CN104592996A - Nano probe for copper ion fluorescence imaging in cells and preparation method for nano probe - Google Patents
Nano probe for copper ion fluorescence imaging in cells and preparation method for nano probe Download PDFInfo
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- CN104592996A CN104592996A CN201510010745.0A CN201510010745A CN104592996A CN 104592996 A CN104592996 A CN 104592996A CN 201510010745 A CN201510010745 A CN 201510010745A CN 104592996 A CN104592996 A CN 104592996A
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Abstract
The invention relates to a nano probe for copper ion fluorescence imaging in cells and a preparation method for the nano probe. The preparation method comprises the following steps: firstly, synthesizing up-conversion nana particles with core-shell structures, CS-UCNPs for short; then, by taking a CTAB (cetyltrimethyl ammonium bromide) as a template agent and a surfactant, coating a layer of mesoporous SiO2 on the surfaces of the CS-UCNPs to obtain mesoporous coated nano particles CS-UCNPs@mSiO2 with compounding functions; finally, performing covalent bond assembly on functional modified rhodamine organic dye RHB precursors capable of identifying metal copper ions in a singular manner and the CS-UCNPs@mSiO2 to construct an organic-inorganic hybrid nano probe CS-UCNPs@mSiO2-RBH, thereby realizing fluorescence detecting and living cell fluorescence imaging of copper ions in an aqueous solution. The preparation method disclosed by the invention has the advantages of being simple in process, convenient to operate and easy to control structure. The prepared nano fluorescence probe has the characteristics of a uniform dimension, a stable structure, low toxicity and good biocompatibility, and a potential application value in the fields of up-conversion fluorescence labeling, fluorescence detecting and the like of cells or tissues.
Description
Technical field
The present invention relates to a kind of nano-probe for intracellular copper ion fluorescence imaging and preparation method thereof.
Background technology
Copper is a kind of required trace element in human body, plays an important role in the metabolic processes of human body.Copper lacks and is reduced by the chromo-oxidase made in brain cell, vigor decline, thus makes amnesia, disturbance in thinking, slow in reacting, even instability of gait, motor disorder etc.; Copper participates in the synthesis of various metals enzyme in human body, and copper is once lack, and the synthesis of this fermentoid reduces, and cardiovascularly just cannot maintain normal morphology and function, thus invades to coronary heart disease with opportunity.On the other hand, but the copper of excess intake may cause poisoning, comprises the illnesss such as acute copper poisoning, hepatolenticular degeneration, children's intrahepatic cholestasis.Therefore, the distribution situation specifying copper in physiological process and cell is significant for the complex physiologic function of research copper.
The design of copper ion fluorescence probe and synthesis are one of the emphasis and focus of fluorescent sensing material research field, and probe material conventional at present mainly contains: organic molecule fluorescent probe, quantum dot etc.There is following shortcoming in them: (1) organic molecular probe structural instability, and light stability is poor, and water-soluble poor, cannot be applied in pure aqueous environment or cell system.(2) quantum dot class fluorescent probe chemical stability or unsatisfactory, also there is larger dispute etc. in its bio-toxicity.(3) exciting light of probe used is positioned at the high-energy light district such as ultraviolet and visible region, and to greatly cell killing, archebiosis fluorescence is strong simultaneously, and signal to noise ratio is low.With this, design and synthesis bio-toxicity is low, good water solubility, and the probe material of what background influence was little can be used for cupric ion fluorescence imaging in viable cell has important theory significance and the using value of reality.
Summary of the invention
An object of the present invention is for the deficiencies in the prior art, provides a kind of nano-probe for intracellular copper ion fluorescence imaging, realizes the trace detection of cupric ion in aqueous phase system and the application of intracellular copper ion fluorescence imaging.
Two of object of the present invention is the preparation method providing this nano-probe.
For achieving the above object, technical scheme provided by the present invention is:
A kind of nano-probe for intracellular copper ion fluorescence imaging, it is characterized in that this probe be coated on the up-conversion luminescence nanometer crystal with nucleocapsid structure on mesoporous silicon oxide, as energy donor, then formed with the bonding as the rhodamine B derivative fluorescence dye precursor molecule of energy acceptor by the mode of covalent bonding, the mass ratio of the up-conversion luminescence nanometer crystal and mesoporous silicon oxide wherein with nucleocapsid structure is 1:10 ~ 1:19; Described energy donor and the mass ratio of energy acceptor are 10:1 ~ 15:1.
The above-mentioned up-conversion luminescence nanometer crystal with nucleocapsid structure is: NaYF
4: Yb, Er@NaYF
4, NaYF
4: Yb, Er@NaYF
4: Yb, Er, NaYF
4: Yb, Er@NaGdF
4or NaYF
4: Yb, Er@NaGdF
4: Yb, Er.
Above-mentioned rhodamine B derivative fluorescence dye precursor molecule can be:
or
.
Prepare a method for the above-mentioned nano-probe for intracellular copper ion fluorescence imaging, it is characterized in that the concrete steps of the method are:
A. by there is nucleocapsid structure up-conversion luminescence nanometer crystal on coating mesoporous silicon-dioxide, obtain CS-UCNPs@mSiO
2;
B. rhodamine B derivative fluorescence dye precursor molecule and isocyanatopropyl triethoxyl silane are dissolved in organic solvent according to the ratio of mol ratio 1:2 ~ 1:10, reflux 2 ~ 10 hours; After being cooled by obtained mixture, rotary evaporation, except desolventizing, obtains the nano-probe for intracellular copper ion fluorescence imaging after being separated deduction.
The concrete grammar of above-mentioned step a is:
A. be dissolved in deionized water by cetyl trimethylammonium bromide and the up-conversion luminescence nanometer crystal with nucleocapsid structure by the mass ratio of 4:1 ~ 5:1, spend the night removing hexanaphthene;
B. the aqueous ethanolic solution of tetraethoxy is joined in step a gained solution, regulate pH to 10 ~ 12, be heated to 70 DEG C, and keep 2 hours, after reaction terminates, by washing with alcohol, obtain nano particle and the CS-UCNPs@SiO of coated with silica
2, and be dispersed in dehydrated alcohol;
C. by ammonium nitrate and step b gained nano particle CS-UCNPs@SiO
2be dissolved in dehydrated alcohol by the mass ratio of 15:1 ~ 20:1, be heated to 60 DEG C, keep 2 ~ 4 hours, cooling, centrifugal, with ethanol, i.e. obtained CS-UCNPs@mSiO
2nano particle.。
The invention has the advantages that: construct nano-probe using rare earth up-conversion luminescence nanometer crystal as energy donor, its exciting light is positioned at 980 nm of near-infrared region, and the light loss that effectively prevent high-energy light injures the strong shortcoming of biological context fluorescence.Secondly, synthesized nano-probe has good biocompatibility and low bio-toxicity, can realize intracellular copper ion fluorescence imaging.In addition, the nano-probe uniform particle diameter prepared by the inventive method, pattern are good, Stability Analysis of Structures, and experiment condition is gentle, and repetition rate is high.
Accompanying drawing explanation
Fig. 1 is UCNPs(a in the embodiment of the present invention 1); CS-UCNPs (b); CS-UCNPs@mSiO
2(c); CS-UCNPs@mSiO
2the TEM figure of-RBH (d).
Fig. 2 is nano-probe CS-UCNPs@mSiO in the embodiment of the present invention 3
2uv-visible absorption spectra figure (A) after different metal ion is added in-RBH;
Fig. 3 is for being nano-probe CS-UCNPs@mSiO in the embodiment of the present invention 3
2the colour-change photo (B) after different metal ion is added in-RBH.
Fig. 4 is nano-probe CS-UCNPs@mSiO in the embodiment of the present invention 3
2fluorescence spectrum figure (A) after-RBH adds different concns cupric ion under 510nm excites,
Fig. 5 be in the embodiment of the present invention 3 nano-probe under 980nm excitation light irradiation cupric ion to nano-probe CS-UCNPs@mSiO
2the up-conversion luminescence spectrum change figure (B) of-RBH.
Fig. 6 be add cupric ion in the embodiment of the present invention 5 after cell confocal fluorescent image.
Embodiment
For making the present invention easier to understand, describe in detail below in conjunction with drawings and Examples.These embodiments only play illustrative effect, are not limited to range of application of the present invention.
The preparation method with the up-conversion luminescence nanometer crystal of nucleocapsid structure refers to document:
27. Li, Z.; Zhang, Y., An efficient and user-friendly method for the synthesis of hexagonal-phase NaYF
4:Yb, Er/Tm nanocrystals with controllable shape and upconversion fluorescence. Nanotechnology 2008, 19 (34), 345606.
Embodiment 1:
The present embodiment provides an example with nano-probe CS-UCNPs@mSiO
2the synthesis of-RBH, it comprises the following steps:
(1) utilize solvent structure to have the upper conversion nano particle CS-UCNPs of nucleocapsid structure, and be distributed in cyclohexane solution, be i.e. the upper conversion nano particle of obtained nucleocapsid structure;
(2) take cetyl trimethylammonium bromide as template and tensio-active agent, the upper conversion nano particle of nucleocapsid structure is transferred in aqueous phase from cyclohexane solution, under alkaline environment, utilize the hydrolysis-condensation reaction of tetraethoxy to make the coated last layer silicon-dioxide of nano grain surface again, then by the method removing tensio-active agent of ion-exchange, obtain the mesoporous coated upper conversion nano particle with complex function, i.e. obtained CS-UCNPs@mSiO
2;
(3) rhodamine B derivative fluorescence dye and triethoxysilicane based isocyanate are reacted, preparation precursor molecule, as the energy acceptor of nano-probe and the presoma with above-mentioned energy donor covalent bonding.
(4) by CS-UCNPs@mSiO
2the fluorescence dye presoma prepared with above-mentioned steps (3) carries out covalent linkage assembling, constructs containing a pair energy donor and energy acceptor, and the nano-probe of transmission ofenergy can effectively occur, and namely prepares CS-UCNPs@mSiO
2-RBH nano-probe.
Described step (1) specifically comprises the following steps:
(1) utilize solvent-thermal method to prepare and change nano particle NaYF
4: Yb, Er.And be dispersed in 20mL cyclohexane solution;
(2) use above-mentioned nano particle, conversion nano particle on the CS-UCNPs utilizing solvent structure to have a nucleocapsid structure, wherein the Shell Materials of nanoparticle is six side phase NaYF
4, the thickness of shell is about 5 nm.
Described step (2) specifically comprises the following steps:
(2.1) conversion nano particle, 2 M 300 μ L sodium hydroxide, 6 mL dehydrated alcohols, 200 ~ 600 μ L tetraethoxys on 0.1 ~ 0.3 g cetyl trimethylammonium bromide, 60 mL deionized waters, 2 ~ 5 mL CS-UCNPs are prepared;
(2.2) by the cetyl trimethylammonium bromide of preparation, 20 mL deionized water mixing, then add conversion nano particle on CS-UCNPs, spend the night removing hexanaphthene;
(2.3) sodium hydroxide of preparation, dehydrated alcohol, 40 mL deionized waters, tetraethoxy are joined above-mentioned solution, be heated to 70 DEG C, and keep 2 hours, after reaction terminates, wash four times with ethanol, obtain nano particle and the CS-UCNPs@SiO of coated with silica
2, be dispersed in 10mL dehydrated alcohol;
(2.4) the nano particle CS-UCNPs@SiO of 0.6 ~ 1.2 g ammonium nitrate, 90 mL dehydrated alcohols, 10 mL coated with silica is prepared
2;
(2.5) by ammonium nitrate, dehydrated alcohol, CS-UCNPs@SiO
2nano particle mix, be heated to 60 DEG C, keep 2 ~ 4 hours, cooling, centrifugal, wash 2 ~ 4 times with ethanol, namely obtain CS-UCNPs@mSiO
2nano particle.
Described step (3) specifically comprises the following steps:
(3.1) rhodamine B hydrazides 30 ~ 200 mg is prepared, isocyanatopropyl triethoxyl silane 300 ~ 2000 mg.
(3.2) the rhodamine B hydrazides of preparation and isocyanatopropyl triethoxyl silane are joined in 20 ~ 60 mL organic solvents according to mol ratio 1:2 ~ 1:10, reflux 2 ~ 10 hours.Organic solvent wherein used comprises but is not limited only to tetrahydrofuran (THF).
(3.3), after mixture cooling above-mentioned steps obtained, rotary evaporation, except desolventizing, utilizes silica gel column chromatography to be separated the precursor molecule obtained containing rhodamine B fluorophore.
Described step (4) specifically comprises the following steps:
(4.1) CS-UCNPs@mSiO prepared by above-mentioned steps (3.2) is prepared
2nano particle 50 ~ 500 mg; Precursor molecule 30 ~ 200 mg prepared by above-mentioned steps (4.3).
(4.2) by the CS-UCNPs@mSiO of preparation
2nano particle and precursor molecule join in 20 ~ 60 mL organic solvents according to mass ratio 2:1 ~ 10:1, reflux 20 ~ 40 hours.Organic solvent wherein used comprises but is not limited only to toluene.
(4.3) after mixture cooling above-mentioned steps obtained, high speed centrifugation, washes 3 ~ 5 times with dehydrated alcohol, is finally dispersed in 20 mL dehydrated alcohols, i.e. obtained inorganic-organic hybridization nano probe CS-UCNPs@mSiO
2-RBH.Result as shown in Figure 1.
Embodiment 2:
The present embodiment provides the spectrogram of nano-probe and different metal ion, and it comprises the following steps:
(1) strong solution (0.1M) of each metal ion species is prepared with deionized water;
(2) nano-probe CS-UCNPs@mSiO is prepared
2-RBH, is then diluted to desired concn with ethanol solution.
(3), in selectivity experiment, the strong solution of getting each metal ion species of certain volume joins 2.0mL nano-probe CS-UCNPs mSiO respectively
2in the solution of-RBH, then stirred at ambient temperature 1min carries out spectrum test, and observes its colour-change.Result as shown in Figure 2.
(4) in titration experiments, with pipette, extract 2.0mL nano-probe CS-UCNPs@mSiO
2-RBH is placed in 1.0cm × 1.0cm quartz colorimetric utensil, dropwise adds Cu with microsyringe in secondary solution
2+solution, often adds the Cu of certain volume
2+after solution, then stirred at ambient temperature 1min carries out spectrum test.
(5), in competitive assay, first certain other metal ions are joined 2.0mL nano-probe CS-UCNPs@mSiO
2in-RBH solution, then add Cu
2+, then stirred at ambient temperature 1min carries out spectrum test.
(6) in fluorescence emission spectrum test, with pipette, extract 2.0mL nano-probe CS-UCNPs@mSiO
2-RBH is placed in 1.0cm × 1.0cm quartz colorimetric utensil, dropwise adds Cu with microsyringe in secondary solution
2+solution, often adds the Cu of certain volume
2+after solution, stirred at ambient temperature 1min, then carries out spectrum test.Result as shown in Figure 3.
Embodiment 3:
The present embodiment provides nano-probe CS-UCNPs@mSiO
2-RBH is applied to cell imaging experiment, and it comprises the following steps:
(1) control group, joins the nano-probe CS-UCNPs@mSiO of 0.2mg/mL
2the RPMI. 1640 water culture liquid of-RBH;
(2) Hela cell is cultivated 2 hours in above-mentioned nutrient solution;
(3) experimental group, then the Cu adding 10 μMs in above-mentioned solution
2+solution, cultivates 2 hours;
(4) use PBS wash buffer cell 3 times, will do not washed away by the nutrient solution of Cell uptake;
(5) cell after cultivation is carried out imaging on Laser Scanning Confocal Microscope, the stable state 980 nm laser apparatus that imaging process uses 0 ~ 650mW power adjustable, continuous wave excites and xenon lamp (510 nm) are as excitation light source, observe the utilizing emitted light being positioned at 520 ~ 560 nm and 630 ~ 670 nm, obvious green glow and red signal light can be observed.Result as shown in Figure 4.
Fig. 1 is UCNPs(a in the embodiment of the present invention 1); CS-UCNPs (b); CS-UCNPs@mSiO
2(c); CS-UCNPs@mSiO
2the TEM figure of-RBH (d).As can be seen from the figure, synthesized UCNPs nanoparticle dispersion is good and size is homogeneous, and the size of nanoparticle is at 30 nm; CS-UCNPs size is at 35nm; Nanoparticle dispersion is good and size is homogeneous.CS-UCNPs@mSiO
2the size of nano particle, at 90nm, can see the pore passage structure on nanometer ball.CS-UCNPs@mSiO
2-RBH is relative to CS-UCNPs@mSiO
2pattern considerable change does not occur, and in grafting after probe molecule, pore passage structure thickens, illustrate that the channel section of nanoparticle is occupied by organic molecule.
Fig. 2 is nano-probe CS-UCNPs@mSiO in the embodiment of the present invention 3
2uv-visible absorption spectra figure after different metal ion is added in-RBH; Fig. 3 is CS-UCNPs@mSiO
2the colour-change photo after different metal ion is added in-RBH.As can be seen from the figure, after adding cupric ion in solution, corresponding uv-visible absorption spectra at the strong absorption peak of 554 nm place appearance one, for other ions, as Mn
2+, Na
+, Ca
2+, Mg
2+, Zn
2+, K
+, Li
+, Ba
2+, Ni
2+, Co
2+, Cr
3+, Hg
2+deng, uv-visible absorption spectra does not have the absorption peak near appearance 554 nm.Corresponding, only under the existence of cupric ion, solution becomes pink from colourless, and does not have colour-change when other ions exist.Nano-probe synthesized by explanation can be single response cupric ion.
Fig. 4 is nano-probe CS-UCNPs@mSiO in the embodiment of the present invention 3
2fluorescence spectrum figure after-RBH adds different concns cupric ion under 510nm excites, and Fig. 5 be under 980nm excitation light irradiation cupric ion to nano-probe CS-UCNPs@mSiO
2the up-conversion luminescence spectrum change figure of-RBH.As seen from Figure 4, after adding cupric ion in solution, there is emission peak at 580 nm places in corresponding fluorescence spectrum, and along with the increase of copper ion concentration, the fluorescence intensity level enhancing at 580 nm places; As seen from Figure 5, under 980 nm exciting lights, along with the increase of copper ion concentration, the fluorescence intensity level that 545nm goes out declines gradually, and 580nm place fluorescence intensity level strengthens gradually, illustrate that rhodamine B derivative can absorb energy in the transmitted wave strong point of up-conversion nanoparticles, pass energy effect better.
Fig. 6 be add cupric ion in the embodiment of the present invention 5 after cell confocal fluorescent image.As can be seen from the figure after adding cupric ion, under 980nm excites, obvious green fluorescence in cell can be observed, under the exciting of 510 nm visible rays, obvious red fluorescence in cell can be observed, illustrate that this material can realize up-conversion fluorescence imaging and down-conversion fluorescent imaging in cell simultaneously.
According to provided by the present invention, rhodamine B derivative is modified the coated rare earth up-conversion luminescence nano grain surface of mesoporous silicon oxide, the product obtained has size homogeneous and favorable dispersity, Stability Analysis of Structures, the advantages such as up-conversion fluorescence is stronger, particularly gained nano-probe can be applicable to intracellular copper ion fluorescence imaging and detection.It is simple that the inventive method has technique, and easy to operate, the advantage of easy control of structure, has potential using value in the field such as up-conversion fluorescent marking, detection of cell or tissue.
As described in the above embodiment the present invention, other nano-probe for intracellular copper ion fluorescence imaging that method same or similar with it obtains is adopted, all in scope.
Claims (5)
1. the nano-probe for intracellular copper ion fluorescence imaging, it is characterized in that this probe be coated on the up-conversion luminescence nanometer crystal with nucleocapsid structure on mesoporous silicon oxide, as energy donor, then formed with the bonding as the rhodamine B derivative fluorescence dye precursor molecule of energy acceptor by the mode of covalent bonding, the mass ratio of the up-conversion luminescence nanometer crystal and mesoporous silicon oxide wherein with nucleocapsid structure is 1:10 ~ 1:19; Described energy donor and the mass ratio of energy acceptor are 10:1 ~ 15:1.
2. the nano-probe for intracellular copper ion fluorescence imaging according to claim 1, is characterized in that the described up-conversion luminescence nanometer crystal with nucleocapsid structure is: NaYF
4: Yb, Er@NaYF
4, NaYF
4: Yb, Er@NaYF
4: Yb, Er, NaYF
4: Yb, Er@NaGdF
4or NaYF
4: Yb, Er@NaGdF
4: Yb, Er.
3. the nano-probe for intracellular copper ion fluorescence imaging according to claim 1, is characterized in that described rhodamine B derivative fluorescence dye precursor molecule can be:
or
.
4. prepare a method for the nano-probe for intracellular copper ion fluorescence imaging according to claim 1,2 or 3, it is characterized in that the concrete steps of the method are:
A. by there is nucleocapsid structure up-conversion luminescence nanometer crystal on coating mesoporous silicon-dioxide, obtain CS-UCNPs@mSiO
2;
B. rhodamine B derivative fluorescence dye precursor molecule and isocyanatopropyl triethoxyl silane are dissolved in organic solvent according to the ratio of mol ratio 1:2 ~ 1:10, reflux 2 ~ 10 hours; After being cooled by obtained mixture, rotary evaporation, except desolventizing, obtains the nano-probe for intracellular copper ion fluorescence imaging after being separated deduction.
5. method according to claim 4, is characterized in that the concrete grammar of described step a is:
A. be dissolved in deionized water by cetyl trimethylammonium bromide and the up-conversion luminescence nanometer crystal with nucleocapsid structure by the mass ratio of 4:1 ~ 5:1, spend the night removing hexanaphthene;
B. the aqueous ethanolic solution of tetraethoxy is joined in step a gained solution, regulate pH to 10 ~ 12, be heated to 70 DEG C, and keep 2 hours, after reaction terminates, by washing with alcohol, obtain nano particle and the CS-UCNPs@SiO of coated with silica
2, and be dispersed in dehydrated alcohol;
C. by ammonium nitrate and step b gained nano particle CS-UCNPs@SiO
2be dissolved in dehydrated alcohol by the mass ratio of 15:1 ~ 20:1, be heated to 60 DEG C, keep 2 ~ 4 hours, cooling, centrifugal, with ethanol, i.e. obtained CS-UCNPs@mSiO
2nano particle.
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| CN109307664A (en) * | 2018-09-30 | 2019-02-05 | 江南大学 | The fluorescent detection probe of metal ion in a kind of detectable living cells |
| CN109307664B (en) * | 2018-09-30 | 2020-06-09 | 江南大学 | Fluorescent detection probe capable of detecting metal ions in living cells |
| CN112358866A (en) * | 2020-11-17 | 2021-02-12 | 上海大学 | Orthogonal up-conversion luminescence nano probe, preparation method and application thereof |
| CN114195722A (en) * | 2021-12-10 | 2022-03-18 | 山东省科学院新材料研究所 | Nano fluorescence sensor and preparation method and application thereof |
| CN114195722B (en) * | 2021-12-10 | 2023-12-01 | 山东省科学院新材料研究所 | Nanometer fluorescence sensor and preparation method and application thereof |
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