CN102590208A - Preparation method for biological scale-based in-situ optical pH value detector - Google Patents
Preparation method for biological scale-based in-situ optical pH value detector Download PDFInfo
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Abstract
一种生物光子晶体材料技术领域的基于生物鳞片的原位光学pH值检测器的制备方法，通过将聚乙烯醇-壳聚糖前驱体溶液加载于石英玻璃上并将鳞翅目生物鳞片浸没其中，然后向生物鳞片上滴加交联剂戊二醛溶液并待自然干燥后进行加热烘干，得到基于生物鳞片的原位光学pH值检测器。本发明规避了染料泄漏污染等缺点，而与pH值敏感PCCA探测器相比，实现了对鳞翅目生物鳞片天然光子晶体内部微观结构和光学性能的调控。为天然生物光子晶体无法进行有效调控的技术困难提供了一种解决途径。
A preparation method of an in-situ optical pH value detector based on biological scales in the technical field of biological photonic crystal materials, by loading polyvinyl alcohol-chitosan precursor solution on quartz glass and immersing Lepidoptera biological scales in it , and then drop the cross-linking agent glutaraldehyde solution on the biological scales and heat and dry after natural drying to obtain an in-situ optical pH value detector based on biological scales. The invention avoids the disadvantages of dye leakage and pollution, and compared with the pH value sensitive PCCA detector, it realizes the control of the internal microstructure and optical properties of the natural photonic crystal of the lepidopteran biological scale. It provides a solution to the technical difficulty that natural biophotonic crystals cannot be effectively regulated.
Description
Technical field
What the present invention relates to is a kind of pick-up unit of bio-photon crystalline material technical field, specifically is a kind of preparation method of the original position optics pH value detecting device based on biological scale.
Background technology
PH value fluorescence detector has been owing to avoided the contact of direct electrochemical surface, reduced corrosion and polluted, thereby in position biomedical fields such as detection great advantage.Optics pH detector commonly used at present is based on the fluorescence polymer dyestuff; (patent No.: 200580033961.1), detector is carried exciting light and is received from the emission light that is fixed in the fluorescent dye on the matrix at least two wavelength like patent fluorescent pH detector system and correlation technique.And based on quick response optics pH detecting device (the Optical pH Sensor with Rapid Response Based on a Fluoresce in-Intercalated Layered Double Hydroxide of the double-deck oxyhydroxide of luciferin interlayer; W.Y.Shi; Et al., Advanced Functional Materials 2010,20; 3856-3863) with the double-colored colorimetric optics pH of system detecting device (Colorimetric optical pH sensor production using a dual-color system; H.X.Chen, et al., Sensors and Actuators B-Chemical 2010; 146,278-282) wait and to be the excitation spectrum that utilizes dyestuff and to change with the Acidity of Aikalinity of environment the pH value is detected and demarcates.This type of device can reach higher precision, but exists poor stability, chemical substance to be prone to aspect problems such as leakage, biocompatibility difference.
One of thinking that addresses the above problem is that (Photonic Crystal Colloidal Assay PCCA) replaces the fluorescence polymer dyestuff as response element to pH value sensitive polymers photonic crystal array in employing.As gather hydroxyl methacrylate photonic crystal: pH and ethanol test material (Polymerized polyHEMA photonic crystals:pH and ethanol sensor materials; X.Xu; Journal ofthe American Chemical Society 2008; 130,3113-3119) based on quick response photonic crystal pH sensor (Fast response photonic crystal pH sensor based on templated photo-polymerized hydrogel inverse opa, the J.Shin of polymkeric substance photon structure counter opal gel template; Sensors and Actuators; B:Chemical 2010,150,183-190) etc.
Intelligent macromolecule PCCA follows the variation of environment pH value that stereomutation can take place, and then influences the space distribution in its dielectric structure cycle, thereby reflective character can change.Yet the self assembling process of PCCA photonic crystal template is had relatively high expectations to synthesis condition, and structure is from topology angle lack diversity.On the other hand, the nature biotechnology body passes through the natural selection in 1 years with superseded, evolved out diversified natural biological photon crystal structure, for example beetle crust, butterfly's wing scale etc.These structures often can not be copied with yardstick is artificial through existing technology, and have meticulous, small scale (sub-micron rank), with low cost, advantage such as be easy to obtain.
Retrieval through to prior art is found; Summary (C.I.Aguirre on 2010 the top periodical of material science " advanced function material " (Advance Functional Materials); Et al., Advanced Functional Materials 2010,20; Point out 2565-2578); New optical devices design and manufacturing will make a breakthrough and should fully use for reference the classification fine structure of bio-photon crystal, yet up to now, the report that does not still utilize biological structure to prepare original position optics pH value detecting device occurs.
Summary of the invention
The present invention is directed to the above-mentioned deficiency that prior art exists; A kind of preparation method of the original position optics pH value detecting device based on biological scale is provided; The wing scale that utilizes Lepidoptera biological (butterfly and moth) is as " physics dyestuff "; With pH value sensitive aquagel, for example chitosan/polyvinyl alcohol (Chitosan/PVA) etc. is filled embedding to single scale (size is about 100 μ m * 200 μ m).Form behind the gel crosslinking curing and can change the macromolecule membrane that expands, shrinks with environment pH value, wherein embedded butterfly wing scale submicron order structure is the optic response core of this pH value sensitive element.
The present invention realizes through following technical scheme; The present invention is through loading on polyvinyl alcohol (PVA)-shitosan precursor solution on the quartz glass and with the biological scale submergence of Lepidoptera wherein; After dripping the crosslinking chemical glutaraldehyde solution on the biological scale and treating air dry, carry out heating, drying then, obtain original position optics pH value detecting device based on biological scale.
Described polyvinyl alcohol (PVA)-shitosan precursor solution prepares in the following manner: shitosan is dissolved in and obtains chitosan solution in the glacial acetic acid aqueous solution; Be dissolved in polyvinyl alcohol (PVA) in the distilled water then and mix and obtain with chitosan solution.
Described crosslinking chemical glutaraldehyde solution is meant: volumetric concentration is 25% glutaraldehyde water solution, is dissolved in solution that distilled water obtains 1% volumetric concentration with as crosslinking chemical; Drip the glutaraldehyde cross-linking agent then, the mass concentration that makes glutaraldehyde account for the macromolecule presoma is 1-4 * 10
-5Mol/g.
The biological scale of described Lepidoptera is meant sun moth scale, and its scale is preferably the sun moth scale with 4 microns following grid distances.
Described heating, drying is meant: in vacuum drying oven, dried 12 hours for 50 ℃.
The present invention relates to a kind of pH value detection method, through the above-mentioned pH value detecting device for preparing is soaked in the solution to be measured, and detect the pH value that obtains solution according to the different spectrum peak positions of reflectance spectrum.
Described immersion is meant: make compound scale of gel and solution reach the bloated balance of swelling/precipitation.
Described different spectrum peak position is meant: at first demarcate pH value detecting device in the optical characteristics of not spending in the potential of hydrogen, i.e. and spectrum peak position, as the standard that detects, the spectrum peak contrast according to solution to be measured obtains the pH value then.
Described pH value detecting device has highest resolution in weakly alkaline environment.
The present invention utilizes the bio-photon crystal structure first, and promptly the biological sun moth of Lepidoptera scale utilizes the responsive gel of chitosan/polyvinyl alcohol pH as matrix material as the optic response core, makes the scale reflectance spectrum follow gel volume to change pH is produced response.
Compare with conventional fluorescent dyestuff optics pH value detector; The present invention has evaded shortcomings such as dyestuff leakage pollution; And compare with the responsive PCCA detector of pH value, it is simple, with low cost that the present invention has preparation, meticulous various, the advantage such as the performance controllability is strong of structure; The employed material of this device is all nontoxic, can be used for human diagnosis and biological medicine apparatus.On the other hand, the intelligent gel that the present invention will be used for artificial muscle and drug first combines with natural photonic crystal, has realized the regulation and control to biological scale natural photon crystals micromechanism of Lepidoptera and optical property.The technical difficulty that can't effectively regulate and control for the natural biological photonic crystal provides a kind of solution route.
Description of drawings
Fig. 1 is preparation flow figure of the present invention;
Among the figure: (a) be the embedding process of primeval life scale in intelligent gel; (b) be the solidification process of complex after the embedding.
Fig. 2 is the embodiment synoptic diagram;
Among the figure: (a) be embodiment pictorial diagram of the present invention; (b) be the electron scanning micrograph of selected sun moth scale structure.
Fig. 3 for spectrum in the embodiment of the present invention with pH value response data synoptic diagram;
Among the figure: (a) acid condition; (b) alkali condition.
Fig. 4 is gel infrared spectrum (FTIR) spectrogram of embodiment.
Embodiment
Elaborate in the face of embodiments of the invention down, present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Embodiment
1, pH detects the response core---the biological scale of Lepidoptera
The wing scale of choosing the biological sun moth of Lepidoptera (Chrysiridia rhipheus) is by landfill material.Sun moth is one type comparatively special in the Lepidoptera biology, has the schemochrome (comprising rare red schemochrome) of nearly all wave band, but also is that minority has one of Lepidoptera biology of outside of belly schemochrome.
Find through sem observation, the constitutional repeating unit of regions of different colours scale, promptly the yardstick difference of positive " window " shape structure is very big, and wherein the grid distance of red area scale is about 4 microns, and green area is merely about 1 micron.This embodiment is chosen the conduct of red area scale by landfill material.
2, the compound scale preparation of devices of gel
From multiple pH sensitive material, choosing polyvinyl alcohol (PVA)/shitosan is example as the high-molecular gel system of embedding and filling.(chitosan is the alkaline polysaccharide of the unique a large amount of existence of nature CS) to shitosan, has favorable tissue compatibility, biodegradability and adhesion, has obtained further investigation and widespread use in medical science, field of biology.Simultaneously, shitosan is the chitinous deacetylation product of scale chemical constitution, and both compositions are approaching, and the good chemical compatibility is provided.Polyvinyl alcohol (PVA) (PVA) is unique water soluble polymer, and its gel is because of having excellent biological compatibility, biodegradability and mechanical property.CS and PVA carried out hybrid reaction in 1: 1～5: 1 with mass ratio, can obtain having the gel network of good swelling property and stimulating responsive.
Shitosan (deacetylation rate 0.76, molecular weight 2 * 10
5), under 50 ℃, be dissolved in 10% the glacial acetic acid aqueous solution, obtain chitosan solution (3.0%, w/w).Polyvinyl alcohol (PVA) under 70 ℃ of conditions, is dissolved in the distilled water, obtains the solution of 10wt%.Two kinds of solution are mixed each other, guarantee that the mass ratio of shitosan and polyvinyl alcohol (PVA) is 1: 1～1: 5, with this forerunner's liquid solution under 50 ℃, with magnetic stirrer 1 hour, until mixing.The glutaraldehyde solution of 25% (v/v) is dissolved in solution that distilled water obtains 1% (v/v) with as crosslinking chemical; Drip the glutaraldehyde cross-linking agent then, the mass concentration that makes glutaraldehyde account for the macromolecule presoma is 2 * 10
-5Mol/g.
The element manufacturing flow process is as shown in Figure 1; Independent sun moth scale is placed on the quartz glass, be immersed in the polyvinyl alcohol (PVA)/shitosan precursor solution for preparing with 1: 1～5: 1 mass ratioes, drip the crosslinking chemical glutaraldehyde solution for preparing; In vacuum drying oven, dried 12 hours for 50 ℃; Precursor solution is fully reacted, and until forming the squamose macromolecule membrane of embedding, thickness is about 100 microns.The squamose part of embedding in the film is cut to 1.0 * 1.5cm size, promptly gets pH original position optical detection device, shown in Fig. 2 (a), wherein the micromechanism of scale is seen Fig. 2 (b).
3, pH detector response performance
According to the different spectrum peak positions of optics pH detecting device reflectance spectrum, can detect the pH value of solution.At first demarcate this pH value detecting device in the optical characteristics of not spending in the potential of hydrogen, as the standard that detects.
The sample of picked at random after with the deionized water swelling; Using pH is that 1～13 solution soaks it respectively; Make compound scale of gel and solution reach the bloated balance of swelling/precipitation; Considering in the sour environment that the reflectance spectrum variation range is less, is gradient with pH value 2, in alkaline environment, is gradient with pH value 1.Treat that pH value detecting device light signal reaches stable, carries out in site measurement to its reflectance spectrum.Never be swelling to swelling, because gel swelling enlarges the scale inner structure, the reflectance spectrum peak is from the about 50nm to 730nm of 680nm red shift, shown in Fig. 3 (a).When pH=3, can reach the wavelength maximal value at reflectance spectrum peak.During from neutral weakly alkaline environment, significant change appears in reflectance spectrum, and intensity of variation is maximum between pH=8～10, and the reflectance spectrum peak is blue shifted to minimal wave length～470nm when pH=13, sees Fig. 3 (b), and the overall movement scope at reflectance spectrum peak reaches～260nm.This device has highest resolution in weakly alkaline environment.
Comparative Examples
Preparation method and material are selected with reference to embodiment 1, and crosslinking chemical glutaraldehyde water solution concentration is respectively 0,1 * 10
-5Mol/g, 4 * 10
-5Mol/g, like table 1, in the Comparative Examples with embodiment 1 (G2) in the infrared spectrum (FTIR) of chitosan/polyvinyl alcohol gel because methylene is constant before and after the reaction, can select to do 2900cm
-1The C-H characteristic peak be reference peak, 1560cm
-1Near shitosan amido link N-H key is compared the C-H absorption intensity with the characteristic peak of one-level amido and is compared A
1560/ A
2900Weaken along with the raising of crosslinker concentration, can know that according to the rich bright law of Bill the N-H linkage content reduces.Infrared spectrum can not detect the characteristic peak of aldehyde because glutaraldehyde and acid amides reactivity are lower, glutaraldehyde almost all with the primary amine radical reaction of shitosan.The azomethine link shitosan chain that forms behind the aldolisation forms three-dimensional macromolecule network, meets PVA again and forms mutual biography network.Along with the raising of glutaraldehyde concentration, the theoretical degree of crosslinking of shitosan improves, and theoretical swelling equilibrium descends.If degree of crosslinking is low excessively, like G1 among Fig. 4 and G2, the high-molecular gel network delivery can cause the later gel-in-matrix of swelling to separate with sun moth scale, if concentration is higher, the swelling ability drop can reduce the moving range at reflectance spectrum spectrum peak, like G3 among Fig. 4.Therefore, the crosslinker concentration among the embodiment 1 is comparatively reasonable.
Crosslinker concentration and theoretical degree of crosslinking are relatively among the different embodiment of table 1.
Claims (10)
1. preparation method based on the original position optics pH value detecting device of biological scale; It is characterized in that; Through polyvinyl alcohol (PVA)-shitosan precursor solution being loaded on the quartz glass and wherein with the biological scale submergence of Lepidoptera; After dripping the crosslinking chemical glutaraldehyde solution on the biological scale and treating air dry, carry out heating, drying then, obtain original position optics pH value detecting device based on biological scale.
2. method according to claim 1 is characterized in that, described polyvinyl alcohol (PVA)-shitosan precursor solution prepares in the following manner: shitosan is dissolved in and obtains chitosan solution in the glacial acetic acid aqueous solution; Be dissolved in polyvinyl alcohol (PVA) in the distilled water then and mix and obtain with chitosan solution.
3. method according to claim 1 is characterized in that, described crosslinking chemical glutaraldehyde solution is meant: volumetric concentration is 25% glutaraldehyde water solution, is dissolved in solution that distilled water obtains 1% volumetric concentration with as crosslinking chemical; Dripping the glutaraldehyde cross-linking agent then obtains.
4. according to claim 1 or 3 described methods, it is characterized in that to account for the mass concentration of macromolecule presoma be 1-4 * 10 to glutaraldehyde in the described crosslinking chemical glutaraldehyde solution
-5Mol/g.
5. according to the described method of above-mentioned arbitrary claim, it is characterized in that the biological scale of described Lepidoptera is meant sun moth scale.
6. method according to claim 5 is characterized in that, the biological scale of described Lepidoptera is the sun moth scale with 4 microns following grid distances.
7. the original position optics pH value detecting device based on biological scale is characterized in that, prepares according to the said method of above-mentioned arbitrary claim.
8. a pH value detection method is characterized in that, through the described original position optics of above-mentioned arbitrary claim pH value detecting device is soaked in the solution to be measured, and detects the pH value that obtains solution according to the different spectrum peak positions of reflectance spectrum.
9. method according to claim 8 is characterized in that, described immersion is meant: make compound scale of gel and solution reach the bloated balance of swelling/precipitation.
10. method according to claim 8; It is characterized in that described different spectrum peak positions are meant: at first demarcate pH value detecting device at the optical characteristics of not spending in the potential of hydrogen, i.e. spectrum peak position; As the standard that detects, the spectrum peak contrast according to solution to be measured obtains the pH value then.
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| CN103163082A (en) * | 2013-02-05 | 2013-06-19 | 哈尔滨工业大学 | Method using three-dimensional photonic crystals to measure potential of hydrogen (pH) |
| CN103399012A (en) * | 2013-07-25 | 2013-11-20 | 厦门斯坦道科学仪器股份有限公司 | Colorimetric sensing paste film and preparation method thereof |
| CN103884710A (en) * | 2014-02-08 | 2014-06-25 | 上海交通大学 | Method for measuring pH by using photonic crystal wettability |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103163082A (en) * | 2013-02-05 | 2013-06-19 | 哈尔滨工业大学 | Method using three-dimensional photonic crystals to measure potential of hydrogen (pH) |
| CN103399012A (en) * | 2013-07-25 | 2013-11-20 | 厦门斯坦道科学仪器股份有限公司 | Colorimetric sensing paste film and preparation method thereof |
| CN103399012B (en) * | 2013-07-25 | 2015-12-23 | 厦门斯坦道科学仪器股份有限公司 | A kind of colorimetric sensing pad pasting and preparation method thereof |
| CN103884710A (en) * | 2014-02-08 | 2014-06-25 | 上海交通大学 | Method for measuring pH by using photonic crystal wettability |
| CN103884710B (en) * | 2014-02-08 | 2016-05-25 | 上海交通大学 | A kind of method of utilizing photonic crystal wellability to measure pH |
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Application publication date: 20120718 |