阅读说明：本技术 一种联萘醛手性荧光探针及其制备方法和应用 (Binaphthyl aldehyde chiral fluorescent probe and preparation method and application thereof ) 是由 余孝其 于珊珊 田俊 蒲林 于 2019-10-31 设计创作，主要内容包括：本发明公开了一种联萘醛手性荧光探针及其制备方法和应用。手性荧光探针的制备是先将(S)-2,2’-甲基溴-1,1’-联萘与碳酸氢钠按0.8～1.5:4～7.5的摩尔比混合后加入二甲基亚砜中,于85～95℃下反应6～8h,得初产物；然后对初产物进行分离提纯,得联萘醛手性荧光探针。本发明中的联萘醛手性荧光探针合成简单,产率较高,主要用于手性分子的对映性选择识别,能够克服传统手性荧光探针识别需要加入金属离子辅助的缺点,在手性识别领域具有广阔的应用前景。(The invention discloses a binaphthyl chiral fluorescent probe and a preparation method and application thereof. The preparation method of the chiral fluorescent probe comprises the steps of mixing (S) -2,2 '-methyl bromide-1, 1' -binaphthyl with sodium bicarbonate according to a molar ratio of 0.8-1.5: 4-7.5, adding the mixture into dimethyl sulfoxide, and reacting for 6-8 hours at 85-95 ℃ to obtain a primary product; then, the primary product is separated and purified to obtain the binaphthyl aldehyde chiral fluorescent probe. The binaphthyl aldehyde chiral fluorescent probe disclosed by the invention is simple to synthesize and high in yield, is mainly used for enantioselective identification of chiral molecules, can overcome the defect that metal ion assistance needs to be added in the traditional chiral fluorescent probe for identification, and has a wide application prospect in the field of chiral identification.)

1. A binaphthyl chiral fluorescent probe is characterized in that the structural formula of the fluorescent probe is shown as a formula I:

2. the method for preparing the binaphthyl aldehyde chiral fluorescent probe as claimed in claim 1, which comprises the following steps:

s1: mixing (S) -2,2 '-methyl bromide-1, 1' -binaphthyl with sodium bicarbonate according to a molar ratio of 0.8-1.5: 4-7.5, adding the mixture into dimethyl sulfoxide, and reacting at 85-95 ℃ for 6-8 hours to obtain a primary product;

s2: separating and purifying the primary product to obtain a binaphthyl aldehyde chiral fluorescent probe;

the synthetic route is shown as the formula (1-1):

3. the method for preparing the binaphthal chiral fluorescent probe according to claim 2, wherein the method comprises the following steps: the molar ratio of the (S) -2,2 '-methyl bromide-1, 1' -binaphthyl to sodium bicarbonate is 1: 5.

4. The method for preparing the binaphthal chiral fluorescent probe according to claim 2, wherein the method comprises the following steps: the reaction temperature is 90 ℃ and the reaction time is 7 h.

5. The method for preparing the binaphthyl aldehyde chiral fluorescent probe according to claim 2, wherein the specific method for separating and purifying S2 comprises the following steps: firstly, extracting the initial product, removing the solvent, then mixing petroleum ether and ethyl acetate according to the volume ratio of 20:1 to obtain eluent, and carrying out column chromatography purification on the initial product after the solvent is removed.

6. Use of the binaphthal chiral fluorescent probe of claim 1 for enantioselective recognition of chiral molecules.

7. Use according to claim 6, characterized in that it comprises the following steps: mixing a binaphthyl aldehyde chiral fluorescent probe, an organic solution, chiral molecules and a cosolvent, wherein the concentration of the fluorescent probe in the mixture is 1 x 10^-5mol/L～3×10^{- 5}mol/L; then measuring the fluorescence response value of the mixture, and judging the configuration or the composition ratio of the enantiomer of the substance to be detected according to the fluorescence response value.

8. Use according to claim 7, characterized in that: the chiral molecule is an amino acid; the organic solution is dichloromethane or methanol solution; the cosolvent is tetrabutylammonium hydroxide.

9. Use according to claim 8, characterized in that: the amino acid is glutamic acid or aspartic acid.

Technical Field

The invention belongs to the technical field of fluorescent probes, and particularly relates to a binaphthyl chiral fluorescent probe and a preparation method and application thereof.

Background

Chirality is the basic attribute of nature, and important biological macromolecules participating in life activities, such as protein, polysaccharide, enzyme and the like, have chirality; various biological and chemical reaction processes occurring in life activities are closely related to chiral recognition and change. Therefore, the design and synthesis of host molecules with enantioselective recognition and sensing properties and the application of the host molecules in the rapid analysis of chiral compositions of chiral compounds have important research significance. Compared with other identification methods, the fluorescence identification has the advantages of high sensitivity, multiple signal modes, zero background interference, real-time property, convenience and easiness in obtaining of instruments and the like, so that the fluorescence method is greatly concerned in identifying chiral molecules.

Disclosure of Invention

Aiming at the problems in the background art, the invention provides a binaphthyl chiral fluorescent probe and a preparation method and application thereof.

In order to achieve the purpose, the invention adopts the technical scheme that: the binaphthyl chiral fluorescent probe is characterized in that the structural formula of the fluorescent probe is shown as formula I:

the binaphthyl aldehyde chiral fluorescent probe is prepared by the following steps:

s1: mixing (S) -2,2 '-methyl bromide-1, 1' -binaphthyl with sodium bicarbonate according to a molar ratio of 0.8-1.5: 4-7.5, adding the mixture into dimethyl sulfoxide, and reacting at 85-95 ℃ for 6-8 hours to obtain a primary product;

s2: separating and purifying the primary product to obtain a binaphthyl aldehyde chiral fluorescent probe;

the synthetic route is shown as the formula (1-1):

on the basis of the preparation method, the invention can be further improved as follows.

Further, in S1, the molar ratio of (S) -2,2 '-methylbromo-1, 1' -binaphthyl to sodium bicarbonate was 1: 5.

Further, the reaction temperature in S1 was 90 ℃ and the reaction time was 7 hours.

Further, the specific method for separating and purifying in S2 comprises the following steps: firstly, extracting the initial product, removing the solvent, then mixing petroleum ether and ethyl acetate according to the volume ratio of 20:1 to obtain eluent, and carrying out column chromatography purification on the initial product after the solvent is removed.

The binaphthyl aldehyde chiral fluorescent probe disclosed by the invention is mainly used for enantioselective identification of chiral molecules, and the specific method for the enantioselective identification of the chiral molecules comprises the following steps: the binaphthyl aldehyde chiral fluorescent probe, the organic solution, the chiral molecules and the cosolvent are mixed, the fluorescence response value is measured, and then the configuration or the enantiomer composition ratio of the substance to be measured is judged according to the fluorescence response value.

The organic solution used in the chiral molecule recognition process is preferably dichloromethane or methanol solution; the cosolvent used is preferably tetrabutylammonium hydroxide. The chiral molecules are mainly chiral amino acids, and the binaphthyl chiral fluorescent probe has good selective recognition capability on glutamic acid, aspartic acid and the like.

The invention has the beneficial effects that: the binaphthyl aldehyde chiral fluorescent probe provided by the invention has the advantages of easily available raw materials and simple synthesis, can be used for enantioselectively identifying glutamic acid and aspartic acid in a methanol solution without metal ions, and has a wide application prospect in the field of chiral identification.

Drawings

FIG. 1 shows probe (S) -3¹H NMR spectrum;

FIG. 2 shows the probe (S) -3¹³C NMR spectrum;

FIG. 3 is a mass spectrum of probe (S) -3;

FIG. 4 shows the fluorescent response of probe (S) -3 to L-glutamic acid in a methanol system, with the abscissa representing the wavelength and the ordinate representing the fluorescence intensity;

FIG. 5 shows the change in concentration of D-glutamic acid by probe (S) -3 in the methanol system, with the abscissa representing the wavelength and the ordinate representing the fluorescence intensity;

FIG. 6 is a graph showing the change in fluorescence intensity with increasing concentration of glutamic acid (D-glutamic acid, L-glutamic acid), the abscissa being equivalent weight and the ordinate being fluorescence intensity;

FIG. 7 shows the fluorescence intensity of probes (S) -3 and (R) -3 in the methanol system as a function of the composition ratio of glutamic acid enantiomer, with the abscissa representing the mass percentage of L-glutamic acid and the ordinate representing the fluorescence intensity;

FIG. 8 shows the fluorescence response of probe (S) -3 to different equivalents of L-aspartic acid in a methanol system; the abscissa is wavelength and the ordinate is fluorescence intensity;

FIG. 9 shows the fluorescence response of probe (S) -3 to different equivalents of D-aspartic acid in a methanol system; the abscissa is wavelength and the ordinate is fluorescence intensity;

FIG. 10 is a graph showing the change in fluorescence intensity with increasing concentration of aspartic acid (D-aspartic acid, L-aspartic acid), with the amino acid concentration on the abscissa and the fluorescence intensity on the ordinate;

FIG. 11 shows the fluorescence intensity of probes (S) -3 and (R) -3 in the methanol system as a function of the enantiomeric composition ratio of aspartic acid, with the abscissa representing the mass percentage of L-aspartic acid and the ordinate representing the fluorescence intensity.

Detailed Description

The following examples are provided to illustrate specific embodiments of the present invention.