CN105294770B - Near-infrared luminous ruthenium complex pH sensors - Google Patents
Near-infrared luminous ruthenium complex pH sensors Download PDFInfo
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Abstract
The invention discloses the preparation method and its near-infrared luminous property and pH sensor applications of a binuclear ruthenium.The ultraviolet-visible absorption spectroscopy and emission spectrum of the compound, calculate luminous quantum efficiency during different pH during by determining different pH, and using pH as abscissa, luminous quantum efficiency is that ordinate draws out standard working curve, for detecting the pH of unknown water sample.This method has high sensitivity and ease for operation.
Description
Technical field
The present invention relates to pH sensory fields, and in particular to the preparation method of binuclear ruthenium and its in detection water sample
Application in pH.
Background technology
Detection pH conventional method has pH meter, pH indicator and pH test paper etc., more accurately determines the acidity used in pH
Meter will use glass electrode, but glass electrode is due to electrochemistry interference being present, and may also result in mechanical damage, therefore
It is not suitable for live body pH detection.Many life processes in human body cell and organelle are all closely related with acid-base value, than
As said, under normal physiological conditions, the pH of extracellular fluid is in 7.40 ([H in human body+]=40nmol/L) left and right, its pH excursion
Typically in 0.1-0.2 pH unit.It is acid too strong or it is alkaline it is too strong can all cause some lesions, may have life danger when serious
Danger.How in real time some enzymes only just have catalytic activity under some specific pH for another example, so accurate detection biosystem
PH, be still one of focus of current scientific research.In recent years, in order to detect the pH in biosystem, there is high sensitivity
Be gradually developed and apply available for the pH phosphorescence probes being imaged into the cell.Compared with organic molecule, coordinated based on ruthenium
The pH sensors of thing have longer life-span, larger stoke shift, and ruthenium complex has certain water solubility, and this is to inspection
The pH for surveying active somatic cell system is extremely important.Because the groups such as imidazoles, hydroxyl, carboxyl, pyridine are very quick to the acid-base property in the external world
Sense, so these groups are incorporated into ruthenium complex, by changing the pH of solution, make these groups that protonation occur or go
Protonation, so that the spectrochemical property of complex changes, therefore play a part of pH sensings.
The most frequently used regulation and control pH construction unit is imidazole ring, so the ruthenium complex based on imidazole ring as regulation and control group
PH sensor researchs it is also a lot, protonated/deprotonated reaction can occur under different pH for the nitrogen-atoms on imidazole ring,
And the gain and loss of proton can change the energy level of part, and then the electric charge transfer (MLCT) for regulating and controlling complex metal to part excites
State, influence its chemical property.(M.Haga, M.M.Ali, S.Koseki, K.Fujimoto, A.Yoshimura, K.Nozaki,
T.Ohno, K.Nakajima, D.J.Stufkens, Photo-induced tuning of electrochemical and
photophysical properties in mononuclear and dinuclear ruthenium complexes
Containing2,2 '-bis (benzimidazol-2-yl) -4,4 '-bipyridine：Synthesis, molecular
Structure, and mixed-valence state and excited-state properties, Inorg.Chem.,
1996,35,3335-3347；M.Haga, T.Ano, K.Kano, S.Yamabe, Proton-induced switching of
metal-metal interactions in dinuclear ruthenium and osmium complexes bridged
By 2,2 '-bis (2-pyridyl) bibenzimidazole.Inorg.Chem., 1991,30,3843-3849；H.Chao,
B.H.Ye, Q.L.Zhang, L.N.Ji, A luminescent pH sensor based on a diruthenium (II)
complex：“off-on-off”switching via the protonation/deprotonation of an
Imidazole-containing ligand, Inorg.Chem.Commun., 1999,2,338-340；F.X.Cheng,
N.Tang.pH-induced molecular switch of a novel trinuclear Ru(II)polypyridyl
Complex, Inorg.Chem.Commun., 2008,11,506-508.).But these ruthenium complex pH sensors reported are more
Light, seldom relate to near-infrared luminous for visual field.
The ruthenium metal complex of imidazole ring-containing part, ground state and Excited State Properties can with imidazole group protonation or go
Protonate and change, therefore the change for outside pH can show obvious spectral response, and the bioactivity of compound
It is largely dependent upon its soda acid property.On the other hand the near-infrared luminous rare report of ruthenium complex pH sensors, because
This, ruthenium complex of the design synthesis with the effect of near-infrared luminous pH sensors has great importance.
The content of the invention
The purpose of the present invention is to disclose the preparation method of a double-core ruthenium containing multiple imidazole rings.
The purpose of the present invention is to disclose the compound to have near-infrared luminous property.
Another object of the present invention is to disclose ultraviolet-visible absorption spectroscopy of the complex under different pH and transmitting light
Spectrum, draws luminous quantum efficiency working curve during different pH.
A further object of the invention is the application for disclosing the compound as pH sensors.
Technical scheme is as follows：
Binuclear ruthenium in this experiment is made up of cation and anion, and the cation is [(bpy)2Ru
(HL1)Ru(H2L2)]4+, structural formula is as shown below：
Binuclear ruthenium of the present invention does not limit the type of anion, and this area conventional anion can be realized
The object of the invention, such as especially inorganic salt anionic, (ClO4)-, chlorion, hexafluorophosphoricacid acid ions etc., as a kind of override
Scheme, the anion of this experiment binuclear ruthenium is (ClO4)-。
The preparation method of the present invention is as follows：
First prepare [Ru (H2L2)Cl3] and [Ru (bpy)2HL1](ClO4)2, then according to stoichiometric mole ratio weigh both in
Reacted 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
Enter saturation NaClO4The aqueous solution, there is reddish brown precipitation precipitation.Suction filtration is dried to obtain crude product, then is carried by silica gel column chromatography separation
It is pure, with V (acetonitrile): V (water): V (saturation KNO3The aqueous solution): the elution of V (ammoniacal liquor)=40: 5: 1: 0.5 mixed solution, revolving remove
After most of eluent, saturation NaClO is added4The aqueous solution causes complex to separate out, and filters acetonitrile/Diethyl ether recrystallization after drying,
Obtain target product.
Britton-Robinson (abbreviation BR) cushioning liquid is prepared, acid base titration is carried out in the cushioning liquid.Prepare
3.75×10-6Mol/L complex prepare liquid, is divided into two parts, a to adjust pH with the concentrated sulfuric acid, determines pH=0.2-2.0 purple
Outer visible absorbance and emission spectrum, another adjusts pH with strong caustic, and the UV, visible light for determining pH=2.0-7.0 is inhaled
Receive and emission spectrum (λex=λMLCT).A data are determined at interval of 0.2 pH, ultravioletvisible absorption during further according to different pH
The integrated intensity of spectrum 505nm absorbances and emission spectrum, luminous quantum efficiency is calculated, draw standard working curve.
And then by determining the ultraviolet-visible absorption spectroscopy and emission spectrum of unknown water sample, calculate luminous quantum efficiency
Compared with standard working curve, so as to obtain the pH value of unknown water sample.
Compared with prior art, advantage of the invention is that：
Binuclear ruthenium Stability Analysis of Structures prepared by the present invention, there is certain water solubility, and with near-infrared luminous
Property.The complex has three imidazole rings, the property of ground state and excitation state can with imidazole group protonation or go matter
Sonization and change, the change for outside pH shows obvious spectral response so that ultraviolet-visible absorption spectroscopy and transmitting light
Spectral intensity strengthens or weakened, and absorbs peak position and emission peak positions and be moved, and the compound be it is near-infrared luminous,
Luminous quantum efficiency when drawing different pH is simple and convenient for detecting the pH of water sample as standard working curve, is easy to grasp
Make, and ensure that accuracy.
Brief description of the drawings
Fig. 1 is complex [(bpy)2Ru(HL1)Ru(H2L2)](ClO4)4Preparation method and structure.
Fig. 2 is complex [(bpy)2Ru(HL1)Ru(H2L2)](ClO4)4Protonated/deprotonated process.
Fig. 3 (a) is ultravioletvisible absorption light of the BR solution (3.75 μM) of complex in pH=0.2-2.4 under difference pH
Spectrogram, illustration are change of the absorption value with pH；Fig. 3 (b) is purple of the BR solution (3.75 μM) of complex in pH=2.4-8.0
Outer visible absorption spectra figure, illustration are change of the absorption value with pH；Fig. 3 (c) is the BR solution (3.75 μM) of complex in pH=
Ultraviolet-visible absorption spectroscopy figure during 8.0-11.4, illustration are change of the absorption value with pH.
Fig. 4 (a) is launching light spectrogram of the BR solution (3.75 μM) of complex in pH=0.2-3.8 under difference pH, is inserted
Figure is the change for launching peak intensity with pH；Fig. 4 (b) is transmitting of the BR solution (3.75 μM) of complex in pH=3.8-7.4
Spectrogram, illustration are the changes for launching peak intensity with pH.
Fig. 5 is change curve of the luminous quantum efficiency with pH, i.e. standard working curve.
Embodiment
Below by embodiment, the present invention is further described.
Embodiment 1：Complex [(bpy)2Ru(HL1)Ru(H2L2)](ClO4)4Preparation process：
(1) part H2L2According to document [Addison, A.W.；Burke, P.J.Heterocycl.Chem.1981,18,
803-805.] synthesis.
(2)[Ru(H2L2)Cl3] it is RuCl3·3H2O and part H2L2System is heated at reflux in ethanol according to 1: 1 mol ratio
.
(3) part HL1[Ru (bpy)2HL1](ClO4)2According to document [Zheng, Z.B.；Duan, Z.M.；Zhang,
J.M.；Wang, K.Z.Chromogenic and fluorogenic sensing properties toward cations
And anions by a terpyridine/phenylimidazo [4,5-f] phenanthroline hybrid.Sensors
Actuators B 2012,169,312 and Ze-Bao Zheng, Zhi-Ming Duan, Ying-Ying Ma, Ke-Zhi
Wang, Highly Sensitive and Selective Difunctional Ruthenium (II) ComplexBased
Chemosensor for Dihydrogen Phosphate Anion and Ferrous Cation,
Inorg.Chem.2013,52,2306-2316] synthesis.
(4) complex [(bpy)2Ru(HL1)Ru(H2L2)](ClO4)4Preparation, weigh [Ru (H2L2)Cl3] (0.0811g,
0.15mmol) it is distributed in 30 milliliters of ethylene glycol, when stirred under nitrogen atmosphere is heated to 100 DEG C, adds [Ru (bpy)2HL1]
(ClO4)2(0.161g, 0.15mmol), mixed solution continue 180 DEG C of heating reflux reactions 12 hours under nitrogen protection.Reaction
After end, treat that solution is cooled to room temperature, add saturation NaClO4The aqueous solution, there is reddish brown precipitation precipitation.Filter, wash, dry
Obtain crude product.Obtained crude product is passed through into silica gel column chromatography separating-purifying again, with V (): V (water): V (saturation KNO3
The aqueous solution): the elution of V (ammoniacal liquor)=40: 5: 1: 0.5 mixed solution, after revolving removes most of eluent, saturation is added dropwise
NaClO4The aqueous solution causes complex to separate out, and filters and uses acetonitrile/Diethyl ether recrystallization again after drying, obtain target product 108mg, produces
Rate is 43%.Elementary analysis C67H46N16Ru2·4ClO4·4H2O (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-4ClO4-H+]3+)(C67H45N16Ru2)3+, 319.0
([M-4ClO4]4+)(C67H46N16Ru2)4+
Hydrogen nuclear magnetic resonance spectrum δ/ppm (400MHz, DMSO-d6)：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 drafting of the measure and working curve of ultraviolet-visible absorption spectroscopy and emission spectrum during different pH
The acid base titration of complex is carried out in Britton-Robinson (abbreviation BR) cushioning liquid.BR bufferings are molten
Liquid is that have 0.04M glacial acetic acid, what 0.04M boric acid and 0.1M sodium chloride mixed.Sodium chloride is to keep the ion of system
Intensity, so as to reduce influence of the external environment to test.Prepare 40 milliliter 3.75 × 10-6Mol/L complex prepare liquid, is divided into
It is two parts, a to adjust pH with the concentrated sulfuric acid, determine Ph=0.2-2.0 ultravioletvisible absorption and emission spectrum.Another is with dense hydrogen
Sodium hydroxide solution adjusts pH, determines pH=2.0-7.0 ultravioletvisible absorption and emission spectrum (excitation wavelength lambdaex=505nm).
A data are determined at interval of 0.2 pH, the absorbance (at 505nm) of ultraviolet-visible absorption spectroscopy and transmitting when reading different pH
The integration luminous intensity of spectrum, luminous quantum efficiency is calculated, draw standard working curve.
Uv-visible absorption spectra determines on UV-2600 spectrophotometry instrument, is buffered with BR during measure molten
Liquid is as reference liquid.It can be seen from absorption spectrum, in pH=0.2-11.4 excursion, ultraviolet-visible absorption spectroscopy change
The continuous deprotonation process of three steps can be divided into：The first step such as Fig. 3 (a), pH are from during 0.2 rises to 2.4, at 347nm
Absworption peak be gradually increasing, and there is isobestic point at 411 and 512nm, this is attributed to part HL1The imidazole ring of upper protonation
Proton dissociation process.Shown in second step such as Fig. 3 (b), pH rises to 8.2 from 2.4, and ultraviolet-visible absorption spectroscopy is in 505nm
The absworption peak at place constantly declines and red shift is to 530nm, there is three isobestic points at 536,401 and 373nm, this process be by
Part H2L2On imidazole ring deprotonation caused by.Occur shown in the deprotonation of final step such as Fig. 3 (c) in pH=8.2-
11.4 sections, it is HL1On neutral imidazole ring deprotonation caused by.
Fluorescence emission spectrum determines on Cary Eclipse sepectrophotofluorometers, excitation wavelength 505nm, excite and
Transmite slit is 10nm.As seen from Figure 4, change of the emission spectrum of complex to pH is very sensitive, change procedure point
For two stages, and to be near-infrared luminous.Complex is hardly luminous during pH=1, with pH increase, intensity of emission spectra
Increase sharply, for peak position from 750nm blue shift to 721nm, in pH=3.8, intensity reaches maximum, and " off-on " (I is presentedpH4.0/
IpH1.0=15, ΦpH4.0/ΦpH1.0=5).Shown in second stage such as Fig. 4 (b), pH is during 3.8 rise to 12.0, excitation state
Proton on complex neutrality imidazole ring starts to dissociate, and the luminous intensity of complex starts to weaken, almost complete in pH=7.0
It is quenched entirely, " off-on " remitted its furys nearly 90%, and peak position has red shift (ΦpH7.0/ΦpH4.0=0.39).
Trying to achieve for luminous quantum efficiency is with tris (bipyridine) ruthenium [Ru (bpy)3]2+It is reference material (Φstd=0.028), survey dense
Spend for 1.0 × 10-6Mol/L [Ru (bpy)3]2+The ultraviolet-visible absorption spectroscopy and emission spectrum of the aqueous solution, read UV, visible light
Absorbance A at absorption spectrum 450nmstdWith the integrated intensity I of emission spectrumstd, according to formula (1)：
Φ=Φstd(Astd/A)(I/Istd) (1)
Φ and ΦstdThe respectively luminous quantum efficiency of determinand and reference material, A and AstdIt is that determinand and reference material excite
Absorbance at wavelength, I and IstdIt is the luminous integrated intensity of non-determinand and standard sample.
The integration of absorbance A and emission spectrum when reading different pH at complex ultraviolet-visible absorption spectroscopy 505nm is strong
I is spent, luminous quantum efficiency Φ during different pH is calculated according to formula.Using pH as abscissa, luminous quantum efficiency is ordinate, is painted
Standard working curve (Fig. 5) processed.As pH increases, complex phosphorescence, which opens the light, to be gradually " on ", and quantum efficiency is from 0.29 × 10-3
Gradually rise to 1.57 × 10-3, then gradually decrease to 0.62 × 10 again-3Left and right reaches balance.
Embodiment 3：Unknown water sample pH measure
Unknown water sample 23ml is taken, it is 0.1M to add sodium chloride to concentration thereto, keeps ionic strength to buffer phase one in BR
Cause.3ml is taken to add the water sample of superchlorination sodium as reference liquid, quantitative complex is added into remaining 20ml water samples makes its concentration be
3.75×10-6Mol/L, it is consistent with concentration during complex acid base titration.Survey the UV absorption and emission spectrum of water sample.
Trying to achieve for luminous quantum efficiency is with tris (bipyridine) ruthenium [Ru (bpy)3]2+It is reference material (Φstd=0.028), survey dense
Spend for 1.0 × 10-6Mol/L [Ru (bpy)3]2+The ultraviolet-visible absorption spectroscopy and emission spectrum of the aqueous solution, read UV, visible light
Absorbance A at absorption spectrum 450nmstdWith the integrated intensity I of emission spectrumstd, according to formula (1)：
Φ=Φstd(Astd/A)(I/Istd) (1)
Φ and ΦstdThe respectively luminous quantum efficiency of determinand and reference material, A and AstdIt is that determinand and reference material excite
Absorbance at wavelength, I and IstdIt is the luminous integrated intensity of non-determinand and standard sample.
The integrated intensity I of the absorbance A and emission spectrum at unknown water sample ultraviolet-visible absorption spectroscopy 505nm is read, from
And, according to standard curve, corresponding pH during the quantum yield can be read in the hope of the photoluminescence quantum yield of complex, so as to learn
The pH of unknown water sample.
Claims (2)
- A kind of 1. binuclear ruthenium [(H2L2)Ru(HL1)Ru(bpy)2](ClO4)4, wherein, part bpy, HL1And H2L2And Binuclear ruthenium cation [(H2L2)Ru(HL1)Ru(bpy)2]4+Structural formula it is as shown below：
- 2. purposes of the binuclear ruthenium described in claim 1 as phosphorescence pH sensors, it is characterised in that can be according to described double The luminous quantum efficiency of core ruthenium complex is ordinate, pH is that the standard working curve that abscissa is drawn tries to achieve unknown water sample pH。
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| CN106366131B (en) * | 2016-08-29 | 2018-10-23 | 北京师范大学 | Physiological pH senses the preparation method and application of binuclear ruthenium |
| 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 |
| 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 |
| 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 |
| CN110511249B (en) * | 2019-08-26 | 2020-10-30 | 北京师范大学 | Preparation and application of near-infrared luminescent 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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