CN112939871A - Nanometer thermometer based on saturated fatty acid and double-response fluorescent molecule - Google Patents
Nanometer thermometer based on saturated fatty acid and double-response fluorescent molecule Download PDFInfo
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Abstract
The invention discloses a nanometer thermometer based on saturated fatty acid and double-response fluorescent molecules, which is prepared by the following method: 1) dissolving a saturated fatty acid double bond derivative and a dual-response fluorescent molecule in the heated and melted saturated fatty acid, cooling to obtain a solid A, and grinding the solid A into powder to obtain powder A; 2) dissolving a double-bond-containing polymerization monomer in water to prepare a monomer aqueous solution; mixing the powder A, the monomer aqueous solution and the MBA solution, adding a catalyst, uniformly mixing by ultrasonic or oscillation, adding an APS aqueous solution, carrying out polymerization reaction, and carrying out dialysis or ultracentrifugation to obtain the final product; the nano thermometer prepared by the invention has the advantages of simple synthesis steps, high yield, easiness in purification, capability of simultaneously evaluating the temperature change by using three fluorescence variables of fluorescence intensity, spectral displacement and fluorescence lifetime, good photostability, high sensitivity, good accuracy, good reversibility, good biocompatibility and the like. In the temperature detection of the biofilm, the method has excellent sensitivity and accuracy.
Description
Technical Field
The invention belongs to the field of biosensing, and relates to a saturated fatty acid and dual-response fluorescent molecule-based nano thermometer and a preparation method thereof.
Background
Temperature is one of the most basic and important physiological parameters, and its dynamic changes are closely related to various physiological activities and pathological states of a living body, such as gene expression, cell division, inflammatory response, and the like. Therefore, the realization of highly sensitive and highly accurate detection of temperature at the subcellular level is of great importance for understanding and revealing various life processes. Among various temperature sensing systems, the fluorescence nano thermometer is receiving attention due to its advantages of high sensitivity, good time-space resolution, non-invasiveness, real-time response, and the like. In such temperature sensing systems, temperature changes are often quantitatively correlated with changes in certain fluorescence parameters (e.g., fluorescence intensity, fluorescence lifetime, and/or spectral position, etc.), thereby indirectly reflecting subtle changes in temperature. Generally, organic/polymer nano thermometers have been widely developed because of their good biocompatibility. Although organic/polymeric nano-thermometers have made great progress in temperature sensing, there are still some challenges to be solved. For example, organic fluorophores do not provide significant signal changes over a particular temperature range; photobleaching readily occurs under continuous light irradiation; certain fluorescence parameters (such as intensity and spectral bandwidth) are more susceptible to the microenvironment in which they are located. These deficiencies limit the sensitivity and accuracy of temperature sensing to some extent. In order to amplify the signal response of organic fluorophores, researchers have developed systems based on thermoresponsive polymers. The system utilizes the change of hydrophilic/hydrophobic property in the phase transition process of the polymer to influence the local microenvironment of the organic fluorophore, thereby realizing temperature sensing. However, due to the heterogeneity of polymer compositions, the thermo-responsive polymers generally have a wide phase transition temperature range and a slow phase transition process, and these disadvantages greatly affect the sensitivity and responsiveness of temperature sensing. In addition, most organic/polymer nano thermometers rely on temperature sensing of a single fluorescence parameter only, and cannot use multiple parameters for cross validation at the same time, which reduces the sensing accuracy to a certain extent. Therefore, there is still a need to develop a new type of fluorescent nano-temperature that has higher sensitivity, responsiveness and accuracy.
In recent years, aggregation-induced emission (AIE) materials have been developed into a new class of organic fluorophores with promising application prospects, and have shown unique research advantages in fluorescence imaging. AIE fluorophores exhibit weak or no luminescence in dilute solutions; in the aggregated state, strong fluorescence is emitted due to restricted intramolecular motion. Generally, the AIE fluorophore has the advantages of high fluorescence quantum yield, large Stokes shift, good light stability and the like, and is particularly suitable for high-quality fluorescence imaging. In addition, functional fluorophores that respond to both molecular aggregation and microenvironment polarities can be obtained by introducing a donor-acceptor (D-a) structure into the AIE molecule, giving it an intramolecular twisted charge transfer (TICT) property. Generally, the emission wavelength of a molecule with the properties of TICT is significantly red-shifted with increasing polarity of the external environment, accompanied by a significant decrease in fluorescence intensity. However, for dual-response fluorescent molecules, the presence of the AIE property can greatly compensate for the intensity reduction due to the TICT effect, so that the total signal output is still maintained at a high level, and thus, the application of the AIE in fluorescence imaging is realized.
Phase Change Materials (PCMs) are a new class of thermally responsive materials that generally have a well-defined molecular structure, a narrow melting point range, and reversible solid-liquid phase transition characteristics. Among various PCMs, natural saturated fatty acids have attracted attention of researchers due to their advantages of low cost, good biocompatibility, biodegradability, and the like. Saturated fatty acids generally have high crystallinity, and thus it is difficult to achieve nanocrystallization thereof without affecting the physical properties thereof.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a dual-response fluorescent molecule.
The second purpose of the invention is to provide a preparation method of the dual-response fluorescent molecule.
It is a third object of the present invention to provide a nanothermometer based on saturated fatty acids and dual-responsive fluorescent molecules.
The fourth purpose of the invention is to provide a preparation method of the nano thermometer based on saturated fatty acid and dual-response fluorescent molecules.
The fifth purpose of the invention is to provide the application of the nano thermometer based on saturated fatty acid and dual-response fluorescent molecules in detecting the temperature of the biofilm.
The technical scheme of the invention is summarized as follows:
a dual-response fluorescent molecule has a structure shown in a formula V,
wherein R is1is-OCH3、-OH、-NH2、-N(CH3)2、-NHCOCH3or-OCOCH3；
R2is-H, -OCH3、-OH、-NH2、-N(CH3)2、-NHCOCH3or-OCOCH3；
R3is-C4H9、-C5H11、-C6H13、-C7H15or-C8H17。
The preparation method of the dual-responsiveness fluorescent molecule V comprises the following steps:
1) dissolving 4-bromo-benzylidene oxazolone I and compound II in ethanol, heating and refluxing under the catalysis of potassium carbonate, and monitoring by thin layer chromatography to obtain compound III;
2) compound III, compound IV, Pd (PPh)3)4Dissolving potassium carbonate in the mixed solvent, vacuumizing and blowing by using dry nitrogen; mixing, reacting and monitoring by thin-layer chromatography to obtain a dual-response fluorescent molecule V, wherein the mixed solvent is tetrahydrofuran aqueous solution with the volume concentration of 50-80%;
the reaction formula is as follows:
wherein R is1is-OCH3、-OH、-NH2、-N(CH3)2、-NHCOCH3or-OCOCH3；
R2is-H, -OCH3、-OH、-NH2、-N(CH3)2、-NHCOCH3or-OCOCH3；
R3is-C4H9、-C5H11、-C6H13、-C7H15or-C8H17。
A preparation method of a nanometer thermometer based on saturated fatty acid and dual-response fluorescent molecules comprises the following steps:
1) according to the mass ratio of 1 (0.01-10) to (89-98.99), dissolving a saturated fatty acid double bond derivative and a dual-response fluorescent molecule V in a heated and melted saturated fatty acid, cooling to obtain a solid A, and grinding the solid A into powder to obtain powder A;
the structure of the saturated fatty acid double bond derivative is shown as a formula IX:
wherein n is 9-17.
2) Dissolving a double-bond-containing polymerization monomer in water to prepare a monomer aqueous solution;
dissolving a cross-linking agent MBA in dimethyl sulfoxide to prepare an MBA solution;
dissolving initiator APS in water to prepare APS aqueous solution;
mixing the powder A, the monomer aqueous solution and the MBA solution, adding a catalyst TEMED, carrying out ultrasonic or oscillation uniform mixing, adding an APS aqueous solution, carrying out polymerization reaction for 1-3h at 0-4 ℃, and removing unreacted double-bond-containing polymerization monomers and water-soluble byproducts through dialysis or ultracentrifugation to prepare the nano thermometer based on saturated fatty acid and dual-responsive fluorescent molecules;
the mass ratio of the powder A to the double-bond-containing polymerized monomer is 1 (4-6);
the molar ratio of the double-bond-containing polymerized monomer to the MBA to the TEMED to the APS is 15 (6-9) to 0.8-1.2 to 1.8; MBA is an abbreviation for N, N-methylenebisacrylamide;
the APS is an abbreviation for ammonium persulfate;
TEMED is an abbreviation for tetramethylethylenediamine.
The saturated fatty acid is at least one of lauric acid, myristic acid, palmitic acid and stearic acid.
The double-bond-containing polymerized monomer is at least one of 2-methacryloyloxyethyl phosphorylcholine, N- [3- (dimethylamino) propyl ] methacrylamide and acrylamide.
The nanometer thermometer prepared by the method based on saturated fatty acid and double-response fluorescent molecules.
The application of a nanometer thermometer based on saturated fatty acid and double-response fluorescent molecules in detecting the temperature of a biofilm.
Has the advantages that:
(1) the saturated fatty acid and double-response fluorescent molecule-based nano thermometer can evaluate the temperature change by simultaneously using three fluorescent variables of fluorescence intensity, spectral displacement and fluorescence lifetime, and has the advantages of good light stability, high sensitivity, good accuracy, good reversibility, good biocompatibility and the like. At 30-42 deg.C, the sensitivity of spectral shift is 10.6 nm/deg.C, the sensitivity of fluorescence intensity is 11.3%/deg.C, and the sensitivity of fluorescence lifetime is 9.9%/deg.C, which is much higher than that of most fluorescence nanotherms (sensitivity of spectral shift <0.5 nm/deg.C and sensitivity of fluorescence intensity < 5%/deg.C).
(2) The preparation of the nanometer thermometer of the invention adopts the technology of combining nanometer precipitation and surface polymerization to obtain the fatty acid nanometer material with stable colloid, and the synthesis steps are simple, the yield is high and the purification is easy.
(3) The nano thermometer of the invention shows excellent sensitivity and accuracy in the temperature detection of the biofilm. Three fluorescence variables, namely fluorescence intensity, spectral shift and fluorescence lifetime, can also be used in temperature detection of biofilms to evaluate temperature changes.
Drawings
FIG. 1 is a photo-physical property characterization of the dual-responsive fluorescent molecule prepared in example 3, including solvation effect and AIE properties.
(A) Shows the fluorescence emission of the dual-response fluorescent molecule in different solvents.
(B) A plot of maximum emission and fluorescence intensity of a dual-responsive fluorescent molecule as a function of moisture content.
FIG. 2 is a graph showing the change of morphology, particle size, fluorescence spectrum and fluorescence lifetime with temperature of the saturated fatty acid and dual-responsive fluorescent molecule-based nano-thermometer prepared in example 4.
(A) Schematic representation of the surface polymerization method for preparing Poly-TICT @ AIE (SolidPCM is solid fatty acid, filtered PCM is Melted fatty acid, and TICT @ AIE is dual-responsive fluorescent molecule).
(B) TEM pictures showing the morphology of Poly-TICT @ AIE.
(C) Particle size distribution of Poly-TICT @ AIE.
(D) Poly-TICT @ AIE maximum emission wavelength as a function of temperature.
(E) Poly-TICT @ AIE changes fluorescence intensity with temperature.
(F) The maximum emission wavelength of Poly-TICT @ AIE was cycled between 25-42 deg.C for a number of cycles.
(G) Poly-TICT @ AIE fluorescence lifetime as a function of temperature.
FIG. 3 is temperature sensing of fluorescence spectrum and fluorescence intensity in biofilm of a nano thermometer based on saturated fatty acid and dual-responsive fluorescent molecule prepared in example 4.
(A) Poly-TICT @ AIE incubated biofilms were imaged by confocal fluorescence at 25 ℃ in two channels, 510-550nm (green, left) and 570-610nm (red, right).
(B) Poly-TICT @ AIE incubated biofilms were imaged by confocal fluorescence at 37 ℃ in two channels, 510-550nm (green, left) and 570-610nm (red, right).
(C) Poly-TICT @ AIE incubated biofilms were imaged by confocal fluorescence at 42 ℃ in two channels, 510-550nm (green, left) and 570-610nm (red, right).
(D) Fluorescence intensities at different depths of the biofilm in the two channels, 510-550nm (green) and 570-610nm (red), at 25 ℃.
(E) Fluorescence intensities at different depths of the biofilm in the two channels, 510-550nm (green) and 570-610nm (red), at 37 ℃.
(F) Fluorescence intensities at different depths of the biofilm in the two channels, 510-550nm (green) and 570-610nm (red), at 42 ℃.
(G) (D-F) and the ratio of the integrated area under the fluorescence curve shown in (D-F) to the integrated areas of the channels at 510-550nm (green) and 570-610nm (red).
(H) Emission spectra of Poly-TICT @ AIE incubated biofilms at different temperatures.
FIG. 4 is temperature sensing of fluorescence lifetime in biofilm of a saturated fatty acid and dual-responsive fluorescent molecule based nano-thermometer prepared in example 4.
(A) Poly-TICT @ AIE incubated biofilm fluorescence lifetime imaging at 25 ℃.
(B) Poly-TICT @ AIE incubated biofilm fluorescence lifetime imaging at 37 ℃.
(C) Poly-TICT @ AIE incubated biofilms were imaged for fluorescence lifetime at 42 ℃.
(D) Fluorescence decay curve and fluorescence lifetime in selected regions at 25 ℃.
(E) Fluorescence decay curve and fluorescence lifetime in selected regions at 37 ℃.
(F) Fluorescence decay curve and fluorescence lifetime in selected regions at 42 ℃.
Detailed Description
The present invention will be further illustrated by the following specific examples.
In each example:
MPC is an abbreviation for 2-methacryloyloxyethyl phosphorylcholine;
MBA is an abbreviation for N, N-methylenebisacrylamide;
APS is an abbreviation for ammonium persulfate;
TEMED is an abbreviation for tetramethylethylenediamine.
Example 1
The structure of the saturated fatty acid double bond derivative is shown as formula IX:
wherein n is 9-17. Specifically, n is 9, 11, 13, 15, 17.
Synthesis of saturated fatty acid double bond derivatives (lauric acid double bond derivatives as an example):
1) under the protection of nitrogen, lauric acid VI-1 is dissolved in dichloromethane at 0 ℃, and catalyst triethylamine and excessive oxalyl chloride are added to react at 0 ℃; after the reaction is finished, concentrating under reduced pressure, and removing dichloromethane and excessive oxalyl chloride; to obtain lauroyl chloride VII-1;
2) dissolving lauroyl chloride in dichloromethane to obtain a lauroyl chloride solution;
adding N- (3-aminopropyl) methacrylic acid hydrochloride VIII into a reaction container, vacuumizing and introducing nitrogen, adding dried dichloromethane to dissolve the N- (3-aminopropyl) methacrylic acid hydrochloride, adding lauroyl chloride solution and triethylamine into the reaction container, stirring at room temperature to react, quenching with water to react, extracting with an extract, washing with water, and drying to obtain a lauric acid double-bond derivative IX-1;
the reaction formula is as follows:
in the formula, when n is 11, VI is VI-1, namely lauric acid; VII is VII-1; IX is IX-1;
n is also 9, 13, 15 or 17, VI is VI-2, VI-3, VI-4, VI-5, IX-2, IX-3, IX-4, IX-5.
Example 2
Preparation of Compound IV (exemplified by IV-1):
4-bromo-N- (4-methoxyphenyl) -N-diphenylamine X-1(700.0mg, 2mmol), potassium acetate (392.0mg, 4mmol), bis (pinacolato) diboron XI (507.0mg, 2mmol) and bis (triphenylphosphine) palladium dichloride (73.0mg, 0.1mmol) were added to the flask. The flask was evacuated and purged three times with dry nitrogen, then 10mL of anhydrous dioxane was added. The mixture was heated to 85 ℃ and reacted for 15 hours. After cooling to room temperature, it was extracted with dichloromethane and dried over magnesium sulfate. Removing solvent under reduced pressure, purifying the crude product by silica gel column chromatography, eluting with mixture of petroleum ether and ethyl acetate (volume ratio 50:1) to obtain OMe-TPA-Bpin (compound IV-1) with yield of 73.18%;
1H-NMR(400MHz,CDCl3):δ7.63(d,J＝6.7Hz,2H),7.22(t,J＝8Hz,2H),7.11–7.04(m,4H),7.02–6.94(m,3H),6.84(d,J＝8.9Hz,2H),3.79(s,3H),1.32(s,12H).13C NMR(100MHz,CDCl3)δ156.54,150.92,147.59,140.28,135.82,129.21,127.77,124.15,122.81,120.47,114.84,83.51,55.50,24.88.HRMS(ESI,m/z,C25H28BNO3,[M+Na+]):calcd,424.1962；found,424.2058；
in the formula, R of X1is-OCH3，R2When is-H, is X-1; r of product IV1is-OCH3，R2When is-H, IV is IV-1.
The method can also comprise the following steps:
r of X1is-OCH3，R2Is para-OCH3When, is X-2;
r of X1is-OH, R2Is ortho-OCH3When, is X-3;
r of X1is-NH2，R2Is meta-OCH3When, is X-4;
r of X1is-N (CH)3)23，R2X-5 when it is para-OH;
r of X1is-NHCOCH3，R2Is para-NH2When, is X-6;
r of X1is-OCOCH3，R2Is para-N (CH)3)2When, is X-7;
r of X1is-OCH3，R2Is para-NHCOCH3When, is X-8;
r of X1is-OCH3，R2Is para-OCOCH3When, is X-9;
in a similar manner to this example, the corresponding compounds IV-2 to IV-9 can be obtained by reaction.
Example 3
Preparation of compound V:
1) preparation of Compound III-1:
n-butylamine (compound II-1) (300. mu.L, 15mmol), ethanol (15mL), 4-bromo-benzylidene oxazolone (compound I) (1.32g, 5mmol) and potassium carbonate (69mg, 0.05mmol) were added to the flask, heated to 80 ℃ and refluxed for 7 hours, monitored by thin layer chromatography, cooled to room temperature, diluted hydrochloric acid and water were added, and extracted with dichloromethane, and the organic phase was dried over magnesium sulfate. After the solvent is removed, the crude product is purified by silica gel column chromatography and eluted by mixed solution (volume ratio is 50:1) of petroleum ether and ethyl acetate to obtain a compound III-1, and the yield is 45.32%;
1H-NMR(400MHz,CDCl3):δ8.00(d,J＝8.3Hz,2H),7.53(d,J＝8.3Hz,2H),6.99(s,1H),3.59(t,J＝7.4Hz,2H),2.38(s,3H),1.66–1.58(m,2H),1.37(h,J＝7.3Hz,2H),0.96(t,J＝7.3Hz,3H).13C-NMR(100MHz,CDCl3):δ170.64,163.17,139.18,133.44,133.22,131.96,125.48,124.52,40.50,31.45,20.03,15.84,13.70.HRMS(ESI,m/z,C15H17BrN2O,[M+H+]):calcd,321.0584；found,321.0599；
2) mixing compound III-1(192mg,0.6mmol), compound IV-1(200mg,0.5mmol), Pd (PPh)3)4(58mg,0.05mmol) and potassium carbonate (690mg,5mmol) were added to the flask, evacuated and purged three times with dry nitrogen. Adding 20mL of tetrahydrofuran aqueous solution (volume concentration is 75%, or any one of volume concentration is 50% or 80%)Arbitrary), heated to 60 ℃, reacted for 15 hours, monitored by thin layer chromatography. After cooling to room temperature, it was quenched with water, extracted with dichloromethane and dried over magnesium sulfate. Removing the solvent under reduced pressure, purifying the crude product by silica gel column chromatography, eluting with mixed solution of petroleum ether and ethyl acetate (volume ratio 10:1) to obtain dual-response fluorescent molecule (compound V-1), with yield of 72.56%;
1H-NMR(400MHz,CDCl3):δ8.16(d,J＝8.1Hz,2H),7.62(d,J＝8.1Hz,2H),7.49(d,J＝8.4Hz,2H),7.27(s,1H),7.23(s,1H),7.17–6.94(m,8H),6.93–6.81(m,2H),3.81(s,3H),3.61(t,J＝7.4Hz,2H),2.40(s,1H),1.67–1.57(m,2H),1.38(q,J＝7.5Hz,2H),0.96(t,J＝7.3Hz,3H).13C-NMR(100MHz,CDCl3):δ170.79,162.24,156.51,148.16,147.76,142.12,140.41,138.37,132.96,132.67,129.26,127.63,126.95,126.60,123.65,122.56,122.21,114.92,55.53,40.48,31.51,24.91,20.07,13.74.HRMS(ESI,m/z,C34H33N3O2,[M+H+]):calcd,516.2633；found,516.2649.
the reaction formula is as follows:
2-methylpropylamine is used,
N-pentylamine, 2-methylbutylamine, 2-dimethylpropylamine,
N-hexylamine, 2-methylpentylamine, 3-methylpentylamine,
N-heptylamine, 2-methylhexylamine, 3-dimethylpentylamine,
N-octylamine, 2-methylheptylamine and 3-methylheptylamine, wherein the codes are II-2 to II-14 respectively; the amines II-2 to II-14 were used to replace n-butylamine (15 mmol was used in the addition) in step 1) of this example, and the other steps were the same as in step 1) of this example, to obtain compounds III-2 to III-14 in this order.
By reacting any of compounds III-2 to III-14 with any of compounds IV-2 to IV-9 as described above, different compounds V can be prepared, as shown in the following Table:
| compound IV | Compound | Compound V | |
| 2 | 2 | 2 | |
| 3 | 3 | 3 | |
| 4 | 4 | 4 | |
| 5 | 5 | 5 | |
| 6 | 6 | 6 | |
| 7 | 7 | 7 | |
| 8 | 8 | 8 | |
| 9 | 9 | 9 | |
| 1 | 10 | 10 | |
| 2 | 11 | 11 | |
| 3 | 12 | 12 | |
| 4 | 13 | 13 | |
| 5 | 14 | 14 |
Example 4
A preparation method of a nanometer thermometer (named Poly-TICT @ AIE) based on saturated fatty acid and double-response fluorescent molecules comprises the following steps:
1) dissolving lauric acid double bond derivative IX-1 and double-response fluorescent molecule V-1 in a low-temperature eutectic (LA/SA) of lauric acid and stearic acid according to the mass ratio of 1:3:96, cooling to obtain solid A, and grinding the solid A into powder to obtain powder A;
the structure of the lauric acid double-bond derivative is shown as a formula IX-1:
2) polymerizing the monomer containing double bond2-Methacryloyloxyethylphosphocholine (MPC) was dissolved in water to a concentration of 100mg mL-1An aqueous MPC solution of (a);
dissolving crosslinking agent MBA in dimethyl sulfoxide to obtain solution with concentration of 100mg mL-1The MBA solution of (1);
dissolving initiator APS in water to obtain solution with concentration of 100mgmL-1An aqueous solution of APS;
mixing the powder A, MPC aqueous solution and MBA solution, adding a catalyst TEMED, ultrasonically mixing uniformly, adding an APS aqueous solution, carrying out polymerization reaction for 2h at 4 ℃, dialyzing, and removing unreacted double-bond-containing polymerization monomer MPC and water-soluble byproducts to prepare the nano thermometer 1 based on saturated fatty acid and double-responsive fluorescent molecules, which is named as Poly-TICT @ AIE;
the mass ratio of the powder A to the MPC is 1: 5;
the molar ratio of MPC, MBA, TEMED and APS is 15:8:1: 1.5.
Example 5
A preparation method of a nanometer thermometer based on saturated fatty acid and dual-response fluorescent molecules comprises the following steps:
1) dissolving IX-2 and a dual-response fluorescent molecule V-2 in heated and melted palmitic acid according to the mass ratio of 1:0.01:98.99, cooling to obtain a solid A, and grinding the obtained solid A into powder to obtain powder A;
2) polymerizing monomer N- [3- (dimethylamino) propyl group containing double bond]Methacrylamide (APM) is dissolved in water to make the concentration of 100mgmL-1An aqueous solution of APM;
dissolving crosslinking agent MBA in dimethyl sulfoxide to obtain solution with concentration of 100mg mL-1The MBA solution of (1);
dissolving initiator APS in water to obtain solution with concentration of 100mgmL-1An aqueous solution of APS;
mixing the powder A, APM aqueous solution and the MBA solution, adding a catalyst TEMED, oscillating and mixing uniformly, adding an APS aqueous solution, carrying out polymerization reaction for 3h at 0 ℃, carrying out ultracentrifugation, and removing unreacted APM and water-soluble byproducts to prepare a nano thermometer 2 based on saturated fatty acid and dual-responsive fluorescent molecules;
the mass ratio of the powder A to the APM is 1: 4;
the molar ratio of APM, MBA, TEMED and APS is 15:6:0.8: 1.2.
Example 6
A preparation method of a nanometer thermometer based on saturated fatty acid and dual-response fluorescent molecules comprises the following steps:
1) dissolving IX-3 and a dual-response fluorescent molecule V-3 in palmitic acid which is melted after heating according to the mass ratio of 1:10:89, cooling to obtain a solid A, and grinding the obtained solid A into powder to obtain powder A;
2) the double bond-containing polymerized monomer acrylamide (AAM) was dissolved in water to a concentration of 100mg mL-1AAM aqueous solution of (a);
dissolving crosslinking agent MBA in dimethyl sulfoxide to obtain solution with concentration of 100mg mL-1The MBA solution of (1);
dissolving initiator APS in water to make the concentration be 100mg mL-1An aqueous solution of APS;
mixing the powder A, AAM aqueous solution and the MBA solution, adding a catalyst TEMED, oscillating and mixing uniformly, adding an APS aqueous solution, carrying out polymerization reaction for 3h at 0 ℃, carrying out ultracentrifugation, removing unreacted AAM and water-soluble byproducts, and preparing to obtain a nano thermometer 3 based on saturated fatty acid and dual-responsive fluorescent molecules;
the mass ratio of the powder A to the AAM is 1: 6;
the molar ratio of AAM, MBA, TEMED and APS is 15:9:1.2: 1.8.
Example 7
A preparation method of a nanometer thermometer based on saturated fatty acid and dual-response fluorescent molecules comprises the following steps:
1) dissolving IX-4 and the double-response fluorescent molecule V-4 in molten myristic acid according to the mass ratio of 1:3:96, cooling to obtain a solid A, and grinding the solid A into powder to obtain powder A;
2) same as example 4, step 2), obtaining the nanometer thermometer 4 based on saturated fatty acid and dual-response fluorescent molecules.
Example 8
A preparation method of a nanometer thermometer based on saturated fatty acid and dual-response fluorescent molecules comprises the following steps:
1) dissolving IX-5 and the double-response fluorescent molecule V-5 in stearic acid which is melted after heating according to the mass ratio of 1:3:96, cooling to obtain a solid A, and grinding the obtained solid A into powder to obtain powder A;
2) same as example 4, step 2), obtaining a nano thermometer 5 based on saturated fatty acid and dual-response fluorescent molecules.
Example 9
A preparation method of a nanometer thermometer based on saturated fatty acid and dual-response fluorescent molecules comprises the following steps:
1) dissolving IX-1 and the double-response fluorescent molecule V-6 in stearic acid which is melted after heating according to the mass ratio of 1:3:96, cooling to obtain a solid A, and grinding the obtained solid A into powder to obtain powder A;
2) same as example 4, step 2), obtaining a nano thermometer 6 based on saturated fatty acid and dual-response fluorescent molecules.
Example 10
A preparation method of a nanometer thermometer based on saturated fatty acid and dual-response fluorescent molecules comprises the following steps:
1) dissolving IX-2 and the dual-response fluorescent molecule V-7 in molten palmitic acid according to the mass ratio of 1:3:96, cooling to obtain a solid A, and grinding the solid A into powder to obtain powder A;
2) same as example 4, step 2), obtaining a nano thermometer 7 based on saturated fatty acid and dual-response fluorescent molecules.
Example 11
A preparation method of a nanometer thermometer based on saturated fatty acid and dual-response fluorescent molecules comprises the following steps:
1) dissolving IX-3 and a dual-response fluorescent molecule V-8 in molten myristic acid according to the mass ratio of 1:3:96, cooling to obtain a solid A, and grinding the obtained solid A into powder to obtain powder A;
2) same as example 4, step 2), obtaining a nano thermometer 8 based on saturated fatty acid and dual-response fluorescent molecules.
Example 12
A preparation method of a nanometer thermometer based on saturated fatty acid and dual-response fluorescent molecules comprises the following steps:
1) dissolving IX-4 and a dual-response fluorescent molecule V-9 in heated and melted lauric acid according to the mass ratio of 1:3:96, cooling to obtain a solid A, and grinding the obtained solid A into powder to obtain powder A;
2) same as example 4, step 2), obtaining a nano thermometer 9 based on saturated fatty acid and dual-response fluorescent molecules.
Example 13
A preparation method of a nanometer thermometer based on saturated fatty acid and dual-response fluorescent molecules comprises the following steps:
1) dissolving IX-5 and the double-response fluorescent molecule V-10 in heated and melted palmitic acid according to the mass ratio of 1:3:96, cooling to obtain a solid A, and grinding the solid A into powder to obtain powder A;
2) same as example 4, step 2), obtaining the nano thermometer 10 based on saturated fatty acid and dual-response fluorescent molecules.
Example 14
A preparation method of a nanometer thermometer based on saturated fatty acid and dual-response fluorescent molecules comprises the following steps:
1) dissolving IX-1 and the double-response fluorescent molecule V-11 in stearic acid which is melted after heating according to the mass ratio of 1:3:96, cooling to obtain a solid A, and grinding the obtained solid A into powder to obtain powder A;
2) same as example 4, step 2), obtaining the nano thermometer 11 based on saturated fatty acid and dual-response fluorescent molecules.
Example 15
A preparation method of a nanometer thermometer based on saturated fatty acid and dual-response fluorescent molecules comprises the following steps:
1) dissolving IX-2 and the dual-response fluorescent molecule V-12 in molten palmitic acid according to the mass ratio of 1:3:96, cooling to obtain a solid A, and grinding the solid A into powder to obtain powder A;
2) same as example 4, step 2), obtaining the nano thermometer 12 based on saturated fatty acid and dual-response fluorescent molecules.
Example 16
A preparation method of a nanometer thermometer based on saturated fatty acid and dual-response fluorescent molecules comprises the following steps:
1) dissolving IX-3 and the double-response fluorescent molecule V-13 in heated and melted palmitic acid according to the mass ratio of 1:3:96, cooling to obtain a solid A, and grinding the solid A into powder to obtain powder A;
2) same as example 4, step 2), obtaining a nano thermometer 13 based on saturated fatty acid and dual-responsive fluorescent molecules.
Example 17
A preparation method of a nanometer thermometer based on saturated fatty acid and dual-response fluorescent molecules comprises the following steps:
1) dissolving IX-4 and the dual-response fluorescent molecule V-14 in heated and melted lauric acid according to the mass ratio of 1:3:96, cooling to obtain a solid A, and grinding the obtained solid A into powder to obtain powder A;
2) same as example 4, step 2), obtaining a nano thermometer 14 based on saturated fatty acid and dual-responsive fluorescent molecules.
Example 18
The double-response fluorescent molecule V-1 has a remarkable solvent color change effect, and experiments show that the maximum emission wavelength of the double-response fluorescent molecule is shifted from 459nm red to 620nm along with the reduction of fluorescence intensity when the polarity of an organic solvent is increased from n-hexane to dimethyl sulfoxide (DMSO) (figure 1A). We also prepared a series of DMSO/water mixtures (percentage of water as f)wRepresentation) to examine the AIE performance of the dual-responsive fluorescent molecule (fig. 1B). When f iswBelow 40%, no significant fluorescence emission is observed due to intramolecular vibration or rotation, but the emission spectrum is slightly red-shifted; when f iswFrom 40% up to 70%, the dual-responsive fluorescent molecules begin to form small aggregates, at which time significant fluorescence emission occurs (about an increase in intensity)70 times) with a blue shift of the emission spectrum, this process is dominated by AIE; when f iswWhen the fluorescence intensity increases to more than 90%, the fluorescence emission intensity begins to decrease, and the emission spectrum is red-shifted, so that the TICT plays a dominant role. These results indicate that the dual-responsive fluorescent molecule can sensitively sense the polarity of the surrounding environment and the change of the aggregation state of the molecule.
Fig. 2A shows a schematic diagram of a preparation method of the saturated fatty acid and dual-responsive fluorescent molecule-based nano thermometer 1 of example 4, where the synthesized saturated fatty acid and dual-responsive fluorescent molecule-based nano thermometer 1 (referred to as nano thermometer 1 for short) has a core-shell structure, where the saturated fatty acid and dual-responsive fluorescent molecule are cores, and a network structure formed by surface polymerization is a shell. To reduce non-specific interactions between Poly-TICT @ AIE and components of a biological system, a zwitterionic monomer, 2-Methacryloyloxyethyl Phosphorylcholine (MPC), was introduced into the polymer network during surface polymerization. Transmission electron microscopy showed that Poly-TICT @ AIE had a spherical structure (FIG. 2B), and dynamic light scattering measurements showed that the particle size distribution of Poly-TICT @ AIE was between 100 and 400nm (FIG. 2C). We then tested the photophysical properties of Poly-TICT @ AIE at various temperatures, as shown in FIG. 2D, with the emission spectrum of Poly-TICT @ AIE gradually shifted toward shorter wavelengths as the temperature was increased from 25 deg.C to 42 deg.C, with a blue shift of the maximum emission wavelength from 591.9nm to 528.5 nm. The sensitivity and resolution of the spectral shift of the nano-thermometer is 3.7 nm/deg.C and 0.35 deg.C respectively between 25-42 deg.C, and since the phase transition temperature of the eutectic fatty acid is about 39 deg.C, the sensitivity and resolution of the spectral shift of the nano-thermometer is improved to 10.6 nm/deg.C and 0.14 deg.C when the temperature range is reduced to between 35-39 deg.C, which is much higher than that of most fluorescent nano-thermometers. Meanwhile, as shown in FIG. 2E, when the temperature rises from 25 ℃ to 42 ℃, the fluorescence intensity of Poly-TICT @ AIE is gradually increased along with the increase of the temperature, the integral area of the fluorescence spectrum is increased by 2.6 times, the sensitivity and resolution of the spectral shift of the nano thermometer are respectively 9.3%/° C and 0.26 ℃ between 25 ℃ and 42 ℃, and the sensitivity and resolution of the spectral shift of the nano thermometer are increased to 11.3%/° C and 0.24 ℃ when the temperature range is reduced to between 35 ℃ and 39 ℃. To ensure the reusability of Poly-TICT @ AIE, we tested its spectral change between 25-42 ℃, as shown in fig. 2F, after 5 cycles of thermal cycling, its maximum emission wavelength did not shift significantly, indicating good spectral reversibility of Poly-TICT @ AIE during temperature sensing. Compared with the fluorescence intensity, the fluorescence lifetime is not easily influenced by external factors such as the concentration of fluorescence molecules, excitation wavelength and the like, so that the change of the fluorescence lifetime of Poly-TICT @ AIE at different temperatures is tested. As shown in FIG. 2G, the fluorescence lifetime showed a decreasing trend of change with increasing temperature, from 2.06ns down to 0.95ns, between 25-42 ℃ with sensitivity and resolution of fluorescence lifetime of 3.2%/deg.C and 0.61 deg.C, respectively, and as the temperature range was reduced to between 35-39 deg.C, the sensitivity and resolution of the spectral shift of the nano-thermometer increased to 9.9%/deg.C and 0.41 deg.C. Therefore, Poly-TICT @ AIE can realize temperature sensing by utilizing three complementary fluorescence parameters of spectral shift, fluorescence intensity and fluorescence lifetime.
To verify that the fluorescence nanothermometer 1 can be applied to biological systems, we tested temperature sensing in bacterial biofilms using Poly-TICT @ AIE. Bacterial biofilms are composed of an extracellular matrix secreted by a bacterial community and protect bacteria from environmental threats. The MPC modified on the outer surface of the Poly-TICT @ AIE can reduce the nonspecific adsorption of the MPC with bacteria, and is beneficial to the efficient penetration of the Poly-TICT @ AIE to a biological capsule. After incubation of Poly-TICT @ AIE with bacterial envelopes, three-dimensional confocal laser scanning of the biological envelopes was performed from two channels (green channel, 510-550 nm; red channel, 570-610nm) at different temperatures. As shown in FIGS. 3A-3C, when the temperature was increased from 25 ℃ to 37 ℃, the two channels, 510-550nm (green, left) and 570-610nm (red, right), showed significant enhancement of the fluorescence signal; when the temperature is increased from 37 ℃ to 42 ℃, the fluorescence signal of the 510-550nm channel is continuously enhanced, and the fluorescence signal of the 570-610nm channel is basically kept unchanged. This trend in signal change can be shown from the integrated area of the fluorescence intensity of the two channels at different depths in the biofilm (fig. 3D-3F) and the total fluorescence intensity of the two channels (fig. 3G), where the ratio of the integrated area between the two channels increases linearly from 1.59 to 2.31. Furthermore, when the temperature was increased from 25 ℃ to 42 ℃, the fluorescence spectrum was blue-shifted by 69nm (FIG. 3H). Since temperature changes also cause changes in fluorescence lifetime, we also explored the use of Poly-TICT @ AIE for biofilm fluorescence lifetime imaging. We performed fluorescence lifetime imaging of biofilms at three temperatures, 25 deg.C, 37 deg.C and 42 deg.C (FIGS. 4A-4C) and extracted fluorescence decay curves from selected regions (FIGS. 4D-4F). As can be seen from the graph, the fluorescence lifetime decreased with increasing temperature, linearly from 2.43ns to 1.49ns, which is consistent with the in vitro test results. In summary, Poly-TICT @ AIE can sense the temperature of the biofilm from three angles of fluorescence intensity, spectrum shift and fluorescence life, and is expected to be developed into a novel fluorescence nano thermometer for high-sensitivity and high-accuracy feedback of the temperature in a biological system.
Experiments prove that the nano thermometers 2-14 have the capability of sensing the temperature of the biological envelope similar to the nano thermometer 1.
Claims (7)
1. A dual-response fluorescent molecule is characterized in that the molecule has a structure shown in a formula (V),
wherein R is1is-OCH3、-OH、-NH2、-N(CH3)2、-NHCOCH3or-OCOCH3；
R2is-H, -OCH3、-OH、-NH2、-N(CH3)2、-NHCOCH3or-OCOCH3；
R3is-C4H9、-C5H11、-C6H13、-C7H15or-C8H17。
2. A method for preparing a dual-responsive fluorescent molecule according to claim 1, characterized by comprising the steps of:
1) dissolving 4-bromo-benzylidene oxazolone (I) and compound (II) in ethanol, heating and refluxing for reaction under the catalysis of potassium carbonate, and monitoring by thin layer chromatography to obtain compound (III);
2) compound (III), compound (IV), Pd (PPh)3)4Dissolving potassium carbonate in the mixed solvent, vacuumizing and blowing by using dry nitrogen; mixing, reacting and monitoring by thin-layer chromatography to obtain a dual-response fluorescent molecule (V), wherein the mixed solvent is tetrahydrofuran aqueous solution with the volume concentration of 50-80%;
the reaction formula is as follows:
wherein R is1is-OCH3、-OH、-NH2、-N(CH3)2、-NHCOCH3or-OCOCH3；
R2is-H, -OCH3、-OH、-NH2、-N(CH3)2、-NHCOCH3or-OCOCH3；
R3is-C4H9、-C5H11、-C6H13、-C7H15or-C8H17。
3. A preparation method of a nanometer thermometer based on saturated fatty acid and dual-response fluorescent molecules is characterized by comprising the following steps:
1) according to the mass ratio of 1 (0.01-10) to (89-98.99), dissolving a saturated fatty acid double bond derivative and the dual-response fluorescent molecule of claim 1 in the saturated fatty acid which is melted after heating, cooling to obtain a solid A, and grinding the solid A into powder to obtain powder A;
the structure of the saturated fatty acid double bond derivative is shown as a formula (IX):
wherein n is 9-17.
2) Dissolving a double-bond-containing polymerization monomer in water to prepare a monomer aqueous solution;
dissolving a cross-linking agent MBA in dimethyl sulfoxide to prepare an MBA solution;
dissolving initiator APS in water to prepare APS aqueous solution;
mixing the powder A, the monomer aqueous solution and the MBA solution, adding a catalyst TEMED, carrying out ultrasonic or oscillation uniform mixing, adding an APS aqueous solution, carrying out polymerization reaction for 1-3h at 0-4 ℃, and removing unreacted double-bond-containing polymerization monomers and water-soluble byproducts through dialysis or ultracentrifugation to prepare the nano thermometer based on saturated fatty acid and dual-responsive fluorescent molecules;
the mass ratio of the powder A to the double-bond-containing polymerized monomer is 1 (4-6);
the molar ratio of the double-bond-containing polymerized monomer to the MBA to the TEMED to the APS is 15 (6-9) to 0.8-1.2 to 1.8; MBA is an abbreviation for N, N-methylenebisacrylamide;
the APS is an abbreviation for ammonium persulfate;
TEMED is an abbreviation for tetramethylethylenediamine.
4. The method according to claim 3, wherein the saturated fatty acid is at least one of lauric acid, myristic acid, palmitic acid, and stearic acid.
5. The method according to claim 3, wherein the double bond-containing monomer is at least one of 2-methacryloyloxyethyl phosphorylcholine, N- [3- (dimethylamino) propyl ] methacrylamide and acrylamide.
6. A nano-thermometer based on saturated fatty acids and dual-responsive fluorescent molecules prepared by the method of any one of claims 3 to 5.
7. Use of a saturated fatty acid and dual-responsive fluorescent molecule based nanothermometer according to claim 6 for detecting biofilm temperature.
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