CN1107685C - 聚乙烯醇接枝4－乙烯基吡啶的制备方法 - Google Patents

聚乙烯醇接枝4－乙烯基吡啶的制备方法 Download PDF

Info

Publication number
CN1107685C
CN1107685C CN96123527A CN96123527A CN1107685C CN 1107685 C CN1107685 C CN 1107685C CN 96123527 A CN96123527 A CN 96123527A CN 96123527 A CN96123527 A CN 96123527A CN 1107685 C CN1107685 C CN 1107685C
Authority
CN
China
Prior art keywords
polyvinyl alcohol
preparation
graft
vinylpyridine
grafting
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
Application number
CN96123527A
Other languages
English (en)
Other versions
CN1186082A (zh
Inventor
李彬
寇文朋
董绍俊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changchun Institute of Applied Chemistry of CAS
Original Assignee
Changchun Institute of Applied Chemistry of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Changchun Institute of Applied Chemistry of CAS filed Critical Changchun Institute of Applied Chemistry of CAS
Priority to CN96123527A priority Critical patent/CN1107685C/zh
Publication of CN1186082A publication Critical patent/CN1186082A/zh
Application granted granted Critical
Publication of CN1107685C publication Critical patent/CN1107685C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Landscapes

  • Graft Or Block Polymers (AREA)

Abstract

本发明属于聚乙烯醇接枝4-乙烯基吡啶的制备方法。本发明以聚乙烯醇为起始物，经硝酸铈铵引发，在酸性水溶液中接枝聚合4-乙烯基吡啶，再经甲醇沉淀和真空干燥得到接枝产物。按照本发明所述方法制备聚乙烯醇接枝接枝4-乙烯基吡啶固定化酶载体，其原材料容易获得且成本低廉，制备过程简单安全；接枝产物分子有利于酶的固定化；接枝产物的含酶水溶液可直接滴涂于电极表面制备生物传感器。

Description

聚乙烯醇接枝4-乙烯基吡啶的制备方法
本发明属于聚乙烯醇接枝4-乙烯基吡啶的制备方法。
已知接枝反应是对高分子材料进行改性的一种有效方法，在亲水高分子链上接枝聚合疏水单体所得的接枝产物中同时含有亲水支链和疏水支链，能分别与酶的亲水区和疏水区相互作用，有利于酶的固定化。德国D.Muller-Schulte在Journal ofChromatography 1990，510，115-121中用钴γ-射线照射引发聚乙烯醇与多种丙烯酰胺类物质的接枝反应，得到可用于分离酶和蛋白质的高载量色谱填料，但放射性同位素的使用有潜在危险。美国专利U.S.Pat.Appl.US104,899公开了一种用H2O2/Fe2+或Ce4+引发，在多糖分子上接枝丙烯氰的技术，其接枝产物作载体能得到高活力的固定化酶，可作为生物反应器的填料，但此接枝产物难以修饰到电极表面。事实上，上述工作及该领域的其它工作虽然利用接枝反应制备了多种不同用途的固定化酶载体，但尚无一种方法能综合考虑接枝反应的起始物、引发剂和接枝物等相关因素，以制备适用于生物传感器的固定化酶载体。
本发明的目的是提供一种适用于生物传感器的新型固定化酶载体的制备方法，即以聚乙烯醇为起始物，经硝酸铈铵引发，在酸性水溶液中接枝聚合4-乙烯基吡啶，再经甲醇沉淀和真空干燥得到接枝产物。
亲水的聚乙烯醇是一种人工合成的多羟基聚合物，具有良好的生物相容性和生物稳定性，能通过自身物理交联成胶并同时包埋酶，在本发明中被选作接枝反应的起始物。聚乙烯醇的分子量和浓度会影响溶液的粘度进而影响接枝效果，本发明的方法可采用任何商业来源的聚乙烯醇。硝酸铈铵作为引发剂的优点是能够有效地降低接枝体系中的自聚副反应。疏水的4-乙烯基吡啶在石墨、玻碳、铂等多种电极表面均有很强的吸附能力、且有定的导电性、在本发明中被选作接枝反应的接枝物。
本发明用2～10％分子量为30,000～115,000的聚乙烯醇作起始物，经1.0～30mmol·L-1的硝酸铈铵引发，接枝聚合0.2～1.5％的4-乙烯基吡啶单体，体系的pH值为1～3，反应时，先抽气除氧50～80分钟，然后在20～40℃反应2.5～3.5小时，再向反应体系中加入3～6倍体积的甲醇来沉淀接枝产物，沉淀用甲醇洗涤三次以除去未反应的4-乙烯基吡啶单体、自聚物及其它杂质，再经真空干燥得聚乙烯醇的4-乙烯基吡啶接枝产物。
接枝产物用傅立叶变换红外光谱进行表征，作为起始物的聚乙烯醇在1650cm-1附近无吸收峰，而接枝产物在此处有吡啶环的伸缩振动峰；另外，接枝产物用元素分析表征，起始物聚乙烯醇中不含氮元素，而接枝产物中含氮。
按照本发明所述方法制备聚乙烯醇接枝接枝4-乙烯基吡啶固定化酶载体，其原材料容易获得且成本低廉，制备过程简单安全；接枝产物分子内含有亲水支链和疏水支链，能分别与酶分子表面的亲水区和疏水区相互作用，有利于酶的固定化；将接枝产物配成浓度为2～15％的含酶水溶液，直接滴涂于电极表面，室温或低温自然干燥后即能自身物理交联成胶并同时包埋酶，且此含酶胶膜能牢固粘附于石墨、玻碳、铂等多种电极表面，而得到有良好安培响应的生物传感器。
本发明提供的实施例如下：
实施例1：5％的分子量为84,000的聚乙烯醇水溶液20ml，加入1NHNO3 5ml，混匀，水泵抽气除氧60分钟后，加入最终浓度为1mmol·L-1的硝酸铈铵，然后加入最终浓度为1.5％的4-乙烯基吡啶，该体系的pH值为1.0，在室温下电磁搅拌2.5小时，加入80ml甲醇，振荡，3000转/分钟离心20分钟，沉淀分别用30ml甲醇充分洗涤并离心3次，最后所得接枝物沉淀室温真空干燥即得产物。
实施例2：10％的分子量为30,000的聚乙烯醇水溶液10ml，加入1NHNO3 3ml，混匀，水泵抽气除氧50分钟后，加入最终浓度为10mmol·L-1的硝酸铈铵，随后加入最终浓度为0.8％的4-乙烯基吡啶，该体系的pH值为1.8，在20℃恒温下振荡水浴反应3.5小时，加入90ml甲醇，振荡，水泵抽滤，沉淀分别用30ml甲醇充分洗涤后抽滤分离3次，最后所得接枝物沉淀室温真空干燥即得产物。
实施例3：2％的分子量为110,000的聚乙烯醇水溶液12.5ml，加入1NHNO3 2ml，混匀，水泵抽气除氧80分钟后，加入最终浓度为0.2％的4-乙烯基吡啶，随后加入最终浓度为30mmol·L-1的硝酸铈铵，该体系的pH值为3.0，在40℃恒温下振荡水浴反应3小时，加入100ml甲醇，振荡，水泵抽滤，沉淀分别用30ml甲醇充分洗涤后抽滤分离3次，最后所得接枝物沉淀室温真空干燥即得产物。

Claims (1)

1.一种聚乙烯醇接枝4-乙烯基吡啶的制备方法，其特征在于用2～10％分子量为30,000～115,000的聚乙烯醇作起始物，经1.0～30mmol·L-1的硝酸铈铵引发，接枝聚合0.2～1.5％的4-乙烯基吡啶单体，体系的pH值为1～3，反应时，先抽气除氧50～80分钟，然后在20～40℃反应2.5～3.5小时，再向反应体系中加入3～6倍体积的甲醇来沉淀接枝产物，沉淀用甲醇洗涤三次以除去未反应的4-乙烯基吡啶单体、自聚物及其它杂质，再经真空干燥得聚乙烯醇的4-乙烯基吡啶接枝产物。
CN96123527A 1996-12-25 1996-12-25 聚乙烯醇接枝4－乙烯基吡啶的制备方法 Expired - Fee Related CN1107685C (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN96123527A CN1107685C (zh) 1996-12-25 1996-12-25 聚乙烯醇接枝4－乙烯基吡啶的制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN96123527A CN1107685C (zh) 1996-12-25 1996-12-25 聚乙烯醇接枝4－乙烯基吡啶的制备方法

Publications (2)

Publication Number Publication Date
CN1186082A CN1186082A (zh) 1998-07-01
CN1107685C true CN1107685C (zh) 2003-05-07

Family

ID=5127672

Family Applications (1)

Application Number Title Priority Date Filing Date
CN96123527A Expired - Fee Related CN1107685C (zh) 1996-12-25 1996-12-25 聚乙烯醇接枝4－乙烯基吡啶的制备方法

Country Status (1)

Country Link
CN (1) CN1107685C (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100434448C (zh) * 2005-11-04 2008-11-19 中国科学院化学研究所 基于羧甲基纤维素钠改性的电极表面修饰材料及其制备方法
CN102115775A (zh) * 2010-10-26 2011-07-06 中国科学院长春应用化学研究所 一种用于生物传感器测定生化需氧量的包埋BODseed的有机-无机杂化材料膜及制法
CN110003559B (zh) * 2019-04-22 2021-07-27 合肥工业大学 一种木塑复合材料及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4781838A (en) * 1985-08-23 1988-11-01 Commissariat A L'energie Atomique Solid polyvinyl alcohol-based support able to adsorb lipoproteins and its use for the separation of low density lipoproteins present in a liquid, such as blood plasma
US4788242A (en) * 1986-10-06 1988-11-29 Shin-Estu Chemical Co., Ltd. Polyvinyl alcohol-based reversibly hydrated gel, highly water-absorptive resin and method for the preparation thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4781838A (en) * 1985-08-23 1988-11-01 Commissariat A L'energie Atomique Solid polyvinyl alcohol-based support able to adsorb lipoproteins and its use for the separation of low density lipoproteins present in a liquid, such as blood plasma
US4788242A (en) * 1986-10-06 1988-11-29 Shin-Estu Chemical Co., Ltd. Polyvinyl alcohol-based reversibly hydrated gel, highly water-absorptive resin and method for the preparation thereof

Also Published As

Publication number Publication date
CN1186082A (zh) 1998-07-01

Similar Documents

Publication Publication Date Title
US4747956A (en) Method of adsorbing subtances
JPH0342076B2 (zh)
US5494815A (en) Immobilization of biochemical substances on a carrier containing a layer of an olefinic-unsaturated, epoxyfunctional polysiloxane
GB2071669A (en) Es as supports of enzymatic activity and copolymers thus oprocess for the preparation of copolymers of polysaccharidbtained
US5389533A (en) Immobilization of biochemical substances on a carrier containing a layer of an olefinic - unsaturated, epoxyfunctional polyether
EP0146329A2 (en) Process for preparing oxirane-bearing polymer carriers for immobilizing enzymes and other materials bearing active hydrogen, and oxirane-bearing polymer carriers
CN1107685C (zh) 聚乙烯醇接枝4－乙烯基吡啶的制备方法
JPH0416219A (ja) アミノ酸を有する複合機能濾過膜の製造方法
CN100564523C (zh) 含环氧基固定化酶载体及制备方法与用途
Caro Jr et al. Reaction of hexamethylene diisocyanate with poly (vinyl alcohol) films for biomedical applications
CN112980826B (zh) 一种脂肪酶/聚丙烯酰胺水凝胶微球催化材料及其制备方法和应用
CN104549178B (zh) 一种叠氮法偶联明胶吸附材料及其制备方法
JP3274844B2 (ja) アクリロニトリルとコーモノマーとの共重合体を基礎とする溶媒および酸に安定な膜
BG61277B1 (en) Process for the preparation of optically activecyanohydrines with enzymes
US3761357A (en) Bonding of enzymes to polymeric materials
Schwark et al. Toward protein-selective membrane adsorbers: A novel surface-selective photo-grafting method
Yoshida et al. Spacer effect of novel bifunctional organophosphorus monomers in metal‐imprinted polymers prepared by surface template polymerization
Zühlke et al. Synthesis and application of new microcarriers for animal cell culture. Part I: design of polystyrene based microcarriers
US5266471A (en) Solid carriers modified with 2,4,6-trichloro-s triazine to immobilize biomolecules
US5401784A (en) Insoluble polymer material with condensed reactive sites, method of preparation of said polymer and applications
Piedade et al. Behaviour of catalase immobilised on poly (acrylonitrile)‐g. co‐hydroxyethyl methacrylate when used in a continuous system
CN110330599B (zh) 一种二维芳香族聚酰胺层状材料及其化学改性方法
AZHARI et al. Oxidative procedure for activation of hydroxyl-containing polymeric carriers(Abstract Only)
Ichijo et al. Immobilization of microorganisms on poly (vinyl alcohol) super fine fibers
CN1059354C (zh) 一种纤维素微孔滤膜及其制备和应用

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C01 Deemed withdrawal of patent application (patent law 1993)
WD01 Invention patent application deemed withdrawn after publication
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee