CN104829787B - 一种吸附蜂王酸的功能材料的制备方法及其应用 - Google Patents
一种吸附蜂王酸的功能材料的制备方法及其应用 Download PDFInfo
- Publication number
- CN104829787B CN104829787B CN201510223157.5A CN201510223157A CN104829787B CN 104829787 B CN104829787 B CN 104829787B CN 201510223157 A CN201510223157 A CN 201510223157A CN 104829787 B CN104829787 B CN 104829787B
- Authority
- CN
- China
- Prior art keywords
- hydroxy
- methanol
- acid
- functional material
- royal
- 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.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 238000001179 sorption measurement Methods 0.000 title abstract description 7
- QHBZHVUGQROELI-UHFFFAOYSA-N Royal Jelly acid Natural products OCCCCCCCC=CC(O)=O QHBZHVUGQROELI-UHFFFAOYSA-N 0.000 title abstract 6
- KUPHXIFBKAORGY-UHFFFAOYSA-N 2-amino-3-iodo-4-methylbenzoic acid Chemical compound CC1=CC=C(C(O)=O)C(N)=C1I KUPHXIFBKAORGY-UHFFFAOYSA-N 0.000 title abstract 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- 229960000583 acetic acid Drugs 0.000 claims description 8
- 239000012362 glacial acetic acid Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 229920000344 molecularly imprinted polymer Polymers 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000000052 vinegar Substances 0.000 claims description 3
- 235000021419 vinegar Nutrition 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000003361 porogen Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims 2
- 238000000605 extraction Methods 0.000 claims 2
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 claims 1
- 238000006392 deoxygenation reaction Methods 0.000 claims 1
- 102000040430 polynucleotide Human genes 0.000 claims 1
- 108091033319 polynucleotide Proteins 0.000 claims 1
- 239000002157 polynucleotide Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 229940109850 royal jelly Drugs 0.000 abstract description 10
- 238000001514 detection method Methods 0.000 abstract description 9
- 239000000499 gel Substances 0.000 abstract description 6
- 238000002414 normal-phase solid-phase extraction Methods 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 5
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000004128 high performance liquid chromatography Methods 0.000 abstract description 4
- QHBZHVUGQROELI-SOFGYWHQSA-N (E)-10-hydroxydec-2-enoic acid Chemical compound OCCCCCCC\C=C\C(O)=O QHBZHVUGQROELI-SOFGYWHQSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 33
- 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 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000012722 thermally initiated polymerization Methods 0.000 description 2
- 201000004384 Alopecia Diseases 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 206010006187 Breast cancer Diseases 0.000 description 1
- 208000026310 Breast neoplasm Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- -1 N,N'-methylene Chemical group 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 201000009613 breast lymphoma Diseases 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940121657 clinical drug Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 208000024963 hair loss Diseases 0.000 description 1
- 230000003676 hair loss Effects 0.000 description 1
- 235000013402 health food Nutrition 0.000 description 1
- 230000036737 immune function Effects 0.000 description 1
- 238000004244 micellar electrokinetic capillary chromatography Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001044 reversed-phase solid-phase extraction Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明创造提供一种吸附蜂王酸的功能材料的制备方法及其应用，该功能材料以蜂王酸为模板分子，4‑乙烯基吡啶为功能单体，N，N’‑亚甲基双丙烯酰胺为交联剂，甲醇为致孔剂，利用溶胶‑凝胶技术和分子印迹技术进行合成，所述功能材料吸附容量可达到22.97mg/g。本发明创造合成过程简单，成本低廉，反应条件容易控制，所制成的蜂王酸特异性吸附材料可用于固相萃取富集与高效液相色谱联用，适用于对蜂王浆及其制品中蜂王酸的检测。
Description
技术领域
本发明属于高分子材料技术领域，尤其是涉及一种吸附蜂王酸的功能材料的制备方法及其应用。
背景技术
随着我国居民生活水平不断提升，市场上推出了品种繁多的保健食品，其中一大类是蜂王浆为原料制成的产品。蜂王酸是蜂王浆的主要功能成分之一，其含量约为蜂王浆总质量的1.4％-2.0％，是其中含量最高的一种脂肪酸。研究表明，蜂王酸能够防治脱发，增强机体免疫功能，防治急性辐射损伤，抑制真菌和细菌的生长，抑制乳腺癌和淋巴癌等多种癌细胞的增长。因此，蜂王酸含量成为了评定蜂王浆产品等级的重要指标。我国食品国家标准GB 9697-2008中明确规定，合格的蜂王浆中蜂王酸的含量不得少于1.4％；优等品中的含量应大于等于1.8％。目前，蜂王酸的定量检测方法主要包括紫外分光光度法、高效液相色谱法、薄层析色谱法、胶束电动毛细管色谱法和气相色谱-质谱联用法等。应用较广泛的配套前处理方法是反相固相萃取法。然而，由于这些方法往往存在操作繁杂和净化不彻底等问题，使检测用时和检测准确度受到影响。
分子印迹技术(Molecular Imprinting Technique，MIT)是当前制备高选择性材料的主要方法之一，所制备的聚合物在仿生传感器、固相萃取、临床药物分析、模拟酶催化等方面表现出了较好的应用前景。分子印迹溶胶-凝胶技术是利用溶胶-凝胶过程，把分子模板引入到无机网络结构中，形成一种刚性材料。通过溶胶-凝胶过程条件的控制，可合成具有特定的平均孔径、孔分布、表面积、折射率和极性的溶胶-凝胶材料，克服了传统分子印迹有机聚合物的刚性与惰性较差、粒径不均匀的缺点，提高了聚合物的分散性。
发明内容
为解决上述技术问题，本发明的目的在于提出一种与溶胶-凝胶技术相结合的对蜂王酸具有高选择性的吸附材料，克服传统分子印迹聚合物传质速度低，粒径不均匀，刚性较差等缺陷。
本发明采用的技术方案是：
一种吸附蜂王酸的功能材料的制备方法，包括如下步骤：
(1)将0.1～0.3g蜂王酸模板分子溶于2～25mL致孔剂甲醇中，依次加入400～700μL功能单体4-乙烯基吡啶，1000～2500mg交联剂N，N’-亚甲基双丙烯酰胺和20～70mg引发剂偶氮二异丁腈，将反应后的溶液通氮气5～20min除氧后置于30～80℃水浴锅中，热引发聚合反应24h；
(2)将甲醇和冰醋酸混合溶液索氏提取24h，再以甲醇为溶剂索氏提取12h洗去残留的冰醋酸，50℃真空干燥得到蜂王酸分子印迹聚合物。
进一步，所述步骤(2)中甲醇和冰醋的体积比为5:1～20:1。
进一步，所述步骤(2)中甲醇和冰醋的体积比为9:1。
进一步，所述步骤(1)中通氮气的时间为10min，水浴锅温度为55℃
进一步，所述功能材料应用于蜂王浆及其制品中蜂王酸的检测。
本发明具有的优点和积极效果是：
1.本发明提供的蜂王酸高选择性材料是按照蜂王酸为模板分子定做，可专一识别蜂王酸，对蜂王酸具有很高的选择特异性，该材料的吸附容量可达到22.97mg/g。
2.本发明聚合反应运用的溶胶-凝胶技术，条件易于控制,可合成具有特定的平均孔径、孔分布、表面积、折射率和极性的溶胶-凝胶材料,使合成的材料刚性与惰性好、粒径均匀,提高了材料的分散性。
3.本发明成本低廉，实验操作简单，反应条件容易控制，制得的对蜂王酸具有高选择性的材料可作为填充材料制备分子印迹固相萃取柱，并与高效液相色谱联用，适用于蜂王酸及其制品中蜂王酸的检测，检出限达到0.94μg·L-1。
附图说明
图1是蜂王酸分子印迹固相萃取-高效液相色谱检测标准曲线
具体实施方式
实施例1
一种吸附蜂王酸的功能材料的制备方法，采用本体聚合法以蜂王酸为模板分子制备分子印迹聚合物。将0.186g蜂王酸溶于10mL甲醇中，依次加入421μL 4-乙烯基吡啶，1514.7mg N，N’-亚甲基双丙烯酰胺和50mg偶氮二异丁腈。将反应后的溶液通氮气10min除氧后置于55℃水浴锅中，热引发聚合反应24h。反应结束后，以体积比为9:1的甲醇和冰醋酸混合溶液索氏提取24h，再以甲醇为溶剂索氏提取12h洗去残留的冰醋酸，50℃真空干燥得到蜂王酸分子印迹聚合物。
准确称取150mg实施例1合成的粉末状蜂王酸吸附材料，装于固相萃取柱中(3.0cm×1.0cm i.d.)，用于样品提取液中蜂王酸的净化和富集，结合高效液相色谱分析技术对蜂王浆及其制品中的蜂王酸进行检测，检出限达到0.94μg·L-1。
实施例2
一种吸附蜂王酸的功能材料的制备方法，采用本体聚合法以蜂王酸为模板分子制备分子印迹聚合物。将0.3g蜂王酸溶于16mL甲醇中，依次加入674μL 4-乙烯基吡啶，2424mgN，N’-亚甲基双丙烯酰胺和80mg偶氮二异丁腈。将反应后的溶液通氮气10min除氧后置于55℃水浴锅中，热引发聚合反应24h。反应结束后，以体积比为9:1的甲醇和冰醋酸混合溶液索氏提取24h，再以甲醇为溶剂索氏提取12h洗去残留的冰醋酸，50℃真空干燥得到蜂王酸分子印迹聚合物。
准确称取150mg实施例2合成的粉末状蜂王酸吸附材料，装于固相萃取柱中(3.0cm×1.0cm i.d.)，用于样品提取液中蜂王酸的净化和富集，结合高效液相色谱分析技术对蜂王浆及其制品中的蜂王酸进行检测，检出限达到0.94μg·L-1。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (2)
1.一种吸附蜂王酸的功能材料的制备方法，其特征在于：包括如下步骤：
(1)将0.1～0.3g蜂王酸模板分子溶于2～25mL致孔剂甲醇中，依次加入400～700μL功能单体4-乙烯基吡啶，1000～2500mg交联剂N，N’-亚甲基双丙烯酰胺和20～70mg引发剂偶氮二异丁腈，将反应后的溶液通氮气10min除氧后置于55℃水浴锅中，热引发聚合反应24h；
(2)将甲醇和冰醋酸混合溶液索氏提取24h，再以甲醇为溶剂索氏提取12h洗去残留的冰醋酸，50℃真空干燥得到蜂王酸分子印迹聚合物。
2.根据权利要求1所述的一种吸附蜂王酸的功能材料的制备方法，其特征在于：所述步骤(2)中甲醇和冰醋的体积比为9:1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510223157.5A CN104829787B (zh) | 2015-05-04 | 2015-05-04 | 一种吸附蜂王酸的功能材料的制备方法及其应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510223157.5A CN104829787B (zh) | 2015-05-04 | 2015-05-04 | 一种吸附蜂王酸的功能材料的制备方法及其应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104829787A CN104829787A (zh) | 2015-08-12 |
| CN104829787B true CN104829787B (zh) | 2017-04-19 |
Family
ID=53808012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510223157.5A Expired - Fee Related CN104829787B (zh) | 2015-05-04 | 2015-05-04 | 一种吸附蜂王酸的功能材料的制备方法及其应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104829787B (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112940558A (zh) * | 2021-01-13 | 2021-06-11 | 浙江潘季新材料股份有限公司 | 一种水溶性好的电泳涂料固化剂及其应用 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177500A (zh) * | 2007-10-30 | 2008-05-14 | 湖北出入境检验检疫局检验检疫技术中心 | 一种双酚a分子印迹聚合物的制备方法 |
| CN102336860A (zh) * | 2010-07-21 | 2012-02-01 | 天津科技大学 | 一种亚胺硫磷分子印迹聚合物的制备方法 |
| CN102432754A (zh) * | 2011-09-30 | 2012-05-02 | 浙江大学 | 乐果分子印迹聚合物的制备方法和使用方法 |
-
2015
- 2015-05-04 CN CN201510223157.5A patent/CN104829787B/zh not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104829787A (zh) | 2015-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20190329221A1 (en) | Synthesis and application of A Nanomaterial for Removal of Patulin | |
| You et al. | One-pot synthesis of zeolitic imidazolate framework-8/poly (methyl methacrylate-ethyleneglycol dimethacrylate) monolith coating for stir bar sorptive extraction of phytohormones from fruit samples followed by high performance liquid chromatography-ultraviolet detection | |
| Chen et al. | Comparison and recent progress of molecular imprinting technology and dummy template molecular imprinting technology | |
| CN104341552B (zh) | 一种氟喹诺酮类替代模板分子印迹聚合物及其应用 | |
| CN108273477A (zh) | 一种多孔聚离子液体吸附剂及其应用 | |
| Ergün et al. | Ion imprinted beads embedded cryogels for in vitro removal of iron from β‐thalassemic human plasma | |
| CN107722178A (zh) | 一种大环内酯类抗生素中空多孔型分子印迹聚合物的制备方法及应用 | |
| Wen et al. | The metal-and covalent-organic frameworks-based molecularly imprinted polymer composites for sample pretreatment | |
| CN105837747B (zh) | 一种用于选择性吸附磺胺间甲氧嘧啶的表面分子印迹聚合物及其制备方法和应用 | |
| CN106146716B (zh) | 一种原花青素b2分子印迹聚合物及其制备方法和应用 | |
| Zhao et al. | Study on an electrochromatography method based on organic–inorganic hybrid molecularly imprinted monolith for determination of trace trichlorfon in vegetables | |
| CN107868181B (zh) | 一种甘宝素替代模板分子印迹聚合物及其制备方法和应用 | |
| CN104829787B (zh) | 一种吸附蜂王酸的功能材料的制备方法及其应用 | |
| CN103396512B (zh) | 混合模板分子印迹聚合物及其固相萃取柱的制备方法和应用 | |
| Long et al. | Highly selective coextraction of rhodamine B and dibenzyl phthalate based on high‐density dual‐template imprinted shells on silica microparticles | |
| CN101747506A (zh) | 一种富集痕量恩诺沙星的分子印迹聚合物的制备方法 | |
| Amalia et al. | Cobalt (II)‐mediated molecularly imprinted polymer as a monolithic stationary phase for separation of racemic citronellal by liquid chromatography | |
| CN103111260A (zh) | 哑铃状分子印迹搅拌棒的制备方法 | |
| CN102585156B (zh) | 一种α-亚麻酸分子印迹聚合物材料的制备方法 | |
| CN102895959A (zh) | 一种吸附痕量组胺的功能材料及其制备方法和应用 | |
| CN105367711B (zh) | 一种分子印迹聚合物及其制备方法 | |
| CN103275271A (zh) | 氯霉素分子印迹聚合物膜的制备方法 | |
| Yuan et al. | Hydrophilic molecularly imprinted chitosan microspheres based on deep eutectic solvents for micro-solid phase extraction of catechin | |
| CN102936315A (zh) | 一种可富集硬毛素的分子印迹聚合物的制备方法 | |
| Yu et al. | Preparation of a composite monolith with functional graphene oxide and its application in the online enrichment of ursolic acid in medicinal plant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170419 |