CN102206223A - Optical probe film and special-purposed organic dye for micro determination of copper ion content in water sample - Google Patents
Optical probe film and special-purposed organic dye for micro determination of copper ion content in water sample Download PDFInfo
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- CN102206223A CN102206223A CN2010101363451A CN201010136345A CN102206223A CN 102206223 A CN102206223 A CN 102206223A CN 2010101363451 A CN2010101363451 A CN 2010101363451A CN 201010136345 A CN201010136345 A CN 201010136345A CN 102206223 A CN102206223 A CN 102206223A
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Abstract
The invention discloses an optical probe film and a special-purposed organic dye for micro determinations of copper ion contents in water sample. The structural formula of the organic dye provided by the present invention is represented by formula I. On the basis of the organic dye, an active group -COCl is introduced. The -COCl group is subject to an amidation reaction with -NH2 on chitosan, and is fixed on a chitosan film through a covalent bond. With the above processes, an optical probe film is produced. The optical probe film has specific response to copper ions. Because copper ions and organic dye molecules are combined through reversible complexations, when the content of the dissociated copper ions in the water sample is changed, the copper ion content still can be reflected instantly. When in use, the film is immersed in a water sample requiring testing, the film is stood in the water sample for 5 minutes, and analysis and determination can be carried out upon the copper-ion-containing water sample through a spectrophotometer. The optical probe film provided by the present invention has advantages of easy production and low cost. According to the present invention, the optical film does not pollute the water system requiring testing, and can be repeatedly used. With the optical film provided by the present invention, an in situ on-line detection can be realized. (Formula I)
Description
Technical field
The present invention relates to a kind of optical probe film and special-purpose organic dye thereof that is used for the micro-investigating copper ion content of water sample.
Background technology
Cupric ion is a kind of common heavy metal ion that extensively is present in the environment, and it benefits the works better of keeping body intravital the having in right amount of people, as participates in intravital hemoposieis, enzyme reaction and some redox processeses or the like.But,, then might cause a series of diseases, as Menkes syndromes and Wilson syndromes etc. as cupric ion shortage or excessive if the metabolic balance of intravital cupric ion is destroyed.Thereby the content that detects cupric ion in the various water quality relevant with the human lives is extremely important.China's drinking water standard (GB 5749-85) regulation copper in drinking water ion content must not be higher than 1.0ppm, and Seawater Quality Standards (GB 3097-1997) requires in the first to fourth class seawater that content of copper ion must not be higher than 0.005,0.01,0.05 respectively, 0.05ppm.
The method that is usually used in analyzing cupric ion at present has anodic stripping method, atomic absorption spectrometry, spectrophotometry and fluorescent spectrometry.Wherein ion chromatography, atomic absorption spectrometry instrument complexity, analytical test is consuming time longer; Spectrophotometry and fluorescent spectrometry instrument are easy, analyze rapidly, are more suitable for the analysis of content of copper ion in water sample.But both common ground of back are directly to use organic dye in solution, and organic dye can only be dissolved in the organic solvent mostly, is easy to cause environmental pollution, and are difficult to reclaim, and can't reuse; Just there is following defective in mensuration cupral spectrophotometry as National Standard Method GB 7474-87 water quality copper: 1) needs use highly toxic organic solvent (as tetracol phenixin) to carry out extracting operation, 2) complex operation, introduce error easily, 3) transition metal ions such as iron, cobalt, nickel disturb bigger, often need to add masking reagent, 4) can not replication, easily pollute system to be measured.
Then can overcome above-mentioned shortcoming if organic dye can be fixed in stromal surface making solid phase transmitters such as glass surface or polymeric membrane, realize the repeated use of transmitter and reduce pollution, and then realize the online detection of original position etc.
Summary of the invention
Defective at prior art exists the invention provides a kind of optical probe film.This optical probe film has specificly-response to cupric ion, and is simple to operate when detecting cupric ion, very strong to the various ion immunity from interferencies beyond the cupric ion, and has reusability.
Optical probe film provided by the present invention, its structural representation are suc as formula shown in the II, and this probe film is to be obtained on chitosan film by covalent bonds by the organic dye shown in the formula I.
It is superpolymer that n among the formula II represents chitosan, and the chitosan molecule amount difference of different deacetylations, n value are also different.
The preparation method of probe film provided by the present invention comprises the steps:
With organic dye and the SOCl shown in the formula I
2In dichloromethane solvent, react, obtain rhodamine B 4-oxyethyl group acyl chlorides salicylic aldehyde schiff bases; And then make in the rhodamine B 4-oxyethyl group acyl chlorides salicylic aldehyde schiff bases-COCl group and chitosan film on the chitosan-NH
2Carry out amidate action, obtain described probe film.
Chitosan film described in the present invention can prepare according to following method:
A) chitosan is dissolved in the acetum that mass concentration is 1%-2%, obtains the chitosan-acetic acid solution that mass concentration is 1%-2%;
B) adding mass concentration in described chitosan-acetic acid solution is 37%～40% formaldehyde solution, stirring at room 1-2 hour, spread film then, the film of being spread is placed under the infrared lamp irradiation 20-24 hour, again resulting film was soaked 10-15 minute with 0.1-0.2mol/LNaOH, then extremely neutral, dry under infrared lamp at last with deionized water rinsing, promptly obtain chitosan film.
Wherein, to can be deacetylation be that 80%-90%, molecular weight are 9.0 * 10 to chitosan described in the step a)
5Da-1.86 * 10
6The chitosan of Da; The volume ratio of chitosan-acetic acid solution described in the step b) and described formaldehyde solution is 100: 1-130: 1.
A further object of the present invention provides the application of described optical probe film.
The application of optical probe film provided by the present invention is its application during content of copper ion is measured in to water sample, is particularly useful for the quantitative assay to 2.5～10 μ M cupric ions in the water sample.
In addition, organic dye shown in the formula I (rhodamine B hydrazides 4-oxyethyl group carboxyl salicylic aldehyde schiff bases) and preparation method thereof also belongs to protection scope of the present invention.
The preparation method of the organic dye shown in the formula I comprises the steps:
1) heating reflux reaction in ethanol with hydrazine hydrate and rhodamine B obtains the rhodamine B hydrazides;
2) heating reflux reaction in ethanol with rhodamine B hydrazides and 4-oxyethyl group carboxyl salicylic aldehyde obtains the organic dye shown in the formula I.
Wherein, the mol ratio 10 of hydrazine hydrate and rhodamine B: 1-20: 1 in the described reaction of step 1); The temperature of reflux described in the step 1) is 78-80 ℃, and the time is 1-2 hour; Step 2) mol ratio of rhodamine B hydrazides and 4-oxyethyl group carboxyl salicylic aldehyde is 1 in the described reaction: 3-1: 4; The temperature of reflux step 2) is 78 ℃-80 ℃, and the time is 5-6 hour.
Organic dye provided by the present invention (rhodamine B hydrazides 4-oxyethyl group carboxyl salicylic aldehyde schiff bases) possess with the cupric ion complexing after solution become red peculiar property by colourless, and has selectivity to the cupric ion height, the advantage of the interference to other metal ions very small (concentration that decuples cupric ion at least is noiseless to the cupric ion assay determination) is so this organic dye can be used for trace copper ionic qualitative and quantitative analysis in the water sample.With this specific specificity to the organic dye of cupric ion colour developing by covalent bonds on the chitosan film, obtained the optical probe film.When adopting this probe film to measure in water sample cupric ion, only need this film is immersed in the cupric ion water sample to be measured, places and take out film after 5 minutes, can be by the content of spectrophotometer cupric ion in 556nm place analysis mensuration water sample.This film is at least the linear response range of cupric ion in tap water and river water sample: 2.5～10 μ M, detectability 0.79 μ M.Most of transition metal ions, inorganic salts are all noiseless.
In addition, because film of the present invention is red to the colour developing of cupric ion, when with water sample to be measured with after film contacts, can qualitatively judge the roughly content of cupric ion in the water sample by the colour-change of film, further can carry out accurate quantitative analysis at the 556nm place, thereby satisfy the demand of field trial by spectrophotometer.
Compared with prior art the present invention has the following advantages:
1, optical probe film provided by the present invention has specificly-response to cupric ion, can be used for the quantitative analysis (variation of 556nm place absorbancy detects cupric ion) of water sample cupric ion.Linearity range is 2.5～10 μ M, and detectability is lower than 0.79 μ M.
2, optical probe film provided by the invention is with low cost, making is simple, easy to use, do not pollute system to be measured.
When 3, optical probe film provided by the invention is used for water sample cupric ion mensuration, be not subjected to the interference (noiseless when interferent concentration decuples copper ion concentration at least) of most of transition metal ions and inorganic salts.
4, optical probe film provided by the invention has reusability and can realize online detection.
Description of drawings
Fig. 1 is the absorbancy and the concentration working curve of 0～10 μ mol/L cupric ion in the water sample that the optical probe film is measured among the embodiment 3.
Fig. 2 is the abosrption spectrogram that the optical probe film is measured 0～50 μ mol/L cupric ion in the water sample among the embodiment 3.
Fig. 3 be among the embodiment 7 EDTA to the influence of chitosan film-cupric ion complex compound absorption spectrum; Wherein curve 1 is represented chitosan film, and curve 2 is represented chitosan film+50 μ mol cupric ions, and curve 3 is represented the EDTA of chitosan film+50 μ mol cupric ion+1mmol, the EDTA+1.5mmol cupric ion of curve 4 generation chitosan film+50 μ mol cupric ion+1mmol.
Embodiment
Below by specific embodiment optical probe film of the present invention is described, but the present invention is not limited thereto.Experimental technique described in the following embodiment if no special instructions, is ordinary method; Described reagent and material if no special instructions, all can obtain from commercial channels.
Add the 1.2g rhodamine B in the 100mL round-bottomed flask, 50mL ethanol and 3mL mass concentration 85% hydrazine hydrate are heated to 80 ℃ and refluxed 2 hours, filter out the precipitation (rhodamine B hydrazides) of generation, oven dry.0.436g gained solid is dissolved in the 20mL ethanol, add 0.78g 4-oxyethyl group carboxyl salicylic aldehyde, being heated to 80 ℃ of oil baths refluxed 6 hours, removal of solvent under reduced pressure, oven dry promptly got organic dye rhodamine B hydrazides 4-oxyethyl group carboxyl salicylic aldehyde schiff bases (RBHCOOH) after solid washed 3 times with ethanol.
The preparation of embodiment 2, optical probe film
1) making of chitosan film:
Take by weighing the chitosan (molecular weight 1.9 * 10 of deacetylation 90%
5) 0.1g is in the 25ml round-bottomed flask, adding 10ml 2%HAc stirring at room one day added 100 μ l (37%～40%) formaldehyde in second day, continued to stir 2 hours.Pipette wherein 500 μ l then at the face upper berth film (perhaps on sheet glass) of glass cuvette inwall, and glass cuvette (or sheet glass) is positioned under the infrared lamp, the crosslinking reaction of chitosan and formaldehyde solution continues 24 hours, afterwards, glass cuvette (or sheet glass) is cooled to room temperature, adds 0.1mol/LNaOH and soak 10 minutes (purpose deprotonation), then with a large amount of deionization washings, dry under infrared lamp, obtain the chitosan film that thickness is 10 μ m.
2) making of RBHCOOCl Covalent Immobilization chitosan film:
The RBHCOOH that accurately takes by weighing 123mg adds the CH of 15ml in the 50ml round-bottomed flask
2Cl
2, the SOCl of adding 138 μ l under the vigorous stirring
2(mol ratio RBHCOOH: SOCl
2=1: 10), oil bath refluxed 3 hours.Boil off solvent C H with Rotary Evaporators again
2Cl
2, obtain red-purple solid rhodamine B 4-oxyethyl group acyl chlorides salicylic aldehyde schiff bases.Add 18ml CH subsequently
2Cl
2, obtain rhodamine B 4-oxyethyl group acyl chlorides salicylic aldehyde schiff bases solution.
Dropwise add 280 μ l triethylamines under the vigorous stirring in above-mentioned rhodamine B 4-oxyethyl group acyl chlorides salicylic aldehyde schiff bases solution, pipette this solution 3.5ml then in the glass cuvette that is covered with chitosan film, make among the RBHCOCl-on COCl and the chitosan-NH
2Carry out acylation reaction.Last earlier with a large amount of water flushing cuvettes, use CH again
2Cl
2Wash, do not have and the covalently bound RBHCOCl of chitosan until removing fully.Afterwards, glass cuvette is positioned over the ventilation film is dried naturally, obtain the optical probe film.
Contain the Tris-HCl buffered soln of 50% acetonitrile (10mM, pH=7.0) in, the solution that 2mL is contained different concns cupric ion (0-50 μ M) adds and to be covered with in the glass cuvette of film.Placed 3～5 minutes down in room temperature (25 ℃), under 556nm, measure (abosrption spectrogram is seen Fig. 2) by spectrophotometer afterwards.At first determine working curve (curvilinear equation y=0.026+0.0062x) by the series of standards sample, have working curve as can be known, method of the present invention is linear good in 2.5～10 μ M copper ion concentration scopes at least.Again water samples such as tap water, river are carried out analytical test, proof utilizes optical probe film of the present invention can realize quantitative analysis to the cupric ion in 2.5～10 μ M scopes in the water sample at least at last.
Interference simultaneously, selectivity test show, most of salts, as sodium, potassium, magnesium, calcium, barium salt, with transition metal ion iron, cobalt, nickel, zinc, cadmium, lead and vitriol, hydrochloride, nitrate, phosphoric acid salt etc., at least all noiseless to measuring method of the present invention under the concentration of cupric ion up to 10 times.
Optical probe film with embodiment 2 preparations is analyzed Tsing-Hua University's drinking public water supply, can not detect absorbancy in the 556nm place, illustrates not record and contains cupric ion (being lower than detectability).Use aas determination also not detect copper, prove that the present invention does not produce any absorbance signal to the water sample of copper ions not.
In addition, behind the cupric ion standard substance (analytical pure Salzburg vitriol) of adding 6.0 μ M, with the film of embodiment 2 preparations it is measured in above-mentioned tap water again, detect cupric ion 5.85 μ M, the rate of recovery is 97.5%.Prove that method of the present invention is very accurate to trace copper ionic measurement in the tap water.
Embodiment 5, utilize the optical probe film that river is analyzed
Film with embodiment 2 preparations is analyzed river, Tsing-Hua University school river, and behind the adding 8.0 μ M cupric ions, it is measured with optical probe film of the present invention again, detects cupric ion 8.23 μ M, the rate of recovery 103.3% in this river.Prove that method of the present invention is very accurate to trace copper ionic measurement in the river.
Embodiment 6, utilize the optical probe film that the copper staining water sample is analyzed
With film of the present invention certain copper staining water sample is analyzed (copper ions 5 μ M, iron 10 μ M, manganese 50 μ M, zinc 50 μ M, each 50 μ M of sodium K-Mg-Ca, chlorion and each 10mM of nitrate radical), detecting copper ion concentration is 5.11 μ M.In addition, in this water sample, behind the adding 5 μ M cupric ions, with film of the present invention it is measured again, detect cupric ion 9.46 μ M, the rate of recovery 106%.
Embodiment 7, optical probe film repeatability detect the cupric ion in the solution
Containing the Tris-HCl buffered soln (10mM of 50% acetonitrile, pH=7.0) in, this film and 50 μ M cupric ion complexings produce the strong back (curve 2 among Fig. 3) that absorbs, if in system, add excessive 1mMEDTA (the strong complexing agent of cupric ion, with chitosan film competition cupric ion), then can make its absorption spectrum (curve 3 among Fig. 3) almost get back to absorption spectrum (curve 1 among Fig. 3) when not having cupric ion to exist; Further in system, add excessive cupric ion then, can embody the ultraviolet-visible absorption spectroscopy (curve 4 among Fig. 3) of cupric ion complex compound again once more.This result has proved that the complexing action of synthetic dyestuff and cupric ion and corresponding absorbancy enhancing signal are reversible, can regulate by adding copper ion complexing agent and cupric ion.Above phenomenon proves absolutely that the complexing of chitosan film and cupric ion is a reversible, and this chitosan film can be regenerated, and can be recycled and reused for the detection cupric ion.
Claims (11)
1. the compound shown in the formula I:
2. the preparation method of compound shown in the formula I comprises the steps:
1) heating reflux reaction in ethanol with hydrazine hydrate and rhodamine B obtains the rhodamine B hydrazides;
2) heating reflux reaction in ethanol with rhodamine B hydrazides and 4-oxyethyl group carboxyl salicylic aldehyde obtains the compound shown in the formula I.
3. method according to claim 2 is characterized in that: the mol ratio 10 of hydrazine hydrate and rhodamine B: 1-20: 1 in the described reaction of step 1); The temperature of reflux described in the step 1) is 78-80 ℃, and the time is 1-2 hour; Step 2) mol ratio of rhodamine B hydrazides and 4-oxyethyl group carboxyl salicylic aldehyde is 1 in the described reaction: 3-1: 4; The temperature of reflux step 2) is 78 ℃-80 ℃, and the time is 5-6 hour.
4. the optical probe film shown in the formula II is obtained on chitosan film by covalent bonds by compound shown in the claim 1 Chinese style I;
5. optical probe film according to claim 4 is characterized in that: described probe film is prepared according to following method: with compound and the SOCl shown in the formula I
2In dichloromethane solvent, react, obtain rhodamine B 4-oxyethyl group acyl chlorides salicylic aldehyde schiff bases; And then make in the rhodamine B 4-oxyethyl group acyl chlorides salicylic aldehyde schiff bases-COCl group and chitosan film on the chitosan-NH
2Carry out amidate action, obtain described probe film.
6. according to claim 4 or 5 described optical probe films, it is characterized in that: described chitosan film prepares according to following method:
A) chitosan is dissolved in the acetum that mass concentration is 1%-2%, obtains the chitosan-acetic acid solution that mass concentration is 1%-2%;
B) adding mass concentration in described chitosan-acetic acid solution is 37%～40% formaldehyde solution, stirring at room 1-2 hour, spread film then, the film of being spread is placed under the infrared lamp irradiation 20-24 hour, again resulting film was soaked 10-15 minute with 0.1-0.2mol/LNaOH, then extremely neutral, dry under infrared lamp at last with deionized water rinsing, promptly obtain chitosan film.
7. optical probe film according to claim 6 is characterized in that: chitosan described in the step a) is that deacetylation is that 80%-90%, molecular weight are 9.0 * 10
5Da-1.86 * 10
6The chitosan of Da; The volume ratio of chitosan-acetic acid solution described in the step b) and described formaldehyde solution is 100: 1-130: 1.
8. the preparation method of the described optical probe film of claim 4 comprises the steps: compound and the SOCl shown in the formula I
2In dichloromethane solvent, react, obtain rhodamine B 4-oxyethyl group acyl chlorides salicylic aldehyde schiff bases; And then make in the rhodamine B 4-oxyethyl group acyl chlorides salicylic aldehyde schiff bases-COCl group and chitosan film on the chitosan-NH
2Carry out amidate action, obtain described probe film.
9. method according to claim 8 is characterized in that: described chitosan film prepares according to following method:
A) chitosan is dissolved in the acetum that mass concentration is 1%-2%, obtains the chitosan-acetic acid solution that mass concentration is 1%-2%; Wherein, described chitosan is that deacetylation is that 80%-90%, molecular weight are 9.0 * 10
5Da-1.86 * 10
6The chitosan of Da;
B) adding mass concentration in described chitosan-acetic acid solution is 37%～40% formaldehyde solution, stirring at room 1-2 hour, spread film then, the film of being spread is placed under the infrared lamp irradiation 20-24 hour, again resulting film was soaked 10-15 minute with 0.1-0.2mol/LNaOH, then extremely neutral, dry under infrared lamp at last with deionized water rinsing, promptly obtain chitosan film; Wherein, the volume ratio of described chitosan-acetic acid solution and described formaldehyde solution is 100: 1-130: 1.
10. the described optical probe film of claim 4 application in the content of copper ion in measuring water sample.
11. application according to claim 10 is characterized in that: content of copper ion is 2.5-10 μ M in the described water sample.
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| CN105400233A (en) * | 2015-12-31 | 2016-03-16 | 东华大学 | Functional reactive dye for zinc ion probe, and preparation method and application thereof |
| CN105885828A (en) * | 2016-04-21 | 2016-08-24 | 湘潭大学 | Method for preparing water-soluble mercury ion fluorescence probe on basis of rhodamine and application of water-soluble mercury ion fluorescence probe |
| CN105885828B (en) * | 2016-04-21 | 2017-12-12 | 湘潭大学 | The preparation method and application of water-soluble mercury ion fluorescence probe based on rhodamine |
| CN105866316A (en) * | 2016-06-24 | 2016-08-17 | 曲阜师范大学 | Analysis method for simultaneous detection of amino acids and biogenic amines in foods |
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