Studies on the resonance Raman spectra of polyaniline obtained with near‐IR excitation

The effects of near‐IR (NIR) laser power over the Raman spectra of poly(aniline) emeraldine salt (PANI‐ES) and base (PANI‐EB) were investigated. The reasons for the existence of several bands from 1324 to 1500 cm⁻¹ in the Raman spectra of poly(aniline) obtained at NIR region were also studied. The bands from 1324 to 1375 cm⁻¹ were associated to νC N of polarons with different conjugation lengths and the bands from 1450 to 1500 cm⁻¹ in Raman spectra of PANI emeraldine and pernigraniline base forms were correlated to νCN modes associated with quinoid units having different conjugation lengths. The increase of laser power at 1064.0 nm causes the deprotonation of PANI‐ES and the formation of cross‐linking segments having phenazine and/or oxazine rings. For PANI‐EB only a small spectral change is observed when the laser power is increased, owing to the low absorption of this form in the NIR region. Copyright © 2007 John Wiley & Sons, Ltd.     

Polymerization of aniline in the galleries of layered HNbMoO6

Insertion of aniline molecules and subsequent polymerization using FeCl₃ as an oxidizing agent were examined in the layers of rutile-type HNbMoO₆. Although the polyaniline/host ratio was variable depending on the amount of intercalated aniline before polymerization, the interlayer spacing was constant as 6.3 Å regardless of the ratios. Comparison of FT-IR and FT-Raman spectra for (PANI)_yNbMoO₆ (0.26≤y≤0.64) clearly showed that both quinoid and benzenoid forms exist in the galleries of inorganic host. IR and Raman active modes of extracted PANI from the matrix were quite similar to those of emeraldine salt.     

The chemical oxidative polymerization of aniline in water: Raman spectroscopy

The structural changes of aniline oligomers and polyaniline, associated with oxidation of aniline with ammonium peroxydisulfate in aqueous solutions without any added acid, were studied. The reaction was quenched at various times and the films deposited on silicon windows have been studied in detail by Raman spectroscopy, at excitation wavelengths 633 and 514 nm. The presence of substituted phenazine structural units, in addition to ordinary benzenoid, quinonoid, and semiquinonoid structures, has been proved by the appearance of characteristic Raman bands at 1645–1630, 1420–1400, 1380–1365, ∼575, and ∼415 cm⁻¹. The remarkable differences of the Raman spectra of oligoanilines, precipitated in the first phase of oxidative polymerization, and polyaniline nanotubes and nanorods, formed in the second stage of reaction, are discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

AC conductivity and dielectric behavior of polyaniline/sodium metavenadate (PANI/NaVO3) composites

The conducting polyaniline/sodium metavenadate (PANI/NaVO₃) composites were synthesized by single step in situ polymerization technique by placing finely grinded powder of NaVO₃ during the polymerization of aniline. The formation of mixed phases of the polymer together with the conducting emeraldine salt phase was confirmed by spectroscopic techniques like FTIR. SEM images indicated a systematic morphological variation of particles aggregated in the composite matrix as compared to the pristine PANI. AC conductivity and dielectric behavior of these composites were investigated in the frequency range 50 Hz to 5 MHz. It is found that AC conductivity obeyed the power law index and the variation of conductivity with wt% of NaVO₃ could be related to conductivity relaxation phenomenon. These composites have shown high dielectric constant, which is related to polarization. It is seen that both dielectric constant and dielectric loss decrease with increase in frequency. Variations in measured parameters of AC response with increasing frequency of these composites are found to follow systematic trends that are similar to those observed with temperature and doping.     

Investigation of the effect of acid dopant on the physical properties of polyaniline prepared using microwave irradiation

The microwave (MW) synthesis of polyaniline (PANI) is performed using potassium iodate (KIO₃) as oxidizing agent in different concentrations of aqueous hydrochloric acid (HCl) at 8 and 93 W applied microwave power for duration of 10 min. The morphological and structural changes in synthesized MW PANI samples are investigated using Scanning Electron Microscopy (SEM) and Fourier transform Infrared Spectroscopy (FTIR). With decreasing pH of the reaction medium the morphology of MW PANI samples changed from slab-like with a small amount of fibrils to porous products which consist of short, rod-like structures. The FTIR spectra confirm that the microwave generated materials structurally consist of PANI, but aniline oligomer peaks are observed in the FTIR at 725 and 686 cm⁻¹ for MW PANI synthesized using 0.5 M aqueous HCl. The influence of acid dopant on the spin concentration of MW PANI synthesized at 8 and 93 W are examined.     

Photodegradation of Carbaryl in Acetonitrile Solution

The photochemical decomposition, induced by UV radiation, of the carbamate pesticide (Carbaryl) in acetonitrile has been examined by means of gas chromatography–Mass spectrometry (GC‐MS). The result of continuous irradiation was almost total degradation of the pesticide examined. In order to investigate the nature of the reaction products, a spectroscopic study (UV‐Vis, steady‐state fluorescence, and fluorescence lifetime) of the products was performed. Phthalic anhydride and traces of 1,4‐naphtalenedione as an intermediate were detected as reaction products. The presence of a trace amount of 1‐naphthol as one of the photoproducts was confirmed by fluorescence lifetime measurements.     

Polyacetylene nanoparticles-based preparation of polyaniline nanofibers

Abstract  

A conjugated polymer polyacetylene (PA) nanoparticles-based preparative strategy toward doped polyaniline (PANI) nanofibers has been demonstrated for the first time, carried out by chemical oxidative polymerization of aniline under rapid stirring using ammonium persulfate as the oxidant in acidic aqueous media in the presence of dodecylsulfate (SDS)-stabilized PA nanoparticles. It is found that only PANI nanoparticulates are formed when the synthesis is performed in the absence of PA nanoparticles. The optical properties and the electronic conductivity of the resulting doped nanofibers and the corresponding dedoped products were studied and the influence of the amount of PA nanoparticles used on the morphologies of PANI nanostructures was also investigated. A possible mechanism is proposed to explain the formation of the PANI nanofibers.     

Ultrasound and ionic-liquid-assisted synthesis and characterization of polyaniline/Y2O3 nanocomposite with controlled conductivity

A sonochemical method has been employed to prepare polyaniline-Y₂O₃ nanocomposite with controlled conductivity with the assistance of an ionic liquid (IL). Ultrasound energy and the IL replace conventional oxidants and metal complexes in promoting the polymerization of aniline monomer for the first time. Structural characterization has revealed that the resulting nanocomposite consists of microspheres of average diameter 3–5 μm. The products were found to consist of regular solid microspheres covered with some 40 nm nanoparticles. Under certain polymerization conditions, polyaniline nanofibers and nanosheet were obtained. The method may open a new pathway for the preparation of nanoscale conducting polymer nanocomposites with the aid of ILs. The conductivity of the product varies with the mass ratio of aniline monomer to Y₂O₃ and IL. TG curves of the products suggest that the thermal degradation process of the PANI/Y₂O₃ composites proceeds in two steps and that the composites are more thermally stable than pure PANI. The reaction conditions have been optimized by varying parameters such as the aniline/Y₂O₃ ratio and the type and amount of IL used. The effect of the ultrasonic irritation time and frequency on the morphology, conductivity and yield were discussed.     

Reactivity of C4‐indolyl substituted 1,4‐dihydropyridines toward superoxide anion (O2•) in dimethylsulfoxide

Reactivity of two new C4‐indolyl substituted 1,4‐dihydropyridines (1,4‐DHPs) toward superoxide anion (O₂^? ) in dimethylsulfoxide (DMSO) is reported. Reactivity was followed by electrochemical and spectroscopic techniques. Gas chromatography‐mass spectrometry (GC–MS) was used to identify the final products of the reaction. C4 indolyl‐substituted‐1,4‐DHPs reacted toward O₂^? at significant rates, according to the calculated kinetic rate constants. Results are compared with 4‐phenyl‐DHP and the commercial 1,4‐DHPs, nimodipine, nisoldipine, and amlodipine. Indolyl‐substituted 1,4‐DHPs were more reactive than the commercial derivatives. The direct participation of proton of the 1‐position of the secondary amine in the quenching of O₂^? was demonstrated. Copyright © 2008 John Wiley & Sons, Ltd.     

Pickering emulsion polymerization of polyaniline/LiCoO2 nanoparticles used as cathode materials for lithium batteries

The oil in water (o/w) emulsions were prepared using aniline dissolved in toluene and LiCoO₂ particles as stabilizers (Pickering emulsions). Pickering emulsions are stabilized by adsorbed solid particles instead of emulsifier molecules. The mean droplet diameter of emulsions was controlled by the mass ratio M (oil)/M (solid particles). The emulsions showed great stability during 3 days. The composite materials containing LiCoO₂ and the conductive polymer polyaniline (PANI) have been prepared by means of polymerization of aniline emulsion stabilized by LiCoO₂ particles. The composite materials were characterized by nanosphere and nanofiber-like structures. The nanofiber-like morphology of the powdered material was distinctly different of the morphologies of the parent materials. The electrochemical reactivity of PANI/LiCoO₂ composites as positive electrode in a lithium battery was examined during lithium ion deinsertion and insertion by galvanostatic charge–discharge testing; PANI/LiCoO₂ (1:4) composite materials exhibited the best electrochemical performance by increasing the reaction reversibility and capacity compared to that of the pristine LiCoO₂ cathode. The first discharge capacity of PANI/LiCoO₂ (1:4) was 167 mAh/g, while that of LiCoO₂ was136 mAh/g.     

The effect of spectral resolution on the Raman spectra of polyaromatic hydrocarbons and beta‐carotene mixtures

The spectroscopic basis for extraterrestrial life‐detection through the molecular signatures of relevant biomaterials is dependent upon several instrumental facilities which could effect the diagnostic interpretation of key Raman bands from relevant substances occurring together in the geological record. To this effect, the Raman spectra of several polyaromatic hydrocarbons have been investigated under different conditions of spectral resolution using FT‐Raman‐spectroscopy operating at 1064 nm laser excitation wavelength. The observed Raman spectra are considerably altered under different conditions of spectral resolution; in particular, the discrimination between several polyaromatic hydrocarbons and beta‐carotene no longer becomes possible as the spectral resolution decreases. These results are relevant for the evaluation of miniaturised Raman spectrometers for space flight missions and incorporation into instrumentation for landers and rovers being proposed for future missions to Mars. Copyright © 2010 John Wiley & Sons, Ltd.     

聚苯胺/碳纳米管复合体的制备及其三阶非线性光学性能研究

通过原位吸附-受限生长聚合法成功制备了聚苯胺/碳纳米管(PANI/MWCNT)复合体.红外光谱和拉曼光谱证实了在碳纳米管(MWCNT)表面的包覆层为聚苯胺(PANI).紫外—可见吸收光谱表明随着MWCNT含量的增加PANI的吸收发生红移且强度提高.扫描电子显微镜和透射电子显微镜观察发现，PANI/MWCNT复合体直径为40—70nm，其中PANI的包覆层厚度约为15—20nm.利用四波混频方法测试它们的三阶非线性光学系数，结果发现PANI/MWCNT复合体的三阶非线性光学系数比纯PANI大，这说明在MWC 关键词： 碳纳米管 聚苯胺 复合体 三阶非线性光学系数     

A Novel Hydrophilic Modification of PTFE Membranes Using In Situ Deposited PANI

A new kind of polyaniline/polytetrafluoroethylene (PANI/PTFE) composite membrane has been successfully prepared by in situ deposition of PANI onto PTFE membranes during the aniline's dispersion polymerization. The PTFE membrane was plasma treated before the aniline polymerization; the induced alteration of morphology and surface properties accelerated the polymerization of aniline and increased the number density of the deposited PANI onto the PTFE surface. The surface properties and morphology of the membranes were characterized. The composite PANI/PTFE membrane exhibited an enhanced flux in salt water separation, which is up to 75% higher than the pristine membrane.     

Raman spectroscopic determination of the acidity constants of salicylaldoxime in aqueous solution

A sensitive and efficient method for the determination of acidity constants of salicylaldoxime (SALO) (2‐hydroxybenzaldehyde oxime), using both Raman spectroscopic and potentiometric methods, at 30 °C in 50% (wt/wt) of ethanol–water mixture and at the constant ionic strength I = 0.1 M is proposed. The effect of pH on the Raman spectra has also been studied. The Raman spectroscopic technique allows the identification of compounds in different molecular and molecular ionic structures. The limit of detection (LOD) was determined to be 0.05 mol dm⁻³ for SALO by means of Raman peak area. Copyright © 2010 John Wiley & Sons, Ltd.     

苯胺和丙烯酸协同聚合一步法制备聚苯胺纳米管

本文通过加入过硫酸铵(APS)引发苯胺和丙烯酸(AA)在水溶液中的协同聚合反应,一步合成出具有中空结构的聚苯胺纳米管. 聚苯胺纳米管的外径平均为180 nm,内径约80 nm,其形成取决于苯胺与丙烯酸的摩尔比(X_{ani/AA}). 当X_{ani/AA}不超过1时,主要得到聚苯胺纳米管. 在三电极体系中测定了所制备的聚苯胺纳米管的电化学性能. 在1 mol/L H₂SO₄为电解液,电流密度为0.5 A/g的条件下,聚苯胺纳米管比电容高达436 F/g,是通常聚苯胺纳米片的七倍. 此外,在0.5 A/g的电流密度下进行500次充放电循环后,其比电容能够保持最初始的89.2%,表现出优异的充放电循环稳定性.     

Quantitative analysis of sugar composition in honey using 532‐nm excitation Raman and Raman optical activity spectra

Raman spectroscopy based on the 1064‐nm laser excitation was suggested as a handy non‐invasive technique allowing to quickly determine sugar content in honey and similar food products. In the present study, the green 532‐nm laser radiation is explored instead as it provides higher‐quality spectra in a shorter time. The sample fluorescence was quenched by purification with activated carbon. For control mixture decomposition of Raman spectra to standard subspectra led to a typical error of the sugar content of 3%. Raman optical activity (ROA) spectra that could be measured at the shorter excitation wavelength as well provided a lower accuracy (~8%) than the Raman spectra because of instrumental sensitivity and noise limitations. The results show that Raman spectroscopy provides elegant and reliable means for fast analyses of sugar‐based food products. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis,Characterization, and AC Conductivity of Polyaniline/Selenium Composites

This study reports structural and thermal properties and temperature-dependent alternating current (AC) conductivity of polyaniline/selenium (PANI/Se) composites in emeraldine salt form prepared by a chemical polymerization method. Fourier transform infrared spectroscopy showed that the doping process significantly affected the N-H bond in PANI chain. The free energy change, which was calculated from the Langmuir adsorption isotherm, showed that Se was electrostatically adsorbed on PANI molecules. From the scanning electron microscopy images it was determined that morphological changes caused by the doping process on PANI surface could affect conductivity. Thermal analysis, which was performed with differential scanning calorimetry, showed that the addition of Se increased the degradation temperature of PANI. Depending on the doping level, significant increase was observed in the AC conductivity of PANI, approximately 11, 13, and 17 times for 300, 350, and 400 K temperatures respectively.     

Nucleophilic reactivity of aniline derivatives towards the nitroso group

This study investigates the reactivity of the electrophilic nitroso group towards nucleophilic aniline derivatives from various nitrosating agents. A relationship between the rate of nitrosation and Edwards' nucleophilic parameter (E_n) is disclosed, indicative of a transition state that is mostly product‐like in nature with respect to cleavage of the nitroso bond in the nitrosating agent. A similar relationship based on the work of Marcus provides a considerably better explanation of the data. Through application of the Marcus equation, the free energy change of reaction is calculated for the nitrosation reactions studied, which in turn is applied to develop an equation linking the free energy of formation of a nitrosamine and its corresponding protonated amine. This equation accounts for the often‐observed Brønsted relationships in nitrosation reactions. The intrinsic barrier to reaction is estimated to be 10 kJ mol^?1, indicating that the main impedance to nitrosation arises from the unfavourable reaction thermodynamics. However, for the nitrosation of aniline derivatives substituted with π‐electron withdrawing groups, an unbalancing of the transition state results in an increased intrinsic barrier, of the order of 19 kJ mol^?1. For electronic‐effect aniline derivatives, a More O'Ferrall–Jencks diagram shows the nitrosation transition state to be synchronously well balanced between reactants and products. This diagram also confirms that the reaction follows a concerted mechanism. The nitrosation of resonance‐stabilised aniline derivatives is somewhat less synchronous, however, due to delocalisation of the lone electron pair on the amino group, induced by π electron withdrawing substituents. Transition states were located according to the theory of harmonic parabolic wells. The results of these calculations agreed with transition state locations predicted using linear free energy relationship techniques. A method is developed which approximates free energy profiles by treating the product and reactant free energy wells as harmonic parabola, while the free energy profile around the transition state is taken as the parabolic barrier to the product and reactant energy wells. Applying this technique, free energy profiles for electronic‐effect and resonance‐stabilised aniline nitrosation are predicted, utilising measured kinetic values and predicted thermodynamic properties. We couple the simulated free energy profiles with their corresponding More O'Ferrall–Jencks diagrams in order to elucidate the three‐dimensional reaction path traversed between reactants and products, in terms of both structure and energy. We also demonstrate that the nitrosonium ion behaves as a soft acid, and should therefore undergo covalent frontier‐orbital controlled bonding. Copyright © 2007 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering and fluorescence emission of gold nanoparticle–multiwalled carbon nanotube hybrids

Multiwalled carbon nanotubes (MWCNTs) are grafted with gold (Au) nanoparticles of different sizes (1–12 and 1–20 nm) to form Au–MWCNT hybrids. The Au nanoparticles pile up at defect sites on the edges of MWCNTs in the form of chains. The micro‐Raman scattering studies of these hybrids were carried using visible to infrared wavelengths (514.5 and 1064 nm). Enhanced Raman scattering and fluorescence is observed at an excitation wavelength of 514.5 nm. It is found that the graphitic (G) mode intensity enhances by 10 times and down shifts by approximately 3 cm⁻¹ for Au–MWCNT hybrids in comparison with pristine carbon nanotubes. This enhancement in G mode due to surface‐enhanced Raman scattering effect is related to the interaction of MWCNTs with Au nanoparticles. The enhancement in Raman scattering and fluorescence for large size nanoparticles for Au–MWCNTs hybrids is corroborated with localized surface plasmon polaritons. The peak position of localized surface plasmons of Au nanoparticles shifts with the change in environment. Further, no enhancement in G mode was observed at an excitation wavelength of 1064 nm. However, the defect mode (D) mode intensity enhances, and peak position is shifted by approximately 40 cm⁻¹ to lower side at the same wavelength. The enhanced intensity of D mode at 1064 nm excitation wavelength is related to the double resonance phenomenon and shift in the particular mode occurs due to more electron phonon interactions near Fermi level. Copyright © 2012 John Wiley & Sons, Ltd.     

Experimental and theoretical FT‐IR and FT‐Raman spectroscopic analysis of N1‐methyl‐2‐chloroaniline

In this work, the experimental and theoretical vibrational spectra of N1‐methyl‐2‐chloroaniline (C₇H₈NCl) were studied. FT‐IR and FT‐Raman spectra of the title molecule in the liquid phase were recorded in the region 4000–400 cm^?1 and 3500–50 cm^?1, respectively. The structural and spectroscopic data of the molecule in the ground state were calculated by using density functional method (B3LYP) with the 6‐311++G(d,p) basis set. The vibrational frequencies were calculated and scaled values were compared with experimental FT‐IR and FT‐Raman spectra. The observed and calculated frequencies are found to be in good agreement. The complete assignments were performed on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. ¹³C and ¹H NMR chemical shifts results were compared with the experimental values. The optimized geometric parameters (bond lengths and bond angles) were given and are in agreement with the corresponding experimental values of aniline and p‐methyl aniline. Copyright © 2008 John Wiley & Sons, Ltd.