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      Enhanced Charge Collection in MOF‐525–PEDOT Nanotube Composites Enable Highly Sensitive Biosensing

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          Abstract

          With the aim of a reliable biosensing exhibiting enhanced sensitivity and selectivity, this study demonstrates a dopamine (DA) sensor composed of conductive poly(3,4‐ethylenedioxythiophene) nanotubes (PEDOT NTs) conformally coated with porphyrin‐based metal–organic framework nanocrystals (MOF‐525). The MOF‐525 serves as an electrocatalytic surface, while the PEDOT NTs act as a charge collector to rapidly transport the electron from MOF nanocrystals. Bundles of these particles form a conductive interpenetrating network film that together: (i) improves charge transport pathways between the MOF‐525 regions and (ii) increases the electrochemical active sites of the film. The electrocatalytic response is measured by cyclic voltammetry and differential pulse voltammetry techniques, where the linear concentration range of DA detection is estimated to be 2 × 10 −6–270 × 10 −6 m and the detection limit is estimated to be 0.04 × 10 −6 m with high selectivity toward DA. Additionally, a real‐time determination of DA released from living rat pheochromocytoma cells is realized. The combination of MOF5‐25 and PEDOT NTs creates a new generation of porous electrodes for highly efficient electrochemical biosensing.

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          Metal-organic framework materials as chemical sensors.

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            A homochiral porous metal-organic framework for highly enantioselective heterogeneous asymmetric catalysis.

            A homochiral porous noninterpenetrating metal-organic framework (MOF), 1, was constructed by linking infinite 1D [Cd(mu-Cl)2]n zigzag chains with axially chiral bipyridine bridging ligands containing orthogonal secondary functional groups. The secondary chiral dihydroxy groups accessible via the large open channels in 1 were utilized to generate a heterogeneous asymmetric catalyst for the addition of diethyzinc to aromatic aldehydes to afford chiral secondary alcohols at up to 93% enantiomeric excess (ee). Control experiments with dendritic aromatic aldehydes of different sizes indicate that the heterogeneous asymmetric catalyst derived from 1 is both highly active and enantioselective as a result of the creation of readily accessible, uniform active catalyst sites inside the porous MOF.
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              Synthesis, structure, and metalation of two new highly porous zirconium metal-organic frameworks.

              Three new metal-organic frameworks [MOF-525, Zr(6)O(4)(OH)(4)(TCPP-H(2))(3); MOF-535, Zr(6)O(4)(OH)(4)(XF)(3); MOF-545, Zr(6)O(8)(H(2)O)(8)(TCPP-H(2))(2), where porphyrin H(4)-TCPP-H(2) = (C(48)H(24)O(8)N(4)) and cruciform H(4)-XF = (C(42)O(8)H(22))] based on two new topologies, ftw and csq, have been synthesized and structurally characterized. MOF-525 and -535 are composed of Zr(6)O(4)(OH)(4) cuboctahedral units linked by either porphyrin (MOF-525) or cruciform (MOF-535). Another zirconium-containing unit, Zr(6)O(8)(H(2)O)(8), is linked by porphyrin to give the MOF-545 structure. The structure of MOF-525 was obtained by analysis of powder X-ray diffraction data. The structures of MOF-535 and -545 were resolved from synchrotron single-crystal data. MOF-525, -535, and -545 have Brunauer-Emmett-Teller surface areas of 2620, 1120, and 2260 m(2)/g, respectively. In addition to their large surface areas, both porphyrin-containing MOFs are exceptionally chemically stable, maintaining their structures under aqueous and organic conditions. MOF-525 and -545 were metalated with iron(III) and copper(II) to yield the metalated analogues without losing their high surface area and chemical stability.
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                Author and article information

                Contributors
                YAMAUCHI.Yusuke@nims.go.jp
                kcho@ntu.edu.tw
                kevinwu@ntu.edu.tw
                Journal
                Adv Sci (Weinh)
                Adv Sci (Weinh)
                10.1002/(ISSN)2198-3844
                ADVS
                Advanced Science
                John Wiley and Sons Inc. (Hoboken )
                2198-3844
                22 September 2017
                November 2017
                : 4
                : 11 ( doiID: 10.1002/advs.v4.11 )
                : 1700261
                Affiliations
                [ 1 ] Department of Chemical Engineering National Taiwan University No. 1, Sec. 4, Roosevelt Road Taipei 10617 Taiwan
                [ 2 ] International Center for Materials Nanoarchitectonics (MANA) National Institute for Materials Science (NIMS) 1‐1 Namiki Tsukuba Ibaraki 305‐0044 Japan
                [ 3 ] Physics Department Jamoum University College Umm Al‐Qura University Makkah 21955 Saudi Arabia
                [ 4 ] Advanced Materials Research Chair Chemistry Department College of Science King Saud University Riyadh 11451 Saudi Arabia
                [ 5 ] Division of Medical Engineering Research National Health Research Institute Keyan Road Zhunan Miaoli City 350 Taiwan
                Author notes
                Author information
                http://orcid.org/0000-0003-0590-1396
                Article
                ADVS406
                10.1002/advs.201700261
                5700651
                c9ca9af4-fdfb-4017-a26a-03b7da90b37d
                © 2017 The Authors. Published by WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim

                This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

                History
                : 02 June 2017
                : 21 July 2017
                Page count
                Figures: 7, Tables: 0, Pages: 8, Words: 5322
                Funding
                Funded by: Ministry of Science and Technology (MOST) of Taiwan
                Award ID: 104‐2628‐E‐002‐008‐MY3
                Award ID: 105‐2221‐E‐002‐227‐MY3
                Funded by: Aim for Top University Project at National Taiwan University
                Award ID: 105R7706
                Funded by: National Health Research Institute (NHRI) of Taiwan
                Award ID: 03A1‐BNMP14‐014
                Funded by: Deanship of Scientific Research, King Saud University
                Categories
                Full Paper
                Full Papers
                Custom metadata
                2.0
                advs406
                November 2017
                Converter:WILEY_ML3GV2_TO_NLMPMC version:5.2.6.1 mode:remove_FC converted:23.11.2017

                biosensing,dopamine,metal‐organic frameworks,nanotubes,pedot,pc12 cells

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