CN102660253A

CN102660253A - Pyrazoline derivative Ni<2+> fluorescence probe and application thereof

Info

Publication number: CN102660253A
Application number: CN2012100581585A
Authority: CN
Inventors: 葛燕青; 段桂运; 曹晓群; 陈红余; 王建武
Original assignee: Taishan Medical University
Current assignee: Taishan Medical University
Priority date: 2012-03-07
Filing date: 2012-03-07
Publication date: 2012-09-12
Anticipated expiration: 2032-03-07
Also published as: CN102660253B

Abstract

The invention discloses a pyrazoline derivative Ni<2+> fluorescence probe and application thereof. The probe is 5-(2-thiophene)-3-(2-benzimidazole)-1-(2-pyridine) pyrazoline with a chemical structural formula as shown in formula (1). The fluorescence probe provided by the invention has special fluorescence selectivity for the Ni<2+>, relatively high sensitivity and relatively strong anti-interference capability to other ions in an ethanol solution and possesses great application prospects.

Description

A kind of pyrazoline derivative class Ni 2+Fluorescent probe and application thereof

Technical field

The present invention relates to organic molecule fluorescent probe field, relate in particular to a kind of Ni ²⁺Fluorescent probe 5-(2-thiophene)-3-(2-benzoglyoxaline)-1-(2-pyridine) pyrazoline and application thereof.

Background technology

Pyrazoline derivative is because of it has good blue emission, high quantum yield and hole transport efficient, often is used to detect the research of the fluorescent probe or the chemical sensor of metals ion behind the structural modification.

Ni ²⁺Can form complex compound with amino acid, polypeptide, phosphoric acid salt and nucleic acid etc., in many physiological processs, bring into play important effect, for example the catalytic activity of many enzymes is just relevant therewith.But organism is considerably less to its requirement, and excessive absorption tends to cause various diseases, like dermatitis, allergy even cancer.Simultaneously; Nickel has a wide range of applications in fields such as electroplating industry, Ni-Cd battery, pottery, welding, dyestuff, surgery and dental prosthesis; Acute or the chronic poisoning form of its potential is prone to cause environmental pollution and harm humans healthy; Therefore, the qualitative and detection by quantitative of nickel ion in the human body or in the environment is become the field that chemists are in recent years paid special attention to.

Summary of the invention

To the deficiency of prior art, the problem that the present invention solves provides a kind of pyrazoline derivative class Ni ²⁺Fluorescent probe and application thereof.

Technical scheme of the present invention is: a kind of pyrazoline derivative class Ni ²⁺Fluorescent probe: 5-(2-thiophene)-3-(2-benzoglyoxaline)-1-(2-pyridine) pyrazoline, its chemical structural formula is suc as formula shown in (1):

The present invention also comprises pyrazoline derivative class Ni ²⁺The application of fluorescent probe, formula (1) compound in small molecular alcohol solution to Ni ²⁺Unique fluorescence selectivity is arranged.

The present invention comprises that also described small molecular alcohol is an ethanol.

The present invention also comprises pyrazoline derivative class Ni ²⁺The compound method of fluorescent probe in alkaline ethanol solution, was under refluxad reacted cinnamophenone and 2-pyridine hydrazine 3.5-5 hour according to 1:3-1:5, obtained 5-(2-thiophene)-3-(2-benzoglyoxaline)-1-(2-pyridine) pyrazoline.

The ethanolic soln of preparation 5-(2-thiophene)-3-(2-benzoglyoxaline)-1-(2-pyridine) pyrazoline adds quantitative CrCl respectively ₃6H ₂O, MnCl ₂4H ₂O, FeCl ₃6H ₂O, CoCl ₂6H ₂O, NiCl ₂6H ₂O, HgCl ₂, ZnCl ₂, CuCl ₂2H ₂O, CdCl ₂2H ₂O, AgNO ₃Ethanolic soln; Test through fluorescence spectrum and to study different metal ionic selectivity, survey its fluorescent emission wave spectrum Strength Changes and find: 5-according to the invention (2-thiophene)-3-(2-benzoglyoxaline)-1-(2-pyridine) pyrazoline is that formula (1) compound is to Ni ²⁺Unique fluorescence selectivity is arranged, add 2 normal Ni ²⁺After, compound 1 at the 460nm place fluorescence intensity cancellation about 85.5%, simultaneously, fluorescence quantum yield is by not adding Ni ²⁺The time 0.26 be reduced to 0.037, as shown in Figure 1.Therefore, 5-(2-thiophene)-3-(2-benzoglyoxaline)-1-(2-pyridine) pyrazoline is as Ni ²⁺Fluorescent probe has huge application.

The invention provides a kind of pyrazoline derivative class Ni ²⁺Fluorescent probe, experiment proof formula according to the invention (1) compound can with Ni ²⁺With stoichiometric ratio 1:1 complexing, the fluorescent quenching effect owing to transition metal in the complexing process reduces the part fluorescence quantum yield greatly in ethanolic soln.Thus susceptible of proof formula according to the invention (1) compound in ethanolic soln to Ni ²⁺There are unique fluorescence selectivity, higher sensitivity to reach stronger anti-other ion interference ability, have great application prospect.

Description of drawings

Fig. 1: formula (1) compound (10 ^-6M) fluorescence intensity in the ethanolic soln behind the different metal ion of adding equivalent changes histogram, and ordinate zou is a light intensity among Fig. 1.

Fig. 2: formula (1) compound (10 ^-6M) carry out Ni in the ethanolic soln ²⁺Fluorometric titration figure.Intensity is a light intensity among the figure, and Wavelength is a wavelength, and eq is a multiple.

Fig. 3: formula (1) compound (10 ^-6M) and the Ni of equivalent ²⁺Fluorescence intensity in the ethanolic soln of coexistence behind other metals ion of adding equivalent changes histogram.

Embodiment

Embodiment 1: the synthetic schemes of formula (1) compound is shown below:

Figure DEST_PATH_725303DEST_PATH_IMAGE002

Concrete synthesis step is following:

In containing 0.254g cinnamophenone 1.0 mmol and 15 mL alcoholic acid, 50 mL round-bottomed flasks, add 0.131 gram 2-hydrazino pyridine 1.2 mmol and 0.12g NaOH3.2 mmol, mixing solutions is heated to backflow, reacts 4 hours.After the TLC detection reaction is accomplished, be chilled to room temperature, add 10 mL cold water, have a large amount of solids to separate out after transferring to neutrality with Hydrogen chloride, decompress filter, filter cake is washed successively, and ethanol is washed, and re-crystallizing in ethyl acetate gets the 0.18g gray solid, productive rate 52.2%.

Fusing point test: mp:146-149 ° C;

Infrared measurement: IR (KBr, cm ^-1): 1639.9,1619.2,1596.6,1472.0,1438.1,1364.8,1134.1,1084.2,764.8,745.7;

Nuclear magnetic resonance hydrogen spectruming determining: ¹H NMR (400 MHz, CD ₃OD): δ 8.07 (d, J=4.2 Hz, 1H), 7.58 (m, 1H), 7.48-7.14 (m; 6H), and 6.97-6.86 (m, 3H), 5.76 (dd, J=6.6; 12.3 Hz, 1H), 4.12 (dd, 1H, J=12.3; 18.0 Hz), 3.59 (dd, 1H, J=6.6,18.0 Hz).

Embodiment 2:

To formula (1) compound (10 ^-6M) add 2 normal Cr in the ethanolic soln respectively ³⁺, Mn ²⁺, Fe ³⁺, Co ²⁺, Ni ²⁺, Cu ²⁺, Zn ²⁺, Cd ²⁺, Hg ²⁺And Ag ⁺After, survey its fluorescent emission wave spectrum Strength Changes and find: formula (1) compound is to Ni ²⁺Unique fluorescence selectivity is arranged, add 2 normal Ni ²⁺After, compound 1 at the 460nm place fluorescence intensity cancellation about 85.5%, simultaneously, fluorescence quantum yield is by not adding Ni ²⁺The time 0.26 be reduced to 0.037, as shown in Figure 1.

Embodiment 3:

In formula (1) compound (10 ^-6M) and 2 normal Ni ²⁺Ethanolic soln in add 2 normal Cr respectively ³⁺, Mn ²⁺, Fe ³⁺, Co ²⁺, Ni ²⁺, Cu ²⁺, Zn ²⁺, Cd ²⁺, Hg ²⁺And Ag ⁺After, survey its fluorescent emission wave spectrum Strength Changes and find: formula (1) compound is to Ni ²⁺Fluorescence select that other ion is had stronger immunity from interference, as shown in Figure 3.

Claims

1. pyrazoline derivative class Ni ²⁺Fluorescent probe is characterized in that: it is 5-(2-thiophene)-3-(2-benzoglyoxaline)-1-(2-pyridine) pyrazoline, and its chemical structural formula is suc as formula shown in (1):

。

2. the described pyrazoline derivative class of claim 1 Ni ²⁺The application of fluorescent probe.

3. pyrazoline derivative class Ni according to claim 2 ²⁺The application of fluorescent probe is characterized in that: formula (1) compound in small molecular alcohol solution to Ni ²⁺Unique fluorescence selectivity is arranged.

4. pyrazoline derivative class Ni according to claim 2 ²⁺The application of fluorescent probe is characterized in that: described small molecular alcohol is an ethanol.

5. the said pyrazoline derivative class of claim 1 Ni ²⁺The compound method of fluorescent probe is characterized in that: in alkaline ethanol solution, cinnamophenone and 2-pyridine hydrazine were under refluxad reacted 3.5-5 hour according to 1:3-1:5, obtain 5-(2-thiophene)-3-(2-benzoglyoxaline)-1-(2-pyridine) pyrazoline.