CN105130787A - Poly-brominated biphenyl homolog semi-antigen and preparation method thereof - Google Patents
Poly-brominated biphenyl homolog semi-antigen and preparation method thereof Download PDFInfo
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- CN105130787A CN105130787A CN201510471283.2A CN201510471283A CN105130787A CN 105130787 A CN105130787 A CN 105130787A CN 201510471283 A CN201510471283 A CN 201510471283A CN 105130787 A CN105130787 A CN 105130787A
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- tbbpa
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- polybrominated biphenyl
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Polymers C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000427 antigen Substances 0.000 title abstract description 15
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 33
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 102000014914 Carrier Proteins Human genes 0.000 claims abstract description 7
- 108010078791 Carrier Proteins Proteins 0.000 claims abstract description 7
- 150000002148 esters Chemical class 0.000 claims abstract description 6
- 150000001718 carbodiimides Chemical class 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001514 detection method Methods 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000004587 chromatography analysis Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004809 thin layer chromatography Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 150000008065 acid anhydrides Chemical class 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 102000036639 antigens Human genes 0.000 description 9
- 108091007433 antigens Proteins 0.000 description 9
- -1 bromo-4-hydroxyphenyl Chemical group 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000002163 immunogen Effects 0.000 description 7
- 239000012043 crude product Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 238000003018 immunoassay Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 230000008034 disappearance Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 230000002688 persistence Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000001900 immune effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000003752 polymerase chain reaction Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- YOETUEMZNOLGDB-UHFFFAOYSA-N 2-methylpropyl carbonochloridate Chemical compound CC(C)COC(Cl)=O YOETUEMZNOLGDB-UHFFFAOYSA-N 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 125000006416 CBr Chemical group BrC* 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000004544 DNA amplification Effects 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 108060003951 Immunoglobulin Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000000890 antigenic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000704 bioconcentration Toxicity 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229940098773 bovine serum albumin Drugs 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000001965 diffuse reflectance infrared spectroscopy Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 231100000507 endocrine disrupting Toxicity 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000028993 immune response Effects 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000003053 immunization Effects 0.000 description 1
- 238000002649 immunization Methods 0.000 description 1
- 230000005847 immunogenicity Effects 0.000 description 1
- 102000018358 immunoglobulin Human genes 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000011587 new zealand white rabbit Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
- C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
- C07C59/68—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings the oxygen atom of the ether group being bound to a non-condensed six-membered aromatic ring
- C07C59/70—Ethers of hydroxy-acetic acid, e.g. substitutes on the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
- C07K14/76—Albumins
- C07K14/765—Serum albumin, e.g. HSA
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
- C07K14/76—Albumins
- C07K14/77—Ovalbumin
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K19/00—Hybrid peptides, i.e. peptides covalently bound to nucleic acids, or non-covalently bound protein-protein complexes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
- G01N33/531—Production of immunochemical test materials
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Molecular Biology (AREA)
- Immunology (AREA)
- Biochemistry (AREA)
- Medicinal Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Hematology (AREA)
- Urology & Nephrology (AREA)
- Genetics & Genomics (AREA)
- Biophysics (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- General Physics & Mathematics (AREA)
- Biotechnology (AREA)
- Physics & Mathematics (AREA)
- Pathology (AREA)
- Food Science & Technology (AREA)
- Cell Biology (AREA)
- Analytical Chemistry (AREA)
- Microbiology (AREA)
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Abstract
The invention provides a poly-brominated biphenyl homolog semi-antigen and a preparation method thereof. The structural formula of the semi-antigen is represented in the description. The preparation method comprises a step of reacting TBBPA with bromo-acetic acid in an alkaline environment to introduce a carboxyl group into the terminal end of the phenolic hydroxyl group of TBBPA so as to obtain the semi-antigen. The provided semi-antigen preparation method has the advantages of simpleness, high stability, low cost, and easiness for industrial production. TBBPA semi-antigen can be coupled to carrier protein to prepare TBBPA artificial holoantigen through a carbodiimide method, a mixed acid anhydride method, or an activated ester method. The holoantigen can be used to prepare antibody having the advantages of high specificity and high titer and establish an immuno-PCR biological bar-code method.
Description
Technical field
The present invention relates to a kind of haptens and preparation method thereof, especially relate to a kind of Polybrominated biphenyl homologue semiantigen and preparation method thereof.
Background technology
Bromide fire retardant is one of organic fire-retardant that at present output is maximum in the world, wherein mainly Poly Brominated Diphenyl Ethers (PBDEs) and Polybrominated biphenyl (PBBs) class material.Wherein, tetrabromo-bisphenol (being called for short TBBPA) is by dihydroxyphenyl propane bromination gained, and it is the main products of the current organic bromine flame retardant of China, belongs to novel bromide fire retardant less to harm in polybrominated biphenyl.TBBPA Chang Zuowei fire retardant is added in the high molecular synthetic materials such as resin, polystyrene and polyurethane foam, be widely used in various production product and the Material Fields such as plastics, textiles, circuit card and Building Decoration Material, and along with the use of these products, slowly spill in environment.
Domestic and international vast environment scholar has done large quantity research to the concentration of TBBPA in various surrounding medium and biological sample and toxic effect.Research shows, TBBPA can exist in the various surrounding mediums such as various water body, bed mud, soil, air, and can move at a distance with aerosol.Obvious bioconcentration is revealed at Different Nutrition level organism intensive amount change list, and toxic and endocrine disrupting to organism.The pollution capacity of TBBPA has very high persistence, and main harm has 3 points: first, and Long Term Contact can hinder brain and skeleton development; Secondly, when being incinerated process, bromination Dioxins and the furans of high carcinogenic can be discharged.Therefore, research thinks that TBBPA is the potential compound with persistence, biological accumulation and toxicity (PBT-persistentbioaccumulativetoxie).As far back as 2003, TBBPA just caused the attention of green peace organization of the world.Originally European Union plans about " 2 instructions " of environmental protection the use limiting all brominated flame-retardants, and imagination substitutes with phosphorus, nitrogen, but because nitrogen, phosphor resource lack, indivedual performance far can not satisfy the demands and may cause the potential risk of the eutrophication of water body, and is not included in by TBBPA.At present, TBBPA has been put into as hazardous substance in the register of " Northeast Atlantic Ocean marine environmental protection regulations " OSPAR.
At present the instrument such as gas-chromatography and high performance liquid chromatography detection method is mainly to the detection means of TBBPA, although these methods accurately and reliably, has very high requirement to the pretreatment process of sample and the professional of operator.Just because of the process of these methods is complicated, consuming time, instrument price is expensive and be not suitable for promoting the use of, be also unfavorable in environmental pollution accident field quick detection.For overcoming these shortcomings, seek the main direction of studying that a kind of quick, easy, sensitive and economical and practical analytical procedure just becomes environmental monitoring field.
The immunoassay (Immunoassay, IA) that the sixties in 20th century grows up is based on antigen and the specificity of antibody, the analytical technology of reversibility association reaction.Immunoassay has the unrivaled selectivity of conventional physical and chemical analysis technology and high sensitivity, is applicable to very much the analysis of trace components in complex dielectrics.Therefore the high specificity, the advantage such as highly sensitive, method is quick and easy, analysis throughput is large, testing cost is low that have of immunoassay, makes these class methods can meet simply, detects the requirement of persistence organic pollutant fast, delicately.K.B.Mullis and R.K.Saiki etc. of Cetus company of the U.S. in 1985 has invented a kind of specific DNA Amplification Technologies, becomes PolymeraseChainReaction, is called for short PCR, i.e. polymerase chain reaction.Immuno analytical method is combined with round pcr by Sano in 1992 etc., develops immune PCR technique.Immune PCR technique has had the feature of the high specificity of immunoassay and the highly sensitive of round pcr concurrently, can be used for contaminant trace species in testing environment.Along with the development of bio-barcode technology, combine with the bio-barcode immuno-PCR biobarcode approach that develops of immune PCR technique can disturb too much problem by loaded down with trivial details, the organic solvent of settlement steps to deal, greatly can improve the sensitivity of detection method in addition.
Immuno-PCR biological bar code detection method is not still had to detect the relevant report of TBBPA at present.For the foundation of TBBPA immunologic surveillance method, the haptens that high purity is suitable is that preparation has the basic of highly sensitive and specific immunogens and high-titer antibody, sets up the key of TBBPA immunologic detection method especially.Therefore, the haptenic preparation of TBBPA is the basis adopting immunization method to measure TBBPA, for the monitoring method setting up Polybrominated biphenyl monomer, has important using value and theoretical significance.
Summary of the invention
For defect of the prior art, the object of the invention is to provide a kind of step simple first, speed is fast, much higher bromo biphenyl homologue semiantigen of productive rate and preparation method thereof.
The object of the invention is to be achieved through the following technical solutions:
The invention provides a kind of Polybrominated biphenyl homologue semiantigen, structural formula is such as formula shown in I:
Described formula I is faint yellow acicular crystals, and fusing point is 167 ~ 170 DEG C.
The invention still further relates to a kind of preparation method of Polybrominated biphenyl homologue semiantigen, comprise step:
TBBPA
react in alkaline environment with bromoacetic acid, introduce a carboxylic group at TBBPA molecule phenolic hydroxy group end.Introduce carboxylic group can with carrier protein couplet.
Preferably, described TBBPA and bromoacetic acid react and specifically comprise in alkaline environment:
A1, TBBPA and alkali metal hydroxide are dissolved in non-proton organic solvent, obtain solution A, heat up gradually;
A2, the bromoacetic acid being dissolved in non-proton organic solvent dropwise to be joined in the solution A after heating up in steps A 1, keep constant temperature back flow reaction subsequently, till raw material point disappears.
Its chemical equation is as follows:
Preferably, described non-proton organic solvent is DMF, methyl-sulphoxide or acetone.
Preferably, the mol ratio of described TBBPA, alkali metal hydroxide and bromoacetic acid is 1:2 ~ 4:1 ~ 2.As shown in chemical reaction equation, ideally the mol ratio of TBBPA, alkali metal hydroxide is 1:2, but carries out smoothly to react, and general alkali metal hydroxide can be more excessive, but can not more than 2 times; Ideally TBBPA and alkali metal hydroxide react the mol ratio of haptens precursor and the bromoacetic acid generated is 1:1, and for guaranteeing that reaction is carried out smoothly to the right, bromoacetic acid is excessive, but can not exceed 2 times of desirable molar weight.
Preferably, described alkali metal hydroxide is sodium hydroxide or potassium hydroxide.
Preferably, in steps A 2, described solution A temperature is 80 ~ 85 DEG C, and constant temperature reflux time is 4 ~ 6 hours.This temperature is more conducive to the carrying out reacted, and detects with thin-layer chromatography, within 4 ~ 6 hours, can react completely.
Preferably, further comprising the steps of:
B, reaction terminate rear concentrated hydrochloric acid and regulate pH termination reaction;
C, in reaction solution, add ethyl acetate, be separated and wash with water, dry organic phase;
D, by dried organic phase desolventizing, cross chromatography column separation and purification, finally obtain faint yellow acicular crystals TBBPA haptens 2-(the bromo-4-of 2, the 6-bis-(2-(3 after purifying, the bromo-4-hydroxyphenyl of 5-bis-) isopropyl ester)) acetic acid, i.e. formula I.TBBPA hapten molecule formula: C
17h
14br
4o
4; Molecular weight: 601.92; Fusing point: 167-170 DEG C.
Preferably, in step B, described pH is 2.0 ~ 4.0.The solution of slant acidity, is conducive to termination reaction, also prevents the generation of reversed reaction.
Preferably, in step D, the thin-layer chromatography developping agent of described chromatography column separation and purification adopts volume ratio to be the acetone of 1:4 and the mixing solutions of normal hexane composition.Because haptens is organic phase material, the present invention surprisingly finds to adopt this developping agent to be more conducive to haptenic purifying, makes the haptens purity of acquisition higher.
Present invention also offers a kind of purposes of Polybrominated biphenyl homologue semiantigen, for the detection of trace brominated flame-retardant TBBPA.
Preferably, the detection method of described trace brominated flame-retardant TBBPA, comprises and formula I is prepared the artificial holoantigen of TBBPA by carbodiimide method, mixed anhydride method or active ester method and carrier protein couplet.
Preferably, the artificial holoantigen of described TBBPA is TBBPA artificial immunogen TBBPA-BSA
or the artificial coating antigen TBBPA-OVA of TBBPA
wherein, BSA is bovine serum albumin, and OVA is oralbumin.
The present invention relates to a kind of Polybrominated biphenyl homologue semiantigen and preparation method thereof, because TBBPA is small-molecule substance, only there is reactionogenicity and there is no immunogenicity, and this molecule there is no the functional group such as amino, carboxyl that directly can be combined with protein molecule, therefore need the carboxyl making its molecule is brought two carbon chain length to TBBPA molecule derivatize.In order to the realization of immune analysis method, by carbodiimide method or active ester method or mixed anhydride method, this carboxylic haptens and protein molecule coupling are prepared artificial holoantigen (comprising artificial immunogen and artificial coating antigen), wherein artificial immunogen immunize New Zealand White Rabbit, by the immunne response in organism and then the specific antibody preparing anti-TBBPA, and artificial coating antigen and TBBPA can with the reaction of anti-TBBPA specific antibody immunoglobulin IgG generation specific recognition, namely artificial coating antigen and TBBPA are the relations of direct competitive, thus set up immune analysis method for water body, soil, the environmental samples such as air and electronic product, textile printing and dyeing product, the detection of trace brominated flame-retardant tetrabromo-bisphenol in the products such as building decoration.
Compared with prior art, the present invention has following beneficial effect:
(1) haptens is practical: the preparation of TBBPA haptens and antibody preparation have important practical value and realistic meaning.This haptens remains the structure of TBBPA, recycling carbodiimide method, active ester method or mixed anhydride method coupling protein matter make it have the antigenic determinant for TBBPA, successfully can prepare the artificial coating antigen TBBPA-OVA of TBBPA artificial immunogen TBBPA-BSA or TBBPA, for preparation specificity is good, the high antibody and set up immuno-PCR biobarcode approach and provide guarantee of tiring.
(2) haptens good stability: the present invention has prepared TBBPA haptens first, and the TBBPA haptens structure of this method synthesis has good stability, can preserve for many years, lost efficacy hardly under room temperature state.
(3) haptens technology of preparing is simple and feasible: haptenic whole preparation process is without the need to special plant and instrument, with low cost, and preparation speed is fast, and productive rate is high, easy commercial scale production.
Accompanying drawing explanation
By reading the detailed description done non-limiting example with reference to the following drawings, other features, objects and advantages of the present invention will become more obvious:
Fig. 1 is the infrared spectrogram of TBBPA;
Fig. 2 is the haptenic infrared spectrogram of TBBPA;
Fig. 3 is the haptenic nmr spectrum of TBBPA;
Fig. 4 is the ultraviolet spectrogram of TBBPA haptens TBBPA-hapten, carrier proteins BSA and artificial holoantigen TBBPA-BSA;
Fig. 5 is the ultraviolet spectrogram of TBBPA haptens TBBPA-hapten, carrier proteins OVA and artificial holoantigen TBBPA-OVA.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
the haptenic preparation of embodiment 1 Polybrominated biphenyl
Take 2g (3.677mmol) TBBPA and 0.294g (7.354mmol) sodium hydroxide and be dissolved in 8mLN, in dinethylformamide, be warmed up to 80 DEG C gradually.Take 0.5109g (3.677mmol) bromoacetic acid and be dissolved in 5mLN, dinethylformamide, it is dropwise joined in 80 DEG C of thermal response liquid, keep constant temperature back flow reaction 4 ~ 6 hours subsequently, till thin plate chromatography (TLC) detects the disappearance of raw material point.Be cooled to room temperature after reaction terminates, in reaction solution, add 30mL distilled water, regulate pH to 3.0 with concentrated hydrochloric acid, now have a large amount of white precipitate and generate; Subsequently, in dirty solution, add 60mL ethyl acetate, be separated and preserve organic layer; Now, with water repeatedly repeated washing organic phase to remove byproduct of reaction as far as possible, use anhydrous sodium sulfate drying more afterwards.Dried organic phase is transferred in Rotary Evaporators and removes unnecessary solvent, obtain faint yellow crude product.Crude product acetone solution, cross chromatography column separation and purification (developping agent, normal hexane: acetone=4:1 (V:V)), finally obtain faint yellow acicular crystals and TBBPA haptens 2-(2, the bromo-4-of 6-bis-(2-(the bromo-4-hydroxyphenyl of 3,5-bis-) isopropyl ester)) acetic acid.TBBPA hapten molecule formula: C
17h
14br
4o
4; Molecular weight: 601.92; Productive rate: 67.5%, fusing point: 167-170 DEG C, purity: 98%.
the haptenic preparation of embodiment 2 Polybrominated biphenyl
Take 2g (3.677mmol) TBBPA and 0.588g (14.708mmol) sodium hydroxide and be dissolved in 8mLN, in dinethylformamide, be warmed up to 85 DEG C gradually.Taking 1.0218g (7.354mmol) bromoacetic acid is dissolved in 5mL methyl-sulphoxide, it is dropwise joined in 85 DEG C of thermal response liquid, keep constant temperature back flow reaction 4 ~ 6 hours subsequently, till thin plate chromatography (TLC) detects the disappearance of raw material point.Be cooled to room temperature after reaction terminates, in reaction solution, add 30mL distilled water, regulate pH to 4.0 with concentrated hydrochloric acid, now have a large amount of white precipitate and generate; Subsequently, in dirty solution, add 60mL ethyl acetate, be separated and preserve organic layer; Now, with water repeatedly repeated washing organic phase to remove byproduct of reaction as far as possible, use anhydrous sodium sulfate drying more afterwards.Dried organic phase is transferred in Rotary Evaporators and removes unnecessary solvent, obtain faint yellow crude product.Crude product acetone solution, cross chromatography column separation and purification (developping agent, normal hexane: acetone=4:1 (V:V)), finally obtain faint yellow acicular crystals and TBBPA haptens 2-(2, the bromo-4-of 6-bis-(2-(the bromo-4-hydroxyphenyl of 3,5-bis-) isopropyl ester)) acetic acid.TBBPA hapten molecule formula: C
17h
14br
4o
4; Molecular weight: 601.92; Productive rate: 68.5%, fusing point: 167-170 DEG C, purity: 98%.
the haptenic preparation of embodiment 3 Polybrominated biphenyl
Take 2g (3.677mmol) TBBPA and 0.294g (7.354mmol) sodium hydroxide and be dissolved in 8mLN, in dinethylformamide, be warmed up to 80 DEG C gradually.Take 1.0218g (7.354mmol) bromoacetic acid and be dissolved in 5mLN, in dinethylformamide, it is dropwise joined in 80 DEG C of thermal response liquid, keep constant temperature back flow reaction 4 ~ 6 hours subsequently, till thin plate chromatography (TLC) detects the disappearance of raw material point.Be cooled to room temperature after reaction terminates, in reaction solution, add 30mL distilled water, regulate pH to 2.0 with concentrated hydrochloric acid, now have a large amount of white precipitate and generate; Subsequently, in dirty solution, add 60mL ethyl acetate, be separated and preserve organic layer; Now, with water repeatedly repeated washing organic phase to remove byproduct of reaction as far as possible, use anhydrous sodium sulfate drying more afterwards.Dried organic phase is transferred in Rotary Evaporators and removes unnecessary solvent, obtain faint yellow crude product.Crude product acetone solution, cross chromatography column separation and purification (developping agent, normal hexane: acetone=4:1 (V:V)), finally obtain faint yellow acicular crystals and TBBPA haptens 2-(2, the bromo-4-of 6-bis-(2-(the bromo-4-hydroxyphenyl of 3,5-bis-) isopropyl ester)) acetic acid.TBBPA hapten molecule formula: C
17h
14br
4o
4; Molecular weight: 601.92; Productive rate: 69%, fusing point: 167-170 DEG C, purity: 98%.
The TBBPA haptens obtained, its structure is by detection means Analysis and Identification such as infrared spectra, uv-vis spectra, nucleus magnetic resonance, and the haptenic diffuse reflectance infrared spectroscopy of TBBPA is as follows: IR (KBr) ν/cm
-1: 3475.69 (O-H stretches), (1733.86 C=O stretches), 1577.22,1472.99 (C=C phenyl ring skeletal vibrations), 875.55,778.72,734.95 (C-H bends), (621.08 C-Br stretches), find out from the infared spectrum interpretation of result of Fig. 1 and Fig. 2, TBBPA haptens has the spectral results with TBBPA molecular mimicry, and in TBBPA haptens infrared spectra, have obvious-COOH group characteristic peak, prove in the TBBPA hapten molecule prepared containing carboxyl functional group.
As shown in Figure 3, its feature is as follows for the haptenic hydrogen nuclear magnetic resonance spectrogram of TBBPA:
1hNMR (CDCl
3) δ (ppm): 11.5 (1H, COOH), 7.31 (2H, AromaticH), 4.19 (2H ， – OCH
2cOOH), 2.50 (1H, OH), 1.60 (6H, 2CH
3).Infrared, nuclear-magnetism characterization result shows, Success in Experiment has prepared TBBPA haptens.
the preparation of the artificial holoantigen of embodiment 4 Polybrominated biphenyl
Polybrominated biphenyl haptens prepared by the present invention, is mainly used in the immunodetection of Polybrominated biphenyl in environment.One of its main application, can be used for exactly directly and protein macromolecule coupling, prepare the immunogen for immune animal, and then prepare corresponding mono-clonal or polyclonal antibody.Set up the method for immunity of Polybrominated biphenyl on this basis.Following applicating example is used as below with regard to haptenic the making of TBBPA:
Adopt active ester method to prepare TBBPA-BSA immunogen, concrete synthesis step: to take 0.3010gTBBPA haptens in fine taper bottle, add 1mLN, N '-dimethyl methane amide makes it to dissolve; Take 0.0575gN-N-Hydroxysuccinimide and 0.103gN, N '-Dicyclohexylcarbodiimide is dissolved in 1mLN, in N '-dimethyl methane amide, by the N containing NHS and DCC, N '-dimethyl formamide soln dropwise joins in TBBPA haptens solution, stirred at ambient temperature reaction 6-12 hour, 4 DEG C are spent the night, low-temperature centrifugation separation of supernatant.Taking 120mgBSA is dissolved in the PBS damping fluid of 10mL0.01MpH7.40, is dropwise added by above-mentioned supernatant liquor in BSA solution, 4 DEG C of reaction 2-6 hour; After reaction, solution is loaded dialysis tubing, dialyse 3 days with the PBS damping fluid of 0.01MpH7.40, within every eight hours, change water once; Centrifugation supernatant liquor after dialysis, obtains TBBPA artificial immunogen TBBPA-BSA, after ultraviolet-visible spectrophotometer qualification, and packing in a small amount ,-20 DEG C of freezen protective.
TBBPA-OVA coating antigen is prepared by mixed anhydride method, concrete synthesis step: take 0.5mmolTBBPA haptens in fine taper bottle, add 1mLN, N '-dimethyl methane amide makes it to dissolve, add equimolar n-Butyl Amine 99 and isobutyl chlorocarbonate in turn, 4 DEG C of magnetic agitation 2-3 hour.Taking 120mgOVA is dissolved in the PBS of 10mL0.01MpH7.40, is dropwise joined by haptens reaction solution in OVA solution, 4 DEG C of stirring reactions 5 hours; After reaction terminates, load dialysis tubing, dialyse 3 days with the PBS of 0.01MpH7.40, within every eight hours, change water once, 4 DEG C of low-temperature centrifugation separation of supernatant, obtain coating antigen TBBPA-OVA.Coating antigen is identified through ultraviolet-visible spectrophotometer, packing in a small amount ,-20 DEG C of freezen protective.
Conjugate is after ultraviolet-visible pectrophotometer scanning qualification, and as can be seen from the TBBPA haptens of Fig. 4 and Fig. 5, carrier proteins and artificial holoantigen ultraviolet spectrogram, the haptenic charateristic avsorption band of TBBPA is positioned at 287nm; The charateristic avsorption band of carrier proteins BSA is positioned at 227nm and 273nm place; The charateristic avsorption band of carrier proteins OVA appears at 219nm, 224nm, 268nm place.Not only comprise the characteristic peak of BSA and OVA in the UV spectrum of conjugate TBBPA-BSA and TBBPA-OVA respectively, also occurred new absorption peak at 317nm and 312nm place, above information shows TBBPA-BSA and TBBPA-OVA coupling success.
These immunogens both may be used for immune animal, and the immune response produced by animal obtains the mono-clonal that can be used for doing immunoassay or polyclonal antibody, can use again as Immune competition object.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (10)
1. a Polybrominated biphenyl homologue semiantigen, is characterized in that, structural formula is such as formula shown in (I):
2. a preparation method for Polybrominated biphenyl homologue semiantigen as claimed in claim 1, is characterized in that, comprise the following steps:
TBBPA
react in alkaline environment with bromoacetic acid.
3. the preparation method of Polybrominated biphenyl homologue semiantigen as claimed in claim 2, it is characterized in that, described TBBPA and bromoacetic acid react and specifically comprise in alkaline environment:
A1, TBBPA and alkali metal hydroxide are dissolved in non-proton organic solvent, obtain solution A, heat up gradually;
A2, the bromoacetic acid being dissolved in non-proton organic solvent dropwise to be joined in the solution A after heating up in steps A 1, keep constant temperature back flow reaction subsequently, till raw material point disappears.
4. the preparation method of Polybrominated biphenyl homologue semiantigen as claimed in claim 3, it is characterized in that, described non-proton organic solvent is DMF, methyl-sulphoxide or acetone.
5. the preparation method of Polybrominated biphenyl homologue semiantigen as claimed in claim 3, it is characterized in that, the mol ratio of described TBBPA, alkali metal hydroxide and bromoacetic acid is 1:2 ~ 4:1 ~ 2.
6. the preparation method of Polybrominated biphenyl homologue semiantigen as claimed in claim 3, it is characterized in that, in steps A 2, the temperature of described solution A is 80 ~ 85 DEG C, and constant temperature reflux time is 4 ~ 6 hours.
7. the preparation method of Polybrominated biphenyl homologue semiantigen as claimed in claim 2, is characterized in that, further comprising the steps of:
B, reaction terminate rear concentrated hydrochloric acid and regulate pH termination reaction;
C, in reaction solution, add ethyl acetate, be separated and wash, dry organic phase;
D, by dried organic phase desolventizing, cross chromatography column separation and purification, obtain the TBBPA haptens after purifying, i.e. described Polybrominated biphenyl homologue semiantigen.
8. the preparation method of Polybrominated biphenyl homologue semiantigen as claimed in claim 7, it is characterized in that, in step B, described pH is 2.5 ~ 3.5; In step D, the thin-layer chromatography developping agent of described chromatography column separation and purification adopts volume ratio to be the acetone of 1:4 and the mixing solutions of normal hexane composition.
9. a purposes for Polybrominated biphenyl homologue semiantigen as claimed in claim 1, is characterized in that, for the detection of trace brominated flame-retardant TBBPA.
10. the purposes of Polybrominated biphenyl homologue semiantigen as claimed in claim 9, it is characterized in that, the detection method of described trace brominated flame-retardant TBBPA, comprises and described Polybrominated biphenyl homologue semiantigen is prepared the artificial holoantigen of TBBPA by carbodiimide method or mixed anhydride method or active ester method and carrier protein couplet.
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| CN106748714A (en) * | 2016-12-21 | 2017-05-31 | 江苏大学 | A kind of tetrabromobisphenol A derivative TBBPA DHEE synthesis of semiantigen and purposes |
| CN111320698A (en) * | 2020-03-26 | 2020-06-23 | 江西省农业科学院农产品质量安全与标准研究所 | Preparation method and application of CdTe labeled antibody and method for detecting polybrominated biphenyls |
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| CN104030913A (en) * | 2014-06-26 | 2014-09-10 | 江南大学 | Synthesis method of tetrabromobisphenol A analog-tetrabromobisphenol A hexanoic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106748714A (en) * | 2016-12-21 | 2017-05-31 | 江苏大学 | A kind of tetrabromobisphenol A derivative TBBPA DHEE synthesis of semiantigen and purposes |
| CN111320698A (en) * | 2020-03-26 | 2020-06-23 | 江西省农业科学院农产品质量安全与标准研究所 | Preparation method and application of CdTe labeled antibody and method for detecting polybrominated biphenyls |
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