CN114832441B - 一种修饰型笼状分子印迹聚合物的制备方法和应用 - Google Patents
一种修饰型笼状分子印迹聚合物的制备方法和应用 Download PDFInfo
- Publication number
- CN114832441B CN114832441B CN202210536323.7A CN202210536323A CN114832441B CN 114832441 B CN114832441 B CN 114832441B CN 202210536323 A CN202210536323 A CN 202210536323A CN 114832441 B CN114832441 B CN 114832441B
- Authority
- CN
- China
- Prior art keywords
- modified
- boric acid
- poss
- hours
- molecularly imprinted
- 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.)
- Active
Links
- 229920000344 molecularly imprinted polymer Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 84
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229920000642 polymer Polymers 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000001914 filtration Methods 0.000 claims abstract description 18
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 11
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 62
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 239000004005 microsphere Substances 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 26
- DRTQHJPVMGBUCF-XVFCMESISA-N Uridine Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1N1C(=O)NC(=O)C=C1 DRTQHJPVMGBUCF-XVFCMESISA-N 0.000 claims description 20
- 238000001704 evaporation Methods 0.000 claims description 17
- 239000000706 filtrate Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 14
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 14
- 229960000583 acetic acid Drugs 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- DRTQHJPVMGBUCF-PSQAKQOGSA-N beta-L-uridine Natural products O[C@H]1[C@@H](O)[C@H](CO)O[C@@H]1N1C(=O)NC(=O)C=C1 DRTQHJPVMGBUCF-PSQAKQOGSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- DRTQHJPVMGBUCF-UHFFFAOYSA-N uracil arabinoside Natural products OC1C(O)C(CO)OC1N1C(=O)NC(=O)C=C1 DRTQHJPVMGBUCF-UHFFFAOYSA-N 0.000 claims description 10
- 229940045145 uridine Drugs 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- HGDQAFSQPJJIFA-UHFFFAOYSA-N 1,3-dibromo-2-methyl-5-nitrobenzene Chemical compound CC1=C(Br)C=C([N+]([O-])=O)C=C1Br HGDQAFSQPJJIFA-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- SKOWZLGOFVSKLB-UHFFFAOYSA-N hypodiboric acid Chemical compound OB(O)B(O)O SKOWZLGOFVSKLB-UHFFFAOYSA-N 0.000 claims description 8
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 7
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 5
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 claims description 5
- IQPNAANSBPBGFQ-UHFFFAOYSA-N luteolin Chemical compound C=1C(O)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(O)C(O)=C1 IQPNAANSBPBGFQ-UHFFFAOYSA-N 0.000 claims description 5
- LRDGATPGVJTWLJ-UHFFFAOYSA-N luteolin Natural products OC1=CC(O)=CC(C=2OC3=CC(O)=CC(O)=C3C(=O)C=2)=C1 LRDGATPGVJTWLJ-UHFFFAOYSA-N 0.000 claims description 5
- 235000009498 luteolin Nutrition 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 235000013305 food Nutrition 0.000 claims description 3
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 3
- 238000011403 purification operation Methods 0.000 claims description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 125000005619 boric acid group Chemical group 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 13
- 239000004327 boric acid Substances 0.000 abstract description 9
- 239000002777 nucleoside Substances 0.000 abstract description 7
- 150000003833 nucleoside derivatives Chemical class 0.000 abstract description 7
- -1 boric acid compound Chemical class 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 3
- OOPSAZSKOMIGFX-UHFFFAOYSA-N boric acid;toluene Chemical class OB(O)O.CC1=CC=CC=C1 OOPSAZSKOMIGFX-UHFFFAOYSA-N 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 238000000605 extraction Methods 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000003480 eluent Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 4
- NYHBQMYGNKIUIF-UUOKFMHZSA-N Guanosine Chemical compound C1=NC=2C(=O)NC(N)=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O NYHBQMYGNKIUIF-UUOKFMHZSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- UTHULKKJYXJZLV-UHFFFAOYSA-N (3-aminophenoxy)boronic acid Chemical compound NC1=CC=CC(OB(O)O)=C1 UTHULKKJYXJZLV-UHFFFAOYSA-N 0.000 description 2
- UHDGCWIWMRVCDJ-UHFFFAOYSA-N 1-beta-D-Xylofuranosyl-NH-Cytosine Natural products O=C1N=C(N)C=CN1C1C(O)C(O)C(CO)O1 UHDGCWIWMRVCDJ-UHFFFAOYSA-N 0.000 description 2
- MIKUYHXYGGJMLM-GIMIYPNGSA-N Crotonoside Natural products C1=NC2=C(N)NC(=O)N=C2N1[C@H]1O[C@@H](CO)[C@H](O)[C@@H]1O MIKUYHXYGGJMLM-GIMIYPNGSA-N 0.000 description 2
- UHDGCWIWMRVCDJ-PSQAKQOGSA-N Cytidine Natural products O=C1N=C(N)C=CN1[C@@H]1[C@@H](O)[C@@H](O)[C@H](CO)O1 UHDGCWIWMRVCDJ-PSQAKQOGSA-N 0.000 description 2
- NYHBQMYGNKIUIF-UHFFFAOYSA-N D-guanosine Natural products C1=2NC(N)=NC(=O)C=2N=CN1C1OC(CO)C(O)C1O NYHBQMYGNKIUIF-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229930010555 Inosine Natural products 0.000 description 2
- UGQMRVRMYYASKQ-KQYNXXCUSA-N Inosine Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1N1C2=NC=NC(O)=C2N=C1 UGQMRVRMYYASKQ-KQYNXXCUSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- UHDGCWIWMRVCDJ-ZAKLUEHWSA-N cytidine Chemical compound O=C1N=C(N)C=CN1[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O1 UHDGCWIWMRVCDJ-ZAKLUEHWSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 229940029575 guanosine Drugs 0.000 description 2
- 229960003786 inosine Drugs 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 235000003255 Carthamus tinctorius Nutrition 0.000 description 1
- 244000020518 Carthamus tinctorius Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- JMZFEHDNIAQMNB-UHFFFAOYSA-N m-aminophenylboronic acid Chemical compound NC1=CC=CC(B(O)O)=C1 JMZFEHDNIAQMNB-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000009870 specific binding Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/38—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36
- B01D15/3852—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36 using imprinted phases or molecular recognition; using imprinted phases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明公开了一种修饰型笼状分子印迹聚合物的制备方法及应用,属于固相萃取材料领域,制备方法包括如下步骤:制备修饰型硼酸;将巯基丙酸与修饰型硼酸按照混合,溶解于甲苯中,搅拌得改性硼酸;以甲苯为溶剂、偶氮二异丁腈为引发剂,将八乙烯基POSS与改性硼酸加入三口烧瓶中,反应、过滤、旋蒸得修饰型POSS;聚合;洗脱模板,干燥。本发明通过在笼形POSS分子上修饰硼酸化合物,应用于固相萃取柱中时,可实现对药品中含有顺式二醇结构的核苷类物质含量的同时检测;本发明将自制的修饰型硼酸与乙烯基POSS接枝、修饰,笼形POSS本身具备多个活性位点,使印迹聚合物上含有数量较多的硼酸基团,能够提高物质含量测试的准确性。
Description
技术领域
本发明涉及固相萃取材料领域,具体地,涉及一种修饰型笼状分子印迹聚合物的制备方法和应用。
背景技术
分子印迹技术是指采用人工方法制备在空间结构和结合位点上对特定分子有专一性结合作用的聚合物技术。分子印迹聚合物(MIPs)是通过模板分子、功能单体和交联剂三者之间相互作用而合成的一种具有三维空间结构的“受体”,对模板分子具有独特的“记忆”功能,因而表现出特殊的亲和性、高度的选择性以及卓越的分子识别能力。
硼酸化学法是利用硼酸基团在碱性水溶液中可以与顺式二醇类物质,如核苷类物质所含的顺式邻位或间位羟基发生可逆反应形成环状二酯,并且在酸性条件下实现可逆地解离,从而对含有顺式二醇结构的核苷进行分离富集。这种pH开关的特性使硼酸成为优良的亲和识别配基。利用硼酸对顺式二醇结构的特异性识别,制备硼酸修饰的POSS,可以实现对木犀草素物质的选择性识别及分离富集。并且,利用苯硼酸和木犀草素中顺式二醇结构的可逆作用,可以增强材料对特定木犀草素的选择性。同时,可以利用pH值控制吸附/解吸过程。
POSS(polyhedralol igomericsilsesquioxane)是一类纳米复合材料,具有无机-有机笼型结构,常见分子式为(RSiO1.5)n。由于POSS具有多重活性功能基和纳米级结构,可通过共聚作用、嫁接或混合法将其混合到传统的聚合物里。由于POSS分子中的八个有机基团可以为修饰提供丰富的反应位点,POSS也应是一种理想的亲和配体扩增支架。
现有技术(申请号为201611191091.7)的专利公开了一种苯硼酸修饰的中空分子印迹聚合物及采用该聚合物制成的萃取柱,该聚合物的合成方法为以3-氨基苯硼酸为修饰剂,对甲基丙烯酸单体进行化学修饰,以尿苷为模板,修饰的甲基丙烯酸作为功能单体,加入基质、交联剂和引发剂制备分子印迹材料,对制得的分子印迹材料进行洗脱模板,并采用氢氟酸腐蚀掉基质,制得中空分子印迹聚合物。该专利虽然能够实现含有硼酸基团修饰的POSS,但是使用的是3-氨基苯硼酸为修饰剂,单个3-氨基苯硼酸仅含有一个硼酸基团,存在活性吸附位点数量少的缺陷,需要进一步改进。
发明内容
针对上述存在的问题和不足,本发明提供一种修饰型笼状分子印迹聚合物的制备方法和应用。
本发明通过在笼形POSS分子上修饰硼酸化合物,再聚合形成聚合物球体,应用于固相萃取柱中时,可实现对药品中含有顺式二醇结构的核苷类物质(胞苷、鸟苷、尿苷及肌苷)含量的同时检测;此外,本发明通过将自制的修饰型硼酸与乙烯基POSS接枝、修饰,笼形POSS本身具备多个活性位点,能够接枝多个硼酸化合物,而自制的硼酸化合物,单个分子上含有两个硼酸基团,活性基团位点翻倍,在叠加作用下,印迹聚合物上含有数量较多的硼酸基团,能够提高物质含量测试的准确性,扩大适用范围。
本发明的目的可以通过以下技术方案实现:
一种修饰型笼状分子印迹聚合物的制备方法,包括如下步骤:
第一步、制备修饰型硼酸;
第二步、将巯基丙酸与修饰型硼酸按照物质的量之比为1:1混合,溶解于甲苯中,室温下搅拌12-18h,旋蒸除去甲苯,得到改性硼酸;
修饰型硼酸分子上的-NH2与巯基丙酸分子上的-COOH在常温发生反应,使巯基丙酸分子链接枝于修饰型硼酸分子上,获得改性硼酸,该改性硼酸分子上含有两个硼酸基团与一个-SH基团,-SH能为后续与乙烯基POSS反应提供反应位点;
第三步、以甲苯为溶剂、偶氮二异丁腈为引发剂,将八乙烯基POSS与改性硼酸加入三口烧瓶中,于80℃反应3h,过滤,取滤液,旋蒸除去甲苯,获得修饰型POSS;甲苯、偶氮二异丁腈、八乙烯基POSS和改性硼酸的用量比为50mL:0.1g:0.03mol:0.18mol;
改性硼酸分子上的-SH与八乙烯基POSS分子上的双键发生巯基-烯点击化学反应,使改性硼酸接枝于笼状POSS上,形成硼酸修饰的POSS;由于改性硼酸的用量摩尔量为八乙烯基POSS分子的6倍,故修饰型POSS上含有未参与反应的双键,能够为后续聚合反应奠定反应位点;
第四步、将修饰型POSS与甲苯混合后,加入模板尿苷,静置4-6h,再加入乙二醇二甲基丙烯酸酯和引发剂AIBN,通入氮气15-20min,升高温度至70-80℃搅拌60-90min,再加入介孔分子筛MCM-48,超声20-30min,在氮气保护下,于50-60℃反应2h,70-75℃反应2h,80-90℃反应2h,制得聚合物微球;尿苷、乙二醇二甲基丙烯酸酯、修饰型POSS、引发剂AIBN、介孔分子筛MCM-48的用量之比为16mmol:50mmol:1mmol:10mg:400mg;
第五步、将聚合物微球抽滤、乙醇洗涤后,用含有HF的乙醇溶液浸泡刻蚀10h,过滤洗涤后,将聚合物微球置于索式提取器中,用甲醇/乙酸混合溶剂洗去模板分子后,放入真空干燥器中干燥至恒重,得到笼状分子印迹聚合物。
进一步地,所述介孔分子筛MCM-48是以正硅酸乙酯为硅源,以十六烷基三甲基溴化胺为活性剂,采用水热合成法合成得到的。
本发明还提供了该修饰型笼状分子印迹聚合物的应用,具体为:将该笼状分子印迹聚合物制成固相萃取柱,固相萃取柱与高效液相色谱检测方法结合,在食品中检测含有顺式二醇结构的木犀草素含量的应用。
具体为:将待检测的样品溶液加入笼状分子印迹聚合物,震荡后离心,将洗脱液过滤后进入高效液相色谱仪进行检测,测定食品中含有顺式二醇结构的核苷类物质含量。
进一步地,修饰型硼酸通过如下步骤制备:
S1、将2,6-二溴-4-硝基甲苯和铁粉混合,加入乙醇,室温下滴加冰乙酸,用油浴控制反应在70℃进行,反应3-4h后,冷却至室温,抽滤,滤液蒸干,用乙酸乙酯和正庚烷(体积比1:4)过柱纯化,蒸干,得中间体;2,6-二溴-4-硝基甲苯、铁粉、乙醇、冰乙酸的用量之比为0.038mol:8.5g:100mL:0.304mol;
在铁粉的作用下,2,6-二溴-4-硝基甲苯分子上的-NO2还原成-NH2,获得中间体,具体反应方程式如下所示:
S2、将中间体、四羟基二硼、NiCl2(dppp)、三苯基膦、二异丙基乙基胺和乙醇置于烧瓶中,氮气保护、升温至70℃,搅拌反应6小时,反应结束后,冷却至室温,抽滤,将滤液蒸干,将所得的粗品进行纯化操作,获得修饰型硼酸;中间体、四羟基二硼、NiCl2、三苯基膦、二异丙基乙基胺、乙醇的用量比为6.3g:6.4g:0.65g:0.63g:9.3g:100mL;
中间体分子上含有两个-Br,在NiCl2的催化作用下,与四羟基二硼反应生成硼酸基团,单个分子上含有两个硼酸基团,具体反应方程式如下所示:
进一步地,纯化操作为:按照固液比1g:10mL将粗品溶于3M盐酸中,乙酸乙酯萃取2次,再用碳酸氢钠将pH值调至5,有大量固体析出,用乙酸乙酯萃取,蒸干,纯化完成。
本发明的有益效果:
本发明通过在笼形POSS分子上修饰硼酸化合物,再聚合形成聚合物球体,应用于固相萃取柱中时,可实现对药品中含有顺式二醇结构的核苷类物质(胞苷、鸟苷、尿苷及肌苷)含量的同时检测;此外,本发明进一步改进创新的将自制的修饰型硼酸与乙烯基POSS接枝、修饰,笼形POSS本身具备多个活性位点,能够接枝多个硼酸化合物,而自制的硼酸化合物,单个分子上含有两个硼酸基团,在活性基团位点翻倍,在叠加作用下,印迹聚合物上含有数量较多的硼酸基团,在测定含有顺式二醇结构的核苷类物质时,硼酸基团活性位点越多,与被测物质的反应概率越高,吸附效率越高,从而提高物质含量测试的准确性;而且,活性位点越多,能够处理更高浓度的被测样品,扩大适用范围;从另一方面来看,笼状的POSS具有更好的包裹性,能够有效提高固相萃取柱吸附和解吸过程的稳定性。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
制备修饰型笼状分子印迹聚合物:
第一步、制备修饰型硼酸:
S1、将0.038mol的2,6-二溴-4-硝基甲苯和8.5g铁粉混合,加入100mL乙醇,室温下滴加0.304mol冰乙酸,用油浴控制反应在70℃进行,反应3-4h后,冷却至室温,抽滤,滤液蒸干,用乙酸乙酯和正庚烷(体积比1:4)过柱纯化,蒸干,得中间体;
S2、将6.3g中间体、6.4g四羟基二硼、0.65g的NiCl2(dppp)、0.63g的三苯基膦、9.3g二异丙基乙基胺和100mL乙醇置于烧瓶中,氮气保护、升温至70℃,搅拌反应6小时,反应结束后,冷却至室温,抽滤,将滤液蒸干,按照固液比1g:10mL将粗品溶于3M盐酸中,乙酸乙酯萃取2次,再用碳酸氢钠将pH值调至5,有大量固体析出,用乙酸乙酯萃取,蒸干,获得修饰型硼酸;
第二步、将0.2mol巯基丙酸与0.2mol修饰型硼酸混合,溶解于300mL甲苯中,室温下搅拌12h,旋蒸除去甲苯,得到改性硼酸;
第三步、以50mL甲苯为溶剂、0.1g偶氮二异丁腈为引发剂,将0.03mol八乙烯基POSS与0.18mol改性硼酸加入三口烧瓶中,于80℃反应3h,过滤,取滤液,旋蒸除去甲苯,获得修饰型POSS;
第四步、将1mmol修饰型POSS与50mL甲苯混合后,加入16mmol模板尿苷,静置4h,再加入50mmol乙二醇二甲基丙烯酸酯和10mg引发剂AIBN,通入氮气15min,升高温度至70℃搅拌60min,再加入400mg介孔分子筛MCM-48,超声20min,在氮气保护下,于50℃反应2h,70℃反应2h,80℃反应2h,制得聚合物微球;
第五步、将聚合物微球抽滤、乙醇洗涤后,用含有HF的乙醇溶液浸泡刻蚀10h,过滤洗涤后,将聚合物微球置于索式提取器中,用甲醇/乙酸混合溶剂洗去模板分子后,放入真空干燥器中干燥至恒重,得到笼状分子印迹聚合物。
实施例2
制备修饰型笼状分子印迹聚合物:
第一步、制备修饰型硼酸:
S1、将0.038mol的2,6-二溴-4-硝基甲苯和8.5g铁粉混合,加入100mL乙醇,室温下滴加0.304mol冰乙酸,用油浴控制反应在70℃进行,反应3.5h后,冷却至室温,抽滤,滤液蒸干,用乙酸乙酯和正庚烷(体积比1:4)过柱纯化,蒸干,得中间体;
S2、将6.3g中间体、6.4g四羟基二硼、0.65g的NiCl2(dppp)、0.63g的三苯基膦、9.3g二异丙基乙基胺和100mL乙醇置于烧瓶中,氮气保护、升温至70℃,搅拌反应6小时,反应结束后,冷却至室温,抽滤,将滤液蒸干,按照固液比1g:10mL将粗品溶于3M盐酸中,乙酸乙酯萃取2次,再用碳酸氢钠将pH值调至5,有大量固体析出,用乙酸乙酯萃取,蒸干,获得修饰型硼酸;
第二步、将0.2mol巯基丙酸与0.2mol修饰型硼酸混合,溶解于300mL甲苯中,室温下搅拌15h,旋蒸除去甲苯,得到改性硼酸;
第三步、以50mL甲苯为溶剂、0.1g偶氮二异丁腈为引发剂,将0.03mol八乙烯基POSS与0.18mol改性硼酸加入三口烧瓶中,于80℃反应3h,过滤,取滤液,旋蒸除去甲苯,获得修饰型POSS;
第四步、将1mmol修饰型POSS与50mL甲苯混合后,加入16mmol模板尿苷,静置5h,再加入50mmol乙二醇二甲基丙烯酸酯和10mg引发剂AIBN,通入氮气18min,升高温度至75℃搅拌75min,再加入400mg介孔分子筛MCM-48,超声25min,在氮气保护下,于55℃反应2h,73℃反应2h,85℃反应2h,制得聚合物微球;
第五步、将聚合物微球抽滤、乙醇洗涤后,用含有HF的乙醇溶液浸泡刻蚀10h,过滤洗涤后,将聚合物微球置于索式提取器中,用甲醇/乙酸混合溶剂洗去模板分子后,放入真空干燥器中干燥至恒重,得到笼状分子印迹聚合物。
实施例3
制备修饰型笼状分子印迹聚合物:
第一步、制备修饰型硼酸:
S1、将0.038mol的2,6-二溴-4-硝基甲苯和8.5g铁粉混合,加入100mL乙醇,室温下滴加0.304mol冰乙酸,用油浴控制反应在70℃进行,反应4h后,冷却至室温,抽滤,滤液蒸干,用乙酸乙酯和正庚烷(体积比1:4)过柱纯化,蒸干,得中间体;
S2、将6.3g中间体、6.4g四羟基二硼、0.65g的NiCl2(dppp)、0.63g的三苯基膦、9.3g二异丙基乙基胺和100mL乙醇置于烧瓶中,氮气保护、升温至70℃,搅拌反应6小时,反应结束后,冷却至室温,抽滤,将滤液蒸干,按照固液比1g:10mL将粗品溶于3M盐酸中,乙酸乙酯萃取2次,再用碳酸氢钠将pH值调至5,有大量固体析出,用乙酸乙酯萃取,蒸干,获得修饰型硼酸;
第二步、将0.2mol巯基丙酸与0.2mol修饰型硼酸混合,溶解于300mL甲苯中,室温下搅拌18h,旋蒸除去甲苯,得到改性硼酸;
第三步、以50mL甲苯为溶剂、0.1g偶氮二异丁腈为引发剂,将0.03mol八乙烯基POSS与0.18mol改性硼酸加入三口烧瓶中,于80℃反应3h,过滤,取滤液,旋蒸除去甲苯,获得修饰型POSS;
第四步、将1mmol修饰型POSS与50mL甲苯混合后,加入16mmol模板尿苷,静置6h,再加入50mmol乙二醇二甲基丙烯酸酯和10mg引发剂AIBN,通入氮气20min,升高温度至80℃搅拌90min,再加入400mg介孔分子筛MCM-48,超声30min,在氮气保护下,于60℃反应2h,75℃反应2h,90℃反应2h,制得聚合物微球;
第五步、将聚合物微球抽滤、乙醇洗涤后,用含有HF的乙醇溶液浸泡刻蚀10h,过滤洗涤后,将聚合物微球置于索式提取器中,用甲醇/乙酸混合溶剂洗去模板分子后,放入真空干燥器中干燥至恒重,得到笼状分子印迹聚合物。
性能测试
取200mg实施例1-3制得的聚合物材料,填充至5mL底部装有筛板的中空固相萃取柱中,再在填料的上方放置筛板并压实。
以红花口服液作为实际样品,进行实际样品的富集和净化,具体的步骤为,精密量取实际样品2mL,置50mL容量瓶中,加流动相稀释至50mL刻度,摇匀,取适量溶液至具塞离心管中,于4000r·min-1条件下离心30min后,过滤,取滤液;
将上述固相萃取柱置于真空固相萃取装置上,依次用5mL乙腈、5mL水在负压状态下活化,并抽干活化溶剂;
将上述滤液在负压状态下连续通过固相萃取柱,抽干溶剂;再以1mL正丁烷做淋洗剂在负压状态下连续通过固相萃取柱进行淋洗,抽干淋洗剂,并保持连续抽干状态;以1.0mL体积比为5:5的1%三氟乙酸/乙腈的混合溶剂作为洗脱剂,在负压状态下连续通过固相萃取柱对分析物进行洗脱,抽干洗脱剂;将洗脱液过滤后进高效液相检测,空白对照组为直接HPLC分析,计算色谱图峰面积,测试结果如下表所示:
由以上数据可知,本发明制得的分子印迹聚合物对核苷类物质具有明显的富集效果,使得由此制得的固相萃取柱具有明显的吸附效果。
以上具体实施方式部分对本发明所涉及的分析方法进行了具体的介绍。应当注意的是,上述介绍仅是为了帮助本领域技术人员更好地理解本发明的方法及思路,而不是对相关内容的限制。在不脱离本发明原理的情况下,本领域技术人员还可以对本发明进行适当的调整或修改,上述调整和修改也应当属于本发明的保护范围。
Claims (8)
1.一种修饰型笼状分子印迹聚合物的制备方法,其特征在于,包括如下步骤:
第一步、制备修饰型硼酸,具体步骤如下:
S1、将2,6-二溴-4-硝基甲苯和铁粉混合,加入乙醇,室温下滴加冰乙酸,用油浴控制反应在70℃进行,反应3-4h后,冷却至室温,抽滤,滤液蒸干,过柱纯化,蒸干,得中间体;
S2、将中间体、四羟基二硼、NiCl2、三苯基膦、二异丙基乙基胺和乙醇置于烧瓶中,氮气保护、升温至70℃,搅拌反应6小时,反应结束后,冷却至室温,抽滤,将滤液蒸干,将所得的粗品进行纯化操作,获得修饰型硼酸;
第二步、将巯基丙酸与修饰型硼酸按照物质的量之比为1:1混合,溶解于甲苯中,室温下搅拌12-18h,旋蒸除去甲苯,得到改性硼酸;
第三步、以甲苯为溶剂、偶氮二异丁腈为引发剂,将八乙烯基POSS与改性硼酸加入三口烧瓶中,于80℃反应3h,过滤,取滤液,旋蒸除去甲苯,获得修饰型POSS;
第四步、将修饰型POSS与甲苯混合后,加入模板尿苷,静置4-6h,再加入乙二醇二甲基丙烯酸酯和引发剂AIBN,通入氮气15-20min,升高温度至70-80℃搅拌60-90min,再加入介孔分子筛MCM-48,超声20-30min,在氮气保护下,于50-60℃反应2h,70-75℃反应2h,80-90℃反应2h,制得聚合物微球;
第五步、对聚合物微球进行洗脱模板,真空干燥至恒重,得到笼状分子印迹聚合物。
2.根据权利要求1所述的一种修饰型笼状分子印迹聚合物的制备方法,其特征在于,第三步中甲苯、偶氮二异丁腈、八乙烯基POSS和改性硼酸的用量比为50mL:0.1g:0.03mol:0.18mol。
3.根据权利要求1所述的一种修饰型笼状分子印迹聚合物的制备方法,其特征在于,所述介孔分子筛MCM-48是以正硅酸乙酯为硅源,以十六烷基三甲基溴化胺为活性剂,采用水热合成法合成得到的。
4.根据权利要求1所述的一种修饰型笼状分子印迹聚合物的制备方法,其特征在于,第四步中尿苷、乙二醇二甲基丙烯酸酯、修饰型POSS、引发剂AIBN、介孔分子筛MCM-48的用量之比为16mmol:50mmol:1mmol:10mg:400mg。
5.根据权利要求1所述的一种修饰型笼状分子印迹聚合物的制备方法,其特征在于,步骤S1中2,6-二溴-4-硝基甲苯、铁粉、乙醇、冰乙酸的用量之比为0.038mol:8.5g:100mL:0.304mol。
6.根据权利要求1所述的一种修饰型笼状分子印迹聚合物的制备方法,其特征在于,步骤S2中中间体、四羟基二硼、NiCl2、三苯基膦、二异丙基乙基胺、乙醇的用量比为6.3g:6.4g:0.65g:0.63g:9.3g:100mL。
7.根据权利要求1所述的一种修饰型笼状分子印迹聚合物的制备方法,其特征在于,步骤S2中纯化操作为:按照固液比1g:10mL将粗品溶于3M盐酸中,乙酸乙酯萃取2次,再用碳酸氢钠将pH值调至5,有大量固体析出,用乙酸乙酯萃取,蒸干,纯化完成。
8.根据权利要求1所述的方法制备的修饰型笼状分子印迹聚合物的应用,其特征在于,将该笼状分子印迹聚合物制成固相萃取柱,固相萃取柱与高效液相色谱检测方法结合,在食品中检测含有顺式二醇结构的木犀草素含量的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210536323.7A CN114832441B (zh) | 2022-05-17 | 2022-05-17 | 一种修饰型笼状分子印迹聚合物的制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210536323.7A CN114832441B (zh) | 2022-05-17 | 2022-05-17 | 一种修饰型笼状分子印迹聚合物的制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114832441A CN114832441A (zh) | 2022-08-02 |
CN114832441B true CN114832441B (zh) | 2024-01-26 |
Family
ID=82569868
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210536323.7A Active CN114832441B (zh) | 2022-05-17 | 2022-05-17 | 一种修饰型笼状分子印迹聚合物的制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114832441B (zh) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107189011A (zh) * | 2016-12-21 | 2017-09-22 | 哈尔滨师范大学 | 中空分子印迹聚合物、固相萃取柱及其制备方法和应用 |
GB202102631D0 (en) * | 2019-11-20 | 2021-04-07 | Anple Laboratory Tech Shanghai Inc | Benzeneboronic Acid Solid-phase Extraction Column Packing and Preperation Method Thereof |
CN113929840A (zh) * | 2021-10-11 | 2022-01-14 | 华中科技大学 | 一种用于分离富集紫杉烷的中空多孔介质、其制备和应用 |
-
2022
- 2022-05-17 CN CN202210536323.7A patent/CN114832441B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107189011A (zh) * | 2016-12-21 | 2017-09-22 | 哈尔滨师范大学 | 中空分子印迹聚合物、固相萃取柱及其制备方法和应用 |
GB202102631D0 (en) * | 2019-11-20 | 2021-04-07 | Anple Laboratory Tech Shanghai Inc | Benzeneboronic Acid Solid-phase Extraction Column Packing and Preperation Method Thereof |
CN113929840A (zh) * | 2021-10-11 | 2022-01-14 | 华中科技大学 | 一种用于分离富集紫杉烷的中空多孔介质、其制备和应用 |
Non-Patent Citations (1)
Title |
---|
Synergistic effect of polyhedral oligomeric semisiloxane and boronate affinity molecularly imprinted polymer in a solid-phase extraction system for selective enrichment of ovalbumin;Baoyue Zhang et al.;《Microchemical Journal》(第168期);前言部分、2.4和2.5部分 * |
Also Published As
Publication number | Publication date |
---|---|
CN114832441A (zh) | 2022-08-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Andersson et al. | A highly selective solid phase extraction sorbent for pre-concentration of sameridine made by molecular imprinting | |
CN104231166B (zh) | 一种仿生青蒿素分子印迹复合膜的制备方法 | |
CN107970788B (zh) | 选择性识别分离依诺沙星分子印迹复合膜材料的制备方法 | |
Liang et al. | Ordered macroporous molecularly imprinted polymers prepared by a surface imprinting method and their applications to the direct extraction of flavonoids from Gingko leaves | |
Wang et al. | Enhanced binding capacity of boronate affinity adsorbent via surface modification of silica by combination of atom transfer radical polymerization and chain-end functionalization for high-efficiency enrichment of cis-diol molecules | |
Wang et al. | The preparation of high-capacity boronate affinity adsorbents by surface initiated reversible addition fragmentation chain transfer polymerization for the enrichment of ribonucleosides in serum | |
Zhu et al. | Using ionic liquid monomer to improve the selective recognition performance of surface imprinted polymer for sulfamonomethoxine in strong polar medium | |
CN104861130A (zh) | 一种高分子刷接枝硼酸亲和分离材料及其制备方法与应用 | |
CN101768238A (zh) | 一种桔青毒素分子印迹材料及其制备方法与应用 | |
AU2020100965A4 (en) | Method For Preparation Of Solid Phase Extraction Column Of Sophocarpine Molecularly Imprinted Polymer | |
CN105153367A (zh) | 一种双氰胺介孔表面分子印迹聚合物微球的制备方法 | |
CN107189011B (zh) | 中空分子印迹聚合物、固相萃取柱及其制备方法和应用 | |
CN114832441B (zh) | 一种修饰型笼状分子印迹聚合物的制备方法和应用 | |
Hu et al. | Hierarchically porous MOFs self-supporting copolymers for ultrafast transport and precise recognition of flavonoids: A triple interfacial crosslinking strategy based on microreactors | |
CN103599755A (zh) | 苯乙醇胺a分子印迹膜及其制备方法与应用 | |
Ling et al. | Polymer‐bound cellulose phenylcarbamate derivatives as chiral stationary phases for enantioselective HPLC | |
CN105854844B (zh) | 青蒿酸磁性印迹微球及其制法与应用 | |
CN104174390A (zh) | 乙氧酰胺苯甲酯分子印迹固相萃取小柱的制备方法及应用 | |
CN113634238B (zh) | 一种柔性多孔硼亲和共聚物吸附剂及其制备方法和应用 | |
Yu et al. | RECENT DEVELOPMENT AND APPLICATION OF MONOLITHIC COLUMNS. | |
CN109851717A (zh) | 一种阴离子型psss/psa微球的制备方法及应用 | |
Churilina et al. | Adsorption preconcentration of 4-nitrophenol from aqueous solutions using polymers based on cyclic N-vinylamides | |
CN105237770A (zh) | 一种分子印迹聚合物的制备方法 | |
CN102539587B (zh) | 常山酮分子印迹固相萃取小柱的制备方法和应用 | |
CN109880148B (zh) | 一种表面印迹材料的制备及其在谷氨酸对映体拆分中的应用 |
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 |