Effect of electroreduction on the EPR spectra due to charge carriers in carbon blacks

The electrochemical reduction of carbon black particles dispersed in methylene chloride was monitored in situ with electron paramagnetic resonance (EPR) spectroscopy. The broad EPR signal is converted to a signal with intermediate linewidth (ΔH_pp ~ 23 G) in both CSX-99 and BP-1300 carbon blacks. This narrowing was coincident with the manifestation of the narrow EPR signal (ΔH_pp ~ 5 G, which has been previously shown to arise during electroreduction. In addition, changes in the cavity Q were also observed under electro-reduction and subsequent electrooxidation. This decrease in the dielectric loss and the narrowing of the EPR linewidth observed upon electroreduction are discussed.     

Electrochemical behaviour and electrochemical polymerization of fluoro‐substituted anilines

The electrochemical behaviour of three fluoro‐substituted aniline monomers, 2‐fluoroaniline (2FAN), 3‐fluoroaniline (3FAN) and 4‐fluoroaniline (4FAN), was investigated in aqueous acidic and organic media by means of cyclic voltammetry (CV) studies. Constant potential electrolysis (CPE) of the monomers in acetonitrile–water mixture (1:1 by volume) using NaClO₄ as supporting electrolyte yielded soluble polymers. The mechanism of electrochemical polymerization was investigated using in situ electron spin resonance (ESR) and in situ UV–VIS spectroscopic techniques for one of the monomers (4FAN). Both CV and in situ UV–VIS measurements indicated that the polymers obtained are in the emeraldine base form. In situ ESR studies indicated that electrochemical polymerization involves a radical‐cation as an intermediate. Characterization of polymer products have been carried out using FTIR and NMR spectroscopic techniques, and thermal behaviour was studied using differential scanning calorimetry (DSC). It was found that conductivity can be imparted to as‐synthesized polyfluoroanilines via iodine doping. © 2002 Society of Chemical Industry     

A Caged,Destabilized, Free Radical Intermediate in the Q‐Cycle

The Rieske/cytochrome b complexes, also known as cytochrome bc complexes, catalyze a unique oxidant‐induced reduction reaction at their quinol oxidase (Q_o) sites, in which substrate hydroquinone reduces two distinct electron transfer chains, one through a series of high‐potential electron carriers, the second through low‐potential cytochrome b. This reaction is a critical step in energy storage by the Q‐cycle. The semiquinone intermediate in this reaction can reduce O₂ to produce deleterious superoxide. It is yet unknown how the enzyme controls this reaction, though numerous models have been proposed. In previous work, we trapped a Q‐cycle semiquinone anion intermediate, termed SQ_o, in bacterial cytochrome bc₁ by rapid freeze‐quenching. In this work, we apply pulsed‐EPR techniques to determine the location and properties of SQ_o in the mitochondrial complex. In contrast to semiquinone intermediates in other enzymes, SQ_o is not thermodynamically stabilized, and can even be destabilized with respect to solution. It is trapped in Q_o at a site that is distinct from previously described inhibitor‐binding sites, yet sufficiently close to cytochrome b_L to allow rapid electron transfer. The binding site and EPR analyses show that SQ_o is not stabilized by hydrogen bonds to proteins. The formation of SQ_o involves “stripping” of both substrate ‐OH protons during the initial oxidation step, as well as conformational changes of the semiquinone and Q_o proteins. The resulting charged radical is kinetically trapped, rather than thermodynamically stabilized (as in most enzymatic semiquinone species), conserving redox energy to drive electron transfer to cytochrome b_L while minimizing certain Q‐cycle bypass reactions, including oxidation of prereduced cytochrome b and reduction of O₂.     

Grafting of polymer chains on the surface of carbon nanotubes via nitroxide radical coupling reaction

Poly(butylene succinate) (PBS) was grafted on the surface of TEMPO (2,2,6,6‐tetramethyl‐1‐piperidinyloxy) modified multi‐walled carbon nanotubes (MWCNTs) via a nitroxide radical coupling reaction. TEMPO functionalized MWCNTs (MWCNTs‐g‐TEMPO) were synthesized using the Cu(I)‐catalyzed azide/alkyne click chemistry approach and the covalent bond of the nitroxide moieties onto the MWCNTs was confirmed via electron paramagnetic resonance (EPR) spectroscopy. The PBS grafting on the sidewalls of MWCNTs was carried out in solution via peroxide‐induced formation of macroradicals and it was confirmed by EPR and attenuated total reflectance Fourier transform infrared analysis. Preliminary rheological and calorimetric analyses revealed that the grafting improves both the quality of stress transfer across the polymer ? nanotube interface and the degree of dispersion of the filler, which also exhibited a moderate nucleating action on the PBS. Overall, our results demonstrate that nitroxide radical coupling is an efficient and feasible ‘grafting to’ method to covalently bond polymer chains on MWCNTs with possible advantages in the final properties of the polymer nanocomposites. © 2015 Society of Chemical Industry     

Chemical copolymerization of aniline with o‐chloroaniline: thermal stability by spectral studies

Poly(aniline‐co‐o‐chloroaniline) salts were synthesized by chemical copolymerization of aniline with o‐chloroaniline using three different acids. The polymer salt samples were heat treated at four different temperatures (150, 200, 275 and 375 °C) and the thermal stability of the polymer salts were studied by conductivity, electron paramagnetic resonance (EPR), infrared (IR) and electronic absorption spectral measurements. The conductivity of the copolymers could be controlled in a broad range from 10 S cm⁻¹ for homopolymer of aniline to 10⁻⁴ S cm⁻¹ for those of o‐chloroaniline. No structural changes took place up to 200 °C and this was confirmed from EPR, IR and electronic absorption spectra. No definite correlation exists between conductivity and spin concentration. © 2000 Society of Chemical Industry     

Oxidation of oleuropein studied by EPR and spectrophotometry

The autoxidation at alkaline pH and enzymatic oxidation by mushroom tyrosinase of oleuropein, the dominant biophenol present in the fruits and leaves of Olea europea, was followed by both electron paramagnetic resonance (EPR) and absorption spectroscopy. For comparison, the same oxidation processes were applied to 4‐methylcatechol, a simple polyphenol present in olive mill wastewaters. EPR spectra of stable o‐semiquinone radicals produced during autoxidation at pH 12 and short‐lived o‐semiquinone free radicals produced during autoxidation at pH 9.0 or tyrosinase action and stabilized by chelation with a diamagnetic metal ion (Mg²⁺) were recorded for both polyphenols, and the corresponding hyperfine splitting constants were determined. The UV‐Vis spectral characteristics of the oxidation of polyphenols were highly dependent on the type of polyphenol, oxidant type and the pH of the reaction. The kinetic behavior of tyrosinase in the presence of oleuropein and 4‐methylcatechol was followed by recording spectral changes at 400 nm (absorption maximum) over time. The tysosinase activity with oleuropein showed a pronounced pH optimum at pH 6.5 and a minor one around pH 8. From the data analysis of the initial rate at pH 6.5, the kinetic parameters K_m = 0.34 ± 0.03 mM and V_max = 0.029 ± 0.002 ΔA₄₀₀ min^–1 were determined for oleuropein.     

Ethylene–propylene copolymer/ordered polysilsesquioxane nanocomposites prepared via organic acid‐ or base‐catalyzed binary silica water‐crosslinking reactions

In situ silica sol–gel‐derived organic–inorganic hybrid materials, which comprise a vinyltrimethoxysilane‐grafted ethylene–propylene copolymer (EPR‐g‐VTMS) and n‐hexyltrimethoxysilane (HTMS), were successfully prepared in the presence of an organic acid and base catalyst. Benzenesulfonic acid and aniline were selected as the organic acid and base catalyst, respectively, to examine the progress and effect of progressive changes in the silane water‐crosslinking reaction of EPR‐g‐VTMS/HTMS composites. The water‐crosslinked EPR‐g‐VTMS/HTMS composites were characterized by means of attenuated total reflectance Fourier transform infrared spectroscopy, gel content, solid‐state ²⁹Si cross‐polarization/magic‐angle spinning NMR, wide‐angle X‐ray scattering, tensile strength and field‐emission scanning electron microscopy measurements. These results revealed that the type of catalyst has a substantial influence on the nature of siloxane bonds and eventually the physical tensile properties of the water‐crosslinked EPR‐g‐VTMS/HTMS composites, which can be explained mainly from knowledge of the traditional acid‐ and base‐catalyzed silica sol–gel reaction. Moreover, an in‐depth analysis of the aniline‐catalyzed composites indicated the formation of ladder‐type poly(n‐hexylsilsesquioxane)s and the presence of a highly ordered structure with a thickness equal to the length of two n‐hexyl groups in all‐trans conformation. We demonstrate potential for the future design of highly ordered silicate‐based organic–inorganic hybrid nanocomposites. Copyright © 2009 Society of Chemical Industry     

Vertically oriented polyaniline‐graphene nanocomposite based on functionalized graphene for supercapacitor electrode

Polyaniline functionalized reduced graphene oxide (PORGO) is prepared by interfacial polymerization and then vertically oriented polyaniline‐graphene (PANI‐PORGO) nanocomposites based on PORGO are developed successfully by in situ polymerization. The morphology and structure are characterized by field emission scanning electron microscopy (FE‐SEM), transmission electron microscopy (TEM), Fourier transform infrared spectra (FT‐IR), Raman spectra and X‐ray diffraction (XRD). The electrochemical tests indicate that the specific capacitance of PORGO and PANI‐PORGO is as high as 291 and 369 F/g, respectively, at the current density of 1 A/g. PANI—PORGO nanocomposite exhibits high electrochemical activity and enhanced cycle stability with a capacitance retention of 81.2% after 500 cycles at 10 A/g. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44808.     

In situ binary sol–gel reaction of various trifunctional alkoxysilane in the silane‐grafted polyolefin matrix and its effect upon the mechanical properties

The vinyltrimethoxysilane‐grafted ethylene‐propylene copolymer/trifunctional methoxysilane (EPR‐g‐VTMS/RTMS) composites were prepared via in situ silica sol–gel reactions. Five trifunctional methoxysilane compounds (n‐hexyltrimethoxysilane, n‐decyltrimethoxysilane, n‐tetradecyltrimethoxysilane, n‐octadecyltrimethoxysilane, and phenyltrimethoxysilane) have been selected for this study. The water‐cross‐linked EPR‐g‐VTMS/RTMS composites were characterized by attenuated total reflectance‐Fourier transform infrared spectroscopy, gel content, solid‐state ²⁹Si CP/MAS NMR, wide‐angle x‐ray scattering, tensile strength, and field emission scanning electron microscopy measurements. The type of RTMS additive has a substantial influence on the nature of siloxane band networks and eventually the mechanical tensile properties. This finding suggests that the interaction and/or entanglement between the EPR‐g‐VTMS matrix and the substituent of the RTMS additives are crucial for the modifying mechanical properties. Moreover, for the water‐cross‐linked EPR‐g‐VTMS/CnTMS (n = 6, 10, 14, and 18) composites, the joint evidence provided by attenuated total reflectance‐Fourier transform infrared spectroscopy, ²⁹Si CP/MAS NMR, and wide‐angle x‐ray scattering results suggested the formation of ladder‐type poly(n‐alkyl silsesquioxane)s and the presence of the highly ordered structure with a thickness equal to the length of two n‐alkyl groups in all‐trans conformation. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers.     

Electrochemical oxidation of aryl cycloheptatrienes

The electrochemical oxidation of various substituted aryl cycloheptatrienes and cyclohepta‐1,3,5‐triene, the parent compound, in acetonitrile is investigated with the aid of cyclic voltammetry (CV), experiments at the rotating ring disk electrode (RRDE) and controlled potential electrolysis. 1‐(p‐methoxyphenyl)‐cycloheptatriene 2c , 1‐ and 3‐(p‐di‐methylaminophenyl)‐cycloheptatriene 2d , 3d are converted by anodic oxidation into the radical cations the main reaction of which is not the deprotonation. According to the proposed mechanism the electrochemical oxidation proceeds along the radical cation dimerization. The dimer cations ( 1 ₂²⁺) decompose under deprotonation into tropylium ions 4 and starting compound. In the case of 1‐(p‐dimethylaminophenyl)‐cycloheptatriene 2d the deprotonation reaction can compete with the dimerization. The oxidation of the cycloheptatriene compounds is kinetically controlled by the homogeneous chemical steps rather than by the initial electron transfer.     

Synthesis,characterization and SEESR spectroscopic investigations of indole/aniline copolymers

Indole/aniline copolymers were synthesized electrochemically and the polymerization mechanism was investigated via in‐situ simultaneous electrochemical electron spin resonance (SEESR) spectroscopy. The Radical cationic intermediates of substituted indole and aniline were detected during the electrochemical oxidation. The resulting ESR‐spectra with hyperfine splitting were simulated and radicalic structures were identified. It was suggested that the polymerization occurs over positions C‐3 and C‐6 of indole molecule and over the nitrogen and para‐position of aniline. Furthermore, aniline, indole and aniline/indole copolymers were investigated depending on applied potential via electrochemical impedance spectroscopy (EIS). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polymerization of monomers initiated by silyl centers in SiO deposits prepared by pulsed laser ablation

Deposits from silicon monoxide prepared by pulsed laser ablation were allowed to react with acrylic and vinyl monomers—styrene, methyl methacrylate and 1,2 ethylene glycol dimethacrylate. It was revealed by means of FTIR, electron paramagnetic resonance (EPR), and NMR spectroscopies that silyl ?Si· reacts with monomer molecules and initiates the consecutive polymerization. Crosslinking is proved by the occurrence of bending δ(? CH₂) absorption peak at about 750 cm^?1 in FTIR spectra. Because of very low concentration of the propagating radical for styrene we used a radical scavenger N‐phenyl‐t‐butylnitrone for trapping. The measured EPR parameters were compared with the calculated ones. In case of styrene, NMR analysis manifested the presence of Si? C bonds in SiC_xO_y (x + y = 2) units, which can be taken as direct evidence of the reaction between silyl centers and monomer molecules. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4488–4492, 2006     

Formation of silver nanoparticles created in situ in an amphiphilic block copolymer film

In this work, silver nanoparticles were synthesized with an amphiphilic diblock copolymer, polystyrene‐block‐poly(1‐vinyl‐2‐pyrrolidone) (PS‐b‐PVP), as a template film. First, microphase‐separated amphiphilic PS‐b‐PVP (70 : 30 wt %) was synthesized through atom transfer radical polymerization. The self‐assembled block copolymer film was used to template the growth of silver nanoparticles by the introduction of a silver trifluoromethanesulfonate precursor and an ultraviolet irradiation process. The in situ formation of silver nanoparticles with an average size of 4–6 nm within the block copolymer template film was confirmed with transmission electron microscopy, ultraviolet–visible spectroscopy, and wide‐angle X‐ray scattering. Fourier transform infrared spectroscopy also demonstrated the selective incorporation and in situ formation of silver nanoparticles within the hydrophilic poly(1‐vinyl‐2‐pyrrolidone) domains, which were mostly due to the stronger interaction strength of the silver with the carbonyl oxygens of poly(1‐vinyl‐2‐pyrrolidone) in the block copolymer. This work provides a simple route for the in situ synthesis of silver nanoparticles within a polymer film. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Effect of composition and component structure on thermal behavior and miscibility of polypropylene catalloys

The thermal behavior and the miscibility of an in‐situ polypropylene blend named polypropylene catalloys (PP‐cats) were investigated by using modulated differential scanning calorimeter (MDSC). It is found that all PP‐cats samples present two glass transitions, one of which is ascribed to the ethylene‐propylene random copolymer (EPR), and the other, to isotactic polypropylene (PP). However, no glass transition of ethylene‐propylene block copolymer (E‐b‐P) responsible for a third component in PP‐cats could be found. With the increase of EPR, the glass transition temperatures responding to PP and EPR components, T_g, _PP and T_g, _EPR, shift to low temperature, because of the enhancement of the interaction between PP and EPR component and the increase of ethylene content in EPR, respectively. Furthermore, the difference between T_g, _PP and T_g, _EPR remarkably decreases with the increase of the total ethylene content in PP‐cats, which indicates that the miscibility of PP‐cats is strongly dependent on the composition. Comparing the T_g, _PP and T_g, _EPR with T_g of fractionated PP and EPR, we ascribe the T_g change of PP fraction to the increase of EPR content; while that of EPR, to the increase of ethylene content in EPR. These experimental results suggest that the existence of E‐b‐P plays an important role in improving the miscibility between propylene homopolymer and EPR in PP‐cats. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

In situ synthesis of cabbage like polyaniline@hydroquinone nanocomposites and electrochemical capacitance investigations

A Cabbage like polyaniline@hydroquinone composite microsphere was synthesized using in situ polymerization and the electrochemical performance was investigated. The core template, p‐benzoquinone, is demonstrated working as an oxidizing agent for the in situ polymerization of PANI, and to be reduced to 1, 4‐hydroquinone after reaction. The morphology and microstructure of samples were examined by field emission scanning electron microscopy, transmission electron microscope, X‐ray photoelectron spectrometer, thermo gravimetric, and Fourier transform infrared spectra. The cyclic voltammetry, impedance and galvanostatic charge/discharge analysis demonstrates that PANI contributes electronic conductive channels for hydroquinone, and hydroquinone works as a pseudocapacitance component. The prepared PANI@hydroquinone nanocomposite exhibits brilliant electrochemical properties of a specific capacitance of 126.0 F g^?1 at a scan rate of 5 mV s^?1 and enhanced stability of about 85.1% of initial capacitance retained after 500 cycles scanning at a current density of 1 A g^?1. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42290.     

Role of phenolic derivatives in photopolymerization of an acrylate coating

The photopolymerization of acrylate resins on wood surfaces suffers from retardation and inhibition effects due to the phenolic derivatives present at the interface. This article details the study of the effect of a set of phenolic compounds on the initiation step. The global effect was recorded by differential scanning calorimetry and photocalorimetry. A comparison between a direct photocleavable initiator such as 2,2‐dimethyloxy‐2‐phenylacetophenone (DMPA) and a two‐component system like benzophenone/N‐methyldiethanolamine (BP/MDEA) suggests that the retardation effect observed in the latter case is due to the interaction between phenols and the triplet state of BP. Subsequently, nanosecond transient absorption (NTA) spectroscopy was used to measure in acetonitrile the quenching rate constants k_Q. A hydrogen abstraction occurred, and the ketyl radical quantum yield was also determined by NTA experiments. In comparison with the photoreduction mechanisms proposed in the literature, the high k_Q values obtained were tentatively correlated to the half‐wave oxidation potentials of phenols in order to discuss the involvement of an electron transfer within the reaction. Some EPR experiments were done to confirm in situ the photoreduction process at the wood surface and the creation of phenoxyl radicals. The interaction of phenols with some initiating radicals was also studied. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2061–2074, 2000     

Influence of cocatalyst on the structure and properties of polypropylene/poly (ethylene‐co‐propylene) in‐reactor alloys prepared by MgCl2/TiCl4/diester type Ziegler‐Natta catalyst

In this work, a series of polypropylene/poly(ethylene‐co‐propylene) (iPP/EPR) in‐reactor alloys were prepared by MgCl₂/TiCl₄/diester type Ziegler‐Natta catalyst with triethylaluminium/triisobutylaluminium (TEA/TIBA) mixture as cocatalyst. The influence of cocatalyst and external electron donor, e.g., diphenyldimethoxysilane (DDS) or dicyclopentyldimethoxysilane (D ‐donor), on the structure and mechanical properties of iPP/EPR in‐reactor alloys were studied and discussed. According to the characterization results, PP/EPR was mainly composed of random poly(ethylene‐co‐propylene), segmented poly(ethylene‐co‐propylene), and high isotactic PP. Using TEA/TIBA mixture as cocatalyst and DDS as external electron donor, as TEA/TIBA ratio increased, the impact strength of iPP/EPR in‐reactor alloys had an increasing trend. Using TEA/TIBA mixture as cocatalyst and D ‐donor as external electron donor, the impact strength of iPP/EPR in‐reactor alloy were dramatically improved. In this case, the iPP/EPR in‐reactor alloy prepared at TEA: TIBA = 4 : 1 was the toughest. The influence of cocatalyst and external electron donor on the flexural modulus and flexural strength could be ignored. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

6‐Pyridinium benzo[a]phenazine‐5‐oxide derivatives as visible photosensitisers for polymerisation

Several 6‐pyridinium benzo[a]phenazine‐5‐oxide derivatives have been synthesised and characterised by proton nuclear magnetic resonance spectroscopy and mass spectrometry. The spectroscopic and electrochemical properties of these dyes were examined. The dyes were used as reducible sensitisers for selected electron donors (phenylthioacetic acid, phenoxyacetic acid, N‐phenylglycine, and ethyl 4‐N,N‐dimethylaminobenzoate) and as oxidisable sensitisers for electron acceptors (onium and N‐alkoxypyridinium salts). These photoredox pairs were found to be effective visible‐wavelength photoinitiators for the free radical polymerisation of trimethylolpropane triacrylate under visible light. The cationic photopolymerisation of cyclohexene oxide by the studied dyes and the onium salt photoredox pairs was ineffective. The obtained results are discussed on the basis of both free energy change for electron transfer to or from the benzo[a]phenazine dyes and the photochemical properties of the dyes, particularly their photobleaching. The proposed mechanism of dye fading is supported by density functional theory calculations and spectroscopic characterisation of the radical cation of the dye.     

In situ EPR spectroelectrochemistry of single-walled carbon nanotubes and C60 fullerene peapods

The first in situ electron paramagnetic resonance (EPR) spectroelectrochemical study of C₆₀ fullerene peapods (C₆₀@SWCNT) as well as that of single-walled carbon nanotubes (SWCNTs) in different electrolyte solutions describes the formation of spin states by charge transfer reactions. Electrochemical reduction of peapods at high negative potentials causes the production of spins at the SWCNT site, while the intratubular fullerene is unchanged.Slightly anisotropic EPR signals were detected during electrochemical reduction of single-walled carbon nanotubes and fullerene peapods in the potential region from −1.75 to −2.15 V vs. decamethylferrocene/decamethylferrocinium couple. They are centered at g = 2.0038 and exhibit a hyperfine structure indicating the presence of functional groups containing N, O, H atoms in neighborhood. They differ from the EPR signals of chemically (potassium) doped SWCNT and C₆₀@SWCNT. As the EPR signal is influenced by the electrolyte counter ions a reaction with electrolysis products of tetraalkylammonium cations is taken into consideration. No EPR lines of fullerene anions were found in electrochemically treated peapods, but these anions are detectable, if a free C₆₀ in solution is cathodically reduced on a SWCNT electrode.     

Preparation of different dendritic‐layered silicate nanocomposites

Several dendrimer–clay nanocomposites have been prepared. Firstly, the dendrimer (DE₁)/clay nanocomposite was obtained via an in situ free radical polymerization of a double bond‐ended dendrimer (DE₁), derived from Behera's amine by using 2,2′‐azobisisobutyronitrile (AIBN), as initiator, and Cloisite 30 B, as nanofiller. Further free radical in situ copolymerization processes were conducted between DE₁, methyl methacrylate (MMA), and styrene (St). Two other dendrimer/clay nanocomposites were prepared by the reaction of second generation (G₂)–36‐acid dendrimer (DE₂) and N,N′,N′,N′‐tetrakis[2‐hydroxy‐1,1‐bis(hydroxylmethyl) ethyl]‐α,α,ω,ω‐alkane‐tetracarboxamide [6]‐10‐[6] Arborols (DE₃) with montmorillonite clay (MMT). POLYM. ENG. SCI., 53:2166–2174, 2013. © 2013 Society of Plastics Engineers