CN114605670B - High-chromatic-aberration formaldehyde color-changing hydrogel based on natural pigment - Google Patents

High-chromatic-aberration formaldehyde color-changing hydrogel based on natural pigment Download PDF

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CN114605670B
CN114605670B CN202210314786.9A CN202210314786A CN114605670B CN 114605670 B CN114605670 B CN 114605670B CN 202210314786 A CN202210314786 A CN 202210314786A CN 114605670 B CN114605670 B CN 114605670B
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formaldehyde
water
natural pigment
hydrogel
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CN114605670A (en
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白剑芸
贲倩岑
田晶
李茹梦
李峰
周磊
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Shanghai Shiyi Brand Management Co ltd
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Abstract

The application discloses a high-chromatic-difference formaldehyde color-changing hydrogel based on natural pigment, which comprises a water-soluble linear polymer, a gel agent, iodine simple substance, iodine ions, natural pigment and water. The hydrogel can react with formaldehyde to produce a visually apparent color difference change from blue or brown-violet to orange or yellow. The hydrogel provided by the application can be used for absorbing, detecting and indicating formaldehyde pollutants. Compared with the prior art, the application has the following beneficial effects: the hydrogel material is mainly based on natural substances, is friendly and safe to home environment, has obvious color change to formaldehyde, can identify color difference change visually, does not need additional identification equipment, and has the advantages of low cost, simple and mild preparation process and convenient application.

Description

High-chromatic-aberration formaldehyde color-changing hydrogel based on natural pigment
Technical Field
The application belongs to the field of daily chemicals, and particularly relates to a high-color-difference formaldehyde color-changing hydrogel based on natural pigments.
Background
Formaldehyde is one of the main polluting gases of the indoor environment with colorless and strong pungent smell, can destroy the protoplasm poison of biological cell proteins, and has potential carcinogenic harm to human bodies. At present, methods for measuring formaldehyde by using an instrument include gas chromatography and mass spectrometry, but the instrument is very expensive and is not suitable for household use; there are also methods of enriching a gas sample with a gas sampling tube, and performing a color reaction with a chemical reagent, and performing the measurement with a spectrophotometer [ analytical laboratories, 2015, 34 (4): 447, sometimes requiring the use of strong acids, strong bases and even strong oxidizing agents [ spectroscopic laboratories, 2010, 27 (3): 881] are very inconvenient for field and home operations.
Hydrogels (hydrogels) are a type of extremely hydrophilic three-dimensional network structure gels, which are colloidal particles or polymer macromolecules interconnected under certain conditions to form a space network structure, and the structural gaps are filled with dispersion media. Due to the existence of the three-dimensional network structure, the hydrogel can swell and hold a large amount of water, the water absorption amount is closely related to the crosslinking degree, the higher the crosslinking degree is, the lower the water absorption amount is, and the soluble active component can diffuse or permeate in the hydrogel, so that the formaldehyde concentration can be detected by utilizing the characteristic.
CN104877184B discloses a supramolecular hydrogel for detecting formaldehyde in environment, the principle is that the guest molecule Tyloxapol has fluorescent effect, and the fluorescence of the Tyloxapol in the hydrogel system is quenched due to pi-pi effect after the Tyloxapol is coated by host molecule cyclodextrin; after contacting formaldehyde molecules, formaldehyde enters the cyclodextrin cavity to replace Tyloxpol, and fluorescent effect is recovered after the Tyloxpol is released, so that formaldehyde detection effect is achieved. The method needs a fluorescence spectrometer, raw materials are not easy to obtain, and the purpose of low-cost and convenient application is difficult to achieve.
CN111701439a discloses a formaldehyde-removing color-changing gel with visual sense, which is characterized in that after alkaline alcohol amine compound reacts with formaldehyde, the pH value of the gel system changes to change the color of the acid-base indicator, thereby achieving the purpose of removing formaldehyde and changing color. The system is indirect in that the color change of formaldehyde is indirect, nearly equivalent level formaldehyde is required to react with alcohol amine to generate obvious pH value change so as to obviously change the color of the indicator, and the design is not much used for detecting the formaldehyde with the ppm concentration level in the actual indoor air.
Therefore, the above prior art has at least the following technical problems: the gel for formaldehyde detection has the advantages that the color change can be identified by an instrument, the indication sensitivity is poor, and the price is high.
Disclosure of Invention
In order to solve the technical problems, the application provides a high-chromatic-aberration formaldehyde color-changing hydrogel based on natural pigments.
The aim of the application is realized by the following technical scheme:
a natural pigment-based high-color-difference formaldehyde color-changing hydrogel, wherein the Gao Secha formaldehyde color-changing hydrogel comprises a water-soluble linear polymer, a gel agent, iodine simple substance, iodine ions, natural pigment and water.
Further, the Gao Secha formaldehyde color-changing hydrogel is prepared by the following method: the water-soluble linear polymer and the gel are heated and dissolved in water, and then iodine simple substance, iodide ions and natural pigment are added, so that the contents of all components in the solution are as follows: 1-50 g/L of water-soluble linear polymer, 1-50 g/L of gel, 0.1-10 g/L of iodine simple substance, 2-30 g/L of iodide ion and 0.02-2 g/L of natural pigment, and cooling to room temperature to obtain the Gao Secha formaldehyde color-changing hydrogel.
The hot water is generally hot water at 50-100 ℃.
Further, the water-soluble linear polymer is one or more of polyvinyl alcohol, water-soluble starch, polyvinylpyrrolidone, water-soluble cellulose, polyethylene glycol and polyacrylamide, preferably polyvinyl alcohol, water-soluble starch or polyvinylpyrrolidone.
Furthermore, the gel is one or more of carrageenan, gellan gum, agar, hyaluronic acid, sodium alginate, konjac gum and gelatin, preferably agar, hyaluronic acid or sodium alginate.
Further, the iodide ion is derived from the group I - The compound containing I - The cation in the compound of (2) is one or more of potassium, sodium, lithium and ammonium. Preferably the iodide ion is from sodium iodide, potassium iodide or ammonium iodide.
In calculating the amount of iodine ions, the iodine ions are added in the form of I - I in the compound (I) - Is measured by the mass of the (c).
Further, the natural pigment is one or more of curcumin, capsanthin, beta-carotene, corn yellow pigment and lycopene, preferably curcumin, capsanthin or beta-carotene.
The application also provides a preparation method of the high-chromatic-aberration formaldehyde color-changing hydrogel based on the natural pigment, which comprises the following steps: the water-soluble linear polymer and the gel agent are dissolved by heating water, and then iodine simple substance and I-containing agent are added - The content of each component in the solution is as follows: 1-50 g/L of water-soluble linear polymer, 1-50 g/L of gel, 0.1-10 g/L of iodine simple substance, 2-30 g/L of iodide ion and 0.02-2 g/L of natural pigment, and cooling to room temperature to obtain the Gao Secha formaldehyde color-changing hydrogel.
The high-color-difference formaldehyde color-changing hydrogel provided by the application can react with formaldehyde and generate visible obvious color-difference change from blue or brown-purple to orange or yellow, so that the high-color-difference formaldehyde color-changing hydrogel can be used for absorbing, detecting and indicating formaldehyde pollutants.
The color change principle of the high-color-difference formaldehyde color-change hydrogel disclosed by the application is as follows:
in the hydrogel system, iodine simple substance I 2 Together with I-form polyiodide (I n - ) After the water-soluble linear polymer is dissolved in water, the water-soluble linear polymer is curled into a spiral shape by means of intramolecular hydrogen bonds, at the moment, polyiodide ions can enter a spiral middle tube cavity, a one-dimensional supermolecular assembly is formed under the action of coordination bonds of polymer hydroxyl groups (providing lone pair electrons) and iodine (providing empty orbitals), and the electron delocalization effect of the polyiodide ions in the one-dimensional assembly is enhanced, so that the absorption spectrum of the polyiodide ions is red shifted to be blue or brown-purple. The supramolecular assemblies are darker in color in the hydrogels and can mask the natural pigment ground color in the hydrogels. When the supermolecule assembly encounters formaldehyde molecules which are air pollutants, polyiodide ions can oxidize formaldehyde, and the supermolecule assembly can oxidize formaldehydeThe reduction to iodide ions causes the assembly to disintegrate and fade (as shown in figure 1), and the color of the natural pigment in the hydrogel is displayed. In order to obtain a relatively obvious color vision contrast effect before and after formaldehyde reaction, the selection of natural pigment endowed with the ground color of the hydrogel is mainly based on the complementary color (orange or yellow) of the blue or brown-purple color of the supramolecular assembly. The molecular structure of the optional natural pigment is shown in figure 2.
In industry and commerce, various factors such as light source, viewing angle, observer's own condition, etc. in visual color measurement may cause differences in color evaluation, and the international commission on illumination (CIE) recommends accurate assessment of product color difference based on Lab color space as a measurement standard. Processing each color into a point (L, a, b) in three-dimensional space by comparing color differences between a sample plate and a detected product by using a color difference meter according to the following standard color difference formula provided by CIE, and then calculating euclidean space distance between the two points to obtain a color difference value (Δe):
because the colors before and after the formaldehyde is changed are in a relative complementary color relationship (shown in figure 3), the hydrogel can obtain a larger color difference value (delta E is more than or equal to 30) and obtain better visual sensitivity.
Compared with the prior art, the application has the following beneficial effects: the formaldehyde color-changing hydrogel material is mainly based on natural substances, is friendly and safe to home environment, has obvious color change to formaldehyde, can identify color difference change visually, does not need additional identification equipment, and has the advantages of low cost, simple and mild preparation process and convenient application.
Drawings
FIG. 1 is a schematic structural diagram of a high-color-difference formaldehyde color-changing hydrogel and a schematic diagram of a formaldehyde color-changing principle.
FIG. 2 shows the molecular structure of natural pigment.
FIG. 3 is a color complementary relationship of hydrogels before and after formaldehyde discoloration.
Detailed Description
The present application will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present application, but are not intended to limit the application in any way. It should be noted that variations and modifications, including any combination of examples, can be made by those skilled in the art without departing from the spirit of the application.
Example 1
A natural pigment-based high-chromatic formaldehyde color-changing hydrogel comprises polyvinyl alcohol, agar, iodine simple substance, potassium iodide and curcumin.
The preparation method comprises the following steps: firstly, dissolving polyvinyl alcohol and agar in hot water at 80 ℃, and then adding iodine simple substance, potassium iodide and curcumin into the solution to ensure that the contents of all components in the solution are as follows: 10g/L polyvinyl alcohol, 10g/L agar, 1g/L iodine simple substance, 10g/L iodide ion and 0.2g/L curcumin are fully and uniformly mixed and dissolved, and cooled to room temperature, so that the high-color-difference formaldehyde color-changing hydrogel is obtained.
The hydrogel is placed in an air detection cabin, the color of the hydrogel is changed from deep blue to yellow visually after 24 hours under the condition that the formaldehyde concentration is 2mg/L, and the color difference delta E value before and after color change is 77.8 measured by a color difference meter, so that the obvious formaldehyde color change effect is achieved.
The hydrogel is placed in an air detection cabin, the color of the hydrogel is changed from deep blue to light yellow visually after 24 hours under the condition that the formaldehyde concentration is 0.08mg/L, and the color difference delta E before and after the color change is measured by a color difference meter to be 41.6, so that the obvious visual color change effect is achieved.
Example 2
A high-chromatic-difference formaldehyde color-changing hydrogel based on natural pigment comprises water-soluble starch, hyaluronic acid, iodine simple substance, sodium iodide and capsanthin.
The preparation method comprises the following steps: firstly, dissolving water-soluble starch and hyaluronic acid in hot water at 50 ℃, and then adding iodine simple substance, sodium iodide and capsanthin into the water-soluble starch and hyaluronic acid to ensure that the contents of all components in the solution are as follows: 1g/L of water-soluble starch, 1g/L of hyaluronic acid, 0.1g/L of iodine simple substance, 2g/L of iodide ions and 0.02g/L of capsanthin, and cooling to room temperature to obtain the high-chromatic-aberration formaldehyde color-changing hydrogel.
The hydrogel is placed in an air detection cabin, after 24 hours of the color of the hydrogel is changed from blue to orange under the condition that the formaldehyde concentration is 2mg/L, and the color difference delta E value before and after color change is 63.4 measured by a color difference meter, so that the obvious formaldehyde color change effect is achieved.
Example 3
A high-color-difference formaldehyde color-changing hydrogel based on natural pigment comprises polyvinylpyrrolidone, sodium alginate, iodine simple substance, ammonium iodide and beta-carotene.
The preparation method comprises the following steps: firstly, dissolving polyvinylpyrrolidone and sodium alginate in hot water at 100 ℃, and then adding iodine simple substance, ammonium iodide and beta-carotene into the solution to ensure that the contents of all components in the solution are as follows: 50g/L polyvinylpyrrolidone, 50g/L sodium alginate, 10g/L iodine simple substance, 30g/L iodine ion and 2g/L beta-carotene are fully and uniformly mixed and dissolved, and cooled to room temperature, thus obtaining the high-color-difference formaldehyde color-changing hydrogel.
The hydrogel is placed in an air detection cabin, the color of the hydrogel is changed from brown purple to orange yellow visually after 24 hours under the condition that the formaldehyde concentration is 2mg/L, and the color difference delta E value before and after the color change is measured by a color difference meter to be 45.9, so that the obvious formaldehyde color change effect is achieved.
Comparative example 1
A formaldehyde color-changing hydrogel comprising polyvinyl alcohol, agar, elemental iodine, and potassium iodide.
The preparation method comprises the following steps: firstly, dissolving polyvinyl alcohol and agar in hot water at 80 ℃, and then adding iodine simple substance and potassium iodide into the solution to ensure that the content of each component in the solution is as follows: 10g/L polyvinyl alcohol, 10g/L agar, 1g/L iodine simple substance and 10g/L iodine ion are fully mixed and dissolved, and cooled to room temperature, thus obtaining the formaldehyde color-changing hydrogel.
The hydrogel is placed in an air detection cabin, after 24 hours of the color of the hydrogel is changed from deep blue to slightly fade under the condition that the formaldehyde concentration is 2mg/L, the color difference delta E of the hydrogel before and after the color change is measured by a color difference meter to be 11.5, and the visual color change effect is not obvious.
The foregoing describes specific embodiments of the present application. It is to be understood that the application is not limited to the particular embodiments described above, and that various changes or modifications may be made by those skilled in the art within the scope of the appended claims without affecting the spirit of the application. The embodiments of the application and the features of the embodiments may be combined with each other arbitrarily without conflict.

Claims (7)

1. A natural pigment-based high-color-difference formaldehyde color-changing hydrogel, which is characterized by comprising a water-soluble linear polymer, a gel agent, an iodine simple substance, iodide ions, a natural pigment and water;
the Gao Secha formaldehyde color-changing hydrogel is prepared by the following steps: the water-soluble linear polymer and the gel are heated and dissolved in water, and then iodine simple substance, iodide ions and natural pigment are added, so that the contents of all components in the solution are as follows: 1 to 50g/L of water-soluble linear polymer, 1 to 50g/L of gel, 0.1 to 10g/L of iodine simple substance, 2 to 30g/L of iodine ions and 0.02 to 2g/L of natural pigment, and cooling to room temperature to obtain the Gao Secha formaldehyde color-changing hydrogel;
the water-soluble linear polymer is one or more of polyvinyl alcohol, water-soluble starch, polyvinylpyrrolidone, water-soluble cellulose, polyethylene glycol and polyacrylamide;
the natural pigment is one or more of curcumin, capsanthin, beta-carotene, zeaxanthin and lycopene.
2. The natural pigment-based high-chromatic formaldehyde color-changing hydrogel according to claim 1, wherein the gel is one or more of agar, hyaluronic acid, sodium alginate, konjac gum and gelatin.
3. The natural pigment-based formulation of claim 1Is characterized in that the iodide ions are derived from a high-color-difference formaldehyde-color-changing hydrogel containing I - The compound containing I - The cation in the compound is one or more of potassium, sodium, lithium and ammonium.
4. The natural pigment-based high color difference formaldehyde color-changing hydrogel according to claim 2, wherein the hot water is hot water of 50 to 100 ℃.
5. The natural pigment-based high color-difference formaldehyde color-changing hydrogel according to one of claims 1 to 4, wherein the hydrogel reacts with formaldehyde to produce a visually distinct color-difference change from blue or brown-violet to orange or yellow.
6. The method for preparing the natural pigment-based high-chromatic formaldehyde color-changing hydrogel, which is characterized in that the method comprises the following steps: the water-soluble linear polymer and the gel agent are dissolved by heating water, and then iodine simple substance and I-containing agent are added - The content of each component in the solution is as follows: 1 to 50g/L of water-soluble linear polymer, 1 to 50g/L of gel, 0.1 to 10g/L of iodine simple substance, 2 to 30g/L of iodine ions and 0.02 to 2g/L of natural pigment, and cooling to room temperature to obtain the Gao Secha formaldehyde color-changing hydrogel.
7. The use of the natural pigment-based high-color-difference formaldehyde color-changing hydrogel according to any one of claims 1 to 4 for absorbing, detecting and indicating formaldehyde pollutants.
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