CN106947467A - It is a kind of to detect arginic up-conversion luminescence nanosensor material and the application in arginine detection - Google Patents
It is a kind of to detect arginic up-conversion luminescence nanosensor material and the application in arginine detection Download PDFInfo
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Abstract
The present invention relates to a kind of new luminous upper conversion nano sensing material of ratio for being used to detect arginic lysosome cellular localization luminescence resonance energy transfer mechanism and preparation method thereof, the nanosensor material is with yttrium, ytterbium, the oxide of erbium obtains rare earth up-conversion luminescence nanometer crystal for raw material, it is modified with polyacrylic acid (PAA), with 2, 3, the carboxylic acid derivates of 3 trimethyl 3H indoles 5 are carried in the polyacrylic acid of rare earth up-conversion luminescence nanometer crystal, excitation wavelength is 980nm, injury to cell is small, it is possible to prevente effectively from the autofluorescence of organism, tissue penetration is strong, arginine is detected in the way of ratio is luminous, and it is used as the new luminous upper conversion sensor of ratio for being used to detect arginic lysosome cellular localization luminescence resonance energy transfer mechanism, with good stability, the advantages of anti-interference is good, the arginine detection that can be applied in solution and living cells.
Description
Technical field
The invention belongs to technical field of analytical chemistry, and in particular to a kind of new for detecting arginic lyase body cell
The luminous upper conversion nano sensing material of the ratio of positioning luminous Resonance energy transfer mechanism.
Background technology
In 20 kinds of amino acid for constituting protein, arginine is the ammonia that protein the most various is may be constructed in animal body
One of base acid, it be not only protein synthesis precursor, be also produce nitric oxide, urea, polyamines, proline, glutamic acid,
The precursor of creatine and agmatine etc..Arginine is played in the release of cell division, wound healing, immunologic function and hormone to pass
Important effect.
But it is due to that arginine has strongly hydrophilic and its weak interaction between acceptor, its detection is faced greatly
Challenge.At present it has been reported that probe seldom, Parveen in 2015, S.D.S. et al. and He in 2014, L. report two respectively
The arginic chemical probe of example detection【Parveen, S.D.S., Affrose, A., Pitchumani, K.,
2015.Sens.Actuators B 221,521-527.He, L.；So, V.L.L.；Xin J.H.；
2014.Sens.Actuators B 192,496-502.】.
Molecular imaging marker material includes organic dyestuff, fluorescin, quantum dot, rare earth nano material etc., traditional
The features such as biomarker dyestuff has good water solubility, is easy to mark, but be generally basede on one-photon excitation, light source is in ultraviolet or can
Jian Guang areas, exciting may be damaged for a long time to biology, and the autofluorescence of organism, tissue penetration energy can not be avoided in addition
Power is poor.Up-conversion luminescent material is excited by near infrared light, and emission band is narrow, and the life-span is normal, anti-Stokes displacement is big, photostability
Strong the features such as.In addition, Ratiometric fluorescent probe can detect the fluorescence intensity at two different wave lengths simultaneously, internal mark is set up
Degree, can overcome single fluorescence probe asking due to factor influence detection signals such as such as instrument efficiency, detection environment, concentration and probe concentrations
Topic.
Lysosome is a kind of important subcellular organelle in cell, the cryptomere particle being made up of inside it single-layer membrane structure, greatly
It is small between 0.025 micron to 0.8 micron.Containing abundant hydrolase inside lysosome, kind more than 60 is up to the present had found,
For example：Proteolytic enzyme, hydrolase nucleic acid, fat hydrolase, phosphate fire-resistant oil enzyme, glycoside hydrolase etc., are mainly used in decomposing
With the albumen and macromolecular in metabolizing cells.The pH value that the hydrolase enriched in lysosome makes it internal is maintained at 5 or so, now
The active highest of lysosome.After extraneous species enter lysosome, the hydrolase in lysosome can play a role alien species
It is decomposed into the material needed for cell.When the membrane structure in lysosome is destroyed, its internal a large amount of hydrolase can be escaped into carefully
Intracellular so that self-dissolving occurs for cell.Therefore, lysosome plays vital effect in the cell.If probe can be real
Existing lysosome positioning, carries out real time imagery, it is possible to in the cytase body under normal and medicine irritation to Cytolysosome
Arginine change carries out correlative study.
The content of the invention
Present invention aims at the up-conversion nano material for providing organic molecular modification, with luminescence resonance energy transfer
The preparation method of the luminous upper conversion nano probe of the ratio of reason, and the application in terms of arginine fluorescence imaging.
To achieve the above object, the technical solution adopted by the present invention is that one kind detects arginic up-conversion luminescence nanometer
Sensing material, is prepared using following methods：Rare earth up-conversion luminescence nanometer crystal is obtained into polyacrylic acid using polyacrylic acid modified
Modification upper conversion nano particle, then by compound 1 be assembled in polyacrylic acid modification up-conversion nano material surface, produce
The arginic up-conversion luminescence nanosensor material of described detection；The structural formula of the compound 1 is as follows：
It is preferred that, the rare earth up-conversion luminescence nanometer crystal is the NaYF of ytterbium and/or Er ions4。
It is preferred that, the rare earth up-conversion luminescence nanometer crystal particle diameter is 13-30nm, and spacing of lattice is 0.30nm, is (110)
Hexagonal crystal phase.
It is preferred that, the preparation method of described rare earth up-conversion luminescence nanometer crystal is as follows：1. by rare earth nitrades and tristearin
The ethanol solution of acid is gradually heated to 78 DEG C of backflows, and NaOH ethanol solution, backflow, mixture filtering, filter cake water is then added dropwise
Wash twice, alcohol is washed once, be dried in vacuo, obtain the stearic acid precursor of rare earth；2. the stearic acid precursor of rare earth and NaF are added
H2In O, EtOH and oleic acid, stirring is transferred in hydrothermal reactor, and reaction cooled down reactant mixture after 24 hours, and it is heavy to isolate
Starch；3. by CHCl3Added with EtOH in sediment, be then centrifuged for obtaining crude product white powder, then use H2O-EtOH washes three
After secondary, alcohol is washed once, described rare earth up-conversion luminescence nanometer crystal is obtained.
It is preferred that, the rare earth nitrades are YNO3、YbNO3And ErNO3Mixture；YNO3、YbNO3And ErNO3Rub
You are than being 0.78: 0.20: 0.02.
It is preferred that, it is described that rare earth up-conversion luminescence nanometer crystal is obtained into the upper of polyacrylic acid modification using polyacrylic acid modified
Conversion nano particle is comprised the following steps that：Rare earth up-conversion luminescence nanometer crystal chloroform is disperseed to obtain rare earth up-conversion luminescence
Nanocrystalline chloroform colloidal solution, is then added dropwise to NOBF4Saturation dichloromethane solution, stirring, be then centrifuged for separation, will precipitate
Thing alcohol flushing is redispersed in DMF (DMF) for three times, adds excessive toluene, is centrifuged, product
It is dispensed into the DMF solution that rare earth up-conversion luminescence nanometer crystal is obtained in DMF；The DMF of polyacrylic acid (PAA) (25% saponification) is molten
Liquid is slowly added into the DMF solution of above-mentioned rare earth up-conversion luminescence nanometer crystal, adds acetone stirring, and then centrifugation is washed, obtained
The upper conversion nano particle modified to polyacrylic acid.
It is preferred that, compound 1 is assembled in the specific steps on surface of the up-conversion nano material of polyacrylic acid modification such as
Under：The up-conversion nano material that polyacrylic acid is modified is dispersed in water, then that the DMSO (dimethyl sulfoxide (DMSO)) of compound 1 is molten
Liquid is added dropwise, and is stirred overnight at room temperature, and centrifugation is precipitated, and is washed, and is obtained the arginic up-conversion luminescence of detection and is received
Rice sensing material.
Application of the described arginic up-conversion luminescence nanosensor material of detection in arginine detection.
On the ratio of the present invention is luminous in conversion nano nano material on conversion nano particle on the one hand play energy and supply
Conversion nano particle plays a part of organic molecule anchored site in the effect of body, another aspect.
The beneficial effect comprise that：The present invention ratio light up-conversion nano material excitation wavelength be
980nm, the injury to cell is small, it is possible to prevente effectively from the autofluorescence of organism, tissue penetration is strong.Lighted with ratio
Mode detects arginine, as sensor, and the fluorescence intensity at two different wave lengths can be detected simultaneously, sets up internal scale,
The problem of single fluorescence probe is due to the factor influence detection signal such as such as instrument efficiency, detection environment, concentration and probe concentration can be overcome.
And it is used as new luminous upper turn of ratio for being used to detect arginic lysosome cellular localization luminescence resonance energy transfer mechanism
Emat sensor, has the advantages that good stability, anti-interference are good, it is adaptable to the ratio biodiversity resources of arginine detection.
Brief description of the drawings
Fig. 1 (a) is NaYF4: the sem image of Yb, Er nano-particle, (b) is the NaYF in situ prepared4: Yb, Er high score
Distinguish images of transmissive electron microscope, the NaYF of (c) polyacrylic acid (PAA) modification4: the sem image of Yb, Er nano-particle, (d) oleic acid
(OA) modified NaYF4: Yb, Er and the modified NaYF of polyacrylic acid (PAA)4: Yb, Er nano-particle XRD sample；
Fig. 2 (a) compounds 1 (7.3 × 10-5M) the absorption spectrum and PAA-UCNPs in water/DMSO solution (8: 2 (v/v))
The luminescent spectrum of (0.15mg/mL) in the case where 980nm light is excited in water；(b) PAA-UCNPs-1 (0.25mg/mL) is in water/DMSO
Up-conversion luminescence spectrum of the arginine aqueous solution in the case where 980nm light is excited is added dropwise in solution (8: 2 (v/v))；(c) it is dense with arginine
With luminous intensity ratio linear relationship chart at 525nm at degree increase 660nm；
Fig. 3 probes PAA-UCNPs-1 [0.25mg/mL is scattered in 8: 2 (v/v) water/DMSO] is at 660nm and at 525nm
Luminous intensity with arginine concentrations (be respectively 1.0 × 10-5M, 5.0 × 10-5M, 1.0 × 10-4M, 1.5 × 10-4M, 2.0 ×
10-4M, 3.0 × 10-4M, 4.0 × 10-4M, 5.0 × 10-4M), excitation wavelength 980nm；(b) 980nm light excites lower probe PAA-
UCNPs-1 [0.25mg/mL is scattered in 8: 2 (v/v) water/DMSO] is at 660nm and at 525nm during luminous intensity ratio
Between change curve；(c) 980nm light excites lower probe PAA-UCNPs-1 [0.25mg/mL is scattered in 8: 2 (v/v) water/DMSO
In] luminous intensity ratio temperature variation curve at 660nm and at 525nm；
Fig. 4 (a) excites lower PAA-UCNPs-1 [0.25mg/mL is scattered in 8: 2 (v/v) water/DMSO] to add in 980nm light
Different biofacies turns down molecule (3.6 × 10-4M up-conversion luminescence response condition and PAA-UCNPs-1 and arginine (concentration)
5.0×10-4M, water is solvent) mixture add the related small molecule (3.6 × 10 of excessive other biological-4M the upper conversion after)
Luminescence response situation, a length of 980nm of excitation light wave, the reaction time is 20 minutes；UCL660And UCL525Represent respectively 660nm and
Up-conversion Intensity at 525nm；Biofacies turns down molecule for Ala, Asp, Glu, Gly, IIe, Leu, Lys, Met, Phe,
Pro, Ser, Thr, Trp, Tyr, Val, Cys, Hcy, Glc, and H2O2；(b) under dark surrounds through probe PAA-UCNPs-1 at
The determination of activity of the HeLa cells of reason；
Fig. 5 is with arginine ((a1) 0, (a2) 2.0 × 10 of 0.006mg/mL PAA-UCNPs-1 and various concentrations-5M, and
(a3)2.8×10-5M the confocal fluorescent image (passage 1 of the HeLa cell of 15 minutes) is dyed：λex=980nm, λem=
660nm)；Arginine ((b1) 0, (b2) 2.0 × 10 of orchil (2.0mM) and various concentrations are positioned with lysosome-5M, and
(b3)2.0×10-5M the confocal fluorescent image (passage 2 of the HeLa cell of 15 minutes) is dyed：λex=543nm, λem=
590nm)；The merging image of (c1, c2and c3) (a) and (b)；
Fig. 6 (a) to add the Laser Scanning Confocal Microscope picture of the HeLa cells after PAA-UCNPs-1 (0.006mg/mL), Fig. 6 (b),
(c) it is addition PAA-UCNPs-1 (0.006mg/mL) and the arginine (b 2.0 × 10 of various concentrations-5M, c 2.8 × 10-5M)
The Laser Scanning Confocal Microscope picture of HeLa cells afterwards；Bright field image (d, e, f).Excitation wavelength is to be collected at 980nm, image 660nm；
Fig. 7 compound PAA-UCNPs, compound 1 and PAA-UCNPs-1 infrared spectrum；
Absorption at graph of a relation (outer figure), 650nm and intensity function relation between the concentration of Fig. 8 compounds 1 and uv-vis spectra
Scheme (illustration)；The concentration of compound 1 is 7.51wt% in the upper conversion nano particle (PAA-UCNPs-1) of organic molecule modification,
The concentration of organic molecule 1 in the upper conversion nano particle (PAA-UCNPs-1) for obtaining organic molecule modification is calculated through function in figure
For 6.6 × 10-5M；
Arginine (the 0-30.0 equivalents of compound 1) 20 minutes compound of reactant aqueous solution 1 [1.0 × 10 is added dropwise in Fig. 9-5M in
8: 2 (v/v) water/DMSO] absorption spectrum；
Figure 10 excitation wavelengths are the 8: 2 of the upper conversion nano particle PAA-UCNPs (0.15mg/mL) that 980nm polyacrylic acid is modified
(v/v) the up-conversion luminescence spectrum of the arginine aqueous solution is added dropwise in water/dimethyl sulphoxide solution；
Upper conversion nano particle PAA-UCNPs-1 [0.25mg/ml in 8: 2 (v/v) water/ of Figure 11 organic molecules modification
DMSO] the fluorescence respective strengths (light post Analyte) of different metal ions (0.11 mol/L) are added in solution and organic
The upper conversion nano particle PAA-UCNPs-1 [0.25mg/ml in 8: 2 (v/v) water/DMSO] and arginine of molecular modification
(2.2×10-3The mol/L aqueous solution) solution add luminous intensity (the dark post Arg+ of excessive specified metal ion
Analyte), excitation wavelength is 980nm, and the reaction time is 20 minutes；UCL660And UCL525Represent respectively at 660nm and 525nm
Up-conversion Intensity；Institute is respectively Na using metal ion+, Mg2+, K+, Ca2+, Mn2+, Co2+And Zn2+；
Upper conversion nano particle PAA-UCNPs-1 [0.25mg/mL in 8: 2 (v/v) water/ of Figure 12 organic molecules modification
DMSO] add in solution different anion (0.11 mol/L) fluorescence respective strengths (light post Analyte) and organic point
The upper conversion nano particle PAA-UCNPs-1 [0.25mg/mL in 8: 2 (v/v) water/DMSO] and arginine of son modification
(2.2×10-3The mol/L aqueous solution) solution add luminous intensity (the dark post Arg+ of excessive specified anion
Analyte), excitation wavelength is 980nm, and the reaction time is 20 minutes；UCL660And UCL525Represent respectively at 660nm and 525nm
Up-conversion Intensity.Institute is respectively F using anion-, Cl-, Br-, I-, N3 -, NO3 -, ClO3 2-, ClO4 -, C2O4 2-, SH-,
S2O3 2-, SO3 2-, HSO3 2-, SO4 2-And HPO4 2-。
Embodiment
Embodiment 1
The preparation of compound 1 uses following synthetic route：
1) synthesis 3- pyrrolidinyl -1- phenol (compound 6)：
By 3- amino-phenols (1.0913g, 10.0mmol), potassium carbonate (1.5203g, 11.0mmol) and Isosorbide-5-Nitrae-dibromobutane
(1340 μ L, 11.0mmol) is dissolved in 10mL DMF.80 DEG C are heated to, reacts 2 hours, is cooled to room temperature.Cross post purification (exhibition
Agent is opened for ethyl acetate: petroleum ether=1: 10), 3- pyrrolidinyl phenol, yield is obtained：58.8%.
It is characterized as below：1H NMR (400MHz, DMSO-d6, TMS)：δH7.10 (t, 1H), 6.19 (t, 2H), 6.09 (s,
1H), (t, the 4H) of 4.86 (s, 1H), 3.28 (t, 4H), 2.0213C NMR (100MHz, DMSO-d6)：δC156.55,149.47,
130.06,104.81,102.57,98.69,47.71, and 25.44.
2) synthesis 2- nitroso -5- pyrrolidines -1- phenol (compound 5)：
3- pyrrolidinyls phenol (324.6 milligrams, 2 mMs) is dissolved in 12 milliliters of concentrated hydrochloric acid (37wt%) and 4mL water
In mixed solvent, 4 milliliters of aqueous solution of natrium nitrosum (138 milligrams, 2 mMs) are added in the above-mentioned solution less than 5 DEG C,
Mixture reacts 1.5 hours and filtered.Solid is washed three times with saturated acetic acid sodium solution, and it is in red brown solid final product to obtain
(340 milligrams, yield：88.4%).
It is characterized as below：1H NMR (400MHz, DMSO-d6, TMS)：δH7.30 (d, 1H), 6.72 (d, 1H), 5.91 (s,
1H), (t, the 4H) of 5.32 (s, 1H), 3.44 (t, 4H), 1.9213C NMR (100MHz, DMSO-d6)：δC173.88,169.19,
156.46,134.66,117.30,96.28,49.63, and 23.49.
3) 3- methyl -7- (pyrrolidines -1-) -2H- benzos [b] [Isosorbide-5-Nitrae] oxazine -2- ketone (compound 4) is synthesized：
2- nitroso -5- pyrrolidines -1- phenol (720.75 milligrams, 2.5 mMs) and 1563 microlitre 80% of hydrazine hydrate are added
Enter into 17 milliliters of ethanol, heat the mixture to 30-40 DEG C, then add 41.5 milligrams of Pd-C catalyst.By above-mentioned mixing
Thing backflow is until the red of solution disappears in argon atmospher.2.5 milliliters of ethyl pyruvates are added, reaction solution is flowed back 4 hours.It is logical
The crude product that vacuum distillation is obtained is crossed, and post purification is crossed for eluent with ethyl acetate/petroleum ether (1/20) and obtains end-product, is produced
Rate is 68%.
It is characterized as below：1H NMR (400MHz, DMSO-d6, TMS)：δH7.40 (d, 1H), 6.56 (d, 1H), 6.37 (s,
1H), (s, the 3H) of 3.31 (t, 4H), 1.98 (t, 4H), 1.2613C NMR (100MHz, DMSO-d6)：δC149.39,148.96,
146.66,129.21,122.24,110.08,97.11,61.96, and 48.04.
4) 7- (pyrrolidines -1-) -2H- benzos [b] [Isosorbide-5-Nitrae] oxazine -3- formaldehyde (compound 3) is synthesized：
By 3- methyl -7- (pyrrolidines -1-) -2H- benzos [b] [Isosorbide-5-Nitrae] oxazine -2- ketone (345.4 milligrams, 1.5 mMs) with
SeO2(204.4 milligrams, 1.8 mMs) are dissolved in 12mL1,4- dioxane, are flowed back 7 hours.Vacuum distillation, crosses post separation
(solvent is dichloromethane/ethanol=500: 1) obtains product (formula III), yield for purification：84.7%.
It is characterized as below：1H NMR (400MHz, CDCl3, TMS)：δH10.08 (s, 1H), 7.67 (d, 1H), 6.68 (d, 1H),
(t, the 4H) of 6.31 (s, 1H), 3.51 (t, 4H), 2.1513C NMR (100MHz, CDCl3)：δC187.86,153.07,152.64,
151.30,134.17,133.42,124.64,112.46,96.96,48.59, and 25.33.
5) preparation of compound 2：
4- hydrazinobenzoic acid hydrochlorides (500mg, 2.46mmol) and NaOH (98.5mg, 2.46mmol) are weighed in 100mL's
In eggplant-shape bottle, add under appropriate EtOH Sonicate, room temperature condition and stir, dissolve 30min, then screw out ethanol, will be remaining
Solid is transferred in 100mL there-necked flasks, is added the dissolving of 16mL glacial acetic acids, is added sodium acetate (405mg, 4.94mmol), ultrasound
Dissolving, is eventually adding 3- methyl -2- butanone (397 μ L, 3.7mmol), is heated to 100 DEG C, and flow back 16h, after question response is complete, stops
Only react, be cooled to room temperature, vacuum distillation screws out glacial acetic acid, 0 DEG C is cooled to frozen water, the sodium carbonate for being slowly added into saturation is molten
Liquid, untill not having bubble generation, pH=4 is adjusted with hydrochloric acid, is extracted three times with dichloromethane, oil phase is collected, uses anhydrous slufuric acid
Sodium is dried, suction filtration, then screws out dichloromethane, obtains red oil 2,3,3- trimethyl -3H- indole -5-carboxylic acids (405mg, yield
For 81%).
By 2,3,3- trimethyl -3H- indole -5-carboxylic acids (1.0g, 4.93mmol) and iodomethane (700mg, 4.93mmol)
It is dissolved in 10 milliliters of acetonitriles.Mixture heating reflux reaction 12 hours, is cooled to room temperature.Filtering revolving removes solvent
Compound 2 (0.76g, 44.7%).
Compound 2 is characterized as below：1H NMR (400MHz, DMSO-d6, TMS)：δH8.38 (s, 1H), 8.19 (d, 1H),
(sd, the 6H) of 8.03 (d, 21H), 4.00 (s, 3H), 2.82 (s, 3H), 1.5713C NMR (100MHz, DMSO-d6)：δC199.48,166.95,142.42,141.72,132.04,130.83,124.68,115.85,54.72,35.52,21.96,
and 15.12。
6) preparation of compound 1：
Compound 3 (209.9 milligrams, 0.64 mM) and compound 2 (155.3 milligrams, 0.64 mM) are dissolved in 17 millis
Rise in ethanol, be heated to 78 DEG C and flow back 12 hours.Reaction solution is cooled to after room temperature and filtered, filter cake washs three with ether
It is secondary, obtain as dark green solid, yield：76.4%.
Compound 1 is characterized as below：HRMS(EI)m/z：calcd for C26H26N3O4[M-I], 444.1923；Found,
444.1921.1H NMR (400MHz, DMSO-d6, TMS)：δH8.39 (s, 1H), 8.24 (s, 1H), 8.19 (d, 1H), 8.02 (d,
1H), 7.80 (d, 1H), 7.66 (d, 1H), 6.96 (d, 1H), 6.67 (s, 1H), 4.04 (s, 3H), 3.59 (t, 4H), 2.00 (t,
4H), 1.79 (s, 6H)13C NMR (100MHz, DMSO-d6)：δC166.99,153.39,145.75,143.88,133.14,
131.55,131.04,127.48,124.22,115.58,114.86,98.14,52.30,49.49,34.98,26.22, and
25.25。
The preparation of rare earth up-conversion luminescence nanometer crystal
By Y2O3(0.8807g, 3.9mmol), Yb2O3(0.3941g, 1.0mmol) and Er2O3(0.0383g, 0.1mmol) dissolves
In 20mL concentrated nitric acids, excessive nitric acid is heated away, the nitrate of the rare earth of white powder, Y is obtained3+, Yb3+And Er3+'s
Mol ratio is 0.78: 0.20: 0.02；By above-mentioned rare earth nitrades and stearic acid 8.5344g (30mmol) 80mL ethanol solutions
78 DEG C of backflows are gradually heated to, NaOH (1.1900g, 30mmol) 20mL ethanol solutions are then added dropwise, are flowed back 1 hour.Mixing
Thing is filtered, and filter cake is washed twice, and alcohol is washed once, and vacuum drying obtains the stearic acid precursor of rare earth for 12 hours.Previous step is obtained
The stearic acid precursor (0.9577g, 1.0mmol) of rare earth and NaF (0.2099g, 5mmol) additions 10mLH2O、15mL EtOH
In the mixed solution of (ethanol) and 5mL oleic acid, stirring is transferred in hydrothermal reactor after 15 minutes.Reacted 24 hours at 150 DEG C
Reactant mixture is cooled to 60 DEG C afterwards, sediment is isolated.By CHCl3Precipitation is added with EtOH (v/v=1: 6) for totally 20 milliliters
In thing, it is then centrifuged for (7800 revs/min, 10 minutes) and obtains crude product white powder, then uses H2O-EtOH (v/v=1: 2) is washed
Three times, after alcohol washes once, obtain described rare earth up-conversion luminescence nanometer crystal (NaYF4: Yb, Er).
Prepare the upper conversion nano particle of polyacrylic acid modification
By rare earth up-conversion luminescence nanometer crystal (NaYF4: Yb, Er) it is scattered in 30 milliliters of chloroforms to obtain changing on rare earth and sends out
Nanocrystalline (NaYF4: Yb, Er) the chloroform colloidal solution of light, is then added dropwise to 50mg NOBF4Saturation dichloromethane solution, stirring
15 minutes.It is then centrifuged for separating (18000 revs/min, 15 minutes), sediment alcohol flushing is redispersed in 20 milliliters of N three times,
In dinethylformamide (DMF).Excessive toluene (50mL) is added, (18000 revs/min, 15 minutes) product point is centrifuged
Spill into 10 milliliters of DMF and obtain NaYF4: Yb, Er DMF solution.By 300 milligrams of polyacrylic acid (PAA) (25% saponification)
10 milliliters of DMF solutions are slowly added into above-mentioned NaYF4: Yb, Er DMF solution, add 60 milliliters of acetone and stir 12 hours, from
The heart (18000 revs/min, 15 minutes), is then washed, and collects the upper conversion nano particle (PAA-UCNPs) of polyacrylic acid modification simultaneously
It is dispersed in water and obtains PAA-UCNPs solution.
Compound 1 is assembled in the surface (PAA-UCNPs-1) of the up-conversion nano material of polyacrylic acid modification：
The prepared PAA-UCNPs in round-bottomed flask is added dropwise in DMSO (0.5mL) solution of compound 1 (45.72mg)
In (5mg/mL) solution, then mixture is stirred overnight obtains homogeneous liquid at room temperature.After mixture centrifugation, rinsed repeatedly with water
Three times, solid phase is collected, the described arginic up-conversion luminescence nanosensor material (PAA-UCNPs-1) of detection is obtained.(PAA-
UCNPs-1 need to disperse to keep in deionized water).
What is prepared in the present embodiment detects application of the arginic up-conversion luminescence nanosensor material as fluorescence probe.
Rare earth nanometer particle in the upper conversion nano particle PAA-UCNPs-1 that organic molecule is modified in the present invention is by solvent
Prepared by hot method, the rare earth nanometer particle of PAA modifications is prepared by ligand exchange processes.Organic molecule modification as shown in Figure 1 upper turn
Change nano material (PAA-UCNPs-1) electron microscopic picture can see nano particle size shape it is homogeneous, particle diameter exists
Between 13nm to 30nm.Its high resolution electron microscopy crystal display cell spacing is 0.30nm, corresponding to NaYF4: Yb, Er nano particle
(110) hexagonal crystal phase.NaYF prepared by (oleic acid) in situ4: Yb, Er and PAA-UCNPs XRD sample are consistent with standard pattern
(JCPDS 28-1192), illustrates that surface modification does not change nano particle crystalline phase.
The absorption spectrum of compound 1 and nano particle PAA-UCNPs are luminous in water in the case where 980nm light is excited in Fig. 2
Spectrum overlaps, the absorption spectrum blue shift of compound 1 after identification arginine so that the upper conversion nano particle of organic molecule modification
Luminous there is rate of change (Fig. 3)；And change is planted with the change of time and temperature not change.
By Fig. 4 it can be seen that arginine influences the absorption spectrum and fluorescence emission spectrum of organic molecular probe, to upper conversion
The luminous of nano particle does not influence, and the other biological in addition to arginine related small molecule Ala, Asp, Glu, Gly, IIe,
Leu, Lys, Met, Phe, Pro, Ser, Thr, Trp, Tyr, Val, Cys, Hcy, Glc, and H2O2On up-conversion luminescence without influence.
Dark toxicity test shows the upper conversion nano particle probe PAA-UCNPs-1 of organic molecule modification at the concentration tested to cell toxicant
Property is smaller；The Laser Scanning Confocal Microscope picture of Fig. 5 HeLa cells confirms that compound cells experiment (Fig. 5, Fig. 6) proves that organic molecule is repaiied
The upper conversion nano probe PAA-UCNPs-1 of decorations can realize lysosome cellular localization, and realize essence in the way of ratio is luminous
The cell detection imaging of propylhomoserin.
It is multiple that Fig. 7 compound PAA-UCNPs, 1 and PAA-UCNPs-1 infrared spectrum confirm that organic fluorescence probe is carried on
Close conversion nano probe；Absorption at graph of a relation and 650nm and intensity between the concentration of Fig. 8 compounds 1 and uv-vis spectra
Function relation figure confirms the amount of the organic fluorescence probe of load；The arginine reactant aqueous solution compound of 20 minutes 1 is added dropwise in Fig. 9
Absorption spectrum and Figure 10 excitation wavelengths are that essence is added dropwise in the upper conversion nano particle PAA-UCNPs solution that 980nm polyacrylic acid is modified
The up-conversion luminescence spectra arginine of the propylhomoserin aqueous solution is to the absorption spectrum of organic compound 1 and upper conversion nano particle
The not same-action of luminescent spectrum, is the important evidence of its mechanism.The upper conversion nano particle PAA- of Figure 11 organic molecules modification
UCNPs-1 recognizes arginic Na+, Mg2+, K+, Ca2+, Mn2+, Co2+And Zn2+Metal ion and F-, Cl-, Br-, I-, N3 -, NO3 -,
ClO3 2-, ClO4 -, C2O4 2-, SH-, S2O3 2-, SO3 2-, HSO3 2-, SO4 2-And HPO4 2-Anion interference experiment is confirmed on organic composite
Conversion nano particle PAA-UCNPs-1 has good anti-interference.
In summary, it is new for detecting arginic lysosome cellular localization light emitting resonator energy the invention provides one kind
Measure the luminous upper conversion nano probe of ratio of transfer mechanism.The nano-probe shows rate of change in arginic light.Should
Sensor has good arginine detection property, good light and thermally stable, anti-interference, it is adaptable to detect arginic
The biodiversity resources of ratio.
Claims (8)
1. the arginic up-conversion luminescence nanosensor material of one kind detection, it is characterised in that prepared using following methods：Will be dilute
Native up-conversion luminescence nanometer crystal is using the polyacrylic acid modified upper conversion nano particle for obtaining polyacrylic acid modification, then by compound
1 is assembled in the surface of the upper conversion nano particle of polyacrylic acid modification, produces the described arginic up-conversion luminescence of detection and receives
Rice sensing material；The structural formula of the compound 1 is as follows：
2. arginic up-conversion luminescence nanosensor material is detected as claimed in claim 1, it is characterised in that on the rare earth
Conversion luminescence nanometer crystal is the NaYF of ytterbium and/or Er ions4。
3. arginic up-conversion luminescence nanosensor material is detected as claimed in claim 1, it is characterised in that on the rare earth
Conversion luminescence nanometer crystal particle diameter is 13-30nm, and spacing of lattice is 0.30nm, is (110) hexagonal crystal phase.
4. arginic up-conversion luminescence nanosensor material is detected as claimed in claim 1, it is characterised in that described rare earth
The preparation method of up-conversion luminescence nanometer crystal is as follows：1. rare earth nitrades and stearic ethanol solution are gradually heated to 78 DEG C
Backflow, is then added dropwise NaOH ethanol solution, and backflow, mixture filtering, filter cake is washed twice, and alcohol is washed once, vacuum drying, is obtained
To the stearic acid precursor of rare earth；2. the stearic acid precursor of rare earth and NaF are added into H2In O, EtOH and oleic acid, stirring is transferred to water
In thermal reactor, reaction cooled down reactant mixture after 24 hours, isolated sediment；3. by CHCl3Add and precipitate with EtOH
In thing, it is then centrifuged for obtaining crude product white powder, then use H2After O-EtOH washes three times, alcohol washes once, described rare earth is obtained
Up-conversion luminescence nanometer crystal.
5. arginic up-conversion luminescence nanosensor material is detected as claimed in claim 4, it is characterised in that the rare earth nitre
Hydrochlorate is YNO3、YbNO3And ErNO3Mixture；YNO3、YbNO3And ErNO3Mol ratio be 0.78: 0.20: 0.02.
6. arginic up-conversion luminescence nanosensor material is detected as claimed in claim 1, it is characterised in that described by rare earth
Up-conversion luminescence nanometer crystal uses the specific steps of the polyacrylic acid modified upper conversion nano particle for obtaining polyacrylic acid modification such as
Under：Rare earth up-conversion luminescence nanometer crystal chloroform is disperseed to obtain rare earth up-conversion luminescence nanometer crystal chloroform colloidal solution, then
It is added dropwise to NOBF4Saturation dichloromethane solution, stir, centrifuge, sediment alcohol flushing is redispersed in DMF three times
In, excessive toluene is added, is centrifuged, product is dispensed into the DMF solution that rare earth up-conversion luminescence nanometer crystal is obtained in DMF；
The DMF solution of polyacrylic acid is slowly added into the DMF solution of above-mentioned rare earth up-conversion luminescence nanometer crystal, acetone is added and stirs
Mix, centrifuge, then wash, obtain the upper conversion nano particle of polyacrylic acid modification.
7. arginic up-conversion luminescence nanosensor material is detected as claimed in claim 1, it is characterised in that by compound 1
The surface for being assembled in the up-conversion nano material of polyacrylic acid modification is comprised the following steps that：The upper conversion that polyacrylic acid is modified
Nano particle is dispersed in water, and then the DMSO solution of compound 1 is added dropwise, is stirred overnight at room temperature, and centrifugation is sunk
Form sediment, washing obtains the arginic up-conversion luminescence nanosensor material of detection.
8. arginic up-conversion luminescence nanosensor material answering in arginine detection is detected as claimed in claim 1
With.
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| CN108130069A (en) * | 2017-12-27 | 2018-06-08 | 深圳大学 | Rare earth upconversion nano diagnosis and treatment agent and preparation method thereof |
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| CN108676554A (en) * | 2018-05-10 | 2018-10-19 | 郑州大学 | A kind of composite Nano probe and preparation method thereof and application |
| CN108676554B (en) * | 2018-05-10 | 2020-12-01 | 郑州大学 | Composite nano probe and preparation method and application thereof |
| 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 |
| CN111234808A (en) * | 2020-03-06 | 2020-06-05 | 安徽师范大学 | Upconversion nano particle modified by nitroso tetrafluoroborate, nano probe, preparation method of nano probe and detection method of sulfur-containing compound |
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