CN107677652A - Upper conversion nano rod/dopamine system of additive Mn and preparation method thereof and the detection method of glutathione or cysteine - Google Patents
Upper conversion nano rod/dopamine system of additive Mn and preparation method thereof and the detection method of glutathione or cysteine Download PDFInfo
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Abstract
The invention discloses a kind of NaYF of additive Mn4:Upper conversion nano rod/dopamine system of Yb, Er and preparation method thereof and the detection method of glutathione or cysteine, the preparation method include：1) water, manganese source, yttrium source, ytterbium source, erbium source, trisodium citrate, CTAB, C1 C3 alcohol and NaF are mixed, is subsequently added into concentrated nitric acid and carries out the obtained UCNRs (Mn of hydro-thermal reaction2+Adulterate NaYF4:The upper conversion nano rod of Yb, Er)；2) UCNRs, PAA (polyacrylic acid) are subjected to ligand exchange reaction in solvent and obtain the UCNRs of PAA modifications；3) the PAA UCNRs modified are scattered in Tris HCl cushioning liquid, are subsequently added into dopamine oscillation incubation so that Mn is made2+The NaYF of doping4:The upper conversion nano rod/dopamine system of Yb, Er.Conversion nano rod/dopamine system has excellent sensitivity and relatively low detection limit for glutathione or cysteine on this.
Description
Technical field
The present invention relates to NaYF4:The upper conversion nano structure of Yb, Er, in particular it relates to the NaYF4 of additive Mn:On Yb, Er
Conversion nano rod/dopamine system and preparation method thereof and the detection method of glutathione or cysteine.
Background technology
Glutathione (GSH) and cysteine (Cys) play vital effect in many physiology courses, and they
The exception of content can trigger different diseases, such as：Hematopoietic cell is reduced, and trichochromes is calm, hepatic injury, skin injury, Chinese mugwort
Disease is grown, Alzheimer disease is caught a cold, and scurvy, severe patient even can trigger cancer.Therefore, to glutathione and cysteine
Detection be particularly important.
Method currently used for detection glutathione and cysteine mainly has electrochemistry, AAS, chromatography and
Using fluorescence probe etc., these methods provide the reliability of experimental result, but the operation of these methods is relative complex, uses instrument
Device costly, introduces to the disagreeableness material of environment in synthesized fluorescence probe.
The content of the invention
It is an object of the invention to provide a kind of NaYF of additive Mn4:The upper conversion nano rod/dopamine system of Yb, Er and its
The detection method of preparation method and glutathione or cysteine, the NaYF4 of the additive Mn:The upper conversion nano rod of Yb, Er/
Dopamine system has excellent sensitivity and relatively low detection limit for glutathione or cysteine and then can realize paddy
The quantitative detection of the sweet peptide of Guang or cysteine, while the preparation method has the advantages of mild condition and raw material are easy to get.
To achieve these goals, the invention provides the invention provides a kind of Mn2+The NaYF of doping4:On Yb, Er
The preparation method of conversion nano rod/dopamine system, the preparation method include：
1) by water, manganese source, yttrium source, ytterbium source, erbium source, trisodium citrate, CTAB (cetyl trimethylammonium bromide), C1-
C3 alcohol and NaF is mixed, and is subsequently added into concentrated nitric acid and is carried out the obtained UCNRs (Mn of hydro-thermal reaction2+Adulterate NaYF4:On Yb, Er
Conversion nano rod)；
2) UCNRs, PAA (polyacrylic acid) are subjected to ligand exchange reaction in solvent and obtain the UCNRs of PAA modifications；
3) the PAA UCNRs modified are scattered in Tris-HCl cushioning liquid, are subsequently added into dopamine oscillation incubation to make
Obtain Mn2+The NaYF of doping4:The upper conversion nano rod/dopamine system of Yb, Er.
Present invention also offers a kind of Mn2+The NaYF of doping4:The upper conversion nano rod/dopamine system of Yb, Er, the Mn2+Mix
Miscellaneous NaYF4:The upper conversion nano rod/dopamine system of Yb, Er is prepared by above-mentioned preparation method.
Invention further provides the detection method of a kind of glutathione or cysteine, the detection method includes：
1) Tris-HCl cushioning liquid, such as above-mentioned PAA-UCNRs and dopamine are formed into mixed liquor, it is then dense by known to
The sample of degree, which is added into mixed liquor, carries out incubation concussion, then carries out luminous signal measure, finally using the concentration of sample as horizontal stroke
Coordinate, the recovery efficiency that lights is ordinate drawing curve or evaluation work curvilinear equation；
2) measuring samples solution is measured into luminous intensity and luminous recovery efficiency according to the method for step 1), then basis
Working curve or working curve equation calculate the concentration of measuring samples solution；
It is known that the sample in the sample and measuring samples solution of concentration is glutathione or cysteine.
In the above-mentioned technical solutions, the principle of preparation of the invention is as shown in figure 8, the Mn that the present invention is built2+Doping
NaYF4:The upper conversion nano rod/dopamine system of Yb, Er：Mn is prepared first2+The NaYF of doping4:Turn nanometer on Yb, ErUCNRs
Rod, then with PAA to Mn2+The NaYF of doping4:Yb, Er UCNRs carry out surface modification link carboxyl, and it is water-soluble and raw to improve it
Thing compatibility, then, dopamine is added under weak basic condition, dopamine, into quinone, passes through hydrogen bond and electrostatic phase by spontaneous oxidation
Interaction is connected, and Photo-induced electron transfer occurs, and forms Mn2+The NaYF of doping4:The upper conversion nano rod/dopamine body of Yb, Er
System.
Again to the Mn of structure2+The NaYF of doping4:In the upper conversion nano rod/dopamine system of Yb, Er add glutathione or
After cysteine, suppress the oxidation of dopamine, prevent the generation of Photo-induced electron transfer, UCNRs luminous recovery.Meanwhile
UCNRs luminous recovery extent is related to the glutathione or the concentration of cysteine that add, it is achieved thereby that to glutathione
Or the quantitative detection of cysteine.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Figure 1A is to detect the Mn that PAA is modified in example 12+Adulterate NaYF4:The upper conversion nano rod TEM figures of Yb, Er；
Figure 1B is the TEM figures for detecting the upper conversion nano rod that dopamine quinone coats in example 1；
Fig. 2 is to detect the Mn that PAA is modified in example 22+Adulterate NaYF4:The emission spectrum and DOPA of the upper conversion nano rod of Yb, Er
The overlapped spectra of amine quinone UV absorption；
Fig. 3 A are quenching design sketch of the DA of various concentrations in detection example 3 to up-conversion luminescence nanometer rods；
Fig. 3 B are that the DA for detecting various concentrations in example 3 adds luminous recovery effects figures of the GSH to up-conversion luminescence nanometer rods；
Fig. 3 C are influence result figures of the different pH to the luminous intensity of the system in detection example 3；
Fig. 3 D are influence result figure of the response time to the luminous intensity of the system in detection example 3；
Fig. 4 is to detect the control experiment figure that the experimental principle is proved in example 4；
Fig. 5 A are the glutathione that various concentrations are added in application examples 1, the luminous spectrogram recovered of upper conversion nano rod；
Fig. 5 B are statistical chart of the luminous recovery strength on the basis of Fig. 5 A to GSH concentration；
Fig. 6 A are the cysteines that various concentrations are added in application examples 2, the luminous spectrogram recovered of upper conversion nano rod；
Fig. 6 B are statistical chart of the luminous recovery strength on the basis of Fig. 6 A to Cys concentration；
Fig. 7 is interference detection results statistical chart；
Fig. 8 is Mn of the present invention2+The NaYF of doping4:The schematic diagram of the upper conversion nano rod/dopamine system of Yb, Er.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The invention provides a kind of Mn2+The NaYF of doping4:The preparation side of the upper conversion nano rod/dopamine system of Yb, Er
Method, the preparation method include：
1) water, manganese source, yttrium source, ytterbium source, erbium source, trisodium citrate, CTAB, C1-C3 alcohol and NaF are mixed, connect
Addition concentrated nitric acid and carry out the obtained UCNRs (Mn of hydro-thermal reaction2+Adulterate NaYF4:The upper conversion nano rod of Yb, Er)；
2) UCNRs, PAA (polyacrylic acid) are subjected to ligand exchange reaction in solvent and obtain the UCNRs of PAA modifications；
3) the PAA UCNRs modified are scattered in Tris-HCl cushioning liquid, are subsequently added into dopamine oscillation incubation to make
Obtain Mn2+The NaYF of doping4:The upper conversion nano rod/dopamine system of Yb, Er.
In the step 1) of above-mentioned preparation method, the dosage of each material can select in wide scope, but in order that
Obtaining obtained UCNRs has excellent luminescent properties, and then causes Mn2+The NaYF of doping4:Yb, Er UCNRs/ dopamines are made
There is more excellent sensitivity, detection limit for system, it is preferable that in step 1), relative to 26-58mg manganese source, the use of water
Measure as 1-3mL, the dosage in yttrium source is 46-138mg, and the dosage in ytterbium source is 19-57mg, and the dosage in erbium source is 2.2-6.7mg, lemon
The dosage of lemon acid trisodium is 29-88mg, and CTAB dosage is 0.05-0.15g, and the dosage of alcohol is 10-20mL, and NaF dosage is
0.21-0.42g, the dosage of concentrated nitric acid is 1-1.5mL and the concentration of concentrated nitric acid is 65-69 weight %；
In the step 1) of above-mentioned preparation method, manganese source, yttrium source, ytterbium source, erbium source, alcohol specific species can be in wide model
Interior selection is enclosed, but in order that obtaining obtained UCNRs has excellent luminescent properties, and then so that Mn2+The NaYF of doping4:Yb,
Er UCNRs/ dopamines as system have more excellent sensitivity, detection limit, it is preferable that erbium source be selected from five nitric hydrate erbiums,
At least one of erbium oxide, anhydrous erbium chloride and eight hydrated sulfuric acid erbiums, manganese source be selected from four chloride hydrate manganese, anhydrous Manganese chloride,
At least one of anhydrous manganous sulfate and Manganous sulfate monohydrate, ytterbium source are selected from ytterbium chloride, five water ytterbium nitrates, ytterbium oxide and ytterbium carbonate
At least one of, yttrium source is selected from least one of yttrium nitrate, yittrium oxide, six chloride hydrate yttriums and yttrium phosphate, and alcohol is selected from first
At least one of alcohol, ethanol and propyl alcohol.
In the step 1) of above-mentioned preparation method, the actual conditions of hydro-thermal reaction can select in wide scope, still
Consider from reaction efficiency and yield, it is preferable that in step 1), in step 1), hydro-thermal reaction at least meets following bar
Part：Reaction temperature is 180-200 DEG C, reaction time 3-5h.
In the step 1) of above-mentioned preparation method, the concrete mode of mixing can select in wide scope, but from behaviour
Consider in the convenience of work, it is preferable that in step 1), mixing is carried out by the way of stirring, and mixing time is 5-
15min。
In the step 2) of above-mentioned preparation method, the dosage of each material can select in wide scope, but in order that
The UCNRs for obtaining obtained PAA modifications has excellent luminescent properties, and then causes Mn2+The NaYF of doping4:Yb,Er UCNRs/
Dopamine has more excellent sensitivity, detection limit as system, it is preferable that in step 2), relative to 34mg UCNRs,
PAA dosage is 0.1-0.3g, and the volume of solvent is 10-20mL.
In the step 2) of above-mentioned preparation method, the specific species of solvent can select in wide scope, but in order to
So that the UCNRs of obtained PAA modifications has excellent luminescent properties, and then cause Mn2+The NaYF of doping4:Yb,Er
UCNRs/ dopamines have more excellent sensitivity, detection limit as system, it is preferable that in step 2), it is sweet that solvent is selected from two
At least one of alcohol, toluene, ethanol.
In the step 2) of above-mentioned preparation method, PAA weight average molecular weight can select in wide scope, but in order to
So that the UCNRs of obtained PAA modifications has excellent luminescent properties, and then cause Mn2+The NaYF of doping4:Yb,Er
UCNRs/ dopamines have more excellent sensitivity, detection limit as system, it is preferable that PAA weight average molecular weight is 1000-
3000。
In the step 2) of above-mentioned preparation method, the actual conditions of ligand exchange reaction can select in wide scope
Select, but consider from reaction yield and speed, it is preferable that in step 2), ligand exchange reaction at least meets following
Condition：Reaction temperature is 150-160 DEG C, reaction time 80-110min.
In the step 3) of above-mentioned preparation method, the dosage of dopamine can select in wide scope, but in order that
Obtaining obtained UCNRs/ dopamines has excellent luminescent properties, and then causes Mn2+The NaYF of doping4:Yb, Er UCNRs/ are more
Bar amine has more excellent sensitivity, detection limit as system, it is preferable that in step 3), relative to 0.14mg PAA-
UCNRs, the dosage of dopamine is 0.09-0.76mg.
In the step 3) of above-mentioned preparation method, the dosage of Tris-HCl cushioning liquid can select in wide scope,
But in order that obtaining obtained UCNRs/ dopamines has excellent luminescent properties, and then so that Mn2+The NaYF of doping4:Yb,Er
UCNRs/ dopamines have more excellent sensitivity, detection limit as system, it is preferable that in step 3), relative to 0.14mg
PAA-UCNRs, the dosage of Tris-HCl cushioning liquid is 0.45-0.7mL；Also, the pH of Tris-HCl cushioning liquid is each
It independently is 7.0-8.5.
In the step 3) of above-mentioned preparation method, the actual conditions of oscillation incubation can select in wide scope, still
In order that obtaining obtained UCNRs/ dopamines has excellent luminescent properties, and then cause Mn2+The NaYF of doping4:Yb,Er
UCNRs/ dopamines have more excellent sensitivity, detection limit as system, it is highly preferred that oscillation incubation at least meets following bar
Part：Vibration temperature is 20-35 DEG C, duration of oscillation 0.5-1h.
In addition, the UCNRs purifications of PAA modifications can use a variety of purification modes, but in order to simplify purification step, preferably
Ground, after ligand exchange reaction terminates, step 2) also includes：Body weight during hydrochloric acid solution is added, then carry out under centrifuging and taking
Layer precipitation；Wherein, the dosage of hydrochloric acid solution and concentration can select in wide scope, but in order to further improve purification
Effect, it is highly preferred that relative to 34mg UCNRs, the dosage of hydrochloric acid solution is 2-3mL and the concentration of hydrochloric acid solution is
0.08-0.15mol/L。
Present invention also offers a kind of Mn2+The NaYF of doping4:The upper conversion nano rod/dopamine system of Yb, Er, the Mn2+Mix
Miscellaneous NaYF4:The upper conversion nano rod/dopamine system of Yb, Er is prepared by above-mentioned preparation method.
Invention further provides the detection method of a kind of glutathione or cysteine, the detection method includes：
1) Tris-HCl cushioning liquid, such as above-mentioned PAA-UCNRs and dopamine are formed into mixed liquor, it is then dense by known to
The sample of degree, which is added into mixed liquor, carries out incubation concussion, then carries out luminous signal measure, finally using the concentration of sample as horizontal stroke
Coordinate, the recovery efficiency that lights is ordinate drawing curve or evaluation work curvilinear equation；
2) measuring samples solution is measured into luminous intensity and luminous recovery efficiency according to the method for step 1), then basis
Working curve or working curve equation calculate the concentration of measuring samples solution；
It is known that the sample in the sample and measuring samples solution of concentration is glutathione or cysteine.
In above-mentioned detection method, Tris-HCl cushioning liquid, such as above-mentioned PAA-UCNRs, dopamine, detection sample solution
Dosage can be selected in wide scope, but in order to further improve the precision of detection, it is preferable that in sample be paddy Guang
During sweet peptide, relative to 0.14mg PAA-UCNRs, the dosage of dopamine is 0.09-0.76mg, and the dosage for detecting sample solution is
0.8-1mL and detection sample solution in glutathione concentrations be 0.25-56.25 μm of ol/L；And/or it is half in sample
During cystine, relative to 0.14mg PAA-UCNRs, the dosage of dopamine is 0.09-0.76mg, detects the dosage of sample solution
It is 0.3125-43.75 μm of ol/L for the semicystinol concentration in 0.8-1mL and detection sample solution.
In above-mentioned detection method, the dosage and pH of cushioning liquid can select in wide scope, but in order to enter
One step improves the precision of detection, it is preferable that relative to 0.14mg PAA-UCNRs, the dosage of cushioning liquid is 0.45-
0.7mL, and the pH of Tris-HCl cushioning liquid is 7.0-8.5.
In above-mentioned detection method, being incubated the condition of concussion can select in wide scope, but in order to further carry
The precision of high detection, it is preferable that be incubated concussion and at least meet following condition：25-30 DEG C of temperature is shaken, duration of oscillation is
0.5-0.75h。
On the basis of the above, different working curve equations can be produced under different testing conditions, but in order to
Further improve the precision of detection, it is preferable that when sample is glutathione, working curve equation is y=0.168+
0.02442x, wherein, y is that luminous intensity recovers efficiency, and x is the concentration of glutathione；And/or it is half Guang ammonia in sample
When sour, working curve equation is y=0.1523+0.03603x, wherein, y is luminous intensity recovery value, and x is the dense of cysteine
Degree.
Finally, measuring samples solution source place can be a variety of, but from the common scope of detection and be easy to promote
The detection method, it is preferable that measuring samples solution is originally water sample.
The present invention will be described in detail by way of examples below.
Embodiment 1
1)UCNRs(Mn2+-NaYF4:Yb, Er/UCNRs) preparation：
First, 2.1mL ultra-pure waters are added into clean 50mL small beaker, concentration is added under conditions of being kept stirring for
For 0.145mLMnCl2Solution (1.2mol/L), 1.2mL Y (NO3)3Solution (0.2mol/L), 1mL YbCl3Solution
(0.1mol/L)、0.1mL Er(NO3)3Solution (0.1mol/L) and 1.75mL citric acid three sodium solutions (0.1mol/L), continue
Stirring is well mixed the solution in beaker.Secondly, 0.1g CTAB are weighed and measure 15mL C2H5OH is added in beaker.Then,
6mL NaF solution (1.0mol/L) is added dropwise into above-mentioned solution, 1mL concentrated nitric acid (concentration 68 is added after being kept stirring for 2h
Weight %) reaction precursor liquid solution is formed, and presoma is transferred in 50mL reactors, 180 DEG C of reaction 4h are set, work as reaction
When solution in kettle is cooled to 25 DEG C, supernatant is outwelled, will obtain below milky turbidity liquid pour into centrifuge tube and centrifuge
(10000rpm, 5min), washed repeatedly with ultra-pure water and ethanol, finally obtain Mn2+The NaYF of doping4:Yb,Er UCNRs。
2)Mn2+-NaYF4:PAA-UCNRs is made in Yb, Er/UCNRs carboxyl modified：
Weigh 0.2g PAA (weight average molecular weight 1000-3000) to add in dry four-neck flask, then added to it
16mL DEG (diethylene glycol (DEG)), 110 DEG C are heated under logical condition of nitrogen gas；34mg Mn2+The NaYF of doping4:Yb,Er UCNRs
Solve homogeneously in 2mL C7H8In and be added in four-neck flask, when temperature is raised to 150 DEG C, at such a temperature keep constant temperature backflow
1.5h.Obtained solution adds 2mL HCl solutions (0.1mol/L) after being cooled to 25 DEG C, and solution is poured into centrifuge tube and centrifuged
(10000rpm, 10min) and centrifuged twice with milli-Q water, finally obtain PAA-UCNRs.
3) the 0.14mg PAA-UCNRs is dissolved in 675 μ L Tris-HCl cushioning liquid (10.00 mmol/L, pH is
7.6) 0.47mg dopamines, are added, mixing concussion forms uniform solution, and concussion 35min is incubated at 30 DEG C, forms Mn2+Mix
Miscellaneous NaYF4:Yb, Er UCNRs/ dopamine systems.
Application examples 1
GSH (glutathione) detection：
Luminous intensity is determined by the use of Hitachi, Ltd's F-4600 XRFs (980nm is used as excitation source), is realized with this
Luminous detection to glutathione.
PAA-UCNRs is dissolved in 675 μ L Tris-HCl cushioning liquid (10.00 mM, pH in 0.14mg detection example 1
7.6) 0.47mg dopamines, are added, mixing concussion forms uniform solution, adds the GSH solution of same volume various concentrations 30
Concussion 35min is incubated at DEG C, as sample solution.
It is luminous to recover detection：It is luminous strong by the use of Hitachi, Ltd's F-4600 XRFs (980nm is used as excitation source) measure
Degree, drawing curve, is as a result shown in Fig. 5 A and Fig. 5 B, wherein, Fig. 5 A be when adding the glutathione of various concentrations on change and receive
The luminous spectrogram recovered of rice rod；Fig. 5 B are statistical chart of the luminous recovery strength on the basis of Fig. 5 A to GSH concentration；By
Figure understands that working curve equation is y=0.168+0.02442x, wherein, y is luminous intensity recovery value, and x is GSH concentration.
Application examples 2
Cys (cysteine) detection：
Luminous intensity is determined by the use of Hitachi, Ltd's F-4600 XRFs (980nm is used as excitation source), is realized with this
Luminous detection to glutathione.
PAA-UCNRs is dissolved in 675 μ L Tris-HCl cushioning liquid (10.00 mM, pH in 0.14mg detection example 1
7.6) 0.47mg dopamines, are added, mixing concussion forms uniform solution, adds the Cys solution of same volume various concentrations 30
Concussion 35min is incubated at DEG C, as sample solution.
It is luminous to recover detection：It is luminous strong by the use of Hitachi, Ltd's F-4600 XRFs (980nm is used as excitation source) measure
Degree, drawing curve, it is upper conversion nano rod hair when adding the cysteine of various concentrations as a result to see Fig. 6 A and Fig. 6 B, Fig. 6 A
The spectrogram that light recovers；Fig. 6 B are statistical chart of the luminous recovery strength on the basis of Fig. 6 A to Cys concentration；As seen from the figure, work
It is y=0.1523+0.03603x to make curvilinear equation, wherein, y is luminous intensity recovery value, and x is Cys concentration.
Embodiment 2
Mn is prepared Following the procedure of Example 12+The NaYF of doping4:Yb, Er UCNRs/ dopamine systems, except that
MnCl2Dosage be 58mg, Y (NO3)3Dosage be 138mg, YbCl3Dosage be 57mg, Er (NO3)3Dosage be 6.7mg,
The dosage of trisodium citrate is 88mg, and CTAB dosage is 0.15g.
Detection according to identical method in application examples 1 and 2 shows, the UCNRs/ dopamine systems for glutathione and
Cysteine can also carry out quantitative detection.
Embodiment 3
Mn is prepared Following the procedure of Example 12+The NaYF of doping4:Yb, Er UCNRs/ dopamine systems, except that
MnCl2Dosage be 26mg, Y (NO3)3Dosage be 46mg, YbCl3Dosage be 19mg, Er (NO3)3Dosage be 2.2mg,
The dosage of trisodium citrate is 29mg, and CTAB dosage is 0.05g.
Detection according to identical method in application examples 1 and 2 shows, the UCNRs/ dopamine systems for glutathione and
Cysteine can also carry out quantitative detection.
Detect example 1
By the trade mark be the 120kV of Hitachi HT 7700 transmission electron microscope (TEM) to PAA-UCNRs in embodiment 1
And Mn2+The NaYF of doping4:Yb, Er UCNRs/ dopamine systems (dopamine is oxidized to quinone and is coated on PAA-UCNRs) enter
Row Shape measure, is specifically shown in Figure 1A and Figure 1B.From Figure 1A, up-conversion nano material is in bar-shaped；From Figure 1B, dopamine
Quinone is coated on PAA-UCNRs surface.
Detect example 2
F-4600 XRFs by the trade mark for Japan, Hi-Tech Optoelectronics Co., Ltd. 980nm is added in addition and is swashed
Light carries out luminescent spectrum measure to PAA-UCNRs in embodiment 1 as excitation source, a curves in testing result such as Fig. 2.
The dopamine quinone in ultraviolet-visible spectrophotometer embodiment 1 for being UV-4100 by the trade mark carries out absorption spectrum
B curves in measure, testing result such as Fig. 2.
As shown in Figure 2, the PAA-UCNRs launching light spectrograms in embodiment 1 and the UV absorption figure of dopamine quinone, the two has
Good spectrogram is overlapping.
Detect example 3
Detected using F-4600 XRF of the trade mark for Japan：
1) carried out according to the method for embodiment 1, except that changing the concentration of DA (dopamine) in step 3), then
The luminous intensity of UCNRs/ dopamine systems is detected, as a result as shown in Figure 3A, as seen from the figure, with the addition of DA (dopamine),
PAA-UCNRs luminous intensity has obvious quenching.
2) according to application examples 1 method carry out, except that change in DA) concentration, then detection architecture recovery
Rate, as a result as shown in Figure 3 B, the optimal recovery concentration for as a result showing DA are 3.125mmol/L.
3) according to application examples 1 method carry out, except that change in cushioning liquid pH, then testing result as scheme
Shown in 3C, as a result show that 7.6 be optimal pH value.
4) carry out according to the method for application examples 1, except that changing the concussion time, as a result as shown in Fig. 3 D, as a result show
It is the optimal oscillation incubation time to show more than 35min.
Detect example 4
The hair of PAA-UCNRs under different condition in embodiment 1 is recorded for the F-4600 XRFs of Japan using the trade mark
Light intensity analysis, as a result such as Fig. 4.As shown in Figure 4, the luminous intensity (Fig. 4 a) during only UCNRs；Add 100.0 μM of paddy of detectable substance
During the sweet peptide of Guang, (Fig. 4 b) almost is not influenceed on UCNRs luminous intensity；3.125mmol/L DA, hair are added in UCNRs solution
Now there is obvious quenching (Fig. 4 c) to the luminous of UCNRs；Followed by above-mentioned Mn2+The NaYF of doping4:Yb,Er UCNRs/DA
When the glutathione of various concentrations is added in system, the luminous of UCNRs has obvious recovery (Fig. 4 d, e), it was demonstrated that the experimental principle
It is feasible.
Application examples 3
Fluorescence radiation detects actual sample：
According to the method for embodiment 1 to being detected to the GSH in originally water sample and Cys.Add expression and pass through standard
Add and standard GSH and Cys sample is added in normal direction system, find to represent after GSH and Cys is added, the luminous intensity measured
Value, according to working curve, the concentration value drawn.Concrete outcome is shown in Table 1, and wherein RSD is that relative standard deviation (takes 3 times averagely
Value).
Table 1
Application examples 4
Interference Detection：
Carried out according to the method for application examples 1, except that adding interfering material (L- dried meat ammonia into luminous detection architecture
Acid, glutamic acid, leucine, glycine, alanine, histidine, threonine, asparatate, glucose, sodium ion, calcium ion,
Potassium ion：500.0μmol/L).According to luminous intensity recovery value, block diagram is drawn, as a result sees Fig. 7, wherein, each English in figure
Represent respectively：L-proline(Pro)：L-PROLINE；Glutamate(Glu)：Glutamic acid；Leucine(Leu)：Leucine；
Glycine(Gly)：Glycine；Alanine(Ala)：Alanine；Histidine(His)：Histidine；Threonine(Thr)：
Threonine；Aspartic acid(Asp)：Asparatate；Glucose glucose；Na+：Sodium ion；Ca2+：Calcium ion；K+：
Potassium ion；GSH：Glutathione；Cys：Cysteine.As seen from the figure, the system has to glutathione and cysteine
Excellent selectivity.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
- A kind of 1. Mn2+The NaYF of doping4:The preparation method of the upper conversion nano rod/dopamine system of Yb, Er, it is characterised in that institute Stating preparation method includes：1) water, manganese source, yttrium source, ytterbium source, erbium source, trisodium citrate, CTAB, C1-C3 alcohol and NaF are mixed, then added Enter concentrated nitric acid and carry out the obtained UCNRs (Mn of hydro-thermal reaction2+Adulterate NaYF4:The upper conversion nano rod of Yb, Er)；2) described UCNRs, PAA (polyacrylic acid) are subjected to ligand exchange reaction in solvent and obtain the UCNRs of PAA modifications；3) PAA UCNRs modified are scattered in Tris-HCl cushioning liquid, are subsequently added into dopamine oscillation incubation to make Obtain the Mn2+The NaYF of doping4:The upper conversion nano rod/dopamine system of Yb, Er.
- 2. preparation method according to claim 1, wherein, in step 1), relative to the 26-58mg manganese source, institute The dosage for stating water is 1-3mL, and the dosage in the yttrium source is 46-138mg, and the dosage in the ytterbium source is 19-57mg, the erbium source Dosage is 2.2-6.7mg, and the dosage of the trisodium citrate is 29-88mg, and the dosage of the CTAB is 0.05-0.15g, described The dosage of alcohol is 10-20mL, and the dosage of the NaF is 0.21-0.42g, and the dosage of the concentrated nitric acid is 1-1.5mL and described dense The concentration of nitric acid is 65-69 weight %；Preferably, the erbium source in five nitric hydrate erbiums, erbium oxide, anhydrous erbium chloride and eight hydrated sulfuric acid erbiums at least one Person, the manganese source are selected from least one of four chloride hydrate manganese, anhydrous Manganese chloride, anhydrous manganous sulfate and Manganous sulfate monohydrate, The ytterbium source is selected from least one of ytterbium chloride, five water ytterbium nitrates, ytterbium oxide and ytterbium carbonate, the yttrium source be selected from yttrium nitrate, At least one of yittrium oxide, six chloride hydrate yttriums and yttrium phosphate, the alcohol in methanol, ethanol and propyl alcohol at least one Person.
- 3. preparation method according to claim 1, wherein, in step 1), in step 1), the hydro-thermal reaction is at least Meet following condition：Reaction temperature is 180-200 DEG C, reaction time 3-5h；Preferably, in step 1), the mixing is carried out by the way of stirring, and mixing time is 5-15min.
- 4. according to the preparation method described in any one in claim 1-3, wherein, in step 2), relative to 34mg institute UCNRs is stated, the dosage of the PAA is 0.1-0.3g, and the volume of the solvent is 10-20mL；It is highly preferred that in step 2), the solvent is selected from least one of diethylene glycol (DEG), toluene, ethanol；More preferably, the weight average molecular weight of the PAA is 1000-3000.
- 5. preparation method according to claim 4, wherein, in step 2), the ligand exchange reaction at least meets Following condition：Reaction temperature is 150-160 DEG C, reaction time 80-110min.
- 6. preparation method according to claim 5, wherein, in step 3), relative to the 0.14mg PAA- UCNRs, the dosage of the dopamine is 0.09-0.76mg；Preferably, in step 3), relative to the 0.14mg PAA-UCNRs, the dosage of the Tris-HCl cushioning liquid For 0.45-0.7mL；Also, the pH of the Tris-HCl cushioning liquid is each independently 7.0-8.5；It is highly preferred that the oscillation incubation at least meets following condition：Vibration temperature is 20-35 DEG C, duration of oscillation 0.5-1h.
- 7. the preparation method according to claim 5 or 6, wherein, after the ligand exchange reaction terminates, step 2) is also Including：Body weight during hydrochloric acid solution is added, then carry out centrifuging and taking lower sediment；Preferably, relative to the 34mg UCNRs, the dosage of the hydrochloric acid solution is dense for 2-3mL and the hydrochloric acid solution Spend for 0.08-0.15mol/L.
- A kind of 8. Mn2+The NaYF of doping4:The upper conversion nano rod/dopamine system of Yb, Er, it is characterised in that the Mn2+Doping NaYF4:Preparation method system of the upper conversion nano rod/dopamine system of Yb, Er described in by any one in claim 1-7 It is standby and obtain.
- 9. the detection method of a kind of glutathione or cysteine, it is characterised in that the detection method includes：1) Tris-HCl cushioning liquid, PAA-UCNRs as claimed in claim 8 and dopamine are formed into mixed liquor, then will The sample of concentration known, which adds, carries out incubation concussion into the mixed liquor, luminous signal measure is then carried out, finally with sample Concentration be abscissa, light recover efficiency be ordinate drawing curve or evaluation work curvilinear equation；2) measuring samples solution is measured into luminous intensity and luminous recovery efficiency according to the method for step 1), then according to Working curve or working curve equation calculate the concentration of measuring samples solution；Wherein, the sample in the sample of the concentration known and measuring samples solution is glutathione or cysteine.
- 10. detection method according to claim 9, wherein, when sample is glutathione, relative to described in 0.14mg PAA-UCNRs, the dosage of the dopamine is 0.09-0.76mg, and the dosage for detecting sample solution is 0.8-1mL and the detection Glutathione concentrations in sample solution are 0.25-56.25 μm of ol/L；And/or when sample is cysteine, relatively In the 0.14mg PAA-UCNRs, the dosage of the dopamine is 0.09-0.76mg, and the dosage for detecting sample solution is 0.8-1mL and it is described detection sample solution in semicystinol concentration be 0.3125-43.75 μm of ol/L；Preferably, relative to the 0.14mg PAA-UCNRs, the dosage of the cushioning liquid is 0.45-0.7mL, and described The pH of Tris-HCl cushioning liquid is 7.0-8.5；It is highly preferred that the incubation concussion at least meets following condition：Shake 25-30 DEG C of temperature, duration of oscillation 0.5- 0.75h；It is further preferred that when sample is glutathione, the working curve equation is y=0.168+0.02442x, its In, y is that luminous intensity recovers efficiency, and x is the concentration of glutathione；And/or when sample is cysteine, the work It is y=0.1523+0.03603x to make curvilinear equation, wherein, y is luminous intensity recovery value, and x is the concentration of cysteine；Still further preferably, the measuring samples solution is originally water sample.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108982440A (en) * | 2018-06-10 | 2018-12-11 | 福建医科大学 | The upper building for converting faint photodetector and its detection for glutathione |
| CN112649406A (en) * | 2020-11-30 | 2021-04-13 | 天津科技大学 | Method for detecting glutathione by fluorescence enhancement method |
| CN115558488A (en) * | 2022-10-14 | 2023-01-03 | 赣南师范大学 | Rare earth composite nano material, preparation method and application thereof, and up-conversion detection method of cysteine |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232849A (en) * | 2013-04-27 | 2013-08-07 | 东南大学 | Preparation method of water-soluble rare earth up-converting luminescence nano particle modified by amino acid |
| CN103540311A (en) * | 2013-10-15 | 2014-01-29 | 上海大学 | Synthetic method of cysteine modified rare earth up-conversion luminescent nanocrystallines |
| CN106268884A (en) * | 2016-08-16 | 2017-01-04 | 福州大学 | A kind of rear-earth-doped NaYF4/ Au@CdS composite photo-catalyst and preparation method thereof |
| CN106987245A (en) * | 2017-03-23 | 2017-07-28 | 安徽师范大学 | The up-conversion luminescence nanomaterial of manganese dioxide nano-plates modification and preparation method, the detection method of hydrogen peroxide or choline and application |
-
2017
- 2017-08-24 CN CN201710733155.XA patent/CN107677652A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232849A (en) * | 2013-04-27 | 2013-08-07 | 东南大学 | Preparation method of water-soluble rare earth up-converting luminescence nano particle modified by amino acid |
| CN103540311A (en) * | 2013-10-15 | 2014-01-29 | 上海大学 | Synthetic method of cysteine modified rare earth up-conversion luminescent nanocrystallines |
| CN106268884A (en) * | 2016-08-16 | 2017-01-04 | 福州大学 | A kind of rear-earth-doped NaYF4/ Au@CdS composite photo-catalyst and preparation method thereof |
| CN106987245A (en) * | 2017-03-23 | 2017-07-28 | 安徽师范大学 | The up-conversion luminescence nanomaterial of manganese dioxide nano-plates modification and preparation method, the detection method of hydrogen peroxide or choline and application |
Non-Patent Citations (4)
| Title |
|---|
| D.W. ET AL.: "Bioinspired Near-Infrared-Excited Sensing Platform for in Vitro Antioxidant Capacity Assay Based on Upconversion Nanoparticles and a Dopamine−Melanin Hybrid System", 《 ACS APPL. MATER. INTERFACES》 * |
| LIPING ZHANG ET AL.: "A near-infrared luminescent Mn2+-doped NaYF4:Yb,Tm/Fe3+ upconversion nanoparticles redox reaction system for the detection of GSH/Cys/AA", 《TALANTA》 * |
| 徐又一等: "多巴胺的自聚-附着行为与膜表面功能化", 《膜科学与技术》 * |
| 罗芳等: "多巴胺修饰制备亲水性ＮaYF4:Yb"Er上转换发光纳米颗粒", 《南京工业大学学报（自然科学版）》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108982440A (en) * | 2018-06-10 | 2018-12-11 | 福建医科大学 | The upper building for converting faint photodetector and its detection for glutathione |
| CN112649406A (en) * | 2020-11-30 | 2021-04-13 | 天津科技大学 | Method for detecting glutathione by fluorescence enhancement method |
| CN115558488A (en) * | 2022-10-14 | 2023-01-03 | 赣南师范大学 | Rare earth composite nano material, preparation method and application thereof, and up-conversion detection method of cysteine |
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