CN104877672A - Two-photon fluorescent probe for identifying palladium (0) and preparation method and application of two-photon fluorescent probe - Google Patents

Abstract

The invention discloses a two-photon fluorescent probe for quickly identifying metal palladium and a preparation method and application of the two-photon fluorescent probe in an environment, belongs to the field of organic small-molecule fluorescent probes. The probe is called GCTPOC-Pd for short, and the chemical structural formula is shown as the formula (I). The synthesis process of the probe comprises only two steps, and the aftertreatment process is relatively simple and easy to operate. According to the two-photon fluorescent probe for identifying palladium (0) and the preparation method and application of the two-photon fluorescent probe, the selective and quick detection on metal palladium is realized, the selectivity is good, and the resistance to interference of other metal ions is high, therefore, the probe can serve as a simple, quick and sensitive specific detection reagent for metal palladium, and has a broad application prospect in the field of biological molecule detection.

Description

A kind ofly identify two-photon fluorescence probe of zeroth order palladium and its preparation method and application

Technical field

The present invention relates to two-photon fluorescence probe of a kind of quick identification heavy metal palladium and preparation method thereof and application in the environment, belong to organic molecule fluorescent probe field.

Background technology

In recent years, along with a large amount of uses of palladium in the catalytic conversion agent and organic catalyst compound of medicine, daily living article, tail gas, the impact about palladium ion environmental pollution and HUMAN HEALTH causes numerous scientists and pays close attention to widely.Research shows: palladium ion can affect their normal physiological functions in vivo in cell containing the amino acid of sulfydryl, protein (casein, fibroin and part enzyme), DNA and other biomacromolecule are combined, thus toxic side effect is produced to human body, destroy normal physiological mechanism.Existing a lot of country strictly limits palladium ion at present, such as: the maximum of food absorption palladium must not higher than 1.5-15 μ g/sky/people.Therefore, study and to palladium ion, there is sensitivity and the strong detection method of selectivity has very important practical significance.

Traditional palladium ion detection method mainly contains: plasma body-mass spectrum, atomic absorption, electrochemical analysis, Catalytic Spectrophotometric Determination and analytical photometry etc., in recent years along with the development of organic molecule fluorescent probe shows distinctive character gradually, such as: highly sensitive, easy and simple to handle, favorable reproducibility, membrane permeability is good, the many merits such as in situ detection, organic molecule fluorescent probe is made day by day to become the indispensable research means in the field such as modern life science and medical diagnosis on disease, be applied to Various Complex biology more and more, metal ion detection in environmental sample and imaging analysis.Therefore, the organic molecule fluorescent probe of Development of Novel is applied in the detection of heavy metal and has stronger using value.

The current palladium ion fluorescent probe of comprehensive analysis all belongs to one-photon excitation, it mainly has the following disadvantages: first, detect in organic solvent or containing in the component of organic solvent to improve the most of heavy metal palladium probe of selectivity, the practicality of environment measuring is reduced greatly; The second, the detection of heavy metal palladium probe is all carry out according to the change of a certain specific wavelength, easily by the interference of extraneous factor; 3rd, most heavy metal palladium probe is all excite under shorter wavelength to the identification of palladium in cell, is difficult to realize long-wavelength excitation.Therefore, the two-photon fluorescence probe of the detection heavy metal palladium of Development of Novel, above shortcoming can be avoided completely, there is significant advantage, such as: dark-field imaging, near infrared excite, avoid fluorescent bleach and photic poison, determine target activation, high-resolution three-dimensional imaging and darker penetration into tissue etc.To having important researching value and scientific meaning with the detection of palladium ion in environment in vivo.

Summary of the invention

For the deficiencies in the prior art, the invention provides a kind of two-photon fluorescence probe identifying zeroth order palladium.

Present invention also offers a kind of preparation method identifying the two-photon fluorescence probe of zeroth order palladium.

Present invention also offers a kind of application identifying the two-photon fluorescence probe of zeroth order palladium.

The present invention is by the following technical solutions:

Identify a two-photon fluorescence probe for zeroth order palladium, this probe be called for short GCTPOC-Pd, its chemical structural formula as shown in the formula (I):

。

The preparation method of the two-photon fluorescence probe of above-mentioned identification zeroth order palladium, it is characterized in that, it comprises the following steps:

1) by 2 of 1.0eq; it is in the mixed solvent of 1:1 that the pimelinketone of 4-Dihydroxy benzaldehyde, 2.5 eq, the DABCO of 1.5eq add water/dioxane volume ratio under nitrogen atmosphere; nitrogen protection, 100 DEG C of reflux, react 2 days; by TCL plate detection reaction; after reacting completely, concentrated, column chromatography; can obtain compound GCTPOC, its structural formula is as follows:

；

2) GCTPOC of 1.0 eq is dissolved in DCM, then stir at the triethylamine adding 1.2 eq is placed on 0 DEG C, 1.2eq allyloxycarbonyl chlorine dropwise adds in above-mentioned solution, and reaction 5h, by TCL plate detection reaction, after reacting completely, be extracted with ethyl acetate, anhydrous sodium sulfate drying, concentrated, column chromatography, can obtain probe GCTPOC-Pd.

The synthetic route of above-mentioned GCTPOC-Pd is as follows:

The application of the two-photon fluorescence probe of described identification zeroth order palladium, is characterized in that, the content sensing that can be applied to Heavy Metals in Water Environment palladium detects; Described sensing detection is mainly fluoroscopic examination.

Advantage of the present invention: 1) synthesis of probe only needs two steps, and last handling process is relatively simple, easy handling; 2) present invention achieves the selectivity rapid detection of heavy metal palladium, and selectivity is good, other metal ion disturbance abilities anti-are strong.In addition, under general ultraviolet lamp (365 nm), can observe fluorescence color change equally, be a kind of two-photon fluorescence probe with the sensing function that adds lustre to.Based on its specificity and significant colour-change, this reagent can be used as the specificity indicator that in the display aqueous solution, heavy metal palladium exists, and can carry out real-time qualitative and the detection of quantitative visual colorimetry.So the present invention is a kind of simple, and fast, the specific detection agents of sensitive heavy metal palladium, has broad application prospects in biomolecule detection field.

Accompanying drawing explanation

Fig. 1 is the high resolution mass spectrum figure of probe GCTPOC-Pd;

Fig. 2 is the changing conditions that add fluorogram of probe GCTPOC-Pd with heavy metal palladium;

Fig. 3 is the changing conditions of probe GCTPOC-Pd to the fluorogram of differential responses time;

Fig. 4 is the selectivity histogram data of probe GCTPOC-Pd to different metal lewis' acid, wherein 1. none; 2. Pd ²⁺+ PPh ₃; 3. K ⁺; 4. K ⁺+ Pd (0); 5. Co ²⁺; 6. Co ²⁺+ Pd (0); 7. Fe ³⁺; 8. Fe ³⁺+ Pd (0); 9. Zn ²⁺; 10. Zn ²⁺+ Pd (0); 11. Fe ²⁺; 12. Fe ²⁺+ Pd (0); 13. Ni ²⁺; 14. Ni ²⁺+ Pd (0); 15. Mg ²⁺; 16. Mg ²⁺+ Pd (0); 17. Cu ²⁺; 18. Cu ²⁺+ Pd (0); 19. Cu ⁺; 20. Cu ⁺+ Pd (0); 21. Ca ²⁺; 22. Ca ²⁺+ Pd (0); 23. Al ³⁺; 24. Al ³⁺+ Pd (0);

Fig. 5 is probe GCTPOC-Pd solution adds front and back solution colour change in heavy metal palladium;

Fig. 6 is the change of probe GCTPOC-Pd solution fluorescence color after heavy metal palladium adds front and back solution ultra violet lamp.

Embodiment

Below in conjunction with specific embodiments and the drawings, the present invention is described in further detail.

embodiment 1

The synthesis of two-photon fluorescence probe GCTPOC-Pd

10 mmol 2,4-Dihydroxy benzaldehydes, 25 mmol pimelinketone, 15 mmol DABCO are added (60 mL, 1:1, v/v) in water/dioxane mixed solvent, nitrogen protection, 100 DEG C of reflux under nitrogen atmosphere, reacts 2 days.By TCL plate detection reaction, after reacting completely, concentrated, column chromatography, can obtain compound GCTPOC, and productive rate is 15%.

0.2 mmol GCTPOC is dissolved in DCM (5.0 mL), add under 0.24 mmol triethylamine is placed on zero degrees celsius and stir, 0.24 mmol allyloxycarbonyl chlorine (AllocC) is dropwise added in above-mentioned solution, reacts 5 h, by TCL plate detection reaction, after reacting completely, be extracted with ethyl acetate, anhydrous sodium sulfate drying, concentrated, column chromatography, obtains probe GCTPOC-Pd, productive rate 80%. ¹h NMR (400 MHz, CDCl ₃) δ=7.41 (d, j=2.2,1H), 7.24 (d, j=8.3,1H), 6.81 (dd, j=8.3,2.3,1H), 6.76 (d, j=2.1,1H), 6.05-5.96 (m, 1H), 5.47-5.34 (m, 2H), 5.04 (m, 1H), 4.75 (td, j=5.9,1.2,2H), 2.63-2.56 (m, 1H), 2.52-2.46 (m, 1H), 2.44-2.35 (m, 1H), 2.14-2.06 (m, 1H), 2.03-1.95 (m, 1H), 1.77-1.65 (m, 1H). HRMS (ESI) m/z calcd for C ₁₇h ₁₇o ₅[M] ⁺: 301.0998; The high resolution mass spectrum of this probe of found 301.1068. is shown in Fig. 1.

embodiment 2

Probe GCTPOC-Pd is with the change adding the increase fluorogram of equivalent of heavy metal Pd (0)

GCTPOC-Pd fluorescent probe prepared by Example 1 is dissolved in acetonitrile, makes 1mmol/L storing solution.From storing solution, take out 30 μ L join in the middle of the centrifuge tube of 5 mL, add Pd (the 0) (Pd (OAc) of different equivalent (0-10 equiv) ₂: PPh ₃=1:1) standardized solution, use MeOH/H ₂o (1:1, v/v) is diluted to 3 mL (10 μMs), with 450 nm for exciting light measures its photoluminescent property.Fluorescence spectrum is as shown in Fig. 2.As seen from Figure 2, the increase fluorescence that the photoluminescence peak of GCTPOC-Pd two-photon fluorescence probe solution adds equivalent along with palladium metal strengthens gradually, and maximum enhancing can reach 130 times.

embodiment 3

Probe GCTPOC-Pd is to the change of time dependent fluorogram

From embodiment 2, in fluorescent probe storing solution, take out 30 μ L join in the middle of the centrifuge tube of 5 mL, add Pd (0) (Pd (OAc) ₂: PPh ₃=1:1) (10 equiv) standardized solution, use MeOH/H ₂o (1:1, v/v) is diluted to 3 mL (10 μMs), with 450 nm for exciting light measures its photoluminescent property.Fluorescence spectrum is as shown in Fig. 3.As seen from Figure 3, the photoluminescence peak of GCTPOC-Pd two-photon fluorescence probe solution strengthens gradually along with its fluorescence of prolongation of time, finds that when 6 min, fluorescence intensity reaches maximum, achieves the rapid detection of palladium metal.

embodiment 4

Probe GCTPOC-Pd is to the selectivity of differing molecular or ion

From embodiment 2, take out 30 μ L in fluorescent probe storing solution joins in the middle of the centrifuge tube of 2 5mL respectively, wherein one adds competition metal ion standardized solution, another is except adding competition metal ion standardized solution, add Pd (0) standardized solution of equimolar amount again, use MeOH/H ₂o (1:1, v/v) 3 mL (10 μMs) are diluted to, the fluorescence emission spectrum change of solution is detected after 6 min, can be found by Fig. 4, the fluorescence of other metal ions on compound GCTPOC-Pd does not almost affect, and adding of Pd (0) solution makes the fluorescence of compound GCTPOC-Pd significantly strengthen.

embodiment 5

GCTPOC-Pd fluorescent probe is to the Visual retrieval of Pd (0)

From embodiment 2, take out 100 μ L in fluorescent probe storing solution joins in the middle of the sample hose of 5mL, add excessive Pd (0) standardized solution as shown in Figure 5, Pd (0) can make the DMF solution of compound GCTPOC-Pd fluorescent probe that obvious colour-change occurs, and solution colour becomes light yellow from colourless.Send bright yellow fluorescence (Fig. 6) along with Pd (0) the induced fluorescence probe of macroscopic under ultraviolet lamp (365nm), explanation is a kind of fluorescent probe with the sensing function that adds lustre to.

Claims (3)

1. identify a two-photon fluorescence probe for zeroth order palladium, its chemical structural formula as shown in the formula (I):

。

2. identify a preparation method for the two-photon fluorescence probe of zeroth order palladium described in claim 1, it is characterized in that, it comprises the following steps:

1) by 2 of 1.0 eq; it is in the mixed solvent of 1:1 that the pimelinketone of 4-Dihydroxy benzaldehyde, 2.5 eq, the DABCO of 1.5 eq add water/dioxane volume ratio under nitrogen atmosphere; nitrogen protection, 100 DEG C of reflux, react 2 days; by TCL plate detection reaction; after reacting completely, concentrated, column chromatography; can obtain compound GCTPOC, its structural formula is as follows:

；

2) GCTPOC of 1.0 eq is dissolved in DCM, then stir at the triethylamine adding 1.2 eq is placed on 0 DEG C, 1.2eq allyloxycarbonyl chlorine dropwise adds in above-mentioned solution, and reaction 5h, by TCL plate detection reaction, after reacting completely, be extracted with ethyl acetate, anhydrous sodium sulfate drying, concentrated, column chromatography, can obtain probe GCTPOC-Pd.

3. an application for the two-photon fluorescence probe of identification zeroth order palladium according to claim 1, is characterized in that, the content sensing that can be applied to Heavy Metals in Water Environment palladium detects; Described sensing detection is mainly fluoroscopic examination.