CN110982515B

CN110982515B - Application of triphenylamine modified binaphthyl derivative

Info

Publication number: CN110982515B
Application number: CN201911127506.8A
Authority: CN
Inventors: 田梅; 张宏; 黄巧茜; 雷鸣
Original assignee: Zhejiang University ZJU
Current assignee: Zhejiang University ZJU
Priority date: 2019-11-18
Filing date: 2019-11-18
Publication date: 2020-10-16
Anticipated expiration: 2039-11-18
Also published as: CN110982515A

Abstract

The invention discloses an application of triphenylamine modified binaphthyl derivative. The compound capable of emitting fluorescence can selectively bind iron ions (Fe) at single site³⁺) Resulting in fluorescence quenching, therefore, the compounds can be used as fluorescent probes for detecting Fe³⁺The probe has high sensitivity and anti-interference characteristic and is easy to synthesize.

Description

Application of triphenylamine modified binaphthyl derivative

Technical Field

The invention relates to application of triphenylamine modified binaphthyl derivatives.

Background

A large number of fluorescent probes for ion and neutral analytes become powerful tools for environmental monitoring, biological research and disease diagnosis due to the characteristics of high sensitivity, good selectivity, fast response, simple synthesis, convenient operation and the like. In the past two decades, fluorescent probes have been developed rapidly by using various fluorophores as signal sources of fluorescent chemical sensors and according to the interaction between the host and the object and the reaction mechanisms such as protonation-deprotonation, complexation, redox reaction, formation and cleavage of covalent bonds, etc. From a photophysical perspective, analyte detection with fluorescence chemical sensors is typically accomplished by chelate-induced enhanced fluorescence (CHEF), Intramolecular Charge Transfer (ICT), light-induced electron transfer (PET), aggregation-induced emission (AIE), and the like.

Iron ion (Fe)³⁺) Is an abundant element and essential ion in human bodies and plants, and plays an important role in various biological processes. Fe³⁺Can lead to various functional disorders as well as insomnia, anemia, Alzheimer's disease, ParisParkinson's disease and other neurodegenerative diseases. Thus, Fe³⁺The selectivity and sensitivity of detection is very important. By introducing specific selective recognition groups and fluorescent groups, probe molecules with application potential can be synthesized. The binding site, fluorophore and mechanism of action are all factors to be considered. Design and Synthesis of Single binding site Fe in comparison with probes with multiple sites of action³⁺The probe strategy is simpler and more economical.

Electron donor-acceptor (D-a) type pi conjugated organic molecules are widely used in Organic Light Emitting Diodes (OLEDs) and solar cells. In addition, they also have potential utility in metal ion fluorescent probes, which may result in migration, enhancement or reduction of fluorescence. In recent years, Triphenylamine (TPA) and Binaphthyl (BINAP) have been widely used in the field of photoelectric materials due to their excellent electron donor and transport properties^[2-11]. TPA-functionalized twisted binaphthyl derivatives have good external quantum efficiency, and some also exhibit high glass transition temperature, good fluorescence quantum yield, excellent thermal stability and morphology stability in thin films, and thus can be used as hole transport layers and electroluminescent materials in OLEDs. In addition, based on hydrogen bonding, 7,7 '-bis (4-diphenylamino-phenyl) -1, 1' -binaphthol can selectively detect fluoride ions, resulting in a change in the spectrum. However, no relevant studies have been made on the use of TPA-bonded BINAP-type probes for the detection of iron ions.

In a TPA-bonded BINAP-type molecule, BINAP is an electron acceptor (a), TPA is a non-planar helical electron donor (D), and the N atom can serve as a binding site. Such a single binding site Fe³⁺The fluorescent probe is formed by N atom and Fe in TPA³⁺The interaction between the two leads to Electron Transfer (ET) and fluorescence quenching, thereby realizing high selectivity and high sensitivity for detecting Fe³ ⁺。

Reference documents:

[1]D.Wu,A.C.Sedgwick,T.Gunnlaugsson,E.U.Akkaya,J-Y.Yoon,T.D.James,Chem.Soc.Rev.2017,46,7105–7123.

[2]B.Daly,J.Ling,A.P.de Silva,Chem.Soc.Rev.2015,44,4203–4211.

[3]a)R.T.K.Kwok,C.W.T.Leung,J.W.Y.Lam,B.Z.Tang,Chem.Soc.Rev.2015,44,4228–4238；b)M.Gao,B.Z.Tang,ACS Sens.2017,2,1382–1399.

[4]S.R.Lynch,Nutr.Rev.1997,55,102–110.

[5]H.Sasabe,J.Kido,J.Mater.Chem.C 2013,1,1699–1707.

[6]a)Y.Zhou,Q.G.He,Y.Yang,H.Z.Zhong,C.He,G.Y.Sang,W.Liu,C.H.Yang,F.L.Bai,Y.F.Li,Adv.Funct.Mater.2008,18,3299–3306；b)Q.G.He,H.Z.Lin,Y.F.Weng,B.Zhang,Z.M.Wang,G.T.Lei,L.D.Wang,Y.Qiu,F.L.Bai,Adv.Funct.Mater.2006,16,1343–1348；c)X.Fan,Z.P.Li,D.D.Yao,Y.W.Zhang,H.Li,X.M.Liu,Y.Wang and Y.Mu,C.R.Chimie2014,17,1102–1108.

[7]C.-H.Chen,M.-kit Leung,Tetrahedron,2011,67,3924–3935.

disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a kind of easily synthesized single binding site Fe³⁺A fluorescent probe.

The specific technical scheme of the invention is as follows:

application of triphenylamine modified binaphthyl derivative, and the compound can be used as fluorescent probe for detecting iron ions Fe³⁺(ii) a Wherein the triphenylamine modified binaphthyl derivative is 6,6-TB-1, 6,6-TB-2, 7,7-TB-1, 7,7-TB-2 or 7,7-OMeTB-1, and the structural formula is as follows:

preferably, triphenylamine modified binaphthyl derivative is used as a fluorescent probe to detect iron ions Fe³⁺The method comprises the following steps:

will contain Fe³⁺Dropwise adding the solution to be detected into a triphenylamine modified binaphthyl derivative solution to enable Fe³⁺After the mixed solution is fully contacted with a sufficient amount of fluorescent probes, measuring the fluorescence emission spectrum of the mixed solution system; then calculating Fe in the solution to be detected according to a standard relation curve of the fluorescence intensity and the concentration of Fe3+³⁺And (4) concentration.

Further, the solution to be detectedContaining a single Fe³⁺Or contain Fe³⁺A plurality of metal ions therein; fluorescent probes capable of selectively binding Fe³⁺Resulting in fluorescence quenching.

Preferably, the triphenylamine modified binaphthyl derivative is 7, 7-OMeTB-1. Further, the fluorescent probe is directed to Fe³⁺Has a detection limit of 1.7 × 10^-7M。

Such a single binding site Fe³⁺The fluorescent probe is formed by N atom and Fe in TPA³⁺The interaction between the two leads to Electron Transfer (ET) and fluorescence quenching, thereby realizing the detection of Fe with high selectivity and sensitivity³⁺. These probes are directed to Fe in the presence of other common metal ions³⁺Shows a fluorescence quenching phenomenon with strong selectivity, and can improve the sensitivity of the probe by introducing an electron donor substituent on TPA, and the detection limit is 1.7 × 10^-7M～8.0×10^-7And M. Therefore, the probe provided by the invention has the characteristics of high sensitivity, interference resistance and easy synthesis.

Drawings

FIG. 1 is a nuclear magnetic hydrogen spectrum of Compound 1;

FIG. 2 is a nuclear magnetic carbon spectrum of Compound 1;

FIG. 3 is the nuclear magnetic hydrogen spectrum of Compound 3;

FIG. 4 is a nuclear magnetic carbon spectrum of Compound 3;

FIG. 5 shows the nuclear magnetic hydrogen spectrum of compound 6, 6-TB-1;

FIG. 6 is a nuclear magnetic carbon spectrum of compound 6, 6-TB-1;

FIG. 7 is the nuclear magnetic hydrogen spectrum of compound 6, 6-TB-2;

FIG. 8 is a nuclear magnetic carbon spectrum of compound 6, 6-TB-2;

FIG. 9 shows the nuclear magnetic hydrogen spectrum of compound 7, 7-TB-1;

FIG. 10 is the nuclear magnetic carbon spectrum of compound 7, 7-TB-1;

FIG. 11 is the nuclear magnetic hydrogen spectrum of compound 7, 7-TB-2;

FIG. 12 is the nuclear magnetic carbon spectrum of compound 7, 7-TB-2;

FIG. 13 is the nuclear magnetic hydrogen spectrum of compound 7, 7-OMeTB-1;

FIG. 14 is the nuclear magnetic carbon spectrum of compound 7, 7-OMeTB-1;

FIG. 15 is a graph of the fluorescence titration curves of iron ions for five compounds;

FIG. 16 shows the fluorescence intensity and Fe of five compounds³⁺A concentration dependence;

FIG. 17 is a fluorescent photograph of a selective assay for five compounds;

FIG. 18 is a bar graph of the selectivity test for five compounds;

FIG. 19 is a bar graph of the anti-interference test for five compounds;

FIG. 20 is a nuclear magnetic hydrogen spectrum map;

FIG. 21 is an ESR map;

FIG. 22 shows 7,7-TB-2 and FeCl₃Mass spectrum of the mixture;

FIG. 23 is an XPS map;

FIG. 24 shows the detection of Fe in a test solution by 7,7-TB-2³⁺Concentration;

FIG. 25 shows the detection of Fe in the solution to be detected by 7,7-OMeTB-1³⁺And (4) concentration.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.

By introducing specific selective recognition groups and fluorescent groups, probe molecules with application potential can be synthesized. Triphenylamine (TPA) and Binaphthyl (BINAP) are widely used in the field of photoelectric materials due to their good electron donor and transport characteristics. However, regarding triphenylamine-bonded binaphthyl derivatives as Fe³⁺There is no work on fluorescence quenching probes. We introduced TPA (electron donor) on BINAP (electron donor) and synthesized a series of selective detection Fe based on charge transfer induced fluorescence quenching³⁺The D-A-D type probe of (1). The series of TPA bonded BINAP probes 6,6-TB-1, 6,6-TB-2, 7,7-TB-1, 7,7-TB-2 and 7,7-OMeTB-1 react on Fe in the presence of other common metal ions³⁺Exhibits a fluorescence quenching phenomenon with strong selectivity and is obtained by introducing electricity to TPAThe substituent of the sub-donor can improve the sensitivity of the probe, and the detection limit is 1.7 × 10^-7And M. Fe is confirmed by analysis such as Nuclear Magnetic Resonance (NMR), Electron Spin Resonance (ESR), mass spectrum (MALDI-TOF-MS), X-ray photoelectron spectroscopy (XPS), etc³⁺Interaction with nitrogen atoms on TPA, Fe³⁺The formation of a complex with the probe leads to a fluorescence quenching phenomenon.

The following examples will aid in the understanding of the invention, but are not intended to limit the invention:

preparation of the Compound of example 1

(1) Synthesis of Compound 1

The synthetic route for compound 1 is shown below:

the specific synthetic procedure for compound 1 is as follows:

a250 mL round bottom flask was charged with 6-bromo-2-naphthol (5g,22.4mmol), FeCl₃·6H₂O (12.1g,44.8mmol) and distilled water (100 mL). After stirring the reaction at 60 ℃ for 24h, it was cooled to room temperature. Dichloromethane (DCM) was added to the reaction solution, and the organic phase was obtained by dissolving sufficiently and extracting the separated liquid. The obtained organic phase was treated with anhydrous Na₂SO₄Drying, filtering and distilling under reduced pressure to obtain a crude product. The crude product was further purified by silica gel column chromatography eluting with n-hexane and ethyl acetate (6: 1) to give a white solid in 74.3% yield (3.7g,8.3 mmol).

The white solid obtained was characterized by means of a nuclear magnetic resonance apparatus, the nuclear magnetic resonance hydrogen spectrum of which is shown in fig. 1:¹HNMR(400MHz,CDCl₃) 8.04(d, J ═ 1.6Hz,2H),7.88(d, J ═ 8.8Hz,2H), 7.40-7.35 (m,4H),6.96(d, J ═ 8.8Hz,2H),5.03(s,2H), the nmr spectrum of which is shown in fig. 2:¹³C NMR(100MHz,CDCl₃):153.0,131.9,130.9,130.7,130.6,130.4,125.9,119.0,118.0,110.6.

(2) synthesis of Compound 3

The synthetic route for compound 3 is shown below:

the synthetic procedure of compound 3 was similar to that of compound 1, using 7-bromo-2-naphthol as the starting material to give a white solid with a yield of 63.8%.

The white solid obtained was characterized by means of a nuclear magnetic resonance apparatus, the nuclear magnetic resonance hydrogen spectrum of which is shown in fig. 3:¹HNMR(400MHz,CDCl₃) 7.90(d, J ═ 9.2Hz,2H),7.73(d, J ═ 8.8Hz,2H), 7.47-7.44 (m,2H),7.33(d, J ═ 8.8Hz,2H),7.21(s,2H),5.04(s,2H), the nmr spectrum is shown in fig. 4:¹³C NMR(100MHz,CDCl₃):153.5,134.6,131.6,130.1,127.9,127.7,125.9,122.4,118.2,109.5.

(3) synthesis of Compound 6,6-TB-1

The synthetic route of compound 6,6-TB-1 is shown below:

the specific synthetic steps of the compound 6,6-TB-1 are as follows:

a250 mL round-bottom flask was charged with Compound 1(2.5g,5.6mmol), Compound 2(3.58g,12.4mmol), Pd (PPh)₃)₄(1.21g,1.0mmol)、K₂CO₃(7.79g,56.4mmol)、H₂O (20mL) and toluene (80 mL). Introducing nitrogen, stirring under reflux for two days, cooling to room temperature, pouring the reaction solution into water, extracting with DCM for three times, and collecting the organic phase with anhydrous Na₂SO₄Drying, filtering and distilling under reduced pressure to obtain a crude product. The crude product was further purified by silica gel column chromatography eluting with n-hexane and ethyl acetate (20: 1) to give a white solid in 82.1% yield with a melting point of 99-100 ℃.

The white solid obtained was characterized by nmr, and its nmr hydrogen spectrum is shown in fig. 5:¹HNMR(400MHz,CD₂Cl₂):8.15(d,J＝1.6Hz,2H),8.11(s,1H),8.08(s,1H),7.64–7.60(m,6H),7.46(s,1H),7.44(s,1H),7.34–7.29(m,8H),7.26(s,1H),7.24(s,1H),7.19–7.14(m,12H),710-7.06 (m,4H),5.24(s,2H) with a nmr thermogram as shown in fig. 6:¹³C NMR(100MHz,CD₂Cl₂):153.3,148.2,147.8,136.7,135.1,133.1,132.1,130.5,129.8,128.3,127.1,126.1,125.3,125.0,124.4,123.6,118.8,111.7,100.6.

(4) synthesis of Compound 6,6-TB-2

The synthetic route for compound 6,6-TB-2 is shown below:

the specific synthetic steps of the compound 6,6-TB-2 are as follows:

a100 mL round-bottom flask was charged with compound 6,6-TB-1(1g,3.9mmol), diiodomethane (1.38g,5.2mmol), K₂CO₃(1.07g,7.7mmol) and acetone (50 mL). Introducing nitrogen, stirring at 90 deg.C for 12 hr, cooling to room temperature, pouring the reaction solution into water, extracting with DCM for three times, and collecting the organic phase with anhydrous Na₂SO₄Drying, filtering and distilling under reduced pressure to obtain a crude product. The crude product was further purified by silica gel column chromatography eluting with n-hexane and ethyl acetate (4: 1) to give a white solid with a yield of 70.9% and a melting point of 148-.

The white solid obtained was characterized by means of a nuclear magnetic resonance apparatus, the nuclear magnetic resonance hydrogen spectrum of which is shown in fig. 7:¹HNMR(400MHz,CD₂Cl₂) 8.16(s,2H),8.07(s,1H),8.05(s,1H), 7.66-7.62 (m,4H),7.59(s,4H),7.53(s,1H),7.51(s,1H), 7.31-7.26 (m,8H), 7.17-7.12 (m,12H), 7.07-7.03 (m,4H),5.71(s,2H), the NMR spectrum of which is shown in FIG. 8:¹³C NMR(100MHz,CD₂Cl₂):151.9,148.2,148.0,137.5,134.8,132.8,131.6,131.1,129.9,128.4,127.8,126.5,125.9,125.8,125.1,124.4,123.6,122.0,103.9.

(5) synthesis of Compound 7,7-TB-1

The synthetic route of compound 7,7-TB-1 is shown below:

the procedure for the synthesis of the compound 7,7-TB-1 was similar to that of the compound 6,6-TB-1, using the

compounds

2 and 3 as the starting materials, giving a white solid with a yield of 72.3% and a melting point of 172-.

The white solid obtained was characterized by nmr, and its nmr hydrogen spectrum is shown in fig. 9:¹HNMR(400MHz,CD₂Cl₂) 8.01(s,1H),7.99(s,1H),7.97(s,1H),7.95(s,1H),7.63(d, J ═ 1.6Hz,1H),7.61(d, J ═ 1.6Hz,1H), 7.37-7.28 (m,8H), 7.24-7.20 (m,8H), 7.05-6.95 (m,16H),5.20(s,2H), whose nmr carbon spectrum is shown in fig. 10:¹³C NMR(100MHz,CD₂Cl₂):153.8,148.1,147.9,140.1,135.2,134.4,131.7,129.8,129.6,129.1,128.5,125.0,124.2,123.9,123.6,121.7,118.1,111.7.

(6) synthesis of Compound 7,7-TB-2

The synthetic route of compound 7,7-TB-2 is shown below:

the procedure for the synthesis of compound 7,7-TB-2 was similar to that of compound 6,6-TB-2, giving a white solid with a yield of 64.2% and a melting point of 242-243 ℃.

The white solid obtained was characterized by nmr, and its nmr hydrogen spectrum is shown in fig. 11:¹HNMR(400MHz,CD₂Cl₂) 8.01(d, J ═ 8.4Hz,4H),7.77(s,2H),7.72(d, J ═ 1.6Hz,1H),7.70(d, J ═ 1.6Hz,1H),7.49(s,1H),7.47(s,1H), 7.22-7.19 (m,12H), 7.02-6.98 (m,12H), 6.92-6.88 (m,4H),5.73(s,2H), whose nmr carbon spectrum is shown in fig. 12:¹³C NMR(100MHz,CD₂Cl₂):152.4,148.1,147.8,138.8,135.1,132.9,131.4,130.6,129.8,129.6,128.4,126.7,125.1,125.0,124.6,124.0,123.6,121.4,103.9.

(7) synthesis of Compound 7,7-OMeTB-1

The synthetic route for compound 7,7-OMeTB-1 is shown below:

the procedure for the synthesis of compound 7,7-OMeTB-1 was similar to that of compound 6,6-TB-1, using

compounds

3 and 4 as starting materials to give a green solid with a yield of 57.5% and a melting point of 169-.

The white solid obtained was characterized by nmr, and its nmr hydrogen spectrum is shown in fig. 13:¹HNMR(400MHz,CDCl₃) 7.95(s,1H),7.93(s,1H),7.91(s,1H),7.89(s,1H),7.59(d, J ═ 1.6Hz,1H),7.57(d, J ═ 1.6Hz,1H),7.34(s,1H),7.31(d, J ═ 3.7Hz,4H),7.21(d, J ═ 8.4Hz,4H),7.01(d, J ═ 8.8Hz,8H),6.84(d, J ═ 8.4Hz,4H), 6.80-6.77 (m,8H),5.13(s,2H),3.76(s,12H), and its nuclear magnetic carbon resonance spectrum is shown in fig. 14:¹³C NMR(100MHz,CDCl₃):155.87,153.11,148.24,140.69,139.86,133.73,132.54,131.10,128.83,128.25,127.80,126.62,123.47,121.00,120.38,117.31,114.65,110.92,55.46.

the compound prepared in this example has the formula:

the 6,6-TB-1, 6,6-TB-2, 7,7-TB-1, 7,7-TB-2 or 7,7-ome TB-1 prepared in this example is applied to examples 2 to 6 to show the specific technical effects thereof, and the preparation methods and structural formulas of the compounds are described in this example and are not described again.

Example 2 iron ion titration experiment and detection Limit calculation

Prepare 250mL 2 × 10 with volumetric flask^-5The THF solution of M probe is precisely 10mL each time by pipette, and 20uL of 0-40equiv FeCl is added during stirring₃Stirring the aqueous solution for 3min to allow the probe to contact with Fe³⁺After sufficient exposure, the fluorescence emission spectra of the respective solutions were determined.

As shown in FIG. 15, Fe was added³⁺Can reduce fluorescence intensity until fluorescence quenching, and can observe different Fe under 365nm ultraviolet lamp³⁺Fluorescent response of probe solution at concentration and in timeAnd (6) recording the photographed image. Wherein, in 6,6-TB-1 THF solution, Fe is added³⁺Increasing the amount from 0 to 40 equivalents, the fluorescence intensity dropped sharply and a slight red shift appeared. And for 7,7-OMeTB-1, 15 equivalents of Fe³⁺The solution fluorescence can be completely quenched. This phenomenon is probably due to the methoxy group having an electron donating effect, increasing the electron cloud density of the TPA donor, thus promoting Fe³⁺Interaction with the binding site.

Increase Fe in sequence³⁺Concentration of (0-8 × 10)^-4M) measurement of the fluorescence intensity, which can be used to calculate the Fe for each probe in THF³⁺LOD of 3SD/S according to the LOD calculation formula, the LOD values of 6,6-TB-1, 6,6-TB-2, 7,7-TB-1, 7,7-TB-2 and 7,7-ome TB-1 were 7.6 × 10, respectively^-7M，6.9×10^-7M，7.9×10^-7M，8.0×10^-7M and 1.7 × 10^-7And M. By plotting fluorescence intensity versus Fe³⁺The slope (S) and correlation coefficient (R2) were obtained from the concentration dependence (fig. 16). The Standard Deviation (SD) was calculated from 10 background measurements. 7,7-OMeTB-1 in Fe due to the electron donating effect of the methoxy group³⁺The highest sensitivity was shown in the detection of (2). .

Example 3 Selective testing experiment

To evaluate probe selectivity, we tested the fluorescent response of the probe with various metal ions, 250mL 2 × 10 was prepared in a volumetric flask^-5The THF solution of M probe is precisely 10mL each time by using a pipette, and 15 equivalents or 40 equivalents of different metal ions (Fe) are respectively added during stirring³⁺，K⁺，Mg²⁺，Na⁺，Ni²⁺，Co²⁺，Ca²⁺，Al³⁺，Ba²⁺，Mn²⁺，Cr³⁺，Cu² ⁺，Cd²⁺，Pd²⁺And Zn²⁺) And measuring the fluorescence emission spectrum of the corresponding solution after fully stirring. Under a 365nm ultraviolet lamp, the fluorescent response condition is recorded by observing and photographing in time (figure 17). In order to observe the influence of various metal ions on the fluorescence intensity of the solution more intuitively, the F/F is used₀As ordinate (F is the fluorescence of the solution after addition of the respective metal ionLight intensity, F₀Fluorescence intensity of the solution without any added ions) was plotted for comparative study (fig. 18). The results show that only Fe³⁺The fluorescence intensity of the solution can be sharply reduced by adding the metal ions, and the addition of other metal ions does not cause obvious influence. This indicates that these fluorescent probes are directed against Fe³⁺Has good selectivity.

Example 4 anti-interference test experiment

To further evaluate these probes for Fe³⁺In the presence of various metal ions (K) we tested⁺，Mg²⁺，Na⁺，Ni²⁺，Co²⁺，Ca²⁺，Al³⁺，Ba²⁺，Mn²⁺，Cr³⁺，Cu²⁺，Cd²⁺，Pd²⁺And Zn²⁺) The interference resistance of the probe in the case of (2). As shown in FIG. 19, for 6,6-TB-1, 6,6-TB-2, 7,7-TB-1 and 7,7-TB-2, the histograms show the change in fluorescence of the probes without any addition of ions and after addition of 40 equivalents of each metal ion, respectively, and the histogram shows the addition of 20 equivalents of Fe to the above solution³⁺Fluorescence of the rear probe changes. It is known that Fe is present in a large amount even if a large amount of interfering ions are present³⁺The fluorescence of the probe solution can be weakened as before, which indicates that the probe is in the presence of Fe³⁺Has good competitiveness in the sensing process. In addition, since 7,7-OMeTB-1 has the highest detection sensitivity, only 15 equivalents of interfering ions and 7 equivalents of Fe were added to 7,7-OMeTB-1³⁺Test research is carried out, and the result also proves that the probe is used for treating Fe under the condition that other common metal ions exist³⁺Is not disturbed.

Example 5 analysis of complexation mechanism

The mechanism of the single-site interaction between the probe and the iron ion is demonstrated by taking the compound 7,7-TB-2 as an example.

(1) Nuclear magnetic hydrogen spectrum control experiment:

taking a 7,7-TB-2 probe sample, dissolving in deuterated dichloromethane, measuring nuclear magnetic hydrogen spectrum by using BRUKER ADVANCE DMX 400(400M), and then adding trace FeCl into the solution₃Measuring nuclear magnetic hydrogen spectrum again, twice before and afterSpectra were compared (fig. 20). By contrast, we found that the nuclear magnetic hydrogen spectrum of the mixture is broad and shifted, which is consistent with the effect of paramagnetic iron. In the presence of FeCl₃After that, the hydrogen peak area on TPA is shifted from 6.89-6.96 ppm to 7.15-7.35 ppm, which is in contrast to Fe³⁺And the interaction between the N atoms.

(2) Electron Spin Resonance (ESR) test experiment:

7,7-TB-2 with FeCl₃The mixture was sampled by mixing FeCl₃THF solution with 7,7-TB-2 (FeCl)₃:7, 7-TB-2 ═ 1: 1) mixing, and rotary evaporating to remove solvent. ESR measurement was performed using an ESRA-300 electron spin resonance spectrometer from BRUKER, Inc., under a nitrogen atmosphere at room temperature. A new signal peak was observed on the EPR spectrum of the mixture, indicating that the probe and Fe³⁺There is electron transfer therebetween (fig. 21).

(3) Mass Spectrometry (MALDI-TOF-MS) test experiment:

mixing 7,7-TB-2 with FeCl₃Sample of the mixture (FeCl)₃:7, 7-TB-2 ═ 1: 1) dissolving in ethanol, mixing by ultrasonic wave, and analyzing and detecting. The complex 7,7-TB-2-FeCl was observed on the MALDI-TOF-MS spectrum₃Isotopic peaks of (a): 984.1m/z (+ K) (FIG. 22), demonstrating the formation of the complex.

(4) Photoelectron Spectroscopy (XPS) test experiments

7,7-TB-2 with FeCl₃Sample of the mixture (FeCl)₃7,7-TB-2 ═ 1: 1) preparation method as described above, samples were irradiated with Al K α (1486.6eV) as an ion source under conditions of a voltage of 15KV and a current of 12mA, and data were collected, and binding energy correction was performed with C1s (284.8eV) whose surface was not contaminated as a standard.

With FeCl₃And 7,7-TB-2 as a control, XPS for 7,7-TB-2 and FeCl₃The electronic structure and chemical state of the elements of interest in the mixture were studied, and the results are shown in fig. 23. With FeCl₃In contrast, the mixture Fe2p_3/2Peak sum Fe2p_1/2The binding energy of the peak is reduced by 1.36 eV; the peak binding energy of mixture N1s was increased by 0.41 compared to 7,7-TB-2eV, while the binding energy of O1s remains almost unchanged. Fe. The relative change in the electronic structure of the N element indicates Fe³⁺And N, revealing that the N atom in the TPA donor is Fe³⁺Thereby causing fluorescence quenching of the probe.

Example 6 detection of iron ion concentration

(1) And (3) preparing a standard curve: adding a ferric ion solution with a standard concentration into a probe solution (the operation method is the same as that of the ferric ion titration experiment and detection limit calculation in the example 2), recording the addition amount of the ferric ion solution and the fluorescence intensity of each solution, determining the relation between the ferric ion concentration and the fluorescence intensity, and making a standard curve;

(2) adding the solution to be detected containing iron ions into the probe solution with the same concentration as that in the step (1), and recording the fluorescence intensity (the intensity value with the wavelength of 340 nm) of the solution;

(3) and calculating the concentration of iron ions in the solution to be detected according to the standard curve.

To evaluate the accuracy of the standard curve, we formulated 1 × 10^-4Adding the iron ion solution to be tested of M into the 7,7-TB-2 probe solution, measuring the fluorescence intensity of 419.0 (figure 24), and substituting the standard curve y into-4.75 × 10⁶x +876.5, calculated as iron ion concentration 9.64 × 10^-5We also formulated 1 × 10^-4The test solution of iron ion M was added to the 7,7-OMeTB-1 probe solution, and the fluorescence intensity was measured to be 402.4 (FIG. 25), and the standard curve y was substituted with-5.24 × 10⁶x +927.0, calculated as iron ion concentration 1 × 10^-4And M. The above results demonstrate that the detection method is reliable. The following table lists the standard curve function for 5 probes.

Probe needle	Standard curve
			6,6-TB-1	y＝-3.9×10⁶x+781.9
6,6-TB-2	y＝-4.37×10⁶x+901.2
		7,7-TB-1	y＝-3.9×10⁶x+781.9
7,7-TB-2	y＝-4.75×10⁶x+876.5
		7,7-OMeTB-1	y＝-5.24×10⁶x+927.0

The above examples are merely illustrative of the preferred embodiments of the present invention and any obvious variations and modifications which would occur to persons skilled in the art without departing from the spirit of the invention are to be considered as part of the present invention.

Claims

1. The application of triphenylamine modified binaphthyl derivative is characterized in that the triphenylamine modified binaphthyl derivative is used as a fluorescent probe to detect iron ions Fe³⁺The triphenylamine modified binaphthyl derivative is 6,6-TB-1, 6,6-TB-2, 7,7-TB-1, 7,7-TB-2 or 7,7-OMeTB-1, and the structural formula is as follows:

2. the use of triphenylamine-modified binaphthyl derivative according to claim 1, wherein the triphenylamine-modified binaphthyl derivative is used as a fluorescent probe for detecting iron ions Fe³⁺The method comprises the following steps:

will contain Fe³⁺Dropwise adding the solution to be detected to triphenylamine modification unitIn solution of naphthalene derivative, Fe³⁺After the mixed solution is fully contacted with a sufficient amount of fluorescent probes, measuring the fluorescence emission spectrum of the mixed solution system; then according to the fluorescence intensity and Fe³⁺Calculating Fe in the solution to be detected according to a standard relation curve of concentration³⁺And (4) concentration.

3. Use of triphenylamine-modified binaphthyl derivative according to claim 2, wherein the solution to be detected contains Fe alone³⁺Or contain Fe³⁺A plurality of metal ions therein; fluorescent probes capable of selectively binding Fe³⁺Resulting in fluorescence quenching.

4. The use of a triphenylamine-modified binaphthyl derivative according to claim 1, wherein the triphenylamine-modified binaphthyl derivative is 7, 7-OMeTB-1.

5. Use of triphenylamine-modified binaphthyl derivative according to claim 4, wherein the fluorescent probe is Fe³⁺Has a detection limit of 1.7 × 10^-7M。