Molecular Recognition and Sensing Based on Ferrocene Derivatives and Ferrocene-Based Polymers

In the field of electrochemical detection, ferrocene has a promising application prospect in view of its impact as a component of molecular receptors and sensing materials. In this review, we aim to describe the principle of ferrocene-based electrochemical detection and further discuss its design and performances. In particular, two forms of detection, molecular recognition and sensing systems, were specified. Ferrocene-based molecular receptors with all kinds of structures covering derivatives, polymers, and supramolecular receptors are presented. Benefits of their structures to the recognition behavior are compared and discussed. In electrochemical sensors, the ferrocene-containing component is used as a mediator or a label. The architectural design, enhancement effect of additives, and the structures of ferrocene-containing components in the corresponding sensors are discussed in this review. Among sensors with different structures, film-type, sandwich-type, and displacement-type sensors are the main a...

[1]  Jian-Ding Qiu,et al.  Nanocomposite film based on graphene oxide for high performance flexible glucose biosensor , 2011 .

[2]  Guonan Chen,et al.  DNAzyme-based magneto-controlled electronic switch for picomolar detection of lead (II) coupling with DNA-based hybridization chain reaction. , 2013, Biosensors & bioelectronics.

[3]  I. Cuadrado,et al.  Ferrocenyl silicon-based dendrimers as mediators in amperometric biosensors , 1997 .

[4]  Mehmet Senel,et al.  Construction of reagentless glucose biosensor based on ferrocene conjugated polypyrrole , 2011 .

[5]  D. Astruc,et al.  The Dendritic Effect in Molecular Recognition: Ferrocene Dendrimers and Their Use as Supramolecular Redox Sensors for the Recognition of Small Inorganic Anions , 1997 .

[6]  M. Şenel,et al.  Novel reagentless glucose biosensor based on ferrocene cored asymmetric PAMAM dendrimers , 2013 .

[7]  J. Landers,et al.  Quenching of the electrochemiluminescence of tris(2,2'-bipyridine)ruthenium(II) by ferrocene and its potential application to quantitative DNA detection. , 2006, Journal of the American Chemical Society.

[8]  Jin Guo,et al.  Amperometric sensor based on ferrocene-modified multiwalled carbon nanotube nanocomposites as electron mediator for the determination of glucose. , 2009, Analytical biochemistry.

[9]  É. Boisselier,et al.  Dendrimers designed for functions: from physical, photophysical, and supramolecular properties to applications in sensing, catalysis, molecular electronics, photonics, and nanomedicine. , 2010, Chemical reviews.

[10]  Li Wang,et al.  Recent progress in synthesis of ferrocenyl dendrimers and their application in anion recognition , 2007 .

[11]  S. Adeloju,et al.  Mediated xanthine oxidase potentiometric biosensors for hypoxanthine based on ferrocene carboxylic acid modified electrode. , 2012, Food chemistry.

[12]  K. Nakatani,et al.  Facile electrochemical biosensor based on a new bifunctional probe for label-free detection of CGG trinucleotide repeat. , 2013, Biosensors & bioelectronics.

[13]  Fushen Lu,et al.  A novel probe density controllable electrochemiluminescence biosensor for ultra-sensitive detection of Hg2+ based on DNA hybridization optimization with gold nanoparticles array patterned self-assembly platform. , 2013, Biosensors & bioelectronics.

[14]  B. Alonso,et al.  Carbosilane based dendritic cores functionalized with interacting ferrocenyl units: synthesis and electrocatalytical properties , 2011 .

[15]  D. Astruc,et al.  Dendritic and Ion-Pairing Effects in Oxo-anion Recognition by Giant Alkylferrocenyl Dendrimers , 2009 .

[16]  S. Yao,et al.  Highly sensitive and selective dopamine biosensor based on a phenylethynyl ferrocene/graphene nanocomposite modified electrode. , 2012, The Analyst.

[17]  Minghui Yang,et al.  Application of hydrogel prepared from ferrocene functionalized amino acid in the design of novel electrochemical immunosensing platform. , 2013, Biosensors & bioelectronics.

[18]  Minghui Yang,et al.  Sensitive immunosensor for tumor necrosis factor α based on dual signal amplification of ferrocene modified self-assembled peptide nanowire and glucose oxidase functionalized gold nanorod. , 2013, Biosensors & bioelectronics.

[19]  D. Astruc,et al.  Redox recognition using “click” chemistry , 2011 .

[20]  Li Wang,et al.  Synthesis and Electrochemical Properties of Phloroglucin-Based Ferrocenyl Compounds and Their Application in Anion Recognition , 2008 .

[21]  Yasuyuki Ikeda,et al.  Ferrocenylnaphthalene diimide-based electrochemical hybridization assay for a heterozygous deficiency of the lipoprotein lipase gene. , 2002, Bioconjugate chemistry.

[22]  S. Otto,et al.  Noncovalent interactions within a synthetic receptor can reinforce guest binding. , 2006, Journal of the American Chemical Society.

[23]  Zhiqiang Gao,et al.  Synthesis of water-soluble and cross-linkable ferrocenyl redox polymers for uses as mediators in biosensors , 2012 .

[24]  Sundargopal Ghosh,et al.  An Efficient Ferrocene Derivative as a Chromogenic, Optical, and Electrochemical Receptor for Selective Recognition of Mercury(II) in an Aqueous Environment , 2012 .

[25]  Jian-Ding Qiu,et al.  A label-free amperometric immunosensor based on biocompatible conductive redox chitosan-ferrocene/gold nanoparticles matrix. , 2009, Biosensors & bioelectronics.

[26]  Yafeng Wu,et al.  Electrochemical biosensing using amplification-by-polymerization. , 2009, Analytical chemistry.

[27]  Li Wang,et al.  Study on synthesis and electrochemical properties of novel ferrocene-based compounds and their applications in anion recognition , 2009 .

[28]  M. Şenel,et al.  Construction of biosensor for determination of galactose with galactose oxidase immobilized on polymeric mediator contains ferrocene , 2010 .

[29]  N. Kuramoto,et al.  Property of thermo-sensitive and redox-active poly(N-cyclopropylacrylamide-co-vinylferrocene) and poly(N-isopropylacrylamide-co-vinylferrocene) , 1998 .

[30]  G. Diao,et al.  Preparation and electrochemical behavior of water-soluble inclusion complex of ferrocene with β-cyclodextrin polymer , 2011 .

[31]  D. Tasis,et al.  Current progress on the chemical modification of carbon nanotubes. , 2010, Chemical reviews.

[32]  S. Fujii,et al.  Amino acid ester salt recognition by ferrocene-based ditopic receptor bearing oligoethylene glycol with pendant bipy subunits: CV, UV-vis and ESR studies. , 2005, Organic & biomolecular chemistry.

[33]  B. Alonso,et al.  Multioperational Oxidase Biosensors Based on Carbosilane Dendrimers with Interacting Ferrocenes , 2011 .

[34]  D. Astruc,et al.  Synthesis of five generations of redox-stable pentamethylamidoferrocenyl dendrimers and comparison of amidoferrocenyl- and pentamethylamidoferrocenyl dendrimers as electrochemical exoreceptors for the selective recognition of H2PO4-, HSO4-, and adenosine 5'-triphosphate (ATP) anions: stereoelectroni , 2003, Chemistry.

[35]  Li Wang,et al.  Synthesis and Properties of a Ferrocene-based Metallomesogenic Polymer Containing Bis(4-hydroxyoctoxyphenyl)sulfone , 2012, Journal of Inorganic and Organometallic Polymers and Materials.

[36]  Jong Seung Kim,et al.  Ferrocene-based anion receptor bearing amide and triazolium donor groups. , 2012, The Analyst.

[37]  K. Yokoyama,et al.  Electrochemical characterization of an enzyme electrode based on a ferrocene-containing redox polymer , 1999 .

[38]  M. Watanabe,et al.  Characterization of poly(vinylferrocene-co-2-hydroxyethyl methacrylate) for use as electron mediator in enzymatic glucose sensor , 1998 .

[39]  Ning Xia,et al.  Amplified voltammetric detection of dopamine using ferrocene-capped gold nanoparticle/streptavidin conjugates. , 2013, Biosensors & bioelectronics.

[40]  C. R. Raj,et al.  Redox-functionalized graphene oxide architecture for the development of amperometric biosensing platform. , 2013, ACS applied materials & interfaces.

[41]  S. Arya,et al.  Anti-EpCAM modified LC-SPDP monolayer on gold microelectrode based electrochemical biosensor for MCF-7 cells detection. , 2013, Biosensors & bioelectronics.

[42]  O. Reynes,et al.  Poly(Ferrocenylalkylammonium): A Molecular Electrode Material for Dihydrogenphosphate Sensing , 2003 .

[43]  P. Beer,et al.  Interlocked host molecules for anion recognition and sensing , 2013 .

[44]  T. Rüffer,et al.  Synthesis and characterization of multiferrocenyl-substituted group 4 metallocene complexes. , 2012, Chemistry.

[45]  N. Kuramoto,et al.  Preparation of thermally responsive and electroactive poly(N-acryloylpyrrolidine-co-vinylferrocene) , 1994 .

[46]  Sundargopal Ghosh,et al.  Sensitive and selective redox, chromogenic, and "turn-on" fluorescent probe for Pb(II) in aqueous environment. , 2013, Analytical chemistry.

[47]  H. Frey,et al.  Electrocatalytic Properties of Carbosilane-Based Hyperbranched Polymers Functionalized with Interacting Ferrocenyl Units †‡ , 2013 .

[48]  O. Reynes,et al.  (Ferrocenylmethyl)trimethylammonium cation: a very simple probe for the electro-chemical sensing of dihydrogen phosphate and ATP anionsElectronic supplementary information (ESI) available: cyclic voltammograms of 1 in the presence of increasing amounts of ATP2– or HSO4–. See http://www.rsc.org/suppd , 2002 .

[49]  M. Sekine,et al.  Synthesis and properties of a pyrrole–imidazole polyamide having a ferrocene dicarboxylic amide linker , 2004 .

[50]  B. Alonso,et al.  New Carbosilane Polymers with Interacting Ferrocenes as Support and Bioelectrocatalysts of Oxidases to Develop Versatile and Specific Amperometric Biodevices , 2012, Applied Biochemistry and Biotechnology.

[51]  Li Wang,et al.  Study on anion electrochemical recognition based on a novel ferrocenyl compound with multiple binding sites. , 2008, The journal of physical chemistry. B.

[52]  R. Murray,et al.  Charge-transfer diffusion rates and activity relationships during oxidation and reduction of plasma-polymerized vinylferrocene films , 1981 .

[53]  Sook Mei Khor,et al.  The impact of antibody/epitope affinity strength on the sensitivity of electrochemical immunosensors for detecting small molecules , 2013, Analytical and Bioanalytical Chemistry.

[54]  J. Ji,et al.  Electrochemically controlled stiffness of multilayers for manipulation of cell adhesion. , 2013, ACS applied materials & interfaces.

[55]  Li Wang,et al.  Synthesis of a Novel Ferrocene-Based Epoxy Compound and Its Electrochemical Behavior , 2008 .

[56]  T. Tu,et al.  Asymmetric catalysis with chiral ferrocene ligands. , 2003, Accounts of chemical research.

[57]  Li Wang,et al.  Study on synthesis and electrochemical properties of a novel ferrocene-based compound and its application in anion recognition. , 2007, The journal of physical chemistry. B.

[58]  H. Gülce,et al.  A new amperometric enzyme electrode for galactose determination , 2002 .

[59]  Li Wang,et al.  Synthesis and curing behavior of a novel ferrocene‐based epoxy compound , 2008 .

[60]  H. Nishihara.  Redox Chemistry and Functionalities of Conjugated Ferrocene Systems , 2003 .

[61]  A. Kaifer,et al.  Pt(II)-activated coupling of aminoethylferrocene with benzonitrile. A facile access route to a new redox-active bis(ferrocenyl-amidine) anion sensor. , 2011, Chemical communications.

[62]  G. Diao,et al.  Electrochemical study of mono-6-thio-beta-cyclodextrin/ferrocene capped on gold nanoparticles: characterization and application to the design of glucose amperometric biosensor. , 2009, Talanta.

[63]  Debra R. Rolison,et al.  Diffusional charge transport through ultrathin films of radiofrequency plasma polymerized vinylferrocene at low temperature , 1980 .

[64]  P. Molina,et al.  Electrochemically induced intermolecular anion transfer. , 2009, Chemistry.

[65]  M. Şenel,et al.  Immobilization of glucose oxidase on reagentless ferrocene-containing polythiophene derivative and its glucose sensing application , 2010 .

[66]  B. Alonso,et al.  Synthesis and Electrochemical Anion-Sensing Properties of a Biferrocenyl-Functionalized Dendrimer , 2012 .

[67]  Shinobu Sato,et al.  Detection of an aberrant methylation of CDH4 gene in PCR product by ferrocenylnaphthalene diimide-based electrochemical hybridization assay. , 2012, Analytica chimica acta.

[68]  M. Şenel,et al.  Amperometric hydrogen peroxide biosensor based on covalent immobilization of horseradish peroxidase on ferrocene containing polymeric mediator , 2010 .

[69]  P. Beer,et al.  A ferrocene redox-active triazolium macrocycle that binds and senses chloride , 2012, Beilstein journal of organic chemistry.

[70]  Ruíz,et al.  Molecular batteries: ferrocenylsilylation of dendrons, dendritic cores, and dendrimers: new convergent and divergent routes to ferrocenyl dendrimers with stable redox activity , 2000, Chemistry.

[71]  C. Fan,et al.  A Conjugated Polymer-Based Electrochemical DNA Sensor: Design and Application of a Multi-Functional and Water-Soluble Conjugated Polymer , 2008 .

[72]  P. Beer,et al.  A ferrocene functionalized rotaxane host system capable of the electrochemical recognition of chloride. , 2011, Organic & biomolecular chemistry.

[73]  B. Fabre.  Ferrocene-terminated monolayers covalently bound to hydrogen-terminated silicon surfaces. Toward the development of charge storage and communication devices. , 2010, Accounts of chemical research.

[74]  Li Wang,et al.  Electrochemical Behaviors and Anion Recognition of Ferrocene Modified Hyperbranched Polyether , 2009 .

[75]  D. Astruc,et al.  Redox-robust pentamethylamidoferrocenyl metallodendrimers that cleanly and selectively recognize the H2PO4- anion. , 2003, Chemical communications.

[76]  Jason J. Davis,et al.  Solution and surface-confined chloride anion templated redox-active ferrocene catenanes , 2012 .

[77]  Sundargopal Ghosh,et al.  A highly selective redox, chromogenic, and fluorescent chemosensor for Hg2+ in aqueous solution based on ferrocene-glycine bioconjugates. , 2011, Inorganic chemistry.

[78]  Ferrocenylnaphthalene diimide-based electrochemical detection of methylated gene. , 2006, Analytica chimica acta.

[79]  P. Molina,et al.  Ferrocene-based multichannel molecular chemosensors with high selectivity and sensitivity for Pb(II) and Hg(II) metal cations. , 2010, Dalton transactions.

[80]  K. Novoselov,et al.  A roadmap for graphene , 2012, Nature.

[81]  Mi-Sook Won,et al.  Gold nanoparticles doped conducting polymer nanorod electrodes: ferrocene catalyzed aptamer-based thrombin immunosensor. , 2009, Analytical chemistry.

[82]  Na Zhang,et al.  An electrochemiluminescent DNA sensor based on nano-gold enhancement and ferrocene quenching. , 2013, Biosensors & bioelectronics.

[83]  Shinobu Sato,et al.  Supramolecular Complex Formation by β-Cyclodextrin and Ferrocenylnaphthalene Diimide-intercalated Double Stranded DNA and Improved Electrochemical Gene Detection , 2005, Molecules.

[84]  M. G. Almeida,et al.  Small electron-transfer proteins as mediators in enzymatic electrochemical biosensors , 2013, Analytical and Bioanalytical Chemistry.

[85]  R. de Marco,et al.  Transport and accumulation of ferrocene tagged poly(vinyl chloride) at the buried interfaces of plasticized membrane electrodes. , 2013, The Analyst.

[86]  Yinan Qin,et al.  Highly sensitive and selective detection of cancer cell with a label-free electrochemical cytosensor. , 2013, Biosensors & bioelectronics.

[87]  Yi‐Hung Liu,et al.  Sodium ions template the formation of rotaxanes from BPX26C6 and nonconjugated amide and urea functionalities. , 2013, Angewandte Chemie.

[88]  P. Beer.  Transition-Metal Receptor Systems for the Selective Recognition and Sensing of Anionic Guest Species , 1998 .

[89]  O. Reynes,et al.  Amplification upon polymerization of the electrochemical anion sensing properties of an amidoferrocene monoreceptor molecule , 2002 .

[90]  D. Astruc,et al.  Click syntheses of 1,2,3-triazolylbiferrocenyl dendrimers and the selective roles of the inner and outer ferrocenyl groups in the redox recognition of ATP2- and Pd2+. , 2010, Angewandte Chemie.

[91]  Philip A. Gale,et al.  Anion Recognition and Sensing: The State of the Art and Future Perspectives. , 2001, Angewandte Chemie.

[92]  N. Raouafi,et al.  Gold nanoparticles decorated with a ferrocene derivative as a potential shift-based transducing system of interest for sensitive immunosensing. , 2013, Journal of materials chemistry. B.

[93]  Wenqiang Lai,et al.  Hybridization-induced isothermal cycling signal amplification for sensitive electronic detection of nucleic acid. , 2013, Biosensors & bioelectronics.

[94]  Minghui Yang,et al.  A water-dispersible, ferrocene-tagged peptide nanowire for amplified electrochemical immunosensing. , 2013, Biosensors & bioelectronics.

[95]  J. Howard,et al.  Selective electrochemical magnesium and calcium sensors based on non-macrocyclic nitrogen-containing ferrocene ligands , 1998 .

[96]  D. Astruc.  Electron-transfer processes in dendrimers and their implication in biology, catalysis, sensing and nanotechnology. , 2012, Nature chemistry.

[97]  I. Bozgeyik,et al.  A novel amperometric galactose biosensor based on galactose oxidase-poly(N-glycidylpyrrole-co-pyrrol , 2011 .

[98]  H. Kondo,et al.  Electrochemical analysis of single nucleotide polymorphisms of p53 gene. , 2002, Talanta.

[99]  B. Alonso,et al.  Anion Receptor Electrochemical Sensing Properties of Poly(propyleneimine) Dendrimers with Ferrocenylamidoalkyl Terminal Groups , 2009 .

[100]  Jason J. Davis,et al.  Amplification of anion sensing by disulfide functionalized ferrocene and ferrocene-calixarene receptors adsorbed onto gold surfaces. , 2010, Dalton transactions.

[101]  P. Molina,et al.  Ion pair recognition receptor based on an unsymmetrically 1,1'-disubstituted ferrocene-triazole derivative. , 2012, The Journal of organic chemistry.

[102]  Eric Bakker,et al.  Ferrocene bound poly(vinyl chloride) as ion to electron transducer in electrochemical ion sensors. , 2010, Analytical chemistry.

[103]  D. Astruc,et al.  “Click” Synthesis of a Heterobifunctional Ferrocenyl Dendrimer with Molecular Recognition Properties and Influence of the Ferrocenyl Redox Potential on the Formation of Gold Nanoparticles , 2010 .

[104]  P. Beer,et al.  A 1,2,3,4,5-pentaphenylferrocene-stoppered rotaxane capable of electrochemical anion recognition. , 2011, Chemistry.

[105]  Shinobu Sato,et al.  Electrochemical gene detection based on supramolecular complex formation by ferrocenyl-β-cyclodextrin and adamantylnaphthalene diimide bound to double stranded DNA , 2004 .

[106]  D. Tang,et al.  Target-induced structure-switching DNA hairpins for sensitive electrochemical monitoring of mercury (II). , 2013, Biosensors & bioelectronics.

[107]  Arthur E. Martell,et al.  Ligand design for selective complexation of metal ions in aqueous solution , 1989 .

[108]  Qiang Yang,et al.  Preparation of N,N'-bisethoxyethane[12]amideferrocenophane and its application in anion recognition. , 2008, The journal of physical chemistry. B.

[109]  Jaime Ruiz,et al.  Dendrimers and gold nanoparticles as exo-receptors sensing biologically important anions. , 2004, Chemical communications.

[110]  R. Hosseinzadeh,et al.  New voltammetric strategy for simultaneous determination of N-acetylcysteine and folic acid using a carbon nanotube modified glassy carbon electrode. , 2013, Colloids and surfaces. B, Biointerfaces.

[111]  B. González,et al.  Aza-crown ethers attached to dendrimers through amidoferrocenyl units , 2006 .

[112]  D. Astruc,et al.  Click dendrimers and triazole-related aspects: catalysts, mechanism, synthesis, and functions. A bridge between dendritic architectures and nanomaterials. , 2012, Accounts of chemical research.

[113]  S. Yao,et al.  Sensitive detection of rutin with novel ferrocene benzyne derivative modified electrodes. , 2013, Biosensors & bioelectronics.

[114]  Xindong Wang,et al.  β-cyclodextrin-ferrocene host-guest complex multifunctional labeling triple amplification strategy for electrochemical immunoassay of subgroup J of avian leukosis viruses. , 2013, Biosensors & bioelectronics.

[115]  S. Yao,et al.  A double signal amplification platform for ultrasensitive and simultaneous detection of ascorbic acid, dopamine, uric acid and acetaminophen based on a nanocomposite of ferrocene thiolate stabilized Fe₃O₄@Au nanoparticles with graphene sheet. , 2013, Biosensors & bioelectronics.

[116]  P. Beer,et al.  A redox-active [3]rotaxane capable of binding and electrochemically sensing chloride and sulfate anions. , 2011, Chemical communications.

[117]  Li Wang,et al.  Electrochemical assessment of the interaction of dihydrogen phosphate with a novel ferrocenyl receptor. , 2009, The journal of physical chemistry. B.

[118]  Jason J. Davis,et al.  Anion templated surface assembly of a redox-active sensory rotaxane. , 2007, Chemical communications.

[119]  Beatriz Alonso,et al.  Amperometric biosensors for NADH based on hyperbranched dendritic ferrocene polymers and Pt nanoparticles , 2014 .

[120]  J. Raoof,et al.  Fabrication of a nanostructure-based electrochemical sensor for simultaneous determination of N-acetylcysteine and acetaminophen. , 2011, Talanta.

[121]  M. Şenel,et al.  Poly(glycidylmethacrylate-co-vinyl ferrocene)-grafted iron oxide nanoparticles as an electron transfer mediator for amperometric phenol detection , 2013 .

[122]  M. Satoh,et al.  Charge/Discharge Properties of Organometallic Batteries Fabricated with Ferrocene–Containing Polymers , 2008 .

[123]  P. Beer,et al.  Anion binding by calix[4]arene ferrocene ureas , 2003 .

[124]  Sundargopal Ghosh,et al.  Click-generated triazole based ferrocene-carbohydrate bioconjugates: A highly selective multisignalling probe for Cu(II) ions , 2012, Journal of Chemical Sciences.

[125]  B. González,et al.  Redox-active ferrocenyl dendrimers and polymers in solution and immobilised on electrode surfaces , 1999 .

[126]  Xuan Zhou,et al.  Electrochemical immunosensor with graphene/gold nanoparticles platform and ferrocene derivatives label. , 2013, Talanta.