CN115975636B - Chiral carbon dot, preparation method and application thereof - Google Patents
Chiral carbon dot, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a chiral carbon dot, a preparation method and application thereof, and belongs to the technical field of chiral identification. The chiral carbon dot is prepared by the following method: dissolving L-cysteine and L-lysine in water, adding sodium hydroxide solution, and reacting at high temperature; after the reaction is finished, cooling to room temperature; the reaction solution is filtered, dialyzed and freeze-dried to obtain chiral carbon dots. The chiral carbon point with the double-emission characteristic is prepared, the chiral identification of tryptophan enantiomer can be realized according to the fluorescent signal change at different emission wavelengths, and the convenience and the accuracy of the chiral identification are improved. The chiral carbon dot has the advantages of environmental protection, low cost, easy synthesis and the like, and the tryptophan fluorescence chiral recognition method based on the chiral carbon dot is simple, convenient, quick, sensitive and wide in application prospect.
Description
Technical Field
The invention belongs to the technical field of chiral recognition, and particularly relates to a chiral carbon dot, a preparation method and application thereof.
Background
Chirality is an essential feature in nature. Many biomolecules, including amino acids, sugars, proteins, and DNA, have chirality. Chiral molecules have the same chemical structure but often have different physiological functions. It is well known that only L-amino acids can be used for the synthesis of human proteins. Amino acid enantiomer recognition has been increasingly studied to facilitate a better understanding of the mechanism of molecular recognition in biological systems, further facilitating accurate diagnosis and treatment of diseases. Tryptophan (Trp) is an essential amino acid that plays a key role in the synthesis of human neurotransmitters and in the synthesis of auxins. In addition, trp levels in plasma are associated with liver disease, and therefore, it is important to identify tryptophan enantiomers and accurately determine their levels. However, accurately recognizing D-Trp and L-Trp remains a challenge because they have the same physicochemical properties except for optical rotation.
At present, methods for identifying Trp enantiomers include chromatography, round dichroism, electroanalytical chemistry, mass spectrometry, surface plasmon resonance, ultraviolet visible spectrometry, colorimetry and the like, but the methods have the problems of complex sample pretreatment, expensive instrument, complex operation, time consumption, low sensitivity, poor repeatability, weak anti-interference capability, requirement of professional technicians and the like. Fluorescence detection methods have been a chiral recognition method which has been favored in recent years because of their high sensitivity, simplicity and rapidity. Conventional fluorescent nanoparticles such as metal and semiconductor quantum dots, although excellent in properties, are not a green nanomaterial and have limited applications in biological systems.
The carbon dots are green nano materials with low biotoxicity, good photoluminescence performance, low cost and easy obtainment, so the synthesis of chiral carbon dots and the establishment of an amino acid enantiomer recognition method have important significance. However, synthesis of chiral carbon sites and their use in chiral recognition are relatively lacking. The chiral carbon point synthesized at present is limited to the identification of lysine and glutamic acid enantiomers in amino acid, and the chiral identification is based on the difference of fluorescence intensity signals under the same emission wavelength, so that the identification of enantiomers can not be realized according to the fluorescence emission peak position.
Disclosure of Invention
The invention aims to provide a chiral carbon point which can rapidly identify tryptophan enantiomers and realize detection of D-Trp and L-Trp.
The technical scheme of the invention is as follows:
a preparation method of chiral carbon dots comprises the following steps:
dissolving L-cysteine and L-lysine in water, adding sodium hydroxide solution, and reacting at high temperature; after the reaction is finished, cooling to room temperature; the reaction solution is filtered, dialyzed and freeze-dried to obtain chiral carbon dots.
In the preparation method, the mass ratio of the L-cysteine to the L-lysine is selected from 0.5-1:0.2-0.5. Preferably 1:0.5.
In the preparation method, the mass volume ratio of the L-cysteine to the water is selected from 0.5-1:50-80. Preferably 1:50, g: mL.
In the preparation method, the volume ratio of the sodium hydroxide solution to the water is selected from 1-2:10-16. Preferably 1:10. The concentration of the sodium hydroxide solution is selected from 0.1 to 0.5mol/L, preferably 0.1mol/L.
In the preparation method, the reaction conditions of the high-temperature reaction are as follows: the reaction temperature is selected from 100-140 ℃, preferably 120 ℃; the reaction time is selected from 4 to 12 hours, preferably 6 hours.
In the preparation method, a 0.22 mu m filter membrane can be adopted to filter the reaction solution; the filtrate can be dialyzed using a 1000Da dialysis bag.
The invention provides chiral carbon dots prepared by the method.
The invention provides application of the chiral carbon point in tryptophan enantiomer fluorescent recognition.
Specifically, in the above application, after incubation of tryptophan sample with chiral carbon point, fluorescence emission spectrum of the incubation system is scanned; if the tryptophan sample is L-tryptophan (L-Trp), the fluorescence intensity is obviously enhanced at 390 nm; if the tryptophan sample is D-tryptophan (D-Trp), the fluorescence intensity is obviously enhanced at 450 nm; if the tryptophan sample is a racemic mixture, the fluorescence intensity is enhanced at both 390nm and 450 nm.
The invention provides a tryptophan enantiomer recognition method, which comprises the following steps:
incubating a tryptophan sample with chiral carbon dots, and then scanning the fluorescence emission spectrum of the incubation system; if the fluorescence intensity is significantly enhanced at 390nm, the tryptophan sample is L-tryptophan; if the fluorescence intensity is significantly enhanced at 450nm, the tryptophan sample is D-tryptophan; if the fluorescence intensity is enhanced at both 390nm and 450nm, the tryptophan sample is a racemic mixture.
In the above identification method, the incubation may be selected from the group consisting of in phosphate buffer solution.
The beneficial effects of the invention are as follows:
the chiral carbon point with the double-emission characteristic is prepared, the chiral identification of tryptophan enantiomer can be realized according to the fluorescent signal change at different emission wavelengths, and the convenience and the accuracy of the chiral identification are improved. The chiral carbon dot has the advantages of environmental protection, low cost, easy synthesis and the like, and the tryptophan fluorescence chiral recognition method based on the chiral carbon dot is simple, convenient, quick, sensitive and wide in application prospect.
Drawings
FIG. 1 is a transmission electron microscope image of chiral carbon dots;
FIG. 2 is an infrared spectrum of chiral carbon dots;
FIG. 3 is an X-ray photoelectron spectrum of a chiral carbon point;
FIG. 4 is a circular dichroism spectrum of chiral carbon dots;
FIG. 5 is a graph of fluorescence emission spectra of chiral carbon dots at different excitation wavelengths;
FIG. 6 is a graph of fluorescence emission spectra of chiral carbon spots after incubation with different concentrations of L-Trp;
FIG. 7 is a graph of L-Trp assay standard;
FIG. 8 is a graph of fluorescence emission spectra of chiral carbon spots after incubation with different concentrations of D-Trp;
FIG. 9 is a D-Trp detection standard curve;
FIG. 10 is a graph of fluorescence emission spectra of chiral carbon spots after incubation with mixtures of Trp enantiomers in different mixing ratios;
FIG. 11 is a test standard curve for Trp enantiomer mixtures;
FIG. 12 is a fluorescence detection map of an actual sample;
fig. 13 is a high performance liquid chromatogram.
Detailed Description
The principle of the invention is as follows:
the chiral carbon point synthesized by the invention has chiral characteristics, two chromophores (the emission wavelength is 390nm and 450nm respectively) are arranged on the surface, and the chiral functional groups on the surface can form different three-dimensional interaction forces with L-Trp and D-Trp. The spatially matched forces between them limit intramolecular vibration and rotation of the functional groups in the chiral carbon sites and reduce non-radiative relaxation of the excited states, resulting in fluorescence enhancement. The different steric interactions between the L-Trp and D-Trp and the different chromophores on the chiral carbon dot surface lead to the change of fluorescence intensity at different emission wavelengths. Thus, L-Trp and D-Trp can be identified by fluorescence spectrum and variation in fluorescence intensity.
Other terms used in the present invention, unless otherwise indicated, generally have meanings commonly understood by those of ordinary skill in the art. The invention will be described in further detail below in connection with specific embodiments and with reference to the data. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
Example 1
Preparing chiral carbon points:
dispersing 1g L-cysteine and 0.5g L-lysine in 50mL of ultrapure water, adding 5mL of 0.1mol/L sodium hydroxide solution, uniformly mixing the solutions, transferring to a reaction kettle, and heating at 120 ℃ for 6 hours; after the reaction kettle is cooled to room temperature, the solution is filtered by a 0.22 mu m filter membrane, the filtrate is placed in a 1000Da dialysis bag for dialysis for 3 days, and the chiral carbon dot powder is obtained after freeze drying. 100mg of chiral carbon dot powder may be dissolved in 1000mL of water to prepare a chiral carbon dot solution having a concentration of 0.1 mg/mL.
Observing the morphology of chiral carbon points through a transmission electron microscope, wherein the synthesized chiral carbon points have good dispersibility and are spherical nano particles as shown in figure 1; by measuring the size of 200 chiral carbon dots in FIG. 1, a statistical distribution of the sizes was obtained, and it was found that the chiral carbon dot size distribution was in the range of 2 to 8nm, and the average size was 3.73nm.
FIG. 2 is an infrared spectrum of chiral carbon dots. As shown in FIG. 2, 3402cm -1 The adsorption peak at the position is derived from the stretching vibration of the N-H and O-H chemical bonds. 3130cm -1 The absorption peak at this point may be derived from the stretching vibration of the C-H bond in the H-c=c-H structure. 2620cm -1 The absorption peak at this point is a characteristic absorption peak of S-H. 1608cm -1 And 1390cm -1 The strong absorption peaks at c=n and C-N, respectively, are from the stretching vibrations. 1118cm -1 The absorption peak at this point is due to C-O stretching vibration. From the above analysis, it can be roughly judged that amino groups, hydroxyl groups, mercapto groups, aromatic groups and N, S doping structures exist in the synthesized chiral carbon dots.
FIG. 3 is an X-ray photoelectron spectrum of chiral carbon sites. As shown in fig. 3, four peaks are present at 283.8eV, 399.2eV, 530.4eV and 162.7eV, due to C1S, N1S, O1S and S2p, respectively. C. The element contents of N, O and S in chiral carbon points are 71.5%, 6.1%, 17.8% and 4.6%, respectively.
The invention researches the chiral characteristic of chiral carbon points through circular dichroism spectrum. FIG. 4 shows the circular dichroism spectrum of L-cysteine, L-lysine and chiral carbon dots, from which it can be seen that the circular dichroism spectrum of chiral carbon dots contains two signal peaks centered at 205nm and 240 nm. A signal peak centered at 205nm was also found in the circular dichroism spectrum of L-cysteine and L-lysine, indicating that the chiral structure represented at 205nm in the chiral carbon spot was derived from the chiral precursor. The special signal at 240nm in the chiral carbon sites indicates the generation of a new chiral structure. Furthermore, the chiral configuration of the new chiral centers is opposite to that of the chiral precursors, since their circular dichroism spectrum signals are opposite.
The fluorescence emission spectra of chiral carbon dots at different excitation wavelengths are shown in fig. 5. It can be seen that the chiral carbon point has two emission peaks, but the two emission peaks partially coincide. When the excitation wavelength is changed from 320nm to 380nm, the maximum emission wavelengths of both peaks are red shifted, indicating that the excitation of chiral carbon dots depends on the emission characteristics.
Example 2
Constructing an L-Trp detection standard curve:
to a 10mL centrifuge tube containing 100. Mu.L of chiral carbon spot solution (0.1 mg/mL), 1mL of L-Trp solution at a concentration of 0M, 0.01M, 0.02M, 0.03M, 0.04M, 0.05M, 0.06M, 0.07M, 0.08M, 0.09M was added, and the volume was made up to 5mL with phosphate buffer solution (pH=7.4), to thereby obtain detection solutions having L-Trp concentrations of 0mM, 2mM, 4mM, 6mM, 8mM, 10mM, 12mM, 14mM, 16mM, 18mM, respectively. Incubation was performed for 1min at room temperature and fluorescence emission spectra of the incubation solutions were determined.
As a result of the experiment, as shown in FIG. 6, the fluorescence intensity signal of the incubation solution at 390nm was gradually increased as the concentration of L-Trp was increased. Fluorescence intensity signal increment (I-I) on the abscissa of L-Trp concentration 0 ) As the ordinate, a standard curve is constructed, as shown in FIG. 7, fluorescenceIntensity signal increment (I-I) 0 ) Is in linear relation with the concentration of L-Trp in the concentration range of 2-18 mM, the regression equation is y=71.41x+99.02, R 2 The limit of detection can reach 0.21mM, = 0.9920, and thus, the L-Trp can be quantitatively analyzed by this standard curve.
Example 3
Constructing a D-Trp detection standard curve:
to a 10mL centrifuge tube containing 100. Mu.L of chiral carbon spot solution (0.1 mg/mL), 1mL of D-Trp solutions each having a concentration of 0M, 0.01M, 0.02M, 0.03M, 0.04M, 0.06M, and 0.07M were added, and the volume was made up to 5mL with phosphate buffer solution (pH=7.4), to thereby obtain detection solutions each having a concentration of D-Trp of 0mM, 2mM, 4mM, 6mM, 8mM, 12mM, and 14 mM. Incubation was performed for 1min at room temperature and fluorescence emission spectra of the incubation solutions were determined.
As a result of the experiment, as shown in FIG. 8, the fluorescence intensity signal of the incubation solution at 450nm was gradually increased as the concentration of D-Trp was increased. Fluorescence intensity signal increment (I-I) on the abscissa of D-Trp concentration 0 ) As shown in FIG. 9, a standard curve was constructed for the ordinate, and the increase in fluorescence intensity signal (I-I 0 ) The regression equation of the compound is y=8.232x+47.06, R is that the compound has a linear relation with the concentration of D-Trp in the concentration range of 2-14 mM 2 The limit of detection can reach 1.69mM, and thus D-Trp can be quantitatively analyzed by this standard curve.
Example 4
Constructing a test standard curve of the Trp enantiomer mixture:
to a 10mL centrifuge tube containing 100. Mu.L of chiral carbon spot solution (0.1 mg/mL), 1mL of a solution of the Trp enantiomer mixture having an L-Trp content of 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100% was added, respectively, and the volume was made up to 5mL with a phosphate buffer solution (pH=7.4). Incubation was performed for 1min at room temperature and fluorescence emission spectra of the incubation solutions were determined.
As a result of the experiment, as shown in FIG. 10, the fluorescence intensity signals of the incubation solutions at 390nm and 450nm increased with an increase in the L-Trp ratio (from 0% to 100%). Fluorescence intensities at 390nm and 450nm, on the abscissa, with the percentage content of L-TrpSignal ratio (I) 390 /I 450 ) As shown in FIG. 11, a standard curve was constructed for the ordinate, the ratio of fluorescence intensity signals at 390nm and 450nm (I 390 /I 450 ) The regression equation is y=0.0091x+0.8345, R, which is linearly related to the percentage content of L-Trp 2 =0.987, therefore, the Trp enantiomer mixtures can be purity-determined by this standard curve.
Application example 1
L-tryptophan is commonly used as a human nutritional supplement as an essential amino acid. Food grade L-tryptophan additives are obtained from the market, and the L-tryptophan content is detected by the method. The specific method comprises the following steps:
1.0g of the food-grade L-tryptophan additive is weighed, dissolved by water, transferred to a 200mL volumetric flask, and added with water to fix the volume to a scale, so as to obtain an actual sample solution of 5mg/mL L-tryptophan. To a 10mL centrifuge tube containing 100. Mu.L of chiral carbon spot solution (0.1 mg/mL), 1mL of the above-mentioned L-tryptophan actual sample solution was added, and the volume was made up to 5mL with phosphate buffer solution (pH=7.4). Incubation was performed for 1min at room temperature and fluorescence emission spectra of the incubation solutions were determined.
As a result of the test, as shown in FIG. 12, the concentration of L-tryptophan in the actual sample solution was measured to be 24.1mM, i.e., 4.92mg/mL, based on the L-Trp assay standard curve, and the content of L-tryptophan in the commercially available food-grade L-tryptophan additive was 0.98g/g, with a purity of about 98%.
And comparing the detection result obtained by the method with data obtained by high performance liquid chromatography, thereby verifying the reliability of the method. The specific method comprises the following steps:
l-tryptophan standard solutions with the concentration of 1mM, 2mM, 4mM, 6mM, 8mM and 10mM are prepared, 1mL of the actual sample solution is additionally taken, and the volume is supplemented to 5mL by a phosphate buffer solution (pH=7.4), so as to obtain an actual sample detection solution. Analysis was performed under 10% methanol/90% ammonium acetate mobile phase conditions and the chromatogram is shown in figure 13. The standard curve is constructed with L-tryptophan concentration as abscissa and chromatographic peak area as ordinate, and regression equation is y=702008 42x+67823.33, R 2 = 0.9963. The concentration of L-tryptophan in the actual sample solution was measured to be 23.7mM based on the quantitative relationship,i.e., 4.84mg/mL, the L-tryptophan content in the commercial food grade L-tryptophan additive was 0.97g/g, with a purity of about 97%. The experimental result shows that the result measured by the method is consistent with the high performance liquid chromatography, and the method is rapid and accurate.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (6)
1. The preparation method of the chiral carbon dot is characterized by comprising the following steps:
dissolving L-cysteine and L-lysine in water, adding sodium hydroxide solution, and reacting at high temperature; after the reaction is finished, cooling to room temperature; filtering, dialyzing and freeze-drying the reaction solution to obtain chiral carbon points;
the mass ratio of the L-cysteine to the L-lysine is selected from 0.5-1:0.2-0.5; the mass volume ratio of the L-cysteine to the water is selected from 0.5-1:50-80; the volume ratio of the sodium hydroxide solution to the water is selected from 1-2:10-16; the concentration of the sodium hydroxide solution is selected from 0.1 to 0.5mol/L; the reaction conditions of the high-temperature reaction are as follows: the reaction temperature is selected from 100-140 ℃, and the reaction time is selected from 4-12 h.
2. The method according to claim 1, wherein the reaction solution is filtered using a 0.22 μm filter; the filtrate was dialyzed using a 1000Da dialysis bag.
3. A chiral carbon dot prepared by the method of any one of claims 1-2.
4. Use of a chiral carbon point according to claim 3 for the fluorescent recognition of tryptophan enantiomers.
5. A tryptophan enantiomer recognition method, which is characterized by comprising the following steps:
incubating a tryptophan sample with the chiral carbon point of claim 3, and then scanning the fluorescence emission spectrum of the incubation system; if the fluorescence intensity is significantly enhanced at 390nm, the tryptophan sample is L-tryptophan; if the fluorescence intensity is significantly enhanced at 450nm, the tryptophan sample is D-tryptophan; if the fluorescence intensity is enhanced at both 390nm and 450nm, the tryptophan sample is a racemic mixture.
6. The method of claim 5, wherein the incubating is in a phosphate buffer solution.
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| CN115386372A (en) * | 2022-09-21 | 2022-11-25 | 中国科学院兰州化学物理研究所 | Preparation of chiral fluorescent carbon dots and application of chiral fluorescent carbon dots in identification and detection of tyrosine enantiomers |
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| CN115386372A (en) * | 2022-09-21 | 2022-11-25 | 中国科学院兰州化学物理研究所 | Preparation of chiral fluorescent carbon dots and application of chiral fluorescent carbon dots in identification and detection of tyrosine enantiomers |
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| "碳点的类酶活性及其在靶向氮信号分子抑制神经元死亡中的应用";欧阳路飞;《中国优秀硕士学位论文全文数据库 医药卫生科技辑》(02);第E066-223页 * |
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