Polyaniline doped by a new class of dopants,benzoic acid and substituted benzoic acid: synthesis and characterization

This work reports on a new class of dopants, benzoic acid and substituted benzoic acids such as 2‐hydroxybenzoic acid, 2‐chlorobenzoic acid, 4‐nitrobenzoic acid, 2‐methoxybenzoic acid, 3‐methylbenzoic acid, 4‐methylbenzoic acid, 3‐aminobenzoic acid and 4‐aminobenzoic acid, for polyaniline. Benzoic acids can be used to dope polyaniline by mixing benzoic acid (or a substituted benzoic acid) with polyaniline in the common solvent 1‐methyl‐2‐pyrrolidone. Properties of benzoic acid doped polyaniline salts are studied using Fourier transform infra‐red, X‐ray diffraction spectroscopy, scanning electron microscopy, thermogravimetric analysis and conductivity measurements. The conductivity of polyaniline‐benzoic acid salt was found to be high (10⁻² S/cm) when compared to polyaniline‐substituted benzoic acid salts (10⁻³–10⁻⁵ S/cm). Copyright © 2005 John Wiley & Sons, Ltd.     

Cation‐ and Anion‐Substituted Potassium Manganese Phosphate,KMnP3O9: Luminescence and Photocatalytic Studies

Phosphates as multifunctional materials were of vital importance in the environmental and energy fields. In the present work, a new cyclophosphate, potassium manganese phosphate (KMnP₃O₉) (hereafter KMPO), was prepared by solid state method. Cations (Ag⁺ and Cu²⁺) and anion (N^3?) were substituted into KMPO lattice via ion‐exchange and solid state methods, respectively. The as‐prepared materials were characterized by powder X–ray diffraction, SEM–EDS and UV–visible diffuse reflectance spectra. Rietveld refinement was carried out for parent material. All the prepared materials were found to crystallize in the hexagonal lattice and isomorphous with KCoP₃O₉. The nitrogen content in N^3?‐substituted KMPO was estimated by EDS and O‐N‐H analysis. The bandgap energy of the cation‐ and anion‐substituted samples was lower compared to that of pristine KMPO. Gouy method was employed to determine the magnetic susceptibility of KMPO. The photoluminescence property of Mn²⁺ in all the samples was studied, and the color coordinates were calculated using CIE 1931 chromaticity. The photocatalytic activity of visible light active material, N^3?‐substituted KMPO, was examined against the degradation of methylene blue and methyl violet at ambient conditions.     

Green synthesis of hematite/TUD-1 nanocomposite as efficient photocatalyst for bromophenol blue and methyl violet degradation

Hematite immobilized on TUD-1 nanocomposite was prepared via sol-gel composite formation of biosynthesized hematite nanoparticles with TUD-1 precursor. The nanocomposite was characterized by various techniques such as X-ray diffraction, scanning electron microscopes/energy-dispersive X-ray spectroscopy, transmission electron microscope, gas sorption analysis, and UV–Visible diffuse reflectance spectrophotometer. Photocatalytic activity of the nanocomposite was examined in bromophenol blue and methyl violet degradation. The results showed that hematite nanoparticles obtained by the biosynthesis has particle size ranging at 20–100 nm. The nanocomposite of hematite/TUD-1 exhibit the homogeneous dispersion of the hematite in the mesoporous structured TUD-1. The smaller dispersed hematite nanoparticles affects to the increasing band gap energy of hematite, and is responsible for the efficient photocatalytic degradation of bromophenol blue and methyl violet. It is found that degradation efficiencies of the reactions over hematite/TUD-1 nanocomposite are 94.6% for bromophenol blue, and 96.7% for methyl violet. The degradation efficiency and kinetics constant of the degradation reaction expressed the effectiveness of the nanocomposite since the values are comparable with the hematite nanoparticles and other reported photocatalysts.     

Synthesis and characterization of N‐substituted polyaniline with mesogen molecules

The N‐substituted polyaniline (PANi) was synthesized by incorporation of bromine‐terminated mesogens onto the emeraldine form of polyaniline. Firsty three liquid crystalline molecules containing biphenyl units were synthesized. These mesogenic molecules are named as: 6‐bromo‐ (4‐hexyloxy‐biphenyl‐4′‐oxy) hexane (C₆? C₆Br), 5‐bromo‐(4‐hexyloxy‐biphenyl‐4′‐oxy) pentane (C₆? C₅Br), 6‐bromo‐(4‐octyloxy‐biphenyl‐4′‐oxy) hexane (C₈? C₆Br). Differential scanning calorimetry (DSC) in combination with polarizing optical microscopy (POM) were used to investigate the thermal properties of them. Optical microscopy showed focal conic texture characteristic of the Smectic A phase for (C₆? C₅Br) and (C₈? C₆Br). For (C₆? C₆? Br) smectic phase was determined. DSC experiments were also found in accord with mesophase formation. For the synthesis of N‐substituted polyaniline with these mesogen molecules, the emeraldine base polyaniline was reacted with BuLi to produce the N‐anionic polyaniline and then deprotonated polyaniline was reacted with bromine‐end mesogen to prepare mesogen‐substituted polyaniline through N‐substitution reaction. The degree of N‐substitution can be controlled by adjusting the molar feed ratio of mesogen to the number of repeat units of PANi. The microstructure and compositions of obtained polymers were characterized by FT‐IR, elemental analysis, DSC, and scanning electron microscopy (SEM). The cyclicvoltammetry show that the electroactivity of N‐substituted polyaniline is strongly dependent on the degree of N‐grafting. The solubility of mesogen‐substituted polyaniline in common organic solvents such as THF and chloroform was improved by increasing the degree of N‐substitution and also the samples are partially soluble in xylene. Liquid crystalline behavior of mesogen‐substituted polyanilines was investigated via POM, but no mesophase was observed. Copyright © 2008 John Wiley & Sons, Ltd.     

Preparation and Regioselective Metalation of Bis(trimethylsilyl)methyl‐Substituted Aryl Derivatives

A range of bis(trimethylsilyl)methyl‐substituted aryl derivatives was prepared by using a Kumada–Corriu cross‐coupling reaction. The regioselective metalation of the resulting bis(trimethylsilyl)methyl‐substituted aryl derivatives bearing this bulky silyl group allowed the generation of functionalized aromatics. A regioselective switch in the presence or in the absence of the bis(trimethylsilyl)methyl group has been demonstrated. Furthermore, this silyl group was converted into a formyl group or a styryl group, enhancing the scope of application of such bis(trimethylsilyl)methyl‐substituted arenes.     

Separation of Dyes from Aqueous Solutions by Paper Adsorption

Separation of the dyes methyl violet, methylene blue, and congo red from aqueous solutions by paper capillary permeation adsorption method was studied using paper. Nearly 100% of the investigated dyes could be separated under the optimum conditions. The effect of pH on the separation efficiency was studied in particular. At pH 5–9, 1.3–11, and 7–11, the maximum separation was achieved for methyl violet, methylene blue and congo red, respectively. The effects of dye concentration and some foreign ions on the separatability were examined. Moreover, the selective separation of some dyes was attempted by elution with chemical reagents.     

Removal of methyl violet from aqueous solution by perlite

The use of perlite for the removal of methyl violet from aqueous solutions at different concentration, pH, and temperature has been investigated. Adsorption equilibrium is reached within 1 h. The capacity of perlite samples for the adsorption of methyl violet was found to increase with increasing pH and temperature and decrease with expansion and increasing acid-activation. The adsorption isotherms are described by means of the Langmuir and Freundlich isotherms. The adsorption isotherm was measured experimentally at different conditions and the experimental data were correlated reasonably well by the adsorption isotherm of Langmuir. The order of heat of adsorption corresponds to a physical reaction. It is concluded that the methyl violet is physically adsorbed onto the perlite. The removal efficiency (P) and dimensionless separation factor (R) have shown that perlite can be used for removal of methyl violet from aqueous solutions, but unexpanded perlite is more effective.     

Solvatochromic effect and kinetics of methyl violet reduction with potassium iodide in water–isopropanol mixtures

The solvent influence on the reduction kinetics of methyl violet with iodide in binary mixture of aqueous isopropanol was investigated spectrophotometrically. The absorption spectra of methyl violet were recorded in water, aqueous isopropanol and absolute isopropanol. In these solvents λ_max was in the range from 580.5 to 582.5 nm. The CNIBS/R-K model was used to calculate the solvatochromic parameters in a binary mixture; polynomial equation was also applied to describe the experimental data. The transition energies (E_T) were calculated. They show bathochromic shift with the decrease in the polarity of the solvent. The temperature was varied from 298–318 K, while the pH of the reaction was maintained at 4.99 and 6.00. The reduction reaction was found to be first order by potassium iodide and zero order by methyl violet. The thermodynamic parameters were also evaluated to support the kinetic data.     

Study on the supramolecular systems of two basic violets with cyclodextrins by MWNTs/Nafion modified glassy carbon electrode

The electrochemical properties of two basic violets(methyl violet and ethyl violet) at the MWNTs/Nafion modified glassy carbon electrode were investigated.The redox of the basic violets is two-electron and two-proton process,and methyl violet presents stronger electron transfer capacity than ethyl violet.Meanwhile,the inclusion constants of the two basic violets with five CDs were determined by differential pulse voltammetry(DPV).The two basic violets and CDs can form 1:1 complexes. The inclusion capacit...     

甲基紫与牛血清白蛋白作用的荧光光谱研究

在pH 7.40的Tris-HC1缓冲溶液体系中,采用荧光光谱法和同步荧光光谱法研究了甲基紫(MV)与牛血清白蛋白(BSA)相互作用.结果表明MV与BSA相互作用两者存在一个结合位点,结合常数(KA)为7.628×103 L/mol,MV与BSA主要发生疏水作用,反应是一个吸热、熵增的自发过程.     

Visible light photodegradation of dyes over mesoporous titania prepared by using chrome azurol S as template

Mesoporous TiO₂ with anatase crystalline structure (MTiO₂/CAS) has been synthesized by using chrome azurol S (CAS, 2″,6″-dichloro-3,3′-dimethyl-4′-hydroxy-3″-sulfofuchson-5,5′-dicarboxylic acid) as template. It was characterized by X-ray diffraction, nitrogen adsorption/desorption, diffuse reflectance UV–visible and FT-IR spectrometry, and transmission electron microscopy. It was found that MTiO₂/CAS had substantial photocatalytic activity in the degradation of methylthionine chloride, rhodamine B, gentian violet, safranin T, methyl violet, and fuchsine basic whereas Degussa P25 (P25) had negligible photodegradation yield (<6%) under visible light irradiation.     

Quantifying Photoinitiation Efficiencies in a Multiphotoinitiated Free‐Radical Polymerization

Online size exclusion chromatography–electrospray ionization–mass spectrometry (SEC/ESI–MS) is employed for quantifying the overall initiation efficiencies of photolytically generated radical fragments. In a unique experiment, we present the first quantitative and systematic study of methyl‐substituted acetophenone‐type photoinitiators being employed in a single cocktail to initiate the free‐radical polymerization of methyl methacrylate (MMA) in bulk. The photoinitiators are constituted of a set of two known and four new molecules, which represent an increasing number of methyl substituents on their benzoyl fragment, that is, benzoin, 4‐methylbenzoin, 2,4‐dimethylbenzoin, 2,4,6‐trimethylbenzoin, 2,3,5,6‐tetramethylbenzoin, and 2,3,4,5,6‐pentamethylbenzoin. The absolute quantitative evaluation of the mass spectra shows a clear difference in the initiation ability of the differently substituted benzoyl‐type radical fragments: Increasing the number of methyl substituents leads to a decrease in incorporation of the radical fragments.     

Coated-wire organic ion-selective electrodes in titrations based on ion-pair formation: Part 3. Determination of cationic triarylmethane dyestuffs

Aqueous solutions of seven cationic triarylmethane dyestuffs can be titrated with sodium tetraphenylborate using as indicator electrode an aluminium wire coated with a PVC membrane plasticized with 2-nitrophenyl 2-ethylhexyl ether or tricresylphosphate. Titrations are possible in unbuffered and buffered media within the pH range 4–10. Characteristic titration data are given for determinations of malachite green B, seto- glaucin 0, brilliant green, fuchsine, methyl violet, crystal violet, and Victoria blue B.     

Resonance Rayleigh scattering method for the determination of trace amounts of cadmium with iodide-basic triphenylmethane dye systems

In dilute phosphoric acid solution, cadmium (II) reacts with a large excess of I^– to form [CdI₄]^2– which reacts further with basic triphenylmethane dyes such as crystal violet (CV), ethyl violet (EV), methyl violet (MV), brilliant green (BG) or malachite green (MG) to form an ion-association complex. This results in a significant enhancement of resonance Rayleigh scattering (RRS) intensity and the appearance of new RRS spectra. The characteristics of RRS spectra of the ion-association complexes, the influencing factors and the optimum conditions of these reactions have been investigated. The intensity of RRS is directly proportional to the concentration of cadmium from ¶0 to 60 ng mL^–1 for EV and MV systems, 0 to 80 ng mL^–1 for CV system, and 0 to 100 ng mL^–1 for BG and MG systems. The methods exhibit high sensitivities and the detection limits for cadmium are between 0.35 and 2.00 ng mL^–1 depending on the different reaction systems. The new RRS method was applied to the direct determination of traces of cadmium in pure zinc and synthetic water samples.     

Magnetic nanocomposite of self‐doped polyaniline–graphene as a novel sorbent for solid‐phase extraction

This work is the first study on the extraction efficiency of self‐doped polyaniline that is immobilized on the graphene‐modified magnetic nanoparticles. The new material was used as a sorbent for the magnetic solid‐phase extraction of methyl‐, propyl‐, and butylparabens. The use of graphene provides a high surface area and prevents aggregation of the nanoparticles. The self‐doped polyaniline also provides multifunctionality, high extraction capacity, and chemical stability even in the basic medium. The parabens were acetylated for determination by gas chromatography with flame ionization detection. The effects of monomer ratio, extraction solvent, sorbent amount, sample volume, desorption solvent volume, adsorption and desorption times, and sample ionic strength were optimized. Preconcentration factors obtained were from 190 to 310. The detection limits of the method were <2.8 μg/L. Linear ranges of the method were 5–2000 μg/L for propyl and butyl parabens, and 10–2000 μg/L for methyl paraben. The method was applied for the determination of the parabens in cosmetic products and extraction recoveries were 89–101% with RSDs ≤7.9%.     

PPh3‐catalyzed knoevenagel condensation: A facile synthesis of 5‐(1H‐indol‐3‐yl)Meth‐ ylene)‐2, 2‐Dimethyl‐1, 3‐Dioxane‐4, 6‐dione,and their N‐alkyl derivatives by using peg‐600 as the reaction medium

Triphenylphosphine (TPP) has been utilized as a novel and efficient catalyst for the Knoevenagel condensation of indole‐3‐carboxaldehydes 1(a–e) , 1‐methyl‐1H‐indole‐3‐carboxaldehydes 4(a–e) , and 1‐ethyl‐1H‐indole‐3‐carboxaldehydes 6(a–e) with the active methylene compound, that is, meldrum's acid ( 2 ), to afford substituted derivatives 5‐((1H‐indol‐3‐yl) methylene)‐2,2‐dimethyl‐1,3‐dioxane‐4,6‐dione 3(a–e) , 2,2‐dimethyl‐5‐((1‐methyl‐1H‐indol‐3‐yl)methylene)‐1,3‐dioxane‐4,6‐dione 5(a–e) , and 2,2‐dimethyl‐5‐((1‐ethyl‐1H‐indol‐3‐yl)methylene)‐1,3‐dioxane‐4,6‐dione 7(a–e) , respectively, in ethanol medium at RT just within 1 h in excellent yields. The products 3(a–e) were reacted independently with alkylating agents, that is, DMS and DES in the presence of PEG‐600 as an efficient and green solvent, to afford the corresponding N‐substituted methyl and ethyl derivatives 5(a–e) and 7(a–e) , respectively. © 2011 Wiley Periodicals, Inc. Heteroatom Chem 23:41–48, 2012; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20750     

Counterion-dye staining method for DNA in agarose gels using crystal violet and methyl orange

Sensitive and safe methods for visualization of DNA in agarose gels are described. 0.001% crystal violet dissolved in distilled water was used for DNA staining on agarose gels and it could detect as little as 16 ng of DNA (3 kb, pGem-7Zf/EcoRI) without destaining procedure. The detection limit is four times lower than that of ethidium bromide. To improve the sensitivity, we studied a counterion-dye staining method using methyl orange as a counterion-dye which contributes to reduce excessive background staining by crystal violet. Dye concentration, pH of staining solution, mixing molar ratio of two dyes, and staining times were optimized for the counterion-dye staining. By the staining with a mixed solution of 0.0025% crystal violet and 0.0005% methyl orange in distilled water, 8 ng of the 3 kb DNA in an agarose gel was detected within 30 min.     

Synthesis of some substituted 6,7-dihydro-4-methoxy-7-methyl-7-substituted-5-oxo-5H-furo[3,2-g]chromene-9-sulfonate derivatives as potent antihypertensive α-blocking and antiarrythmic agents

Russian Journal of General Chemistry - A number of substituted 4-methoxy-7-methyl-6-(substituted methyl)-5-oxo-5H-furo[3,2-g]-chromene-9-sulfonates 3a–3f and 4a–4c were synthesized....     

Sorption of mercury on chemically synthesized polyaniline

Summary Sorption of inorganic mercury (Hg²⁺) and methyl mercury, on chemically synthesized polyaniline, in 0.1-10N HCl solutions has been studied. Hg²⁺ is strongly sorbed at low acidities and the extent of sorption decreases with increase in acidity. The sorption of methyl mercury is very low in the HCl concentration range studied. Sorption of Hg²⁺ on polyaniline in 0.1-10N LiCl and H₂SO₄ solutions has also been studied. The analysis of the data indicates that the sorption of Hg²⁺ depends on the degree of protonation of polyaniline and the nature of mercury(II) chloride complexes in solution. X-ray photoelectron spectroscopy analysis (XPS) of polyaniline sorbed with mercury show that mercury is bound as Hg²⁺. Sorbed mercury is quantitatively eluted from polyaniline with 0.5N HNO₃. Polyaniline can be used for separation and pre-concentration of inorganic mercury from aqueous samples.     

Effect of Inorganic Ions on the Oxidation of Methyl Violet with Gliding Arc Plasma Discharge

Gliding arc discharge process was used for the treatment of methyl violet wastewater. First, the intermediate products were studied by gas chromatography coupled with mass spectrometry and Fourier transform infrared spectrometry, and ultraviolet–visible spectrometer. Second, the effects of inorganic anions including chloride (Cl^?), carbonate (CO₃ ^2?), sulfate (SO₄ ^2?), phosphate (PO₄ ^3?), nitrate (NO₃ ^?) on the degradation efficiency of methyl violet were examined. The research results indicated that hydroxyl radicals attacked carbon atom that situated in the center of dye molecule, and the conjugating structure of methyl violet was destroyed, and dye was degraded and decolored, so a possible degradation pathway was proposed by the analysis of intermediate products detected. The methyl violet degradation rate decreased with increasing anions concentrations, and their order of sequence according to the inhibition reaction was CO₃ ^2? > Cl^? > SO₄ ^2? > NO₃ ^?.