CN113004315B - Histidine-triggered organic hydrogel fluorescent probe and preparation method and application thereof - Google Patents

Histidine-triggered organic hydrogel fluorescent probe and preparation method and application thereof Download PDF

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CN113004315B
CN113004315B CN202110175668.XA CN202110175668A CN113004315B CN 113004315 B CN113004315 B CN 113004315B CN 202110175668 A CN202110175668 A CN 202110175668A CN 113004315 B CN113004315 B CN 113004315B
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牛和林
刘文胜
杨勇
廉笑
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Abstract

The invention discloses a histidine-triggered organic hydrogel fluorescent probe, a preparation method and application thereof, wherein histidine is used as a fluorescent trigger, and Zr is used as a fluorescent trigger 4+ As precursors and gel inducers, N-dimethylformamide and H are used 2 O is used as a mixed solvent to construct a histidine-triggered metal organic hydrogel fluorescent switch probe Zr-MOG-His. The method is used for stably, selectively and highly sensitively detecting and capturing the vitamins, amino acids and antibiotics remained in water, and the detection results show specificity to Rutin (RUT), beta-Carotene (CAR), vancomycin (VHE) and nitrofurantoin (FAN), good fluorescence change efficiency and excellent detection limit and practicability.

Description

Histidine-triggered organic hydrogel fluorescent probe and preparation method and application thereof
Technical Field
The invention relates to the field of material chemistry and sensing, in particular to a histidine-triggered organic hydrogel fluorescent probe, and a preparation method and application thereof.
Background
Development of a multifunctional fluorescent probe is important for selection and optimization of optical sensor substrate materials. Luminescent metal-organic gels have been attracting attention as an emerging class of metal-organic hybrid materials that combine some of the properties of metal-organic complexes and colloids, and have been increasingly used in the field of optical sensors.
Vitamins are trace elements necessary for maintaining normal physiological functions of human beings, and have important functions and effects on the life health of human beings. Rutin (vitamin P, rut) is a flavonoid vitamin that needs to be ingested by the human body for eliminating excessive free radicals in the human body. It has subtle effects on the development of various body systems and the removal of disease factors. However, although Rut has many benefits to humans, such as allergic people, obese patients and people with weak capillaries are not suitable to ingest such substances too much, and it is also notable that rutin is a serious hazard to aquatic organisms. Beta-carotene is a classical carotenoid which is effective in preventing diseases such as cancers, but is erroneously added to partial foods such as fried foods, which can cause toxic and side effects on human bodies. Antibiotics are broad spectrum drugs used to treat human diseases and bacterial infections. Vancomycin and nitrofurantoin are two common classes of anti-staphylococcus aureus, sensitive bacterial drugs, often used in clinical medicine. However, both antibiotics have been prohibited from being added to food. Illegally added into foods to achieve the effect of food preservation is a common means of illegal merchants. Therefore, it is necessary to effectively detect food additives and antibiotics in these foods.
The optical sensor has the advantages of high recognition efficiency, visual effect and good expression effect. Fluorescence sensors based on fluorescence quenching mode are a very classical type of optical detector and have been favored by many researchers. In addition, fluorescence sensors based on fluorescence enhancement modes have been attracting attention by researchers due to their excellent sensitivity and other characteristics. Both have advantages and disadvantages. Here, we have constructed a multifunctional fluorescence sensor using a metal organic gel as an optical substrate material for detecting and identifying these common food additives and antibiotics.
Disclosure of Invention
Histidine (His) is an essential basic amino acid in human body, contains carboxylic acid and a plurality of N binding sites, and has very important functions of regulating the steady state of the human body, balancing acid and alkali, controlling inflammatory reaction and improving the immunity of the human body. The invention provides a zirconium-based metal organic gel Zr-MOG-His with coordination induction luminescence effect triggered by amino acid, which is used for specifically and sensitively identifying and capturing Rut by taking His as a fluorescence starting 'key' and aiming at the defects of the existing experience and technology such as electrochemical method, colorimetric method, chromatographic method and the like. The electron-rich structure of His forms a good bridging site with trimesic acid that is strongly competitive. His serves as a good Lewis base in the system to regulate the pH, reduce the acidic environment of the system and promote the formation of a gel system. And the acidic environment easily causes His to be protonated, and positively charged N-containing functional groups block Zr 4+ Is of the interaction of (a) to indirectly induce Zr 4+ Form stable interaction force with-COO-.
Preparation method of histidine-triggered organic hydrogel fluorescent probe, which uses histidine as fluorescent trigger, zr 4+ As precursors and gel inducers, N-dimethylformamide and H are used 2 O is used as a mixed solvent to construct a histidine-triggered metal organic hydrogel fluorescent switch probe Zr-MOG-His.
The preparation method comprises the steps of DMF and H 2 O was transferred into the reaction vessel and then shaken well until thoroughly mixed, DMF and H 2 The volume ratio of O is 3:5-9:1; adding the ligand into the reaction container, and mixing and dissolving; the reaction vessel is sufficiently vibrated for 10-30min until the organic ligand in the system is completely dissolved, then 0.05mmoL-1 mole of Zr is added 4+ Adding into a mixed solvent; heating and vibrating the reaction system, and then placing the reaction system into an electrothermal blowing drying box, and heating the reaction system for 30min to 12h at the temperature of 80 to 120 ℃ to form white columnar gel.
The ligand is trimesic acid, terephthalic acid, graphene quantum dots, perovskite quantum dots, melamine and g-C 3 N 4 And organic acid or inorganic-organic hybrid nanodots having a plurality of carboxyl groups or amino groups.
According to the preparation method, the ligand is trimesic acid, and the molar ratio of His to trimesic acid is 1:1
The preparation method comprises DMF and H 2 The volume ratio of O is 7:3.
An organic hydrogel fluorescent probe prepared according to any one of the preparation methods.
The application of the organic hydrogel fluorescent probe is used for stably, selectively and highly sensitively detecting and capturing the vitamins, amino acids and antibiotics remained in water, and the detection results show specificity, good fluorescence change efficiency, excellent detection limit and practicability to Rutin (RUT), beta-Carotene (CAR), vancomycin (VHE) and nitrofurantoin (FAN).
DMF and H 2 O was transferred into the reaction vessel and then shaken well until thoroughly mixed, DMF and H 2 The volume ratio of O is 7:3 (at a mixing ratio of 3:5 to 9:1Any condition is satisfied); trimesic acid (ligands can be replaced by terephthalic acid, graphene quantum dots, perovskite quantum dots, melamine, g-C 3 N 4 Organic acid or inorganic-organic hybrid nanodots with a plurality of carboxyl groups or amino groups, etc.) are added into the reaction vessel, and His and trimesic acid are added according to the mole ratio of 1:1 (the mole ratio can be optionally regulated according to the requirement, the photoluminescence of other amino acids forming gel is verified or excluded through a plurality of experiments, and the experimental results show that after tryptophan, tyrosine, phenylalanine, arginine and histidine form metal organic gel, no obvious photoluminescence exists in the wavelength range of 300-500nm, and experimental record data are shown in table 1). His is used as an alkaline bridging ligand and Zr 4+ Coordination, thereby triggering the action of Zr-MOG-His fluorescence on. Sufficiently shaking the reaction vessel for 10-30min until the organic ligand in the system is completely dissolved, and then adding Zr 4+ (between 0.05mmoL and 1 mole of salt which can be fully dissolved or dispersed in the mixed solvent of DMF and water is added into the mixed solvent; heating and vibrating the reaction system, and then placing the reaction system into an electrothermal blowing drying oven for heating for 30min-12h at 80-120 ℃ in which the heating temperature is inversely proportional to the time, the higher the temperature is, the shorter the synthesis time is, the synthesis temperature is controlled within 25-170 ℃ to form white columnar gel, and the heating time is determined by the conditions of material ratio and the like. His triggered coordination induced luminescence metal organic gel prepared by the preparation method is fluorescent on after gel is formed, and the fluorescent on efficiency is enhanced according to the increase of His concentration; meanwhile, rutin, beta-carotene, vancomycin and nitrofurantoin have good stimulus response to the freeze-dried xerogel so as to generate quenching effect, and L-alanine and D-arginine have certain fluorescence enhancement effect to the freeze-dried xerogel.
Table 1 Metal organic gel formed by partial amino acids and its luminous mechanism
Figure BDA0002939702470000031
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Figure BDA0002939702470000041
The invention has the following advantages:
1. the target detection object can be specifically identified in water or serum;
2. a fluorescent switch probe with ligand-to-metal ligand coordination induced luminescence effect resulting in probe fluorescence on. And the effects of rapidly identifying and capturing rutin, beta-carotene, vancomycin and nitrofurantoin are achieved through energy resonance transfer or internal filtering effect.
3. Mixing detection with other food additives or antibiotics still does not affect the detection effect of the target detection object, and the quenching effect is instantly completed due to the synergistic effect of internal filtration effect or energy resonance transfer between the host and the object, so that the fluorescent probe has the advantages of rapid detection, sensitivity and good selectivity.
Drawings
FIG. 1 is an optical physical diagram of Zr-MOG-His gel;
FIG. 2 is a UV photopic image of Zr-MOG-His gel;
FIG. 3 optimization experiment of histidine to BTC ratio;
FIG. 4 is a scanning electron microscope and transmission electron microscope photograph of Zr-MOG-His xerogel;
FIG. 5 (a) structural formula of histidine, structural formula (b) trimesic acid;
FIG. 6 structural formulas of a target detection object and a target antibiotic;
FIG. 7 (a) fluorescence emission spectra of Zr-MOG-His xerogel identifying different kinds of food additives, (b) concentration gradient fluorescence emission spectra of Zr-MOG-His xerogel captured for Rut identification, (c) Rut Linear fitting map;
FIG. 8 (a) fluorescence change efficiency of Zr-MOG-His xerogel to recognize different antibiotics, (b) concentration gradient fluorescence emission spectrum of Zr-MOG-His xerogel to FAN recognition capture, (c) FAN linear fitting map;
FIG. 9 Zr-MOG-His xerogel, BTC, his, rut, zr-MOG-His+Rut solid state ultraviolet absorbance spectra;
FIG. 10 Zr-MOG-His xerogel recognizes and captures solid state fluorescence lifetimes before and after Rut;
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1:
the preparation method comprises the following concrete implementation steps:
1. hydrothermal solvothermal method: DMF and H 2 O was mixed in any ratio and transferred to a glass vial, and then shaken well until thoroughly mixed. BTC (0.1 g,0.05 mmol) and His were separately added to vials. And carrying out ultrasonic vibration treatment on the small glass bottle for 20s-3min until the ligand in the system is completely dispersed and dissolved. Then ZrCl is added 4 (0.046 g,0.2 mmol) was added to the mixed solvent. And finally, placing the reaction system into an electrothermal blowing drying oven, and heating at 80-120 ℃ for 30min-12h to form white columnar gel. The gel is then eluted with double distilled water or ethanol. In a high-speed centrifuge at 12000r min -1 High speed centrifugation was used to aid in removal of residual DMF from the gel. Finally, the eluted hydrogel is placed in a freeze drying box and dried in vacuum at the temperature of minus 110 ℃ to further remove residual DMF and uncrystallized H in the gel 2 O。
2. Ultrasonic assisted thermal method: the specific reactant amounts are the same as above. And placing the fully mixed and dissolved precursor in an ultrasonic heater, and carrying out ultrasonic heating to obtain the white columnar gel.
3. Microwave assisted method: the specific reactant consumption is the same as above, and the reaction vessel is replaced by a reaction kettle and a polytetrafluoroethylene lining. And (5) fully mixing the dissolved precursors in a microwave oven, and heating by microwaves to obtain the white columnar gel.
His: optimization of BTC ratio
Weighing a certain amount of His and BTC according to different molar ratios, respectively, pouring into a container containing DMF and H 2 The O mixed solvent is fully shaken in a glass bottle until the O mixed solvent is completely dissolved. ZrCl of the same mass 4 Respectively adding into the above small glass bottles. Stirring was carried out well at room temperature until complete dissolution. Finally, the mixed precursor is processedPlacing in an electrothermal blowing drying oven for heating at 120deg.C for 12 hr after fully sealing. Obtaining the Zr-MOG-His with different proportions of His and BTC. The residual DMF was removed by treatment with double distilled water and absolute ethanol and washing 3-10 times, respectively. The experimental results showed that the fluorescence intensity was highest when the ratio was 1:1 (FIG. 3).
Example 2: detection of Rut with Zr-MOG-His as fluorescent probe
The xerogel after freeze-drying of Zr-MOG-His hydrogels was used for Rut detection. Zr-MOG-His xerogel (100 mg) was dispersed in 5mL H 2 O or DMSO, sonicated for 30min until completely dispersed. The formulated dispersion was used to identify capture experiments.
Remove 100. Mu.L of Zr-MOG-His to centrifuge tubes with solutions of various target analytes (2.9 mL) and incubate at room temperature for 30-60min. After complete mixing of Zr-MOG-His and target analyte, the samples were used for subsequent stimulus response experiments of target analyte to Zr-MOG-His. Fluorescence spectra were recorded by excitation at 370 nm.
Rutin and beta-carotene selective identification (rutin is taken as an example)
His: freeze-dried gel of BTC-optimized gel was used for the stimulus response experiment of rutin. Zr-MOG-His xerogel (200 mg) was dispersed in 5mL DMF and sonicated for 20-50min until completely dispersed. The finally obtained dispersion liquid is used for a stimulus response experiment on rutin.
mu.L of Zr-MOG-His was transferred to a centrifuge tube containing solutions of different target analytes and incubated at room temperature for 30min. And finally, the obtained mixed dispersion liquid is used for selectively verifying rutin. The following food additives were selected as target analytes for rutin to conduct the selectivity experiments: rutin (RUT), carotene (CAR), L-aspartic acid (L-Asp), L-valine (L-Val), L-glutamic acid (L-Ula), L-histidine (L-His), DL-arginine (DL-Arg), melamine (Mel), sucrose (Suc), glucose (Glu), D-fructose (D-Fru), lactose (Lac), L-leucine (L-Lea), L-methionine (L-Met), L-isoleucine (L-Iso).
As can be seen from FIG. 7 (a), different food additives have different levels of quenching effect, wherein RUT and CAR significantly quench the fluorescence of Zr-MOG-HisAnd the fluorescent quenching efficiency is high. In addition, it is notable that the relative fluorescence intensity of Zr-MOG-His showed a linear decrease with increasing RUT concentration (FIG. 7 b). According to the Stern-Volmer (SV) formula: f (F) 0 /F＝1+K SV [M]Standard calculation formula lod=3σ/K of detection limit SV The value of Ksv and LOD are estimated. Wherein F is 0 And F is the fluorescence intensity of Zr-MOG-His gel dispersion before and after adding a certain concentration of RUT. [ M ]]Is the molar concentration of Zr-MOG-His gel, and K SV Is the quenching constant and σ is the standard deviation of the blank amount. With reference to fig. 7c, the detection limit of the RUT is calculated to be 0.011 μm, so that the RUT has good practical application potential and low sensitivity.
As shown in FIG. 7, rutin has excellent stimulus response results to Zr-MOG-His, and the energy resonance transfer efficiency is as high as 97.4% according to fluorescence lifetime. This may be due to the strong interaction between the host (Zr-MOG-His) and the guest (Rut) leading to fluorescence resonance energy transfer. This point is further demonstrated by the broad integrated overlap between the fluorescence emission spectrum of the Zr-MOG-His xerogel and the UV absorption spectrum of Rut. In addition, the solid state ultraviolet absorption spectrum of the Zr-MOG-His xerogel appears to be a distinct absorption band around 350nm-500nm after recognizing Rut, which suggests that a certain interaction is formed between the Zr-MOG-His xerogel and Rut, which may be attributed to the stable conjugated structure of the Zr-MOG-His xerogel itself, namely BTC, and stable pi-pi interaction is formed between His and Rut, so that the Zr-MOG-His xerogel can selectively capture Rut and generate fluorescent off signals. Based on the fluorescence lifetime before and after recognition, the mechanism of static quenching between hosts and guests is excluded (static quenching does not lead to a change in fluorescence lifetime). Therefore, the Zr-MOG-His xerogel becomes a sensing material with great potential for selectively identifying and capturing rutin.
Example 3: the selective identification of the antibiotics vancomycin and nitrofurantoin (as exemplified by nitrofurantoin), the procedure is as above, and the specific target antibiotics are selected as follows:
procaine Penicillin (PPG), thiamphenicol (TPL), vancomycin Hydrochloride (VHE), azithromycin (ATN), ceftazidime (CAE), cefoxitin sodium (CXN), cefuroxime (CRM), penicillin sodium (PCN), cefixime (CIE), amoxicillin (AMO), aztreonam (AEM), clarithromycin (CTN), tinidazole (TDE), metronidazole (MIE), nitrofurantoin (FAN).
Different antibiotics have different degrees of quenching or fluorescence enhancement effects, wherein FAN significantly quenched the fluorescence of Zr-MOG-His and had higher fluorescence quenching efficiency (fig. 8 a). In addition, it is notable that the relative fluorescence intensity of Zr-MOG-His showed a linear decrease with increasing FAN concentration (FIG. 8 b). According to the Stern-Volmer (SV) formula: f (F) 0 /F＝1+K SV [M]Standard calculation formula lod=3σ/K of detection limit SV The value of Ksv and LOD are estimated. Wherein F is 0 And F is the fluorescence intensity of Zr-MOG-His gel dispersion before and after adding certain concentration of FAN. [ M ]]Is the molar concentration of Zr-MOG-His gel, and K SV Is the quenching constant and σ is the standard deviation of the blank amount. Referring to FIG. 7c, the detection limit of the obtained FAN was calculated to be 0.597. Mu.M, so that the obtained Zr-MOG-His has good recognition ability for FAN.
It will be understood that modifications and variations will be apparent to those skilled in the art from the foregoing description, and it is intended that all such modifications and variations be included within the scope of the following claims.

Claims (4)

1. A preparation method of a histidine-triggered organic hydrogel fluorescent probe is characterized in that histidine is used as a fluorescent trigger, and Zr is used as a fluorescent trigger 4+ As precursors and gel inducers, N-dimethylformamide and H are used 2 O is used as a mixed solvent to construct a histidine-triggered metal organic hydrogel fluorescent switch probe Zr-MOG-His; DMF and H 2 O was transferred into the reaction vessel and then shaken well until thoroughly mixed, DMF and H 2 The volume ratio of O is 3:5-9:1; adding ligand trimesic acid into the reaction vessel, wherein the molar ratio of His to trimesic acid is 1:1, mixing and dissolving; the reaction vessel is sufficiently vibrated for 10-30min until the organic ligand in the system is completely dissolved, then 0.05mmoL-1 mole of Zr is added 4+ Adding into a mixed solvent; the reaction bodyHeating and vibrating, and then placing into a drying oven, heating at 80-120deg.C for 30min-12 min h to form white columnar gel.
2. The process according to claim 1, wherein DMF and H 2 The volume ratio of O is 7:3.
3. An organic hydrogel fluorescent probe prepared by the preparation method according to claim 1 or 2.
4. Use of the organic hydrogel fluorescent probe according to claim 3 for the preparation of a probe for detecting and capturing vitamins or antibiotics remaining in water, said vitamins or antibiotics being: rutin, beta-carotene, vancomycin, nitrofurantoin.
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CN110358109A (en) * 2019-08-14 2019-10-22 安徽大学 A kind of luminous Zr-MOG metal organogel and its synthetic method
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