CN103193826A - Nanocluster, as well as preparation method and application thereof - Google Patents
Nanocluster, as well as preparation method and application thereof Download PDFInfo
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- CN103193826A CN103193826A CN201310128428XA CN201310128428A CN103193826A CN 103193826 A CN103193826 A CN 103193826A CN 201310128428X A CN201310128428X A CN 201310128428XA CN 201310128428 A CN201310128428 A CN 201310128428A CN 103193826 A CN103193826 A CN 103193826A
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Abstract
The invention discloses a nanocluster, as well as a preparation method and application thereof. The preparation method of the nanocluster provided by the invention comprises the following steps of: evenly mixing a coordination compound with a compound shown in ligand in a formula I to carry out olefin crossmetathesis, so as to obtain the nanocluster after the reaction is finished, wherein the light-emitting wavelength of the nanocluster can be adjusted along with different ratios of surface functional group. The invention further provides an application of the nanocluster in detection of a ferric ion. The nanocluster provided by the invention can be used for achieving high-selectivity and high-sensitivity detection of the ferric ion, thus providing possibility for building a fluorescent chemical sensor for high-selectivity and high-sensitivity detection of the ferric ion. The iridium nanocluster provided by the invention can be used for not only imaging cell endogenous Fe<3+>, but also detecting exogenous Fe<3+>, and is expected to be used for detection of Fe<3+> in physiological and pathological processes.
Description
Technical field
The present invention relates to a kind of nanocluster and preparation method thereof and application.
Background technology
Iron is the trace element of needed by human, is keeping running balance in a variety of forms in vivo, is the necessary metallic element of nearly all biomass cells normal growth.Iron mainly is present in the red corpuscle of circulation with the form of oxyphorase in human body and participates in the synthetic of oxyphorase, cytopigment and various enzymes, for the balance of keeping the human body intracellular metabolic is being brought into play crucial effects.Iron ion content is crossed and low or too highly all can be caused a series of pathologies, when iron ion lacks, can cause many metabolism disorders such as the transportation of the transportation of oxygen and storage, carbonic acid gas and release, electronics transmission, redox, and infringement immunity of organism mechanism, thereby many physiology, pathological change produced; When iron ion is excessive, cause liver cell by virus infection easily, body oxidation and antioxidant system are unbalance, and coup injury DNA brings out sudden change, cause cancer.Therefore, along with the reach of science, biological and medical field all presses for development has high selectivity to iron ion optical probe.Yet, up to now, still lack and can identify iron ion and the water-soluble probe that can in actual living things system, use with specific oxidation state by high selectivity.
Summary of the invention
The purpose of this invention is to provide a kind of nanocluster and preparation method thereof and application.
The method for preparing coordination compound provided by the invention, comprise the steps: metal-salt and sodium-acetate are carried out reduction reaction in solvent, reaction is cooled to organic solution that room temperature adds dodecyne again after finishing and stirs and carry out the part replacement(metathesis)reaction, collects the gained black powder and is described coordination compound.
In the aforesaid method, described metal-salt is selected from least a in three hydration iridous chlorides, ruthenium trichloride and the Trichlororhodium;
The molar ratio of described metal-salt and sodium-acetate and dodecyne is 1: (8-20): (2-4), be specially 1: 10: 3;
In the described reduction reaction step, temperature is 160-170 ℃, is specially 165 ℃, and the time is 1-2 hour, is specially 1 hour;
Described solvent is selected from 1,2-propylene glycol and 1, at least a in the ammediol;
In the organic solution of described dodecyne, organic solvent is selected from least a in toluene and the tetrahydrofuran (THF);
In the described part replacement(metathesis)reaction step, temperature is room temperature, and the time is 15-30 hour, is specially 24 hours.
This method gained coordination compound (also be the nanoparticle of dodecyne dodecyne protection, be called for short MD) is by as the M of central atom with as being connected to form by M-C ≡ d π key between the dodecyne molecule of part; The mol ratio of described central atom and part is 1: 2-4;
Described M is selected from least a among Ir, Ru and the Rh.
Concrete, the mol ratio of described central atom and part is 1: 3;
The structural representation of this coordination compound is as follows:
The present invention also provides compound shown in a kind of formula I,
Formula I
The method of ligand compound shown in the described formula I of preparation provided by the invention; comprise the steps: under the nitrogen protection condition; 4-1-chloro-4-methyl-benzene and 2-(2-picolyl) amine and triethylamine mixing in organic solvent are carried out nucleophilic reaction, and reaction finishes and obtains ligand compound shown in the described formula I.
In the aforesaid method, the molar ratio of described 4-1-chloro-4-methyl-benzene and 2 (2-picolyl) amine and triethylamine is (6-10): (4-6): (30-50), be specially 8: 5: 40;
Described organic solvent is selected from least a in methylene dichloride, ethylene dichloride, tetrahydrofuran (THF) and the acetonitrile;
In the described nucleophilic reaction step, temperature is room temperature, and the time is 6-10 hour, is specially 8 hours.
The method for preparing nanocluster provided by the invention comprises the steps: compound mixing shown in described coordination compound and the described formula I is carried out olefin metathesis reaction, and reaction finishes and obtains described nanocluster;
In the aforesaid method, the mass ratio that feeds intake of compound shown in described compound MD and the formula I was specially 1: 6,1: 1,1: 3,1: 3-6,1: 1-3,1: 1-6;
In the described olefin metathesis reaction step, temperature is room temperature, and the time is 2～4 days, is specially 3 days.
The schematic construction of this nanocluster is as follows:
Wherein, M is selected from least a among Ir, Ru and the Rh.
The nanocluster that the invention described above provides and contain the nano-probe of nanocluster, and this nanocluster and the application of nano-probe in detecting ferric ion also belong to protection scope of the present invention.Wherein, described detection is for to carry out in the aqueous solution of ferric ion.The median size of this nanocluster is 0.8-2.5nm, specifically can be 1.3 ± 0.4nm, 1.4 ± 0.4nm, 1.6 ± 0.4nm, 1.8 ± 0.4nm.
Nanocluster provided by the invention, especially iridium nanocluster M
xL
y, its emission wavelength can change adjustable with the ratio of surface functional group, is specially 386～420nm, and blue light-emitting under the 365nm ultra violet lamp, maximum emission wavelength are positioned at about 420nm; Under the normal temperature, this iridium nanocluster and Fe
3+Blue light cancellation after effect for some time is until disappearance.Under the same terms, other metal ion (as: potassium ion, sodium ion, calcium ion, magnesium ion, mn ion, cadmium ion, zine ion, lead ion, cobalt ion, ferrous ion, nickel ion, cupric ion and mercury ion) and amino acid (as: L-Ala, arginine, Histidine, halfcystine, aspartic acid, tyrosine, Isoleucine, Methionin, methionine(Met), phenylalanine, proline(Pro), leucine, Serine, homocysteine, Threonine, tryptophane and glutamine) and M
xL
yAfter the effect, its emission wavelength and luminous intensity all do not have considerable change, further discover, this iridium nanoparticle is (with ML
6Be example) to Fe
3+Detectability be low to moderate 10nmol, thereby iridium nanocluster provided by the invention can realize highly selective, the high-sensitivity detection of ferric ion, for the sensor that makes up a kind of highly selective, high-sensitivity detection ferric ion provides may; And metal iridium nanocluster provided by the invention has stronger recognition function to intracellular ferric ion, particularly importantly, this iridium nanocluster can evenly disperse in the aqueous solution, and emission wavelength can regulate with the difference of surface functional group ratio, is expected to for physiology, pathologic process Fe
3+Detection.
Description of drawings
Fig. 1 is iridium nanoparticle ML provided by the present invention
6Transmission electron microscope picture and size distribution figure;
Fig. 2 is the difference provided by the present invention iridium nanocluster M that mass ratio forms that feeds intake
xL
yThe variation of emmission spectrum figure;
Fig. 3 is iridium nanocluster ML provided by the invention
6With the emmission spectrum figure after the different metal ionization;
Fig. 4 is iridium nanocluster ML provided by the invention
6With the emmission spectrum figure after the different aminoacids effect;
Fig. 5 is iridium nanocluster ML provided by the invention
6With Fe
3+Laser co-focusing imaging after the effect wherein, (a) is the laser co-focusing imaging of HeLa cell, (b) is that the HeLa cell is through this iridium nanocluster ML
6Laser co-focusing imaging after hatching is that the HeLa cell is through injecting exogenous Fe (c)
3+With iridium nanocluster ML
6Laser co-focusing imaging after mixing solutions is hatched.
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can get from open commercial sources if no special instructions.
The preparation of embodiment 1, coordination compound MD
Take by weighing the IrCl of 0.28mmol
3H
2The NaAc of O and 2.0mmol is dissolved in 200mL1, in the 2-propylene glycol, carry out reduction reaction 1h in 165 ℃ of reflux, the toluene solution (molar weight of dodecyne is 0.84mmol) that adds 200 μ L dodecynes to the room temperature to be cooled, stirring was carried out ligand exchange reaction after 24 hours, and the separatory suction filtration is drying to obtain black powder.Transmission electron microscope picture shows that the particle diameter of this nanoparticle MD is 1.2 ± 0.4nm.
1H?NMR(300MHz，CDCl
3)：δppm0.9(s，CH
3)，1.2(s，CH
2)。
As from the foregoing, the unimodal ownership at 0.9ppm place is dodecyne terminal methyl group-CH
3Proton split swarming, though dodecyne monomer terminal methyl group proton is triple branches that split, be modified on the iridium nanoparticle after, it splits branch and is subjected to central metal iridium atom influence, is become unimodal by triplet; 1.2ppm the unimodal ownership of locating is dodecyne part methylene radical-CH
2Proton split swarming, it splits the branch mode and also is subjected to central metal iridium atom influence, is become unimodal by triplet; And the monomer dodecyne is in the unimodal disappearance of the ≡ at 2.83ppm place CH, thereby explanation compound MD successfully synthesizes; And as the Ir of central atom with as being connected to form by M-C ≡ d π key between the dodecyne molecule of part.
The preparation of 2-shown in embodiment 2, the formula I (2-pyridylmethyl)-4-vinyl benzene ethamine
Taking by weighing 1.3g (8.0mmol) 4-1-chloro-4-methyl-benzene, 1.0g (5.0mmol) 2-(2-picolyl) amine and 4mL (40.0mmol) triethylamine is dissolved in the methylene dichloride of 30mL, stirring at room is carried out nucleophilic reaction 8h, suction filtration, underpressure distillation get weak yellow liquid then, productive rate: 68%.
1H?NMR(300MHz，CDCl
3)：δppm3.59(s，2H，NCH
2Ph)，3.73(s，4H，pyCH
2)，5.12(d，1H，cis-CH
2CH)，5.60(1H，trans-CH
2CH)，6.60(dd，1H，CH
2CH)，7.0-7.6(m，10H，aromatic?H)，8.41(m，2H，pyH
6)。
Infared spectrum (KBr compressing tablet, cm
-1): v=2974,2938 (aromatic C-H), 1629 (C=C), 1589,1568 (aromatic C=C), 1261,1096 (C-N), 803 (=C-H),
Mass spectrum: m/z (%) 316.2 (C
21H
21N
3).
As from the foregoing, this product structure is correct, is target compound.
The preparation of embodiment 3, iridium nanocluster ML (mass ratio x: the y that feeds intake of compound shown in MD and the formula I is 1: 1)
Take by weighing that ligand compound is dissolved in the 50mL anhydrous methylene chloride shown in 30mg embodiment 1 preparation gained compound MD and 30mg (0.10mmol) the embodiment 2 preparation gained formula I, stirring at room was carried out olefin metathesis reaction 2 days, suction filtration, the gained solid with washing with alcohol repeatedly, namely get the iridium nanoparticle, then its photophysical property is measured.
Transmission electron microscope picture shows that the median size of this iridium nanocluster is 1.3 ± 0.4nm.
Embodiment 4, iridium nanocluster ML
3Preparation (mass ratio x: the y that feeds intake of compound shown in MD and the formula I is that x: y is 1: 3)
According to the method for embodiment 3, only the quality with the described ligand compound of formula I replaces with 90mg (0.29mmol).
Transmission electron microscope picture shows that the median size of this iridium nanocluster is 1.4 ± 0.4nm.
According to the method for embodiment 3, only the quality with the described ligand compound of formula I replaces with 180mg (0.57mmol).
Transmission electron microscope picture shown in Figure 1 shows that the median size of this iridium nanocluster is 1.6 ± 0.4nm.
EDX analyzes (energy dispersion X-ray spectral analysis) and shows, contain a certain amount of N element on the embodiment 5 gained iridium nanoparticle ML, and the content of N element can reach 25.63%, and the 2-of part shown in the formula I (2-pyridylmethyl)-4-vinyl benzene ethamine is successfully modified on the nanoparticle MD.(the no photoluminescent property of nanoparticle shown in the factor I itself, and nanoparticle ML in addition,
6Strong emission light wave is arranged at the 420nm place, and also part 2-shown in the Ming Dynasty style I (2-pyridylmethyl)-4-vinyl benzene ethamine is successfully modified shown in the formula I on the nanoparticle MD furtherly.)
Embodiment 6, iridium nanocluster ML
10Preparation (mass ratio x: the y that feeds intake of compound shown in MD and the formula I is 1: 10)
According to the method for embodiment 3, only the quality with the described ligand compound of formula I replaces with 300mg (0.95mmol).
Transmission electron microscope picture shows that the median size of this iridium nanocluster is 1.8 ± 0.4nm.
The M of the different feed ratio of above-mentioned gained (mass ratio)
xL
yThe fluorescence spectrum figure of nanocluster as shown in Figure 2.
As seen from the figure, along with the raw material mass ratio that feeds intake increases the iridium nanocluster M of formula I
xL
yThe red shift gradually of emission maximum spectrum.When raw material feeds intake mass ratio when increasing to 1: 6 from 1: 1, the emission maximum spectrum of the iridium nanocluster of formula I from 386nm (ML) red shift to 420nm (ML
6), the nearly 40nm of red shift; Continue to increase the raw material mass ratio to 1 that feeds intake: 10, find iridium nanocluster ML
10Maximum emission wavelength is with respect to ML
6No considerable change, this may be because the part of formula I reaches capacity in the nanocluster finishing, energy is shifted reach due to the maximum value.Because the mass ratio of compound MD and formula I is 1: 6 o'clock gained iridium nanocluster emission peak is positioned at visible region and more economical during with respect to 1: 10 feed ratio, so the iridium nanocluster ML that makes under this ratio condition is all adopted in following experiment
6Iridium nanocluster ML
6Interaction with the different metal ion:
Iridium nanocluster ML with these embodiment 5 preparations
6Pressed powder is scattered in the aqueous solution, and the preparation ultimate density is the ML of 0.06mg/mL
6Solution adds different metal ion (wherein, the Na of equal-volume, different concns again
+, K
+, Ca
2+, Mg
2+Concentration is 100 μ M, and other concentration of metal ions are 10 μ M) normal-temperature reaction 5min, carry out the mensuration of photophysical property then respectively to it.
Iridium nanocluster ML
6Interaction with different aminoacids:
Iridium nanocluster ML with this embodiment preparation
6Pressed powder is scattered in the aqueous solution, and the preparation final concentration is the ML of 0.06mg/mL
6Solution adds the amino acid of equal-volume, isoconcentration (final concentration is 100 μ M) again, and normal-temperature reaction 5min carries out the mensuration of photophysical property then respectively.
Above-mentioned detected result is shown in Fig. 3 and 4.
As seen from the figure, iridium nanocluster ML6 aqueous solution emission wavelength is positioned at the 420nm place, presents strong blue light, and quantum yield is up to 28.4%, when adding Fe
3+After, fluorescence is immediately by cancellation, and under the same terms, common amino acid (as: L-Ala, arginine, Histidine, halfcystine, aspartic acid, tyrosine, Isoleucine, Methionin, methionine(Met), phenylalanine, proline(Pro), leucine, Serine, homocysteine, Threonine, tryptophane and glutamine) and ML in other metal ion (as: potassium ion, sodium ion, calcium ion, magnesium ion, mn ion, cadmium ion, zine ion, lead ion, cobalt ion, ferrous ion, nickel ion, cupric ion and mercury ion) and the organism
6After the effect, considerable change does not take place in its emission wavelength and luminous intensity, and ML
6To Fe
3+Detectability be low to moderate 10nmol/L, thereby iridium nanocluster probe provided by the invention can be realized highly selective and the high-sensitivity detection of ferric ion.
Used cell is HeLa cell (cervical cancer cell), purchases in BJ Union Hospital.
The iridium nanocluster ML of preparation different concns (0,0.02,0.04,0.06,0.08,0.10mg/mL)
6Solution is treated cell in adherent growth in 96 orifice plates after 5～6 hours, and (PBS pH7.4) cleans twice, respectively adds the ML of 100 μ L different concns again with phosphate buffer solution
6Solution is hatched 24h, cleans twice with PBS solution again, adds the CCK-8 staining reagent at last, surveys absorbancy in microplate reader after 2 hours and changes.
Experimental result shows that the HeLa cell is the ML of 0.04mg/mL and 0.06mg/mL in concentration
6After hatching 24h in the solution, cell survival rate can reach more than 95% and 90%, works as ML
6When concentration reached 0.1mg/mL, cell survival rate illustrated that still up to more than 80% iridium nanocluster provided by the invention has hypotoxicity and good bio-compatibility.
With this iridium nanocluster ML
6Be scattered in PBS (0.01M, pH7.4) in, prepare the ML that final concentration is 0.06mg/mL
6Solution, hatch HeLa cell 1h after, clean twice with PBS solution, under Olympus FV1000 laser scanning co-focusing microscope, adopt 405nm to excite then, gather the emission light in 420～520nm scope.
The result shown in Fig. 5 a, the cell autofluorescence a little less than, when adding this iridium nanocluster ML
6After solution is hatched 1h, the luminous obvious grow of tenuigenin part (Fig. 5 b); It is to be noted Fe in the cell
3+Content is (nmole is to the micromole) seldom, so the fluorescence of Fig. 5 b comes from ML
6Nanocluster is expressed crossing of intracytoplasmic fluorescence intensity; And add exogenous Fe in the ban
3+(final concentration is 10 μ M) hatches 10min, again with the ML of 0.06mg/mL
6After hatching 1h, the fluorescent quenching of HeLa cell matter part almost completely disappears (Fig. 5 c), and iridium nanocluster ML provided by the invention is described
6Can enter tenuigenin by cytolemma, can not only be to cell endogenous Fe
3+Imaging also can be to exogenous Fe
3+Detect, this is to research Fe
3+Relevant bio-imaging and the variation in some physiology, pathologic process thereof are significant.
In addition, the ruthenium nanocluster that the invention described above provides and the above-mentioned detected result of rhodium nanocluster and iridium nanocluster do not have substantive difference, repeat no more.
Claims (10)
1. method for preparing coordination compound, comprise the steps: metal-salt and sodium-acetate are carried out reduction reaction in solvent, reaction is cooled to organic solution that room temperature adds dodecyne again after finishing and stirs and carry out the part replacement(metathesis)reaction, and reaction finishes and collects the gained black powder and be described coordination compound.
2. method according to claim 1 is characterized in that: described metal-salt is selected from least a in three hydration iridous chlorides, ruthenium trichloride and the Trichlororhodium; Or,
The molar ratio of described metal-salt and sodium-acetate and dodecyne is 1: (8-20): (2-4), be specially 1: 10: 3; Or,
In the described reduction reaction step, temperature is 160-170 ℃, is specially 165 ℃, and the time is 1-2 hour, is specially 1 hour; Or,
Described solvent is selected from 1,2-propylene glycol and 1, at least a in the ammediol; Or,
In the organic solution of described dodecyne, organic solvent is selected from least a in toluene and the tetrahydrofuran (THF); Or,
In the described part replacement(metathesis)reaction reactions steps, temperature is room temperature, and the time is 15-30 hour, is specially 24 hours.
3. the coordination compound for preparing of the arbitrary described method of claim 1-2.
4. compound shown in the formula I,
Formula I.
5. method for preparing compound shown in the described formula I of claim 4; comprise the steps: under the nitrogen protection condition; 4-1-chloro-4-methyl-benzene and 2-(2-picolyl) amine and triethylamine mixing in organic solvent are carried out nucleophilic reaction, and reaction finishes and obtains compound shown in the described formula I.
6. method according to claim 5 is characterized in that: the molar ratio of described 4-1-chloro-4-methyl-benzene and 2 (2-picolyl) amine and triethylamine is (6-10): (4-6): (30-50), be specially 8: 5: 40; Or,
Described organic solvent is selected from least a in methylene dichloride, ethylene dichloride, tetrahydrofuran (THF) and the acetonitrile; Or,
In the described nucleophilic reaction step, temperature is room temperature, and the time is 6-10 hour, is specially 8 hours.
7. a method for preparing nanocluster comprises the steps: the described coordination compound of claim 3 and the described formula I compound of claim 4 mixing are carried out olefin metathesis reaction, and reaction finishes and obtains described nanocluster.
8. method according to claim 7, it is characterized in that: the mass ratio that feeds intake of the described coordination compound of described claim 3 and the described formula I compound of claim 4 is 1: (1～10) was specially 1: 6; Or,
In the described olefin metathesis reaction step, temperature is room temperature, and the time is 2～4 days, is specially 3 days.
9. the nanocluster for preparing of claim 7 or 8 described methods;
The nano-probe that contains described nanocluster.
10. the described nanocluster of claim 9 or the described nano-probe application in detecting ferric ion; Or described detection is for to carry out in the aqueous solution of ferric ion.
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Cited By (5)
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|---|---|---|---|---|
| CN103611946A (en) * | 2013-12-08 | 2014-03-05 | 福建医科大学 | Preparation method of gold nanocluster fluorescent materials protected by methionine |
| CN105885832A (en) * | 2016-05-13 | 2016-08-24 | 湖南大学 | Preparation method and application of nano-copper cluster probe used for detecting iron ions |
| CN106053416A (en) * | 2016-07-14 | 2016-10-26 | 中南大学 | Application of silver nanocluster in detecting Fe3+ |
| CN109396415A (en) * | 2017-08-17 | 2019-03-01 | 清华大学 | Gold nano cluster and preparation method thereof |
| CN115609001A (en) * | 2022-07-15 | 2023-01-17 | 西北工业大学 | Method for preparing functionalized gold nanoparticles by using acetylene compounds |
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| WO2007138345A1 (en) * | 2006-05-26 | 2007-12-06 | Johnson Matthey Public Limited Company | Process for producing stabilised metal nanoparticles |
| WO2008139204A2 (en) * | 2007-05-15 | 2008-11-20 | Imperial Innovations Ltd | Functional group imprinted polymers |
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| WO2007138345A1 (en) * | 2006-05-26 | 2007-12-06 | Johnson Matthey Public Limited Company | Process for producing stabilised metal nanoparticles |
| WO2008139204A2 (en) * | 2007-05-15 | 2008-11-20 | Imperial Innovations Ltd | Functional group imprinted polymers |
| CN102802782A (en) * | 2009-05-19 | 2012-11-28 | 百特基公司 | Porous polymeric separation material |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103611946A (en) * | 2013-12-08 | 2014-03-05 | 福建医科大学 | Preparation method of gold nanocluster fluorescent materials protected by methionine |
| CN105885832A (en) * | 2016-05-13 | 2016-08-24 | 湖南大学 | Preparation method and application of nano-copper cluster probe used for detecting iron ions |
| CN106053416A (en) * | 2016-07-14 | 2016-10-26 | 中南大学 | Application of silver nanocluster in detecting Fe3+ |
| CN109396415A (en) * | 2017-08-17 | 2019-03-01 | 清华大学 | Gold nano cluster and preparation method thereof |
| CN109396415B (en) * | 2017-08-17 | 2019-11-22 | 清华大学 | Gold nano cluster and preparation method thereof |
| CN115609001A (en) * | 2022-07-15 | 2023-01-17 | 西北工业大学 | Method for preparing functionalized gold nanoparticles by using acetylene compounds |
| CN115609001B (en) * | 2022-07-15 | 2023-10-10 | 西北工业大学 | Method for preparing functionalized gold nanoparticles by using alkyne compounds |
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| CN103193826B (en) | 2016-01-06 |
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