Preparation, characterization and application of a chiral thermo-sensitive membrane for phenylalanine separation of the racemic mixture

Feng, Xia; Zhang, Qiang; Liang, Xiaotong; Li, Jinling; Zhao, Yiping; Chen, Li

doi:10.1007/s10965-014-0475-7

Cited by 16 publications

(4 citation statements)

References 28 publications

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“…P(NIPAAm-co-Phe-OMe) and P(NIPAAm-co-Trp-OMe5)-modified silica columns. There are many reports of functional polymers synthesized by introducing amino acid derivatives to synthetic polymers [23][24][25] and novel packing materials composed of poly(N-alanine)grafted porous silica or poly(octadecyl acrylate-alt-N-octadecylmaleimide)-grafted silica with separation mechanisms explained by π-π interactions or shape-selectivity. 26,27 However, we believe the present research is the first report to successfully demonstrate dual temperature-response and molecular recognition characteristics in a separation system utilizing temperature-responsive polymers bearing aromatic amino acid derivatives.…”

Section: Discussionmentioning

confidence: 99%

Temperature-responsive molecular recognition chromatography using phenylalanine and tryptophan derived polymer modified silica beads

Hiruta

Kanazashi

Ayano

et al. 2016

Analyst

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Temperature-responsive polymers incorporating molecular-recognition sites were developed as stationary phases for high-performance liquid chromatography (HPLC). The grafted stationary phases consisted of functional copolymers composed of N-isopropylacrylamide (NIPAAm) and N-acryloyl aromatic amino acid methyl esters, i.e., phenylalanine and tryptophan methyl esters (Phe-OMe and Trp-OMe). Three novel temperature-responsive polymers, P(NIPAAm-co-Phe-OMe5), P(NIPAAm-co-Phe-OMe10), and P(NIPAAm-co-Trp-OMe5), were synthesized. These copolymers exhibited a reversible hydrophilic/hydrophobic phase transition at their lower critical solution temperatures (LCSTs). The polymers were grafted onto aminopropyl silica using an activated ester-amine coupling method, and were packed into a stainless steel column, which was connected to an HPLC system. Temperature-responsive chromatography was conducted using water as the sole mobile phase. More hydrophobic analytes were retained longer, and the retention times of aromatic steroids and aromatic amino acids were dramatically increased. This indicated that π-π interactions occurred between the phenyl or indole moieties of phenylalanine or tryptophan, respectively, and the aromatic compounds. Furthermore, the retention times of compounds with hydrogen bond acceptors were higher with P(NIPAAm-co-Trp-OMe5), which contained indole as a hydrogen bond donor, than with P(NIPAAm-co-Phe-OMe5). This indicated that hydrogen bonding occurred between the stationary phase and the analytes. These results indicate that hydrophobic, π-π, and hydrogen bonding interactions all affected the separation mode of the temperature-responsive chromatography, and led to selective separation with molecular recognition. Both temperature-response and molecular recognition characteristics are present in the proposed separation system that utilizes a temperature-responsive polymer bearing aromatic amino acid derivatives.

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Section: Discussionmentioning

confidence: 99%

Temperature-responsive molecular recognition chromatography using phenylalanine and tryptophan derived polymer modified silica beads

Hiruta

Kanazashi

Ayano

et al. 2016

Analyst

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“…Chiral compounds, especially chiral drugs, have identical physical and chemical properties but very often exhibit different biological, pharmacological, toxicological activities, and metabolism pathways in living system. Diverse analytical techniques have been developed for separating chiral compounds including various chromatography, CE , membrane separation, crystallization, metal organic framework, and chemical recognition . However, most techniques require time‐consuming procedures, high cost, quite large consumption of solvents, as well as complicated pre‐treatment steps for samples.…”

Section: Methodsmentioning

confidence: 99%

Facile Synthesis and Enantioseparation of Chiral Drugs Using Zirconia Magnetic Microspheres Coated with Cyclodextrin/Poly(amidoamine) Dendrimers

Kim

Lee

2016

Bulletin Korean Chem Soc

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Chirality is a universal and important phenomenon in nature. It refers to the property of a molecule or system which is not identical to its mirror image. In chemical field, chirality is used to describe the lack of a symmetric plane in molecules. Chiral compounds, especially chiral drugs, have identical physical and chemical properties but very often exhibit different biological, pharmacological, toxicological activities, and metabolism pathways in living system. Diverse analytical techniques have been developed for separating chiral compounds including various chromatography, 1-5 CE, 6 membrane separation, 7,8 crystallization 9 , metal organic framework, 10 and chemical recognition. 11 However, most techniques require time-consuming procedures, high cost, quite large consumption of solvents, as well as complicated pre-treatment steps for samples. Thus, it leads to an increasing demand for developing simple and efficient methods for chiral separation.Cyclodextrin and their derivatives, such as carboxymethylβ-cyclodextrin (CMCD), which consist of a hydrophobic internal cavity and a hydrophilic outer surface have been used widely as a chiral selector because of their excellent chiral recognition capabilities. [12][13][14] In this study, we report the synthesis of carboxymethyl-β-cyclodextrin modified zirconiapoly(amidoamine) (PAMAM) dendrimer-magnetic microspheres (CMCD-ZPMMs) that was carried out via repetitive Michael addition reactions by using microwave irradiation. The product was tried to apply in selective enantioseparation of racemic drugs using polarimetric technique. To the best of our knowledge, the direct separation of racemic drugs by using CMCD-ZPMMs has not been reported yet.The scheme of the preparation for CMCD-ZPMMs is displayed in Scheme 1. Firstly, magnetic microspheres, Fe 3 O 4 were synthesized via solvothermal reaction, and then coated with glucose by hydrothermal reaction before coating with zirconia. The surface of Zirconia magnetic microspheres was modified with (3-aminopropyl) triethoxysilane (APTES) to form primary amine groups. The morphologies of obtained products were investigated in our previous report. 15 Subsequently, to make more bonding sites for efficient conjugation with chiral selector, PAMAM dendrimers were grown onto ZPMMs by repeating the Michael addition and amidation reaction by using ultrasonic system. The synthetic procedures for preparing CMCD-ZPMMs are presented in Supporting information (Appendix S1).Initial assessments of CMCD-ZPMMs for separating chiral drugs were performed using ketopropen, propranolol, and acebutolol. Sample solutions containing these three drugs showed no optical activity because they are comprised of equal amounts of the (+) and (−) enantiomers, called a racemic mixture. It is well-known that the sign (+/−) of the rotation change depends on the nature and macroscopic behavior of the compound, such as the substituents attached to the stereocenter, the number of molecules in the path of the light. The scheme of the separation of racemic drugs vi...

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“…After the first article on chiral solid membranes was published in 1986, 7 various enantioselective membranes have been studied. [16][17][18][19][20][21][22][23][24][25][26][27][28][29] To the best of our knowledge, only one original research article on chiral-separation-mechanism-based solid enantioselective membranes appeared, in 2001, 30 which has since been introduced and referenced often. [16][17][18][19][20][21][22][23][24][25][26][27][28][29] To the best of our knowledge, only one original research article on chiral-separation-mechanism-based solid enantioselective membranes appeared, in 2001, 30 which has since been introduced and referenced often.…”

Section: Introductionmentioning

confidence: 99%

“…[8][9][10][11][12][13][14][15] Recently, some new optical resolution membranes have also been reported. [16][17][18][19][20][21][22][23][24][25][26][27][28][29] To the best of our knowledge, only one original research article on chiral-separation-mechanism-based solid enantioselective membranes appeared, in 2001, 30 which has since been introduced and referenced often. 9,10 The article was a theoretical study including some mathematical † Contributed equally to this work.…”

Section: Introductionmentioning

confidence: 99%

Optical resolution and mechanism using enantioselective cellulose, sodium alginate and hydroxypropyl‐β‐cyclodextrin membranes

Yuan

et al. 2017

Chirality

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Chiral solid membranes of cellulose, sodium alginate, and hydroxypropyl-β-cyclodextrin were prepared for chiral dialysis separations. After optimizing the membrane material concentrations, the membrane preparation conditions and the feed concentrations, enantiomeric excesses of 89.1%, 42.6%, and 59.1% were obtained for mandelic acid on the cellulose membrane, p-hydroxy phenylglycine on the sodium alginate membrane, and p-hydroxy phenylglycine on the hydroxypropyl-β-cyclodextrin membrane, respectively. To study the optical resolution mechanism, chiral discrimination by membrane adsorption, solid phase extraction, membrane chromatography, high-pressure liquid chromatography ultrafiltration were performed. All of the experimental results showed that the first adsorbed enantiomer was not the enantiomer that first permeated the membrane. The crystal structures of mandelic acid and p-hydroxy phenylglycine are the racematic compounds. We suggest that the chiral separation mechanism of the solid membrane is "adsorption - association - diffusion," which is able to explain the optical resolution of the enantioselective membrane. This is also the first report in which solid membranes of sodium alginate and hydroxypropyl-β-cyclodextrin were used in the chiral separation of p-hydroxy phenylglycine.

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Preparation, characterization and application of a chiral thermo-sensitive membrane for phenylalanine separation of the racemic mixture

Cited by 16 publications

References 28 publications

Temperature-responsive molecular recognition chromatography using phenylalanine and tryptophan derived polymer modified silica beads

Temperature-responsive molecular recognition chromatography using phenylalanine and tryptophan derived polymer modified silica beads

Facile Synthesis and Enantioseparation of Chiral Drugs Using Zirconia Magnetic Microspheres Coated with Cyclodextrin/Poly(amidoamine) Dendrimers

Optical resolution and mechanism using enantioselective cellulose, sodium alginate and hydroxypropyl‐β‐cyclodextrin membranes

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