CN105802609B - A kind of photoresponse room temperature phosphorimetry supermolecule anti-fake material and preparation method thereof - Google Patents

Abstract

The invention proposes a photoresponsive room temperature phosphorescent supramolecular anti-counterfeiting material with adjustable luminous intensity and a preparation method thereof. In the present invention, tetracarbonylphenylpalladium porphyrin (Pd-TCPP) and o-nitrobenzaldehyde (NBA ) is added to a supramolecular gel formed by self-assembly of DBS in a mixed solvent composed of an organic solvent and water. The advantage of the present invention is that the supramolecular material cannot produce room temperature phosphorescence by photoexcitation before ultraviolet irradiation; and when the supramolecular material is subjected to ultraviolet irradiation of 365 nm, when the excitation wavelength is 417 nm, it can produce Room temperature phosphorescence with a wavelength of 700nm is emitted, and the phosphorescence intensity of the supramolecular material can be regulated by NBA concentration and ultraviolet light irradiation time. The obtained supramolecular gel material has potential application value in the field of anti-counterfeiting.

Description

A light-responsive room temperature phosphorescent supramolecular anti-counterfeiting material and its preparation method

technical field

The invention belongs to the field of luminous anti-counterfeiting materials, and in particular relates to a light-responsive room-temperature phosphorescent supramolecular anti-counterfeiting material with adjustable luminous intensity and a preparation method thereof.

Background technique

Compared with fluorescence, phosphorescence has a larger Stokes shift, which can avoid the interference of excitation light. At the same time, phosphorescence has a longer lifetime, which can avoid the interference of short-lived fluorescence and scattered light, thereby obtaining a lower detection limit. Fluorescence has been widely used in the field of anti-counterfeiting due to its simple lighting conditions and convenient use. For example, fluorescence technology is used in the anti-counterfeiting of RMB. However, phosphorescence requires low temperature conditions in order to control the non-radiative transition of phosphorescent molecules, which greatly limits the application of phosphorescence. The room-temperature phosphorescence developed later is widely used in the fields of life science, environmental science, clinical medicine, industrial energy and anti-counterfeiting due to the control of the non-radiative transition of phosphorescent molecules and the mild luminescence conditions. Room-temperature phosphorescence has achieved control methods such as temperature response and mechanical stimulus response to regulate the turn-on and intensity of room-temperature phosphorescence, but these methods are often destructive and the operation process is complicated. Photoresponse is a non-destructive, non-contact and simple control method, which can conveniently realize the turning on of phosphorescence at room temperature and the regulation of phosphorescence intensity. It has been reported that the reversible switch of room temperature phosphorescence can be achieved by decyclization and cyclization of photochromic compounds, but the synthesis of the reported compounds is complicated, the cost is high, and the phosphorescence intensity cannot be adjusted, which is very inconvenient to use. Especially in the field of anti-counterfeiting, the anti-counterfeiting level has been reduced.

Contents of the invention

Aiming at the deficiencies of the prior art, the invention provides a photoresponsive room temperature phosphorescent supramolecular material and a preparation method thereof. Using 1,3(R):2,4(S)-benzyl-D-sorbitol (DBS) as the gelling factor, supramolecular gels were prepared by self-assembly of DBS in organic/water mixed solvents, as The room temperature induction matrix of the phosphorescent molecule tetracarbonylphenylpalladium porphyrin (Pd-TCPP). At room temperature, the induction matrix can induce the phosphorescent molecule Pd-TCPP to produce strong phosphorescence; sodium sulfite is used as an antioxidant to prevent phosphorescence quenching ; In addition, adding o-nitrobenzaldehyde (NBA) in the supramolecular gel system, the photoresponsiveness of room temperature phosphorescent supramolecular materials can be realized by adding NBA, and by adjusting the concentration of NBA and the illumination time of supramolecular materials to Regulates phosphorescence intensity. Compared with other systems that regulate room temperature phosphorescence, the method of this system is simple, and the phosphorescence intensity can be adjusted. Therefore, when used in anti-counterfeiting materials, the anti-counterfeiting level is improved due to the "password" for phosphorescence opening and the "password" for intensity regulation.

The present invention adopts the following technical solutions: a photoresponsive room temperature phosphorescent supramolecular anti-counterfeiting material, comprising phosphorescent molecules, antioxidants, inducing substrates, water and organic solvents, the phosphorescent molecules are tetracarbonylphenyl palladium porphyrin (Pd-TCPP), The antioxidant is sodium sulfite, and the induction matrix is 1,3 (R): 2,4 (S)-benzyl-D-sorbitol (DBS), which is characterized in that the supramolecular anti-counterfeiting material also contains the photoresponse factor o-nitro Nylbenzaldehyde (NBA);

The preparation steps of the room temperature phosphorescent supramolecular anti-counterfeiting material are:

① Dissolving tetracarbonylphenylpalladium porphyrin (Pd-TCPP) in an appropriate amount of organic solvent to obtain a solution A with a concentration of 1×10 ^-2 mol/L;

②Dissolve o-nitrobenzaldehyde (NBA) in an appropriate amount of organic solvent to obtain a solution B with a concentration of 5×10 ^-1 mol/L;

③Dissolve sodium sulfite in an appropriate amount of water to obtain a solution C with a concentration of 1mol/L;

④Dissolve an appropriate amount of 1,3(R):2,4(S)-benzyl-D-sorbitol (DBS) in an organic solvent to obtain a solution D with a concentration of 1.5×10 ^-2 mol/L;

⑤ Mix the three solutions of solution A, solution B and solution C obtained above according to the formula quantity, the stirring speed is 300 rpm, and heat to 50°C-90°C, keep warm for 8-10 minutes, and then add solution D to obtain Mixed solution, continue to stir at 300 rpm for 5-10 minutes;

⑥ Cool the above mixed solution to room temperature to obtain a supramolecular gel, which is the photoresponsive room temperature phosphorescent supramolecular anti-counterfeiting material;

In the above mixed solution, the volume percentage of each solution is:

Preferably, the volume percent of each solution in the above-mentioned mixed solution is:

The organic solvent can be one of N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), ethylene glycol, butanediol, polyethylene glycol (PEG) and ethanol.

The remarkable advantage of the present invention is that the photoresponsiveness of the room-temperature phosphorescent supramolecular anti-counterfeiting material is realized by adding NBA, and the phosphorescence intensity is adjusted by adjusting the concentration of NBA or the illumination time of the room-temperature phosphorescent supramolecular anti-counterfeiting material. When the gel system is added to NBA, the room temperature phosphorescence of palladium porphyrin is quenched by NBA, and the degree of quenching increases with the concentration of NBA. Different concentrations of NBA have different degrees of phosphorescence quenching of palladium porphyrin. Change to adjust the intensity of room temperature phosphorescence. The room temperature phosphorescent supramolecular anti-counterfeiting material gradually recovers after being irradiated with 365nm ultraviolet light. The reason is that the charge of the product after NBA irradiation becomes negative charge, which repulses with anionic palladium porphyrin and cannot quench its phosphorescence.

The supramolecular anti-counterfeiting material prepared by the above preparation method was directly tested for room temperature phosphorescence, and it was found that the phosphorescence effect was weak or no phosphorescence effect was produced. After being illuminated for a certain period of time under 365nm ultraviolet light, the room temperature phosphorescence test is carried out. When the excitation light is 410nm, the material can produce room temperature phosphorescence of 700nm, and the phosphorescence intensity increases with the increase of the illumination time. When the illumination time When reaching a certain value, the phosphorescent intensity reaches the maximum value.

The room-temperature phosphorescent supramolecular anti-counterfeiting material has a phosphorescence opening method and an intensity control method, but the specific formula and illumination method are not known in advance, so the anti-counterfeiting level is extremely high.

Detailed ways

The present invention will be further described below in conjunction with embodiment.

Example 1:

This example provides a photoresponsive room temperature phosphorescent supramolecular anti-counterfeiting material. The preparation method is as follows: take a clean test tube, add 5mL 1×10 ^-2 mol/L Pd-TCPP DMSO solution, 15mL 5×10 ^-1 mol/ L NBA DMSO solution, 55mL 1mol/L sodium sulfite aqueous solution, at a stirring speed of 300 rpm, heat the water bath to 70°C, keep warm for 8 minutes, add 25mL 1.5mol/L DBS DMSO solution, continue to press 300 rpm Stir at a speed of 5 minutes, and then statically cool to obtain a supramolecular gel that is a photoresponsive room temperature phosphorescent supramolecular anti-counterfeiting material.

Example 2:

This example provides a photoresponsive room temperature phosphorescent supramolecular anti-counterfeiting material, and its preparation method is as follows: take a clean test tube, add 15mL of 1×10 ^-2 mol/L Pd-TCPP in DMSO solution, 25mL of 5×10 ^-1 mol/L NBA DMSO solution, 25mL 1mol/L sodium sulfite aqueous solution, at a stirring speed of 300 rpm, heated to 70°C in a water bath, kept warm for 10 minutes, added 35mL 1.5mol/L DBS DMSO solution, and continued to press 300 rpm Stir for 10 minutes at a speed of 10 minutes, and then statically cool to obtain the supramolecular gel, which is the photoresponsive room temperature phosphorescent supramolecular anti-counterfeiting material.

Example 3:

This example provides a light-responsive room temperature phosphorescent supramolecular anti-counterfeiting material. The preparation method is as follows: take a clean test tube, add 10mL 1×10 ^-2 mol/L Pd-TCPP butanediol solution, 20mL 5×(10 ^{- 1} mol/L NBA butanediol solution, 30mL 1mol/L sodium sulfite aqueous solution, at a stirring speed of 300 rpm, heated to 70°C in a water bath, kept warm for 9 minutes, and added 40mL of 1.5mol/L DBS butanediol Continue to stir the alcohol solution at a speed of 300 rpm for 8 minutes, and then statically cool the obtained supramolecular gel, which is the photoresponsive room temperature phosphorescent supramolecular anti-counterfeiting material.

Example 4:

This example provides a photoresponsive room temperature phosphorescent supramolecular anti-counterfeiting material. The preparation method is as follows: take a clean test tube, add 5mL 1×10 ^-2 mol/L Pd-TCPP DMSO solution, 5mL 5×10 ^-1 mol/ L NBA DMF solution, 30mL 1mol/L sodium sulfite aqueous solution, at a stirring speed of 300 rpm, heated to 70°C in a water bath, kept warm for 10 minutes, added 60mL of 1.5mol/L DBS ethanol solution, continued to press 300 rpm Stir at a speed of 5 minutes, and then statically cool to obtain a supramolecular gel that is a photoresponsive room temperature phosphorescent supramolecular anti-counterfeiting material.

The supramolecular anti-counterfeiting material prepared by the above preparation method was directly tested for room temperature phosphorescence, and it was found that the phosphorescence effect was weak or no phosphorescence effect was produced. After being illuminated for a certain period of time under 365nm ultraviolet light, the room temperature phosphorescence test is carried out. When the excitation light is 410nm, the material can produce room temperature phosphorescence of 700nm, and the phosphorescence intensity increases with the increase of the illumination time. When the illumination time When reaching a certain value, the phosphorescent intensity reaches the maximum value.

Claims (6)

1. a kind of photoresponse room temperature phosphorimetry supermolecule anti-fake material, including phosphorescent molecules, antioxidant, inducer substance, water and organic Solvent, phosphorescent molecules are four carbonyl phenyl palladium porphyrins（Pd-TCPP）, antioxidant is sodium sulfite, inducer substance 1,3 (R):2, 4 (S)-benzyl-D-glucitol（DBS）, which is characterized in that also contain photoresponse factor ortho-nitrophenyl first in supermolecule anti-fake material Aldehyde (NBA)；

The preparation process of the room temperature phosphorimetry supermolecule anti-fake material is：

By four carbonyl phenyl palladium porphyrins（Pd-TCPP）It is dissolved in appropriate organic solvent, obtains a concentration of 1 × 10^-2The solution of mol/L A；

By o-nitrobenzaldehyde（NBA）It is dissolved in suitable organic solvent, obtains a concentration of 5 × 10^-1The solution B of mol/L；

Sodium sulfite is dissolved in suitable water, the solution C of a concentration of 1mol/L is obtained；

By appropriate 1,3 (R):2,4 (S)-benzyl-D-glucitol（DBS）It is dissolved in organic solvent and obtains a concentration of 1.5 × 10^{- 2}The solution D of mol/L；

Three kinds of solution A obtained above, solution B and solution C solution are mixed by formula ratio, mixing speed be 300 turns/ Point, and 50 DEG C -90 DEG C are heated to, 8-10 minutes are kept the temperature, solution D is then added and obtains mixed liquor, continues to stir by 300 revs/min It mixes 5-10 minutes；

Above-mentioned mixed liquor is cooled to room temperature, supermolecular gel is obtained, which is photoresponse room temperature phosphorimetry oversubscription Sub- anti-fake material；

In above-mentioned mixed liquor, the percent by volume of each solution is：

Solution A 5 ~ 15

Solution B 5 ~ 25

Solution C 25 ~ 80

Solution D 10 ~ 60.

2. a kind of photoresponse room temperature phosphorimetry supermolecule anti-fake material as described in claim 1, it is characterised in that described is each molten The percent by volume of liquid is：

Solution A 10 ~ 15

Solution B 10 ~ 20

Solution C 30 ~ 60

Solution D 20 ~ 50.

3. a kind of photoresponse room temperature phosphorimetry supermolecule anti-fake material as described in claim 1, the photoresponse factor is ortho-nitrophenyl Formaldehyde (NBA).

4. a kind of photoresponse room temperature phosphorimetry supermolecule anti-fake material as described in claim 1, it is characterised in that described is organic Solvent is N,N-dimethylformamide（DMF）, dimethyl sulfoxide（DMSO）, ethylene glycol, butanediol, polyethylene glycol（PEG）, in ethyl alcohol One kind.

5. a kind of preparation method of photoresponse room temperature phosphorimetry supermolecule anti-fake material, it is characterised in that use following steps：

1. by four carbonyl phenyl palladium porphyrins（Pd-TCPP）It is dissolved in appropriate organic solvent, obtains a concentration of 1 × 10^-2Mol/L's is molten Liquid A；

2. by o-nitrobenzaldehyde（NBA）It is dissolved in suitable organic solvent, obtains a concentration of 5 × 10^-1The solution B of mol/L；

3. sodium sulfite is dissolved in suitable water, the solution C of a concentration of 1mol/L is obtained；

4. by appropriate 1,3 (R):2,4 (S)-benzyl-D-glucitol（DBS）It is dissolved in organic solvent and obtains a concentration of 1.5 × 10^{- 2}The solution D of mol/L；

5. three kinds of solution A obtained above, solution B and solution C solution are mixed by formula ratio, mixing speed be 300 turns/ Point, and 50 DEG C -90 DEG C are heated to, 8-10 minutes are kept the temperature, solution D is then added and obtains mixed liquor, continues to stir by 300 revs/min It mixes 5-10 minutes；

6. above-mentioned mixed liquor is cooled to room temperature, supermolecular gel is obtained, which is that photoresponse room temperature phosphorimetry is super Molecule anti-fake material；

In above-mentioned mixed liquor, the percent by volume of each solution is：

Solution A 5 ~ 15

Solution B 5 ~ 25

Solution C 25 ~ 80

Solution D 10 ~ 60.

6. a kind of photoresponse room temperature phosphorimetry supermolecule anti-fake material as described in claim 1, which is characterized in that by oversubscription The sub- anti-fake material ultraviolet lighting time changes to realize the regulation and control to phosphorescence intensity.