ACQ fluorescent probe composition, cmc determination method, stain removal concentration determination method, and detergent dispensing control method and system

Abstract

An ACQ fluorescent probe composition, which is a probe solution used for directly determining the cmc concentration of a surfactant and comprises probe molecules and an auxiliary agent, the probe molecules being fluorescent molecules having aggregation-caused quenching (ACQ) properties and the auxiliary agent comprising one or more non-volatile organic solvents, wherein the boiling point of the organic solvent is 100℃ or more, and the distance between the Hansen solubility parameters, i.e. the HSP distance Ra, of the probe molecules and the organic solvent is less than 17 (MPa)1 / 2. Further provided are a cmc determination method which uses the ACQ fluorescent probe composition, a stain removal concentration determination method, a detergent dispensing control method, and a detergent dispensing control system.

Description

ACQ fluorescent probe composition, CMC measurement method, stain cleaning concentration determination method, detergent dosing control method and system Technical Field

[0001] The present invention relates to an ACQ fluorescent probe composition, a CMC measurement method using the ACQ fluorescent probe composition, a stain cleaning concentration determination method, and a detergent dosing control method and system. Background Art

[0002] Detergents typically consist of surfactants, builders, and additives. Current automatic washing machines primarily rely on the weight of the fabric load to add detergent, but detergent dosage varies significantly between washing machine brands, limiting their adaptability and flexibility for different detergents and washing scenarios.

[0003] The inventors have discovered that when the concentration of surfactants in the wash water reaches the critical micelle concentration (CMC), the washing effect reaches the optimal cost-effective balance point. Therefore, they hope to use monitoring whether the concentration of surfactants in the wash water reaches the CMC as a basis for automatically adding detergent.

[0004] Furthermore, cleaning clothes with different stains requires different detergent concentrations, which may be greater than or equal to the critical micelle concentration (cmc) described above. Therefore, different threshold concentrations can be determined for each of the three types of stains: oil, color, and invisible. When the detergent concentration in the wash water reaches or exceeds the threshold concentration, it can be assumed that the stains have been cleaned. Therefore, it is also desirable to monitor whether the surfactant concentration in the wash water has reached the threshold concentration as a basis for automatically dispensing detergent.

[0005] In other words, the automatic detergent dispensing control can be based on the following two methods: using the CMC concentration as the best cost-effectiveness factor, which provides the highest cleaning efficiency; or using the stain removal threshold concentration as the best cleaning performance factor. Typically, the stain removal threshold concentration is ≥ CMC.

[0006] Conventional methods for detecting the cmc of surfactants include surface tension method, conductivity method and fluorescent probe method, but the surface tension method requires a series of complicated operations; the conductivity method cannot detect nonionic surfactants and surfactants with lower conductivity; the fluorescent probe method has the problem that the sensitivity and accuracy of the probe are not high. For example, pyrene is usually used as a probe in the fluorescent probe method, and the cmc is determined by measuring the fluorescence peak intensity and ratio of the first and third emission peaks (373nm and 384nm) of pyrene. However, when the pyrene probe is used for online testing of cmc, there may be a peak position drift that causes the selected 373nm and 384nm to be not at the peak inflection point, thereby detecting the problem of insufficient sensitivity, and it is necessary to find a probe molecule with more suitable fluorescent properties. In addition, current fluorescence spectrophotometers also have the problem that instrumentation is difficult to miniaturize and the cost is high.

[0007] Fluorescent probe molecules are roughly divided into AIE molecules that adopt the aggregation-induced emission (AIE) strategy and ACQ molecules that adopt the aggregation-induced luminescence quenching (ACQ) strategy. We have previously successfully developed an AIE fluorescent probe composition comprising AIE molecules and auxiliary agents (Patent Document 1). However, compared with AIE molecules, the types and sources of ACQ molecules are more extensive. Most ACQ molecules already have efficient preparation methods and commercially available products. At the same time, compared with AIE molecules, ACQ molecules have lower probe costs and higher application cost-effectiveness while ensuring similar detection accuracy. Therefore, it is expected to develop a low-cost and easy-to-use ACQ fluorescent probe composition that can be used in various scenarios such as monitoring the cmc of washing water, and has huge application prospects.

[0008] The current problem is that most of the ACQ probe molecules used to measure cmc are poorly water-soluble substances. In order to dissolve these hydrophobic substances, they are usually dissolved in organic solvents such as tetrahydrofuran and ethanol. However, it is generally believed in the art that the presence of these organic solvents can cause deviations in the cmc measurement results. Therefore, in order to avoid such problems, it is necessary to control the amount of organic solvent to a very small amount (non-patent document 1), or evaporate the volatile organic solvent before measurement or wait for it to evaporate naturally and remove it (non-patent documents 2 and 3). Because these organic solvents are easily volatile, in actual application environments, ACQ probe solutions are not easy to store and keep for a long time, or need to be processed in advance before use, resulting in cumbersome operations in the cmc measurement process, reduced accuracy of measurement sampling, and lack of ease of use.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: CN116554861A

[0012] Non-patent literature

[0013] Non-patent document 1: "Role of Curcumin on The Determination of The Critical Micellar Concentration by Absorbance, Fluorescence and Fluorescence Anisotropy Techniques, J Photochem. Photobiol., B, 2012, 115(3), 9-15

[0014] Non-patent literature 2: Determination of CTAB critical micelle concentration by pyrene fluorescence probe spectroscopy, Petrochemical Technology and Application, 2007, 25(1), 48-50

[0015] Non-patent document 3: Fluorescence Emission of Pyrene in Surfactant Solution, Advance in Colloid and Interface Science, 215 (2015), 1-12

[0016] Summary of the Invention

[0017] Problems to be solved by the invention

[0018] The present invention was developed in response to the aforementioned challenges and aims to provide an inexpensive, easy-to-use ACQ fluorescent probe composition that can be stored as a stable solution for long periods of time and can be directly used to measure the cmc concentration of surfactant solutions. The present invention also provides a method for measuring the cmc concentration of surfactant solutions, a method for determining stain cleaning concentration, and a method for controlling detergent dosage using this ACQ fluorescent probe composition.

[0019] Methods used to solve problems

[0020] The inventors conducted in-depth research to address the above-mentioned issues and discovered that by using a specific combination of ACQ probe molecules and an auxiliary agent, not only can the ACQ molecules be well dissolved in the auxiliary agent, forming a stable probe solution that can be stored for a long time and directly used to measure the cmc of the surfactant solution; but the effect of the presence of the auxiliary agent on the cmc measurement results is also controlled within an allowable range, enabling accurate measurement results to be obtained, thus effectively solving the above-mentioned problems.

[0021] The present invention provides an ACQ fluorescent probe composition, characterized in that it is a probe solution for directly measuring the cmc concentration of a surfactant, comprising a probe molecule and an auxiliary agent, wherein the probe molecule is a fluorescent molecule having an aggregation-induced luminescence quenching (ACQ) property, and the auxiliary agent comprises one or more non-volatile organic solvents, wherein the boiling point of the organic solvent is above 100°C, and the distance between the probe molecule and the organic solvent, i.e., the Hansen solubility parameter (HSP) distance Ra, is within 17 (MPa). 1 / 2 the following.

[0022] Preferably, the Hansen Solubility Parameter (HSP) of the probe molecule is 15 (MPa) 1 / 2 ~35(MPa) 1 / 2 .

[0023] Preferably, the solubility of the probe molecule in the auxiliary agent is classified as soluble or above.

[0024] Preferably, the difference Δδ between the Hansen solubility parameter of the auxiliary agent and the probe molecule is -3 (MPa) 1 / 2 ~+12(MPa) 1 / 2 .

[0025] Preferably, the viscosity of the auxiliary agent is 30 mPa·s or less.

[0026] Preferably, the additive is soluble in water and has a density of 0.9 g / cm 3 ~1.2g / cm 3 .

[0027] Preferably, the flash point of the auxiliary agent is above 60°C.

[0028] Preferably, the probe molecule is an ACQ molecule whose luminescence strategy is based on changes in fluorescence intensity or characteristic wavelength, including ACQ molecules with blue-shift characteristics of characteristic wavelength, ACQ molecules with red-shift characteristics of characteristic wavelength, and ACQ molecules with unchanged characteristic wavelength.

[0029] Preferably, the probe molecule is one or more ACQ molecules selected from curcumin (CUR), Nile red (NR), coumarin (C480), rhodamine B (RhB), N-phenyl-1-naphthylamine (NPN) and pyrene (PYR).

[0030] Preferably, the auxiliary agent contains one or more organic solvents selected from n-butanol, ethylene glycol, N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), dimethylformamide (DMF), diethylene glycol monoethyl ether (DGME), ethyl glycolate, polyethylene glycol 200 (PEG200), 1,3-butanediol and 1,5-pentanediol.

[0031] Preferably, the probe molecule is at least one ACQ molecule selected from curcumin (CUR), Nile red (NR) and coumarin (C480), and the auxiliary agent contains at least one organic solvent selected from N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), polyethylene glycol 200 (PEG200) and diethylene glycol monoethyl ether (DGME).

[0032] The present invention also provides a method for measuring the cmc of a surfactant solution, which is characterized by comprising the following steps in sequence:

[0033] Preparation steps: prepare a series of surfactant solutions at different concentrations.

[0034] Probe adding step: adding a certain amount of probe solution to the surfactant solution,

[0035] Detection steps: Use the detection mechanism to detect the fluorescence response value of each surfactant solution, and

[0036] Determining step: drawing a fluorescence response value-concentration curve based on the results obtained in the detecting step, wherein the fluorescence response value-concentration curve has at least a first platform region and an ascending region, and determining the concentration corresponding to the inflection point where the fluorescence response value changes from the first platform region to the ascending region as the cmc of the surfactant solution;

[0037] Wherein, the probe solution is the ACQ fluorescent probe composition of the present invention.

[0038] Preferably, in the determining step, the concentration corresponding to the intersection of the fitting straight line of the first platform area and the fitting straight line of the rising area in the fluorescence response value-concentration curve is determined as the cmc of the surfactant solution.

[0039] Preferably, relative to 10 ml of the surfactant solution, the amount of solvent added to the probe solution does not exceed 400 μl, and the probe working concentration of the probe molecule does not exceed 10 ug / ml.

[0040] Preferably, the surfactant comprises at least one of anionic surfactants, nonionic surfactants and amphoteric surfactants.

[0041] Preferably, the surfactant solution further comprises a fluorescent whitening agent.

[0042] The present invention also provides a method for determining the concentration of stain cleaning, which is characterized by comprising the following steps:

[0043] Liquid preparation step: adding a first predetermined amount of detergent into a washing machine filled with a predetermined amount of water and clothes, stirring and mixing to obtain washing water,

[0044] Sampling step: sampling from the washing water and adding a small amount of probe solution to obtain the washing water to be tested.

[0045] Detection step: using the detection mechanism to detect the fluorescence response value S of the washing water to be tested,

[0046] Determination step: judging whether the detergent concentration of the washing water to be tested is a stain cleaning concentration according to whether the detected fluorescence response value S reaches or exceeds a preset cleaning response threshold S0; if it does not reach the preset cleaning response threshold S0, the determination result is "no"; if it reaches or exceeds the preset cleaning response threshold S0, the determination result is "yes", and

[0047] A control step: based on the determination result of the determination step, controlling the subsequent addition of the detergent in the liquid preparation step, wherein, if the determination result is "no", returning to the liquid preparation step to continue adding a second predetermined amount of detergent, and then performing subsequent sampling steps, detection steps and determination steps; if the determination result is "yes", stopping the addition of the detergent and outputting the determination result.

[0048] Wherein, the probe solution is the ACQ fluorescent probe composition of the present invention.

[0049] Preferably, the cleaning response threshold S0 is a fluorescence response value corresponding to the critical micelle concentration cmc of the washing water, or a fluorescence response value corresponding to the stain cleaning threshold concentration Ct.

[0050] The stain cleaning threshold concentration Ct is the minimum concentration required to clean clothes with different stains, and is determined by the following formula 3: Ct = cmc × (1 + a) (Formula 3)

[0051] In Formula 3, cmc is the critical micelle concentration of the washing water, and a is the cleaning coefficient, which ranges from 0≤a≤10. Depending on the type and degree of dirtiness of the stains, a may take different values.

[0052] Preferably, the washing response threshold S0 is determined by the following formula 4 or formula 5: S0 = β × S max (Equation 4) S0=S blank +β×(S max -S blank ) (Formula 5)

[0053] Where S maxS is the maximum fluorescence intensity or maximum voltage response value of the washing water, or the second platform value in the fluorescence response value-concentration curve of the washing water; blank is the background fluorescence intensity or minimum voltage response value of the washing water, or the first platform value in the fluorescence response value-concentration curve of the washing water; β is the threshold percentage, the unit is 100%, and the range is 0<β<1. Corresponding to different types and degrees of dirtiness of stains, β can take different values.

[0054] The present invention also provides a detergent dispensing control method, which is characterized by comprising the following steps:

[0055] Liquid preparation step: adding a first predetermined amount of the detergent into the inner tub according to the weight of the laundry and the amount of water inlet in the washing device, and mixing and stirring with the water in the inner tub to obtain washing water or detergent solution;

[0056] Sampling step: collecting a predetermined amount of the washing water or detergent solution from the inner barrel as a sample;

[0057] Liquid collection step: Take out a small amount of probe solution and add it to the sample.

[0058] Mixing step: mixing the sample and the probe solution to obtain a test solution;

[0059] Detection step: detecting the fluorescence response value of the test liquid and outputting a detection signal S;

[0060] Determination step: receiving the detection signal S, and determining whether the detergent concentration of the test liquid reaches the critical micelle concentration cmc or the preset cleaning threshold concentration Ct according to whether the detection signal S reaches or exceeds a preset response threshold S0, wherein the cleaning threshold concentration Ct is greater than or equal to the critical micelle concentration cmc; and

[0061] Controlling step: Based on the judgment result of the judging step, controlling the subsequent addition of the detergent, wherein, if the judgment result is that the critical micelle concentration or the preset cleaning threshold concentration has not been reached, returning to the liquid preparation step to continue adding a second predetermined amount of the detergent into the inner barrel; if the judgment result is that the critical micelle concentration or the preset cleaning threshold concentration has been reached, stopping the addition of the detergent,

[0062] Wherein, the probe solution is the ACQ fluorescent probe composition of the present invention.

[0063] Preferably, the control step also includes a number limiting step: a number threshold representing the maximum number of times the detergent is added is pre-set. If, after the detergent has been added more than once, although the judgment result of the judgment step is still that the critical micelle concentration or the preset cleaning threshold concentration has not been reached, the number of times the detergent has been added has reached the number threshold, then the detergent is stopped from being added in the liquid preparation step.

[0064] The present invention also provides a detergent dispensing control system for automatically controlling the amount of detergent dispensed into a washing device, wherein the washing device comprises: an inner tub for placing laundry and water to be washed; a storage device for storing detergent; and a dispensing device for dispensing a first predetermined amount of the detergent into the inner tub and mixing the detergent with the water in the inner tub to obtain washing water or a detergent solution, wherein:

[0065] The detergent delivery control system comprises:

[0066] a liquid storage device for storing a probe solution;

[0067] a sampling device for collecting a predetermined amount of the wash water or detergent solution from the inner tub as a sample;

[0068] a liquid taking device, used for taking out a small amount of probe solution from the liquid storage device and adding it to the sample;

[0069] Mixing device: used for mixing the sample and the probe solution to obtain the test solution;

[0070] A detection device, used to detect the fluorescence response value of the test liquid and output a detection signal S;

[0071] a judgment device for receiving the detection signal S and judging whether the detergent concentration of the test liquid reaches the critical micelle concentration cmc or the preset cleaning threshold concentration Ct according to whether the detection signal S reaches or exceeds a preset response threshold S0, wherein the cleaning threshold concentration Ct is greater than or equal to the critical micelle concentration cmc;

[0072] a CMC determining device for, under the condition that there is no laundry in the inner tub, using the dispensing device to dispense a predetermined amount of the detergent into the inner tub in batches, and repeatedly performing multiple sets of measurements using the liquid storage device, the sampling device, the liquid collection device, the mixing device, and the detection device, to determine the critical micelle concentration of the detergent solution based on a plurality of detection data corresponding to different detergent concentrations output by the detection device; and

[0073] a control device for controlling the subsequent delivery of the detergent by the delivery device of the washing device based on the determination result of the determination device;

[0074] If the judgment result of the judgment device is that the critical micelle concentration cmc or the preset cleaning threshold concentration Ct has not been reached, the control device controls the dispensing device to continue dispensing the second predetermined amount of the detergent into the inner drum of the washing device; if the judgment result of the judgment device is that the critical micelle concentration cmc or the preset cleaning threshold concentration Ct has been reached or exceeded, the control device controls the dispensing device to stop dispensing the detergent;

[0075] Wherein, the probe solution is the ACQ fluorescent probe composition of the present invention.

[0076] Preferably, the cleaning response threshold S0 is a fluorescence response value corresponding to the critical micelle concentration cmc of the detergent solution, or a fluorescence response value corresponding to the stain cleaning threshold concentration Ct.

[0077] The critical micelle concentration cmc is a pre-determined critical micelle concentration of a detergent solution, or a critical micelle concentration of a detergent solution or washing water determined online by the cmc determination device.

[0078] The cleaning threshold concentration Ct is calculated using the following formula 3: Ct = cmc × (1 + a) (Formula 3)

[0079] Where a is the cleaning coefficient, ranging from 0≤a≤10. It can take different values ​​depending on the type and degree of dirtiness of the stains.

[0080] Alternatively, the wash response threshold S0 is determined by the following formula 4 or formula 5: S0 = β × S max (Equation 4) S0=S blank +β×(S max -S blank ) (Formula 5)

[0081] Where S max S is the maximum fluorescence intensity or maximum voltage response value of the washing water, or the second platform value in the fluorescence response value-concentration curve of the washing water; blank is the background fluorescence intensity or minimum voltage response value of the washing water, or the first platform value in the fluorescence response value-concentration curve of the washing water; β is the threshold percentage, the unit is 100%, and the range is 0<β<1. Corresponding to different types and degrees of dirtiness of stains, β can take different values.

[0082] Preferably, a number threshold indicating the maximum number of times the detergent is dispensed is also set in the control device. After the dispensing device has dispensed the detergent more than once, if the judgment result of the judgment device is still that the critical micelle concentration or the preset cleaning threshold concentration has not been reached, but the number of times the detergent has been dispensed has reached the number threshold, the control device controls the dispensing device to stop dispensing the detergent.

[0083] Effects of the Invention

[0084] The ACQ fluorescent probe composition of the present invention utilizes a specific combination of ACQ probe molecules and an auxiliary agent. The ACQ molecules can be dissolved in the auxiliary agent to form a stable probe solution that can be stored for a long time and has good operability during measurement. Furthermore, the composition can accurately detect cmc within a suitable concentration range, thereby providing an inexpensive and easy-to-use ACQ fluorescent probe composition that is expected to be applied in a wide range of fields, including the laundry, detergent, and washing machine industries.

[0085] By using the above-mentioned ACQ fluorescent probe composition, a more convenient and accurate cmc measurement method, a stain cleaning concentration determination method for online judgment of whether clothes with different stains can be washed, and a detergent dispensing control method and detergent dispensing control system for automatically controlling the amount of detergent in the washing machine based on cost-effectiveness or cleaning effect can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0086] FIG1 shows the fluorescence spectra of the ACQ fluorescent probe composition (CUR-DGME) in Example 1 of the present invention measured in different concentrations of Supreme Biotechnology (Bright White) detergent solutions (abbreviated as ZZLB) using a fluorescence spectrophotometer.

[0087] Figure 2 is a fluorescence response value-detergent concentration curve plotted by selecting the peak height data of the fluorescence intensity at the maximum emission wavelength Em = 495 nm in the ACQ fluorescent probe composition (CUR-DGME) in Example 1 of the present invention as the fluorescence response value, and the cmc value or cmc range is determined using the fitted straight line intersection method.

[0088] Figure 3 is a fluorescence response value-detergent concentration curve plotted using the voltage value obtained by using a fluorescence photodetector (CD detector) as the fluorescence response value of the ACQ fluorescent probe composition (NR-NMP) in Example 2 of the present invention in different concentrations of Supreme Biotechnology (Bright White) washing water, and the inflection point method is used to determine the cmc value or cmc range.

[0089] Figure 4 shows the fluorescence response value-detergent concentration curve obtained when the cmc of Supreme Biotechnology (Bright White) detergent solution (abbreviated as ZZLB) was measured using various ACQ fluorescent probe compositions in Example 3 of the present invention. (A) CUR probe composition, the adjuvants are BUT, EG, NMP, and PEG200 (labeled as PEG in the figure); (B) NR probe composition, the adjuvants are BUT, NMP, and PEG200.

[0090] FIG5 is a graph showing the cmc of detergent solutions of various brands measured using a surface tension method in Example 4 of the present invention.

[0091] FIG6 is a graph showing fluorescence response values ​​versus detergent concentration when two ACQ fluorescent probe compositions of the present invention are used to measure the cmc of detergent solutions of various brands in Example 4 of the present invention, (A) CUR probe composition; (B) NR probe composition.

[0092] FIG7 is a graph showing fluorescence response values ​​versus detergent concentration when two ACQ fluorescent probe compositions are used to test the cmc of detergent solutions or washing water in different scenarios in Example 5 of the present invention, (A) CUR probe composition; (B) NR probe composition.

[0093] Figure 8 is a graph showing the fluorescence response value-detergent concentration curve when the cmc of other types of products containing surfactant ingredients (softener, oxygen bleach, disinfectant) is tested using two ACQ fluorescent probe compositions in Example 6 of the present invention: (A) CUR probe composition; (B) NR probe composition. DETAILED DESCRIPTION

[0094] Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments and can be implemented with appropriate modifications within the scope of the purpose of the present invention.

[0095] In this specification, the numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the minimum and maximum values, respectively. Unless otherwise specified, the maximum and minimum values ​​representing each preferred range can be combined with each other.

[0096] In this specification, a "surfactant solution" refers to an aqueous solution containing a surfactant. When a surfactant is used to wash clothes or articles (referred to as clothing or laundry), the surfactant is referred to as a "detergent," and the aqueous solution of the surfactant is referred to as a "detergent solution" or "washing water." Specifically, a "detergent solution" includes an aqueous solution prepared by directly mixing and diluting a detergent with water. This includes an aqueous solution obtained by adding detergent and water to the inner drum of an industrial washing machine or a domestic washing machine without adding clothes or fabrics. On the other hand, a detergent solution obtained by placing clothes or fabrics in an industrial washing machine or a domestic washing machine, adding detergent and water, and mixing the detergent and water in the inner drum is referred to as "washing water." Furthermore, if the surfactant concentration is present in a surfactant solution containing multiple surfactant components, unless otherwise specified, the concentration refers to the total concentration of the multiple surfactant components present in the surfactant solution.

[0097] In this specification, the “fluorescence response value” refers to the FL fluorescence intensity (au) when measured using a fluorescence spectrophotometer, and refers to the response voltage value (V) when measured using a fluorescence photodetector (abbreviated as CD detector).

[0098] In this specification, the units of Hansen solubility parameter HSP values ​​(δd, δp, δh) and HSP distance Ra are (MPa). 1 / 2 However, for the sake of simplicity, the units of Ra values ​​and HSP values ​​are sometimes omitted and only numerical values ​​are expressed.

[0099] (ACQ fluorescent probe composition)

[0100] The ACQ fluorescent probe composition of the present invention is characterized in that it is a probe solution for directly measuring the cmc concentration of a surfactant, comprising a probe molecule and an auxiliary agent, wherein the probe molecule is a fluorescent molecule having an aggregation-induced luminescence quenching (ACQ) property, and the auxiliary agent comprises one or more non-volatile organic solvents, wherein the boiling point of the organic solvent is above 100°C; and the distance Ra between the Hansen solubility parameter of the probe molecule and the organic solvent is within 17 (MPa). 1 / 2 the following.

[0101] In the present invention, "direct measurement" means that the ACQ fluorescent probe composition of the present invention can be directly added to the test solution in the form of a probe solution without pretreatment (such as waiting for the organic solvent to evaporate after adding the test solution) for subsequent CMC measurement.

[0102] In the present invention, "non-volatility" refers to the property of an organic solvent that maintains its volume over long periods of storage at room temperature and pressure. Generally, the higher the boiling point of an organic solvent, the lower its volatility. Therefore, in the present invention, the boiling point of the organic solvent contained in the additive is specified to be 100°C or higher, thereby providing non-volatility. If the organic solvent is non-volatile, the probe solution formed by dissolving the probe of the present invention in the additive is considered to be stable and can be stored for a long time.

[0103] In the present invention, the Hansen solubility parameter (HSP) is used to measure the molecular polarity and intermolecular forces of the ACQ probe molecule. In the following description, the Hansen solubility parameter is sometimes appropriately expressed as "HSP". In order to form a stable probe solution in an aqueous system of a surfactant solution and to show obvious aggregation-induced luminescence quenching (ACQ) phenomenon at an appropriate cmc concentration, the Hansen solubility parameter δ of the ACQ probe molecule of the present invention is preferably set to 15 (MPa) 1 / 2 ~35(MPa) 1 / 2 , more preferably 20 (MPa) 1 / 2 ~25(MPa) 1 / 2 In this specification, the unit of the Hansen solubility parameter may be omitted and expressed, that is, the Hansen solubility parameter δ is preferably 15 to 35, and more preferably 20 to 25.

[0104] Furthermore, the Hansen Solubility Parameter (HSP) distance Ra can be used to predict the solubility of ACQ probe molecules in organic solvents. Generally, when the absolute value of the HSP distance Ra between the ACQ probe molecule and the organic solvent is 17 or less, it can be considered that the ACQ probe molecule is fully soluble in the organic solvent, forming a relatively stable probe solution.

[0105] In the auxiliary agent of the present invention, the organic solvent that meets the above requirements can be used alone or in combination of multiple. In addition, in addition to the above-mentioned non-volatile organic solvent as an essential component, the auxiliary agent can also contain a small amount of volatile organic solvent or inorganic solvent (such as water) as an optional component without affecting the solubility of the probe or the accuracy of the CMC measurement results. That is, in the present invention, the auxiliary agent can be only one organic solvent, a mixed solvent of multiple organic solvents, or a mixed solvent of an organic solvent and an inorganic solvent.

[0106] The content of the non-volatile organic solvent in the auxiliary agent is not particularly limited. As an essential component, its content exceeds 0%, and can be 10% by volume or more, preferably 30% by volume or more, more preferably 50% by volume or more, further preferably 70% by volume or more, further preferably 90% by volume or more, and most preferably 100% by volume.

[0107] In order to form a stable and clear probe solution with sufficient probe stock solution concentration, the ACQ probe molecules of the present invention must have good solubility in the organic solvent used as an auxiliary agent.

[0108] When the ACQ probe molecule is soluble in an additive, the cmc can sometimes be determined even with a low solubility. Therefore, conventional quantitative descriptions of solubility may not be able to accurately characterize it. Furthermore, considering the applicability of different probe molecules, the concept of solubility classification is adopted in the present invention to qualitatively classify the solubility of ACQ probe molecules.

[0109] According to the solubility classification reference standard described in Table 1 below, the solubility of the ACQ probe molecule of the present invention in the additive is classified as "soluble" or higher, preferably "relatively soluble" or higher, and more preferably "freely soluble." In other words, the solubility of the ACQ probe molecule in the additive is ≥ 0.1 mg / ml (≥ 0.01%), preferably ≥ 1 mg / ml (≥ 0.1%), and more preferably ≥ 10 mg / ml (≥ 1%).

[0110] For example, if the solubility of CUR (curcumin) in a specific solvent at room temperature is ≥0.1 mg / ml (i.e., ≥0.01%), it can be classified as "soluble" or higher in that solvent. This CUR molecule can be used as a probe in conjunction with that solvent to form the ACQ fluorescent probe composition of the present invention. In fact, in the present invention, when CUR is formulated into a probe solution at a concentration of 1.0 mg / ml, it exhibits suitable fluorescence properties and can be measured using CMC.

[0111] Table 1

[0112] In the fluorescent probe composition of the present invention, since the ACQ probe molecules are dissolved in the auxiliary agent, and the auxiliary agent contains a non-volatile organic solvent with a boiling point of more than 100°C, a stable and homogeneous probe solution can be formed, which is convenient for long-term storage and preservation, and no volume reduction or concentration change will occur even after long-term storage. In addition, the fluorescent probe composition can be transferred and taken out before use, and can be directly used to measure the cmc concentration of the surfactant without volatilization of the solvent, thereby shortening the operation time. In addition, if the ACQ molecule is not dissolved in the organic solvent and added directly, the amount of probe added will be inaccurate and the mixing will be uneven, affecting the accuracy of the cmc measurement results. Since the fluorescent probe composition of the present invention exists in the form of a solution, a sampling mechanism (such as a peristaltic pump and matching pipelines) can be used for accurate weighing, transfer and sample addition, which is convenient for operation.

[0113] Practical applications of the ACQ fluorescent probe composition of the present invention include using the ACQ fluorescent probe composition as a probe solution to measure the cmc of a surfactant solution, or determining whether stains on clothing with different stains can be cleaned, thereby providing a suitable judgment basis for controlling the dosage of detergent in washing equipment.

[0114] Hereinafter, various components contained in the ACQ fluorescent probe composition of the present invention will be described in detail.

[0115] [ACQ molecule]

[0116] The probe molecule of the present invention is a fluorescent molecule with ACQ properties.

[0117] Aggregation-Caused Quenching (ACQ) is a phenomenon observed in ACQ fluorescent molecules. While fluorescent molecules emit light in dilute solutions, their fluorescence intensity significantly decreases or even disappears once they aggregate or solidify. Common ACQ molecules include curcumin, fluorescein, rhodamine, Nile Red, pyrene, and perylene. These molecules typically possess a planar conjugated system and are relatively rigid. In good solvents and low-concentration solutions, fluorescent molecules exist as independent molecules, emitting strong fluorescence upon excitation by specific light. However, in poor solvents or when the concentration increases to a certain level, aggregation occurs, increasing the intermolecular π-π forces. Most of the excitation energy is then converted into non-radiative transitions (such as molecular thermal motion), resulting in a decrease or disappearance of fluorescence.

[0118] ACQ molecules exhibit completely different fluorescence properties in different aggregation or dispersion states in solution and micelles, including fluorescence emission intensity (none / weak / strong) and characteristic wavelength (spectral blue shift / unchanged / red shift). Based on these characteristics, it can be used as a probe to determine the cmc of surfactant solutions.

[0119] In the present invention, hydrophobic ACQ molecules can be used for cmc measurement. These ACQ molecules are dissolved as probes in a suitable organic solvent to form a probe solution, i.e., an ACQ fluorescent probe composition. When such a probe solution is added to water or a low-concentration aqueous surfactant solution, the ACQ molecules aggregate due to their hydrophobicity and exhibit low or no fluorescence. However, when the surfactant reaches the cmc concentration and forms micelles, the hydrophobic core of the micelles acts as a good solvent for the ACQ fluorescent molecules and promotes their dissolution. When the ACQ molecules are dissolved as single molecules in the micelles, they emit strong characteristic fluorescence, thus demonstrating a distinct ACQ signature within a suitable concentration range.

[0120] In addition, some hydrophilic or partially hydrophilic ACQ molecules can also be used for CMC determination. For example, Rhodamine B is a hydrophilic ACQ molecule that is completely soluble in water, forming a homogeneous and stable solution. In aqueous solution, Rhodamine B is dispersed at low concentrations and emits strong fluorescence, while at high concentrations, it aggregates and loses fluorescence, consistent with the ACQ characteristic of fluorescing when dissolved and dispersed in a dilute, good solvent and quenching when aggregated. The inventors speculate that the mechanism is that Rhodamine B's hydrophilic-hydrophobic amphiphilic structure enables it to insert into the micelle barrier layer of the surfactant and participate in micelle formation, with the hydrophilic end located in the hydrophilic surface layer of the micelle and the hydrophobic end remaining in the barrier layer. Increased local concentration leads to enhanced fluorescence intensity or wavelength shift, resulting in different fluorescence characteristics in different systems with and without micelles. However, based on its structural characteristics and pH test results, the accuracy of measurement results using Rhodamine B as a probe may be significantly affected by the pH value of the solution.

[0121] As described above, the luminescence mechanism of the ACQ probe molecules that can be used in the present invention can be based not only on changes in fluorescence intensity caused by solubilization of the hydrophobic core, but also on red-shifts / blue-shifts in the characteristic emission wavelength caused by the amphiphilic structure of the molecule entering the palisade layer or the interior of the micelle. In other words, the luminescence strategy of the ACQ probe molecules of the present invention is based on, but not limited to, changes in fluorescence intensity or changes in characteristic wavelength, wherein the change in fluorescence intensity can be a change from none to one or from weak to strong, and the change in characteristic wavelength includes a change in wavelength red-shift (Red-Shift) or wavelength blue-shift (Blue-Shift).

[0122] That is, the ACQ probe molecules of the present invention include ACQ molecules having a blue-shifted characteristic wavelength, ACQ molecules having a red-shifted characteristic wavelength, and ACQ molecules having a constant characteristic wavelength. Specific examples include pyrene, Nile Red, curcumin, coumarin, sodium 8-anilino-1-naphthalenesulfonate, N-phenyl-1-naphthylamine, rhodamine B, dansyl chloride, 6-propionyl-2-(dimethylamino)naphthalene, neutral red, fluorescein, anthracene, and lycopene. Preferred are Nile Red, curcumin, coumarin, N-phenyl-1-naphthylamine, rhodamine B, and pyrene. More preferred are ACQ molecules having a constant characteristic wavelength or a blue-shifted characteristic, such as curcumin, Nile Red, and coumarin.

[0123] The present inventors first preliminarily screened several commonly used fluorescent probe molecules based on the requirements of easy availability and low toxicity of fluorescent reagents, including the following substances: PYR (pyrene): It is a molecule with fluorescent properties and is often used in the research of biological markers and fluorescent probes; NR (Nile Red): It is a common lipophilic fluorescent dye, which is often used to stain lipid substances such as lipids; CUR (Curcumin): It is a multi-purpose natural fluorescent probe and drug molecule; C480 (Coumarin): It is a common (heavy) metal detection fluorescent probe; ANS (8-anilino-1-naphthalenesulfonate sodium): It is a fluorescent probe widely used in the study of protein structure and conformational changes; NPN (N-phenyl-1-naphthylamine): It is a commonly used fluorescent dye with a wide range of applications, including biomedicine, materials science and chemical analysis; RhB (Rhodamine B): It is a cell fluorescent stain commonly used in laboratories.

[0124] The chemical structures of these fluorescent molecules are shown below:

[0125] In order to determine whether these fluorescent probe molecules can form stable probe solutions, the present inventors dissolved these probe molecules in N-methylpyrrolidone (NMP). The results showed that all of them could form clear solutions and emit fluorescence of various colors in the solution state.

[0126] Using the probe solution formed above, we tested detergent solutions prepared at a range of concentrations (including a directly prepared Supreme Clean solution and a Supreme Brightening detergent solution containing a fluorescent brightener). Specifically, based on the fluorescence spectrophotometer's measurement results, we selected an appropriate wavelength and plotted a fluorescence response value-concentration curve, with detergent concentration plotted on the abscissa and fluorescence intensity plotted on the ordinate. The transition interval from the plateau to the rising zone of the curve was visually determined, corresponding to the range of CMC values. The results are shown in Table 2 below.

[0127] Meanings of the abbreviations in Table 2: PYR: pyrene; ANS: 8-anilino-1-naphthalenesulfonic acid sodium salt; NPN: N-phenyl-1-naphthylamine; C480: coumarin 480 (density is 1.3 g / cm 3 ); CUR: curcumin; NR: Nile red. " / " indicates not measured. In addition, the meanings of the comprehensive evaluation column in the table are as follows: ×: not measurable; △: available, but with large errors or weak anti-interference ability; ○: preferred result; ◎: more preferred result.

[0128] In addition, the spectral parameters of various probes, the values of solubility parameter δ, the changes in characteristic wavelengths, and the cmc control results measured by the surface tension method are also shown in Table 2.

[0129] Table 2

[0130] * The solubility parameters δ of PYR, CUR, and RhB are the reported values in the literature. The solubility parameters δ of the remaining probe molecules are HSP values calculated based on the functional group contribution method. There is no numerical reference for the sulfonic acid functional group in ANS, and it is calculated based on the phosphoric acid functional group.

[0131] As shown in Table 2, the characteristic wavelength of the fluorescent probe molecule may change before and after the cmc of the surfactant. △λ = λ (surfactant concentration ≥ cmc) - λ (surfactant concentration < cmc). When △λ > 0, it is a red shift (i.e., the wavelength becomes larger); when △λ < 0, it is a blue shift (i.e., the wavelength becomes smaller); when △λ = 0, the wavelength remains unchanged.

[0132] The results in Table 2 show that in the system of the probe composition with NMP as the additive, the fluorescence response value of the water-soluble ANS probe basically shows a linear relationship with the detergent concentration, without an obvious inflection point. Therefore, it is difficult to measure the cmc. PYR and NPN can be used as probes to measure the cmc in the directly prepared Supreme Clean solution, and the deviation of the measurement results is small. However, the measurement results of PYR in the actually used Supreme Bright White washing water are affected by various factors and have a large deviation. NPN is greatly affected by the fluorescent whitening agent in the measurement of the Supreme Bright White washing water, resulting in the inability to measure the cmc. The comprehensive evaluation results show that the four fluorescent molecules C480, CUR, NR, and RhB are suitable for measuring the cmc concentration of the surfactant solution or the actually used washing water in the system with NMP as the additive, and they are preferred ACQ molecules.

[0133] Table 2 also shows that the deviations between the RhB and C480 results are slightly larger. Curcumin (CUR) and Nile Red (NR) are more preferred ACQ molecules in the present invention. The cmc values ​​measured for the directly prepared Supreme Clean solution (excluding fluorescent whitening agents) both validate each other and are consistent with the result obtained by surface tension analysis (0.066 g / L), demonstrating high accuracy. Furthermore, in the actual Supreme Brightening wash water containing fluorescent whitening agents, the cmc values ​​measured by both methods also match the result obtained by surface tension analysis (0.3 g / L), demonstrating no interference from the fluorescent whitening agents (CBS or FB-33) present. The inventors speculate that this is because the Ex / Em of fluorescent whitening agent 33# (FB-33) is 370 / 430nm, and the Ex / Em of sodium distyryl biphenyl disulfonate (CBS) is 340 / 425nm; and the emission peak of NR is at 638nm, which is not within the emission peak range of the fluorescent whitening agent, so NR is not affected by it; although the emission wavelength of CUR falls within the fluorescence emission peak range of the fluorescent whitening agent, the response of the fluorescent whitening agent at its excitation wavelength of 430nm is not obvious, that is, the fluorescent whitening agent has no fluorescent emission at this excitation wavelength, so the interference of the fluorescent whitening agent can also be avoided.

[0134] In the present invention, the Hansen Solubility Parameter (HSP) δ is used to measure the molecular polarity and intermolecular forces of the ACQ probe molecule. Referring to the data in Table 2, it can be seen that the solubility parameter δ of the ACQ probe molecule capable of forming a stable probe solution is generally in the range of 15 to 35. Therefore, the Hansen Solubility Parameter δ of the ACQ probe molecule is preferably 15 to 35. In addition, from the perspective of the accuracy of the cmc measurement, the solubility parameter of the ACQ probe molecule is more preferably in the range of 20 to 25.

[0135] The above screening results are merely illustrative of the ACQ fluorescent probe compositions of the present invention. When using different organic solvents as additives, different ACQ fluorescent probe compositions may exhibit different fluorescence properties and ACQ characteristics. Therefore, the ACQ fluorescent molecules used in the present invention are not limited to the aforementioned RhB, C480, CUR, and NR, and the additive is not limited to NMP. Suitable combinations of ACQ fluorescent molecules and additives can be screened based on specific application scenarios and needs.

[0136] [Additives]

[0137] The auxiliary agent in the ACQ fluorescent probe composition of the present invention comprises one or more non-volatile organic solvents. The type of the organic solvent mainly depends on its volatility, the solubility and fluorescence properties of the ACQ molecule in the organic solvent, and the like.

[0138] In the present invention, when the auxiliary agent contains only one organic solvent, the properties of the auxiliary agent (viscosity, density, flash point, etc.) refer to the properties of the organic solvent; when the auxiliary agent is a mixed solvent of multiple organic solvents or a mixed solvent of an organic solvent and an inorganic solvent, the properties of the auxiliary agent refer to the properties of the mixed solvent.

[0139] In the prior art, to measure cmc using ACQ molecules as probes, the molecules are typically pre-dissolved in a volatile organic solvent, such as methanol, ethanol, benzene, tetrahydrofuran, or dioxane, and then the solvent is removed before measurement. However, these organic solvents are highly volatile, colorless liquids with low boiling and flash points. When formulated into the probe solution of the present invention, the prepared mother solution is difficult to store for long periods of time, and the solution volume and probe concentration are susceptible to fluctuations.

[0140] The inventors used curcumin (CUR) as a specific probe molecule and, through studying and screening the physical properties of a series of organic solvents, identified some specific organic solvents that can serve as adjuvants for the aforementioned ACQ molecules. These organic solvents have sufficient solubility for ACQ molecules, are nonvolatile, and enable curcumin (CUR) to exhibit distinct ACQ properties within an appropriate concentration range of a specific surfactant solution.

[0141] Table 3 shows the volatility, water solubility, density, viscosity and probe solubility of a series of organic solvents investigated by the present inventors.

[0142] Table 3. Properties of each solvent

[0143] * 1 The ACQ probe molecule is CUR, and its solubility is described in the solubility classification above, where >1% is readily soluble, 0.1-1% is relatively soluble, 0.01-0.1% is soluble, and <0.01% is poorly soluble / insoluble.

[0144] * 2 The solubility of solvents in water was classified according to the solvent data in Pub Chem, where >10% was readily soluble, 1-10% was soluble, 0.01-1% was slightly soluble, and <0.01% was poorly soluble / insoluble.

[0145] In order to form a stable probe solution that can be stored for a long time, the auxiliary agent in the ACQ fluorescent probe composition of the present invention must contain one or more non-volatile organic solvents.

[0146] In the present invention, the boiling point value is used to evaluate the volatility of the organic solvent. Generally speaking, the lower the boiling point of the organic solvent, the greater its volatility. As can be seen from Table 3, the volatile organic solvents commonly used in the art (such as acetone) have low boiling points and are too volatile, making them unsuitable as auxiliary agents for the stable probe solution of the present invention.

[0147] As a suitable auxiliary agent, the boiling point of the nonvolatile organic solvent of the present invention is specified to be 100° C. or higher, preferably 120° C. or higher, and more preferably 150° C. or higher.

[0148] In addition, in order to form a uniform, clear solution with sufficient probe concentration, the ACQ probe molecule of the present invention must have good solubility in the organic solvent used as an auxiliary agent. Preferably, the solubility grade of the probe is at least soluble, that is, the solubility of the probe molecule in the organic solvent is preferably above 0.1 mg / ml (0.01%).

[0149] When screening suitable organic solvents for a selected probe molecule, it is difficult to conduct solubility tests on each of a large number of solvents. If the solubility of the solvent relative to the probe can be evaluated and predicted in advance, the time and cost required for screening auxiliary agents can be greatly reduced.

[0150] In the present invention, in order to establish the intrinsic relationship between the microstructure and macroscopic solubility of the probe molecule, the Hansen Solubility Parameter theory (HSP theory) is used to evaluate and predict the solubility of ACQ molecules in organic solvents.

[0151] There are many ways to calculate solubility parameters. In HSP theory, the surface energy of solute and solvent is classified by three energy terms. These three energy terms are dispersion δd, polarity δp, and hydrogen bond δh, and the unit is MPa. 1 / 2 Based on the HSP theory, if the HSP values ​​of the solute are (δd1, δp1, δh1) and the HSP values ​​of the solvent are (δd2, δp2, δh2), then the distance Ra of the Hansen solubility parameters between these solutes and the solvent (abbreviated as HSP distance Ra) can be expressed by the following formula 1.

[0152] Ra 2 =4(δd1-δd2) 2 +(δp1-δp2) 2 +(δh1-δh2) 2 (Formula 1)

[0153] The smaller the HSP distance Ra, the easier it is for the solute to dissolve in the solvent. In a probe-organic solvent system, the organic solvent serves as the dispersion medium, and the probe molecules, acting as the solute, serve as the dispersed phase. Generally speaking, a dispersed state is achieved when Ra ≤ 20, a moderately dispersed state when Ra ≤ 15, a highly dispersed state when Ra ≤ 10, and an ultra-highly dispersed state when Ra ≤ 5. By comparing the Ra values ​​between the solute and different solvents, a solvent with similar interaction forces with the solute can be found to achieve higher solubility.

[0154] The present inventors used the probe molecule curcumin (CUR) as an example of solute and investigated the literature values ​​or calculated values ​​of the solubility parameters of various organic solvents or mixed solvents of organic solvents and inorganic solvents, as well as the measured results of solubility fractionation. The results are shown in Table 4-1 below.

[0155] Table 4-1 Solubility parameters of curcumin (CUR) and various solvents

[0156] *: Indicates that the listed δ values ​​are calculated values, where the δ values ​​of single solvents are calculated based on the functional group contribution method, and the δ values ​​of mixed solvents are calculated based on the δ values ​​of single solvents and the solvent ratio contribution method.

[0157] As can be seen from Table 4-1, except for a few non-polar organic solvents (such as cyclohexane and toluene), the HSP distance Ra value has a roughly corresponding relationship with the measured solubility classification. Among them, the vast majority of organic solvents or mixed solvents with HSP distance Ra values ​​below 17 have good solubility for the ACQ probe molecule (CUR), and their solubility classification is soluble or above; when the Ra value is below 15, preferably below 12, the solubility of the ACQ probe molecule in the solvent predicted by the HSP distance Ra value is more consistent with the results of the measured solubility classification.

[0158] Therefore, in the present invention, in order to obtain good probe solubility, the HSP distance Ra value between the ACQ probe molecule and the organic solvent or mixed solvent as an auxiliary agent is set to 17 or less, preferably 15 or less, and more preferably 12 or less.

[0159] However, predicting solubility using the HSP distance Ra value can sometimes result in errors. For example, the HSP distance Ra value between acetonitrile and the probe molecule (16.858) is much larger than the HSP distance Ra value between n-octanol and the probe molecule (3.753). However, actual measurements show that acetonitrile solubility is significantly better than n-octanol solubility. The reason for this is unclear, but it may be due to the influence of intermolecular forces (such as hydrogen bonds), polarity, or molecular conformation on solubility. To address this, we further introduce the difference Δδ in the Hansen solubility parameter δ to correct the prediction results.

[0160] According to the solubility parameter theory proposed by Hildebrand, the total δ value of the solubility parameter (abbreviated as δ) is the vector sum of the three components of dispersion δd, polarity δp, and hydrogen bond δh (see Equation 2 below). When the difference between the total δ of the solute and the solution, that is, the δ difference (△δ), is less than a constant value, the solution is relatively stable, which is the so-called compatibility theory.

[0161] δ 2 =δd 2 +δp 2 +δh 2 (Formula 2)

[0162] As can be seen from Table 4-1, the total δ value of the CUR molecule as the ACQ probe molecule is 22.579, while the total δ values ​​of most organic solvents or mixed solvents that have good solubility for the CUR molecule (solubility classification is soluble or above) are in the range of 19 to 34.

[0163] Therefore, in the present invention, from the perspective of compatibility between the solute and the solvent, the δ difference between the total δ of the organic solvent or mixed solvent serving as the auxiliary agent and the total δ of the ACQ probe molecules (i.e., Δδ = total δ of the auxiliary agent minus total δ of the ACQ probe molecules) is preferably in the range of -3 to +12, more preferably in the range of -2.5 to +10, even more preferably in the range of -2 to +4, and even more preferably in the range of -2.0 to +2.5. Furthermore, from the perspective of achieving a more stable probe solution, the absolute value of the δ difference is preferably 2 or less, and more preferably 1 or less.

[0164] As can be seen from Table 4-1, first, based on the requirement that the organic solvent must be non-volatile, acetone, acetonitrile, and ethanol (see Table 3) need to be excluded. Secondly, organic solvents or mixed solvents that simultaneously meet the requirements of an HSP distance Ra of 17 or less and a δ difference of -3 to +12 include: dibutyl phthalate, n-octanol, polyethylene glycol 200 (PEG200), diethylene glycol ethyl ether (DGME), ethylene glycol monophenyl ether, N-ethylpyrrolidone (NEP), N-methylpyrrolidone (NMP), n-butanol, ethyl glycolate, dimethylformamide (DMF), dimethyl sulfoxide, 1,5-pentanediol, 1,3-butanediol (1,3-BDO), ethylene glycol, and mixed solvents of these organic solvents (such as DGME, 1,3-BDO, and NMP) with water in specific ratios. These solvents have good solubility and compatibility with the ACQ probe molecules of the present invention and can be used as adjuvants of the present invention.

[0165] Furthermore, as preferred adjuvants of the present invention, solvents that simultaneously meet the requirements of the organic solvent HSP distance Ra being less than 15, the δ difference being -2.5 to +10, and non-volatility include: dibutyl phthalate, n-octanol, polyethylene glycol 200 (PEG200), diethylene glycol ethyl ether (DGME), ethylene glycol monophenyl ether, N-ethylpyrrolidone (NEP), N-methylpyrrolidone (NMP), n-butanol, ethyl glycolate, dimethylformamide (DMF), dimethyl sulfoxide, 1,5-pentanediol, 1,3-butanediol (1,3-BDO), and mixtures of these organic solvents and water. Mixed solvents with specific ratios include, for example, a mixed solvent of DGME and water (9:1), a mixed solvent of DGME and water (7:3), a mixed solvent of 1,3-BDO and water (8:2), etc.; as more preferred adjuvants of the present invention, solvents that simultaneously meet the requirements that the HSP distance Ra of the organic solvent is less than 12 and the δ difference is in the range of -2.0 to +2.5 include: diethylene glycol monoethyl ether (DGME), ethylene glycol monophenyl ether, N-ethylpyrrolidone (NEP), N-methylpyrrolidone (NMP), n-butanol, a mixed solvent of DGME and water (9:1), and dimethylformamide (DMF).

[0166] The range of organic solvents selected by the above method is essentially consistent with the range of organic solvents subsequently screened by the inventors through extensive experimentation. Therefore, the present invention can predict and screen suitable combinations of ACQ probe molecules and additives by combining factors such as the boiling point of the organic solvent and the solubility parameter δ of the probe molecule and the organic solvent.

[0167] That is, when determining the combination of probes and auxiliary agents in the ACQ fluorescent probe composition of the present invention, the volatility of the auxiliary agent itself is first considered. With reference to the boiling point value of the solvent, a large number of organic solvents can be selected as alternative auxiliary agents. Then, by pre-checking or calculating the values ​​of the solubility parameters of the selected probe molecule and the alternative organic solvent, the solubility and compatibility of the probe molecule in various auxiliary agents can be better predicted, thereby greatly improving the screening efficiency of auxiliary agents and saving costs. This has important guiding significance in the preparation of the ACQ fluorescent probe composition of the present invention.

[0168] Generally speaking, HSP values ​​(δd, δp, δh) for most small molecules can be found in the literature, but polymers usually require calculation. δd, δp, and δh values ​​for different substances can be found in the Hansen Solubility Parameters manual and the accompanying tables in the Edproperties of polymer. Calculations based on the functional group contribution method are also possible, but this method may underestimate δh values ​​because it doesn't account for intermolecular interactions.

[0169] When preparing the ACQ fluorescent probe composition of the present invention, the organic solvent in the auxiliary agent must not only be non-volatile and have good solubility for the probe, but also other properties of the auxiliary agent (such as viscosity, water solubility, density, flash point, etc.) must be considered.

[0170] From the perspective of easy and uniform dispersion of the prepared probe solution, convenient sampling and accurate weighing, the viscosity of the organic solvent used as an auxiliary agent is preferably 30 mPa·s or less, more preferably 25 mPa·s or less, and even more preferably 10 mPa·s or less.

[0171] For organic solvents with high viscosity, the viscosity can be reduced by combining multiple solvents to form a mixed solvent. For example, the viscosity of 1,3-butanediol (1,3-BDO) is 130 mPa·s. By adding a certain proportion of a low-viscosity solvent such as NMP, DGME, or water to create a mixed solvent, the viscosity can be significantly reduced.

[0172] In order to form a stable test solution system, the organic solvent is preferably miscible with water. In the present invention, "miscible with water" means that the organic solvent has a certain solubility in water, specifically, it can be slightly soluble, soluble or readily soluble in water (see Table 3).

[0173] In addition, in order to ensure that the probe solution can be uniformly dispersed in the surfactant solution during the CMC measurement, the density of the organic solvent in the additive is preferably 0.9 to 1.2 g / cm 3In this way, the probe solution can be easily evenly diffused in the water; if the density difference between the organic solvent and water is large, uneven diffusion is likely to occur. Since the probe solution is generally added from above the liquid to be tested, the density of the organic solvent can be slightly greater than the density of water, preferably controlled at 1.2g / cm 3 If the density is less than 0.9g / cm 3 , it is easy to float above the aqueous solution, which is not conducive to the diffusion of probe molecules in the aqueous solution.

[0174] The density of the mixed solvent can be adjusted by combining multiple solvents. For example, the density of n-butanol is only 0.811 g / cm 3 , can be mixed with solvents with higher density such as ethylene glycol or NMP to obtain a mixed solvent with appropriate density.

[0175] In addition, from the perspective of safety, the auxiliary agent of the present invention is preferably a low-toxic, slightly toxic or non-toxic organic solvent with a flash point of 60° C. or higher, preferably 70° C. or higher, and more preferably 75° C. or higher.

[0176] Similarly, a combination of multiple solvents can also be used to adjust the flash point of the mixed solvent. For example, n-butanol has a better solubility (more soluble) for the probe (CUR), but its flash point is relatively low, only 37°C, while ethylene glycol has a slightly worse solubility for the probe (CUR), but its flash point is 110°C. Therefore, by mixing a small amount of n-butanol into ethylene glycol (for example, 995 ethylene glycol-5 n-butanol (v / v)), a good balance can be achieved in terms of solubility and flash point properties.

[0177] Taking into account the various property parameters of the organic solvent, it can be seen that the auxiliary agent of the present invention is preferably selected from one or more of n-butanol, ethylene glycol, NMP, NEP, DMF, DGME, ethyl glycolate, polyethylene glycol 200, 1.3-butanediol and 1,5-pentanediol, more preferably selected from one or more of n-butanol, ethylene glycol, NMP, NEP, DGME, polyethylene glycol 200, more preferably NMP, NEP, DGME, polyethylene glycol 200.

[0178] In addition, when the type of ACQ molecule changes, the preferred range of the corresponding adjuvant may also change accordingly. As mentioned above, this mainly depends on the matching degree of the solubility parameters of the two.

[0179] For example, when pyrene or rhodamine B is used as a solute, the solubility parameters in Tables 4-2 and 4-3 below can be used to evaluate and predict its solubility in various solvents.

[0180] Table 4-2 Solubility parameters of pyrene in various solvents

[0181] Table 4-3 Solubility parameters of Rhodamine B in various solvents

[0182] In Table 4-3, the HSP distance Ra between Rhodamine B and water is 23.968, but it is "soluble" in water. The inventors speculate that the reason may be that Rhodamine B itself is an ionic form of a quaternary ammonium salt, and the tertiary amine groups it contains can form hydrogen bonds after protonation in an aqueous solution, that is, there is a strong intermolecular interaction between Rhodamine B and water. However, this strong interaction cannot be taken into account when calculating using HSP parameters, so the calculated results are not completely consistent with the actual test results.

[0183] When determining the specific combination of fluorescent molecules and auxiliary agents in the ACQ fluorescent probe composition of the present invention, the difference from the AIE fluorescent probe composition we studied before is that, unlike the AIE fluorescent probe composition that focuses on the hydrophilic-hydrophobic amphiphilic molecular structure of the auxiliary agent, the present invention pays more attention to the differences in properties such as solubility, dispersibility, and molecular polarity between the auxiliary agent and the ACQ molecule. This may be because most AIE molecules are non-polar macromolecular structures, and the auxiliary agent has a hydrophilic-hydrophobic amphiphilic structure. The hydrophobic site is adsorbed on the surface of the AIE molecule to form a hydrophilic layer, which is beneficial for its stable dispersion in the aqueous system. Therefore, in a low-concentration surfactant solution, the AIE molecules exist in a dispersed state and do not emit light. When the concentration exceeds the cmc and micelles are formed, the auxiliary agent follows the AIE molecules into the fence layer of the micelles and aggregates to emit light. In the fluorescent probe composition of the present invention, the auxiliary agent has a high solubility in water, and there is a competitive relationship between the dissolution of the auxiliary agent and the ACQ molecules in the hydrophilic-hydrophobic system. When the ACQ fluorescent probe composition is added to a surfactant solution or washing water, the diffusion rate of the auxiliary agent is significantly faster than that of the ACQ probe molecules. The auxiliary agent preferentially dissolves in water, while the probe tends to aggregate in water due to its hydrophobicity. Since the auxiliary agent molecules can only affect the solubility and stability of the ACQ probe molecules in water to a certain extent, in a low-concentration surfactant solution, the ACQ probe molecules exist in an aggregated state and do not emit light. When the concentration of the surfactant exceeds the cmc and micelles are formed, the auxiliary agent cannot follow the ACQ molecules into the micelles, and the ACQ molecules enter the interior of the micelles as monomers and emit light.

[0184] [Other ingredients]

[0185] The ACQ fluorescent probe composition of the present invention may include, in addition to the ACQ molecules and auxiliary agents as probes, other components such as stabilizers, preservatives and other additives without affecting the ACQ effect.

[0186] When other components are contained, the total content of the other components is preferably less than 5% by mass, more preferably less than 1% by mass, relative to the total amount of the ACQ probe composition.

[0187] [ACQ fluorescent probe composition]

[0188] The ACQ fluorescent probe composition of the present invention comprises ACQ molecules as probes and auxiliary agents, wherein the auxiliary agents comprise one or more non-volatile organic solvents.

[0189] The fluorescence emission spectrum of ACQ molecules is inherently characterized by their fluorescent groups. However, the properties of their fluorescence emission (including excitation / emission wavelengths and fluorescence intensity) vary depending on the environment in which the molecules are placed. Therefore, further investigation of the fluorescence performance and measurement feasibility of specific combinations of ACQ molecules and additives in actual measurement environments is required.

[0190] The inventors used CUR and NR as specific probe compounds. Based on the screening results of the above method, they studied the solubility and fluorescence properties of these two probe molecules in various solvents. They also investigated the feasibility of using the ACQ fluorescent probe composition containing the probe and the auxiliary agent as a probe solution to actually measure the cmc of the surfactant solution. The results are shown in Table 5.

[0191] Table 5

[0192] *NR is poorly soluble in EG, and a large amount of NR cannot be dissolved. As a result, when NR-EG is used as a probe combination for measurement, the fluorescence intensity of the probe is extremely weak after being added to the test solution.

[0193] In Table 5, "UV irradiation results" refer to the fluorescence emission observed when the target probe molecule (such as 1 mg / ml CUR or 1 mM NR) is dissolved in the corresponding solvent and the clarified mother liquor or the supernatant of the mother liquor is irradiated under UV light. At this time, no surfactant is added. Therefore, this result can reflect the following situations from a macroscopic perspective: 1) the solubility of the probe, 2) the homogeneity / dispersibility of the probe, 3) whether there is an interaction between the probe and the solvent, and 4) the change in the peak wavelength of the fluorescence emission of the probe.

[0194] Generally speaking, strong fluorescence can only be emitted when the probe molecules have a certain solubility in the additive, good homogeneity / dispersion, and no or only weak interaction with the solvent. The color change of the fluorescence can reflect the wavelength shift of the maximum emission intensity of the corresponding probe.

[0195] Therefore, the “UV irradiation results” in Table 5 help illustrate the dispersibility of the probe in the solvent on a macroscopic level. For example, the probe molecules CUR and NR are strongly fluorescent in good solvents, but non-fluorescent / weakly fluorescent in poor solvents. They also reflect the interaction between the solvent and the probe. For example, the benzene ring structure of ethylene glycol monophenyl ether may cause the probe molecules CUR and NR to exhibit similar aggregation quenching results, resulting in a significant decrease in fluorescence intensity.

[0196] The results in the "CMC Measurement" column in Table 5 indicate the feasibility of using the probe-solvent composition (probe solution) for actual CMC measurement. Specifically, the corresponding probe-solvent composition was added to surfactant solutions of varying concentrations. The fluorescence of the homogeneously dispersed probe-solvent-surfactant aqueous solution was measured to determine whether a fluorescence difference existed, thereby determining whether CMC measurement was feasible.

[0197] The results in Table 5 show that when using n-butanol, n-octanol, dibutyl phthalate, NMP, polyethylene glycol 200, DGME, ethyl glycolate, 1,3-butanediol, and 1,5-pentanediol as solvents, both CUR and NR emit strong or weak fluorescence, indicating that the probe molecules have certain solubility and dispersibility in these solvents. In contrast, when using ethylene glycol as a solvent, CUR can be partially dissolved but the fluorescence intensity is weak. NR has poor solubility or dispersibility, showing poor solubility and almost no visible fluorescence.

[0198] In addition, although ethylene glycol monophenyl ether meets the requirements of low volatility and good probe solubility of organic solvents, the probe molecules only emit extremely weak fluorescence after being dissolved in ethylene glycol monophenyl ether. This may be because the benzene ring structure of the solvent molecules themselves produces an interaction force with the probe molecules, resulting in a weakened ability of the probe molecules to convert excitation light into fluorescence, so only extremely weak fluorescence is produced in this solvent.

[0199] And then, use the various single solvents or mixed solvents in table 5 to carry out the test of cmc determination to same detergent (Supreme Biotechnology laundry detergent) respectively.Result shows, the probe composition that n-octanol, dibutyl phthalate and these three kinds of solvents of ethylene glycol monophenyl ether are formulated has all occurred the oil-water stratification of washing water solution and probe solution in testing process, and probe is more inclined to be dissolved in organic solvent layer rather than aqueous phase.When adopting ethylene glycol monophenyl ether as auxiliary agent, because ethylene glycol monophenyl ether is partially soluble in water, though stratification occurs, the cmc determination of detergent can still be achieved, and n-octanol and dibutyl phthalate are immiscible with water (referring to table 3), therefore, obvious oil-water stratification occurs in the probe solution prepared after adding surfactant solution, the density of n-octanol is less, thus probe composition is in upper strata, the density of dibutyl phthalate is larger, thus probe composition is in lower floor, because oil-water stratification causes the solution that can't obtain homogeneous dispersion, and all without obvious fluorescence difference between different concentrations surfactant solution aqueous phase and organic phase, therefore can't carry out cmc determination. This indicates that the water solubility of the adjuvant will also significantly affect the measurement results of the probe composition.

[0200] In addition, the measured results in Table 5 show that when CUR and NR are used as probes and n-butanol, ethylene glycol, NMP, polyethylene glycol 200, DGME, ethyl glycolate, 1,3-butanediol, and 1,5-pentanediol are used as auxiliary agents, detectable fluorescence signal changes are generated when the probe solution is added to the aqueous solution of the surfactant. That is, the above organic solvents can be used alone as auxiliary agents to more accurately monitor cmc.

[0201] In addition to the non-volatility of the organic solvent, the solubility and water solubility of the probe, and the ability of the fluorescence characteristics to monitor CMC, other physical and chemical properties of the probe solution also need to be considered comprehensively, such as viscosity, density, flash point, safety, etc.

[0202] For example, although ethylene glycol, 1,3-butanediol, and 1,5-pentanediol meet the characteristics of low volatility and good water solubility, their high viscosity and low fluidity are not conducive to the dissolution, addition, and diffusion of the probe; the density of n-butanol is relatively small, and when the probe-butanol composition is added to the washing water solution, it is not easy to diffuse or diffuses slowly, which will lead to uneven distribution of the probe in the solution; although ethyl glycolate meets the requirements of low volatility and probe solubility of organic solvents, and the probe solution emits strong fluorescence, its flash point is relatively low (62°C), and there are many things to pay attention to in the storage and safety of the probe composition.

[0203] Taking into account the physicochemical properties of each solvent and multiple parameters such as probe solubility, it can be seen that NMP, NEP, polyethylene glycol 200 (PEG200), and DGME are the more preferred solvents screened, which can be used to directly dissolve the probe molecules and accurately monitor cmc.

[0204] In addition, when Nile Red (NR) was used as the ACQ molecule, the present inventors obtained similar screening results for the preferred adjuvant types.

[0205] Specifically, the most preferred probe+adjuvant combinations in the ACQ fluorescent probe composition of the present invention include: CUR+NMP, CUR+DGME, CUR+NEP, CUR+PEG200, NR+NMP, NR+DGME, NR+NEP, and NR+PEG200.

[0206] On the other hand, for single solvents such as n-butanol, ethylene glycol, ethyl glycolate, 1,3-butanediol, and 1,5-pentanediol, which have some deficient properties, a solution can be achieved by mixing them with solvents with different properties. For example, organic solvents with high viscosity, such as ethylene glycol, butanediol, and pentanediol, can be mixed in a certain proportion with solvents with good probe solubility and low viscosity, such as n-butanol or DGME. Organic solvents with relatively low density, such as butanol, can be mixed with denser solvents, such as ethylene glycol or NMP, to obtain a mixed solvent with appropriate density, thereby accelerating the diffusion rate of the probe in the washing solution.

[0207] Similarly, the above-mentioned preferred solvents can also be mixed with other different types of solvents in different proportions to improve the application potential of the solvent in the probe composition, including but not limited to various physicochemical properties, safety, stability, cost, etc.

[0208] That is, according to the above research contents of the present invention, based on the various properties of the probe molecules and the organic solvent themselves, a specific combination of preferred probe molecules and auxiliary agents can be obtained directly or through appropriate adjustments.

[0209] Furthermore, the inventors discovered that the amount of probe solution, primarily the organic solvent therein, added to the test solution has a certain impact on CMC measurement results. To reduce the amount of organic solvent used in the probe solution and suppress its impact on CMC measurement results, it is preferable to reduce the amount of organic solvent added to the surfactant solution. On the other hand, to ensure good fluorescence sensitivity and convenient detection, the probe solution needs to be added in a certain amount to ensure a sufficient working concentration of the probe in the surfactant solution.

[0210] As shown in Table 6, the inventors investigated the effects of varying solvent additions to the probe solution (CUR-NMP) on CMC test results. The test solution was Supreme Biotech (Bright White) detergent solution (ZZLB), and the detector used a custom photodetector (CD detector).

[0211] In addition, since a single organic solvent composition system of CUR-NMP was used, the solvent addition amounts in Table 6 can be considered equivalent to the probe solution addition amounts. The cmc value was determined using the fitted straight line intersection method: based on the measurement results of the fluorescence spectrophotometer, an appropriate wavelength within the corresponding fluorescence emission peak range was selected, and a fluorescence response value-concentration curve was plotted with detergent concentration as the abscissa and fluorescence intensity as the ordinate. Linear regression fitting was performed on the plateau and rising regions of the curve, and the intersection of the two fitted lines was determined. The surfactant concentration on the abscissa corresponding to this intersection was the cmc concentration (measured value).

[0212] Table 6: Effect of solvent addition on CMC test results

[0213] *1 The conversion method is: cmc conversion value = cmc measured value / (1 + solvent addition volume / sample volume).

[0214] *2 The cmc value was obtained by fluorescence spectrophotometry. The amount of NMP added was 40 μl and the probe working concentration was 4 μg / ml.

[0215] The CMC conversion value in Table 6 is the actual CMC concentration calculated after taking into account the dilution effect of the solvent on the surfactant. Specifically, CMC conversion concentration = CMC measured concentration / (1 + solvent addition volume / sample volume), where the solvent addition volume is equivalent to the volume of the added probe solution, and the sample volume is the volume of the surfactant solution to be tested.

[0216] Since the probe solution is formed by dissolving the probe molecules in a solvent serving as an auxiliary agent, the amount of solvent added can be roughly considered the amount of probe solution added. When the amount of probe solution added is small, the CMC conversion value in the table is the same as the actual CMC measured value. However, when the amount of probe solution added is too large, the solvent in it will significantly dilute the surfactant concentration in the original test solution. Therefore, the raw data used as the measurement result needs to be converted. For example, when the amount of probe solution added is 5000ul, the CMC conversion value is 3.341 = 5.012 / (1 + 5ml / 10ml). In other words, the CMC conversion concentration already takes into account the change in solution volume and the dilution of the surfactant concentration caused by the addition of the probe solution. When the amount of probe solution added is small, its dilution effect can be basically ignored.

[0217] As shown in Table 6, when using the probe solution in which the probe-adjuvant is CUR-NMP, in a 10ml surfactant solution, the solvent addition in the solution to be tested is preferably no more than 1000ul (i.e. no more than 10%), more preferably no more than 400ul (i.e. no more than 4%). In this case, the range of the cmc measured values ​​in the table is relatively stable and close to the cmc measured value (0.100g / L) obtained using a fluorescence spectrophotometer and the cmc value (0.067g / L) obtained by the surface tension method. When using other organic solvents, the difference in the solvent addition also results in similar results.

[0218] Therefore, in order to reduce the influence of the organic solvent in the auxiliary agent on the cmc determination result, the addition of probe solution (also referred to as probe mother liquor) in liquid to be measured is suppressed to be lower by the present invention, and its preferred range can be set with reference to the preferred range of solvent addition, that is, relative to the surfactant solution of 10ml, the upper limit of the addition of probe mother liquor is preferably below 1000μl, preferably below 400μl. The lower limit of the addition of probe mother liquor is determined according to the sensitivity of probe and the concentration of probe in probe mother liquor, for example, more than 1μl, preferably more than 10μl, more preferably more than 20μl, and when probe concentration is higher, the lower limit of the addition of probe mother liquor can be appropriately reduced. When using a mixed solvent, the addition of probe mother liquor can be applicable to and meet the preferred scope of organic solvent after conversion according to the ratio shared by its mixed solvent, that is, organic solvent ratio in solvent addition=probe mother liquor*probe mother liquor addition.

[0219] In this case, the cmc measurement results obtained using a customized miniaturized photodetector (CD detector) in Table 6 range from 0.084 g / L to 0.107 g / L, which is close to the value (0.100 g / L) obtained using a fluorescence spectrophotometer in the examples described below. Here, the customized miniaturized detector is a detector of fluorescence response values ​​at a specific single wavelength, while the fluorescence photometer can scan the entire wavelength range of the fluorescence spectrum. Both are fluorescence detection instruments. The former is small, simple to operate, and has a fast detection rate, while the latter provides more spectral information and higher accuracy. Both can adjust spectral parameters according to the corresponding fluorescent probe and be used in various tests.

[0220] As can also be seen from Table 6, the cmc test value measured by fluorescence spectroscopy using a CD detector or fluorescence spectrophotometer is slightly higher than the value measured by the surface tension method (0.067 g / L). The inventor speculates that the reason is that when the surfactant begins to form aggregates in the solution after adsorption saturation at the gas-liquid surface, the cmc measured by the surface tension method is the concentration corresponding to the initial formation of aggregates; while the fluorescence spectroscopy method measures the concentration corresponding to the formation of a large number of aggregates in the solution and the presence of fluorescent molecules in the form of single molecules in the micelles. When micelles are just beginning to form, because the number of probe molecules may be greater than the number of micelles, there may be more than one probe molecule in each micelle. Therefore, the cmc result measured by the fluorescence spectroscopy method will be slightly greater than the cmc result of the surface tension method.

[0221] When the amount of NMP added is higher than the above range (1000 μl), the cmc measurement results are significantly higher. The inventors speculate that the mechanism is as follows: NMP is a short-chain hydrophilic molecule. During the micelle formation process, the hydrophilicity of NMP affects the hydrophobic interaction between surfactant molecules, thereby affecting micelle formation. When the NMP concentration is low, the effect on the cmc value measurement result is small. As the NMP concentration increases and exceeds a certain value, the degree to which it reduces the hydrophobic interaction increases significantly, thereby increasing the cmc value.

[0222] Based on the above speculation, the inventors also used the surface tension method to observe the changes in cmc values ​​at different addition amounts of NMP solvent (not containing probe) used in the CUR-NMP probe solution. The results are shown in Table 7. When the NMP addition amount is less than 10%, the measured cmc value is affected to a certain extent, but the effect is small; when it is less than 4%, the measured cmc value is basically unaffected. This result is basically consistent with the measurement results of the fluorescence spectroscopy method and is consistent with the inference.

[0223] Table 7: Effect of solvent addition on CMC results in surface tension method

[0224] Furthermore, the inventors have discovered that the working concentration of the probe in the test solution also has a certain impact on the CMC measurement results. In this specification, the probe stock concentration refers to the concentration of the probe in the probe solution, while the probe working concentration refers to the probe concentration after the probe stock solution containing the probe is added to the surfactant aqueous solution or wash water.

[0225] The present inventors took the CUR-DGME probe composition as an example to conduct an experiment on the effect of the probe working concentration on the cmc determination results. The results are shown in Table 8.

[0226] Table 8: Effect of CUR probe working concentration

[0227] *1 The cmc value was obtained by fluorescence spectrophotometry. The amount of DGME added was 40 μl and the probe working concentration was 4 μg / ml.

[0228] As shown in Table 8, the probe working concentration is closely correlated with the measured cmc concentration. When the probe working concentration in the test solution is below 10 μg / ml, the cmc values ​​differ slightly from those determined by surface tension. However, as the probe working concentration increases, and when the CUR working concentration exceeds 20 μg / ml, the cmc values ​​deviate significantly. This may be due to the fact that when the probe concentration is too high, fluorescence quenching occurs due to probe aggregation at the inflection point in the curve corresponding to the initial formation of micelles. Furthermore, the second plateau following the rising zone cannot be observed within the original concentration range, resulting in a significantly biased cmc result.

[0229] The inventors speculate that the mechanism is as follows: CUR is a hydrophobic ACQ molecule that can only emit fluorescence when dissolved in a good solvent. When the CUR working concentration is low, CUR enters the micelles as a single molecule, dissolves, and emits fluorescence. However, as the CUR working concentration increases, the proportion of CUR molecules entering the micelles as single molecules decreases, while the proportion of CUR aggregates entering the micelles increases. This results in insignificant fluorescence at the cmc concentration. Only when the number of micelle molecules increases further, allowing more CUR molecules to enter the micelles as single molecules, can they be detected. Therefore, excessive CUR working concentrations will lead to an increase in the measured cmc value.

[0230] Based on the comparative results of surface tension and fluorescence spectroscopy, it can be seen that for the detergent solution or wash water as the target test liquid, the working concentration of the probe used can be selected to be above 0.04 μg / ml, but not more than 20 μg / ml, and preferably not more than 10 μg / ml. Therefore, the preferred range of the probe working concentration is 0.04-10 μg / ml, more preferably 0.4-6 μg / ml, and particularly preferably 0.8-4 μg / ml.

[0231] The ACQ fluorescent probe composition of the present invention can be stored for a long time as a stable probe solution. After adding the sample to be tested, the cmc can be accurately measured without evaporating the solvent, reducing the step of waiting for the organic solvent to evaporate, greatly improving the ease of use in practical scenarios, and can meet the actual needs of ACQ fluorescent probes in application fields such as measuring the cmc of surfactant solutions.

[0232] (Method for measuring CMC of surfactant solution)

[0233] The ACQ fluorescent probe composition of the present invention can be directly used in the form of a stable solution to measure the cmc concentration of a surfactant solution.

[0234] The method for determining the cmc of a surfactant solution of the present invention comprises the following steps:

[0235] Preparation steps: prepare a series of surfactant solutions at different concentrations.

[0236] Probe adding step: adding a certain amount of probe solution to the surfactant solution,

[0237] Detection steps: Use the detection mechanism to detect the fluorescence response value of each surfactant solution, and

[0238] Determining step: drawing a fluorescence response value-concentration curve based on the results obtained in the detecting step, wherein the fluorescence response value-concentration curve has at least a first platform region and an ascending region, and determining the concentration corresponding to the inflection point where the fluorescence response value changes from the first platform region to the ascending region as the cmc of the surfactant solution;

[0239] It is characterized in that the probe solution is the ACQ fluorescent probe composition of the present invention.

[0240] In the fluorescence response value-concentration curve obtained by the determination step, with the horizontal axis representing concentration and the vertical axis representing fluorescence intensity or voltage value, the detergent solution to which the ACQ fluorescent probe composition of the present invention is added generally does not fluoresce or the fluorescence intensity is very weak within a lower concentration range, and is maintained in a stable platform region (also referred to as the first platform region), indicating that the ACQ probe molecules are in a state of aggregation with each other in the aqueous system, and therefore do not emit light or emit low fluorescence; as the detergent concentration increases to a specific value (cmc), the fluorescence intensity begins to increase significantly, indicating that at this time, detergent micelles begin to form and the ACQ probe molecules transfer from the aqueous solution to the hydrophobic core of the micelles. Due to the good solvent environment, the probe molecules can exist in a single form, thereby emitting fluorescence. As the number of micelles increases, the fluorescence intensity of the probe also increases, and the fluorescence curve rises rapidly; when all the fluorescent probe molecules exist in the form of single molecules in the micelles or surfactant aggregates, the fluorescence intensity tends to stabilize again (second platform region).

[0241] In a fluorescence response value-concentration curve, the presence of a second plateau after the rising zone is not mandatory; it is related to the relative relationship between the number of fluorescent probe molecules and the number of micelles. However, the concentration corresponding to the plateau before the rising zone (the first plateau) and the inflection point of the rising zone is necessarily the concentration at which micelles begin to form (i.e., the cmc). Therefore, if the inflection point of the change from the plateau to the rising zone in the fluorescence response value (e.g., fluorescence intensity or voltage value) can be detected by a detector and transmitted to a determination mechanism, the determination mechanism can determine the concentration corresponding to the inflection point as the cmc measurement value.

[0242] The inflection point of the change in the fluorescence response value can be determined by the fitted straight line intersection method and the inflection point judgment method. The fitted straight line intersection method is to find the intersection of the fitted straight line in the platform area and the fitted straight line in the rising area in the obtained fluorescence response value-concentration curve, and set the concentration of the detergent solution corresponding to the intersection as cmc (see Figure 2); the inflection point judgment method is to compare the changing trend of the fluorescence intensity at the two data points before and after the obtained fluorescence response value-concentration curve, and directly determine the inflection point based on the phenomenon that the change in the fluorescence intensity at the latter data point is significantly greater than the change in the fluorescence intensity at the previous data point, and set the concentration of the detergent solution corresponding to the inflection point as cmc (see Figure 3).

[0243] Determining CMC using the inflection point method is relatively simple, but the accuracy of CMC values ​​depends on the interval between the measured concentrations. When the concentration interval is too large (fewer data points are used for the measured concentration), accuracy decreases and errors become larger. The fitted line intersection method, on the other hand, integrates multiple data sets to draw a fitted line and find the intersection point, resulting in more stable and accurate CMC measurements. Therefore, the fitted line intersection method is preferred for determining CMC.

[0244] The surfactant solution of the present invention comprises at least one of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants. More preferably, the surfactant comprises at least anionic surfactants and / or nonionic surfactants.

[0245] Examples of the anionic surfactant include surfactants such as alkyl carboxylate type, alkyl sulfate type, alkyl sulfonate type, alkyl ether sulfate ester salt, and phosphate type.

[0246] Examples of the nonionic surfactant include alkyl glucoside, alkyl alcohol ether glucoside, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, alkyl amine oxide, alkylamidopropyl amine oxide, and fatty acid alkanolamide.

[0247] The above-mentioned surfactants may be used alone or in combination of two or more. In addition, the surfactant solution may further contain a fluorescent whitening agent or the like.

[0248] Furthermore, the detection mechanism employed in the present invention includes an existing fluorescence spectrophotometer and a fluorescence photodetector (CD detector) customized for the spectral characteristics of the specific ACQ molecule. The fluorescence spectrophotometer's excitation wavelength can be set to any wavelength within the fluorescence excitation peak wavelength range corresponding to the probe molecule, and the emission wavelength can be selected to any wavelength within the fluorescence emission peak wavelength range. Detergent CMC can be measured based on either fluorescence intensity or the voltage response curve of the fluorescence.

[0249] The difference between customized fluorescence photoelectric detectors and existing fluorescence spectrophotometers lies in cost, accuracy, size, speed and modularity. Fluorescence spectrophotometers have high accuracy and can distinguish red / blue shifts, but they are expensive, the instrument is relatively large, and the applicability is poor. Customized detectors can only detect target wavelengths and cannot distinguish red / blue shifts, but they are small in size, have a fast detection rate, are modular, and have strong applicability.

[0250] In this specification, the “fluorescence response value” in the fluorescence response value-concentration curve refers to the fluorescence intensity when measuring using a fluorescence spectrophotometer, and refers to the voltage value when measuring using a CD detector.

[0251] The fluorescence photodetector used in the present invention includes any of the following:

[0252] 1) Includes an excitation filter (430 nm), a dichroic mirror, and an emission filter (495 nm). The light source has a peak wavelength of 430 nm and a wavelength range of 420 to 440 nm. The operating current is 0.02 A and the operating voltage is 5 V. The detector has an acceptable wavelength range of at least 480 to 510 nm.

[0253] 2) Includes an excitation filter (550 nm), a dichroic mirror, and an emission filter (638 nm); light source: peak wavelength 550 nm, wavelength range 540-560 nm, operating current: 0.02 A, operating voltage: 5 V; the detector's acceptable wavelength range includes at least 620-650 nm.

[0254] The above-mentioned fluorescence photodetector is customized according to the fluorescence spectral characteristics of the ACQ probe molecules of the present invention. Specifically, corresponding to the two ACQ molecules CUR and NR, the test results show that both CD detectors have good responsiveness and sensitivity.

[0255] In addition, in the present invention, the steps of preparing the probe composition, preparing the detergent solution to be tested, preparing the washing water, adding the probe, fluorescence detection, and judging the cmc value can all be achieved based on high-precision metering equipment (sensors, peristaltic pumps, solenoid valves) and automated control.

[0256] For example: the probe composition stock solution can be pre-configured using an electronic balance and a volumetric flask, or after the probe is quantitatively weighed using a pressure sensor, the solvent can be pumped in using a peristaltic pump to prepare a probe composition stock solution of 0.001 mg / ml-100 mg / ml; different concentrations of detergent solutions / washing water to be tested can be prepared by pumping in different amounts of detergent and water using a peristaltic pump respectively; corresponding doses of detergent solution / washing water to be tested and the probe composition stock solution can be transferred using a peristaltic pump respectively for mixing, and the amount of organic solvent added to the washing water to be tested is controlled to not exceed 10%, and the working concentration of the probe is controlled to not exceed 20 uM; a photoelectric sensor can be used to detect changes in the fluorescence response value, and the measurement can be automatically judged and controlled based on the response value result, and finally the cmc value measurement result of the detergent is output.

[0257] In addition, for the qualitative judgment of CMC, improvements can be made to its convenience. For example, when the CMC determination method of the present invention is used to qualitatively determine whether the detergent in the liquid to be tested has reached the CMC value, a threshold value corresponding to the CMC value (threshold concentration ≥ CMC value concentration) can be set based on the measured data. When the measurement result is lower than the threshold, it is determined that the CMC value has not been reached. When the measurement result is greater than or equal to the threshold, it is determined that the CMC value has been reached or exceeded. When used in the washing industry, the threshold value can be set according to the purpose of washing, the required detergent concentration, and the specific washing scene.

[0258] (Stain cleaning concentration determination method)

[0259] In the laundry industry, the standard for setting the amount of detergent to be added is not only related to the cost-effectiveness of the detergent, i.e., the cleaning efficiency, but also to the degree of stain removal, i.e., the cleaning effect. According to extensive research by the inventors, different detergent concentrations are required to clean different stains. In this specification, the minimum concentration required to clean clothes with different stains is referred to as the "stain removal threshold concentration C". t ” (sometimes referred to as “cleaning threshold concentration C t " or "threshold concentration C t ”), the fluorescence response value corresponding to the threshold concentration is called the “stain cleaning response threshold S0” (sometimes referred to as “cleaning response threshold S0” or “response threshold S0”). Usually, the stain cleaning threshold concentration C t ≥Critical micelle concentration (cmc) of wash water.

[0260] Stains are generally divided into three categories according to the washing principles: oil stains, color stains, and invisible stains; oil stains include but are not limited to collar stains, food oil stains, cosmetic oil stains and other stains with animal and plant fats or mineral oils as the main components; color stains include but are not limited to blood stains, fruit stains, aging yellowing stains, pigment stains, dye stains and other colored stains; invisible stains include milk stains, saliva stains, rice porridge stains and other stains that are not easy to see with the naked eye, usually protein stains and starch stains.

[0261] In the present invention, different threshold concentrations of stain cleaning C can be set for the three types of stains: oil stains, color stains and invisible stains. t In the case of actual machine washing, when it is detected that the concentration of detergent put into the washing water has reached or exceeded the above-mentioned stain cleaning threshold concentration, it is considered that the washing water at this concentration can clean the stained clothes, and the detergent concentration at this time can be determined as the "stain cleaning concentration".

[0262] Therefore, in the stain cleaning concentration determination method of the present invention, whether the detected concentration of the washing water can clean the clothes can be determined based on whether the concentration of the washing water reaches or exceeds the preset cleaning threshold concentration corresponding to different stains. In this case, the preset cleaning threshold concentration ≥ cmc.

[0263] The stain cleaning concentration determination method of the present invention comprises the following steps:

[0264] Liquid preparation step: adding a first predetermined amount of detergent into a washing machine filled with a predetermined amount of water and clothes, stirring and mixing to obtain washing water,

[0265] Sampling step: sampling from the washing water and adding a small amount of probe solution to obtain the washing water to be tested.

[0266] Detection step: using the detection mechanism to detect the fluorescence response value S of the washing water to be tested,

[0267] Determination step: judging whether the detergent concentration of the washing water to be tested is a stain cleaning concentration according to whether the detected fluorescence response value S reaches or exceeds a preset cleaning response threshold S0; if it does not reach the preset cleaning response threshold S0, the determination result is "no"; if it reaches or exceeds the preset cleaning response threshold S0, the determination result is "yes", and

[0268] Controlling step: Based on the determination result of the determining step, controlling the number of times the detergent is added in the liquid preparation step; if the determination result is "no", continuing to add a second predetermined amount of detergent in the liquid preparation step, and then performing subsequent sampling steps, detection steps and determining steps; if the determination result is "yes", stopping adding the detergent, outputting the determination result, or starting the washing equipment to continue washing.

[0269] The probe solution may be the ACQ fluorescent probe composition of the present invention.

[0270] The preset washing response threshold S0 in the above determination step can be a fluorescence response value corresponding to the cmc of the washing water, or a washing threshold concentration C of the washing water. t The corresponding fluorescence response value.

[0271] The CMC of the washing water can be measured in advance by the CMC measurement method of the present invention, or the liquid preparation step to the measurement step can be repeated multiple times in the stain cleaning concentration determination method of the present invention, and a fluorescence response value-concentration curve is drawn based on the results obtained in the detection step. The concentration corresponding to the inflection point where the fluorescence response value changes is determined as the CMC.

[0272] The stain removal threshold concentration Ct can be determined based on actual machine washing results. Specifically, by washing stained clothing with water at a range of detergent concentrations, the lowest concentration that demonstrates satisfactory cleaning results is determined as the stain removal threshold concentration. Alternatively, after measuring the cmc of the detergent solution, the stain removal threshold concentration Ct can be set to a fixed value greater than or equal to the cmc concentration.

[0273] In the present invention, a fluorescence response value-concentration curve is plotted based on the detection results in the detection step. This curve generally includes two plateaus and a rising region between them. Taking into account both the cleaning effect and the cost-effectiveness of the detergent, the stain removal threshold concentration Ct is preferably set within the rising region of the curve. In other words, the cleaning threshold concentration Ct is preferably set at any value between the two plateaus and the inflection point of the rising region, as needed.

[0274] The stain removal threshold concentration Ct can be set based on the washing purpose, different scene requirements, load / stain (clothing load, stain type, stain amount, etc.), and scene (household washing machine, industrial washing equipment, etc.). When applied to the detergent dispensing control method for washing equipment, the amount of detergent required during the washing process is related to the load of the washed fabric and the type and degree of dirt. When the load in the washing equipment is large and the stains are numerous and complex, a higher threshold value can be considered (for example, the fluorescence response threshold of the fluorescent photodetector can be set to 0.22, corresponding to a detergent removal threshold concentration of approximately 0.45g / L) to improve the cleaning rate of the clothes. When the load in the washing equipment is small and the stains are few and simple, a conventional threshold value can be considered (the fluorescence response threshold of the fluorescent photodetector can be set to 0.15, corresponding to a detergent removal threshold concentration of approximately 0.35g / L). In this way, while ensuring the washing effect, the amount of detergent can be saved to obtain the highest cost-effectiveness of detergent addition.

[0275] Considering that the cmc values ​​of various detergents in different scenarios can vary and are not constant, the stain removal threshold concentration Ct can be determined based on cmc and the cleaning coefficient a (a unitless coefficient). That is, the stain removal threshold concentration Ct is determined by the following formula 3: Ct = cmc × (1 + a) (Formula 3)

[0276] In Equation 3, cmc is the measured cmc of the wash water, and a is the cleaning coefficient, which ranges from 0 ≤ a ≤ 10, preferably from 0.1 ≤ a ≤ 5, and more preferably from 0.15 ≤ a ≤ 3.5. a can take different values ​​depending on the type and degree of soiling.

[0277] In addition, the preset cleaning response threshold S0 in the above determination step may also be based on the maximum fluorescence intensity response value (S max ) or the percentage of fluorescence increase (S max -S blank ), wherein the detergent concentration corresponding to the response value of the set percentage or increment percentage is still greater than or equal to the cmc concentration. In this specification, the percentage of the maximum response value of the fluorescence intensity or the percentage of the fluorescence increment is referred to as the threshold percentage β, and the unit is 100%.

[0278] For example: in industrial and household scenarios, the relationship between the cleaning rate of common oil stains, color stains, invisible stains, etc., the amount of detergent used, and the detection value (voltage value) of the customized fluorescent photoelectric detector is measured, and the threshold percentage (β) can be arbitrarily set within the range of 0 < β < 1 (i.e., the range of 0 to 100%, but excluding the endpoint value). Considering that industrial washing scenarios involve more pretreatment steps such as pre-coating and color stain soaking before washing, β can be set lower, for example, to 0.35, that is, the cleaning response threshold S0 can be set to 0.35×S max In household washing scenarios, pretreatment is usually not involved or the treatment method is relatively simple, and the mechanical force of household washing machines is smaller than that of industrial washing machines. That is, household scenarios require higher detergent concentrations than industrial scenarios to achieve similar washing effects. β can be set higher, for example, to 0.55, that is, the washing response threshold S0 can be set to 0.55×S max Alternatively, you can set the increment of the cleaning response threshold S0 to 0.2×(S max -S blank ), the threshold value in the home scenario is 0.4×(S max -S blank ).

[0279] That is, the wash response threshold S0 is determined by the following formula 4 or formula 5: S0 = β × S max (Equation 4) S0=S blank +β×(Smax -S blank ) (Formula 5)

[0280] Where S max is the maximum fluorescence intensity or maximum voltage response value of the washing water, or the second platform value in the fluorescence response value-concentration curve, S blank is the background fluorescence intensity of the washing water or the minimum voltage response value, or the first platform value in the fluorescence response value-concentration curve diagram, β is the threshold percentage, the unit is 100%, and the range is 0<β<1. Corresponding to different types and degrees of dirtiness of stains and different washing application scenarios, β can take different values, preferably 0.1≤β≤0.9, and more preferably 0.2≤β≤0.8.

[0281] In the stain cleaning concentration determination method of the present invention, the "first predetermined amount" and "second predetermined amount" of detergent dosage can be set as needed. Furthermore, there are no specific regulations regarding the water volume, laundry volume, wash water sampling volume, and probe solution addition amount; these can be appropriately set based on the actual usage scenario and the preferred range of the probe's working concentration.

[0282] The ACQ fluorescent probe composition of the present invention is particularly suitable for determining whether the clothes are clean by comparing the real-time concentration of the detergent with the size of the stain cleaning threshold concentration. The reason is that: by comparing the difference between the fluorescence response value-concentration curve of the ACQ probe and the AIE probe, it can be seen that in the curve obtained using the ACQ fluorescent probe composition, the first inflection point from the platform area to the rising area is cmc. After exceeding cmc, its fluorescence response gradually increases until the second platform area, which is very suitable for monitoring concentrations greater than cmc (see Figure 2); in contrast, in the fluorescence response value-concentration curve obtained using the AIE fluorescent probe composition (such as HPS), only the highest point of the curve corresponds to cmc, and the ordinate value (fluorescence intensity or voltage) below the highest point may correspond to two concentration values ​​on the horizontal axis, so it is impossible to accurately monitor concentrations greater than cmc. In addition, in the curve obtained using the ACQ fluorescent probe composition, there is a relatively gentle change interval between the platform areas, which is convenient for adjusting the set value of the stain cleaning threshold concentration.

[0283] Since the curve obtained by the ACQ probe molecule is more suitable for determining the stain cleaning concentration and adjusting the stain cleaning threshold concentration, the ACQ fluorescent probe composition of the present invention is more advantageous than the AIE fluorescent probe composition in controlling the automatic dispensing of detergent by setting and adjusting the stain cleaning threshold concentration.

[0284] (Detergent dispensing control method)

[0285] One practical application field of the ACQ fluorescent probe composition of the present invention is the control of detergent dosage in automatic washing equipment.

[0286] In detergent dosing control for automatic washing equipment, the amount of detergent required during the washing process is related to the amount of water, the load of the washed fabric, and the type and degree of soiling. The present invention can employ multiple quantitative dosing methods to add detergent, automatically determining the required dosing amount by measuring whether the surfactant concentration of the washing water solution is above the CMC or above the cleaning threshold concentration. The present invention can provide a detergent dosing control method, characterized by comprising:

[0287] Liquid preparation step: adding a first predetermined amount of the detergent into the inner tub according to the weight of the laundry and the amount of water inlet in the washing device, and mixing and stirring with the water in the inner tub to obtain washing water or detergent solution;

[0288] Sampling step: collecting a predetermined amount of the washing water or detergent solution from the inner barrel as a sample;

[0289] Liquid collection step: Take out a small amount of probe solution and add it to the sample.

[0290] Mixing step: mixing the sample and the probe solution to obtain a test solution;

[0291] Detection step: detecting the fluorescence response value of the test liquid and outputting a detection signal S;

[0292] Determination step: receiving the detection signal S, and determining whether the detergent concentration of the test liquid reaches a critical micelle concentration or a preset cleaning threshold concentration based on whether the detection signal S reaches or exceeds a preset response threshold S0, wherein the cleaning threshold concentration is greater than or equal to the critical micelle concentration; and

[0293] Controlling step: Based on the judgment result of the judging step, controlling the subsequent addition of the detergent, wherein, if the judgment result is that the critical micelle concentration or the preset cleaning threshold concentration has not been reached, continuing to add the second predetermined amount of the detergent into the inner barrel in the liquid preparation step; if the judgment result is that the critical micelle concentration or the preset cleaning threshold concentration has been reached, stopping adding the detergent.

[0294] The probe solution may be the ACQ fluorescent probe composition of the present invention.

[0295] In order to realize the judgment of detergent dosage control, it is necessary to output the fluorescence intensity F of the washing water detected by the fluorescence detector in the detection step as a detection signal S. The detection signal S is a voltage signal corresponding to the fluorescence intensity F of the washing water at a specific wavelength. The detection signal S is output to the judgment step and control step described later.

[0296] A series of test solutions with increasing concentrations of detergents can be prepared in advance in multiple sample pools or a single sample pool, or washing water can be directly sampled from the inner barrel of the washing equipment into the sample pool in real time when the equipment is running and washing is in progress. Through the cmc determination method of the surfactant solution of the present invention, the detection signal corresponding to the inflection point where the platform area of ​​the detected curve changes to the rising area is set as the response threshold S0 corresponding to the critical micelle concentration cmc, or a specific stain cleaning threshold concentration Ct is selected in the platform area of ​​the curve according to the situation, and the detection signal corresponding to the stain cleaning threshold concentration Ct is set to the response threshold S0 (sometimes also called St) corresponding to the cleaning threshold concentration Ct, wherein the stain cleaning threshold concentration Ct is greater than or equal to the critical micelle concentration cmc.

[0297] Then, in the above judgment step, if the detection signal S is equal to or higher than the preset response threshold S0, the judgment result is yes (the detergent concentration C has reached cmc or the cleaning threshold concentration Ct), and the further addition of detergent is stopped at this time; if the detection signal S is lower than the preset response threshold S0, the judgment result is no (the detergent concentration C has not yet reached cmc or the cleaning threshold concentration Ct), then return to the liquid preparation step and continue to add detergent.

[0298] The CMC concentration of wash water actually used in washing equipment is affected by many factors (such as fabric type, quantity, amount of dirt, water temperature, etc.). Analysis of Gibbs free energy data shows that surfactants preferentially adsorb (on fabric, dirt) at gas-liquid, liquid-liquid, and solid-liquid interfaces, and then form aggregates (such as micelles) in the solution. The surfactants in actual machine-washed wash water preferentially adsorb to gas-liquid, solid-liquid, and liquid-liquid interfaces before forming micelles. This consumes some of the surfactant, leading to a CMC greater than that of the detergent solution. This is understandable. Based on this principle, we use online monitoring to determine whether the detergent concentration in the wash water reaches the CMC or exceeds the cleaning threshold concentration as the basis for automatic detergent addition.

[0299] In the washing water of actual machine washing, the detection signal S corresponding to the inflection point value when the platform area of ​​the detected curve changes to the rising area can also be set as the critical micelle concentration value S0, and the detection signal S corresponding to the judgment that the stain can be washed can be set as the washing response threshold St. The surfactant concentration (washing threshold concentration Ct) corresponding to the washing response threshold St is usually greater than the critical micelle concentration cmc.

[0300] During actual machine washing, the cleaning response threshold St can be preset. First, a certain amount of detergent is added, and the fluorescence response value of the washing water is monitored to see if it reaches the cleaning response threshold St. If not, continue to add detergent and continue to monitor whether the fluorescence response value of the washing water reaches the cleaning response threshold St. If it has reached or exceeded the cleaning response threshold St, no more detergent is added.

[0301] In addition, a maximum number of additions may be set during actual machine washing to avoid excessive addition of detergent due to a detector failure.

[0302] Therefore, it is preferred that the control step also includes a number limiting step: a number threshold representing the maximum number of times the detergent is added is pre-set. If, after the detergent is added more than once, although the judgment result is still that the critical micelle concentration or the preset cleaning threshold concentration has not been reached, the number of times the detergent is added has reached the number threshold, then the detergent is stopped from being added in the liquid preparation step.

[0303] Specifically, the detergent dosage control of the present invention can be performed in the following two ways.

[0304] (Method 1) Determine whether the washing water concentration is above the cmc by online monitoring

[0305] In industrial washing machines, when the concentration of Supreme Biotech laundry detergent reaches the cmc (cmd) value, the overall detergency reaches or approaches the plateau. Table 9 shows that the cmc concentration of Supreme Biotech wash water in actual machine washes reaches at least 0.3 (±0.01) g / L, significantly higher than the cmc of a directly prepared detergent solution. Therefore, in actual machine washes, it is recommended to add detergent in multiple, equal amounts, preferably to a concentration that matches the cmc value for the second-to-last addition.

[0306] Table 9. CMC of Supreme Laundry Detergent and Supreme Washing Water Solution

[0307] (Method 2) Determine whether the concentration of washing water is above the stain cleaning threshold concentration by online monitoring

[0308] The decision logic is to determine whether the measured concentration of the washing water is greater than the stain cleaning threshold concentration. If it is greater than or equal to the threshold concentration, it means that the cleaning point has been reached.

[0309] When a 5 kg simple stained fabric load is added to an industrial washing machine, the fluorescence response threshold corresponding to the stain cleaning threshold concentration Ct can be 0.15. In the actual washing scenario shown in Table 10, the preferred number of detergent applications is 1. At this time, the stain is cleaned and the amount of detergent and water used are both small. At the end of the application, the fluorescence response value is 0.161 V and the detergent concentration is 0.41 g / L, which is 37% higher than the cmc measured value of 0.3 g / L during actual machine washing (i.e., the cleaning coefficient a = 0.37) (see Table 10).

[0310] Table 10. Example of loading with a 5kg load in an industrial washing machine

[0311] (Detergent dispensing control system)

[0312] The present invention also provides a detergent dispensing control system for automatically controlling the amount of detergent dispensed into a washing device, wherein the washing device comprises: an inner tub for placing laundry and water to be washed; a storage device for storing detergent; and a dispensing device for dispensing a first predetermined amount of the detergent into the inner tub and mixing the detergent with the water in the inner tub to obtain washing water or a detergent solution, wherein:

[0313] The detergent delivery control system comprises:

[0314] a liquid storage device for storing a probe solution;

[0315] a sampling device for collecting a predetermined amount of the wash water or detergent solution from the inner tub as a sample;

[0316] a liquid taking device, used for taking out a small amount of probe solution from the liquid storage device and adding it to the sample;

[0317] Mixing device: used for mixing the sample and the probe solution to obtain the test solution;

[0318] A detection device, used to detect the fluorescence response value of the test liquid and output a detection signal S;

[0319] a judgment device for receiving the detection signal S and judging whether the detergent concentration of the test liquid reaches the critical micelle concentration cmc or the preset cleaning threshold concentration Ct according to whether the detection signal S reaches or exceeds a preset response threshold S0, wherein the cleaning threshold concentration Ct is greater than or equal to the critical micelle concentration cmc;

[0320] a CMC determining device for, under the condition that there is no laundry in the inner tub, using the dispensing device to dispense a predetermined amount of the detergent into the inner tub in batches, and repeatedly performing multiple sets of measurements using the liquid storage device, the sampling device, the liquid collection device, the mixing device, and the detection device, to determine the critical micelle concentration of the detergent solution based on a plurality of detection data corresponding to different detergent concentrations output by the detection device; and

[0321] a control device for controlling the subsequent delivery of the detergent by the delivery device of the washing device based on the determination result of the determination device;

[0322] If the judgment result of the judgment device is that the critical micelle concentration cmc or the preset cleaning threshold concentration Ct has not been reached, the control device controls the dispensing device to continue dispensing the second predetermined amount of the detergent into the inner drum of the washing device; if the judgment result of the judgment device is that the critical micelle concentration cmc or the preset cleaning threshold concentration Ct has been reached or exceeded, the control device controls the dispensing device to stop dispensing the detergent;

[0323] The probe solution may be the ACQ fluorescent probe composition of the present invention.

[0324] In one embodiment of the detergent dispensing control system of the present invention, the control device may control the subsequent dispensing of the detergent by the dispensing device of the washing machine based on the determination result of the determination device.

[0325] The cleaning response threshold S0 is a fluorescence response value corresponding to the critical micelle concentration cmc of the detergent solution, or a fluorescence response value corresponding to the stain cleaning threshold concentration Ct.

[0326] The critical micelle concentration cmc is the critical micelle concentration of the detergent solution measured in advance, or the critical micelle concentration of the detergent solution or the washing water determined online by the cmc determination device. The cleaning threshold concentration Ct is calculated using the following formula 3: Ct = cmc × (1 + a) (Formula 3)

[0327] Where a is the cleaning coefficient, ranging from 0≤a≤10. Depending on the type and degree of dirtiness of the stains, a can take different values.

[0328] Alternatively, the wash response threshold S0 is determined by the following formula 4 or formula 5: S0 = β × S max (Equation 4) S0=S blank +β×(S max -S blank ) (Formula 5)

[0329] Where Smax S is the maximum fluorescence intensity or maximum voltage response value of the washing water, or the second platform value in the fluorescence response value-concentration curve of the washing water; blank is the background fluorescence intensity or minimum voltage response value of the washing water, or the first platform value in the fluorescence response value-concentration curve of the washing water; β is the threshold percentage, the unit is 100%, and the range is 0<β<1. Corresponding to different types and degrees of dirtiness of stains, β can take different values.

[0330] Preferably, a number threshold indicating the maximum number of times the detergent is dispensed is also set in the control device. If, after the dispensing device has dispensed the detergent more than once, although the judgment result is still that the critical micelle concentration or the preset cleaning threshold concentration has not been reached, the number of times the detergent has been dispensed has reached the preset number threshold, the control device controls the dispensing device to stop dispensing the detergent.

[0331] Example

[0332] Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following Examples unless it departs from the gist of the present invention.

[0333] (Example 1)

[0334] The CUR-DGME probe combination was used to detect the cmc value of Supreme Biotechnology (Bright White) detergent solution.

[0335] <1> Preparation of CUR-DGME fluorescent probe composition:

[0336] Accurately weigh the CUR probe into a clean beaker, add DGME, and transfer the solution to a volumetric flask to a fixed volume, so that the final concentration of the CUR-DGME probe composition stock solution is 1 mg / ml.

[0337] <2> Preparation of the detergent solution to be tested:

[0338] Use the weighing method or gradient dilution method to prepare Supreme Biotechnology (Bright Whitening) detergent (production batch number AHA 20260206, abbreviated as ZZLB) into a series of detergent solutions with concentrations including 0.02g / L, 0.05g / L, 0.1g / L, 0.2g / L, 0.5g / L, 1g / L, 2g / L, 10g / L, and 20g / L.

[0339] <3> Addition and handling of probe composition:

[0340] Use a pipette to accurately transfer 40 uL of the CUR-DGME probe composition into 10 mL of the detergent solution to be tested, so that the working concentration of the probe in the detergent solution to be tested is 4 ug / mL (minor volume changes are not considered).

[0341] <4> Fluorescence intensity detection:

[0342] The spectrophotometer's spectral parameters were set as follows: excitation wavelength Ex = 430 nm, slit width 5 nm, scan speed 1200 nm / min, and emission wavelength scanning range 440-700 nm. Accurately pipette 2 mL of the mixed detergent solution containing the probe into a fluorescence cuvette and measure the fluorescence emission of solutions with different detergent concentrations using the fluorescence spectrophotometer. The scan results are shown in Figure 1.

[0343] <5> Determination of cmc value:

[0344] Referring to the results shown in Figure 1, the peak height data at the maximum emission wavelength Em = 495 nm was selected as the fluorescence response value of the target detergent solution to be tested. This fluorescence response value was plotted against the detergent concentration, as shown in Figure 2. Based on the fluorescence response value (fluorescence intensity)-detergent concentration curve in Figure 2, a fitting straight line was obtained for the plateau region and the rising region of the curve. The concentration coordinate corresponding to the intersection of the two fitting lines is the cmc value of the detergent.

[0345] As can be seen from Figure 2, the cmc of the directly prepared Supreme Biotechnology (Bright White) detergent solution is approximately 0.1 g / L.

[0346] (Example 2)

[0347] The NR-NMP composition was used to detect the cmc value of Supreme Biotechnology (Bright White) washing water.

[0348] <1> Preparation of NR-NMP fluorescent probe composition:

[0349] Accurately weigh the NR probe into a clean beaker, add NMP to dissolve it directly, and transfer the solution to a volumetric flask to make it constant to volume so that the final stock solution concentration of the NR-NMP probe composition is 1 mM.

[0350] <2> Preparation of washing water to be tested:

[0351] The preparation parameters for Supreme Biotechnology (Bright Whitening) washing water are: Supreme Biotechnology (Bright Whitening) detergent (production batch number is AHA 20260206) + 12 kinds of dirty cloths (carbon black, clay, egg white, whole egg, blood stains, sebum, vegetable oil, lipstick, butter, rice starch, etc.) + 2.5kg clothing load, the water quality is 250ppm hard water, the washing equipment is a drum washing machine, and the pre-water volume is 13L.

[0352] Using the same dirty cloth, clothing load, water quality and the same washing equipment, by adding different amounts of Supreme Biotechnology (Bright White Edition) detergent, wash water containing different detergent concentrations was prepared. The converted concentrations include 0.025g / L, 0.075g / L, 0.15g / L, 0.3g / L, 0.6g / L, 0.9g / L, 1.2g / L, 1.5g / L, 1.8g / L, and 2.4g / L.

[0353] <3> Addition and handling of probe composition:

[0354] Use a pipette to accurately transfer 20 uL of the NR-NMP probe stock solution to 10 mL of the wash water to be tested, so that the working concentration of the probe in the wash water to be tested is 2 uM (minor volume changes are not considered).

[0355] <4> Fluorescence intensity detection:

[0356] 10 ml of the wash water to be tested containing the probe was transferred to a glass sample bottle, and the fluorescence response value (voltage value) of the wash water under different detergent concentrations was measured using a customized fluorescence photodetector (including excitation filter (550 nm), dichroic mirror, emission filter (638 nm), light source: peak wavelength 550 nm, band 540-560 nm, working current: 0.02 A, working voltage: 5 V).

[0357] <5> Determination of cmc value:

[0358] According to the results of the customized fluorescence photodetector, the fluorescence response value was used to plot the washing water concentration, and the results are shown in Figure 3. Based on the fluorescence response value (voltage value)-detergent concentration curve in Figure 3, the cmc value corresponding to the detergent at the inflection point of the curve can be directly determined.

[0359] As can be seen from Figure 3, the cmc value of Supreme Biotechnology (Bright White) washing water is about 0.3g / L.

[0360] (Example 3)

[0361] Referring to Example 1 or Example 2, a Supreme Biotech (Bright White) detergent solution was prepared to be tested. The probe and adjuvant types in the fluorescent probe composition were adjusted. The probes were CUR and NR, and the adjuvants included BUT, EG, NMP, and PEG200. Detection was performed using a custom CD detector. The resulting fluorescence response value (voltage value)-detergent concentration curve is shown in Figure 4. Due to the weak detection signal of NR-EG, its results are not shown in Figure 4(B).

[0362] As can be seen from Figure 4, using various combinations of probes and adjuvants in the fluorescent probe composition of the present invention, the cmc value of the detergent solution can be determined based on the change curve of the characteristic emission peak in the obtained fluorescence response value (voltage value)-detergent concentration curve and using the fitted straight line intersection method or the inflection point judgment method. Among them, when NMP and PEG200 are used as adjuvants, the resulting curves are more consistent, indicating that they have less impact on the cmc measurement results and are more preferred adjuvants of the present invention.

[0363] (Example 4)

[0364] The detergent to be tested was adjusted to detergent solutions of other commercially available brands, including GB, LYL, AM, CN, WLS, LBJH, SGY, TZ, etc. The meanings of the abbreviations of each detergent are shown in Table 11.

[0365] The measurement was performed in the same manner as in Example 1 or Example 2 except that the type of detergent was changed to the detergent shown in Table 11. The measurement results are shown in Table 11 below.

[0366] Table 11

[0367] FIG5 is a graph showing the cmc of the detergent solutions of the above-mentioned various brands measured by the surface tension method.

[0368] FIG6 is a graph showing the fluorescence response value-detergent concentration curve when the cmc of the above-mentioned detergent solutions of different brands is measured using a fluorescence spectrophotometer using two ACQ fluorescent probe compositions, respectively: (A) CUR probe composition; (B) NR probe composition.

[0369] As can be seen from Table 11 and Figures 5 and 6, the probe composition of the present invention can be used to determine the cmc of various commercially available detergents by fluorescence spectroscopy, and the measurement results are basically consistent with the cmc results determined by conventional surface tension method. The error is within the allowable range and does not affect actual use.

[0370] (Example 5)

[0371] The detergent solution to be tested was adjusted to a directly prepared detergent solution and washing water used in different machine washing scenarios (industrial machine washing or household washing machine washing), wherein some detergents contained fluorescent whitening agents. The two ACQ fluorescent probe compositions of the present invention, namely (A) CUR probe composition and (B) NR probe composition, were used to perform CMC measurements in the same manner as in Example 1 or Example 2. The obtained fluorescence response value-detergent concentration curve is shown in Figure 7.

[0372] As can be seen from Figure 7, the probe composition of the present invention can be used to determine the cmc of detergent solutions or washing water in various usage scenarios by fluorescence spectroscopy, and the measurement results are basically consistent. The cmc concentration of actual machine washing washing water is greater than the cmc concentration of directly prepared detergent solutions, and the fluorescent whitening agent has little effect on the results and does not affect actual use.

[0373] (Example 6)

[0374] The detergent solution to be tested was adjusted to other commercially available products containing surfactant components, such as softener, oxygen bleach, disinfectant, etc., and the same test was carried out as in Example 1 or Example 2. The results showed that the CMC value of the detergent could be measured.

[0375] FIG8 is a graph showing the fluorescence response value-detergent concentration curve obtained by using the fluorescent probe composition of the present invention to test the cmc of other types of products containing surfactant ingredients (softener, oxygen bleach, disinfectant), (A) CUR probe composition; (B) NR probe composition.

[0376] As can be seen from the results of Figure 8, for other types of products with added surfactants, the fluorescent probe method using the fluorescent probe composition of the present invention can still measure the fluorescence intensity response value, and the cmc value obtained by the measurement is strongly correlated with the amount of surfactant added in the product, indicating that the fluorescent probe composition of the present invention has strong applicability.

[0377] In addition, it can be seen from Figure 8 that when the concentration of the softener is very high, the increase in the softener concentration will significantly reduce the clarity of the solution, thereby causing the transmittance of the solution to decrease. Therefore, the curve shows a downward trend after reaching the highest point.

[0378] (Example 7)

[0379] Referring to Examples 1 and 3, a Supreme Biotechnology (bright white version) detergent solution was prepared, and a CUR probe composition (probe mother liquor) with a probe concentration of 0.001 mg / ml was used, and the amount of probe mother liquor added was adjusted to 400 ul, or a NR probe composition with a probe concentration of 100 mg / ml was used, and the amount of probe mother liquor added was adjusted to 1 ul, so that the amount of organic solvent (auxiliary agent) added to the washing water to be tested and the probe working concentration both met the preferred range of the present invention (i.e., the solvent addition amount does not exceed 4%, and the probe working concentration does not exceed 10 ug / ml). The CD detector was used for measurement under the above two conditions respectively.

[0380] The measurement results are shown in Table 12. The CMC values ​​measured in both cases were 0.061 g / L and 0.171 g / L, respectively, demonstrating that the CMC of Supreme Biotech (Bright White) detergent can be measured. When compared with the results in Table 8 (Reference Examples 1 and 2) using the same probe working concentration, the errors are all within the allowable range. This indicates that when the amount of probe solution added and the probe working concentration are within the ranges specified by the present invention, the CMC value of the detergent can be measured with accuracy that meets practical requirements.

[0381] Table 12

[0382] (Example 8)

[0383] In order to achieve the miniaturization of washing equipment or detergent dispensing control systems, we customized the following fluorescence photodetector with the following specifications: 1) Including excitation filter (430nm), dichroic mirror, emission filter (495nm), light source: peak wavelength 430nm, band 420~440nm, working current: 0.02A, working voltage: 5V, the detector's acceptable wavelength range includes at least 480-510nm; 2) Including excitation filter (550nm), dichroic mirror, emission filter (638nm), light source: peak wavelength 550nm, band 540~560nm, working current: 0.02A, working voltage: 5V, the detector's acceptable wavelength range includes at least 620-650nm.

[0384] The CMC of the aqueous solution of Supreme Biotechnology (Bright White) laundry detergent was measured using a fluorescence spectrophotometer and the customized fluorescence photodetector, respectively, with reference to Example 1 or Example 2. The results are shown in Table 13 below.

[0385] Table 13 Comparison of customized fluorescence photoelectric detection and fluorescence spectrum detection data

[0386] *Due to the poor solubility of NR in ethylene glycol (poor insolubility), after adding it to the detergent solution to be tested, no effective fluorescence signal was detected using the custom fluorescence photodetector, so no results were obtained.

[0387] It can be seen from Table 13 that the test results of the customized fluorescence photoelectric detector of the present invention are repeatable and highly accurate, and can be applied to miniaturized washing equipment.

[0388] Industrial applicability

[0389] By adopting the ACQ fluorescent probe composition of the present invention, it can be stored for a long time in the form of a stable probe solution and can be directly used for CMC determination of surfactant solutions and determination of stain cleaning concentration. It has important applications in the control of detergent dosage in industrial water washing equipment, household washing machines, and household washer-dryers.

Claims

1. An ACQ fluorescent probe composition, characterized in that: It is a probe solution for directly measuring the cmc concentration of surfactants, containing probe molecules and additives. The probe molecule is a fluorescent molecule with aggregation-induced luminescence quenching (ACQ) properties. The auxiliary agent comprises one or more non-volatile organic solvents, wherein the boiling point of the organic solvent is above 100°C. The distance between the probe molecule and the organic solvent, i.e., the HSP distance Ra, is 17 (MPa). 1 / 2 the following.

2. The ACQ fluorescent probe composition according to claim 1, wherein The Hansen solubility parameter (HSP) of the probe molecule is 15 (MPa) 1 / 2 ~35(MPa) 1 / 2 .

3. The ACQ fluorescent probe composition according to claim 1, wherein The solubility of the probe molecule in the auxiliary agent is classified as soluble or above.

4. The ACQ fluorescent probe composition according to any one of claims 1 to 3, wherein The difference in Hansen solubility parameters between the adjuvant and the probe molecule is -3 (MPa). 1 / 2 ~+12(MPa) 1 / 2 .

5. The ACQ fluorescent probe composition according to any one of claims 1 to 3, wherein The viscosity of the auxiliary agent is less than 30 mPa·s.

6. The ACQ fluorescent probe composition according to any one of claims 1 to 3, wherein The additive is soluble in water and has a density of 0.9 g / cm 3 ~1.2g / cm 3 .

7. The ACQ fluorescent probe composition according to any one of claims 1 to 3, wherein The flash point of the auxiliary agent is above 60°C.

8. The ACQ fluorescent probe composition according to any one of claims 1 to 3, wherein The probe molecule is an ACQ that emits light based on changes in fluorescence intensity or characteristic wavelength. molecular, These include ACQ molecules whose characteristic wavelength has a blue-shift characteristic, ACQ molecules whose characteristic wavelength has a red-shift characteristic, and ACQ molecules whose characteristic wavelength has an unchanged characteristic.

9. The ACQ fluorescent probe composition according to any one of claims 1 to 3, wherein The probe molecule is one or more ACQ molecules selected from curcumin (CUR), Nile red (NR), coumarin (C480), rhodamine B (RhB), N-phenyl-1-naphthylamine (NPN) and pyrene (PYR), The auxiliary agent contains one or more organic solvents selected from n-butanol, ethylene glycol, N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), dimethylformamide (DMF), diethylene glycol monoethyl ether (DGME), ethyl glycolate, polyethylene glycol 200 (PEG200), 1,3-butanediol and 1,5-pentanediol.

10. The ACQ fluorescent probe composition according to any one of claims 1 to 3, wherein The probe molecule is at least one ACQ molecule selected from curcumin (CUR), Nile red (NR) and coumarin (C480), The auxiliary agent comprises at least one organic solvent selected from N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), polyethylene glycol 200 (PEG200) and diethylene glycol monoethyl ether (DGME).

11. A method for measuring the cmc of a surfactant solution, characterized in that: The method includes the following steps in sequence: Preparation steps: prepare a series of surfactant solutions at different concentrations. Probe adding step: adding a certain amount of probe solution to the surfactant solution, Detection steps: Use the detection mechanism to detect the fluorescence response value of each surfactant solution, and Determining step: drawing a fluorescence response value-concentration curve based on the results obtained in the detecting step, wherein the fluorescence response value-concentration curve has at least a first platform region and an ascending region, and determining the concentration corresponding to the inflection point where the fluorescence response value changes from the first platform region to the ascending region as the cmc of the surfactant solution; Wherein, the probe solution is the ACQ fluorescent probe according to any one of claims 1 to 10 composition.

12. The cmc measurement method according to claim 11, wherein In the determining step, the concentration corresponding to the intersection of the fitting straight line of the first platform region and the fitting straight line of the rising region in the fluorescence response value-concentration curve is determined as the cmc of the surfactant solution.

13. The cmc measurement method according to claim 11 or 12, wherein Relative to 10 ml of the surfactant solution, the amount of solvent added to the probe solution does not exceed 400 μl, and the probe working concentration of the probe molecule does not exceed 10 ug / ml.

14. The cmc measurement method according to claim 11 or 12, wherein The surfactant includes at least one of anionic surfactants, nonionic surfactants, and amphoteric surfactants.

15. The cmc measurement method according to claim 11 or 12, wherein The surfactant solution also contains a fluorescent whitening agent.

16. A method for determining stain cleaning concentration, characterized in that: The steps include: Liquid preparation step: adding a first predetermined amount of detergent into a washing machine filled with a predetermined amount of water and clothes, stirring and mixing to obtain washing water, Sampling step: sampling from the washing water and adding a small amount of probe solution to obtain the washing water to be tested. Detection step: using the detection mechanism to detect the fluorescence response value S of the washing water to be tested, Determination step: judging whether the detergent concentration of the washing water to be tested is a stain cleaning concentration according to whether the detected fluorescence response value S reaches or exceeds a preset cleaning response threshold value S0; if it does not reach the preset cleaning response threshold value S0, the determination result is "no"; if it reaches or exceeds the preset cleaning response threshold value S0, the determination result is "yes", and Controlling step: Based on the determination result of the determining step, controlling the subsequent addition of the detergent in the dispensing step, wherein if the determination result is "no", returning to the In the liquid preparation step, the second predetermined amount of detergent is continued to be added, and then the subsequent sampling step, detection step and judgment step are performed; if the judgment result is "yes", the detergent is stopped and the judgment result is output. Wherein, the probe solution is the ACQ fluorescent probe composition according to any one of claims 1 to 10.

17. The stain cleaning concentration determination method according to claim 16, wherein: The cleaning response threshold S0 is a fluorescence response value corresponding to the critical micelle concentration cmc of the washing water, or a fluorescence response value corresponding to the stain cleaning threshold concentration Ct. The stain removal threshold concentration Ct is the minimum concentration required to clean clothes with different stains, and is determined by the following formula 3: Ct=cmc×(1+a) (Formula 3) In Formula 3, cmc is the critical micelle concentration of the washing water, and a is the cleaning coefficient, which ranges from 0≤a≤10. Depending on the type and degree of dirtiness of the stains, a may take different values.

18. The stain cleaning concentration determination method according to claim 16, wherein: The cleaning response threshold S0 is determined by the following formula 4 or formula 5: S0=β×S max (Formula 4) S0 = S blank + β×(S max - S blank ) (Equation 5) Where S max S is the maximum fluorescence intensity or maximum voltage response value of the washing water, or the second platform value in the fluorescence response value-concentration curve of the washing water; blank is the background fluorescence intensity or minimum voltage response value of the washing water, or the first platform value in the fluorescence response value-concentration curve of the washing water; β is the threshold percentage, the unit is 100%, and the range is 0<β<1. Corresponding to different types and degrees of dirtiness of stains, β can take different values.

19. A detergent dispensing control method, characterized in that: The following steps are included: Liquid preparation step: adding a first predetermined amount of the detergent into the inner tub according to the weight of the laundry and the amount of water inlet in the washing device, and mixing and stirring with the water in the inner tub to obtain washing water or detergent solution; Sampling step: collecting a predetermined amount of the washing water or detergent solution from the inner barrel as a sample Taste; Liquid collection step: Take out a small amount of probe solution and add it to the sample. Mixing step: mixing the sample and the probe solution to obtain a test solution; Detection step: detecting the fluorescence response value of the test liquid and outputting a detection signal S; Determination step: receiving the detection signal S, and determining whether the detergent concentration of the test liquid reaches the critical micelle concentration cmc or the preset cleaning threshold concentration Ct according to whether the detection signal S reaches or exceeds a preset response threshold S0, wherein the cleaning threshold concentration Ct is greater than or equal to the critical micelle concentration cmc; and Controlling step: Based on the judgment result of the judging step, controlling the subsequent addition of the detergent, wherein, if the judgment result is that the critical micelle concentration or the preset cleaning threshold concentration has not been reached, returning to the liquid preparation step to continue adding a second predetermined amount of the detergent into the inner barrel; if the judgment result is that the critical micelle concentration or the preset cleaning threshold concentration has been reached, stopping the addition of the detergent, Wherein, the probe solution is the ACQ fluorescent probe composition according to any one of claims 1 to 10.

20. The detergent dispensing control method according to claim 19, wherein: The control step also includes a number limiting step: a number threshold representing the maximum number of times the detergent is added is pre-set. If, after the detergent is added more than once, although the judgment result of the judgment step is still that the critical micelle concentration or the preset cleaning threshold concentration has not been reached, the number of times the detergent has been added has reached the number threshold, then the detergent is stopped from being added in the liquid preparation step.

21. A detergent dispensing control system for automatically controlling the amount of detergent dispensed into a washing device, the washing device comprising: An inner tub for placing laundry and water to be washed; a storage device for storing detergent; and a dosing device for adding a first predetermined amount of the detergent into the inner barrel, mixing and stirring with the water in the inner barrel to obtain washing water or detergent solution, characterized in that: The detergent delivery control system comprises: a liquid storage device for storing a probe solution; A sampling device for collecting a predetermined amount of the washing water or detergent solution from the inner barrel as a For samples; a liquid taking device, used for taking out a small amount of probe solution from the liquid storage device and adding it to the sample; Mixing device: used for mixing the sample and the probe solution to obtain the test solution; A detection device, used to detect the fluorescence response value of the test liquid and output a detection signal S; a judgment device for receiving the detection signal S and judging whether the detergent concentration of the test liquid reaches the critical micelle concentration cmc or the preset cleaning threshold concentration Ct according to whether the detection signal S reaches or exceeds a preset response threshold S0, wherein the cleaning threshold concentration Ct is greater than or equal to the critical micelle concentration cmc; a CMC determining device for, under the condition that there is no laundry in the inner tub, using the dispensing device to dispense a predetermined amount of the detergent into the inner tub in batches, and repeatedly performing multiple sets of measurements using the liquid storage device, the sampling device, the liquid collection device, the mixing device, and the detection device, to determine the critical micelle concentration of the detergent solution based on a plurality of detection data corresponding to different detergent concentrations output by the detection device; and a control device for controlling the subsequent delivery of the detergent by the delivery device of the washing device based on the determination result of the determination device; If the judgment result of the judgment device is that the critical micelle concentration cmc or the preset cleaning threshold concentration Ct has not been reached, the control device controls the dispensing device to continue dispensing the second predetermined amount of the detergent into the inner drum of the washing device; if the judgment result of the judgment device is that the critical micelle concentration cmc or the preset cleaning threshold concentration Ct has been reached or exceeded, the control device controls the dispensing device to stop dispensing the detergent; Wherein, the probe solution is the ACQ fluorescent probe composition according to any one of claims 1 to 10.

22. The detergent dispensing control system according to claim 21, wherein: The cleaning response threshold S0 is the fluorescence response value corresponding to the critical micelle concentration cmc of the detergent solution, or the fluorescence response value corresponding to the stain cleaning threshold concentration Ct. The critical micelle concentration cmc is a pre-determined critical micelle concentration of a detergent solution, or a critical micelle concentration of a detergent solution or washing water determined online by the cmc determination device. The cleaning threshold concentration Ct is calculated using the following formula 3: Ct=cmc×(1+a) (Formula 3) Where a is the cleaning coefficient, ranging from 0≤a≤10. It can take different values depending on the type and degree of dirtiness of the stains. Alternatively, the wash response threshold S0 is determined by the following formula 4 or formula 5: S0=β×S max (Formula 4) S0 = S blank + β × (S max - S blank ) (Equation 5) Where S max S is the maximum fluorescence intensity or maximum voltage response value of the washing water, or the second platform value in the fluorescence response value-concentration curve of the washing water; blank is the background fluorescence intensity or minimum voltage response value of the washing water, or the first platform value in the fluorescence response value-concentration curve of the washing water; β is the threshold percentage, the unit is 100%, and the range is 0<β<1. Corresponding to different types and degrees of dirtiness of stains, β can take different values.

23. The detergent dispensing control system according to claim 21 or 22, wherein: The control device also sets a number threshold indicating the maximum number of times the detergent is dispensed. After the dispensing device has dispensed the detergent more than once, if the judgment result of the judgment device is still that the critical micelle concentration or the preset cleaning threshold concentration has not been reached, but the number of times the detergent has been dispensed has reached the number threshold, the control device controls the dispensing device to stop dispensing the detergent.

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