CN108398395B - Light-operated reversible color changing method and device - Google Patents
Light-operated reversible color changing method and device Download PDFInfo
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- CN108398395B CN108398395B CN201810017735.3A CN201810017735A CN108398395B CN 108398395 B CN108398395 B CN 108398395B CN 201810017735 A CN201810017735 A CN 201810017735A CN 108398395 B CN108398395 B CN 108398395B
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000002441 reversible effect Effects 0.000 title claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 84
- 238000003860 storage Methods 0.000 claims abstract description 36
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 15
- 108091003079 Bovine Serum Albumin Proteins 0.000 claims abstract description 11
- 229940098773 bovine serum albumin Drugs 0.000 claims abstract description 11
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 31
- 238000002347 injection Methods 0.000 claims description 21
- 239000007924 injection Substances 0.000 claims description 21
- 230000031700 light absorption Effects 0.000 claims description 18
- 230000008859 change Effects 0.000 claims description 8
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 238000000862 absorption spectrum Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000005562 fading Methods 0.000 claims description 4
- 230000000149 penetrating effect Effects 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- -1 Methylene Chemical group 0.000 claims description 2
- 108010071390 Serum Albumin Proteins 0.000 claims description 2
- 102000007562 Serum Albumin Human genes 0.000 claims description 2
- 239000012888 bovine serum Substances 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 7
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- 238000013461 design Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
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- 239000004065 semiconductor Substances 0.000 description 2
- 239000000516 sunscreening agent Substances 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- QTWZICCBKBYHDM-UHFFFAOYSA-N leucomethylene blue Chemical compound C1=C(N(C)C)C=C2SC3=CC(N(C)C)=CC=C3NC2=C1 QTWZICCBKBYHDM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
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- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000000430 tryptophan group Chemical group [H]N([H])C(C(=O)O*)C([H])([H])C1=C([H])N([H])C2=C([H])C([H])=C([H])C([H])=C12 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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Abstract
The invention belongs to the technical field of light-operated switches, and discloses a light-operated reversible color changing method and a light-operated reversible color changing device. The method is a reversible color regulation method of titanium dioxide to methylene blue under the mediation of bovine serum albumin controlled by switching an ultraviolet lamp. The device is designed for this purpose: the electric torch liquid filling device comprises an electric torch, a rotary cover, a liquid storage chamber and a liquid filling opening rubber plug, wherein a cylindrical groove is formed in the top surface of the rotary cover, a lamp holder of the electric torch is placed into the cylindrical groove downwards, internal threads are formed in the inner wall of the lower half portion of the rotary cover, external threads are formed in the outer wall of the upper opening of the liquid storage chamber, the rotary cover and the liquid storage chamber are connected and sealed through threads, the top surface of the liquid storage chamber is sealed, a liquid filling opening is formed in the side wall of the liquid storage chamber, the liquid filling opening rubber plug is plugged into the. The method has the advantages of easily available raw materials, low cost, quick, simple and convenient operation, high efficiency and stability, and has application prospect in the fields of photoswitches and photochromic materials; the design and manufacturing device can be used for detecting the ultraviolet absorption effect of cosmetics and sun-screening products.
Description
Technical Field
The invention belongs to the technical field of light-operated switches, and particularly relates to a light-operated reversible color changing method and a light-operated reversible color changing device.
Background
Methylene Blue (MB) is a cationic biological stain of the phenothiazine class, and is also a lipophilic photosensitizer. Blue MB can be reduced to colorless reduced methylene blue (LMB), and O2The oxidizing agent oxidizes LMB back to the initial state of MB, which shows stable and good reversibility in electrochemistry.
Bovine Serum Albumin (BSA) is a carrier protein in organisms. It has rich source and low purification cost, and may be used as template for synthesizing material and interacting with MB and other small molecules. Meanwhile, BSA has photosensitivity and oxidation resistance, has a maximum absorption value at about 280nm, and tryptophan residues at about 350nm are easily oxidized to generate fluorescence quenching.
Titanium dioxide (TiO)2) Is a white inorganic pigment with ultraviolet screening effect, and is often used as a physical sunscreen agent for scattering ultraviolet rays to be blended into textile fibers and sunscreen cosmetics. At the same time, the user can select the desired position,TiO2belongs to a wide-gap semiconductor, can absorb ultraviolet light to generate a photoproduction electron-hole pair with strong oxidation reduction property, but the performance is not intuitive, and can also cause the skin to generate photochemical oxidation in a sun-screening product. In TiO2UV-excited TiO in the/MB/water system2Photoelectrons may be generated and transferred to MB, which are reduced to colorless LMB. Under dark conditions, the LMB can be replaced by O in solution2Oxidized to blue colored MB. The resulting cavities oxidize BSA and thus prevent oxidative decomposition of MB, which is also used for O2The detection sensor of (1). Because ultraviolet light is often used under dark conditions, the fading and recovery processes become difficult to observe, a great deal of difficulty is brought to the experiment, and the existing system can not realize in-situ discoloration detection.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention mainly aims to provide a light-operated reversible color changing method.
It is still another object of the present invention to provide a photo-controlled reversible color-changing device for implementing the above method. The device can observe the color changing process, and can also excite other reactions in a mode of changing the wavelength of the light source.
The purpose of the invention is realized by the following technical scheme:
a light-operated reversible color-changing method, comprising the steps of: uniformly mixing a bovine serum albumin solution, a methylene blue solution and a titanium dioxide dispersion liquid to obtain a solution to be detected; irradiating the solution to be detected with light to fade the solution; then the solution to be tested is put in the dark, and the color of the solution is recovered.
The solution to be detected contains 0.0001-100 g.L-10.01 to 100 mol.L of titanium dioxide-1Bovine serum albumin and 0.01 to 100 mol.L-1Methylene blue (c).
The time for irradiating the liquid to be detected with light is 0.1-60 min; the time for placing in the dark is 0.1-120 min.
And accurately measuring the light absorption value of the liquid to be measured by ultraviolet absorption spectrum, wherein the light absorption value of the liquid to be measured before being irradiated by light is a, the light absorption value of the liquid to be measured after being irradiated by the light is b, the light absorption value of the liquid to be measured after being placed in the dark is c, the fading efficiency is (a-b) ÷ a, and the recovery efficiency is (c-b) ÷ a-b.
The device comprises a flashlight, a rotary cover, a liquid storage chamber and a liquid injection hole rubber plug, wherein a cylindrical groove is formed in the top surface of the rotary cover, a lamp holder of the flashlight is placed into the cylindrical groove downwards, an internal thread is formed in the inner wall of the lower half portion of the rotary cover, an external thread is formed in the outer wall of the upper opening of the liquid storage chamber, the rotary cover and the liquid storage chamber are connected and sealed through threads, the top surface of the liquid storage chamber is sealed, the liquid injection hole is formed in the side wall of the liquid storage chamber, the liquid injection hole rubber plug is plugged into the liquid injection hole to form sealing, and the liquid storage chamber is made of a transparent.
The liquid to be measured is injected into the liquid storage chamber through the liquid injection port, the light intensity of the light source of the flashlight and the light intensity penetrating through the bottom of the liquid storage chamber are measured by a photometer, and the light absorption of the liquid to be measured on the light source is observed and calculated.
The device can use bovine serum albumin solution, methylene blue solution and titanium dioxide dispersion mixed solution as the liquid to be detected, and can also use other solvents and solutes which can absorb ultraviolet light or visible light, so that the simple detection can be carried out on the light absorption of different wavelengths.
Compared with the prior art, the invention has the following advantages and effects: the invention adopts MB with reversible oxidation-reduction color change and BSA with photosensitivity, oxidation resistance and biocompatibility to compensate TiO2The three parts are combined to realize photosensitive sensing of the photoswitch and photosensitive color change of the photochromic material; the method has the advantages of easily available raw materials, low cost, quick, simple and convenient operation, high efficiency and stability, and has application prospect in the fields of photoswitches and photochromic materials; the design and manufacturing device can be used for detecting the ultraviolet absorption effect of cosmetics and sun-screening products.
Drawings
FIG. 1 is a structural view of the appearance of the device of the present invention, wherein 1 is a flashlight, 8 is a cylindrical groove, 9 is an internal thread, 10 is a liquid injection hole rubber plug, 11 is a liquid storage chamber, and 12 is an external thread.
FIG. 2 is a perspective view of the device of the present invention, wherein 1 is a flashlight, 2 is a circuit board, 3 is a reflective cup, 4 is a flashlight switch, 5 is a battery cathode, 6 is a battery anode, 7 is a 365nm LED ultraviolet lamp, 8 is a cylindrical groove, 9 is an internal thread, 10 is a liquid injection hole plug, 11 is a liquid storage chamber, and 12 is an external thread.
Fig. 3 shows a schematic view of a reservoir according to the invention, wherein 8 is a cylindrical recess and 9 is an internal thread.
Fig. 4 is a schematic structural view of the screw cap of the present invention, wherein 10 is a rubber plug of a liquid injection port, 11 is a liquid storage chamber, and 12 is an external thread.
FIG. 5 is a diagram of a light-controlled TiO compound in example 3 of the present invention2And the absorption spectrum of BSA-MB reversible color change, wherein a is the light absorption value of the liquid to be detected before the lamp is turned on, b is the light absorption value of the liquid to be detected after the liquid to be detected is illuminated for 2min, and c is the light absorption value of the liquid to be detected after a dark box is kept stand for 5 min.
Detailed description of the invention
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. For the purposes of the present invention, simple substitution of the same species and changes in size and shape, such as changing the size and type of semiconductor, changing the type of dye and photosensitive material, changing the specific size of the device, shape, wavelength of light source, power of light source and time of turning on and off the lamp, changing the amount of solute used or the temperature, pH of the solution, etc., are intended to be within the scope of the present invention; the test methods used in the following examples are conventional methods existing in the art unless otherwise specified; the materials, reagents and the like used are commercially available unless otherwise specified.
EXAMPLE 1 construction of the device
As shown in fig. 1-4, 1 is a flashlight, 2 is a circuit board, 3 is a reflective cup, 4 is a flashlight switch, 5 is a battery cathode, 6 is a battery anode, 7 is a 365nm LED ultraviolet lamp, 8 is a cylindrical groove, 9 is an internal thread, 10 is a liquid injection hole rubber plug, 11 is a liquid storage chamber, and 12 is an external thread.
The device comprises a flashlight 1, a rotary cover, a liquid storage chamber 11 and a liquid injection hole rubber plug 10, wherein a cylindrical groove 8 is formed in the top surface of the rotary cover, a lamp holder of the flashlight 1 is placed into the cylindrical groove 8 downwards, internal threads 9 are formed in the inner wall of the lower half portion of the rotary cover, external threads 12 are formed in the outer wall of the upper opening of the liquid storage chamber, the rotary cover and the liquid storage chamber 11 are connected and sealed through threads, the top surface of the liquid storage chamber is sealed, the side wall of the liquid storage chamber is provided with a liquid injection hole, the liquid injection hole rubber plug is plugged into the liquid injection hole to form sealing, and the.
Example 2 ethanol and TiO2Absorption measurement of 365nm ultraviolet light
This example ethanol and TiO2The 365nm ultraviolet light absorption measurement is realized by adopting the device described in the embodiment 1 and adopting the following method:
(1) dispersion of 10mg of PM 25TiO sintered at 450 ℃ in 5mL of ethanol2A solution of the powder is ready for use.
(2) An LS 123A ultraviolet power meter is selected to measure the following three groups of light intensity for the constructed device: (a) the 365nm light source intensity is 5700-6000 mu W cm-2(b) the intensity of the light source after the light source penetrates through the upper opening glass sheet of the liquid storage chamber is 5200-5500 μ W-cm-2(c) the intensity of the light source after the light source penetrates the bottom surface of the liquid storage chamber is 1800-2000 μ W-cm-2。
(3) Adding 5mL of ethanol into the liquid storage chamber from the liquid injection port, and measuring the intensity of the light source after the light source penetrates through the bottom surface of the liquid storage chamber to be 1200-1500 muW-cm-2。
(4) 5mL of ethanol is added into the liquid storage chamber from the liquid injection port to disperse TiO2The intensity of the light source after the light source penetrates the bottom surface of the liquid storage chamber is 0-5 muW cm-2。
As can be seen from the above data, ethanol absorbs less ultraviolet light at 365nm, and TiO2The absorption for the light source is good. The substance to be detected and the light sources with different wavelengths can be changed to repeat the operation, so that the absorption conditions of different substances to different lights can be analyzed simply and conveniently.
Example 3 light-controlling TiO2-BSA-MB reversible discoloration
Light-operated TiO in this example2-reversible color change of BSA-MB, achieved by:
(5) 0.02 mol. L of pH 7.2 was prepared using an acidimeter-1Tris-hydroxymethyl aminomethane/0.10 mol. L-1NaCl buffer solution, and 0.10 mmol. multidot.L was prepared therefrom-1And BSA solution of 0.05mmol·L-1The MB solution of (1). 10mg of PM 25TiO sintered at 450 ℃ are dispersed in 1mL of ethanol2A solution of the powder is ready for use.
(6) Preparing a solution to be detected: mu.L of BSA solution, 8. mu.L of MB solution, and 10. mu.L of TiO solution were added to the cuvette, respectively21.9mL of 0.02 mol. L at pH 7.2-1Tris-hydroxymethyl aminomethane/0.10 mol. L-1NaCl buffer solution, shake evenly and then stand for 2 min.
(7) At 0.02 mol. L of pH 7.2-1Tris hydroxymethyl aminomethane/0.1 mol. L-1NaCl buffer was a blank.
(8) Absorption spectrum UV-2700 UV-visible spectrophotometer (Shimadzu, japan) was selected, and parameters were set: the wavelength range is 500-750 nm, and the sweeping speed is high; irradiating a color dish with 365nm ultraviolet flashlight, and respectively measuring light absorption values of a liquid to be measured before (a) illumination of the light source, after (b) illumination of the light source for 2min and after (c) standing and recovering in a dark box for 5min, wherein the result is shown in fig. 5;
as can be seen from FIG. 5, the absorbance values of the solution to be measured before illumination at 614nm and 664nm reach 1.145 and 1.777 respectively; after 2min of illumination, the light absorption values of the two parts are respectively reduced to 0.259 and 0.459; after the dark box is recovered for 5min, the light absorption values of the two parts are recovered to 1.110 and 1.717; according to calculation, the fading efficiency of the substance concentration to the liquid to be detected after being illuminated for 2min is 74.17%, and the recovery efficiency of 5min after being placed in a dark box for recovery is 95.44%; the cuvette can also be visually displayed before and after switching on and off the lamp.
(9) Injecting the solution to be tested before the same concentration of light is irradiated into the injection port of the device in the embodiment 1, standing for 2min, turning on the 365nm ultraviolet flashlight of the device, rapidly changing the solution to be tested from blue to white within 2min, and measuring the intensity of the light source penetrating through the bottom surface of the liquid storage chamber in the process to be 0-5 muW cm-2。
The data show that the liquid system to be detected has good absorption to the light source, and the reversible color change effect of the method in the device is also high-efficient and obvious.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. A light-operated reversible color-changing method is characterized in that: the method comprises the following steps: uniformly mixing a bovine serum albumin solution, a methylene blue solution and a titanium dioxide dispersion liquid to obtain a solution to be detected; irradiating the solution to be detected with light to fade the solution; then the solution to be tested is put in the dark, and the color of the solution is recovered.
2. A light-operated reversible color change method according to claim 1, characterized in that: the solution to be detected contains 0.0001-100 g.L-10.01 to 100 mol.L of titanium dioxide-1Bovine serum albumin and 0.01 to 100 mol.L-1Methylene blue (c).
3. A light-operated reversible color change method according to claim 1, characterized in that: the time for irradiating the liquid to be detected with light is 0.1-60 min; the time for placing in the dark is 0.1-120 min.
4. A light-operated reversible color change method according to claim 1, characterized in that: and accurately measuring the light absorption value of the liquid to be measured by ultraviolet absorption spectrum, wherein the light absorption value of the liquid to be measured before being irradiated by light is a, the light absorption value of the liquid to be measured after being irradiated by the light is b, the light absorption value of the liquid to be measured after being placed in the dark is c, the fading efficiency is (a-b)/a, and the recovery efficiency is (c-b)/(a-b).
5. An optically controlled reversible color-changing device for carrying out the method of claim 1, wherein: the device comprises a flashlight, a rotary cover, a liquid storage chamber and a liquid injection hole rubber plug, wherein a cylindrical groove is formed in the top surface of the rotary cover, a lamp holder of the flashlight is placed into the cylindrical groove downwards, internal threads are formed in the inner wall of the lower half portion of the rotary cover, external threads are formed in the outer wall of the upper opening of the liquid storage chamber, the rotary cover and the liquid storage chamber are connected and sealed through threads, the top surface of the liquid storage chamber is sealed, a liquid injection hole is formed in the side wall of the liquid storage chamber, the liquid injection hole rubber plug is plugged into the liquid injection hole to form sealing, and.
6. The optically controlled reversible color-changing device according to claim 5, wherein: the liquid to be measured is injected into the liquid storage chamber through the liquid injection port, the light intensity of the light source of the flashlight and the light intensity penetrating through the bottom of the liquid storage chamber are measured by a photometer, and the light absorption of the liquid to be measured on the light source is observed and calculated.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881422A (en) * | 2014-03-21 | 2014-06-25 | 西南交通大学 | Light-operated switch type TiO2 nano-particles surfactant and preparation method thereof |
| WO2017002115A2 (en) * | 2015-06-29 | 2017-01-05 | Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd | Hybrid nanoparticles as photoinitiators |
| CN107635787A (en) * | 2015-05-19 | 2018-01-26 | 爱克发-格法特公司 | Laser-markable composition, material and file |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881422A (en) * | 2014-03-21 | 2014-06-25 | 西南交通大学 | Light-operated switch type TiO2 nano-particles surfactant and preparation method thereof |
| CN107635787A (en) * | 2015-05-19 | 2018-01-26 | 爱克发-格法特公司 | Laser-markable composition, material and file |
| WO2017002115A2 (en) * | 2015-06-29 | 2017-01-05 | Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd | Hybrid nanoparticles as photoinitiators |
Non-Patent Citations (1)
| Title |
|---|
| 亚甲基蓝介导抗坏血酸氧化动力学的研究;赵倩雯;《华南师范大学学报(自然科学版)》;20181231;25－30 * |
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