WO2023142326A1 - AIE荧光探针组合物、表面活性剂溶液的cmc测定方法及装置、cmc判断方法及装置 - Google Patents

AIE荧光探针组合物、表面活性剂溶液的cmc测定方法及装置、cmc判断方法及装置 Download PDF

Info

Publication number
WO2023142326A1
WO2023142326A1 PCT/CN2022/096821 CN2022096821W WO2023142326A1 WO 2023142326 A1 WO2023142326 A1 WO 2023142326A1 CN 2022096821 W CN2022096821 W CN 2022096821W WO 2023142326 A1 WO2023142326 A1 WO 2023142326A1
Authority
WO
WIPO (PCT)
Prior art keywords
solution
cmc
aie
probe
fluorescent probe
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2022/096821
Other languages
English (en)
French (fr)
Inventor
蒋赞
郑翔龙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Moon House China Co Ltd
Original Assignee
Moon House China Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Moon House China Co Ltd filed Critical Moon House China Co Ltd
Priority to JP2024501763A priority Critical patent/JP7665089B2/ja
Priority to US18/265,230 priority patent/US20240263068A1/en
Priority to EP22923138.6A priority patent/EP4471106A4/en
Publication of WO2023142326A1 publication Critical patent/WO2023142326A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms

Definitions

  • the present invention relates to an AIE fluorescent probe composition, a cmc measurement method and device of a surfactant solution using the AIE fluorescent probe composition, and a cmc judgment method and device based on the AIE fluorescent probe.
  • Critical micelle concentration (Critical Micelle Concentration, referred to as cmc) is an important dividing line of the solution properties of surfactants. Before and after cmc, many physical and chemical properties of surfactant solutions such as surface tension, light scattering, molar conductivity, density, Osmotic pressure, solubilization, etc. have significant changes.
  • AIE aggregation-induced emission
  • AIE fluorescent probes made of organic molecules with the above-mentioned AIE phenomenon can simply, quickly and efficiently measure the cmc of surfactant solutions without the help of sophisticated instruments due to their aggregation-induced luminescent properties, so they can be effectively used in various fields, such as It is used in the washing industry to monitor the surfactant content in the washing water solution, which has practical guiding significance.
  • Prototype AIE molecules include, for example, common tetraphenylethylene (TPE), hexaphenylsilole (ie hexaphenylsilacyclopentadiene, HPS) and distyryl anthracene (DSA), etc., which have high Quantum yield and high chemical stability and photostability and other advantages, but the hydrophobicity of the unsubstituted prototype AIE molecule limits its application in aqueous systems such as surfactant solutions.
  • TPE common tetraphenylethylene
  • HPS hexaphenylsilole
  • DSA distyryl anthracene
  • Non-Patent Document 1 reports that hydrophobic AIE molecules are first dissolved in volatile organic solvents such as n-hexane, then added to a surfactant solution, mixed by ultrasonic waves, and AIE characteristics appear after the soluble organic solvents are completely volatilized. However, since this method includes steps such as ultrasonic mixing and organic solvent volatilization, it lacks convenience in practical application environments.
  • AIE fluorescent probes In order to overcome the hydrophobicity of AIE fluorescent probes, current research ideas mainly focus on introducing charged functional groups, such as ammonium groups and sulfonic acid groups, into the hydrophobic AIE molecular structure to improve its hydrophilicity.
  • a series of hydrophilic AIE fluorescent probes were prepared in Patent Document 1. This kind of fluorescent probes is based on benzoquinoline structural unit and added sulfonic acid group as the main water-soluble group. The critical micelle concentration of the surfactant solution was obtained by observing the sudden change of fluorescence from none to the strongest under the ultraviolet lamp.
  • Patent Document 2 reports the synthesis of an amphiphilic molecule in which a hydrophilic unit is introduced into the hydrophobic backbone of an HPS molecule or a TPE molecule, and its application in the field of biology.
  • the synthetic technique of derivatizing unsubstituted hydrophobic AIE molecules to obtain hydrophilic AIE molecules is relatively difficult, and the production cost is high, so it is difficult to be widely applied in the industrial field.
  • Non-Patent Document 1 "Detection of the critical micelle concentration of cationic and anionic surfactants based on aggregation-induced emission property of hexaphenylsilole derivatives" TANG Li et.al, Sci China Ser B-Chem, Jun.2009, vol.52, no .6,755-759
  • Patent Document 1 CN110028446A
  • Patent Document 2 CN106566532A
  • the present invention is carried out in view of the above-mentioned circumstances, and the purpose is to provide a kind of AIE fluorescent probe composition that can be directly used for measuring the cmc concentration of surfactant solution without derivatizing hydrophobic AIE molecules, and provide the use
  • the cmc measurement method and device of the surfactant solution of the AIE fluorescent probe composition, and the cmc judgment method and device based on the AIE fluorescent probe are disclosed.
  • hydrophobic AIE molecules can be dissolved in organic solvents with specific structures to form a stable solution, which can be manifested in a suitable concentration range without waiting for the volatilization of organic solvents.
  • AIE features. Therefore, by using a fluorescent probe composition comprising such a hydrophobic AIE molecule and a specific organic solvent, it can be directly used to measure the cmc concentration of a surfactant solution, and the above-mentioned problem is well solved.
  • the present invention provides a kind of AIE fluorescent probe composition, it is the probe solution that is used for measuring the critical micelle concentration cmc of surfactant solution, it is characterized in that: comprise probe compound and auxiliary agent, described probe compound is Hydrophobic AIE molecules, the auxiliary agent is at least one organic solvent represented by the following general formula (1),
  • R is a substituted or unsubstituted linear or branched alkyl group with 3 to 10 carbon atoms, and n is an integer of 1 or 2.
  • n is 2, the two Rs can be the same or different;
  • X is any polar group selected from hydroxyl, amino, cyano, halogen, amide, carbonyl, aldehyde, ester, ether.
  • the present invention also provides a kind of cmc assay method of surfactant solution, comprises the following steps successively:
  • Solution preparation step prepare a series of solutions to be tested with increasing concentrations of surfactants in multiple sample pools,
  • Step of adding probes adding a certain amount of probe solutions to the plurality of sample pools respectively,
  • Detection step using a detection mechanism to detect the fluorescence intensity of each solution to be tested, and
  • the probe solution is the AIE fluorescent probe composition of the present invention.
  • the present invention also provides a kind of cmc measuring device of surfactant solution, comprising:
  • a sample adding mechanism used to take a certain amount of probe solution from the probe container and add it to the plurality of sample pools
  • a detection mechanism for detecting the fluorescence intensity of the solution to be tested in the plurality of sample pools
  • the determining mechanism determines the cmc concentration of the surfactant solution according to the variation trend of the fluorescence intensity of each solution to be tested detected by the detection mechanism,
  • the probe solution is the AIE fluorescent probe composition of the present invention.
  • the present invention also provides a cmc judgment method based on an AIE fluorescent probe, which is a judgment method for judging whether a surfactant solution reaches a critical micelle concentration cmc, and is characterized in that it includes the following steps in sequence:
  • Liquid preparation step add an initial amount of surfactant in water, stir it, and prepare the solution to be tested;
  • Sampling step take a small amount of the solution to be tested and transfer it to the sample pool;
  • Probe adding step add AIE fluorescent probe into the sample cell, and apply slight vibration to form a mixed solution
  • Detection step detecting the fluorescence intensity of the mixed solution by a fluorescence detector, and outputting a detection signal S;
  • Judging step judging whether the critical micelle concentration cmc is reached according to the variation trend of the detection signal S, if the judgment result is yes, then output the concentration of the solution to be tested as the cmc concentration, and end all steps; if the judgment result is no , then empty the sample pool, return to the liquid preparation step, add a specified amount of surfactant to the solution to be tested, and continue to perform the next sampling step, probe adding step, detection step and judgment step ,
  • the judging step if the judging result is negative, but the number of additions of the predetermined amount of surfactant in the dosing step has reached a predetermined threshold, all steps are ended.
  • the present invention also provides a cmc judging device based on an AIE fluorescent probe, which is a judging device for judging whether the surfactant solution reaches the critical micelle concentration cmc, including a surfactant storage mechanism, an adding mechanism, and a sampling mechanism , the sample pool, the storage mechanism of the AIE fluorescent probe, the sample loading mechanism, the detection mechanism, the cmc judgment mechanism, and the decision mechanism, wherein the following operations are performed in sequence:
  • the adding mechanism takes out a certain amount of surfactant from the storage mechanism of the surfactant and mixes it with water to prepare a solution to be tested,
  • the sampling mechanism takes a small amount of the solution to be tested and transfers it to the sample pool,
  • the sample loading mechanism takes out a small amount of probe solution from the storage mechanism of the AIE fluorescent probe and adds it to the sample pool, and applies slight vibration to form a mixed solution,
  • the detection mechanism detects the fluorescence intensity of the mixed solution, and transmits the obtained detection signal to the cmc judgment mechanism,
  • the cmc judging mechanism judges whether the critical micelle concentration cmc is reached through the change trend of the detection signal
  • the concentration of the solution to be tested is output by the decision mechanism as the cmc concentration, and all operations are ended;
  • the sample pool is emptied, and the adding mechanism adds a specified amount of surface activity to the solution to be tested. Agent, and continue to perform subsequent operations,
  • AIE fluorescent probe composition of the present invention unsubstituted hydrophobic AIE molecules are used.
  • an appropriate organic solvent as an auxiliary agent, it can be stably and well dispersed in an aqueous system, thereby solving the problem of unsubstituted AIE molecules.
  • a stable dispersion structure is formed in the aggregate, and the cmc concentration of the surfactant solution can be measured without the volatilization step of the auxiliary agent, which greatly improves the convenience of use in the actual scene; and, the AIE fluorescent probe composition of the present invention is used as a probe Acupuncture solution can accurately detect the change of fluorescence intensity corresponding to the cmc concentration within a suitable concentration range using a conventional fluorescence detector, thus bringing new solutions and research directions to the application of AIE fluorescent molecules in a wider range of fields .
  • Fig. 1 is a schematic diagram showing the molecular simulation results of the auxiliary agent of the present invention on the solubilization effect of hydrophobic AIE molecules in the mixed micelles of surfactants,
  • auxiliary agent is butylamine
  • B auxiliary agent For butanol.
  • Fig. 2 shows the fluorescence when adding the AIE fluorescent probe composition of the present invention (embodiment 1) and not adding the AIE fluorescent probe composition of the present invention (reference example 1) in the supreme clean detergent aqueous solution prepared directly A graph of intensity (voltage) versus concentration.
  • FIG. 3 is a graph showing the surface tension as a function of concentration of an aqueous direct-made Supreme Cleansing Detergent solution employed in Example 1.
  • FIG. 3 is a graph showing the surface tension as a function of concentration of an aqueous direct-made Supreme Cleansing Detergent solution employed in Example 1.
  • Fig. 4 is a graph showing that the fluorescence intensity (voltage) varies with the concentration when the AIE fluorescent probe composition of the present invention is added to the aqueous solution of the extreme cleansing detergent for actual machine washing in Example 7.
  • FIG. 5 is a graph showing interfacial tension as a function of concentration for an actual machine washable aqueous solution of Supreme Clean detergent employed in Example 7.
  • FIG. 5 is a graph showing interfacial tension as a function of concentration for an actual machine washable aqueous solution of Supreme Clean detergent employed in Example 7.
  • the numerical range represented using “-” means the range which includes the numerical value described before and after "-" as a minimum value and a maximum value, respectively.
  • the concentration of a surfactant refers to the concentration of the surface active agent (sometimes referred to as a detergent), unless otherwise specified, when there are multiple surfactant components in a surfactant solution (sometimes referred to as a detergent solution).
  • concentration of a surfactant refers to the concentration of the surface active agent (sometimes referred to as a detergent), unless otherwise specified, when there are multiple surfactant components in a surfactant solution (sometimes referred to as a detergent solution).
  • the AIE fluorescent probe composition of the present invention is a probe solution for measuring the critical micelle concentration cmc of a surfactant solution, and is characterized in that: it comprises a probe compound and an auxiliary agent, and the probe compound is a hydrophobic AIE molecule , the auxiliary agent is at least one organic solvent represented by the following general formula (1),
  • R is a substituted or unsubstituted linear or branched alkyl group with 3 to 10 carbon atoms, and n is an integer of 1 or 2.
  • n is 2, the two Rs can be the same or different,
  • X is any polar group selected from hydroxyl, amino, cyano, halogen, amide, carbonyl, aldehyde, ester, ether.
  • the probe compound of the present invention is a hydrophobic AIE molecule with aggregation-induced luminescence properties.
  • AIE Aggregation-Induced Emission
  • AIE molecules with aggregation-induced luminescent properties can be roughly classified into pure hydrocarbon systems, heteroatom-containing systems, macromolecular systems, and metal-containing systems. Most of these molecules have aromatic conjugated planar skeletons, which can form a helical structure in space and change their conjugation properties under the influence of different aggregation states, thus showing AIE characteristics in the fluorescence spectrum. Due to the presence of aromatic skeletons, most of these molecules are insoluble in water and hydrophobic in their unsubstituted native state.
  • the probe compound of the present invention is preferably a hydrophobic AIE molecule comprising a compound represented by any one of the following chemical formulas 1 to 12 as a basic skeleton:
  • the hydrophobic AIE molecules used in the present invention preferably include tetraphenylethylene (Tetraphenylethylene, referred to as TPE) represented by chemical formula 1, hexaphenylsilole (Hexaphenylsilole, referred to as HPS) represented by chemical formula 7, represented by chemical formula
  • Unsubstituted AIE molecules such as distyrenylanthracene (DSA for short) represented by 2 and benzoperylene (1,12-Benzoperylene, BP for short) represented by chemical formula 10 can also be the basic skeletons containing these AIE molecules
  • DSA distyrenylanthracene
  • BP benzoperylene
  • Derivatives of the structure, polymers or metal complexes, etc. are hydrophobic to aqueous solutions.
  • hydroophobicity refers to the property of being insoluble or poorly soluble in water.
  • the above-mentioned AIE molecules exhibit completely different fluorescent properties in different aggregation states and dispersion states.
  • the luminescence mechanism of different kinds of AIE molecules in different solution systems may also be different.
  • TPE tetraphenylethylene
  • the principle of using TPE molecules to detect the cmc of various surfactant solutions is that when the surfactant is at a low concentration, most of the TPE molecules gather in the water phase.
  • TPE molecules Since water is a poor solvent for TPE molecules, Therefore, it will gather to produce strong fluorescence; when the concentration of surfactant is high, TPE molecules will be wrapped into the hydrophobic core of micelles, and TPE molecules will be dispersed by each micelles, and in the micelles Scattered inside the inner core, the internal rotation of TPE molecules will not be restricted, so the fluorescence of TPE molecules will be greatly reduced. Considering the completely different fluorescent properties of TPE in aggregated and dispersed states, it can be used to detect the cmc of surfactant solutions and to track the assembly and disassembly of amphiphilic molecules.
  • non-patent literature 1 has reported the use of hydrophobic hexaphenylsilole (HPS) molecules as probes to measure the cmc of surfactant solutions.
  • HPS hydrophobic hexaphenylsilole
  • the approach is to first dissolve HPS in a volatile organic solvent (such as n-hexane ), and then add it to the aqueous solution of the surfactant, HPS is difficult to disperse in water due to its hydrophobicity, so it forms a covering layer, which must be uniformly mixed by ultrasonic waves, and then the cyclohexane is volatilized, and the HPS enters the In micelles formed by surfactant molecules, it emits strong fluorescence.
  • a volatile organic solvent such as n-hexane
  • n-hexane itself is a highly volatile colorless liquid with low boiling point and flash point, and the probe solution is not easy to store after preparation, and a solvent volatilization step must be included in the process of measuring cmc. If the AIE molecule is not dissolved in an organic solvent and added directly, it may lead to inaccurate addition of AIE and uneven mixing, thereby affecting the accuracy of the test results.
  • organic solvents with specific structures as auxiliary agents for hydrophobic AIE molecules. These organic solvents are not volatile, and can make AIE probe molecules exhibit obvious AIE features.
  • HPS hexaphenylsilacyclopentadiene
  • the present inventors studied the solubility of HPS in a series of organic solvents and its AIE performance in surfactant solutions (for example, Blue Moon Supreme detergent aqueous solution), and the results are shown in Table 1.
  • HPS exhibits obvious AIE phenomenon in solvents such as n-butanol and n-pentanol in a certain detergent concentration range, and has slightly soluble in water, Slightly soluble in HPS and non-volatile, it is suitable as an auxiliary agent contained in the probe composition of the present invention.
  • n-butanol which can exhibit obvious AIE phenomenon in a suitable detergent concentration range (for example, 0.1g/L-0.2g/L), is more preferably used as the auxiliary agent of the present invention.
  • organic solvents with specific amphiphilic structures can be used as auxiliary agents of the present invention.
  • the characteristics of these organic solvents are that they have an alkyl chain of a certain length in the molecule, and have a polar group (functional group) at the end or in the middle of the alkyl chain, thus forming an organic solvent with both polar groups in the molecule.
  • the auxiliary agent contained in the AIE fluorescent probe composition of the present invention is at least one organic solvent represented by the following general formula (1),
  • R is a substituted or unsubstituted linear or branched alkyl group with 3 to 10 carbon atoms, and n is an integer of 1 or 2.
  • n is 2, the two Rs can be the same or different,
  • X is any polar group selected from hydroxyl, amino, cyano, halogen, amide, carbonyl, aldehyde, ester, ether.
  • the solubility of the hydrophobic AIE molecules of the present invention in auxiliary agents is soluble or slightly soluble, which is higher than that in water.
  • the probe composition when the probe composition is added to an aqueous system such as a low-concentration surfactant solution, the probe compound tends to be preferentially dissolved in the adjuvant, and is stably dispersed in the aqueous system with the help of the adjuvant. Therefore, the hydrophobic AIE molecule of the present invention dissolves in the auxiliary agent to form a stable probe solution.
  • these additive molecules are preferably non-volatile organic solvents.
  • the boiling point of the additive is preferably greater than 70°C, more preferably 70-155°C, and even more preferably 75-150°C.
  • n in the general formula (1) is preferably 1, that is, the hydrophilic region composed of the polar group X is preferably located at the end of the alkyl molecular chain.
  • R in the general formula (1) is a substituted or unsubstituted linear or branched chain alkyl group with 3 to 10 carbon atoms, wherein the carbon number of R reflects the size of the alkyl chain in the additive molecule. length. If the alkyl chain is too short, the formed hydrophobic region may not be enough to stabilize the AIE molecule, and the solubilization effect of the AIE molecule entering the surfactant micelle is insufficient, and if the number of carbon atoms is too small, the concentration of the auxiliary agent molecule Volatility may be too large, which is not conducive to the storage stability of the probe solution; on the other hand, if the alkyl chain is too long, the water solubility of the additive itself will be reduced, which is also not conducive to the stability of the probe solution, and may not be able to play a role.
  • R in the general formula (1) is preferably an unsubstituted straight-chain or branched-chain alkyl group with 3 to 6 carbon atoms , more preferably having 4-5 carbon atoms.
  • the polar group X in the general formula (1) is preferably selected from hydroxyl or amino groups.
  • the auxiliary agent is at least one selected from n-propanol, isopropanol, tert-butanol, n-butanol, n-butylamine, and pentylamine.
  • Auxiliaries can be a single type or a mixture of two or more types.
  • the AIE fluorescent probe composition of the present invention as a preferred combination of hydrophobic AIE molecules and auxiliary agents, the AIE molecules are unsubstituted HPS, TPE, DSA or benzoperylene, and the auxiliary agent has 3 carbon atoms. ⁇ 5 combinations of organic alcohols or organic amines.
  • the preparation method of the probe solution will also have a certain impact on the fluorescence performance of the AIE fluorescent probe composition.
  • the additive uses a mixed solvent of organic alcohol with 3 to 5 carbon atoms and acetone, due to the influence of the volatility of acetone on the aggregation state of AIE molecules, sometimes a stable and obvious AIE phenomenon cannot be produced; however, when the When the AIE probe molecule is pre-dissolved in acetone, then evaporated to dryness, and finally added with the above-mentioned organic alcohol to obtain the solution of the AIE fluorescent probe composition, a stable and obvious AIE phenomenon will be generated within an appropriate concentration range. It is speculated that this may be because the microcoagulation state of the AIE probe molecules was changed after they were first dissolved in acetone and then volatilized and dried.
  • the present inventors speculate on the mechanism of the AIE phenomenon produced by the AIE fluorescent probe composition in the surfactant solution as follows.
  • hydrophobic AIE molecules are dissolved in an organic solvent as an auxiliary agent to form a probe solution.
  • the probe solution comprising the probe compound and the auxiliary agent
  • the auxiliary agent has a specific amphiphilic structure, It will adsorb or wrap hydrophobic AIE molecules and stably disperse in the aqueous solution of surfactants; when the concentration of surfactants increases to the critical micelle concentration cmc, a large number of surfactant molecules begin to self-assemble and form micelles.
  • the additive molecules do not need additional volatilization, but enter the inner cavity of the micelles formed by the surfactant molecules together with the hydrophobic AIE molecules, and intersperse with the surfactant molecules forming the micelles to form a "barrier".
  • "(Palisade) structure AIE molecules are aggregated near the barrier layer of micelles, and this aggregation state triggers strong AIE luminescence.
  • the auxiliary agent not only plays a role as a solvent for hydrophobic AIE molecules, but also can assist Hydrophobic AIE molecules enter the barrier layer of surfactant micelles, have the effect of solubilizing in micelles, and exhibit obvious AIE characteristics in a suitable concentration range.
  • Fig. 1 is a schematic diagram showing the molecular simulation results of the auxiliary agent of the present invention on the solubilization effect of hydrophobic AIE molecules in the mixed micelles of surfactants, wherein (A) auxiliary agent is butylamine, (B) auxiliary agent The agent is butanol.
  • additive molecules various polar organic solvents such as butylamine, pentylamine, pentanol, propylamine, butanol, butyraldehyde, butyric acid, isopropanol, n-propanol, and tert-butanol were selected in the molecular simulation experiments;
  • AIE fluorescent probe molecule benzoperylene was selected, and the molecules solubilized in the mixed micelles (1:1) of fatty alcohol polyether sulfate sodium (AES) and fatty alcohol polyoxyethylene ether (AEO) were carried out. Simulation experiment.
  • a spherical micellar cubic water box of 21nm*21nm*21nm was built.
  • Each molecule used the United-Atom force field and the gromacs software to perform a 50ns NPT control pressure simulation. It was found that stable micelles were formed in each system, but due to the different solubility of the additive molecules in water, the size and shape of the formed micelles were different, and the additive molecules in the solubilized micelles and The number of additive molecules dispersed in water varies.
  • auxiliary agent 1 is (A) butylamine, (B) butanol, all obtained stable spherical micelle model, as the benzopyrene 2 of fluorescent probe molecule (Fig. The large dark spots in 1) were all solubilized inside the micelles.
  • Surfactant molecules 3 form micellar skeletons and cover fluorescent probe molecules. It can be seen that the micelles formed when butylamine is used as an auxiliary agent are more regular than butanol.
  • the inventors also calculated the distance between each fluorescent probe molecule and the water molecule layer, and the results were all greater than 0.2nm, which further indicated that the fluorescent probe molecule and water molecule were isolated and solubilized in the micelle core.
  • the number of hydrogen bonds it can be seen that butylamine has low solubility in water and is more likely to form micelles with surfactants, which can stabilize the micelles.
  • each system of the AIE fluorescent probe composition of the present invention can form stable micelles, and it can be seen that the auxiliary agent molecule participates in the formation of micelles, and it is in the middle of the surfactant micelles.
  • the barrier layer is close to the side of the polar group, which has a positive contribution to the formation of mixed surfactant micelles and the coating of AIE fluorescent probe molecules.
  • the AIE fluorescent probe composition of the present invention in addition to the hydrophobic AIE molecule as a probe compound and the specific organic solvent as an auxiliary agent, it can also include other components without affecting its AIE effect, such as a stabilizer , preservatives and other additives.
  • the total content of other components is preferably less than 5% by mass, more preferably less than 1% by mass, based on the total amount of the AIE fluorescent probe composition.
  • the content ratio of the auxiliary agent and the probe compound in the AIE fluorescent probe composition there is no particular limitation on the content ratio of the auxiliary agent and the probe compound in the AIE fluorescent probe composition.
  • the content ratio of the auxiliary agent relative to the overall AIE fluorescent probe composition is 40% by mass to 90% by mass, more preferably 50% by mass to 80% by mass; the preferred content of the probe compound relative to the overall AIE fluorescent probe composition The ratio is 10% by mass to 60% by mass, more preferably 20% by mass to 50% by mass.
  • the AIE fluorescent probe composition can also only contain auxiliary agents and probe compounds.
  • the concentration of the hydrophobic AIE molecule as the probe compound is preferably 500 to 2000 ⁇ mol/L, More preferably, it is 600 to 1500 ⁇ mol/L.
  • the concentration of the probe compound in the surfactant solution is preferably 1-1000 ⁇ mol/L, preferably 10-500 ⁇ mol/L.
  • the probe composition of the present invention can form a stable probe solution by using hydrophobic AIE molecules as probe compounds and organic solvents with specific amphiphilic structures as auxiliary agents; moreover, the auxiliary agents play a role in hydrophobic AIE molecules
  • the effect of solubilization in the mixed micelles of surfactants shows obvious AIE characteristics in a suitable concentration range; furthermore, after the probe solution of the present invention is added to the test sample, the cmc can be accurately measured without volatile solvent , which greatly improves the convenience of use in the actual scene, and can meet the actual application requirements of the AIE fluorescent probe in the determination of the cmc concentration of the surfactant solution.
  • AIE fluorescent probe composition comprising hydrophobic AIE molecules as probe molecules and specific organic solvents as auxiliary agents of the present invention can be directly used in the determination of surfactant solutions (detergent solutions) in the form of stable probe solutions ) cmc concentration.
  • the AIE fluorescent probe composition of the present invention contains hydrophobic AIE molecules with neutral charge, compared with derivatized hydrophilic AIE molecules, it is not easily disturbed by charge interactions, therefore, it can be applied to various types of surfactants.
  • the surfactant of the present invention may contain at least one of anionic surfactants, nonionic surfactants, cationic surfactants, and amphiphilic surfactants. More preferably, the surfactant of the present invention contains at least an anionic surfactant and/or a nonionic surfactant.
  • anionic surfactant examples include surfactants such as alkyl sulfate type, alkyl alcohol polyether sulfate type, alkyl carboxylate type, alkylsulfonate type, and phosphate type.
  • nonionic surfactants include alkyl glucoside, alkyl alcohol ether glucoside, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene fatty acid ester, fatty acid alkanolamides etc.
  • the above-mentioned surfactant components may be used alone or in combination of two or more.
  • a fluorescent whitening agent and the like may also be contained in the surfactant solution.
  • the assay method of the critical micelle concentration cmc of surfactant solution of the present invention comprises the steps:
  • Solution preparation step prepare a series of solutions to be tested with increasing concentrations of surfactants in multiple sample pools,
  • Step of adding probes adding a certain amount of probe solutions to the plurality of sample pools respectively,
  • Detection step using a detection mechanism to detect the fluorescence intensity of each solution to be tested, and
  • the probe solution is the AIE fluorescent probe composition of the present invention.
  • the concentration of the solution to be tested in the sample pool corresponding to the detected maximum fluorescence intensity is used as the cmc concentration of the surfactant solution.
  • the concentration of the probe compound in the AIE fluorescent probe composition is 500-2000 ⁇ mol/L, in addition, the concentration of the probe compound in the surfactant solution is 1-1000 ⁇ mol/L .
  • a series of increasing concentrations of the above-mentioned surfactants range from 0 to 20 g/L, and the probe solution is added in a volume ratio of 1:1000 to 100:1000 relative to the surfactant solution .
  • a surfactant solution with an initial concentration is prepared in the sample pool, and a certain amount of fluorescent probe is added to form a mixed solution, and the mixed solution is detected. Then, a certain amount of surfactant can be added to the sample cell within a specified number of times, and the fluorescence intensity of the mixed solution is measured after each addition, and the surface activity is determined according to the change trend of the detected fluorescence intensity.
  • the cmc concentration of the agent solution since it is only necessary to add a probe once and add a predetermined number of additional surfactants, it has the advantages of reducing the amount of reagents used and saving costs.
  • the present invention also provides a kind of measuring device of the critical micelle concentration cmc of surfactant solution, comprising:
  • a sample adding mechanism used to take a certain amount of probe solution from the probe container and add it to the plurality of sample pools
  • a detection mechanism for detecting the fluorescence intensity of the solution to be tested in the plurality of sample pools
  • the determining mechanism determines the cmc concentration of the surfactant solution according to the variation trend of the fluorescence intensity of each solution to be tested detected by the detection mechanism,
  • the probe solution is the above-mentioned AIE fluorescent probe composition of the present invention.
  • the probe compound is an HPS molecule.
  • the HPS molecule is used as a fluorescent probe, the detected fluorescence intensity changes from low to high, and produces the strongest fluorescence intensity in the sample pool corresponding to the cmc concentration .
  • the detection mechanism is preferably a fluorescence sensor with an excitation wavelength range of 275-375nm and an acceptable wavelength range that includes at least 350-370nm or 720-740nm. Fluorescence emission peak intensity changes within the wavelength range to output a detection signal of fluorescence intensity.
  • AIE fluorescent probe composition of the present invention is as an intelligent marker for the online judgment of the intelligent delivery system of detergent in washing equipment.
  • the present inventors have found through research that when the concentration of detergent containing surfactant components reaches the critical micelle concentration, its washing effect has reached the best balance point of cost performance. Therefore, whether the aqueous detergent solution reaches the cmc concentration can be used as the Judgment basis for detergent smart delivery.
  • the present invention also provides a cmc judgment method based on the AIE fluorescent probe, which is a judgment method for judging whether the surfactant reaches the critical micelle concentration cmc, and is characterized in that it comprises the following steps in turn:
  • Liquid preparation step add an initial amount of surfactant in water, stir it, and prepare the solution to be tested;
  • Sampling step take a small amount of the solution to be tested and transfer it to the sample pool;
  • Probe adding step add AIE fluorescent probe into the sample cell, and apply slight vibration to form a mixed solution
  • Detection step detecting the fluorescence intensity of the mixed solution by a fluorescence detector, and outputting a detection signal S;
  • Judging step judging whether the critical micelle concentration cmc is reached according to the variation trend of the detection signal S, if the judgment result is yes, then output the concentration of the solution to be tested as the cmc concentration, and end all steps; if the judgment result is no , then empty the sample pool, return to the liquid preparation step, add a specified amount of surfactant to the solution to be tested, and continue to perform the next sampling step, probe adding step, detection step and judgment step ,
  • the judging step if the judging result is negative, but the number of additions of the predetermined amount of surfactant in the dosing step has reached a predetermined threshold, all steps are ended.
  • the surfactant solution used in the cmc judging method of the present invention may be an aqueous detergent solution directly configured, or an aqueous detergent solution used in washing equipment for actual machine washing.
  • the above-mentioned aqueous detergent solution is an aqueous detergent solution containing one or more surfactant components, including at least an anionic surfactant and/or a nonionic surfactant.
  • the AIE fluorescent probe with aggregation-induced luminescence characteristics is used as a marker in the present invention
  • a conventional fluorescence detector with low sensitivity can be used to accurately measure the fluorescence intensity of the detergent aqueous solution, by converting the fluorescence intensity into The signal S is detected to realize the online judgment of cmc and the intelligent control of the amount of detergent added.
  • the AIE fluorescent probe used in the cmc determination method of the present invention may be an aqueous fluorescent probe solution containing water-soluble AIE molecules, or the AIE fluorescent probe composition containing hydrophobic AIE molecules and auxiliary agents of the present invention. Considering cost, applicability and convenience, the AIE fluorescent probe composition of the present invention is preferably used.
  • the aqueous detergent solution added with HPS molecules as AIE fluorescent probes has yellow-green fluorescence observed by the naked eye within a certain range, and the fluorescence intensity first increases and then decreases significantly.
  • the concentration range corresponding to the strongest fluorescence intensity roughly observed by the naked eye is around 0.1g/L to 0.2g/L, and when the detergent concentration>2g/L, the fluorescence intensity drops significantly .
  • a detection signal S which is a voltage signal corresponding to the fluorescence intensity F at a specific wavelength
  • a series of solutions to be tested with increasing concentrations of surfactants can be prepared in advance in multiple sample pools or a single sample pool by the above-mentioned cmc assay method for surfactant solutions, and the detected The detection signal S corresponding to the maximum fluorescence intensity is set as the threshold S 0 .
  • the judgment result is yes (the detergent aqueous solution has reached the cmc concentration); if the detection signal S is lower than the threshold S 0 , Then the judgment result is no (the detergent aqueous solution has not reached the cmc concentration).
  • the preset threshold value S does not correspond to the actual cmc concentration.
  • the actual The apparent cmc concentration of the detergent aqueous solution of machine washing is far greater than the cmc concentration corresponding to the above-mentioned threshold value S0 .
  • the concentration of the surfactant reaches the critical micelle by observing the difference between the detection signals S X and S Y of two adjacent times. Concentration cmc.
  • the judgment result is yes (the aqueous detergent solution has reached the cmc concentration); if the difference S Y -S X is greater than 0, the judgment result is no (the aqueous detergent solution has not reached the cmc concentration).
  • the judging step is mainly used to decide whether to add detergent. After the detergent is added for the first time, the washing equipment can start washing, and multiple sampling and judgment can be carried out during the washing process; washing can also be started after all steps are completed.
  • the cmc judgment method based on the AIE fluorescent probe of the present invention since the AIE fluorescent probe with aggregation-induced luminescence characteristics is used, it is possible to use a common low-sensitivity fluorescence detector without resorting to precision instruments, or even sometimes only by The change of AIE fluorescence intensity can be recognized by the naked eye, so the cmc of the detergent aqueous solution can be determined simply, quickly and efficiently, and it can be effectively applied in the washing industry for online monitoring of the detergent content in the washing aqueous solution. In the intelligent delivery of detergent It has practical guiding significance.
  • the present invention also provides a cmc judging device based on an AIE fluorescent probe, which is a judging device for judging whether the surfactant solution has reached the critical micelle concentration cmc, including a surfactant storage mechanism, an adding mechanism, and a sampling mechanism , the sample pool, the storage mechanism of the AIE fluorescent probe, the sample loading mechanism, the detection mechanism, the cmc judgment mechanism, and the decision mechanism, wherein the following operations are performed in sequence:
  • the adding mechanism takes out a certain amount of surfactant from the storage mechanism of the surfactant and mixes it with water to prepare a solution to be tested,
  • the sampling mechanism takes a small amount of the solution to be tested and transfers it to the sample pool,
  • the sample loading mechanism takes out a small amount of probe solution from the storage mechanism of the AIE fluorescent probe and adds it to the sample pool, and applies slight vibration to form a mixed solution,
  • the detection mechanism detects the fluorescence intensity of the mixed solution, and transmits the obtained detection signal to the cmc judgment mechanism,
  • the cmc judging mechanism judges whether the critical micelle concentration cmc is reached by the variation trend of the detection signal
  • the concentration of the solution to be tested is output by the decision mechanism as the cmc concentration, and all operations are ended;
  • the sample pool is emptied, and the adding mechanism adds a specified amount of surface activity to the solution to be tested. Agent, and continue to perform subsequent operations,
  • the AIE fluorescent probe used in the device is preferably the above-mentioned AIE fluorescent probe composition of the present invention.
  • the cmc concentration may not be output, and whether to add a surfactant (detergent) is determined only according to the judgment result of the cmc judging mechanism.
  • the decision mechanism may control the washing device to start washing after the initial detection operation is completed or after all operations are completed.
  • the detection mechanism can be a fluorescence sensor with an excitation wavelength range of 275-375nm and an acceptable emission wavelength range of 350-750nm, preferably an excitation wavelength range of 275-375nm and an acceptable wavelength range of at least 350-370nm or 720- 740nm fluorescent sensor.
  • the HPS molecule as an AIE fluorescent probe mainly has two emission peaks of fluorescence intensity: a sharp and high-intensity fluorescence peak in the range of 350-370nm, and a relatively strong fluorescence peak in the range of 720-740nm.
  • fluorescent whitening agents such as CBS
  • the actual detergent aqueous solution such as the Supreme Cleansing Detergent and Supreme Brightening Detergent produced by Blue Moon Company
  • cmc judgment method and device based on the AIE fluorescent probe of the present invention can be practically applied in washing equipment, and carry out online detection of cmc, online judgment and automatic addition of detergent, so it can be applied to the determination of detergent in washing equipment. Smart delivery system.
  • Supreme Cleansing Detergent B1-B10 (trade name, manufactured by Blue Moon Company) was directly prepared into a series of concentrations of 0.02g/L, 0.05g/L, 0.1g/L, 0.2g/L, 0.5g/L, 1g/L, 2g/L, 5g/L, 10g/L, 20g/L detergent aqueous solution, each take 150 ⁇ L of the above probe solution and add to 5mL of the above detergent aqueous solution , prepared as a solution to be tested, the concentration of the HPS probe in the solution to be tested was 30 ⁇ mol/L.
  • test solution containing the surfactant of Reference Example 1 was prepared in the same manner as in Example 1 for comparison.
  • a custom-assembled fluorescence detector filters include excitation filter (365nm), dichroic mirror, emission filter (729nm), light source: peak wavelength 365nm, band 300-400nm, working current: 0.02A , operating voltage: 5V), the above-mentioned solution to be tested that is added with HPS probe is carried out fluorescence detection, detects fluorescence intensity according to the brightness of fluorescence (luminescence intensity is converted into effective voltage readable number).
  • the results of Example 1 and Reference Example 1 are shown in FIG. 2 .
  • Fig. 2 shows that the AIE fluorescent probe composition of the present invention (embodiment 1, marked as a black dot) of the present invention is added in the above-mentioned directly prepared supreme cleaning detergent aqueous solution and the AIE fluorescent probe combination of the present invention is not added (reference example 1, marked as a black square in the figure) is a graph of the fluorescence intensity as a function of concentration.
  • the concentration of the aqueous detergent solution in the system reaches or exceeds cmc (less than 10 times cmc)
  • surfactant molecules start to self-assemble in large quantities to form micelles.
  • the micelles are mostly spherical, and the size and shape of the micelles are roughly unchanged.
  • the lipophilic (hydrophobic) HPS probe molecules enter and gather in the hydrophobic core of the spherical micelles with the assistance of the auxiliary agent (n-butanol), and the In the concentration range of /L, the AIE characteristic with strong fluorescence intensity was exhibited.
  • the concentration of the solution to be tested corresponding to the peak (maximum fluorescence intensity) of the curve in Fig. 2 is 0.1g/L place, therefore, this concentration can be determined as the cmc concentration of the detergent aqueous solution of direct preparation.
  • the fluorescence emission intensity decreases obviously, which may be due to the anisotropy of spherical micelles to form worm-like micelles or vesicles due to excessive surfactant concentration.
  • HPS is distributed into micelles or aggregates of different shapes, the ⁇ - ⁇ interaction between HPS molecules is destroyed, the movement restriction in HPS molecules becomes weaker, and the molecules in the excited state transfer the light energy through the form of vibration It is consumed in the form of heat energy, etc., resulting in the weakening of the fluorescence of HPS.
  • the fluorescence intensity observed by the naked eye is obviously weaker due to the influence of the fluorescence anisotropy of the HPS probe in the non-spherical micellar aggregate environment.
  • the change of the AIE fluorescence intensity of the above-mentioned supreme cleaning detergent aqueous solution can only be identified by the naked eye, and the concentration of the solution to be tested with the strongest fluorescence intensity seen by the naked eye is determined as the cmc concentration.
  • the results of the measurements were basically the same.
  • HPS-propanol n-butanol means that HPS is dissolved in acetone first, and n-butanol is added after the acetone has evaporated.
  • 3* indicates the measurement result after the acetone has been volatilized.
  • Example 6 when HPS is pre-dissolved in acetone, and n-butanol is added after volatilization and drying, a stable and obvious AIE phenomenon is also produced in an appropriate concentration range, and at the cmc concentration The maximum fluorescence intensity is shown nearby.
  • acetone was directly used as an auxiliary agent, and the measurement was carried out after the acetone was completely volatilized. From the experimental results, although acetone shows obvious AIE phenomenon after it is completely volatilized, it cannot be formulated into a stable probe solution due to the extremely volatile characteristics of acetone, and it is not suitable to wait for the volatilization of the solvent during the measurement process. As a probe solution of the present invention, it was excluded from the scope of the present invention, and it was used as a comparative example.
  • Example 7 except that the above-mentioned aqueous detergent solution for actual machine washing was used instead of the directly prepared aqueous detergent solution used in Example 1, the fluorescence intensity was measured in the same manner as in Example 1, and the results are shown in Fig. 4.
  • Fig. 4 is a graph showing the change of the fluorescence intensity with the concentration when the AIE fluorescent probe composition (HPS-n-butanol) of the present invention is added to the aqueous solution of the super clean detergent for actual machine washing.
  • the cmc concentration of the aqueous detergent solution for actual machine washing is 0.62 g/L.
  • This cmc concentration is higher than the cmc concentration measured by the directly configured aqueous detergent solution adopted in Example 1. This is because the aqueous detergent solution used for actual machine washing contains a large amount of clothing, which has certain adsorption to the detergent. Therefore, the apparent cmc concentration is increased, and this result is reasonable.
  • the AIE fluorescent probe composition of the present invention can form a stable probe solution, which has applicability in direct preparation or in the aqueous detergent solution adopted in actual machine washing, and can avoid The interference of fluorescent whitening agents in aqueous detergent solutions shows AIE characteristics in a suitable cmc concentration range, so it can be applied to practical purposes such as washing equipment to accurately and conveniently measure the cmc concentration of aqueous detergent solutions.
  • the AIE fluorescent probe composition of the present invention By adopting the AIE fluorescent probe composition of the present invention, it is not necessary to use high-precision testing instruments, and the on-line measurement and on-line measurement of the cmc concentration of the surfactant solution can be realized only with a simple assembled fluorescence detector in the range of ultraviolet and visible light. Judgment is convenient for industrialization, especially in the intelligent addition system of detergent for washing equipment, which plays an important role.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Pathology (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Molecular Biology (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)

Abstract

一种用于测定表面活性剂溶液的临界胶束浓度cmc的AIE荧光探针组合物，其包含探针化合物和助剂，所述探针化合物为疏水性AIE分子，所述助剂为由下述通式（1）表示的至少一种有机溶剂，（R） n-X（1），其中，R为碳原子数为3-10的取代或无取代的直链或支链烷基，n为1或2的整数，当n为2时，两个R可以相同也可以不同，X为选自羟基、氨基、氰基、卤素基、酰胺基、羰基、醛基、酯基、醚基中的任一种的极性基团。还提供使用了上述AIE荧光探针组合物的表面活性剂溶液的cmc测定方法及装置、以及基于AIE荧光探针的cmc判断方法及装置。

Description

AIE荧光探针组合物、表面活性剂溶液的cmc测定方法及装置、cmc判断方法及装置 技术领域
本发明涉及一种AIE荧光探针组合物、使用了该AIE荧光探针组合物的表面活性剂溶液的cmc测定方法及装置、以及基于AIE荧光探针的cmc判断方法及装置。
背景技术
临界胶束浓度(Critical Micelle Concentration，简称cmc)是表面活性剂的溶液性质的重要分界线，在cmc前后，表面活性剂溶液的许多物理化学性质如表面张力、光散射、摩尔电导率、密度、渗透压、增溶作用等均有显著的变化。
常规检测cmc的方法包括表面张力法、电导率法以及荧光光谱法(PL)等，但这些方法在实际应用的时候会有一些限制。例如，表面张力法测定cmc的时候，需要一系列复杂的操作；电导率方法无法对非离子性表面活性剂和电导率较低的表面活性剂进行检测；荧光光谱法存在灵敏度低、有赖于高精度的测试仪器等问题。
近年来，发现了一些有机分子在溶液中不发光，而在聚集状态或固体薄膜下发光强度大大增强。因为该发光增强的性质是由分子聚集所导致的，故将此现象定义为“聚集诱导发光”(Aggregation-Induced Emission，简称AIE)。
使用具有上述AIE现象的有机分子制成的AIE荧光探针因其聚集诱导发光特性，可以不借助精密仪器而简单、快速、高效测定表面活性剂溶液的cmc，因此可有效应用在各个领域，例如在洗涤行业等中用于监测洗涤水溶液中的表面活性剂含量，具有实际的指导意义。
原型AIE分子例如包括常见的四苯乙烯(TPE)、六苯基噻咯(即六苯基硅杂环戊二烯，HPS)和二苯乙烯基蒽(DSA)等，具有固态情况下的高量子产率以及高化学稳定性和光稳定性等优势，但无取代的原型AIE 分子因其疏水性而限制了其在表面活性剂溶液等水性体系中的应用。非专利文献1报道了将疏水性的AIE分子首先溶解于正己烷等挥发性有机溶剂，然后加入表面活性剂溶液中，通过超声波进行混合，等易溶的有机溶剂完全挥发完毕后呈现AIE特性。但是，由于该方法包括超声波混合、有机溶剂挥发等步骤，因此在实际应用环境中缺乏使用方便性。
为了克服AIE荧光探针的疏水性问题，目前的研究思路主要集中在向疏水性的AIE分子结构中引入了带电的功能基团、比如铵基、磺酸基以提高其亲水性。例如，专利文献1中制备了一系列亲水性的AIE荧光探针，该类荧光探针以苯并喹啉结构单元为母体、加入磺酸基为主要的水溶性基团，可通过波长365nm的紫外灯观察荧光发生从无到最强的突变来得到表面活性剂溶液的临界胶束浓度。专利文献2中报道了在HPS分子或TPE分子的疏水性骨架上引入了亲水性单元而成的两亲性分子的合成、及其在生物学领域的应用。但是，在这些方法中，对无取代的疏水性AIE分子进行衍生化从而得到亲水性AIE分子的合成技术较为困难，生产成本高，很难普遍适用于工业领域。
现有技术文献
非专利文献
非专利文献1：“Detection of the critical micelle concentration of cationic and anionic surfactants based on aggregation-induced emission property of hexaphenylsilole derivatives”TANG Li et.al,Sci China Ser B-Chem,Jun.2009,vol.52,No.6,755-759
专利文献
专利文献1：CN110028446A
专利文献2：CN106566532A
发明概要
发明所要解决的问题
本发明是鉴于上述情况而进行的，目的在于提供一种无需对疏水性AIE分子进行衍生化而能够将其直接用于测定表面活性剂溶液的cmc浓度的AIE荧光探针组合物，并且提供使用了该AIE荧光探针组合物的表面活 性剂溶液的cmc测定方法及装置、以及基于AIE荧光探针的cmc判断方法及装置。
用于解决问题的方法
本发明们针对上述问题进行了深入研究，发现有一些疏水性AIE分子可以溶解在具有特定结构的有机溶剂中形成稳定的溶液，可以无需等待有机溶剂的挥发而在合适的浓度范围内体现出明显的AIE特性。因此，通过使用包含这样的疏水性AIE分子和特定有机溶剂的荧光探针组合物，能够直接用于测定表面活性剂溶液的cmc浓度，很好地解决了上述问题。
本发明提供一种AIE荧光探针组合物，其是用于测定表面活性剂溶液的临界胶束浓度cmc的探针溶液，其特征在于：包含探针化合物和助剂，所述探针化合物为疏水性AIE分子，所述助剂为由下述通式(1)表示的至少一种有机溶剂，
(R) n-X    (1)
其中，R为碳原子数为3～10的取代或无取代的直链或支链烷基，n为1或2的整数，当n为2时，两个R可以相同也可以不同；
X为选自羟基、氨基、氰基、卤素基、酰胺基、羰基、醛基、酯基、醚基中的任一种的极性基团。
本发明还提供一种表面活性剂溶液的cmc测定方法，依次包括下述步骤：
配液步骤：在多个样品池中配制一系列具有递增浓度的表面活性剂的待测溶液，
加入探针步骤：在所述多个样品池中分别添加一定量的探针溶液，
检测步骤：利用检测机构检测出各待测溶液的荧光强度，以及
决定步骤：根据所检测出的各待测溶液的荧光强度的变化趋势来决定所述表面活性剂溶液的cmc浓度，
其特征在于，所述探针溶液为本发明的AIE荧光探针组合物。
此外，本发明还提供一种表面活性剂溶液的cmc测定装置，包括：
多个样品池，其中配制有一系列具有递增浓度的表面活性剂的待测溶液，
探针容器，其中容纳有包含探针化合物的探针溶液，
加样机构，用于从所述探针容器中取出一定量的探针溶液加入所述多个样品池中，
检测机构，用于检测出所述多个样品池中的所述待测溶液的荧光强度，和
决定机构，根据所述检测机构检测出的各待测溶液的荧光强度的变化趋势来决定所述表面活性剂溶液的cmc浓度，
其特征在于，所述探针溶液为本发明的AIE荧光探针组合物。
此外，本发明还提供一种基于AIE荧光探针的cmc判断方法，是用于判断表面活性剂溶液是否达到临界胶束浓度cmc的判断方法，其特征在于：依次包括下述步骤：
配液步骤：在水中加入初始量的表面活性剂，施以搅拌，配制成待测溶液；
取样步骤：从所述待测溶液中取出少量转移至样品池；
探针加入步骤：在所述样品池中加入AIE荧光探针，并施加轻微振动，形成混合液；
检测步骤：通过荧光检测器检测所述混合液的荧光强度，输出检测信号S；和
判断步骤：根据所述检测信号S的变化趋势来判断是否达到临界胶束浓度cmc，如果判断结果为是，则输出所述待测溶液的浓度作为cmc浓度，结束所有步骤；如果判断结果为否，则清空所述样品池，返回到所述配液步骤，向所述待测溶液中追加规定量的表面活性剂，并继续执行接下来的取样步骤、探针加入步骤、检测步骤和判断步骤，
在所述判断步骤中，如果所述判断结果为否、但所述配液步骤中的所述规定量的表面活性剂的追加次数已经达到预定的阈值，则结束所有步骤。
此外，本发明还提供一种基于AIE荧光探针的cmc判断装置，是用于判断表面活性剂溶液是否达到临界胶束浓度cmc的判断装置，包括表面活性剂的储存机构、添加机构、取样机构、样品池、AIE荧光探针的储存机构、加样机构、检测机构、cmc判断机构、以及决定机构，其中，依次执行以下的操作：
所述添加机构从所述表面活性剂的储存机构中取出一定量的表面活性剂与水混合搅拌，配制成待测溶液，
所述取样机构从所述待测溶液中取出少量转移至所述样品池中，
所述加样机构从所述AIE荧光探针的储存机构中取出微量探针溶液加入所述样品池中，并施加轻微振动，形成混合液，
所述检测机构检测所述混合液的荧光强度，将得到的检测信号传送至 所述cmc判断机构，
所述cmc判断机构通过所述检测信号的变化趋势来判断是否达到临界胶束浓度cmc，
如果所述cmc判断机构的判断结果为是，则所述决定机构输出所述待测溶液的浓度作为cmc浓度，结束所有操作；
如果所述cmc判断机构的判断结果为否、且所述添加机构的执行次数低于预定的阈值，则清空所述样品池，所述添加机构向所述待测溶液中追加规定量的表面活性剂，并继续执行后续的操作，
如果所述cmc判断机构的判断结果为否、且所述添加机构的执行次数已达到预定的阈值，则结束所有操作。
发明效果
本发明的AIE荧光探针组合物中采用了无取代的疏水性AIE分子，通过引入适当的有机溶剂作为助剂，可以使其稳定且良好地分散在水性体系中，从而解决了无取代的AIE探针分子的疏水性问题；在将本发明的AIE荧光探针组合物加入表面活性剂溶液中后，所述助剂(即有机溶剂)协助疏水性AIE分子在表面活性剂溶液的胶束等聚集体中形成稳定的分散结构，无需助剂的挥发步骤即可测定表面活性剂溶液的cmc浓度，大大提升了实际场景下的使用方便性；并且，本发明的AIE荧光探针组合物作为探针溶液，能够在合适的浓度范围内利用常规的荧光检测器等准确检测到与cmc浓度对应的荧光强度变化，从而给AIE荧光分子在更广泛领域的运用带来了新的解决思路和研究方向。
附图说明
图1是例示地表示本发明的助剂对疏水性AIE分子在表面活性剂的混合胶束中的增溶效果的分子模拟结果的示意图，(A)助剂为丁胺，(B)助剂为丁醇。
图2是表示在直接配制的至尊洁净洗涤剂水溶液中添加了本发明的AIE荧光探针组合物(实施例1)以及不添加本发明的AIE荧光探针组合物(参考例1)时的荧光强度(电压)随浓度变化的曲线图。
图3是表示实施例1中采用的直接配制的至尊洁净洗涤剂水溶液的表面张力随浓度变化的曲线图。
图4是表示实施例7在实际机洗的至尊洁净洗涤剂水溶液中添加了本发明的AIE荧光探针组合物时的荧光强度(电压)随浓度变化的曲线图。
图5是表示实施例7中采用的实际机洗的至尊洁净洗涤剂水溶液的界面张力随浓度变化的曲线图。
具体实施方式
以下，对本发明的具体实施方式进行说明，但本发明并不受以下的实施方式的任何限定，在本发明的目的范围内，可以加以适当变更来实施。
本说明书中，使用“～”表示的数值范围是指包含“～”的前后记载的数值分别作为最小值及最大值的范围。
本说明书中，关于表面活性剂(有时指洗涤剂)的浓度，在表面活性剂溶液(有时指洗涤剂溶液)中存在多种表面活性剂成分的情况下，只要没有特别说明，则是指表面活性剂溶液中存在的多种表面活性剂成分的合计量。
(AIE荧光探针组合物)
本发明的AIE荧光探针组合物是用于测定表面活性剂溶液的临界胶束浓度cmc的探针溶液，其特征在于：包含探针化合物和助剂，所述探针化合物为疏水性AIE分子，所述助剂为由下述通式(1)表示的至少一种有机溶剂，
(R) n-X    (1)
其中，R为碳原子数为3～10的取代或无取代的直链或支链烷基，n为1或2的整数，当n为2时，两个R可以相同也可以不同，
X为选自羟基、氨基、氰基、卤素基、酰胺基、羰基、醛基、酯基、醚基中的任一种的极性基团。
以下，对本发明的AIE荧光探针组合物中含有的各成分进行详细说明。
[探针化合物]
本发明的探针化合物为具有聚集诱导发光性质的疏水性AIE分子。
聚集诱导发光(Aggregation-Induced Emission，AIE)是唐本忠院士团队在2001年偶然发现的现象：一些噻咯分子(HPS，如1,1,2,3,4,5-六苯基噻咯)在溶液中几乎不发光，而在聚集状态或固体薄膜下发光大大增强。因为该发光增强是由聚集所导致的，故将此现象定义为“聚集诱导发光”。
从结构上来看，常见的具有聚集诱导发光性质的AIE分子大致分类为纯烃体系、含杂原子体系、大分子体系和含金属体系。这些分子大多数具有芳香系的共轭平面骨架，能够在空间形成螺旋结构，并受到不同的聚集状态的影响而改变其共轭性质，从而在荧光光谱中体现出AIE特性。由于芳香系骨架的存在，这些分子在无取代的原生状态，大多呈现不溶于水的疏水性质。
本发明的探针化合物优选为包含由下述化学式1～12中任一种表示的化合物作为基本骨架的疏水性AIE分子：
Figure PCTCN2022096821-appb-000001
本发明所采用的疏水性AIE分子优选包括由化学式1表示的四苯基乙烯(Tetraphenylethylene，简称TPE)、由化学式7表示的六苯基硅杂环戊二烯(Hexaphenylsilole，简称HPS)、由化学式2表示的二苯乙烯基蒽(Distyrenylanthracene，简称DSA)和由化学式10表示的苯并苝(1,12-Benzoperylene，简称BP)等无取代的AIE分子，也可以是包含这些AIE分子的基本骨架结构的衍生物、聚合物或金属络合物等，对于水溶液呈现疏水性。本发明中，“疏水性”是指在水中呈现不溶或难溶状态的性质。
上述AIE分子在不同的聚集状态和分散状态体现出完全不同的荧光性能。此外，不同种类的AIE分子在不同溶液体系中的发光机理也可能不同。例如四苯基乙烯(TPE)在溶解在良溶剂中时没有荧光发射，当处于不良溶剂中时会产生很高的荧光发射。现有技术中，利用TPE分子来检测各种表面活性剂溶液的cmc的原理是，在表面活性剂为低浓度时，大部分的TPE分子聚集在水相，由于水是TPE分子的不良溶剂，所以会聚集而产生很强的荧光；当表面活性剂的浓度很高时，TPE分子会被包裹到胶束分子的疏水核内，此时TPE分子会被各个胶束分子分散、以及在胶束内核里面分散，TPE分子的内旋转不会受到限制，因此TPE分子的荧光会降低很多。考虑到TPE在聚集状态和分散状态完全不同的荧光性能，可用来检测表面活性剂溶液的cmc和用于跟踪两亲性分子的组装和解组装。
此外，非专利文献1中报道了使用疏水性的六苯基噻咯(HPS)分子作为探针来测定表面活性剂溶液的cmc，其做法是先将HPS溶解于挥发性有机溶剂(例如正己烷)中，然后将其添加到表面活性剂的水溶液中，HPS由于其疏水性而很难分散在水中，因此形成覆盖层，必须通过超声波进行均匀混合，然后等环己烷挥发完毕，HPS进入由表面活性剂分子所形成的胶束中，从而发出强荧光。也就是说，当使用正己烷作为良溶剂来溶解HPS探针分子时，溶剂是否挥发对荧光结果有决定性影响：溶剂未挥发时，HPS探针分子会优先溶解在溶剂中，HPS无荧光发射，表面活性剂溶液不发光；必须等溶剂挥发后，HPS有不同程度的析出，有一部分进入并聚集到表面活性剂胶束的疏水核中，才能表现出可聚集发光的AIE特性。
但是，正己烷本身是高度挥发性的无色液体，沸点和闪点较低，探针溶液配制后不易储存，而且在测定cmc的过程中必须具备溶剂挥发的步骤。 若不将AIE分子溶解于有机溶剂而直接添加，则有可能导致AIE添加量不准确、混合不均匀，从而影响测试结果的准确性。
[助剂]
本发明者们通过深入研究和筛选，找到了一些具有特定结构的有机溶剂作为疏水性AIE分子的助剂，这些有机溶剂不易挥发，且能使AIE探针分子在合适的浓度范围内表现出明显的AIE特性。
作为一种典型的疏水性AIE分子，六苯基硅杂环戊二烯(HPS)非常易溶于乙腈、四氢呋喃、氯仿等良溶剂中，微溶于甲醇等醇类，但在水中完全不溶。通常认为溶剂的种类或极性对HPS的荧光吸收或发射光谱几乎没有影响。
本发明者们对HPS在一系列有机溶剂中的溶解性、及其在表面活性剂溶液(例如，蓝月亮至尊洗涤剂水溶液)中的AIE性能进行了研究，结果示于表1。
表1.各溶剂的性质及HPS在各溶剂中的AIE性能测试对比
Figure PCTCN2022096821-appb-000002
由表1的结果可知，在作为溶剂的各种有机溶剂中，HPS在正丁醇、正戊醇等溶剂在一定的洗涤剂浓度范围内表现出明显的AIE现象，且具有微溶于水、对HPS微溶以及不易挥发的性质，适合作为本发明的探针组合物中所包含的助剂。尤其是正丁醇，可以在合适的洗涤剂浓度范围(例如 0.1g/L～0.2g/L)内表现出明显的AIE现象，更优选作为本发明的助剂。
进一步的研究结果表明，不仅是有机醇类，只要是具有特定的两亲性结构的有机溶剂，都可以作为本发明的助剂。这些有机溶剂的特点在于：在分子中具有一定长度的烷基链，而且在烷基链的末端或中间具有极性基团(官能团)，从而形成在分子中既具备由极性基团构成的亲水区域、又具备由烷基链构成的疏水区域的两亲性结构。
也就是说，本发明的AIE荧光探针组合物中所包含的助剂为由下述通式(1)表示的至少一种有机溶剂，
(R) n-X    (1)
其中，R为碳原子数为3～10的取代或无取代的直链或支链烷基，n为1或2的整数，当n为2时，两个R可以相同也可以不同，
X为选自羟基、氨基、氰基、卤素基、酰胺基、羰基、醛基、酯基、醚基中的任一种的极性基团。
本发明的疏水性AIE分子在助剂中的溶解性是可溶或微溶，高于在水中的溶解度。这样，当将探针组合物加入低浓度的表面活性剂溶液等水性体系中时，探针化合物趋向于优先溶解于助剂中，并在助剂的帮助下稳定地分散在水性体系中。因此，本发明的疏水性AIE分子溶解于助剂中形成稳定的探针溶液。
从长期储存稳定性的角度出发，这些助剂分子优选为不易挥发的有机溶剂。一般来说，有机溶剂的挥发性越强则沸点越低，沸点越高则越不容易挥发。因此，本发明中，助剂的沸点优选大于70℃，更优选为70～155℃，进一步优选为75～150℃。
从更稳定地分散探针化合物的角度出发，通式(1)中的n优选为1，即，由极性基团X构成的亲水区域优选位于烷基分子链的末端。
通式(1)中的R为碳原子数为3～10的取代或无取代的直链或支链烷基，其中，R的碳原子数的大小反映出助剂分子中的烷基链的长短。如果烷基链过短，则所形成的疏水区域有可能不足以使AIE分子稳定，且对于AIE分子进入表面活性剂胶束的增溶效果不足，而且，碳原子数过小则助剂分子的挥发性可能过大，不利于探针溶液的储存稳定性；另一方面，如果烷基链过长，则助剂本身的水溶性降低，同样不利于探针溶液的稳定，而且有可能无法起到对于AIE分子进入表面活性剂胶束的增溶效果。从进 一步提高对胶束的增溶效果、并保持探针溶液的稳定性的角度出发，通式(1)中R优选为碳原子数为3～6的无取代的直链或支链烷基，更优选碳原子数为4～5。
此外，从助剂分子的安全性、易得性和水溶性的角度出发，通式(1)中的极性基团X优选选自羟基或氨基。
更优选助剂为选自正丙醇、异丙醇、叔丁醇、正丁醇、正丁胺、戊胺中的一种以上。助剂可以是单独一种，也可以是两种以上的混合物。
对于不同的AIE分子，可以选择不同的助剂种类，没有特别的限制。本发明的AIE荧光探针组合物中，作为疏水性AIE分子与助剂的优选组合，可列举出AIE分子为无取代的HPS、TPE、DSA或苯并苝、助剂为碳原子数为3～5的有机醇或有机胺的组合。
此外，本发明者们发现，探针溶液的配制方法对于AIE荧光探针组合物的荧光性能也会产生一定影响。例如，当助剂采用碳原子数为3～5的有机醇与丙酮的混合溶剂时，由于丙酮的挥发性对AIE分子聚集状态的影响，有时不能产生稳定且明显的AIE现象；但是，当将AIE探针分子预先溶解于丙酮，然后使其挥发变干，最后加入上述有机醇而得到AIE荧光探针组合物的溶液的情况下，会在合适的浓度范围内产生稳定且明显的AIE现象。据推测，这可能是因为AIE探针分子先溶解于丙酮再挥发变干后，其分子的微观凝聚状态发生了改变。
本发明者们对AIE荧光探针组合物在表面活性剂溶液中产生AIE现象的机理推测如下。
首先，疏水性AIE分子溶解于作为助剂的有机溶剂中，形成探针溶液。在将包含探针化合物和助剂的探针溶液加入表面活性剂溶液中的情况下，当表面活性剂浓度较低、尚未达到临界胶束浓度时，助剂由于具有特定的两亲性结构，会吸附或包裹疏水性AIE分子而稳定地分散在表面活性剂的水溶液中；当表面活性剂浓度增大至临界胶束浓度cmc时，大量的表面活性剂分子开始自组装而形成胶束，此时，助剂分子无需额外的挥发，而是带着疏水性AIE分子一起进入表面活性剂分子所形成的胶束的内部空腔，并与形成胶束的表面活性剂分子穿插排列，形成“栅栏”(Palisade)结构，AIE分子聚集在胶束的栅栏层附近，该聚集状态引发了强烈的AIE发光。
也就是说，在本发明的AIE荧光探针组合物中，助剂不仅起到了作为疏水性AIE分子的溶剂的作用，而且由于其具有亲水区域和疏水区域的两亲性结构特征，能够协助疏水性的AIE分子进入表面活性剂的胶束的栅栏层，具有在胶束中增溶的效果，并在合适的浓度范围内体现出明显的AIE特性。
为了验证上述推测的机理，本发明者们进行了下述的分子模拟实验。
图1是例示地表示本发明的助剂对疏水性AIE分子在表面活性剂的混合胶束中的增溶效果的分子模拟结果的示意图，其中(A)助剂为丁胺，(B)助剂为丁醇。
关于助剂分子，分子模拟实验中共选用了丁胺、戊胺、戊醇、丙胺、丁醇、丁醛、丁酸、异丙醇、正丙醇、叔丁醇等多种极性有机溶剂；关于AIE荧光探针分子，选用了苯并苝，进行了在脂肪醇聚醚硫酸酯钠(AES)和脂肪醇聚氧乙烯醚(AEO)的混合胶束(1:1)中增溶的分子模拟实验。
首先搭建了一个21nm*21nm*21nm的球型胶束立方水盒子，各分子使用United-Atom力场，使用gromacs软件，进行了50ns的NPT控压模拟。结果发现，各体系中均形成了稳定的胶束，但由于助剂分子在水中的溶解性不同，所形成的胶束大小、形状有所不同，且增溶在胶束中的助剂分子和分散在水中的助剂分子数量不同。
从图1可以看出，在助剂1为(A)丁胺、(B)丁醇的情况下，均得到了稳定的球型胶束模型，作为荧光探针分子的苯并芘2(图1中的深色大斑点)均被增溶在胶束的内部。表面活性剂分子3形成为胶束骨架，包覆荧光探针分子。可以看出，丁胺作为助剂时所形成的胶束比丁醇更为规整。
此外，发明者们还计算了各荧光探针分子距离水分子层的距离，结果均大于0.2nm，这进一步说明了荧光探针分子与水分子被隔离，增溶在胶束内核。另外，通过比较氢键数目，可知丁胺等在水中溶解性较低，更易与表面活性剂形成胶束，能够起到稳定胶束的作用。
由上述分子模拟的结果可以看出，本发明的AIE荧光探针组合物的各体系均能形成稳定胶束，并可以看出助剂分子参与了胶束形成，其处于表面活性剂胶束的栅栏层靠近极性基一侧，对混合表面活性剂胶束的形成和包覆AIE荧光探针分子具有积极贡献。
从目前结果来看，所建的分子模型合理，方法可行，结果亦合理。
[其他成分]
本发明的AIE荧光探针组合物中，除了作为探针化合物的疏水性AIE分子和作为助剂的特定的有机溶剂以外，还可以在不影响其AIE效果的情况下包括其他成分，例如稳定剂、防腐剂等添加剂。
在包含其他成分的情况下，其他成分的合计含量相对于AIE荧光探针组合物的总量优选低于5质量％，更优选低于1质量％。
本发明中，只要能够达到合适的AIE强度，对助剂和探针化合物在AIE荧光探针组合物中的含量比例没有特别的限制。优选助剂相对于AIE荧光探针组合物整体的含量比例为40质量％～90质量％，更优选为50质量％～80质量％；优选探针化合物相对于AIE荧光探针组合物整体的含量比例为10质量％～60质量％，更优选为20质量％～50质量％。此外，AIE荧光探针组合物也可以仅包含助剂和探针化合物。
从探针溶液的溶解性、储存稳定性和AIE发光强度的角度出发，在本发明的AIE荧光探针组合物中，作为探针化合物的疏水性AIE分子的浓度优选为500～2000μmol/L，更优选为600～1500μmol/L。当将AIE荧光探针组合物加入待测的表面活性剂溶液中之后，探针化合物在表面活性剂溶液中的浓度优选为1～1000μmol/L，优选为10～500μmol/L。
本发明的探针组合物通过采用疏水性AIE分子作为探针化合物以及具有特定两亲性结构的有机溶剂作为助剂，能够形成稳定的探针溶液；而且，助剂对疏水性AIE分子起到在表面活性剂的混合胶束中增溶的效果，在合适的浓度范围内体现出明显的AIE特性；进而，本发明的探针溶液在加入测试样品后，不需挥发溶剂即可准确测定cmc，大大提升了实际场景下的使用方便性，可以满足AIE荧光探针在测定表面活性剂溶液的cmc浓度中的实际应用需求。
(表面活性剂溶液的cmc测定方法)
使用本发明这样的包含疏水性AIE分子作为探针分子和特定有机溶剂作为助剂的AIE荧光探针组合物，能够以稳定的探针溶液的形式直接用于测定表面活性剂溶液(洗涤剂溶液)的cmc浓度。
由于本发明的AIE荧光探针组合物中包含的是电荷中性的疏水性AIE分子，与衍生化的亲水性AIE分子相比，不易受到电荷相互作用的干扰， 因此，可以适用于各种类型的表面活性剂。
本发明的表面活性剂可以包含阴离子性表面活性剂、非离子性表面活性剂、阳离子性表面活性剂和两亲性表面活性剂中的至少一种。更优选本发明的表面活性剂至少包含阴离子性表面活性剂和/或非离子性表面活性剂。
作为阴离子性表面活性剂的例子，可列举出烷基硫酸盐型、烷基醇聚醚硫酸酯盐型、烷基羧酸盐型、烷基磺酸盐型、磷酸盐型等表面活性剂。
作为非离子性表面活性剂的例子，可列举出烷基葡萄糖苷、烷基醇醚葡萄糖苷、聚氧乙烯烷基醚、聚氧乙烯聚氧丙烯烷基醚、聚氧乙烯脂肪酸酯、脂肪酸烷醇酰胺等。
在作为待测溶液的表面活性剂溶液中，上述的表面活性剂成分可以单独使用1种，也可以将2种以上并用。
此外，表面活性剂溶液中还可以包含荧光增白剂等。
本发明的表面活性剂溶液的临界胶束浓度cmc的测定方法包括下述步骤：
配液步骤：在多个样品池中配制一系列具有递增浓度的表面活性剂的待测溶液，
加入探针步骤：在所述多个样品池中分别添加一定量的探针溶液，
检测步骤：利用检测机构检测出各待测溶液的荧光强度，以及
决定步骤：根据所检测出的各待测溶液的荧光强度的变化趋势来决定所述表面活性剂溶液的cmc浓度，
其特征在于，所述探针溶液为本发明的AIE荧光探针组合物。
当采用六苯基硅杂环戊二烯(HPS)作为探针化合物时，在检测步骤中发现，多个样品池中的各待测溶液的荧光强度发生从低到高的突变，到达最大荧光强度后逐渐减弱，因此，在决定步骤中，将检测出的最大荧光强度所对应的样品池中的待测溶液的浓度作为所述表面活性剂溶液的cmc浓度。
优选地，所述探针化合物在所述AIE荧光探针组合物中的浓度为500～2000μmol/L，此外，所述探针化合物在所述表面活性剂溶液中的浓度为1～1000μmol/L。
优选地，上述表面活性剂的一系列递增浓度的范围为0～20g/L，所述 探针溶液相对于所述表面活性剂的溶液以体积比计为1:1000～100:1000的比例添加。
通过上述方法，由于具有多个样品池，其中分别具备一系列递增浓度的表面活性剂，因此可以直观地判断各样品池中的荧光的强弱，即使没有荧光检测设备，有时通过肉眼也可以判断出荧光强度最大的样品池，从而容易地测定表面活性剂溶液的cmc浓度。
此外，也可以代替多个样品池而仅采用一个样品池，此时，在该样品池中配制初始浓度的表面活性剂溶液，并添加一定量的荧光探针形成混合液，检测出该混合液的荧光强度，然后，可以在规定的次数内向该样品池中追加一定量的表面活性剂，每次追加后分别测定混合液的荧光强度，根据所检测出的荧光强度的变化趋势来决定表面活性剂溶液的cmc浓度。该测定方法中，由于仅需要添加一次探针和追加规定次数的表面活性剂，具有试剂使用量减少、节约成本的优点。
(表面活性剂溶液的cmc测定装置)
本发明还提供一种表面活性剂溶液的临界胶束浓度cmc的测定装置，包括：
多个样品池，其中配制有一系列具有递增浓度的表面活性剂的待测溶液，
探针容器，其中容纳有包含探针化合物的探针溶液，
加样机构，用于从所述探针容器中取出一定量的探针溶液加入所述多个样品池中，
检测机构，用于检测出所述多个样品池中的所述待测溶液的荧光强度，和
决定机构，根据所述检测机构检测出的各待测溶液的荧光强度的变化趋势来决定所述表面活性剂溶液的cmc浓度，
其特征在于，所述探针溶液为本发明上述的AIE荧光探针组合物。
优选地，所述探针化合物为HPS分子，当采用HPS分子作为荧光探针时，检测出的荧光强度产生从低到高的变化，并在对应cmc浓度的样品池中产生最强的荧光强度。
所述检测机构优选为激发波长范围为275～375nm、且可接收的波长范围中至少包含350～370nm或720～740nm的荧光传感器，通过检测所述表面 活性剂溶液在350～370nm或720～740nm波长范围内的荧光发射峰波峰强度的变化，来输出荧光强度的检测信号。
(基于AIE荧光探针的cmc判断方法)
本发明的AIE荧光探针组合物的一个应用领域是作为智能标记物，用于洗涤设备中的洗涤剂的智能投放系统的在线判断。
目前的洗涤设备例如自动投放洗衣机主要依赖织物负载的重量来添加洗涤剂，并不智能，针对不同洗涤剂的普适性以及针对各洗涤场景的灵活性均不佳，存在较大的改善空间。洗衣机自动投放系统的智能判断所需解决的标志物问题，目标不是要指示完全洗净或基本洗净的点，而是指示去污效率最佳的点或性价比最高的点。
本发明者们经研究发现，当包含表面活性剂成分的洗涤剂浓度达到临界胶束浓度后，其洗涤效果即达到了性价比最佳的平衡点，因此，可以利用洗涤剂水溶液是否达到cmc浓度作为洗涤剂智能投放的判断依据。
因此，本发明还提供一种基于AIE荧光探针的cmc判断方法，是用于判断表面活性剂是否达到临界胶束浓度cmc的判断方法，其特征在于，依次包括下述步骤：
配液步骤：在水中加入初始量的表面活性剂，施以搅拌，配制成待测溶液；
取样步骤：从所述待测溶液中取出少量转移至样品池；
探针加入步骤：在所述样品池中加入AIE荧光探针，并施加轻微振动，形成混合液；
检测步骤：通过荧光检测器检测所述混合液的荧光强度，输出检测信号S；和
判断步骤：根据所述检测信号S的变化趋势来判断是否达到临界胶束浓度cmc，如果判断结果为是，则输出所述待测溶液的浓度作为cmc浓度，结束所有步骤；如果判断结果为否，则清空所述样品池，返回到所述配液步骤，向所述待测溶液中追加规定量的表面活性剂，并继续执行接下来的取样步骤、探针加入步骤、检测步骤和判断步骤，
在所述判断步骤中，如果所述判断结果为否、但所述配液步骤中的所述规定量的表面活性剂的追加次数已经达到预定的阈值，则结束所有步骤。
本发明的cmc判断方法中所采用的表面活性剂溶液可以是直接配置的洗涤剂水溶液，也可以是用于实际机洗的洗涤设备中的洗涤剂水溶液。上 述洗涤剂水溶液是包含一种或多种表面活性剂成分的洗涤剂的水溶液，其中至少包含阴离子性表面活性剂和/或非离子性表面活性剂。
由于本发明中采用了具有聚集诱导发光特性的AIE荧光探针作为标记物，因此，可以采用灵敏度不高的常规的荧光检测器来准确地测定洗涤剂水溶液的荧光强度，通过将荧光强度变换为检测信号S而实现cmc的在线判断和洗涤剂添加量的智能控制。
本发明的cmc判断方法中采用的AIE荧光探针可以是包含水溶性AIE分子的荧光探针水溶液，也可以是本发明的包含疏水性AIE分子和助剂的AIE荧光探针组合物。从成本、适用性和方便性考虑，优选采用本发明的AIE荧光探针组合物。
添加有作为AIE荧光探针的HPS分子的洗涤剂水溶液在一定的范围内均有肉眼观察到的黄绿色荧光，且荧光强度先增加、然后显著减弱。在直接配制的洗涤剂水溶液的情况下，肉眼粗略观察到的最强荧光强度对应的浓度范围在0.1g/L～0.2g/L附近，当洗涤剂浓度＞2g/L时，荧光强度明显下降。
为了实现洗涤设备的自动控制，需要将荧光检测器检测出的混合液的荧光强度输出为检测信号S，所述检测信号S为对应于特定波长下的荧光强度F的电压信号，将其输出至后述的判断机构或决定机构。
关于阈值S 0，可以通过前面所述的表面活性剂溶液的cmc测定方法，预先在多个样品池或单个样品池中配制一系列具有递增浓度的表面活性剂的待测溶液，将检测出的最大荧光强度所对应的检测信号S设定为阈值S 0。
然后，在判断步骤中，如果检测信号S等于或高于预先设定的阈值S 0，则判断结果为是(洗涤剂水溶液已达到cmc浓度)；如果检测信号S低于所述阈值S 0，则判断结果为否(洗涤剂水溶液未达到cmc浓度)。
但是，由于实际机洗的洗涤设备中的洗涤剂水溶液的cmc浓度受到多方面因素(例如水温、织物重量等)影响，有时预设的阈值S 0并不对应于实际的cmc浓度，通常，实际机洗的洗涤剂水溶液的表观cmc浓度远远大于上述阈值S 0对应的cmc浓度，在这种情况下，优选在实际的洗涤过程中分批少量添加洗涤剂，通过本发明的cmc判断方法，对洗涤剂水溶液的表观cmc浓度进行在线判断，从而实现洗涤剂的智能添加。
优选在执行两次以上的所述判断步骤中，通过观察相邻两次的所述检测信号S X、S Y之间的差值变化，来判断所述表面活性剂的浓度是否达到临界胶束浓度cmc。
更具体来说，在所述相邻两次的检测信号中，如果后一次的检测信号S Y与前一次的检测信号S X之间的差值S Y-S X为0或者变为负值，则所述判断结果为是(洗涤剂水溶液已达到cmc浓度)；如果所述差值S Y-S X大于0，则所述判断结果为否(洗涤剂水溶液未达到cmc浓度)。
当将上述cmc判断方法应用于洗涤设备的实际洗涤过程中时，判断步骤主要用于决定是否需要补加洗涤剂。在第一次加入洗涤剂后，洗涤设备即可开始进行洗涤，洗涤过程中可进行多次取样、判断；也可以在所有步骤结束后开始洗涤。
在本发明的基于AIE荧光探针的cmc判断方法中，由于采用了具有聚集诱导发光特性的AIE荧光探针，因此可以不借助精密仪器、采用通常的低灵敏度的荧光检测器、甚至有时仅通过肉眼即可识别AIE荧光强度变化，因此可简单、快速、高效地确定洗涤剂水溶液的cmc，可有效应用在洗涤行业中用于在线监测洗涤水溶液中的洗涤剂含量，在洗涤剂的智能投放中具有实际的指导意义。
(基于AIE荧光探针的cmc判断装置)
进而，本发明还提供一种基于AIE荧光探针的cmc判断装置，是用于判断表面活性剂溶液是否达到临界胶束浓度cmc的判断装置，包括表面活性剂的储存机构、添加机构、取样机构、样品池、AIE荧光探针的储存机构、加样机构、检测机构、cmc判断机构、以及决定机构，其中，依次执行以下的操作：
所述添加机构从所述表面活性剂的储存机构中取出一定量的表面活性剂与水混合搅拌，配制成待测溶液，
所述取样机构从所述待测溶液中取出少量转移至所述样品池中，
所述加样机构从所述AIE荧光探针的储存机构中取出微量探针溶液加入所述样品池中，并施加轻微振动，形成混合液，
所述检测机构检测所述混合液的荧光强度，将得到的检测信号传送至所述cmc判断机构，
所述cmc判断机构通过所述检测信号的变化趋势来判断是否达到临界 胶束浓度cmc，
如果所述cmc判断机构的判断结果为是，则所述决定机构输出所述待测溶液的浓度作为cmc浓度，结束所有操作；
如果所述cmc判断机构的判断结果为否、且所述添加机构的执行次数低于预定的阈值，则清空所述样品池，所述添加机构向所述待测溶液中追加规定量的表面活性剂，并继续执行后续的操作，
如果所述cmc判断机构的判断结果为否、且所述添加机构的执行次数已达到预定的阈值，则结束所有操作。
该装置中所采用的AIE荧光探针优选为本发明上述的AIE荧光探针组合物。
当将上述装置应用于实际洗涤设备中时，也可以不输出所述cmc浓度，仅根据cmc判断机构的判断结果来决定是否追加表面活性剂(洗涤剂)。所述决定机构可以在初次的检测操作结束后、或者结束所有操作之后，控制洗涤设备开始洗涤。
检测机构可以是激发波长范围为275～375nm、可接收的发射波长范围为350～750nm的荧光传感器，优选为激发波长范围为275～375nm、可接收的波长范围中至少包含350～370nm或720～740nm的荧光传感器。
作为AIE荧光探针的HPS分子在365nm紫外光激发下，主要有两个荧光强度的发射峰：在350～370nm范围内的尖锐、强度较大的荧光峰、和在720～740nm范围内强度相对较小、宽矮的荧光峰，且与实际的洗涤剂水溶液(例如蓝月亮公司出品的至尊洁净洗涤剂和至尊亮白洗涤剂)中包含的荧光增白剂(例如CBS)的发射峰不重合，即，避开了出现荧光增白剂CBS的发射峰的400～550nm的波长范围。这样，可以避免荧光增白剂对cmc判断结果的干扰。
通过采用本发明的基于AIE荧光探针的cmc判断方法及装置，可以实际运用到洗涤设备中，进行cmc的在线检测、在线判断和洗涤剂的自动添加，因此能够应用于洗涤设备的洗涤剂的智能投放系统。
实施例
以下，通过实施例对本发明更具体地进行说明，但本发明只要不脱离其主旨，则不限定于以下的实施例。
(实施例1)
<AIE荧光探针组合物的配制>
将作为探针化合物的HPS(98％纯度，分子量M＝938)以浓度成为0.001mol/L的方式溶解在作为助剂的正丁醇中，配制为探针溶液。
<包含表面活性剂的待测溶液的配制>
作为包含表面活性剂的待测溶液，将至尊洁净洗涤剂B1-B10(商品名，蓝月亮公司制)直接配制为一系列浓度分别为0.02g/L、0.05g/L、0.1g/L、0.2g/L、0.5g/L、1g/L、2g/L、5g/L、10g/L、20g/L的洗涤剂水溶液，各取150μL的上述探针溶液加入到5mL的上述洗涤剂水溶液中，配制成待测溶液，待测溶液中HPS探针的浓度为30μmol/L。
(参考例1)
除了不加入探针溶液以外，与实施例1同样地配制了参考例1的包含表面活性剂的待测溶液，进行对照。
<荧光强度的测定>
采用订制组装的荧光检测器(滤光片包括激发滤光片(365nm)、二向色镜、发射滤光片(729nm)，光源：峰值波长365nm，波段300～400nm，工作电流:0.02A，工作电压:5V)，对上述添加有HPS探针的待测溶液进行荧光检测，根据荧光发光的明亮程度(发光强度转换为有效的电压可读示数)来检测荧光强度。将实施例1和参考例1的结果示于图2。
<洗涤剂水溶液的cmc浓度的确定>
图2是表示在上述直接配制的至尊洁净洗涤剂水溶液中添加了本发明的AIE荧光探针组合物(实施例1，图中标记为黑圆点)以及不添加本发明的AIE荧光探针组合物(参考例1，图中标记为黑方块)时的荧光强度随浓度变化的曲线图。
从图2可以看出，当未加入探针溶液时，洗涤剂水溶液的荧光强度很低，而且其强度随洗涤剂浓度的增加几乎不产生变化(参考例1)。
与此相对照，在实施例1的添加了本发明的探针溶液(HPS-正丁醇)的洗涤剂水溶液中，当洗涤剂水溶液的浓度较低(低于cmc)时，也观察到一定强度的荧光。推测这是因为当体系中添加了洗涤剂和HPS探针分子后，在洗涤剂中的表面活性剂的烷基链之间的疏水相互作用以及HPS分子 之间的π-π相互作用的驱动下，HPS/表面活性剂的混合物开始聚集，它们可以形成有序结构或复合结构，有效地限制了分子内的运动，从而表现出一定的聚集发光特性。
当体系中洗涤剂水溶液的浓度达到或高于cmc(小于10倍cmc)时，表面活性剂分子开始大量自组装形成胶束。此时胶束大多成球形，且胶束的大小和形状大致不变。在亲水-疏水相互作用的驱动下，亲油(疏水)的HPS探针分子在助剂(正丁醇)的协助下，进入并聚集在球形胶束的疏水核中，并在0.1～2g/L浓度范围内表现出荧光强度较强的AIE特性。图2中曲线的峰值(最大荧光强度)所对应的待测溶液的浓度为0.1g/L处，因此，可以将该浓度确定为直接配制的洗涤剂水溶液的cmc浓度。
当体系中洗涤剂水溶液浓度过高(例如10倍cmc以上)时，荧光发射强度明显下降，这可能是因为过量的表面活性剂浓度导致球形胶束形成蠕虫状胶束或囊泡等各向异性聚集体，HPS被分布到不同形状的胶束或聚集体中，HPS分子之间的π-π相互作用被破坏，HPS分子内运动限制变弱，处于激发态的分子通过振转形式将光能以热能等形式消耗，导致HPS的荧光减弱。推测也可能是由于在非球形胶束聚集体环境中HPS探针荧光各向异性的影响，造成在肉眼上观察到的荧光强度明显变弱。
另外，上述至尊洁净洗涤剂水溶液的AIE荧光强度的变化也可仅通过肉眼进行识别，将肉眼所见的荧光强度最强的待测溶液的浓度确定为cmc浓度，其观察结果与上述采用荧光检测器的测定结果基本一致。
为了进一步验证采用了本发明的AIE荧光探针组合物的cmc测定结果的准确性，我们使用K100C表面张力仪，对实施例1中采用的至尊洁净洗涤剂水溶液测定了cmc，得到如图3所示的表面张力随浓度变化的曲线。
通过对图3中的变化曲线进行拟合，推测出直接配制的至尊洁净洗涤剂水溶液的cmc≈0.09g/L，与本发明的采用AIE荧光探针法的测定结果(0.1g/L)比较接近，表明本发明的采用AIE荧光探针组合物的cmc测定方法可行有效。
(实施例2～6、比较例1～3、参考例2)
除了采用包含荧光增白剂CBS的至尊亮白洗涤剂A0-A10(商品名，蓝月亮公司制)代替至尊洁净洗涤剂B1-B10、并且将AIE荧光探针组合物 的组成如下述表2-1、表2-2那样变更后，与实施例1同样地直接配制了实施例2～6、比较例1～3的待测溶液，并进行了同样的测定。
此外，除了不加入探针溶液以外，与实施例2同样地配制了参考例2的待测溶液进行对照。结果如表2-1、表2-2所示。表中，关于电压值的一栏中黑体的数字表示对应于最大荧光强度(峰值)的电压值。
表2-1：
Figure PCTCN2022096821-appb-000003
表2-2：
Figure PCTCN2022096821-appb-000004
注：1*“HPS-丙干正丁醇”表示将HPS先溶解于丙酮，等丙酮挥发完毕后加入正丁醇。
2*表中的“-”表示未测定。
3*表示将丙酮挥发完毕后的测定结果。
由表2-1、表2-2可以看出，在本发明的实施例2～6中，虽然采用了不同的助剂种类，但最大荧光强度对应的待测溶液的浓度均为0.2g/L，因此，可以将该浓度确定为直接配制的至尊亮白洗涤剂水溶液的cmc浓度。
进而，如实施例6所示，当将HPS预先溶解于丙酮、等挥发变干后加入正丁醇的情况下，同样在合适的浓度范围内产生了稳定且明显的AIE现象，并且在cmc浓度附近显示了最大的荧光强度。
与此相对照，比较例1中所采用的助剂分子(氨甲基丙酮)中的烷基链的碳原子数不满足本发明的通式(1)的规定，因此，在0～20g/L的浓度范围内未显示出明显的AIE现象。
比较例2中采用了正丁醇与丙酮的混合溶剂，但丙酮本身不满足本发 明的通式(1)的规定，而且，由于丙酮在混合溶剂中挥发程度的不确定性，导致待测溶液的发光强度的变化趋势不稳定，不能准确测定cmc浓度。这个结果表明，如果探针溶液中的挥发性溶剂未挥发完全，会导致测定结果的不准确。
比较例3直接采用了丙酮作为助剂，并且在丙酮完全挥发后进行了测定。从实验结果来看，虽然丙酮在完全挥发后显示了明显的AIE现象，但由于丙酮极易挥发的特性而不能配制成稳定的探针溶液，且测定过程中需要等待溶剂的挥发，因此不适合作为本发明的探针溶液，被排除在本发明的范围之外，成为比较例。
(实施例7)
<实际机洗的洗涤剂水溶液的配制>
将重量为2.5kg的衣服加入滚筒洗衣机中，并加入13L的水和1g的至尊洁净洗涤剂B0-B10(商品名，蓝月亮公司制)进行搅拌，然后，在洗衣机的洗涤过程中不断追加一定量的洗涤剂，使得加入13L水中的洗涤剂用量分别为1g、2g、4g、8g、12g、16g、20g、24g、28g、32g，对应的至尊洁净洗涤剂浓度分别为0.075g/L、0.15g/L、0.31g/L、0.62g/L、0.92g/L、1.23g/L、1.54g/L、1.85g/L、2.15g/L、2.46g/L，从滚筒洗衣机中依次取出这一系列包含不同浓度的洗涤剂的实际机洗的洗涤剂水溶液作为待测溶液。
在实施例7中，除了采用上述实际机洗用的洗涤剂水溶液来代替实施例1中采用的直接配制的洗涤剂水溶液以外，与实施例1同样地进行了荧光强度的测定，结果示于图4。
图4是表示在实际机洗的至尊洁净洗涤剂水溶液中添加了本发明的AIE荧光探针组合物(HPS-正丁醇)时的荧光强度随浓度变化的曲线图。
如图4所示，与图2的变化趋势相同，随着洗涤剂水溶液中的洗涤剂浓度的逐渐升高，各洗涤剂水溶液的荧光强度发生了从低到高的突变，并且在到达最大荧光强度后逐渐减弱，但与图2不同之处在于，曲线中出现的峰值(最大荧光强度)所对应的洗涤剂水溶液的浓度为0.62g/L。
由此可以确定，在实施例7所示的使用场景下，实际机洗用的洗涤剂水溶液的cmc浓度为0.62g/L。该cmc浓度高于实施例1中采用的直接配置的洗涤剂水溶液所测得的cmc浓度，这是因为，用于实际机洗的洗涤剂 水溶液中包含大量衣物，对洗涤剂有一定的吸附，因此表观cmc浓度升高，这个结果是合理的。
为了进一步验证采用了本发明的AIE荧光探针组合物的cmc测定结果的准确性，我们使用K100C表面张力仪，对实施例7中采用的实际机洗的至尊洁净洗涤剂水溶液测定了cmc，得到如图5所示的界面张力随浓度变化的曲线。
通过对图5中的变化曲线进行拟合，推测出实际机洗的至尊洁净洗涤剂水溶液的cmc≈0.7g/L，与本发明的采用AIE荧光探针法的测定结果(0.62g/L)比较接近，表明本发明的采用AIE荧光探针组合物的cmc测定方法可行有效。
从上述实施例1～7的结果可知，本发明的AIE荧光探针组合物可以形成稳定的探针溶液，在直接配制或实际机洗中采用的洗涤剂水溶液中均具有适用性，而且可避免洗涤剂水溶液中荧光增白剂的干扰，在合适的cmc浓度范围内显示AIE特性，因此可以应用于洗涤设备等实际用途，准确且方便地测出洗涤剂水溶液的cmc浓度。
工业上的可利用性
通过采用本发明的AIE荧光探针组合物，可以无需采用高精度的测试仪器，仅用简单组装的紫外可见光范围内的荧光检测器就可以实现对表面活性剂溶液的cmc浓度的在线测定和在线判断，便于工业化，特别是在洗涤设备的洗涤剂的智能添加系统中具有重要的作用。

Claims (20)

  1. 一种AIE荧光探针组合物，其是用于测定表面活性剂溶液的临界胶束浓度cmc的探针溶液，其特征在于：
    包含探针化合物和助剂，所述探针化合物为疏水性AIE分子，所述助剂为由下述通式(1)表示的至少一种有机溶剂，
    (R) n-X  (1)
    其中，R为碳原子数为3～10的取代或无取代的直链或支链烷基，n为1或2的整数，当n为2时，两个R可以相同也可以不同，
    X为选自羟基、氨基、氰基、卤素基、酰胺基、羰基、醛基、酯基、醚基中的任一种的极性基团。
  2. 根据权利要求1或2所述的AIE荧光探针组合物，其中，所述助剂的沸点大于70℃。
  3. 根据权利要求1或2所述的AIE荧光探针组合物，其中，所述通式(1)中，所述R为碳原子数为3～6的无取代的直链或支链烷基，所述X选自羟基或氨基。
  4. 根据权利要求1或2所述的AIE荧光探针组合物，其中，所述助剂为选自正丙醇、异丙醇、叔丁醇、正丁醇、正丁胺、戊胺中的一种以上。
  5. 根据权利要求1或2所述的AIE荧光探针组合物，其中，所述助剂具备两亲性结构，在分子中具有由所述极性基团构成的亲水区域和由所述烷基构成的疏水区域，所述探针化合物在所述助剂中的溶解度高于在水中的溶解度。
  6. 根据权利要求1或2所述的AIE荧光探针组合物，其中，
    所述助剂为碳原子数为3～6的烷基醇，所述探针溶液的配制方法是：将所述探针化合物预先溶解于丙酮，然后使其挥发变干，最后加入所述烷基醇，从而得到所述AIE荧光探针组合物。
  7. 根据权利要求1或2所述的AIE荧光探针组合物，其中，所述探针 化合物为包含由下述化学式1～12中任一种表示的化合物作为基本骨架的疏水性AIE分子：
    Figure PCTCN2022096821-appb-100001
  8. 根据权利要求7所述的AIE荧光探针组合物，其中，
    所述疏水性AIE分子为由所述化学式1表示的无取代的四苯基乙烯(TPE)、由所述化学式2表示的无取代的二苯乙烯基蒽(DSA)、由所述化学式7表示的无取代的六苯基硅杂环戊二烯(HPS)、或由所述化学式10表示的无取代的苯并苝(BP)。
  9. 根据权利要求1或2所述的AIE荧光探针组合物，其中，
    所述表面活性剂溶液中至少包含阴离子性表面活性剂和/或非离子性表面活性剂。
  10. 根据权利要求1或2所述的AIE荧光探针组合物，其中，
    所述探针化合物在所述AIE荧光探针组合物中的浓度为500～2000μmol/L，所述探针化合物在所述表面活性剂溶液中的浓度为1～1000μmol/L。
  11. 根据权利要求1或2所述的AIE荧光探针组合物，其中，所述助剂相对于所述AIE荧光探针组合物整体的含量比例为70质量％～99质量％，所述探针化合物相对于所述AIE荧光探针组合物整体的含量比例为1质量％～30质量％。
  12. 一种表面活性剂溶液的cmc测定方法，依次包括下述步骤：
    配液步骤：在多个样品池中配制一系列具有递增浓度的表面活性剂的待测溶液，
    加入探针步骤：在所述多个样品池中分别添加一定量的探针溶液，
    检测步骤：利用检测机构检测出各待测溶液的荧光强度，以及
    决定步骤：根据所检测出的各待测溶液的荧光强度的变化趋势来决定所述表面活性剂溶液的cmc浓度，
    其特征在于，
    所述探针溶液为权利要求1～11中任一项所述的AIE荧光探针组合物。
  13. 根据权利要求12所述的cmc测定方法，其中，所述探针化合物为无取代的六苯基硅杂环戊二烯(HPS)，
    在所述检测步骤中，所述多个样品池中的各待测溶液的荧光强度发生从低到高的突变，到达最大荧光强度后逐渐减弱，
    在所述决定步骤中，将检测出的所述最大荧光强度所对应的样品池中的所述待测溶液的浓度作为所述表面活性剂溶液的cmc浓度。
  14. 一种表面活性剂溶液的cmc测定装置，包括：
    多个样品池，其中配制有一系列具有递增浓度的表面活性剂的待测溶 液，
    探针容器，其中容纳有包含探针化合物的探针溶液，
    加样机构，用于从所述探针容器中取出一定量的探针溶液加入所述多个样品池中，
    检测机构，用于检测出所述多个样品池中的所述待测溶液的荧光强度，和
    决定机构，根据所述检测机构检测出的各待测溶液的荧光强度的变化趋势来决定所述表面活性剂溶液的cmc浓度，
    其特征在于，
    所述探针溶液为权利要求1～11中任一项所述的AIE荧光探针组合物。
  15. 一种基于AIE荧光探针的cmc判断方法，是用于判断表面活性剂溶液是否达到临界胶束浓度cmc的判断方法，其特征在于：依次包括下述步骤：
    配液步骤：在水中加入初始量的表面活性剂，施以搅拌，配制成待测溶液；
    取样步骤：从所述待测溶液中取出少量转移至样品池；
    探针加入步骤：在所述样品池中加入AIE荧光探针，并施加轻微振动，形成混合液；
    检测步骤：通过荧光检测器检测所述混合液的荧光强度，输出检测信号S；和
    判断步骤：根据所述检测信号S的变化趋势来判断是否达到临界胶束浓度cmc，如果判断结果为是，则输出所述待测溶液的浓度作为cmc浓度，结束所有步骤；如果判断结果为否，则清空所述样品池，返回到所述配液步骤，向所述待测溶液中追加规定量的表面活性剂，并继续执行接下来的取样步骤、探针加入步骤、检测步骤和判断步骤，
    在所述判断步骤中，如果所述判断结果为否、但所述配液步骤中的所述规定量的表面活性剂的追加次数已经达到预定的阈值，则结束所有步骤。
  16. 根据权利要求15所述的cmc判断方法，其中，所述AIE荧光探针为权利要求1～11中任一项所述的AIE荧光探针组合物。
  17. 根据权利要求15所述的cmc判断方法，其中，
    在所述判断步骤中，如果所述检测信号S等于或高于预先设定的阈值S 0，则判断结果为是；如果所述检测信号S低于所述阈值S 0，则判断结果为否。
  18. 根据权利要求15所述的cmc判断方法，其中，在所述判断步骤中，如果相邻两次检测步骤所得到的检测信号中的后一次的检测信号S Y与前一次的检测信号S X之间的差值S Y-S X为0或者变为负值，则所述判断结果为是；如果所述差值S Y-S X大于0，则所述判断结果为否。
  19. 一种基于AIE荧光探针的cmc判断装置，是用于判断表面活性剂溶液是否达到临界胶束浓度cmc的判断装置，包括表面活性剂的储存机构、添加机构、取样机构、样品池、AIE荧光探针的储存机构、加样机构、检测机构、cmc判断机构、以及决定机构，其中，依次执行以下的操作：
    所述添加机构从所述表面活性剂的储存机构中取出一定量的表面活性剂与水混合搅拌，配制成待测溶液，
    所述取样机构从所述待测溶液中取出少量转移至所述样品池中，
    所述加样机构从所述AIE荧光探针的储存机构中取出微量探针溶液加入所述样品池中，并施加轻微振动，形成混合液，
    所述检测机构检测所述混合液的荧光强度，将得到的检测信号传送至所述cmc判断机构，
    所述cmc判断机构通过所述检测信号的变化趋势来判断是否达到临界胶束浓度cmc，
    如果所述cmc判断机构的判断结果为是，则所述决定机构输出所述待测溶液的浓度作为cmc浓度，结束所有操作；
    如果所述cmc判断机构的判断结果为否、且所述添加机构的执行次数低于预定的阈值，则清空所述样品池，所述添加机构向所述待测溶液中追加规定量的表面活性剂，并继续执行后续的操作，
    如果所述cmc判断机构的判断结果为否、且所述添加机构的执行次数已达到预定的阈值，则结束所有操作。
  20. 根据权利要求19所述的cmc判断装置，其中，所述AIE荧光探针为权利要求1～11中任一项所述的AIE荧光探针组合物。
PCT/CN2022/096821 2022-01-30 2022-06-02 AIE荧光探针组合物、表面活性剂溶液的cmc测定方法及装置、cmc判断方法及装置 Ceased WO2023142326A1 (zh)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2024501763A JP7665089B2 (ja) 2022-01-30 2022-06-02 ＡＩＥ蛍光プローブ組成物、界面活性剤溶液のｃｍｃ測定方法及び装置、ｃｍｃ判定方法及び装置
US18/265,230 US20240263068A1 (en) 2022-01-30 2022-06-02 AIE Fluorescent Probe Composition, Method and Device for Measuring CMC of Surfactant Solution, and Method and Device for CMC Determination
EP22923138.6A EP4471106A4 (en) 2022-01-30 2022-06-02 Composition of an AIE fluorescent probe, method and device for measuring CMC in surfactant solution, and method and device for determining CMC

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210113645.0 2022-01-30
CN202210113645.0A CN116554861B (zh) 2022-01-30 2022-01-30 AIE荧光探针组合物、表面活性剂溶液的cmc测定方法及装置、cmc判断方法及装置

Publications (1)

Publication Number Publication Date
WO2023142326A1 true WO2023142326A1 (zh) 2023-08-03

Family

ID=87470258

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/096821 Ceased WO2023142326A1 (zh) 2022-01-30 2022-06-02 AIE荧光探针组合物、表面活性剂溶液的cmc测定方法及装置、cmc判断方法及装置

Country Status (5)

Country Link
US (1) US20240263068A1 (zh)
EP (1) EP4471106A4 (zh)
JP (1) JP7665089B2 (zh)
CN (1) CN116554861B (zh)
WO (1) WO2023142326A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116990505B (zh) * 2023-09-27 2024-01-19 广东省大湾区华南理工大学聚集诱导发光高等研究院 一种白介素-6aie荧光免疫层析试纸条、试剂盒及其应用
WO2025167122A1 (zh) 2024-09-24 2025-08-14 广州蓝月亮实业有限公司 ACQ荧光探针组合物、cmc测定方法、污渍洗净浓度判定方法、洗涤剂投放控制方法及系统

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103411961A (zh) * 2013-07-15 2013-11-27 南方医科大学 一种测定表面活性剂临界胶束浓度灵敏的荧光点亮探针法
CN104974745A (zh) * 2014-04-07 2015-10-14 香港科技大学深圳研究院 两亲性的具有聚集诱导发光特性的发光物及其应用
WO2016078603A1 (en) * 2014-11-21 2016-05-26 The Hong Kong University Of Science And Technology Aie luminogens for bacteria imaging, killing, photodynamic therapy and antibiotics screening, and their methods of manufacturing
CN110028446A (zh) 2019-04-10 2019-07-19 华东理工大学 一种基于聚集诱导发光特征的荧光探针及其测定临界胶束浓度的方法和应用

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7960439B1 (en) 2006-06-12 2011-06-14 Iowa State University Research Foundation, Inc. Environmentally sensitive foldable oligomers
JP2010195750A (ja) * 2009-02-27 2010-09-09 Osaka Municipal Technical Research Institute 両親媒性物質、界面活性剤、および、界面活性剤の使用方法
JP2012185041A (ja) * 2011-03-04 2012-09-27 Saitama Univ ウィルス、微生物類及び毒素の検出方法
US9511152B2 (en) 2012-04-05 2016-12-06 The Board Of Regents Of The University Of Texas System Multicolored pH-activatable fluorescence nanoplatform
CN104193666B (zh) 2014-07-30 2017-07-11 南方医科大学 一种1,3‑二取代马来酰亚胺化合物及其作为表面活性剂临界胶束浓度荧光探针的应用
EP3281644A1 (en) 2016-08-08 2018-02-14 Consejo Superior De Investigaciones Científicas Stable fluorescent nanovesicles, method for obtaining them and uses thereof
CN106546564B (zh) * 2016-09-27 2019-05-21 南方医科大学 五取代四氢嘧啶化合物在滴定法测定表面活性剂临界胶束浓度中的应用
CN108387559B (zh) * 2018-01-15 2023-05-12 南方医科大学 一种表面活性剂临界胶束浓度试纸及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103411961A (zh) * 2013-07-15 2013-11-27 南方医科大学 一种测定表面活性剂临界胶束浓度灵敏的荧光点亮探针法
CN104974745A (zh) * 2014-04-07 2015-10-14 香港科技大学深圳研究院 两亲性的具有聚集诱导发光特性的发光物及其应用
CN106566532A (zh) 2014-04-07 2017-04-19 香港科技大学深圳研究院 两亲性的具有聚集诱导发光特性的发光物及其应用
WO2016078603A1 (en) * 2014-11-21 2016-05-26 The Hong Kong University Of Science And Technology Aie luminogens for bacteria imaging, killing, photodynamic therapy and antibiotics screening, and their methods of manufacturing
CN110028446A (zh) 2019-04-10 2019-07-19 华东理工大学 一种基于聚集诱导发光特征的荧光探针及其测定临界胶束浓度的方法和应用

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
See also references of EP4471106A4
TANG LI, JIN JIAKE, ZHANG SHUANG, MAO YU, SUN JINGZHI, YUAN WANGZHANG, ZHAO HUI, XU HAIPENG, QIN ANJUN, TANG BEN ZHONG: "Detection of the critical micelle concentration of cationic and anionic surfactants based on aggregation-induced emission property of hexaphenylsilole derivatives", SCIENCE IN CHINA. SERIES B: CHEMISTRY, ZHONGGUO KEXUE ZAZHISHE, BEIJING, CN, vol. 52, no. 6, 1 June 2009 (2009-06-01), CN , pages 755 - 759, XP093080650, ISSN: 1006-9291, DOI: 10.1007/s11426-009-0119-7 *
TANG LI: "Detection of the critical micelle concentration of cationic and anionic surfactants based on aggregation-induced emission property of hexaphenylsilole derivatives", SCI CHINA SER B-CHEM, vol. 52, no. 6, June 2009 (2009-06-01), pages 755 - 759, XP093080650, DOI: 10.1007/s11426-009-0119-7
ZHU CONGSHAN, PANG SHAOPENG, XU JIANPING, JIA LAN, XU FANGMING, MEI JU, QIN ANJUN, SUN JINGZHI, JI JIAN, TANG BENZHONG: "Aggregation-induced emission of tetraphenylethene derivative as a fluorescence method for probing the assembling/disassembling of amphiphilic molecules", ANALYST, ROYAL SOCIETY OF CHEMISTRY, UK, vol. 136, no. 16, 1 January 2011 (2011-01-01), UK , pages 3343, XP093080648, ISSN: 0003-2654, DOI: 10.1039/c1an15176b *

Also Published As

Publication number Publication date
EP4471106A1 (en) 2024-12-04
JP2024526333A (ja) 2024-07-17
US20240263068A1 (en) 2024-08-08
CN116554861B (zh) 2025-10-21
CN116554861A (zh) 2023-08-08
EP4471106A4 (en) 2026-03-04
JP7665089B2 (ja) 2025-04-18

Similar Documents

Publication Publication Date Title
Stuart et al. The use of Nile Red to monitor the aggregation behavior in ternary surfactant–water–organic solvent systems
Song et al. Ratiometric fluorescent detection of biomakers for biological warfare agents with carbon dots chelated europium-based nanoscale coordination polymers
WO2023142326A1 (zh) AIE荧光探针组合物、表面活性剂溶液的cmc测定方法及装置、cmc判断方法及装置
CN110028446B (zh) 一种基于聚集诱导发光特征的荧光探针及其测定临界胶束浓度的方法和应用
KR101311224B1 (ko) 과산화수소 검출용 형광 나노 프로브 및 그 제조방법
Ji et al. Selection of an aggregation-caused quenching-based fluorescent tracer for imaging studies in nano drug delivery systems
Geng et al. Red-Emissive Chemiluminescent Nanoparticles with Aggregation-Induced Emission Characteristics for In Vivo Hydrogen Peroxide Imaging.
CN114672302A (zh) 一种基于硅罗丹明的近红外mof荧光探针的制备和应用
CN106478731A (zh) 一类双发射比率型氧气探针及应用
CN113999679B (zh) 一种基于上转换纳米材料“关-开”型荧光传感器高灵敏检测甲砜霉素的方法
Xie et al. Micelle-mediated chemiluminescence as an indicator for micellar transitions
Zhao et al. An environmentally friendly AIE probe for CMC determination
Mocanu et al. New flexible molecular probes bearing dansyl and TEMPO moieties for host–guest interactions in solution and gels
Lemon et al. Comparison of self-assembled and micelle encapsulated QD chemosensor constructs for biological sensing
CN116556020A (zh) 洗涤设备、用于洗涤设备的洗涤剂的投放控制方法及系统
Liu et al. Graphene oxide functionalization with aminocoumarin nanosheet fluorescent dye: Preparation, electrochemistry, spectroscopy and imaging in the living cells
Zhu et al. Determination of nucleic acids by near-infrared fluorescence quenching of hydrophobic thiacyanine dye in the presence of Triton X-100
CN118777399A (zh) 一种同时测定阳离子表面活性剂临界聚集浓度和临界胶束浓度的方法
Kaur et al. A perylene-based fluorescent probe for highly efficient SDS detection
Yan-Min et al. Combined fluorescence and electrochemical investigation on the binding interaction between organic acid and human serum albumin
CN109708996B (zh) 基于手性单壁碳纳米管的粘度探针及其应用
Elhassan et al. Lipophilic molecular rotor to assess the viscosity of oil core in nano-emulsion droplets
WO2025167122A1 (zh) ACQ荧光探针组合物、cmc测定方法、污渍洗净浓度判定方法、洗涤剂投放控制方法及系统
CN108387559A (zh) 一种表面活性剂临界胶束浓度试纸及其制备方法
Thorve et al. Partitioning of gentamicin and oxytetracycline in spherical and rod-shaped micellar systems of tetradecyltrimethylammonium bromide with addition of sodium salicylate and delivery to bovine serum albumin: Thermodynamic insight

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 18265230

Country of ref document: US

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22923138

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2024501763

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2022923138

Country of ref document: EP

Effective date: 20240830