Pine and cypress hydroformylation salicyl ester molecular device as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of analysis and detection of liquid nutritional agents, and provides a coniferous and cypress hydroformylation salicyl ester molecular device and a preparation method and application thereof. The method comprises the following steps: mixing a coniferyl aldehyde solution, a dehydrating agent dispersion liquid and a salicyl ester derivative solution, and carrying out a dehydration condensation reaction on the mixed solution to obtain the coniferyl hydroformylated salicyl ester molecular device. The coniferous hydroformylated salicylate molecular device has the advantages of high viscosity sensitivity coefficient, stable chemical structure, strong visualization effect, release of stable optical signals in a wide pH range, insensitivity to the polarity of the solvent, and good solvent tolerance; the device can be used as a molecular tool for in-situ measurement of viscosity in a nutritional agent microenvironment, detection can be realized without depending on shearing and relative movement in the measurement process, consumption of a large amount of samples can be avoided, the whole process is rapid, efficient and convenient, and viscosity change of a liquid nutritional agent containing a large amount of pseudoplastic fluid can be effectively measured.

Description

Technical Field

[0001] The present invention relates to the technical field of liquid nutrient analysis and detection, and in particular to a coniferous aldehyde salicylate molecular device, a preparation method and an application thereof. Background Art

[0002] Liquid nutrients are plant nutritional supplements prepared using water-soluble or emulsified technologies. Their complex composition includes inorganic salts, trace elements, organic additives, and functional adjuvants, demonstrating unparalleled advantages in agricultural planting, horticultural cultivation, and plant breeding. As a liquid functional fluid, its physical micro-domain viscosity directly impacts the ultimate application effect. As a core parameter of rheological properties, viscosity influences the fluidity, leaf adhesion, pipeline transport efficiency, and nutrient release rate of liquid nutrients. For example, high-viscosity liquid nutrients may clog drip irrigation systems but can prolong leaf residence time, offering advantages such as long-term residence time, delayed nutrient release, and reduced dissipation. Low-viscosity liquid nutrients, while prone to loss, are more suitable for mechanized spraying, offering easier diffusion, greater permeability, and improved short-term release efficiency. The micro-area viscosity of liquid nutrients is mainly determined by the concentration of ingredients and functional nutritional additives, including high nitrate concentration, high concentration of colloid addition, and nonlinear and sharp increase in viscosity caused by emulsification. Therefore, accurate measurement of micro-area viscosity is crucial for formula optimization and quality control of liquid nutrient products.

[0003] Different users have different demands for liquid nutrients, which is reflected in the different requirements for the relative viscosity of liquid nutrients. At present, liquid nutrients with various functions have been developed. With the continuous rise of crop economy, controlling the appropriate spraying amount and rapid spraying effect can significantly improve the growth status and apparent morphology of crops. It has become a key auxiliary agent for improving crop growth efficiency. In fact, the added value in this field is huge. Traditional liquid nutrient viscosity analysis methods mostly rely on various viscometers for measurement. The sample volume required is large, the measurement time is long, and there are more stringent requirements on transparency and single-phase components. More importantly, it is difficult to accurately measure the micro-area viscosity of liquid nutrients containing a large amount of pseudoplastic fluid, because pseudoplastic fluids will experience shear thinning effect during the shear measurement process. At the same time, it is also difficult to achieve in-situ viscosity measurement at the molecular level.

[0004] In the field of liquid nutrient analysis and testing, photochemical technology can use molecular tools to measure the viscosity of liquid nutrients in micro-areas, ultimately manifesting as a visual light signal. This static response method can effectively avoid the errors caused by traditional shear thinning and effectively improve the optimization and control of liquid nutrient viscosity. Based on this, there is an urgent need to develop a molecular-level tool suitable for liquid nutrient viscosity testing to effectively address the current detection technology bottleneck and promote the refined monitoring and modulation of nutritional supplements. Summary of the Invention

[0005] The purpose of the present invention is to provide a coniferous aldehyde salicylate molecular device and its preparation method and application in order to overcome the shortcomings of the existing technology, and solve the problem that the viscosity of the liquid nutrient micro-area is difficult to accurately measure in the existing technology.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides a coniferous aldehyde salicylate molecular device, the structural formula of the coniferous aldehyde salicylate molecular device is:

[0008]

[0009] The present invention also provides a method for preparing the coniferous aldehyde salicylate molecular device, comprising the following steps:

[0010] The coniferaldehyde solution, the dehydrating agent dispersion and the salicylate derivative solution are mixed, and the mixed solution is subjected to a dehydration condensation reaction to obtain the coniferaldehyde salicylate molecular device.

[0011] Preferably, the concentration of the coniferaldehyde solution is 1-5 mol / L, the concentration of the dehydrating agent dispersion is 1-6 mol / L, and the concentration of the salicylate derivative solution is 1-3 mol / L.

[0012] Preferably, in the mixed solution, the molar ratio of the salicylate derivative, coniferyl aldehyde and the dehydrating agent is 1:1-5:1-6.

[0013] Preferably, in the coniferaldehyde solution, the solvent is one or more of methanol, tetrahydrofuran, ethanol, N,N-dimethylformamide, ethyl acetate and dimethyl sulfoxide; in the salicylate derivative solution, the solvent is an alcohol solvent, and the salicylate derivative is methyl 5-aminosalicylate.

[0014] Preferably, in the dehydrating agent dispersion, the solvent is one or more of methanol, ethanol, propanol, n-butanol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol and 1,3-butanediol, and the dehydrating agent is one or more of sodium carbonate, cesium carbonate, aluminum hydroxide, sodium bicarbonate, potassium carbonate, potassium bicarbonate and magnesium hydroxide.

[0015] Preferably, the specific process of the mixing is: after mixing the coniferyl aldehyde solution and the dehydrating agent dispersion, the salicylate derivative solution is added dropwise, and after the addition is completed, stirring is continued to obtain a mixed solution; the salicylate derivative solution is added dropwise at a rate of 2 to 8 mL / min.

[0016] Preferably, the process of mixing the coniferaldehyde solution and the dehydrating agent dispersion is as follows: first stirring at low speed at room temperature, then heating under high-speed stirring, the low-speed stirring rate is 100-900 rpm, the time is 0.1-2h; the high-speed stirring rate is 900-1800 rpm, the temperature is raised to 70-110°C, and the heating rate is 1-5°C / min;

[0017] The stirring speed is 900-1800 rpm, and the stirring time is 2-24 hours.

[0018] Preferably, the product obtained by the dehydration condensation reaction is sequentially subjected to extraction, crystallization, centrifugation and drying to obtain a coniferous aldehyde salicylate molecular device.

[0019] The present invention also provides an application of the coniferous aldehyde salicylate molecular device in measuring the micro-area viscosity of a liquid nutrient. The molar volume ratio of the coniferous aldehyde salicylate molecular device to the liquid nutrient is 5-80 μmol:0.005L.

[0020] The beneficial effects of the present invention include the following:

[0021] 1) The coniferaldehyde-modified salicylate molecular device of the present invention couples a natural conifer extract (coniferaldehyde) with a natural salicylate derivative (5-aminosalicylic acid methyl ester) to achieve the effective construction of natural organic functional molecules. The required raw materials are abundant in source and belong to natural plant extracts and their derivatives, realizing the development of high-value-added molecular tools for the organic reconstruction of natural products. The overall preparation process adopts a one-step method, which is simple and easy. The amount used during use is extremely small (milligram level), and the application cost is extremely low. In addition, this method of targeted modification of plant extracts is very consistent with the concept of low-carbon sustainable development, avoiding the low yield and large consumption of organic reagents caused by a complicated preparation process.

[0022] 2) The pine aldehyde salicylate molecular device (MHMAAB) of the present invention can respond to changes in the viscosity of the liquid nutrient micro-area, which is helpful for in situ detection of changes in its physical micro-area viscosity. Its viscosity sensitivity coefficient is high (x=0.65), and a flexible and rotatable state can be formed by introducing a Schiff base conjugated single and double bond alternating structure; and its chemical structure is relatively stable, and it can exist for a long time in complex liquid nutrients. Its release wavelength peak is 508nm, which is a typical green light with bright color and extremely strong visualization effect; in addition, the molecular device of the present invention can also release a relatively stable light signal within a relatively wide pH range (3.0~10.0), and can maintain good light stability during long-term irradiation. At the same time, it is insensitive to the polarity of the solvent and has good solvent tolerance.

[0023] 3) The MHMAAB molecular device of the present invention is added to the liquid nutrient and can be used as a molecular tool to measure the viscosity in situ in the microenvironment of the nutrient. The measurement process does not rely on shear and relative motion to achieve detection, and can avoid the consumption of a large amount of sample. The whole process is fast, efficient and convenient, and can effectively measure the viscosity changes of liquid nutrients containing a large amount of pseudoplastic fluid. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 Schematic diagram of the mechanism of the coniferous aldehyde salicylate molecular device of the present invention for detecting the viscosity of liquid nutrient in micro-areas;

[0025] Figure 2 This is a high-resolution mass spectrum of the coniferous aldehyde salicylate molecular device prepared in Example 1;

[0026] Figure 3 This is the nuclear magnetic resonance spectrum of the coniferous aldehyde salicylate molecular device prepared in Example 1;

[0027] Figure 4 Spectra of the coniferyl salicylate molecular device prepared in Example 1 in solutions with different viscosities;

[0028] Figure 5 This is a linear fitting diagram between the optical signal intensity and solution viscosity of the coniferous aldehyde salicylate molecular device prepared in Example 1;

[0029] Figure 6 Spectra of the coniferyl aldehyde salicylate molecular device prepared in Example 1 in solutions with different pH values;

[0030] Figure 7 The results of photostability tests of the coniferous aldehyde salicylate molecular device prepared in Example 1 in glycerol solution and purified water are shown;

[0031] Figure 8 The absorption spectra of the coniferyl salicylate molecular device prepared in Example 1 in different solvents;

[0032] Figure 9 This is the emission spectrum of the coniferyl salicylate molecular device prepared in Example 1 in different liquid nutrients. DETAILED DESCRIPTION

[0033] The present invention provides a coniferous aldehyde salicylate molecular device, the structural formula of the coniferous aldehyde salicylate molecular device is:

[0034]

[0035] In the present invention, the cypress aldehyde salicylate molecular device is methyl 2-hydroxy-5-((3-(4-hydroxy-3-methoxyphenyl)allyl)amino)benzoate, referred to as MHMAAB, with a molecular formula of C 18 H 17 NO5, the theoretical relative molecular mass is 327.33600.

[0036] The present invention also provides a method for preparing the coniferous aldehyde salicylate molecular device, comprising the following steps:

[0037] The coniferaldehyde solution, the dehydrating agent dispersion and the salicylate derivative solution are mixed, and the mixed solution is subjected to a dehydration condensation reaction to obtain the coniferaldehyde salicylate molecular device.

[0038] In the present invention, the concentration of the coniferaldehyde solution is preferably 1 to 5 mol / L, more preferably 2 to 4 mol / L, and more preferably 3 mol / L. The concentration of the dehydrating agent dispersion is preferably 1 to 6 mol / L, more preferably 2 to 5 mol / L, and more preferably 3 to 4 mol / L. The concentration of the salicylate derivative solution is preferably 1 to 3 mol / L, more preferably 1.5 to 2.5 mol / L, and more preferably 2 mol / L.

[0039] In the mixed solution of the present invention, the molar ratio of the salicylates derivative, coniferyl aldehyde and the dehydrating agent is preferably 1:1-5:1-6, more preferably 1:2-4:2-5, and even more preferably 1:3:3-4.

[0040] In the coniferaldehyde solution of the present invention, the solvent is preferably one or more of methanol, tetrahydrofuran, ethanol, N,N-dimethylformamide, ethyl acetate and dimethyl sulfoxide; in the salicylate derivative solution, the solvent is preferably an alcohol solvent, and the salicylate derivative is preferably methyl 5-aminosalicylate.

[0041] In the present invention, coniferaldehyde is dissolved in a solvent and stirred to obtain a coniferaldehyde solution; the stirring temperature is preferably 25-50°C, more preferably 30-45°C, more preferably 35-40°C, and the stirring rate is preferably 300-1000 rpm, more preferably 400-800 rpm, more preferably 500-600 rpm; coniferaldehyde is a natural organic product extracted from the xylem of coniferous trees; a salicylate derivative is dissolved in a solvent and stirred to obtain a salicylate derivative solution, the stirring rate is preferably 300-1000 rpm, more preferably 400-800 rpm, more preferably 500-600 rpm, and the stirring temperature is preferably 25-50°C, more preferably 30-45°C, more preferably 35-40°C.

[0042] In the dehydrating agent dispersion of the present invention, the solvent is preferably one or more of methanol, ethanol, propanol, n-butanol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol and 1,3-butylene glycol, and the dehydrating agent is preferably one or more of sodium carbonate, cesium carbonate, aluminum hydroxide, sodium bicarbonate, potassium carbonate, potassium bicarbonate and magnesium hydroxide.

[0043] In the present invention, the dehydrating agent is dispersed in the solvent and stirred to obtain a dehydrating agent dispersion; the stirring rate is preferably 600-1600 rpm, more preferably 800-1500 rpm, more preferably 1000-1100 rpm, and the stirring temperature is preferably 25-60°C, more preferably 30-55°C, and more preferably 40-45°C.

[0044] In the present invention, the specific process of the mixing is: after the coniferyl aldehyde solution and the dehydrating agent dispersion are mixed, the salicylate derivative solution is added dropwise, and after the addition is completed, stirring is continued to obtain a mixed solution; the salicylate derivative solution is added dropwise at a rate of preferably 2 to 8 mL / min, more preferably 3 to 7 mL / min, and more preferably 5 to 6 mL / min.

[0045] In the present invention, the process of mixing the coniferyl aldehyde solution and the dehydrating agent dispersion is: first stirring at low speed at room temperature, and then heating under high-speed stirring, the low-speed stirring rate is preferably 100-900 rpm, more preferably 200-800 rpm, more preferably 400-500 rpm, and the time is preferably 0.1-2 h, more preferably 0.5-1.5 h, more preferably 1 h; the high-speed stirring rate is preferably 900-1800 rpm, more preferably 1000-1600 rpm, more preferably 1200-1400 rpm, preferably heating to a temperature of 70-110 ° C, more preferably 80-100 ° C, more preferably 90 ° C, and the heating rate is preferably 1-5 ° C / min, more preferably 2-4 ° C / min, more preferably 3 ° C / min;

[0046] The continuous stirring rate is preferably 900-1800 rpm, more preferably 1000-1600 rpm, more preferably 1200-1400 rpm, and the continuous stirring time is preferably 2-24 h, more preferably 5-20 h, more preferably 13-14 h.

[0047] In the present invention, the product obtained by the dehydration condensation reaction is preferably subjected to extraction, crystallization, centrifugation and drying in sequence to obtain the coniferous aldehyde salicylate molecular device.

[0048] In the present invention, the specific process of the extraction is: removing the solvent from the obtained product at -0.09 MPa to -0.07 MPa, preferably at -0.08 MPa, and then extracting with a mixed solution of ethyl acetate and water, collecting the organic phase and removing the solvent under reduced pressure; the volume ratio of ethyl acetate to water is preferably 1 to 5:1, more preferably 2 to 4:1, and more preferably 3:1, and the pressure for removing the solvent under reduced pressure is preferably -0.09 MPa to -0.07 MPa, more preferably -0.08 MPa;

[0049] The specific process of the crystallization is: the extracted product is mixed with ethanol, and the mixed solution is allowed to stand; the volume ratio of water to anhydrous ethanol in the ethanol is preferably 1:1-10, more preferably 1:3-7, more preferably 1:5-6, the solid content of the mixed solution is preferably 10-80 mg / mL, more preferably 20-60 mg / mL, more preferably 40-50 mg / mL, the standing temperature is preferably 1-8°C, more preferably 3-6°C, more preferably 4-5°C, and the standing time is preferably 10-30 hours, more preferably 15-25 hours, more preferably 20 hours;

[0050] The specific process of the centrifugation is as follows: the crystalline solid obtained by crystallization is mixed with ethanol, and the mixed solution is centrifuged; the volume ratio of water to anhydrous ethanol in the ethanol is preferably 1-20:1, more preferably 5-15:1, and more preferably 10:1; the solid content of the mixed solution is preferably 10-80 mg / mL, more preferably 20-70 mg / mL, and more preferably 40-50 mg / mL; the centrifugal speed is preferably 5000-10000 r / min, more preferably 6000-9000 r / min, and more preferably 7000-8000 r / min; the number of centrifugations is preferably 1-3 times, and more preferably 2 times; the time for each centrifugation is preferably 0.1-1.0 h, more preferably 0.3-0.8 h, and more preferably 0.5 h;

[0051] The drying temperature is preferably 50 to 90° C., more preferably 60 to 80° C., and more preferably 70° C. The drying time is preferably 10 to 24 hours, more preferably 13 to 20 hours, and more preferably 14 to 16 hours.

[0052] The present invention also provides an application of the coniferous aldehyde salicylate molecular device in measuring the micro-area viscosity of a liquid nutrient. The molar volume ratio of the coniferous aldehyde salicylate molecular device to the liquid nutrient is 5-80 μmol:0.005L.

[0053] In the present invention, the molar volume ratio of the coniferyl aldehyde salicylate molecular device to the liquid nutrient is preferably 10-70 μmol:0.005L, more preferably 20-60 μmol:0.005L, and even more preferably 40-45 μmol:0.005L.

[0054] The present invention dehydrates and condenses a natural salicylate derivative (5-aminosalicylic acid methyl ester) and coniferaldehyde to obtain a conjugated coupling structure - a coniferaldehyde salicylate molecular device. The preparation process is achieved through a one-step method, and finally presents a conjugated chromogenic chemical structure with rotatable single and double bonds. The structure can rotate freely in a low-viscosity liquid nutrient, and the dissipation mode of the excited state energy is mainly mechanical rotation. The apparent light signal is weak or even unobservable. In contrast, in a high-viscosity liquid nutrient, the rotation is inhibited, and the excited state energy is mainly dissipated through radiation transition. The apparent light signal is strong, making it observable to the naked eye, thereby realizing the in-situ measurement of the viscosity of the liquid nutrient micro-area. As a molecular tool, the cypress aldehyde salicylate molecular device is added to the liquid nutrient and can judge the viscosity of the liquid nutrient according to the intensity of the light signal presented. The stronger the light signal, the thicker the liquid nutrient, the greater the hysteresis force during the flow process, the stronger the relative covering power, adhesion and coating properties, and the longer it can stay at the plant spraying site after spraying. In contrast, when the light signal is weaker, its fluidity, expandability and permeability are stronger, and it can better diffuse to the vicinity of the spraying site and play a wider coverage role. The schematic diagram of the mechanism of the cypress aldehyde salicylate molecular device for detecting the viscosity of the liquid nutrient micro-area is shown in the figure below. Figure 1 shown.

[0055] The coniferous aldehyde salicylate molecular device of the present invention can be used as a signal switch to effectively measure the relative size of micro-area viscosity, which helps to improve the formulation process of liquid nutrients and improve the control effect of their viscosity, better meeting customers' needs for liquid nutrients with different viscosities. The coniferous aldehyde salicylate molecular device prepared based on coniferous tree extract of the present invention can release a strong light signal in the wavelength range of 340 to 680 nm under the excitation of an external light source of 420 nm, with a peak wavelength at 508 nm. It can effectively measure the micro-area viscosity of liquid nutrients and provide a better solution to the problem of difficult measurement of the viscosity of liquid nutrients and microscopic viscosity changes.

[0056] The technical solutions provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0057] In the embodiment, the vacuum oven model is VO-53.

[0058] Example 1

[0059] 356.4 g of coniferaldehyde was dissolved in tetrahydrofuran and stirred at 500 rpm at 35° C. to obtain a 2 mol / L coniferaldehyde solution; 167.2 g of 5-aminosalicylic acid methyl ester was dissolved in methanol and stirred at 500 rpm at 35° C. to obtain a 1 mol / L 5-aminosalicylic acid methyl ester solution; 252 g of sodium bicarbonate was dispersed in anhydrous ethanol and stirred at 1200 rpm at 40° C. to obtain a 3 mol / L dehydrating agent dispersion;

[0060] The coniferyl aldehyde solution and the dehydrating agent dispersion were first stirred at room temperature at a rate of 400 rpm for 1 h, and then the stirring rate was increased to 1300 rpm, and the temperature was raised to 80°C at a rate of 3°C / min. After heating to 80°C, the 5-aminosalicylic acid methyl ester solution was added dropwise to the above-mentioned mixture at a rate of 5 mL / min (the mixed solution was stirred at a rate of 1300 rpm during the addition process). After the addition was completed, the mixture was continuously stirred at a rate of 1300 rpm for 12 h for dehydration condensation reaction to obtain a crude product;

[0061] The crude product was freed of solvent at -0.08 MPa, and then extracted with a mixed solution of ethyl acetate and purified water (the volume ratio of ethyl acetate and purified water was 3:1). The organic phase was collected and then the pressure was reduced to -0.08 MPa to remove the solvent ethyl acetate. The extracted product was mixed with ethanol (the volume ratio of purified water and anhydrous ethanol was 1:5), and the solid content of the mixture was 50 mg / mL. The mixture was allowed to stand at 4°C for 20 hours for crystallization. The crystalline solid obtained by crystallization was mixed with ethanol (the volume ratio of purified water and anhydrous ethanol was 10:1), and the solid content of the mixture was 50 mg / mL. The mixture was centrifuged at a speed of 7000 r / min, the number of centrifugations was 2, and the time of each centrifugation was 0.5 hours. The product after centrifugation was placed in a vacuum oven and dried at 70°C for 16 hours to obtain a cypress aldehyde salicylate molecular device, recorded as MHMAAB.

[0062] The coniferous aldehyde salicylate molecular device obtained in this example weighed 302.1 g, with a yield of 92.3%.

[0063] The relative molecular mass of the coniferous aldehyde salicylate molecular device MHMAAB prepared in Example 1 was analyzed by mass spectrometry. The high-resolution mass spectrum of the coniferous aldehyde salicylate molecular device MHMAAB is shown in FIG. Figure 2 As shown. Figure 2 It can be seen that the relative molecular mass of the cypress aldehyde salicylate molecular device MHMAAB is 327.32914[M] + , the molecular formula of formula I is C 18 H 17NO5, its theoretical relative molecular mass is 327.33600. In terms of relative molecular mass, it can be found that the coniferous aldehyde salicylate molecular device MHMAAB prepared in Example 1 is consistent with the target product formula I.

[0064] The chemical structure of the coniferous aldehyde salicylate molecular device MHMAAB prepared in Example 1 was confirmed by nuclear magnetic resonance. The nuclear magnetic resonance spectrum of the coniferous aldehyde salicylate molecular device MHMAAB is shown in FIG. Figure 3 As shown. Figure 3 It can be seen that 13 CNMR (101MHz, DMSO-d6)δ170.13,164.68,161.93,149.11,148.21,144.82,133.83,127.83,126.78,124.10,122.35,120.18,117.62,116.71,116.01,113.89,55.91,52.68, the carbon skeleton displacement in its molecular structure was confirmed, and it was determined to be the target product, the coniferous aldehyde salicylate molecular device described in Formula I.

[0065] Example 2

[0066] 178.2 g of coniferaldehyde was dissolved in tetrahydrofuran and stirred at 1000 rpm at 25° C. to obtain a coniferaldehyde solution with a concentration of 1 mol / L; 167.2 g of 5-aminosalicylic acid methyl ester was dissolved in methanol and stirred at 1000 rpm at 25° C. to obtain a 5-aminosalicylic acid methyl ester solution with a concentration of 1 mol / L; 84 g of sodium bicarbonate was dispersed in anhydrous ethanol and stirred at 1600 rpm at 25° C. to obtain a dehydrating agent dispersion with a concentration of 1 mol / L;

[0067] The coniferyl aldehyde solution and the dehydrating agent dispersion were first stirred at room temperature at a rate of 900 rpm for 0.1 h, and then the stirring rate was increased to 1800 rpm, and the temperature was raised to 70° C. at a rate of 1° C. / min. After heating to 70° C., the 5-aminosalicylic acid methyl ester solution was added dropwise to the aforementioned mixture at a rate of 2 mL / min (the mixture was stirred at a rate of 1800 rpm during the addition process). After the addition was completed, the mixture was continuously stirred at a rate of 1800 rpm for 2 h for dehydration condensation reaction to obtain a crude product;

[0068] The crude product was freed of solvent at -0.07 MPa, and then extracted with a mixed solution of ethyl acetate and purified water (the volume ratio of ethyl acetate and purified water was 1:1). The organic phase was collected and then the pressure was reduced to -0.07 MPa to remove the solvent ethyl acetate. The extracted product was mixed with ethanol (the volume ratio of purified water and anhydrous ethanol was 1:1), and the solid content of the mixture was 10 mg / mL. The mixture was allowed to stand at 1°C for 10 hours for crystallization. The crystalline solid obtained by crystallization was mixed with ethanol (the volume ratio of purified water and anhydrous ethanol was 1:1), and the solid content of the mixture was 10 mg / mL. The mixture was centrifuged at a speed of 5000 r / min, the number of centrifugations was 1, and the centrifugation time was 1 hour. The product after centrifugation was placed in a vacuum oven and dried at 50°C for 24 hours to obtain a cypress aldehyde salicylate molecular device, recorded as MHMAAB.

[0069] The coniferous aldehyde salicylate molecular device obtained in this example weighed 285.7 g, with a yield of 87.3%.

[0070] The high-resolution mass spectrometry results and nuclear magnetic resonance test results of the coniferous aldehyde salicylate molecular device MHMAAB prepared in this example are consistent with the results obtained in Example 1.

[0071] Example 3

[0072] 891.0 g of coniferaldehyde was dissolved in tetrahydrofuran and stirred at 300 rpm at 50° C. to obtain a coniferaldehyde solution with a concentration of 1 mol / L. 167.2 g of methyl 5-aminosalicylate was dissolved in methanol and stirred at 300 rpm at 50° C. to obtain a 3 mol / L methyl 5-aminosalicylate solution. 504 g of sodium bicarbonate was dispersed in anhydrous ethanol and stirred at 60° C. at 600 rpm to obtain a dehydrating agent dispersion with a concentration of 6 mol / L.

[0073] The coniferyl aldehyde solution and the dehydrating agent dispersion were first stirred at room temperature at a rate of 100 rpm for 2 h, and then the stirring rate was increased to 900 rpm, and the temperature was raised to 110 ° C. at a rate of 5 ° C. / min. After heating to 110 ° C., the 5-aminosalicylic acid methyl ester solution was added dropwise to the aforementioned mixed solution at a rate of 8 mL / min (the mixed solution was stirred at a rate of 900 rpm during the addition process). After the addition was completed, the mixture was continuously stirred at a rate of 900 rpm for 24 h for dehydration condensation reaction to obtain a crude product;

[0074] The crude product was freed of solvent at -0.09 MPa, and then extracted with a mixed solution of ethyl acetate and purified water (the volume ratio of ethyl acetate and purified water was 5:1). The organic phase was collected and then reduced pressure to -0.09 MPa to remove the solvent ethyl acetate. The extracted product was mixed with ethanol (the volume ratio of purified water and anhydrous ethanol was 1:10), and the solid content of the mixture was 80 mg / mL. The mixture was allowed to stand at 8°C for 30 hours for crystallization. The crystalline solid obtained by crystallization was mixed with ethanol (the volume ratio of purified water and anhydrous ethanol was 10:1), and the solid content of the mixture was 80 mg / mL. The mixture was centrifuged at a speed of 10,000 r / min, the number of centrifugations was 3, and the time of each centrifugation was 0.1 hour. The product after centrifugation was placed in a vacuum oven and dried at 90°C for 10 hours to obtain a cypress aldehyde salicylate molecular device, recorded as MHMAAB.

[0075] The coniferous aldehyde salicylate molecular device obtained in this example weighed 294.9 g, with a yield of 90.1%.

[0076] The high-resolution mass spectrometry results and nuclear magnetic resonance test results of the coniferous aldehyde salicylate molecular device MHMAAB prepared in this example are consistent with the results obtained in Example 1.

[0077] Example 4

[0078] 534.6 g of coniferaldehyde was dissolved in N,N-dimethylformamide and stirred at 500 rpm at 35°C to obtain a coniferaldehyde solution with a concentration of 3 mol / L; 167.2 g of 5-aminosalicylic acid methyl ester was dissolved in methanol and stirred at 500 rpm at 35°C to obtain a 5-aminosalicylic acid methyl ester solution with a concentration of 1 mol / L; 212 g of sodium carbonate was dispersed in propanol and stirred at 1200 rpm at 40°C to obtain a dehydrating agent dispersion with a concentration of 2 mol / L; other conditions were the same as in Example 1.

[0079] Example 5

[0080] 712.8 g of coniferaldehyde was dissolved in ethyl acetate and stirred at 1000 rpm at 25° C. to obtain a coniferaldehyde solution with a concentration of 4 mol / L; 167.2 g of 5-aminosalicylic acid methyl ester was dissolved in methanol and stirred at 1000 rpm at 25° C. to obtain a 5-aminosalicylic acid methyl ester solution with a concentration of 1 mol / L; 200.24 g of potassium bicarbonate was dispersed in ethylene glycol and stirred at 1600 rpm at 25° C. to obtain a dehydrating agent dispersion with a concentration of 2 mol / L; other conditions were the same as those in Example 2.

[0081] The coniferous aldehyde salicylate molecular device MHMAAB prepared in Example 1 was subjected to various spectroscopic tests, including viscosity sensitivity test, photostability test, pH stability test, and detection limit test.

[0082] (1) Viscosity sensitivity test of the MHMAAB molecular device of cypress aldehyde salicylate prepared in Example 1: Solutions of different viscosities (1.0 to 956.0 cP) were obtained by mixing glycerol and purified water in different proportions (the corresponding relationship between the viscosity of the solution and the glycerol content in the solution is shown in Table 1, and the sum of the volume fractions of glycerol and purified water remains unchanged). A tetrahydrofuran solution of the MHMAAB molecular device of cypress aldehyde salicylate was added to the solution to make the concentration of MHMAAB 10 μmol / L. The external excitation wavelength was controlled to 420 nm and the test was carried out at room temperature. The spectrum obtained by the test is shown in FIG. Figure 4 shown.

[0083] Table 1 Corresponding relationship between solution viscosity and glycerol content in solution

[0084]

[0085]

[0086] Depend on Figure 4 It can be seen that as the solution viscosity increases from 1.00 cP to 956.00 cP, the observable light signal intensity gradually increases, especially when the volume percentage of glycerol exceeds 50%, the released light signal intensity increases sharply until the volume fraction of purified water is 0% (the volume fraction of glycerol is 99%, and the volume fraction of tetrahydrofuran is 1%), the light signal intensity reaches its maximum value. Compared with the solution system without glycerol added, the light signal intensity increases by 90.6 times.

[0087] The relationship between the optical signal intensity and the solution viscosity is established, where the solution viscosity ranges from 1.00 to 956.00 cP. The optical signal intensity and solution viscosity are converted into logarithmic functions and then fitted into a straight line, which is consistent with -Hoffmann relationship, as shown in the following example: Figure 5 As shown, where x is the viscosity sensitivity coefficient, R 2 is the fitting coefficient, and the specific logarithmic function values ​​are shown in Table 2.

[0088] Table 2 Corresponding relationship between the logarithm of solution viscosity and the logarithm of fluorescence intensity

[0089]

[0090] Depend on Figure 5As shown in Table 2, the viscosity sensitivity coefficient of MHMAAB is 0.65, and the fitting coefficient is 0.99, demonstrating high sensitivity to viscosity. These results demonstrate that the coniferous aldehyde salicylates molecular device MHMAAB can be used as a molecular tool for measuring the viscosity of liquid nutrients at microscales. The apparent light signal strength can be used to determine the viscosity of liquid nutrients, providing a solution for rapid, efficient, and visual formulation.

[0091] (2) pH stability test of the MHMAAB molecular device of cypress aldehyde salicylate prepared in Example 1: 0.63 mg of MHMAAB molecular device of cypress aldehyde salicylate was dissolved in fulvic acid, wherein the concentration of MHMAAB was 2 mmol / L, and added to buffer solutions with pH values ​​of 3 to 10 (pH value 3 to 5: ammonium dihydrogen phosphate / diammonium hydrogen phosphate mixture; pH value 5 to 7: potassium dihydrogen phosphate / dipotassium hydrogen phosphate mixture; pH value 7 to 9: Tris buffer; pH value 9 to 10: sodium bicarbonate / sodium carbonate mixture) respectively, so that the concentration of MHMAAB in the buffer solution was 10 μmol / L. The change of its optical signal intensity was tested at room temperature. The test results are as follows: Figure 6 shown.

[0092] like Figure 6 It can be seen that the fluorescence intensity of the cypress aldehyde salicylate molecular device MHMAAB does not change much in the pH range of 3 to 10, can show good light signal release stability, is not easily affected by pH fluctuations, and has high pH tolerance and universality.

[0093] (3) Light stability test of the cypress aldehyde salicylate molecular device MHMAAB prepared in Example 1: 1.26 mg of the cypress aldehyde salicylate molecular device MHMAAB was dissolved in fulvic acid, wherein the concentration of MHMAAB was 4 mmol / L, and then added to low-viscosity purified water (1.0 cP) and high-viscosity glycerol solution (glycerol volume fraction of 99%, viscosity of 956.0 cP), respectively, so that the concentration of MHMAAB was 10 μmol / L. Under continuous irradiation with an external excitation light source of 420 nm, the change of its light signal intensity within 60 minutes was tested. The test results are as follows: Figure 7 The fluorescence test results are shown in Table 3.

[0094] Table 3 Fluorescence test results

[0095]

[0096] Depend on Figure 7As can be seen from the data obtained in Table 3, the MHMAAB molecular device of coniferyl aldehyde salicylate prepared in Example 1 can still maintain stable light signal release under continuous irradiation of an external light source. It has light signal stability whether in a high-viscosity propylene glycol solution or in a low-viscosity purified water, and is suitable for the micro-area viscosity response of liquid nutrients. It will not be greatly affected even under long-term irradiation.

[0097] (4) Polarity tolerance test of the MHMAAB molecular device prepared in Example 1: 1.88 mg of the MHMAAB molecular device was dissolved in anhydrous ethanol, wherein the concentration of MHMAAB was 6 mmol / L, and then added to a variety of conventional solvents of different polarities so that the concentration of MHMAAB was 10 μmol / L. The optical signal absorption law of the MHMAAB in the atmosphere of solvents with different polarities was tested. The above test was carried out at room temperature. The results are as follows: Figure 8 shown.

[0098] Depend on Figure 8 It can be seen that in a variety of solvents (toluene, dichloromethane, dimethyl sulfoxide, methanol, acetonitrile, tetrahydrofuran, ethyl acetate), the absorbance of the coniferous aldehyde salicylate molecular device MHMAAB is around 0.3, and the peak of its absorption spectrum is around 420nm. The results show that the molecular device MHMAAB is insensitive to the polarity of the solution and is suitable for regulating and monitoring the viscosity changes of liquid nutrients containing multiple polar components.

[0099] Application Example 1

[0100] 1.57 mg of the coniferous aldehyde salicylate molecular device MHMAAB prepared in Example 1 was dissolved in anhydrous ethanol to obtain a 5 mmol / L MHMAAB solution, which was added to liquid nutrient 1, liquid nutrient 2, and liquid nutrient 3, respectively. The concentration of MHMAAB in each liquid nutrient was 10 μmol / L. Then, the emission spectra of the liquid nutrient 1 (General Hydroponics Flora Series), liquid nutrient 2 (CANNATerraAqua), and liquid nutrient 3 (Advanced Nutrients Sensi Grow) added with MHMAAB were tested at room temperature, with an external excitation light source of 420 nm. The obtained emission spectra are shown in the figure below. Figure 9 The optical signal intensity and viscosity of different mixed solutions are shown in Table 4.

[0101] Table 4 Light signal intensity and viscosity of different liquid nutrients

[0102] Sample Optical signal intensity (au) Viscosity (cP) Liquid Nutrition 1 478.1 52.0 Liquid Nutrition 2 831.7 120.2 Liquid Nutrition 3 1555.9 314.8

[0103] Depend on Figure 9 As can be seen from Table 4, the viscosities of the three liquid nutrients are quite different, which leads to large differences in light signal intensities. The light signal intensity of liquid nutrient 1 is the lowest, indicating that its consistency is thinner, and the test data shows that its viscosity is 52.0 cP; the light signal intensity of liquid nutrient 2 is medium, indicating that its consistency has improved to a certain extent, with an overall medium consistency, and the test data shows that its viscosity is 120.2 cP; the light signal intensity of liquid nutrient 3 further increases, and the overall consistency is larger, and the test data shows that its viscosity is 314.8 cP. Different consistencies indicate that there are large differences in their final spraying and retention performance. Liquid nutrients with high viscosity can make the liquid nutrients stay on the leaves longer, while liquid nutrients with low viscosity show better spraying coverage efficiency and can better infiltrate more leaf surfaces.

[0104] The above test results show that the coniferaldehyde salicylate molecular device (MHMAAB) prepared based on coniferaldehyde and salicylate derivatives in the present invention can present light signals of different intensities to liquid nutrients with different micro-area viscosities. The peak wavelength of the released light is 508nm, which is bright green light and has a visual monitoring effect.

[0105] As can be seen from the above embodiments, the present invention provides a coniferous aldolase molecular device and its preparation method and application. The coniferous aldehyde of the present invention and the salicylate derivative are conjugated and coupled in a one-step manner to obtain a functional molecule containing a chromophore, i.e., a coniferous aldolase molecular device (MHMAAB). The coniferous aldolase molecular device of the present invention has a structure of alternating conjugation of single and double bonds, and can present different rotational states in solution atmospheres of different viscosities, and then converted into light signals and released, thereby realizing rapid, efficient, and visual detection of the viscosity of the liquid nutrient microregion. Especially for liquid nutrients containing a large amount of pseudoplastic polymers, traditional detection methods mostly complete the measurement through a shear process, which is difficult to cope with the viscosity measurement of such shear-thinning fluids, while the molecular device of the present invention can be presented in situ by the strength of the light signal, and there is no need to consume a large amount of test samples. Various test results show that the coniferous aldolase molecular device of the present invention has a high sensitivity coefficient (x=0.65), good pH stability and excellent light stability. In addition, the solvent tolerance of the coniferous aldolase molecular device is strong, and it is suitable for sensing the slight changes in the viscosity of the liquid nutrient microregion. In addition, the preparation process of pine cypress aldehyde salicylate molecular device (MHMAAB) does not add any toxic catalysts and heavy metal ions, is green, environmentally friendly and easy to operate, and has a high final yield. The raw materials are derived from natural products, which are abundant and have high added value, and are suitable for large-scale industrial production applications.

[0106] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A coniferous aldehyde salicylate molecular device, characterized in that: The structural formula of the coniferous aldehyde salicylate molecular device is:

2. The method for preparing the coniferous salicylate molecular device according to claim 1, characterized in that: The following steps are included: The coniferaldehyde solution, the dehydrating agent dispersion and the salicylate derivative solution are mixed, and the mixed solution is subjected to a dehydration condensation reaction to obtain the coniferaldehyde salicylate molecular device.

3. The preparation method according to claim 2, characterized in that The concentration of the coniferaldehyde solution is 1-5 mol / L, the concentration of the dehydrating agent dispersion is 1-6 mol / L, and the concentration of the salicylate derivative solution is 1-3 mol / L.

4. The preparation method according to claim 3, characterized in that In the mixed solution, the molar ratio of the salicylate derivative, coniferaldehyde and the dehydrating agent is 1:1-5:1-6.

5. The preparation method according to claim 2 or 4, characterized in that In the coniferaldehyde solution, the solvent is one or more of methanol, tetrahydrofuran, ethanol, N,N-dimethylformamide, ethyl acetate and dimethyl sulfoxide; in the salicylate derivative solution, the solvent is an alcohol solvent, and the salicylate derivative is 5-aminosalicylic acid methyl ester.

6. The preparation method according to claim 5, characterized in that In the dehydrating agent dispersion, the solvent is one or more of methanol, ethanol, propanol, n-butanol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol and 1,3-butylene glycol, and the dehydrating agent is one or more of sodium carbonate, cesium carbonate, aluminum hydroxide, sodium bicarbonate, potassium carbonate, potassium bicarbonate and magnesium hydroxide.

7. The preparation method according to claim 6, characterized in that The specific mixing process is: after the coniferyl aldehyde solution and the dehydrating agent dispersion are mixed, the salicylate derivative solution is added dropwise, and after the addition is completed, stirring is continued to obtain a mixed solution; the salicylate derivative solution is added dropwise at a rate of 2 to 8 mL / min.

8. The preparation method according to claim 7, characterized in that The process of mixing the coniferaldehyde solution and the dehydrating agent dispersion is as follows: first stirring at low speed at room temperature, then heating under high-speed stirring, the low-speed stirring rate is 100-900 rpm, the time is 0.1-2 hours; the high-speed stirring rate is 900-1800 rpm, the temperature is raised to 70-110°C, and the heating rate is 1-5°C / min; The stirring speed is 900-1800 rpm, and the stirring time is 2-24 hours.

9. The preparation method according to claim 7, characterized in that The product obtained by the dehydration condensation reaction is sequentially subjected to extraction, crystallization, centrifugation and drying to obtain the coniferous aldehyde salicylate molecular device.

10. Application of the coniferous aldehyde salicylate molecular device according to claim 1 in measuring the viscosity of liquid nutrient in micro-areas, characterized in that: The molar volume ratio of the coniferous aldehyde salicylate molecular device to the liquid nutrient is 5-80 μmol:0.005L.

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