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Publication
Journal: Biochimica et Biophysica Acta - General Subjects
October/21/1998
Abstract
A gene encoding a novel member of the PPP family of protein serine/threonine phosphatases, termed PPN 58A, was cloned from Drosophila melanogaster. The deduced amino acid sequence of PPN 58A exhibits 59-62% identity to D. melanogaster PP1 isoforms, 51% identity to D. melanogaster PPY 55A and < or = 40% identity to other members of the PPP family. The single copy gene PPN 58A maps to chromosome 2 locus 58A. Analysis of PPN 58A mRNA reveals that, like PPY 55A, PPN 58A is a testis specific enzyme.
Publication
Journal: International Journal of Biological Macromolecules
September/16/2013
Abstract
1-3,4-Dihydroxy phenylalanine called as l-Dopa is a precursor of dopamine and an important neural message transmitter and it has been a preferred drug for the treatment of Parkinson's disease. In this study, with regards to the synthesis of L-Dopa two types of biosensors were designed by immobilizing tyrosinase on conducting polymers: thiophene capped poly(ethyleneoxide)/polypyrrole (PEO-co-PPy) and 3-methylthienyl methacrylate-co-p-vinylbenzyloxy poly(ethyleneoxide)/polypyrrole (CP-co-PPy). PEO-co-PPy and CP-co-PPy were synthesized electrochemically and tyrosinase immobilized by entrapment during electropolymerization. L-Tyrosine was used as the substrate for L-Dopa synthesis. The kinetic parameters of the designed biosensors, maximum reaction rate of the enzyme (Vmax) and Michaelis Menten constant (Km) were determined. Vmax were found as 0.007 μmol/(minelectrode) for PEO-co-PPy matrix and 0.012 μmol/(minelectrode) for CP-co-PPy matrix. Km values were determined as 3.4 and 9.2 mM for PEO-co-PPy and CP-co-PPy matrices, respectively. Optimum temperature and pH, operational and shelf life stabilities of immobilized enzyme were also examined.
Publication
Journal: ACS Applied Materials & Interfaces
May/10/2019
Abstract
Self-healing and electrically conductive silk fibroin (SF)-based hydrogels were developed based on the dynamic assembly/disassembly nature of supramolecular complexes and the conductive nature of polypyrrole (PPy). The self-healing properties of the hydrogels were achieved through host-guest interactions between β-cyclodextrin and amino acid side chains (tyrosine, tryptophan, phenylalanine, and histidine) on SF. PPy deposition was achieved via in situ polymerization of pyrrole using ammonium persulfate as an oxidant and laccase as a catalyst. The PPy-coated hydrogels behaved as an elastomer and displayed excellent electrical properties, with adjustable electrical conductivities ranging from 0.8 ± 0.2 to (1.0 ± 0.3) × 10-3 S·cm-1. Furthermore, possibility of potential utilization of the hydrogels in electrochemistry applications as flexible yet self-healable electrode materials was explored. This study not only shows great potential in expanding the role of silk-based devices for various applications but also provides a useful approach for designing multifunctional self-healing protein-based hydrogels.
Publication
Journal: Carcinogenesis
September/20/1993
Abstract
Arylalkynes such as 4-phenyl-1-butyne (PBY), 5-phenyl-1-pentyne (PPY) and 2-ethynylnaphthalene (2-EN) are suicide inhibitors of cytochrome P450 enzymes. Arylalkyl isothiocyanates such as 6-phenylhexyl isothiocyanate (PHITC) are structurally related to arylalkynes and are known to inhibit the cytochrome P450 mediated metabolic activation and tumorigenicity of a tobacco-specific lung carcinogen, 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK). In this study, we compared the ability of PBY, PPY, 2-EN and PHITC to inhibit A/J mouse lung tumorigenesis by NNK. Groups of 20 female mice were gavaged with 5 mumol of arylalkyne or PHITC in corn oil. Two hours later they were given a single i.p. injection of 10 mumol NNK. The mice were killed 16 weeks later. PPY and PHITC were both potent inhibitors of tumorigenesis by NNK, reducing lung tumor multiplicity from 8.35 tumors per mouse to 0.40 and 0.35 respectively. PBY and 2-EN also significantly inhibited tumor multiplicity. The results of this study demonstrate that arylalkynes and PHITC are potent inhibitors of NNK induced lung tumorigenesis in A/J mice, consistent with the hypothesis that inhibition of specific cytochrome P450 enzymes is involved in inhibition of tumorigenesis.
Publication
Journal: IEEE Transactions on Ultrasonics, Ferroelectrics, and Frequency Control
December/13/2009
Abstract
The gas sensing properties of organic polypyrrole (PPS) film, deposited onto LiNbO(3) substrate by Langmuir-Blodgett (LB) technique, have been monitored by surface acoustic wave (SAW) delay lines and studied with respect to sensitivity, selectivity, response time, stability, repeatability, and aging. The SAW PPy elements demonstrate high sensitivity toward NH(3) gas with high selectivity against CH(4), CO, H(2), and O(2). The detectable threshold concentration has been estimated as 20 ppm NH(3) in air; the response time is in the 10s range, and the recovery time is about 15 min; the repeatability of the SAW response toward eight sequential NH(3) gas exposures is within 6%; the aging of the PPy film is within 4% over a month; and the effect of humidity on SAW NH(3) gas response is negligible for the typical conditions at room ambient air. Partially reversible SAW response recognizing NH(3) gas as one component of an interfering gases-mixture has been observed. Simultaneous chemoresponses of SAW phase and insertion loss have been performed in order to investigate the sensing mechanisms. By merging with electrical conductivity gas response, the dominant SAW sensing effects for NH(3 ) gas detection are defined as elastic loading.
Publication
Journal: Materials Science and Engineering C
December/27/2016
Abstract
Polypyrrole (PPy) was synthesized by enzyme mediated oxidation of pyrrole using naturally occurring compounds as redox mediators. The catalytic mechanism is an enzymatic cascade reaction in which hydrogen peroxide is the oxidizer and soybean peroxidase, in the presence of acetosyringone, syringaldehyde or vanillin, acts as a natural catalysts. The effect of the initial reaction composition on the polymerization yield and electrical conductivity of PPy was analyzed. Morphology of the PPy particles was studied by scanning electron microscopy and transmission electron microscopy whereas the chemical structure was studied by X-ray photoelectron and Fourier transformed infrared spectroscopic techniques. The redox mediators increased the polymerization yield without a significant modification of the electronic structure of PPy. The highest conductivity of PPy was reached when chondroitin sulfate was used simultaneously as dopant and template during pyrrole polymerization. Electroactive properties of PPy obtained from natural precursors were successfully used in the amperometric quantification of uric acid concentrations. PPy increases the amperometric sensitivity of carbon nanotube screen-printed electrodes toward uric acid detection.
Publication
Journal: Journal of Nanoscience and Nanotechnology
December/5/2011
Abstract
Thermal polymerization of pyrrole was performed using silver nitrate as source of silver ions followed by its conversion to Polypyrrole (PPy)/Ag nano-comoposites without using any external oxidizing agent or solvent. The formation of PPy was monitored by UV-Visible absorption spectroscopy showing a band at approximately 464 nm. XRD measurement confirmed characteristic peaks for face centered cubic (fcc) silver and presence of PPy at 2 theta of approximately 23 degrees suggesting the formation of PPy/Ag nanocomposite. Transmission electron microscopy (TEM) images showed non-aggregated spherical Ag nano-particles of about 5-10 nm. PPy/Ag thick film acts as a NH3 sensor at 100 degrees C, a H2S sensor at 250 degrees C and CO2 sensor at 350 degrees C. The thick films showed capability to recognize various gases at different operating temperature.
Publication
Journal: ACS Applied Materials & Interfaces
November/22/2015
Abstract
With the advantages of high stickiness and stretchability of the hydrogel electrolyte as well as the resilient properties of film electrodes, the facile "prestrain-stick-release" strategy can be utilized for the assembly of a stretchable supercapacitor. Two major issues of concern are the relatively low mechanical strength of the hydrogel electrolyte and the low energy density of the assembled device. Herein, vinyl group grafted silica (CH2═CH-SiO2) nanoparticles were used as a nanoparticle cross-linker for polyacrylamide (PAAM), enhancing the tensile strength of 844 kPa at the strain of 3400% for the KCl-CH2═CH-SiO2/PAAM hydrogel electrolyte. Besides, carbon nanotube supported polypyrrole (CNT@PPy) and manganese dioxide (CNT@MnO2) film electrodes are prepared to assemble the stretchable asymmetric CNT@MnO2//KCl-CH2═CH-SiO2/PAAM//CNT@PPy supercapacitor, significantly enhancing the potential window to 0-2.0 V and achieving a high energy density of 40 Wh kg(-1) at the power density of 519 kW kg(-1) with the strain of 100%, which is the best known for the reported stretchable supercapacitors.
Publication
Journal: Angewandte Chemie - International Edition
June/26/2017
Abstract
Constructing inorganic-organic hybrids with superior properties in terms of water adsorption and activation will lead to catalysts with significantly enhanced electrocatalytic activity in the hydrogen evolution reaction (HER) in environmentally benign neutral media. Herein, we report SiO2 -polypyrrole (PPy) hybrid nanotubes supported on carbon fibers (CFs) (SiO2 /PPy NTs-CFs) as inexpensive and high-performance electrocatalysts for the HER in neutral media. Because of the strong electronic interactions between SiO2 and PPy, the SiO2 uniquely serves as the centers for water adsorption and activation, and accordingly promotes the HER. The metal-free SiO2 /PPy NTs-CFs displayed high catalytic activity in the HER in neutral media, such as a low onset potential and small Tafel slope, as well as excellent long-term durability.
Publication
Journal: Dalton Transactions
June/9/2013
Abstract
Magnetic separation with composite microspheres presents an alternative strategy for applications in biomedical and bioengineering fields. However, the synthesis of core-shell structured magnetic composites universally assumes the surfactant-directing and/or silica-assisting polymerization approach to modify and stabilize the magnetic cores. In this paper, we report on the surfactant-free synthesis of well-defined core-shell structured Fe(3)O(4)@PANI and Fe(3)O(4)@PPy microspheres with high magnetization. The temperature dependence of magnetization of the samples was examined as a function of temperature between 3 and 300 K in an applied field of 500 Oe. It was found that the blocking temperature (T(B)) values of the composite spheres are well above the room temperature. The small variation in magnetization as the temperature changes renders the composite spheres a suitable candidate when used at elevated temperatures. Also, the genomic DNA can be effectively isolated from Aspergillus niger (A. niger) cells with the composite microspheres, using a PEG-NaCl binding buffer and a phosphate eluting buffer. The magnetic isolation of genomic DNA with the composite microspheres was shown to be superior to the conventional phenol-chloroform extraction, which was confirmed by agarose gel eletrophoresis and polymerase chain reaction (PCR) diagnosis. The Fe(3)O(4)@PANI and Fe(3)O(4)@PPy microspheres presented here have great potential in enzyme immobilization, drug delivery, catalysis, and sensors.
Publication
Journal: Nanoscale
August/11/2014
Abstract
Establishing a biology-device interface might enable the interaction between microelectronics and biotechnology. In this study, electroactive hydrogels have been produced using bacterial cellulose (BC) and conducting polymer (CP) deposited on the BC hydrogel surface to cover the BC fibers. The structures of these composites thus have double networks, one of which is a layer of electroactive hydrogels combined with BC and CP. The electroconductivity provides the composites with capabilities for voltage and current response, and the BC hydrogel layer provides good biocompatibility, biodegradability, bioadhesion and mass transport properties. Such a system might allow selective biological functions such as molecular recognition and specific catalysis and also for probing the detailed genetic and molecular mechanisms of life. A BC-CP composite hydrogel could then lead to a biology-device interface. Cyclic voltammetry and electrochemical impedance spectroscopy (EIS) are used here to study the composite hydrogels' electroactive property. BC-PAni and BC-PPy respond to voltage changes. This provides a mechanism to amplify electrochemical signals for analysis or detection. BC hydrogels were found to be able to support the growth, spreading and migration of human normal skin fibroblasts without causing any cytotoxic effect on the cells in the cell culture. These double network BC-CP hydrogels are biphasic Janus hydrogels which integrate electroactivity with biocompatibility, and might provide a biology-device interface to produce implantable devices for personalized and regenerative medicine.
Publication
Journal: Journal of Physical Chemistry B
June/10/2009
Abstract
This work investigates the movement of anions during potentiostatic controlled reduction of novel composite materials consisting of high surface area cellulose substrates, extracted from the Cladophora sp. algae, coated with thin ( approximately 50 nm) layers of the intrinsically conducting polymer (ICP) polypyrrole. The coating was achieved by chemical polymerization of pyrrole on the cellulose fibers with iron(III) chloride and phosphomolybdic acid, respectively. The composites are in the form of paper sheets and can be directly immersed into an electrolyte solution for ion absorption/desorption. The motion of glutamate and aspartate anions during cathodic polarization was investigated as a function of preceding anodic polarization at various potentials. The composite was found to exhibit memory effect as the response to a cathodic polarization of constant magnitude produced different responses depending on the magnitude of the preceding anodic potential. After the application of a cathodic potential to the composite, the reduction current curvesgenerated by anions leaving the compositewere found to initially increase in magnitude followed by a monotonic decay. A similar response has not been described and analyzed for electrochemical reduction of anion containing ICP materials earlier. A theoretical model was developed to aid the analysis of the experimental data. The model accounts for both freely mobile anions and anions that may be temporarily trapped in a contracting PPy network during cathodic polarization. By fitting the recorded reduction current curves to this model, detailed information about the ionic movement in the composite could be obtained, which may be used to further optimize the materials properties of conducting polymer systems aimed for specific electrochemical ion exchange processes.
Publication
Journal: Carbohydrate Polymers
December/18/2016
Abstract
Polypyrrole (PPy) and copper sulfide (CuS) have been successfully deposited on bacterial cellulose (BC) membranes to prepare nanofibrous composite electrodes of PPy/CuS/BC for flexible supercapacitor applications. The introduction of CuS remarkably improves the specific capacitance and cycling stability of BC-based electrodes. The specific capacitance of the supercapacitors based on the PPy/CuS/BC electrodes can reach to about 580Fg-1 at a current density of 0.8mAcm-2 and can retain about 73% of their initial value after 300 cycles, while the PPy/BC-based device could retain only 21.7% after 300 cycles. This work provides a promising approach to fabricate cost-effective and flexible nanofibrous composite membranes for high-performance supercapacitor electrodes.
Publication
Journal: Analytical Chemistry
October/4/2004
Abstract
Amperometric biosensors based on new composite carbon paste (CPE) electrodes have been designed for the determination of phenolic compounds. The composite CPEs were prepared by in situ generation of polypyrrole (PPy) within a paste containing the enzyme polyphenol oxidase (PPO). The best paste composition (enzyme/pyrrole monomer/carbon particles/Nujol) was determined for a model enzyme, glucose oxidase, according to the enzymatic activity of the resulting electrodes and to the enzyme leakage from the paste during storage in phosphate buffer. The in situ electrogenerated PPy enables improvement in enzyme immobilization within the paste since practically no enzyme was lost in solution after 72 h of immersion. Moreover, the enzyme activity remains particularly stable under storage since the biocomposite structure maintains 80% of its activity after 1-month storage. Following the optimization of the paste composition, PPO-based carbon paste biosensors were prepared and presented excellent analytical properties toward catechol detection with a sensitivity of 4.7 A M(-1) cm(-2) and a response time lower than 20 s. The resulting biosensors were finally applied to the determination of epicatechin and ferulic acid as flavonol and polyphenol model, respectively.
Publication
Journal: Biosensors and Bioelectronics
August/20/2013
Abstract
A glucose biosensor was assembled using gold microelectrodes (diameter of 250 μm) coated by Single-Walled Carbon Nanotubes (SWCNTs), via the Electrophoresis Deposition Process (EPD). This nanostructured platform was successfully used to deposit the poly(pyrrole)/glucose oxidase film (PPy/GOx). The most important result of this biosensors was the wide linear range of concentration, ranging from 4 to100 mM (covering the hypo- and hyper-glycemia range, useful in diabetes). This extended linearity offered the possibility to measure glucose from 0.560 to 12.0 mM, with a detection limit of 50 μM (useful for hypo-glycemia disease).
Publication
Journal: Journal of Biomedical Materials Research - Part A
December/13/2007
Abstract
Polypyrrole (PPy) is a conducting polymer that may be electrochemically generated with the incorporation of any anionic species, including net-negatively charged biological molecules such as proteins and polysaccharides. In this article, dermatan and chloride-loaded PPy films were prepared on gold sputter-coated coverslips and various skin derived cells were studied on them by electrochemical impedance spectroscopy. Impedance spectra in the frequency range 1-100 kHz were either determined at specific times or impedance was monitored continuously at specific frequencies. An equivalent impedance circuit was fitted to the recorded impedance spectra to obtain parameters whose contributions could be mapped to intracellular and intercellular current pathways, and the membrane properties of cells. Results show cell-induced impedance changes were detected over PPy modified electrodes and were dependent on cell density and type, monitoring frequency, material composition, and treatment. Lower cell densities were detected on PPy when compared with bare gold. Keratinocyte confluence, as determined by impedimetric analysis, was reached more rapidly on PPy than on gold. This was consistent with previous, more cumbersome, biochemical assays. Electrical equivalent circuit analysis provided evidence that the technique may be extended to discriminate cell type because of the intracellular and intercellular resistance, and cell membrane capacitance being related to cell morphology.
Publication
Journal: Journal of Colloid and Interface Science
August/26/1997
Abstract
DNA adsorption onto polypyrrole (PPy) powder, a colloidal silica sol, and three polypyrrole-silica nanocomposite particles (untreated and amine- or carboxylic acid-functionalized) was investigated at neutral pH using sodium phosphate buffer. The extent of DNA adsorption was found to be 32 and 22 mg/g for the aminated silica sol and aminated PPy-silica particles respectively, and 6.5 mg/g for the carboxylated particles. DNA adsorption onto the unfunctionalized PPy-silica particles occurs to a lesser extent, whereas no adsorption was detected for the colloidal silica sol. Our results suggest that DNA adsorption is mainly governed by electrostatic and hydrophobic interactions. DNA is adsorbed onto polypyrrole chloride bulk powder and also onto the aminated PPy-silica particles, which both have cationic binding sites. The silica sol and the unfunctionalized PPy-silica particles both possess a net negative surface charge at this pH, which probably accounts for the zero or very low adsorbed amounts of DNA on these substrates. DNA adsorption onto the carboxylated PPy-silica particles may be enhanced by hydrogen bonding relative to the unfunctionalized polypyrrole-silica particles.
Publication
Journal: Biosensors and Bioelectronics
August/4/1998
Abstract
The in situ potentiostatic electropolymerization of pyrrole (Py) on a Pt electrode in a thin-layer amperometric cell and the entrapment of the enzyme glucose oxidase (GOx) for the determination of glucose are reported. Polypyrrole (PPy) is directly formed by continuous passage of a buffered solution of the monomer (0.4 M) and enzyme (250 U mL-1) at pH 7 at a flow rate of 0.05-0.1 mL min-1 under a constant applied potential of +0.85 V vs Ag/AgCl decreases. The electrosynthesis of PPy by injection of 500 microL of a Py + GOx solution in a carrier electrolyte consisting of 0.05 M phosphate buffer and 0.1 M KCl at pH 7.0 was also assayed. The influence of the electropolymerization conditions on the analytical response of the sensor to glucose was investigated. The analytical performance of the PPy/GOx sensor was also studied in terms of durability and storage life, as well as selectivity against electroactive species such as ascorbic acid and uric acid as a function of the thickness of the polymer film formed.
Publication
Journal: Bioelectrochemistry
August/18/2013
Abstract
Emerging evidences have pointed out that the release of cytochrome c (cyt c) from mitochondria into cytosol is a critical step in the activation of apoptosis. This article presents a novel approach for the detection of mitochondrial cyt c release for the first time using cytochrome c reductase (CcR) immobilized on nanoparticles decorated electrodes. Two kinds of nanomaterial-based biosensor platforms were used: (a) carbon nanotubes (CNT) incorporated polypyrrole (PPy) matrix on Pt electrode and (b) self-assembled monolayer (SAM) functionalized gold nanoparticles (GNP) in PPy-Pt. Scanning electron microscope was used to characterize the surface morphologies of the nanomaterial modified electrodes. Cyclic voltammograms of both the biosensors showed reversible redox peaks at -0.45 and -0.34 V vs Ag/AgCl, characteristic of CcR. In comparison, the CcR-CNT biosensor gave a detection limit of 0.5±0.03 μM cyt c, which was 4-fold better than the CcR-GNP biosensor (2±0.03 μM). Moreover, the CcR-CNT biosensor achieved a much larger linear range (1-1000 μM) over the CcR-GNP biosensor (5-600 μM) with 2-fold better sensitivity. The CcR-CNT-PPy-Pt biosensor was further applied to quantify the mitochondrial cyt c released in cytosol of A549 cells upon induction of apoptosis with doxorubicin, the results agreed well with standard western blot analysis.
Publication
Journal: Nanotechnology
October/1/2012
Abstract
In this study, the functionalization process for nanopillar enhanced electrodes (NEEs) using glucose oxidase (GOx) with polypyrrole (PPY) is optimized for the purpose of achieving enhanced sensing performances for these electrodes in glucose detection. Specifically, an optimal roughness factor for the NEEs and an optimal set of electro-polymerization/deposition parameters for their functionalization using GOx/PPY are identified. Results show that NEEs with a roughness factor of about 60 are optimal for enhancing the amperometric current responses and that for such electrodes an electro-functionalization/deposition process at a deposition current of 50 µA cm(-2) and a total charge of 150 mC cm(-2) will give rise to a high sensing performance with a sensitivity as high as 36 µA cm(-2) mM(-1).
Publication
Journal: Micro and Nano Letters
February/19/2017
Abstract
Patterned carbon nanotubes arrays (PCNTA) with reduced density and length were developed with polystyrene sphere masked catalyst dots followed by plasma enhanced chemical vapor deposition method. The nanotubes were then uniformly coated with electropolymerized polypyrrole (PPy). The coating thickness was conformally adjustable. Gold nanoparticles (AuNP) together with glucose oxidase (Gox) were doped into the PPy film on the nanotubes to develop a high performance PCNTA glucose sensor. The sensitivity of the sensor was improved by the co-existence of Gox and AuNP on the carbon nanotube. Moreover, in contrast to previous reported PCNTA glucose sensors, the design herein utilized the entire surface of nanotubes as active sensing areas in order to maximize the Faradic currents. This research outlines a practical avenue to fabricate high performance PCNTA sensor chips with multiple molecules and functional nano-architectures.
Publication
Journal: Analytical Chemistry
March/12/2007
Abstract
An optical sensing probe has been developed by taking advantage of the polypyrrole (PPy) chromophore. The absorbance of the oxidation product of pyrrole, i.e., solubilized PPy colloids, is shown to be directly proportional to the concentration of hydrogen peroxide, when H2O2 is used as an oxidant for pyrrole in the presence of a surfactant, sodium dodecyl sulfate, and Fe(II) in a slightly acidic aqueous solution. Based on this result, a new optical sensing method has been developed for the determination of H2O2. The probe has also been applied to optical sensing of ethanol by biocatalyzed generation of H2O2 in the presence of O2, ethanol, and alcohol oxidase. The novel methodology is expected to provide a general protocol for the determination of H2O2 as well as for numerous other oxidase-based reactions producing H2O2 as a product.
Publication
Journal: Inorganic Chemistry
May/13/2012
Abstract
Metallamacrocycles 1, 2, and 3 of the general formula [{Ir(ppy)(2)}(2)(μ-BL)(2)](OTf)(2) (ppyH = 2-phenyl pyridine; BL = 1,2-bis(4-pyridyl)ethane (bpa) (1), 1,3-bis(4-pyridyl)propane (bpp) (2), and trans-1,2-bis(4-pyridyl)ethylene (bpe) (3)) have been synthesized by the reaction of [{(ppy)(2)Ir}(2)(μ-Cl)(2)], first with AgOTf to effect dechlorination and later with various bridging ligands. Open-frame dimers [{Ir(ppy)(2)}(2)(μ-BL)](OTf)(2) were obtained in a similar manner by utilizing N,N'-bis(2-pyridyl)methylene-hydrazine (abp) and N,N'-(bis(2-pyridyl)formylidene)ethane-1,2-diamine (bpfd) (for compounds 4 and 5, respectively) as bridging ligands. Molecular structures of 1, 3, 4, and 5 were established by X-ray crystallography. Cyclic voltammetry experiments reveal weakly interacting "Ir(ppy)(2)" units bridged by ethylene-linked bpe ligand in 3; on the contrary the metal centers are electronically isolated in 1 and 2 where the bridging ligands are based on ethane and propane linkers. The dimer 4 exhibits two accessible reversible reduction couples separated by 570 mV indicating the stability of the one-electron reduced species located on the diimine-based bridge abp. The "Ir(ppy)(2)" units in compound 5 are noninteracting as the electronic conduit is truncated by the ethane spacer in the bpfd bridge. The dinuclear compounds 1-5 show ligand centered (LC) transitions involving ppy ligands and mixed metal to ligand/ligand to ligand charge transfer (MLCT/LLCT) transitions involving both the cyclometalating ppy and bridging ligands (BL) in the UV-vis spectra. For the conjugated bridge bpe in compound 3 and abp in compound 4, the lowest-energy charge-transfer absorptions are red-shifted with enhanced intensity. In accordance with their similar electronic structures, compounds 1 and 2 exhibit identical emissions. The presence of vibronic structures in these compounds indicates a predominantly (3)LC excited states. On the contrary, broad and unstructured phosphorescence bands in compounds 3-5 strongly suggest emissive states of mixed (3)MLCT/(3)LLCT character. Density functional theory (DFT) calculations have been carried out to gain insight on the frontier orbitals, and to rationalize the electrochemical and photophysical properties of the compounds based on their electronic structures.
Publication
Journal: Sensors
May/13/2017
Abstract
Today, significant attention has been brought to the development of sensitive, specific, cheap, and reliable sensors for real-time monitoring. Molecular imprinting technology is a versatile and promising technology for practical applications in many areas, particularly chemical sensors. Here, we present a chemical sensor for detecting formaldehyde, a toxic common indoor pollutant gas. Polypyrrole-based molecularly-imprinted polymer (PPy-based MIP) is employed as the sensing recognition layer and synthesized on a titanium dioxide nanotube array (TiO₂-NTA) for increasing its surface-to-volume ratio, thereby improving the sensor performance. Our sensor selectively detects formaldehyde in the parts per million (ppm) range at room temperature. It also shows a long-term stability and small fluctuation to humidity variations. These are attributed to the thin fishnet-like structure of the PPy-based MIP on the highly-ordered and vertically-aligned TiO₂-NTA.
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