CN106093018A - Detection tea polyphenols multilamellar sensor and preparation method thereof and the application of this sensor - Google Patents
Detection tea polyphenols multilamellar sensor and preparation method thereof and the application of this sensor Download PDFInfo
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- CN106093018A CN106093018A CN201610369941.1A CN201610369941A CN106093018A CN 106093018 A CN106093018 A CN 106093018A CN 201610369941 A CN201610369941 A CN 201610369941A CN 106093018 A CN106093018 A CN 106093018A
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- tea polyphenols
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
Abstract
The present invention provides a kind of sensor for detecting tea polyphenols multilamellar, and the preparation method of described multilamellar sensor, and the method detecting Tea Polyphenols in Tea with this sensor.Use the present invention for the quick detection to Tea Polyphenols in Tea, with low cost, different according to the tea polyphenols concentration detected, occur different colors to change, accomplish Visual retrieval, detection limit is low, need not large-scale instrument, sample need not pre-treatment, simple to operate, good stability, can be as a kind of cheap, convenient, simple and effective " electronic tongues " of the plant-derived beverage of real time discriminating different brands or quality.Further, tea polyphenols, without detection sample is carried out pre-treatment, is directly used for quickly detecting by the present invention.
Description
Technical field
The present invention relates to technical field of food detection, be specifically related to detect tea polyphenols multilamellar sensor and preparation method thereof and
The application of this sensor.
Background technology
Natural antioxidant polyphenol can participate in the metabolic response of human body, prevents the oxidative damage that free radical causes, logical
Cross the Accurate Determining to antioxidant activity and polyphenol component, it is achieved various plant-derived the objective of food and drink physiological function are commented
Valency has become as one of study hotspot the most popular in Related Research Domain.Wherein using forint phenol colorimetry is detection total polyphenols
The classical way of content.But, due to other reducing agents such as interference of aminoacid, ascorbic acid and other sugar, make repeatability
It is deteriorated, significantly hinders it and extensively apply.From the point of view of the performance analyzing detection, those are depended on by most efficient method beyond doubt
The method of large-scale instrument and equipment, including high effective liquid chromatography for measuring, capillary electrophoresis, flow injection spectrum etc..But due to
The complexity of sample pre-treatments and the shortage of professional operator, cause underestimating of Determination of Polyphenols, the most inevitably
High experimental cost and the operation sequence wasted time and energy.Owing to most of polyphenol have stronger chemism, papery senses
Device class, low consumption, in-situ study, in real time detection, easy popularization easy and simple to handle, reduce and operation and instrument and reagent are wanted
Asking, it is possible to achieve the detection real-time outside laboratory, cost is substantially reduced, and makes marketization commercialization be possibly realized, at environment
The aspects such as protection, health monitoring have the biggest potentiality.
CN201510688617.1 is disclosed " polyphenol content quick detection test paper and preparation method thereof ", there is following asking
Topic: utilizing ferrous iron as developer, the instability of reagent own easily aoxidizes；The load mode that reagent paper is each layer is directly leaching
Profit, uncontrollable to the amount of infiltration, it is not only a kind of waste to reagent, and the repeatability between batch cannot be ensured；Prepared
Journey needs reagent paper is carried out lyophilization, add the triviality of operation；Last obtains semiquantitative result to polyphenol.
Summary of the invention
For deficiencies of the prior art, present invention solves the technical problem that it is how to provide a kind of for soon
The speed detection sensor of tea polyphenols and the preparation method of this sensor, enable this sensor quick, sensitive, can visually semidefinite
Polyphenol content in volume production product, and the preparation method of this reagent paper is simple to operation.
The present invention also provides for the method for this sensor detection Tea Polyphenols in Tea.
The present invention uses following technological means: one detects tea polyphenols multilamellar sensor, it is characterised in that by Fe3+Complexation
Thing, chitosan layer and sodium alginate layer on the filter paper film of titanium dioxide membrane modifying from inside to outside LBL self-assembly form.
Further, the preparation method of described detection tea polyphenols multilamellar sensor, comprise the steps:
1) qualitative filter paper is cut into 2.0cm × 2.0cm square, dehydrated alcohol infiltrates 12-15h, is dried under room temperature；
2) the butyl titanate solution of 10 μ L pipettor is dripped at the center of the scraps of paper, allow solution spread on the scraps of paper, room temperature
Lower dry；Wherein, butyl titanate solution, by 1mL butyl titanate is added to 9mL dehydrated alcohol, is subsequently added into 100 μ L second
Acid is formulated；
3) through step 2) add 10 μ L dye solutions on the filter paper that processes, add after drying at room temperature 10 μ L chitosan solutions and
10 μ L sodium alginate solns；Wherein, dye solution is by by 0.5 mol L-1Liquor ferri trichloridi 5mL adds 1.5 mol L-1Sulfur
The cyanic acid ammonia 5mL dehydrated alcohol of 10% volume parts is diluted to 25 mL configurations；2.5mg•mL-1Chitosan and 2.0mg
mL-1Sodium alginate is respectively with the acetic acid of 2% volume parts and deionized water preparation, and the two solution is with stirring before
24-26h；
4) on the filter paper that step 3) processes, drip 10 μ L butyl titanate solution, complete a circulation of multilamellar sensor；
5) step 2 is repeated)-4) five circulations, constitute the sensor of multiple structure.
Compared to existing technology, there is advantages that
1, inventive sensor applies common material and simple technique to prepare, and has the feature of low cost.Further, layer is utilized
Multilayer film is prepared in layer self assembly, makes solution spread evenly, and hydrophobicity is higher, and colour developing becomes apparent from；By relatively different circulations time
The number sensor responsiveness to tea polyphenols, finds to repeat five secondary responses the highest.Utilize Ferric sulfocyanate in glycan substrate
Diffusion, get rid of Ferric sulfocyanate solution itself color disturb, it is ensured that the accuracy of result；Realize the inspection to different brackets green tea
Survey.
2, the present invention uses more stable ferric iron as developer, eliminates what the uncertain factor of reagent own was brought
Interference；Each layer of reagent paper all passes through liquid-transfering gun and accurately drips, it is ensured that good repeatability；Preparation process only needs drying at room temperature i.e.
Can；Finally RGB and the gray value of scraps of paper color are extracted, obtain the quantitative result accuracy to polyphenol high.
3, rich in tea polyphenols in Folium Camelliae sinensis, all it is contained in Folium Camelliae sinensis lixiviating solution.Use multilamellar sensor of the present invention directly to Folium Camelliae sinensis
Lixiviating solution carries out detecting, it is not necessary to detection sample (Folium Camelliae sinensis lixiviating solution) carry out complexity pre-treatment, it is achieved to tea polyphenols can
Depending on changing detection.For the quick detection of Tea Polyphenols in Tea, with low cost, different according to the tea polyphenols concentration detected, occur
Different color changes, accomplishes Visual retrieval, and detection limit is low, it is not necessary to large-scale instrument, simple to operate, and good stability is permissible
A kind of cheap, convenient, simple and effective " electronic tongues " as the plant-derived beverage of real time discriminating different brands or quality.
Accompanying drawing explanation
Fig. 1 is multilayer colorimetric sensor manufacture process schematic diagram.
Fig. 2 is the response diagram before and after cellulosic filter paper is modified by surface with tea polyphenols.
Fig. 3 is polyphenol Detection results figure and the Linear Fit Chart (i.e. standard curve) of variable concentrations in aqueous solution.
Fig. 4 is the Detection results figure of five kinds of green tea.
In Fig. 2, (A) is the rgb value before and after cellulosic filter paper is modified by surface with tea polyphenols response；(B) cellulosic filter paper
Before and after being modified by surface, the surface color with tea polyphenols response spreads and hydrophilic and hydrophobic situation.；Wherein a, b are cellulose filter respectively
The surface color spread condition that paper responds with tea polyphenols before and after being modified by surface；C is to drip tea polyphenols again after surface is modified
The hydrophobicity of its surface of solution.
Detailed description of the invention
Below in conjunction with specific embodiments and the drawings, the present invention is described in further detail.
1. the preparation of multilamellar sensor and the configuration of solution
Seeing Fig. 1, multilamellar sensor preparation process is as follows, first will in experiment used qualitative filter paper be cut into 2.0cm ×
2.0cm square, infiltrates 12-15h in dehydrated alcohol, is dried under room temperature；Then by the butyl titanate solution of 10 μ L with moving liquid
Device drips at the center of the scraps of paper, and solution quickly spreads on the scraps of paper, is dried under room temperature；Add 10 μ L dye solutions, room temperature afterwards
Dried addition 10 μ L chitosan solutions and 10 μ L sodium alginate solns；Finally drip 10 μ L butyl titanate solution again, so
One circulation of multilamellar sensor just completes.It is repeated 5 times above-mentioned steps and can build multiple structure.
Wherein, butyl titanate solution, by 1mL butyl titanate is added to 9mL dehydrated alcohol, is subsequently added into 100 μ L second
Acid preparation.Dye solution is by by 0.5 mol L-1Liquor ferri trichloridi 5mL adds 1.5 mol L-1Ammonium thiocyanate 5mL is with 10%
The dehydrated alcohol of volume parts is diluted to 25 mL configurations.2.5mg•mL-1Chitosan and 2.0mg mL-1Sodium alginate divides
Not with acetic acid and the deionized water preparation of 2% volume parts.The two solution is with stirring at least 24h before.Experiment is used
The polyphenol sample solution 1mg mL arrived-1Dilution, noting must be now with the current.
Cleaning Principle: based on polyphenol and Fe3+Between complex reaction, the present invention have studied the most sensitive simple multilamellar ratio
Colour sensor.In the making of sensor, chitosan layer, Fe3+Complex and sodium alginate layer are in the filter of titanium dioxide membrane modifying
LBL self-assembly in paper membrane.After repeating for five times to assemble, the sensor obtained not only has a good super-hydrophobicity, and because of
For the specificity affinity of chitosan, the polyphenol in aqueous solution has the process of a preenrichment on the surface of sensor, thus
Improve the sensitivity of sensor.Under the effect of multi-functional test-paper the most after treatment, colour developing particle spreads evenly, face
Color is deepened, and sensitivity improves.See Fig. 2.
2. standard curve and data process:
First, 1mg mL is configured with deionized water-1Polyphenol stock solution, with deionized water be diluted to concentration be respectively 0.02mM,
The standard solution of 0.04 mM, 0.06mM, 0.2mM, 0.4mM, 0.6mM, 2mM, 4mM and 6mM；
Then, by central at the described multilamellar sensor scraps of paper for the standard solution dropping of above-mentioned 9 variable concentrations obtained, wait
10min completes detection；Wherein, the solution filter paper not evaporated sops up and waits that at least 5min makes it thoroughly be dried, it is ensured that reaction
Carry out completely；
Finally, the imagery exploitation scanner scanning that multilamellar sensor and standard solution are reacted, utilize Image J software to color
Intensity quantifies, and obtains standard curve, wherein R2=0.9952.See Fig. 3.
3. the detection of green tea sample
First the green tea of 5 kinds of different quality grades is placed in 35 DEG C of baking ovens and is dried 2h, then pulverized 40 mesh sieves, and took 1g and add
The distilled water of 100mL boiling, is placed in 100 DEG C of thermostat water baths extraction 30min, is settled to by gained millet paste sucking filtration afterwards
100mL is standby.Utilize this sensor that it is detected, drip in described multilamellar sensor scraps of paper central authorities, wait that 10min completes
Detection；Wherein, the solution filter paper not evaporated sops up and waits that at least 5min makes it thoroughly be dried, it is ensured that reaction is carried out completely.
Imagery exploitation scanner scanning multilamellar sensor and detected solution reacted, utilizes Image J software to carry out color intensity
Quantify；The data obtained then carries out follow-up quantitative and statistical analysis.Testing result sees Fig. 4.
Finally, reacted color intensity value is deducted by the color intensity value before reaction, it is thus achieved that color change rgb value,
Again by this result and standard curve control, the content of the polyphenol of detected sample i.e. can be obtained.
Concrete operations are i.e. chosen every the scraps of paper color even region more than 90% with circle and are carried out subsequent analysis, every
The scraps of paper intercept and are averaged intensity level three times.Color intensity value before the reaction of color change rgb value deducts reacted color intensity
Value obtains.
Finally illustrating, above example is only in order to illustrate technical scheme and unrestricted, although with reference to relatively
The present invention has been described in detail by good embodiment, it will be understood by those within the art that, can be to the present invention's
Technical scheme is modified or equivalent, and without deviating from objective and the scope of technical solution of the present invention, it all should be contained
In the middle of scope of the presently claimed invention.
Claims (4)
1. a detection tea polyphenols multilamellar sensor, it is characterised in that by Fe3+Complex, chitosan layer and sodium alginate layer exist
On the filter paper film of titanium dioxide membrane modifying, LBL self-assembly forms from inside to outside.
2. detect a preparation method for tea polyphenols multilamellar sensor, comprise the steps:
1) qualitative filter paper is cut into 2.0cm × 2.0cm square, dehydrated alcohol infiltrates 12-15h, is dried under room temperature；
2) the butyl titanate solution of 10 μ L pipettor is dripped at the center of the scraps of paper, allow solution spread on the scraps of paper, room temperature
Lower dry；Wherein, butyl titanate solution, by 1mL butyl titanate is added to 9mL dehydrated alcohol, is subsequently added into 100 μ L second
Acid is formulated；
3) through step 2) add 10 μ L dye solutions on the filter paper that processes, add after drying at room temperature 10 μ L chitosan solutions and
10 μ L sodium alginate solns；Wherein, dye solution is by by 0.5 mol L-1Liquor ferri trichloridi 5mL adds 1.5 mol L-1Sulfur
The cyanic acid ammonia 5mL dehydrated alcohol of 10% volume parts is diluted to 25 mL configurations；2.5mg•mL-1Chitosan and 2.0mg
mL-1Sodium alginate is respectively with the acetic acid of 2% volume parts and deionized water preparation, and the two solution is with stirring before
24-26h；
4) on the filter paper that step 3) processes, drip 10 μ L butyl titanate solution, complete a circulation of multilamellar sensor；
5) step 2 is repeated)-4) five circulations, constitute the sensor of multiple structure.
3. detect the application of tea polyphenols multilamellar sensor, it is characterised in that use detection tea polyphenols described in claim 1 or 2 many
Layer sensor is for the method detecting tea polyphenols, and concrete steps include:
1) standard curve and data process:
First, 1mg mL is configured with deionized water-1Polyphenol stock solution, with deionized water be diluted to concentration be respectively 0.02mM,
The standard solution of 0.04 mM, 0.06mM, 0.2mM, 0.4mM, 0.6mM, 2mM, 4mM and 6mM；
Then, the standard solution of above-mentioned 9 variable concentrations obtained is dripped at multilamellar sensor paper described in claim 1 or 2
Sheet central authorities, wait that 10min completes detection；Wherein, the solution filter paper not evaporated sops up and waits that at least 5min makes it thoroughly do
Dry, it is ensured that reaction is carried out completely；
Finally, the imagery exploitation scanner scanning that multilamellar sensor and standard solution are reacted, utilize Image J software to color
Intensity quantifies, and obtains standard curve；
2) detection of polyphenol sample:
Sample is directly dripped in multilamellar sensor scraps of paper central authorities described in claim 1 or 2, wait that 10min completes detection；
Wherein, the solution filter paper not evaporated sops up and waits that at least 5min makes it thoroughly be dried, it is ensured that reaction is carried out completely；
Then, the imagery exploitation scanner scanning that multilamellar sensor and detected solution are reacted, utilize Image J software to color
Intensity quantifies；
Finally, reacted color intensity value is deducted by the color intensity value before reaction, it is thus achieved that color change rgb value table
Show, then by this result and standard curve control, i.e. can obtain the content of the polyphenol of detected sample.
The method detecting Tea Polyphenols in Tea the most according to claim 2, it is characterised in that Image J software in step 3)
Quantifying color intensity, it is follow-up to carry out that concrete operations circle chooses every the scraps of paper color even region more than 90%
Analyzing, every scraps of paper intercept and are averaged intensity level three times；Color change rgb value deducts reaction by the color intensity value before reaction
After color intensity value obtain.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610369941.1A CN106093018A (en) | 2016-05-30 | 2016-05-30 | Detection tea polyphenols multilamellar sensor and preparation method thereof and the application of this sensor |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108918516A (en) * | 2018-10-22 | 2018-11-30 | 李素媛 | It is a kind of for detecting the detection device and its application method of Tea Polyphenols in Tea |
| CN114720541A (en) * | 2022-05-07 | 2022-07-08 | 中国标准化研究院 | Method for improving accuracy of classifying tingling strength of zanthoxylum piperitum |
| DE102021209448A1 (en) | 2021-08-27 | 2023-03-02 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein | Method for detecting substances released from a plant and medium for a plant |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070218166A1 (en) * | 2004-04-21 | 2007-09-20 | Dieter Tanzer | Test Kit and Method for the Determination of Nitrogen Components in Wine |
| CN103645182A (en) * | 2013-12-13 | 2014-03-19 | 重庆大学 | Method for identifying white spirit flavor type by using electronic tongue system |
| CN105067607A (en) * | 2015-07-26 | 2015-11-18 | 滁州学院 | Colorimetric sensor, and preparation method and new application thereof in food detection |
-
2016
- 2016-05-30 CN CN201610369941.1A patent/CN106093018A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070218166A1 (en) * | 2004-04-21 | 2007-09-20 | Dieter Tanzer | Test Kit and Method for the Determination of Nitrogen Components in Wine |
| CN103645182A (en) * | 2013-12-13 | 2014-03-19 | 重庆大学 | Method for identifying white spirit flavor type by using electronic tongue system |
| CN105067607A (en) * | 2015-07-26 | 2015-11-18 | 滁州学院 | Colorimetric sensor, and preparation method and new application thereof in food detection |
Non-Patent Citations (1)
| Title |
|---|
| JUNJIE LI ET.AL.: ""A colorimetric multilayer sensor for discriminating red wine and green tea by measurement of antioxidant activity"", 《ANALYTICAL METHODS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108918516A (en) * | 2018-10-22 | 2018-11-30 | 李素媛 | It is a kind of for detecting the detection device and its application method of Tea Polyphenols in Tea |
| CN108918516B (en) * | 2018-10-22 | 2020-11-24 | 李素媛 | Detection device for detecting tea polyphenol in tea and use method thereof |
| DE102021209448A1 (en) | 2021-08-27 | 2023-03-02 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein | Method for detecting substances released from a plant and medium for a plant |
| DE102021209448B4 (en) | 2021-08-27 | 2023-06-29 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein | Method for detecting substances released from a plant and medium for a plant |
| CN114720541A (en) * | 2022-05-07 | 2022-07-08 | 中国标准化研究院 | Method for improving accuracy of classifying tingling strength of zanthoxylum piperitum |
| CN114720541B (en) * | 2022-05-07 | 2023-10-27 | 中国标准化研究院 | Method for improving accuracy of classifying spicy intensity of red peppers |
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