WO2019015448A1 - 一种用于检测水体镉离子的识别膜及其制备方法、应用 - Google Patents

一种用于检测水体镉离子的识别膜及其制备方法、应用 Download PDF

Info

Publication number
WO2019015448A1
WO2019015448A1 PCT/CN2018/092965 CN2018092965W WO2019015448A1 WO 2019015448 A1 WO2019015448 A1 WO 2019015448A1 CN 2018092965 W CN2018092965 W CN 2018092965W WO 2019015448 A1 WO2019015448 A1 WO 2019015448A1
Authority
WO
WIPO (PCT)
Prior art keywords
cadmium ions
water
film
water body
detecting cadmium
Prior art date
Application number
PCT/CN2018/092965
Other languages
English (en)
French (fr)
Inventor
刘长坤
王琳
Original Assignee
深圳大学
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 深圳大学 filed Critical 深圳大学
Publication of WO2019015448A1 publication Critical patent/WO2019015448A1/zh

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour

Definitions

  • the invention relates to the field of heavy metal detection, in particular to a recognition film for detecting cadmium ions in water, a preparation method thereof and an application thereof.
  • Cadmium is mainly derived from industrial wastewater, such as electroplating wastewater discharge, nickel-cadmium battery manufacturing, fertilizer and pesticide production, pigments, dyes and textiles, smelting and alloy manufacturing, steel, cement production, sewage sludge, mining and ore. Refining and so on.
  • industrial wastewater such as electroplating wastewater discharge, nickel-cadmium battery manufacturing, fertilizer and pesticide production, pigments, dyes and textiles, smelting and alloy manufacturing, steel, cement production, sewage sludge, mining and ore. Refining and so on.
  • Cadmium one of the heavy metals, accumulates in the human body and causes damage to important organs such as kidney, bone, liver, central and lung.
  • the pollution of cadmium to water can spread and spread rapidly in a short period of time. In order to control the deterioration of the situation and formulate corresponding countermeasures, it is necessary to timely discover and identify cadmium ions in water.
  • an object of the present invention is to provide a recognition film for detecting cadmium ions in a water body, a preparation method thereof and an application thereof, and aim to solve the problem that the prior art has complicated operation when detecting cadmium ions in a water body.
  • a method for preparing a recognition film for detecting cadmium ions in a water body comprising the steps of:
  • the polysulfone membrane is placed in a monomer solution of potassium sulfonate propyl sulfonate, and after ultraviolet irradiation for 20-60 minutes, a polysulfone having a potassium sulfonate 3-sulfonate potassium salt monomer is obtained.
  • the polysulfone membrane with the propyl sulfonate propyl sulfonate potassium salt monomer is placed in the porphyrin solution, and after 15-24 hours, a recognition membrane for detecting cadmium ions in the water is prepared.
  • the method for preparing a recognition film for detecting cadmium ions in a water wherein the porphyrin is 5,10,15,20-tetrakis(1-methyl-4-pyridyl)porphyrin IV (p-toluenesulfonate), the chemical formula is Where R is
  • the preparation method of the identification film for detecting cadmium ions in a water body wherein before the step A, the method further comprises:
  • the polysulfone membrane was previously immersed in a methanol solution for 1-3 h, and the polysulfone membrane was taken out and placed in a benzophenone solution for 1-3 hours to obtain a surface-activated polysulfone membrane.
  • step A further comprises:
  • the polysulfone membrane with methacrylic acid propyl sulfonate potassium salt monomer was rinsed with deionized water for 1-10 min.
  • the method for preparing a recognition film for detecting cadmium ions in a water wherein the volume ratio of the mass of the polysulfone membrane in the step A to the potassium sulfonate 3-sulfonate potassium salt monomer solution is 0.1-0.5 g: 100-200 ml.
  • the method for preparing a recognition film for detecting cadmium ions in a water body wherein the concentration of the methacrylic acid propyl sulfonate potassium salt monomer solution in the step A is 0.15 g/mL.
  • the preparation method of the identification film for detecting cadmium ions in a water body wherein the concentration of the porphyrin solution in the step B is 35 mg/L.
  • An identification film for detecting cadmium ions in a water body which is prepared by the preparation method of any one of the above.
  • the application of the identification film for detecting cadmium ions in a water body includes the steps of:
  • the identification film is taken out and automatically dried. If the color of the identification film changes, it is determined that cadmium ions are present in the water to be tested.
  • the present invention provides a preparation method of a recognition film for detecting cadmium ions in a water body, which first introduces a hydrophilic potassium sulfonate 3-sulfonate methacrylate salt into a polysulfone membrane material by ultraviolet irradiation. The reaction time is greatly reduced, and the experiment is completed in one step, and then the positively charged porphyrin group is grafted onto the surface of the modified negatively charged polysulfone membrane to prepare a recognition film for detecting cadmium ions in water.
  • the whole preparation process is simple and easy to realize, the experiment time is greatly shortened, and the identification film prepared by the invention can quickly and accurately detect trace amounts of cadmium ions in the water to be tested.
  • FIG. 1 is a flow chart of a preferred embodiment of a method for preparing a recognition film for detecting cadmium ions in water according to the present invention.
  • the present invention provides a recognition film for detecting cadmium ions in a water body, a preparation method thereof, and an application thereof.
  • the present invention will be further described in detail below in order to make the objects, technical solutions and effects of the present invention more clear and clear. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
  • FIG. 1 is a flow chart of a preferred embodiment of a method for preparing a recognition film for detecting cadmium ions in water according to the present invention. As shown in the figure, the method includes the following steps:
  • the rapid identification technology of heavy metals has been developed to some extent.
  • the main principle is to form a complex by a ligand on the surface of the material and a heavy metal ion in the form of a coordination bond, which is represented by a color change displayed on the macroscopic surface.
  • the presence of certain heavy metals is to form a complex by a ligand on the surface of the material and a heavy metal ion in the form of a coordination bond, which is represented by a color change displayed on the macroscopic surface.
  • polysulfone is preferred as a matrix material for the recognition membrane, and TMPyP (5,10,15,20-tetrakis(1-methyl-4-pyridyl)porphyrin tetra(p-toluene) which is highly sensitive to cadmium and discoloration is recognized.
  • the acid salt)) is fixed on the polysulfone membrane in the form of a "polymer brush" to prepare a recognition film capable of rapidly detecting cadmium ions in water.
  • the prior art generally performs surface graft modification of materials by the method of SI-ATRP, which has a long experimental period, many operation steps, and cumbersome reaction, and the present invention will use a UV irradiation method to carry a hydrophilic sulfonic acid group.
  • the polymer brush methyl 3-sulfonate propyl methacrylate monomer
  • PSF polysulfone
  • the reaction time is greatly reduced, and the experimental procedure is simple.
  • the identification film prepared by the invention is used for detecting cadmium ions in water, and the recognition function of the trace cadmium ions in the water body can be realized by color change, so that the trace cadmium in the water body can be detected quickly and sensitively. Ions to take emergency measures in a timely manner.
  • the polysulfone material has good rigidity and toughness, is resistant to temperature, heat and oxidation, excellent in creep resistance, corrosion resistant to inorganic acids, alkalis, and salt solutions, non-toxic, good in insulation and self-extinguishing, and easy to form.
  • the present invention preferably uses polysulfone as a matrix material for the modified film.
  • the method further comprises: pre-soaking the polysulfone membrane into a methanol solution for 1-3 hours, taking out the polysulfone membrane and then immersing in a benzophenone solution for 1-3 hours to obtain surface activation. Polysulfone membrane.
  • 0.1-0.5 g of the polysulfone membrane is firstly immersed in a methanol solution for 2 hours to remove impurities on the surface of the polysulfone membrane; then the polysulfone membrane is taken out from the methanol solution and placed in 0.1- A 0.2 mol/L benzophenone (BP) solution in methanol was immersed for two hours, and the benzophenone was used as a photoinitiator to activate the surface of the polysulfone membrane.
  • BP benzophenone
  • the polysulfone membrane is placed in a monomer solution of potassium sulfonate propyl sulfonate, and after ultraviolet irradiation for 20-60 minutes, a propyl 3-sulfonate methacrylate is obtained.
  • a polysulfone membrane of a potassium salt monomer Specifically, the chemical formula of the potassium propyl sulfonate sulfonate is The surface-activated polysulfone membrane was first placed in a 0.15 g/mL methacrylic acid propyl sulfonate potassium salt monomer solution, and then placed in an ultraviolet light box for 30 minutes to obtain methacrylic acid.
  • a polysulfone membrane of a propyl sulfonate potassium salt monomer preferably, the solvent in the propyl sulfonate propyl sulfonate potassium salt monomer solution is a ratio of water to methanol of 1:4. Proportioned in proportion.
  • a piece of quartz glass can be placed in the ultraviolet light box to reduce the solvent evaporation of the potassium sulfonate 3-sulfonate potassium salt monomer to cause a change in the monomer concentration, thereby reducing experimental errors.
  • the volume ratio of the mass of the polysulfone membrane to the potassium sulfonate 3-sulfonate potassium salt monomer solution is from 0.1 to 0.5 g: 100 to 200 ml.
  • the invention adopts an ultraviolet irradiation method to introduce a polymer brush with a hydrophilic sulfonic acid group (potassium 3-sulfonate methacrylate) onto a polysulfone (PSF) membrane material, and the operation is simple and the reaction time is Significantly reduced, the experiment is completed in one step.
  • a hydrophilic sulfonic acid group potassium 3-sulfonate methacrylate
  • the polysulfone membrane with the potassium sulfonate propyl sulfonate methacrylate monomer is rinsed with deionized water for 1-10 min, preferably for 5 min, to make a residual sheet on the polysulfone membrane.
  • the body is removed clean.
  • the polysulfone membrane with the potassium sulfonate 3-sulfonate potassium salt monomer is placed in the porphyrin solution, and the reaction is prepared for 15-24 hours.
  • the porphyrin is 5,10,15,20-tetrakis(1-methyl-4-pyridyl)porphyrin tetra(p-toluenesulfonate), the chemical formula of which is Where R is
  • the 5,10,15,20-tetrakis(1-methyl-4-pyridyl)porphyrin tetra(p-toluenesulfonate) can bind to cadmium ions in a water body with high sensitivity and undergo a color reaction, thereby The color of the identification film changes.
  • the washed polysulfone membrane is placed in a 100 ml concentration of 35 mg/L porphyrin solution for 20 hours to obtain a highly sensitive identification film for detecting cadmium ions in water.
  • the present invention also provides an identification film for detecting cadmium ions in a water body, which is prepared by the preparation method of any one of the above.
  • the present invention also provides an application for detecting a cadmium ion in a water body, comprising the steps of:
  • the identification film is taken out and automatically dried. If the color of the identification film changes, it is determined that cadmium ions are present in the water to be tested.
  • the present invention provides a method for preparing a recognition film for detecting cadmium ions in water, first introducing hydrophilic potassium sulfonate 3-sulfonate methacrylate into the polymerization by ultraviolet irradiation. On the sulfone membrane material, the reaction time is greatly reduced, and the experiment is completed in one step, and then the positively charged porphyrin group is grafted onto the surface of the modified negatively charged polysulfone membrane to prepare for detecting cadmium ions in water.
  • the identification film is simple and easy to realize, the experimental time is greatly shortened, and the identification film prepared by the invention can quickly and accurately detect trace amounts of cadmium ions in the water to be tested.

Abstract

一种用于检测水体镉离子的识别膜的制备方法，其中，所述制备方法包括：将聚砜膜放入甲基丙烯酸3-磺酸丙酯钾盐单体溶液中，紫外照射20-60min后，得到接有甲基丙烯酸3-磺酸丙酯钾盐单体的聚砜膜；将所述接有甲基丙烯酸3-磺酸丙酯钾盐单体的聚砜膜放入卟啉溶液中，反应15-24h后，制得用于检测水体镉离子的识别膜。一种采用上述方法制备得到的识别膜。一种所述用于检测水体镉离子识别膜的应用，能够快速、准确地检测到待测水体中的微量镉离子。

Description

一种用于检测水体镉离子的识别膜及其制备方法、应用 技术领域
本发明涉及重金属检测领域，尤其涉及一种用于检测水体镉离子的识别膜及其制备方法、应用。
背景技术
近年来，随着科学技术的快速发展，镉的使用变得越来越广泛，镉的需求和产量也在逐年增长，相应地镉进入到环境含量也逐渐增多。镉主要来源于工业废水，例如电镀废水排放、镍镉电池制造业、化肥和农药的生产、颜料、染料和纺织行业、冶炼和合金制造、钢铁、水泥的生产、污水污泥、矿山开采和矿石提炼等。镉作为重金属之一，在人体内蓄积将导致肾、骨、肝、中枢、肺等重要器官受到损害。而且镉对水体的污染可在很短的时间内迅速扩散和蔓延，为了控制事态的恶化以及制定相应的处理对策，及时的发现和识别水体中的镉离子是非常必要的。
传统识别水体镉元素的检测方法有仪器分析法、酶分析法、免疫分析法、生物化学传感器等，其中，仪器分析方法大多需要昂贵的大型仪器，并且存在样品保存条件严格、分析方法成本高、分析时间长、操作专业性强等缺点；酶法选择性较差，对单一重金属离子的检测存在一定的困难；免疫分析法对金属离子单克隆抗体的制备非常困难，而较容易制备的多克隆抗体又难以满足对金属离子的特异性要求；传统的生物化学传感器制作工艺困难，成本相对较高。
因此，现有技术还有待于改进和发展。
发明内容
鉴于上述现有技术的不足，本发明的目的在于提供一种用于检测水体镉离子的识别膜及其制备方法、应用，旨在解决现有技术在检测水体中的镉离子时存在操作复杂、检测灵敏度低、周期长以及成本高的问题。
本发明的技术方案如下：
一种用于检测水体镉离子的识别膜的制备方法，其特征在于，包括步骤：
A、将聚砜膜放入甲基丙烯酸3-磺酸丙酯钾盐单体溶液中，紫外照射20-60min后，得到接有甲基丙烯酸3-磺酸丙酯钾盐单体的聚砜膜；
B、将所述接有甲基丙烯酸3-磺酸丙酯钾盐单体的聚砜膜放入卟啉溶液中，反应15-24h后，制得用于检测水体镉离子的识别膜。
较佳地，所述的用于检测水体镉离子的识别膜的制备方法，其中，所述卟啉为5,10,15,20-四(1-甲基-4-吡啶基)卟啉四(对甲苯磺酸盐)，其化学式为
Figure PCTCN2018092965-appb-000001
其中R为
Figure PCTCN2018092965-appb-000002
所述的用于检测水体镉离子的识别膜的制备方法，其中，所述步骤A之前还包括：
A0、预先将聚砜膜放入甲醇溶液中浸泡1-3h，取出所述聚砜膜再放入二苯甲酮溶液中浸泡1-3h，得到表面活化后的聚砜膜。
所述的用于检测水体镉离子的识别膜的制备方法，其中，所述步骤A之后还包括：
A1、用去离子水对接有甲基丙烯酸3-磺酸丙酯钾盐单体的聚砜膜冲洗1-10min。
所述的用于检测水体镉离子的识别膜的制备方法，其中，所述步骤A中聚砜膜的质量与甲基丙烯酸3-磺酸丙酯钾盐单体溶液的体积比为0.1-0.5g：100-200ml。
所述的用于检测水体镉离子的识别膜的制备方法，其中，所述步骤A中的甲基丙烯酸3-磺酸丙酯钾盐单体溶液的浓度为0.15g/mL。
所述的用于检测水体镉离子的识别膜的制备方法，其中，所述步骤B中的卟啉溶液浓度为35mg/L。
一种用于检测水体镉离子的识别膜，其中，采用如上任意一项制备方法制备而得。
所述的用于检测水体镉离子的识别膜的应用，其中，包括步骤：
将识别膜加入到待测水体中，室温下搅拌5-20min；
取出所述识别膜并自动晾干，若识别膜发生颜色变化，判定待测水体中存在镉离子。
所述的用于检测水体镉离子的识别膜的应用，其中，所述搅拌转速为 200-400r/min。
有益效果：本发明提供一种用于检测水体镉离子的识别膜的制备方法，首先通过紫外辐照的方式将亲水性的甲基丙烯酸3-磺酸丙酯钾盐引入到聚砜膜材料上，反应时间大幅减少，实验一步完成，然后再将带正电荷的卟啉基团接枝到经改性后的带负电荷的聚砜膜表面，制得用于检测水体镉离子的识别膜，整个制备过程简单易实现，实验时间大大缩短，并且通过本发明制备的识别膜能够快速、准确地检测到待测水体中的微量镉离子。
附图说明
图1为本发明一种用于检测水体镉离子的识别膜的制备方法较佳实施例的流程图。
具体实施方式
本发明提供一种用于检测水体镉离子的识别膜及其制备方法、应用，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
请参阅图1，图1为本发明一种用于检测水体镉离子的识别膜的制备方法较佳实施例流程图，如图所示，其中，包括步骤：
S10、将聚砜膜放入甲基丙烯酸3-磺酸丙酯钾盐单体溶液中，紫外照射20-60min后，得到接有甲基丙烯酸3-磺酸丙酯钾盐单体的聚砜膜；
S20、将所述接有甲基丙烯酸3-磺酸丙酯钾盐单体的聚砜膜放入卟啉溶液中，反应15-24h后，制得用于检测水体镉离子的识别膜。
具体来说，现如今重金属的快速识别技术得到了一定发展，其主要原理是通过材料表面的配位体与重金属离子以配位键形式形成络合物，通过在宏观上显示的颜色变化来表示某种重金属的存在。
本发明优选聚砜作为识别膜的基质材料，将高灵敏识别镉并发生变色的TMPyP(5,10,15,20-四(1-甲基-4-吡啶基)卟啉四(对甲苯磺酸盐))以“聚合物刷”的形式固定聚砜膜上，制备出能够快速检测水体镉离子的识别膜。
现有技术通常是通过SI-ATRP的方法进行材料的表面接枝改性，其实验周期长，操作步骤多，反应繁琐，而本发明将利用紫外辐照方法将带有亲水性磺酸基团的聚合物刷(甲基丙烯酸3-磺酸丙酯钾盐单体)引入到聚砜(PSF)膜材料上，然 后利用正负电子相吸，将带正电荷的卟啉基团接到改性后带负电荷的聚砜膜上，其反应时间大幅减少，实验步骤简单。
进一步，将本发明制备的识别膜用于检测水体中的镉离子，通过颜色变化便可实现其对水体中微量镉离子的识别功能，使其能够快速、高灵敏地检测出水体中的微量镉离子，以便及时采取应急措施。
具体地，由于聚砜材料具有刚性和韧性好，耐温、耐热氧化，抗蠕变性能优良，耐无机酸、碱、盐溶液的腐蚀，无毒，绝缘性和自熄性好，容易成型加工等多种优点，因此，本发明优选聚砜作为改性膜的基质材料。
进一步，在所述步骤S10之前还包括：预先将聚砜膜放入甲醇溶液中浸泡1-3h，取出所述聚砜膜再放入二苯甲酮溶液中浸泡1-3h，得到表面活化后的聚砜膜。具体来说，先将0.1-0.5g的聚砜膜放入到甲醇溶液中浸泡2h，使聚砜膜表面杂质被清除干净；然后将所述聚砜膜从甲醇溶液中取出并放入0.1-0.2mol/L二苯甲酮(BP)的甲醇溶液中浸泡两小时，所述二苯甲酮作为光引发剂，可使聚砜膜表面活化。
进一步，在所述步骤S10中，将聚砜膜放入甲基丙烯酸3-磺酸丙酯钾盐单体溶液中，紫外照射20-60min后，得到接有甲基丙烯酸3-磺酸丙酯钾盐单体的聚砜膜。具体来说，所述甲基丙烯酸3-磺酸丙酯钾盐的化学式为
Figure PCTCN2018092965-appb-000003
先将表面活化的聚砜膜放入浓度为0.15g/mL的甲基丙烯酸3-磺酸丙酯钾盐单体溶液中，然后放入紫外灯箱中紫外光照30min，得到接有甲基丙烯酸3-磺酸丙酯钾盐单体的聚砜膜；较佳地，所述甲基丙烯酸3-磺酸丙酯钾盐单体溶液中的溶剂是按照水和甲醇的体积比为1：4的比例配制而成。优选地，可在所述紫外灯箱中放置一片石英玻璃片，以减小甲基丙烯酸3-磺酸丙酯钾盐单体溶剂挥发导致所述单体浓度发生变化，从而减小实验误差。更优选地，所述聚砜膜的质量与甲基丙烯酸3-磺酸丙酯钾盐单体溶液的体积比为0.1-0.5g：100-200ml。
本发明利用紫外辐照方法将带有亲水性磺酸基团的聚合物刷(甲基丙烯酸3-磺酸丙酯钾盐)引入到聚砜(PSF)膜材料上，操作简单，反应时间大幅减少，实验一步完成。
进一步，所述步骤S10之后还包括；用去离子水对接有甲基丙烯酸3-磺酸丙酯钾盐单体的聚砜膜冲洗1-10min，优选冲洗5min，使聚砜膜上的残留单体去除干净。
更进一步，在所述步骤S20中，将所述接有甲基丙烯酸3-磺酸丙酯钾盐单体的聚砜膜放入卟啉溶液中，反应15-24h后，制得用于检测水体镉离子的识别膜。具体来说，所述卟啉为5,10,15,20-四(1-甲基-4-吡啶基)卟啉四(对甲苯磺酸盐)，其化学式为
Figure PCTCN2018092965-appb-000004
其中R为
Figure PCTCN2018092965-appb-000005
所述5,10,15,20-四(1-甲基-4-吡啶基)卟啉四(对甲苯磺酸盐)能够高灵敏度地与水体中的镉离子结合并发生显色反应，从而使识别膜发生颜色变化。优选地，将洗净后的聚砜膜放入100ml浓度35mg/L卟啉溶液中进行反应20小时，便可制得用于检测水体镉离子的高灵敏度识别膜。
进一步，本发明还提供一种用于检测水体镉离子的识别膜，其中，采用如上任意一项制备方法制备而得。
更进一步，本发明还提供一种用于检测水体镉离子的识别膜的应用，其中，包括步骤：
将识别膜加入到待测水体中，室温下搅拌5-20min；
取出所述识别膜并自动晾干，若识别膜发生颜色变化，判定待测水体中存在镉离子。
具体地，将待测水体的pH调节至3-7，将50mg的识别膜和磁力搅拌子放入干净的烧杯中，同时迅速倒入50mL的待测水体溶液，在室温下，以200-400r/min转速的磁力搅拌机上进行反应，反应2-120min，将膜放置在滤纸上自动晾干，通过观察识别膜是否发生颜色，来判定待测水体中是否存在镉离子；若识别膜发生颜色变化，说明待测水体中存在镉离子；若识别膜没有发生颜色变化，则说明待测水体中不存在镉离子。
综上所述，本发明提供的一种用于检测水体镉离子的识别膜的制备方法，首先通过紫外辐照的方式将亲水性的甲基丙烯酸3-磺酸丙酯钾盐引入到聚砜膜材 料上，反应时间大幅减少，实验一步完成，然后再将带正电荷的卟啉基团接枝到经改性后的带负电荷的聚砜膜表面，制得用于检测水体镉离子的识别膜，整个制备过程简单易实现，实验时间大大缩短，并且通过本发明制备的识别膜能够快速、准确地检测到待测水体中的微量镉离子。
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。

Claims (10)

  1. 一种用于检测水体镉离子的识别膜的制备方法，其特征在于，包括步骤：
    A、将聚砜膜放入甲基丙烯酸3-磺酸丙酯钾盐单体溶液中，紫外照射20-60min后，得到接有甲基丙烯酸3-磺酸丙酯钾盐单体的聚砜膜；
    B、将所述接有甲基丙烯酸3-磺酸丙酯钾盐单体的聚砜膜放入卟啉溶液中，反应15-24h后，制得用于检测水体镉离子的识别膜。
  2. 根据权利要求1所述的用于检测水体镉离子的识别膜的制备方法，其特征在于，所述卟啉为5,10,15,20-四(1-甲基-4-吡啶基)卟啉四(对甲苯磺酸盐)，其化学式为
    Figure PCTCN2018092965-appb-100001
    其中R为
    Figure PCTCN2018092965-appb-100002
  3. 根据权利要求1所述的用于检测水体镉离子的识别膜的制备方法，其特征在于，所述步骤A之前还包括：
    A0、预先将聚砜膜放入甲醇溶液中浸泡1-3h，取出所述聚砜膜再放入二苯甲酮溶液中浸泡1-3h，得到表面活化后的聚砜膜。
  4. 根据权利要求1所述的用于检测水体镉离子的识别膜的制备方法，其特征在于，所述步骤A之后还包括：
    A1、用去离子水对接有甲基丙烯酸3-磺酸丙酯钾盐单体的聚砜膜冲洗1-10min。
  5. 根据权利要求1所述的用于检测水体镉离子的识别膜的制备方法，其特征在于，所述步骤A中聚砜膜的质量与甲基丙烯酸3-磺酸丙酯钾盐单体溶液的体积比为0.1-0.5g：100-200ml。
  6. 根据权利要求1所述的用于检测水体镉离子的识别膜的制备方法，其特征在于，所述步骤A中的甲基丙烯酸3-磺酸丙酯钾盐单体溶液的浓度为0.15g/mL。
  7. 根据权利要求1所述的用于检测水体镉离子的识别膜的制备方法，其特征在于，所述步骤B中的卟啉溶液浓度为35mg/L。
  8. 一种用于检测水体镉离子的识别膜，其特征在于，采用权利要求1-7任意一项制备方法制备而得。
  9. 一种如权利要求8所述的用于检测水体镉离子的识别膜的应用，其特征 在于，包括步骤：
    将识别膜加入到待测水体中，室温下搅拌5-20min；
    取出所述识别膜并自动晾干，若识别膜发生颜色变化，判定待测水体中存在镉离子。
  10. 根据权利要求9所述的用于检测水体镉离子的识别膜的应用，其特征在于，所述搅拌转速为200-400r/min。
PCT/CN2018/092965 2017-07-21 2018-06-27 一种用于检测水体镉离子的识别膜及其制备方法、应用 WO2019015448A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710601256.1 2017-07-21
CN201710601256.1A CN107290339B (zh) 2017-07-21 2017-07-21 一种用于检测水体镉离子的识别膜及其制备方法、应用

Publications (1)

Publication Number Publication Date
WO2019015448A1 true WO2019015448A1 (zh) 2019-01-24

Family

ID=60102842

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/092965 WO2019015448A1 (zh) 2017-07-21 2018-06-27 一种用于检测水体镉离子的识别膜及其制备方法、应用

Country Status (2)

Country Link
CN (1) CN107290339B (zh)
WO (1) WO2019015448A1 (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107290339B (zh) * 2017-07-21 2020-06-23 深圳大学 一种用于检测水体镉离子的识别膜及其制备方法、应用
CN107930692A (zh) * 2017-12-07 2018-04-20 天津工业大学 一种基于多孔膜基质的单分散卟啉可见光催化剂及其制备方法
CN109824820B (zh) * 2019-01-09 2021-05-14 山西大学 一种含氮和钾的复合型高分子吸水树脂及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19935180A1 (de) * 1999-07-27 2001-02-15 Fraunhofer Ges Forschung Solarzellen-Sensoren, Verfahren zu ihrer Herstellung und ihrer Anwendung
CN101787130A (zh) * 2010-03-04 2010-07-28 浙江大学 含卟啉的聚酰亚胺及其制备方法和应用
CA2870065A1 (en) * 2012-04-24 2013-10-31 University Health Network Porphyrin-lipid stabilized nanoparticles for surface enhanced raman scattering based imaging
CN104345043A (zh) * 2014-07-16 2015-02-11 天津工业大学 一种适用于重金属离子检测的卟啉光学传感功能膜及其制备方法
CN107290339A (zh) * 2017-07-21 2017-10-24 深圳大学 一种用于检测水体镉离子的识别膜及其制备方法、应用

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1586702A (zh) * 2004-07-29 2005-03-02 复旦大学 一种用表面接枝技术制备纳滤膜的方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19935180A1 (de) * 1999-07-27 2001-02-15 Fraunhofer Ges Forschung Solarzellen-Sensoren, Verfahren zu ihrer Herstellung und ihrer Anwendung
CN101787130A (zh) * 2010-03-04 2010-07-28 浙江大学 含卟啉的聚酰亚胺及其制备方法和应用
CA2870065A1 (en) * 2012-04-24 2013-10-31 University Health Network Porphyrin-lipid stabilized nanoparticles for surface enhanced raman scattering based imaging
CN104345043A (zh) * 2014-07-16 2015-02-11 天津工业大学 一种适用于重金属离子检测的卟啉光学传感功能膜及其制备方法
CN107290339A (zh) * 2017-07-21 2017-10-24 深圳大学 一种用于检测水体镉离子的识别膜及其制备方法、应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LIANG, XIAOYAN: "Preparation of Multifunctional Cotton Fiber and Its Application Research in Adsorption and Detection of Copper and Cadmium Ions in Water", SCIENCE -ENGINEERING (A), CHINA MASTER'S THESES FULL-TEXT DATABASE, 15 July 2017 (2017-07-15), pages 30 - 34, ISSN: 1674-0246 *

Also Published As

Publication number Publication date
CN107290339A (zh) 2017-10-24
CN107290339B (zh) 2020-06-23

Similar Documents

Publication Publication Date Title
WO2019015448A1 (zh) 一种用于检测水体镉离子的识别膜及其制备方法、应用
Yi et al. Smartphone-based ratiometric fluorescent definable system for phosphate by merged metal− organic frameworks
Zhu et al. Amperometric immunosensor for simultaneous detection of three analytes in one interface using dual functionalized graphene sheets integrated with redox-probes as tracer matrixes
CN105572197B (zh) 一种基于磁性纳米光敏材料的光电化学雌二醇传感器的制备方法及应用
CN107576704B (zh) 微囊藻毒素-lr分子印迹光电化学传感器及其制备与应用
CN104133067B (zh) 一种基于磁性Fe3O4Au复合纳米材料电化学检测人免疫球蛋白E的方法
CN107543809B (zh) 一种谷胱甘肽分子检测用试纸条及检测方法
CN104292381A (zh) 一种荧光离子印迹探针的制备及其应用
CN108344792B (zh) 一种水体中总砷快速检测方法
CN110530965A (zh) 一种硅纳米线阵列芯片检测细胞代谢物、脂质的方法
CN113552199B (zh) 基于FeS2/C/MQDs/GCE修饰电极的分子印迹电化学传感器及其制备方法
Li et al. A single-layer structured microbial sensor for fast detection of biochemical oxygen demand
CN111504909B (zh) 一种无标记检测甲胎蛋白的光电化学生物传感器、制备方法及其应用
CN108957010A (zh) 一种可检测过敏反应的纸基传感器及其制备和应用
Su-Ping et al. Progress in molecular imprinting electrochemiluminescence analysis
CN108067311A (zh) 一种用于微囊藻毒素检测的微流控芯片及检测方法
Li et al. A copper-based biosensor for dual-mode glucose detection
CN112067647B (zh) 一种检测液体生物样本葡萄糖含量的弛豫核磁共振方法
CN108593610A (zh) 一种基于纳米mv-mof的用于生物标记物检测的荧光增强型试纸的制备方法
CN105527277A (zh) 一种雌酮分子印迹电化学发光传感器的制备方法及应用
CN111965136A (zh) 一种类过氧化物纳米酶β-FeOOH的制备方法及其在H2O2检测中的应用
CN107782721A (zh) 一种基于膜的生物样品化学发光检测方法和相关检测试剂盒
CN110903444B (zh) 一种聚合物包银微纳颗粒及其检测尿液小分子的方法
CN108776077B (zh) 一种生物传感器及检测方法
CN109900665B (zh) 一种分子印迹选择荧光猝灭法测量水体中ddt的方法

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: 18835652

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

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 25/05/2020)

122 Ep: pct application non-entry in european phase

Ref document number: 18835652

Country of ref document: EP

Kind code of ref document: A1