CN107245334B (en) * | 2017-06-23 | 2019-05-03 | 东华大学 | A kind of water soluble polymer fluoresceins fluorescence probe and preparation method thereof detecting mercury ion |
| CN109761992B (en) * | 2018-12-17 | 2021-03-12 | 齐鲁工业大学 | Triazolyl benzaldehyde rhodamine hydrazine hydrate Schiff base and preparation method thereof |
| CN113061139A (en) * | 2021-03-26 | 2021-07-02 | 辽宁大学 | Hexabasic spiro rhodamine fluorescent probe containing aminourea structure and preparation method and application thereof |
| CN113070050B (en) * | 2021-04-28 | 2022-06-21 | 山东大学 | Chitosan-based hydrogel adsorbent capable of visually identifying and removing mercury ions and preparation method and application thereof |
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