CN104926844B - Cup [8] areneboronic acid derivative and preparation, the composite containing the derivative and application - Google Patents
Cup [8] areneboronic acid derivative and preparation, the composite containing the derivative and application Download PDFInfo
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- CN104926844B CN104926844B CN201510267208.4A CN201510267208A CN104926844B CN 104926844 B CN104926844 B CN 104926844B CN 201510267208 A CN201510267208 A CN 201510267208A CN 104926844 B CN104926844 B CN 104926844B
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- 239000002253 acid Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 56
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- -1 calixarenes phenyl boronic acid derivative Chemical class 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 58
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 55
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 19
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000010992 reflux Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 13
- 239000012043 crude product Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- DGUWACLYDSWXRZ-UHFFFAOYSA-N (2-formylphenyl)boronic acid Chemical class OB(O)C1=CC=CC=C1C=O DGUWACLYDSWXRZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 125000004494 ethyl ester group Chemical group 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
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- 239000002904 solvent Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
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- 238000002156 mixing Methods 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims 1
- 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 abstract description 35
- 239000007772 electrode material Substances 0.000 abstract description 18
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- 239000002041 carbon nanotube Substances 0.000 abstract description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract 2
- 150000007513 acids Chemical class 0.000 abstract 1
- 238000002848 electrochemical method Methods 0.000 abstract 1
- 238000002484 cyclic voltammetry Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
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- 239000011734 sodium Substances 0.000 description 8
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000002255 enzymatic effect Effects 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- QBKSWRVVCFFDOT-UHFFFAOYSA-N gossypol Chemical compound CC(C)C1=C(O)C(O)=C(C=O)C2=C(O)C(C=3C(O)=C4C(C=O)=C(O)C(O)=C(C4=CC=3C)C(C)C)=C(C)C=C21 QBKSWRVVCFFDOT-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- RFSUNEUAIZKAJO-VRPWFDPXSA-N D-Fructose Natural products OC[C@H]1OC(O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-VRPWFDPXSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- QHOPXUFELLHKAS-UHFFFAOYSA-N Thespesin Natural products CC(C)c1c(O)c(O)c2C(O)Oc3c(c(C)cc1c23)-c1c2OC(O)c3c(O)c(O)c(C(C)C)c(cc1C)c23 QHOPXUFELLHKAS-UHFFFAOYSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- GZCGUPFRVQAUEE-KVTDHHQDSA-N aldehydo-D-mannose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)C=O GZCGUPFRVQAUEE-KVTDHHQDSA-N 0.000 description 1
- GZCGUPFRVQAUEE-VANKVMQKSA-N aldehydo-L-glucose Chemical compound OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)C=O GZCGUPFRVQAUEE-VANKVMQKSA-N 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
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- 210000004369 blood Anatomy 0.000 description 1
- 238000011095 buffer preparation Methods 0.000 description 1
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- 238000003759 clinical diagnosis Methods 0.000 description 1
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- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 229930000755 gossypol Natural products 0.000 description 1
- 229950005277 gossypol Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001906 matrix-assisted laser desorption--ionisation mass spectrometry Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
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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
- C07F5/025—Boronic and borinic acid compounds
-
- 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)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Molecular Biology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to cup [8] areneboronic acid derivative and preparation, the composite containing the derivative and application, the chemical formula of derivative is C146H202O20N16B6, using 2 formylphenylboronic acids as co-ligand, the hydrazide derivatives of cup [8] aromatic hydrocarbons four are main part, after cup [8] areneboronic acid derivative is combined with multi-walled carbon nano-tubes, obtain the calixarenes phenyl boronic acid derivative multi-walled carbon nano-tubes compound of black powder.The big cup of specific surface area [8] areneboronic acid derivative carbon nanotube electrode material is prepared using the inventive method, with excellent electric conductivity and selection identity, the inventive method is simple to operation, it is easy to control, cup [8] aromatic hydrocarbons phenyl boronic acid derivative multi-walled carbon nanotube electrode material is prepared, understands that the compound has selection recognition reaction to D glucose by electrochemical method.
Description
Technical field
The present invention relates to a kind of composite for recognizing D-Glucose, derive more particularly, to a kind of cup [8] areneboronic acid
The preparation method and applications of thing, derivative-multi-walled carbon nanotube electrode material.
Background technology
Glucose is a kind of important carbohydrate in animal and plant body, and important work is played during vital movement
With being also the human body indispensable energy and physiological activator.The detection of glucose is in clinical diagnosis, food inspection, life
The numerous areas such as science have extremely important application.As the material of storage energy, carbohydrate can be oxidized generation energy
Metabolic process is driven, the other biological molecule such as protein and fat can also be converted into.The detection of glucose would is that one long
Phase problem.
Glucose sensor and non-enzymatic glucose sensor of the development experience of glucose sensor based on enzyme, although base
The continuous differentiation of three generations is experienced in the glucose sensor of enzyme, but they all do not break away from enzyme and originally experienced temperature, pH, humidity
Influence with oxygen content and this unstable shortcoming.In addition, enzyme is expensive so that the glucose sensor based on enzyme begins
Cost this problem is faced with eventually.Based on factors above, the development of non-enzymatic glucose sensor has obtained great concern.Document
In largely reported a series of various metals and metal oxide, bimetal nano material, alloy and metal/metal oxygen
Compound-carbon nano tube compound material non-enzyme type glucose sensor.But calixarenes-carbon nano tube compound material is made into grape
Sugared sensor is not reported also in the literature.
Chinese patent CN 103864830A disclose calixarenes boronic acid derivatives, preparation method and applications.With 2- formyls
Base phenyl boric acid is co-ligand；Using 5,17- bis--amido -25,26,27,28- tetrahydroxys cup [4] aromatic hydrocarbons as main part.Prepared cup
Areneboronic acid derivative all has combination and recognition reaction to D-Glucose, D-Fructose, D-MANNOSE and D- galactolipins.It is logical
Cross fluorescent spectrometry and understand that derivative has recognition reaction to four kinds of monose, but this method detection limit is not high, linear correlation
Coefficient is not very high, it is necessary to which complicated pre-treatment step, agents useful for same amount is larger.
The content of the invention
The purpose of the present invention is exactly the defect in order to overcome above-mentioned prior art presence and provides a kind of cup [8] areneboronic acid
Derivative.
It is a further object to provide the preparation method of cup [8] areneboronic acid derivative.
Another object of the present invention is to prepare cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material
Material.
Another object of the present invention is cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material in identification
Application in D-Glucose.
The purpose of the present invention can be achieved through the following technical solutions：
Cup [8] areneboronic acid derivative, chemical formula is C146H202O20N16B6, using 2- formylphenylboronic acids as co-ligand, cup
[8] hydrazide derivatives of aromatic hydrocarbons four are main part, and structural formula is as follows：
The preparation method of cup [8] areneboronic acid derivative, using following steps：
(1) hydrazide derivatives of cup [8] aromatic hydrocarbons four are synthesized, white powder is obtained；
(2) crude product and 2- formylphenylboronic acids obtained step (1) is 1 in molar ratio:It is dissolved in after 10 mixing anhydrous
In the mixed solvent of methanol and glacial acetic acid, heating water bath, temperature control is flowed back at 60~70 DEG C, under agitation after 7~8h, rotation
Methanol removed by evaporation and acetic acid, obtain buff powder；
(3) absolute methanol and sodium borohydride are added into step (2) products therefrom, temperature control is at 40~50 DEG C, stirring
Flow back 6~7h, then reaction 10h is stirred at room temperature, and volatilize first alcohol and water under natural environment, obtains powdered light yellow thick production
Thing；
(4) the crude product silica gel column chromatography post separation for obtaining step (3) processing, then rotary evaporation eluant, eluent, is obtained
Powdery product is cup [8] areneboronic acid derivative.
Step (1) specifically uses following steps：Cup [8] tetrem acetoacetic ester is added in toluene and methanol mixed solvent to derive
The mol ratio of thing and hydrazine hydrate aqueous solution, cup [8] tetraacethyl ethyl ester derivative and hydrazine hydrate is 1：34,12h is stirred at reflux, is depressurized
Solvent is steamed, the white powder obtained after drying is the hydrazide derivatives of cup [8] aromatic hydrocarbons four, and yield is about 60%.
The sodium borohydride added in step (3) is 4 with the mol ratio of the hydrazide derivatives of cup [8] aromatic hydrocarbons four:25.
Multi-wall carbon nano-tube composite material containing cup [8] areneboronic acid derivative, is prepared using following methods：
(1) in the nitration mixture of the multi-walled carbon nano-tubes concentrated sulfuric acid and concentrated nitric acid, will be heated to reflux 6 hours, temperature control at 80 DEG C,
Centrifuge decantation and remove supernatant liquid, obtain sediment, use deionized water cyclic washing, centrifugation is until supernatant liquor pH value
Close to neutrality, under conditions of 50 DEG C, 12h dries the CNT after being acidified；
(2) added into the CNT after acidifying at thionyl chloride, 80 DEG C, flow back 24h, outstanding that thionyl chloride is evaporated off,
Obtain the multi-walled carbon nano-tubes of chloride；
(3) DMF dissolving cup [8] areneboronic acid derivative is utilized, many wall carbon of chloride are then added
Nanotube, at 60-70 DEG C, flows back 24 hours, obtains dispersed black particle suspension well, successively with tetrahydrofuran, food
Salt solution, second distillation water washing remove unreacted phenyl boric acid, centrifuge, and drying obtains black powder product, as cup
[8] multi-wall carbon nano-tube composite material of areneboronic acid derivative.
The volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 1 in step (1):3.
Described cup [8] areneboronic acid derivative and the weight ratio of the multi-walled carbon nano-tubes of chloride are 10:9.
The composite has selection recognition reaction to D-Glucose.Many wall carbon of cup [8] areneboronic acid derivative are received
Mitron composite is dissolved among ethanol, and decorating liquid is made, using drop-coating, and modified electrode is made, using cyclic voltammetry, is obtained
To modified electrode in the cyclic voltammogram of D-Glucose, it can be seen that there are obvious redox peaks to go out from cyclic voltammogram
Existing, illustrate the multi-wall carbon nano-tube composite material of cup [8] areneboronic acid derivative has recognition reaction to D-Glucose.
Compared with prior art, cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode that the present invention is prepared
Material can be combined with D-Glucose, and play the role of to recognize D-Glucose.Glucose and cup [8] areneboronic acid derivative
Multi-walled carbon nano-tubes combine, because the phenyl boric acid group on the multi-walled carbon nano-tubes of cup [8] areneboronic acid derivative can be with
Hydroxyl reaction in saccharides glucose, forms the borate ester of five-membered ring and hexatomic ring, and redox peaks occurs, in addition, root
Go out the difference of peak position according to cyclic voltammogram, can also distinguish between out D- glucose sugar and L- glucose.
Brief description of the drawings
Fig. 1 is the SEM figures of the multi-walled carbon nano-tubes used；
Fig. 2 is the SEM figures of cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material；
Fig. 3 is cup [8] aromatic hydrocarbons phenyl boronic acid derivative, multi-walled carbon nano-tubes, cup [8] aromatic hydrocarbons phenyl boronic acid derivative-many walls carbon
The XRD of nanotube electrode material；
Fig. 4 is cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material in Na2HPO4-NaH2PO4Ion delays
In electuary solution, the cyclic voltammogram that contrast Different electrodes are acted on D-Glucose；
Fig. 5 is cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material in Na2HPO4-NaH2PO4Ion delays
In electuary solution, difference repaiies the influence figure of reagent dosage；
Fig. 6 is cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material in Na2HPO4-NaH2PO4Ion delays
In electuary solution, the influence figure of different scanning speed；
Fig. 7 is cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material in Na2HPO4-NaH2PO4Ion delays
In electuary solution, different pH influence figure.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
The synthesis of cup [8] aromatic hydrocarbons phenyl boronic acid derivative
1. p-t-butyl phenol (5g, 33mmol) is added in 1000mL three-necked bottles, paraformaldehyde (1.75g, 55mmol),
0.1mL (10mol/L) the NaOH aqueous solution, and 30mL dimethylbenzene, heating stirring, are brought rapidly up, and by reaction temperature control
At 135~140 DEG C or so.Reactant dissolves, the transparent clear that reactant becomes after about 5min, as homogeneous, gradually becomes sticky, and reacts
Constantly having in liquid in bubble generation, water knockout drum constantly has moisture to go out, and after about 4~4.5h, reaction solution becomes light orange, first there is white
Color solid is generated, rear yellowing, is stopped heating, is cooled to room temperature.Filtering, filtrate successively with 2mL toluene, 20mL ether,
20mL acetone and treat 20mL distill water washing, dry, dry to obtain white powder crude product.Crude product Gossypol recrystallized from chloroform, is obtained
White crystal 3g.Yield：72%.
2. step (1) product (0.3g, 0.23mmol) is weighed, potassium carbonate (1g), anhydrous propanone (8mL), 0.23g iodate
Potassium, a certain amount of ethyl chloroacetate is added in 50mL three-necked bottles, controls ultrasonic wave range, and system is carried out to be heated to reflux several points
Stop reaction after clock, be cooled to room temperature, suction filtration by filtrate rotary evaporation, is obtained a little oily liquids, obtained with 95% ethyl alcohol recrystallization
White solid product.
3. step (2) product (1.9840g, 1mmol) is weighed to be dissolved in the mixed solution of 50mL methanol and 50mL toluene, plus
Enter 20mL hydrazine hydrate aqueous solutions (content 85%), be stirred at reflux 12h.Decompression steams solvent, and white powder is obtained after drying.Yield
60%.
4. adding step (3) products obtained therefrom (1.56g, 0.8333mmol) in three-neck flask, 2- formylphenylboronic acids are added
(1.2510g, 8.34mmol), adds 100mL absolute methanols and 1.5mL glacial acetic acid, is heated to reflux after 7-8h, rotary evaporation goes out
Remove methanol and glacial acetic acid.Buff powder is obtained, the sodium borohydride of 120mL absolute ethyl alcohols and about 6 times of desired products is added
(NaBH4) (0.19g, 5mmol), temperature control is stirred at reflux 6~7h at 40~50 DEG C, then is stirred at room temperature reaction 10h,
The first alcohol and water that volatilized under natural environment is taken out, yellow powder crude product is obtained.Yield about 65%.
5. the crude product silica gel column chromatography post separation that step (4) processing is obtained, with methanol/ethyl acetate (5:2, v/v)
Elution, can obtain product 0.2356g.Yield is 50.8%.1H-NMR(CDCl3,TMS,400MHz):
6.82~7.16 (m, 40H, Ar-H)
4.21 (s, 16H, Ar-O-CH2-)
3.89 (s, 12H, Ar-CH2-N-)
3.61 (d, 16H, Ar-CH2-Ar)
3.20 (s, 16H, Ar-O-C-CH2-N-)
2.21 (s, 12H, Ar-B-OH)
2.00 (s, 18H, Ar-C-NH-NH-)
0.88~1.25 (s, 72H ,-C (CH3)3)
MALDI-MS for a1:Calcd.m/z=2565.85 (M+H)+
Embodiment 2
The synthesis of cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nano-tubes
1. 0.15g multi-walled carbon nano-tubes (SEM figures are as shown in Figure 1) is weighed in the 10mL concentrated sulfuric acids and 30mL concentrated nitric acid (volumes
Than 1:3) in nitration mixture, it is heated to reflux 6 hours, temperature control centrifuges decantation and remove supernatant liquid, obtain at 80 DEG C or so
Sediment, is using deionized water cyclic washing, centrifugation is up to supernatant liquor pH value is close to neutrality, under conditions of 50 DEG C, 12h,
Dry the CNT MWCNTs-COOH after being acidified.
2. step (1) products therefrom is added at 50mL thionyl chlorides, 80 DEG C, flow back 24h, outstanding that thionyl chloride is evaporated off,
Obtain the multi-walled carbon nano-tubes MWCNTs-COCl of chloride.
3. with material obtained by the step (5) of 5mL DMFs dissolving 0.1986g embodiments 1, add step (2)
In reaction, at 60-70 DEG C, flow back 24 hours, obtain dispersed black particle suspension well, successively with tetrahydrofuran, food
Salt solution, second distillation water washing remove unreacted phenyl boric acid, centrifuge, and drying obtains 0.11g black powder products, i.e.,
For cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material, SEM figures are as shown in Figure 2.Fig. 3 is cup [8] aromatic hydrocarbons benzene
Boronic acid derivatives, multi-walled carbon nano-tubes, the XRD of cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material.From
In figure it can be seen that 25.5 ° be multi-walled carbon nano-tubes characteristic peak, 31 ° be cup [8] aromatic hydrocarbons phenyl boronic acid derivative characteristic peak.Two
After person combines, the characteristic peak that at 26 ° with 30.8 ° two all to occur in that shape similar has illustrated cup [8] aromatic hydrocarbons phenyl boronic acid derivative
Through being successfully accessed on multi-walled carbon nano-tubes.
Embodiment 3
The electrochemical sensing of cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material and D-Glucose is tested：
Laboratory apparatus：CHI660C electrochemical analysers
Supporting electrolyte：0.1mol/L phosphate buffer solution is prepared, required pH is transferred to as needed and obtains supporting electricity
Solve liquid.With the buffer preparation 0.01mol/L matched somebody with somebody D-Glucose sugar juice, during experiment, as needed with being diluted to
Required concentration.
Experimental method：Cycle voltammetry
Instrument parameter：High potential：0.6V, low potential：- 1.2V, sweep speed 0.1mv/s, sensitivity 10-4
The preparation of modified electrode：Glassy carbon electrode surface is polished with the abrasive paper for metallograph of No. 1-6 successively, then on deerskin according to
Secondary is in minute surface with 0.3 μm, 0.05 μm of alundum (Al2O3) powder polishing, uses absolute ethyl alcohol and deionized water respectively after polishing every time
It is cleaned by ultrasonic 30 seconds.Activation process is carried out in 0.5-1.0mol/L sulfuric acid solution, be repeatedly scanned with cyclic voltammetry until
Untill the circulation Fuan figure stablized, sweep speed is 100mV/s, and sweep limits is -1.0-1.0V.
5mg glasss of [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nano-tubes are weighed, are dispersed in 10mL absolute ethyl alcohols, ultrasound
2h, obtains the black suspension of 0.5mg/L two bottles of stable homogeneous.Using drop-coating modified electrode.Drawn with microsyringe
Above-mentioned suspension, drop coating is dried in the surface of glass-carbon electrode, in atmosphere volatilization.Before each drop coating electrode, it is required for modifying
Ultrasonically treated 30min makees decentralized processing to liquid again.
As a result show：Cup [8] aromatic hydrocarbons phenyl boronic acid derivative-Multiwalled Carbon Nanotubes Modified Electrode can occur with D-Glucose
Recognition reaction.
Fig. 4 is cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material in Na2HPO4-NaH2PO4Ion delays
In electuary solution, the cyclic voltammogram that contrast Different electrodes are acted on D-Glucose, it can be seen that in identical conditions
Under, the cyclic voltammogram of three kinds of electrodes differs greatly.Current signal of the bare glassy carbon electrode in PBS cushioning liquid hardly may be used
Survey；Cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode is in PBS cushioning liquid, and cup [8] aromatic hydrocarbons phenyl boric acid derives
Thing-multi-walled carbon nanotube electrode in the PBS cushioning liquid for adding D-Glucose in solution on, can be seen in cyclic voltammogram
Observe an obvious reduction peak.Because cup [8] aromatic hydrocarbons phenyl boronic acid derivative combines to form five yuan or six with glucose
First cyclic ester so that cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode greatly increases to the adsorption capacity of glucose
Plus, the sensitivity of identification is refer to significantly.
Fig. 5 is cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material in Na2HPO4-NaH2PO4Ion delays
In electuary solution, difference repaiies the influence figure of reagent dosage, and when dressing agent consumption is less than 20 μ L, peak current is with dressing agent consumption
Increase and significantly increase, because the consumption of increase dressing agent, cup [8] aromatic hydrocarbons phenyl boronic acid derivative-many walls of electrode surface
Carbon mano-tube composite is gradually paved with, and causes electric conductivity to increase, electric signal be exaggerated, while so that active site therewith
Increase, bioaccumulation efficiency is improved, and both collective effects cause peak current to increase.After dressing agent consumption is more than 20 μ L, peak current
Gradually reduce on the contrary, background current becomes larger, reappearance is deteriorated.Because after dressing agent exceedes a certain amount, electrode
Surface modification film is too thick, is difficult to be fixed on electrode surface, is easily fallen off in experimentation, under the stability of electrode is also understood
Drop.Therefore, this experiment dressing agent consumption selects 20 μ L.
Fig. 6 is cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material in Na2HPO4-NaH2PO4Ion delays
In electuary solution, the influence figure of different scanning speed, when sweep speed progressively increases to 300mV/s from 50mV/s, reduction peak
All gradually increase with oxidation peak, its reduction peak current IpcWith oxidation peak current IpaWith the square root v of sweep speed1/2In good
Linear relationship, illustrates the electrode reaction mainly by diffusion control.
Fig. 7 is cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material in Na2HPO4-NaH2PO4Ion delays
In electuary solution, different pH influence figure, as can be seen from Fig. when neutrality is close under the conditions of weakly alkaline, peak current maximum；
Under acid and alkalescence condition, peak current is gradually reduced.And there is skew slightly.PH among blood of human body is 7.35~7.45
In the range of, thus illustrate that this material can play a role in the range of the pH that human body has again.
Embodiment 4
Cup [8] areneboronic acid derivative, chemical formula is C146H202O20N16B6, using 2- formylphenylboronic acids as co-ligand, cup
[8] hydrazide derivatives of aromatic hydrocarbons four are main part, and structural formula is as follows：
The preparation method of cup [8] areneboronic acid derivative, using following steps：
(1) cup [8] tetraacethyl ethyl ester derivative and hydrazine hydrate aqueous solution, cup are added in toluene and methanol mixed solvent
[8] mol ratio of tetraacethyl ethyl ester derivative and hydrazine hydrate is 1：34,12h is stirred at reflux, decompression steams solvent, is obtained after drying
White powder be the hydrazide derivatives of cup [8] aromatic hydrocarbons four, yield is about 60%；
(2) crude product and 2- formylphenylboronic acids obtained step (1) is 1 in molar ratio:It is dissolved in after 10 mixing anhydrous
In the mixed solvent of methanol and glacial acetic acid, heating water bath, temperature control is flowed back at 60 DEG C, under agitation after 7h, and rotary evaporation is removed
Methanol and acetic acid are removed, buff powder is obtained；
(3) absolute methanol and sodium borohydride, sodium borohydride and cup [8] virtue of addition are added into step (2) products therefrom
The mol ratio of the hydrazide derivatives of hydrocarbon four is 4:25, temperature control is stirred at reflux 6h at 40 DEG C, then is stirred at room temperature reaction 10h,
Volatilize first alcohol and water under natural environment, obtains powdered light yellow raw material；
(4) the crude product silica gel column chromatography post separation for obtaining step (3) processing, then rotary evaporation eluant, eluent, is obtained
Powdery product is cup [8] areneboronic acid derivative.
Prepared using cup [8] the areneboronic acid derivative prepared as raw material many containing cup [8] areneboronic acid derivative
Wall carbon nano-tube composite material, specifically using following methods：
(1) by (volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 1 in the nitration mixture of the multi-walled carbon nano-tubes concentrated sulfuric acid and concentrated nitric acid:3),
It is heated to reflux 6 hours, temperature control centrifuges decantation and remove supernatant liquid, obtain sediment, with deionized water at 80 DEG C
Cyclic washing, centrifugation are until supernatant liquor pH value is close to neutrality, and under conditions of 50 DEG C, 12h, the carbon after drying is acidified is received
Mitron；
(2) added into the CNT after acidifying at thionyl chloride, 80 DEG C, flow back 24h, outstanding that thionyl chloride is evaporated off,
Obtain the multi-walled carbon nano-tubes of chloride；
(3) DMF dissolving cup [8] areneboronic acid derivative is utilized, many wall carbon of chloride are then added
The weight ratio of the multi-walled carbon nano-tubes of nanotube, cup [8] areneboronic acid derivative and chloride is 10:9, at 60 DEG C, backflow 24
Hour, dispersed black particle suspension well is obtained, is removed successively with tetrahydrofuran, saline solution, second distillation water washing
Unreacted phenyl boric acid, is centrifuged, and drying obtains many walls of black powder product, as cup [8] areneboronic acid derivative
Carbon nano tube compound material.
The composite has selection recognition reaction to D-Glucose.Many wall carbon of cup [8] areneboronic acid derivative are received
Mitron composite is dissolved among ethanol, and decorating liquid is made, using drop-coating, and modified electrode is made, using cyclic voltammetry, is obtained
To modified electrode in the cyclic voltammogram of D-Glucose, it can be seen that there are obvious redox peaks to go out from cyclic voltammogram
Existing, illustrate the multi-wall carbon nano-tube composite material of cup [8] areneboronic acid derivative has recognition reaction to D-Glucose.
Embodiment 5
Cup [8] areneboronic acid derivative, chemical formula is C146H202O20N16B6, using 2- formylphenylboronic acids as co-ligand, cup
[8] hydrazide derivatives of aromatic hydrocarbons four are main part, and structural formula is as follows：
The preparation method of cup [8] areneboronic acid derivative, using following steps：
(1) cup [8] tetraacethyl ethyl ester derivative and hydrazine hydrate aqueous solution, cup are added in toluene and methanol mixed solvent
[8] mol ratio of tetraacethyl ethyl ester derivative and hydrazine hydrate is 1：34,12h is stirred at reflux, decompression steams solvent, is obtained after drying
White powder be the hydrazide derivatives of cup [8] aromatic hydrocarbons four, yield is about 60%；
(2) crude product and 2- formylphenylboronic acids obtained step (1) is 1 in molar ratio:It is dissolved in after 10 mixing anhydrous
In the mixed solvent of methanol and glacial acetic acid, heating water bath, temperature control is flowed back at 70 DEG C, under agitation after 8h, and rotary evaporation is removed
Methanol and acetic acid are removed, buff powder is obtained；
(3) absolute methanol and sodium borohydride, sodium borohydride and cup [8] virtue of addition are added into step (2) products therefrom
The mol ratio of the hydrazide derivatives of hydrocarbon four is 4:25, temperature control is stirred at reflux 7h at 50 DEG C, then is stirred at room temperature reaction 10h,
Volatilize first alcohol and water under natural environment, obtains powdered light yellow raw material；
(4) the crude product silica gel column chromatography post separation for obtaining step (3) processing, then rotary evaporation eluant, eluent, is obtained
Powdery product is cup [8] areneboronic acid derivative.
Prepared using cup [8] the areneboronic acid derivative prepared as raw material many containing cup [8] areneboronic acid derivative
Wall carbon nano-tube composite material, specifically using following methods：
(1) by (volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 1 in the nitration mixture of the multi-walled carbon nano-tubes concentrated sulfuric acid and concentrated nitric acid:3),
It is heated to reflux 6 hours, temperature control centrifuges decantation and remove supernatant liquid, obtain sediment, with deionized water at 80 DEG C
Cyclic washing, centrifugation are until supernatant liquor pH value is close to neutrality, and under conditions of 50 DEG C, 12h, the carbon after drying is acidified is received
Mitron；
(2) added into the CNT after acidifying at thionyl chloride, 80 DEG C, flow back 24h, outstanding that thionyl chloride is evaporated off,
Obtain the multi-walled carbon nano-tubes of chloride；
(3) DMF dissolving cup [8] areneboronic acid derivative is utilized, many wall carbon of chloride are then added
The weight ratio of the multi-walled carbon nano-tubes of nanotube, cup [8] areneboronic acid derivative and chloride is 10:9, at 70 DEG C, backflow 24
Hour, dispersed black particle suspension well is obtained, is removed successively with tetrahydrofuran, saline solution, second distillation water washing
Unreacted phenyl boric acid, is centrifuged, and drying obtains many walls of black powder product, as cup [8] areneboronic acid derivative
Carbon nano tube compound material.
The composite has selection recognition reaction to D-Glucose.Many wall carbon of cup [8] areneboronic acid derivative are received
Mitron composite is dissolved among ethanol, and decorating liquid is made, using drop-coating, and modified electrode is made, using cyclic voltammetry, is obtained
To modified electrode in the cyclic voltammogram of D-Glucose, it can be seen that there are obvious redox peaks to go out from cyclic voltammogram
Existing, illustrate the multi-wall carbon nano-tube composite material of cup [8] areneboronic acid derivative has recognition reaction to D-Glucose.
Claims (7)
1. glass [8] areneboronic acid derivative, it is characterised in that the chemical formula of derivative is C146H202O20N16B6, with 2- formoxyls
Phenyl boric acid is co-ligand, and the hydrazide derivatives of cup [8] aromatic hydrocarbons four are main part, and structural formula is as follows：
2. the preparation method of cup [8] areneboronic acid derivative as claimed in claim 1, it is characterised in that this method use with
Lower step：
(1) hydrazide derivatives of cup [8] aromatic hydrocarbons four are synthesized, white powder is obtained；
(2) crude product and 2- formylphenylboronic acids obtained step (1) is 1 in molar ratio:Absolute methanol is dissolved in after 10 mixing
In the mixed solvent of glacial acetic acid, heating water bath, temperature control is flowed back at 60~70 DEG C, under agitation after 7~8h, rotary evaporation
Methanol and acetic acid are removed, buff powder is obtained；
(3) absolute methanol and sodium borohydride are added into step (2) products therefrom, temperature control is stirred at reflux 6 at 40~50 DEG C
~7h, then reaction 10h is stirred at room temperature, volatilize first alcohol and water under natural environment, obtains powdered light yellow raw material；
(4) the crude product silica gel column chromatography post separation for obtaining step (3) processing, then rotary evaporation eluant, eluent, obtains powder
Shape product is cup [8] areneboronic acid derivative.
3. the preparation method of cup [8] areneboronic acid derivative as claimed in claim 2, it is characterised in that step (1) is specifically adopted
Use following steps：Cup [8] tetraacethyl ethyl ester derivative and hydrazine hydrate aqueous solution, cup are added in toluene and methanol mixed solvent
[8] mol ratio of tetraacethyl ethyl ester derivative and hydrazine hydrate is 1:34,12h is stirred at reflux, decompression steams solvent, is obtained after drying
White powder be the hydrazide derivatives of cup [8] aromatic hydrocarbons four.
4. the preparation method of cup [8] areneboronic acid derivative as claimed in claim 2, it is characterised in that added in step (3)
The mol ratios of sodium borohydride and the hydrazide derivatives of cup [8] aromatic hydrocarbons four be 4:25.
5. the multi-wall carbon nano-tube composite material containing cup as claimed in claim 1 [8] areneboronic acid derivative, its feature exists
In the composite is prepared using following methods：
(1) multi-walled carbon nano-tubes is placed in the nitration mixture of the concentrated sulfuric acid and concentrated nitric acid, is heated to reflux 6 hours, temperature control at 80 DEG C,
Centrifuge decantation and remove supernatant liquid, obtain sediment, then use deionized water cyclic washing, centrifugation is until supernatant liquor pH value
Close to neutrality, under conditions of 50 DEG C, 12h dries the CNT after being acidified；
(2) added into the CNT after acidifying at thionyl chloride, 80 DEG C, flow back 24h, revolving removes thionyl chloride, obtained
The multi-walled carbon nano-tubes of chloride；
(3) DMF dissolving cup [8] areneboronic acid derivative is utilized, the multi-wall carbon nano-tube of chloride is then added
Pipe, at 60-70 DEG C, flows back 24 hours, obtains dispersed black particle suspension well, successively with tetrahydrofuran, saline solution,
Second distillation water washing removes unreacted phenyl boric acid, centrifuges, and drying obtains black powder product, as cup [8] virtue
The multi-wall carbon nano-tube composite material of hydrocarbon boronic acid derivatives.
6. containing the multi-wall carbon nano-tube composite material of cup [8] areneboronic acid derivative as claimed in claim 5, its feature exists
In the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 1 in step (1):3.
7. containing the multi-wall carbon nano-tube composite material of cup [8] areneboronic acid derivative as claimed in claim 5, its feature exists
In described cup [8] areneboronic acid derivative and the weight ratio of the multi-walled carbon nano-tubes of chloride are 10:9.
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