Electro-templating of prussian blue nanoparticles in PEDOT:PSS and soluble silkworm protein for hydrogen peroxide sensing.

Herein, we demonstrate a high-accuracy H2O2 selective organic-inorganic 3D-heterointerface based on catalytically in-situ reduced Prussian-blue nanoparticles (PBNPs), Poly (3,4-ethylene dioxythiophene):poly (styrene sulfonic acid) (PEDOT:PSS) and water-soluble Silkworm protein (SWp). PBNPs were immobilized on an indium tin oxide-coated glass (ITO) electrode through the electrochemical polymerization process of PEDOT:PSS and the yielding intertwining composite was templated by the use of SWp, simultaneously. Since PSS and SWp act as poly-anionic and poly-cationic charge compensating elements, the sensing system's potential cycling and amperometric response stability have been significantly enhanced thanks to the arising physical blockage effect. Constructed sensing system showed a substantially high sensitivity (1031.7 µA mM-1 cm-2) and a low limit of detection value (LOD, 0.29 µM) between 1 and 130 µM H2O2. Eliminating the possible signal disruptions by common anion and cations in tap water, the (PEDOT:PSS:PB):SWp interface successfully selected H2O2 between the concentration of 10-40 µM with high recovery and relatively low RSDs oscillating between 94.2-110.9% and 2.9-5.1%, respectively. It is thought that the proposed heterointerface can be used in the field of sensor, biosensor and fuel cell systems run by H2O2 assay based on 3D scaffold-templated conductive polymer-PBNPs network.

Enzyme-free detection of hydrogen peroxide with a hybrid transducing system based on sodium carboxymethyl cellulose, poly(3,4-ethylenedioxythiophene) and prussian blue nanoparticles.

Herein, we report a two-layered hybrid catalytic interface composed of carboxymethyl cellulose (CMC), poly (3,4-ethylene dioxythiophene) (PEDOT), Prussian blue (PB) nanoparticles and Nickel-Hexacyanoferrate (Ni-HCF) layer for the enzyme-free detection of hydrogen peroxide (H2O2). Whereas the first layer, CMC:PEDOT:PB, is responsible for generating amperometric signals toward H2O2, Ni-HCF on CMC:PEDOT:PB layer is playing an active role as an operational stability-enhancer. In the study, where the systematic optimization of the sensor electrode is presented using cyclic voltammetry (CV), amperometry and electrochemical impedance spectroscopy (EIS) technique, the physical and chemical properties of the hybrid composite systems constructed is also supported by scanning electron microscopy (SEM) and Fourier-transform infrared spectroscopy (FTIR) techniques. The amperometric signal generation of the H2O2 sensor was linear between 1 and 100 µM (R2 = 0.999) with a sensitivity of 416.11 µA mM-1cm-2, providing a limit of detection (LOD) of 0.33 µM. The sensing system, which was not affected by the various interfering molecules, creates a successful sensor platform for H2O2 measurements in tap water with a high recovery value between 94.0% and 110.5% and relatively small RSD in the range of 0.4-5.2%.

Novel nonperipheral octa-3-hydroxypropylthio substituted metallo-phthalocyanines: synthesis, characterization, and investigation of their electrochemical, photochemical and computational properties.

The current study describes the synthesis, electrochemical, computational, and photochemical properties of octa (3-hydroxypropylthio) substituted cobalt (II) ( 4 ), copper (II) ( 5 ), nickel (II) ( 6 ) and zinc(II) ( 7 ) phthalocyanine derivatives. These novel compounds were characterized by elemental analysis,1H,13C NMR, FT-IR, UV-Vis, and MS. The redox behaviors of these metallo-phthalocyanines were investigated by the cyclic voltammetric method. The optimized molecular structure and gauge-including atomic orbital (GIAO)1H and13C NMR chemical shift values of these phthalocyanines in the ground state had been calculated by using B3LYP/6-31G(d,p) basis set. The outcomes of the optimized molecular structure were given and compared with the experimental NMR values. The photochemical properties including photodegradation and singlet oxygen generation of zinc(II) phthalocyanine were studied in DMSO solution for the determination of its photosensitizer behaviors.

Use of the monodisperse Pt/Ni@rGO nanocomposite synthesized by ultrasonic hydroxide assisted reduction method in electrochemical nonenzymatic glucose detection.

An electrochemical non-enzymatic sensor was developed for the detection of glucose based on an electrode modified with monodisperse platinum-nickel nanocomposites-decorated on reduced graphene oxide (Pt/Ni@rGO) which was synthesized using a new ultrasonic hydroxide assisted reduction method. Because the nanocomposites prepared by using NaOH (OH- ligands) are much smaller nanocomposites on the supports compared to the ones without OH- ligands. Such a monodisperse Pt/Ni@rGO nanocomposites-based electrode exhibited a high electrochemical activity for electrocatalytic oxidation of glucose in alkaline solution. Amperometric analysis showed a glucose sensitivity of 171.92 µA/mM cm2 of, the detection limit of 6.3 µM and a linear range of 0.02-5.0 mM glucose concentration. Fabricated sensor platform demonstrated long-term stability and good reproducibility, in addition to high selectivity.

Experimental and Theoretical Investigations of an Electrochromic Azobenzene and 3,4-Ethylenedioxythiophene-based Electrochemically Formed Polymeric Semiconductor.

An electrochromic material based on azobenzene and 3,4-ethylenedioxythiophene (EDOT) semiconducting layer was electrochemically deposited on an indium tin oxide coated glass electrode. Chemical synthesis of the azobenzene and EDOT-based chromophore (DAE) and electrochemical formation of its corresponding polymer (pDAE) are reported. The electrochromic properties of the synthesized polymer pDAE were investigated by electrochemical and spectroelectrochemical methods. pDAE exhibited an optical bandgap of 1.82 eV and three distinct colored states in its reduced, neutral, and oxidized forms. The pDAE polymer showed 44 % optical contrast at 710 nm between its reduced and oxidized states and a fast electrochromic switching time of 1.0 s. The frontier molecular orbitals, Raman shifts, and semiconducting properties of this electrochromic polymer were evaluated by density functional theory calculations. The optical absorption bands of the polymer charged states were assigned and investigated.

Comparative Investigation of Peripheral and Nonperipheral Zinc Phthalocyanine-Based Polycarbazoles in Terms of Optical, Electrical, and Sensing Properties.

In this study, nonperipherally alkyl-linked carbazole conjugated novel zinc(II) phthalocyanine was synthesized by cyclotetramerization reaction of 6-(9 H-carbazol-9-yl)hexane-1-thiol and 3,6-bis(tosyloxy) phthalonitrile in a one-step reaction. Optical, electrical, and sensing properties of this super structured polycarbazole obtained by electropolymerization are compared with peripherally alkyl-linked polycarbazole-based zinc(II) phthalocyanine. It has been found that the attachment of alkyl-linked carbazoles to the phthalocyanine molecule in either peripheral or nonperipheral positions has a great effect on the optical and electrical properties and sensing ability of the resulting polycarbazole derivatives. P(n-ZnPc) has the highest electrochromic contrast (70.5%) among the derivatives of zinc(II) phthalocyanines in the literature. In addition to these, the sensor platform has been successfully established, and analytical optimizations have been carried out. When the sensors prepared with zinc(II) phthalocyanine are examined, it was specified that the n-ZnPc- co-TP/GOx was ranked first in the literature with high sensor response and stability. As a result, by changing of the peripheral and nonperipheral position of phthalocyanines, their physical properties can be tuned to meet the requirements of desired technological application.

Copolymer based multifunctional conducting polymer film for fluorescence sensing of glucose.

A simple, rapid and effective fluorescence sensing platform has been fabricated using a fluorescent conducting polymer surface. For this purpose, a rhodamine based electroactive monomer (RDC) and a functional group containing monomer (SNS) have been copolymerized to develop a conducting polymer based sensor platform having a fluorescence and enzyme-binding surface on ITO electrode. The proposed fluorescence sensing mechanism for detection of glucose is related to the consumption of dissolved oxygen at the double layer of the electrode which is fluorescence quenching agent by glucose-GOx reaction. Concentration of glucose was investigated quantitatively from 0.05 to 1 mM via fluorescence signal measurement. This novel approach could be adapted for the production of various rapid and effective fluorescence sensing platforms for glucose.

Rhodamine-based conjugated polymers: potentiometric, colorimetric and voltammetric sensing of mercury ions in aqueous medium.

Herein, we report the synthesis and characterization of a new rhodamine-based monomer (RD-CZ), and an investigation of the optical and electrochemical properties of the corresponding polymer (P(RD-CZ)), which was electropolymerized on an ITO electrode. The resulting P(RD-CZ) polymer film was used as a simple and novel multi-signal sensor platform, which demonstrates ion-selective potentiometric, colorimetric and voltammetric responses in aqueous media for the first time. P(RD-CZ) exhibits excellent selectivity for Hg2+ ions compared with Cd2+, Cu2+ Zn2+, and Fe3+ using the potentiometric technique, which depends on the increasing charge carrier transport through rhodamine-bound Hg2+ with a limit of detection (LOD) of 9.77 × 10-8 M. The P(RD-CZ) polymer film also exhibits a distinct color change from orange to purple, which is detectable even by the naked eye, in the presence of Hg2+ ions. The LOD for Hg2+ ions obtained using the colorimetric method is 3.16 × 10-8 M. The same material has also been used for the voltammetric sensing of Hg2+ in aqueous media with a detection limit of 1 × 10-7 M. In this study, a conductive polymer-based sensor platform for detecting mercury ions via three different methods has been designed for the first time. By doing so, a disposable planar paper-based ion-sensing platform, which is suitable for low-cost point-of-care and in-field testing applications, could be fabricated with a highly reproducible and linear response towards different concentrations of analyte ions in aqueous and biological samples.

Zinc(II) phthalocyanine fused in peripheral positions octa-substituted with alkyl linked carbazole: Synthesis, electropolymerization and its electro-optic and biosensor applications.

Zinc(II) phthalocyanine fused in peripheral positions octa-substituted with alkyl linked carbazole has been prepared by cyclomerization reaction of 4,5-bis(6-carbazole-9-yl-hexylsulfanil)phthalonitrile in the presence of anhydro Zn(II) acetate and a strong organic base (DBU). Synthesis steps were optimized and higher efficiency synthesis was achieved. The purpose of combining of carbazole moieties with phthalocyanine on the peripheral position is to enhance some properties such as photo and electrochemical properties because of strong electron-donating properties of carbazole group. This molecule has been electrochemically polymerized and the electrical and optical properties of the resulting conductive polymer have been investigated. Amperometric detection was carried out following oxygen consumption at -0.7V vs. the Ag reference electrode in phosphate buffer (50mM, pH 6.0). The novel biosensor showed a linear amperometric response for glucose within a concentration range of 0.05mM to 1.5mM (LOD: 0.024mM). This result shows that modification of the proposed biosensor by copolymerization have provided to give perfect response to different glucose concentrations. Because of its superior spectral and electrochemical properties and contained zinc metal which can act as a mediator during biochemical reactions, this material has been used as a glucose biosensor platform to detection for real samples.

Rhodamine functionalized conducting polymers for dual intention: electrochemical sensing and fluorescence imaging of cells.

We report here the electrochemical co-polymerization of two functional monomers, one containing fluorescent rhodamine dye (RF) and the other monomer having amine groups (RD), onto electroactive Indium Tin Oxide (ITO) glass. After one step preparation of these surfaces, a three peptide called ArginylGlysylAspartic acid (RGD) was immobilized via EDC chemistry by using amine groups (P(RF-co-RD)/RGD) of the co-polymer, for further use in various bio-applications such as cell adhesion and imaging as well as electrochemical cell sensing. The resultant RGD bound and also fluorescent platforms were utilized as targeted adhesion materials towards integrin avb3 receptor positive (U87-MG) cells and the selectivity was checked by using HaCaT cells as a control. Finally, electrochemical measurements were carried out to characterize step by step surface modification and detection of cell attachment. As a result, P(RF-co-RD)/RGD is a promising material for multi-purpose uses, such as fluorescence imaging without the need for an additional dye for cell visualization and as a targeted adhesion and electrochemical cell sensing platform.

Enhancing biosensor properties of conducting polymers via copolymerization: Synthesis of EDOT-substituted bis(2-pyridylimino)isoindolato-palladium complex and electrochemical sensing of glucose by its copolymerized film.

1,3-Bis(2-pyridylimino)isoindoline derivative bearing 3,4-ethylenedioxythiophene (EDOT-BPI) and its palladium complex (EDOT-PdBPI) were synthesized and characterized by FT-IR, 1H NMR, 13C NMR, UV-Vis spectroscopies and via mass spectrometric analysis. Polymerization of EDOT-PdBPI and copolymerization with 4-amino-N-(2,5-di(thiophene-2-yl)-1H-pyrrol-1-yl)benzamide (HKCN) were carried out by an electrochemical method. In addition, P(EDOT-PdBPI-co-HKCN) modified graphite rod electrode was improved for amperometric glucose sensor based on glucose oxidase (GOx). In this novel biosensor matrix, amino groups in HKCN were used for the enzyme immobilization. On the other hand, EDOT-PdBPI used to mediate the bioelectrocatalytic reaction. Amperometric detection was carried out following oxygen consumption at -0.7V vs. the Ag reference electrode in phosphate buffer (50mM, pH 6.0). The novel biosensor showed a linear amperometric response for glucose within a concentration range of 0.25mM to 2.5mM (LOD: 0.176mM). Amperometric signals at 1mM of glucose were 17.9µA under anaerobic conditions. Amperometric response of the P(EDOT-PdBPI-co-HKCN)/GOx electrode decreased only by 13% within eight weeks. The P(EDOT-PdBPI-co-HKCN)/GOx electrode showed good selectivity in the presence of ethanol and phenol. This result shows that, modification of the proposed biosensor by copolymerization of amine functionalized monomer, which is indispensable to the enzyme immobilization, with palladium complex bearing monomer, which is mediate the bioelectrocatalytic reaction, have provided to give perfect response to different glucose concentrations.

Smart windows application of carbazole and triazine based star shaped architecture.

A novel triazine-based, star shape and electroactive monomer, 2,4,6-tris(2-(9H-carbazol-9-yl)ethoxy)-1,3,5-triazine (TCZ) which contains 2,4,6-trichloro-1,3,5-triazine as the core and 2-(9H-carbazol-9-yl)ethanol as the arms, was successfully synthesized. After electrochemical polymerization of the TCZ monomer, called PTCZ, the polymer shows superior optoelectronic and thermal properties due to its unique three-dimensional shape and highly-branched structure in comparison with linear analogues. Electrochromic studies exhibited that PTCZ has turquoise color in the oxidized state and is transparent in the neutral state. Due to the fact that the redox color characteristics of PTCZ are indispensable for smart windows, a PTCZ-based electrochromic device was formed with PEDOT as complementary coloring material. A potential range of -1.5 to +1.8 V was determined to be suitable for operating the PTCZ/PEDOT device between transparent and blue colors. Characterizations of the device were performed in term of switching times, optical contrast, optical memory and redox stability.

A soluble and fluorescent new type thienylpyrrole based conjugated polymer: optical, electrical and electrochemical properties.

Recently, increased attention has been focused on the synthesis of soluble and processable conducting polymers due to interest in their potential application. For this purpose a new type electroactive 2,5-di(2-thienyl)pyrrole derivative was synthesized and its novel solution-processable and fluorescent polymer, namely poly(N-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl)-3,4,5-tris(dodecyloxy)benzamide) (P(TPDOB)), was electrochemically synthesized. Characterization of the monomer and the polymer was performed by (1)H-NMR, (13)C-NMR, cyclic voltammetry, and UV-vis and fluorescence spectroscopy. This soluble polymer has very well-defined and reversible redox processes in the acetonitrile-lithium perchlorate (ACN/LiClO4) couple. Moreover, P(TPDOB) shows multielectrochromic behavior: blue in the oxidized state, caesious in the intermediate state and greenish in the neutral state. Also the copolymer consists of EDOT and TPDOB was synthesized by cyclic voltammetry. A copolymer film has superior electrochromic and electrical properties when compared with a homopolymer. Furthermore, the fluorescence features of the monomer and the polymer were investigated. Although the monomer is a violet light emitter, its polymer is a yellow light emitter. Synthesis of this new type solution-processable and fluorescent conducting polymer is an alternative to the conventional synthesis of soluble conducting polymers which allows the direct application of the conductive polymer to any desired surface for potential technological applications.

Ferrocene-functionalized 4-(2,5-Di(thiophen-2-yl)-1H-pyrrol-1-yl)aniline: a novel design in conducting polymer-based electrochemical biosensors.

Herein, we report a novel ferrocenyldithiophosphonate functional conducting polymer and its use as an immobilization matrix in amperometric biosensor applications. Initially, 4-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl)amidoferrocenyldithiophosphonate was synthesized and copolymerized with 4-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl)benzenamine at graphite electrodes. The amino groups on the polymer were utilized for covalent attachment of the enzyme glucose oxidase. Besides, ferrocene on the backbone was used as a redox mediator during the electrochemical measurements. Prior to the analytical characterization, optimization studies were carried out. The changes in current signals at +0.45 V were proportional to glucose concentration from 0.5 to 5.0 mM. Finally, the resulting biosensor was applied for glucose analysis in real samples and the data were compared with the spectrophotometric Trinder method.

Theoretical study of the structure-properties relationship in new class of 2,5-di(2-thienyl)pyrrole compounds.

Detailed studies of the structure-property relationships for conductive polymers are important for the proper understanding of the impact of morphological details on chemical and physical properties. This understanding is necessary for the development of realistic theoretical models. The particular cases of thienyl pyrroles are described. Ab initio methods based on Hartree-Fock (HF) and Density Functional Theory (DFT) calculations with the basis set of 6-31G(d) are performed to determine the molecular structural properties and to calculate FT-IR and NMR spectrum of the title molecule. Moreover, assignments of the vibrational modes are made on the basis of potential energy distribution (PED). Furthermore, the correlations between the observed and calculated frequencies are found to be in good agreement with each other as well as the correlation of the NMR data. A comparison of the experimental and theoretical calculations can be very useful in making correct assignment and understanding the properties and molecular structure relations.

A novel functional conducting polymer as an immobilization platform.

Here, we present the fabrication of conducting polymer based enzymatic and microbial biosensors. To obtain immobilization platforms for both pyranose oxidase (PyOx) and Gluconobacter oxydans, the graphite electrode surface was modified with the polymer of 4-amino-N-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl)benzamide (HKCN) which has free amino groups on the surface for further bioconjugation reactions with the biomolecules. Initially, the electrode surface was covered with HKCN via electropolymerization. Then, either PyOx or G. oxydans cell was stabilized using glutaraldehyde as a cross-linker. After optimization of biosensors, analytical characterization and surface imaging studies were investigated. The change of current depends on glucose concentration between 0.05-1.0mM and 0.25-2.5mM with HKCN/PyOx and HKCN/G. oxydans biosensors in batch systems. Also, the calibration graphs were obtained for glucose in FIA mode, and in this case, linear ranges were found to be 0.01-1.0mM and 0.1-7.5mM for HKCN/PyOx and HKCN/G. oxydans, respectively.

Transition metal cations extraction by ester and ketone derivatives of chromogenic azocalix[4]arenes.

The molecule of azocalix[n]arene is a macrocyclic used effectively in the complexation of the heavy metal pollutants (like silver and mercury). In this work, our main aim is to prepare new chromogenic azocalix[n]arene molecules to elaborate an extractant with high extractant selectivity for metal ions able to detect this type of pollutant. The solvent extraction properties of four acetyls, four methyl ketones and four benzoyls derivatives from azocalix[4]arenes which were prepared by linking 4-ethyl, 4-n-butyl, 4-acetamid anilin and 2-aminothiazol to calix[4]arene through a diazo-coupling reaction, the alkaline earth (Sr2+) and the transition (Ag+, Hg2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Cr3+) metal cations have been determined by extraction studies with metal picrates. Both ketones are better extractants than esters, and show a strong preference for Ag+, while Cu2+ and Cr3+ are the most extracted cation with the esters. Both acetyl and benzoyl esters are good carriers for Ag+ and Hg2+.