CN110575824A - 一种杂化多孔整体材料及其制备和应用 - Google Patents
一种杂化多孔整体材料及其制备和应用 Download PDFInfo
- Publication number
- CN110575824A CN110575824A CN201810584148.2A CN201810584148A CN110575824A CN 110575824 A CN110575824 A CN 110575824A CN 201810584148 A CN201810584148 A CN 201810584148A CN 110575824 A CN110575824 A CN 110575824A
- Authority
- CN
- China
- Prior art keywords
- poss
- pore
- hybrid
- acrylate
- solution
- 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
- 239000000463 material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 8
- 239000012472 biological sample Substances 0.000 claims abstract description 5
- 238000013375 chromatographic separation Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- -1 3-mercaptopropyl Chemical group 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 230000002255 enzymatic effect Effects 0.000 claims description 11
- 239000004088 foaming agent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000413 hydrolysate Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 7
- 108091003079 Bovine Serum Albumin Proteins 0.000 claims description 6
- 229940098773 bovine serum albumin Drugs 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 125000004386 diacrylate group Chemical group 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 238000004587 chromatography analysis Methods 0.000 claims description 3
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 claims 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims 4
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims 2
- 150000001448 anilines Chemical class 0.000 claims 1
- INDXRDWMTVLQID-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO.OCCCCO INDXRDWMTVLQID-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- USGIERNETOEMNR-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO.CCCO USGIERNETOEMNR-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 7
- 238000004458 analytical method Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 2
- DAWJJMYZJQJLPZ-UHFFFAOYSA-N 2-sulfanylprop-2-enoic acid Chemical compound OC(=O)C(S)=C DAWJJMYZJQJLPZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 229920000058 polyacrylate Polymers 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 24
- 238000000926 separation method Methods 0.000 description 23
- 238000003981 capillary liquid chromatography Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 150000002989 phenols Chemical class 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001555 benzenes Chemical class 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000009396 hybridization Methods 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 108010033276 Peptide Fragments Proteins 0.000 description 3
- 102000007079 Peptide Fragments Human genes 0.000 description 3
- 108010009736 Protein Hydrolysates Proteins 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 238000004366 reverse phase liquid chromatography Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000004885 tandem mass spectrometry Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- OQHHSGRZCKGLCY-UHFFFAOYSA-N 8-nitroquinoline Chemical compound C1=CN=C2C([N+](=O)[O-])=CC=CC2=C1 OQHHSGRZCKGLCY-UHFFFAOYSA-N 0.000 description 1
- CFRFHWQYWJMEJN-UHFFFAOYSA-N 9h-fluoren-2-amine Chemical compound C1=CC=C2C3=CC=C(N)C=C3CC2=C1 CFRFHWQYWJMEJN-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XBJFCYDKBDVADW-UHFFFAOYSA-N acetonitrile;formic acid Chemical compound CC#N.OC=O XBJFCYDKBDVADW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002045 capillary electrochromatography Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- HQVFCQRVQFYGRJ-UHFFFAOYSA-N formic acid;hydrate Chemical compound O.OC=O HQVFCQRVQFYGRJ-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 238000001121 post-column derivatisation Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/58—Use in a single column
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明涉及一种添加多面体低聚半硅氧烷试剂(POSS)的聚丙烯酸酯类杂化整体材料的制备。首先是将带有巯基的多面体低聚半硅氧烷试剂与其他两种丙烯酸酯类单体混合,加入致孔溶剂超声溶解;通过紫外光引发,原位发生丙烯酸酯自聚反应以及巯基‑丙烯酸酯点击化学反应,即可得到该杂化整体材料。该整体材料制备过程简单快速、反应条件温和,并且具有均一的孔结构和良好的热稳定性,可以应用于小分子化合物和复杂生物样品的高效色谱分离分析。
Description
技术领域
本发明涉及一种基于光引发的巯基自由基介导的聚合反应快速制备有机–无机杂化多孔整体材料及其制备方法和应用,具体是将经巯丙基三甲氧基硅烷修饰后含有八个巯基的多面体低聚倍半硅氧烷,丙烯酸酯类化合物和光引发剂在致孔溶剂中超声溶解,利用光引发的丙烯酸酯自聚反应以及巯基–丙烯酸酯点击化学反应(photoinduced thiol-eneclick polymerization reaction)原位形成有机–无机杂化多孔整体材料。通过调节单体的浓度、巯基的加入量和致孔剂的比例,最终可制备出一种具有优异色谱性能的多孔杂化整体材料,具体为一种杂化多孔整体材料及其制备和应用。
背景技术
近年来,微型化已经成为液相色谱的主要发展趋势之一,同时也追求着高速分离和高柱效。因此,毛细管色谱就成为微纳米尺度分离分析的领域中的研究热点之一,它主要分为毛细管电色谱和毛细管液相色谱。毛细管柱是毛细管色谱分离中的核心,分离效果的优劣与毛细管柱固定相的化学和物理特性密切相关。多孔整体材料作为一种新型多孔微分离介质,具有高容量、快速分离和易于与质谱联用等优点,已经广泛应用于毛细管液相色谱。
根据多孔整体材料的基质不同性质,可将毛细管整体柱分为有机整体柱,无机整体柱和杂化整体柱三种类型。其中有机整体柱具有制备过程简单、生物兼容性好、pH适用范围宽等优点。但是,有机整体柱机械强度较差、稳定性不好,且在一些有机溶剂中易发生溶胀。许多研究人员致力于解决该问题,目前主要分为两种方法。一种是系统地优化有机整体柱的制备条件,其中包括单体的、交联剂的选择、致孔剂的选择、聚合时间和反应温度的优化以及柱后衍生等,以此获得令人满意的多孔有机整体材料;另一种方法是在有机整体柱中加入纳米粒子,利用其特殊的物理和化学性质来提高多孔有机整体材料的分离性能。
多面体低聚倍半硅氧烷是一种纳米级的有机-无机杂化分子,由于其独特的笼状结构,具有多种优异的功能。所以,具有不同功能基团多面体低聚倍半硅氧烷试剂可以被用来制备杂化整体柱,发生自由基聚合、巯基为基础的点击化学和开环聚合等反应。利用一锅法,将具有特定功能基团的多面体低聚倍半硅氧烷试剂添加到反应体系中,参与整体材料的制备。这就在一定程度上克服了无机整体材料和有机整体材料的缺陷,最终获得机械强度高、制备过程简单、性能优越的多孔杂化整体材料。
通过添加多面体低聚倍半硅氧烷试剂,使多孔杂化整体材料具有性能稳定、通透性好等优点。它可作为固定相被应用于毛细管液相色谱中,实现快速制备与快速分离。多孔杂化整体材料作为一种出色的色谱分离介质,可广泛应用在药物学、环境科学和生命科学等领域。
发明内容
本发明提供了一种基于丙烯酸酯自聚合反应和巯基–丙烯酸酯点击化学反应制备多孔杂化整体材料的方法。具有是将含有八个巯基的多面体低聚倍半硅氧烷、两种丙烯酸酯类单体、致孔剂和光引发剂通过超声混合均匀,在紫外交联仪中曝光,通过光引发的聚合反应制备有机–无机杂化整体材料。
本发明采用的技术方案为:
将经巯丙基三甲氧基硅烷修饰后的含有八个巯基的多面体低聚倍半硅氧烷、含有丙烯酸酯的两个功能单体和光引发剂溶解在致孔溶剂中,超声混合至成均匀透明溶液,利用巯基介导的逐步聚合反应制备出有机–无机多孔杂化整体材料,并根据不同的需求,通过调节单体浓度和致孔剂比例,可以制备出不同性质的有机–无机多孔杂化整体材料。
本发明所制备的杂化多孔整体材料可应用于色谱分析,尤其适用于毛细管液相色谱,同时可实现小分子和复杂生物样品的分离及鉴定。分离对象分别为五种苯系物、胺类化合物、酚类化合物以及复杂生物样品如蛋白酶解液。结果显示在反相色谱模式下五种苯系物、九种酚类化合物和五种胺类化合物分别达到基线分离且峰形对称,同时在液质联用中,此材料可实现复杂样品中多种肽段的分离及蛋白鉴定。
本发明的有益效果和优势为:
本方法采用的是光引发的巯基介导的逐步聚合反应(photoinduced thiol-enepolymerization reaction),由于适量巯基的存在氧聚阻作用被消除,使制备过程更加简单、制备时间缩短。杂化多孔整体材料的形成只需要在紫外交联仪中曝光反应即可,而且其孔径、孔结构和通透性可以通过改变加入交联剂和功能单体浓度和改变致孔溶剂的组成或者含量来进行调控。
本发明所制备的杂化整体材料具有较为均一的多孔结构,适于色谱分离分析。液相色谱考察结果表明,杂化多孔整体材料表面具有疏水性质,对中性化合物表现出典型的反相保留机制。本实验中选用的巯基化合物为丙烯酸十八酯,具有较强的疏水性,所制备的杂化多孔整体柱表现出较强的疏水性和较高的柱效。
本发明所制备的杂化多孔整体材料具有通透性好,生物兼容性好,热稳定性好,功能修饰方法简便,同时通用性较强,可采用其它甲基丙烯酸酯或丙烯酸酯功能单体为原料。
附图说明
图1毛细管杂化整体柱的扫描电镜图(a为10000倍,b为1000倍)。
图2为多孔杂化整体材料的热重分析图。
图3为多孔杂化整体材料的孔径分布图。
图4为苯系物在毛细管杂化整体柱的毛细管液相色谱分离图。
图5为苯系物在毛细管杂化整体柱的van Deemter图。
图6为乙腈含量对保留因子的影响。
图7为酚类以及胺类化合物在毛细管杂化整体柱的毛细管液相色谱分离图(a为酚类化合物,b为胺类化合物)。
图8为牛血清白蛋白酶解液和HeLa细胞酶解液在毛细管杂化整体柱的cLC-MS/MS分离图(a为牛血清白蛋白酶解液,b为HeLa细胞酶解液)。
图9为基于巯基–丙烯酸酯点击聚合反应原位制备杂化多孔整体材料的反应式。
具体实施方式
实施例1
POSS-SH功能单体的制备:首先取15mL巯丙基三甲氧基硅烷(MPTS)溶解在360mL甲醇中,向溶液中滴加30mL浓盐酸(36%~38%),在90℃油浴中回流反应24h;反应完成后,将反应液在冰浴(-4℃-4℃)中冷却得到粗产物,用甲醇洗涤粗产物三次,除去残留的巯丙基三甲氧基硅烷;然后,用二氯甲烷溶解所得粗产物,在该溶液中加入水进行萃取,收集二氯甲烷层,再加入水萃取,重复三次,最终收集二氯甲烷,在其中加入无水硫酸钠干燥过夜;最后,将所得溶液进行减压蒸馏,得到产物POSS-SH。所得POSS-SH溶于四氢呋喃溶液(50.0%,w/v,mg/ml)备用。
制备步骤如下:
1)向离心管中加入单体丙烯酸十八酯60mg;
2)向步骤1)的离心管中加入158μL的正丙醇作为致孔剂;
3)向离心管中加入60mg的功能单体1,6-己二醇乙氧酸二丙烯酸酯;
4)向步骤3)的离心管中加入46μL的1,4-丁二醇作为致孔剂;
5)向步骤4)的离心管中加入10μL功能单体POSS-SH;
6)向步骤5)的离心管中加入36μL的THF作为致孔剂;
7)将步骤6)的离心管在室温下超声2min,使其完全溶解形成均匀透明溶液;
8)将步骤5)中得到的预聚液1μL用注射器引入到已预先经过3-(甲基丙烯酰氧)丙基三甲氧基硅烷活化处理的75μm(内径)的毛细管中,随后毛细管两端用硅胶封口,然后将装有剩余混合液的离心管密封。
9)将步骤8)中密封着混合溶液的反应器置于波长为365nm的紫外交联仪中,反应7min,至离心管中的混合液反应变成白色的固体;
10)用乙醇洗涤至少3次步骤9)反应器得到的产物,将致孔剂及未反应或未结合上的物质冲出,得到杂化多孔整体材料。
11)用乙醇冲洗毛细管,将其中的致孔剂及一些未参与反应的物质冲出即制备成毛细管杂化整体柱。毛细管杂化整体柱的扫描电镜图见图1(a,b);多孔杂化整体材料的热重分析图见图2;多孔杂化整体材料的孔径分布图见图3;毛细管液相色谱分离图见图4;毛细管杂化整体柱的van Deemter见图5;乙腈含量对保留因子的影响见图6。
图2为多孔杂化整体材料的热重分析图。整体材料的失重范围是345-550℃,说明材料具有良好的热稳定性。
图3为多孔杂化整体材料的孔径分布图。多孔杂化整体材料的孔径主要是1μm左右的大孔。
图4为苯系物在毛细管杂化整体柱的毛细管液相色谱分离图。色谱条件为毛细管柱(19.8cm×75μm i.d.),流动相为乙腈/水(60/40,v/v),流速为200μL/min(分流前)。色谱图中的峰依次为(1)硫脲、(2)苯、(3)甲苯、(4)乙苯、(5)丙苯和(6)丁苯。出峰顺序按疏水性由弱到强出峰,为典型的反相色谱保留机理。
图5为苯系物在毛细管杂化整体柱的van Deemter图。分析物为(▲)苯、(○)甲苯、(●)乙苯、(□)丙苯和(■)丁苯;色谱条件为毛细管柱(19.8cm×75μm i.d.),流动相为乙腈/水(60/40,v/v),流速为20-220μL/min(分流前)。
图6为乙腈含量对保留因子的影响图。色谱条件为毛细管柱(19.8cm×75μmi.d.),流动相为乙腈/水(50/50-80/20,v/v),流为100μL/min(分流前)。
图7为酚类以及胺类化合物在毛细管杂化整体柱的毛细管液相色谱分离图(a为酚类化合物,b为胺类化合物)。色谱图中的峰依次为(a)(1)间苯三酚、(2)邻苯三酚、(3)苯酚、(4)间甲酚、(5)双酚A、(6)邻甲酚、(7)2,6-二甲苯酚、(8)萘酚、(9)对叔丁基苯酚;(b)(1)8-硝基喹啉、(2)对硝基苯胺、(3)邻硝基苯胺、(4)1-萘胺、(5)2-氨基芴。流动相为(a)乙腈/水(40/60,v/v),(b)乙腈/水(45/55,v/v);流速为175μL/min(分流前)。在反相色谱模式下九种酚类化合物和五种胺类化合物分别达到基线分离且峰形对称。
图8为牛血清白蛋白酶解液和HeLa细胞酶解液在毛细管杂化整体柱的cLC-MS/MS分离图(a为牛血清白蛋白酶解液,b为HeLa细胞酶解液)。色谱条件为毛细管柱(37.0cm×100μm i.d.);流动相A相为0.1%甲酸水溶液,B相为0.1%甲酸乙腈溶液;流动相梯度(a)0-5%B(0-2min),5-35%B(2-32min),35-80%B(32-62min),80%B(62-72min),(b)0-5%B(0-2min),5-35%B(2-95min),35-80%B(95-103min),80%B(103-113min);流速为80μL/min(分流前)。结果表明,对牛血清蛋白酶解液分析,鉴定出有108条非冗余的肽段,蛋白覆盖率在85%以上;对HeLa细胞酶解液分析,最高鉴定了出1,287个蛋白质和5,038条肽段。
由实施例和附图可见,该方法制备过程简单,所需时间短,所制备的杂化整体柱热稳定性好,孔形貌均一,可将其应用于小分子和复杂生物样品的分离。它具有适宜的通透性,高柱效,分离能力强等优点。同时,通过替换该反应体系中任意单体,可制备出多种应用于不同分离模式的毛细管液相色谱整体柱,这改善了整体柱的选择性,拓宽其在分离分析科学中的应用范围。
Claims (7)
1.一种丙烯酸酯杂化整体材料;该整体材料是利用致孔溶剂将含巯基的八(3-巯基丙基)多面体低聚倍半硅氧烷(POSS-SH)试剂与两种不同的丙烯酸酯类单体溶解,加入光引发剂超声混匀,将均一的预聚液置入紫外交联仪中曝光,原位形成一种杂化多孔整体材料;所述含有多巯基的POSS试剂为八(3-巯基丙基)多面体低聚半硅氧烷(octakis(3-Mercaptopropyl)octasilsesquioxane,POSS-SH),其他两种丙烯酸酯类单体分别1,6-己二醇乙氧酸二丙烯酸酯(1,6-Hexanediol ethoxylate diacrylate,HDEA)和丙烯酸十八酯(Stearyl acrylate,SA)。
2.一种权利要求1所述杂化多孔整体材料的制备方法,其特征在于:
所述含有多巯基的POSS试剂为八(3-巯基丙基)多面体低聚半硅氧烷(octakis(3-Mercaptopropyl)octasilsesquioxane,POSS-SH),其他两种丙烯酸酯类单体分别1,6-己二醇乙氧酸二丙烯酸酯(1,6-Hexanediol ethoxylate diacrylate,HDEA)和丙烯酸十八酯(Stearyl acrylate,SA);所述致孔剂为四氢呋喃(Tetrahydrofuran,THF)、1,4-丁二醇(1,4-Butanediol)和正丙醇(1-Propanol);
可按如下步骤操作,
1)POSS-SH功能单体的制备;
2)取步骤1)所得POSS-SH溶于四氢呋喃溶液(49.5~50.5%,w/v,mg/ml)备用;
3)取一个离心管,向其中加入丙烯酸十八酯50~70mg;
4)向步骤3)的离心管中加入正丙醇0.14~0.20mL为致孔剂;
5)向步骤4)的离心管加入中功能单体1,6-己二醇乙氧酸二丙烯酸酯50~70mg;
6)向步骤5)的离心管中加入1,4-丁二醇0.00~0.08mL(优选0.04~0.08mL)为致孔剂;
7)向步骤6)的离心管中加入四氢呋喃0.03~0.12mL为致孔剂;
8)向步骤7)的离心管加入中功能单体POSS-SH 10~30μL;
9)向步骤8)的离心管加入中光引发剂2,2-二甲氧基-苯基苯乙酮0.10~0.12mg;
10)将步骤9)所获溶液超声,使单体等完全溶解形成均匀透明溶液;
11)将步骤10)所获装有均匀预聚液的离心管放入紫外交联仪中曝光,得到白色不透明固体;
12)用乙醇洗涤步骤11)离心管中所得产物,将致孔剂及残留物质冲出,得到杂化多孔整体材料。
3.根据权利要求2所述的制备方法,其特征在于:
POSS-SH功能单体的制备:首先取15mL巯丙基三甲氧基硅烷(MPTS)溶解在358~362mL甲醇中,向溶液中滴加28~32mL浓盐酸(质量分数36%~38%),在88~92℃油浴中回流反应24~26h;反应完成后,将反应液在冰浴(-4℃~4℃)中冷却得到粗产物,用甲醇洗涤粗产物三至五次,除去残留的巯丙基三甲氧基硅烷;然后用二氯甲烷溶解所得粗产物,在该溶液中加入水进行萃取,收集二氯甲烷层,再加入水萃取,重复三至五次,最终收集二氯甲烷,在其中加入无水硫酸钠干燥过夜(通常12h~14h);最后,将所得溶液进行减压蒸馏,得到产物POSS-SH。
4.根据权利要求2所述的制备方法,其特征在于:所述含有丙烯酸酯基团的单体均为50~70mg;含有巯基的POSS试剂为10~30μL;致孔剂为0.2~0.4mL;光引发剂为2,2-二甲氧基-苯基苯乙酮0.10~0.12mg;所述致孔溶剂中正丙醇、1,4-丁二醇和四氢呋喃的体积比为4:1:1~5:0:1。
5.根据权利要求2所述的制备方法,其特征在于:将步骤10)超声后的透明溶液引入毛细管中,再进行毛细管端口密封,进行步骤11)的光引发反应,然后进行步骤12)的乙醇洗涤步骤,即得到毛细管杂化整体柱。
6.根据权利要求2或5所述的制备方法,其特征在于:权利要求2步骤10)超声时间为3~4min,室温下进行权利要求2中步骤11)的光引发反应,反应时间为7~8min。
7.一种权利要求1所述多孔杂化整体材料可以应用于小分子化合物(包括苯酚和/或苯胺类化合物)的高效色谱分离和/或复杂生物样品(包括牛血清白蛋白酶解液和/或HeLa细胞酶解液)的色谱分析。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810584148.2A CN110575824B (zh) | 2018-06-08 | 2018-06-08 | 一种杂化多孔整体材料及其制备和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810584148.2A CN110575824B (zh) | 2018-06-08 | 2018-06-08 | 一种杂化多孔整体材料及其制备和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110575824A true CN110575824A (zh) | 2019-12-17 |
CN110575824B CN110575824B (zh) | 2021-08-31 |
Family
ID=68808924
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810584148.2A Active CN110575824B (zh) | 2018-06-08 | 2018-06-08 | 一种杂化多孔整体材料及其制备和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110575824B (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112920787A (zh) * | 2021-02-05 | 2021-06-08 | 西华师范大学 | 一种笼形两亲纳米颗粒及其制备方法和应用 |
CN115212853A (zh) * | 2021-04-14 | 2022-10-21 | 中国科学院大连化学物理研究所 | 一种异植醇修饰聚丙烯酸酯微球及其制备与应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102757535A (zh) * | 2012-06-29 | 2012-10-31 | 天津大学 | 含poss的聚丙烯酸接枝pdms共聚物及制备和应用 |
CN104109222A (zh) * | 2013-04-22 | 2014-10-22 | 中国科学院大连化学物理研究所 | 一种含多面体寡聚倍半硅烷试剂的杂化整体材料的制备 |
CN105985474A (zh) * | 2015-02-13 | 2016-10-05 | 中国科学院大连化学物理研究所 | 基于光引发的巯基–丙烯酸酯聚合反应快速制备有机–无机杂化多孔整体材料的方法 |
CN107434833A (zh) * | 2016-05-25 | 2017-12-05 | 中国科学院大连化学物理研究所 | 一种有机多孔整体材料及其制备方法和应用 |
-
2018
- 2018-06-08 CN CN201810584148.2A patent/CN110575824B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102757535A (zh) * | 2012-06-29 | 2012-10-31 | 天津大学 | 含poss的聚丙烯酸接枝pdms共聚物及制备和应用 |
CN104109222A (zh) * | 2013-04-22 | 2014-10-22 | 中国科学院大连化学物理研究所 | 一种含多面体寡聚倍半硅烷试剂的杂化整体材料的制备 |
CN105985474A (zh) * | 2015-02-13 | 2016-10-05 | 中国科学院大连化学物理研究所 | 基于光引发的巯基–丙烯酸酯聚合反应快速制备有机–无机杂化多孔整体材料的方法 |
CN107434833A (zh) * | 2016-05-25 | 2017-12-05 | 中国科学院大连化学物理研究所 | 一种有机多孔整体材料及其制备方法和应用 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112920787A (zh) * | 2021-02-05 | 2021-06-08 | 西华师范大学 | 一种笼形两亲纳米颗粒及其制备方法和应用 |
CN112920787B (zh) * | 2021-02-05 | 2021-09-21 | 西华师范大学 | 一种笼形两亲纳米颗粒及其制备方法和应用 |
CN115212853A (zh) * | 2021-04-14 | 2022-10-21 | 中国科学院大连化学物理研究所 | 一种异植醇修饰聚丙烯酸酯微球及其制备与应用 |
CN115212853B (zh) * | 2021-04-14 | 2023-11-21 | 中国科学院大连化学物理研究所 | 一种异植醇修饰聚丙烯酸酯微球及其制备与应用 |
Also Published As
Publication number | Publication date |
---|---|
CN110575824B (zh) | 2021-08-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Hong et al. | Recent advances in the preparation and application of monolithic capillary columns in separation science | |
Cao et al. | Polymer monoliths with exchangeable chemistries: use of gold nanoparticles as intermediate ligands for capillary columns with varying surface functionalities | |
CN105504331B (zh) | 一种多孔整体材料的制备方法 | |
Dulay et al. | Photopolymerized sol− gel monoliths for capillary electrochromatography | |
CN108107144B (zh) | 一种核酸适配体功能化的poss交联有机-硅胶杂化整体柱及其制备方法 | |
US20090280997A1 (en) | Microarray system | |
CN110575824B (zh) | 一种杂化多孔整体材料及其制备和应用 | |
JPH021747A (ja) | マクロ多孔性ポリマー膜及びその製造方法 | |
Krenkova et al. | Less common applications of monoliths: V. Monolithic scaffolds modified with nanostructures for chromatographic separations and tissue engineering | |
CN106478980B (zh) | 基于巯基-环氧点击聚合反应的杂化多孔整体材料的制备方法 | |
Calleri et al. | New monolithic chromatographic supports for macromolecules immobilization: challenges and opportunities | |
CN110314673B (zh) | 一种基于光引发混杂聚合的核酸适配体功能化亲和整体柱及其制备方法 | |
Hajba et al. | Recent advances in capillary electrochromatography of proteins and carbohydrates in the biopharmaceutical and biomedical field | |
CN107474254B (zh) | 有机–无机亲水性杂化整体材料的制备及应用 | |
CN109400823B (zh) | 八乙烯基-poss和二甲基丙烯酸乙二醇酯共交联的硼亲和整体柱及其制备方法 | |
US10119003B2 (en) | Surfactant-based monolithic columns, methods for making the same, and methods for using the same | |
Amalia et al. | Immobilization of trypsin onto porous methacrylate-based monolith for flow-through protein digestion and its potential application to chiral separation using liquid chromatography | |
CN100435935C (zh) | 十八烷基型整体式液相色谱微柱的制备方法 | |
Khaparde et al. | Development of a metal/chelate polyhydroxyethylmethacrylate monolith capillary for selective depletion of immunoglobulin G from human plasma for proteomics | |
CN111468087B (zh) | 一种修饰杂化整体材料及其制备和应用 | |
de Paula Lima et al. | Monolithic stationary phases preparation for use in chromatographic and electromigration techniques: The state-of-the-art | |
US20050042363A1 (en) | Method for fabrication of biochips with a macroporous polymer substrate | |
CN111019067B (zh) | 一种有机-无机杂化多孔整体材料及制备和应用 | |
CN115121234B (zh) | 离子液体内嵌烷基酯混合模式色谱固定相及制备方法和应用 | |
CN108828114B (zh) | 一种固相微萃取-质谱联用在线富集检测烟草中烟碱类化合物的方法 |
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 |