CN107033176B - Cup [4] aromatic hydrocarbons phenyl boronic acid derivative/multi-wall carbon nano-tube composite material preparation method and applications - Google Patents
Cup [4] aromatic hydrocarbons phenyl boronic acid derivative/multi-wall carbon nano-tube composite material preparation method and applications Download PDFInfo
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- CN107033176B CN107033176B CN201710259981.5A CN201710259981A CN107033176B CN 107033176 B CN107033176 B CN 107033176B CN 201710259981 A CN201710259981 A CN 201710259981A CN 107033176 B CN107033176 B CN 107033176B
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- aromatic hydrocarbons
- boronic acid
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- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000002048 multi walled nanotube Substances 0.000 title claims abstract description 29
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 13
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 13
- -1 aromatic hydrocarbons dibromo compound Chemical class 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012074 organic phase Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000012043 crude product Substances 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 8
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- CVISDVLTGPAQGC-UHFFFAOYSA-N (3-hydroxyphenoxy)boronic acid Chemical compound OB(O)OC1=CC=CC(O)=C1 CVISDVLTGPAQGC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 238000010908 decantation Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910002027 silica gel Inorganic materials 0.000 claims 1
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 abstract 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 22
- 239000008103 glucose Substances 0.000 description 20
- 238000001514 detection method Methods 0.000 description 9
- 239000007853 buffer solution Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 description 6
- 239000008280 blood Substances 0.000 description 5
- 210000004369 blood Anatomy 0.000 description 5
- 206010012601 diabetes mellitus Diseases 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 238000004566 IR spectroscopy Methods 0.000 description 3
- 229960002645 boric acid Drugs 0.000 description 3
- 235000010338 boric acid Nutrition 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 238000001903 differential pulse voltammetry Methods 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000001548 drop coating Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 208000017667 Chronic Disease Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000013016 Hypoglycemia Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 241001481789 Rupicapra Species 0.000 description 1
- 238000011095 buffer preparation Methods 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000003862 health status Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 201000001421 hyperglycemia Diseases 0.000 description 1
- 230000002218 hypoglycaemic effect Effects 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
-
- 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
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
-
- 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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Cup [4] aromatic hydrocarbons phenyl boronic acid derivative/multi-wall carbon nano-tube composite material preparation method and applications.Specifically: 3- hydroxyl phenyl boric acid and potassium carbonate are dissolved in anhydrous acetonitrile by the first step, oil bath agitating and heating.Cup [4] aromatic hydrocarbons dibromo compound and potassium iodide are dissolved in acetonitrile, oil bath agitating and heating.After a period of time, the acetonitrile solution containing 3- hydroxyl phenyl boric acid and potassium carbonate is added into cup [4] aromatic hydrocarbons dibromo compound and the acetonitrile solution of potassium iodide in batches, is heated at reflux.Gained crude product is extracted, washing organic phase to neutrality.Rotary evaporation obtains the solid powder of yellow after removing methylene chloride and micro residue distilled water, isolates and purifies.Second step is by multi-walled carbon nanotube in 4molL‑1It is heated to reflux in nitric acid, is centrifuged, washs repeatedly, until pH value is dried close to neutrality.Multi-walled carbon nanotube and cup [4] aromatic hydrocarbons the phenyl boronic acid derivative ultrasonic disperse in alcohol solvent are weighed, cup [4] aromatic hydrocarbons phenyl boronic acid derivative/multi-wall carbon nano-tube composite material is obtained.
Description
Technical field
The present invention relates to a kind of cup [4] aromatic hydrocarbons phenyl boronic acid derivatives, cup [4] aromatic hydrocarbons phenyl boronic acid derivative/multi-wall carbon nano-tube
The preparation method and applications of pipe composite material.
Background technique
As the glucose with human health status close relation, it all has for organism in all fields can not
The effect of substitution.It is the main source of energy needed for vital movement process, accounts for 70% to the contribution of body energy.Grape
Sugar is one of ingredient of blood of human body, and the exception of Glucose in Blood by Cyclic implies the generation of disease.Medically, normal person
It is 3.61~6.11mmol/L in fasting plasma glucose concentration, fasting plasma glucose concentration is more than that 7.0mmol/L is then diagnosed as hyperglycemia, blood
Sugared concentration is then diagnosed as hypoglycemia lower than 3.61mmol/L.Contacting most close disease with blood glucose level is exactly diabetes,
The sole criterion of diagnosis is exactly Glucose in Blood by Cyclic.The diabetes data of the World Health Organization is shown: the whole world is extremely at present
Few to have had more than 1.8 hundred million people with diabetes, this number to the year two thousand thirty will rise to 3.6 hundred million.Diabetes have become after
The third-largest chronic disease for seriously threatening human health after tumour, cardiovascular disease.Therefore, easy, easy-operating glucose
Quantitative measurement technology have very great meaning for the Clinics and Practices of diabetes.
Recent years, the macromolecular compound containing boric acid receive very big concern in chemistry, biomedicine field etc.,
Many researchs concentrate on the macromolecular compound containing boric acid in terms of the sensing of carbohydrate, but the macromolecular chemical combination containing boric acid
Object often haves the shortcomings that signal intensity is small to the spectral method of detection of the identification of glucose.In order to overcome this disadvantage, grind
Study carefully the supermolecule for synthesizing boracic acid groups in conjunction with Gold nanoparticle, detect glucose, but there is also detection material expensive,
The disadvantages of signal intensity is unobvious.Therefore, the detection for using other detection means optimization glucose instead is most important, electrochemical sensing
The principle of device is the characteristic signal that compound can be issued after test substance is in conjunction with molecular recognition elements, is then turned again through signal
Parallel operation is transformed into the exportable signal of electricity, to achieve the purpose that detect glucose, compared with other detection methods, electrochemistry is passed
The detection to specific substrates may be implemented in sensor, while recognition component itself is easy to operate, time-saving and efficiency, practical, electrochemistry
Detection means has evolved into a kind of very active detection means in sensing detection field, by the concern of each area research person.
Summary of the invention
The purpose of the present invention is to provide cup [4] aromatic hydrocarbons phenyl boronic acid derivative/multi wall carbon that one kind can measure glucose
Nanometer tube composite materials, and study cup [4] aromatic hydrocarbons phenyl boronic acid derivative/multi-wall carbon nano-tube composite material and passed as electrochemistry
Sensor is for measuring glucose.
The purpose of the present invention can be achieved through the following technical solutions:
1. the chemical formula of glass [4] aromatic hydrocarbons phenyl boronic acid derivative is C62H78B2O10.The ligand supplemented by 3- hydroxyl phenyl boric acid, cup
[4] aromatic hydrocarbons dibromo compound is main ligand, so constitutes following formula cup [4] aromatic hydrocarbons phenyl boronic acid derivative:
Cup [4] the aromatic hydrocarbons phenyl boronic acid derivative and multi-walled carbon nanotube according to claim 1 adulterate to obtain cup [4]
Aromatic hydrocarbons phenyl boronic acid derivative/multi-walled carbon nanotube compound, which is characterized in that wherein the derivative has formula:
The preparation method of described cup [4] aromatic hydrocarbons phenyl boronic acid derivative/multi-wall carbon nano-tube composite material, feature exist
In, method includes the following steps:
(1) cup [4] aromatic hydrocarbons dibromo compound is synthesized, white powder is obtained.3.2g pairs is successively separately added into round-bottomed flask
Tert-butyl p tertButylcalixarene, 10.1g 1,3- dibromopropane, 1.73g Anhydrous potassium carbonate, the anhydrous acetonitrile of 125mL；Logical nitrogen, oil
Bath is heated to reflux 48 hours, is stopped heating, is cooled to room temperature, rotary evaporation obtains residue；100mL is sequentially added into residue
The chloroform of 5% HCl and 200mL, liquid separation extraction repeatedly, separate organic phase, with saturated salt solution and distilled water wash repeatedly to
PH value is neutrality.Add anhydrous sodium sulfate 24 hours dry, filter, obtains white powder after rotary evaporation removing solvent and slightly produce
Product.Column chromatography separating purification (VPetroleum ether:VEthyl acetate=4:3), obtain white powder product.
(2) in round-bottomed flask, product 0.1780g (about 0.2mmol), 0.0266g that (1) step process obtains is added
(about 0.16mmol) KI, 5mL acetonitrile, oil bath agitating and heating 30min.Another round-bottomed flask is taken, 0.2g is added (about
1.44mmol) Anhydrous potassium carbonate, 0.0662g (about 0.48mmol) 3- hydroxyl phenyl boric acid, 3mL acetonitrile, oil bath agitating and heating
30min.Solution by portions in second round-bottomed flask is added in first flask, oil bath is stirred at reflux 48 hours, has been reacted
Stop heating after complete, be cooled to room temperature, rotary evaporation removes partial solvent.
(3) step (2) resulting product is extracted into liquid separation using the dilute hydrochloric acid solution of methylene chloride and 5%, merged organic
Phase is neutral with distillation washing organic phase to pH.Rotary evaporation obtains consolidating for yellow after removing methylene chloride and minimal amount of water
Solid powder is put in 40 DEG C of drying in baking oven, obtains crude product by body powder.
(4) crude product that step (3) processing obtains is isolated and purified into (V with the big plate of silica gelEthyl acetate: VPetroleum ether=1:4), it obtains
20mg yellow solid powder, yield 10%.
(5) 0.3g multi-walled carbon nanotube is weighed, is flowed back in the nitric acid of 4mol/L for 24 hours, after reflux, by the carbon of purifying
Nanotube centrifugation after decantation remove supernatant liquor, be added secondary distilled water, be centrifuged repeatedly washing until pH for neutrality, be put into drying
Case is in 60 DEG C of baking 12h.
(6) the product 5mg for taking step (5) gains 5mg and step (4) to obtain is dissolved in 10mL ethyl alcohol, ultrasonic disperse 3h,
Obtain cup [4] aromatic hydrocarbons phenyl boronic acid derivative/multi-wall carbon nano-tube composite material.
Cup [4] aromatic hydrocarbons phenyl boronic acid derivative/multi-wall carbon nano-tube composite material application, the compound can measure glucose.
Cup [4] aromatic hydrocarbons phenyl boronic acid derivative/multi-wall carbon nano-tube composite material measures glucose, the results showed that cup
The specific recognition of aromatic hydrocarbons enhances the recognition capability to glucose, and electrochemical signals intensity is remarkably reinforced, and sensitivity is mentioned
Height, strong interference immunity.
Carried out hydrogen spectrum (1H NMR), electrospray ionization mass spectrum (ES-MS) and infrared spectroscopy (IR) characterization.Utilize Electrochemical Detection
Means measure glucose using cup [4] aromatic hydrocarbons phenyl boronic acid derivative/multi-wall carbon nano-tube composite material of designed synthesis.
Detailed description of the invention
Fig. 1 is the SEM figure of cup acquired in the present invention [4] aromatic hydrocarbons phenyl boronic acid derivative/multi-wall carbon nano-tube composite material；
Fig. 2 is acquired in the present invention in Na2HPO4-NaH2PO4In ion buffer solution, cup [4] aromatic hydrocarbons phenyl boric acid spreads out
Biology/multi-wall carbon nano-tube composite material modified electrode compares Multiwalled Carbon Nanotubes Modified Electrode current versus time curve figure；
Fig. 3 is acquired in the present invention in Na2HPO4-NaH2PO4In ion buffer solution, Different electrodes and Portugal are compared
The differential pulse voltammetry figure of grape sugar effect；
Fig. 4 is acquired in the present invention in Na2HPO4-NaH2PO4In ion buffer solution, difference repairs reagent dosage
Influence diagram；
Fig. 5 is acquired in the present invention in Na2HPO4-NaH2PO4In ion buffer solution, the influence diagram of different pH；
Fig. 6 is acquired in the present invention in Na2HPO4-NaH2PO4In ion buffer solution, anti-interference ability figure
In Na acquired in Fig. 7 present invention2HPO4-NaH2PO4In ion buffer solution, electrode stability figure
Specific embodiment
The present invention is described in detail with reference to embodiments.
Embodiment 1
The synthesis of novel p tertButylcalixarene phenyl boronic acid derivative
1,3.2g is successively separately added into round-bottomed flask to tert-butyl p tertButylcalixarene, 10.1g 1,3- dibromopropane,
1.73g Anhydrous potassium carbonate, the anhydrous acetonitrile of 125mL；Logical nitrogen, oil bath heating flow back 48 hours, stop heating, are cooled to room
Temperature, rotary evaporation obtain residue；The chloroform of the HCl and 200mL of 100mL 5% are sequentially added into residue, liquid separation extraction is more
It is secondary, organic phase is separated, it is neutral for being washed repeatedly with saturated salt solution and distilled water to pH value.Add anhydrous sodium sulfate dry 24 small
When, filtering, rotary evaporation obtains white powder crude product after removing solvent.Column chromatography separating purification (VPetroleum ether:VEthyl acetate=4:
3) white powder product, is obtained.
2, in round-bottomed flask, step (1) is added and handles obtained product 0.1780g (about 0.2mmol), 0.0266g is (about
0.16mmol) KI, 5mL acetonitrile, oil bath agitating and heating 30min.Another round-bottomed flask is taken, 0.2g (about 1.44mmol) nothing is added
Aqueous carbonate potassium, 0.0662g (about 0.48mmol) 3- hydroxyl phenyl boric acid, 3mL acetonitrile, oil bath agitating and heating 30min.By second circle
Solution by portions in the flask of bottom is added in first flask, and oil bath is stirred at reflux 48 hours, stops heating after fully reacting, is cooled to
Room temperature, rotary evaporation remove partial solvent.
3, step 2 resulting product is extracted into liquid separation using the dilute hydrochloric acid solution of methylene chloride and 5%, merges organic phase,
It is neutral with distillation washing organic phase to pH.Rotary evaporation obtains the solid powder of yellow after removing methylene chloride and minimal amount of water
Solid powder is put in 40 DEG C of drying in baking oven, obtains crude product by end.
4, the crude product that step 3 processing obtains is isolated and purified into (V with the big plate of silica gelEthyl acetate: VPetroleum ether=1:4), obtain 20mg
Yellow solid powder, yield 10%.
IR (KBr): υ/cm-1
1H NMR(400MHz,CDCl3)δ
9.89(s,2H,ArH),
7.87(s,2H,BOH),
7.84(s,2H,BOH),
7.74(s,2H,OH),
7.26(s,2H,ArH),
7.10(s,2H,ArH),
7.09(s,4H,ArH),
7.06(s,2H,ArH),
4.51(t,4H,BrCH2CH2CH2),
4.27(s,2H,ArCH2Ar),
4.24(s,2H,ArCH2Ar),
4.16(t,4H,BrCH2CH2CH2),
3.39(s,2H,ArCH2Ar),
3.16(s,2H,ArCH2Ar),
2.38(m,4H,BrCH2CH2CH2),
1.32(s,18H,C(CH3)3),
1.04(s,18H,C(CH3)3).
ESI-MS:m/z-=1005.62, (M+H+)
Embodiment 2
The synthesis of cup [4] aromatic hydrocarbons phenyl boronic acid derivative/multi-walled carbon nanotube
1,0.3g multi-walled carbon nanotube is weighed, is flowed back in the nitric acid of 4mol/L for 24 hours, after reflux, by the carbon of purifying
Nanotube centrifugation after decantation remove supernatant liquor, be added secondary distilled water, be centrifuged repeatedly washing until pH for neutrality, be put into drying
Case is in 60 DEG C of baking 12h.
2, step example 1 gains 5mg and product 5mg obtained in the previous step is taken to be dissolved in 10mL ethyl alcohol, ultrasonic disperse 3h,
Obtain cup [4] aromatic hydrocarbons phenyl boronic acid derivative/multi-wall carbon nano-tube composite material.
Embodiment 3
The electrochemical sensing experiment of cup [4] aromatic hydrocarbons phenyl boronic acid derivative/multi-wall carbon nano-tube composite material measurement glucose:
Laboratory apparatus: CHI660C electrochemical analyser
Supporting electrolyte: preparing the phosphate buffer solution of 0.1mol/L, is transferred to required pH as needed and obtains supporting electricity
Solve liquid.It is dilute with buffer solution as needed when experiment with the glucose solution of the buffer preparation 0.01mol/L matched
Release required concentration.
Experimental method: differential pulse voltammetry cyclic voltammetry current versus time curve
Instrument parameter: differential pulse voltammetry initial potential: 0.6V terminates current potential: -0.8V, sensitivity: 1 × 10-4.It follows
Ring voltammetry: high potential: 0.6V, low potential: -1.4V, scanning speed 0.1mv/s, sensitivity: 1 × 10-4.Current-vs-time is bent
Line: take-off potential: -0.4V, sensitivity: 1 × 10-4, runing time: 400s.
The preparation of modified electrode: successively being polished glassy carbon electrode surface with No. 1-6 abrasive paper for metallograph, then on chamois leather according to
The secondary aluminum oxide powder polishing with 0.3 μm, 0.05 μm is in mirror surface, uses dehydrated alcohol and deionized water respectively after polishing every time
Ultrasonic cleaning 30 seconds.Be activated in the sulfuric acid solution of 0.5-1.0mol/L, be repeatedly scanned with cyclic voltammetry until
Until obtaining stable circulation Fuan figure, sweep speed 100mV/s, scanning range is -1.0-1.0V.
The cup dispersed in ethanol [4] aromatic hydrocarbons phenyl boronic acid derivative/multi-wall carbon nano-tube composite material is used into drop-coating
Modification, by decorating liquid ultrasound 10min, draws above-mentioned suspension with microsyringe, uniform drop coating exists before electrode surface, modification
Then it is spare to be placed on shady place naturally dry by the surface of glass-carbon electrode for electrode.Unmodified calixarenes is made with same method
Carbon nanotube modified electrode.
The result shows that: cup [4] aromatic hydrocarbons phenyl boronic acid derivative/Multiwalled Carbon Nanotubes Modified Electrode can measure glucose.
Claims (1)
1. a kind of preparation method of cup [4] aromatic hydrocarbons phenyl boronic acid derivative/multi-walled carbon nanotube, which is characterized in that the derivative
Chemical formula be C62H78B2O10, with the main ligand of cup [4] aromatic hydrocarbons dibromo compound, ligand supplemented by 3- hydroxyl phenyl boric acid, structural formula
It is as follows:
Specific step is as follows:
One, preliminary step
(1) cup [4] aromatic hydrocarbons dibromo compound is synthesized, white powder is obtained；
3.2g is successively separately added into round-bottomed flask to tert-butyl p tertButylcalixarene, 10.1g1,3- dibromopropane, the anhydrous carbon of 1.73g
Sour potassium, the anhydrous acetonitrile of 125mL；
Logical nitrogen, oil bath heating flow back 48 hours, stop heating, are cooled to room temperature, rotary evaporation obtains residue；
Sequentially add the chloroform of the HCl and 200mL of 100mL5% into residue, liquid separation extraction repeatedly, separates organic phase, with full
Being washed repeatedly with saline solution and distilled water to pH value is neutrality；
Add anhydrous sodium sulfate 24 hours dry, filtering, rotary evaporation obtains white powder crude product after removing solvent；Column chromatography
It isolates and purifies, obtains cup [4] aromatic hydrocarbons dibromo compound solid 3.0g of fine white powder shape；
Two, the reaction step of cup [4] aromatic hydrocarbons phenyl boronic acid derivative:
(1) in round-bottomed flask, product 0.1780g, 0.0266gKI, the 5mL acetonitrile that preliminary step is handled, oil bath is added
Agitating and heating 30min；Another round-bottomed flask is taken, 0.2g Anhydrous potassium carbonate, 0.0662g3- hydroxyl phenyl boric acid, 3mL second is added
Nitrile, oil bath agitating and heating 30min；Solution by portions in second round-bottomed flask is added in first flask, oil bath is stirred back
Stream 48 hours stops heating after fully reacting, be cooled to room temperature, and rotary evaporation removes partial solvent；
(2) step (1) resulting product is extracted into liquid separation using the dilute hydrochloric acid solution of methylene chloride and 5%, merges organic phase, uses
Distillation washing organic phase is neutrality to pH, and rotary evaporation obtains the solid powder of yellow after removing methylene chloride and minimal amount of water
Solid powder is put in 40 DEG C of drying in baking oven, obtains crude product by end；
(3) crude product that step (2) processing obtains is isolated and purified with the big plate of silica gel, VEthyl acetate: VPetroleum ether=1:4 obtains 20mg Huang
Color solid powder, yield 10%；
Three, the synthesis step of cup [4] aromatic hydrocarbons phenyl boronic acid derivative/multi-wall carbon nano-tube composite material:
(1) 0.3g multi-walled carbon nanotube is weighed, is flowed back in the nitric acid of 4mol/L for 24 hours, after reflux, by the carbon nanometer of purifying
Pipe centrifugation after decantation remove supernatant liquor, be added secondary distilled water, be centrifuged repeatedly washing until pH for neutrality, be put into drying box in
60 DEG C of baking 12h；
(2) the product 5mg for taking step in this synthesis step (1) gains 5mg and step (3) to obtain is dissolved in 10mL ethyl alcohol, is surpassed
Sound disperses 3h, obtains cup [4] aromatic hydrocarbons phenyl boronic acid derivative/multi-walled carbon nanotube compound.
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| CN103864830A (en) * | 2014-03-26 | 2014-06-18 | 同济大学 | Calixarene boric acid derivative as well as preparation method and application of calixarene boric acid derivative |
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| CN104926844A (en) * | 2015-05-22 | 2015-09-23 | 同济大学 | Calix [8] areneboronic acid derivative and preparation thereof, as well as composite containing derivative and application of composite |
| CN105175356A (en) * | 2015-09-17 | 2015-12-23 | 同济大学 | Calix [4] arene thiadiazole derivative, calix [4] arene thiadiazole derivative-multi-walled carbon nanotube complex as well as preparation method and application of complex |
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