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

通过本研究项目获得了以下结果：研究了寡肽衍生物的氨基酸保留量的影响，寡肽衍生物是构造分子识别位点的候选材料，研究了手性识别能力。手性识别位点是由寡肽衍生物形成的，其中构建氨基酸保留数为三到六，通过采用替代分子印记。 It was made clear That the number four, in other words, the telepeptide derivative, is the best candidate material to from a chiral recognition site.Molecularly imprinted polymeric membranes were prepared from polystyrene resin bearing telepeptide derivatives H-Asp(OcHex)-Leu-Asp(OcHex)-Glu(OBzl)-OCH_2- (DLDE) consisting of D-amino acid残留物或L-氨基酸残留物。不仅使用光学纯的BOC-TRP，而且还使用Racemic Boc-Trps作为印刷Mo…更易于刺激，将静脉穿刺剂衍生物转化为手性识别位点。手性识别能力取决于印刷分子的绝对构型和构成氨基酸保留的结合。由DLDE衍生物制备的膜由D-Amino酸组成，并由BOC-D-TRP印记，识别出d-isomer，而不是相应的L-异构体，反之亦然。在本研究中，生成的手性识别位点的亲和力常数确定为9.6 x 10^3 mol dm^<-3>，它与分子烙印条件无关。通过施加电透析来连接对映选择性渗透。连接了与吸附选择性相对应的5.9的最佳选择性。通过采用BOC-D-TRP或BOC-L-TRP作为印刷分子，从各种寡肽Tweezer中制备了分子上的iMpprinted聚合物膜。形成的分子识别位点的手性识别能力取决于膜制剂（分子印迹）过程中采用的印刷分子的绝对构型，而候选寡肽镊子由L-氨基酸保留。换句话说，D-ISOMER印记的膜识别出与相应的L-异构体相比，反之亦然。来自寡肽肽镊子的靶分子和手性识别位点之间的亲和力常数高于单链寡肽衍生物的亲和力。这些膜选择性地运输了参与度，该膜优先通过透析将其掺入膜中。这些膜的允许选择性超过了它们的吸附选择性。一种新型候选聚合物材料，具有5元的环酸盐碳酸盐，Poly [（2-oxo-1,3-二氧烷-4-基）甲基丙烯酸甲基丙烯酸甲酯-CO-CO-丙烯腈]，通过使用AC-DRP转化为chir识别材料或AC-DRP，分子不张纸的聚合物表现出手性识别能力，而AC-D-TRP的D-异构体的材料则识别出比相应的L-异构体的D-异构体，反之亦然。手性识别位点的形成通过分子烙印材料的明显吸附等温线得到证实。较少的

项目成果

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

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

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）