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CN-121975146-A - Zinc-orotic acid complex crystal material, preparation method and fluorescent identification application thereof

CN121975146ACN 121975146 ACN121975146 ACN 121975146ACN-121975146-A

Abstract

The invention discloses a zinc-orotic acid complex crystal material, a preparation method and fluorescent identification application thereof. The chemical formula of the complex is [ Zn 2 (HOA) 2 (1,3-dpp)(H 2 O) 2 ] n ], and the complex has a 2-weight-interpenetration two-dimensional network structure. The preparation method comprises respectively preparing orotic acid, potassium hydroxide and zinc acetate into solutions, mixing with 1, 3-bis (4-pyridyl) propane and water, and performing ultrasonic treatment and heating treatment to obtain crystals. The material has characteristic fluorescence emission at 370 nm, the intensity of the material can be changed obviously when encountering specific substances, and the characteristic can be used as a fluorescence sensing material for identifying solvents such as methanol, DMSO, water and the like, specifically detecting Fe 3+ ions, identifying antibiotics minocycline hydrochloride, furacilin and nitrofurantoin, identifying medicine curcumin, and identifying food additives potassium sorbate and sodium benzoate.

Inventors

  • CUI PEIPEI
  • Guan Peiyan
  • LIU LU
  • WANG CHUANFEN
  • Han Shenru
  • ZHANG QING
  • ZHANG JUFANG

Assignees

  • 德州学院

Dates

Publication Date
20260505
Application Date
20260409

Claims (13)

  1. 1. A zinc-orotic acid complex crystalline material characterized by: The chemical formula of the zinc-orotic acid coordination polymer crystal material is [ Zn 2 (HOA) 2 (1,3-dpp)(H 2 O) 2 ] n , which is named as R-Zn-1, the first ligand is orotic acid H 3 OA,HOA 2- , H 3 OA, which is caused by 2 loss of H + , and the chemical structural formula of H 3 OA is shown as follows: ; The second ligand is 1, 3-di (4-pyridyl) propane 1,3-dpp, and the chemical structural formula is shown as follows: 。
  2. 2. a zinc-orotic acid complex crystalline material according to claim 1, characterized in that: from the structural connection construction point of view, the zinc-orotic acid complex crystal material R-Zn-1 is a 2-weight interpenetration two-dimensional network structure, the crystal structure belongs to tetragonal system I41/acd space group, and unit cell parameters are a= 18.725 (4) a, b= 18.725 (4) a, c= 30.285 (7), a=90, β=90, and γ=90.
  3. 3. A zinc-orotic acid complex crystalline material according to claim 1, characterized in that: The asymmetric structural unit of R-Zn-1 comprises a Zn (II), an HOA 2- ligand, half 1,3-dpp and a coordinated water molecule, wherein the coordination number of Zn (II) is 5, the coordination number is respectively coordinated with two O from HOA 2- , one N from HOA 2- , one N from 1,3-dpp and one O from the coordinated water molecule, four Zn (II) are connected through HOA 2- to form a small [ Zn 4 (HOA) 4 ] four-membered ring secondary structural unit, which is called SBU for short, the four-membered ring SBU is connected with the four 1,3-dpp coordinates to form a 2D layered structure, the side length of a quadrilateral grid formed by four [ Zn 4 (HOA) 4 ] SBUs and the four 1,3-dpp is 18.6 X18.6A, and the two identical quadrilateral grids are interleaved in space to finally form a 2-inserted layered structure.
  4. 4. A process for the preparation of a zinc-orotic acid complex crystalline material according to any one of claims 1 to 3, characterized in that: The method comprises the following steps: (1) Dissolving orotic acid and potassium hydroxide in water, and stirring and reacting for at least 2 hours to obtain an R-1 solution; (2) Dissolving zinc acetate in water, and stirring until the zinc acetate is dissolved to obtain Zn-1 solution; (3) Mixing the R-1 solution obtained in the step (1), the Zn-1 solution obtained in the step (2), 1, 3-bis (4-pyridyl) propane 1,3-dpp and purified water; (4) And (3) carrying out ultrasonic treatment on the mixed solution obtained in the step (3) for not less than 0.5 hour, then heating at 90 ℃ for 72 hours, and then slowly cooling to room temperature to obtain colorless transparent crystals.
  5. 5. The method for producing a zinc-orotic acid complex crystal material according to claim 4, wherein: In the step (1), the molar ratio of the orotic acid to the potassium hydroxide is 1:1, and the orotic acid is subjected to H proton removal in the mixed solution, and the concentration of the deprotonated orotic acid is 0.1 mmol/mL.
  6. 6. The method for producing a zinc-orotic acid complex crystal material according to claim 4, wherein: the concentration of zinc acetate in the Zn-1 solution in the step (2) is 0.1 mmol/mL.
  7. 7. The method for producing a zinc-orotic acid complex crystal material according to claim 4, wherein: in the step (3), the volume ratio of the R-1 solution to the Zn-1 solution is 2:1, and the mole ratio of the 3-dpp to the zinc acetate is 2:1.
  8. 8. Use of a zinc-orotic acid complex crystalline material according to any one of claims 1 to 3 in the preparation of a fluorescent sensing material.
  9. 9. The use of the zinc-orotic acid complex crystal material according to claim 8 for preparing a fluorescent sensing material, wherein 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.
  10. 10. The use of the zinc-orotic acid complex crystal material according to claim 8 for preparing a fluorescence sensing material, wherein the zinc-orotic acid complex crystal material is used for metal ion detection and can specifically identify Fe 3+ .
  11. 11. The use of the zinc-orotic acid complex crystal material according to claim 8 for preparing a fluorescence sensing material, wherein the zinc-orotic acid complex crystal material is used for antibiotic detection and can specifically identify at least one of minocycline hydrochloride, furacilin and nitrofurantoin.
  12. 12. The application of the zinc-orotic acid complex crystal material in preparing fluorescent sensing materials, as claimed in claim 8, wherein the zinc-orotic acid complex crystal material is used for drug detection and can specifically identify curcumin.
  13. 13. The application of the zinc-orotic acid complex crystal material in preparing fluorescent sensing materials, as claimed in claim 8, wherein the zinc-orotic acid complex crystal material is used for detecting food additives and can specifically identify potassium sorbate.

Description

Zinc-orotic acid complex crystal material, preparation method and fluorescent identification application thereof Technical Field The invention belongs to the technical field of crystalline materials, and relates to a metal-organic coordination polymer material, in particular to a zinc-orotic acid complex crystalline material, a preparation method thereof and fluorescent identification application. Background The emission and accumulation of various types of pollutants is a major contributor to environmental problems. The method realizes the efficient detection and accurate identification of pollutants in the environment, and is a key technical link for solving the environmental treatment problem. Fluorescent detection is widely applied to detection of pollutants at present because of the advantages of simple operation, short response time, high sensitivity and the like. Iron is a core component of key proteins such as hydrogen peroxidase, cytochrome oxidase and the like in organisms and hemoglobin, myoglobin and the like, and participates in a plurality of important physiological processes such as oxygen transportation, energy metabolism, DNA synthesis and the like. However, excessive Fe 3+ can catalyze and generate hydroxyl free radicals with strong oxidability, so that DNA and cell membranes are damaged, the incidence risk of diseases such as Alzheimer disease, parkinson disease and liver fibrosis is increased, iron deficiency anemia is caused by iron deficiency, and the hematopoietic function and the immunocompetence of an organism are adversely affected. Meanwhile, the content of iron ions is also one of important monitoring indexes of the environmental quality of water and soil. However, industrial wastewater discharged from industries such as metallurgy, electroplating, chemical industry and the like often causes the concentration of iron ions in water body to exceed the standard. The excessive iron ions can cause the water body to be in a turbid yellow brown color, reduce the transparency of the water quality and obstruct the photosynthesis of aquatic plants, and simultaneously, the iron ions can also be combined with phosphate in the water to form precipitation, so that the nutrition balance of the water body is destroyed, and the eutrophication problem of the water body is induced. In addition, the iron ion concentration in the soil is too high, so that the absorption of trace elements such as zinc, manganese and the like by plants can be inhibited, and the plant growth is malformed and the yield of crops is reduced. The food additive is used as a core component of the modern food industry and plays a key role in improving the food quality, prolonging the shelf life, optimizing the processing characteristics and the like, but problems such as out-of-range and out-of-limit use or illegal addition can cause health risks, so that the accurate and efficient detection of the food additive is a core support of a food safety guarantee system. In addition, detection of antibiotics that are widely used in animal husbandry and aquaculture is also necessary. Although antibiotics can be used as antibacterial drugs and growth promoters, with abuse and improper discharge of antibiotics, the problem of residue is increasingly prominent, and the problem of residue is gradually becoming a prominent hidden trouble threatening ecological safety and human health. Excessive administration of antibiotics can result in drug residues in various foods such as meat, eggs, milk, aquatic products, etc. The long-term intake of the food containing antibiotic residues by human body can not only destroy the balance of intestinal flora and reduce the immunity of the organism, but also induce the generation of drug-resistant bacteria, thereby seriously weakening the effectiveness of clinical anti-infection treatment. Therefore, a set of efficient, sensitive and rapid food additive and antibiotic detection system is established, and the method has important practical significance. Compared with the traditional detection technologies such as atomic absorption spectrum and inductively coupled plasma, the fluorescent identification technology does not need a complex sample pretreatment flow, can realize on-site rapid detection, can timely and accurately master pollution conditions such as iron ions, food additives and antibiotics, and provides a solid scientific basis for environmental quality assessment, pollution source tracing and environmental protection policy formulation. Metal-organic coordination polymers (Metal-Organic Coordination Polymers, MOCPs) are crystalline materials formed by self-assembly of Metal ions/clusters with organic ligands through weak interactions such as coordination bonds, hydrogen bonds, pi-pi stacking, etc. The fluorescent dye has the adjustability of inorganic metal ions and the functionality of organic ligands, has diversified topological structures, rich active sites, adjustable optical properties and