CN109135729A - A kind of temperature response type luminescent gold nano-micelle and preparation method thereof and the application in visualization temperature detection - Google Patents
A kind of temperature response type luminescent gold nano-micelle and preparation method thereof and the application in visualization temperature detection Download PDFInfo
- Publication number
- CN109135729A CN109135729A CN201810686627.5A CN201810686627A CN109135729A CN 109135729 A CN109135729 A CN 109135729A CN 201810686627 A CN201810686627 A CN 201810686627A CN 109135729 A CN109135729 A CN 109135729A
- Authority
- CN
- China
- Prior art keywords
- temperature
- micelle
- response type
- gold nano
- preparation
- 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.)
- Granted
Links
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, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
-
- 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
-
- 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
- G01N21/6447—Fluorescence; Phosphorescence by visual observation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Biochemistry (AREA)
- Pathology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a kind of temperature response type luminescent gold nano-micelles and preparation method thereof and the application in visualization temperature detection.This method comprises the following steps: fluorescent dye and surfactant being dissolved in organic solvent, is sufficiently mixed uniformly, organic solvent is spin-dried for；Solvent, sulfydryl small molecule, sufficiently dissolution is added；Gold chloride is added, in 80-120 DEG C of reaction 2-10 h；After reaction, by dialysing and being centrifuged off impurity, a kind of temperature response type luminescent gold nano-micelle is obtained.The temperature response type luminescent gold nano-micelle synthetic method is simple, at low cost, is easy to large-scale industrial production.The variation of apparent fluorescence radiation color can be observed with the variation of temperature in the temperature response type luminescent gold nano-micelle of this method synthesis under ultraviolet light.The temperature response type luminescent gold nano-micelle has the series of advantages such as simple and efficient, highly sensitive, practicability, universality, repeatability and strong antijamming capability in application aspect.
Description
Technical field
The present invention relates to function Illuminant nanometer Material Fields, and in particular to a kind of temperature response type luminescent gold nano-micelle and
Preparation method and the application in visualization temperature detection.
Background technique
Temperature is to characterize the physical quantity of the cold and hot degree of object, is pole in daily life, scientific research and new and high technology exploitation
Its universal and important one of measurement parameter.Temperature control fault may cause production safety, product quality and food safety
A series of problems, such as, therefore the meaning that temperature in system is accurately sensed and detected is increasing.With the development of science and technology and people
The increasingly raising of people's living standard, the abnormal experiment such as high temperature, low temperature and ultralow temperature and engineer application are more and more, survey to temperature
The requirement of amount is higher and higher, is in daily life especially more intuitive, visualization and quickly to the requirement of temperature detection.Cause
This, constantly explores new thermometry, improves original measuring technique, with meet it is various under the conditions of temperature measurement demand carve
Do not allow to delay (Sensor Actuat.B:Chem, 2003,96,180；Anal.Chem.,1993,65,1868).
Fluorescence analysis method and have the characteristics that high sensitivity, reproducible and easy to operate with its imaging technique, has become
For one of the area researches important tools of analysis such as bio-sensing, medical diagnosis and food product environment safety (Mater.Today,
2013,16,477；J.Am.Chem.Soc., 2016,138,6380), therefore there is the fluorescence of highly sensitive optic response to visit for synthesis
Needle has great importance and practical value.There is detection to limit low, high sensitivity, good, the sampling amount of selectivity for molecular fluorescence analysis
The advantages that few, dynamic linear response range is wide, favorable reproducibility, and instrument and equipment is simple and analysis method is simple and direct quick is a kind of important
Optical analysis means.Luminescent metal nano material has fluorescence probe and nano material as a kind of novel fluorescent nano probe
Attribute, rapidly developed in recent years, imaging in biological tissues, chemical detection, medical diagnosis on disease and treatment and sensing etc. lead
Domain shows huge application potential, attracted researcher extensive concern (Nanoscale, 2012,4,4073；
Angew.Chem.,Int.Ed.,2013,52,12572；J.Am.Chem.Soc.,2003,125,14676).However, temperature is rung
The luminous gold nano-material of type is answered to be rarely reported in the application of temperature sensing and context of detection.
Current thermometry generally comprises expansion type thermometric, electricity quantity type thermometric, contact photoelectric and thermocolour thermometric
With sound wave or microwave temp measuring method etc..These temperature checking methods require the support of complex instrument, and complex steps are not easy
Operation and a series of disadvantages such as the cost is relatively high (ACS Sens., 2016,16,99；Chem.Soc.Rev.,2016,45,
1738；J.Phys.Chem.B, 2006,110,13508；Sensor Actuat.B:Chem, 2012,173,250；Lab Chip,
2011,11,3411).Therefore to quickly obtain accurately and reliably temperature analysis as a result, it is desirable to be familiar with the original of various measurement methods
Reason and its feature require to select suitable measurement method in conjunction with measurand.To overcome disadvantages mentioned above, meet Current Temperatures sensing
With the demand of detection, innovation and improve temperature checking method and technology it is imperative.In recent years, a kind of with simple and efficient and high
The temperature sensing material of sensitivity comes into being, and receive numerous researchers concern (Macromolecules, 2004,37,
7861；Nat.Chem.,2017,9,171；Polym.Chem.,2017,8,177).However, most of temperature-responsive at present
The preparation of type polymer is to polymerize the temperature sensitive block for obtaining having close and distant water-bound using reversible addion-fragmentation chain transfer (RAFT)
Copolymer.Many RAFT polymerization studies show can there is the defects of retardance, cross termination and inducing phenomena in polymerization, cause it
The disadvantages such as polymerization process is complicated and changeable, easy purification, stability is not poor and practicability is low.Therefore, research has highly sensitive with design
Degree, practicability, universality and repeatability optics temperature-sensitive nano material, realize temperature quick visualization sensing have very
Important meaning and practical application value.
Summary of the invention
The shortcomings that in order to overcome existing thermometry and deficiency, the present invention provide a kind of luminous Jenner of temperature response type
Rice glue beam and preparation method thereof and the application in visualization temperature detection.Temperature detection technology provided by the invention, can pass through
Several analysis means Simultaneous Monitorings below: general fluorescenes spectrum instrument detects luminescent gold nano-micelle fluorescence intensity change；Luminescent gold
Ratio (the I of two wave crests of nano-micelle1/I2) relationship that varies with temperature；More importantly temperature change can also be passed through
When, it can observe that the variation (transformation between such as Red-Blue) of the material fluorescence color quickly may be used to realize under ultraviolet light
Sensitive Detection depending on changing temperature.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of temperature response type luminescent gold nano-micelle, includes the following steps:
(1) dyestuff and surfactant are dissolved in organic solvent, are spin-dried for after mixing；
(2) under agitation, solvent is added into step (1) obtained solid powder, stirs to being completely dissolved, adds
Sulfydryl small molecule compound simultaneously stirs evenly；
(3) Au (III) being added into mixed liquor obtained by step (2), stirring to solution becomes colorless, pH value of solution is adjusted,
The lower sufficiently reaction of constant temperature oil bath stirring；The Au (III) is containing Au3+Compound；
(4) sample obtained by step (3) is obtained into the luminous Jenner of temperature response type by dialysis, centrifugal purification
Rice glue beam.Composition principle is as shown in Figure 9.
Preferably, step (1) dyestuff is aminocoumarin, diamidino phenyl indole, monochloro amine and 2,2- (4,4-
Diphenylethyllene) one of double benzoxazoles or a variety of.
Preferably, step (1) surfactant is F108, P104, L22, P123, F127 or with similar structure
Triblock polymer (PEO/PPO/PEO) it is one or more.
Preferably, step (1) organic solvent is chloroform, ethyl alcohol, styrene, tetrahydrofuran, toluene and glycerol
It is one or more.
Preferably, described be uniformly mixed of step (1) is uniformly mixed under magnetic stirrer or ultrasound condition；It is described to be spin-dried for
It is to be threaded to sufficiently do with Rotary Evaporators.
Preferably, step (2) solvent is one or more of ethyl alcohol, methanol, acetone, glycerol, toluene and water.
Preferably, step (2) the sulfydryl small molecule compound is thioacetic acid, mercaptoethylmaine, 1,6- ethanthiol, two
Thionitrobenzoate, four (3- mercaptopropionic acid) pentaerythritol esters are with R- (SH)nThe compound of chemical structural formula, formula
Middle R is alkyl chain or heterocycle compound, and n is sulfydryl number, value range 1-8.
Preferably, in step (3), the ratio between amount of substance of small molecule compound and Au (III) containing sulfydryl is 1.4:1.
Preferably, step (3) stirring to the time that solution becomes colorless is 15-30min.
Preferably, step (3) pH value is 8-10.
Preferably, the temperature of step (3) described constant temperature oil bath is 80-120 DEG C.
Preferably, step (3) time sufficiently reacted is 2-10h.
Preferably, the mixing speed of step (3) described constant temperature oil bath is 500-1500rpm/min.
Preferably, the molecular cut off of bag filter used in step (4) described dialysis is 3000-14000Da.
Preferably, the time of step (4) described dialysis is for 24 hours, wherein to change water primary by every 8h.
Preferably, the speed of step (4) described centrifugation is 21000rpm/min, and the time of centrifugation is 10min.
A kind of temperature response type luminescent gold nano-micelle as made from above-described preparation method.With the change of temperature
Change, the variation (transformation between such as Red-Blue) of the material fluorescence color can be observed under ultraviolet light.
A kind of above-described temperature response type luminescent gold nano-micelle is applied in visualization temperature sensing or detection.
A kind of temperature response type luminescent gold nano-micelle (can be made into temperature sensitive test paper etc.) that the present invention synthesizes, works as temperature change
When, fluorescence (the intensity I of dye molecule can be significantly observed by Fluorescence Spectrometer detection luminescent gold nano-micelle1, wavelength
For λ1) and gold nanoparticle fluorescence (intensity I2, wavelength λ2) between conversion；On this basis, the gold nano that shines is calculated
Ratio (the I of two wave crests of micella1/I2) relationship that varies with temperature, it can intuitively obtain relevant temperature；It is more intuitively also
It, can to realize by the variation (such as between Red-Blue) of its fluorescence radiation color under ultraviolet light when can pass through temperature change
Detection depending on changing temperature.In terms of temperature detection, the present invention provides a kind of new thinkings, have prepared a kind of with easy to be fast
The temperature response type luminescent gold nano-micelle of the advantages such as victory, high sensitivity, practicability, universality, repeatability, further to mention
Design and synthesis new way and innovation temperature checking method for novel optical nanoparticle, have further established theoretical and experiment
Basis, in luminescence display, chemical detection, the fields such as biomedical and food safety have broad application prospects.
Compared with prior art, the invention has the advantages that and technical effect:
(1) the temperature response type luminescent gold nano-micelle synthesized by the present invention, synthesis technology is simple, and consume energy low, cost
It is low, it is easy to large-scale industrial production.
(2) the temperature response type luminescent gold nano-micelle synthesized by the present invention, in use because of Ratio-type fluorescence
Probe possesses self-calibration function, therefore not vulnerable to the influence of microenvironment.
(3) the temperature response type luminescent gold nano-micelle synthesized by the present invention, the detection means used can be by a variety of
Approach is realized, is detected including Fluorescence Spectrometer, the ratio (I of two wave crests of luminescent gold nano-micelle1/I2) figure that varies with temperature
Picture and macroscopic color change.
(4) the temperature response type luminescent gold nano-micelle synthesized by the present invention, in visualization temperature detection application aspect
With advantages such as simple and efficient, highly sensitive, practicability, repeatability and universalities.
Detailed description of the invention
Fluorescence spectra of the Fig. 1 for dye molecule used in 1 synthesis process of embodiment in organic solvent.
Fig. 2 is transmission electron microscope (TEM) figure for the temperature response type luminescent gold nano-micelle that embodiment 1 synthesizes.
Fig. 3 is that the fluorescence signal for the temperature response type luminescent gold nano-micelle that embodiment 2 synthesizes varies with temperature fluorescence light
Spectrogram.
Fig. 4 is the visualization temperature variation for the temperature response type luminescent gold nano micellar solution that embodiment 2 synthesizes.
Fig. 5 is the dynamic light scattering of the temperature response type luminescent gold nano-micelle of the synthesis of embodiment 3 at different temperatures
(DLS) characterization result figure.
Fig. 6 is that the partial size for the temperature response type luminescent gold nano-micelle that embodiment 3 synthesizes varies with temperature figure.
Fig. 7 is reversible change figure of the temperature response type luminescent gold nano-micelle to temperature-responsive of the synthesis of embodiment 4.
Fig. 8 is the temperature response type luminescent gold of the dye molecule synthesis of different material amount under the conditions of embodiment 1-5 is 30 DEG C
The fluorescence spectra of nano-micelle.
Fig. 9 is the composition principle schematic diagram of temperature response type luminescent gold nano-micelle of the present invention.
Specific embodiment
Technical solution of the present invention is described in further detail below in conjunction with specific embodiments and drawings, but of the invention
Protection scope and embodiment are without being limited thereto.
In specific embodiment, the Fluorescence Spectrometer of the fluorescence intensity change for observing luminescent gold nano-micelle is the U.S.
PerkinElmer fluorescent/phosphorescent/luminometer (LS-55)；It is Britain Malvern Ma Er for test its particle size
Literary nano-particle size analysis instrument (ZS Nano S) and Other Instruments etc..
Embodiment 1
(1) under room temperature, by the double benzoxazoles of 2,2- (4,4- diphenylethyllene) and 0.2667g of 8 μ L 0.00015g/ml
The tetrahydrofuran of surfactant F127 and 2ml are placed in the single-necked flask of 50ml, in magnetic stirrer 1000rpm/min or super
It is uniformly mixed under the conditions of sound.Under room temperature, it is threaded to Rotary Evaporators sufficiently dry；
(2) under room temperature, 10ml secondary water is added in step (1) obtained solid powder, under magnetic stirrer stirring
(1000rpm/min) is stirred to being completely dissolved, and is added (3- mercaptopropionic acid) pentaerythritol ester of 0.01813g tetra- and is stirred equal
It is even；
(3) 290 μ will be added dropwise for 1.4:1 according to the ratio between amount of substance according to sulfydryl small molecule compound and Au (III)
The HAuCl of L 89.94M4Solution, stirring 15-30min to solution become colorless, and adjusting pH value of solution is 8, in 95 DEG C of constant temperature oil bath
Under stirring (1000rpm/min), sufficiently reaction 6h.
(4) above-mentioned gained sample (is changed into water/8h) for 24 hours by the bag filter dialysis that molecular cut off is 14000Da, then
In the case where centrifugal speed is 21000rpm/min, the purifying such as centrifugation 10min obtain sample.
The fluorescence of dye molecule used in organic solvent during the temperature response type luminescent gold nano-micelle of synthesis
Spectrogram is shown in Fig. 1, and the maximum excitation wavelength of the dye molecule in organic solvent is 374nm and maximum emission wavelength 434nm.
The partial size of gold nanoparticle in the temperature response type luminescent gold nano-micelle of synthesis is 1-3nm, sees Fig. 2.
Embodiment 2
(1) under room temperature, by the double benzoxazoles of 2,2- (4,4- diphenylethyllene) and 0.2667g of 10 μ L 0.00015g/ml
Surfactant F127 and 2ml tetrahydrofuran is placed in the single-necked flask of 50ml, in magnetic stirrer 1000rpm/min or ultrasound
Under the conditions of be uniformly mixed.Under room temperature, it is threaded to Rotary Evaporators sufficiently dry；
(2) under room temperature, 10ml secondary water is added in step (1) obtained solid powder, under magnetic stirrer stirring
(1000rpm/min) is stirred to being completely dissolved, and is added (3- mercaptopropionic acid) pentaerythritol ester of 0.01813g tetra- and is stirred equal
It is even；
(3) 290 μ will be added dropwise for 1.4:1 according to the ratio between amount of substance according to sulfydryl small molecule compound and Au (III)
L 89.94M HAuCl4Solution, stirring 15-30min to solution become colorless, and adjusting pH value of solution is 8, stir in 95 DEG C of constant temperature oil baths
(1000rpm/min) is mixed down, sufficiently reaction 6h.
(4) above-mentioned gained sample (is changed into water/8h) for 24 hours by the bag filter dialysis that molecular cut off is 14000Da, then
In the case where centrifugal speed is 21000rpm/min, the purifying such as centrifugation 10min obtain sample.
The fluorescence signal of the temperature response type luminescent gold nano-micelle of synthesis varies with temperature fluorescence spectra and sees Fig. 3, can
See as the temperature rises, fluorescence intensity of the small molecule dyes in 434nm gradually rises；The gold nanoparticle of formation is in 640nm
The fluorescence intensity at place gradually decreases.Above-mentioned phenomenon is attributed to: under cryogenic, the hydrophobicity of block subtracts in surfactant
It is weak, weaken with the hydrophobic interaction power of dyestuff or gold nanoparticle, its gap is caused to become larger, permeability enhancing, moisture
Son enters, and dye molecule gathers inside surfactant, assembles fluorescent quenching；It is embedding in surfactant as the temperature rises
Duan Jituan dehydration, hydrophobicity enhancing, causes micella under hydrophobic effect, and partial size reduces, and dye molecule is scattered in micella again
Core has the absorption being remarkably reinforced in 434nm；Sulfydryl small molecule compound modification hydrophobic luminous gold nanoparticle then show compared with
Stable temperature-responsive.
The visualization temperature variation of the temperature response type luminescent gold nano-micelle of synthesis is shown in Fig. 4, it is seen that with temperature
It increases, the variation (changing between such as Red-Blue) of apparent fluorescence radiation color can be observed under ultraviolet light.
Embodiment 3
(1) under room temperature, by the double benzoxazoles of 2,2- (4,4- diphenylethyllene) and 0.2667g of 15 μ L 0.00015g/ml
Surfactant F127 and 2ml tetrahydrofuran is placed in the single-necked flask of 50ml, in magnetic stirrer 1000rpm/min or ultrasound
Under the conditions of be uniformly mixed.Under room temperature, it is threaded to Rotary Evaporators sufficiently dry；
(2) under room temperature, 10ml secondary water is added in step (1) obtained solid powder, under magnetic stirrer stirring
(1000rpm/min) is stirred to being completely dissolved, and is added (3- mercaptopropionic acid) pentaerythritol ester of 0.01813g tetra- and is stirred equal
It is even；
(3) 290 μ will be added dropwise for 1.4:1 according to the ratio between amount of substance according to sulfydryl small molecule compound and Au (III)
L 89.94M HAuCl4Solution, stirring 15-30min to solution become colorless, and adjusting pH value of solution is 8, stir in 95 DEG C of constant temperature oil baths
(1000rpm/min) is mixed down, sufficiently reaction 6h.
(4) above-mentioned gained sample (is changed into water/8h) for 24 hours by the bag filter dialysis that molecular cut off is 14000Da, then
In the case where centrifugal speed is 21000rpm/min, the purifying such as centrifugation 10min obtain sample.
Dynamic light scattering (DLS) phenogram of the temperature response type luminescent gold nano-micelle of synthesis at different temperatures is shown in figure
5, it is seen that the particle size of the luminescent gold nano-micelle under condition of different temperatures.
The partial size of the temperature response type luminescent gold nano-micelle of synthesis varies with temperature figure and sees Fig. 6, it is seen that at 20-30 DEG C,
Its change of size is more obvious.Above-mentioned phenomenon is attributed to: under cryogenic, the hydrophobicity of block weakens in surfactant,
It weakens with the hydrophobic interaction power of dyestuff or gold nanoparticle, and micellar particle size, which increases, even scatters, and gold nano at this time
The Jenner's grain of rice formed in micella can stablize fixation surface activating agent micella in low temperature, guarantee that its basic framework is constant；With
Blocking group dehydration in the elevation surface activating agent of temperature, hydrophobicity enhancing cause micella under hydrophobic effect, partial size subtracts
It is small.
Embodiment 4
(1) under room temperature, by the double benzoxazoles of 2,2- (4,4- diphenylethyllene) and 0.2667g of 20 μ L 0.00015g/ml
Surfactant F127 and 2ml tetrahydrofuran is placed in the single-necked flask of 50ml, in magnetic stirrer 1000rpm/min or ultrasound
Under the conditions of be uniformly mixed.Under room temperature, it is threaded to Rotary Evaporators sufficiently dry；
(2) under room temperature, 10ml secondary water is added in step (1) obtained solid powder, under magnetic stirrer stirring
(1000rpm/min) is stirred to being completely dissolved, and is added (3- mercaptopropionic acid) pentaerythritol ester of 0.01813g tetra- and is stirred equal
It is even；
(3) 290 μ will be added dropwise for 1.4:1 according to the ratio between amount of substance according to sulfydryl small molecule compound and Au (III)
L 89.94M HAuCl4Solution, stirring 15-30min to solution become colorless, and adjusting pH value of solution is 8, stir in 95 DEG C of constant temperature oil baths
(1000rpm/min) is mixed down, sufficiently reaction 6h.
(4) above-mentioned gained sample (is changed into water/8h) for 24 hours by the bag filter dialysis that molecular cut off is 14000Da, then
In the case where centrifugal speed is 21000rpm/min, the purifying such as centrifugation 10min obtain sample.
The temperature response type luminescent gold nano-micelle of synthesis is shown in Fig. 7 to the reversible change figure of temperature-responsive, it is seen that in temperature
During circulation, with preferable invertibity, illustrate that the luminescent gold nano-micelle is reusable.
Embodiment 5
(1) under room temperature, by the double benzoxazoles of 2,2- (4,4- diphenylethyllene) and 0.2667g of 25 μ L 0.00015g/ml
Surfactant F127 and 2ml tetrahydrofuran is placed in the single-necked flask of 50ml, in magnetic stirrer 1000rpm/min or ultrasound
Under the conditions of be uniformly mixed.Under room temperature, it is threaded to Rotary Evaporators sufficiently dry；
(2) under room temperature, 10ml secondary water is added in step (1) obtained solid powder, under magnetic stirrer stirring
(1000rpm/min) is stirred to being completely dissolved, and is added (3- mercaptopropionic acid) pentaerythritol ester of 0.01813g tetra- and is stirred equal
It is even；
(3) 290 μ will be added dropwise for 1.4:1 according to the ratio between amount of substance according to sulfydryl small molecule compound and Au (III)
L 89.94M HAuCl4Solution, stirring 15-30min to solution become colorless, and adjusting pH value of solution is 8, stir in 95 DEG C of constant temperature oil baths
(1000rpm/min) is mixed down, sufficiently reaction 6h.
(4) above-mentioned gained sample (is changed into water/8h) for 24 hours by the bag filter dialysis that molecular cut off is 14000Da, then
In the case where centrifugal speed is 21000rpm/min, the purifying such as centrifugation 10min obtain sample.
Under the conditions of embodiment 1-5 is 30 DEG C, the temperature response type luminescent gold nanometre glue of the Dyestuff synthesis of the amount of different material
The fluorescence spectra of beam is shown in Fig. 8, it is seen that with the increase of the amount of fluorescent dye material, gradually increases in the fluorescence intensity of 434nm
By force.
Above-described embodiment is the preferable specific embodiment of the present invention, and wherein the temperature-responsive effect of embodiment 2 is best, but
Scope of protection of the present invention is not limited thereto, it is other it is any without departing from the spirit and principles of the present invention made by change
Become, modification, substitution, combination, simplify, should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of temperature response type luminescent gold nano-micelle, which comprises the steps of:
(1) dyestuff and surfactant are dissolved in organic solvent, are spin-dried for after mixing；
(2) under agitation, solvent is added into step (1) obtained solid powder, stirs to being completely dissolved, adds sulfydryl
Small molecule compound simultaneously stirs evenly；
(3) Au(III is added into mixed liquor obtained by step (2)), stirring to solution becomes colorless, and pH value of solution is adjusted, in constant temperature
The lower sufficiently reaction of oil bath stirring；The Au(III) it is containing Au3+Compound；
(4) sample obtained by step (3) is obtained into temperature response type luminescent gold nano-micelle by dialysis, centrifugal purification.
2. preparation method according to claim 1, which is characterized in that step (1) dyestuff is aminocoumarin, two amidines
One of base Phenylindole, monochloro amine and 2,2- (4,4- diphenylethyllene) double benzoxazoles are a variety of；The surface is living
Property agent be F108, P104, L22, P123, F127, PEO, PPO and PEO it is one or more；The organic solvent is three chloromethanes
Alkane, ethyl alcohol, styrene, tetrahydrofuran, toluene and glycerol it is one or more.
3. preparation method according to claim 1, which is characterized in that step (2) solvent be ethyl alcohol, methanol, acetone,
One or more of glycerol, toluene and water.
4. preparation method according to claim 1, which is characterized in that step (2) the sulfydryl small molecule compound is mercapto
Guanidine-acetic acid, mercaptoethylmaine, 1,6- ethanthiol, two thionitrobenzoates, four (3- mercaptopropionic acid) pentaerythritol esters are
With R-(SH)nThe compound of chemical structural formula, R is alkyl chain or heterocycle compound in formula, and n is sulfydryl number, value model
It encloses for 1-8.
5. preparation method according to claim 1, which is characterized in that in step (3), small molecule compound containing sulfydryl with
Au(III the ratio between amount of substance) is 1.4:1.
6. preparation method according to claim 1, which is characterized in that step (3) stirring becomes colorless to solution
Time is 15-30 min；The pH value is 8-10.
7. preparation method according to claim 1, which is characterized in that the temperature of step (3) described constant temperature oil bath is 80-
120℃；The time sufficiently reacted is 2-10 h；The mixing speed of the constant temperature oil bath is 500-1500 rpm/min.
8. preparation method according to claim 1, which is characterized in that the retention of bag filter used in step (4) described dialysis
Molecular weight is 3000-14000Da；The time of the dialysis is 24 h, wherein to change water primary by every 8h；The speed of the centrifugation is
21000 rpm/min, the time of centrifugation are 10 min.
9. a kind of temperature response type luminescent gold nano-micelle as made from the described in any item preparation methods of claim 1-8.
10. a kind of temperature response type luminescent gold nano-micelle as claimed in claim 9 is applied to visualization temperature sensing or detection
In.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810686627.5A CN109135729B (en) | 2018-06-28 | 2018-06-28 | Temperature response type luminescent gold nano micelle, preparation method thereof and application thereof in visual temperature detection |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810686627.5A CN109135729B (en) | 2018-06-28 | 2018-06-28 | Temperature response type luminescent gold nano micelle, preparation method thereof and application thereof in visual temperature detection |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109135729A true CN109135729A (en) | 2019-01-04 |
| CN109135729B CN109135729B (en) | 2020-10-27 |
Family
ID=64802493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810686627.5A Active CN109135729B (en) | 2018-06-28 | 2018-06-28 | Temperature response type luminescent gold nano micelle, preparation method thereof and application thereof in visual temperature detection |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109135729B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111687428A (en) * | 2020-05-13 | 2020-09-22 | 华南理工大学 | Amphiphilic polymer mediated gold nanoparticle controllable assembly and preparation and application thereof |
| CN112798141A (en) * | 2020-12-28 | 2021-05-14 | 苏州缔因安生物科技有限公司 | Measuring method for surface temperature of gold nanorod, heat transmission device constructed by using measuring method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104117073A (en) * | 2014-07-22 | 2014-10-29 | 国家纳米科学中心 | Dual-mode imaging nano-micelle as well as preparation method and application thereof |
| CN104371069A (en) * | 2014-10-22 | 2015-02-25 | 同济大学 | Preparation method of gold nanoparticle/dendrimer hybrid material |
-
2018
- 2018-06-28 CN CN201810686627.5A patent/CN109135729B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104117073A (en) * | 2014-07-22 | 2014-10-29 | 国家纳米科学中心 | Dual-mode imaging nano-micelle as well as preparation method and application thereof |
| CN104371069A (en) * | 2014-10-22 | 2015-02-25 | 同济大学 | Preparation method of gold nanoparticle/dendrimer hybrid material |
Non-Patent Citations (1)
| Title |
|---|
| SARTHAK MANDAL 等: "Pluronic Micellar Aggregates Loaded with Gold Nanoparticles (Au NPs) and Fluorescent Dyes: A Study of Controlled Nanometal Surface Energy Transfer", 《J. PHYS. CHEM. C》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111687428A (en) * | 2020-05-13 | 2020-09-22 | 华南理工大学 | Amphiphilic polymer mediated gold nanoparticle controllable assembly and preparation and application thereof |
| CN111687428B (en) * | 2020-05-13 | 2021-11-19 | 华南理工大学 | Amphiphilic polymer mediated gold nanoparticle controllable assembly and preparation and application thereof |
| CN112798141A (en) * | 2020-12-28 | 2021-05-14 | 苏州缔因安生物科技有限公司 | Measuring method for surface temperature of gold nanorod, heat transmission device constructed by using measuring method and application |
| CN112798141B (en) * | 2020-12-28 | 2024-02-23 | 苏州缔因安生物科技有限公司 | Gold nanorod surface temperature measurement method, heat transmission device constructed by using same and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109135729B (en) | 2020-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | New near-infrared rhodamine dyes with large Stokes shifts for sensitive sensing of intracellular pH changes and fluctuations | |
| Qin et al. | Organic fluorescent thermometers: Highlights from 2013 to 2017 | |
| Peng et al. | Ratiometric fluorescent nanoparticles for sensing temperature | |
| Ji et al. | Synthesis and application of submicrometer fluorescence sensing particles for lysosomal pH measurements in murine macrophages | |
| CN103087545B (en) | Fluorochrome taking fluorescein as matrix, as well as preparation method and application thereof | |
| CN108033907A (en) | A kind of Heptamethine cyanines active fluoro probe and preparation method and application | |
| CN103382313B (en) | Naphthalimide fluorochrome and its preparation and application | |
| CN101805603A (en) | FITC-doped silica fluorescent nanoparticle and preparation method thereof | |
| CN109897634B (en) | pH-sensitive long-wavelength fluorescent carbon dot and biological application thereof | |
| CN109187473A (en) | Fluorescence resonance energy transfer based on up-conversion nano material and tetramethylrhodamine is used for the detection of excretion body | |
| CN106318372B (en) | A kind of fluorescent nano particle and its synthetic method, application | |
| Chao et al. | A novel ‘‘donor-π-acceptor’’type fluorescence probe for sensing pH: mechanism and application in vivo | |
| Gao et al. | Core-shell fluorescent silica nanoparticles for sensing near-neutral pH values | |
| CN109135729A (en) | A kind of temperature response type luminescent gold nano-micelle and preparation method thereof and the application in visualization temperature detection | |
| Ding et al. | Ratiometric pH sensing by fluorescence resonance energy transfer-based hybrid semiconducting polymer dots in living cells | |
| Wang et al. | Highly efficient red-emitting carbon dots as a “turn-on” temperature probe in living cells | |
| CN108333162A (en) | Fluorescent oxygen probe and preparation method and application thereof | |
| Song et al. | Self-Assembled Micellar Nanosensor toward pH with high photo-stability and its application in living cells | |
| CN109320537A (en) | A kind of soluble two-photon fluorescence probe and its preparation method and application of for flour and in vivo benzoyl peroxide detection | |
| CN109456250A (en) | Hot activation delayed fluorescence (TADF) nano-probe and preparation method thereof and the application in bio-imaging | |
| CN106892870B (en) | Lysosome targeted two-photon viscosity fluorescent probe and preparation method and application thereof | |
| CN111573654A (en) | Green fluorescent carbon quantum dot for detecting pH value in acidic environment and preparation method thereof | |
| Wang et al. | Ratiometric fluorescent sensor with large pseudo-Stokes shifts for precise sensing and imaging of pH without interferential background fluorescence | |
| Chen et al. | Sensitive quantitative image analysis of bisulfite based on near-infrared upconversion luminescence total internal reflection platform | |
| CN104845610B (en) | A kind of fluorescent probe and preparation method thereof, application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |