An infrared and Raman spectroscopic study of polyanilines co-doped with metal ions and H+

Polyanilines doped with (HCl+KCl) and (HCl+CoCl2) were prepared by co-doping method, respectively. For comparison, polyaniline emeraldine salt (ES) by doping with HCl and its emeraldine base (EB) form were also synthesized. The co-doped polyanilines, ES and EB samples were all characterized by Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy aiming to understand the transformations in the different doping status. The results show that the doping degree of K+ ions is considerably higher than that of Co2+ ions under the same co-doping conditions possibly due to different pseudoprotonation constants of EB with K+ ions and Co2+ ions. Moreover, morphology difference of polyaniline co-doped with alkaline metal ions or transition meal ions may arise from different coordination geometry of metal ions. Nevertheless, there are similar chemical transformations of quinoid units to benzenoid ones on polyaniline backbones for the ES and both co-doped samples. And the polyaniline backbones co-doped with H+ and metal cations are found to attain weaker charge delocalization than the ES which is doped solely with H+.     

Origin and removal of adducts (molecular mass = 98 u) attached to peptide and protein ions in electrospray ionization mass spectra

Electrospray ionization of peptides and proteins often produces intense adduct ions resulting from the attachment of a moeity with mass 98 u. The formation of these adduct ions results in a substantial reduction in the mass spectrometric sensitivity and an undesirable increase in the complexity of the mass spectra. In the present study it was shown that the removal of the attached adducts from peptide and protein ions can be affected by collisional activation and that the adducts arise from the attachment of sulfuric acid or phosphoric acid to peptide and protein ions. When sulfate and phosphate ions are removed from the samples by chemical means, adduct free ions are obtained from proteins yielding spectra with improved quality and sensitivity.     

Doping and metallic‐support effect evidenced on SERS spectra of polyaniline thin films

Surface‐enhanced Raman scattering (SERS) is a process with origins, electromagnetic and chemical. The electromagnetic enhancement consists of the excitation of surface plasmons in the metallic support of the thin film. With only the electromagnetic enhancement mechanism, the surface spectra should not differ from volume Raman spectra. However, between SERS and volume Raman spectra, there are differences resulting from the chemical reactions taking place at the polymer/metal interface, intermediated by solvent molecules, that finally depend on the types of polymers and metallic supports. Polyaniline (PAN) is an excellent material to emphasize the chemical component of SERS. This is due to its particular structure with a repeating unit that contains two entities at different weights—a reduced state and an oxidized state–that, in turn, react differently with a metallic substrate. SERS spectra depend on the oxidizing properties of the metal surface, which involves an intermediate compound of the types Ag₂O and Au₂O₃ when N‐methyl‐2‐pyrrolidinone is used as the solvent. This article presents new results concerning the surface chemical effects that produce variations of the PAN SERS spectra. The SERS spectra of the PAN emeraldine base (PAN‐EB) layered on Au support are characterized by a semiquinoid structure that we believe is induced on the intermediate compound Au₂O₃. In the presence of H₂SO₄, the SERS spectra change gradually as the degree of acid protonation doping increases. The SERS spectra of the fully protonated PAN‐EB are identical to those obtained on PAN emeraldine salt (PAN‐ES) synthesized by cyclic voltammetry in an acid medium and are invariable with the type of metallic support. The SERS spectra show that the emeraldine salt can be partially or totally deprotonated with water or NH₄OH. The deprotonation is complete for the Ag support and partial for the Au support. The SERS spectra of the fully protonated PAN‐EB are characterized by a double band with maxima at about 1330 and 1370 cm⁻¹. Although the generation process of positive charge on the macromolecular chain of PAN‐EB doped in the presence of (C₄H₉)₄NBF₄ is similar to that due to protonic acid doping, involving cation addition (C₄H or H⁺ ions, respectively) in SERS spectra, the complex band situated at about 1330–1370 cm⁻¹ no longer appears. The doping of PAN‐EB with FeCl₃ produces two polymer forms: a salt type characterized by a protonated structure similar to that found for PAN‐ES and a base type similar to the leucoemeraldine form. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2599–2609, 2000     

Acidification of three-dimensional emeraldine polymers: Search for minimum energy paths from base to salt

We present a numerical simulation of the HCl acidification process of a three-dimensional semiconducting emeraldine base (EB) polymer leading to the corresponding metallic emeraldine salt form. We have searched minimum energy paths connecting the initial configuration, composed of two EB polymer chains per cell each one attached by two HCl molecules, with the Pc2a polaronic configuration which is the final state of the acidification process. For this aim, the variational nudged elastic band method has been adopted. We provide a pictorial representation of the acidification process at T=0 K, monitoring the EB protonation and the evolution of the polymeric chains and of the positions of the Cl(-) counterions on the lowest potential energy surface. To include also temperature effects, we have explored the potential energy surface around the final equilibrium configuration, heating the system and following its dynamics by the Car-Parrinello procedure.     

Doping of polyaniline films with organic sulfonic acids in aqueous media and the effect of water on these doped films

Polyaniline (PANI) films in the form of emeraldine salt (ES) doped with aqueous organic sulfonic acids such as camphorsulfonic acid (CSA), p-toluenesulfonic acid (p-TSA) and dodecylbenzenesulfonic acid (DBSA) were studied. The ES films were obtained by treating the PANI in the form of emeraldine base (EB) with the aqueous solution of the acids. The dopant weight fraction (w), which is related to the mass gain during the redoping of EB, was in situ determined using a quartz crystal microbalance (QCM). The behaviour of PANI doping with different acids indicates that the uptake shows a slow diffusion process. The kinetics of the doping reaction is dominated by Fickian diffusion kinetics. The diffusion coefficients (D) of the dopant ions into the PANI chains were determined and were found to vary within the range of (1.6-18) × 10⁻¹⁵ cm² s⁻¹. Moreover, the effect of water on these doped ES films was studied. The starting point is the fact that PANI-coated the electrode of QCM shows significant frequency shifts on exposure to water. The changes in the frequency as a function of treatment time in water were quantitatively measured. The response of the device suggests that the mass decrease under water exposure is due to dopant ions release. The latter films were dedoped by exposure to ammonia solution to obtain the EB film form. A further decrease in the mass of the films was observed. The percentage of the mass loss due to water exposure is found to be less than w determined during the dedoping process.     

Theoretical Investigation of the Protonation Mechanism of Doped Polyaniline

The theoretical calculation of polyaniline tetramers were performed in implicit water solvent medium using the polarizable continuum model with density functional theory. In order to explore the protonation mechanism of polyaniline, the geometry characteristics, charge distribution, frontier molecular orbitals (MOs) and stability of emeraldine base and emeraldine salts in tetramer were investigated by B3LYP/6-31G+(d,p), and the significant increase mechanism of the electrical conductivity of polyaniline upon protonation was researched in detail. It was shown that optimized molecular geometry by protonation doping suggested a tendency towards bipolaron delocalization and a greater π-conjugation proved by bond length alternation and the torsional angles. Furthermore, the NBO of ES3 was distributed equably and should be conducive to the electrical conductivity, the frontier MOs were effectively established, and an electronic transition from HOMO to LUMO+1 is turned out to be a ππ* transition finally. In addition, compared with the computed energies of different emeraldine salt configurations, the bipolaronic lattice was taken for the most stable structure.     

Kinetics and thermodynamics of the attack of a phosphate ore by acid solutions at different temperatures

A calorimetric study of the kinetics and thermodynamics of the attack of a phosphate ore from Gafsa region (Tunisia) by phosphoric acid and by a mixture of phosphoric acid and sulfuric acids is undertaken at different temperatures. Two samples of the same ore having different grain size have been used. At 25 °C, the dissolution enthalpy in phosphoric acid solution equals −233.6 ± 2.2 J/g for both of the samples. Attack by the mixture of acids is strongly dependent on the solid granulometry. Interpretation of the calorimetric results by Avrami model shows the existence of three domains attributed to phosphate ore dissolution/H₂PO₄⁻ neutralisation, hemihydrate (HH) precipitation and hemihydrate/dihydrate (DH) transformation. The attack by the acid mixture was performed at higher temperatures and showed in addition the transitional formation of the anhydrous sulfate (AH) at T ≥ 55 °C, which transforms into dihydrate after the HH/DH transformation.     

电位滴定法测定抛光液中的三酸含量

探讨了利用自动电位滴定仪对抛光液中磷酸、硫酸及硝酸的分析方法,以及对溶剂的标定方法。电位滴定法测定三酸,先用硫酸亚铁铵滴定硝酸,再用氢氧化钠滴定磷酸和硫酸,从而计算三酸含量。结果表明,与传统滴定法相比,电位滴定法标定硫酸亚铁铵的相对标准偏差(RSD)从1.1%降至0.13%,标定氢氧化钠的RSD从0.72%降至0.06%。电位滴定法测定自配样品及工厂抛光产品中的硝酸,回收率分别在96%及93%以上。电位滴定法测定自配样品及工厂抛光产品中磷酸和硫酸的回收率偏差在3%以内。手动滴定法测定磷酸和硫酸的回收率偏差在5%~10%,回收效果不如电位滴定法。电位滴定法测定工厂抛光液的三酸加标回收率偏差均小于3%。自动电位滴定法比手工滴定的准确性和精密度明显提高,弥补了手工滴定法只能分析磷酸和硫酸,而无法测定硝酸的缺陷。     

The chromatography of a number of metals on cellulose phosphate layers in sulfuric acid and ammonium sulfate media

Summary The thin-layer chromatographic behavior of 58 metals on an intermediately acidic cation exchanger, cellulose phosphate (P-cellulose), has been surveyed systematically in sulfuric acid and ammonium sulfate media (0.01–2.0 M). The R_f values for many bivalent and univalent metal ions on P-cellulose plates increase with increasing concentration of sulfate ions. Howerver, manganese (II), arsenic (III) and selenium (IV) are not adsorbed on the cellulose to any great extent. Beryllium (II) and other metals, which form either strong phosphate complexes or insoluble sulfate precipitates, are strongly retained on the P-cellulose. The thin-layer chromatographic separations of various metal ions of analytical interest were accomplished to demonstrate the use of R_f measurements for predicting separations in the acid and the sulfate media.     

Electrochemical polymerization of aniline in phosphoric acid

The electrochemical synthesis of common conductive polymers such as polyaniline in phosphoric acid is a little different from that in other acidic media such as sulfuric acid. Electropolymerization in phosphoric acid is difficult, and this electrolyte medium is not applicable for this purpose. However, it is possible to overcome this problem by the addition of a small amount of sulfuric acid. In this case, the electropolymerization process can be successfully performed when the phosphate ion is doped. For instance, polyaniline films electrodeposited from an electrolyte solution of phosphoric acid have good stabilities and useful morphologies. Interestingly, phosphate doping results in the formation of nanostructures, whereas the polymer surface is macroscopically smooth. In an appropriate ratio, a mixed electrolyte of H₃PO₄ and H₂SO₄ can be used for the electropolymerization of aniline; thus, H₂SO₄ acts as a required agent for successful polymer growth, and H₃PO₄ acts as a doping agent. In this case, a small amount of sulfate is incorporated into the polymer matrix, which does not participate in the electrochemical insertion/extraction process. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3304–3311, 2006     

Extraction of oxalic acid from solutions of electrolyte mixture

Extraction of oxalic acid with tributyl phosphate and triisoamyl phosphate from solutions of its mixtures with nitric, phosphoric, sulfuric, and hydrochloric acid and with ammonium nitrate and chloride was studied. In the extractability series, oxalic acid occupies the position between nitric and phosphoric acids, with sulfuric and hydrochloric acids acting as strong salting-out agents. Nitric acid salts drastically decrease the distribution ratios of oxalic acid.     

Unusual light absorption of gem-polyfurylalkanes in sulfuric acid solution

The UV spectra of gem-polyfurylalkanes in concentrated sulfuric acid have intense bands that are shifted bathochromically as a function of the number of furan rings in the molecule. It was concluded that the conjugation between the rings through the formally nonconducting carbon bridge develops in an ionizing medium. An interpretation of the results is proposed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 613–615, May, 1993.     

The heterometric microdetermination of sulfuric acid as barium sulfate. A general study

The influence of the medium on the precipitation of barium sulfate both in the presence and in the absence of various concentrations of acids, was studied.The coprecipitation, which occurs in the presence of varying concentrations of phosphoric and nitric acids, as well as in the presence of iron(III), chromium or potassium ions, was studied quantitatively.A quick method is presented for the micro-determination of sulfuric acid.     

Determination of trace anions in concentrated weak acids by ion chromatography

Ion-exclusion chromatography (ICE) followed by ion chromatography (IC) was used for the determination of trace anionic contaminants in concentrated weak acids. The ICE separation was used as a pretreatment step to isolate the contaminant anions of strong acids from the excess of matrix ions. Then a fraction containing the analyte ions was separated using IC with suppressed conductivity detection. Microbore–ion-exchange columns were chosen to address the increased purity requirements for use of these concentrated acids in semiconductor applications. The chromatographic conditions were optimized for determining trace chloride, sulfate, phosphate, and nitrate in concentrated 24.5% (v/v) hydrofluoric acid; trace chloride, sulfate, and nitrate in concentrated 85% (w/w) phosphoric acid and trace chloride and sulfate in concentrated 0.7% (v/v) glycolic acid. Method detection limits for the anions of interest were below 100 μg/l.     

Synchrotron radiation circular dichroism spectroscopy of ribose and deoxyribose sugars, adenosine, AMP and dAMP nucleotides.

Synchrotron radiation circular dichroism (SRCD) spectra of ribose and deoxyribose sugars, adenosine, AMP and dAMP nucleotides and cyclic derivatives were measured in the vacuum ultraviolet region (down to 168 nm for sugars and 175 nm for adenine derivatives) and at different pH values (3, 6-7, 9-10) and temperatures (between 5 and 45 degrees C). The information content in the VUV region is important since the CD bands strongly depend on the chemical structure of the sugar, the presence and orientation of a phosphate group and the protonation state of adenine. On the other hand, single or double deprotonation of the phosphoric acid group has no influence on the spectra. We assign the vacuum ultraviolet (VUV) CD bands of the nucleoside and nucleotides to be due mainly to n-->pi* transitions in the adenine nucleobase based on a comparison with the absorption spectra. The CD bands of the sugars are due to n(O -->sigma*) transitions and are much smaller than the CD signal from the nucleotides in the VUV region. Bands are assigned to both pyranose and open-chain forms.     

Raman based pH measurements with polyaniline

The reversible acid–base equilibrium between the emeraldine salt (ES) and the emeraldine base (EB) form of thin electropolymerized films of polyaniline (PANI) has been studied between pH 2 and 9 with in situ Raman spectroscopy using the 514, 633 and 780 nm laser excitation wavelengths. The electropolymerization of PANI was done with cyclic voltammetry in a flow cell from a solution consisting of 50 mM aniline and 1.0 M HCl. It is shown that the Raman signal of the CN stretching vibration at 1439 cm⁻¹, originating from the quinoid units of the EB form, can be used for pH measurements between pH 3 and 6 with the 633 nm laser. This vibration is strongly resonance enhanced by the 633 nm laser and its intensity grows therefore considerably in the pH interval where the ES–EB transition mainly takes place (pH 3–6). The influence of the film conditioning pH was also studied as well as the reproducibility of the Raman spectra when pH was changed several times from pH 6 to 3.     

A spectral study of transition-metal complexes on a chelating ion-exchange resin containing aminophosphonic acid groups

The coordination mode of a commercial chelating ion-exchange resin, ES 467, containing aminomethylphosphonic acid groups anchored on a macroporous styrenedivinylbenzene copolymer, with several metal ions, such as chromium(III), cobalt(II), nickel(II), copper(II) and zinc(II) has been studied with the aid of IR, ligand field and ESR spectra. The chelating group of ES 467, aminomethylphosphonic acid, appears to bind different metal ions mainly through oxygen atoms of the phosphonic acid group, though, in the case of those species containing low-loading of metal ions, the secondary amine nitrogen atom also appears to take part in coordination. Most of the metal ions studied seem to be present as six-coordinated species in the polymeric matrix, whereas cobalt(II) species show electronic spectra which are consistent with the presence of both four-coordinated (tetrahedral) and six-coordinated (octahedral) structures of these species. The distribution coefficients for cobalt(II), nickel(II), copper(II) and zinc(II) have been determined and it appears that the resin ES 467 binds copper(II) ions selectively. An attempt has been made to find a possible relationship between the selectivity of the chelating resin and the stereochemistry of the adsorbed metal ions.     

PHOTOCHEMISTRY OF HYPOCRELLIN A (Ⅶ)——PHOTO-INDUCED ONE-ELECTRON REDUCTION OF HYPOCRELLIN PIGMENTS

The photo-induced one-electron reduction of hypocrellin A (abbreviated as HA) and hy-pocrellin B (abbreviated as HB) in the presence of cysteine or ascorbic acid has been studied in this paper. The semiquinone radical anions of HA and HB obtained from the photo-reduction of HA and HB respectively, and the following protonation and disproportionation of these radical anions were detected via the ESR and UV-Vis spectra. Through comparison of their UV-Vis spectra with those of the chemically synthesized compounds of similar structures, it has been suggested that the metastable products formed after the acceptance of net two electrons and two protons in the photoreduction of HA and HB were tetrahydroxyl-per-ylene derivatives.     

Sodium sulfate solubilities in high temperature aqueous sodium chloride and sulfuric acid solutions—predictions of solubility,vapor pressure,acidity, and speciation

Experimental measurements of the solubility of sodium sulfate in aqueous solutions containing both sodium chloride and sulfuric acid in the temperature range 250 to 374°C are reported. These measurements have been combined with previous data on the solubility of sodium sulfate in water, in aqueous sodium chloride, and in sulfuric acid solutions to produce a comprehensive model describing the solubility of sodium sulfate in such solutions. Calculations and predictions of solubility, vapor pressure, boiling point elevation, acidity, and speciation are presented. This model is of fundamental interest in itself and also is of importance because the precipitation of sodium sulfate may be a contributing factor in enhancing crevice corrosion in metals exposed to high-temperature water containing chloride and sulfate ions as impurities.     

紫外光-热双固化聚苯胺防腐涂料

以酸性磷酸酯为掺杂剂对本征态聚苯胺(EB)进行掺杂,制备了可在聚氨酯和聚氨酯丙烯酸酯中进行纳米分散的导电聚苯胺(ES),其粒径分布在80~750 nm之间可控。 在此基础上,制备了不含重金属的紫外光-热双固化聚苯胺防腐涂料。 该防腐涂料先后经过3~5 s紫外光固化和80 ℃下1~3 min的热固化,即可完成紫外光-热双固化过程。 由于ES与聚氨酯或聚氨酯丙烯酸酯之间是不相容体系,因此随着ES质量分数的增大,会导致ES的团聚,分散粒径增大。 当ES质量分数从1.0%增大到5.0%时,ES的粒径从80~119 nm增加到500~750 nm。 ES的分散粒径增大会导致防腐涂层的致密性变差,降低防腐效果。 与普通紫外光固化聚苯胺防腐涂层相比,当ES为1.0%时,紫外光-热双固化防腐涂层在质量分数为3.5%的NaCl水溶液中浸泡2160 h后,其0.1 Hz下的绝对阻抗值(|Z|_{0.1 Hz})仍高于1.0×10⁸ Ω·cm²,优于普通紫外光固化聚苯胺防腐涂层的|Z|_{0.1 Hz}(1.0×10⁷ Ω·cm²),表明紫外光-热双固化涂层的防腐效果有了显著改善。 经过500 h划叉中性盐雾试验后,普通紫外光固化防腐涂层的板面出现了锈蚀宽度小于1 mm的锈蚀,而紫外光-热双固化防腐涂层经过500 h划叉中性盐雾试验,板面没有出现生锈、起泡的现象,表明紫外光-热双固化路线对提高涂层的防腐性能具有较大的价值。