CN104926844A - Calix [8] areneboronic acid derivative and preparation thereof, as well as composite containing derivative and application of composite - Google Patents
Calix [8] areneboronic acid derivative and preparation thereof, as well as composite containing derivative and application of composite Download PDFInfo
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- CN104926844A CN104926844A CN201510267208.4A CN201510267208A CN104926844A CN 104926844 A CN104926844 A CN 104926844A CN 201510267208 A CN201510267208 A CN 201510267208A CN 104926844 A CN104926844 A CN 104926844A
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- 239000002253 acid Substances 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 71
- 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 claims abstract description 40
- 230000000694 effects Effects 0.000 claims abstract description 14
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 13
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 13
- DGUWACLYDSWXRZ-UHFFFAOYSA-N (2-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1C=O DGUWACLYDSWXRZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003446 ligand Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 39
- 239000000047 product Substances 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 238000010992 reflux Methods 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000002484 cyclic voltammetry Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 13
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 10
- 238000002390 rotary evaporation Methods 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-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
- 239000012279 sodium borohydride Substances 0.000 claims description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 9
- 125000004494 ethyl ester group Chemical group 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 239000011159 matrix material Substances 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
- 238000001035 drying Methods 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 230000006837 decompression Effects 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000001548 drop coating Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000006396 nitration reaction Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 230000003252 repetitive effect Effects 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 238000005201 scrubbing Methods 0.000 claims description 5
- 238000010898 silica gel chromatography Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000010025 steaming Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical class OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 abstract description 52
- 239000007772 electrode material Substances 0.000 abstract description 19
- HDPRHRZFFPXZIL-UHFFFAOYSA-N calix[8]arene Chemical compound OC1=C(CC=2C(=C(CC=3C(=C(CC=4C(=C(CC=5C(=C(CC=6C(=C(CC=7C(=C(C8)C=CC=7)O)C=CC=6)O)C=CC=5)O)C=CC=4)O)C=CC=3)O)C=CC=2)O)C=CC=C1CC1=C(O)C8=CC=C1 HDPRHRZFFPXZIL-UHFFFAOYSA-N 0.000 abstract 2
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound 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 abstract 1
- 238000002848 electrochemical method Methods 0.000 abstract 1
- 239000008103 glucose Substances 0.000 description 15
- -1 calixarene boric acid derivatives Chemical class 0.000 description 9
- 239000007853 buffer solution Substances 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 102000004190 Enzymes Human genes 0.000 description 6
- 108090000790 Enzymes Proteins 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000003607 modifier Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 0 C*(CC(**(*)=*)C1)*(C)(C)*1=C Chemical compound C*(CC(**(*)=*)C1)*(C)(C)*1=C 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 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
- 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 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000002255 enzymatic effect Effects 0.000 description 2
- 239000000706 filtrate Substances 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
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
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- 239000000376 reactant Substances 0.000 description 2
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- 239000003115 supporting electrolyte Substances 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-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
- WQZGKKKJIJFFOK-ZZWDRFIYSA-N L-glucose Chemical compound OC[C@@H]1OC(O)[C@@H](O)[C@H](O)[C@H]1O WQZGKKKJIJFFOK-ZZWDRFIYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- 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
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 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
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 238000011095 buffer preparation Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003759 clinical diagnosis Methods 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 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
- 238000005304 joining 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
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 229960004839 potassium iodide Drugs 0.000 description 1
- 235000007715 potassium iodide Nutrition 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
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 238000004383 yellowing 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
- C07F5/025—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)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a calix [8] areneboronic acid derivative and preparation thereof, as well as a composite containing the derivative and an application of the composite. A chemical formula of the derivative is C146H202O20N16B6. With 2-formylphenylboronic acid as an auxiliary ligand and a calix[8] arene tetrahydrazide derivative as a main ligand, the calix [8] areneboronic acid derivative and multi-walled carbon nanotubes are compounded to obtain black powdered calix arene phenylboronic acid derivative-multi-walled carbon nanotube composite. The large-specific-area calix [8] areneboronic acid derivative-carbon nanotube electrode material prepared by using the method has excellent heat conductivity and selective recognition property. The method disclosed by the invention is simple and easy to operate and easy to control. The prepared calix [8] arene phenylboronic acid derivative-carbon nanotube electrode material, namely the composite has a selective recognition effect on D-glucose through an electrochemical method.
Description
Technical field
The present invention relates to a kind of matrix material identifying D-Glucose, especially relate to a kind of cup [8] areneboronic acid derivative, the preparation method of derivative-multi-walled carbon nanotube electrode material and application thereof.
Background technology
Glucose is a kind of important carbohydrate in animal and plant body, plays an important role in vital movement process, is also the indispensable energy of human body and physiologically active substance.The detection of glucose has extremely important application at numerous areas such as clinical diagnosis, food inspection, life sciences.As the material of storage energy, carbohydrate oxidized generate energy can drive metabolic process, also can be converted into the other biological such as protein and fat molecule.The detection of glucose will be a long-standing issues.
The development experience of glucose sensor is based on the glucose sensor of enzyme and non-enzymatic glucose sensor, although the glucose sensor based on enzyme experienced by the continuous differentiation of three generations, they are not all broken away from enzyme and originally to experience the impact of temperature, pH, humidity and oxygen content and this shortcoming unstable.In addition, enzyme expensive, makes the glucose sensor based on enzyme be faced with this problem of cost all the time.Based on above factor, the development of non-enzymatic glucose sensor obtains great concern.A series of various metal and metal oxide, bimetal nano material, alloy and metal/metal oxide-carbon nano tube compound material non-enzyme type glucose sensor has been reported in a large number in document.But calixarene-carbon nano tube compound material is made glucose sensor and also do not reported in the literature.
Chinese patent CN 103864830A discloses calixarene boric acid derivatives, preparation method and application thereof.With 2-formylphenylboronic acid for co-ligand; Be main part with 5,17-, bis--amido-25,26,27,28-tetrahydroxy cup [4] aromatic hydrocarbons.Prepared calixarene boric acid derivatives all has keying action and recognition reaction to D-Glucose, D-Fructose, D-MANNOSE and D-semi-lactosi.All have recognition reaction by the known derivative of fluorescent spectrometry to four kinds of monose, but this method detection limit is not high, linearly dependent coefficient is not very high, and need complicated pre-treatment step, agents useful for same amount is larger.
Summary of the invention
Object of the present invention be exactly in order to overcome above-mentioned prior art exist defect and a kind of cup [8] areneboronic acid derivative is provided.
Another object of the present invention is to provide the preparation method of cup [8] areneboronic acid derivative.
Another object of the present invention prepares cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material.
Another object of the present invention is that cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material is identifying the application in D-Glucose.
Object of the present invention can be achieved through the following technical solutions:
Cup [8] areneboronic acid derivative, chemical formula is C
146h
202o
20n
16b
6, with 2-formylphenylboronic acid for co-ligand, cup [8] aromatic hydrocarbons four hydrazide derivatives is main part, and structural formula is as follows:
The preparation method of cup [8] areneboronic acid derivative, adopts following steps:
(1) synthesize cup [8] aromatic hydrocarbons four hydrazide derivatives, obtain white powder;
(2) thick product step (1) obtained and 2-formylphenylboronic acid are in molar ratio for being dissolved in the mixed solvent of anhydrous methanol and Glacial acetic acid after 1:10 mixing, heating in water bath, temperature controls at 60 ~ 70 DEG C, under agitation reflux after 7 ~ 8h, rotary evaporation removing methyl alcohol and acetic acid, obtain buff powder;
(3) in step (2) products therefrom, anhydrous methanol and sodium borohydride is added, temperature controls at 40 ~ 50 DEG C, stirring and refluxing 6 ~ 7h, more at room temperature stirring reaction 10h, first of volatilizing under physical environment alcohol and water, obtains Powdered light yellow raw material;
(4) step (3) is processed the thick product silica gel column chromatography obtained to be separated, then rotary evaporation eluent, obtains powdery product and is cup [8] areneboronic acid derivative.
Step (1) specifically adopts following steps: in toluene and methanol mixed solvent, add cup [8] tetraacethyl ethyl ester derivative and hydrazine hydrate aqueous solution, the mol ratio of cup [8] tetraacethyl ethyl ester derivative and hydrazine hydrate is 1:34, stirring and refluxing 12h, decompression steams solvent, the white powder obtained after drying is cup [8] aromatic hydrocarbons four hydrazide derivatives, and productive rate is probably 60%.
The mol ratio of the sodium borohydride added in step (3) and cup [8] aromatic hydrocarbons four hydrazide derivatives is 4:25.
Multi-wall carbon nano-tube composite material containing cup [8] areneboronic acid derivative, adopts following methods to prepare:
(1) by the nitration mixture of the multi-walled carbon nano-tubes vitriol oil and concentrated nitric acid, reflux 6 hours, temperature controls at 80 DEG C, centrifugation decant removes supernatant liquid, is precipitated thing, is using deionized water repetitive scrubbing, it is centrifugal until supernatant liquid pH value is close to neutral, under the condition of 50 DEG C, 12h, dries the carbon nanotube after obtaining acidifying;
(2) in the carbon nanotube after acidifying, thionyl chloride is added, at 80 DEG C, backflow 24h, outstanding steaming removes thionyl chloride, obtains the multi-walled carbon nano-tubes of chloride;
(3) N is utilized, dinethylformamide dissolving cup [8] areneboronic acid derivative, then the multi-walled carbon nano-tubes of chloride is added, at 60-70 DEG C, reflux 24 hours, obtain dispersed well black particle suspension liquid, unreacted phenylo boric acid is removed successively with tetrahydrofuran (THF), salt solution, second distillation water washing, centrifugation, dries and obtains black powder product, be the multi-wall carbon nano-tube composite material of cup [8] areneboronic acid derivative.
In step (1), the volume ratio of the vitriol oil and concentrated nitric acid is 1:3.
The weight ratio of described cup [8] areneboronic acid derivative and the multi-walled carbon nano-tubes of chloride is 10:9.
This matrix material has selective recognition effect to D-Glucose.The multi-wall carbon nano-tube composite material of cup [8] areneboronic acid derivative is dissolved in the middle of ethanol, make decorating liquid, adopt drop-coating, make modified electrode, adopt cyclic voltammetry, obtain the cyclic voltammogram of modified electrode at D-Glucose, can find out from cyclic voltammogram and have obvious redox peak to occur, illustrate that 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 material that the present invention prepares can combine with D-Glucose, and has the effect identifying D-Glucose.The multi-walled carbon nano-tubes of glucose and cup [8] areneboronic acid derivative combines, because the phenylo boric acid group on the multi-walled carbon nano-tubes of cup [8] areneboronic acid derivative can with the hydroxyl reaction in saccharides glucose, form the borate ester of five-ring and six-ring, and there is redox peak, in addition, go out the difference of peak position according to cyclic voltammogram, D-glucose sugar and L-glucose can also be distinguished.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the multi-walled carbon nano-tubes adopted;
Fig. 2 is the SEM figure 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, the XRD figure of cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material;
Fig. 4 is that cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material is at Na
2hPO
4-NaH
2pO
4in ion buffer solution, the cyclic voltammogram of contrast Different electrodes and D-Glucose effect;
Fig. 5 is that cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material is at Na
2hPO
4-NaH
2pO
4in ion buffer solution, difference repaiies the effect diagram of reagent dosage;
Fig. 6 is that cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material is at Na
2hPO
4-NaH
2pO
4in ion buffer solution, the effect diagram of different scanning speed;
Fig. 7 is that cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material is at Na
2hPO
4-NaH
2pO
4in ion buffer solution, the effect diagram of different pH.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
The synthesis of cup [8] aromatic hydrocarbons phenyl boronic acid derivative
1. in 1000mL three-necked bottle, add p-tert-butylphenol (5g, 33mmol), paraformaldehyde (1.75g, 55mmol), the aqueous solution of the NaOH of 0.1mL (10mol/L), and 30mL dimethylbenzene, heated and stirred, rapid temperature increases, and temperature of reaction is controlled at about 135 ~ 140 DEG C.Reactants dissolved, the transparent clear that after about 5min, reactant becomes, becomes homogeneous phase, becomes sticky gradually, bubble is constantly had to produce in reaction solution, constantly have moisture to go out in water trap, after about 4 ~ 4.5h, reaction soln becomes light orange, first adularescent solid generates, rear yellowing, stops heating, is cooled to room temperature.Filter, filtrate is successively with 2mL toluene, 20mL ether, 20mL acetone with treat 20mL distilled water wash, and drying, dries to obtain the thick product of white powder.Thick product Gossypol recrystallized from chloroform, obtains white crystal 3g.Productive rate: 72%.
2. take step (1) product (0.3g, 0.23mmol), salt of wormwood (1g), anhydrous propanone (8mL), 0.23g potassiumiodide, a certain amount of ethyl chloroacetate, adds in 50mL three-necked bottle, controls ultrasonic wave range, stopped reaction after reflux number minute is carried out to system, be cooled to room temperature, suction filtration, by filtrate rotary evaporation, obtain a little oily liquids, obtain white solid product with 95% ethyl alcohol recrystallization.
3. take step (2) product (1.9840g, 1mmol) to be dissolved in the mixing solutions of 50mL methyl alcohol and 50mL toluene, add 20mL hydrazine hydrate aqueous solution (content 85%), stirring and refluxing 12h.Decompression steams solvent, obtains white powder after drying.Productive rate 60%.
4. in three-necked flask, add step (3) products obtained therefrom (1.56g; 0.8333mmol); add 2-formylphenylboronic acid (1.2510g; 8.34mmol); add 100mL anhydrous methanol and 1.5mL Glacial acetic acid again; after reflux 7-8h, rotary evaporation goes out methyl alcohol and Glacial acetic acid.Obtain buff powder, then add 120mL dehydrated alcohol and about 6 times to the sodium borohydride (NaBH of desired product
4) (0.19g, 5mmol), temperature controls at 40 ~ 50 DEG C, stirring and refluxing 6 ~ 7h, more at room temperature stirring reaction 10h, takes out the first alcohol and water that to volatilize under physical environment, obtains yellow powder crude product.Productive rate about 65%.
5. step (4) is processed the thick product silica gel column chromatography obtained to be separated, with methanol/ethyl acetate (5:2, v/v) wash-out, product 0.2356g can be obtained.Productive rate is 50.8%.
1H-NMR(CDCl
3,TMS,400MHz):
6.82～7.16(m，40H，Ar-H)
4.21(s，16H，Ar-O-CH
2-)
3.89(s，12H，Ar-CH
2-N-)
3.61(d，16H，Ar-CH
2-Ar)
3.20(s，16H，Ar-O-C-CH
2-N-)
2.21(s，12H，Ar-B-OH)
2.00(s，18H，Ar-C-NH-NH-)
0.88～1.25(s，72H，-C(CH
3)
3)
MALDI-MS for a1:calcd.m/z＝2565.85(M+2Na)
2+
Embodiment 2
The synthesis of cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nano-tubes
1. take 0.15g multi-walled carbon nano-tubes (SEM figure as shown in Figure 1) in the nitration mixture of the 10mL vitriol oil and 30mL concentrated nitric acid (volume ratio 1:3), reflux 6 hours, temperature controls at about 80 DEG C, centrifugation decant removes supernatant liquid, is precipitated thing, is using deionized water repetitive scrubbing, it is centrifugal until supernatant liquid pH value is close to neutral, under the condition of 50 DEG C, 12h, dries the carbon nanotube MWCNTs-COOH after obtaining acidifying.
2. step (1) products therefrom is added 50mL thionyl chloride, at 80 DEG C, backflow 24h, outstanding steaming removes thionyl chloride, obtains the multi-walled carbon nano-tubes MWCNTs-COCl of chloride.
3. use 5mL N, dinethylformamide dissolves 0.1986g embodiment 1 step (5) gained material, add in step (2) reaction, at 60-70 DEG C, reflux 24 hours, obtain dispersed well black particle suspension liquid, unreacted phenylo boric acid is removed successively with tetrahydrofuran (THF), salt solution, second distillation water washing, centrifugation, oven dry obtains 0.11g black powder product, be cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material, SEM figure as shown in Figure 2.Fig. 3 is cup [8] aromatic hydrocarbons phenyl boronic acid derivative, multi-walled carbon nano-tubes, the XRD figure of cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material.As can be seen from the figure 25.5 ° is the characteristic peak of multi-walled carbon nano-tubes, and 31 ° is the characteristic peak of cup [8] aromatic hydrocarbons phenyl boronic acid derivative.All having there is with 30.8 ° of two place the characteristic peak that shape is similar at 26 ° after combining in the two, illustrates that cup [8] aromatic hydrocarbons phenyl boronic acid derivative has 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 analyser
Supporting electrolyte: the phosphate buffer soln of preparation 0.1mol/L, is transferred to required pH as required and obtains supporting electrolyte.With the D-Glucose sugar soln of buffer preparation 0.01mol/L of joining, during experiment, as required with being diluted to desired concn.
Experimental technique: cycle voltammetry
Instrument parameter: noble potential: 0.6V, low potential :-1.2V, sweep velocity 0.1mv/s, sensitivity 10
-4
The preparation of modified electrode: use the abrasive paper for metallograph of No. 1-6 by glassy carbon electrode surface polishing successively, then the aluminium sesquioxide powder polishing successively with 0.3 μm, 0.05 μm on deerskin is minute surface, uses dehydrated alcohol and deionized water ultrasonic cleaning 30 seconds after each polishing respectively.In the sulphuric acid soln of 0.5-1.0mol/L, carry out activation treatment, repeatedly scan till obtaining stable circulation Fuan figure by cyclic voltammetry, scanning speed is 100mV/s, and sweep limit is-1.0-1.0V.
Take 5mg cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nano-tubes, be dispersed in 10mL dehydrated alcohol, ultrasonic 2h, obtain the black suspension of two bottles of stable homogeneous of 0.5mg/L.Adopt drop-coating modified electrode.Draw above-mentioned suspension liquid with microsyringe, drip the surface being coated in glass-carbon electrode, volatilization is dried in atmosphere.Each drip be coated with electrode before, all need by decorating liquid again supersound process 30min make dispersion treatment.
Result shows: cup [8] aromatic hydrocarbons phenyl boronic acid derivative-Multiwalled Carbon Nanotubes Modified Electrode can with D-Glucose generation recognition reaction.
Fig. 4 is that cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material is at Na
2hPO
4-NaH
2pO
4in ion buffer solution, the cyclic voltammogram of contrast Different electrodes and D-Glucose effect, as can be seen from the figure, under identical conditions, the cyclic voltammogram of three kinds of electrodes differs greatly.The current signal of naked glass-carbon electrode in PBS buffered soln can be surveyed hardly; Cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode is in PBS buffered soln, cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode in the PBS buffered soln adding D-Glucose in solution on, an obvious reduction peak can be observed in cyclic voltammogram.This is because cup [8] aromatic hydrocarbons phenyl boronic acid derivative and glucose are in conjunction with formation five yuan or hexa-atomic cyclic ester, the adsorptive power of cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode to glucose is increased greatly, greatly refer to the sensitivity of identification.
Fig. 5 is that cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material is at Na
2hPO
4-NaH
2pO
4in ion buffer solution, difference repaiies the effect diagram of reagent dosage, when modifier consumption is less than 20 μ L, peak current enlarges markedly with the increase of modifier consumption, this is because increase the consumption of modifier, cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nano-tubes mixture of electrode surface is paved with gradually, cause electroconductibility to increase, electrical signal is exaggerated, and makes active site increase simultaneously thereupon, bioaccumulation efficiency improves, and both actings in conjunction cause peak current to increase.After modifier consumption is more than 20 μ L, peak current reduces on the contrary gradually, and background current becomes comparatively large, and circulation ratio is deteriorated.This is because after modifier exceedes certain amount, electrode face finish film is too thick, is not easily fixed on electrode surface, easily comes off in experimentation, and the stability of electrode also can decline.Therefore, this experiment modifier consumption selects 20 μ L.
Fig. 6 is that cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material is at Na
2hPO
4-NaH
2pO
4in ion buffer solution, the effect diagram of different scanning speed, when sweep velocity is increased to 300mV/s gradually from 50mV/s, reduction peak and oxidation peak increase all gradually, its reduction peak current I
pcwith oxidation peak current I
pawith the square root v of sweep velocity
1/2in good linear relationship, this electrode reaction is described mainly by diffusion control.
Fig. 7 is that cup [8] aromatic hydrocarbons phenyl boronic acid derivative-multi-walled carbon nanotube electrode material is at Na
2hPO
4-NaH
2pO
4in ion buffer solution, the effect diagram of different pH, as can be seen from Fig. when neutrality is close under weakly alkaline condition, peak current is maximum; Under acidity and alkaline condition, peak current reduces gradually.And there is skew slightly.PH in the middle of blood of human body, in the scope of 7.35 ~ 7.45, illustrates that this material can play a role within the scope of the pH that human body has again thus.
Embodiment 4
Cup [8] areneboronic acid derivative, chemical formula is C
146h
202o
20n
16b
6, with 2-formylphenylboronic acid for co-ligand, cup [8] aromatic hydrocarbons four hydrazide derivatives is main part, and structural formula is as follows:
The preparation method of cup [8] areneboronic acid derivative, adopts following steps:
(1) in toluene and methanol mixed solvent, cup [8] tetraacethyl ethyl ester derivative and hydrazine hydrate aqueous solution is added, the mol ratio of cup [8] tetraacethyl ethyl ester derivative and hydrazine hydrate is 1:34, stirring and refluxing 12h, decompression steams solvent, the white powder obtained after drying is cup [8] aromatic hydrocarbons four hydrazide derivatives, and productive rate is probably 60%;
(2) thick product step (1) obtained and 2-formylphenylboronic acid are in molar ratio for being dissolved in the mixed solvent of anhydrous methanol and Glacial acetic acid after 1:10 mixing, heating in water bath, temperature controls at 60 DEG C, under agitation after backflow 7h, rotary evaporation removing methyl alcohol and acetic acid, obtain buff powder;
(3) in step (2) products therefrom, anhydrous methanol and sodium borohydride is added, the mol ratio of the sodium borohydride added and cup [8] aromatic hydrocarbons four hydrazide derivatives is 4:25, temperature controls at 40 DEG C, stirring and refluxing 6h, at room temperature stirring reaction 10h again, first of volatilizing under physical environment alcohol and water, obtains Powdered light yellow raw material;
(4) step (3) is processed the thick product silica gel column chromatography obtained to be separated, then rotary evaporation eluent, obtains powdery product and is cup [8] areneboronic acid derivative.
With the cup prepared [8] areneboronic acid derivative be raw material preparation containing the multi-wall carbon nano-tube composite material of cup [8] areneboronic acid derivative, specifically adopt following methods:
(1) by the nitration mixture of the multi-walled carbon nano-tubes vitriol oil and concentrated nitric acid (volume ratio of the vitriol oil and concentrated nitric acid is 1:3), reflux 6 hours, temperature controls at 80 DEG C, centrifugation decant removes supernatant liquid, is precipitated thing, is using deionized water repetitive scrubbing, it is centrifugal until supernatant liquid pH value is close to neutral, under the condition of 50 DEG C, 12h, dries the carbon nanotube after obtaining acidifying;
(2) in the carbon nanotube after acidifying, thionyl chloride is added, at 80 DEG C, backflow 24h, outstanding steaming removes thionyl chloride, obtains the multi-walled carbon nano-tubes of chloride;
(3) N is utilized, dinethylformamide dissolving cup [8] areneboronic acid derivative, then the multi-walled carbon nano-tubes of chloride is added, the weight ratio of the multi-walled carbon nano-tubes of cup [8] areneboronic acid derivative and chloride is 10:9, at 60 DEG C, reflux 24 hours, obtain dispersed well black particle suspension liquid, unreacted phenylo boric acid is removed successively with tetrahydrofuran (THF), salt solution, second distillation water washing, centrifugation, oven dry obtains black powder product, is the multi-wall carbon nano-tube composite material of cup [8] areneboronic acid derivative.
This matrix material has selective recognition effect to D-Glucose.The multi-wall carbon nano-tube composite material of cup [8] areneboronic acid derivative is dissolved in the middle of ethanol, make decorating liquid, adopt drop-coating, make modified electrode, adopt cyclic voltammetry, obtain the cyclic voltammogram of modified electrode at D-Glucose, can find out from cyclic voltammogram and have obvious redox peak to occur, illustrate that 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 C
146h
202o
20n
16b
6, with 2-formylphenylboronic acid for co-ligand, cup [8] aromatic hydrocarbons four hydrazide derivatives is main part, and structural formula is as follows:
The preparation method of cup [8] areneboronic acid derivative, adopts following steps:
(1) in toluene and methanol mixed solvent, cup [8] tetraacethyl ethyl ester derivative and hydrazine hydrate aqueous solution is added, the mol ratio of cup [8] tetraacethyl ethyl ester derivative and hydrazine hydrate is 1:34, stirring and refluxing 12h, decompression steams solvent, the white powder obtained after drying is cup [8] aromatic hydrocarbons four hydrazide derivatives, and productive rate is probably 60%;
(2) thick product step (1) obtained and 2-formylphenylboronic acid are in molar ratio for being dissolved in the mixed solvent of anhydrous methanol and Glacial acetic acid after 1:10 mixing, heating in water bath, temperature controls at 70 DEG C, under agitation after backflow 8h, rotary evaporation removing methyl alcohol and acetic acid, obtain buff powder;
(3) in step (2) products therefrom, anhydrous methanol and sodium borohydride is added, the mol ratio of the sodium borohydride added and cup [8] aromatic hydrocarbons four hydrazide derivatives is 4:25, temperature controls at 50 DEG C, stirring and refluxing 7h, at room temperature stirring reaction 10h again, first of volatilizing under physical environment alcohol and water, obtains Powdered light yellow raw material;
(4) step (3) is processed the thick product silica gel column chromatography obtained to be separated, then rotary evaporation eluent, obtains powdery product and is cup [8] areneboronic acid derivative.
With the cup prepared [8] areneboronic acid derivative be raw material preparation containing the multi-wall carbon nano-tube composite material of cup [8] areneboronic acid derivative, specifically adopt following methods:
(1) by the nitration mixture of the multi-walled carbon nano-tubes vitriol oil and concentrated nitric acid (volume ratio of the vitriol oil and concentrated nitric acid is 1:3), reflux 6 hours, temperature controls at 80 DEG C, centrifugation decant removes supernatant liquid, is precipitated thing, is using deionized water repetitive scrubbing, it is centrifugal until supernatant liquid pH value is close to neutral, under the condition of 50 DEG C, 12h, dries the carbon nanotube after obtaining acidifying;
(2) in the carbon nanotube after acidifying, thionyl chloride is added, at 80 DEG C, backflow 24h, outstanding steaming removes thionyl chloride, obtains the multi-walled carbon nano-tubes of chloride;
(3) N is utilized, dinethylformamide dissolving cup [8] areneboronic acid derivative, then the multi-walled carbon nano-tubes of chloride is added, the weight ratio of the multi-walled carbon nano-tubes of cup [8] areneboronic acid derivative and chloride is 10:9, at 70 DEG C, reflux 24 hours, obtain dispersed well black particle suspension liquid, unreacted phenylo boric acid is removed successively with tetrahydrofuran (THF), salt solution, second distillation water washing, centrifugation, oven dry obtains black powder product, is the multi-wall carbon nano-tube composite material of cup [8] areneboronic acid derivative.
This matrix material has selective recognition effect to D-Glucose.The multi-wall carbon nano-tube composite material of cup [8] areneboronic acid derivative is dissolved in the middle of ethanol, make decorating liquid, adopt drop-coating, make modified electrode, adopt cyclic voltammetry, obtain the cyclic voltammogram of modified electrode at D-Glucose, can find out from cyclic voltammogram and have obvious redox peak to occur, illustrate that the multi-wall carbon nano-tube composite material of cup [8] areneboronic acid derivative has recognition reaction to D-Glucose.
Claims (9)
1. glass [8] areneboronic acid derivative, is characterized in that, the chemical formula of derivative is C
146h
202o
20n
16b
6, with 2-formylphenylboronic acid for co-ligand, cup [8] aromatic hydrocarbons four hydrazide derivatives is main part, and structural formula is as follows:
2. the preparation method of cup [8] areneboronic acid derivative as claimed in claim 1, is characterized in that, the method adopts following steps:
(1) synthesize cup [8] aromatic hydrocarbons four hydrazide derivatives, obtain white powder;
(2) thick product step (1) obtained and 2-formylphenylboronic acid are in molar ratio for being dissolved in the mixed solvent of anhydrous methanol and Glacial acetic acid after 1:10 mixing, heating in water bath, temperature controls at 60 ~ 70 DEG C, under agitation reflux after 7 ~ 8h, rotary evaporation removing methyl alcohol and acetic acid, obtain buff powder;
(3) in step (2) products therefrom, anhydrous methanol and sodium borohydride is added, temperature controls at 40 ~ 50 DEG C, stirring and refluxing 6 ~ 7h, more at room temperature stirring reaction 10h, first of volatilizing under physical environment alcohol and water, obtains Powdered light yellow raw material;
(4) step (3) is processed the thick product silica gel column chromatography obtained to be separated, then rotary evaporation eluent, obtains powdery product and is cup [8] areneboronic acid derivative.
3. the preparation method of cup [8] areneboronic acid derivative as claimed in claim 2, it is characterized in that, step (1) specifically adopts following steps: in toluene and methanol mixed solvent, add cup [8] tetraacethyl ethyl ester derivative and hydrazine hydrate aqueous solution, the mol ratio of cup [8] tetraacethyl ethyl ester derivative and hydrazine hydrate is 1:34, stirring and refluxing 12h, decompression steams solvent, and the white powder obtained after drying is cup [8] aromatic hydrocarbons four hydrazide derivatives.
4. the preparation method of cup [8] areneboronic acid derivative as claimed in claim 2, it is characterized in that, the mol ratio of the sodium borohydride added in step (3) and cup [8] aromatic hydrocarbons four hydrazide derivatives is 4:25.
5. containing, for example the multi-wall carbon nano-tube composite material of cup according to claim 1 [8] areneboronic acid derivative, it is characterized in that, this matrix material adopts following methods to prepare:
(1) by the nitration mixture of the multi-walled carbon nano-tubes vitriol oil and concentrated nitric acid, reflux 6 hours, temperature controls at 80 DEG C, centrifugation decant removes supernatant liquid, is precipitated thing, is using deionized water repetitive scrubbing, it is centrifugal until supernatant liquid pH value is close to neutral, under the condition of 50 DEG C, 12h, dries the carbon nanotube after obtaining acidifying;
(2) in the carbon nanotube after acidifying, thionyl chloride is added, at 80 DEG C, backflow 24h, outstanding steaming removes thionyl chloride, obtains the multi-walled carbon nano-tubes of chloride;
(3) N is utilized, dinethylformamide dissolving cup [8] areneboronic acid derivative, then the multi-walled carbon nano-tubes of chloride is added, at 60-70 DEG C, reflux 24 hours, obtain dispersed well black particle suspension liquid, unreacted phenylo boric acid is removed successively with tetrahydrofuran (THF), salt solution, second distillation water washing, centrifugation, dries and obtains black powder product, be the multi-wall carbon nano-tube composite material of cup [8] areneboronic acid derivative.
6. the multi-wall carbon nano-tube composite material containing cup [8] areneboronic acid derivative as claimed in claim 5, is characterized in that, in step (1), the volume ratio of the vitriol oil and concentrated nitric acid is 1:3.
7. the multi-wall carbon nano-tube composite material containing cup [8] areneboronic acid derivative as claimed in claim 5, it is characterized in that, the weight ratio of described cup [8] areneboronic acid derivative and the multi-walled carbon nano-tubes of chloride is 10:9.
8. the application of the multi-wall carbon nano-tube composite material containing cup [8] areneboronic acid derivative as claimed in claim 5, it is characterized in that, this matrix material has selective recognition effect to D-Glucose.
9. the application of the multi-wall carbon nano-tube composite material containing cup [8] areneboronic acid derivative as claimed in claim 8, it is characterized in that, the multi-wall carbon nano-tube composite material of cup [8] areneboronic acid derivative is dissolved in ethanol and makes decorating liquid, adopt drop-coating, make modified electrode, adopt cyclic voltammetry, obtain the cyclic voltammogram of modified electrode at D-Glucose, can find out from cyclic voltammogram and have obvious redox peak to occur, illustrate that the multi-wall carbon nano-tube composite material of cup [8] areneboronic acid derivative has recognition reaction to D-Glucose.
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| CN113820378A (en) * | 2021-10-29 | 2021-12-21 | 重庆医科大学 | GNFs/CC (GNFs/CC) and glucose sensor and application thereof |
| CN113820378B (en) * | 2021-10-29 | 2023-06-16 | 重庆医科大学 | GNFs/CC, glucose sensor and application thereof |
| CN117816249A (en) * | 2024-03-04 | 2024-04-05 | 潍坊职业学院 | Lindqvist molybdenum polyacid-calix [4] arene inorganic-organic hybrid complex, and preparation method and application thereof |
| CN117816249B (en) * | 2024-03-04 | 2024-05-28 | 潍坊职业学院 | LINDQVIST type molybdenum polyacid-calix [4] arene inorganic-organic hybrid complex, and preparation method and application thereof |
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