CN116789660A - 1, 8-naphthalimide derivative, preparation method thereof and application thereof as Hg 2+ Application of colorimetric probe and fluorescent switch - Google Patents

Abstract

The application discloses a 1, 8-naphthalimide derivative, a preparation method thereof and a preparation method thereof as Hg ²⁺ And (3) reacting the BBN compound with 2-aminothiazole to obtain the 1, 8-naphthalimide derivative by using a colorimetric probe and a fluorescent switch. The application designs and synthesizes a novel 1, 8-naphthalimide derivative (BBNS) with an aminothiazole structure at the 4-position. BBNS can recognize Hg in multiple channels ²⁺ : not only can colorimetric detection of Hg in solution ²⁺ But also can be made into test paper type portable sensor for naked eye recognition Hg ²⁺ Also can be used as a response range to reach the picomolar level of hypersensitive Hg ²⁺ And (3) a fluorescent switch.

Description

1, 8-naphthalimide derivative, preparation method thereof and application thereof as Hg 2+ Application of colorimetric probe and fluorescent switch

Technical Field

The application belongs to the new material technology, in particular to a 1, 8-naphthalimide Hg ²⁺ Colorimetric probes and fluorescent switches and methods of making the same.

Background

Hg ²⁺ Is a toxic material which is concerned withHeavy metal ions, and sensitive and accurate detection of Hg ²⁺ Is critical to the environment and human health. The fluorescent probe is widely applied to heavy metal ion detection due to good selectivity, high sensitivity, simple operation and in-situ real-time use. 1, 8-naphthalimide derivatives are an important heavy metal ion fluorescent probe, wherein Hg ²⁺ Fluorescent probes are very active. The prior art reports a disulfide bond-linked 1, 8-naphthalimide dimer fluorescent probe against Hg ²⁺ The detection range of (2) is 0-150 mu M, and the detection limit is 0.38 mu M; the prior art reports a 1, 8-naphthalimide fluorescent probe with thiosemicarbazide group at C-4 position of naphthalene ring, and the probe is used for Hg ²⁺ The detection range of (2) is 18-40 mu M, and the detection limit is 0.138 mu M; the prior art reports a photocrosslinked solid fluorescent sensing film containing 1, 8-naphthalimide for Hg in aqueous solutions ²⁺ Is performed on Hg ²⁺ The detection range of (2) is 0-400 mu M, and the detection limit is 2.5 mu M; the prior art reports a fluorescent probe of the analog type 1, 8-naphthalimide type for Hg in acetonitrile/water (1:1, v/v, pH=7.0, HEPES buffer) ²⁺ The detection range of (2) is 0-100 mu M, and the detection limit is 17.4 nM; the prior art reports a Schiff base type 1, 8-naphthalimide Hg ²⁺ Fluorescent probe for Hg ²⁺ The detection range of (2) is 50-400 nM, and the detection limit is 0.16 mu M.

The existing 1, 8-naphthalimide Hg ²⁺ Fluorescent probes are used for detecting Hg in solution ²⁺ Few portable sensors can be made; hg for existing probe pair ²⁺ The response range of (2) is generally between micro-molar and nanomolar, and the fluorescence performance of the probe is along with Hg ²⁺ The concentration is increased gradually over a wide range. At very narrow Hg ²⁺ Fluorescence properties with Hg in the concentration range ²⁺ The concentration change has surging property, and the response concentration reaches picomolar level of 1, 8-naphthalimide Hg ²⁺ Fluorescent switches are not reported.

Disclosure of Invention

The application synthesizes a novel multichannel Hg through two-step reaction ²⁺ Colorimetric and fluorescent probes which can colorimetrically detect Hg in solution ²⁺ But also can be made into test paper type toiletNaked eye Hg identification of portable sensor ²⁺ Also can be used as the hypersensitive Hg of the picomolar concentration response range ²⁺ And (3) a fluorescent switch.

The application adopts the following technical scheme:

a1, 8-naphthalimide derivative has the chemical structural formula as follows:

the application discloses a preparation method of the 1, 8-naphthalimide derivative, which comprises the step of reacting a BBN compound with 2-aminothiazole to obtain the 1, 8-naphthalimide derivative. Preferably, the reaction is carried out in the presence of a noble metal catalyst, an inorganic base, an organic ligand, and a solvent. Further preferably, the noble metal catalyst comprises a palladium catalyst, preferably an inorganic palladium catalyst; inorganic bases include cesium salts, potassium salts, sodium salts, and the like, preferably carbonates; the organic ligands include phosphine ligands, preferably phenylphosphine containing; the solvent is an organic solvent such as DMF.

In the present application, the reaction is carried out under an inert gas such as nitrogen at a temperature of 100 to 150 ℃, preferably 110 to 130 ℃, for a time of 1 to 5 hours, preferably 2 to 4 hours.

In the application, the molar ratio of BBN compound, 2-aminothiazole, noble metal catalyst, inorganic base and organic ligand is 1:1-2:0.1-0.3:1-2:0.3-0.65.

The application discloses the 1, 8-naphthalimide derivative as the Hg preparation ²⁺ Use of colorimetric probes, preferably in solution as Hg ²⁺ Use of colorimetric probes.

The application discloses the 1, 8-naphthalimide derivative as the Hg preparation ²⁺ Application of fluorescent switches.

The application discloses Hg ²⁺ A detection sensor comprising the above 1, 8-naphthalimide derivative and a substrate; the 1, 8-naphthalimide derivative is adsorbed on a substrate. The substrate is a conventional product such as filter paper and the like; the specific adsorption operation (mode) is conventional technologyAnd (5) performing surgery.

The application discloses a method for detecting Hg in liquid ²⁺ The method of (2) comprises the steps of mixing the above 1, 8-naphthalimide-type derivative with a detection liquid according to A ₅₂₅ /A ₄₃₅ Is used for detecting Hg in liquid ²⁺ Qualitative and quantitative analysis of (2); or mixing the above 1, 8-naphthalimide derivative with a detection liquid, and detecting Hg in the liquid according to the fluorescence intensity at 550 nm ²⁺ Qualitative and quantitative analysis of (2); or dripping the detection liquid on a sensor containing the 1, 8-naphthalimide derivative, and detecting Hg in the liquid according to the color change of the sensor ²⁺ Qualitative and quantitative analysis of (c).

Positive effects and advantages compared with the prior art:

(1) The application designs and synthesizes a novel 1, 8-naphthalimide derivative with a higher yield than similar products in literature;

(2) Realize the detection of Hg by one probe in multiple channels ²⁺ (Hg can be detected colorimetrically in solution) ²⁺ Can also be made into a portable sensor for identifying Hg ²⁺ Can also be used as Hg ²⁺ A fluorescent switch);

(3) Can be made into test paper type portable sensor for naked eye recognition of Hg ²⁺ ；；

(4) As Hg ²⁺ The picomolar hypersensitive response Hg can be achieved when the fluorescent switch is used ²⁺ ；

(5) The detection and identification process has good selectivity, sensitivity and strong anti-interference capability;

(6) For Hg ²⁺ Is fast and reversible.

Drawings

FIG. 1 is a schematic diagram of the synthesis of the 1, 8-naphthalimide derivative BBNS, the chemical structural formula of BBN compound and the chemical structural formula of BBNS according to the application.

FIG. 2 is an ultraviolet-visible absorption spectrum of BBNS before and after adding 17 metal ions, where a is the absorption spectrum and b is the ratio of the absorbance of BBNS solution at 525 nm and 435 nm; solvent: DMSO/H ₂ O (10/90, v/v); concentration: BBNS of 10. Mu.M, metal ion100. Mu.M.

FIG. 3 is Hg ²⁺ Ultraviolet-visible absorption spectrum of BBNS at concentration of 0-100 μm (a), ratio A of absorbance of BBNS at 525 nm to 435 nm ₅₂₅ /A ₄₃₅ With Hg ²⁺ A linear plot (b) of concentrations of 0, 1, 3, 5, 7, 9, 10, 11, 13, 15, 17, 19, 20 μm; solvent: DMSO/H ₂ O (10/90, v/v); concentration: BBNS is 10. Mu.M.

FIG. 4 is a coexisting metal ion pair BBNS-Hg ²⁺ In DMSO/H ₂ The ratio A of the maximum absorbance at 525 nm to 435 nm in O (10/90, v/v) ₅₂₅ /A ₄₃₅ Is a function of (1); concentration: BBNS is 10. Mu.M, and each metal ion is 20. Mu.M.

FIG. 5 is BBNS-Hg ²⁺ In DMSO/H ₂ The ratio A of the absorbance at 525 nm to 435 nm in O (10/90, v/v) ₅₂₅ /A ₄₃₅ Is a time response of (2); concentration: BBNS of 10. Mu.M, hg ²⁺ 20. Mu.M.

FIG. 6 is a chart of indicating Hg with BBNS test paper ²⁺ A photograph of the concentration; BBNS concentration of 0.265, 2.65, 13.25 mg/g, hg from left to right ²⁺ The concentration was 0, 1, 10, 100, 1000. Mu.M.

FIG. 7 is a graph of fluorescence emission spectra of BBNS solutions before and after addition of 17 metal ions; solvent: DMF/H ₂ O (1/99, v/v); concentration: BBNS is 10. Mu.M, and metal ion is 100. Mu.M; excitation wavelength: 435 nm, slit width: 10 nm.

FIG. 8 shows the content of Hg at various concentrations ²⁺ Fluorescent emission spectrum of BBNS solution of (a) and fluorescent intensity at 550 nm with Hg ²⁺ Relationship of concentration. Solvent: DMF/H ₂ O (1/99, v/v), concentration: BBNS is 10 mu M, hg from top to bottom ²⁺ Concentrations of 0, 100, 300, 500, 700, 900, 1000, 3000, 7000 pM (blue dot) 10, 30, 50, 70, 90 nM (green dot) 100, 150, 200, 250, 300 nM (red dot) 400, 500, 600 nM (black dot); excitation wavelength: 435 nm, emission wavelength: 550 nm, slit width: 10 nm.

FIG. 9 is a coexisting metal ion pair BBNS-Hg ²⁺ In DMF/H ₂ O（1/99，v/v) effect of maximum fluorescence intensity at 550 nm; concentration: BBNS 10 μM, various metal ions 7000 pM; excitation wavelength: 435 nm, slit width: 10 nm.

FIG. 10 is a BBNS-Hg ²⁺ In DMF/H ₂ The circularity test of the fluorescent switch at 550 nm in O (1/99, v/v); concentration: BBNS of 10. Mu.M, hg ²⁺ 7000 pM. Excitation wavelength: 435 nm, slit width: 10 nm.

Detailed Description

The prior art reports a 1, 8-naphthalimide derivative whose imide site is modified with a pyridine group, but the compound is Ag ⁺ Probe to Hg ²⁺ Has low response and can not be used as Hg ²⁺ And (3) a probe. The application designs and synthesizes a novel 1, 8-naphthalimide derivative (BBNS) with an aminothiazole structure at the 4-position. BBNS can recognize Hg in multiple channels ²⁺ : not only can colorimetric detection of Hg in solution ²⁺ But also can be made into test paper type portable sensor for naked eye recognition Hg ²⁺ Also can be used as a response range to reach the picomolar level of hypersensitive Hg ²⁺ And (3) a fluorescent switch. The synthesis method comprises the following steps:

synthesis of intermediate BBN: dissolving 4-bromo-1, 8-naphthyridine in absolute ethanol, at N ₂ Under the protection, stirring and heating to 40-60 ℃, adding n-butylamine, carrying out reflux reaction for 15-30 h, stopping the reaction, cooling to room temperature, pouring into ice water, precipitating dark yellow, filtering, washing a filter cake with deionized water, drying, and recrystallizing with absolute ethyl alcohol to obtain a pale yellow crystalline solid.

Synthesis of 1, 8-naphthalimide derivative BBNS: BBN (80 mg,0.24 mmol), cesium carbonate (78~156 mg,0.24~0.48 mmol), bis (triphenylphosphine) palladium (II) dichloride (PdCl) ₂ (PPh ₃ ) ₂ (25~50 mg,0.036~0.072 mmol) triphenylphosphine PPh ₃ (20-39 mg, 0.075-0.15 mmol) and heating, dropwise adding 2-aminothiazole (24~48 mg,0.24~0.48 mmol) dissolved in DMF (DMF) by using a dropping funnel at the dropwise speed of 4-6 drops per minute, heating to 100-120 ℃ after the dropwise adding, reacting for 1-3 h, and cooling the reaction mixture to room temperature; the heating rate is 10-15 ℃/min, and the reaction is finishedThe reaction temperature is 100-120 ℃. Post-treatment was performed in two ways: (1) Adding 10mL deionized water, mixing, extracting the mixed solution with dichloromethane (3×10-3×20 mL), collecting the lower solution, rotary evaporating to remove solvent, and purifying the residue with petroleum ether/ethyl acetate (5/1, v/v) as eluent and silica gel column. (2) The reaction solution was transferred to a centrifuge tube and centrifuged, the supernatant was removed by rotary evaporation, and the residue was purified by a silica gel column using petroleum ether/ethyl acetate (5/1, v/v) as a eluting agent. The final brown yellow solid (BBNS) 9.4-36.0. 36.0 mg was obtained in 11.1-42.9% yield.

The raw materials involved in the application are all existing products, and specific preparation operation and performance test are conventional technologies. FIG. 1 is a schematic diagram of the synthesis of the 1, 8-naphthalimide derivative BBNS, the chemical structural formula of BBN, and the chemical structural formula of BBNS.

The compound for preparing mercury ions is HgCl ₂ (AR, national medicine group chemical reagent Co., ltd.) the compound for preparing other metal ions is AlCl ₃ ·6H ₂ O、FeCl ₂ ·7H ₂ O、MgCl ₂ ·6H ₂ O、CrCl ₃ ·6H ₂ O、CuSO ₄ ·5H ₂ O、Pb(CH ₃ COO) ₂ ·3H ₂ O、CdCl ₂ ·5H ₂ O、Ni(CH ₃ COO) ₂ ·4H ₂ O, anhydrous FeCl ₃ 、MnSO ₄ ·H ₂ O、CoCl ₂ ·6H ₂ O、CaCl ₂ 、KCl、AgNO ₃ 、ZnCl ₂ NaCl (AR, national medicine group chemical Co., ltd.).

The present application mixes the metal compound with the solution system using conventional methods.

EXAMPLE preparation of intermediate (BBN)

Intermediate BBN synthesis: 4-bromo-1, 8-naphthyridine (1.0 g,3.61 mmol) was dissolved in absolute ethanol (15 mL) at room temperature, N ₂ Under protection, stirring and heating to 50deg.C, adding n-butylamine (0.75 mL,10.25 mmol), reflux reacting for 24-h, stopping the reaction, cooling to room temperature, pouring into 30-mL ice water, precipitating with dark yellow precipitate, filtering, and removing filter cakeWashing twice with ionized water, drying and recrystallizing with absolute ethyl alcohol to obtain light yellow crystalline solid with the yield of 0.75-g and 62.6%.

EXAMPLE two preparation of 1, 8-naphthalimide derivative (BBNS)

BBN (80 mg,0.24 mmol) was dissolved in DMF (3 mL), N ₂ Cesium carbonate (156 mg,0.48 mmol) and PdCl were added under protection ₂ (PPh ₃ ) ₂ (50 mg,0.072 mmol) and PPh ₃ (39 mg,0.15 mmol), heating was started, 2-aminothiazole (24 mg,0.24 mmol) dissolved in 5 mL of DMF was added dropwise with a dropping funnel at a dropping rate of 4 to 6 drops per minute, and after completion of the addition, the reaction was carried out at 120℃for 3 h. The reaction solution was cooled to room temperature, then 10mL deionized water was added and mixed well, the mixed solution was extracted with dichloromethane (3×10 mL), the lower layer solution was collected, the solvent was removed by rotary evaporation, and the residue was purified by a silica gel column using petroleum ether/ethyl acetate (5/1, v/v) as a eluent to give brown yellow solid (BBNS) 13 mg in 15.5% yield. ¹ H NMR（400 MHz，DMSO-d6，δ /ppm): 10.81(s,1H), 8.88(d, J=8.47 Hz, 1H), 8.80(d, J=8.13 Hz, 1H), 8.50(d, J=6.99 Hz, 1H), 8.43(d, J=8.59 Hz, 1H), 7.84(t, J=7.67 Hz, 1H), 7.48(d, J=3.09 Hz, 1H), 7.22(d, J=2.29 Hz, 1H), 4.02(t, J=7.44 Hz, 2H), 1.60(m, J=7.79 Hz, 2H), 1.33(m, J=6.99 Hz, 2H), 0.92(t, J=7.33 Hz, 3H)。LC-MSm/z calcd. For C ₁₉ H ₁₇ N ₃ O ₂ S: 352.14 [M+H] ⁺ , found: 352.30。FT-IR: 1087.17(C-S-C)，1237.27(C-N)，1364.17，1388.91，1515.40，1566.98(ArH)，1641.30(C=O)，1692.41(C=N)，2868.05，2921.73，2946.84(CH ₃ ,CH ₂ )，3296.47(NH)。

EXAMPLE preparation of Tri-1, 8-naphthalimide derivative (BBNS)

BBN (80 mg,0.24 mmol) was dissolved in DMF (3 mL), N ₂ Cesium carbonate (78 mg,0.24 mmol) and PdCl were added under protection ₂ (PPh ₃ ) ₂ (25 mg,0.036 mmol) and PPh ₃ (20 mg, 0.075 mmol), heating is started and 2-aminothiazole (24 mg, 0) dissolved in 5 mL of DMF is added dropwise with a dropping funnel.24 mmol), the dropping speed is 4-6 drops per minute, and the reaction is carried out at 120 ℃ for 3 h after the dropping is completed. The reaction solution was cooled to room temperature, then 10mL deionized water was added and mixed well, the mixed solution was extracted with dichloromethane (3×10 mL), the lower layer solution was collected, the solvent was removed by rotary evaporation, and the residue was purified by a silica gel column using petroleum ether/ethyl acetate (5/1, v/v) as a eluent to give brown yellow solid (BBNS) 9.4 mg in 11.1% yield.

EXAMPLE four preparation of 1, 8-naphthalimide derivative (BBNS)

BBN (80 mg,0.24 mmol) was dissolved in DMF (3 mL), N ₂ Cesium carbonate (156 mg,0.48 mmol) and PdCl were added under protection ₂ (PPh ₃ ) ₂ (50 mg,0.072 mmol) and PPh ₃ (39 mg,0.15 mmol), heating was started, 2-aminothiazole (24 mg,0.24 mmol) dissolved in 5 mL of DMF was added dropwise with a dropping funnel at a dropping speed of 4 to 6 drops per minute, and after completion of the addition, 1 h was reacted at 100℃and then 2-aminothiazole (15 mg,0.15 mmol) was added dropwise again, and the reaction was continued to 1 h. The reaction solution was cooled to room temperature, then 10mL deionized water was added and mixed well, the mixed solution was extracted with dichloromethane (3×20 mL), the lower layer solution was collected, the solvent was removed by rotary evaporation, and the residue was purified by silica gel column using petroleum ether/ethyl acetate (5/1, v/v) as a eluent to give brown yellow solid (BBNS) 15.3 mg in 18.2% yield.

EXAMPLE five preparation of 1, 8-naphthalimide derivative (BBNS)

BBN (80 mg,0.24 mmol) was dissolved in DMF (3 mL), N ₂ Cesium carbonate (156 mg,0.48 mmol) and PdCl were added under protection ₂ (PPh ₃ ) ₂ (50 mg,0.072 mmol) and PPh ₃ (39 mg,0.15 mmol), heating was started, 2-aminothiazole (48 mg,0.48 mmol) dissolved in 5 mL of DMF was added dropwise with a dropping funnel at a dropping rate of 4 to 6 drops per minute, and after completion of the addition, the reaction was carried out at 120℃for 3 h. The reaction solution was cooled to room temperature, then 10mL deionized water was added and mixed well, the mixed solution was extracted with methylene chloride (3×20 mL), the lower layer solution was collected, the solvent was removed by rotary evaporation, and the residue was petroleum ether/ethyl acetate(5/1, v/v) purification of the eluent on a silica gel column gave brown yellow solid (BBNS) 25.7. 25.7 mg in 30.5% yield.

EXAMPLE six 1, 8-naphthalimide derivative (BBNS) preparation

BBN (80 mg,0.24 mmol) was dissolved in DMF (3 mL), N ₂ Cesium carbonate (156 mg,0.48 mmol) and PdCl were added under protection ₂ (PPh ₃ ) ₂ (50 mg,0.072 mmol) and PPh ₃ (39 mg,0.15 mmol), heating was started, 2-aminothiazole (48 mg,0.48 mmol) dissolved in 5 mL of DMF was added dropwise with a dropping funnel at a dropping rate of 4 to 6 drops per minute, and after completion of the addition, the reaction was carried out at 120℃for 3 h. The reaction solution was cooled to room temperature, then transferred to a centrifuge tube for centrifugation, the solvent was removed by rotary evaporation of the supernatant, and the residue was purified by a silica gel column using petroleum ether/ethyl acetate (5/1, v/v) as a eluent to give brown yellow solid (BBNS) 36.0. 36.0 mg in a yield of 42.9%.

EXAMPLE seven in DMSO/H ₂ Selectivity of BBNS for metal ions in O (10/90, v/v) system

As shown in FIG. 2a, in DMSO/H ₂ In O (10/90, v/v), hg ²⁺ The absorbance of the BBNS solution is obviously reduced at 435 and nm, the absorption is enhanced at 525 and nm, and the absorption spectrum of the BBNS is not greatly influenced by other metal ions. Calculate the ratio A of the absorbance of 17 metal ions at 525 nm and 435 nm ₅₂₅ /A ₄₃₅ And plotted on its ordinate with the metal ion on its abscissa (FIG. 2 b), hg can be seen ²⁺ Make A ₅₂₅ /A ₄₃₅ The increase of 33.6 times, other metal ion pairs A ₅₂₅ /A ₄₃₅ The influence is not great. Elucidation of BBNS in DMSO/H ₂ Hg in O (10/90, v/v) ²⁺ Has remarkable response and can possibly be used as a ratio Hg ²⁺ Colorimetric probes.

EXAMPLE eight in DMSO/H ₂ Absorbance of BBNS and Hg in O (10/90, v/v) system ²⁺ Relationship of concentration

Further investigation of DMSO/H of BBNS ₂ UV-visible absorption spectrum and Hg of O (10/90, v/v) solution ²⁺ Relationship between concentrations. From FIG. 3a, with Hg ²⁺ Is added continuously, the absorbance of BBNS solution at 435 and nm is gradually reduced, the absorbance at 525 and nm is gradually increased, and the absorbance is calculated as Hg ²⁺ The ratio A of absorbance at 525 nm to 435 nm increases to 20. Mu.M ₅₂₅ /A ₄₃₅ Is basically stable. As shown in fig. 3b, in Hg ²⁺ Concentration (0-20. Mu.M), A ₅₂₅ /A ₄₃₅ With Hg ²⁺ The concentration shows good linear relation, and the linear equation is A ₅₂₅ /A ₄₃₅ =0.0252×[Hg ²⁺ ]+0.0157, correlation coefficient R ² 0.99341, the limit of detection was 0.28. Mu.M.

EXAMPLE nine Co-existence of Metal ion pair BBNS in DMSO/H ₂ Colorimetric detection of Hg in O (10/90, v/v) systems ²⁺ Influence of (2)

Detection of Hg for BBNS for investigation of co-existing other metal ions ²⁺ In the presence of Hg ²⁺ Ag is added to BBNS solution of (C) ⁺ 、Al ³⁺ 、Ca ²⁺ 、Cd ²⁺ 、Co ²⁺ 、Cr ³⁺ 、Cu ²⁺ 、Fe ²⁺ 、Fe ³⁺ 、K ⁺ 、Mg ²⁺ 、Mn ²⁺ 、Na ⁺ 、Ni ²⁺ 、Pb ²⁺ 、Zn ²⁺ Comparing the ultraviolet-visible absorption spectra of the solution before and after the ion addition with the ratio A of the absorbance at 525 nm and 435 nm ₅₂₅ /A ₄₃₅ Mapping the metal ions, as shown in FIG. 4, after adding the coexisting metal ions, A of the system ₅₂₅ /A ₄₃₅ No significant change, indicating that BBNS detects Hg ²⁺ The metal ion interference resistance is better.

EXAMPLE ten DMSO/H ₂ BBNS detection of Hg in O (10/90, v/v) system ²⁺ Time responsiveness of (2)

Next, BBNS was studied in DMSO/H ₂ Detection of Hg in O (10/90, v/v) System ²⁺ As shown in FIG. 5, A ₅₂₅ /A ₄₃₅ Rises very quickly to near maximum within 3 minutes and stabilizes substantially near maximum after 9 minutes. Elucidation of BBNS in DMSO/H ₂ O (10/90, v/v) system with rapid detection of Hg ²⁺ Is provided.

Example eleven BBNS as a colorimetric Probe for detection of Hg ²⁺ Is to be used in the following

To investigate the utility of BBNS, the pool water and tap water from the university of soldier lake district of su zhou was labeled with BBNS and the results are shown in table 1. Measured Hg ²⁺ Concentration and Hg added ²⁺ The concentration is close to Hg ²⁺ The recovery rate of the water sample is between 101.7 and 109.6 percent, and the relative standard deviation of three parallel experiments is lower than 4.5 percent, so that the BBNS can effectively detect Hg in the water sample in the actual environment ²⁺ Has better practicability.

Solvent system: DMSO/H ₂ O (10/90, v/v), BBNS concentration: 10.μM, RSD: a relative standard deviation; the detection method is described in example twelve.

Example twelve BBNS as a colorimetric Probe for detection of Hg ²⁺ Is a method of (2)

Hg is added to ²⁺ Adding a water sample to be tested into a DMSO solution of BBNS, and using DMSO and H ₂ Constant volume of O, make DMSO/H ₂ The volume ratio of O is 10/90, wherein the concentration of BBNS is 10 mu M, and the solution to be detected is obtained; measuring ultraviolet-visible absorption spectrum of the solution to be measured and finding A ₅₂₅ And A ₄₃₅ Calculate A ₅₂₅ /A ₄₃₅ According to the linear equation A ₅₂₅ /A ₄₃₅ =0.0252×[Hg ²⁺ ]+0.0157 Hg in the sample to be measured is calculated ²⁺ Concentration.

Method for preparing test paper of example thirteen BBNS

BBNS samples 3.53 mg, 8.83 mg were dissolved in 10mL and 5 mL ethanol, respectively, to give stock solutions at concentrations of 1 mM, 5 mM, respectively, and then 1 mL BBNS stock solution (1 mM) was pipetted into 10mL volumes, diluted 10-fold with ethanol, to prepare a stock solution of 0.1 mM. Cutting conventional filter paper into round paper sheets with the diameter of 0.6 and cm, dripping 20 mu L of stock solution with the concentration of 0.1 (1 or 5) mM on the paper sheets as required, standing for 30 min at room temperature, putting into a vacuum drying oven, drying for 5 min to obtain BBNS test paper capable of being used for detection, and putting on a porcelain point drip tray for standby. The concentration of BBNS on the test paper is expressed in mass fraction: BNAS milligrams (mg) adsorbed per gram (g) of filter paper was 0.265 (2.65 or 13.25) mg/g. (the filter paper has an average weight of 0.002. 0.002 g).

Examples fourteen BBNS test paper as a portable sensor to indicate Hg ²⁺

To investigate whether BBNS is portable, BBNS is adsorbed onto filter paper to make test paper for Hg detection ²⁺ . Dripping Hg with different concentrations on BBNS test paper ²⁺ DMSO/H of (E) ₂ The O (10/90, v/v) solution, the color of which was immediately changed under natural light, was observed, and the photographic result was shown in FIG. 6. Along with Hg ²⁺ The concentration is increased, and the colors of test papers with BBNS concentration of 0.265mg/g, 2.65mg/g and 13.25 mg/g are gradually changed from yellow to orange, so that the BBNS test papers with three concentrations can effectively indicate Hg by observing the color change through naked eyes ²⁺ 。

EXAMPLE fifteen in DMF/H ₂ Selectivity of BBNS fluorescence for metal ions in O (1/99, v/v) system

FIG. 7 shows DMF/H at BBNS ₂ Fluorescence emission spectra of O (1/99, v/v) solution before and after adding 17 metal ions. As can be seen, hg ²⁺ DMF/H of BBNS ₂ O (1/99, v/v) solution fluorescence quenching, about 3.5 times at wavelength 550 nm, thus demonstrating a fluorescence quenching in DMF/H ₂ BBNS in O (1/99, v/v) system may be useful as quenched Hg ²⁺ A fluorescent probe.

EXAMPLE sixteen BBNS fluorescence and Hg ²⁺ Relationship between concentrations

DMF/H in the study of BBNS ₂ Fluorescence intensity of O (1/99, v/v) solution and Hg ²⁺ In relation to the concentration, a conventional concentration of Hg of 1 to 10. Mu.M was found ²⁺ The fluorescence of the solution was completely quenched (black panel curve of fig. 8 a). Hg reduction ²⁺ Concentration of 100 nM-1. Mu.M Hg was studied ²⁺ Effect on BBNS fluorescence emission spectrum, it was found that even 100 nM Hg ²⁺ Also, the BBNS fluorescence was quenched by about 3/4 (FIG. 8a red set of curves). Continue to study Hg in the range of 10-100 nM ²⁺ Shadow of BBNS fluorescence emission spectrumRinging, hg was found to be 10 nM ²⁺ The BBNS fluorescence can be quenched by about 1/2 (FIG. 8a green set of curves). Further investigation of Hg of 100 pM-10 nM ²⁺ Influence on BBNS fluorescence emission spectrum, along with Hg ²⁺ The increase in concentration, the fluorescence of BBNS gradually decreased (fig. 8a blue panel curve). BBNS vs Hg ²⁺ Has reached picomolar scale and has hypersensitive properties. When Hg is ²⁺ The fluorescence intensity of BBNS decreases almost linearly (dark blue dots arranged almost vertically in FIG. 8 b) from 0 to 7000 pM, with switching characteristics. Thus in DMF/H ₂ In O (1/99, v/v) system, BBNS can be used as hypersensitive Hg ²⁺ And (3) a fluorescent switch.

EXAMPLE seventeen coexisting metal ion pair BBNS as hypersensitive Hg ²⁺ Influence of fluorescent switch

To investigate other coexisting metal ion pairs BBNS as hypersensitive Hg ²⁺ Interference condition of fluorescent switch, in the presence of Hg ^{2 +} Respectively adding Ag into BBNS solution of (C) ⁺ 、Al ³⁺ 、Ca ²⁺ 、Cd ²⁺ 、Co ²⁺ 、Cr ³⁺ 、Cu ²⁺ 、Fe ²⁺ 、Fe ³⁺ 、K ⁺ 、Mg ²⁺ 、Mn ²⁺ 、Na ⁺ 、Ni ²⁺ 、Pb ²⁺ 、Zn ²⁺ The maximum fluorescence intensity of the solution after adding the coexisting metal ions was not significantly changed, as shown in FIG. 9, which indicates that these coexisting ions were hypersensitive Hg to BBNS ²⁺ The fluorescent switch has little effect.

EXAMPLE eighteen BBNS as hypersensitive Hg ²⁺ Recyclability of fluorescent switch

As shown in FIG. 10, BBNS is in DMF/H ₂ The O (1/99, v/v) solution has fluorescence (on) and Hg is added ²⁺ The fluorescence of the solution was quenched (off) and excess Na was added ₂ S, the fluorescence intensity of the solution is increased back to be close to that of Hg ²⁺ And Na (Na) ₂ Fluorescence intensity before S (on), hg was added ²⁺ The fluorescence of the solution was quenched again (off) and excess Na was added ₂ S, the fluorescence of the solution is recovered (turned on). Visible in the lightBBNS as hypersensitive Hg ²⁺ The fluorescent switch has better circularity; na (Na) ₂ The amount of S is 10 nM (i.e. 10000 pM).

In summary, the application discloses a novel 1, 8-naphthalimide derivative which can be used as Hg with high selectivity, high sensitivity and high anti-interference ²⁺ Colorimetric probe and test paper type portable Hg capable of observing indication result with naked eyes ²⁺ The sensor can also be used as a sensor for Hg ²⁺ A fluorescent switch with hypersensitive response.

Claims (10)

1. A1, 8-naphthalimide derivative has the chemical structural formula as follows:

。

2. the process for producing a 1, 8-naphthalimide derivative according to claim 1, wherein the BBN compound is reacted with 2-aminothiazole to obtain the 1, 8-naphthalimide derivative.

3. The process for producing a 1, 8-naphthalimide derivative according to claim 2, wherein the reaction temperature is 100 to 150℃and the reaction time is 1 to 5 hours.

4. The process for producing a 1, 8-naphthalimide derivative according to claim 2, wherein the reaction is carried out in the presence of a noble metal catalyst, an inorganic base, an organic ligand, a solvent and an inert gas.

5. The process for producing a 1, 8-naphthalimide derivative according to claim 4, wherein the noble metal catalyst comprises a palladium catalyst; inorganic bases include cesium salts, potassium salts, sodium salts; the organic ligands include phosphine ligands; the solvent is an organic solvent.

6. The process for producing a 1, 8-naphthalimide derivative according to claim 4, wherein the molar ratio of the BBN compound, the 2-aminothiazole, the noble metal catalyst, the inorganic base and the organic ligand is 1:1-2:0.1-0.3:1-2:0.3-0.65.

7. The 1, 8-naphthalimide derivative according to claim 1 as or in the preparation of Hg ²⁺ The application of colorimetric probes; or the 1, 8-naphthalimide derivative according to claim 1 as or in the preparation of Hg ²⁺ Application of fluorescent switches.

8. Hg system ²⁺ A detection sensor comprising the 1, 8-naphthalimide derivative according to claim 1 and a substrate.

9. Detection of Hg in a liquid ²⁺ The method of (1) wherein Hg in a liquid is carried out by a colorimetric probe method, a fluorescent switch method or a sensor discoloration method using the 1, 8-naphthalimide derivative according to claim 1 as an active material ²⁺ Is detected.

10. Detection of Hg in liquids according to claim 9 ²⁺ The method of (1), comprising the steps of mixing the 1, 8-naphthalimide type derivative according to claim 1 with a detection liquid according to A ₅₂₅ /A ₄₃₅ Is used for detecting Hg in liquid ²⁺ Qualitative and quantitative analysis of (2); or mixing the 1, 8-naphthalimide derivative according to claim 1 with a detection liquid, and detecting Hg in the liquid based on the fluorescence intensity at 550 nm ²⁺ Qualitative and quantitative analysis of (2); or by dropping a detection liquid onto a sensor containing the 1, 8-naphthalimide-type derivative according to claim 1, and detecting Hg in the liquid based on the color change of the sensor ²⁺ Qualitative and quantitative analysis of (c).