Chiral Separation of Racemates with Molecularly Imprinted Polymeric Membranes

用分子印迹聚合物膜手性分离外消旋体

• 批准号: 15360412
• 负责人: YOSHIKAWA Masakazu
• 金额: $ 4.74万
• 依托单位: Kyoto Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-15360412/
• 关键词: Optical resolution; Chiral recognition; Molecular recognition; Molecular imprinting; Chiral environment; Peptide; Membrane; Print molecule; 簡易分子インプリント; 好熱菌; ポリスルホン; 鋳型膜; 膜分離; ナノメートルスケール; ナノスケール

The following results have been obtained through the present research project : The effect of constituting amino acid residue number of oligopeptide derivatives, which are candidate materials to construct molecular recognition sites, on chiral recognition ability was investigated. Chiral recognition sites were formed from oligopeptide derivatives, of which constituting amino acid residue numbers were three to six, by adopting an alternative molecular imprinting. It was made clear that the number four, in other words, the tetrapeptide derivative, is the best candidate material to from a chiral recognition site.Molecularly imprinted polymeric membranes were prepared from polystyrene resin bearing tetrapeptide derivatives H-Asp(OcHex)-Leu-Asp(OcHex)-Glu(OBzl)-OCH_2- (DLDE) consisting of D-amino acid residues or L-amino acid residues. The tetrapeptide derivatives were converted into chiral recognition sites by using not only an optically pure Boc-Trp but also racemic Boc-Trps as a print mo … More lecule. The chiral recognition ability depends on the combination of the absolute configuration of the print molecule and that of constituting amino acid residues. The membrane prepared from DLDE derivative consisting of D-amino acid residues and imprinted by Boc-D-Trp recognized the D-isomer in preference to the corresponding L-isomer and vice versa. In the present study, it was also made clear that racemic print molecules were effective in generating chiral recognition sites. The affinity constant of the generated chiral recognition site was determined to be 9.6 x 10^3 mol dm^<-3>, which was independent of the molecular imprinting conditions. Enantioselective permeation was attained by applying electrodialysis. An optimum selectivity of 5.9, which corresponds to the adsorption selectivity, was attained.Molecularly imprinted polymeric membranes were prepared from various oligopeptide tweezers by the adoption of Boc-D-Trp or Boc-L-Trp as a print molecule. The chiral recognition ability of the formed molecular recognition sites was dependent on the absolute configuration of the print molecule adopted in the membrane preparation (molecular imprinting) process, whereas the candidate oligopeptide tweezers consisted of the L-amino acid residues. In other words, the membranes imprinted by the D-isomer recognized the D-isomer in preference to the corresponding L-isomer, and vice versa. The affinity constant between the target molecule and the chiral recognition site from oligopeptide tweezers was higher than that from a single-strand oligopeptide derivative. Those membranes selectively transported the enantiomer, which was preferentially incorporated into the membrane by dialysis. The permselectivities for these membranes exceeded their adsorption selectivities.A novel candidate polymeric material bearing 5-membered cyclic carbonate, poly[(2-oxo-1,3-dioxolan-4-yl)methyl methacrylate-co-acrylonitrile], converted into a chiral recognition material by adopting Ac-D-Trp or Ac-L-Trp as a print molecule. The molecularly imprinted polymer showed chiral recognition ability, and the material imprinted by the D-isomer of Ac-D-Trp recognized the D-isomer in preference to the corresponding L-isomer, and vice versa. The formation of the chiral recognition site was confirmed by apparent adsorption isotherms of the molecularly imprinted materials. Less

本研究取得了以下成果：研究了作为构建分子识别位点候选材料的寡肽衍生物的组成氨基酸残基数目对手性识别能力的影响。采用交替分子印迹法，从氨基酸残基数为3 ~ 6的寡肽衍生物中形成手性识别位点。以聚苯乙烯树脂为载体，制备了含有D-氨基酸残基或L-氨基酸残基的四肽衍生物H-Asp（OcHex）-Leu-Asp（OcHex）-Glu（OBzl）-OCH_2-（DLDE）的分子印迹聚合物膜。以光学纯的Boc-Trp和外消旋的Boc-Trp为模板，将四肽衍生物转化为手性识别位点 ...更多信息 莱库莱手性识别能力取决于印迹分子的绝对构型和组成氨基酸残基的绝对构型的组合。由D-氨基酸残基组成的DLDE衍生物制备的Boc-D-Trp印迹膜优先识别D-异构体而不是相应的L-异构体，反之亦然。在本研究中，还明确了外消旋印刷分子在产生手性识别位点方面是有效的。所产生的手性识别位点的亲和常数被确定为9.6 × 10^3 mol dm^<-3>，这与分子印迹条件无关。采用电渗析法实现了对映体选择性渗透。以Boc-D-Trp和Boc-L-Trp为印迹分子，制备了寡肽分子印迹聚合物膜。所形成的分子识别位点的手性识别能力取决于膜制备（分子印迹）过程中所采用的印迹分子的绝对构型，而候选寡肽镊子由L-氨基酸残基组成。换句话说，被D-异构体印迹的膜优先识别D-异构体而不是相应的L-异构体，反之亦然。寡肽镊子的手性识别位点与靶分子之间的亲和常数高于单链寡肽衍生物。这些膜选择性地运输对映体，其通过透析优先并入膜中。以Ac-D-Trp或Ac-L-Trp为印迹分子，将一种新型的含5元环碳酸酯的聚合物材料聚[（2-氧代-1，3-二氧戊环-4-基）甲基丙烯酸甲酯-co-丙烯腈]转化为手性识别材料。分子印迹聚合物对Ac-D-Trp的D-异构体具有较强的手性识别能力，对D-异构体的识别优先于对L-异构体的识别，反之亦然。分子印迹材料的表观吸附等温线证实了手性识别位点的形成。少

项目成果

Chiral recognition ability of oligopeptide derivatives consisting of glutamyl residues

谷氨酰残基寡肽衍生物的手性识别能力

• 发表时间: 2005
• 期刊: J.Appl.Polym.Sci. 95巻
• 作者: M.Miyahara;S.Watanabe;Y.Gotoh;K.Higashitani;Masakazu Yoshikawa;Masakazu Yoshikawa
• 通讯作者: Masakazu Yoshikawa

Molecularly imprinted films from Torlon^<【○!R】> polyamide-imide

Torlon 分子印迹薄膜^<【○!R】>聚酰胺酰亚胺

• 发表时间: 2005
• 期刊: J.Mol.Struct. 739巻
• 作者: M.Yoshikawa;M.D.Guiver;G.P.Robertson
• 通讯作者: G.P.Robertson

ABA triblock copolymer POE-block-PDMS-block-POE as a component for liquid

ABA三嵌段共聚物POE-嵌段-PDMS-嵌段-POE作为液体组分

• 发表时间: 2004
• 期刊: Maku(Membrane) 29巻
• 作者: G.P.Robertson;M.D.Guiver;M.Yoshikawa;S.Brownstein;G.P.Robertson et al.;M.Yoshikawa et al.;T.Sakiyama et al.
• 通讯作者: T.Sakiyama et al.

Evaluation of the recognition ability of molecularly imprinted materials by surface plasmon resonance (SPR) spectroscopy

通过表面等离子共振（SPR）光谱评估分子印迹材料的识别能力

• 发表时间: 2003
• 期刊: Anal.Chim.Acta 489巻
• 作者: G.P.Robertson;M.D.Guiver;M.Yoshikawa;S.Brownstein;G.P.Robertson et al.;M.Yoshikawa et al.;T.Sakiyama et al.;M.Yoshikawa et al.;Masakazu Yoshikawa;Yoshiko Kondo;Gilles P.Robertson;Koichi Taniwaki
• 通讯作者: Koichi Taniwaki

Gilles P.Robertson et al.: "Modified polysulfones. VI. Preparation of polymer membrane materials containing benzimine and benzylamine groups as precursors for molecularly imprinted sensor devices"J.Polym.Sci. : Part A : Polym.Chem.. 41巻. 1316-1329 (2003)

Gilles P. Robertson 等人：“改性聚砜。VI。含有苯亚胺和苯甲胺基团作为分子印迹传感器装置前体的聚合物膜材料的制备”J.Polym.Sci：A 部分：Polym.Chem. 第 41 卷。 1316-1329（2003）