Synthesis and characterization of chiral PEDOT enantiomers bearing chiral moieties in side chains: chiral recognition and its mechanism using electrochemical sensing technology

Dong, Liqi; Zhang, Long; Duan, Xuemin; Mo, Daize; Xu, Jingkun; Zhu, Xiaofei

doi:10.1039/c5ra20871h

Cited by 14 publications

(11 citation statements)

References 81 publications

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“…Successive CVs of ( R )-EDTM (A) and ( S )-EDTM (B) were recorded in an aqueous LiClO 4 electrolyte at a potential scan rate of 50 mV s –1 (Figure ). The onset oxidation potentials ( E ox ) of ( R )-EDTM (0.99 V, Figure A, inset) and ( S )-EDTM (0.98 V, Figure B, inset) were essentially equal, and both were lower than that of other EDOT derivative analogues such as ( R )-/( S )-EDOT-MeCl (1.26 and 1.27 V vs Ag/AgCl), , ( R )-/( S )-EDTM-PP (1.24 and 1.14 V vs Ag/AgCl), EDOT-MeNH 2 (1.25 V vs Ag/AgCl), and C4-EDOT-COOH (1.00 V vs Ag/AgCl) . These results indicated that the introduction of a hydroxyl group reduced the E ox of ( R )-EDTM and ( S )-EDTM.…”

Section: Resultsmentioning

confidence: 98%

“…( R )-/( S )-(2,3-Dihydrothieno[3,4- b ][1,4]dioxin-2-yl)methanol (( R )-/( S )-EDTM) was synthesized as described in Scheme . ( R )-/( S )-2-(Chloromethyl)-2,3-dihydrothieno[3,4- b ][1,4]dioxine (( R )-/( S )-EDOT-MeCl) was prepared according to previously reported procedures. , …”

Section: Methodsmentioning

confidence: 99%

“…Poly(3,4-ethylenedioxythiophene) (PEDOT), one of the most stable and promising conducting polymers (CPs) available, has been employed for chemo/biosensors because of its high electrical conductivity, low bandgap, and outstanding environmental stability. − Therefore, chiral PEDOT is a promising electrode modification material for electrochemical chiral recognition. We previously reported the syntheses of various chiral substituted PEDOT species, such as chloromethyl-, l -leucine-, ( R )-/( S )-2-phenylpropionic acid-, and d -/ l -methionine-substituted PEDOT, by grafting a chiral moiety to a side-chain functionalized PEDOT (Scheme ). This common and effective synthesis strategy counterbalances the achirality of PEDOT.…”

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confidence: 99%

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Chiral PEDOT-Based Enantioselective Electrode Modification Material for Chiral Electrochemical Sensing: Mechanism and Model of Chiral Recognition

et al. 2017

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The development of electrochemical methods for enantioselective recognition is a focus of research in pharmaceuticals and biotechnology. In this study, a pair of water-soluble chiral 3,4-ethylenedioxythiophene (EDOT) derivatives, (R)-2'-hydroxymethyl-3,4-ethylenedioxythiophene ((R)-EDTM) and (S)-2'-hydroxymethyl-3,4-ethylenedioxythiophene ((S)-EDTM), were synthesized and electrodeposited on the surface of a glassy carbon electrode (GCE) via current-time (I-t) polymerization in an aqueous LiClO electrolyte. These chiral PEDOT polymers were used to fabricate chiral sensors and to investigate the enantioselective recognition of d-/l-3,4-dihydroxyphenylalanine, d-/l-tryptophan, and (R)-/(S)-propranolol enantiomers, respectively. The results indicated that the (R)-PEDTM/GCE sensor showed a higher peak current response toward the levo or (S) forms of the tested enantiomers, while the opposite phenomenon occurred for (S)-PEDTM/GCE. The mechanism of the stereospecific interaction between these enantiomers and the chiral polymers was determined. Therefore, a model of the chiral recognition by the chiral conducting polymer electrodes and an electrochemical method was proposed. The chirality of the enantiomers was confirmed by two parameters: the chirality of the electrode and the peak current response. These findings pave the way for the application of chiral PEDOT as electrode modification material in the electrochemical chiral recognition field.

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Section: Resultsmentioning

confidence: 98%

Section: Methodsmentioning

confidence: 99%

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confidence: 99%

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Chiral PEDOT-Based Enantioselective Electrode Modification Material for Chiral Electrochemical Sensing: Mechanism and Model of Chiral Recognition

et al. 2017

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“…3,4-Alkylenedioxythiophene monomers, such as 3,4-ethylenedioxythiophene (EDOT) and 3,4-propylenedioxythiophene (ProDOT), have proven to be highly versatile platforms for functional conductive polymers ( Figure 1 ) [ 22 , 23 , 24 , 25 , 26 , 27 , 28 ] and present many advantages over 3-hexylthiophene. Namely, the electron-donating ether substituents lower the polymer’s oxidation potential and increase its stability in the doped state [ 29 , 30 ].…”

Section: Introductionmentioning

confidence: 99%

Enabling Conducting Polymer Applications: Methods for Achieving High Molecular Weight in Chemical Oxidative Polymerization in Alkyl- and Ether-Substituted Thiophenes

et al. 2021

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Polythiophenes (PTs) constitute a diverse array of promising materials for conducting polymer applications. However, many of the synthetic methods to produce PTs have been optimized only for the prototypical alkyl-substituted example poly(3-hexylthiophene) (P3HT). Improvement of these methods beyond P3HT is key to enabling the widespread application of PTs. In this work, P3HT and two ether-substituted PTs poly(2-dodecyl-2H,3H-thieno[3,4-b][1,4]dioxine) (PEDOT-C12) and poly(3,4-bis(hexyloxy)thiophene) (PBHOT) are synthesized by the FeCl3-initiated oxidative method under different conditions. Polymerization was carried out according to a common literature procedure (“reverse addition”) and a modified method (“standard addition”), which differ by the solvent system and the order of addition of reagents to the reaction mixture. Gel-permeation chromatography (GPC) was performed to determine the impact of the different methods on the molecular weights (Mw) and degree of polymerization (Xw) of the polymers relative to polystyrene standards. The standard addition method produced ether-substituted PTs with higher Mw and Xw than those produced using the reverse addition method for sterically unhindered monomers. For P3HT, the highest Mw and Xw were obtained using the reverse addition method. The results show the oxidation potential of the monomer and solution has the greatest impact on the yield and Xw obtained and should be carefully considered when optimizing the reaction conditions for different monomers.

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“…Most of the known methods to solve this problem are based on chromatography and capillary electrophoresis . Modified enantioselective sensors may be efficient for this, as their analytical signals depend on the isomer type …”

Section: Introductionmentioning

confidence: 99%

Molecular Dynamics Simulation and Density Functional Theory Study of Chemisorption of Propranolol Optical Isomers on a Uracil‐modified Carbon Paste Electrode

Khamitov

Shayakhmetova

Sidel’nikov

et al. 2017

J Chinese Chemical Soc

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To reveal the nature of the interaction of the optical isomers of propranolol with the surface of carbon paste electrodes modified by uracil, we performed a combined computational and experimental study. Our study comprised the different modes of complexation between propranolol and uracil molecules covering the carbon paste electrode within two approaches: molecular dynamics simulation (MD) and quantum mechanics (QM) modeling. A graphene layer was used as a model of the carbon paste electrode. The computations showed that uracil modification of the carbon paste electrode surface enhanced the selectivity toward the D-isomer of propranolol as compared to the unmodified case. These theoretical results agree with our voltammetric measurements.

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Synthesis and characterization of chiral PEDOT enantiomers bearing chiral moieties in side chains: chiral recognition and its mechanism using electrochemical sensing technology

Abstract: This manuscript reports a couple of novel polymers of side-chain functionalized PEDOT. The new polymers can be employed to successfully recognize 3,4-dihydroxyphenylalanine enantiomers and we also discuss the mechanism of chiral recognition.

Cited by 14 publications

References 81 publications

Chiral PEDOT-Based Enantioselective Electrode Modification Material for Chiral Electrochemical Sensing: Mechanism and Model of Chiral Recognition

Chiral PEDOT-Based Enantioselective Electrode Modification Material for Chiral Electrochemical Sensing: Mechanism and Model of Chiral Recognition

Enabling Conducting Polymer Applications: Methods for Achieving High Molecular Weight in Chemical Oxidative Polymerization in Alkyl- and Ether-Substituted Thiophenes

Molecular Dynamics Simulation and Density Functional Theory Study of Chemisorption of Propranolol Optical Isomers on a Uracil‐modified Carbon Paste Electrode

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