CN107576701B - A kind of preparation method and application of porous metals organic framework loaded Ag nanocomposite - Google Patents

A kind of preparation method and application of porous metals organic framework loaded Ag nanocomposite Download PDF

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CN107576701B
CN107576701B CN201710792047.XA CN201710792047A CN107576701B CN 107576701 B CN107576701 B CN 107576701B CN 201710792047 A CN201710792047 A CN 201710792047A CN 107576701 B CN107576701 B CN 107576701B
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organic framework
porous metals
nanocomposite
penicillamine
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CN107576701A (en
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王志玲
杨小凤
崔玉
郑鲁沂
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University of Jinan
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Abstract

It is used to detect the application of enantiomers of chiral drugs the invention discloses a kind of preparation method of porous metals organic framework loaded Ag nanocomposite and based on the composite material, belongs to nano material, Metal-organic frame, analytical chemistry and chiral sensing detection technical field.It, which has main steps that, first prepares Metal-organic frame [(AgL) ClO4] n nanocrystal, it continuously adds potassium bromide in-situ reducing and porous metals organic framework loaded Ag nanocomposite is made.The sensor constructed using the hybrid material, Sensitive Detection enantiomers of chiral drugs.

Description

A kind of preparation method of porous metals organic framework loaded Ag nanocomposite and Using
Technical field
The present invention relates to a kind of preparation method of porous metals organic framework loaded Ag nanocomposite and it is based on The composite material electrochemical sensing detects the application of penicillamine enantiomer, belongs to nano material, catalysis technique, metal organic frame Object field of material technology.
Background technique
Metal-organic framework object (MOFs) is to pass through coordination by metal ion or metal ion cluster and multiple tooth organic ligand The porous material that key driving force is self-assembly of, in the more than ten years in past, Metal-organic frame material has been widely used in It Industrial Catalysis, gas storage, molecular recognition and separates in more technologies such as gas absorption and storage, catalysis, proton conductive, sensing and identification Field.This aspect benefits from the diversification for constructing metal-organic framework object metal species and organic precursor, in addition opens up with it It is directly related to flutter the characteristics such as structure-rich, specific surface area high, structure designability strong, duct easy-regulating, easy functionalization.
The exploitation of exploration and nano-scale for nanometer MOFs synthetic strategy has become the frontier of MOFs research. In general, nanometer MOFs synthesizes the simplest method and is control and adjusts chemical reaction, that is, passes through control physical parameter Regulate and control its growth, including addition modifying agent and surfactant, controls the ratio and reaction time and temperature of reactant.Most Closely also there are many new methods, for example, the heating etc. of ultrasonic wave or microwave (MW) auxiliary.
Noble metal nanometer material is with the property of its superior light, electricity, magnetic etc., by the favor of researchers.At present Common metal nano material includes gold, silver, copper, platinum etc., is widely used in the building of electrochemical sensor.Wherein silver is received Rice material have cheap price, stronger adsorption capacity, good biocompatibility, efficient electro catalytic activity and quickly The incomparable special nature of other nano materials such as electron transfer rate, pays close attention to more and more widely to receive.
There is significance differences in the intracorporal pharmacological activity of people, distribution, metabolic process and toxicity etc. for enantiomers of chiral drugs Different, significant difference behavior is mainly manifested in: 1. one of two enantiomers enantiomer has a pharmacological activity, and another pharmacology Activity is not significant.For example, the anti-inflammatory effect and analgesic activity of S- ketorolac drug are 60 times 230 times of R- ketorolac respectively;S- The anti-inflammatory effect of naproxen is 35 times of R-NAP.2. the pharmacological action of two kinds of structure phases of chiral drug is completely different.Example Such as, R- tetramisole is antidepressant, and S- is that tetramisole is dehelminthization drug, and dextropropoxyphene is a kind of analgestic, and left-handed Dextropropoxyphene is a kind of antitussive.3. a kind of structure of enantiomer mutually has pharmacological activity, and another kind generates serious side effect.Example Such as, the ketamine as non-barbiturates central depressant, S- configuration has anesthesia and analgesic activity, and R- configuration has excitement Maincenter leads to mental symptom;Although two enantiomers of Thalidomide have identical sedation, but S- structure mutually will lead to abnormal resistance Effect.In recent years, some brought by racemic modification drug in order to solve the problems, such as, many developed countries constantly promulgate related hand The guiding performance guide or policy of property drug development.In the U.S., the food and Drug Administration (FICA) of chiral drug require to apply The chiral component contained in person's mandatory declaration novel drugs and the respective pharmacological action of enantiomer, clinical effectiveness and toxicity, and taste Examination separates stereoisomer therein.Canada, European Community etc. have also formulated relevant policy.Therefore, the identification of chiral drug, To research chiral drug reasonably accurate using and control chiral drug quality the problems such as have great importance.
Development of metallic-organic framework nano material and the load expensive doping metals of nanometer-organic framework composite material Preparation method, and for detect identification chiral drug have great importance.
Summary of the invention
Technical assignment of the invention first is that in order to make up for the deficiencies of the prior art, providing a kind of porous metals organic frame The preparation method of object loaded Ag nanocomposite, preparation process used in this method is simple, and energy consumption of reaction is low, has industrial application Prospect.
The two of technical assignment of the invention are to provide the use of the porous metals organic framework loaded Ag nanocomposite On the way, i.e., the porous metals organic framework loaded Ag nanocomposite is used for efficient detection chiral drug penicillamine enantiomer Content, the detecting instrument is at low cost, analysis efficiency is high, easy to operate, operating technology require it is low.
A kind of preparation method of porous metals organic framework loaded Ag nanocomposite, steps are as follows:
(1) porous metals organic framework MOF crystal is prepared
By 0.52 g AgClO4It is dissolved in 1-1.5 mL water, obtains AgClO4Aqueous solution;0.68 g ligand L is dissolved in 0.5- 1.0 mL n,N-Dimethylformamide DMF, obtain the DMF solution of ligand L;AgClO4Aqueous solution and the DMF solution of ligand L shake Blending is shaken, the gel for being inverted no mobility is obtained;By 85 DEG C of gel 24 h of ageing, methanol is added, centrifuge washing 3 times, is made more Mesoporous metal organic framework MOF crystal;
(2) porous metals organic framework loaded Ag nanocomposite
By porous metals organic framework MOF nanocrystal obtained, 1-1.5 mL is added, mass fraction is 5 %'s The ethanol solution of KBr mixes, is stored at room temperature 24 h, is centrifugated and uses ethanol washing 3 times, 70 DEG C of dryings, obtained porous metals Organic framework loaded Ag nanocomposite.
Step (1) described ligand L, structural formula are as follows:
The ligand L, preparation step are as follows:
Under stirring condition, 1, the 2- ethylenediamine of 0.10 mol is mixed with the acidum nicotinicum of 0.20 mol, heating point It evaporates, maintains 103-105 DEG C of temperature of fractionation capital, dropped at a temperature of being fractionated capital, show that reaction is completed, liquid cooling will be mixed But 10-20 DEG C is arrived, is filtered, and three times with ethanol washing, with ethyl alcohol recrystallization, obtains ligand L, 65 % of yield.
Step (1) and (2) described porous metals organic framework MOF crystal are the crystal grain structures for being 40-50 nm by partial size At with micropore, mesoporous and 50 nm-3.0 μm of macropore porous material, chemical formula is [(AgL) ClO4] n, a structure Unit is by 1 Ag (I) cationic species, 1 ligand L, 1 ClO4(I) anion forms.
The porous metals organic framework loaded Ag nanocomposite, the average grain diameter of Ag are 4 nm.
2. the porous metals organic framework loaded Ag nanocomposite of preparation method preparation as described above is as electricity Chemical sensitisation detects the application of penicillamine enantiomer, and steps are as follows:
(1) porous metals organic framework loaded Ag nanocomposite chiral sensor working electrode is prepared
It has polished in alumina powder, the basal electrode glassy carbon electrode surface of water and ethyl alcohol cleaning, drop coating 6uL metal Organic framework loaded Ag Nanocomposite solution, room temperature are dried, and have been obtained porous metals organic framework loaded Ag and have been received The chiral sensor working electrode of nano composite material building;
The porous metals organic framework loaded Ag Nanocomposite solution is by 3 mg porous metals organic frames Ultrasound 10-15min is blended with 250 uL isopropanols, 720 uL water, 30 uL Nafion and is made for object loaded Ag nanocomposite;
(2) porous metals organic framework loaded Ag nanocomposite electrochemistry chiral sensor is prepared
By working electrode, reference electrode made from step (1) and electrode is connected on electrochemical workstation, has been made more Mesoporous metal organic framework loaded Ag nanocomposite electrochemistry chiral sensor;
The reference electrode is saturated calomel electrode, is platinum electrode to electrode;
(3) D- (-)-penicillamine and L- (+)-penicillamine enantiomer are detected
With pH 7,0.1 mol L-1Phosphate buffer solution PBS, had using porous metals made from step (2) Machine frame object loaded Ag nanocomposite electrochemistry chiral sensor, using differential pulse voltammetry, measurement is different dense respectively D- (-)-penicillamine and L- (+)-penicillamine standard solution current value of degree are drawn porous metals organic framework loaded Ag and are received D- (-)-penicillamine and L- (+) of nano composite material sensor-penicillamine enantiomer working curve;By sample to be tested D- (-)-blueness Mould amine and L- (+)-mould amine aqueous solution replace D- (-)-penicillamine or L- (+)-penicillamine standard solution, carry out D- (-)-in sample Penicillamine and the detection of L- (+)-mould amine content.
The chiral sensor is 0.1-1.0 to D- (-)-penicillamine and L- (+)-penicillamine mapping liquid solution detection range ×10-10 g/mL。
The beneficial technical effect of the present invention is as follows:
(1) method is easy
The preparation method of porous metals organic framework loaded Ag nanocomposite of the present invention, it is old by gel-first The method of change, is made porous metals organic framework MOF nanocrystal, and the preparation of gel is that one-step method system is blended by raw material , the generation of gel is based in solvent for use because material concentration is high and central ion and ligands key, hydrogen bond etc. are made Caused by firmly acting on;The ageing of gel so that the further growth of MOF nucleus at porous [(AgL) ClO4] n crystal.Porous MOF is brilliant The preparation of body, process is simple, easily operated, at low cost, less energy consumption, is easy to industrialize;[(AgL) made from the preparation method ClO4] n crystal, it is made of the crystal grain that partial size is 40-50 nm with micropore, mesoporous and 50 nm-3 μm of porous materials.And it adopts The MOF crystal made from 3 days is heated with 120 DEG C of solvent-thermal method, long preparation period, energy consumption is high, and average crystal grain diameter is about 20-30 um, is not belonging to nanocrystal.
The preparation of nanometer Ag in Metal-organic frame loaded Ag nanocomposite, the present invention is by being added appropriate Br (I) ion captures [(AgL) ClO4] n plane of crystal Ag (I) ion, AgBr is formed in situ, AgBr decomposes in light in-situ preparation Nano Ag particles, since the effect of crystal is so that Ag nanoparticle average grain diameter is only 4 nm.
Preparation method solvent usage of the invention significantly reduces, and not only reduces cost, has been significantly reduced spent solvent production Raw pollution, increases economic and social benefit.
(2) have the function of Sensitive Detection D- (-)-penicillamine and L- (+)-penicillamine enantiomer
The present invention provides a kind of electrochemistry chirality of porous metals organic framework loaded Ag nanocomposite sensings Device, the sensor are simply to modify Metal-organic frame loaded Ag nanocomposite to be made in glassy carbon electrode surface, system Preparation Method is simple, easy to operate.Since Metal-organic frame loaded Ag nanocomposite is by porous nano MOF crystal and nanometer Ag composition, exposes more and different active sites, has played synergistic effect, so that the chirality based on composite material preparation Sensor detects D- (-)-penicillamine and L- (+)-penicillamine chiral enantiomer content, has quick response, detection range Width, high sensitivity, it is easy to operate the features such as.
Specific embodiment
The present invention will be further described below with reference to examples, but protection scope of the present invention is not only limited to implement Example, professionals in the field change to made by technical solution of the present invention, are within the scope of protection of the invention interior.
Embodiment 1
1. a kind of preparation method of porous metals organic framework loaded Ag nanocomposite, steps are as follows:
(1) porous metals organic framework MOF crystal is prepared
By 0.52 g AgClO4It is dissolved in 1 mL water, obtains AgClO4Aqueous solution;0.68 g ligand L is dissolved in 0.5 mL N, Dinethylformamide DMF obtains the DMF solution of ligand L;AgClO4Aqueous solution is blended with the shaking of the DMF solution of ligand L, obtains To gel of the inversion without mobility;By 85 DEG C of gel 24 h of ageing, methanol is added, centrifuge washing 3 times, obtained porous metals have Machine frame object MOF crystal;
(2) porous metals organic framework loaded Ag nanocomposite
By porous metals organic framework MOF nanocrystal obtained, 1 mL is added, KBr that mass fraction is 5 % Ethanol solution mixes, is stored at room temperature 24 h, is centrifugated and uses ethanol washing 3 times, 70 DEG C of dryings, and obtained porous metals are organic Framework supported Ag nanocomposite.
Embodiment 2
1. a kind of preparation method of porous metals organic framework loaded Ag nanocomposite, steps are as follows:
(1) porous metals organic framework MOF crystal is prepared
By 0.52 g AgClO41.5 mL water are dissolved in, AgClO is obtained4Aqueous solution;0.68 g ligand L is dissolved in 1.0 mL N,N-Dimethylformamide DMF obtains the DMF solution of ligand L;AgClO4Aqueous solution is blended with the shaking of the DMF solution of ligand L, Obtain the gel for being inverted no mobility;By 85 DEG C of gel 24 h of ageing, methanol is added, centrifuge washing 3 times, porous metals are made Organic framework MOF crystal;
(2) porous metals organic framework loaded Ag nanocomposite
By Metal-organic frame MOF nanocrystal obtained, 1.5 mL are added, the second for the KBr that mass fraction is 5 % Alcoholic solution mixes, is stored at room temperature 24 h, is centrifugated and with ethanol washing 3 times, and 70 DEG C of dryings, obtained porous metals have machine frame Frame object loaded Ag nanocomposite.
Embodiment 3
1. a kind of preparation method of porous metals organic framework loaded Ag nanocomposite, steps are as follows:
(1) porous metals organic framework MOF crystal is prepared
By 0.52 g AgClO41.3 mL water are dissolved in, AgClO is obtained4Aqueous solution;0.68 g ligand L is dissolved in 0.75 mL N,N-Dimethylformamide DMF obtains the DMF solution of ligand L;AgClO4Aqueous solution is blended with the shaking of the DMF solution of ligand L, Obtain the gel for being inverted no mobility;By 85 DEG C of gel 24 h of ageing, methanol is added, centrifuge washing 3 times, porous metals are made Organic framework MOF crystal;
(2) porous metals organic framework loaded Ag nanocomposite
By porous metals organic framework MOF nanocrystal obtained, 1.3 mL are added, the KBr that mass fraction is 5 % Ethanol solution, mix, be stored at room temperature 24 h, be centrifugated and with ethanol washing 3 times, 70 DEG C of dryings, obtained porous metals have Machine frame object loaded Ag nanocomposite.
The preparation of 4 ligand L of embodiment
Under stirring condition, 1, the 2- ethylenediamine of 0.10 mol is mixed with the acidum nicotinicum of 0.20 mol, heating point It evaporates, maintains 103-105 DEG C of temperature of fractionation capital, dropped at a temperature of being fractionated capital, show that reaction is completed, liquid cooling will be mixed But 10-20 DEG C is arrived, is filtered, and three times with ethanol washing, obtains ligand L, yield 65% with ethyl alcohol recrystallization;
Ligand L, structural formula are as follows:
Embodiment 5
Porous metals organic framework MOF crystal described in embodiment 1-3 is made of the crystal grain that partial size is 40-50 nm With micropore, mesoporous and 50 nm-3.0 μm of macropore porous material, chemical formula is [(AgL) ClO4] n, a structural unit By 1 Ag (I) cationic species, 1 ligand L, 1 ClO4(I) anion forms;
The porous metals organic framework loaded Ag nanocomposite, the average grain diameter of Ag are 4 nm.
6 porous metals organic framework loaded Ag nanocomposite of embodiment detects penicillamine as electrochemical sensing The application of enantiomer
(1) porous metals organic framework loaded Ag nanocomposite chiral sensor working electrode is prepared
It has polished in alumina powder, the basal electrode glassy carbon electrode surface of water and ethyl alcohol cleaning, 6 uL of drop coating is real It applies porous metals organic framework loaded Ag Nanocomposite solution, room temperature made from example 1 to dry, has obtained porous metals The chiral sensor working electrode of organic framework loaded Ag nanocomposite building;
The porous metals organic framework loaded Ag Nanocomposite solution is to bear 3 mg Metal-organic frames Ultrasound 10-15 min is blended with 250 uL isopropanols, 720 uL water, 30 uL Nafion and is made for load Ag nanocomposite;
(2) porous metals organic framework loaded Ag nanocomposite electrochemistry chiral sensor is prepared
By working electrode, reference electrode made from step (1) and electrode is connected on electrochemical workstation, has been made more Mesoporous metal organic framework loaded Ag nanocomposite electrochemistry chiral sensor;
The reference electrode is saturated calomel electrode, is platinum electrode to electrode;
(3) D- (-)-penicillamine and L- (+)-penicillamine enantiomer are detected
With pH 7,0.1 mol L-1Phosphate buffer solution PBS, had using porous metals made from step (2) Machine frame object loaded Ag nanocomposite electrochemistry chiral sensor, using differential pulse voltammetry, measurement is different dense respectively D- (-)-penicillamine and L- (+)-penicillamine standard solution current value of degree are drawn porous metals organic framework loaded Ag and are received D- (-)-penicillamine and L- (+) of nano composite material sensor-penicillamine enantiomer working curve;By sample to be tested D- (-)-blueness Mould amine and L- (+)-mould amine aqueous solution replace D- (-)-penicillamine or L- (+)-penicillamine standard solution, carry out D- (-)-in sample Penicillamine and the detection of L- (+)-mould amine content.
Embodiment 7
Method embodiment 6, only will the wherein nano combined material of porous metals organic framework loaded Ag made from embodiment 1 Material replaces with porous metals organic framework loaded Ag nanocomposite made from embodiment 2.
Embodiment 8
Method embodiment 6, only will the wherein nano combined material of porous metals organic framework loaded Ag made from embodiment 1 Material replaces with porous metals organic framework loaded Ag nanocomposite made from embodiment 3.
Embodiment 9
Chiral sensor made from embodiment 6-8 is to D- (-)-penicillamine and the detection of L- (+)-penicillamine mapping liquid solution Range is 0.1-1.0 × 10-10 g/mL。

Claims (3)

1. a kind of preparation method of porous metals organic framework loaded Ag nanocomposite, which is characterized in that steps are as follows:
(1) Metal-organic frame MOF crystal is prepared
By 0.52g AgClO4It is dissolved in 1-1.5mL water, obtains AgClO4Aqueous solution;0.68g ligand L is dissolved in 0.5-1.0mL N, Dinethylformamide DMF obtains the DMF solution of ligand L;AgClO4Aqueous solution is blended with the shaking of the DMF solution of ligand L, obtains To gel of the inversion without mobility;For 24 hours by 85 DEG C of gel ageings, methanol is added, centrifuge washing 3 times, it is organic that porous metals are made Frame object MOF crystal;
(2) porous metals organic framework loaded Ag nanocomposite
By porous metals organic framework MOF nanocrystal obtained, 1-1.5mL is added, the KBr ethyl alcohol that mass fraction is 5% Solution mixes, and is stored at room temperature for 24 hours, is centrifugated and uses ethanol washing 3 times, 70 DEG C of dryings, obtained porous metals organic framework Loaded Ag nanocomposite;
The ligand L, structural formula are as follows:
The preparation step of ligand L is as follows:
Under stirring condition, 1, the 2- ethylenediamine of 0.10mol is mixed with the acidum nicotinicum of 0.20mol, heating fractionation maintains to divide 103-105 DEG C of the temperature on fractional distillation column top drops at a temperature of being fractionated capital, shows that reaction is completed, mixed liquor is cooled to 10-20 DEG C, it filters, and three times with ethanol washing, with ethyl alcohol recrystallization, obtain ligand L, yield 65%;
The porous metals organic framework MOF crystal is that have micropore, mesoporous by what the crystal grain that partial size is 40-50nm was constituted With the porous material of 50nm-3.0 μm of macropore, chemical formula is [(AgL) ClO4] n, a structural unit by 1 Ag (I) sun from Subcenter, 1 ligand L, 1 ClO4(I) anion forms;
The porous metals organic framework loaded Ag nanocomposite, the average grain diameter of Ag are 4nm.
2. the porous metals organic framework loaded Ag nanocomposite of preparation method preparation as described in claim 1 is as electricity The application of chemical sensitisation detection penicillamine enantiomer.
3. the application of electrochemical sensing detection penicillamine enantiomer as claimed in claim 2, which is characterized in that steps are as follows:
(1) porous metals organic framework loaded Ag nanocomposite chiral sensor working electrode is prepared
It has polished in alumina powder, the basal electrode glassy carbon electrode surface of water and ethyl alcohol cleaning, drop coating 6uL porous metals Organic framework loaded Ag Nanocomposite solution, room temperature are dried, and have been obtained porous metals organic framework loaded Ag and have been received The chiral sensor working electrode of nano composite material building;
The porous metals organic framework loaded Ag Nanocomposite solution is to bear 3mg porous metals organic framework Ultrasound 10-15min is blended with 250uL isopropanol, 720uL water, 30uLNafion and is made for load Ag nanocomposite;
(2) porous metals organic framework loaded Ag nanocomposite electrochemistry chiral sensor is prepared
By working electrode, reference electrode made from step (1) and electrode is connected on electrochemical workstation, porous gold has been made Belong to organic framework loaded Ag nanocomposite electrochemistry chiral sensor;
The reference electrode is saturated calomel electrode, is platinum electrode to electrode;
(3) D- (-)-penicillamine and L- (+)-penicillamine enantiomer are detected
With pH7,0.1molL-1Phosphate buffer solution PBS, using porous metals organic framework made from step (2) Loaded Ag nanocomposite electrochemistry chiral sensor measures the D- of various concentration using differential pulse voltammetry respectively It is nano combined to draw porous metals organic framework loaded Ag for (-)-penicillamine and L- (+)-penicillamine standard solution current value D- (-)-penicillamine and L- (+) of material sensors-penicillamine enantiomer working curve;By sample to be tested D- (-)-penicillamine and L- (+)-mould amine aqueous solution replaces D- (-)-penicillamine or L- (+)-penicillamine standard solution, carries out D- (-)-penicillamine in sample With the detection of L- (+)-mould amine content.
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