CN105294770A - pH sensor made of near-infrared light-emitting Ru complex - Google Patents
pH sensor made of near-infrared light-emitting Ru complex Download PDFInfo
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Abstract
The invention discloses a preparation method and the near-infrared light-emitting property of a dual-core Ru complex, as well as application of a pH sensor. The application comprises the following steps: calculating light-emitting quantum efficiencies at different pH values by measuring ultraviolet visible absorption spectrums and ultraviolet visible emission spectrums of the dual-core Ru complex at the pH values, and drawing a standard working curve by taking the pH values as abscissa values and the light-emitting quantum efficiencies as ordinate values, so as to detect the pH of an unknown water sample. The application is high in sensitivity and easy to operate.
Description
Technical field
The present invention relates to pH sensory field, be specifically related to the preparation method of a binuclear ruthenium and detecting the application in water sample pH.
Background technology
The traditional method detecting pH has pH meter, pH indicator and pH test paper etc., the acidometer measuring pH used comparatively accurately all will use glass electrode, but owing to there is electrochemistry interference in glass electrode, but also may cause physical abuse, is therefore not suitable for the detection of live body pH.Many vital processes in human body cell and organoid all follow potential of hydrogen closely related, such as under normal physiological conditions, in human body, the pH of extracellular fluid is at 7.40 ([H
+]=40nmol/L) left and right, its pH variation range is generally at 0.1-0.2 pH unit.Acidity crosses strong or alkaline mistake all can cause some pathologies by force, may be in peril of one's life time serious.Some enzyme only just has catalytic activity under certain specific pH for another example, so how to detect the pH of living things system in real time accurately, remains one of focus of current scientific research.In recent years, in order to detect the pH in living things system, there is the highly sensitive pH phosphorescence probe that can be used for imaging in cell and be developed gradually and apply.Compared with organic molecule, the pH sensor based on ruthenium complexe has the longer life-span, larger stoke shift, and ruthenium complexe has certain water-soluble, and this is extremely important to the pH detecting active somatic cell system.Because the group acid-basicity to external world such as imidazoles, hydroxyl, carboxyl, pyridine are very responsive, so these groups are incorporated in ruthenium complexe, by changing the pH of solution, make these groups that protonated or deprotonation occur, thus the spectrochemical property of title complex is changed, therefore play the effect of pH sensing.
The structural unit of the most frequently used regulation and control pH is imidazole ring, so based on ruthenium complexe pH sensor research also a lot of of imidazole ring as regulation and control group, protonated/deprotonated reaction can be there is in the nitrogen-atoms on imidazole ring under different pH, and the gain and loss of proton can change the energy level of part, and then regulation and control title complex metal is to charge transfer (MLCT) excited state of part, affects its chemical property.(M.Haga，M.M.Ali，S.Koseki，K.Fujimoto，A.Yoshimura，K.Nozaki，T.Ohno，K.Nakajima，D.J.Stufkens，Photo-inducedtuningofelectrochemicalandphotophysicalpropertiesinmononuclearanddinuclearrutheniumcomplexescontaining2，2’-bis(benzimidazol-2-yl)-4，4’-bipyridine：synthesis，molecularstructure，andmixed-valencestateandexcited-stateproperties，Inorg.Chem.，1996，35，3335-3347；M.Haga，T.Ano，K.Kano，S.Yamabe，Proton-inducedswitchingofmetal-metalinteractionsindinuclearrutheniumandosmiumcomplexesbridgedby2，2’-bis(2-pyridyl)bibenzimidazole.Inorg.Chem.，1991，30，3843-3849；H.Chao，B.H.Ye，Q.L.Zhang，L.N.Ji，AluminescentpHsensorbasedonadiruthenium(II)complex：“off-on-off”switchingviatheprotonation/deprotonationofanimidazole-containingligand，Inorg.Chem.Commun.，1999，2，338-340；F.X.Cheng，N.Tang.pH-inducedmolecularswitchofanoveltrinuclearRu(II)polypyridylcomplex，Inorg.Chem.Commun.，2008，11，506-508.)。But these ruthenium complexe pH sensors reported mostly are visible region luminescence, seldom have relate to near-infrared luminous.
The ruthenium metal complexes of imidazole ring-containing part, ground state and Excited State Properties can change along with the protonated of imidazole group or deprotonation, therefore the change for outside pH can show obvious spectral response, and the biological activity of compound depends on its soda acid character to a great extent.The rare report of ruthenium complexe pH sensor near-infrared luminous on the other hand, therefore, the ruthenium complexe that design and synthesis has the effect of near-infrared luminous pH sensor has great importance.
Summary of the invention
The object of the invention is to disclose a preparation method containing the double-core ruthenium of multiple imidazole ring.
The object of the invention is to disclose this compound and there is near-infrared luminous character.
Another object of the present invention discloses the ultraviolet-visible absorption spectroscopy of this title complex under different pH and emmission spectrum, draws luminous quantum efficiency working curve during different pH.
A further object of the invention discloses the application of this compound as pH sensor.
Technical scheme of the present invention is as follows:
Binuclear ruthenium in this experiment is made up of positively charged ion and negatively charged ion, and described positively charged ion is [(bpy)
2ru (HL
1) Ru (H
2l
2)]
4+, structural formula is as follows:
Binuclear ruthenium of the present invention does not limit the type of negatively charged ion, and this area conventional anion all can realize the object of the invention, especially inorganic salt negatively charged ion, as (ClO
4)
-, chlorion, hexafluorophosphoricacid acid ions etc., as the prepreerence scheme of one, this negatively charged ion of testing described binuclear ruthenium is (ClO
4)
-.
Preparation method of the present invention is as follows:
First prepare [Ru (H
2l
2) Cl
3] and [Ru (bpy)
2hL
1] (ClO
4)
2, then take both according to stoichiometric mole ratio and react in ethylene glycol, nitrogen protection, 180 DEG C of heating reflux reactions 12 hours, after reaction terminates, treat that solution is cooled to room temperature, add saturated NaClO
4the aqueous solution, has reddish brown precipitation to separate out.Suction filtration drying obtains thick product, then through silica gel column chromatography separating-purifying, with V (acetonitrile): V (water): V (saturated KNO
3the aqueous solution): V (ammoniacal liquor)=40: 5: 1: 0.5 mixing solutions wash-out, revolves after steaming the most of elutriant of removing, adds saturated NaClO
4the aqueous solution makes title complex separate out, and after suction filtration drying, acetonitrile/Diethyl ether recrystallization, obtains target product.
Preparation Britton-Robinson (being called for short BR) buffered soln, acid base titration carries out in this buffered soln.Preparation 3.75 × 10
-6the title complex liquid to be measured of mol/L, be divided into two parts, the portion vitriol oil regulates pH, measures ultravioletvisible absorption and the emmission spectrum of pH=0.2-2.0, another part regulates pH by strong caustic, measures ultravioletvisible absorption and the emmission spectrum (λ of pH=2.0-7.0
ex=λ
mLCT).Measure data at interval of 0.2 pH, then according to the integrated intensity of ultraviolet-visible absorption spectroscopy 505nm absorbancy during different pH and emmission spectrum, calculate luminous quantum efficiency, drawing standard working curve.
And then, by measuring ultraviolet-visible absorption spectroscopy and the emmission spectrum of unknown water sample, calculate luminous quantum efficiency and standard working curve compares, thus obtain the pH value of unknown water sample.
Compared with prior art, advantage of the present invention is:
Binuclear ruthenium Stability Analysis of Structures prepared by the present invention, has certain water-soluble, and has near-infrared luminous character.This title complex has three imidazole rings, the character of ground state and excited state can change along with the protonated of imidazole group or deprotonation, change list for outside pH reveals obvious spectral response, ultraviolet-visible absorption spectroscopy and intensity of emission spectra is made to strengthen or weaken, and absorption peak position and emission peak positions are moved, and this compound is near-infrared luminous, luminous quantum efficiency when drawing different pH is as standard working curve, for detecting the pH of water sample, simple and convenient, easy handling, and ensure that accuracy.
Accompanying drawing explanation
Fig. 1 is title complex [(bpy)
2ru (HL
1) Ru (H
2l
2)] (ClO
4)
4preparation method and structure.
Fig. 2 is title complex [(bpy)
2ru (HL
1) Ru (H
2l
2)] (ClO
4)
4protonated/deprotonated process.
Fig. 3 (a) is the ultraviolet-visible absorption spectroscopy figure of BR solution (3.75 μMs) when pH=0.2-2.4 under different pH of title complex, and illustration is the change of absorption value with pH; Fig. 3 (b) is BR solution (3.75 μMs) the ultraviolet-visible absorption spectroscopy figure when pH=2.4-8.0 of title complex, and illustration is the change of absorption value with pH; Fig. 3 (c) is BR solution (3.75 μMs) the ultraviolet-visible absorption spectroscopy figure when pH=8.0-11.4 of title complex, and illustration is the change of absorption value with pH.
Fig. 4 (a) is the utilizing emitted light spectrogram of BR solution (3.75 μMs) when pH=0.2-3.8 under different pH of title complex, and illustration is the change of emission peak intensity pH; Fig. 4 (b) is BR solution (3.75 μMs) the utilizing emitted light spectrogram when pH=3.8-7.4 of title complex, and illustration is the change of emission peak intensity pH.
Fig. 5 is the change curve of luminous quantum efficiency with pH, i.e. standard working curve.
Embodiment
Below by embodiment, the present invention is further described.
Embodiment 1: title complex [(bpy)
2ru (HL
1) Ru (H
2l
2)] (ClO
4)
4preparation process:
(1) part H
2l
2according to document [Addison, A.W.; Burke, P.J.Heterocycl.Chem.1981,18,803-805.] synthesis.
(2) [Ru (H
2l
2) Cl
3] be RuCl
33H
2o and part H
2l
2according to 1: 1 mol ratio, reflux is obtained in ethanol.
(3) part HL
1[Ru (bpy)
2hL
1] (ClO
4)
2according to document [Zheng, Z.B., Duan, Z.M., Zhang, J.M., Wang, K.Z.Chromogenicandfluorogenicsensingpropertiestowardcati onsandanionsbyaterpyridine/phenylimidazo [4, 5-f] phenanthrolinehybrid.SensorsActuatorsB2012, 169, 312 and Ze-BaoZheng, Zhi-MingDuan, Ying-YingMa, Ke-ZhiWang, HighlySensitiveandSelectiveDifunctionalRuthenium (II) ComplexBasedChemosensorforDihydrogenPhosphateAnionandFer rousCation, Inorg.Chem.2013, 52, 2306-2316] synthesis.
(4) title complex [(bpy)
2ru (HL
1) Ru (H
2l
2)] (ClO
4)
4preparation, take [Ru (H
2l
2) Cl
3] (0.0811g, 0.15mmol) be distributed in 30 milliliters of ethylene glycol, when stirred under nitrogen atmosphere is heated to 100 DEG C, adds [Ru (bpy)
2hL
1] (ClO
4)
2(0.161g, 0.15mmol), mixing solutions continues 180 DEG C of heating reflux reactions 12 hours under nitrogen protection.After reaction terminates, treat that solution is cooled to room temperature, add saturated NaClO
4the aqueous solution, has reddish brown precipitation to separate out.Suction filtration, washing, drying obtains thick product.By the thick product that obtains again through silica gel column chromatography separating-purifying, with V (): V (water): V (saturated KNO
3the aqueous solution): V (ammoniacal liquor)=40: 5: 1: 0.5 mixing solutions wash-out, revolves after steaming the most of elutriant of removing, dropwise adds saturated NaClO
4the aqueous solution makes title complex separate out, and uses acetonitrile/Diethyl ether recrystallization again after suction filtration drying, obtains target product 108mg, and productive rate is 43%.Ultimate analysis C
67h
46n
16ru
24ClO
44H
2o (F.M.=1746): C, 46.05%; N, 12.83%; H, 3.09%.Found:C, 46.11%; N, 12.98%; H, 3.35%.
Mass spectrum ESI-MS (positive, CH3CN) m/z:425.2 ([M-4ClO
4-H
+]
3+) (C
67h
45n
16ru
2)
3+, 319.0 ([M-4ClO
4]
4+) (C
67h
46n
16ru
2)
4+
Hydrogen nuclear magnetic resonance spectrum δ/ppm (400MHz, DMSO-d
6): 9.83 (s, 2H, H5), 9.22 (d, 2H, J=20Hz, H4), 8.93-8.81 (m, 8H, 2H17+2H6+4H9), 8.69 (t, 1H, J=16Hz, H18), 8.26 (t, 2H, J=15.8Hz, H2), 8.22-8.10 (m, 4H, 2H10+2H8), 8.04-8.15 (m, 4H, 2H10+2H7), 7.88 (d, 2H, J=5.24Hz, H12), 7.70-7.58 (m, 8H, 2Hl+4H11+2H12), 7.43 (t, 2H, J=12.4Hz, H13), 7.34 (t, 2H, J=13.1Hz, H3), 7.29 (t, 2H, J=15.4Hz, H14), 6.98 (t, 2H, J=15.6Hz, H15), 6.11 (d, 2H, J=8.2Hz, H16).
Embodiment 2: the mensuration of ultraviolet-visible absorption spectroscopy and emmission spectrum and the drafting of working curve during different pH
The acid base titration of title complex carries out in Britton-Robinson (being called for short BR) buffered soln.BR buffered soln has 0.04M Glacial acetic acid, and 0.04M boric acid and 0.1M sodium-chlor mix.Sodium-chlor is the ionic strength in order to keep system, thus reduces the impact of external environment on test.Prepare 40 milliliter 3.75 × 10
-6the title complex liquid to be measured of mol/L, be divided into two parts, the portion vitriol oil regulates pH, measures ultravioletvisible absorption and the emmission spectrum of Ph=0.2-2.0.Another part regulates pH by strong caustic, measures ultravioletvisible absorption and the emmission spectrum (excitation wavelength lambda of pH=2.0-7.0
ex=505nm).Measure data at interval of 0.2 pH, read the absorbancy (505nm place) of ultraviolet-visible absorption spectroscopy during different pH and the integration luminous intensity of emmission spectrum, calculate luminous quantum efficiency, drawing standard working curve.
Uv-visible absorption spectra measures on UV-2600 spectrophotometry instrument, using BR buffered soln as reference liquid during mensuration.According to absorption spectrum, in the variation range of pH=0.2-11.4, ultraviolet-visible absorption spectroscopy change can be divided into three step continuous print deprotonation processes: the first step is as Fig. 3 (a), pH rises to the process of 2.4 from 0.2, the absorption peak at 347nm place rises gradually, and there is isobestic point in 411 and 512nm place, this is owing to part HL
1the dissociation process of the proton of upper protonated imidazole ring.Second step is as shown in Fig. 3 (b), and pH rises to 8.2 from 2.4, the absorption peak of ultraviolet-visible absorption spectroscopy at 505nm place constantly decline and red shift to 530nm, 536,401 and 373nm place have three isobestic points, this process is by part H
2l
2on imidazole ring deprotonation cause.The deprotonation of final step occurs in pH=8.2-11.4 interval as shown in Fig. 3 (c), is HL
1on neutral imidazole ring deprotonation cause.
Fluorescence emission spectrum measures on CaryEclipse spectrophotofluorometer, and excitation wavelength is 505nm, excites and launch slit to be 10nm.As seen from Figure 4, the emmission spectrum of title complex is very responsive to the change of pH, and change procedure is divided into two stages, and is near-infrared luminous.During pH=1, title complex is luminous hardly, and along with the increase of pH, intensity of emission spectra increases sharply, and peak position is from 750nm blue shift to 721nm, and when pH=3.8, intensity reaches maximum, presents " off-on " (I
pH4.0/ I
pH1.0=15, Φ
pH4.0/ Φ
pH1.0=5).Subordinate phase is as shown in Fig. 4 (b), pH rises to 12.0 processes from 3.8, proton on the neutral imidazole ring of excited state title complex starts to dissociate, the luminous intensity of title complex starts to weaken, the almost cancellation completely when pH=7.0; " off-on " strength reduction nearly 90%, and peak position has red shift (Φ
pH7.0/ Φ
pH4.0=0.39).
Trying to achieve of luminous quantum efficiency is with tris (bipyridine) ruthenium [Ru (bpy)
3]
2+be standard substance (Φ
std=0.028), surveying concentration is 1.0 × 10
-6[the Ru (bpy) of mol/L
3]
2+the ultraviolet-visible absorption spectroscopy of the aqueous solution and emmission spectrum, read the absorbance A at ultraviolet-visible absorption spectroscopy 450nm place
stdwith the integrated intensity I of emmission spectrum
std, according to formula (1):
Φ＝Φ
std(A
std/A)(I/I
std)(1)
Φ and Φ
stdbe respectively the luminous quantum efficiency of determinand and standard substance, A and A
stdthe absorbancy of determinand and standard substance excitation wave strong point, I and I
stdit is the luminous integrated intensity of non-determinand and standard.
The absorbance A at title complex ultraviolet-visible absorption spectroscopy 505nm place and the integrated intensity I of emmission spectrum when reading different pH, luminous quantum efficiency Φ when calculating different pH according to formula.Take pH as X-coordinate, luminous quantum efficiency is ordinate zou, drawing standard working curve (Fig. 5).Along with pH increases, complex phosphorescence opens the light and is " unpacked " gradually, and quantum yield is from 0.29 × 10
-3rise to 1.57 × 10 gradually
-3, then drop to 0.62 × 10 gradually again
-3left and right reaches balance.
Embodiment 3: the mensuration of unknown water sample pH
Get unknown water sample 23ml, adding sodium-chlor to concentration is wherein 0.1M, keeps ionic strength consistent in BR buffering.Get 3ml and add the water sample of superchlorination sodium as reference liquid, in remaining 20ml water sample, add quantitative title complex make its concentration be 3.75 × 10
-6mol/L, is consistent with concentration during title complex acid base titration.Survey uv-absorbing and the emmission spectrum of water sample.
Trying to achieve of luminous quantum efficiency is with tris (bipyridine) ruthenium [Ru (bpy)
3]
2+be standard substance (Φ
std=0.028), surveying concentration is 1.0 × 10
-6[the Ru (bpy) of mol/L
3]
2+the ultraviolet-visible absorption spectroscopy of the aqueous solution and emmission spectrum, read the absorbance A at ultraviolet-visible absorption spectroscopy 450nm place
stdwith the integrated intensity I of emmission spectrum
std, according to formula (1):
Φ＝Φ
std(A
std/A)(I/I
std)(1)
Φ and Φ
stdbe respectively the luminous quantum efficiency of determinand and standard substance, A and A
stdthe absorbancy of determinand and standard substance excitation wave strong point, I and I
stdit is the luminous integrated intensity of non-determinand and standard.
Read the unknown absorbance A at water sample ultraviolet-visible absorption spectroscopy 505nm place and the integrated intensity I of emmission spectrum, thus can in the hope of the photoluminescence quantum yield of title complex, according to typical curve, pH corresponding when reading this quantum yield, thus learn the pH of unknown water sample.
Claims (6)
1. the binuclear ruthenium in the present invention, is made up of positively charged ion and negatively charged ion, it is characterized in that, described positively charged ion is [(bpy)
2ru (HL
1) Ru (H
2l
2)]
4+, structural formula is as follows:
2. binuclear ruthenium according to claim 1, it is characterized in that, described negatively charged ion is inorganic salt negatively charged ion.
3. binuclear ruthenium according to claim 2, it is characterized in that, described inorganic salt negatively charged ion is (ClO
4)
-.
4. the preparation method of binuclear ruthenium according to claim 1, it is characterized in that, preparation process is simple to operation:
First prepare [Ru (H
2l
2) Cl
3] and [Ru (bpy)
2hL
1] (ClO
4)
2, then take both according to stoichiometric mole ratio and react in ethylene glycol, nitrogen protection, 180 DEG C of heating reflux reactions 12 hours, after reaction terminates, treat that solution is cooled to room temperature, add saturated NaClO
4the aqueous solution, has reddish brown precipitation to separate out.Suction filtration drying obtains thick product, then through silica gel column chromatography separating-purifying, with V (): V (water): V (saturated KNO
3the aqueous solution): V (ammoniacal liquor)=40: 5: 1: 0.5 mixing solutions wash-out, revolves after steaming the most of elutriant of removing, adds high density NaClO
4the aqueous solution makes title complex separate out, and after suction filtration drying, acetonitrile/Diethyl ether recrystallization, obtains target product.
5. binuclear ruthenium according to claim 5, it is characterized in that, the luminescence of this title complex is near-infrared luminous.
6. binuclear ruthenium according to claim 3, is characterized in that, can be ordinate zou according to luminous quantum efficiency, pH is the pH that standard working curve that X-coordinate is drawn tries to achieve unknown water sample.
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| CN107118235B (en) * | 2017-05-12 | 2019-05-14 | 北京师范大学 | Application of the near-infrared luminous ruthenium complex in cellular pH sensing |
| CN107389574A (en) * | 2017-07-31 | 2017-11-24 | 北京师范大学 | Physiological pH senses the preparation method and application of three core ruthenium complexes |
| CN111735781A (en) * | 2017-11-14 | 2020-10-02 | 北京师范大学 | Triphenylamine grafted ruthenium complex ratio luminescence pH sensor |
| CN108409796A (en) * | 2018-03-06 | 2018-08-17 | 北京师范大学 | Application of the near-infrared luminous ruthenium complex in normal mouse imaging organs |
| CN108409796B (en) * | 2018-03-06 | 2020-09-04 | 北京师范大学 | Application of near-infrared luminescent ruthenium complex in normal mouse organ imaging |
| CN109251746A (en) * | 2018-11-23 | 2019-01-22 | 曲靖师范学院 | The preparation and its application of anthracene nucleus bridged binuclear ruthenium complex fluorescence probe |
| CN109251746B (en) * | 2018-11-23 | 2021-10-08 | 曲靖师范学院 | Preparation and application of anthracene ring bridged binuclear ruthenium complex fluorescent probe |
| CN110511249A (en) * | 2019-08-26 | 2019-11-29 | 北京师范大学 | The preparation and application of near-infrared luminous ruthenium complex |
| CN110967326A (en) * | 2019-12-12 | 2020-04-07 | 北京师范大学 | Near-infrared light-emitting binuclear ruthenium complex as tumor cell recognition and imaging reagent |
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