CN104062271A - Xerogel for detecting substances in water phase and detecting device thereof - Google Patents
Xerogel for detecting substances in water phase and detecting device thereof Download PDFInfo
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- CN104062271A CN104062271A CN201310086591.4A CN201310086591A CN104062271A CN 104062271 A CN104062271 A CN 104062271A CN 201310086591 A CN201310086591 A CN 201310086591A CN 104062271 A CN104062271 A CN 104062271A
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Abstract
The invention provides xerogel loaded with a fluorescence probe, and a detecting device containing the xerogel and used for detecting substances in a water phase. The device of the invention is simple in structure, and high in identification speed for substances in a water phase, and can adopt non-water-soluble fluorescence probes for a single water phase system.
Description
Technical field
The invention belongs to the molecular recognition field in analytical chemistry field, particularly fluorescent probe molecule detects material in water.
Background technology
Molecular recognition is one of core content of supramolecular chemistry research, is by organic chemist and biochemist, to simulate native compound on molecular level to be proposed at first.Molecular recognition refers to main body (acceptor) to object (substrate) selective binding and produces the process of certain specific function, maintains the synergy that intermolecular acting force is several weak interaction forces (non-covalent bond).Molecular recognition can be divided into the identification of ion object and the identification of neutral molecule.When object is when the recognition group of acceptor is combined, physics or the chemical property of induction acceptor change, and are converted to detectable macroscopical signal.
Optochemical sensor due to the high sensitivity of fluorescence inherence, can detect in real time and can realize the superiority such as remote detection, it obtains flourish in molecular recognition and sensing, therefore becomes rapidly one of research frontier of Modern Analytical Chemistry.
Because traditional fluorescent probe molecule major part is not water-soluble, and may be due to the affecting cancellation it is luminous of water in water environment, therefore at pure water, the application of the fluorescent probe molecule in be mutually limited by very large.
The saturated water absorbing properties of height based on xerogel itself, is scattered in xerogel surface by water-insoluble molecular adsorption, can realize water-insoluble molecule and detect for the material in water.
Summary of the invention
The object of the present invention is to provide a kind of xerogel for detection of the material in water and preparation method thereof, described xerogel load has water-insoluble fluorescent probe molecule.
Another object of the present invention is to provide a kind of detection means for detection of material in water and preparation method thereof.
Another object of the present invention is to provide a kind of method of using detection means of the present invention to detect material in water.
The invention provides a kind of xerogel, it is characterized in that, described xerogel load has water-insoluble fluorescent probe molecule.
A kind of load according to the present invention has the xerogel of water-insoluble fluorescent probe molecule, and wherein said xerogel is for can the undissolvable cross-linked polymer of swelling in water, alcohol equal solvent.Described xerogel can form gel with solvent, wherein forms hydrogel (hydrogel) with water.
According to the present invention, described xerogel comprises natural polymer and the large class of synthetic macromolecule two, natural hydrophilic macromolecule comprises polysaccharide (for example starch, cellulose, alginic acid, hyaluronic acid, shitosan, agarose etc.), polypeptide class (such as collagen, polylysine, poly-L-GLU etc.), synthetic hydrophilic macromolecule comprise tygon, polyalcohols, polyacrylic acid and their derivant class (for example polymethylacrylic acid, polyacrylamide).
Load on water-insoluble fluorescent probe molecule on xerogel and can be non-water-soluble fluorescence probe arbitrarily, for example in patent CN102250134A, a disclosed class detects the fluorescence probe of fluorine ion, in CN101735277A, a disclosed class detects the rhodamine fluorescence probe of palladium ion, and above-mentioned two pieces of full patent texts are introduced in the present invention as a reference.
Xerogel of the present invention can be for detection of the material to be checked in water, the material of described material to be detected for reacting with described water-insoluble fluorescent probe molecule, for example metallic ion, nonmetallic ion, little molecule etc., wherein said water refers to simple aqueous solution.
The present invention further provides a kind of method of preparing above-mentioned xerogel, comprise the following steps:
(1) water-insoluble fluorescent probe molecule is dissolved in solvent, the more above-mentioned solution that contains probe molecule is mixed with xerogel, make its abundant saturated absorption;
(2), by the gel evaporate to dryness liquid of the saturated absorption in step (1), form the xerogel that load has fluorescent probe molecule.
According to the present invention, the middle evaporate to dryness liquid of step (2) is evaporate to dryness liquid in environment under low pressure preferably, and wherein environment under low pressure is preferably 0.01～1 atmospheric pressure.
The present invention further provides a kind of detection means for detection of material to be detected in water, it is characterized in that, comprising load of the present invention, have the xerogel of water-insoluble fluorescent probe molecule.
According to the present invention, described detection means comprises substrate, xerogel of the present invention and macromolecular material.
According to the present invention, described substrate is used for loading xerogel of the present invention.
According to the present invention, described macromolecular material is for being encapsulated in described substrate by xerogel of the present invention, and described macromolecular material is permeable at least partly, and described macromolecular material and/or substrate are for transparent or semitransparent at least partly.
According to the present invention, in described detection means, the consumption of xerogel of the present invention (i.e. the volume of the xerogel of filling) is based on for example, selecting for loading the volume in the space (groove) of xerogel of the present invention in substrate, preferably, the volume of described xerogel after fully absorbing water is more than or equal to the volume in the space (for example groove) for loading xerogel of the present invention.
According to the present invention, macromolecular material and/or substrate are set to transparent or semitransparent at least partly, are in order to detect the wherein luminescent spectrum of the fluorescence molecule on the xerogel surface of encapsulation.
According to the present invention, the effect of described substrate is only that it can be arbitrary shape as the container of fixing xerogel of the present invention.The material of described substrate can be metal, macromolecular material, glass, quartz.In described substrate, for loading the space of xerogel of the present invention, can be groove, through hole or other, arbitrary position that it can be in substrate, also can be arbitrary shape.
According to the present invention, described substrate is preferably a rectangle, preferred, and substrate thickness is 1～20mm, and area is 1-100cm
2.Describedly for loading the part of xerogel of the present invention, be preferably groove, particularly preferably the center in substrate.Described groove is preferably a cylindrical aperture.Preferred, the diameter of described aperture is 1～10mm, and the degree of depth is preferably 0.5-10mm.
The preferred polymeric membrane of described macromolecular material, described macromolecular material for example can be tygon, polystyrene or Polyvinylchloride.
Described at least part of permeable macromolecular material is preferably provided with one or more holes on macromolecular material, preferred, uses pin on macromolecular material, to prick hole.
Further preferred, detection means of the present invention, comprise the reeded substrate of tool, xerogel of the present invention is housed in described groove, and on groove, be packaged with permeable macromolecular material at least partly, described macromolecular material and/or substrate are for transparent or semitransparent at least partly.
The preparation method who the present invention further provides a kind of detection means for detection of material to be detected in water, comprises the following steps:
(1) xerogel described in the present invention is loaded in substrate;
(2) substrate after filling step (1) being obtained encapsulates with macromolecular material, wherein said macromolecular material part is permeable (preferably arranges one or more holes on macromolecular material, for example use pinprick hole), the macromolecular material that wherein used and/or substrate are substantial transparent or translucent.
The present invention also provides a kind of preparation method of the device for detection of material in water, comprises the following steps:
(1) xerogel is loaded in substrate;
(2) water-insoluble fluorescent probe molecule is dissolved in solvent, the more above-mentioned solution that contains probe molecule is mixed with xerogel, make its abundant saturated absorption;
(3), by the gel evaporate to dryness liquid of the saturated absorption in step (2), form the xerogel that load has fluorescent probe molecule;
(4) substrate that is filled with xerogel in step (3) is encapsulated with macromolecular material, wherein said macromolecular material part is permeable (preferably arranges one or more holes on macromolecular material, for example use pinprick hole), the macromolecular material using and/or substrate are substantial transparent or semi-transparent.
The invention further relates to the method for using described detection means to detect material to be detected in water, comprise the following steps:
(1) measure the luminescent spectrum of the xerogel surface fluorescence molecule of detection means of the present invention;
(2) detection means of the present invention is soaked in the aqueous solution that contains material to be detected, until fully taking out after water suction;
(3) luminescent spectrum of the hydrogel surface fluorescence molecule after abundant water suction in measuring process (2);
(4) by two luminescent spectrums that obtain in comparison step (1) and step (3), can determine in aqueous solution, whether to contain material to be detected, and the concentration of material to be detected in can computational analysis aqueous solution.
In computational analysis aqueous solution, the method for the concentration of material to be detected is as follows: known in this field, the size of material luminescence intensity is directly proportional to amount of substance, in two luminescent spectrums that obtain, can obtain the luminous intensity of the material that the luminous intensity of fluorescence molecule before and after reaction and fluorescence molecule and substance reaction to be detected obtain from above-mentioned steps (1) and step (3), owing to being adsorbed on the amount of the fluorescence molecule on xerogel, be known, therefore can calculate the amount of substance to be detected reacting with fluorescence molecule.Volume based on groove can calculate the volume of the aqueous solution that contains material to be detected of absorption in above-mentioned steps (2), can calculate thus the concentration of the aqueous solution that contains material to be detected.
Time detection means of the present invention being soaked in the aqueous solution that contains material to be detected can be selected by the absorbent time based on xerogel, is preferably 1～1000 second, more preferably 1-60 second.
Of the present invention for water substance detector part due to the loaded article and the disperse phase that adopt xerogel as fluorescence molecule, strong absorptive energy based on xerogel, can make rapidly fluorescence probe fully contact with water, and can effectively adsorb and fix its surperficial fluorescent probe molecule and make to present monodispersed existence form in its hydrogel after water suction.Thereby the water suction volume that adopts the coated mode of macromolecular material can effectively control hydrogel can carry out the content of material to be detected in quantitative test water.Device architecture of the present invention is simple, and can use water-insoluble fluorescence probe for the detection of single aqueous phase system, fast to the recognition speed of material to be detected in water, required detection time is very short, only use the time of minimum 15s, be far smaller than detection time of the prior art.
Accompanying drawing explanation
Fig. 1: the present invention is for detection of the structural representation of the detection means of material in water.
Fig. 2: the hydrogel that contains BTBPA probe molecule and the reacted spectrogram of variable concentrations fluorine ion, and the spectrogram of the hydrogel of BTHPA molecule load.
Reference numeral
1. macromolecule hyaline membrane; 2. groove; 3. dry hydrogel; 4. substrate.
Specific embodiments
Embodiment 1
Detect the fluorinion concentration (being the fluorinion concentration in single water) in aqueous solution, the fluorescence probe of employing be a kind of silylation of proton translocation compounds derivant (N-(3-(benzo [d] thiazol-2-yl)-4-(tert-butyl group hexichol siloxy) phenyl) acetamide) (BTBPA).By the fluorine ion in the idiosyncrasy identification water of fluorine and silicon oxygen bond.
The device detecting for aqueous solution material is referring to accompanying drawing 1, and it comprises: substrate 4, be seated in xerogel 3, encapsulation macromolecule hyaline membrane 1 in groove 2.
(1) base material using is aluminium sheet, and the thickness of aluminium sheet is 2mm, and the size of aluminium sheet is a square that 1cm is square.In the center of aluminium sheet, have a cylindrical aperture, the diameter of aperture is 2mm, and volume is 6mm
3;
(2) configuration concentration is 2 * 10
-4the methanol solution of the fluorescent probe molecule BTBPA of mol/L, gets 2 microliter methanol solution and 4mm
3xerogel polyvinylpyrrolidone (PVP) (swelling ratio is 1.5) mixes;
(3) by gel evaporate to dryness liquid under 0.5 atmospheric pressure of saturated adsorption in step (2);
(4) xerogel step (3) being obtained is loaded in the aperture of substrate and is encapsulated with macromolecule hyaline membrane, and uses pinprick hole on film surface;
(5) luminescent spectrum of the xerogel surface fluorescence molecule of encapsulated device in measuring process (4);
(6) encapsulated device of step (4) is soaked in the aqueous solution that contains fluorine ion, after 15s, takes out;
(7) luminescent spectrum of the hydrogel surface fluorescence molecule after abundant water suction in measuring process (6);
(8) by two luminescent spectrums that obtain in comparison step (5) and step (7), can computational analysis aqueous solution in the concentration of fluorine ion.
Fluorescent probe molecule BTBPA(compound of Formula I) being luminously blue, there is 1:1 with fluorine ion and react in it, and wherein silicon oxygen bond disconnects, and obtains general formula I I compound (BTHPA), generation proton translocation in molecule, its luminous green (seeing accompanying drawing 2) that is.
The calculating of concentration is the spectrum change based on before and after reaction.Because the luminous intensity of material is directly proportional to amount of substance, the known amount of substance that is adsorbed in the fluorescence probe on xerogel in the present embodiment, the volume of the aqueous solution that absorption contains fluorine ion with detection means, therefore can the luminous intensity based on before and after reaction calculate the amount of substance of the fluorine ion of detection means absorption, and then calculate the concentration of the fluorine ion of detected aqueous solution.
For example: when above-mentioned extent of reaction is 100%, compound of Formula I is converted into general formula I I compound completely, and the concentration of fluorine ion is for being more than or equal to 4ppm;
When extent of reaction is less than 100%, compound of Formula I Partial Conversion is general formula I I compound, and the concentration of fluorine ion is less than 4ppm, and for example, when compound of Formula I only reacts 25%, the concentration of fluorine ion is 1ppm.
Known based on foregoing description, the Cmax of the fluorine ion that detection means in the present embodiment is measured is only 4ppm.If need to detect the fluorinion concentration of certain concentration, only need simply to change the concentration of initial probe.
Claims (10)
1. an xerogel, is characterized in that, described xerogel load has water-insoluble fluorescent probe molecule.
2. xerogel as claimed in claim 1, wherein said xerogel is natural hydrophilic macromolecule or synthetic hydrophilic macromolecule, described natural hydrophilic macromolecule comprises polysaccharide (for example starch, cellulose, alginic acid, hyaluronic acid, shitosan, agarose etc.), polypeptide class (such as collagen, polylysine, poly-L-GLU etc.), described synthetic hydrophilic macromolecule comprises tygon, polyalcohols, polyacrylic acid and their derivant class (for example polymethylacrylic acid, polyacrylamide).
3. the preparation method of the xerogel described in claim 1-2 any one, comprises the following steps:
(1) water-insoluble fluorescent probe molecule is dissolved in solvent, the more above-mentioned solution that contains probe molecule is mixed with xerogel, make its abundant saturated absorption;
(2), by the gel evaporate to dryness liquid of saturated absorption in step (1), form the xerogel that load has water-insoluble fluorescent probe molecule.
4. the purposes of the xerogel described in claim 1-2 any one, it is for detection of the material to be checked in water, described material to be detected is the material that can react with described water-insoluble fluorescent probe molecule, for example metallic ion, nonmetallic ion, little molecule etc.
5. a detection means, is characterized in that, comprising the xerogel as described in claim 1-2 any one.
6. detection means as claimed in claim 5, it is characterized in that, described detection means comprises xerogel and the macromolecular material described in substrate, claim 1-2 any one, described substrate is for loading the xerogel described in claim 1-2 any one, described macromolecular material is for being encapsulated in described substrate by described xerogel, described macromolecular material is permeable at least partly, and described macromolecular material and/or substrate are for transparent or semitransparent at least partly.
7. detection means as claimed in claim 6, described base material is metal, macromolecular material, glass, quartz, described macromolecular material is tygon, polystyrene, Polyvinylchloride, in described substrate, for loading the space of the xerogel described in claim 1-2 any one, is groove or through hole.
8. the preparation method of the detection means described in claim 6-7 any one, comprises the following steps:
(1) xerogel described in claim 1-2 any one is loaded in substrate;
(2) substrate after filling step (1) being obtained encapsulates with macromolecular material, wherein said macromolecular material part is permeable (preferably arranges one or more holes on macromolecular material, for example use pinprick hole), the macromolecular material that wherein used and/or substrate are substantial transparent or translucent;
Or comprise the following steps:
(1) xerogel is loaded in substrate;
(2) water-insoluble fluorescent probe molecule is dissolved in solvent, the more above-mentioned solution that contains probe molecule is mixed with xerogel, make its abundant saturated absorption;
(3), by the gel evaporate to dryness liquid of saturated absorption in step (2), form the xerogel that load has fluorescent probe molecule;
(4) substrate that is filled with xerogel in step (3) is encapsulated with macromolecular material, described macromolecular material part is permeable (preferably arranges one or more holes on macromolecular material, for example use pinprick hole), the macromolecular material that wherein used and/or substrate are substantial transparent or semi-transparent.
9. the purposes of the detection means described in claim 5-7 any one, it is for detection of the material to be checked in water.
10. the detection means of use as described in claim 5-7 any one detects a method for material to be checked in water, comprises the following steps:
(1) measure the luminescent spectrum of the xerogel surface fluorescence molecule in described detection means;
(2) described detection means is soaked in the aqueous solution that contains material to be detected, fully after water suction, takes out;
(3) luminescent spectrum of the hydrogel surface fluorescence molecule after abundant water suction in measuring process (2);
(4) by two luminescent spectrums that obtain in comparison step (1) and step (3), can determine in aqueous solution, whether to contain material to be detected, and the concentration of material to be detected in can computational analysis aqueous solution.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310086591.4A CN104062271A (en) | 2013-03-19 | 2013-03-19 | Xerogel for detecting substances in water phase and detecting device thereof |
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| CN201310086591.4A CN104062271A (en) | 2013-03-19 | 2013-03-19 | Xerogel for detecting substances in water phase and detecting device thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105784664A (en) * | 2016-05-10 | 2016-07-20 | 南京工业大学 | Hydrogel microsphere type fluorescence sensor, preparation method and application |
| WO2016188533A1 (en) | 2015-05-26 | 2016-12-01 | Københavns Universitet (Ku) | Enzyme activity assay system and devices |
| CN111501122A (en) * | 2020-05-08 | 2020-08-07 | 广东工业大学 | Luminescent hydrogel fiber and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735277A (en) * | 2010-01-15 | 2010-06-16 | 大连理工大学 | Fluorescent probe compounds, preparation method and use thereof |
| CN102250134A (en) * | 2010-05-21 | 2011-11-23 | 中国科学院化学研究所 | Fluorescent probe for identifying fluorine ions and preparation method and use thereof |
-
2013
- 2013-03-19 CN CN201310086591.4A patent/CN104062271A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735277A (en) * | 2010-01-15 | 2010-06-16 | 大连理工大学 | Fluorescent probe compounds, preparation method and use thereof |
| CN102250134A (en) * | 2010-05-21 | 2011-11-23 | 中国科学院化学研究所 | Fluorescent probe for identifying fluorine ions and preparation method and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| LEI XIONG ET AL.: "Sensing in 15 s for Aqueous Fluoride Anion by Water-Insoluble Fluorescent Probe Incorporating Hydrogel", 《ANALYTICAL CHEMISTRY》 * |
| LILIAN C. LOPERGOLO ET AL.,: "Direct UV photocrosslinking of poly(N-vinyl-2-pyrrolidone) (PVP) to produce hydrogels", 《POLYMER》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016188533A1 (en) | 2015-05-26 | 2016-12-01 | Københavns Universitet (Ku) | Enzyme activity assay system and devices |
| CN105784664A (en) * | 2016-05-10 | 2016-07-20 | 南京工业大学 | Hydrogel microsphere type fluorescence sensor, preparation method and application |
| CN111501122A (en) * | 2020-05-08 | 2020-08-07 | 广东工业大学 | Luminescent hydrogel fiber and preparation method and application thereof |
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Application publication date: 20140924 |