CN103242368A - Nano chelating agent and preparation method thereof - Google Patents
Nano chelating agent and preparation method thereof Download PDFInfo
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- CN103242368A CN103242368A CN2013101475094A CN201310147509A CN103242368A CN 103242368 A CN103242368 A CN 103242368A CN 2013101475094 A CN2013101475094 A CN 2013101475094A CN 201310147509 A CN201310147509 A CN 201310147509A CN 103242368 A CN103242368 A CN 103242368A
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Abstract
The invention discloses a nano chelating agent and a preparation method thereof, and belongs to the field of chelating agents. The nano chelating agent has the following structural formula. The preparation method comprises the steps as follows: carrying out amidation reaction on a carboxyl arsenazo solution and an NH2-POSS solution to obtain a solution of the nano chelating agent under the action of a condensating agent. According to the nano chelating agent, the metal ion enrichment efficiency can be improved, and trace metal ions, even ultratrace metal ions, can be detected by adopting a spectrophotometric method. According to the preparation method, the process is simple, the reaction conditions are easy to meet and the nano chelating agent is easy to prepare.
Description
Technical field
The present invention relates to the sequestrant field, particularly a kind of nanometer sequestrant and preparation method thereof.
Background technology
Sequestrant has another name called complexing agent, is that a kind of energy and heavy metal ion generation sequestering action form stable water soluble complex, and sequestrant is by generating colored material with metal ion reaction, and with the content of this metal ion of spectrophotometry.
Existing sequestrant is used the content of spectrophotometry metal ion more, and for the metal ion of trace even ultra-trace, because its content seldom, be combined the back to be difficult to be detected by spectrophotometry with sequestrant, therefore, can only adopt atomic absorption spectrometry to detect the content of its metal ion.
In realizing process of the present invention, the contriver finds that there is following problem at least in prior art:
The equipment that atomic absorption spectrometry adopts is expensive more a lot of than the equipment that light splitting light-intensity method adopts, and the maintenance cost of atomic absorption spectrometry equipment used is also very high, so for the ion that detects trace, cost is higher.
Summary of the invention
In order to solve the metal ion cost problem of higher that prior art detects trace even ultra-trace, the embodiment of the invention provides a kind of nanometer sequestrant and preparation method thereof.Described technical scheme is as follows:
On the one hand, the invention provides a kind of nanometer sequestrant, the structural formula of nanometer sequestrant is:
Wherein, POSS is cage-type silsesquioxane, and molecular formula is C
31H
71NO
12Si
8, the structure of described POSS is:
Wherein, R is isobutyl-.
On the other hand, the invention provides a kind of preparation method of above-mentioned nanometer sequestrant, described method comprises: will be to carboxyl arsenazo and NH
2-POSS makes respectively carboxyl arsenazo solution and NH
2-POSS solution and under the condensing agent effect, to described to carboxyl arsenazo solution and described NH
2-POSS solution carries out amidate action, obtains the solution of described nanometer sequestrant, and is described to carboxyl arsenazo and described NH
2The mol ratio of-POSS is 1:1-3, described condensing agent is dicyclohexylcarbodiimide or 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, described condensing agent and described mol ratio to the carboxyl arsenazo are 1.2-3.6:1, the temperature of described amidate action is 0-40 ℃, obtain the solution of described nanometer sequestrant, make the nanometer sequestrant by the solution of described nanometer sequestrant.
Preferably, the temperature of described amidate action is 20 ℃.
Alternatively, described solute to carboxyl arsenazo solution is described to the carboxyl arsenazo, and described solvent to carboxyl arsenazo solution is dehydrated alcohol or anhydrous methanol, and described mass concentration to carboxyl arsenazo solution is 0.671 * 10
-2G/mL～1.342 * 10
-2G/mL.
Alternatively, described NH
2The solute of-POSS solution is described NH
2-POSS, described NH
2The solvent of-POSS solution is trichloromethane or tetrahydrofuran (THF), described NH
2The mass concentration of-POSS solution is 2.5 * 10
-2G/mL～2.9 * 10
-2G/mL.
Alternatively, described amidate action also comprises catalyzer, and described catalyzer is 4-Dimethylamino pyridine or carbonyl dimidazoles, and described catalyzer and described mol ratio to the carboxyl arsenazo are 1-3:20, and the time of described amidate action is 12-24h.
Alternatively, described solution by described nanometer sequestrant makes the nanometer sequestrant, comprising:
The solution of described nanometer sequestrant is air-dry, add distilled water and obtain first filter cake to having solid to separate out and carrying out suction filtration, described first filter cake is dried under infrared lamp, obtain described nanometer sequestrant.
Alternatively, described is that the diazonium salt solution of para-amino benzoic acid of 0.031g/mL and arsenazo solution that mass concentration is 0.12g/mL carry out the azo reaction and obtains by mass concentration to carboxyl arsenazo solution, the volume ratio of the diazonium salt solution of described para-amino benzoic acid and described arsenazo solution is 0.9-1.2:1, the pH regulator agent of described azo reaction is lithium hydroxide, the mass ratio of described arsenazo and described lithium hydroxide is 4:5-15, the temperature of described azo reaction is 0-5 ℃, the time of described azo reaction is 5-10min, described azo reaction pH value is 8-10, obtains described to carboxyl arsenazo solution.
Alternatively, the temperature of described azo reaction is 0 ℃, and the time of described azo reaction is 8min, and described azo reaction pH value is 9.
Alternatively, the diazonium salt solution of described para-amino benzoic acid prepares by the following method: under 0 ℃ of condition, be that the described para-amino benzoic acid of 0.035g/mL is dissolved in the hydrochloric acid that concentration is 6mol/L and makes mixing solutions with mass concentration, the sodium nitrite solution that with concentration is 0.5g/mL again splashes into to described mixing solutions, make the diazonium salt solution of described para-amino benzoic acid, the volume ratio of described sodium nitrite solution and described mixing solutions is 1:8.
Alternatively, to described be that 37% concentrated hydrochloric acid obtains second filter cake to having solid to separate out and carrying out suction filtration to adding massfraction in the carboxylic arsenazo solution, described second filter cake is dried under infrared lamp, obtain described to the carboxylic arsenazo.
The beneficial effect that the technical scheme that the embodiment of the invention provides is brought is: nanometer sequestrant provided by the invention, can improve the bioaccumulation efficiency to metal ion, make the metal ion of trace even ultra-trace can adopt spectrophotometry to detect, preparation method provided by the invention, technology is simple, reaction conditions easily reaches, and product easily makes.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, below with embodiment of the present invention is described further in detail.
On the one hand, the invention provides a kind of nanometer sequestrant, the structural formula of this nanometer sequestrant is:
Wherein, POSS is cage-type silsesquioxane, and molecular formula is C
31H
71NO
12Si
8, the structure of POSS is:
Wherein, R is isobutyl-.
Nanometer sequestrant and NH that the embodiment of the invention provides
2-POSS compares: the nanometer sequestrant can either be dissolved in the ethanolic soln, and also can evenly be suspended in the aqueous solution, and keep not precipitating at least two days, and NH
2-POSS then is water insoluble and white precipitate ethanol; In addition, the tetrahydrofuran solution of nanometer sequestrant is red-purple, and NH
2The tetrahydrofuran solution of-POSS then is clear, colorless, and these significant solvabilities and change in physical show that the keyed jointing to the carboxylic arsenazo has changed NH
2The solvability of-POSS nano particle has generated the nanometer sequestrant with selective separation and enriched in metals ion.
On the other hand, the invention provides a kind of preparation method of above-mentioned nanometer sequestrant, this method comprises: alternatively, the diazonium salt solution of para-amino benzoic acid can prepare by the following method: under 0 ℃ of condition, be that the para-amino benzoic acid of 0.035g/mL is dissolved in the hydrochloric acid that concentration is 6mol/L and makes mixing solutions with mass concentration, the sodium nitrite solution that with concentration is 0.5g/mL again splashes into to mixing solutions, make the diazonium salt solution of para-amino benzoic acid, the volume ratio of sodium nitrite solution and mixing solutions is 1:8.
Alternatively, the temperature of azo reaction is 0 ℃, and the time of azo reaction is 8min, and the azo reaction pH value is 9.
Alternatively, can be that the diazonium salt solution of para-amino benzoic acid of 0.031g/mL and arsenazo solution that mass concentration is 0.12g/mL carry out the azo reaction and obtains by mass concentration to carboxyl arsenazo solution, the volume ratio of the diazonium salt solution of para-amino benzoic acid and arsenazo solution is 0.9-1.2:1, the pH regulator agent of azo reaction is lithium hydroxide, the mass ratio of arsenazo and lithium hydroxide is 4:5-15, the temperature of azo reaction is 0-5 ℃, the time of azo reaction is 5-10min, the azo reaction pH value is 8-10, obtains carboxyl arsenazo solution.
Alternatively, obtain second filter cake to the concentrated hydrochloric acid that to adding massfraction in the carboxylic arsenazo solution is 37% to having solid to separate out and carrying out suction filtration, second filter cake is dried under infrared lamp, obtain the carboxylic arsenazo.
Will be to carboxyl arsenazo and NH
2-POSS makes respectively carboxyl arsenazo solution and NH
2-POSS solution and under the condensing agent effect, to carboxyl arsenazo solution and NH
2-POSS solution carries out amidate action, obtains the solution of nanometer sequestrant, to carboxyl arsenazo and NH
2The mol ratio of-POSS is 1:1-3, condensing agent is dicyclohexylcarbodiimide or 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, the dicyclohexylcarbodiimide condensing agent be 1.2-3.6:1 to the mol ratio of carboxyl arsenazo, the temperature of amidate action is 0-40 ℃, obtain the solution of nanometer sequestrant, make the nanometer sequestrant by the solution of nanometer sequestrant.
Preferably, the temperature of amidate action is 20 ℃.
Alternatively, be to the carboxyl arsenazo to the solute of carboxyl arsenazo solution, be dehydrated alcohol or anhydrous methanol to the solvent of carboxyl arsenazo solution, be 0.671 * 10 to the mass concentration of carboxyl arsenazo solution
-2G/mL～1.342 * 10
-2G/mL.
Alternatively, NH
2The solute of-POSS solution is NH
2-POSS, NH
2The solvent of-POSS solution is trichloromethane or tetrahydrofuran (THF), NH
2The mass concentration of-POSS solution is 2.5 * 10
-2G/mL～2.9 * 10
-2G/mL.
Alternatively, amidate action also comprises catalyzer, and catalyzer is 4-Dimethylamino pyridine or carbonyl dimidazoles, catalyzer be 1-3:20 to the mol ratio of carboxyl arsenazo, the time of amidate action is 12-24h.
Alternatively, make the nanometer sequestrant by the solution of nanometer sequestrant, comprising: the solution of nanometer sequestrant is air-dry, add distilled water and obtain first filter cake to having solid to separate out and carrying out suction filtration, first filter cake is dried under infrared lamp, obtain the nanometer sequestrant.
Preparation method provided by the invention, technology is simple, and reaction conditions easily reaches, and product easily makes.
The nanometer sequestrant that adopts the embodiment of the invention to provide is measured Cu
2+Method be to get The addition of C u
2+, the CH of pH=4.6
3COOH-CH
3The nanometer sequestrant that COONa and the embodiment of the invention provide behind the constant volume, carries out centrifugation in the 50mL centrifuge tube; Inner complex enrichment after separating is settled to 1.5mL with dehydrated alcohol, measures at spectrophotometer, its chromophoric solution volume concentrates 33 times after separation, and namely the enrichment multiple reaches 33 times.Adopt sequestrant of the prior art (to the carboxylic arsenazo) to measure Cu with same method
2+, finding that it only can be combined with metal ion chelatropic reaction takes place forms inner complex, can not realize the enrichment reaction.
Embodiment one
Under 0 ℃ of condition of ice bath, be that the para-amino benzoic acid of 0.035g/mL is dissolved in the hydrochloric acid that concentration is 6mol/L and makes mixing solutions with mass concentration, the sodium nitrite solution that with concentration is 0.5g/mL again splashes into to this mixing solutions, make the diazonium salt solution of para-amino benzoic acid, wherein, the volume ratio of sodium nitrite solution and mixing solutions is 1:8.
Other gets the 1.2g arsenazo and is dissolved in and makes arsenazo solution in the 10mL water, add the agent of 1.5g lithium hydroxide pH regulator, place 0 ℃ of ice bath, the diazonium salt solution of para-amino benzoic acid was splashed in the arsenazo solution fully at 8 minutes, wherein, the volume ratio of the diazonium salt solution of para-amino benzoic acid and arsenazo solution is 0.9:1, after dripping, add 1+1HCl and regulate pH value to 9, behind the placement 12h, adding 20mL massfraction is 37% concentrated hydrochloric acid, make having solid to separate out in the carboxylic arsenazo solution, carry out suction filtration and obtain filter cake, this filter cake is dried under infrared lamp, obtain the carboxyl arsenazo.
Get the carboxylic arsenazo of 0.671g, be dissolved in that to make mass concentration in the 100mL dehydrated alcohol be 0.671 * 10
-2G/mL to carboxylic arsenazo solution, get 0.875g NH more respectively
2-POSS, 0.2472g dicyclohexylcarbodiimide condensing agent and 0.0061g4-Dimethylamino pyridine catalyst mix are dissolved in mixture in the 30mL trichloromethane, and making mass concentration is 2.9 * 10
-2The NH that contains condensing agent and catalyzer of g/mL
2-POSS solution, the temperature of amidate action are 0 ℃, with above-mentioned prepare to carboxylic arsenazo solution and NH
2-POSS solution mixes, and after stirring 24h under the magnetic stirring apparatus, leaves standstill air-dryly, obtains the nanometer sequestrant.
The nanometer sequestrant that the embodiment of the invention provides with the carboxylic arsenazo is compared: the nanometer sequestrant has not only kept the highly selective chelating properties to carboxylic arsenazo and special metal ion, this specific metal ion has: copper, iron, aluminium etc., have simultaneously special metal ions such as copper, iron, aluminium are carried out efficiently concentrating and stalling characteristic, the present invention reaches 33 times at least to the enrichment multiple of copper.
Embodiment two
Under 0 ℃ of condition of ice bath, be that the para-amino benzoic acid of 0.035g/mL is dissolved in the hydrochloric acid that concentration is 6mol/L and makes mixing solutions with mass concentration, the sodium nitrite solution that with concentration is 0.5g/mL again splashes into to this mixing solutions, make the diazonium salt solution of para-amino benzoic acid, wherein, the volume ratio of sodium nitrite solution and mixing solutions is 1:8.
Other gets the 1.2g arsenazo and is dissolved in and makes arsenazo solution in the 10mL water, add the agent of 3g lithium hydroxide pH regulator, place 2 ℃ of ice baths, the diazonium salt solution of para-amino benzoic acid was splashed in the arsenazo solution fully at 10 minutes, wherein, the volume ratio of the diazonium salt solution of para-amino benzoic acid and arsenazo solution is 1.2:1, after dripping, add 1+1HCl and regulate pH value to 10, behind the placement 12h, adding 20mL massfraction is 37% concentrated hydrochloric acid, make having solid to separate out in the carboxylic arsenazo solution, carry out suction filtration and obtain filter cake, filter cake is dried under infrared lamp, obtain the carboxyl arsenazo.
Get the carboxylic arsenazo of 0.671g, be dissolved in that to make mass concentration in the 75mL anhydrous methanol be 1.0065 * 10
-2G/mL to carboxylic arsenazo solution, get 0.875g NH more respectively
2-POSS, 0.4944g dicyclohexylcarbodiimide condensing agent and 0.0122g4-Dimethylamino pyridine catalyst mix are dissolved in mixture in the 32.5mL trichloromethane, and making mass concentration is 2.7 * 10
-2The NH that contains condensing agent and catalyzer of g/mL
2-POSS solution, the temperature of amidate action are 20 ℃, with above-mentioned prepare to carboxylic arsenazo solution and NH
2-POSS solution mixes, and after stirring 18h under the magnetic stirring apparatus, leaves standstill air-dryly, obtains the nanometer sequestrant.
The nanometer sequestrant that the embodiment of the invention provides with the carboxylic arsenazo is compared: the nanometer sequestrant has not only kept the highly selective chelating properties to carboxylic arsenazo and special metal ion, have simultaneously the special metal ion is carried out efficiently concentrating and stalling characteristic, enrichment multiple of the present invention reaches 33 times at least.
Embodiment three
Under 0 ℃ of condition of ice bath, be that the para-amino benzoic acid of 0.035g/mL is dissolved in the hydrochloric acid that concentration is 6mol/L and makes mixing solutions with mass concentration, the sodium nitrite solution that with concentration is 0.5g/mL again splashes into to this mixing solutions, make the diazonium salt solution of para-amino benzoic acid, wherein, the volume ratio of sodium nitrite solution and mixing solutions is 1:8.
Other gets the 1.2g arsenazo and is dissolved in and makes arsenazo solution in the 10mL water, add the agent of 4.5g lithium hydroxide pH regulator, place 5 ℃ of ice baths, the diazonium salt solution of para-amino benzoic acid was splashed in the arsenazo solution fully at 5 minutes, wherein, the volume ratio of the diazonium salt solution of para-amino benzoic acid and arsenazo solution is 1:1, after dripping, add 1+1HCl and regulate pH value to 8, behind the placement 12h, adding 20mL massfraction is 37% concentrated hydrochloric acid, make having solid to separate out in the carboxylic arsenazo solution, carry out suction filtration and obtain filter cake, this filter cake is dried under infrared lamp, obtain the carboxyl arsenazo.
Get the carboxylic arsenazo of 0.671g, be dissolved in that to make mass concentration in the 50mL dehydrated alcohol be 1.342 * 10
-2The alcoholic solution to the carboxylic arsenazo of g/mL is got 0.875g NH more respectively
2-POSS, 0.7416g dicyclohexylcarbodiimide condensing agent and 0.0183g4-Dimethylamino pyridine catalyst mix are dissolved in mixture in the 35mL tetrahydrofuran (THF), and making mass concentration is 2.5 * 10
-2The NH that contains condensing agent and catalyzer of g/mL
2-POSS solution, the temperature of amidate action are 40 ℃, with above-mentioned to carboxylic arsenazo solution and NH
2-POSS solution mixes, and after stirring 12h under the magnetic stirring apparatus, leaves standstill air-dryly, obtains the nanometer sequestrant.
Embodiment four
Under 0 ℃ of condition of ice bath, be that the para-amino benzoic acid of 0.035g/mL is dissolved in the hydrochloric acid that concentration is 6mol/L and makes mixing solutions with mass concentration, the sodium nitrite solution that with concentration is 0.5g/mL again splashes into to this mixing solutions, make the diazonium salt solution of para-amino benzoic acid, wherein, the volume ratio of sodium nitrite solution and mixing solutions is 1:8.
Other gets the 1.2g arsenazo and is dissolved in and makes arsenazo solution in the 10mL water, add the agent of 4g lithium hydroxide pH regulator, place 1 ℃ of ice bath, the diazonium salt solution of para-amino benzoic acid was splashed in the arsenazo solution fully at 5 minutes, wherein, the volume ratio of the diazonium salt solution of para-amino benzoic acid and arsenazo solution is 1.1:1, after dripping, add 1+1HCl and regulate pH value to 9, behind the placement 12h, adding 20mL massfraction is 37% concentrated hydrochloric acid, make having solid to separate out in the carboxylic arsenazo solution, carry out suction filtration and obtain filter cake, this filter cake is dried under infrared lamp, obtain the carboxyl arsenazo.
Get the carboxylic arsenazo of 0.671g, be dissolved in that to make mass concentration in the 80mL dehydrated alcohol be 0.839 * 10
-2The alcoholic solution to the carboxylic arsenazo of g/mL is got 0.875g NH more respectively
2-POSS and 0.2472g dicyclohexylcarbodiimide condensing agent mix, and mixture is dissolved in the 34mL tetrahydrofuran (THF), and making mass concentration is 2.6 * 10
-2The NH that contains condensing agent of g/mL
2-POSS solution, the temperature of amidate action are 30 ℃, with above-mentioned to carboxylic arsenazo solution and NH
2-POSS solution mixes, and after stirring 72h under the magnetic stirring apparatus, leaves standstill air-dryly, obtains the nanometer sequestrant.
Embodiment five
Under 0 ℃ of condition of ice bath, be that the para-amino benzoic acid of 0.035g/mL is dissolved in the hydrochloric acid that concentration is 6mol/L and makes mixing solutions with mass concentration, the sodium nitrite solution that with concentration is 0.5g/mL again splashes into to this mixing solutions, make the diazonium salt solution of para-amino benzoic acid, wherein, the volume ratio of sodium nitrite solution and mixing solutions is 1:8.
Other gets the 1.2g arsenazo and is dissolved in and makes arsenazo solution in the 10mL water, add the agent of 1.5g lithium hydroxide pH regulator, place 0 ℃ of ice bath, the diazonium salt solution of para-amino benzoic acid was splashed in the arsenazo solution fully at 8 minutes, wherein, the volume ratio of the diazonium salt solution of para-amino benzoic acid and arsenazo solution is 0.9:1, after dripping, add 1+1HCl and regulate pH value to 9, behind the placement 12h, adding 20mL massfraction is 37% concentrated hydrochloric acid, make having solid to separate out in the carboxylic arsenazo solution, carry out suction filtration and obtain filter cake, this filter cake is dried under infrared lamp, obtain the carboxyl arsenazo.
Get the carboxylic arsenazo of 0.671g, be dissolved in that to make mass concentration in the 100mL dehydrated alcohol be 0.671 * 10
-2G/mL to carboxylic arsenazo solution, get 0.875g NH more respectively
2-POSS, 0.2292g1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride condensing agent and 0.0081g carbonyl dimidazoles catalyst mix are dissolved in mixture in the 30mL trichloromethane, and making mass concentration is 2.9 * 10
-2The NH that contains condensing agent and catalyzer of g/mL
2-POSS solution, the temperature of amidate action are 0 ℃, with above-mentioned prepare to carboxylic arsenazo solution and NH
2-POSS solution mixes, and after stirring 24h under the magnetic stirring apparatus, leaves standstill air-dryly, obtains the nanometer sequestrant.
Embodiment six
Under 0 ℃ of condition of ice bath, be that the para-amino benzoic acid of 0.035g/mL is dissolved in the hydrochloric acid that concentration is 6mol/L and makes mixing solutions with mass concentration, the sodium nitrite solution that with concentration is 0.5g/mL again splashes into to this mixing solutions, make the diazonium salt solution of para-amino benzoic acid, wherein, the volume ratio of sodium nitrite solution and mixing solutions is 1:8.
Other gets the 1.2g arsenazo and is dissolved in and makes arsenazo solution in the 10mL water, add the agent of 3g lithium hydroxide pH regulator, place 2 ℃ of ice baths, the diazonium salt solution of para-amino benzoic acid was splashed in the arsenazo solution fully at 10 minutes, wherein, the volume ratio of the diazonium salt solution of para-amino benzoic acid and arsenazo solution is 1.2:1, after dripping, add 1+1HCl and regulate pH value to 10, behind the placement 12h, adding 20mL massfraction is 37% concentrated hydrochloric acid, make having solid to separate out in the carboxylic arsenazo solution, carry out suction filtration and obtain filter cake, filter cake is dried under infrared lamp, obtain the carboxyl arsenazo.
Get the carboxylic arsenazo of 0.671g, be dissolved in that to make mass concentration in the 75mL anhydrous methanol be 1.0065 * 10
-2G/mL to carboxylic arsenazo solution, get 0.875g NH more respectively
2-POSS, 0.4584g1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride condensing agent and 0.0162g carbonyl dimidazoles catalyst mix are dissolved in mixture in the 32.5mL trichloromethane, and making mass concentration is 2.7 * 10
-2The NH that contains condensing agent and catalyzer of g/mL
2-POSS solution, the temperature of amidate action are 20 ℃, with above-mentioned prepare to carboxylic arsenazo solution and NH
2-POSS solution mixes, and after stirring 18h under the magnetic stirring apparatus, leaves standstill air-dryly, obtains the nanometer sequestrant.
Embodiment seven
Under 0 ℃ of condition of ice bath, be that the para-amino benzoic acid of 0.035g/mL is dissolved in the hydrochloric acid that concentration is 6mol/L and makes mixing solutions with mass concentration, the sodium nitrite solution that with concentration is 0.5g/mL again splashes into to this mixing solutions, make the diazonium salt solution of para-amino benzoic acid, wherein, the volume ratio of sodium nitrite solution and mixing solutions is 1:8.
Other gets the 1.2g arsenazo and is dissolved in and makes arsenazo solution in the 10mL water, add the agent of 4.5g lithium hydroxide pH regulator, place 5 ℃ of ice baths, the diazonium salt solution of para-amino benzoic acid was splashed in the arsenazo solution fully at 5 minutes, wherein, the volume ratio of the diazonium salt solution of para-amino benzoic acid and arsenazo solution is 1:1, after dripping, add 1+1HCl and regulate pH value to 8, behind the placement 12h, adding 20mL massfraction is 37% concentrated hydrochloric acid, make having solid to separate out in the carboxylic arsenazo solution, carry out suction filtration and obtain filter cake, this filter cake is dried under infrared lamp, obtain the carboxyl arsenazo.
Get the carboxylic arsenazo of 0.671g, be dissolved in that to make mass concentration in the 50mL dehydrated alcohol be 1.342 * 10
-2The alcoholic solution to the carboxylic arsenazo of g/mL is got 0.875g NH more respectively
2-POSS, 0.6876g1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride condensing agent and 0.0243g carbonyl dimidazoles catalyst mix are dissolved in mixture in the 35mL tetrahydrofuran (THF), and making mass concentration is 2.5 * 10
-2The NH that contains condensing agent and catalyzer of g/mL
2-POSS solution, the temperature of amidate action are 40 ℃, with above-mentioned to carboxylic arsenazo solution and NH
2-POSS solution mixes, and after stirring 12h under the magnetic stirring apparatus, leaves standstill air-dryly, obtains the nanometer sequestrant.
Nanometer sequestrant provided by the invention and Cu
2+CH at pH=4.6
3COOH-CH
3All can form stable blue title complex in COONa, phosphoric acid or the hydrochloric acid medium, adopt its maximum absorption of spectrophotometry at the 610nm place, absorbance and Cu
2+Linear in 0.2-10 μ g scope, its linear equation is A=0.06365C+0.0277, and wherein C represents the Cu in every 50mL solution to be measured
2+Quality (μ g/50mL), the molar absorptivity of title complex is 2.13 * 10
5Lmol
-1Cm
-1Provided by the present invention to carboxylic arsenazo raw material (being sequestrant of the prior art) and Cu
2+CH at pH=4.6
3COOH-CH
3All can form stable blue title complex in COONa, phosphoric acid or the hydrochloric acid medium, adopt its maximum absorption of spectrophotometry at the 610nm place, absorbance and Cu
2+Linear in 2-10 μ g scope, its linear equation is A=0.003925C-0.00185, wherein the unit of C: μ g/50mL, C represent the Cu in every 50mL solution to be measured
2+Quality, the molar absorptivity of title complex is 5.83 * 10
3Lmol
-1Cm
-1From the contrast of above data as can be known: the inner complex of nanometer sequestrant and cupric ion formation, its molar absorptivity be apparently higher than to carboxylic arsenazo sequestrant, and its chelating effect is also just apparently higher than to carboxylic arsenazo sequestrant.
The nanometer sequestrant that the embodiment of the invention provides with the carboxylic arsenazo is compared: the nanometer sequestrant has not only kept the highly selective chelating properties to carboxylic arsenazo and special metal ion, have simultaneously the special metal ion is carried out efficiently concentrating and stalling characteristic, enrichment multiple of the present invention reaches 33 times at least.
The invention described above embodiment sequence number does not represent the quality of embodiment just to description.
The above only is preferred embodiment of the present invention, and is in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a nanometer sequestrant is characterized in that, the structural formula of nanometer sequestrant is:
Wherein, POSS is cage-type silsesquioxane, and molecular formula is C
31H
71NO
12Si
8, the structure of described POSS is:
Wherein, R is isobutyl-.
2. the preparation method of a nanometer sequestrant as claimed in claim 1 is characterized in that, described method comprises:
Will be to carboxyl arsenazo and NH
2-POSS makes respectively carboxyl arsenazo solution and NH
2-POSS solution and under the condensing agent effect, to described to carboxyl arsenazo solution and described NH
2-POSS solution carries out amidate action, obtains the solution of described nanometer sequestrant, and is described to carboxyl arsenazo and described NH
2The mol ratio of-POSS is 1:1-3, described condensing agent is dicyclohexylcarbodiimide or 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, described condensing agent and described mol ratio to the carboxyl arsenazo are 1.2-3.6:1, the temperature of described amidate action is 0-40 ℃, makes the nanometer sequestrant by the solution of described nanometer sequestrant.
3. preparation method according to claim 2, it is characterized in that, described solute to carboxyl arsenazo solution is described to the carboxyl arsenazo, and described solvent to carboxyl arsenazo solution is dehydrated alcohol or anhydrous methanol, and described mass concentration to carboxyl arsenazo solution is 0.671 * 10
-2G/mL～1.342 * 10
-2G/mL.
4. preparation method according to claim 2 is characterized in that, described NH
2The solute of-POSS solution is described NH
2-POSS, described NH
2The solvent of-POSS solution is trichloromethane or tetrahydrofuran (THF), described NH
2The mass concentration of-POSS solution is 2.5 * 10
-2G/mL～2.9 * 10
-2G/mL.
5. preparation method according to claim 2, it is characterized in that, described amidate action also comprises catalyzer, described catalyzer is 4-Dimethylamino pyridine or carbonyl dimidazoles, described catalyzer and described mol ratio to the carboxyl arsenazo are 1-3:20, and the time of described amidate action is 12-24h.
6. preparation method according to claim 2 is characterized in that, described solution by described nanometer sequestrant makes the nanometer sequestrant, comprising:
The solution of described nanometer sequestrant is air-dry, add distilled water and obtain first filter cake to having solid to separate out and carrying out suction filtration, described first filter cake is dried under infrared lamp, obtain described nanometer sequestrant.
7. according to each described preparation method of claim 2-6, it is characterized in that, described is that the diazonium salt solution of para-amino benzoic acid of 0.031g/mL and arsenazo solution that mass concentration is 0.12g/mL carry out the azo reaction and obtains by mass concentration to carboxyl arsenazo solution, the volume ratio of the diazonium salt solution of described para-amino benzoic acid and described arsenazo solution is 0.9-1.2:1, the pH regulator agent of described azo reaction is lithium hydroxide, the mass ratio of described arsenazo and described lithium hydroxide is 4:5-15, the temperature of described azo reaction is 0-5 ℃, the time of described azo reaction is 5-10min, and described azo reaction pH value is 8-10.
8. preparation method according to claim 7 is characterized in that, the temperature of described azo reaction is 0 ℃, and the time of described azo reaction is 8min, and described azo reaction pH value is 9.
9. preparation method according to claim 7, it is characterized in that, the diazonium salt solution of described para-amino benzoic acid prepares by the following method: under 0 ℃ of condition, be that the described para-amino benzoic acid of 0.035g/mL is dissolved in the hydrochloric acid that concentration is 6mol/L and makes mixing solutions with mass concentration, the sodium nitrite solution that with concentration is 0.5g/mL again splashes into to described mixing solutions, make the diazonium salt solution of described para-amino benzoic acid, the volume ratio of described sodium nitrite solution and described mixing solutions is 1:8.
10. preparation method according to claim 7, it is characterized in that, to described be that 37% concentrated hydrochloric acid obtains second filter cake to having solid to separate out and carrying out suction filtration to adding massfraction in the carboxylic arsenazo solution, described second filter cake is dried under infrared lamp, obtain described to the carboxylic arsenazo.
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