CN107991273A - A kind of imdazole derivatives class mercury ion and sulphion relay fluoroscopic examination and application method - Google Patents

Abstract

The present invention relates to a kind of relay fluoroscopic examination Hg²⁺And S^2–The foundation of method.The present invention is to solve the existing fluoroscopic examination of relay in aqueous Hg²⁺And S^2–Fluorescence probe it is few, to Hg²⁺Easily by Au during identification³⁺,Fe²⁺And Fe³⁺The problem of influence.Adjacent benzene 23 (1 amyl group benzimidazole) antifebrin chloride [L] of probe 1,4 of the present invention can be with Hg in HEPES aqueous solutions²⁺Stable complex compound is formed, makes L fluorescent quenchings；In the range of pH value is 2.0 ~ 11.3, which can be used for Hg²⁺Detection, fluorescence property stablize；Hg²⁺Detection limit can reach 4.0 × 10^–7mol/L.Compound [L Hg²⁺] can also realize to S^2–Fluoroscopic examination, therefore, the probe can be realized in aqueous to Hg²⁺And S^2–Relay fluoroscopic examination, this will have huge application prospect in fields such as environmental science, analytical chemistry, life sciences.

Description

A kind of imdazole derivatives class mercury ion and sulphion relay fluoroscopic examination and application method

Technical field

The present invention relates to a kind of relay fluoroscopic examination mercury ion (Hg²⁺) and sulphion (S^2–) method foundation.

Background technology

In the past few decades, ion identification in the key effect of biology, environment and chemical field because causing people Greatly concern.Although in the past it has been reported that many selectivity fluorescence probes, can be achieved on the multi-functional of relay identification Fluorescence probe is relatively fewer.Therefore, it is very significant to develop recyclable, inexpensive and high performance relay identification fluorescence probe 's.

Novel probe of the exploitation with Selective recognition toxic heavy metal ion and anion is increasingly subject to people Concern.The article that Mehdi Amirnasr in 2016 et al. are published on Sensors and Actuators B《A fluorescent carboxamide ligand, having combined ionophore/fluorophore moieties, exhibiting “On-Off” switching toward Zn²⁺ion》It is related to Zn²⁺Detection.In addition Also some researchers have reported that some are to Cu²⁺, Fe³⁺And Cr³⁺Deng the report of cation detection.Hyun Yong Jo in 2015 et al. exist The article published on Inorganic Chemistry Communications《A colorimetric Schiff base chemosensor for CN^–by naked-eye in aqueous solution》It is related to CN^–Detection.In addition with Researcher reports some to F^–, AcO^–, H₂PO₄ ^–And HPO₄ ^2–Deng the report of Anionic recognition.Hg is the heavy metal of toxicity maximum One of element, because mercury element and mercury ion can be converted into methyl mercury by bacterium in the environment, then passes through food chain Biological accumulation.Due to its acidophilus property in protein and enzyme, it causes the function of brain, kidney, stomach and central nervous system to hinder Hinder.Hydrogen sulfide（H₂S）It is prevalent in environmental and biological materials, its existence form is mainly S^2–And HS^–Deng.S^2–In human body Content is excessive, can make a big impact to person's physiological processes, including digestive system, central nervous system and internal system Deng.Therefore, Hg in aqueous solution how is detected²⁺And S^2–Content become research work a vital task.

The identification Hg reported at present²⁺Probe still detect in a solvent mostly, selectivity it is not high, easily by Au³⁺、Fe²⁺ And Fe³⁺Influence.Such as the article that Ceren Canturk et al. are published on RSC Advances《A BODIPY- based fluorescent probe for the differential recognition of Hg(II) and Au (III) ions》It is accomplished that fluorescence probe detects Hg²⁺And Au³⁺, it is impossible to single detection Hg²⁺；Kaushik Ghosh et al. exist The article published on Eurjic European Journal of Inorganic Chemistry《A Simple Fluorescent Probe Derived from Naphthylamine for Selective Detection of Hg^II, Fe^II and Fe^III Ions in Mixed Aqueous Media: Applications in Living Cells and Logic Gates》It is accomplished that fluorescence probe detects Hg²⁺、Fe²⁺And Fe³⁺, it is impossible to single detection Hg²⁺；Yutao Yang et al. The article published on Sensors and Actuators B《Highly selective relay recognition of hydrogen sulfide and Hg(II) by a commercially available fluorescent chemosensor and its application in bioimaging》It is accomplished that the mixing in dimethyl sulfoxide (DMSO) and water To Hg in solution²⁺And HS^–Relay fluoroscopic examination；Ramesh C.Gupta et al. are on Sensors and Actuators B The article published《An efficient Hg²⁺ ensemble based on a triazole bridged anthracene and quinoline system for selective detection of cyanide through fluorescence turn-off-on response in solution and live cell》It is accomplished that in tetrahydrochysene furan Mutter with the mixed solution of water to Hg²⁺And CN^–Relay fluoroscopic examination；Richa Goel et al. are in Sensors and The article published on Actuators B《Naphthalimide based chromofluorescent sensor and DNA intercalator: Triggered by Hg²⁺/ HSO₄ ^–cleavage reaction》It is accomplished that molten in methanol To Hg in liquid²⁺And HSO₄ ^–Relay fluoroscopic examination；K.Muthu Vengaian et al. are in Sensors and Actuators B On the article published《Phenothiazine-diaminomalenonitrile based Colorimetric and Fluorescence “Turn-off-on” Sensing of Hg²⁺ and S^2–》It is accomplished that the mixed solution in second alcohol and water In to Hg²⁺And S^2–Relay fluoroscopic examination.Can high selectivity relay fluorescence in aqueous the present invention relates to one kind has been synthesized Detect Hg²⁺And S^2–A kind of imidazole derivatives species fluorescent molecular probe, and in aqueous to Hg²⁺With stronger single choosing The fluorescent quenching of selecting property identifies that recognition effect is good, and detection limit is low.Based on Hg²⁺The probe of ionic complex, itself and H₂After S is combined, gold Belong to ion and S^2–Form precipitation（HgS）, the fluorescence of probe molecule recovers, and then realizes probe in aqueous to Hg²⁺And S^2–'s Relay fluoroscopic examination.This will have huge application prospect in fields such as environmental science, analytical chemistry, life sciences.

The content of the invention

The present invention is to solve the existing fluoroscopic examination of relay in aqueous Hg²⁺And S^2–Fluorescence probe it is few, to Hg^{2 +}Easily by Au during identification³⁺, Fe²⁺And Fe³⁺The problem of influence, so as to provide a kind of imidazole derivatives species Hg²⁺And S^2–Relay fluorescence Detection and application method

Imidazole derivatives species fluorescence probe 1,4- neighbour benzene two -3- (1- amyl groups benzimidazole) antifebrin chloride of the present invention [L], its structural formula are：

Hg is tested using the method for the present invention²⁺, using HEPES as buffer solution, the solvent of buffer solution is deionized water, energy The single detection Hg of high selectivity²⁺, from other metal ions in aqueous solution（Al³⁺, Zn²⁺, Ag⁺, Ca²⁺, Mg²⁺, Fe^{3 +}, Pb²⁺, Na⁺, Ba²⁺, Ni²⁺, K⁺, Cu²⁺, Cr³⁺, Cd²⁺, Co²⁺）Interference, there is stronger antijamming capability. PH value is that the probe can be used in Hg in the range of 2.0 ~ 11.3²⁺Detection, fluorescence property stablize.Detection is limited to 4.0 × 10^–7 mol/L.Based on Hg²⁺The probe of ionic complex, it is possible to achieve relay fluoroscopic examination S in aqueous^2–.In conclusion this hair Bright has the technical effect that obviously, and provides a kind of environmentally protective, and detection is simple and quick, high selectivity relay is glimmering Light detects Hg²⁺And S^2–Method.

The imidazole derivatives species fluorescence probe of the present invention can relay fluoroscopic examination Hg in aqueous²⁺And S^2–, there is high answer With value.

Brief description of the drawings

Fig. 1 is two -3- of 1,4- neighbour's benzene (1- amyl groups benzimidazole) antifebrin chloride [L] fluorescence probe of embodiment 1 To the fluorescence emission spectrogram of compound of different cations.

Fig. 2 is two -3- of 1,4- neighbour's benzene (1- amyl groups benzimidazole) antifebrin chloride [L] of embodiment 2 different Hg²⁺Fluorescence spectrum variation diagram during concentration.

Fig. 3 is the other common metal ions and Hg of embodiment 3²⁺During competition, Isosorbide-5-Nitrae-two -3- of neighbour's benzene (1- amyl group benzo miaows Azoles) antifebrin chloride [L] change in fluorescence figure.

Fig. 4 is 5 [L-Hg of embodiment²⁺] fluorescence probe is to the fluorescence emission spectrogram of compound of different anions.

Fig. 5 is that embodiment 8 is separately added into Hg into L²⁺And S^2–, circulate 5 obtained figure of fluorescence intensity changes.

Embodiment

Embodiment 1

Solvent is made with the HEPES buffer solutions of pH=7.4, measured concentration is 1.0 × 10^–5The L solution of mol/L is common to 16 kinds The fluorescence emission spectrum of cation.16 kinds of cations of 6.0 equiv. are added into L solution（Al³⁺, Zn²⁺, Ag⁺, Ca^{2 +}, Mg²⁺, Fe³⁺, Hg²⁺, Pb²⁺, Na⁺, Ba²⁺, Ni²⁺, K⁺, Cu²⁺, Cr³⁺, Cd²⁺, Co²⁺）Solution, only 6.0 equiv. Hg²⁺L fluorescence can be made to occur significantly to be quenched, amplitude is quenched as 83%.In contrast, other metal ions only cause very Small change.Show, fluorescence probe L of the invention is to Hg²⁺With single selection fluorescent detection features.Wherein：Ordinate represents Fluorescence intensity, abscissa represent wavelength of fluorescence.

Embodiment 2

Solvent is made with the HEPES buffer solutions of pH=7.4, by various concentrations（0~11.0 equiv.）Hg²⁺It is added to 1.0 × 10^–5In the L solution of mol/L, the result of variations of its fluorescence emission spectrum is observed.With Hg²⁺The increase of concentration, L is in 370 nm The fluorescence intensity at place gradually reduces, and the above results show L to Hg²⁺With higher sensitiveness.Wherein：Ordinate represents that fluorescence is strong Degree, abscissa represent wavelength of fluorescence.

Embodiment 3

It is 1.0 × 10 in concentration^–515 kinds of cations of 12.0 equiv. are added in the L solution of mol/L（Al³⁺, Zn²⁺, Ag⁺, Ca²⁺, Mg²⁺, Fe³⁺, Pb²⁺, Na⁺, Ba²⁺, Ni²⁺, K⁺, Cu²⁺, Cr³⁺, Cd²⁺, Co²⁺）Solution, shakes up rear quiet 5min is put, is then separately added into 6.0 equiv. Hg again²⁺Solution, shakes up.The above-mentioned 15 kinds of cations of 6.0 equiv. are added in L Fluorescence intensity and the fluorescence intensity of L approach.As above-mentioned 15 kinds of cations and Hg²⁺Coexist, and cation concn is Hg²⁺Concentration 2 times when, disturb L to Hg²⁺Detection, system still has obvious fluorescent quenching to respond, shows L to Hg²⁺Detection have Excellent interference free performance, can be used as a kind of detection Hg²⁺Fluorescent quenching type probe.Wherein：Ordinate represents fluorescence intensity, horizontal Coordinate representation species of metal ion, (0) blank, (1) Al³⁺, (2) Zn²⁺, (3) Ag⁺, (4) Ca²⁺, (5) Mg²⁺, (6) Fe³⁺, (7) Pb²⁺, (8) Na⁺, (9) Ba²⁺, (10) Ni²⁺, (11) K⁺, (12) Cu²⁺, (13) Cr³⁺, (14) Cd²⁺, (15) Co²⁺。

Embodiment 4

It is 1.0 × 10 by concentration^–5The L aqueous solutions of mol/L and contain 6.0 equiv. Hg²⁺ L aqueous solutions nitric acid or hydrogen Sodium hydroxide solution adjusts pH value, measures change of the solution fluorescence intensity with pH value.Compare what two fluorescence intensities changed with pH value Curve, it is known that pH scopes are at 2.0 ~ 11.3, Hg²⁺With L-shaped into stable complex, solution fluorescence is caused to occur significantly to be quenched.I.e. L can be realized in the range of wider pH, to Hg under the conditions of particularly physiological environment pH 7.35 ~ 7.45²⁺ Recognition detection.

Embodiment 5

After identification is quenched in selectivity, [L-Hg is studied using fluorescence spectrum²⁺] in water（HEPES, pH=7.4）To 18 kinds in solution Anion（I^–, Cl^–, Br^–, F^–, HCO₃ ^–, CO₃ ^2–, SO₃ ^2–, HSO₃ ^–, SO₄ ^2–, NO₃ ^–, NO₂ ^–, HPO₄ ^2–, H₂PO₄ ^–, BrO₃ ^–, SCN^–, AcO^–, PO₄ ^3–, S^2–）Relay capabilities of fluorescence detection.In compound [L-Hg²⁺] (1.0× 10^–5Mol/L above-mentioned 18 kinds of anion of 6.0 equiv., only 6.0 equiv. S) are added in solution^2–It can recover completely To main body L fluorescent values.In contrast, other anion only cause the change of very little.Due to S^2–Go to grab Hg²⁺Formed and stablized HgS compounds, cause the release of probe L.Obviously, compound [L-Hg²⁺] can be in relay fluoroscopic examination as a kind of glimmering Light probe, for bioanalysis.Wherein：Ordinate represents fluorescence intensity, and abscissa represents wavelength of fluorescence.

Embodiment 6

In the HEPES buffer solutions of pH=7.4, by various concentrations（0~10.0 equiv.）S^2–It is added to 1.0 × 10^–5 [the L-Hg of mol/L²⁺] in solution, observe the result of variations of its fluorescence emission spectrum.With S^2–The increase of concentration, [L-Hg²⁺] Fluorescence intensity gradually strengthens, until adding 6.0 equiv. S^2–, fluorescence intensity returns to the fluorescent value of main body L.

Embodiment 7

It is 1.0 × 10 in concentration^–5[the L-Hg of mol/L²⁺] anion of 12.0 equiv. is added in solution（I^–, Cl^–, Br^–, F^–, HCO₃ ^–, CO₃ ^2–, SO₃ ^2–, HSO₃ ^–, SO₄ ^2–, NO₃ ^–, NO₂ ^–, HPO₄ ^2–, H₂PO₄ ^–, BrO₃ ^–, SCN^–, AcO^–, PO₄ ^3–）Solution, stands 5 min after shaking up, be then separately added into 6.0 equiv. S again^2–Solution, shakes up.When above-mentioned 17 Kind anion and S^2–Coexist, and anion concentration is S^2–At 2 times of concentration, [L-Hg is not disturbed²⁺] to S^2–Detection, show [L-Hg²⁺] to S^2–Detection there is excellent interference free performance.

Embodiment 8

It is 1.0 × 10 in concentration^–5The L solution of mol/L, Hg²⁺And S^2–Concentration is 6.0 equiv., measures its fluorescence intensity. Successively Hg is added into L solution²⁺And S^2–, circulation obtain for 5 times fluorescence intensity be respectively 247.3,47.2,247.0,52.2, 238.0、50.2、231.1、49.0、222.2、50.0、216.0.Show L to Hg²⁺Identification has invertibity.Wherein：Ordinate table Show fluorescence intensity, abscissa represents cycle-index.

Embodiment 9

In the HEPES buffer solutions of pH=7.4, by various concentrations（0~11.0 equiv.）Hg²⁺It is added to 1.0 × 10^–5 In the L solution of mol/L, the change of its fluorescence emission spectrum is observed.With Hg²⁺The increase of concentration, the fluorescence intensity of L gradually drop It is low, Hg²⁺For concentration at 0-1.0 μM, fluorescence intensity is to Hg²⁺It is in a linear relationship, linear equation for Y=238.1331- 93.2289X (linearly dependent coefficient：R²=0.9949)；To blank sample carry out 20 parallel determinations, by 3 σ/K(σ is zero standard Deviation,KFor the slope of regression equation), calculate detection and be limited to 4.0 × 10^–7mol/L.This is the result shows that probe L can height Sensitive qualitative detection Hg²⁺。

Claims (1)

1. A kind of 1. imidazole derivatives species Hg²⁺And S^2–Relay fluoroscopic examination and application method, it is characterised in that：With pH=7.4 HEPES aqueous solutions are alternately added Hg as buffer solution in probe solution²⁺And S^2–, can make fluorescence intensity that invertibity occur Change.Two -3- of fluorescence probe 1,4- neighbour benzene (1- amyl groups benzimidazole) antifebrin chloride [L] of the present invention can be with Hg²⁺Shape Into stable complex compound, realize to Hg²⁺Fluorescent quenching detection, and from other metal ion (Al³⁺, Zn²⁺, Ag⁺, Ca²⁺, Mg²⁺, Fe³⁺, Pb²⁺, Na⁺, Ba²⁺, Ni²⁺, K⁺, Cu²⁺, Cr³⁺, Cd²⁺, Co²⁺) interference；It is in pH value In the range of 2.0 ~ 11.3, which can be used in Hg²⁺Detection, fluorescence property stablize, detection be limited to 4.0 × 10^–7 mol/L。 Compound [L-Hg²⁺] can also realize to S^2–Relay fluoroscopic examination.