CN108503620B - Formaldehyde fluorescent donor molecule and preparation method and application thereof - Google Patents
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Abstract
The invention relates to a formaldehyde fluorescence donor molecule and a preparation method and application thereof, wherein the formaldehyde fluorescence donor molecule has a structure shown in a formula I or II. The formaldehyde fluorescent donor molecules of the present invention are themselves non-fluorescent in aqueous solutions, but can be gradually converted to fluorescent products with the release of formaldehyde. Meanwhile, the formaldehyde releasing speed of the formaldehyde fluorescence donor molecule is related to the pH value of the aqueous solution, and the formaldehyde fluorescence donor molecule can be used for quantitatively researching the formaldehyde releasing speed and the total formaldehyde releasing amount in the aqueous solution by fluorescence so as to research the mutual relation between formaldehyde and other chemical and biological effects, and has potential application value. The preparation method of the formaldehyde fluorescence donor molecule is simple and has high yield.
Description
Technical Field
The invention relates to a formaldehyde fluorescence donor molecule and a preparation method and application thereof, belonging to the technical field of donor fluorescence probes.
Background
Formaldehyde is a colorless gas with pungent odor, generally exists in the form of an aqueous solution called formalin, has bleaching, preservative and disinfection effects, and is widely used in various fields. Formaldehyde is toxic and can also be used directly as a disinfectant, a bactericide, a preservative and the like.
Conventional formaldehyde donors include paraformaldehyde, urotropin, imidazolidinyl urea, diazolidinyl urea, and the like. Among them, paraformaldehyde is often used in the pharmaceutical industry and in disinfection of pharmacy, bedding, clothes, etc., and is a common fumigation disinfectant, insecticide and bactericide. Urotropin is used as a chemical synthetic material and as a drug for the treatment of bacterial urinary tract infections. The compound can be decomposed into ammonia and formaldehyde in acidic urine, and the formaldehyde has broad-spectrum antibacterial effect on a plurality of bacteria. Imidazolidinyl urea and diazoalkyl urea are frequently used as preservatives in products such as cosmetics, and formaldehyde released by the imidazolidinyl urea and the diazoalkyl urea has an antibacterial effect.
However, the existing formaldehyde donor has no way to control and judge how much formaldehyde is released, so that the development of formaldehyde fluorescence donor molecules capable of quantitatively researching the release of formaldehyde according to the change of fluorescence signals while releasing formaldehyde is very meaningful, and the tool can be used for researching the mutual relation between formaldehyde and other chemical and biological actions and has potential application value.
Disclosure of Invention
In order to solve the above technical problems in the art, the present invention provides the following technical solutions.
In one aspect, the invention provides a class of formaldehyde fluorescent donor molecules having a structure represented by formula i or ii:
in one embodiment, R is alkyl.
Preferably, R is methyl, ethyl, propyl or n-butyl.
Further preferably, formula I is of the following formula I-1, and formula II is of the following formula II-1
In another aspect, the present invention provides a process for the preparation of the formaldehyde fluorescence donor molecules represented by formulae I and II in claim 1, by the following preparative route:
in one embodiment:
reacting 4-bit N-maleimide derivative of naphthalimide with benzylamine in tetrahydrofuran solution at room temperature for 1 hour to obtain an intermediate 1;
and (3) reacting the intermediate 1 in tetrahydrofuran and an aqueous solution of sodium hydroxide for 30 minutes, and then adding formaldehyde to react for 1 hour to obtain the compounds shown in the formulas I and II.
In one embodiment:
the molar ratio of the 4-position N-maleimide derivative of the naphthalimide to the benzylamine is 1: 1;
the molar ratio of the intermediate 1 to the formaldehyde is 1: 5 to 1: 25.
in a further aspect, the present invention provides the use of a formaldehyde fluorescent donor molecule for releasing formaldehyde in an aqueous solution, wherein the aqueous solution contains formaldehyde or is formaldehyde free, while monitoring the release of formaldehyde. Preferably, the rate and amount of formaldehyde release is monitored.
In a further aspect, the present invention provides the use of a formaldehyde fluorescent donor molecule in combination with formaldehyde probes Na-FA for monitoring the release of formaldehyde while releasing formaldehyde. Preferably, the rate and amount of formaldehyde release is monitored.
In a further aspect, the present invention provides the use of a formaldehyde fluorescent donor molecule for disinfection, disinsection or sterilization. Preferably, the method is used in an environment with pH of 5.0-7.4.
The preparation method of the formaldehyde fluorescence donor molecule is described in detail as follows, and comprises the following steps:
taking the compounds shown in the formula I and the formula II as examples, reacting 4-site N-maleimide derivative of naphthalimide with benzylamine in tetrahydrofuran solution at room temperature for 1 hour, and after the reaction is finished, concentrating and purifying by column chromatography to obtain an intermediate 1; and (3) reacting the intermediate 1 in tetrahydrofuran and a sodium hydroxide aqueous solution for 30 minutes, adding formaldehyde for reacting for 1 hour, and extracting, drying and purifying by column chromatography to obtain the compounds shown in the formulas I and II.
In the first reaction step of the above preparation method, the molar ratio of the 4-position N-maleimide derivative of naphthalimide to benzylamine is 1: 1.
In the first reaction step of the above preparation method, benzylamine is added dropwise.
In the first step of the preparation method, tetrahydrofuran in the reaction is removed by reduced pressure distillation by using a rotary evaporator.
In the first reaction step of the above preparation method, the obtained intermediate 1 is purified by silica gel column chromatography.
In the second reaction step of the above preparation method, the molar ratio of the intermediate 1 to formaldehyde may be 1: 5 to 1: 25.
in the second reaction step of the above preparation method, the reaction solution was extracted with ethyl acetate.
In the second reaction step of the above preparation method, the organic phase obtained by extraction is dried over anhydrous sodium sulfate.
In the second reaction step of the above preparation method, the organic phase obtained by extraction is removed by reduced pressure distillation using a rotary evaporator.
In the second step of the preparation method, the obtained formaldehyde fluorescence donor molecule is purified by silica gel column chromatography.
The detailed description of the application of the formaldehyde fluorescent donor molecule as described above includes:
observing the fluorescence intensity change of different pH values (pH 5.0 and pH 7.4) of aqueous solutions of the donor fluorescent probe shown in the formula I or II along with the change of time, wherein the fluorescence excitation wavelength is 359nm, and the emission wavelength is 470 nm; the change in fluorescence intensity refers to: the fluorescence intensity gradually increased at 470nm with time, and the increase rate was faster at pH 5.0 than at pH 7.4.
Or observing the fluorescence intensity change of the formaldehyde aqueous solution with time according to different pH values (pH value is 5.0 and pH value is 7.4) of the donor fluorescent probe shown in the formula I or II, wherein the fluorescence excitation wavelength is 359nm, and the emission wavelength is 470 nm; the change in fluorescence intensity refers to: when a large amount of formaldehyde was contained in the aqueous solution, the fluorescence intensity at 470nm rapidly increased in the solution at pH 5.0 with time, and the fluorescence intensity at 470nm did not significantly increase at pH 7.4.
Alternatively, the addition of the existing formaldehyde probe Na-FA to an aqueous solution of the donor fluorescent probe of formula I or II was observed, while the change in fluorescence intensity of both compounds with time was observed. The excitation wavelength of the formaldehyde fluorescence donor molecule is 359nm, the emission wavelength is 470nm, the excitation wavelength of the formaldehyde fluorescence probe Na-FA is 440nm, and the emission wavelength is 543 nm. The change in fluorescence intensity refers to: the fluorescence intensity at 470nm gradually increases with time, and the fluorescence intensity at 543nm gradually increases in the existing fluorescence spectrogram of the formaldehyde probe Na-FA.
The invention has the following beneficial technical effects:
the formaldehyde fluorescence donor molecule can gradually release formaldehyde in aqueous solution, has a release speed under an acidic condition which is faster than that under an alkaline condition, is not interfered by the existing formaldehyde concentration in the aqueous solution, generates obvious fluorescence signal change while releasing the formaldehyde, can be used for quantitatively researching the formaldehyde release speed and the total formaldehyde release amount in the aqueous solution, and has potential application value by researching the mutual relation between the formaldehyde and other chemical and biological effects.
The preparation method is simple and has high yield.
Drawings
The advantages and features of the present invention will become more readily apparent to those skilled in the art from the following drawings.
FIG. 1 shows the preparation of the fluorescent donor molecule I-1 of formaldehyde according to the example1H NMR spectrum.
FIG. 2 shows the preparation of the fluorescent donor molecule I-1 of formaldehyde according to the example13C NMR spectrum.
FIG. 3 shows the preparation of the fluorescent donor molecule II-1 of formaldehyde according to the example1H NMR spectrum.
FIG. 4 shows the preparation of the fluorescent donor molecule II-1 of formaldehyde according to the example13C NMR spectrum.
FIG. 5 is a graph of fluorescence intensity at 470nm over 5h of the example formaldehyde fluorescent donor molecule I-1 at a concentration of 1. mu. mol/L in PBS (pH 5.0) as a function of reaction time (slit width 2/2 nm).
FIG. 6 is a graph of fluorescence intensity at 470nm over 5h of the example formaldehyde fluorescent donor molecule I-1 at a concentration of 1. mu. mol/L in PBS (pH 7.4) as a function of reaction time (slit width 2/2 nm).
FIG. 7 is a graph showing the change of fluorescence intensity at 470nm over 5h (slit width 2/2nm) of the example formaldehyde fluorescence donor molecule I-1 at a concentration of 1. mu. mol/L in PBS (pH 5.0) at a formaldehyde concentration of 500. mu. mol/L as a function of reaction time.
FIG. 8 is a graph showing the change of fluorescence intensity at 470nm over 5h (slit width 2/2nm) of the example formaldehyde fluorescence donor molecule I-1 at a concentration of 1. mu. mol/L in PBS (pH 7.4) at a formaldehyde concentration of 500. mu. mol/L as a function of reaction time.
FIG. 9 shows the change of fluorescence spectrum within 5h after adding 60. mu. mol/L of the example formaldehyde fluorescence donor molecule I-1 in PBS (pH 7.4) and 2. mu. mol/L of the existing formaldehyde fluorescence probe Na-FA, the excitation wavelength being 359nm, showing the change of fluorescence spectrum of the formaldehyde fluorescence donor molecule (slit width 1/1 nm).
FIG. 10 shows the change of fluorescence spectrum within 5 hours after adding 60. mu. mol/L of the fluorescence donor molecule I-1 of example formaldehyde to PBS (pH 7.4) and 2. mu. mol/L of the conventional formaldehyde fluorescence probe Na-FA, the excitation wavelength is 440nm, and the change of fluorescence spectrum is shown as the change of fluorescence spectrum of the formaldehyde fluorescence probe Na-FA (slit width 2/2 nm).
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be merely illustrative and not limiting of the invention.
The starting materials and equipment used in the examples are well known to those skilled in the art and are either commercially available or readily available or manufactured.
Example 1 Synthesis of Formaldehyde fluorescent donor molecules I-1 and II-1:
109mg of the maleimide derivative of the starting naphthalimide (0.31mmol) was dissolved in 2mL of tetrahydrofuran, followed by slowly dropping 35. mu.L of benzylamine (0.32mmol), and the reaction solution was stirred at room temperature for 1 hour to complete the reaction. And (4) carrying out reduced pressure distillation by using a rotary evaporator to remove tetrahydrofuran in the reaction liquid to obtain a crude product. The volume ratio is 500: purification of 1 with dichloromethane and methanol as eluent on a silica gel column chromatography gave 86mg of intermediate 1-1 (60% yield, product as a mixture of two rotamers of 1: 1).1H NMR(400MHz,CDCl3):8.69-8.63(m,2H),7.94-7.74(m,2H),7.64-7.56(m,1H),7.42-7.31(m,5H),4.21-4.08(m,3H),4.07-3.95(m,2H),3.28-3.16(m,1H),2.97-2.86(m,1H),2.43(br s,1H),1.71(quint,J＝7.6Hz,2H),1.45(sextet,J＝7.6Hz,2H),0.98(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3):(176.9,176.8),(174.1,173.9),163.8,(163.4,163.4),(138.4,138.4),(134.0,133.8),(132.0,131.9),(131.0,130.9),(129.2,129.2),129.0(2C),(128.6,128.4),128.5(2C),(128.2,127.9),128.0,(128.1,127.8),(127.5,127.3),(124.2,124.1),(123.6,123.5),(56.1,55.8),(52.1,51.9),40.4,(37.1,37.0),30.1,20.3,13.8。
53mg of intermediate 1-1(0.12mmol) was dissolved in 4mL of tetrahydrofuran, and 2mL of 0.5N aqueous NaOH solution was added thereto, followed by stirring at room temperature for 30 minutes. Then, 90. mu.L (1.2mmol) of 37% formaldehyde solution was added thereto, and the reaction solution was left to stir at room temperature for 1 hour, after which the reaction was completed. Dropwise adding 6N hydrochloric acid into the reaction liquid until the pH value of the reaction liquid is less than 5, repeatedly extracting the reaction liquid with ethyl acetate for 3 times, washing the organic phase with saturated salt solution once, drying with anhydrous sodium sulfate, and removing the solvent in the organic phase by reduced pressure distillation with a rotary evaporator to obtain a crude product. The volume ratio of 20: 1 with methanol as eluent, and purified by silica gel column chromatography to give 28mg of formaldehyde fluorescence donor molecule I-1 (48% yield) and 7mg of formaldehyde fluorescence donor molecule II-1 (12% yield).
Spectral data for I-1:1HNMR(400MHz,CDCl3):8.61-8.56(m,2H),8.19-8.12(m,1H),7.78-7.71(m,1H),7.61-7.53(m,1H),7.39-7.30(m,5H),4.81-4.73(m,1H),4.41-4.29(m,1H),4.18-4.04(m,5H),3.18-3.02(m,2H),1.72-1.67(m,2H),1.43(sextet,J＝7.2Hz,2H),0.97(t,J＝7.2Hz,3H)；13C NMR(125MHz,CDCl3):(173.5,173.2),(168.7,168.3),(164.1,164.0),(163.7,163.6),(143.1,142.8),(136.3,136.1),131.9,(131.6,131.5),(129.5,129.3),(129.0,128.9),128.9,(128.8,128.7),128.4,(128.4,128.3),(127.9,127.9),(126.5 126.3),(123.5,123.4),(123.0,122.8),(68.4,67.8),(58.4,58.2),56.5,40.5,(31.9,31.5),30.3,20.5,13.9。
spectrogram data of II-1:1HNMR(400MHz,CDCl3):8.54(d,J＝7.4Hz,2H),8.24(d,J＝8.3Hz,1H),7.73(t,J＝7.8Hz,1H),7.56(d,J＝7.8Hz,1H),7.39-7.30(m,5H),4.62(d,J＝4.2Hz,1H),4.50(d,J＝4.2Hz,1H),4.25(d,J＝12.9Hz,1H),4.15(t,J＝7.4Hz,2H),3.89(br s,1H),3.81(d,J＝12.9Hz,1H),3.12(dd,J＝16.6,3.3Hz,1H),2.96(dd,J＝16.6,5.1Hz,1H),1.68(quint,J＝7.6Hz,2H),1.43(sextet,J＝7.6Hz,2H),0.97(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3):171.6,167.9,164.0,163.6,138.8,135.9,132.0,131.1,130.0,129.3,129.1(2C),129.0(2C),128.4,128.0,127.7,124.2,123.1,122.7,71.3,62.2,58.0,40.3,30.2,29.7,20.4,13.8
example 2 fluorescence intensity of Formaldehyde fluorescent donor molecule I-1 in aqueous solution at pH 5.0 as a function of time
The formaldehyde fluorescence donor molecule I-1 prepared in example 1 was dissolved in DMSO to prepare a fluorescence probe mother liquor with a concentration of 1 mmol/L. The required aqueous PBS solution (20mM, pH 5.0) was added to a 1cm X1 cm quartz cuvette (volume 3.5mL) in accordance with the concentration of the probe, and 3. mu.L of the probe stock solution was added to the aqueous PBS solution to prepare a total of 3mL of a test solution having a probe concentration of 1. mu. mol/L. The increase in fluorescence intensity at 470nm with time was measured using 359nm as excitation wavelength (slit width 2/2 nm). As shown in FIG. 5, the fluorescence intensity value gradually increased at 470 nm.
Example 3 fluorescence intensity of Formaldehyde fluorescent donor molecule I-1 in aqueous solution at pH 7.4 as a function of time
The required aqueous PBS (10mM, pH 7.4) was added to a 1cm X1 cm quartz cuvette (volume 3.5mL) according to the concentration of the probe, and 3. mu.L of the formaldehyde fluorescence donor molecule stock solution of example 2 was added to the aqueous PBS to prepare a total of 3mL of a test solution having a probe concentration of 1. mu. mol/L. The increase in fluorescence intensity at 470nm with time was measured using 359nm as excitation wavelength (slit width 2/2 nm). As shown in FIG. 6, the fluorescence intensity value gradually increased at 470 nm.
Example 4 fluorescence intensity of Formaldehyde fluorescent donor molecule I-1 in aqueous solution containing a large amount of Formaldehyde at pH 5.0 with time
Adding a formaldehyde solution with the mass fraction of 37% into distilled water to prepare a formaldehyde mother liquor with the concentration of 150 mmol/L. The required aqueous PBS solution (20mM, pH 5.0) was added to a 1cm X1 cm quartz cuvette (volume 3.5mL) in accordance with the concentration of the probe and formaldehyde, and 3. mu.L of the formaldehyde fluorescence donor molecule stock solution of example 2 was added to the aqueous PBS solution, followed by 10. mu.L of formaldehyde stock solution, to prepare a total of 3mL of a test solution having a probe concentration of 1. mu. mol/L and a formaldehyde concentration of 500. mu. mol/L. The increase in fluorescence intensity at 470nm with time was measured using 359nm as excitation wavelength (slit width 2/2 nm). As shown in FIG. 7, the fluorescence intensity value gradually increased at 470 nm.
Example 5 fluorescence intensity of Formaldehyde fluorescent donor molecule I-1 in aqueous solution containing a large amount of Formaldehyde at pH 7.4 with time
The required aqueous solution of PBS (10mM, pH 7.4) was added to a 1cm X1 cm quartz cuvette (volume 3.5mL) in accordance with the concentration of the probe and formaldehyde, and 3. mu.L of the formaldehyde fluorescence donor stock solution of example 2 was added to the aqueous solution of PBS and 10. mu.L of formaldehyde stock solution was added to prepare a total of 3mL of a test solution having a probe concentration of 1. mu. mol/L and a formaldehyde concentration of 500. mu. mol/L. The increase in fluorescence intensity at 470nm with time was measured using 359nm as excitation wavelength (slit width 2/2 nm). As shown in FIG. 8, the fluorescence intensity at 470nm did not increase significantly.
Example 6 fluorescence intensity of two probes, formaldehyde fluorescence donor molecule I-1 and formaldehyde fluorescence probe Na-FA, coexisting in aqueous solution at pH 7.4, as a function of time
The formaldehyde fluorescence donor molecule I-1 prepared in the example 1 is dissolved in DMSO to prepare a fluorescence probe mother liquor with the concentration of 10 mmol/L. The required aqueous PBS solution (10mM, pH 7.4) was added to a 1cm X1 cm quartz cuvette (volume 3.5mL) in accordance with the concentration of the probe, 18. mu.L of the probe stock solution was added to the aqueous PBS solution, and then the formaldehyde fluorescence probe Na-FA was added to prepare a total of 3mL of a test solution having a probe concentration of 60. mu. mol/L and a Na-FA concentration of 2. mu. mol/L. The fluorescence spectrum was measured as a function of time using 359nm as the excitation wavelength (slit width 1/1 nm). The fluorescence spectrum was also measured as a function of time using 440nm as the excitation wavelength (slit width 2/2 nm). As shown in fig. 9 and 10, the fluorescence intensity gradually increased.
Thus, it should be appreciated by those skilled in the art that while a number of exemplary embodiments of the invention have been illustrated and described in detail herein, many other variations or modifications consistent with the principles of the invention may be directly determined or derived from the disclosure of the present invention without departing from the spirit and scope of the invention. Accordingly, the scope of the invention should be understood and interpreted to cover all such other variations or modifications.
Claims (9)
1. A formaldehyde fluorescence donor molecule is characterized in that the formaldehyde fluorescence donor molecule has a structure shown in a formula I or II:
and R is alkyl.
2. The formaldehyde fluorescent donor molecule according to claim 1, wherein R is methyl, ethyl, propyl, or n-butyl.
3. The formaldehyde fluorescent donor molecule according to claim 1, wherein the formula I is of the following formula I-1, and the formula II is of the following formula II-1
4. A process for the preparation of the formaldehyde fluorescence donor molecules of formulae I and II according to claim 1, characterized in that it is carried out by the following preparation route:
said R is as defined in claim 1.
5. The method of preparing a formaldehyde fluorescent donor molecule according to claim 4, characterized in that:
reacting 4-bit N-maleimide derivative of naphthalimide with benzylamine in tetrahydrofuran solution at room temperature for 1 hour to obtain an intermediate 1;
and (3) reacting the intermediate 1 in tetrahydrofuran and an aqueous solution of sodium hydroxide for 30 minutes, adding a formaldehyde solution, and reacting at room temperature for 1 hour to obtain the compounds shown in the formulas I and II.
6. The method of preparing a formaldehyde fluorescent donor molecule according to claim 4, characterized in that:
the molar ratio of the 4-position N-maleimide derivative of the naphthalimide to the benzylamine is 1: 1;
the molar ratio of the intermediate 1 to the formaldehyde is 1: 5 to 1: 25.
7. use of a formaldehyde fluorescent donor molecule according to claim 1 for releasing formaldehyde in an aqueous solution with or without formaldehyde while monitoring the release of formaldehyde.
8. Use of the formaldehyde fluorescent donor molecule according to claim 1, characterized in that the formaldehyde fluorescent donor molecule is used in combination with formaldehyde probe Na-FA to monitor the release of formaldehyde at the same time as the release of formaldehyde.
9. Use of the formaldehyde fluorescent donor molecule according to claim 1 for the preparation of disinfectants, insecticides and bactericides.
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