CN116675668B - Molecular probe based on vanillin modification and preparation method and application thereof - Google Patents

Molecular probe based on vanillin modification and preparation method and application thereof Download PDF

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CN116675668B
CN116675668B CN202310655714.5A CN202310655714A CN116675668B CN 116675668 B CN116675668 B CN 116675668B CN 202310655714 A CN202310655714 A CN 202310655714A CN 116675668 B CN116675668 B CN 116675668B
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vanillin
molecular probe
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viscosity
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CN116675668A (en
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徐灵峰
王依雪
彭辉
赵静怡
钟敏
姚培
刘欣雅
余莎莎
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Jinggangshan University
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Abstract

本发明提供了一种基于香兰素改性的分子探针及其制备方法和应用，本发明首先将脱水剂分散液、香兰素溶液顺次和米氏酸分散液混合，之后进行Knoevenagel缩合反应，即可得到基于香兰素改性的分子探针。本发明提供的基于香兰素改性的分子探针化学性能稳定，在复杂的美妆乳液中依旧能稳定存在，信号释放不易受到干扰，对粘度的敏感性高于其它因素，且在多种极性、多种pH的溶液中能保持较好的光稳定性。

The present invention provides a vanillin-modified molecular probe and a preparation method and application thereof. The present invention firstly mixes a dehydrating agent dispersion, a vanillin solution and a Michaelis acid dispersion in sequence, and then performs a Knoevenagel condensation reaction to obtain a vanillin-modified molecular probe. The vanillin-modified molecular probe provided by the present invention has stable chemical properties, can still exist stably in complex cosmetic emulsions, signal release is not easily disturbed, is more sensitive to viscosity than other factors, and can maintain good light stability in solutions of various polarities and various pH values.

Description

Molecular probe based on vanillin modification and preparation method and application thereof
Technical Field
The invention relates to the technical field of cosmetic analysis and detection, in particular to a molecular probe based on vanillin modification and a preparation method and application thereof.
Background
With the advent of people's fine life, the "face value" commodity has become one of the necessities of the public. Cosmetic products have become a necessary tool for improving the "color value", and not only have the necessary expense of female consumers, but also have become part of the expense content of male consumers in recent years, and in fact, the consumption in this field is extremely huge. Among them, the emulsion is used as a key component of three general types of traditional make-up such as water, cream and frost, and is widely applied to the face or other parts of the body, and the spreading and wetting degree on the skin can seriously affect the experience of consumers, and the performances are closely related to the consistency. Even sometimes, manufacturers can enhance the texture of make-up emulsions by formulating a consistency that allows consumers to have a better texture experience when in use. It follows that in the preparation of make-up emulsions, control of the consistency is critical, essentially in relation to the domain viscosity of the make-up emulsion. The viscosity of the micro-region, which is a property capable of reacting fluid to resist deformation or prevent relative flow of adjacent fluid layers, is used as a physical parameter and has a profound relationship with the apparent properties of development, wetting, coverage and the like of cosmetic emulsions. The change in the consistency of make-up emulsions is often inherent and the appearance is difficult to define precisely, in contrast to the micro-domain viscosity which can be measured and even defined precisely. However, conventional viscosity measurement is mostly dependent on various types of viscometers (falling ball viscometer, rotational viscometer, vibrating viscometer, etc.), which are designed for macroscopic viscosity, are severely dependent on equipment in measurement, and require a large volume of sample to be measured, and more importantly, are difficult to realize molecular level measurement for microscopic viscosity.
In the technical field of cosmetic detection, the photochemical technology has the advantages of sensitive response, convenient use, imaging in situ, real time and the like, and particularly, the method can realize the measurement of micro-area viscosity by means of a molecular-level tool, and the method has important significance for the quick visual observation of the micro-area viscosity of the cosmetic emulsion and the improvement of the refinement of the process of the cosmetic emulsion (thin consistency), particularly the development, wetting, coating and other performances of the emulsion. Therefore, development of a molecular probe based on vanillin modification and a preparation method thereof are of great significance in detection of the viscosity of cosmetic emulsion.
Disclosure of Invention
The invention aims to provide a molecular probe based on vanillin modification, and a preparation method and application thereof, so as to solve the technical problem that the viscosity of a micro-region of a cosmetic emulsion is difficult to accurately measure in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides a molecular probe based on vanillin modification, which has a structure shown in a formula I:
The invention provides a preparation method of a molecular probe based on vanillin modification, which comprises the steps of sequentially mixing dehydrating agent dispersion liquid, vanillin solution and Mi's acid dispersion liquid, and then carrying out Knoevenagel condensation reaction to obtain the molecular probe based on vanillin modification.
Preferably, the dehydrating agent dispersion liquid is composed of a dehydrating agent and a solvent, wherein the dehydrating agent contains one or more of sodium carbonate, calcium hydroxide, sodium bicarbonate, cesium carbonate, potassium bicarbonate, magnesium hydroxide, calcium carbonate, calcium acetate and tin acetate.
Preferably, the vanillin solution consists of vanillin and a solvent, the Mitsubishi acid dispersion consists of Mitsubishi acid and the solvent, and the solvent independently comprises one or more of tetrahydrofuran, N-dimethylformamide, ethyl acetate, ethanol, dimethyl sulfoxide and methanol.
Preferably, the content of the dehydrating agent in the dehydrating agent dispersion liquid is 1-150 mol/L, the concentration of the vanillin solution is 1-300 mol/L, and the content of the Mitiglinide in the Mitiglinide dispersion liquid is 1-15 mol/L.
Preferably, the molar ratio of the dehydrating agent to the Michaelis acid to the vanillin is 1-150:1:1-20.
Preferably, the temperature of the Knoevenagel condensation reaction is 20-100 ℃ and the time is 1-96 h.
The invention provides an application of a molecular probe based on vanillin modification in detecting the viscosity of cosmetic emulsion, which is prepared by mixing the molecular probe based on vanillin modification with the cosmetic emulsion, wherein the mixing concentration of the molecular probe based on vanillin modification is 5-15 mu mol/L.
The molecular probe based on vanillin modification has a freely rotatable single double bond conjugate structure, the conjugate structure shows certain flexibility, can freely and mechanically rotate in a cosmetic emulsion with lower viscosity, and can dissipate excitation state energy in a mechanical motion mode, so that the finally released optical signal intensity is weaker, the cosmetic emulsion is thinner, the coating and unfolding effects are better, along with gradual pasting of the cosmetic emulsion, the mechanical rotation of the molecular probe based on vanillin modification in the cosmetic emulsion is more difficult, the excitation state energy is consumed in a radiation transition mode, the released optical signal intensity is higher, the light signal intensity is gradually enhanced along with gradual rising of the cosmetic viscosity, and the visual imaging effect of turn-on can be realized. The molecular probe based on vanillin modification can emit strong fluorescence at 540-800 nm under external excitation of 500-520 nm, and can measure the viscosity of cosmetic emulsion, so that the viscosity of the cosmetic emulsion can be further judged, and a data reference is provided for process development.
The invention has the beneficial effects that:
(1) The molecular probe based on vanillin modification is prepared by further modification of a natural product vanillin, is prepared by a one-step method, has rich sources of required raw materials, belongs to natural plant extracts, is low in price, is low in overall application preparation cost, does not need a complex preparation process in the whole process, is suitable for large-scale preparation, is high in final yield, is relatively green and environment-friendly in process, and accords with the concept of low-carbon sustainable development.
(2) The molecular probe based on vanillin modification provided by the invention can realize visual imaging on cosmetic emulsions with different viscosities, and can be used for preparing process and controlling the consistency of the cosmetic emulsions.
(3) The molecular probe based on vanillin modification provided by the invention has stable chemical performance, can still exist stably in complex cosmetic emulsion, is not easy to interfere signal release, has higher sensitivity to viscosity than other factors, and can keep better light stability in solutions with various polarities and various pH values.
Drawings
Fig. 1 is a schematic diagram of a mechanism of detection of viscosity of a cosmetic emulsion based on a vanillin modified molecular probe provided by the invention;
FIG. 2 is a mass spectrum of a molecular probe based on vanillin modification prepared in example 1;
FIG. 3 is a graph showing fluorescence spectra of the vanillin-modified molecular probe prepared in example 1 in a series of glycerol/water mixed solutions;
FIG. 4 is a graph of the fluorescence intensity versus viscosity number of the vanillin-modified molecular probe prepared in example 1;
FIG. 5 is a graph showing the photostability test of the vanillin-based modified molecular probe prepared in example 1 in high-viscosity and low-viscosity solutions;
FIG. 6 is a graph showing the absorption spectra of vanillin-modified molecular probes prepared in example 1 in solutions of different polarities;
FIG. 7 is a graph showing emission spectra of vanillin-modified molecular probes prepared in example 1 in solutions of different pH;
FIG. 8 is a graph showing the emission spectra of vanillin-based modified molecular probes prepared in example 1 in various commercially available cosmetic emulsions.
Detailed Description
The invention provides a molecular probe based on vanillin modification, which has a structure shown in a formula I:
The name of the molecular probe based on vanillin modification is 5- (4-hydroxy-3-methoxybenzyl) -2, 2-dimethyl-1, 3-dioxane-4, 6-dione (HMBDDD), the molecular formula is C 14H14O6, the relative molecular weight is 278.08, and the molecular probe is further modified based on a natural product vanillin (formula II), is light yellow (light white) powder, and is easily dissolved in various common solvents such as ethyl acetate, methanol, ethanol, N-dimethylformamide, tetrahydrofuran, dimethyl sulfoxide and the like. The molecular probe has good aromaticity, good light stability, stable chemical structure, long-term storage, low hygroscopicity and difficult deterioration. The conjugated single double bond capable of freely rotating exists in the molecular structure, and a typical flexible conjugated structure is displayed, the conjugated structure can freely rotate in a thin solution, is limited in a thick solution and is converted into an optical signal to be released, so that the control of the whole thin consistency is visualized. And the main components of the emulsion such as common surfactant, various cosmetic aids (such as nicotinamide, palmitic acid, isopropyl isostearate and the like) and enzyme can not influence the function of the emulsion, so that the emulsion is particularly suitable for measuring the viscosity of the cosmetic emulsion.
The vanillin has a structure shown in a formula II:
The invention provides a preparation method of a molecular probe based on vanillin modification, which comprises the steps of sequentially mixing dehydrating agent dispersion liquid, vanillin solution and Mi's acid dispersion liquid, and then carrying out Knoevenagel condensation reaction to obtain the molecular probe based on vanillin modification.
In the present invention, the dehydrating agent dispersion is composed of a dehydrating agent and a solvent, wherein the dehydrating agent contains one or more of sodium carbonate, calcium hydroxide, sodium bicarbonate, cesium carbonate, potassium bicarbonate, magnesium hydroxide, calcium carbonate, calcium acetate and tin acetate, preferably one or more of sodium carbonate, calcium hydroxide, potassium carbonate, sodium bicarbonate and calcium carbonate, more preferably one or more of sodium carbonate, potassium carbonate and calcium carbonate.
The dehydrating agent used in the invention has the function of removing moisture generated in the reaction process and promoting the reaction to go right.
In the invention, the vanillin solution consists of vanillin and a solvent, the Mi's acid dispersion consists of Mi's acid and a solvent, and the solvent independently comprises one or more of tetrahydrofuran, N-dimethylformamide, ethyl acetate, ethanol, dimethyl sulfoxide and methanol, preferably one or more of N, N-dimethylformamide, ethyl acetate, ethanol and methanol, and more preferably one or more of ethyl acetate, ethanol and methanol.
In the invention, the content of the dehydrating agent in the dehydrating agent dispersion liquid is 1-150 mol/L, preferably 10-130 mol/L, more preferably 50-100 mol/L, the concentration of the vanillin solution is 1-300 mol/L, preferably 30-200 mol/L, more preferably 50-150 mol/L, and the content of the Mitiglic acid in the Mitiglic acid dispersion liquid is 1-15 mol/L, preferably 2-12 mol/L, more preferably 3-10 mol/L.
In the invention, the molar ratio of the dehydrating agent to the Michaelis acid to the vanillin is 1-150:1:1-20, preferably 5-120:1:2-15, and more preferably 10-110:1:3-12.
In the present invention, when the dehydrating agent dispersion and the Mi's acid dispersion are mixed, the mixing is preferably performed by dropwise addition, and the dropwise addition rate is 1 to 10 drops/s, preferably 2 to 9 drops/s, and more preferably 3 to 8 drops/s.
In the present invention, the mixing of the dehydrating agent dispersion and the Mi's acid dispersion is preferably performed under stirring conditions at a stirring rate of 100 to 1000rpm, preferably 200 to 800rpm, more preferably 300 to 700rpm, and for a stirring time of 1 to 24 hours, preferably 5 to 20 hours, more preferably 10 to 15 hours.
In the invention, the temperature of the Knoevenagel condensation reaction is 20-100 ℃, preferably 40-80 ℃, more preferably 50-70 ℃, and the time is 1-96 h, preferably 10-90 h, more preferably 20-80 h.
In the present invention, the initiation of the Knoevenagel condensation reaction is desirably performed in an inert atmosphere, wherein the inert atmosphere comprises a helium atmosphere, an argon atmosphere, a neon atmosphere, or a krypton atmosphere, preferably a helium atmosphere, an argon atmosphere, or a neon atmosphere, and more preferably a helium atmosphere or an argon atmosphere.
In the present invention, the equation of Knoevenagel condensation reaction is as follows:
In the invention, after the Knoevenagel condensation reaction is finished, the Knoevenagel condensation reaction product is preferably purified, the reaction product is preferably subjected to reduced pressure distillation, extraction, concentration, chromatography and drying in sequence, wherein the reduced pressure distillation is performed in a rotary evaporator, the pressure of the rotary evaporator is-0.09 MPa to-0.08 MPa, preferably-0.085 MPa, a mixed system of ethyl acetate and deionized water is preferably adopted in the extraction process, the volume ratio of the ethyl acetate to the deionized water is 1-10:1, preferably 2-8:1, more preferably 4-6:1, the concentration is that the solution obtained after the extraction is further dried by anhydrous Na 2SO4, then the solution obtained after the drying is removed by adopting the rotary evaporator, the crude product is preferably further purified by adopting a silica gel chromatographic column in the chromatography, the purification process is performed in a mixed system of methanol and ethyl acetate, the volume ratio of the methanol to the ethyl acetate is 1:1-10, preferably 1:2-8, further preferably 1:4-6, the drying is preferably adopted in the drying process, the drying temperature is preferably 20 ℃ and the drying is preferably 20 ℃ for 60-30 h, the drying is preferably carried out in the vacuum condition, and the drying time is preferably 20h is preferably 1-30-5 h.
The invention provides an application of a molecular probe based on vanillin modification in detecting the viscosity of cosmetic emulsion, which is prepared by mixing the molecular probe based on vanillin modification with the cosmetic emulsion, wherein the mixing concentration of the molecular probe based on vanillin modification is 5-15 mu mol/L, preferably 8-12 mu mol/L, and more preferably 10 mu mol/L.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Dissolving 10mmol of vanillin in ethanol, stirring uniformly to obtain vanillin solution with concentration of 10mol/L, dispersing 2mmol of Mirabilic acid in ethanol, stirring uniformly to obtain Mirabilic acid dispersion with Mirabilic acid content of 2mol/L, dispersing 100mmol of calcium carbonate in ethanol to obtain calcium carbonate dispersion with calcium carbonate content of 100mol/L, adding the calcium carbonate dispersion into the Mirabilic acid dispersion at a dropping rate of 3 drops/s, mixing at 25 ℃, controlling the stirring rate to be 800rpm, stirring for 18h, pouring the vanillin solution after uniform mixing, carrying out Knoevenagel condensation reaction in helium atmosphere at a reaction temperature of 60 ℃ for 24h.
Purifying the reaction product of Knoevenagel condensation reaction, namely sequentially performing reduced pressure distillation, extraction, concentration, chromatography and drying, wherein the reduced pressure distillation is performed in a rotary evaporator, removing residual solvent in the reaction under the pressure of-0.09 MPa, then extracting by using a mixed system of ethyl acetate and deionized water, wherein the volume ratio of the ethyl acetate to the deionized water is 8:1, drying an organic solvent layer obtained by extraction by using anhydrous Na 2SO4, removing the dried solution by using the rotary evaporator, further purifying the obtained crude product by using a silica gel chromatographic column, performing the purification process in a methanol/ethyl acetate mixed system (methanol/ethyl acetate, V/V=1:3), and finally drying for 24 hours in a vacuum oven at 50 ℃ to obtain 478.16mg of powder, namely the molecular probe based on vanillin modification, which is recorded as HMBDDD, and the yield is 86%.
The high-resolution mass spectrum detection of the molecular probe based on vanillin modification prepared in example 1 is shown in fig. 2. As can be seen from FIG. 2, the molecular probe based on vanillin modification prepared in example 1 has a relative molecular mass of 279.209703 [ M+H ] + and a theoretical relative mass estimated value of 278.07904, and the synthesized product is determined to be natural product modified molecular probe 5- (4-hydroxy-3-methoxybenzylidene) -2, 2-dimethyl-1, 3-dioxane-4, 6-dione, which has a structural formula shown in formula I, and a molecular formula of formula I is C 14H14O6.
Example 2
Dissolving 1mmol of vanillin in methanol, stirring uniformly to obtain vanillin solution with concentration of 1mol/L, dispersing 1mmol of Mi's acid in methanol, stirring uniformly to obtain Mi's acid dispersion with Mi's acid content of 1mol/L, dispersing 1mmol of sodium carbonate in methanol to obtain sodium carbonate dispersion with sodium carbonate content of 1mol/L, adding the sodium carbonate dispersion into the Mi's acid dispersion at a dropping rate of 1 drop/s, mixing at 25 ℃, controlling the stirring rate to be 1000rpm, stirring for 1h, pouring the vanillin solution after uniform mixing, carrying out Knoevenagel condensation reaction in neon atmosphere at a reaction temperature of 20 ℃ for 96h.
Purifying the reaction product of Knoevenagel condensation reaction, namely sequentially performing reduced pressure distillation, extraction, concentration, chromatography and drying, wherein the reduced pressure distillation is performed in a rotary evaporator, removing residual solvent in the reaction under the pressure of-0.08 MPa, then extracting by using a mixed system of ethyl acetate and deionized water, wherein the volume ratio of the ethyl acetate to the deionized water is 1:1, drying an organic solvent layer obtained by extraction by using anhydrous Na 2SO4, removing the dried solution by using the rotary evaporator, further purifying the obtained crude product by using a silica gel chromatographic column, performing the purification process in a methanol/ethyl acetate mixed system (methanol/ethyl acetate, V/V=1:1), and finally drying for 1h in a vacuum oven at 60 ℃ to obtain 227.9mg of powder, namely the molecular probe based on vanillin modification, which is recorded as HMBDDD, and the yield is 82%.
The mass spectrum results of the vanillin-modified molecular probe prepared in example 2 were identical to those obtained in example 1.
Example 3
Dissolving 30mmol of vanillin in methanol, stirring uniformly to obtain vanillin solution with concentration of 300mol/L, dispersing 1.5mmol of Mi's acid in methanol, stirring uniformly to obtain Mi's acid dispersion with Mi's acid content of 15mol/L, dispersing 225mmol of potassium carbonate in methanol to obtain potassium carbonate dispersion with potassium carbonate content of 150mol/L, adding the potassium carbonate dispersion into the Mi's acid dispersion at a dropping rate of 10 drops/s, mixing at 25 ℃, controlling the stirring rate to be 100rpm, stirring for 24 hours, pouring the vanillin solution after uniform mixing, carrying out Knoevel condensation reaction in neon atmosphere at a reaction temperature of 100 ℃ for 1 hour.
Purifying the reaction product of Knoevenagel condensation reaction, namely sequentially performing reduced pressure distillation, extraction, concentration, chromatography and drying, wherein the reduced pressure distillation is performed in a rotary evaporator, removing residual solvent in the reaction under the pressure of-0.085 MPa, then extracting by using a mixed system of ethyl acetate and deionized water, wherein the volume ratio of the ethyl acetate to the deionized water is 10:1, drying an organic solvent layer obtained by extraction by using anhydrous Na 2SO4, removing the dried solution by using the rotary evaporator, further purifying the obtained crude product by using a silica gel chromatographic column, performing the purification process in a mixed system of methanol and ethyl acetate (methanol/ethyl acetate, V/V=1:10), and finally drying for 48 hours in a vacuum oven under the condition of 30 ℃ to obtain 333.6mg of powder, namely the molecular probe based on vanillin modification, which is recorded as HMBDDD, and the yield is 80%.
The mass spectrum results of the vanillin-modified molecular probe prepared in example 3 were identical to those obtained in example 1.
Application example 1
5.56Mg of the vanillin-based modified molecular probe prepared in example 1 was dissolved in a volume of DMF, the concentration was controlled to be 2mmol/L, then the vanillin-based modified molecular probe solution was added to a common 3 different cosmetic emulsions respectively, and the test was performed under the conditions that the vanillin-based modified molecular probe mixed concentration was 10 mu mol/L and 25 ℃, and the excitation wavelength of an external light source was controlled to be 520nm, and the test result is shown in FIG. 8.
As can be seen from fig. 8, the light signal release intensities of the 3 kinds of make-up emulsions are different, which indicates that the 3 kinds of make-up emulsions have certain viscosity differences, which may be related to the difference of the components contained in the make-up emulsions, and the 3 kinds of make-up emulsions are seen from the final test result that the make-up emulsion 1 belongs to the low-viscosity emulsion, the make-up emulsion 2 belongs to the medium-viscosity emulsion, the whole is of medium consistency, the make-up emulsion 3 belongs to the high-viscosity emulsion, and the whole is in the state of cream (paste). The test result shows that the molecular probe (HMBDDD) based on vanillin modification provided by the invention can fully sense the change of viscosity (thin consistency) of a micro-area in the make-up emulsion and release the change through a visual light signal, and has important significance for researching the optimal process of different types of make-up emulsions.
Performance test:
The vanillin-modified molecular probe prepared in example 1 was subjected to a viscosity response test, a photostability test, a universality test, and a pH stability test.
(1) Response test of vanillin-modified molecular probe (HMBDDD) based on viscosity
Mixed solutions containing glycerol and deionized water with different volume fractions were prepared, wherein the volume fractions of the deionized water and the glycerol are shown in table 1, the excitation external excitation wavelength was set to be 520nm, the concentration of the vanillin-modified molecular probe in the test solution was controlled to be 10 μm, and the test was performed at room temperature, and the test results are shown in fig. 3.
TABLE 1 glycerol and deionized water volume fractions
Deionized water volume fraction Volume fraction of glycerol
100% 0%
70% 30%
50% 50%
30% 70%
10% 90%
0% 100%
At room temperature, the viscosity of deionized water is 1.0cp, the viscosity of glycerol is 956.0cp, and the viscosity of the mixed solution can be adjusted by adjusting the volume concentration of the glycerol and the glycerol. The specific test results are shown in fig. 3, and the intensity of the released optical signal is gradually increased as the viscosity of the solution is gradually increased. In particular, when the volume fraction of glycerol exceeds 50%, the viscosity of the mixed system increases more and more, and the optical signal intensity of the mixed system increases more and more, and the maximum increases by 16 times compared with a solution system without glycerol.
Further, the test found that the logarithmic function of the optical signal intensity of the mixed solution and the solution viscosity value could be fitted to a straight line, as shown in fig. 4.
As can be seen from FIG. 4, the vanillin-modification-based molecular probe HMBDDD provided by the invention can release stronger light signals along with the rising of the viscosity value, and the logarithmic function of the fluorescence signal intensity and the logarithmic function of the viscosity value of the make-up emulsion are compared with each otherThe Hoffmann relation is matched, the viscosity sensitivity coefficient of HMBDDD is 0.40, and the fitting coefficient is 0.97. The test result shows that the molecular probe HMBDDD based on vanillin modification provided by the invention has better detection sensitivity on the micro-area viscosity of the solution, and can be used as supporting data of a cosmetic emulsion viscosity (thin consistency) blending process. The specific logarithmic function values are shown in Table 2.
Table 2 logarithm of viscosity versus logarithm of fluorescence intensity
Logarithm of viscosity (log eta) 0.01 0.24 0.57 1.03 1.77 2.99
Logarithm of fluorescence intensity (log I) 2.37 2.48 2.75 2.90 3.20 3.58
2. Light stability test based on vanillin modified molecular probes (HMBDDD)
2.78Mg of 5- (4-hydroxy-3-methoxybenzylidene) -2, 2-dimethyl-1, 3-dioxane-4, 6-dione (HMBDDD) prepared in example 1 was dissolved in N, N-Dimethylformamide (DMF) to a concentration of 10mM, diluted to 10. Mu.M at the time of test, and added to deionized water and glycerol, respectively, and continuously excited under an excitation light source of 520nm for 60 minutes, the change rule of the optical signal intensity was measured, the test result was shown in FIG. 5, and the obtained data were shown in Table 3.
TABLE 3 fluorescence test results
Time/min 0 10 20 30 60
Fluorescence intensity in deionized water/a.u. 232.0 227.2 222.1 216.7 213.4
Fluorescence intensity in glycerol/a.u. 3688.2 3680.8 3672.4 3663.5 3650.4
As is clear from the data shown in fig. 5 and table 3, the vanillin-modified molecular probe (HMBDDD) has better photostability, can release stable optical signals under the irradiation of a long-time excitation light source, and can maintain higher signal release strength in not only a high-viscosity solution but also a low-viscosity solution.
3. Universal test based on vanillin modified molecular probes (HMBDDD)
1.39Mg of vanillin-modified molecular probe-based 5- (4-hydroxy-3-methoxybenzylidene) -2, 2-dimethyl-1, 3-dioxane-4, 6-dione (HMBDDD) of example 1 was dissolved in DMF at a concentration of 2mM, diluted further to 10. Mu.M at the time of test, and added to 6 common solutions of different polarities, toluene, dichloromethane, tetrahydrofuran, ethanol, dimethyl sulfoxide and glycerol, respectively, to test the change law of absorbance. The above test was performed at room temperature and the results are shown in fig. 6.
The results obtained in fig. 6 show that the absorbance and absorption wavelength in the other 5 common solvents are not greatly changed except for the experimental group of glycerol, and the absorbance change is not obvious in the experimental group of glycerol, but the absorbance change is red-shifted to a certain extent, which is probably because in the solution atmosphere with higher viscosity, the conformation is spatially conjugated, the conjugation degree is indirectly prolonged, which indicates that the molecular probe (HMBDDD) based on the vanillin modification can effectively absorb the energy of excitation light in various solutions with different polarities, the absorption spectrum is not changed due to the change of the polarity of the solution, and the effect of the molecular probe on the viscosity measurement is not influenced by the polarity fluctuation.
4. PH stability test of molecular probes based on vanillin modification
8.34Mg of the vanillin-modified molecular probe 5- (4-hydroxy-3-methoxybenzylidene) -2, 2-dimethyl-1, 3-dioxane-4, 6-dione (HMBDDD) prepared in example 1 was dissolved in DMF at a concentration of 3mM, further diluted to 10. Mu.M at the time of testing, and added to solutions of pH=3, 5, 6.8, 7.4, 8, 9, respectively, to test the change rule of absorbance, and the test was performed at room temperature, and the test results are shown in FIG. 7.
From the test results obtained in fig. 7, it can be seen that the fluorescence intensity of the vanillin-based modified molecular probe (HMBDDD) does not significantly change in a wider pH range, and the vanillin-based modified molecular probe shows better light signal release stability in the pH range, which indicates that the vanillin-based modified molecular probe can be used in cosmetic emulsions in various pH atmospheres.
The vanillin-modified molecular probe-based 5- (4-hydroxy-3-methoxyl benzylidene) -2, 2-dimethyl-1, 3-dioxane-4, 6-dione (HMBDDD) has a flexible conjugated structure, can show different rotation states in environments with different micro-region viscosities, can convert the change of the micro-region viscosities in cosmetic emulsion into optical signals for presentation, and can realize effective detection of the physical index of the micro-region viscosity (thin consistency) from a brand new molecular level angle. Various test results show that the molecular probe HMBDDD based on vanillin modification can still keep better optical signal intensity under the condition of long-time irradiation, can still keep optical signals stable in a wide pH range, has little absorbance change in various polar solutions, is suitable for complex cosmetic emulsion, has the emission wavelength of 604nm, and can effectively avoid background optical signal interference possibly caused by various additives of the cosmetic emulsion. In addition, the molecular probe based on vanillin modification is prepared by a one-step method, the preparation process is green and environment-friendly, the final yield is high, the required raw material sources belong to natural products, the cost is low, the preparation is simple and easy to obtain, the post-treatment process is simple and easy to implement, the whole process is low-carbon and environment-friendly, the cost performance is high, and the molecular probe is suitable for industrial application.
As can be seen from the above examples, the present invention provides a molecular probe based on vanillin modification, a preparation method and application thereof, according to the invention, firstly, a dehydrating agent dispersion liquid and a vanillin solution are sequentially mixed with a Mi acid dispersion liquid, and then Knoevenagel condensation reaction is carried out, so that the molecular probe based on vanillin modification can be obtained. The molecular probe based on vanillin modification provided by the invention has stable chemical performance, can still exist stably in complex cosmetic emulsion, is not easy to interfere signal release, has higher sensitivity to viscosity than other factors, and can keep better light stability in solutions with various polarities and various pH values.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (7)

1. The application of the molecular probe based on the vanillin modification in detecting the viscosity of the make-up emulsion is characterized in that the molecular probe based on the vanillin modification and the make-up emulsion are mixed, and the mixing concentration of the molecular probe based on the vanillin modification is 5-15 mu mol/L;
The molecular probe has a structure shown in a formula I:
the vanillin has a structure shown in a formula II:
2. the use of a molecular probe based on vanillin modification according to claim 1, characterized in that a molecular probe based on vanillin modification is obtained by mixing a dehydrating agent dispersion, a vanillin solution and a milbezier acid dispersion in sequence and then performing Knoevenagel condensation reaction.
3. The use of a vanillin-modification-based molecular probe according to claim 2, wherein said dehydrating agent dispersion is composed of a dehydrating agent and a solvent, wherein the dehydrating agent contains one or more of sodium carbonate, calcium hydroxide, sodium bicarbonate, cesium carbonate, potassium bicarbonate, magnesium hydroxide, calcium carbonate, calcium acetate and tin acetate.
4. Use of a molecular probe based on vanillin modification according to claim 2 or 3 for detecting the viscosity of cosmetic emulsion, wherein said vanillin solution is composed of vanillin and a solvent, said mie acid dispersion is composed of mie acid and a solvent, said solvent independently comprises one or several of tetrahydrofuran, N-dimethylformamide, ethyl acetate, ethanol, dimethyl sulfoxide and methanol.
5. The application of the molecular probe based on vanillin modification in detecting the viscosity of cosmetic emulsion, which is characterized in that the content of a dehydrating agent in a dehydrating agent dispersion is 1-150 mol/L, the concentration of vanillin solution is 1-300 mol/L, and the content of Mi's acid in a Mi's acid dispersion is 1-15 mol/L.
6. The use of a molecular probe based on vanillin modification according to claim 5, which is characterized in that the molar ratio of the dehydrating agent, the milbezier acid and the vanillin is 1-150:1:1-20.
7. The use of a molecular probe based on vanillin modification according to claim 2, 5 or 6 for detecting the viscosity of cosmetic emulsion, characterized in that the Knoevenagel condensation reaction is carried out at a temperature of 20-100 ℃ for a time of 1-96 h.
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Title
"Facile Knoevenagel and Domino Knoevenagel/Michael Reactions Using Gel Entrapped Base Catalysts";Shital Shinde等;《HELVETICA CHIMICA ACTA》;20111114;第第94卷卷(第第11期期);第1943-1951页 *
"以 Knoevenagel 反应构建粘度荧光探针的综合实验设计";陈杜刚等;《实验技术与管理》;20220822;第第39卷卷(第第8期期);第46-64页 *
Shital Shinde等."Facile Knoevenagel and Domino Knoevenagel/Michael Reactions Using Gel Entrapped Base Catalysts".《HELVETICA CHIMICA ACTA》.2011,第第94卷卷(第第11期期),第1943-1951页. *

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