CN102053079B - Fluorescent sensor for magnesium ions and preparation method thereof - Google Patents
Fluorescent sensor for magnesium ions and preparation method thereof Download PDFInfo
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- CN102053079B CN102053079B CN2010105679858A CN201010567985A CN102053079B CN 102053079 B CN102053079 B CN 102053079B CN 2010105679858 A CN2010105679858 A CN 2010105679858A CN 201010567985 A CN201010567985 A CN 201010567985A CN 102053079 B CN102053079 B CN 102053079B
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Abstract
The invention discloses a fluorescent sensor for magnesium ions, which is made of an organic-inorganic composite material, and a preparation method thereof, and belongs to the technical field of fluorescent sensor preparation. Due to exchangeability of anions among hydrotalcite layers, 1-naphthylamine-3,6,8-trisulfonic acid is inserted among the hydrotalcite layers through an ion exchange method, a film is prepared by an electrochemical deposition method, and the fluorescence response of a film sensor to the magnesium ions is examined. In the prepared fluorescent sensor for the magnesium ions, the hydrotalcite is nontoxic and stable, and has high biocompatibility; different from a polymer carrier, an inorganic laminate of the hydrotalcite is difficult to age and can be stored for a long time so as to keep the optical stability of fluorescent ions and obviously improve the thermal stability of the fluorescent ions; and the sensor has high selectivity for the magnesium ions, shows a linear relationship in a certain range, and has repeated operability.
Description
Technical field
The invention belongs to the fluorescent optical sensor preparing technical field, particularly provide a kind of composite organic-inorganic material as magnesium ion fluorescent optical sensor and preparation method thereof.
Background technology
Fluorescent optical sensor is with highly sensitive, but advantage such as acquired signal is abundant and easy to use extremely people pay close attention to, obtained in recent years developing rapidly.Fluorescent optical sensor mainly is divided into two types, homogeneous fluorescent sensor that promptly in solution, uses and the film fluorescent optical sensor that is easy to reuse and can carry out the gas phase sensing.The research of film fluorescent optical sensor in recent years receives people's special concern.
Use homogeneous fluorescent chemical sensor principle, designing and preparing film fluorescent optical sensor is an effective way of fluorescent optical sensor being pushed to practical application or expanding application.With respect to the homogeneous fluorescent sensor, the film fluorescent optical sensor has and can use repeatedly, does not pollute system to be measured, and no reagent consumption is easy to advantages such as device.Therefore, the research of film fluorescent optical sensor has constituted the important content of current unimolecular layer chemical research, also becomes a wherein most active branch.Yet up to the present, the research of film fluorescent optical sensor is also very weak, and most researchs still are in conceptual phase.Be difficult to deeply carry out because of characterizing difficulty with distribution, existence and the surface chemistry Study on Problems such as state variation in the sensing process thereof of the closely-related sensing element of film fluorescent optical sensor designing and preparing in stromal surface, relevant theoretical modeling is also very preliminary.Meanwhile, real device, the film fluorescent optical sensor that can put into practical application is few in number.Therefore, hold on and deepen constantly the surface chemistry fundamental research relevant with the film fluorescent optical sensor, expanding existing applied research is the main contents of following film fluorescent optical sensor research.
The thermometal complex hydroxide is called hydrotalcite (Layered Double Hydroxides again; Be abbreviated as LDHs) be a kind of novel multifunctional stratified material; Its chemical stability is good, has strong heat resistanceheat resistant performance, also is being widely used aspect the slowly-releasing of medicine; And LDHs laminate species of metal ion and adjustable ratio become, and interlayer anion has interchangeability.Utilize this kind performance can be with naphthalidine-3,6, the 8-trisulfonic acid inserts hydrotalcite layers, forms the supramolecular structure system, develops the application of hydrotalcite aspect fluorescent optical sensor thus.
Summary of the invention
The object of the present invention is to provide a kind of hydrotalcite that utilizes the method that the naphthylamines analog derivative carries out inclusion to be prepared fluorescent optical sensor, and realized the good fluorescence response of magnesium ion for carrier.
The present invention utilizes the hydrotalcite layers negative ion to have interchangeability; With naphthalidine-3,6, the 8-trisulfonic acid is inserted into hydrotalcite layers through ion exchange process; Method through electrochemical deposition prepares film forming then, investigates the fluorescence response of thin film sensor to magnesium ion at last.
Concrete preparation process of the present invention is:
A. prepare the hydrotalcite precursor, the chemical formula of said hydrotalcite precursor is Zn
1-xAl
x(OH)
2(NO
3)
xMH
2O, 0.2≤x≤0.33 wherein, m is a water of crystallization quantity, span is 0.5-9;
B. compound concentration is the naphthalidine-3,6 of 1-10g/L, and 8-trisulfonic acid solution adds the hydrotalcite precursor of 0.1-1g step a preparation after using sodium hydrate regulator solution pH value as 6-7, at N
2Protection is stirred down, and 25-30 ℃ was reacted 24-60 hour down, and product spends CO
2Water washing, centrifugal obtains naphthalidine-3,6,8-trisulfonic acid intercalated houghite;
C. get the naphthalidine-3,6 of 0.5-2g step b preparation, 8-trisulfonic acid intercalated houghite is dissolved in the 50-100ml ethanolic solution ultrasonic 5-15 minute; Mixed solution is placed supercentrifuge; It is 3000-10000 rev/min that rotating speed is set, and centrifugal 5-10 minute, gets upper strata colloidal solution;
D. getting the upper strata colloidal solution 10-30ml that step c obtains and place electrochemical deposition liquid pond, is 2-6cm with area
2Electro-conductive glass FTO sheet is sandwiched on two electrodes, and it is 30-80v that voltage is set, and the electro-conductive glass FTO sheet with negative electrode after 1-6 minute takes out, and oven dry is the magnesium ion fluorescent optical sensor.
Described hydrotalcite precursor adopts coprecipitation, nucleation crystallization/isolation method, non-equilibrium crystallization method or hydrothermal synthesis method preparation.
The fluorescent optical sensor performance test:
A. the magnesium ion fluorescent optical sensor of getting preparation places the variable concentrations magnesium ion solution, investigates its fluorescence response value and changes;
B. the magnesium ion fluorescent optical sensor of getting preparation places the solution of different ions, investigates the variation of its fluorescence response value.
The invention has the advantages that: the magnesium ion fluorescent optical sensor of preparation, wherein hydrotalcite nontoxic, stablize, have good Bc; Different with polymer support, the inorganic laminate of hydrotalcite is difficult for aging, preservation that can be permanent, thereby the optical stability of maintenance fluorescence molecule, and significantly improve its thermal stability and the pH scope of application; This sensor has good selectivity and demonstrates linear relationship within the specific limits magnesium ion, and has repetitive operation property.
Description of drawings
Fig. 1 is hydrotalcite precursor and a naphthalidine-3,6 among the embodiment 1, the X-ray powder diffraction figure of 8-trisulfonic acid intercalated houghite, and wherein horizontal ordinate is 2 θ, unit: degree; Ordinate is an intensity; A is the hydrotalcite precursor, and b is a naphthalidine-3,6,8-trisulfonic acid intercalated houghite.
Fig. 2 is hydrotalcite precursor among the embodiment 1, naphthalidine-3,6,8-trisulfonic acid intercalated houghite and naphthalidine-3,6, and the infrared absorption figure of 8-trisulfonic acid, wherein horizontal ordinate is a wave number, unit: cm
-1Ordinate is an absorption intensity; A is a naphthalidine-3,6, and 8-trisulfonic acid, b are the hydrotalcite precursor, and c is a naphthalidine-3,6,8-trisulfonic acid intercalated houghite.
Fig. 3 is the magnesium ion solution fluorescence response value figure of the magnesium ion fluorescent optical sensor of embodiment 1 preparation to variable concentrations, and wherein horizontal ordinate is a wavelength, unit: nm; Ordinate is a fluorescent value, and magnesium ion concentration is followed successively by 0.1 * 10 from top to bottom
-6, 5 * 10
-6, 1 * 10
-5, 5 * 10
-5, 1 * 10
-4, 5 * 10
-4, 1 * 10
-3, 5 * 10
-3, 1 * 10
-2The solution fluorescence response value figure of mol/L.
Fig. 4 is the magnesium ion solution fluorescence response value linear graph of the magnesium ion fluorescent optical sensor of embodiment 1 preparation to variable concentrations, and wherein horizontal ordinate is a concentration, and unit: mol/L, ordinate are fluorescent value.
Fig. 5 is the fluorescence response relative changing value histogram of the magnesium ion fluorescent optical sensor of embodiment 1 preparation to the solution of different ions, and wherein horizontal ordinate is followed successively by 1 * 10
-4The K of mol/L
+, Na
+, Ca
2+, Fe
3+Metallic ion; Ordinate is the fluorescence response relative changing value, i.e. the ratio of changing value and initial fluorescence value.
Embodiment
A. the preparation of hydrotalcite precursor: adopt hydro-thermal method, take by weighing 53.55g Zn (NO
3)
26H
2O and 33.75gAL (NO
3)
39H
2O is dissolved in 100ml and removes CO
2Water in be mixed with salt solusion; Other gets 21.6g NaOH and is dissolved in 100ml and removes CO
2Water in preparation NaOH solution; Stir in the colloid mill with salt solusion and NaOH solution adding high-speed stirred and obtained pulpous state liquid in 1 minute; Pulpous state liquid is placed Pressure solution bullet, in 110 ℃ of reaction 10h, product is centrifugal, washing; The chemical formula of the hydrotalcite precursor of preparation is Zn
2Al (OH)
6(NO
3) 6H
2O;
B. compound concentration is the naphthalidine-3,6 of 3g/L, 8-trisulfonic acid solution, and using sodium hydrate regulator solution pH value is the hydrotalcite precursor that 6.5 backs add 0.5g step a preparation, at N
2Protection is stirred down, and 25 ℃ were reacted 48 hours down, and product spends CO
2Water washing, centrifugal obtains naphthalidine-3,6,8-trisulfonic acid intercalated houghite;
C. get the naphthalidine-3,6 of 1g step b preparation, 8-trisulfonic acid intercalated houghite is dissolved in the 60ml ethanolic solution ultrasonic 10 minutes, and mixed solution is placed supercentrifuge, and it is 7500 rev/mins that rotating speed is set, and centrifugal 8 minutes, gets upper strata colloidal solution;
D. get the upper strata colloidal solution 20ml that step c obtains and place electrochemical deposition liquid pond, 4cm
2Electro-conductive glass FTO sheet is sandwiched on two electrodes, and it is 50v that voltage is set, and the electro-conductive glass FTO sheet with negative electrode after 3 minutes takes out, and oven dry is the magnesium ion fluorescent optical sensor.
Can be known that by XRD, FT-IR spectrogram step b is with naphthalidine-3,6, the 8-trisulfonic acid is inserted into hydrotalcite layers.
The fluorescent optical sensor performance test
(1) the fluorescence response value to the variable concentrations magnesium ion solution changes:
Obtained magnesium ion fluorescent optical sensor is placed liquid cell, add 2000 μ L deionized water solutions, detect its initial fluorescence value.Measure the magnesium ion solution 10 μ L that configure with microsyringe and make that magnesium ion concentration reaches 1 * 10 in the liquid cell
-6Mol/L investigates its fluorescence pattern and changes and record.Measuring magnesium ion concentration then successively is 5 * 10
-6, 1 * 10
-5, 5 * 10
-5, 1 * 10
-4, 5 * 10
-4, 1 * 10
-3, 5 * 10
-3, 1 * 10
-2Solution, investigate its fluorescence pattern and change and record.Can find out that by fluorescence pattern behind the adding magnesium ion, fluorescent value obviously weakens, and demonstrates linear relationship within the specific limits.
(2) the fluorescent value response to the solution of different ions changes:
Obtained magnesium ion fluorescent optical sensor is placed liquid cell, add 2000 μ L deionized water solutions, detect its initial fluorescence value.Measure the Mg that configures with microsyringe
2+Solution 10 μ L make that magnesium ion concentration reaches 1 * 10 in the liquid cell
-4Mol/L investigates its fluorescence pattern and changes and record.
Repeat above-mentioned steps, measure 1 * 10 respectively
-4The K of mol/L
+, Na
+, Ca
2+, Fe
3+Solution.Investigating its fluorescence pattern changes and record.
Can find out that through the variation of fluorescence pattern this magnesium ion fluorescent optical sensor has good selectivity and demonstrates linear relationship within the specific limits magnesium ion.
A. with the step a of embodiment 1;
B. compound concentration is the naphthalidine-3,6 of 5g/L, 8-trisulfonic acid solution, and using sodium hydrate regulator solution pH value is the hydrotalcite precursor that 6 backs add 0.8g step a preparation, at N
2Protection is stirred down, and 28 ℃ were reacted 48 hours down, and product spends C0
2Water washing, centrifugal obtains naphthalidine-3,6,8-trisulfonic acid intercalated houghite;
C. get the naphthalidine-3,6 of 1g step b preparation, 8-trisulfonic acid intercalated houghite is dissolved in the 80ml ethanolic solution ultrasonic 6 minutes, and mixed solution is placed supercentrifuge, and it is 7500 rev/mins that rotating speed is set, and centrifugal 6 minutes, gets upper strata colloidal solution;
D. get the upper strata colloidal solution 20ml that step c obtains and place electrochemical deposition liquid pond, 5cm
2Electro-conductive glass FTO sheet is sandwiched on two electrodes, and it is 65v that voltage is set, and the electro-conductive glass FTO sheet with negative electrode after 4 minutes takes out, and oven dry is the magnesium ion fluorescent optical sensor.
A. with the step a of embodiment 1;
B. compound concentration is the naphthalidine-3,6 of 8g/L, 8-trisulfonic acid solution, and using sodium hydrate regulator solution pH value is the hydrotalcite precursor that 7 backs add 0.2g step a preparation, at N
2Protection is stirred down, and 30 ℃ were reacted 48 hours down, and product spends CO
2Water washing, centrifugal obtains naphthalidine-3,6,8-trisulfonic acid intercalated houghite;
C. get the naphthalidine-3,6 of 1g step b preparation, 8-trisulfonic acid intercalated houghite is dissolved in the 90ml ethanolic solution ultrasonic 12 minutes, and mixed solution is placed supercentrifuge, and it is 7500 rev/mins that rotating speed is set, and centrifugal 9 minutes, gets upper strata colloidal solution;
D. get the upper strata colloidal solution 20ml that step c obtains and place electrochemical deposition liquid pond, 3cm
2Electro-conductive glass FTO sheet is sandwiched on two electrodes, and it is 80v that voltage is set, and the electro-conductive glass FTO sheet with negative electrode after 5 minutes takes out, and oven dry is the magnesium ion fluorescent optical sensor.
Claims (2)
1. the preparation method of a magnesium ion fluorescent optical sensor is characterized in that, its concrete preparation process is:
A. prepare the hydrotalcite precursor, the chemical formula of said hydrotalcite precursor is Zn
1-xAl
x(OH)
2(NO
3)
xMH
2O, 0.2≤x≤0.33 wherein, m is a water of crystallization quantity, span is 0.5-9;
B. compound concentration is the naphthalidine-3,6 of 1-10g/L, and 8-trisulfonic acid solution adds the hydrotalcite precursor of 0.1-1g step a preparation after using sodium hydrate regulator solution pH value as 6-7, at N
2Protection is stirred down, and 25-30 ℃ was reacted 24-60 hour down, and product spends CO
2Water washing, centrifugal obtains naphthalidine-3,6,8-trisulfonic acid intercalated houghite;
C. get the naphthalidine-3,6 of 0.5-2g step b preparation, 8-trisulfonic acid intercalated houghite is dissolved in the 50-100ml ethanolic solution ultrasonic 5-15 minute; Mixed solution is placed supercentrifuge; It is 3000-10000 rev/min that rotating speed is set, and centrifugal 5-10 minute, gets upper strata colloidal solution;
D. getting the upper strata colloidal solution 10-30ml that step c obtains and place electrochemical deposition liquid pond, is 2-6cm with area
2Electro-conductive glass FTO sheet is sandwiched on two electrodes, and it is 30-80v that voltage is set, and the electro-conductive glass FTO sheet with negative electrode after 1-6 minute takes out, and oven dry is the magnesium ion fluorescent optical sensor.
2. the preparation method of a kind of magnesium ion fluorescent optical sensor according to claim 1 is characterized in that, described hydrotalcite precursor adopts coprecipitation, nucleation crystallization/isolation method, non-equilibrium crystallization method or hydrothermal synthesis method preparation.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1089940A (en) * | 1992-09-08 | 1994-07-27 | 拜尔公司 | 2-naphthylamines-1,5, the separation method of 7-trisulfonic acid |
| JP2007031189A (en) * | 2005-07-25 | 2007-02-08 | National Institute For Materials Science | Method for peeling layered double hydroxide, double hydroxide nanosheet, composite thin film material thereof, method for producing the same, and method for producing layered double hydroxide thin film material |
| CN101173118A (en) * | 2007-11-09 | 2008-05-07 | 北京化工大学 | Supramolecular structured 2-naphthylamine-1,5-disulfonic acid intercalation ultraviolet absorption material and method for producing the same |
| US20080170978A1 (en) * | 2007-01-12 | 2008-07-17 | Beijing University Of Chemical Technology | Clean method for preparing layered double hydroxides |
-
2010
- 2010-12-01 CN CN2010105679858A patent/CN102053079B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1089940A (en) * | 1992-09-08 | 1994-07-27 | 拜尔公司 | 2-naphthylamines-1,5, the separation method of 7-trisulfonic acid |
| JP2007031189A (en) * | 2005-07-25 | 2007-02-08 | National Institute For Materials Science | Method for peeling layered double hydroxide, double hydroxide nanosheet, composite thin film material thereof, method for producing the same, and method for producing layered double hydroxide thin film material |
| US20080170978A1 (en) * | 2007-01-12 | 2008-07-17 | Beijing University Of Chemical Technology | Clean method for preparing layered double hydroxides |
| CN101173118A (en) * | 2007-11-09 | 2008-05-07 | 北京化工大学 | Supramolecular structured 2-naphthylamine-1,5-disulfonic acid intercalation ultraviolet absorption material and method for producing the same |
Non-Patent Citations (1)
| Title |
|---|
| 王心蕊 等.酸性橙5插层Zn-Al水滑石薄膜的光致变色性能研究.《中国化学会第26届学术年会纳米化学分会场论文集》.2008,全文. * |
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