A zinc-orotic acid complex crystal material, its preparation method, and its fluorescence recognition application.

Abstract

This invention discloses a zinc-orotic acid complex crystal material, its preparation method, and its fluorescence recognition application. The chemical formula of the complex is [Zn2(HOA)2(1,3-dpp)(H2O)2]. n It possesses a two-dimensional, double-interlaced network structure. Its preparation method involves preparing solutions of orotic acid, potassium hydroxide, and zinc acetate, mixing them with 1,3-bis(4-pyridyl)propane and water, and then subjecting the mixture to ultrasonic and heat treatment to obtain crystals. This material exhibits characteristic fluorescence emission at 370 nm, the intensity of which changes significantly upon contact with specific substances. This property can be utilized as a fluorescent sensing material to identify solvents such as methanol, DMSO, and water, and to specifically detect Fe. 3+ Ions that can identify antibiotics such as dimethylaminetetracycline hydrochloride, nitrofurazone, and nitrofurantoin; drugs such as curcumin; and food additives such as potassium sorbate and sodium benzoate.

Description

Technical Field

[0001] This invention belongs to the technical field of crystalline materials, specifically metal-organic coordination polymer materials, and more specifically, a zinc-orotic acid complex crystalline material, its preparation method, and its fluorescent recognition application. Background Technology

[0002] The emission and accumulation of various pollutants are the main causes of environmental problems. Achieving efficient detection and accurate identification of pollutants in the environment is a key technological step in solving environmental governance challenges. Fluorescence detection, due to its advantages of simple operation, short response time, and high sensitivity, is currently widely used in pollutant detection.

[0003] Iron is a core component of many enzymes in living organisms, such as catalase and cytochrome oxidase, as well as key proteins like hemoglobin and myoglobin, participating in numerous important physiological processes including oxygen transport, energy metabolism, and DNA synthesis. Simultaneously, iron ion content is also a crucial indicator for monitoring water and soil environmental quality. Excessive iron ions can cause water to appear turbid and yellowish-brown, reducing water transparency and hindering photosynthesis in aquatic plants. Furthermore, iron ions can combine with phosphates in the water to form precipitates, disrupting the nutrient balance of aquatic bodies and inducing eutrophication. In addition, excessively high iron ion concentrations in the soil can inhibit the absorption of micronutrients such as zinc and manganese by plants, leading to malformed plant growth and reduced crop yields.

[0004] Food additives, as a core component of the modern food industry, play a crucial role in improving food quality, extending shelf life, and optimizing processing characteristics. However, their use beyond permitted scope or limits, or illegal addition, can pose health risks. Therefore, accurate and efficient detection of food additives is a core support for the food safety assurance system. Furthermore, the detection of antibiotics, widely used in livestock and aquaculture, is also essential. Thus, establishing an efficient, sensitive, and rapid detection system for food additives and antibiotics is of paramount practical significance.

[0005] Compared to traditional detection technologies such as atomic absorption spectroscopy and inductively coupled plasma, fluorescence recognition technology does not require complex sample pretreatment procedures and can achieve rapid on-site detection, enabling timely and accurate assessment of contamination levels such as iron ions, food additives, and antibiotics.

[0006] Metal-organic coordination polymers (MOCPs) are crystalline materials formed by the self-assembly of metal ions / clusters and organic ligands through weak interactions such as coordination bonds, hydrogen bonds, and π-π stacking. They combine the tunability of inorganic metal ions with the functionality of organic ligands, possessing diverse topological structures, abundant active sites, tunable optical properties, and excellent host-guest recognition capabilities. They exhibit unique advantages in fluorescence sensing and recognition, becoming important research carriers in environmental monitoring, biomedicine, and food safety. Among the ligands used in the synthesis of MOCPs, biomolecular applications are relatively limited. However, biomolecular synthesis of complexes is not only green, sustainable, and environmentally friendly, but also has relatively good biocompatibility, which is beneficial for applying these complex materials in the biological field. Orotic acid, also known as vitamin B13, is a nutritional supplement with the molecular formula C5H4N2O4. The orotic acid structure contains both -COOH and N atoms that can coordinate; therefore, orotic acid can be used to synthesize complexes. This invention, guided by the synthesis of novel complex fluorescent probes, selects orotic acid (H3OA) and 1,3-bis(4-pyridyl)propane (1,3-dpp) as ligands to precisely design and synthesize a probe capable of rapidly identifying H2O and Fe. 3+ A Zn complex of potassium sorbate, sodium benzoate, and curcumin (R-Zn-1). Structural analysis shows that R-Zn-1 has a 2-fold interpenetrating layered structure with excellent stability. It reacts with H₂O and Fe. 3+ Fluorescence quenching occurs, and the phenomenon is obvious; it can be used to detect H2O and Fe. 3+ The presence of [a specific compound] was observed. In the identification of food additives, this complex showed good recognition effects for potassium sorbate and sodium benzoate, with a fluorescence quenching rate exceeding 99%. Furthermore, it exhibited some recognition activity for antibiotics; the strongest peak position shifted significantly after the addition of nitrofurazone, nitrofurantoin, and methaqualone hydrochloride. The fluorescence recognition method is simple to operate, produces obvious phenomena, and has high detection efficiency. Therefore, this complex (R-Zn-1) is effective for detecting Fe in the ecological environment. 3+ And antibiotics, food quality and safety H2O, Fe 3+ Potassium sorbate, sodium benzoate, etc. have potential application value. Summary of the Invention

[0007] One of the objectives of this invention is to provide a zinc-orotic acid complex crystal material.

[0008] The chemical formula of the zinc-orotic acid coordination polymer crystal material is [Zn2(HOA)2(1,3-dpp)(H2O)2]. n It was named R-Zn-1, with orotic acid H3OA as its first ligand. 2- H3OA loses 2 H's+ This is due to the fact that H3OA has CAS number 65-86-1 and its chemical structure is shown below:

[0009] ;

[0010] The second ligand is 1,3-bis(4-pyridyl)propane 1,3-dpp, CAS: 17252-51-6, and its chemical structure is shown below:

[0011] .

[0012] Furthermore, from the perspective of structural connection construction, the zinc-orotic acid complex crystal material R-Zn-1 is a 2-fold interpenetrating two-dimensional network structure, and its crystal structure belongs to the tetragonal crystal system. I Space group 41 / acd, cell parameters: a = 18.725(4) Å, b = 18.725(4) Å, c = 30.285(7) Å. α =90, β =90, γ =90.

[0013] Furthermore, the asymmetric structural unit of R-Zn-1 contains one Zn(II) and one HOA. 2- The ligand consists of half a 1,3-dpp molecule and a coordinating water molecule; the Zn(II) molecule has a coordination number of 5 and binds to two molecules from HOA. 2- O, a from HOA 2- One N from 1,3-dpp and one O from the coordinated water molecule are coordinated; four Zn(II) molecules are coordinated via HOA. 2- The connections form a small [Zn4(HOA)4] quadrivalent ring secondary building unit, abbreviated as SBU; this SBU is coordinated with four 1,3-dpp units to form a 2D layered structure. Therefore, according to topological knowledge, the [Zn4(HOA)4] SBU can be simplified to a 4-node, and the 2D layered structure can be simplified to a (4,4)-mesh. In this layered structure, the quadrilateral mesh formed by the four [Zn4(HOA)4] SBUs and the four 1,3-dpp units has a side length of 18.6 Å × 18.6 Å. Due to the large space of this mesh, two identical meshes intersect in space, ultimately forming a 2-fold intersecting layered structure.

[0014] The present invention also provides a method for preparing the crystalline material R-Zn-1, comprising the following steps:

[0015] A method for preparing a metal-organic framework material includes the following steps:

[0016] (1) Dissolve orotic acid and potassium hydroxide in water and stir for at least 2 hours to obtain solution R-1;

[0017] (2) Dissolve zinc acetate in water and stir until dissolved to obtain a Zn-1 solution;

[0018] (3) Mix the R-1 solution obtained in step (1), the Zn-1 solution obtained in step (2), 1,3-bis(4-pyridyl)propane 1,3-dpp and pure water;

[0019] (4) The mixture obtained in step (3) is subjected to ultrasonic treatment for no less than 0.5 hours, then heated at 90°C for 72 hours, and then slowly cooled to room temperature to obtain colorless transparent crystals.

[0020] Furthermore, in step (1), the molar ratio of orotic acid to potassium hydroxide is 1:1. In the mixed solution, orotic acid loses one H proton, and the concentration of deprotonated orotic acid is 0.1 mmol / mL.

[0021] Furthermore, in step (2), the concentration of zinc acetate in the Zn-1 solution is 0.1 mmol / mL.

[0022] Furthermore, in S3, the volume ratio of R-1 solution to Zn-1 solution is 2:1, and the molar ratio of 1,3-dpp to zinc acetate is 2:1.

[0023] The present invention also provides the application of the coordination polymer material R-Zn-1 described in the above technical solution in the preparation of fluorescent sensing materials.

[0024] Furthermore, the R-Zn-1 is used for solvent detection and can specifically identify at least one of methanol, dimethyl sulfoxide, and water.

[0025] Furthermore, the R-Zn-1 is used for metal ion detection and can specifically identify Fe. 3+ .

[0026] Furthermore, the R-Zn-1 is used in the detection of Fe 3+ At that time, for K + Ag + Co 2+ Ni 2+ Zn 2+ Cd 2+ Pb 2+ Cu 2+ Cr 3+ Plasma has anti-interference capabilities.

[0027] Furthermore, the R-Zn-1 is used for antibiotic detection and can specifically identify at least one of dimethylaminetetracycline hydrochloride, nitrofurazone, and nitrofurantoin.

[0028] Furthermore, the R-Zn-1 is used for drug detection and can specifically identify curcumin.

[0029] Furthermore, the R-Zn-1 is used for food additive detection and can specifically identify potassium sorbate.

[0030] Beneficial technical effects of the present invention:

[0031] This invention successfully prepared and characterized a chemical formula [Zn2(HOA)2(1,3-dpp)(H2O)2]. n A novel zinc-orotic acid coordination polymer crystal material (R-Zn-1) was developed. This material possesses a unique 2-fold interpenetrating two-dimensional layered structure, exhibiting excellent thermal stability and solid-state fluorescence properties. Compared with the single ligands (orotic acid and 1,3-bis(4-pyridyl)propane), the fluorescence emission peak of this complex shows a blue shift, indicating that its optical properties are effectively regulated by metal coordination.

[0032] This R-Zn-1 material has been proven to be a highly efficient and selective multifunctional fluorescent probe. Experiments show that its fluorescence emission (at approximately 370 nm) undergoes significant quenching upon encountering specific substances, enabling rapid and sensitive identification of a variety of targets. Specifically, it can highly selectively detect water and dimethyl sulfoxide solvents, with a fluorescence quenching rate exceeding 99% for water and DMSO; it can specifically identify Fe... 3+ This material exhibits a quenching rate of 99.06% and is unaffected by interference from other metal ions. Among antibiotics, it effectively identifies doxycycline, dimethylaminetetracycline hydrochloride, nitrofurazone, and nitrofurantoin. In food additives, it specifically detects potassium sorbate and sodium benzoate, with a quenching rate exceeding 99%. Furthermore, its recognition of curcumin is also remarkably effective. This material combines biomolecules with functional ligands, offering advantages such as simple preparation methods, intuitive responses, and diverse recognition capabilities. It holds immense application potential in environmental pollutant monitoring, food safety testing, and biosensing. Attached Figure Description

[0033] Figure 1 A schematic diagram of the coordination environment of Zn(II) in R-Zn-1 of this invention (symmetric code: #1 3 / 4 - x, 1 / 4 + y, 5 / 4 - z; #2 2-x, 1 / 2-y, z.

[0034] Figure 2 The R-Zn-1 of this invention contains orotic acid (H3OA), 1,3-dpp and Zn. 2+ A 2D mesh structure.

[0035] Figure 3 This is the 2-fold interpenetration structure present in R-Zn-1 of the present invention.

[0036] Figure 4 This is the infrared spectrum of R-Zn-1 of the present invention.

[0037] Figure 5 This is a thermogravimetric analysis diagram of R-Zn-1 of the present invention.

[0038] Figure 6 This is the X-ray powder diffraction pattern of R-Zn-1 of the present invention.

[0039] Figure 7 The fluorescence emission spectra of R-Zn-1, ligand H3OA, and 1,3-dpp of this invention are shown.

[0040] Figure 8 This is the fluorescence emission spectrum of R-Zn-1 in common solvents according to the present invention.

[0041] Figure 9 This is a bar chart showing the intensity of the strongest emission peak of R-Zn-1 in common solvents in this invention.

[0042] Figure 10 This is an image (254 nm wavelength) of R-Zn-1 in aqueous solution under ultraviolet light.

[0043] Figure 11 This is an image (254 nm wavelength) of R-Zn-1 in DMSO solution under ultraviolet light.

[0044] Figure 12 For the present invention R-Zn-1 in 10 -3 Fluorescence emission spectrum in mmol / mL non-rare earth metal salt solution.

[0045] Figure 13 For the present invention R-Zn-1 in 10 -3 Bar graph of the strongest emission peak intensity in mmol / mL non-rare earth metal salt solution.

[0046] Figure 14 Adding Fe to R-Zn-1 in this invention 3+ Images taken before and after exposure to 254 nm wavelength ultraviolet light.

[0047] Figure 15 For the present invention R-Zn-1 in 10 -3 Fluorescence emission spectrum in mmol / mL rare earth salt solution.

[0048] Figure 16 The addition of other non-rare earth metal ions to R-Zn-1 in this invention affects the Fe... 3+ Bar graph of anti-interference experiment.

[0049] Figure 17 For the present invention R-Zn-1 in 10 -4 Fluorescence emission spectrum of antibiotic solution at mmol / mL.

[0050] Figure 18 For the present invention R-Zn-1 in 10 -4 Bar graph of emission peak intensity near 370 nm in mmol / mL antibiotic solution.

[0051] Figure 19 For the present invention R-Zn-1 in 10 -3 Fluorescence emission spectrum of mmol / mL drug solution.

[0052] Figure 20 For the present invention R-Zn-1 in 10 -3 Fluorescence emission spectrum of amino acid solution at mmol / mL.

[0053] Figure 21 The fluorescence emission spectrum of R-Zn-1 in a 1.0 mg / mL inorganic salt food additive solution is shown.

[0054] Figure 22 This is a bar graph showing the intensity of the strongest emission peak of R-Zn-1 near 305 nm in an inorganic salt food additive solution according to the present invention.

[0055] Figure 23 This is a bar graph showing the intensity of the strongest emission peak of R-Zn-1 near 370 nm in an inorganic salt food additive solution according to the present invention.

[0056] Figure 24 Images of R-Zn-1 before and after the addition of potassium sorbate under ultraviolet light at a wavelength of 254 nm.

[0057] Figure 25 Images of R-Zn-1 before and after the addition of sodium benzoate under ultraviolet light at a wavelength of 254 nm.

[0058] Figure 26 The fluorescence emission spectrum of R-Zn-1 in a 1.0 mg / mL organic food additive solution is shown.

[0059] Figure 27 This is a bar graph showing the intensity of the strongest emission peak of R-Zn-1 near 305 nm in an organic food additive solution.

[0060] Figure 28 This is a bar graph showing the intensity of the strongest emission peak of R-Zn-1 near 370 nm in an organic food additive solution. Detailed Implementation

[0061] The present invention will be further described below with reference to the embodiments, but the present invention is not limited to the following embodiments.

[0062] Example 1

[0063] Weigh 1.56 g of orotic acid and 0.56 g of KOH into a small beaker, add 100 mL of purified water, and stir with a magnetic stir bar for more than 2 hours. We name this solution R-1, which is actually 0.1 mmol / mL orotic acid with two hydrogen atoms removed. Weigh 2.2 g of zinc acetate into a small beaker, add 100 mL of purified water, and stir until dissolved. We name this solution Zn-1. Finally, use a syringe to draw 1 mL of the above R-1 solution and 0.5 mL of the Zn-1 solution into a 20 mL sample vial. Weigh 20 mg (0.1 mmol) of 1,3-dpp, add 6 mL of purified water, and seal the vial. Place the vial in an ultrasonicator and sonicate for more than half an hour. After sonication, place the vial in an oven at 90°C for 72 hours. Allow the temperature to slowly cool to room temperature to obtain colorless transparent crystals (referred to as complex R-Zn-1).

[0064] See below for details:

[0065] (1) Determination of crystal structure:

[0066] Crystals with good growth and few cracks were selected and adhered to thinned glass wires. Diffraction data of R-Zn-1 were collected at room temperature under Mo-Kα radiation (λ=0.71073Å) using a Bruker APEX-II CCD single-crystal diffractometer. The structure was solved using the XS structure solver and optimized using the SHELXTL software package using the least squares method. Anisotropic shift parameters of non-hydrogen atoms were provided during the improvement process. The positions of hydrogen atoms on the ligands were determined using theoretical hydrogenation. Crystallographic data are shown in Table 1.

[0067] Table 1 Crystallographic data of R-Zn-1 materials

[0068]

[0069] The structural diagram of the complex R-Zn-1 is as follows: Figure 1-3 As shown, Figure 1 This indicates the coordination environment of Zn(II), showing that the asymmetric structural unit of R-Zn-1 contains one Zn(II) and one HOA. 2- The ligand consists of half a 1,3-dpp molecule and a coordinating water molecule; the Zn(II) molecule has a coordination number of 5 and binds to two molecules from HOA. 2- O, a from HOA 2-One N from 1,3-dpp and one O from the coordinated water molecule are coordinated; four Zn(II) molecules are coordinated via HOA. 2- The connections form a small [Zn4(HOA)4] quaternary ring secondary building unit; this quaternary ring secondary building unit is interconnected with four 1,3-dpp coordinated units to form a 2D layered structure. Figure 2 Therefore, based on topological knowledge, the [Zn4(HOA)4] quadrature ring secondary building units are simplified to 4-nodes, and the 2D layered structure can be simplified to a (4,4)-mesh. In this layered structure, the quadrilateral mesh formed by four [Zn4(HOA)4] quadrature ring secondary building units and four 1,3-dpp units has a side length of 18.6Å × 18.6Å. Due to the large space of this mesh, two identical meshes intersect in space, ultimately forming a 2-fold intersecting layered structure. Figure 3 ).

[0070] Figure 4 The Fourier transform infrared spectrum shows that, using a Shimadzu FTIR-8400S spectrometer, the wavelength range is 4000-500 cm⁻¹. −1 FT-IR spectra of R-Zn-1 were collected within the range of [specific range], and the corresponding characteristic absorption peaks were characterized. Major absorption peaks (KBr, cm⁻¹) -1 The major absorption peaks were: 3138.06 (w), 2360.63 (w), 1668.99 (m), 1607.89 (s), 1471.50 (w), 1418.24 (m), 1397.21 (m), 1337.16 (w), 1025.56 (w), 948.21 (w), 855.02 (w), 805.14 (m), 779.93 (w), 668.06 (w), and 505.02 (w). No -COOH was observed at 1710 cm⁻¹. -1 The strong characteristic peaks near the metal indicate that the carboxyl group has lost its protons and participated in coordination, confirming the coordination between the metal and the ligand. This is consistent with the results of X-ray single-crystal diffraction data analysis.

[0071] Figure 5 The thermogravimetric analysis results show that the R-Zn-1 framework structure is very stable, and can remain stable at temperatures above 200℃.

[0072] Figure 6 This is the X-ray powder diffraction pattern of R-Zn-1 of the present invention. Within the 5-50° range, the simulation and experimental data of this complex show good fit, indicating that the complex has high purity.

[0073] Figure 7This is the solid-state fluorescence emission spectrum of R-Zn-1 and its ligands according to the present invention. The solid-state emission spectra of R-Zn-1 and its ligands were studied at room temperature. H3OA exhibited its strongest emission peak at 393 nm with an excitation wavelength of 275 nm, while the strongest emission peak of 1,3-dpp appeared at 401 nm. In the R-Zn-1 complex, the strongest emission peak appeared at 379 nm with an excitation wavelength of 275 nm. Compared to the ligand, the strongest excitation peak of R-Zn-1 showed a slight blue shift, which is related to the coordination between the ligand and the metal ion.

[0074] Example 2 Solvent Identification Experiment

[0075] At room temperature, a powder sample (3 mg) of complex R-Zn-1 was immersed in 3 mL of 10 different organic solvents: 1,4-dioxane, acetonitrile (CH3CN), n-hexane, anhydrous methanol (MeOH), anhydrous ethanol (EtOH), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), and water (H2O). The mixture was then sonicated for 15 min to obtain a suspension for fluorescence detection.

[0076] The fluorescence spectra of R-Zn-1 in different solvents indicate that ( Figure 8 When the excitation wavelength is 275 nm, the strongest emission peaks are all around 370 nm. Compared with solid-state fluorescence, its strongest emission peak undergoes a slight blue shift, and the fluorescence intensity varies greatly in different solvents. In 1,4-dioxane, the strongest emission peak intensity is highest around 370 nm, and in addition to the strongest emission peak around 370 nm, there is also a shoulder peak around 305 nm. When added to anhydrous methanol (MeOH), dimethyl sulfoxide (DMSO), and water (H2O), fluorescence quenching occurs. In dimethyl sulfoxide (DMSO) and water (H2O), the fluorescence quenching rate reaches over 99%. Therefore, this complex has recognition effects on MeOH, DMSO, and H2O, with better recognition effects on DMSO and H2O. Among these 10 different solvents, the intensity of the strongest emission peak near 370 nm decreased in the following order: Dioxane > CH3CN > n-Hexane > EtOH > DMA > NMP > DMF > MeOH > DMSO > H2O Figure 9 The above phenomenon can be attributed to the interaction between the complex and solvents with different polarities, which is an intermolecular interaction caused by the difference in solvent polarity.

[0077] Figure 10This is an image (254 nm wavelength) of R-Zn-1 in aqueous solution under ultraviolet light. The quenching phenomenon in water is significant compared to that in the solvent 1,4-dioxane.

[0078] Figure 11 This is an image (254 nm wavelength) of R-Zn-1 in DMSO solution under ultraviolet light. The quenching phenomenon is significant in DMSO compared to the complex in the solvent 1,4-dioxane.

[0079] Example 3 Metal Ion Recognition Experiment

[0080] R-Zn-1 was added to a 0.001 mmol / mL solution of 11 non-rare earth metal salts (KNO3, Al(NO3)3, Cr(NO3)3, Fe(NO3)3, Co(NO3)2, Ni(NO3)2, Cu(NO3)2, Zn(NO3)2, Pb(NO3)2, AgNO3, Cd(NO3)2) and 14 rare earth metal salts (Y(NO3)3, La(NO3)3, Ce(NO3)3, Pr(NO3)3, Nd(NO3)3, Sm(NO3)3, Eu(NO3)3, Gd(NO3)3, Tb(NO3)3, Dy(NO3)3, Er(NO3)3, Tm(NO3)3, Yb(NO3)3, and Lu(NO3)3) prepared in 1,4-dioxane as solvent. Figure 12 The fluorescence emission spectra of R-Zn-1 in solutions of different non-rare earth metal ions are shown. Figure 13 This is a bar chart showing the intensity of the strongest emission peak of R-Zn-1 in different non-rare earth metal ion solutions. Compared with the blank sample without added metal salt, the strongest peak position is still around 370 nm, but the fluorescence intensity changes significantly. Fluorescence intensity order: K + >Zn 2+ >Blank>Co 2+ >Pb 2+ >Ag + >Cr 3+ >Ni 2+ >Cd 2+ >Al 3+ >Cu 2+ >Fe 3+ Notably, upon addition of Fe(NO3)3 solution, R-Zn-1 underwent fluorescence quenching, with the strongest peak fluorescence intensity quenching rate reaching 99.06%. This indicates that the complex R-Zn-1 exhibits fluorescence quenching on Fe... 3+ It exhibits strong fluorescence recognition effect and has the potential to be used as Fe 3+ The potential of fluorescence sensors.

[0081] Figure 14 Adding Fe to R-Zn-1 in this invention 3+ Images taken before and after exposure to 254 nm UV light. Compared to the blank control experiment with the complex in the solvent 1,4-dioxane, the addition of Fe... 3+ The phenomenon of sudden death in the middle stage is obvious.

[0082] Figure 15 The images show the fluorescence emission spectra of R-Zn-1 in different rare earth metal ion solutions. R-Zn-1 was added to 10... -3 In mmol / mL solutions of rare earth salts Y(NO3)3, La(NO3)3, Ce(NO3)3, Pr(NO3)3, Nd(NO3)3, Sm(NO3)3, Eu(NO3)3, Gd(NO3)3, Tb(NO3)3, Dy(NO3)3, Er(NO3)3, Tm(NO3)3, Yb(NO3)3, and Lu(NO3)3, the fluorescence emission spectra are similar in shape, with the strongest emission peak around 370 nm, but the fluorescence intensities differ. In Lu... 3+ The highest intensity is medium, Gd 3+ The medium intensity is the lowest, but the quenching phenomenon is not obvious, and the recognition effect is not obvious.

[0083] Figure 16 The present invention provides R-Zn-1 for Fe 3+ Bar graph of anti-interference experiment. At room temperature, the addition of R-Zn-1 to test whether or not K was added... + Ag + Co 2+ Ni 2+ Zn 2+ Cd 2+ Pb 2+ Cu 2+ Cr 3+ Fe 3+ Solution fluorescence emission spectrum. At K + Ag + Co 2+ Ni 2 + Zn 2+ Cd 2+ Pb 2+ Cu 2+ Cr 3+ Add Fe to the solution 3+ A significant fluorescence quenching phenomenon subsequently occurred. Therefore, in the R-Zn-1 detection of Fe... 3+ In the middle, is there a K? + Ag + Co 2+ Ni2+ Zn 2+ Cd 2+ Pb 2+ Cu 2+ Cr 3+ The effect on the test results was minimal, with all results showing fluorescence quenching. The results indicate that R-Zn-1 significantly affects Fe... 3+ The identification is selective and has strong anti-interference capabilities.

[0084] Example 4 Detection of Antibiotics

[0085] R-Zn-1 (3.0 mg) was dispersed in a solution containing 1.0 × 10⁻⁶ mg. -4 The 1,4-dioxane solution containing mmol / mL of antibiotics contains 15 main antibiotics: erythromycin (EM), florfenicol (FFC), amoxicillin (AMX), metronidazole (MTZ), dimetridazole (DMZ), chloramphenicol (CAP), sulfadiazine sodium (SM2-Na), sulfadiazine (SD), sulfathiazole (ST), doxycycline (DOX), tetracycline (TC), oxytetracycline (OTC), dimethylaminotetracycline hydrochloride (MH), nitrofurazone (NF), and nitrofurantoin (NFT).

[0086] Figure 17 The fluorescence emission spectra of R-Zn-1 in different antibiotic solutions are shown below. In the antibiotic recognition experiment, all fluorescence spectra exhibited shoulder peaks. Specifically, the peak shapes and positions of erythromycin (EM), florfenicol (FFC), amoxicillin (AMX), metronidazole (MTZ), dimetridazole (DMZ), chloramphenicol (CAP), sulfadiazine sodium (SM2-Na), sulfadiazine (SD), sulfathiazole (ST), dimethylaminotetracycline hydrochloride (MH), nitrofurazone (NF), and nitrofurantoin (NFT) were consistent with the blank experiment without antibiotics, with shoulder peaks around 305 nm and the strongest peak around 370 nm. The fluorescence intensity of erythromycin (EM), florfenicol (FFC), and amoxicillin (AMX) showed a slight increase compared to the blank solution, while the fluorescence intensity of the other antibiotics decreased to varying degrees compared to the blank solution. However, the peak shapes of doxycycline (DOX), tetracycline (TC), and oxytetracycline (OTC) differed from the blank control, with the strongest peak located around 520 nm and a shoulder peak present around 370 nm. Figure 18 For the present invention R-Zn-1 in 10 -4Bar graph showing the emission peak intensity near 370 nm in mmol / mL antibiotic solutions. Fluorescence intensity analysis showed that the position of the strongest emission peak remained unchanged near 370 nm after the addition of erythromycin (EM), florfenicol (FFC), and amoxicillin (AMX), but the peak intensity increased. The addition of doxycycline (DOX) resulted in the most significant quenching of the strongest peak near 370 nm, with a quenching rate of 96%. Therefore, this complex exhibits good recognition ability for dimethylaminetetracycline hydrochloride (MH), nitrofurazone (NF), and nitrofurantoin (NFT).

[0087] Example 5 Drug Detection

[0088] 3 mg R-Zn-1 was dispersed in a solution containing 1.0 × 10⁻⁶ mg / L. -3 The solution of 1,4-dioxane at a concentration of mmol / mL contains the following drugs: ibuprofen (IBP), busulfan, vitamin C (Vc), aspirin (asa), gentamicin (GC), nicotinamide (nia), and curcumin (CUR). Figure 19 The images show the fluorescence emission spectra of R-Zn-1 in different drug solutions. The results show that the position of the strongest emission peak remained almost unchanged, all around 373 nm, but the intensity was weaker compared to the blank sample. Curcumin (CUR) induced a significant fluorescence quenching effect, with a quenching rate of 99.99%. This indicates that the complex R-Zn-1 has a strong fluorescence recognition effect on curcumin (CUR) and has the potential to serve as a curcumin (CUR) fluorescence sensor.

[0089] Example 6 Amino Acid Detection

[0090] 3 mg of R-Zn-1 was dispersed in a solution of 1,4-dioxane containing 0.001 mmol / mL amino acids, the main amino acids being: L-alanine (L-Ala), L-glycine (L-Gly), N-benzyloxycarbonyl-L-aspartic acid (N-Cbz-L-Asp), L-histidine (L-His), L-glutamic acid (L-Glu), L-aspartic acid (L-Asp), N-benzyloxycarbonyl-L-glutamic acid (N-Cbz-L-Glu), L-valine (L-Val), L-proline (L-Pro), L-tryptophan (L-Try), L-cysteine ​​(L-Cys), and N,N'-dimethylglycine (i.e., vitamin B16). Figure 20The fluorescence emission spectra of R-Zn-1 in different amino acid solutions of this invention are shown. The results show that the emission spectrum shapes are similar, and the position of the strongest emission peak is almost unchanged, with the strongest emission peak around 373 nm. However, the fluorescence intensity varies. The intensity of the strongest emission peak decreases in the following order: L-Ala > blank > L-Gly > N-Cbz-L-Asp > L-His > L-Glu > L-Asp > N-Cbz-L-Glu > L-Val > L-Pro > L-Try > L-Cys > B16. The intensity is highest in L-alanine (L-Ala) and lowest in vitamin B16, but there is no significant fluorescence enhancement or quenching compared to the blank sample.

[0091] Example 7 Fluorescent Recognition Detection of Food Additives

[0092] Seven inorganic salt additives (sodium bicarbonate, calcium propionate, sodium propionate, sodium benzoate, potassium sorbate, sodium distannous citrate, sodium diacetate) and nine organic additives (butylated hydroxyanisole, benzimidazole, dehydroacetic acid, vitamin C, tert-butylhydroquinone, methylparaben, ethylparaben, 2,4-dichlorophenoxyacetic acid, ethoxyquinoline) were selected. 3 mg of R-Zn-1 and 3.0 mg of the above food additives were weighed and added to 3.0 mL of 1,4-dioxane solution. Suspensions were prepared by sonication and then subjected to fluorescence detection.

[0093] Figure 21 This is the fluorescence emission spectrum of R-Zn-1 in a 1.0 mg / mL inorganic salt food additive solution. Compared with the blank control experiment, the position and intensity of the strongest emission peak changed significantly after the addition of the inorganic salt food additive, with the peak intensity significantly weakened. Sodium distannous citrate showed strong emission peaks near 305 nm and 370 nm, while the strongest emission peaks of other additives were all near 305 nm. Sodium benzoate and potassium sorbate showed no obvious emission peaks near 305 nm and 370 nm, indicating that the addition of these two additives led to fluorescence quenching. Based on structural analysis, the reason for the fluorescence quenching may be that after potassium sorbate dissolved, sorbate ions separated out, and the sorbate ions reacted with the central metal ion Zn. 2+ Non-covalent bonding occurs, forming a non-fluorescent complex, which reduces the concentration of the originally luminescent complex and decreases the fluorescence intensity.

[0094] Figure 22 This is a bar graph showing the intensity of the strongest emission peak of R-Zn-1 near 305 nm in an inorganic salt food additive solution. Based on the peak intensity, the fluorescence quenching rate of potassium sorbate at this point is calculated to be over 99%. Therefore, after the addition of potassium sorbate, the fluorescence emission of the complex R-Zn-1 is quenched, and this complex has a recognition effect on potassium sorbate.

[0095] Figure 23 This is a bar graph showing the intensity of the strongest emission peak of R-Zn-1 near 370 nm in an inorganic salt food additive solution. Sodium benzoate and potassium sorbate exhibit fluorescence quenching rates exceeding 99% at this point.

[0096] Figure 24 Images of R-Zn-1 before and after the addition of potassium sorbate under 254 nm ultraviolet light. The difference in appearance before and after the addition of potassium sorbate is obvious, indicating good recognition effect.

[0097] Figure 25 Images of R-Zn-1 before and after the addition of sodium benzoate, under 254 nm ultraviolet light. The difference between the two is obvious, indicating good recognition performance.

[0098] Figure 26 This is the fluorescence emission spectrum of R-Zn-1 in a 1.0 mg / mL organic food additive solution. Compared with the blank control experiment, the strongest emission peaks of these nine organic food additives were significantly weakened after their addition. Except for benzimidazole and butylated hydroxyanisole, whose strongest emission peaks were weakened less, the other seven additives all showed obvious fluorescence quenching.

[0099] Figure 27 This is a bar graph showing the intensity of the strongest emission peak of R-Zn-1 near 305 nm in an organic additive solution according to the present invention. Benzimidazole has the strongest emission peak near 305 nm, and the intensity of this peak is strongest at this location.

[0100] Figure 28 This is a bar graph showing the intensity of the strongest emission peak of R-Zn-1 near 370 nm in the organic additive solution of this invention. As can be seen from the graph, the emission peak intensity is strongest near 370 nm in the blank control experiment, and it significantly decreases after the addition of the organic additive.

Claims

1. A zinc-orotic acid complex crystalline material, characterized in that: The chemical formula of the zinc-orotic acid complex crystal material is [Zn2(HOA)2(1,3-dpp)(H2O)2]. n It was named R-Zn-1, with orotic acid H3OA as its first ligand. 2- H3OA loses 2 Hs + As a result; the chemical structural formula of H3OA is shown below: ； The second ligand is 1,3-bis(4-pyridyl)propane 1,3-dpp, with the chemical structure shown below: ； The asymmetric structural unit of R-Zn-1 contains one Zn(II) and one HOA. 2- The ligand consists of half a 1,3-dpp molecule and a coordinating water molecule; the Zn(II) molecule has a coordination number of 5 and binds to two molecules from HOA. 2- O, a from HOA 2- One N from 1,3-dpp and one O from the coordinated water molecule are coordinated; four Zn(II) molecules are coordinated via HOA. 2- The connections form a small [Zn4(HOA)4] quaternary ring secondary building unit, abbreviated as SBU; the quaternary ring SBU is coordinated with four 1,3-dpp to form a 2D layered structure; in the layered structure, the quadrilateral mesh formed by the four [Zn4(HOA)4] SBUs and the four 1,3-dpp has a side length of 18.6 Å × 18.6 Å; in space, two identical quadrilateral meshes intersect, eventually forming a 2-fold intersecting layered structure.

2. The zinc-orotic acid complex crystal material according to claim 1, characterized in that: From the perspective of structural connection construction, the zinc-orotic acid complex crystal material R-Zn-1 is a 2-fold interpenetrating two-dimensional network structure, and its crystal structure belongs to the tetragonal crystal system. I Space group 41 / acd, cell parameters: a = 18.725(4) Å, b = 18.725(4) Å, c = 30.285(7) Å. α =90, β =90, γ =90.

3. A method for preparing a zinc-orotic acid complex crystal material as described in any one of claims 1-2, characterized in that: Includes the following steps: (1) Dissolve orotic acid and potassium hydroxide in water and stir for at least 2 hours to obtain solution R-1; (2) Dissolve zinc acetate in water and stir until dissolved to obtain a Zn-1 solution; (3) Mix the R-1 solution obtained in step (1), the Zn-1 solution obtained in step (2), 1,3-bis(4-pyridyl)propane 1,3-dpp and pure water; (4) The mixture obtained in step (3) is subjected to ultrasonic treatment for no less than 0.5 hours, then heated at 90°C for 72 hours, and then slowly cooled to room temperature to obtain colorless transparent crystals.

4. The method for preparing the zinc-orotic acid complex crystal material according to claim 3, characterized in that: In step (1), the molar ratio of orotic acid to potassium hydroxide is 1:

1. In the mixed solution, orotic acid loses one H proton, and the concentration of deprotonated orotic acid is 0.1 mmol / mL.

5. The method for preparing the zinc-orotic acid complex crystal material according to claim 3, characterized in that: In step (2), the concentration of zinc acetate in the Zn-1 solution is 0.1 mmol / mL.

6. The method for preparing the zinc-orotic acid complex crystal material according to claim 3, characterized in that: In step (3), the volume ratio of R-1 solution to Zn-1 solution is 2:1, and the molar ratio of 1,3-dpp to zinc acetate is 2:

1.

7. The application of a zinc-orotic acid complex crystal material as described in any one of claims 1-2 in the preparation of fluorescent sensing materials.

8. The application of the zinc-orotic acid complex crystal material according to claim 7 in the preparation of fluorescent sensing materials, characterized in that: The zinc-orotic acid complex crystal material is used for solvent detection and can specifically identify at least one of methanol, dimethyl sulfoxide, and water.

9. The application of the zinc-orotic acid complex crystal material according to claim 7 in the preparation of fluorescent sensing materials, characterized in that: The zinc-orotic acid complex crystal material is used for metal ion detection and can specifically identify Fe. 3+ .

10. The application of the zinc-orotic acid complex crystal material according to claim 7 in the preparation of fluorescent sensing materials, characterized in that: The zinc-orotic acid complex crystal material is used for antibiotic detection and can specifically identify at least one of dimethylamine tetracycline hydrochloride, nitrofurazone, and nitrofurantoin.

11. The application of the zinc-orotic acid complex crystal material according to claim 7 in the preparation of fluorescent sensing materials, characterized in that: The zinc-orotic acid complex crystal material is used for drug detection and can specifically recognize curcumin.

12. The application of the zinc-orotic acid complex crystal material according to claim 7 in the preparation of fluorescent sensing materials, characterized in that: The zinc-orotic acid complex crystal material is used for the detection of food additives and can specifically identify potassium sorbate.

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