CN102584899B - Phosphorescent iridium complex, and preparation method and application thereof - Google Patents

Phosphorescent iridium complex, and preparation method and application thereof Download PDF

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CN102584899B
CN102584899B CN201110459462.6A CN201110459462A CN102584899B CN 102584899 B CN102584899 B CN 102584899B CN 201110459462 A CN201110459462 A CN 201110459462A CN 102584899 B CN102584899 B CN 102584899B
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iridium complex
phosphorescent iridium
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pba
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毛兰群
杨丽芬
姜琴
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Institute of Chemistry CAS
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Abstract

The invention discloses a phosphorescent iridium complex, and a preparation method and application thereof. A chemical formula of the phosphorescent iridium complex is [Ir(pba)2(DMSO)2]PF6 and a structural formula of the phosphorescent iridium complex is shown as a formula (I), wherein pba is expressed as 4-(2-pyridyl)benzaldehyde, DMSO is expressed as dimethylsulfoxide. A method for preparing the phosphorescent iridium complex comprises the following steps of: reacting a complex shown as a formula (II) with the dimethylsulfoxide; and adding potassium hexafluorophosphate into a reaction system and stirring to obtain the phosphorescent iridium complex. The invention also provides application of the phosphorescent iridium complex to the detection of glutamine. By the phosphorescent iridium complex, the high-selectivity and high-sensitivity detection of the glutamine can be realized, and a possibility for constructing a fluorescent chemical sensor for detecting the glutamine in high selectivity and high sensitivity is provided; and the phosphorescent iridium complex has a high dyeing effect on the glutamine in cells, and is expected to be used for detecting the Gln in the physiological and pathological processes.

Description

A kind of phosphorescent iridium complex and preparation method thereof and application
Technical field
The present invention relates to a kind of phosphorescent iridium complex and preparation method thereof and application.
Background technology
Glutamine (Glutamine is called for short Gln) is one of the abundantest amino acid of Mammals in-vivo content, and in human normal plasma, concentration is 0.6～0.9mmol/L, accounts for 20% of blood plasma total free amino acid, accounts for 60% of the interior total free amino acid of body.Nineteen thirty-five, Kerbs finds the ability that Mammals kidney is synthetic and decompose Gln first, emphasizes that " most amino acid has several functions, but the function of Gln is the abundantest." Eagle (H.Eagle.J.Biol.Chem.1955, 214, 839-852), Windmueller (H.G. Windmueller.Advanced in Enzymology and Related Areas of Molecular Biology.1982, 53, 210-237), Kapadia (C.R.Kapadia, M.F.Colpoys, Z.M.Jiang, D.J.Johnson, R.J.Smith, D.W. Wilmore.J.Parenter. Enter. Nutr.1985, 9, 583-589), Alverdy (J.C.Alverdy.J.Parenter. Enter.Nutr. 1990, 14, S109-S113), Souba (W. W. Souba.Ann. Surg.1993, 218, 715-728, 217,655-667) point out that respectively the mammalian cell of cultivating needs Gln, and emphasize that Gln is a kind of important nutrient substance, it is the precursor substance of synthesizing amino acid, protein, nucleic acid and many other biological molecules, not only in liver, kidney, small intestine and muscle metabolism, play important regulative, and be the main carriers that in body, each organ is transported amino acid and nitrogen, be the main fuel of the rapid cell of growth.Gln, as a kind of special nutritive substance, has caused people's common concern, and becomes study hotspot in recent years.1998, the people such as Pittner were developed a kind of flow injection method based on glutamine content in enzyme linked immunological indirect detection cell culture medium; 1998, Hernandez etc. reported a kind of and have detected the glutamine content in first stream Cerebrospinal Fluid in Patients based on capillary zone electrophoresis-via Laser-induced Fluorescence Method, but these methods all exist the shortcomings such as complex operation, instrument is expensive, detectability is high.
Phosphorescent metal title complex (Re i, Ru iI, Os iI, Rh iII, Ir iII) etc. generally there is unique d 6, d 8, d 10electronic structure, between heavy metal atom, can there is spin coupling, singlet state and triplet state are mixed, the symmetry of triplet exciton is destroyed, and decay accelerates, and metal-ligand electric charge occurs and shift (MLCT), make singlet state also there is some triplet state character simultaneously, fall time is elongated, has improved (ISC) efficiency that jumps that leaps up between system from singlet state to triplet state, thereby has sent high efficiency phosphorescent.Compared with organic fluorescent dye, phosphorescence heavy metal complex has larger Stokes displacement and longer emission lifetime, and its long emission lifetime is conducive to duration of service resolution techniques distinguishes phosphorescent signal and the fluorescent signal of background mutually.
In common several heavy metal complexes, Ir iIItitle complex because phosphorescent lifetime is relatively short, luminescent quantum productive rate is high, whole visibility region is adjustable etc., advantage receives much concern in fields such as electroluminescent, fluorescent probe, bio-imagings glow color, therefore, be necessary Ir iIItitle complex is further studied.
Summary of the invention
The object of this invention is to provide a kind of phosphorescent iridium complex and preparation method thereof and application.
A kind of phosphorescent iridium complex provided by the invention, its chemical formula is: [Ir (pba) 2(DMSO) 2] PF 6, wherein pba represents 4-(2-pyridyl) phenyl aldehyde, DMSO represents methyl-sulphoxide;
The structural formula of described phosphorescent iridium complex is suc as formula shown in (I),
Figure BDA0000128059900000021
The present invention also provides the preparation method of above-mentioned phosphorescent iridium complex, comprises the steps:
Suc as formula title complex shown in (II), (chemical formula is [(pba) to structural formula 2ir (μ-Cl 2) Ir (pba) 2], pba represents 4-(2-pyridyl) phenyl aldehyde) react with methyl-sulphoxide;
In described reacted reaction system, add Potassium Hexafluorophosphate through stirring and obtain product;
Figure BDA0000128059900000022
In above-mentioned preparation method, title complex shown in formula (II) can be 1 with the molfraction ratio of methyl-sulphoxide: (3～5), and as 1: 5.
In above-mentioned preparation method, the temperature of described reaction can be 110 ℃～150 ℃, as 120 ℃; The time of described reaction can be 2 hours～and 4 hours, as 2 hours.
In above-mentioned preparation method, title complex shown in formula (II) can be 1 with the molfraction ratio of Potassium Hexafluorophosphate: (4～6), and as 1: 4.
In above-mentioned preparation method, title complex shown in formula (II) can be prepared according to the method comprising the steps: three hydration iridous chlorides react and get final product with 4-(2-pyridyl) phenyl aldehyde in the mixing solutions of ethylene glycol ethyl ether and water, the volume parts ratio of ethylene glycol ethyl ether and water can be 3: 1, specifically can under reflux conditions react 24 hours.
The present invention also provides above-mentioned phosphorescent iridium complex in the application detecting in glutamine; In described application, can in methyl-sulphoxide and phosphate buffer soln, to glutamine, detect, the pH value of described phosphate buffer soln can be 7.0, and concentration is 50mM.
Phosphorescent iridium complex provided by the invention, issues orange light at 365nm ultra violet lamp, and maximum emission wavelength is positioned at 557nm left and right, under normal temperature condition, this complex of iridium and after glutamine effect for some time (glutamine can with Ir iIIcoordination, forms a five-membered ring structure, and can with part on-CHO forms hydrogen bond, the energy of realizing between metal and part shifts), can send brighter blue light, its maximum emission peak is positioned at 475nm, its emissive porwer is [Ir (pba) 2(DMSO) 2] PF 6title complex has improved nearly 100 times, under the same terms, other amino acid and containing the polypeptide (as: arginine of glutamine residue, Histidine, L-glutamic acid, halfcystine, aspartic acid, glycine, tyrosine, L-Ala, Isoleucine, Methionin, l-asparagine, gsh, L-proglu-dipeptide) with this complex of iridium effect after, its emissive porwer does not significantly change, thereby complex of iridium provided by the invention can be realized the highly selective of glutamine, high-sensitivity detection, for building a kind of highly selective, the fluorescence chemical sensor of high-sensitivity detection glutamine provides may, and phosphorescent iridium complex provided by the invention has stronger dyeing function to intracellular glutamine, is expected to the detection for the Gln of physiology, pathologic process.
Accompanying drawing explanation
Fig. 1 is the image under 365nm ultra violet lamp after complex of iridium provided by the invention and different aminoacids effect, wherein, Fig. 1 (a) be after complex of iridium provided by the invention and different aminoacids effect in 365nm ultra violet lamp figure, Fig. 1 (b) is for complex of iridium of the present invention and glutamine effect front and back are in 365nm ultra violet lamp figure.
Fig. 2 is the utilizing emitted light spectrogram after complex of iridium provided by the invention and different aminoacids effect.
Fig. 3 is the cyclic voltammogram after complex of iridium provided by the invention and glutamine effect.
Fig. 4 is the laser confocal imaging after complex of iridium provided by the invention and glutamine effect, and wherein, Fig. 4 (a) is the laser confocal imaging of Hela cell, and Fig. 4 (b) is that Hela cell is through [Ir (pba) 2(DMSO) 2] PF 6laser confocal imaging after title complex is hatched, Fig. 4 (c) is that Hela cell is through [Ir (pba) 2(DMSO) 2] PF 6laser confocal imaging after the mixing solutions of title complex and glutamine is hatched.
Embodiment
The experimental technique using in following embodiment if no special instructions, is ordinary method.
In following embodiment, material used, reagent etc., if no special instructions, all can obtain from commercial channels.
Preparation and the application thereof of phosphorescent iridium complex shown in formula (I)
1, title complex shown in formula (II) [(pba) 2ir (μ-Cl 2) Ir (pba) 2] preparation
Reference literature (W. Tan, Q.Zhang, J.J.Zhang, H.Tian.Org.Lett.2009,11,161-164).
Take the IrCl of 1mmol 3h 2o and 2.5mmol 4-(2-pyridyl) phenyl aldehyde is dissolved in the mixing solutions of ethylene glycol ethyl ether and water (volume ratio 3: 1), and heating, stirring and refluxing 24h, obtain yellow mercury oxide; Suction filtration is drying to obtain [(pba) 2ir (μ-Cl 2) Ir (pba) 2].
1H?NMR(300MHz?CDCl 3)δppm：9.52(s，4H；CHO)，9.27(dd，4H)，8.06(d，4H)，7.94(dt，4H)，7.68(d，4H)，7.31(dd，4H)，6.98(dt，4H)，6.37(d，4H)。MALDI-TOF mass spectrum m/z[M +]: 556.62{[Ir (pba) 2] +.
2, [the Ir (pba) of phosphorescent iridium complex shown in formula (I) 2(DMSO) 2] PF 6preparation
Take 0.085g (0.079mmol) [(pba) 2ir (μ-Cl 2) Ir (pba) 2] and 30mL DMSO reaction, wherein, [(pba) 2ir (μ-Cl 2) Ir (pba) 2] with the mol ratio of DMSO be 1: 5, be heated to 120 ℃ and keep reaction 2h, obtain yellow solution, be cooled to room temperature, then add Potassium Hexafluorophosphate, the Potassium Hexafluorophosphate adding with [(pba) 2ir (μ-Cl 2) Ir (pba) 2] mol ratio be 4: 1, stir 1h, then suction filtration, underpressure distillation; Solid is take methylene dichloride and acetone (volume ratio 15: 1) as eluent, separates with silicagel column, obtains [the Ir (pba) of orange red solid shown in formula (I) 2(DMSO) 2] PF 6, productive rate: 65.8%.
1HNMR(300MHz，DMSO-d 6，TMS)δppm：9.88(s，2H；CHO)，9.58(s，2H)，8.49(d，2H)，8.25(t，2H)，8.00-8.07(m，4H)，7.74(t，1H)，7.64(t，1H)，7.47(m，1H)，7.43(m，2H)，6.75(s，1H)，2.51(s，4H)。MALDI-TOF mass spectrum m/z[M +]: 556.62{[Ir (pba) 2] +.Ultimate analysis: calculated value (is pressed C 28h 28irN 2s 2o 4h 2oCH 2cl 2calculate): C:42.66; N:3.44; H:3.92; Measured value: C:42.99; N:3.29; H:3.89.
3, [the Ir (pba) of phosphorescent iridium complex shown in formula (I) 2(DMSO) 2] PF 6interaction with different aminoacids molecule
By [the Ir (pba) of preparation 2(DMSO) 2] PF 6pressed powder is dissolved in DMSO solution, and with DMSO/ (phosphate buffer soln, PBS (pH 7.0,50mM)) (volume ratio 1: 49) dilution, final preparation concentration is the Ir complex solution of 10 μ M, add equal-volume, isocyatic different aminoacids (final concentration is 500 μ M), normal-temperature reaction two days, then carries out respectively the mensuration of photophysical property to it again.
Test result as illustrated in fig. 1 and 2, with [Ir (pba) 2(DMSO) 2] PF 6complex solution is compared, when adding after glutamine, solution presents stronger blue light, emission wavelength is blue shifted to 475nm by 557nm, fluorescence intensity increases nearly 100 times, and phosphorescent lifetime is also reduced to 7ns by 100ns, and this is because glutamine replaces after DMSO, this title complex triplet excitation changes singlet state into and excites, and the time that excited state electronics returns to ground state shortens greatly; Under the same terms, other amino acid and polypeptide (as: arginine, Histidine, L-glutamic acid, halfcystine, aspartic acid, glycine, tyrosine, L-Ala, Isoleucine, Methionin, l-asparagine, gsh and L-proglu-dipeptide) and [Ir (pba) containing glutamine residue 2(DMSO) 2] PF 6after title complex effect, its emissive porwer does not significantly change, thereby complex of iridium probe provided by the invention can be realized highly selective and the high-sensitivity detection of glutamine; From above-mentioned experiment, complex of iridium provided by the invention can reach 500nmol/L to the minimum limit of determination of glutamine.
4, [the Ir (pba) of phosphorescent iridium complex shown in formula (I) 2(DMSO) 2] PF 6electro-chemical test
Adopt three-electrode system, glass-carbon electrode is working electrode, platinum electrode is supporting electrode, Ag/AgCl (saturated KCl) electrode is reference electrode, solvent: anhydrous acetonitrile, supporting electrolyte: phosphofluoric acid 4-butyl amine, adopts cyclic voltammetry to complete on electrochemical workstation (CHI 660B).
Test result as shown in Figure 3, as can be seen from the figure [Ir (pba) 2(DMSO) 2] PF 6there is good redox reversible peak in title complex, and redox peak-to-peak current potential difference DELTA E=67mV near+1.22V (vsAg/AgCl, saturated KCl), substantially close to theoretical value 59mV.Add after glutamine, oxidation peak peak current is significantly increased, and reduction peak peak current almost remains unchanged, this also illustrates between this complex of iridium and glutamine to exist from another angle and interacts, and peak current to change inconsistent possible cause be oxidation state Ir iVwith reduction-state Ir iIIdifferent from glutamine coordination ability, the spread coefficient of oxidation state complex of iridium from solution bulk diffusion to electrode surface accelerates, thereby it is inconsistent to cause redox peak to peak current to change.
5, [the Ir (pba) of phosphorescent iridium complex shown in formula (I) 2(DMSO) 2] PF 6cell toxicity test
The cell that the present invention tests employing is Hela cell (cervical cancer cell), is purchased from BJ Union Hospital.
Prepare [the Ir (pba) of different concns (10,20,40,60,80,100 μ M) 2(DMSO) 2] PF 6complex solution, after 5～6 hours, uses PBS solution to clean twice until cell adherent growth in 96 orifice plates, respectively adds [the Ir (pba) of 100 μ L different concns 2(DMSO) 2] PF 6solution is hatched 2h, then with PBS solution cleaning twice, finally adds CCK-8 staining reagent, surveys absorbancy and change after 2 hours in microplate reader.
Experimental result demonstration, Hela cell is the [Ir (pba) of 10 μ M and 20 μ M in concentration 2(DMSO) 2] PF 6in complex solution, hatch after 2h, cell viability still can reach more than 95% and 90%, illustrates that complex of iridium provided by the invention has hypotoxicity.
6, [the Ir (pba) of phosphorescent iridium complex shown in formula (I) 2(DMSO) 2] PF 6laser confocal imaging
By [Ir (pba) 2(DMSO) 2] PF 6title complex is dissolved in DMSO/PBS (volume ratio 1: 49) (pH 7.0,50mM), in PBS, adding final concentration is that this complex solution of 10 μ M is hatched after Hela cell 2h, with twice of PBS solution cleaning, then under Olympus FV1000 laser scanning co-focusing microscope, in 405nm, excite, gather the utilizing emitted light within the scope of 440～480nm.
Result as shown in Figure 4, cellular autofluorescence a little less than, when adding [Ir (pba) 2(DMSO) 2] PF 6solution was hatched after for some time, the luminous grow of tenuigenin part; And add [Ir (pba) 2(DMSO) 2] PF 6hatch after for some time with the mixing solutions of Gln, tenuigenin part fluorescence becomes brighter, illustrate that complex of iridium provided by the invention can enter cell by cytolemma, intracellular glutamine is had to stronger dyeing function, the variation of glutamine in bio-imaging and studying physiological, pathologic process is had great importance.

Claims (6)

1. a phosphorescent iridium complex, its chemical formula is: [Ir (pba) 2(DMSO) 2] PF 6, wherein pba represents 4-(2-pyridyl) and phenyl aldehyde, DMSO represents methyl-sulphoxide;
The structural formula of described phosphorescent iridium complex as shown in formula I,
2. the preparation method of phosphorescent iridium complex described in claim 1, comprises the steps:
Structural formula title complex as shown in formula II reacts with methyl-sulphoxide;
In described reacted reaction system, add Potassium Hexafluorophosphate through stirring and obtain product;
Figure FDA0000460178800000012
3. method according to claim 2, is characterized in that: title complex shown in formula II is 1:(3～5 with the molfraction ratio of methyl-sulphoxide).
4. it is characterized in that according to the method in claim 2 or 3: the temperature of described reaction is 110 ℃～150 ℃; The time of described reaction is 2 hours～4 hours.
5. it is characterized in that according to the method in claim 2 or 3: title complex shown in formula II is 1:(4～6 with the molfraction ratio of Potassium Hexafluorophosphate).
6. it is characterized in that according to the method in claim 2 or 3: title complex shown in formula II is to prepare according to the method comprising the steps: three hydration iridous chlorides and 4-(2-pyridyl) phenyl aldehyde reacts and get final product in the mixing solutions of ethylene glycol ethyl ether and water.
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