Preparation method of multifunctional wearable colorimetric sensor

Abstract

The invention belongs to the technical field of sensors, and relates to a preparation method of a multifunctional wearable colorimetric sensor, laccase is utilized to catalyze anthocyanidin to be grafted on a textile and catalyze the anthocyanidin to be subjected to a self-polymerization reaction, and then the textile is directly used as the multifunctional wearable colorimetric sensor, or the multi-functional wearable colorimetric sensor can be used as a multifunctional wearable colorimetric sensor. The textile is further processed into the multifunctional wearable colorimetric sensor, and the textile is a protein textile or a chinlon textile. The colorimetric sensor successfully solves the problem that a colorimetric sensor in the prior art is narrow in color development range, the sensor can more accurately monitor and indicate biochemical changes of human body fluid and external environment stimulation, and therefore the accuracy and reliability of health monitoring and environment monitoring are improved.

Description

Technical Field

[0001] The invention belongs to the technical field of sensors and relates to a method for preparing a multifunctional wearable colorimetric sensor. Background Art

[0002] With the advancement of science and technology and the growing demand for health monitoring, wearable smart devices are gradually entering people's daily lives. Textile materials have become the preferred materials for the development of wearable flexible smart devices due to their stable softness, good mechanical properties, breathability, low-cost weaving technology and lightness. Among them, functional smart textiles have shown great application potential in the fields of mechanical sensing and human health monitoring.

[0003] In smart textiles, colorimetric sensors have attracted much attention due to their simple functions and visual detection capabilities. Colorimetric sensors can quickly judge biochemical changes by naked eyes, without the need for complex electronic components and supporting electronic equipment, nor do they require trained professionals. Therefore, they are considered to be a very simple, cheap and efficient real-time detection technology. The use of colorimetry for human body fluid monitoring or indicating external environmental stimuli and changes has the advantages of being simple, easy to use and non-invasive.

[0004] Anthocyanin, as a natural phenolic compound acid-base sensor, is widely used for pH indication because it can show a variety of colors (including blue, green, red, yellow, purple, etc.) in aqueous solutions with different pH values. Anthocyanin not only has good biocompatibility, antioxidant and anti-inflammatory biological activities, but also has high biosafety and is often used as food coloring in food. In addition, anthocyanin is quite stable in the temperature range below 80°C, which makes it an ideal material for the preparation of wearable biochromic sensors.

[0005] The document (Preparation of green and sustainable colorimetric cotton assay using natural anthocyanins for sweat sensing [J]. International Journal of Biological Macromolecules, 2021, 894-903.) discloses a cotton fiber sensor prepared using anthocyanins extracted from cabbage. Although the sensor can sense human sweat, its color range is limited. When the pH value reaches 8, the fabric sensor no longer changes color and cannot respond well to the stimulation of a higher alkaline environment. This shows that the color range of the sensor fails to cover a wider range of pH values, limiting its versatility in practical applications.

[0006] The literature (Kinetic investigation into pH-dependent color of anthocyanin and its sensing performance [J]. Dyes and Pigments, 2019, 170: 107643.) discloses a sensor prepared by directly dyeing silk fabrics with anthocyanins from purple sweet potatoes. Although the sensor appears pink under acidic conditions and green under strong alkaline conditions, its color change is not significant in the pH range of 2-8, and the naked eye cannot distinguish obvious color changes. Therefore, the sensor cannot make a visible response under the stimulation of acidic to neutral pH values, and also has the problem of a narrow color range.

[0007] The literature (Design and fabrication of green and sustainable vapochromiccellulose fibers embedded with natural anthocyanin for detection of toxicammonia[J].Talanta,2021,122292.) uses metal ions as mordants to dye anthocyanins onto fabrics to prepare pH-responsive sensors. However, the complexation between metal ions and anthocyanins will change the original color development law of anthocyanins and is not environmentally friendly. The literature (Anthocyanin dyes extracted from grape pomace for the purpose of textile dyeing[J].Journal of the Science of Food and Agriculture,2007,87(14):2589-2595.) uses organic molecules as mordants, which may also affect the color development effect of anthocyanins. In addition, the color development range of these sensors is often limited to a specific pH range and cannot meet the needs of a wider range of applications.

[0008] The literature (Chitosan-pectin multilayer coating with anthocyanin grape dye as pH indicating wound dressing: Synthesis and characterization [J]. Carbohydrate Polymers, 2022, 293: 119776.) modified the surface of the fabric with functionalization and then used anthocyanin dyeing to prepare a wound dressing sensor. Although the color change occurred when the pH value of the wound changed from 6 to 7, its color range was still narrow and the process was complicated and cumbersome.

[0009] In summary, the existing colorimetric sensors generally have a narrow color range, which limits the accuracy and reliability of colorimetric sensors in real-time monitoring and indicating biochemical changes of human body fluids and external environmental stimuli. Therefore, it is of great significance to develop a colorimetric sensor with a wide color range. Summary of the invention

[0010] The purpose of the present invention is to solve the problems existing in the prior art and provide a method for preparing a multifunctional wearable colorimetric sensor.

[0011] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0012] A method for preparing a multifunctional wearable colorimetric sensor, wherein laccase is used to catalyze the grafting of anthocyanins onto textiles, and after catalyzing the self-polymerization reaction of anthocyanins, the textiles are directly used as multifunctional wearable colorimetric sensors, or the textiles are further processed into multifunctional wearable colorimetric sensors, wherein the textiles are protein textiles or nylon textiles.

[0013] As the preferred technical solution:

[0014] A method for preparing a multifunctional wearable colorimetric sensor as described above, wherein the multifunctional wearable colorimetric sensor exhibits a color change after being exposed to liquids of different pH values;

[0015] The anthocyanin is butterfly pea anthocyanin; when the pH value of the liquid is in the interval (1,2), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [2,5), the multifunctional wearable colorimetric sensor is purple; when the pH value of the liquid is in the interval [5,7), the multifunctional wearable colorimetric sensor is blue; when the pH value of the liquid is in the interval [7,9), the multifunctional wearable colorimetric sensor is lake blue; when the pH value of the liquid is in the interval [9,11), the multifunctional wearable colorimetric sensor is dark green; when the pH value of the liquid is in the interval [11,13], the multifunctional wearable colorimetric sensor is yellow-brown;

[0016] The anthocyanin is blueberry anthocyanin; when the pH value of the liquid is in the interval (1,2), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [2,5), the multifunctional wearable colorimetric sensor is pink; when the pH value of the liquid is in the interval [5,7), the multifunctional wearable colorimetric sensor is extremely light pink or even colorless; when the pH value of the liquid is in the interval [7,9), the multifunctional wearable colorimetric sensor is dark purple; when the pH value of the liquid is in the interval [9,12), the multifunctional wearable colorimetric sensor is blue-green;

[0017] The anthocyanin is purple cabbage anthocyanin; when the pH value of the liquid is in the interval (1,4), the multifunctional wearable colorimetric sensor is pink; when the pH value of the liquid is in the interval [4,7), the multifunctional wearable colorimetric sensor is blue-purple; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue;

[0018] The anthocyanin is black rice anthocyanin; when the pH value of the liquid is in the interval (1,4), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [4,7), the multifunctional wearable colorimetric sensor is pink; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue;

[0019] The anthocyanin is purple sweet potato anthocyanin; when the pH value of the liquid is in the interval (1,3), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [3,7), the multifunctional wearable colorimetric sensor is pink; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue; when the pH value of the liquid is in the interval [10,12), the multifunctional wearable colorimetric sensor is dark green;

[0020] Anthocyanin is anthocyanin from grape skin; when the pH value of the liquid is in the interval (1,3), the multifunctional wearable colorimetric sensor is pink; when the pH value of the liquid is in the interval [3,7), the multifunctional wearable colorimetric sensor is purple; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue-green; when the pH value of the liquid is in the interval [10,12), the multifunctional wearable colorimetric sensor is dark yellow;

[0021] The anthocyanin is mulberry anthocyanin; when the pH value of the liquid is in the interval (1,3), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [3,5), the multifunctional wearable colorimetric sensor is pink; when the pH value of the liquid is in the interval [5,7), the multifunctional wearable colorimetric sensor is purple; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue;

[0022] Anthocyanin is anthocyanin from eggplant skin; when the pH value of the liquid is in the interval (1,3), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [3,5), the multifunctional wearable colorimetric sensor is purple; when the pH value of the liquid is in the interval [5,7), the multifunctional wearable colorimetric sensor is blue-purple; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue; when the pH value of the liquid is in the interval [10,11), the multifunctional wearable colorimetric sensor is green; when the pH value of the liquid is in the interval [11,13), the multifunctional wearable colorimetric sensor is yellow-green;

[0023] The anthocyanin is blackcurrant anthocyanin; when the pH value of the liquid is in the interval (1,2), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [2,5), the multifunctional wearable colorimetric sensor is pink; when the pH value of the liquid is in the interval [5,7), the multifunctional wearable colorimetric sensor is purple; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue; when the pH value of the liquid is in the interval [10,13), the multifunctional wearable colorimetric sensor is yellow-brown;

[0024] Anthocyanin is a mixture of butterfly pea anthocyanin and blueberry anthocyanin in a mass ratio of 1:3; when the pH value of the liquid is in the interval (1,2), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [2,5), the multifunctional wearable colorimetric sensor is purple-red; when the pH value of the liquid is in the interval [5,7), the multifunctional wearable colorimetric sensor is extremely light purple; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue-purple; when the pH value of the liquid is in the interval [10,11), the multifunctional wearable colorimetric sensor is blue-green; when the pH value of the liquid is in the interval [11,13), the multifunctional wearable colorimetric sensor is brown.

[0025] Natural dyes, including anthocyanins, have rich colors, but there is a common problem that they can only dye light colors when dyeing fibers / fabrics. Even if the concentration of natural dyes is increased, the dyeing rate is still limited, resulting in the dyed fabrics not being colorful enough. However, after anthocyanins are self-polymerized under the catalysis of laccase, they are dyed onto fabrics to achieve a very dark dyeing effect, making up for the defect that the fabrics dyed with single-molecule natural dyes (anthocyanins) are light in color. The present invention unexpectedly discovered that after anthocyanins self-polymerize and cause the color to darken, they can respond quickly and change color under different pH environments. This high pH response sensitivity makes the color change easier to be recognized by the naked eye, thereby greatly improving the accuracy of recognition.

[0026] Overall, the multifunctional wearable colorimetric sensor prepared by the present invention has a wide color rendering range and a wide range of applications. It presents different color responses according to different anthocyanin types and changes in the pH value of the liquid. This high pH response sensitivity greatly improves the recognition accuracy and reliability of color changes. For example, the sensor prepared using blueberry anthocyanin can be used to monitor female watery secretions, the purple cabbage anthocyanin sensor is suitable for the pH detection of human sweat, the black rice anthocyanin sensor can be used for acid rain monitoring, and the purple potato anthocyanin sensor is suitable for NH 3 Detection.

[0027] The preparation method of the multifunctional wearable colorimetric sensor as described above specifically comprises the following steps: placing the textile in a dye solution containing both laccase and anthocyanin, reacting at 30-60°C for 0.5-4h, taking out the textile, rinsing, and drying.

[0028] In the preparation method of a multifunctional wearable colorimetric sensor as described above, in the dye solution, the concentration of laccase is 0.1-3U / mL, and the concentration of anthocyanin is 0.2-5g / L; the mass ratio of textile to dye solution is 1:10-100.

[0029] According to the preparation method of the multifunctional wearable colorimetric sensor as described above, the textile is a protein fabric or a nylon fabric, and the multifunctional wearable colorimetric sensor can be obtained by drying.

[0030] In the preparation method of a multifunctional wearable colorimetric sensor as described above, the textile is a protein yarn or a nylon yarn, which is blended or interwoven with undyed white yarn after drying to obtain a multifunctional wearable colorimetric sensor, so that different patterns can be designed for pH response.

[0031] The preparation method of a multifunctional wearable colorimetric sensor as described above specifically comprises the following steps: spraying an aqueous solution containing laccase evenly on the surface of the textile, drying it, and then printing a printing paste containing anthocyanins on the surface of the textile by screen printing (a personalized pattern can be designed during the printing process), placing it in air at a temperature of 30-60°C and a relative humidity of 50-100% for 0.5-4h, rinsing it, and drying it.

[0032] According to the preparation method of the multifunctional wearable colorimetric sensor as described above, the concentration of laccase in the aqueous solution containing laccase is 0.1-3U / mL; the spraying amount of the aqueous solution containing laccase is 5-500g / m 2 ; In the printing paste containing anthocyanins, the concentration of anthocyanins is 0.2-10g / L.

[0033] According to the preparation method of the multifunctional wearable colorimetric sensor as described above, the textile is a protein fabric or a nylon fabric, and the multifunctional wearable colorimetric sensor can be obtained by drying.

[0034] Invention mechanism:

[0035] The reason why anthocyanins can change color is that their molecular structure changes at different pH values. Figure 1 As shown in Figure 2, some anthocyanins are mainly present as red flavonoid cations (AH + ) exists in the form of, gradually transforming into colorless methanol pseudobase (B) under weak acidic conditions, gradually transforming into blue quinone base (A) under weak alkaline conditions, and then degrading into yellow chalcone (C) under strong alkaline conditions. Different anthocyanins have different color change rules because of their different molecular structures and the substituent R 1 , R 2 , R 3 It may be a hydrogen atom, methoxyl group, phenolic hydroxyl group or complex glycoside structure, and the glycosidic bond structure and length of anthocyanin molecules from different sources are different. Anthocyanins with different structures have different ionization degrees and structural changes under different pH conditions, resulting in great differences in color tone within different pH value ranges.

[0036] The existing technology generally uses single-molecule anthocyanins to prepare colorimetric sensors, which have the problem of narrow color display range. This is mainly because the molecular structure changes of single-molecule anthocyanins at different pH values ​​are relatively limited, and their color transitions are often limited to a specific pH range. In addition, single-molecule anthocyanins are prone to degradation under extreme pH conditions (such as strong acid or strong alkaline environments), resulting in insufficient color stability, which further limits their color display range.

[0037] Laccase is an oxidase containing multiple copper ions, which has the ability to catalyze the oxidation reaction of phenolic compounds. In this process, laccase not only promotes the generation of free radicals, but also further induces the self-polymerization reaction of phenolic compounds. Through its catalytic action, laccase can convert monomeric phenolic compounds into polymers or construct more complex chemical structures. Anthocyanin molecules are polyphenolic structures that can self-polymerize into low molecular weight dimers or trimers under the catalysis of laccase. Compared with single-molecule anthocyanins, these self-polymerized polyphenolic structures (anthocyanin dimers and trimers) have a larger molecular weight, and the glycosidic bond structure on the polymer increases, making the molecular structure of the anthocyanin polymer more stable.

[0038] Specifically, many single-molecule anthocyanins undergo a transformation from red flavonoid cations (AH+) to colorless methanol pseudobases (B), then to blue quinone bases (A), and finally degrade to yellow chalcone (C) during pH changes. However, when anthocyanins are polymerized under the catalysis of laccase, as the pH value of the solution increases, the anthocyanin polymers will significantly reduce and delay the production of colorless methanol pseudobases (B) during the ionization process, making the color change of the solution more significant. In addition, when the pH value continues to rise to a strong alkaline state, the anthocyanin polymers can delay or reduce the degree of degradation under alkaline conditions due to the increase in glycosidic bond structures in their molecules and the enhanced stability of their molecular structures. Therefore, the use of laccase to catalyze the self-polymerization of anthocyanins can not only deepen the color, but also broaden the color range, making it easier for the naked eye to identify color changes.

[0039] Beneficial effects:

[0040] (1) The present invention successfully solves the problem of narrow color display range of colorimetric sensors in the prior art, enabling the sensor to more accurately monitor and indicate biochemical changes in human body fluids and external environmental stimuli, thereby improving the accuracy and reliability of health monitoring and environmental monitoring.

[0041] (2) The method of the present invention is simple and environmentally friendly, which is conducive to the promotion and application of sensors and conforms to the concept of sustainable development. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 Schematic diagram of the molecular conformational transition of anthocyanin color change;

[0043] Figure 2 It is the XPS test result of Example A1; wherein, a is the overall test graph of SF, Ac-DSF, and Ac-DSF-Lac, b is the N1s spectrum of the SF surface, c is the N1s spectrum of the Ac-DSF surface, and d is the N1s spectrum of the Ac-DSF-Lac surface. DETAILED DESCRIPTION

[0044] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0045] The testing methods of the relevant performance indicators in the following embodiments are as follows:

[0046] Lab value: Tested in accordance with GB / T 8424.1-2001 standard;

[0047] UVA band ultraviolet transmittance (UVA%), UVB band ultraviolet transmittance (TUVB%), ultraviolet protection factor (UPF): tested in accordance with the "AATCC 183-2014" standard;

[0048] Dry / wet friction staining level, dry / wet friction discoloration level: Test in accordance with GB / T 3920-2008 standard; When testing the dry / wet friction discoloration level, use the gray scale that complies with GB / T 250 standard;

[0049] Washing discoloration level, washing cotton staining level: Tested in accordance with GB / T 5713-2013 standard;

[0050] Color: Refer to GB / T 6688-2008 for comparison.

[0051] In the following embodiments, the preparation process of butterfly pea anthocyanin is as follows: butterfly pea flower is added to an ethanol aqueous solution with a volume fraction of 80% to obtain a mixed solution, a 1M hydrochloric acid aqueous solution is used to adjust the pH value of the mixed solution to 3, and then the mixed solution is heated at 50°C for 1h and filtered, and then centrifuged at a speed of 6000r / min for 5min, the supernatant is taken, and the solvent is removed under a dark light condition of 60°C, and freeze-dried to obtain butterfly pea anthocyanin powder; wherein the mass volume ratio of butterfly pea flower to the ethanol aqueous solution is 1g:15mL;

[0052] The preparation process of blueberry anthocyanin is as follows: blueberry powder is added to an ethanol aqueous solution with a volume fraction of 80% to obtain a mixed solution, the pH value of the mixed solution is adjusted to 4 using a hydrochloric acid aqueous solution with a concentration of 1M, the mixed solution is heated at 45°C for 2h and then filtered, and then centrifuged at a speed of 5000r / min for 8min, the supernatant is taken, and the solvent is removed under dark light conditions at 60°C, and freeze-dried to obtain blueberry anthocyanin powder; wherein the mass volume ratio of blueberry powder to ethanol aqueous solution is 1g:10mL;

[0053] The preparation process of purple cabbage anthocyanin is as follows: adding purple cabbage leaves to an ethanol aqueous solution with a volume fraction of 80% to obtain a mixed solution, adjusting the pH value of the mixed solution to 3.5 using a hydrochloric acid aqueous solution with a concentration of 1M, heating the mixed solution at 55°C for 1.5h, filtering, centrifuging at a speed of 6000r / min for 6min, taking the supernatant, removing the solvent under dark light conditions at 55°C, and freeze-drying to obtain purple cabbage anthocyanin powder; wherein the mass volume ratio of purple cabbage leaves to the ethanol aqueous solution is 1g:20mL;

[0054] The preparation process of black rice anthocyanin is as follows: black rice powder is added to an ethanol aqueous solution with a volume fraction of 80% to obtain a mixed solution, a 1M hydrochloric acid aqueous solution is used to adjust the pH value of the mixed solution to 3, the mixed solution is heated at 65° C. for 1 hour and then filtered, and then centrifuged at a speed of 5500 r / min for 12 minutes, the supernatant is taken, and the solvent is removed under dark light conditions at 65° C., and freeze-dried to obtain black rice anthocyanin powder; wherein the mass volume ratio of black rice powder to ethanol aqueous solution is 1g:30mL;

[0055] The preparation process of purple sweet potato anthocyanin is as follows: purple sweet potato powder is added to an ethanol aqueous solution with a volume fraction of 80% to obtain a mixed solution, a 1M hydrochloric acid aqueous solution is used to adjust the pH value of the mixed solution to 3.5, the mixed solution is heated at 50°C for 2 hours, filtered, centrifuged at a speed of 5000r / min for 15 minutes, the supernatant is taken, the solvent is removed under dark light conditions at 60°C, and the purple sweet potato anthocyanin powder is freeze-dried; wherein the mass volume ratio of the purple sweet potato powder to the ethanol aqueous solution is 1g:15mL;

[0056] The preparation process of grape skin anthocyanin is as follows: add grape skin to an ethanol aqueous solution with a volume fraction of 80% to obtain a mixed solution, adjust the pH value of the mixed solution to 3 with a hydrochloric acid aqueous solution with a concentration of 1M, heat the mixed solution at 65°C for 1.5h, filter it, centrifuge it at a speed of 6500r / min for 8min, take the supernatant, remove the solvent under dark light conditions at 65°C, and freeze-dry to obtain grape skin anthocyanin powder; wherein the mass volume ratio of grape skin to ethanol aqueous solution is 1g:20mL;

[0057] The preparation process of mulberry anthocyanidin is as follows: mulberry dry powder is added to an ethanol aqueous solution with a volume fraction of 80% to obtain a mixed solution, the pH value of the mixed solution is adjusted to 3.5 using a hydrochloric acid aqueous solution with a concentration of 1M, the mixed solution is heated at 55°C for 2h and then filtered, and then centrifuged at a speed of 6000r / min for 12min, the supernatant is taken, and the solvent is removed under dark light conditions at 55°C, and lyophilized to obtain mulberry anthocyanidin powder; wherein the mass volume ratio of mulberry dry powder to ethanol aqueous solution is 1g:15mL;

[0058] The preparation process of eggplant peel anthocyanin is as follows: adding eggplant peel dry powder to an ethanol aqueous solution with a volume fraction of 80% to obtain a mixed solution, adjusting the pH value of the mixed solution to 3 using a hydrochloric acid aqueous solution with a concentration of 1M, heating the mixed solution at 55°C for 2h and filtering it, centrifuging it at a speed of 5000r / min for 15min, taking the supernatant, removing the solvent under dark light conditions at 60°C, and freeze-drying to obtain eggplant peel anthocyanin powder; wherein the mass volume ratio of eggplant peel dry powder to ethanol aqueous solution is 1g:30mL;

[0059] The preparation process of blackcurrant anthocyanin is as follows: blackcurrant dry powder is added to an ethanol aqueous solution with a volume fraction of 80% to obtain a mixed solution, the pH value of the mixed solution is adjusted to 3.5 using a hydrochloric acid aqueous solution with a concentration of 1M, the mixed solution is heated at 60°C for 1.5 hours and then filtered, and then centrifuged at a speed of 6000r / min for 10 minutes, the supernatant is taken, and the solvent is removed under dark light conditions at 65°C, and freeze-dried to obtain blackcurrant anthocyanin powder; wherein the mass volume ratio of blackcurrant dry powder to ethanol aqueous solution is 1g:15mL.

[0060] Example A1

[0061] A method for preparing a multifunctional wearable colorimetric sensor, the specific steps are as follows:

[0062] (1) Preparation of raw materials;

[0063] Butterfly pea anthocyanins;

[0064] Laccase: manufacturer is Shanghai Yuanye Biotechnology Co., Ltd., product number is S10189;

[0065] water;

[0066] Textiles: Silk fabrics that comply with GB / T 7568.6-2002;

[0067] (2) preparing dye solution;

[0068] The dye solution is composed of laccase, butterfly pea anthocyanin and water, the concentration of laccase is 3U / mL, and the concentration of butterfly pea anthocyanin is 1g / L;

[0069] (3) Preparation of multifunctional wearable colorimetric sensors;

[0070] The textile is placed in a dye solution, reacted at 50°C for 0.5h, the textile is taken out, rinsed, and dried to obtain a multifunctional wearable colorimetric sensor. Alternatively, after drying, the textile is blended or interwoven with undyed white yarn to obtain a multifunctional wearable colorimetric sensor; wherein the mass ratio of the textile to the dye solution is 1:50.

[0071] The multifunctional wearable colorimetric sensor finally prepared will show color changes after contacting liquids with different pH values; when the pH value of the liquid is in the interval (1,2), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [2,5), the multifunctional wearable colorimetric sensor is purple; when the pH value of the liquid is in the interval [5,7), the multifunctional wearable colorimetric sensor is blue; when the pH value of the liquid is in the interval [7,9), the multifunctional wearable colorimetric sensor is lake blue; when the pH value of the liquid is in the interval [9,11), the multifunctional wearable colorimetric sensor is dark green; when the pH value of the liquid is in the interval [11,13], the multifunctional wearable colorimetric sensor is yellow-brown.

[0072] After the multifunctional wearable colorimetric sensor prepared in this embodiment is exposed to liquids with different pH values, the changes in the Lab value of the color, UVA%, TUVB%, and UPF are shown in Table 1:

[0073] Table 1

[0074] pH L value a value b-value UVA % TUVB% UPF 2 53.89 23.88 -9.46 1.99 0.58 129.16 3 52.04 17.28 -13.23 1.88 0.88 102.45 4 51.58 11.53 -15.01 1.49 0.89 105.77 5 50.27 8.45 -12.77 2.01 0.89 105.02 6 50.10 3.64 -11.98 1.99 0.88 105.51 7 49.85 0.65 -12.56 1.99 0.89 103.88 8 49.57 -9.27 -5.58 2.01 0.89 103.30 9 48.32 -11.58 -3.71 2.03 0.90 102.48 10 47.82 -13.34 3.53 2.03 0.92 100.32 11 47.15 -10.12 9.90 1.97 0.91 102.13 12 45.81 -8.56 14.35 1.93 0.90 102.92

[0075] XPS test was performed on the surfaces of the raw textile (SF), anthocyanin dyed textile (Ac-DSF, the preparation process is basically the same as that of this embodiment, except that laccase is not added during the preparation of the dye solution) and the product of this embodiment, the multifunctional wearable colorimetric sensor (Ac-DSF-Lac). The test results showed that the surfaces of SF, Ac-DSF and Ac-DSF-Lac all contained C, N and O elements (such as Figure 2 As shown in a); Figure 2 As shown in (b), on the SF surface, the peaks of the N1s spectrum at 399.7 eV and 401.3 eV correspond to the NC in the peptide chain (accounting for 88.62%) and the salt bond -NH in the tertiary structure of the protein, respectively. 3+ (accounting for 11.38%); in contrast, Figure 2 As shown in middle c, a large amount of NC and -NH at 401.6 eV were still detected on the Ac-DSF surface. 3+ , no new chemical bonds were observed to form, indicating that anthocyanins may be adsorbed on the fibers mainly through physical forces such as hydrogen bonding and π-π stacking; however, Figure 2 As shown in (d), on the surface of Ac-DSF-Lac, in addition to a large amount of NC (accounting for 89.71%) and salt-NH 3+ In addition to the new chemical bond =NR (accounting for 3.24%) at 398.5 eV, this proves that part of the -NH 3+ Under the catalysis of laccase, the Schiff base reaction with anthocyanin occurred, and a very small amount of -NH3+ Michael addition reaction occurred (accounting for about 1%); these results show that the catalytic action of laccase promotes the chemical reaction between anthocyanin and silk fiber, thereby improving the fastness of the modification. The dry friction discoloration grade, wet friction discoloration grade, washing discoloration grade, washing cotton staining grade, dry friction staining grade and wet friction staining grade of Ac-DSF and Ac-DSF-Lac listed in Table 2 can support this view:

[0076] Table 2

[0077]

[0078] The UVA%, TUVB%, and UPF of SF and Ac-DSF after contacting the liquid with a pH value of 7 are shown in Table 3:

[0079] Table 3

[0080] sample UVA % TUVB% UPF SF 11.89 8.25 7.27 Ac-DSF 2.50 2.35 91.58

[0081] Comparing Table 1 and Table 3, it can be seen that after contacting the liquid with a pH value of 7, the anti-ultraviolet effect of Ac-DSF-Lac is significantly better.

[0082] Example A2

[0083] A method for preparing a multifunctional wearable colorimetric sensor, the specific steps are as follows:

[0084] (1) Preparation of raw materials;

[0085] Blueberry anthocyanins;

[0086] Laccase: manufacturer is Shanghai Yuanye Biotechnology Co., Ltd., product number is S10189;

[0087] water;

[0088] Textiles: Silk fabrics that comply with GB / T 7568.6-2002;

[0089] (2) preparing dye solution;

[0090] The dye solution consisted of laccase, blueberry anthocyanin and water, with the concentration of laccase being 1.5 U / mL and the concentration of blueberry anthocyanin being 2 g / L;

[0091] (3) Preparation of multifunctional wearable colorimetric sensors;

[0092] The textile is placed in a dye solution, reacted at 55°C for 3 hours, the textile is taken out, rinsed, and dried to obtain a multifunctional wearable colorimetric sensor. Alternatively, after drying, the textile is blended or interwoven with undyed white yarn to obtain a multifunctional wearable colorimetric sensor; wherein the mass ratio of the textile to the dye solution is 1:15.

[0093] The multifunctional wearable colorimetric sensor finally prepared will show color changes after contacting liquids with different pH values; when the pH value of the liquid is in the interval (1,2), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [2,5), the multifunctional wearable colorimetric sensor is pink; when the pH value of the liquid is in the interval [5,7), the multifunctional wearable colorimetric sensor is extremely light pink or even colorless; when the pH value of the liquid is in the interval [7,9), the multifunctional wearable colorimetric sensor is dark purple; when the pH value of the liquid is in the interval [9,12), the multifunctional wearable colorimetric sensor is blue-green.

[0094] The dry friction discoloration grade, wet friction discoloration grade, washing discoloration grade, washing cotton staining grade, dry friction staining grade and wet friction staining grade of the multifunctional wearable colorimetric sensor and anthocyanin dyed textile (the preparation process is basically the same as that of the present embodiment, except that laccase is not added during the preparation of the dye solution) of the product of this embodiment are shown in Table 4:

[0095] Table 4

[0096]

[0097] Example A3

[0098] A method for preparing a multifunctional wearable colorimetric sensor, the specific steps are as follows:

[0099] (1) Preparation of raw materials;

[0100] Purple cabbage anthocyanins;

[0101] Laccase: manufacturer is Shanghai Aladdin Biochemical Technology Co., Ltd., product number is L757850;

[0102] water;

[0103] Textiles: Silk fabrics that comply with GB / T 7568.6-2002;

[0104] (2) preparing dye solution;

[0105] The dye solution consisted of laccase, red cabbage anthocyanin and water, the concentration of laccase was 0.2 U / mL, and the concentration of red cabbage anthocyanin was 0.2 g / L;

[0106] (3) Preparation of multifunctional wearable colorimetric sensors;

[0107] The textile is placed in a dye solution, reacted at 45°C for 4 hours, the textile is taken out, rinsed, and dried to obtain a multifunctional wearable colorimetric sensor. Alternatively, after drying, the textile is blended or interwoven with undyed white yarn to obtain a multifunctional wearable colorimetric sensor; wherein the mass ratio of the textile to the dye solution is 1:30.

[0108] The multifunctional wearable colorimetric sensor finally prepared will show color changes after coming into contact with liquids of different pH values; when the pH value of the liquid is in the interval (1,4), the multifunctional wearable colorimetric sensor is pink; when the pH value of the liquid is in the interval [4,7), the multifunctional wearable colorimetric sensor is bluish-purple; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue.

[0109] The dry friction discoloration grade, wet friction discoloration grade, washing discoloration grade, washing cotton staining grade, dry friction staining grade and wet friction staining grade of the multifunctional wearable colorimetric sensor and anthocyanin dyed textile (the preparation process is basically the same as that of the present embodiment, except that laccase is not added during the preparation of the dye solution) of the product of this embodiment are shown in Table 5:

[0110] Table 5

[0111]

[0112] Example A4

[0113] A method for preparing a multifunctional wearable colorimetric sensor, the specific steps are as follows:

[0114] (1) Preparation of raw materials;

[0115] Black rice anthocyanins;

[0116] Laccase: manufacturer is Shanghai Yuanye Biotechnology Co., Ltd., product number is S10189;

[0117] water;

[0118] Textiles: wool fabrics that comply with GB / T 7568.1-2002;

[0119] (2) preparing dye solution;

[0120] The dye solution consisted of laccase, black rice anthocyanin and water, with the concentration of laccase being 3U / mL and the concentration of black rice anthocyanin being 5g / L;

[0121] (3) Preparation of multifunctional wearable colorimetric sensors;

[0122] The textile is placed in a dye solution, reacted at 35°C for 0.5h, the textile is taken out, rinsed, and dried to obtain a multifunctional wearable colorimetric sensor. Alternatively, after drying, the textile is blended or interwoven with undyed white yarn to obtain a multifunctional wearable colorimetric sensor; wherein the mass ratio of the textile to the dye solution is 1:100.

[0123] The multifunctional wearable colorimetric sensor finally prepared will show color changes after coming into contact with liquids of different pH values; when the pH value of the liquid is in the interval (1,4), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [4,7), the multifunctional wearable colorimetric sensor is pink; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue.

[0124] The dry friction discoloration grade, wet friction discoloration grade, washing discoloration grade, washing cotton staining grade, dry friction staining grade and wet friction staining grade of the multifunctional wearable colorimetric sensor and anthocyanin dyed textile (the preparation process is basically the same as that of the present embodiment, except that laccase is not added during the preparation of the dye solution) of the product of this embodiment are shown in Table 6:

[0125] Table 6

[0126]

[0127] Example A5

[0128] A method for preparing a multifunctional wearable colorimetric sensor, the specific steps are as follows:

[0129] (1) Preparation of raw materials;

[0130] Purple potato anthocyanins;

[0131] Laccase: manufacturer is Shanghai Yuanye Biotechnology Co., Ltd., product number is S10189;

[0132] water;

[0133] Textiles: Nylon fabrics that comply with GB / T 7568.3-2008;

[0134] (2) preparing dye solution;

[0135] The dye solution is composed of laccase, purple sweet potato anthocyanin and water, the concentration of laccase is 2U / mL, and the concentration of purple sweet potato anthocyanin is 3g / L;

[0136] (3) Preparation of multifunctional wearable colorimetric sensors;

[0137] The textile is placed in a dye solution, reacted at 60°C for 2 hours, the textile is taken out, rinsed, and dried to obtain a multifunctional wearable colorimetric sensor. Alternatively, after drying, the textile is blended or interwoven with undyed white yarn to obtain a multifunctional wearable colorimetric sensor; wherein the mass ratio of the textile to the dye solution is 1:50.

[0138] The multifunctional wearable colorimetric sensor finally prepared will show color changes after contacting liquids with different pH values; when the pH value of the liquid is in the interval (1,3), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [3,7), the multifunctional wearable colorimetric sensor is pink; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue; when the pH value of the liquid is in the interval [10,12), the multifunctional wearable colorimetric sensor is dark green.

[0139] The dry friction discoloration grade, wet friction discoloration grade, washing discoloration grade, washing cotton staining grade, dry friction staining grade and wet friction staining grade of the multifunctional wearable colorimetric sensor and anthocyanin dyed textile (the preparation process is basically the same as that of the present embodiment, except that laccase is not added during the preparation of the dye solution) of the product of this embodiment are shown in Table 7:

[0140] Table 7

[0141]

[0142] Example A6

[0143] A method for preparing a multifunctional wearable colorimetric sensor, the specific steps are as follows:

[0144] (1) Preparation of raw materials;

[0145] Butterfly pea anthocyanins;

[0146] Blueberry anthocyanins;

[0147] Laccase: manufacturer is Shanghai Yuanye Biotechnology Co., Ltd., product number is S10188;

[0148] water;

[0149] Textiles: Silk fabrics that comply with GB / T 7568.6-2002;

[0150] (2) preparing dye solution;

[0151] The dye solution is composed of laccase, mixed anthocyanins and water. The concentration of laccase is 1U / mL. The mixed anthocyanins are butterfly pea anthocyanins and blueberry anthocyanins in a mass ratio of 1:3. The concentration of the mixed anthocyanins is 3g / L.

[0152] (3) Preparation of multifunctional wearable colorimetric sensors;

[0153] The textile is placed in a dye solution, reacted at 50°C for 2 hours, the textile is taken out, rinsed, and dried to obtain a multifunctional wearable colorimetric sensor. Alternatively, after drying, the textile is blended or interwoven with undyed white yarn to obtain a multifunctional wearable colorimetric sensor; wherein the mass ratio of the textile to the dye solution is 1:20.

[0154] The multifunctional wearable colorimetric sensor finally prepared will show color changes after contacting liquids with different pH values; when the pH value of the liquid is in the interval (1,2), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [2,5), the multifunctional wearable colorimetric sensor is purple-red; when the pH value of the liquid is in the interval [5,7), the multifunctional wearable colorimetric sensor is extremely light purple; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue-purple; when the pH value of the liquid is in the interval [10,11), the multifunctional wearable colorimetric sensor is blue-green; when the pH value of the liquid is in the interval [11,13), the multifunctional wearable colorimetric sensor is brown.

[0155] The dry friction discoloration grade, wet friction discoloration grade, washing discoloration grade, washing cotton staining grade, dry friction staining grade and wet friction staining grade of the multifunctional wearable colorimetric sensor and anthocyanin dyed textile (the preparation process is basically the same as that of the present embodiment, except that laccase is not added during the preparation of the dye solution) of the product of this embodiment are shown in Table 8:

[0156] Table 8

[0157]

[0158] Example B1

[0159] A method for preparing a multifunctional wearable colorimetric sensor, the specific steps are as follows:

[0160] (1) Preparation of raw materials;

[0161] Grape skin anthocyanins;

[0162] Laccase: manufacturer is Shanghai Yuanye Biotechnology Co., Ltd., product number is S10188;

[0163] Corn starch: the manufacturer is Shanghai Yuanye Biotechnology Co., Ltd., the product number is S11002;

[0164] water;

[0165] Textiles: Silk fabrics that comply with GB / T 7568.6-2002;

[0166] (2) separately preparing an aqueous solution containing laccase and a printing paste;

[0167] The aqueous solution containing laccase consists of laccase and water, and the concentration of laccase is 1 U / mL;

[0168] The preparation process of the printing paste is as follows: under room temperature, corn starch is added into water and stirred evenly, during which the temperature is gradually raised to 95°C, then the temperature is kept constant and stirred for 1 hour, then the temperature is lowered to 50°C, grape skin anthocyanidin is added, stirred evenly, and the printing paste is obtained; the concentration of corn starch in the printing paste is 10 g / L, and the concentration of grape skin anthocyanidin is 4 g / L;

[0169] (3) Preparation of multifunctional wearable colorimetric sensors;

[0170] The aqueous solution containing laccase is uniformly sprayed on the surface of the textile and dried, and then the printing paste containing anthocyanin is printed on the surface of the textile by screen printing, and then placed in air at a temperature of 55°C and a relative humidity of 50% for 2 hours, rinsed, and dried to obtain a multifunctional wearable colorimetric sensor; wherein the spraying amount of the aqueous solution containing laccase is 200g / m 2 .

[0171] The multifunctional wearable colorimetric sensor finally prepared will show color changes after contacting liquids with different pH values; when the pH value of the liquid is in the interval (1,3), the multifunctional wearable colorimetric sensor is pink; when the pH value of the liquid is in the interval [3,7), the multifunctional wearable colorimetric sensor is purple; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue-green; when the pH value of the liquid is in the interval [10,12), the multifunctional wearable colorimetric sensor is dark yellow.

[0172] The dry friction discoloration grade, wet friction discoloration grade, washing discoloration grade, washing cotton staining grade, dry friction staining grade and wet friction staining grade of the multifunctional wearable colorimetric sensor and anthocyanin printed textile (the preparation process is basically the same as that of the present embodiment, the only difference being that the aqueous solution containing laccase is replaced with water of equal mass) of the products of this embodiment are shown in Table 9:

[0173] Table 9

[0174]

[0175] Example B2

[0176] A method for preparing a multifunctional wearable colorimetric sensor, the specific steps are as follows:

[0177] (1) Preparation of raw materials;

[0178] Mulberry anthocyanins;

[0179] Laccase: manufacturer is Shanghai Yuanye Biotechnology Co., Ltd., product number is S10188;

[0180] Corn starch: the manufacturer is Shanghai Yuanye Biotechnology Co., Ltd., the product number is S11002;

[0181] water;

[0182] Textiles: Silk fabrics that comply with GB / T 7568.6-2002;

[0183] (2) separately preparing an aqueous solution containing laccase and a printing paste;

[0184] The aqueous solution containing laccase consists of laccase and water, and the concentration of laccase is 3U / mL;

[0185] The preparation process of the printing paste is as follows: under room temperature, corn starch is added into water and stirred evenly, during which the temperature is gradually raised to 95°C, then the temperature is kept constant and stirred for 1 hour, then the temperature is lowered to 50°C, mulberry anthocyanidin is added, stirred evenly, and the printing paste is obtained; the concentration of corn starch in the printing paste is 25 g / L, and the concentration of mulberry anthocyanidin is 10 g / L;

[0186] (3) Preparation of multifunctional wearable colorimetric sensors;

[0187] The aqueous solution containing laccase is uniformly sprayed on the surface of the textile and dried, and then the printing paste containing anthocyanin is printed on the surface of the textile by screen printing, and then placed in air at a temperature of 30°C and a relative humidity of 100% for 0.5 h, rinsed, and dried to obtain a multifunctional wearable colorimetric sensor; wherein the spraying amount of the aqueous solution containing laccase is 5 g / m 2 .

[0188] The multifunctional wearable colorimetric sensor finally prepared will show color changes after contacting liquids with different pH values; when the pH value of the liquid is in the interval (1,3), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [3,5), the multifunctional wearable colorimetric sensor is pink; when the pH value of the liquid is in the interval [5,7), the multifunctional wearable colorimetric sensor is purple; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue.

[0189] The dry friction discoloration grade, wet friction discoloration grade, washing discoloration grade, washing cotton staining grade, dry friction staining grade and wet friction staining grade of the multifunctional wearable colorimetric sensor and anthocyanin printed textile (the preparation process is basically the same as that of the present embodiment, the only difference being that the aqueous solution containing laccase is replaced with water of equal mass) of the products of this embodiment are shown in Table 10:

[0190] Table 10

[0191]

[0192] Example B3

[0193] A method for preparing a multifunctional wearable colorimetric sensor, the specific steps are as follows:

[0194] (1) Preparation of raw materials;

[0195] Eggplant skin anthocyanins;

[0196] Laccase: manufacturer is Shanghai Yuanye Biotechnology Co., Ltd., brand number is S10188;

[0197] Corn starch: manufacturer is Shanghai Aladdin Biochemical Technology Co., Ltd., product number is A120984;

[0198] water;

[0199] Textiles: wool fabrics that comply with GB / T 7568.1-2002;

[0200] (2) separately preparing an aqueous solution containing laccase and a printing paste;

[0201] The aqueous solution containing laccase consists of laccase and water, and the concentration of laccase is 2U / mL;

[0202] The preparation process of the printing paste is as follows: under room temperature, corn starch is added into water and stirred evenly, during which the temperature is gradually raised to 95°C, then the temperature is kept constant and stirred for 1 hour, then the temperature is lowered to 50°C, anthocyanidins from eggplant skin are added, stirred evenly, and the printing paste is obtained; the concentration of corn starch in the printing paste is 40 g / L, and the concentration of anthocyanidins from eggplant skin is 0.3 g / L;

[0203] (3) Preparation of multifunctional wearable colorimetric sensors;

[0204] The laccase-containing aqueous solution is uniformly sprayed on the surface of the textile and dried, and then the anthocyanin-containing printing paste is screen-printed on the surface of the textile, placed in air at a temperature of 45°C and a relative humidity of 70% for 1 hour, rinsed, and dried to obtain a multifunctional wearable colorimetric sensor; wherein the spraying amount of the laccase-containing aqueous solution is 100 g / m 2 .

[0205] The multifunctional wearable colorimetric sensor finally prepared will show color changes after contacting liquids with different pH values; when the pH value of the liquid is in the interval (1,3), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [3,5), the multifunctional wearable colorimetric sensor is purple; when the pH value of the liquid is in the interval [5,7), the multifunctional wearable colorimetric sensor is blue-purple; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue; when the pH value of the liquid is in the interval [10,11), the multifunctional wearable colorimetric sensor is green; when the pH value of the liquid is in the interval [11,13), the multifunctional wearable colorimetric sensor is yellow-green.

[0206] The dry friction discoloration grade, wet friction discoloration grade, washing discoloration grade, washing cotton staining grade, dry friction staining grade and wet friction staining grade of the multifunctional wearable colorimetric sensor and anthocyanin printed textile (the preparation process is basically the same as that of the present embodiment, the only difference being that the aqueous solution containing laccase is replaced with water of equal mass) of the products of this embodiment are shown in Table 11:

[0207] Table 11

[0208]

[0209] Example B4

[0210] A method for preparing a multifunctional wearable colorimetric sensor, the specific steps are as follows:

[0211] (1) Preparation of raw materials;

[0212] Blackcurrant anthocyanins;

[0213] Laccase: manufacturer is Sigma-Aldrich, product number is 38429;

[0214] Corn starch: manufacturer is Shanghai Aladdin Biochemical Technology Co., Ltd., product number is A120984;

[0215] water;

[0216] Textiles: Nylon fabrics that comply with GB / T 7568.3-2008;

[0217] (2) separately preparing an aqueous solution containing laccase and a printing paste;

[0218] The aqueous solution containing laccase consists of laccase and water, and the concentration of laccase is 0.1U / mL;

[0219] The preparation process of the printing paste is as follows: under room temperature, corn starch is added into water and stirred evenly, during which the temperature is gradually raised to 95°C, then the temperature is kept constant and stirred for 1 hour, then the temperature is lowered to 50°C, blackcurrant anthocyanidin is added, stirred evenly, and the printing paste is obtained; the concentration of corn starch in the printing paste is 25 g / L, and the concentration of blackcurrant anthocyanidin is 6 g / L;

[0220] (3) Preparation of multifunctional wearable colorimetric sensors;

[0221] The aqueous solution containing laccase is evenly sprayed on the surface of the textile and dried, and then the printing paste containing anthocyanin is printed on the surface of the textile by screen printing, and then placed in air at a temperature of 60°C and a relative humidity of 85% for 4 hours, rinsed, and dried to obtain a multifunctional wearable colorimetric sensor; wherein the spraying amount of the aqueous solution containing laccase is 500g / m 2 .

[0222] The multifunctional wearable colorimetric sensor finally prepared will show color changes after contacting liquids with different pH values; when the pH value of the liquid is in the interval (1,2), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [2,5), the multifunctional wearable colorimetric sensor is pink; when the pH value of the liquid is in the interval [5,7), the multifunctional wearable colorimetric sensor is purple; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue; when the pH value of the liquid is in the interval [10,13), the multifunctional wearable colorimetric sensor is yellow-brown.

[0223] The dry friction discoloration grade, wet friction discoloration grade, washing discoloration grade, washing cotton staining grade, dry friction staining grade and wet friction staining grade of the multifunctional wearable colorimetric sensor and anthocyanin printed textile (the preparation process is basically the same as that of the present embodiment, the only difference being that the aqueous solution containing laccase is replaced with water of equal mass) of the products of this embodiment are shown in Table 12:

[0224] Table 12

[0225]

Claims

1. A method for preparing a multifunctional wearable colorimetric sensor, characterized in that: Laccase is used to catalyze the grafting of anthocyanins onto textiles, and after catalyzing the self-polymerization reaction of anthocyanins, the textiles are directly used as multifunctional wearable colorimetric sensors, or the textiles are further processed into multifunctional wearable colorimetric sensors, wherein the textiles are protein textiles or nylon textiles.

2. The method for preparing a multifunctional wearable colorimetric sensor according to claim 1, characterized in that: The multifunctional wearable colorimetric sensor will show color changes when it comes into contact with liquids of different pH values; The anthocyanin is butterfly pea anthocyanin; when the pH value of the liquid is in the interval (1,2), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [2,5), the multifunctional wearable colorimetric sensor is purple; when the pH value of the liquid is in the interval [5,7), the multifunctional wearable colorimetric sensor is blue; when the pH value of the liquid is in the interval [7,9), the multifunctional wearable colorimetric sensor is lake blue; when the pH value of the liquid is in the interval [9,11), the multifunctional wearable colorimetric sensor is dark green; when the pH value of the liquid is in the interval [11,13], the multifunctional wearable colorimetric sensor is yellow-brown; The anthocyanin is blueberry anthocyanin; when the pH value of the liquid is in the interval (1,2), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [2,5), the multifunctional wearable colorimetric sensor is pink; when the pH value of the liquid is in the interval [5,7), the multifunctional wearable colorimetric sensor is extremely light pink or even colorless; when the pH value of the liquid is in the interval [7,9), the multifunctional wearable colorimetric sensor is dark purple; when the pH value of the liquid is in the interval [9,12), the multifunctional wearable colorimetric sensor is blue-green; The anthocyanin is purple cabbage anthocyanin; when the pH value of the liquid is in the interval (1,4), the multifunctional wearable colorimetric sensor is pink; when the pH value of the liquid is in the interval [4,7), the multifunctional wearable colorimetric sensor is blue-purple; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue; The anthocyanin is black rice anthocyanin; when the pH value of the liquid is in the interval (1,4), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [4,7), the multifunctional wearable colorimetric sensor is pink; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue; The anthocyanin is purple sweet potato anthocyanin; when the pH value of the liquid is in the interval (1,3), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [3,7), the multifunctional wearable colorimetric sensor is pink; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue; when the pH value of the liquid is in the interval [10,12), the multifunctional wearable colorimetric sensor is dark green; Anthocyanin is anthocyanin from grape skin; when the pH value of the liquid is in the interval (1,3), the multifunctional wearable colorimetric sensor is pink; when the pH value of the liquid is in the interval [3,7), the multifunctional wearable colorimetric sensor is purple; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue-green; when the pH value of the liquid is in the interval [10,12), the multifunctional wearable colorimetric sensor is dark yellow; The anthocyanin is mulberry anthocyanin; when the pH value of the liquid is in the interval (1,3), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [3,5), the multifunctional wearable colorimetric sensor is pink; when the pH value of the liquid is in the interval [5,7), the multifunctional wearable colorimetric sensor is purple; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue; Anthocyanin is anthocyanin from eggplant skin; when the pH value of the liquid is in the interval (1,3), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [3,5), the multifunctional wearable colorimetric sensor is purple; when the pH value of the liquid is in the interval [5,7), the multifunctional wearable colorimetric sensor is blue-purple; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue; when the pH value of the liquid is in the interval [10,11), the multifunctional wearable colorimetric sensor is green; when the pH value of the liquid is in the interval [11,13), the multifunctional wearable colorimetric sensor is yellow-green; The anthocyanin is blackcurrant anthocyanin; when the pH value of the liquid is in the interval (1,2), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [2,5), the multifunctional wearable colorimetric sensor is pink; when the pH value of the liquid is in the interval [5,7), the multifunctional wearable colorimetric sensor is purple; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue; when the pH value of the liquid is in the interval [10,13), the multifunctional wearable colorimetric sensor is yellow-brown; Anthocyanin is a mixture of butterfly pea anthocyanin and blueberry anthocyanin in a mass ratio of 1:3; when the pH value of the liquid is in the interval (1,2), the multifunctional wearable colorimetric sensor is red; when the pH value of the liquid is in the interval [2,5), the multifunctional wearable colorimetric sensor is purple-red; when the pH value of the liquid is in the interval [5,7), the multifunctional wearable colorimetric sensor is extremely light purple; when the pH value of the liquid is in the interval [7,10), the multifunctional wearable colorimetric sensor is blue-purple; when the pH value of the liquid is in the interval [10,11), the multifunctional wearable colorimetric sensor is blue-green; when the pH value of the liquid is in the interval [11,13), the multifunctional wearable colorimetric sensor is brown.

3. The method for preparing a multifunctional wearable colorimetric sensor according to claim 1, characterized in that: The specific process is: placing the textiles in a dye solution containing laccase and anthocyanin, reacting at 30-60°C for 0.5-4h, taking out the textiles, rinsing, and drying.

4. The method for preparing a multifunctional wearable colorimetric sensor according to claim 3, characterized in that: In the dye solution, the concentration of laccase is 0.1-3U / mL, and the concentration of anthocyanin is 0.2-5g / L; the mass ratio of textile to dye solution is 1:10-100.

5. The method for preparing a multifunctional wearable colorimetric sensor according to claim 3, characterized in that: The textile is a protein fabric or a nylon fabric, which can be made into a multifunctional wearable colorimetric sensor by drying.

6. The method for preparing a multifunctional wearable colorimetric sensor according to claim 3, characterized in that: The textile is a protein yarn or a nylon yarn, which is blended or interwoven with undyed white yarn after drying to obtain a multifunctional wearable colorimetric sensor.

7. The method for preparing a multifunctional wearable colorimetric sensor according to claim 1, characterized in that: The specific process is: spray the aqueous solution containing laccase evenly on the surface of the textile, dry it, then print the printing paste containing anthocyanin on the surface of the textile by screen printing, place it in air at a temperature of 30-60℃ and a relative humidity of 50-100% for 0.5-4h, rinse it, and dry it.

8. The method for preparing a multifunctional wearable colorimetric sensor according to claim 7, characterized in that: The concentration of laccase in the aqueous solution containing laccase is 0.1-3U / mL; the spraying amount of the aqueous solution containing laccase is 5-500g / m 2 ; In the printing paste containing anthocyanins, the concentration of anthocyanins is 0.2-10g / L.

9. The method for preparing a multifunctional wearable colorimetric sensor according to claim 7, characterized in that: The textile is a protein fabric or a nylon fabric, which can be made into a multifunctional wearable colorimetric sensor by drying.

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