CN113930237A - 一种改性g-C3N4@MOF荧光复合材料及其制法和应用 - Google Patents
一种改性g-C3N4@MOF荧光复合材料及其制法和应用 Download PDFInfo
- Publication number
- CN113930237A CN113930237A CN202111267186.3A CN202111267186A CN113930237A CN 113930237 A CN113930237 A CN 113930237A CN 202111267186 A CN202111267186 A CN 202111267186A CN 113930237 A CN113930237 A CN 113930237A
- Authority
- CN
- China
- Prior art keywords
- mof
- composite material
- modified
- fluorescence
- fluorescent composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000001514 detection method Methods 0.000 claims abstract description 32
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 29
- 229940088710 antibiotic agent Drugs 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 6
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000013110 organic ligand Substances 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 230000003115 biocidal effect Effects 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 16
- 239000012452 mother liquor Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 230000005284 excitation Effects 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 238000001917 fluorescence detection Methods 0.000 claims description 5
- 229940124530 sulfonamide Drugs 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000004098 Tetracycline Substances 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 150000007660 quinolones Chemical class 0.000 claims description 4
- 150000003456 sulfonamides Chemical class 0.000 claims description 4
- 235000019364 tetracycline Nutrition 0.000 claims description 4
- 150000003522 tetracyclines Chemical class 0.000 claims description 4
- 229940040944 tetracyclines Drugs 0.000 claims description 4
- 229940126575 aminoglycoside Drugs 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000012984 antibiotic solution Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- PZKFSRWSQOQYNR-UHFFFAOYSA-N 5-methyl-1h-1,2,4-triazole Chemical compound CC1=NC=NN1 PZKFSRWSQOQYNR-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 238000011534 incubation Methods 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 238000009395 breeding Methods 0.000 abstract description 4
- 230000001488 breeding effect Effects 0.000 abstract description 4
- 244000144972 livestock Species 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 235000013305 food Nutrition 0.000 abstract description 3
- 238000011895 specific detection Methods 0.000 abstract description 3
- 239000003550 marker Substances 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- GTXSTEDIVHHJQL-UHFFFAOYSA-N 2-[[3-methyl-2-(phenylmethoxycarbonylamino)pentanoyl]amino]-4-methylsulfanylbutanoic acid Chemical compound CSCCC(C(O)=O)NC(=O)C(C(C)CC)NC(=O)OCC1=CC=CC=C1 GTXSTEDIVHHJQL-UHFFFAOYSA-N 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000007853 buffer solution Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 229960000973 sulfadimethoxine Drugs 0.000 description 5
- ZZORFUFYDOWNEF-UHFFFAOYSA-N sulfadimethoxine Chemical compound COC1=NC(OC)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ZZORFUFYDOWNEF-UHFFFAOYSA-N 0.000 description 5
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 239000007850 fluorescent dye Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- RDEIXVOBVLKYNT-VQBXQJRRSA-N (2r,3r,4r,5r)-2-[(1s,2s,3r,4s,6r)-4,6-diamino-3-[(2r,3r,6s)-3-amino-6-(1-aminoethyl)oxan-2-yl]oxy-2-hydroxycyclohexyl]oxy-5-methyl-4-(methylamino)oxane-3,5-diol;(2r,3r,4r,5r)-2-[(1s,2s,3r,4s,6r)-4,6-diamino-3-[(2r,3r,6s)-3-amino-6-(aminomethyl)oxan-2-yl]o Chemical compound OS(O)(=O)=O.O1C[C@@](O)(C)[C@H](NC)[C@@H](O)[C@H]1O[C@@H]1[C@@H](O)[C@H](O[C@@H]2[C@@H](CC[C@@H](CN)O2)N)[C@@H](N)C[C@H]1N.O1C[C@@](O)(C)[C@H](NC)[C@@H](O)[C@H]1O[C@@H]1[C@@H](O)[C@H](O[C@@H]2[C@@H](CC[C@H](O2)C(C)N)N)[C@@H](N)C[C@H]1N.O1[C@H](C(C)NC)CC[C@@H](N)[C@H]1O[C@H]1[C@H](O)[C@@H](O[C@@H]2[C@@H]([C@@H](NC)[C@@](C)(O)CO2)O)[C@H](N)C[C@@H]1N RDEIXVOBVLKYNT-VQBXQJRRSA-N 0.000 description 1
- 208000004429 Bacillary Dysentery Diseases 0.000 description 1
- 206010007882 Cellulitis Diseases 0.000 description 1
- 208000004232 Enteritis Diseases 0.000 description 1
- 206010017915 Gastroenteritis shigella Diseases 0.000 description 1
- 208000033809 Suppuration Diseases 0.000 description 1
- 206010070863 Toxicity to various agents Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 231100000570 acute poisoning Toxicity 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 229940124350 antibacterial drug Drugs 0.000 description 1
- FCPVYOBCFFNJFS-LQDWTQKMSA-M benzylpenicillin sodium Chemical compound [Na+].N([C@H]1[C@H]2SC([C@@H](N2C1=O)C([O-])=O)(C)C)C(=O)CC1=CC=CC=C1 FCPVYOBCFFNJFS-LQDWTQKMSA-M 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 1
- 229960005091 chloramphenicol Drugs 0.000 description 1
- WIIZWVCIJKGZOK-RKDXNWHRSA-N chloramphenicol Chemical compound ClC(Cl)C(=O)N[C@H](CO)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 WIIZWVCIJKGZOK-RKDXNWHRSA-N 0.000 description 1
- 231100000739 chronic poisoning Toxicity 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- POUMFISTNHIPTI-BOMBIWCESA-N hydron;(2s,4r)-n-[(1r,2r)-2-hydroxy-1-[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-methylsulfanyloxan-2-yl]propyl]-1-methyl-4-propylpyrrolidine-2-carboxamide;chloride Chemical compound Cl.CN1C[C@H](CCC)C[C@H]1C(=O)N[C@H]([C@@H](C)O)[C@@H]1[C@H](O)[C@H](O)[C@@H](O)[C@@H](SC)O1 POUMFISTNHIPTI-BOMBIWCESA-N 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000003907 kidney function Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229960001595 lincomycin hydrochloride Drugs 0.000 description 1
- -1 lincosamines Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- GWKKVWOEQGDUSY-UHFFFAOYSA-N pyridine;sodium Chemical compound [Na].C1=CC=NC=C1 GWKKVWOEQGDUSY-UHFFFAOYSA-N 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 201000005113 shigellosis Diseases 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
- 229960004306 sulfadiazine Drugs 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 230000009747 swallowing Effects 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- GJWMYLFHBXEWNZ-UHFFFAOYSA-N tert-butyl (4-ethenylphenyl) carbonate Chemical compound CC(C)(C)OC(=O)OC1=CC=C(C=C)C=C1 GJWMYLFHBXEWNZ-UHFFFAOYSA-N 0.000 description 1
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 1
- 229960000707 tobramycin Drugs 0.000 description 1
- NLVFBUXFDBBNBW-PBSUHMDJSA-N tobramycin Chemical compound N[C@@H]1C[C@H](O)[C@@H](CN)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O[C@@H]2[C@@H]([C@@H](N)[C@H](O)[C@@H](CO)O2)O)[C@H](N)C[C@@H]1N NLVFBUXFDBBNBW-PBSUHMDJSA-N 0.000 description 1
- 206010044008 tonsillitis Diseases 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 208000019206 urinary tract infection Diseases 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/0883—Arsenides; Nitrides; Phosphides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Polymers & Plastics (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Inorganic Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Optics & Photonics (AREA)
- Molecular Biology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
本发明公开了一种改性g‑C3N4@MOF荧光复合材料及其制备方法和应用,改性g‑C3N4@MOF为g‑C3N4‑O@MOF,是将氧掺杂的石墨相氮化碳g‑C3N4‑O与金属中心离子和有机配体原位合成的g‑C3N4‑O@MOF荧光复合材料。本发明的基于改性g‑C3N4@MOF荧光复合材料构建的荧光传感器,无需任何化学标记和荧光染料的添加,操作简便,灵敏度、可重复性以及稳定性都很高,可在复杂样品中实现特异性检测,具有良好的经济实用价值,有望应用于医疗、环境、食品及畜牧养殖业中抗生素的检测。
Description
技术领域
本发明涉及荧光复合材料及其制备方法和应用,具体涉及改性g-C3N4@MOF荧光复合材料的制备方法以及用以检测抗生素的应用。
背景技术
石墨相氮化碳(g-C3N4)具有优异的物理结构、低毒性和发光特性,广泛用于传感、生物成像和光催化领域。然而,其发光特性在溶液中存在水性光致发光量子产率差、易聚集和团聚的缺陷,此外g-C3N4的水稳定性、分散性和光物理性质在很大程度上取决于它们的表面状态和环境。因此为了更好的提高g-C3N4的应用性,可复合其他材料弥补缺陷。
金属-有机骨架化合物是指无机金属中心与有机官能团通过共价键或离子共价键相互连接,共同构筑的具有规则或者孔穴结构的晶态多孔材料。其中含氮类配体与金属离子所形成的的骨架结构稳定性较高,能够减少材料的团聚。
每年约有大量抗生素用于饲料添加剂,75%的抗生素不被动物机体吸收而随动物粪便排出,导致畜禽养殖废水成为自然界水体环境中抗生素污染的主要来源。抗生素残留对人体健康有着十分严重的危害,包括“三致”(致癌、致畸、致突变)作用、人体对此类药物的长期暴露,通常不会造成急性中毒,而主要是引起慢性中毒。抗生素污染已被视为一类新型的重要的水体污染物而成为国际研究的前沿课题。
磺胺类药物为人工合成的抗菌药,用于临床已近50年,它具有抗菌谱较广、性质稳定、使用简便、生产时不耗用粮食等优点。磺胺间二甲氧嘧啶,常温下为一种白色或类白色结晶或结晶形粉末,几乎无味。不溶于水、氯仿,微溶于乙醇,可溶于丙酮,易溶于稀无机酸和强碱溶液。遇光易变质,色渐变深。磺胺间二甲氧嘧啶是一种长效磺胺原药,其抗菌谱与磺胺嘧啶相似,但抗菌作用较强,适用于菌痢、肠炎、扁桃体炎、泌尿道感染、蜂窝织炎、皮肤化脓感染等疾病,吸入粉尘,皮肤接触和不慎吞咽有害。对眼睛、呼吸道和皮肤有刺激作用。长期服用容易损伤肾功能及神经系统,磺胺药中毒。
目前对抗生素的检测常用的有仪器检测和试剂盒检测,前者检测步骤繁琐,成本过高,耗时长,后者检测灵敏度低,易受环境因素干扰。
发明内容
发明目的:本发明的目的在于提供一种改性g-C3N4@MOF荧光复合材料,该材料灵敏度高、稳定性好,可重复利用,且该荧光复合材料可作为荧光传感器检测抗生素的浓度。本发明另一个目的是提供了所述荧光复合材料的制备方法。本发明还有一个目的是提供了所述荧光复合材料在检测抗生素中的应用。
技术方案:本发明所述的改性g-C3N4@MOF荧光复合材料,改性g-C3N4@MOF为g-C3N4-O@MOF,是将氧掺杂的石墨相氮化碳g-C3N4-O与金属中心离子和有机配体原位合成的g-C3N4-O@MOF荧光复合材料。
所述的改性g-C3N4@MOF荧光复合材料,氧掺杂的石墨相氮化碳g-C3N4-O是将氮化碳高温处理或酸剥离所得。
所述的改性g-C3N4@MOF荧光复合材料,所述的MOF材料为MAF-7。
所述的改性g-C3N4@MOF荧光复合材料的制备方法,包括如下步骤:
(1)将草酸和尿素溶于水中,搅拌混合均匀并搅拌蒸干,蒸干得到的粉末高温处理,待降至室温后取出,水洗烘干得到粉末为g-C3N4-O;将g-C3N4-O粉末中加入浓酸,混合均匀,加热反应使瓶内悬浊液逐渐转变为溶胶,将反应得到溶胶加入水中,并加入氯化铵,搅拌后,离心后取上清液得到g-C3N4-O溶液,与去离子水按比例配置为母液A;或,将草酸和尿素烧制氮化碳块状材料,通过酸剥离得到对应的g-C3N4-O溶液为母液A;
(2)将Zn (NO3)2·6H2O水溶液和3-甲基-1H-1,2,4-三氮唑Hmtz溶解在母液A中,与NH3·H2O混合,离心、洗涤得到g-C3N4@MOF荧光复合材料。
所述的改性g-C3N4@MOF荧光复合材料的制备方法,步骤(1)所述高温处理是将蒸干得到的粉末升温至300-700℃并保持1-7h。
所述的改性g-C3N4@MOF荧光复合材料的制备方法,步骤(1)所述g-C3N4-O溶液与去离子水按体积比1∶1-1∶99混合;步骤(2)中Zn(NO3)2·6H2O水溶液与Hmtz浓度比按1∶1-1∶99混合。
所述的改性g-C3N4@MOF荧光复合材料在检测抗生素中的应用。
荧光传感器,包含所述改性g-C3N4@MOF荧光复合材料。
利用所述的荧光传感器的检测方法,将改性g-C3N4@MOF荧光复合材料作为荧光传感器,加入抗生素溶液,在室温下孵育,然后转移至四通比色皿中,测定荧光强度。
所述的荧光传感器的检测方法,所述抗生素包括氨基糖苷类、酰胺醇类、磺胺类、喹诺酮类、四环素类中的一种或者多种。
所述的荧光传感器的检测方法,所述测定荧光强度的检测条件为:在320-480nm范围内进行荧光检测,激发波长为240-270nm。
所述的荧光传感器的检测方法,具体包括如下步骤:
(a)构建荧光传感器:将剥离的g-C3N4-O溶液溶液与去离子水按1∶1-1∶99的体积比混合,加入PBS缓冲液,室温孵育构建荧光传感器或者传感体系;
(b)向传感体系中加入不同体积或不同浓度的的抗生素溶液,在室温下孵育时间范围在30min以内;
(c)转移至四通比色皿中,测每个样品的荧光强度。
上述步骤(b)所述加入不同种类抗生素溶液,具体为设置了多种类型抗生素,分类出与g-C3N4-O无明显荧光响应效果的抗生素、有效淬灭g-C3N4-O荧光强度的抗生素以及有效进一步增强量子点荧光强度的抗生素三大类。之后再设置多个体积不同的实验,其范围为0.1uL~100uL,探索三大类抗生素浓度各自与荧光强度的关系。上述步骤(c)具体为:将样品在激发波长为255nm,测定375nm处的荧光值。
本发明将g-C3N4-O与MAF-7复合后具有优异的光学性能,并对抗生素表现出特异性响应,不同的抗生素可产生不同的荧光增强或淬灭效果,利用加入抗生素前后体系荧光信号的变化,实现对目标物的定性定量检测。
本发明对g-C3N4改性得到氧掺杂的g-C3N4(g-C3N4-O),并由g-C3N4-O作为前驱体参与MAF-7的合成。MAF-7的给电子效应显著提高了作为发光中心的g-C3N4-O的π结构上的电子密度,此外MAF-7的刚性结构有效地抑制了聚集和非辐射能量耗散。作为荧光探针,由此增大的表面积和电子密度有利于g-C3N4-O通过π-π相互作用非共价连接抗生素,其荧光强度可以被抗生素选择性淬灭或增强。
加入抗生素前后的荧光差距明显,且抗生素浓度与荧光强度之间具有一定的关系,进而可对目标物进行定量分析,同时由此提供了一种高灵敏度的抗生素检测新方法。能够克服现有分析检测方法灵敏度低,检测耗时,成本过高以及步骤繁琐的缺陷。
原理:本发明首先通过制备具有优异光学性能的氧掺石墨相氮化碳,作为前驱体参与MAF-7的合成,最终合成g-C3N4@MOF荧光复合材料,该复合材料作为传感的平台,未加入目标物时,g-C3N4-O在MAF-7的增强效果下,荧光强度高,加入目标物后,g-C3N4-O和目标物相互作用,其荧光被淬灭或者增强,通过这种信号淬灭或者增强变化来实现对目标物的特异性检测。
本发明基于改性g-C3N4@MOF荧光复合材料构建的传感器是一种信号衰减或者增强性型的荧光传感器,传感器可以实现信号转换,可以有效利用加入目标物前后的荧光信号变化,由此这种信号衰减或者增强模式的传感器用于检测抗生素。
本发明通过调节氧掺石墨相氮化碳的堆叠结构获得具有优异光学性能的氧掺氮化碳材料,作为前驱体参与MAF-7的合成,所得复合材料的光学性能较之氧掺氮化碳有明显的的提高。MAF-7的给电子效应显著提高了作为发光中心的氧掺石墨相氮化碳的π结构上的电子密度,此外MAF-7的刚性结构有效地抑制了聚集和非辐射能量耗散。作为荧光探针,由此增大的比表面积和电子密度有利于氧掺石墨相氮化碳通过π-π相互作用非共价连接抗生素,其荧光强度可以被抗生素选择性淬灭或增强。
有益效果:与现有技术相比,本发明具有如下优点:(1)本发明的荧光性能得到有效增强。(2)将该改性g-C3N4@MOF荧光复合材料应用于构建简单、快速、灵敏的荧光传感器,能够快速检测磺胺类、氨基糖苷类、酰胺醇类、喹诺酮类、林可胺类、四环素类等多种抗生素,为今后抗生素的监管提供了方便。(3)荧光传感器无需任何化学标记和荧光染料的添加,操作简便,灵敏度、可重复性以及稳定性都很高,可在复杂样品中实现特异性检测,具有良好的经济实用价值,有望应用于医疗、环境、食品及畜牧养殖业中抗生素的检测。(4)g-C3N4@MOF荧光复合材料制备成本低,作为荧光传感器检测污染物不需使用大型精密仪器以及对样品的额外处理,方法简便,灵敏度高,在食品领域该检测方法能够有效的对日常食用产品进行快速检测,在环境领域则能短时间内检测出水样和土壤中的微量抗生素残留物质,另外在医疗及畜牧养殖业中也有着广泛的应用,是一种在复杂样品中能够保持稳定性和可重复性的高效检测方法。
附图说明
图1是本发明合成的氧掺石墨相氮化碳纳米材料透射电镜图;
图2是本发明合成的g-C3N4-O@MOF荧光复合材料扫描电镜图;
图3是g-C3N4-O@MOF荧光复合材料光子发射和吸收图;
图4是g-C3N4-O和g-C3N4-O@MOF荧光复合材料的荧光强度对比图;
图5是本发明基于g-C3N4-O@MOF荧光复合材料构建的荧光传感器在长时间持续检测中得到的稳定荧光数值图(荧光强度不随时间变化的稳定数值图);
图6是g-C3N4-O@MOF荧光复合材料构建的检测抗生素体系,荧光强度随不同浓度抗生素变化的荧光光谱图。
具体实施方式
实施例中所述实验方法,如无特殊说明,均为常规方法;所述试剂和材料,如无特殊说明,均可从商业途径获得。
材料/试剂:各种类抗生素购买于麦克林试剂公司、生工试剂公司和阿拉丁试剂公司。
各缓冲液配方:
10×PBS(pH值7.4):80mMNa2HPO4,20mMKH2PO4,1370mM NaCl,27mM KCl
20×SSC(pH值7.0):300mM Sodium Citrate,3M NaCl
4×Tris-HCl(pH值6.8):500mM Tris-HCl
20×TBS(pH值7.4):500mM Tris-HCl,2800mM NaCl,60mM KCl
20×TBSM(pH值7.4):500mM Tris-HCl,2800mM NaCl,60mM KCl,40mM MgCl2
实施例1
(1)制备g-C3N4-O溶液:称取5g草酸和13g尿素混合放置烧杯中,加入25mL去离子水,搅拌均匀后在60℃恒温水浴下继续搅拌,待有结晶析出后将温度调至70℃搅拌直至蒸干。蒸干得到的粉末放入陶瓷坩埚中升温至550℃并保持300min。待降至室温后取出,水洗烘干得到g-C3N4-O粉末。
称取0.6g的g-C3N4-O粉末放于圆底烧瓶中,然后向其中加入7mL 98%硫酸,混合均匀,85℃并900rpm磁力搅拌1h,将反应得到溶胶加85mL水中,并加入8g氯化铵,搅拌2h,离心后取上清液得到g-C3N4-O溶液。
(2)制备实验体系所需g-C3N4-O母液A:按照g-C3N4-O溶液与去离子水体积比为1:49配置成后续实验所用的g-C3N4-O母液A。
(3)制备复合材料:12mM Zn(NO3)2·6H2O水溶液和12mM Hmtz溶解在50mL母液A中,与1mL 10%NH3·H2O混合2h,8000rpm离心15min后,收集沉淀物,超纯水洗涤数次。将所得产物重新分散在80mL去离子水中为g-C3N4-O@M7母液B,储存在暗处以备后续实验使用。
(4)在74uL去离子水中依次加入2uL pH值为8.0的10×PBS缓冲液、20uL母液B并混合均匀,构成传感体系。向传感体系中加入浓度为1mM抗生素溶液4μL,在室温下孵育时间范围在5min~30min。
(5)将溶液转移至四通比色皿中,加入目标物后通过荧光光谱检测界面对信号进行记录。
实施例2
石墨相氮化碳经过氧掺改性后具有了较好的光学性能,而当与MAF-7复合后,光学性能进一步提高,现以不同氧掺比例为自变量,探索与MAF-7复合的最优氧掺比例。
方法:将草酸和尿素按不同质量比0∶24、2.4∶24、4.8∶24、10.8∶24烧制氮化碳块状材料,通过酸剥离得到对应的0%g-C3N4-O、10%g-C3N4-O、20%g-C3N4-O和45%g-C3N4-O,同实施例1中的步骤,将上述不同比例的氧掺氮化碳作为前驱体与金属中心和有机配体结合得到相应复合材料:0%g-C3N4-O@M7、10%g-C3N4-O@M7、20%g-C3N4-O@M7和45%g-C3N4-O@M7,利用瞬态荧光测量不同氧掺比例复合材料的绝对荧光量子产率。
结果:根据图3所示的发射光子数和吸收光子数,测得氧掺比例为10%的氮化碳材料与MAF-7复合后有最高的绝对量子产率。
实施例3
本发明中的g-C3N4-O@M7复合材料以荧光分光光度计的实际测量后,确定激发波长为255nm,发射光谱的范围为320-480nm。
本发明中不同种类抗生素对g-C3N4-O@M7复合材料的荧光响应效果各不相同,一部分种类抗生素如磺胺类、喹诺酮类能够有效淬灭g-C3N4-O@M7复合材料的荧光强度,一部分种类抗生素如氨基糖苷类能够有效增强g-C3N4-O@M7复合材料的荧光强度,酰胺醇类和四环素类也对g-C3N4-O@M7复合材料的荧光响应有影响。
以下以磺胺二甲氧嘧啶钠盐溶液,为信号衰减模式测定本发明的荧光传感器的各个性能:
抗生素检测方法:
配制混合液1:在0.5mL离心管中依次加入78uL去离子水、2μL pH值为7.0的10×PBS缓冲液、20uL的实施例1的g-C3N4-O@M7母液B混合均匀,室温孵育30min。
配制混合液2:在0.5mL离心管中依次加入74uL去离子水、2μL pH值为7.00的10×PBS缓冲液、20uL的实施例1的g-C3N4-O@M7母液B、4uL浓度梯度为1-150mM的磺胺二甲氧嘧啶钠盐水溶液混合均匀,室温孵育30min。
荧光检测结果:利用荧光分光光度计测定在激发波长为255nm,发射波长范围在320-480nm内测定混合液1和2的荧光强度,如图6所示,能够看出在375nm处有最大发射峰,且仅存在g-C3N4-O@M7时荧光强度很高,说明制备的g-C3N4-O@M7复合材料荧光性能优异,而在发射波长范围内加入目标物磺胺二甲氧嘧啶钠盐溶液的混合液2荧光强度明显比未加目标物的混合液1要低,说明目标物磺胺二甲氧嘧啶钠盐溶液可以有效淬灭g-C3N4-O@M7的荧光,同时随着抗生素浓度的增加(0-150μM)荧光强度逐渐降低,实现本发明制备的荧光传感器的抗生素检测。
检测稳定性:
利用荧光分光光度计测量混合液1在连续一小时的荧光强度,激发波长选定255nm处,发射波长选定375nm,光电倍增管电压为600V,激发狭缝和发射狭缝宽度为10nm,扫描速度为2000nm min-1。
结果如图5所示,荧光强度在一个小时的连续测量时间内浮动不大,说明制备的g-C3N4-O@M7复合材料荧光性能稳定,所构造的荧光传感器稳定性高,同时也保证了后续实验的可重复性。
检测特异性:
取7个0.5ml离心管,每个离心管中依次加入74uL去离子水、2μL pH值为7.00的10×PBS缓冲液、20uL g-C3N4-O@M7母液B后,再分别向7个离心管中加入4uL浓度为1mM的盐酸林可霉素、青霉素G钠盐、硫酸庆大霉素、盐酸四环素、妥布霉素、氯霉素和磺胺二甲氧嘧啶钠盐的水溶液,混合均匀,室温孵育30min。
荧光检测结果:利用荧光分光光度计测定在激发波长为255nm,发射波长范围在350-450nm内测定样品荧光强度,在众多抗生素中只有磺胺二甲氧嘧啶钠盐可以明显淬灭g-C3N4-O@M7的荧光强度,说明本发明所构造的荧光传感器具有良好的选择性,具有在复杂水样中特异性检测磺胺二甲氧嘧啶抗生素的潜力。
磺胺二甲氧嘧啶定量检测:
在0.5mL离心管中依次加入74uL去离子水、2μL pH值为7.0的10×PBS缓冲液、20uLg-C3N4-O@M7母液B后再分别加入4uL浓度为0.1mM、1mM、5mM、10mM、50mM、150mM磺胺二甲氧嘧啶钠盐水溶液混合均匀,室温孵育30min。
荧光检测结果:利用荧光分光光度计测定在激发波长为255nm,发射波长范围在320-450nm内测定样品荧光强度,随着磺胺二甲氧嘧啶钠盐溶液浓度的不断增加,荧光强度不断降低,如图6所示,说明通过该荧光传感器可以对磺胺二甲氧嘧啶进行定量检测,检测范围较宽,灵敏度高,检测限低。
Claims (10)
1.一种改性g-C3N4@MOF荧光复合材料,其特征在于,改性g-C3N4@MOF为g-C3N4-O@MOF,是将氧掺杂的石墨相氮化碳g-C3N4-O与金属中心离子和有机配体原位合成的g-C3N4-O@MOF荧光复合材料。
2.根据权利要求1所述的改性g-C3N4@MOF荧光复合材料,其特征在于,所述的MOF材料为MAF-7。
3.一种权利要求1所述的改性g-C3N4@MOF荧光复合材料的制备方法,其特征在于,包括如下步骤:
(1)将草酸和尿素溶于水中,搅拌混合均匀并搅拌蒸干,蒸干得到的粉末高温处理,待降至室温后取出,水洗烘干得到粉末为g-C3N4-O;将g-C3N4-O粉末中加入浓酸,混合均匀,加热反应使瓶内悬浊液逐渐转变为溶胶,将反应得到溶胶加入水中,并加入氯化铵,搅拌后,离心后取上清液得到g-C3N4-O溶液,与去离子水按比例配置为母液A;或,将草酸和尿素烧制氮化碳块状材料,通过酸剥离得到对应的g-C3N4-O溶液为母液A;
(2)将Zn(NO3)2·6H2O水溶液和3-甲基-1H-1,2,4-三氮唑Hmtz溶解在母液A中,与NH3·H2O混合,离心、洗涤得到g-C3N4@MOF荧光复合材料。
4.根据权利要求3所述的改性g-C3N4@MOF荧光复合材料的制备方法,其特征在于,步骤(1)所述高温处理是将蒸干得到的粉末升温至300-700℃并保持1-7h。
5.根据权利要求3所述的改性g-C3N4@MOF荧光复合材料的制备方法,其特征在于,步骤(1)所述g-C3N4-O溶液与去离子水按体积比1∶1-1∶99混合;步骤(2)中Zn(NO3)2·6H2O水溶液与Hmtz浓度比按1∶1-1∶99混合。
6.一种权利要求1所述的改性g-C3N4@MOF荧光复合材料在检测抗生素中的应用。
7.一种荧光传感器,其特征在于,包含权利要求1所述改性g-C3N4@MOF荧光复合材料。
8.一种利用权利要求7所述的荧光传感器的检测方法,其特征在于,将改性g-C3N4@MOF荧光复合材料作为荧光传感器,加入抗生素溶液,在室温下孵育,然后转移至四通比色皿中,测定荧光强度。
9.根据权利要求8所述的荧光传感器的检测方法,其特征在于,所述抗生素包括氨基糖苷类、酰胺醇类、磺胺类、喹诺酮类、四环素类中的一种或者多种。
10.根据权利要求8所述的荧光传感器的检测方法,其特征在于,所述测定荧光强度的检测条件为:在320-480nm范围内进行荧光检测,激发波长为240-270nm。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111267186.3A CN113930237B (zh) | 2021-10-28 | 2021-10-28 | 一种改性g-C3N4@MOF荧光复合材料及其制法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111267186.3A CN113930237B (zh) | 2021-10-28 | 2021-10-28 | 一种改性g-C3N4@MOF荧光复合材料及其制法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113930237A true CN113930237A (zh) | 2022-01-14 |
CN113930237B CN113930237B (zh) | 2023-07-21 |
Family
ID=79284792
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111267186.3A Active CN113930237B (zh) | 2021-10-28 | 2021-10-28 | 一种改性g-C3N4@MOF荧光复合材料及其制法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113930237B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116554149A (zh) * | 2023-03-27 | 2023-08-08 | 岭南师范学院 | 一种有机金属化合物m-pyta-taa及其制备方法与应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104722335A (zh) * | 2015-01-30 | 2015-06-24 | 湖南大学 | 石墨型氮化碳-金属有机框架复合光催化剂及其制备方法和应用 |
CN105903439A (zh) * | 2016-04-26 | 2016-08-31 | 福州大学 | 三维层状石墨相碳化氮/mof复合材料及其制备方法 |
CN107576714A (zh) * | 2017-09-05 | 2018-01-12 | 济南大学 | 一种石墨相氮化碳@mof纳米晶体的制备方法和应用 |
CN112014365A (zh) * | 2020-08-07 | 2020-12-01 | 南京师范大学 | 一种基于功能纳米材料的荧光传感器及其制备方法和应用 |
-
2021
- 2021-10-28 CN CN202111267186.3A patent/CN113930237B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104722335A (zh) * | 2015-01-30 | 2015-06-24 | 湖南大学 | 石墨型氮化碳-金属有机框架复合光催化剂及其制备方法和应用 |
CN105903439A (zh) * | 2016-04-26 | 2016-08-31 | 福州大学 | 三维层状石墨相碳化氮/mof复合材料及其制备方法 |
CN107576714A (zh) * | 2017-09-05 | 2018-01-12 | 济南大学 | 一种石墨相氮化碳@mof纳米晶体的制备方法和应用 |
CN112014365A (zh) * | 2020-08-07 | 2020-12-01 | 南京师范大学 | 一种基于功能纳米材料的荧光传感器及其制备方法和应用 |
Non-Patent Citations (2)
Title |
---|
汤雨林;游少鸿;兰华春;张学洪;安晓强;: "氧掺杂g-C_3N_4光催化降解Cu-EDTA络合物的反应机理研究", 环境科学学报 * |
蒋晓华;胡水生;丁文捷;: "基于MOFs复合材料构建的生物传感器在凝血酶检测中的应用", 闽江学院学报 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116554149A (zh) * | 2023-03-27 | 2023-08-08 | 岭南师范学院 | 一种有机金属化合物m-pyta-taa及其制备方法与应用 |
CN116554149B (zh) * | 2023-03-27 | 2024-06-11 | 岭南师范学院 | 一种有机金属化合物m-pyta-taa及其制备方法与应用 |
Also Published As
Publication number | Publication date |
---|---|
CN113930237B (zh) | 2023-07-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109762558B (zh) | 一种用于定量检测尿液中PPi含量的比率型荧光探针的制备方法 | |
CN109490269B (zh) | 双发射比色荧光纳米微球制备方法及其细菌检测的应用 | |
CN112014365B (zh) | 一种基于功能纳米材料的荧光传感器及其制备方法和应用 | |
Guo et al. | Facile synthesis of highly efficient fluorescent carbon dots for tetracycline detection | |
Liang et al. | Hydrothermal growth of nitrogen-rich carbon dots as a precise multifunctional probe for both Fe3+ detection and cellular bio-imaging | |
Lin et al. | Role of novel silicon nanoparticles in luminescence detection of a family of antibiotics | |
CN110128674B (zh) | 一种用于荧光检测磺胺类抗生素的、水稳定的稀土金属有机框架材料及其制备方法 | |
Deng et al. | Preparation of N/S doped carbon dots and their application in nitrite detection | |
CN109303923B (zh) | 一种制备类羟基磷灰石成分的纳米簇凝胶的方法 | |
CN111715890A (zh) | 一种聚乙烯吡咯烷酮-铜纳米团簇的制备方法、产品及应用 | |
Yan et al. | Two birds with one stone: Ratiometric sensing platform overcoming cross-interference for multiple-scenario detection and accurate discrimination of tetracycline analogs | |
CN113930237B (zh) | 一种改性g-C3N4@MOF荧光复合材料及其制法和应用 | |
CN115308169A (zh) | 一种基于硫量子点和铜纳米簇的比率型荧光探针及其应用 | |
CN112175605A (zh) | 一种近红外荧光磁性Fe NCs双模探针及其合成方法与应用 | |
CN108426867B (zh) | 在水中检测Fe3+和抗生素头孢曲松钠的MOF-Cd探针及其制备方法和应用 | |
CN108680547B (zh) | 铜纳米簇作为荧光探针特异性检测溶液中利福平药物含量方面的应用 | |
CN112705195B (zh) | 一种降解和测定四环素的功能材料及制备方法和应用 | |
CN107817230B (zh) | 基于石墨烯量子点与铕离子复合体系的四环素类抗生素检测方法 | |
CN111363542B (zh) | 一种全色荧光CaF2和利用CaF2制备的糠醛类分子印迹比率荧光传感器及其制备方法 | |
CN111715891A (zh) | 一种铜纳米颗粒溶液及其制备方法和应用 | |
CN108866157B (zh) | 基于链置换和暗态银簇的生物传感器及其应用方法 | |
Ao et al. | Coordinate bonding-induced emission of gold-glutathione complex for sensitive detection of aluminum species | |
CN113281315B (zh) | 基于发夹结构dna为模板的铜纳米簇荧光探针快速定量检测溶液中链霉素的方法 | |
CN114609112B (zh) | 一种简单快速检测美他环素和/或强力霉素的方法 | |
CN110132911B (zh) | 基于复合物比率荧光探针的水样中总磷检测方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |