WO2021072958A1 - 一种金属-有机框架材料的制备方法及其应用 - Google Patents

一种金属-有机框架材料的制备方法及其应用 Download PDF

Info

Publication number
WO2021072958A1
WO2021072958A1 PCT/CN2019/125090 CN2019125090W WO2021072958A1 WO 2021072958 A1 WO2021072958 A1 WO 2021072958A1 CN 2019125090 W CN2019125090 W CN 2019125090W WO 2021072958 A1 WO2021072958 A1 WO 2021072958A1
Authority
WO
WIPO (PCT)
Prior art keywords
solution
metal
organic framework
framework material
phe
Prior art date
Application number
PCT/CN2019/125090
Other languages
English (en)
French (fr)
Inventor
陈中慧
孙一峰
林梓榕
陈俊
张译方
Original Assignee
广东省测试分析研究所（中国广州分析测试中心）
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 广东省测试分析研究所（中国广州分析测试中心） filed Critical 广东省测试分析研究所（中国广州分析测试中心）
Publication of WO2021072958A1 publication Critical patent/WO2021072958A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K5/00—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof
    • C07K5/04—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof containing only normal peptide links
    • C07K5/06—Dipeptides
    • C07K5/06008—Dipeptides with the first amino acid being neutral
    • C07K5/06078—Dipeptides with the first amino acid being neutral and aromatic or cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon

Definitions

  • the present invention relates to the technical field of metal-organic framework materials, in particular to a preparation method and application of metal-organic framework materials.
  • Methylene blue is a dye compound belonging to the thiazide class. It was first used in the treatment of bacillary dysentery, and was subsequently used in the treatment of certain diseases in clinical medicine, such as malaria, methemoglobinosis, cancer chemotherapy, and central nervous system diseases .
  • methylene blue is used as a disinfectant and bactericide for aquatic product breeding and treatment of certain fish diseases. Methylene blue has been proven to have a low redox potential, which is characterized by the ability of the molecule to efficiently cyclically switch between the oxidized state and the reduced state. For example, methylene blue molecules have an antioxidant effect, can carry out effective electron transfer within the mitochondria, and reduce the production of superoxide in the mitochondria.
  • methylene blue has high water solubility and fat solubility, which leads to its high permeability in biological membranes and easier entry into cell organelles. Therefore, these substances have applications in the fields of industry, medicine, and skin care.
  • methylene blue itself contains triphenylmethane structure, and high concentrations of methylene blue can poison animals and cause death.
  • FDA Food Supervision and Administration
  • EU Directive 6/23/EC EU Directive 6/23/EC
  • Japan "Positive List” have all established testing standards for the residues of methylene blue in aquatic products, while domestic regulations have not yet formulated relevant regulations on the residue limits of methylene blue. .
  • Metal-organic framework materials are a type of porous polymer materials formed by the assembly of metal ions and organic ligands through coordination bonds. Compared with pure inorganic molecular sieves, metal-organic frameworks have structural diversity and designability, and can form framework structures of different shapes, sizes, pores, and different degrees of rigidity and flexibility by introducing different metal ions and organic overseas ligands. This feature can play an important role in the adsorption/desorption process.
  • the present invention provides a method for preparing a metal-organic framework material and its application.
  • the present invention uses dipeptide molecules with specific effects on methylene blue as organic ligands through coordination of carboxyl and amino groups of oligopeptide molecules with copper ions. Function, developed a metal organic framework material that can effectively and selectively adsorb methylene blue, and further used for its electrochemical detection.
  • An object of the present invention is to provide a metal-organic framework material, the metal-organic framework material is composed of phenylalanine dipeptide and copper ions, and the chemical formula of the metal-organic framework material is Cu(L -Phe-L-Phe) 2 , the structural formula of L-Phe-L-Phe is shown in formula (1),
  • L-Phe-L-Phe (abbreviated as FF), its linear molecular formula is C 6 H 5 CH 2 CH(NH 2 )CONHCH(CH 2 C 6 H 5 )COOH.
  • Another object of the present invention is to provide a method for preparing the above-mentioned metal-organic framework material, which includes the following steps:
  • the phenylalanine dipeptide is added to the alcohol solution and mixed uniformly, and the solid-liquid ratio of the phenylalanine dipeptide to the alcohol solution is 0.01 to 0.02 g/mL to obtain a mixed solution;
  • step (2) Add copper ion solution dropwise to the mixed solution obtained in step (1), and when the mixed solution changes from white turbidity to navy blue clear and transparent solution, stop adding copper ion solution;
  • step (3) Place the royal blue clear and transparent solution obtained in step (2) in a dry environment. After reacting for 6 to 48 hours, cool to room temperature to obtain a mixed solution with the precipitation of royal blue block crystals. The royal blue block crystal mixed solution is centrifuged, and the precipitate is washed and dried to finally obtain the metal organic framework material.
  • the copper ion solution is a copper acetate solution, and the molar concentration of the copper acetate solution is 0.1-0.2M.
  • the alcohol solution is an ethanol solution, and the volume fraction of ethanol in the ethanol solution is 75% to 90%.
  • step (3) the navy blue clear and transparent solution obtained in step (2) is placed in a dry environment at 80-90°C
  • the mixed solution with royal blue block crystals described in step (3) is centrifuged, and the specific steps of precipitation washing and drying are: put the mixed solution with royal blue block crystals into a centrifuge tube, and use centrifugation.
  • the machine is centrifuged to obtain the royal blue block crystal precipitation.
  • the speed of the centrifuge is 3000r/min and the centrifugation time is 3min.
  • the invention also provides the application of the metal-organic framework material modified electrode in the detection of methylene blue.
  • Metal-organic framework materials are used for the selective adsorption and separation of methylene blue dye in a complex mixed solution matrix.
  • the preparation process of the metal-organic framework material proposed by the present invention is simple, the reaction conditions are mild, and the safety factor is high.
  • the high boiling point solvent is not used in the entire reaction process, and the preparation process is environmentally friendly and green;
  • the present invention uses the dipeptide L-phenylalanine-L-phenylalanine as an organic ligand, and the interaction of biomolecules with methylene blue improves the material's selectivity to methylene blue;
  • the electrode modified by this material can be used for the specific electrochemical detection of methylene blue.
  • Figure 1 is the XRD spectrum of the phenylalanine dipeptide Phe-Phe and the royal blue bulk crystal product Cu(FF) 2 of Example 1 of the present invention
  • Figure 2 is the FTIR spectrum of the phenylalanine dipeptide Phe-Phe and the royal blue block crystal product Cu(FF) 2 of Example 1 of the present invention
  • Example 3 is the XPS spectrum of the phenylalanine dipeptide, copper acetate monohydrate and the royal blue product of Example 1 of the present invention
  • Example 4 is an XPS spectrum of Cu of Example 1 of the present invention, where a is the XPS spectrum of Cu of copper acetate monohydrate, and b is the XPS spectrum of Cu of the royal blue bulk crystal material;
  • Example 5 is an XPS spectrum of C element in Example 1 of the present invention, wherein a is the XPS spectrum of C element of phenylalanine dipeptide, and b is the XPS spectrum of C element of the royal blue bulk crystal material;
  • Example 6 is the N element XPS spectrum of Example 1 of the present invention, where a is the N element XPS spectrum of the phenylalanine dipeptide, and b is the N element XPS spectrum of the royal blue bulk crystal material;
  • Example 7 is the O element XPS spectrum of Example 1 of the present invention, where a is the O element XPS spectrum of the phenylalanine dipeptide, and b is the O element XPS spectrum of the royal blue bulk crystal material;
  • FIG. 8 is a SEM topography diagram of the royal blue bulk crystal material in Example 1 of the present invention under different scales
  • Fig. 9 is a SEM topography diagram of the royal blue bulk crystal material at different scales in Comparative Example 1 of the present invention.
  • Figure 10 is a graph showing the CV cycle of the bare glassy carbon electrode, the glassy carbon electrode modified with Nafion film, and the glassy carbon electrode modified with Nafion/Cu(FF) 2 mixed film in Example 2 of the present invention after being stabilized in a 0.1M KCl solution ;
  • Example 11 is a graph showing the change of the CV curve of the glassy carbon electrode modified with the Nafion/Cu(FF) 2 mixed film in Example 2 of the present invention with the increase of methylene blue concentration;
  • Example 12 is a graph showing the change of the CV curve of the glassy carbon electrode modified with the Nafion/Cu(FF) 2 mixed film in Example 2 of the present invention with increasing tetracycline concentration;
  • Example 13 is a graph showing the change of the CV curve of the glassy carbon electrode modified with the Nafion/Cu(FF) 2 mixed film in Example 2 of the present invention with the increase of the concentration of bisphenol A;
  • Example 14 is a graph showing the change of the CV curve of the glassy carbon electrode modified by the Nafion/Cu(FF) 2 mixed film in Example 2 of the present invention as the concentration of 2'-bromodiphenyl ether increases;
  • Example 15 is a graph showing the change of the CV curve of the glassy carbon electrode modified with the Nafion/Cu(FF) 2 mixed film in Example 2 of the present invention with increasing bromophenol blue concentration.
  • the dipeptide L-Phe-L-Phe was purchased from Shanghai Qiangyao Biotechnology Co., Ltd., and copper acetate monohydrate (98%, 500 g) and absolute ethanol (AR) were purchased from Shanghai Sinopharm Chemical Reagent Co., Ltd.
  • the powder X-ray diffraction spectrum was collected by Rigaku Ultima IV automatic multi-function X-ray diffractometer; the Fourier infrared spectrum was collected by Bruker Vertex 80v vacuum infrared spectrometer; the X-ray photoelectron spectrum was collected by ESCALAB 250Xi X-ray photoelectron spectrum
  • the scanning electron microscope image was collected by Hitachi S-3700N scanning electron microscope; the electrochemical detection experiment was collected by Shanghai Chenhua electrochemical workstation CHI660E.
  • the metal-organic framework material is prepared by the following steps:
  • the chemical formula of the obtained royal blue block crystal is Cu(L-Phe-L-Phe) 2 , and the weight of the product is about 0.186g, where: L-Phe-L-Phe is L-phenylalanine-L -Phenylalanine, its linear molecular formula is C 6 H 5 CH 2 CH(NH 2 )CONHCH(CH 2 C 6 H 5 )COOH as an organic ligand, and its structural formula is as follows:
  • the chemical composition analysis of the product the PXRD pattern of the obtained royal blue block crystal material and the PXRD pattern comparison chart of the raw material L-Phe-L-Phe dipeptide are shown in Figure 1.
  • the dipeptide as an organic ligand molecule, complexes with copper ions and generates a new product, and the reaction product has a better crystal form.
  • the infrared spectrum of the phenylalanine dipeptide and the infrared spectrum of the reaction product navy blue bulk crystal material are shown in Figure 2.
  • the bond (1685cm -1 ) has undergone a significant change, indicating that the carboxyl group of the dipeptide and the carbon-oxygen double bond in the amide bond have complexed with the copper ion through the coordination bond.
  • Figure 3 shows the XPS spectra of phenylalanine dipeptide, copper acetate monohydrate, and royal blue block crystal products. It can be found that N and Cu are present in the products, and the peak intensity of C is significantly increased.
  • the element content ratio obtained by XPS analysis is shown in Table 1. The comparison of the relative atomic content ratio changes of the elements C, N, O and Cu contained in the above three samples also further verified that the copper ion and the dipeptide have complexed. Cooperation, and formed a new product.
  • Figure 4 compares the XPS spectra of Cu element of the raw material copper acetate monohydrate (Figure 4a) and the royal blue bulk crystal material (Figure 4b), which can indicate that the binding energy of Cu2p of the reaction product hardly changes significantly, and the valence state before and after the reaction And the chemical environment has not changed.
  • the relative atomic content ratios of phenylalanine dipeptide, copper acetate monohydrate, and royal blue crystal products obtained by XPS in FIG. 4 are shown in Table 1.
  • the morphology analysis of the product As shown in Figure 8, the morphology of the obtained royal blue block crystal product mainly exists in fibrous shape, with very few block-shaped products.
  • the diameter of the fiber is mainly between 0.1 and 0.3 ⁇ m, and the length is different; the diameter of the bulk product is mainly above 2 ⁇ m.
  • Step (1) The solid-liquid ratio of the phenylalanine dipeptide to the ethanol solution is 0.01g/mL, the volume fraction of ethanol in the ethanol solution is 90%, and the step (2) the molar concentration of the copper acetate solution is 0.1M, step ( 3) The clear and transparent medium blue solution is placed in an oven at 85°C and reacted for 6 hours.
  • Step (1) The solid-liquid ratio of the phenylalanine dipeptide to the ethanol solution is 0.02g/mL, the volume fraction of ethanol in the ethanol solution is 75%, and the step (2) the molar concentration of the copper acetate solution is 0.2M, and the step ( 3) The clear and transparent medium blue solution is placed in an oven at 85°C and reacted for 48 hours.
  • reaction time is 48 hours.
  • phenylalanine dipeptide L-Phe-L-Phe
  • ethanol solution 20 mL of ethanol solution
  • the mixed solution was put into an ultrasonic device and sonicated for 5 minutes to fully disperse uniformly to obtain a milky white turbid solution.
  • the obtained royal blue clear and transparent solution in an oven at 85°C, react for 48 hours, and cool to room temperature to obtain a mixed solution with royal blue block crystals precipitated; centrifuge the obtained mixed solution with royal blue block crystals After washing with ethanol solution and centrifuging for 3 times, it is placed in an oven at 60° C. for heat preservation for 6 hours to obtain dry royal blue block crystals that are metal-organic framework materials.
  • the obtained metal-organic frame material needs to be packaged and stored in a refrigerator at 4°C.
  • Example 1 Compared with Example 1, the influence of the reaction time on the morphology of the product is mainly discussed.
  • the morphology of the obtained royal blue crystalline material is shown in Figure 9. Compared with Figure 8, it can be seen that the morphological characteristics of the product can be effectively affected by changing the reaction conditions parameters, and the honeycomb-shaped ellipsoidal material can be obtained, and it can be clearly observed
  • the honeycomb sphere is formed by assembling and entangled many fibrous materials. Among them, the diameter of the fibers involved in the assembly is about 0.2 to 1 ⁇ m.
  • the blue product contains C (38.03%), N (3.27%), H (4.35%), O (22.98%), and the molecular ratio of Cu element to FF dipeptide is 1:2.
  • the results show that prolonging the reaction time only changes the morphology of the product, and has no significant effect on its molecular composition.
  • the obtained mixed solution was placed in 30mL glass screw-top sample bottle A and sample bottle B, respectively, to the milky white turbid liquid in bottle A and bottle B, respectively, about 5.5mL of 0.1M copper acetate aqueous solution and 2.5mL of 0.2M copper acetate aqueous solution. Place the obtained sapphire blue clear and transparent solution in an oven at 85°C. After reacting for 6 hours, cool to room temperature to obtain a mixed solution with sapphire blue block crystals; centrifuge the obtained mixed solution with sapphire block crystals After washing with ethanol solution and centrifuging for 3 times, it is placed in an oven at 60°C for 6 hours to keep the dry navy blue block crystals, which is the metal-organic framework material, and weighed. Under the above two ethanol volume fraction conditions, the mass of the metal-organic framework material obtained under the condition of sample bottle A is 0.087g, and the mass of the product obtained under the condition of sample bottle B is 0.102g.
  • the electrochemical analysis station was used to detect different types of aromatic ring organic pollutants by cyclic voltammetry, and the characteristics and changes of the CV curve were observed and compared to determine the organic pollutants.
  • concentration on electrochemical signal Among them, methylene blue, bromophenol blue, 2'-bromodiphenyl ether, bisphenol A and tetracycline are used as molecular models of organic pollutants.
  • Electrode preparation uses a three-electrode system, in which a glassy carbon electrode with a diameter of 3 mm is a working electrode, a platinum wire electrode is an auxiliary electrode, and an Ag/AgCl electrode is a reference electrode.
  • the glassy carbon electrode is first polished to the mirror surface with W0.3 ⁇ m aluminum oxide polishing powder, and the surface dirt is washed off with ultrapure water and ethanol, dried, and then activated in a 0.5-1.0M sulfuric acid solution. Dissolve 5 mg of the royal blue crystal product obtained in Example 1 in 100 ⁇ L of Nafion ethanol solution (0.5% by mass), and sonicate for 5-15 minutes to fully disperse uniformly.
  • Cyclic voltammetry measurement CV curve as shown in Figure 10 are bare glassy carbon electrode, Nafion film modified glassy carbon electrode and product/Nafion film modified glassy carbon electrode. Cyclic voltammetry is used in 0.1M KCl aqueous solution. CV curve after stabilization. It can be seen from the figure that the above three electrodes show different characteristic CV curves in 0.1M KCl solution. It can be seen that the product/Nafion film has been successfully modified on the surface of the glassy carbon electrode and exhibits different interface properties. Insert the electrode into 10 mL of KCl solution and measure the CV curve of organic molecule solutions at different concentrations.
  • Figure 11 is the CV curve of the product/Nafion membrane modified glassy carbon electrode in different concentrations of methylene blue solution. With the addition of 5mM methylene blue to the KCl solution, the measured CV curve peaks around -0.04V gradually disappear. At the same time, a new peak formed near -0.29V.
  • Figure 12 shows the change of the CV curve of the product/Nafion membrane modified glassy carbon electrode in different concentrations of tetracycline solution. As the concentration of tetracycline in the electrolyte increases, the peak of the CV curve around 0.025V gradually disappears, and there is nothing new The peaks are generated.
  • FIG. 13-15 are the CV-concentration curves of 10mM bisphenol A, 5mM 2'-bromodiphenyl ether and 2mM bromophenol blue in the electrolyte where the modified electrode is placed.
  • the experimental results show that there is no obvious The relationship with the concentration. It can be seen from the CV-analyte concentration change graph that the modified electrode has the ability to selectively recognize methylene blue, and the CV curve characteristics change significantly, which can be used as a means of identification.
  • the change of the characteristic peak of the CV curve can achieve the purpose of analyzing the existence of methylene blue.
  • the lowest limit of the detection range is 5 ⁇ 10 -4 mM.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Biochemistry (AREA)
  • Electrochemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Analytical Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Biophysics (AREA)
  • Genetics & Genomics (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

一种金属-有机框架材料的制备方法及其应用。所述的金属-有机框架材料的化学式为Cu(L-Phe-L-Phe) 2，L-Phe-L-Phe的结构式如式(1)所示。该金属-有机框架材料的制备工艺简单，反应条件温和，安全系数高，整个反应过程中未采用高沸点溶剂，制备工艺环保绿色。

Description

一种金属-有机框架材料的制备方法及其应用 技术领域
本发明涉及金属有机框架材料技术领域，具体涉及一种金属-有机框架材料的制备方法及其应用。
背景技术
亚甲基蓝是一种属于噻嗪类的染料化合物，最早用于治疗细菌性痢疾，随后又被应用于一些临床医学上的某些疾病的治疗，如疟疾、高铁血红蛋白症、癌症化疗以及中枢神经系统疾病。此外，亚甲基蓝作为消毒剂和杀菌剂用于水产品的养殖，治疗某些鱼病等。亚甲基蓝被证明具有较低的氧化还原电位，其特点是分子能够以氧化态和还原态之间有效循环转换。例如，亚甲基蓝分子具有抗氧化的作用，能够在线粒体内进行有效的电子传递，并减少线粒体中超氧化物的产生。另外，亚甲基蓝具有较高的水溶性和脂溶性，即导致了它在生物膜具有高渗透性，比较轻易的进入细胞内的细胞器等。因此，这类物质在工业、医药以及皮肤护理等领域都有应用。然而，亚甲基蓝自身含有三苯甲烷结构，高浓度的亚甲基蓝会使得动物中毒并导致死亡。目前，美国食品监督管理局(FDA)、欧盟6/23/EC指令以及日本的《肯定列表》都对亚甲基蓝在水产品中残留量制定了检测标准，而国内对亚甲基蓝的残留限量尚未制定相关规定。此外，关于亚甲基蓝在动物体内代谢的研究相对较少，因此需要对亚甲基蓝的检测及其在动物体内代谢问题进行深入研究。特别是，如何从复杂的基质中快速充分富集并分离出微量/痕量的亚甲基蓝分子，并进一步用于定性定量分析检测，是目前需要解决的问题和挑战。
金属有机框架材料是一类通过金属离子与有机配体通过配位键组装形成的多孔聚合物 材料。与纯无机分子筛相比，金属有机框架具有结构多样性和可设计性，可通过引入不同的金属离子和有机侨联配体形成不同形状、尺寸、孔径，和不同刚柔程度的框架结构。该特征能够在吸附/脱附过程中发挥重要的作用。
发明内容
本发明提供了一种金属-有机框架材料的制备方法及其应用，本发明使用对亚甲基蓝具有特异性作用的二肽分子作为有机配体，通过寡肽分子的羧基和氨基与铜离子的配位作用，开发了一种能够有效地选择性吸附亚甲基蓝的金属有机框架材料，并进一步用于对其的电化学检测。
本发明的一个目的是提出了一种金属-有机框架材料，所述的金属-有机框架材料由苯丙氨酸二肽和铜离子组成，所述的金属-有机框架材料的化学式为Cu(L-Phe-L-Phe) 2，L-Phe-L-Phe的结构式如式(1)所示，
Figure PCTCN2019125090-appb-000001
L-Phe-L-Phe(缩写FF)，其线性分子式为C 6H 5CH 2CH(NH 2)CONHCH(CH 2C 6H 5)COOH。
本发明的另一个目的是提出了上述的金属-有机框架材料的制备方法，包括如下步骤：
(1)将苯丙氨酸二肽加入到醇类溶液中混合均匀，所述的苯丙氨酸二肽与醇类溶液的固液比为0.01～0.02g/mL，得到混合溶液；
(2)向步骤(1)得到的混合溶液中逐滴滴加铜离子溶液，当所述的混合溶液由白色 浑浊变为宝蓝色澄清透明溶液时，停止滴加铜离子溶液；
(3)将步骤(2)得到的宝蓝色澄清透明溶液静置于干燥环境中，反应6～48小时后，冷却到室温后得到有宝蓝色块状晶体析出的混合溶液，将所述的有宝蓝色块状晶体混合溶液离心分离，沉淀洗涤干燥后，最终得到所述的金属有机框架材料。
优选地，所述的铜离子溶液为醋酸铜溶液，所述的醋酸铜溶液的摩尔浓度为0.1～0.2M。
优选地，所述的醇类溶液为乙醇溶液，所述的乙醇溶液中乙醇的体积分数为75％～90％。
优选地，步骤(3)中将步骤(2)得到的宝蓝色澄清透明溶液静置于80～90℃的干燥环境中
优选地，步骤(3)中所述的有宝蓝色块状晶体混合溶液离心分离，沉淀洗涤干燥的具体步骤是：将所述的有宝蓝色块状晶体混合溶液放入离心管中，采用离心机离心获得宝蓝色块状晶体沉淀，离心机的转速为3000r/min，离心时长3min；将离心后的上清液除去后，再加入醇类溶剂并充分混匀后再次进行离心分离，反复操作3～5次，直到离心后的上清液澄清后，再将宝蓝色块状晶体沉淀置于烘箱中在60℃的温度下烘干处理，烘干时长为6小时。
本发明还提供了上述的金属-有机框架材料修饰的电极在亚甲基蓝检测中的应用。金属-有机框架材料用于复杂混合溶液基质中对亚甲基蓝染料的选择性吸附分离。
与现有技术相比，本发明的有益效果是：
(1)本发明提出的金属-有机框架材料的制备工艺简单，反应条件温和，安全系数高，整个反应过程中未采用高沸点溶剂，制备工艺环保绿色；
(2)本发明使用了二肽L-苯丙氨酸-L-苯丙氨酸作为有机配体，利用生物分子对亚甲 基蓝的相互作用提高了材料对亚甲基蓝的选择性；
(3)该材料修饰的电极可用于亚甲基蓝的特异性电化学检测。
附图说明
图1为本发明实施例1苯丙氨酸二肽Phe-Phe和宝蓝色块状晶体产物Cu(FF) 2的XRD谱图；
图2为本发明实施例1苯丙氨酸二肽Phe-Phe和宝蓝色块状晶体产物Cu(FF) 2的FTIR谱图；
图3为本发明实施例1苯丙氨酸二肽、一水合醋酸铜和宝蓝色产物的XPS谱图；
图4为本发明实施例1的Cu元素XPS谱图，其中a为一水醋酸铜的Cu元素XPS谱图，b为宝蓝色块状晶体材料的Cu元素XPS谱图；
图5为本发明实施例1的C元素XPS谱图，其中a为苯丙氨酸二肽的C元素XPS谱图，b为宝蓝色块状晶体材料的C元素XPS谱图；
图6为本发明实施例1的N元素XPS谱图，其中a为苯丙氨酸二肽的N元素XPS谱图，b为宝蓝色块状晶体材料的N元素XPS谱图；
图7为本发明实施例1的O元素XPS图谱，其中a为苯丙氨酸二肽的O元素XPS图谱，b为宝蓝色块状晶体材料的O元素XPS图谱；
图8为本发明实施例1中宝蓝色块状晶体材料不同比例尺下的SEM形貌图；
图9为本发明对比例1中宝蓝色块状晶体材料不同比例尺下的SEM形貌图；
图10为本发明实施例2中裸的玻碳电极、Nafion膜修饰的玻碳电极以及Nafion/Cu(FF) 2混合膜修饰的玻碳电极在0.1M KCl溶液中稳定后的CV循环曲线图；
图11为本发明实施例2中Nafion/Cu(FF) 2混合膜修饰的玻碳电极随亚甲基蓝浓度升高的CV曲线变化图；
图12为本发明实施例2中Nafion/Cu(FF) 2混合膜修饰的玻碳电极随四环素浓度升高的CV曲线变化图；
图13为本发明实施例2中Nafion/Cu(FF) 2混合膜修饰的玻碳电极随双酚A浓度升高的CV曲线变化图；
图14为本发明实施例2中Nafion/Cu(FF) 2混合膜修饰的玻碳电极随2‘-溴联苯醚浓度升高的CV曲线变化图；
图15为本发明实施例2中Nafion/Cu(FF) 2混合膜修饰的玻碳电极随溴酚蓝浓度升高的CV曲线变化图。
具体实施方式
以下实施例是对本发明的进一步说明，而不是对本发明的限制。
下述实施例中所用原料及设备：
二肽L-Phe-L-Phe由上海强耀生物科技有限公司购得，一水醋酸铜(98％，500g)，无水乙醇(AR)由上海国药化学试剂有限公司购得。粉末X射线衍射光谱由Rigaku日本理学UltimaⅣ全自动多功能X射线衍射仪采集；傅里叶红外光谱由Bruker布鲁克Vertex 80v型真空红外光谱仪采集；X射线光电子能谱由ESCALAB 250Xi型X射线光电子能谱仪采集；扫描电子显微镜图像由Hitachi日立S-3700N扫描电子显微镜采集；电化学检测实验由上海辰华电化学工作站CHI660E采集。
实施例1
金属-有机框架材料由如下步骤制备得到：
(1)将0.312g的苯丙氨酸二肽(L-Phe-L-Phe)加入到20mL的乙醇溶液中，乙醇溶液 中乙醇的体积分数为80％，并将该混合液放入超声装置中下超声5min充分分散均匀，得到乳白色的浑浊混合溶液；
(2)将得到的混合溶液置于30mL的玻璃螺口样品瓶中，向该乳白色浑浊液中逐滴滴加约2.5mL的0.2M醋酸铜水溶液，待白色浑浊溶液全部变为宝蓝色的澄清透明溶液时，停止滴加醋酸铜溶液；
(3)将得到的宝蓝色澄清透明溶液静置于85℃的烘箱中，反应10小时后，冷却到室温后得到有宝蓝色块状晶体析出的混合溶液；将得到的有宝蓝色块状晶体混合溶液离心，并采用乙醇类溶液清洗并离心3次后，置于60℃的烘箱中保温6小时，得到干燥的宝蓝色块状晶体即为金属-有机框架材料。得到的金属-有机框架材料需封装好并置于4℃的冰箱中保存。
其中，得到的宝蓝色块状晶体的化学式为Cu(L-Phe-L-Phe) 2，产物重量约为0.186g，式中：L-Phe-L-Phe为L-苯丙氨酸-L-苯丙氨酸，其线性分子式为C 6H 5CH 2CH(NH 2)CONHCH(CH 2C 6H 5)COOH的有机配体，其结构式如下：
Figure PCTCN2019125090-appb-000002
产品的化学组分分析：得到的宝蓝色块状晶体材料的PXRD图谱和原料L-Phe-L-Phe二肽的PXRD图谱对照图如图1所示。与原料二肽L-Phe-L-Phe的PXRD图谱对照相比，可知二肽作为有机配体分子与铜离子发生络合并生成了新的产物，且反应产物具有较好的 晶型。苯丙氨酸二肽的红外以及反应产物宝蓝色块状晶体材料的红外光谱如图2所示，对比二肽的羧羟基和氨基峰(3500到3100cm -1)以及酰胺键的C＝O双键(1685cm -1)发生了明显的变化，说明了二肽的羧基及酰胺键中的碳氧双键均与铜离子通过配位键发生了络合作用。
图3分别展示了苯丙氨酸二肽、一水合醋酸铜以及宝蓝色块状晶体产物的XPS谱图，可以发现产物中出现了N元素和Cu元素，且C元素的峰强明显增大。通过XPS分析得到的元素含量比例在表1中展示，对比以上三种样品所含元素C、N、O和Cu的相对原子含量比例变化，也进一步验证了铜离子与二肽之间发生了络合作用，并形成了新的产物。
图4对比了原料一水醋酸铜(图4a)和宝蓝色块状晶体材料(图4b)的Cu元素XPS谱图，可以表明反应产物的Cu2p的结合能几乎没有发生明显改变，反应前后价态和化学环境没有发生改变。图4中由XPS得到的关于苯丙氨酸二肽、一水合醋酸铜以及宝蓝色晶体产物的相对原子含量比例如表1所示。
表1
Figure PCTCN2019125090-appb-000003
同理，苯丙氨酸二肽和反应产物的C1s的结合能改变也不明显(图5)。而产物由二肽和铜离子发生配位络合，因此对比产物和二肽的氮离子和氧离子的峰位，结果发现这两种元素的离子峰结合能发生了明显的变化，N1s由398.68eV和397.38eV处的峰(图6a)变为了 397.68eV和395.88eV(图6b)，说明二肽的氨基-NH 2与铜离子发生了配位作用使得电荷发生转移，N1s的电子密度增加，进而导致了N1s结合能的降低，同时O1s由528.98eV(图7a)位移到了529.28eV(图7b)，则是由于C＝O的O与铜离子发生配位作用，导致了O1s的电子密度降低，进而导致了其结合能的升高。XPS谱图分析表明二肽的氨基和羧基都与铜离子发生了配位作用。根据元素分析，蓝色产物的C(37.47％)，N(3.25％)、H(4.09％)、O(21.4％)，分析得Cu元素与FF二肽的分子比例为1：2。
产品的形貌分析：如图8所示，得到的宝蓝色块状晶体产物形貌主要以纤维状存在，并伴随极少的方块状产物。纤维直径主要在0.1至0.3μm之间，且长度不等；块状产物直径主要在2μm以上。
实施例2
与实施例1相同，不同之处在于：
步骤(1)苯丙氨酸二肽与乙醇溶液的固液比为0.01g/mL，乙醇溶液中乙醇的体积分数为90％，步骤(2)醋酸铜溶液的摩尔浓度为0.1M，步骤(3)中宝蓝色澄清透明溶液静置于85℃的烘箱中，反应6小时。
实施例3
与实施例1相同，不同之处在于：
步骤(1)苯丙氨酸二肽与乙醇溶液的固液比为0.02g/mL，乙醇溶液中乙醇的体积分数为75％，步骤(2)醋酸铜溶液的摩尔浓度为0.2M，步骤(3)中宝蓝色澄清透明溶液静置于85℃的烘箱中，反应48小时。
对比例1
为了进一步说明制备条件对材料性能的影响，以研究反应时长对材料形貌的影响为例。与实施例1相同，不同之处在于，反应时间为48小时。
将0.312g的苯丙氨酸二肽(L-Phe-L-Phe)加入到20mL的乙醇溶液中，并将该混合液放入超声装置中下超声5min充分分散均匀，得到乳白色的浑浊溶液。将得到的混合溶液置于30mL的玻璃螺口样品瓶中，向该乳白色浑浊液中逐滴滴加约2.5mL的0.2M醋酸铜水溶液，待白色浑浊溶液全部变为宝蓝色的澄清透明溶液时，停止滴加醋酸铜溶液。将得到的宝蓝色澄清透明溶液静置于85℃的烘箱中，反应48小时后，冷却到室温后得到有宝蓝色块状晶体析出的混合溶液；将得到的有宝蓝色块状晶体混合溶液离心，并采用乙醇类溶液清洗并离心3次后，置于60℃的烘箱中保温6小时，得到干燥的宝蓝色块状晶体即为金属-有机框架材料。得到的金属-有机框架材料需封装好并置于4℃的冰箱中保存。
与实施例1相比，主要探讨了反应时长对产物形貌的影响。得到的宝蓝色晶体材料的形貌图如图9所示，与图8相比可知，通过改变反应条件参数可有效影响产物的形貌特征，得到蜂窝状的椭球形材料，且可明显观察到该蜂窝球体由许多根纤维状材料组装纠缠一起形成。其中，参与组装的纤维直径约为0.2～1μm。
根据元素分析，蓝色产物的C(38.03％)，N(3.27％)、H(4.35％)、O(22.98％)，分析得Cu元素与FF二肽的分子比例为1：2。结果表明，延长反应时间仅改变产物的形貌，对其分子组成成分不会有明显影响。
对比例2
为了进一步研究反应过程中乙醇水混合溶液中乙醇的体积分数对产率的影响，对比了 乙醇体积分数分别约为75％和90％条件下对产物产率的影响。
分别称取两份0.312g的苯丙氨酸二肽(L-Phe-L-Phe)加入到16.85mL(乙醇溶液中乙醇的体积分数约为75％)和20.25mL(乙醇溶液中乙醇的体积分数约为90％)的乙醇溶液中，并将该混合液放入超声装置中下超声5min充分分散均匀，得到乳白色的浑浊溶液。将得到的混合溶液分别置于30mL的玻璃螺口样品瓶A和样品瓶B中，向A瓶和B瓶中的乳白色浑浊液中分别滴加约5.5mL的0.1M醋酸铜水溶液和2.5mL的0.2M醋酸铜水溶液。将得到的宝蓝色澄清透明溶液静置于85℃的烘箱中，反应6小时后，冷却到室温后得到有宝蓝色块状晶体析出的混合溶液；将得到的有宝蓝色块状晶体混合溶液离心，并采用乙醇类溶液清洗并离心3次后，置于60℃的烘箱中保温6小时，得到干燥的宝蓝色块状晶体即为金属-有机框架材料并称重。在以上两种乙醇体积分数条件下，样品瓶A条件下得到的金属-有机框架材料的质量为0.087g，样品瓶B条件下得到的产物质量和0.102g。
以上实验结果表明，乙醇的体积分数会影响到产物的产量。
实施例4
实施例1制备得到的宝蓝色晶体产物修饰的电极，采用电化学分析站对不同种类的芳香环类有机污染物模型进行循环伏安法检测，观察并对比CV曲线特征及变化，判断有机污染物浓度对电化学信号的影响。其中，采用了亚甲基蓝、溴酚蓝、2’-溴联苯醚、双酚A和四环素作为有机污染物分子模型。
电极的制备：本实施例采用三电极体系，其中，直径为3mm直径玻碳电极为工作电极，铂丝电极为辅助电极，Ag/AgCl电极为参比电极。玻碳电极先经过W0.3μm三氧化二铝抛光粉打磨至镜面后，分别采用超纯水和乙醇洗去表面污物、干燥，然后在0.5～1.0M浓度的 硫酸溶液中活化。将5mg的实施例1得到的宝蓝色晶体产物溶于100μL的Nafion乙醇溶液(质量分数为0.5％)中，超声5～15min充分分散均匀。取10μL的宝蓝色晶体产物/Nafion混合溶液滴在玻碳电极表面，待干燥后开始测量修饰后的电极对不同种类的有机污染物分子在-0.4V～0.8V之间的CV曲线随分析物浓度变化图。
循环伏安法测量CV曲线：如图10所示分别为裸的玻碳电极、Nafion膜修饰的玻碳电极以及产物/Nafion膜修饰的玻碳电极在0.1M KCl的水溶液中采用循环伏安法稳定后的CV曲线。由图可知，以上三种电极在0.1M KCl的溶液中表现出不同特征的CV曲线，可知产物/Nafion膜已经成功修饰到了玻碳电极表面，且表现出了不同的界面性质。将该电极插入到10mL的KCl溶液中，测量不同浓度下的有机分子溶液的CV曲线，每测量一次后，再加入5μL的待测样品，等待30s后再测定CV曲线。图11为产物/Nafion膜修饰的玻碳电极在不同浓度的亚甲基蓝溶液中的CV曲线，随着5mM浓度的亚甲基蓝加入到KCl溶液中，测量的CV曲线分别在-0.04V附近的峰逐渐消失，同时在-0.29V附近形成的新的峰。图12为产物/Nafion膜修饰的玻碳电极在不同浓度的四环素溶液中CV曲线变化图，随着电解液中四环素浓度的增大，CV曲线在0.025V附近的峰逐渐消失，且并没有新的峰生成。为了体现材料对亚甲基蓝的选择性，另外采用了双酚A、2’-溴联苯醚和溴酚蓝三种分子作为参照对比。图13-15分别为修饰后的电极所在电解液中依次滴加10mM双酚A、5mM 2’-溴联苯醚和2mM溴酚蓝的CV-浓度变化曲线图，实验结果表明，并没有明显的随浓度变化关系。由CV-分析物浓度变化图可知，该修饰电极对亚甲基蓝具有选择性识别的能力，CV曲线特征变化明显，可作为一种鉴别手段，通过CV曲线特征峰值的变化达到分析亚甲基蓝是否存在的目的，检测范围最低限值为5×10 -4mM。
以上仅是本发明的优选实施方式，应当指出的是，上述优选实施方式不应视为对本发明的限制，本发明的保护范围应当以权利要求所限定的范围为准。对于本技术领域的普通技术人员来说，在不脱离本发明的精神和范围内，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (7)

  1. 一种金属-有机框架材料，其特征在于，所述的金属-有机框架材料的化学式为Cu(L-Phe-L-Phe) 2，L-Phe-L-Phe的结构式如式(1)所示，
    Figure PCTCN2019125090-appb-100001
  2. 权利要求1所述的金属-有机框架材料的制备方法，其特征在于，包括如下步骤：
    (1)将苯丙氨酸二肽加入到醇类溶液中混合均匀，所述的苯丙氨酸二肽与醇类溶液的固液比为0.01～0.02g/mL，得到混合溶液；
    (2)向步骤(1)得到的混合溶液中逐滴滴加铜离子溶液，当所述的混合溶液由白色浑浊变为宝蓝色澄清透明溶液时，停止滴加铜离子溶液；
    (3)将步骤(2)得到的宝蓝色澄清透明溶液静置于干燥环境中，反应6～48小时后，冷却到室温后得到有宝蓝色块状晶体析出的混合溶液，将所述的有宝蓝色块状晶体混合溶液离心分离，沉淀洗涤干燥后，最终得到所述的金属有机框架材料。
  3. 根据权利要求2所述的金属-有机框架材料的制备方法，其特征在于，所述的铜离子溶液为醋酸铜溶液，所述的醋酸铜溶液的摩尔浓度为0.1～0.2M。
  4. 根据权利要求2所述的金属-有机框架材料的制备方法，其特征在于，所述的醇类溶液为乙醇溶液，所述的乙醇溶液中乙醇的体积分数为75％～90％。
  5. 根据权利要求2所述的金属-有机框架材料的制备方法，其特征在于，步骤(3)中将步 骤(2)得到的宝蓝色澄清透明溶液静置于80～90℃的干燥环境中。
  6. 根据权利要求2所述的金属-有机框架材料的制备方法，其特征在于，步骤(3)中所述的有宝蓝色块状晶体混合溶液离心分离，沉淀洗涤干燥的具体步骤是：将所述的有宝蓝色块状晶体混合溶液放入离心管中，采用离心机离心获得宝蓝色块状晶体沉淀，离心机的转速为3000r/min，离心时长3min；将离心后的上清液除去后，再加入醇类溶剂并充分混匀后再次进行离心分离，反复操作3～5次，直到离心后的上清液澄清后，再将宝蓝色块状晶体沉淀置于烘箱中在60℃的温度下烘干处理，烘干时长为6小时。
  7. 权利要求1所述的金属-有机框架材料修饰的电极在亚甲基蓝检测中的应用。
PCT/CN2019/125090 2019-10-18 2019-12-13 一种金属-有机框架材料的制备方法及其应用 WO2021072958A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910995016.3A CN111057126A (zh) 2019-10-18 2019-10-18 一种金属-有机框架材料的制备方法及其应用
CN201910995016.3 2019-10-18

Publications (1)

Publication Number Publication Date
WO2021072958A1 true WO2021072958A1 (zh) 2021-04-22

Family

ID=70297547

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/125090 WO2021072958A1 (zh) 2019-10-18 2019-12-13 一种金属-有机框架材料的制备方法及其应用

Country Status (2)

Country Link
CN (1) CN111057126A (zh)
WO (1) WO2021072958A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112159528A (zh) * 2020-09-17 2021-01-01 浙大宁波理工学院 一种磷-氮基超分子稀土配合物及其制备方法和应用
CN114011470A (zh) * 2021-11-29 2022-02-08 首都师范大学 一种用于水解三磷酸腺苷的催化剂及其制备方法和应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114470150B (zh) * 2021-12-13 2022-12-27 完美（广东）日用品有限公司 一种鸡源性小分子肽在制备预防和改善肝损伤及其继发症状产品中的应用及该产品

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW387896B (en) * 1996-02-16 2000-04-21 Wang Huei Bo Novel dipeptide and tripeptide mimic compounds for treating Parkinson's disease
CN105541874A (zh) * 2016-01-25 2016-05-04 辽宁大学 一种基于CuII金属的多孔金属有机骨架及其制备方法和应用
CN107497402A (zh) * 2017-09-25 2017-12-22 江苏大学 一种水稳定染料吸附剂及制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013192146A1 (en) * 2012-06-18 2013-12-27 Northwestern University Metal-organic framework materials with ultrahigh surface areas
CN105061474B (zh) * 2015-07-16 2016-09-28 山西大学 一种铜配合物及其制备方法和应用
CN105254901A (zh) * 2015-11-04 2016-01-20 中国科学院化学研究所 一种金属有机骨架材料及其制备方法与应用
CN106111196B (zh) * 2016-06-07 2018-08-07 青岛大学 一种铁卟啉氯化物/亚甲基蓝@金属有机骨架复合材料电极的制备方法和应用
CN109351334A (zh) * 2018-09-12 2019-02-19 内蒙古大学 一种水稳定的亚甲基蓝吸附材料及其制备方法和应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW387896B (en) * 1996-02-16 2000-04-21 Wang Huei Bo Novel dipeptide and tripeptide mimic compounds for treating Parkinson's disease
CN105541874A (zh) * 2016-01-25 2016-05-04 辽宁大学 一种基于CuII金属的多孔金属有机骨架及其制备方法和应用
CN107497402A (zh) * 2017-09-25 2017-12-22 江苏大学 一种水稳定染料吸附剂及制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112159528A (zh) * 2020-09-17 2021-01-01 浙大宁波理工学院 一种磷-氮基超分子稀土配合物及其制备方法和应用
CN114011470A (zh) * 2021-11-29 2022-02-08 首都师范大学 一种用于水解三磷酸腺苷的催化剂及其制备方法和应用

Also Published As

Publication number Publication date
CN111057126A (zh) 2020-04-24

Similar Documents

Publication Publication Date Title
WO2021072958A1 (zh) 一种金属-有机框架材料的制备方法及其应用
CN109100404B (zh) 类水滑石纳米片@zif-67复合材料修饰电极及其制备方法和检测应用
Wu et al. Controllable synthesis of Ag/AgCl@ MIL-88A via in situ growth method for morphology-dependent photocatalytic performance
CN114409913B (zh) 一种磁性金属有机框架材料及其制备方法和应用
CN106432117A (zh) 一种功能性纳米铈配合物的制备方法和应用
Yu et al. Combination of a graphene SERS substrate and magnetic solid phase micro-extraction used for the rapid detection of trace illegal additives
CN105879919A (zh) Au/ZIF-8-TiO2催化剂及其制备方法与应用
CN107917904B (zh) 一种快速检测Fe3+的方法
CN114505058B (zh) 一种金属有机框架材料辅助的高灵敏度氢气检测纳米材料及其制备方法
CN108623815B (zh) 一种镉基金属有机框架材料的制备方法及其在离子识别中的应用
CN109187687B (zh) 共轭有机微孔材料修饰电极的制备及作为过氧亚硝基阴离子电化学传感器的应用
CN107828066B (zh) 四巯基卟啉修饰的金属有机框架纳米材料及其制备方法和用途
CN117347336A (zh) 一种检测卡那霉素的荧光适配体生物传感器及其制备方法和应用
CN106248749B (zh) 一种手性金属有机纳米晶传感器及其制备方法和应用
CN109254037A (zh) 一种石墨烯量子点修饰的金属卟啉纳米管-硫化镉复合光敏传感材料的制备方法
CN108760716B (zh) 一种表面增强拉曼光谱湿巾及其制备方法与应用
CN114989806B (zh) 一种快速检测孔雀石绿的复合探针及其检测方法
WO2020113706A1 (zh) 半导体化合物在苯甲醛特异性检测中的应用及检测方法
CN112573612B (zh) 一种利用亚胺型共价有机框架同时吸附苏丹红i-iv的方法和应用
CN115160590A (zh) 双金属金属有机框架表面增强拉曼光谱基底的制备方法
Martynov et al. New hybrid materials based on nanostructured aluminum oxyhydroxide and terbium (III) bis (tetra-15-crown-5-phthalocyaninate)
CN114314641A (zh) 一种超薄纳米亚基组装的空心硫化铟纳米棒的制备和应用
CN111569835A (zh) 一种亚甲基蓝吸附剂及其制备方法和应用
CN113049718A (zh) 一种碳载金属氧化物复合微球的制备及其对水产品中孔雀石绿和结晶紫的萃取
CN111141802A (zh) 一种纳米材料及其制备方法和应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19949358

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19949358

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 19949358

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 13/10/2022)

122 Ep: pct application non-entry in european phase

Ref document number: 19949358

Country of ref document: EP

Kind code of ref document: A1