CN108484583A - 一种比色法检测水中Cu2+和Ni2+探针的合成与应用 - Google Patents
一种比色法检测水中Cu2+和Ni2+探针的合成与应用 Download PDFInfo
- Publication number
- CN108484583A CN108484583A CN201810275247.2A CN201810275247A CN108484583A CN 108484583 A CN108484583 A CN 108484583A CN 201810275247 A CN201810275247 A CN 201810275247A CN 108484583 A CN108484583 A CN 108484583A
- Authority
- CN
- China
- Prior art keywords
- probe
- water
- cumarin
- colorimetric determination
- reaction
- 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
- 239000000523 sample Substances 0.000 title claims abstract description 56
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000003068 molecular probe Substances 0.000 claims abstract description 19
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002798 spectrophotometry method Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 23
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- PQMOXTJVIYEOQL-UHFFFAOYSA-N Cumarin Natural products CC(C)=CCC1=C(O)C(C(=O)C(C)CC)=C(O)C2=C1OC(=O)C=C2CCC PQMOXTJVIYEOQL-UHFFFAOYSA-N 0.000 claims description 11
- FSOGIJPGPZWNGO-UHFFFAOYSA-N Meomammein Natural products CCC(C)C(=O)C1=C(O)C(CC=C(C)C)=C(O)C2=C1OC(=O)C=C2CCC FSOGIJPGPZWNGO-UHFFFAOYSA-N 0.000 claims description 11
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 claims description 11
- NNJVILVZKWQKPM-UHFFFAOYSA-N Lidocaine Chemical compound CCN(CC)CC(=O)NC1=C(C)C=CC=C1C NNJVILVZKWQKPM-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- QXAMGWKESXGGNV-UHFFFAOYSA-N 7-(diethylamino)-1-benzopyran-2-one Chemical compound C1=CC(=O)OC2=CC(N(CC)CC)=CC=C21 QXAMGWKESXGGNV-UHFFFAOYSA-N 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000003651 drinking water Substances 0.000 claims description 4
- 235000020188 drinking water Nutrition 0.000 claims description 4
- DDWAPSXNXHYQLK-UHFFFAOYSA-N (5-nitropyridin-2-yl)hydrazine Chemical class NNC1=CC=C([N+]([O-])=O)C=N1 DDWAPSXNXHYQLK-UHFFFAOYSA-N 0.000 claims description 3
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 229960004194 lidocaine Drugs 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 150000003053 piperidines Chemical class 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910019213 POCl3 Inorganic materials 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 238000004737 colorimetric analysis Methods 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000008399 tap water Substances 0.000 claims description 2
- 235000020679 tap water Nutrition 0.000 claims description 2
- 239000010949 copper Substances 0.000 abstract description 34
- 238000001514 detection method Methods 0.000 abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 9
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 238000004458 analytical method Methods 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 abstract description 5
- 229910001431 copper ion Inorganic materials 0.000 abstract description 4
- 229910001453 nickel ion Inorganic materials 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 230000000536 complexating effect Effects 0.000 abstract 2
- 239000003086 colorant Substances 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 15
- 239000000126 substance Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 206010070834 Sensitisation Diseases 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 235000011167 hydrochloric acid Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 238000012800 visualization Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 208000002972 Hepatolenticular Degeneration Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 206010028767 Nasal sinus cancer Diseases 0.000 description 1
- 208000012902 Nervous system disease Diseases 0.000 description 1
- 208000025966 Neurological disease Diseases 0.000 description 1
- -1 Ni (NO3)2 Chemical class 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 208000018839 Wilson disease Diseases 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 1
- 229910000369 cadmium(II) sulfate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- AFYCEAFSNDLKSX-UHFFFAOYSA-N coumarin 460 Chemical compound CC1=CC(=O)OC2=CC(N(CC)CC)=CC=C21 AFYCEAFSNDLKSX-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 208000005069 pulmonary fibrosis Diseases 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 230000019491 signal transduction Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Inorganic materials [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 1
- LBVWQMVSUSYKGQ-UHFFFAOYSA-J zirconium(4+) tetranitrite Chemical compound [Zr+4].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O LBVWQMVSUSYKGQ-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- 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
-
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- 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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Pathology (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Immunology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Plasma & Fusion (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
本发明公开了一种比色法检测铜离子(Cu2+)和镍离子(Ni2+)探针的合成及在水样中检测Cu2+和Ni2+的应用，该分子探针的结构式如下：。该分子探针在水溶液中能与Cu2+和Ni2+发生不同的络合反应呈现出不同的颜色而达到同时比色检测这两种金属离子的目的，探针与Cu2+络合后检测液由黄色变为鲜红色，而与Ni2+络合后则变为紫色，颜色变化明显，检测速度快且易于区分。结合紫外分光光度法可实现对Cu2+和Ni2+高灵敏度检测，该探针可以直接检测水中微量级的Cu2+和Ni2+，检测限分别低至2.1 nM和1.2 nM。在pH=4‑10范围内均可高灵敏度检测水样中的Cu2+和Ni2+，操作简单，选择性好，在环境科学、分析检测等领域具有较大的应用价值。
Description
技术领域
本发明属于分析化学技术领域，具体涉及一种比色法检测水中Cu2+和Ni2+探针的合成，以及该探针在不同水样中检测Cu2+和Ni2+含量等方面的应用。
背景技术
铜作为人体中第三种必需的微量金属元素，在一些生理过程中，如细胞能量的产生，氧转运和激活以及信号传导等方面起着重要作用（Chemical Reviews, 2008, 108,1517-1549），然而，近年来由于一些含重金属铜及其化合物的污染物的不达标排放，造成严重的水污染，极易造成生活环境、饮用水、粮食中铜离子（Cu2+）含量过高，过量摄入铜离子会损害人体健康，导致严重的神经疾病如威尔逊氏病和阿尔茨海默病（Annual Review ofNeuroscience, 2007, 30, 317-337）。根据美国国家环境保护局（EPA）的标准，饮用水中Cu2+最高浓度为20 μM。另一方面，镍（Ni）被广泛应用于各种工业生产中，例如电镀，镍镉电池，油漆颜料，陶瓷，氢化反应催化剂等。此外，镍离子（Ni2+）是微生物、植物的酶催化能量和氮代谢必不可少的辅助因子。然而，镍离子的生物累积会导致皮肤过敏、肺纤维化和鼻窦癌等疾病（Nature Immunology, 2010, 11, 781-782）。铜和镍这两种人体所需的微量金属元素均可通过鱼类，谷类等食物最终富集于人体内，摄入超标会严重危害人民的健康。因此，对于环境水样中的Cu2+和Ni2+含量监测具有重要意义。
常规检测金属离子的分析方法包括原子吸收/发射光谱法、电化学方法和色谱法等直接检测法，此外还有利用铜离子和指示剂（分子探针）之间的特异性化学反应后的信号变化对特定金属离子进行分析检测的间接检测法，即化学传感法。化学传感法因具有速度快，操作简单，成本低，可视化等优点而得到了广泛的研究（CN 105949160 A）。近年来，基于化学传感方法已报道相当多的文献或专利用于高选择性检测Cu2+或者Ni2+（Biosensorsand Bioelectronics, 2016, 77, 13–18; Dyes and Pigments, 2017, 139, 50–64; CN104771607 A; CN 104830315 A 等）。但在这些已报到的文献或专利中，大多数只能利用荧光法或比色法检测Cu2+和Ni2+中的一种，能在纯水相环境中检测Cu2+或Ni2+的报道则更少（Dalton Transcations, 2015, 44, 17326-17334）。基于同一分子探针高灵敏度、可视化比色检测环境（不同水样）中Cu2+和Ni2+的文献或专利鲜有报道。因此，开发可视化、高灵敏度、高选择性化学传感技术来监测环境水样中Cu2+和Ni2+浓度在环境保护和实际水样实时监测中具有重要意义。
发明内容
鉴于上述情况，克服一些现有技术的不足，本发明的目的在于提供一种比色法检测水中Cu2+和Ni2+两种金属离子的分子探针，能够高灵敏度、高选择性比色检测水样中的Cu2 +和Ni2+，并通过标准曲线准确测定它们的实际浓度达到定量的目的。
本发明的目的还在于提供一种制备方法简单、高灵敏度、检测限低和成本较低的上述分子探针的合成与应用方法。
本发明解决问题采取的具体技术方案为，一种比色法检测水中Cu2+和Ni2+探针的合成与应用，其探针的化学结构式如下：
。
一种比色法检测水中Cu2+和Ni2+探针的合成，其特征在于，所述的分子探针的制备方法包括以下步骤：
步骤1. 合成7-（二乙基氨基）香豆素
a. 将丙二酸二乙酯与4-（二乙氨基）水杨醛加入适量无水乙醇中，加入几滴哌啶回流反应18-24小时，待反应完毕后，通过旋转蒸发仪蒸去乙醇；
b. 往步骤a中加入适量等体积的浓盐酸和冰醋酸，继续回流反应18-24小时；
c. 将步骤b中反应液倒入冰水中，调节pH至6，过滤，滤饼水洗3次，真空干燥得黄绿色固体7-（二乙基氨基）香豆素；
步骤2. 合成7-(二乙氨基基)香豆素-3-甲醛
．氮气保护条件下，将适量干燥重蒸的N,N-二甲基甲酰胺（DMF）滴加入等体积的三氯氧磷（POCl3）中，在20-50℃下搅拌30分钟，得红色溶液；
．将7-（二乙基氨基）香豆素溶于适量DMF中，逐滴加入到步骤的混合溶液中，混合物继续在氮气保护下60℃搅拌反应12-20小时；
．将步骤中的反应液倒入冰水中，用20%的NaOH溶液调节pH至5~6，产生大量沉淀，过滤，适量去离子水洗涤滤饼3次，所得固体真空干燥，得7-(二乙氨基基)香豆素-3-甲醛；
步骤3. 分子探针7-（二乙基氨基）-3-（（E）-（（（E）-5-硝基吡啶-2（1H）亚基）亚肼基）甲基）-2H-色烯-2-酮的合成
A. 将7-(二乙氨基基)香豆素-3-甲醛和2-肼基-5-硝基吡啶加入适量无水乙醇中，回流反应4-6小时；
B. 将步骤A中反应液过滤，滤饼用乙醇洗涤3次，所得固体真空干燥得目标分子探针。
本发明的分子探针检测水中Cu2+和Ni2+使用方法：在室温下将探针分子溶解在二甲基亚砜（DMSO）中，然后加入含检测物的水溶液即可，检测速度快，颜色变化明显，结合紫外可见分光光度计可以选择性高灵敏度检测水样中的Cu2+和Ni2+含量。
本发明的一种比色法检测水中Cu2+和Ni2+探针的具体特征如下：该分子荧光探针用二甲基亚砜(DMSO)溶解，探针在纯水溶液中最大紫外吸收波长为469 nm，且吸光度很小，溶液颜色为淡黄色，当加入2倍当量Cu2+后，探针溶液迅速变为鲜红色，紫外吸收红移至538nm，紫外吸收增强12 倍以上；而当加入2倍当量Ni2+后，探针溶液迅速变为紫色，紫外吸收红移至494 nm，紫外吸收增强约6 倍。上述分子探针实现了在水溶液中同时检测Cu2+和Ni2+，对Ag+, Bi3+, Zr4+, Fe2+, Cd2+, Pb2+, Fe3+, Ba2+, Mg2+, Mn2+,Zn2+, Hg2+, Ca2+, Cr3+,Ru3+ , Hg+, Ti3+, Al3+等金属离子均无明显响应。该分子探针对Cu2+和Ni2+检测限分别低至2.1 nM和1.2 nM，对于自来水与饮用水等不同水样中的Cu2+和Ni2+检测均有较理想的结果。
附图说明
图1为本发明的一种比色法检测水中Cu2+和Ni2+探针的紫外吸收光谱随加入不同浓度的Cu2+的变化情况，横坐标为波长，纵坐标为吸光度。
图2为本发明的一种比色法检测水中Cu2+和Ni2+探针的紫外吸收光谱随加入不同浓度的Ni2+的变化情况，横坐标为波长，纵坐标为吸光度。
图3为本发明的一种比色法检测水中Cu2+和Ni2+探针的核磁共振氢谱图。
具体实施方式
下面结合附图对本发明做进一步的说明。
本发明所述的荧光分子探针的合成路线如下式所示：
。
实施例1. 合成7-（二乙基氨基）香豆素
a. 将24.87 g（155.2 mmol）丙二酸二乙酯与15 g（77.6 mmol）4-（二乙氨基）水杨醛加入100 mL无水乙醇中，加入5滴哌啶回流反应18小时，待反应完毕后，蒸去乙醇；再往除去乙醇的反应体系中加入100 mL浓盐酸和100 mL冰醋酸，继续回流反应18小时；将上述反应液倒入300 mL冰水中，调节pH至6，过滤，滤饼水洗3次，真空干燥得黄绿色固体7-（二乙基氨基）香豆素10.4 g（产率61.7%）。
实施例2. 合成7-(二乙氨基基)香豆素-3-甲醛
在氮气保护条件下，将2.8 mL干燥重蒸的DMF 缓慢滴加到2.8 mL三氯氧磷中，在20-50℃下搅拌30分钟，得红色溶液；将0.5 g（2.3 mmol）7-（二乙基氨基）香豆素溶于5 mL DMF中，逐滴加入到上述红色混合溶液中，混合物继续在氮气保护下60℃搅拌反应12小时；反应完毕后将反应液倒入60 mL冰水中，用20%的NaOH溶液调节pH至6，产生大量沉淀，过滤，适量去离子水洗涤滤饼3次，固体真空干燥，得7-(二乙氨基基)香豆素-3-甲醛310 mg（产率54.9%）。
实施例3. 分子探针7-（二乙基氨基）-3-（（E）-（（（E）-5-硝基吡啶-2（1H）亚基）亚肼基）甲基）-2H-色烯-2-酮的合成
往25 mL圆底烧瓶中加入0.2 g（0.815 mmol）7-(二乙氨基基)香豆素-3-甲醛和126 mg（0.815 mmol）2-肼基-5-硝基吡啶，10 mL无水乙醇，回流反应4-6小时；反应完毕后过滤，滤饼用乙醇洗涤3次，真空干燥得目标分子探针156 mg（产率50.1%）。
实施例4. 分子探针在水样中检测Cu2+和Ni2+的应用
本发明所述的分子探针光谱性质实验：将探针溶解在二甲基亚砜（DMSO）中配置成1 mM的探针溶液，分别配置1mM的CuSO4和NiSO4水溶液（其他水溶性铜盐和镍盐均可，如Ni(NO3)2、CuCl2、Cu(NO3)2等），10 mM的AgNO3, Bi2(SO4)3, Zr(NO3)4, FeSO4, CdSO4，Pb(NO3)2,FeCl3, BaCl2, MgSO4, MnSO4, ZnSO4, Al2(SO4)3, HgCl2, CaCl2, Cr(NO3)3, RuCl3,HgCl和TiCl3水溶液，检测Cu2+和Ni2+的测试均在纯水相室温条件下测试。具体测试方式为：取20μL 1 mM的探针溶液，所需量的1mM的Cu2+或Ni2+水溶液和所需量的去离子水溶液于2 mL的样品管中，每一个测试样品总体积为2 mL，探针终浓度为10 μM。例如当要求测试Cu2+浓度为10 μM时探针与Cu2+反应后的吸光度，配制样品情况为20 μL 1 mM的探针溶液，20 μL 1 mM的CuSO4水溶液和1960 μL的去离子水于2 mL的样品管中，检测液颜色迅速变为鲜红色，摇匀后即可测试吸光度。从图1-图3可以看出，探针对水样中的Cu2+和Ni2+具有极高的灵敏度和选择性，对不同水样中的Cu2+和Ni2+都有很好的响应。本发明提供的探针分子能将不同水样中的Cu2+和Ni2+区别检测出来，在环境科学、分析检测等领域具有较高的应用价值。
本发明的一种比色法检测水中Cu2+和Ni2+探针的合成与应用，基于同一探针，针对不同的检测对象，利用不同的检测现象和紫外吸收信号，高灵敏度高选择性快速检测水样中Cu2+和Ni2+含量，在环境科学、分析检测等领域都具较高的实用价值。同时为今后金属离子探针的发展与应用提供了一些思路。尽管本发明的内容已经通过上述优选实施例作了详细的介绍，但应当认识到上述的描述不应被认为是对本发明的限制。在本领域技术人员阅读了上述内容后，对于本发明的多种修改和替代都将是显而易见的。因此，具有本文所述技术特征的一种比色法检测水中Cu2+和Ni2+探针的合成与应用，均落入本专利的保护范围。
Claims (5)
1.一种比色法检测水中Cu2+和Ni2+探针，其特征在于，所述分子探针的结构式如(1)所示：
(1)。
2.如权利要求1所述的一种比色法检测水中Cu2+和Ni2+探针的合成，其特征在于，所述分子探针的制备方法包括以下步骤：
步骤1. 合成7-（二乙基氨基）香豆素
a. 将丙二酸二乙酯与4-（二乙氨基）水杨醛加入适量无水乙醇中，加入几滴哌啶回流反应18-24小时，待反应完毕后，通过旋转蒸发仪蒸去乙醇；
b. 往步骤a中加入适量等体积的浓盐酸和冰醋酸，继续回流反应18-24小时；
c. 将步骤b中反应液倒入冰水中，调节pH至6，过滤，滤饼水洗3次，真空干燥得黄绿色固体7-（二乙基氨基）香豆素；
步骤2. 合成7-(二乙氨基基)香豆素-3-甲醛
．氮气保护条件下，将适量干燥重蒸的N,N-二甲基甲酰胺（DMF）滴加入等体积的三氯氧磷（POCl3）中，在20-50℃下搅拌30分钟，得红色溶液；
． 将7-（二乙基氨基）香豆素溶于适量DMF中，逐滴加入到步骤的混合溶液中，混合物继续在氮气保护下60℃搅拌反应12-20小时；
．将步骤中的反应液倒入冰水中，用20%的NaOH溶液调节pH至5~6，产生大量沉淀，过滤，适量去离子水洗涤滤饼3次，所得固体真空干燥，得7-(二乙氨基基)香豆素-3-甲醛；
步骤3. 分子探针7-（二乙基氨基）-3-（（E）-（（（E）-5-硝基吡啶-2（1H）亚基）亚肼基）甲基）-2H-色烯-2-酮的合成
A. 将7-(二乙氨基基)香豆素-3-甲醛和2-肼基-5-硝基吡啶加入适量无水乙醇中，回流反应4-6小时；
B. 将步骤A中反应液过滤，滤饼用乙醇洗涤3次，所得固体真空干燥得目标分子探针。
3.如权利要求2所述的一种比色法检测水中Cu2+和Ni2+探针的合成，其特征在于，所述步骤A中7-(二乙氨基基)香豆素-3-甲醛和2-肼基-5-硝基吡啶的摩尔比为1:1-2。
4.如权利要求1所述的一种比色法检测水中Cu2+和Ni2+探针的应用，其特征在于，所述的分子探针能够用比色法和紫外分光光度法检测水样中Cu2+和Ni2+含量的应用。
5.如权利要求1所述的一种比色法检测水中Cu2+和Ni2+探针的应用，其特征在于，所述的分子探针能够在自来水、饮用水、河水和湖水等不同水样中选择性检测Cu2+和Ni2+含量的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810275247.2A CN108484583B (zh) | 2018-03-30 | 2018-03-30 | 一种比色法检测水中Cu2+和Ni2+探针的合成与应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810275247.2A CN108484583B (zh) | 2018-03-30 | 2018-03-30 | 一种比色法检测水中Cu2+和Ni2+探针的合成与应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108484583A true CN108484583A (zh) | 2018-09-04 |
| CN108484583B CN108484583B (zh) | 2021-03-02 |
Family
ID=63317633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810275247.2A Active CN108484583B (zh) | 2018-03-30 | 2018-03-30 | 一种比色法检测水中Cu2+和Ni2+探针的合成与应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108484583B (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109959628A (zh) * | 2019-04-29 | 2019-07-02 | 中南大学 | 一种基于极-光谱融合的锌溶液杂质离子浓度检测方法 |
| CN110003175A (zh) * | 2019-03-25 | 2019-07-12 | 天津农学院 | 一种用于检测水中金属离子含量的化合物及其应用 |
| CN112250681A (zh) * | 2020-10-21 | 2021-01-22 | 浙江工业大学 | 一种咪唑并[1,5-a]吡啶类染料及其合成方法和应用 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102519949A (zh) * | 2011-11-25 | 2012-06-27 | 江南大学 | 一种基于裸眼目视比色法检测镍离子探针的制备及其应用 |
| CN102702154A (zh) * | 2012-05-31 | 2012-10-03 | 西北师范大学 | 用于比色检测铜离子的受体化合物及其制备和应用 |
| CN104402853A (zh) * | 2014-09-30 | 2015-03-11 | 天津理工大学 | 一种识别谷胱甘肽的特异性荧光探针的制备方法及其应用 |
| CN105315264A (zh) * | 2015-11-24 | 2016-02-10 | 山西大同大学 | 一种n′-（喹啉-2-亚甲基）-7-二乙胺基香豆素-3-甲酰肼及其制备方法和应用 |
| CN105669708A (zh) * | 2016-01-18 | 2016-06-15 | 新乡医学院 | 一种基于香豆素席夫碱铜离子配合物硫醇荧光探针及其制备方法和应用 |
-
2018
- 2018-03-30 CN CN201810275247.2A patent/CN108484583B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102519949A (zh) * | 2011-11-25 | 2012-06-27 | 江南大学 | 一种基于裸眼目视比色法检测镍离子探针的制备及其应用 |
| CN102702154A (zh) * | 2012-05-31 | 2012-10-03 | 西北师范大学 | 用于比色检测铜离子的受体化合物及其制备和应用 |
| CN104402853A (zh) * | 2014-09-30 | 2015-03-11 | 天津理工大学 | 一种识别谷胱甘肽的特异性荧光探针的制备方法及其应用 |
| CN105315264A (zh) * | 2015-11-24 | 2016-02-10 | 山西大同大学 | 一种n′-（喹啉-2-亚甲基）-7-二乙胺基香豆素-3-甲酰肼及其制备方法和应用 |
| CN105669708A (zh) * | 2016-01-18 | 2016-06-15 | 新乡医学院 | 一种基于香豆素席夫碱铜离子配合物硫醇荧光探针及其制备方法和应用 |
Non-Patent Citations (2)
| Title |
|---|
| LINGYUN WANG，等: "A novel coumarin Schiff-base as a Ni(II) ion colorimetric sensor", 《SPECTROCHIMICA ACTA PART A》 * |
| 赵秀文，等: "基于香豆酰肼的高选择性的铜离子荧光探针", 《发光学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003175A (zh) * | 2019-03-25 | 2019-07-12 | 天津农学院 | 一种用于检测水中金属离子含量的化合物及其应用 |
| CN109959628A (zh) * | 2019-04-29 | 2019-07-02 | 中南大学 | 一种基于极-光谱融合的锌溶液杂质离子浓度检测方法 |
| CN112250681A (zh) * | 2020-10-21 | 2021-01-22 | 浙江工业大学 | 一种咪唑并[1,5-a]吡啶类染料及其合成方法和应用 |
| CN112250681B (zh) * | 2020-10-21 | 2022-01-04 | 浙江工业大学 | 一种咪唑并[1,5-a]吡啶类染料及其合成方法和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108484583B (zh) | 2021-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11505530B2 (en) | 1,8-naphthalimide derivative, preparation method therefor and use thereof | |
| Ravichandiran et al. | A phenoxazine-based fluorescent chemosensor for dual channel detection of Cd2+ and CN− ions and its application to bio-imaging in live cells and zebrafish | |
| Ghorai et al. | A reversible fluorescent-colorimetric imino-pyridyl bis-Schiff base sensor for expeditious detection of Al 3+ and HSO 3− in aqueous media | |
| Vanjare et al. | Novel rhodamine based chemosensor for detection of Hg2+: Nanomolar detection, real water sample analysis, and intracellular cell imaging | |
| CN106632064B (zh) | 可逆双羟基菲并咪唑Hg2+荧光探针合成与使用方法 | |
| CN110055056B (zh) | 苯并咪唑基取代的喹啉酮类荧光探针及其制备方法和应用 | |
| CN108484583A (zh) | 一种比色法检测水中Cu2+和Ni2+探针的合成与应用 | |
| CN107056779B (zh) | 一种希夫碱荧光探针qcs及其制备方法 | |
| CN112409292B (zh) | 一种多功能荧光探针及制备方法和应用 | |
| Aziz et al. | Design of a highly sensitive and selective bulk optode based on fluorescence enhancement of N, N′-bis-(1-hydroxyphenylimine) 2, 2′-pyridil Schiff base: Monitoring of zinc (II) ion in real samples and DFT calculation | |
| CN107417681B (zh) | 一种含有香豆素-噻二唑基席夫碱荧光探针化合物及其制备方法和用途 | |
| CN107698557B (zh) | 基于吡啶联吡唑酰腙衍生物的荧光探针及其制备方法和应用 | |
| CN113087651B (zh) | 一种含有吲哚基团的化合物及其制备方法和应用 | |
| CN108276371A (zh) | 香豆素硫代卡巴腙衍生物及其制备方法和应用 | |
| CN108395403A (zh) | 一种1,8-萘酰亚胺衍生物及其制备方法与应用 | |
| CN109053711B (zh) | 一种用于汞离子检测的探针化合物及其制备方法和应用 | |
| CN110627737A (zh) | 一种检测锌离子的水溶性苯并恶唑类荧光探针及制备方法和应用 | |
| CN114539181B (zh) | 一种用于铝离子和锌离子快速检测的荧光探针及其制备方法 | |
| CN111732574B (zh) | 一种萘酰亚胺-肼吡啶衍生物荧光探针及其制备方法和用途 | |
| CN113234046B (zh) | 一种检测次氯酸根离子的荧光探针及其应用 | |
| CN109912633B (zh) | Eu-配合物荧光探针及其制备方法和应用 | |
| CN113563353A (zh) | 用于水溶液中Hg2+和pH实时检测的双功能荧光探针 | |
| CN103992787B (zh) | 一种三[4-(4-吗啡啉基)-1,8-萘二甲酰亚胺乙基]胺荧光试剂及其制备和应用 | |
| CN113527283A (zh) | 一种小分子荧光HClO探针、制备方法及其应用 | |
| CN117050019B (zh) | 一种亚锡离子荧光探针及其合成方法 |
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 |