Polysulfonic Acids Research Articles

Comparison of Optical Ammonia-Sensing Properties of Conducting Polymer Complexes with Polysulfonic Acids

Thin films of conducting polymer complexes with polysulfonic acids of various structures were electrochemically deposited onto transparent FTO electrodes. The behavior of the polymer-based optical ammonia vapor sensors in response to various concentrations of ammonia vapors, ranging from 5 to 135 ppm, was investigated, including the response time and response amplitude. It was found that the nature of the conducting polymers (poly (3,4-ethylenedioxythiophene), polypyrrole, polyaniline), as well as the structure of the polyacids, affected the sensing performance of the obtained complexes.

Polysulfonate-doped polyanilines—oxidation of ascorbic acid and dopamine in neutral solution

The redox behavior of polyaniline (PANI) doped with polysulfonic acids is studied in slightly acidic and neutral solutions (from pH 4 to pH 7). The dopants used are polystyrene sulfonic acid (PSSA), poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPSA), and poly-(4,4′-(2,2′-disulfonic acid)-diphenylene-tere-phthalamide) (t-PASA). Thin PANI layers are used in order to identify clearly the redox peak structure. Based on deconvolution of the reductive currents, the pH dependence of the constituent peaks is studied and pathways of the reductive transitions are suggested. With increasing pH, a loss of electroactivity is observed for all three dopants but to a different extent: the largest for PAMPSA- and the smallest PSSA-doped PANIs. In the same time, a stabilization of the conductive emeraldine salt state is observed at pH 7 for all PANIs with the largest extent of stabilization in the PANI/PAMPSA case. The electrocatalytic properties of the polysulfonic acid-doped PANIs are comparatively studied for ascorbic acid (AA) and dopamine (DA) oxidation at pH 7. It is found that all three types of PANI are good electrocatalysts for both reactions with advantage of the PAMPSA-doped layers showing higher absolute oxidative currents for both reactions. The results concerning DA oxidation demonstrate the possibility to involve polysulfonic acid-doped PANIs in electrocatalytic reactions in neutral solutions occurring at high positive potentials beyond the peak potential of the PANI oxidative transition.

Electrochemically-Obtained Polysulfonic-Acids Doped Polyaniline Films-A Comparative Study by Electrochemical, Microgravimetric and XPS Methods.

Polyaniline (PANI) layers are electrochemically obtained in the presence of four polysulfonic acids with different rigidities of the polymer backbone-iso-(and tere-)poly-(4,4′-(2,2′-disulfonic acid)-diphenylene-iso(tere)-phthalamide (i-PASA and t-PASA), polystyrenesulfonic acid (PSSA) and poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPSA). Combined microgravimetric (EQCM) and electrochemical measurements are carried out in the course of polymerization and repetitive redox switching. It is found that after synthesis PASA-doped PANIs shows good stability with low exchange of mass in the course of voltammetric scans, while PAMPSA-doped PANI contains a large amount of water that gradually becomes expelled in the repetitive redox switching. PANI obtained in the presence of PSSA takes an intermediate position with respect to mass exchanged in the electrochemical redox process. XPS studies are used to obtain data for the extent of doping of the different PANI materials. The results show high doping level (about 0.5) for PASA- and PAMPSA- and lower level (0.32) for PSSA-doped PANI layers. Repeated electrochemical studies carried out with the specimens investigated by XPS after long-term storage in the dry state give evidence for structural rearrangement, perfect recuperation of the initial electrochemical activity and high stability of the electrochemical response.

The influence of the surface structure of polyaniline films on the adsorption of influenza A viruses and antibodies to them

Adsorption of influenza A viruses and their antibodies on golden surfaces, thin films of polyaniline and polyaniline complex with polysulfonic acids, has been studied. The composition of interpolymer complexes was found to influence both the surface relief of synthesized films and the adsorption efficiency. Moreover, it has been shown that the adsorption of bio-objects increased with a growth of surface roughness of the polymer coatings. It has been suggested that this effect was caused by an tight contact between the studied bioobjects and the surface relief elements of close size. In addition, the surface protuberances can act as active centers of adsorption due to their larger accessibility. The results testify to the potential of application of films composed of interpolymer polyaniline complexes with a developed surface relief as a basis to prepare biosensors that are sensitive to viruses and antibodies.

Doped Interlayers for Improved Selectivity in Bulk Heterojunction Organic Photovoltaic Devices

Poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is less selective for holes in an inverted‐architecture organic photovoltaic (OPV) than it is in a conventional‐architecture OPV device due to differences between the interfacial‐PSS concentration at the top and bottom of the PEDOT:PSS layer. In this work, thin layers of polysulfonic acids are inserted between the poly(3‐hexylthiophene) (P3HT):indene‐C60 bisadduct (ICBA) bulk heterojunction (BHJ) active layer and PEDOT:PSS to create a higher concentration of acid at this interface and, therefore, mimic the distribution of materials present in a conventional device. Upon thermal annealing, this acid layer oxidizes P3HT, creating a thin p‐type interlayer of P3HT+/acid− on top of the BHJ. Using X‐ray absorption spectroscopy, Kelvin probe, and ellipsometry measurements, this P3HT+/acid− layer is shown to be insoluble in water, indicating it remains intact during the subsequent deposition of PEDOT:PSS. Current density–voltage measurements show this doped interlayer reduces injected dark current while increasing both open‐circuit voltage and fill factor through the creation of a more hole selective BHJ‐PEDOT:PSS interface.

Molecular Rectangles with Rod‐Shaped Disulfonic Acids

Polysulfonic acids and their compounds have been scarcely investigated, despite the huge knowledge that we have of the respective polycarboxylic acids and polycarboxylates. This is because of the limited availability of polysulfonic acids, for which reliable synthetic protocols are often lacking. Here, we present the first compound of the recently reported disulfonic acid 1,4-bis(4-sulfophenyl)butadiyne (H2DPBDS) prepared in our groups and a new compound of the commercially available 4,4′-biphenyldisulfonic acid (H2BPDS). The zinc sulfonates [Zn2(BPDS)2(NMP)6]·2NMP [I, NMP = N-methylpyrrolidone; triclinic, P, Z = 2, a = 972.8(2), b = 981.5(2), c = 1915.2(2) pm, α = 87.73(3)°, β = 77.68(3)°, γ = 89.36(3)°, V = 1785.0(6) A3] and [Zn2(DPBDS)2(DMA)6]·2DMA [II, DMA = dimethylacetamide; triclinic, P, Z = 2, a = 973.79(2), b = 1347.53(2), c = 1411.08(2) pm, α = 110.531(1)°, β = 92.445(1)°, γ = 101.931(1)° V = 1683.11(5) A3] display rigid molecular rectangles constructed from two zinc atoms and two sulfonate ligands. The rectangles are assembled through weak interactions to form soft host lattices that incorporate the solvent DMA or NMP molecules, partly through Zn2+ coordination. Thermal analysis shows that the solvent molecules can be completely removed without decomposition of the coordination polymers.

1,2,4,5-Benzenetetrasulfonic acid and 1,4-benzenedisulfonic acid as sulfo analogues of pyromellitic and terephthalic acids for building coordination polymers of manganese

New polysulfonic acids have been used for the preparation of manganese coordination polymers.

Rigid Rod Poly(Phenylene Sulfonic Acid) PEMs and MEAs with Grafted and Crosslinked Biphenyl Groups: Mechanical and Electrical Properties

Biphenyl was grafted on rigid-rod aromatic polysulfonic acids (IEC~8 mEq/gm.) to generate crosslinkable polyelectrolytes. Crosslinking conditions were studied and film properties before and after crosslinking were studied. All films broke at 6 to 9% elongation. The elastic moduli were between 0.8 and 2.2 GPa at relative humidities between 22 to 30%; it rises as RH drops and can drop drastically at high humidity if not crosslinked. As is usual for this class of materials, conductivity was high, even at low humidity and with the loss of 24% of starting sulfonic acids by grafting and crosslinking. The sample reported here had a conductivity of 100 mS/cm at 120oC and 30% RH. Fuel cell testing of an MEA by the FSEC showed properties that paralleled those of NRE211® films (power was ~95% that of the standard over the cell working range) in spite of high hydrogen permeation due to nano-tears in the MEA.

Membrane Preparation of Polysulfonic Acid Complexes by Layer‐by‐Layer Adsorption

AbstractSummary: The water‐insoluble, thermostable and homogeneous polymer complex membrane formation of polysulfonic acids was examined by modifying the preparation conditions of the layer‐by‐layer adsorption method of the acid and base polymers. The complexation of poly(4‐styrenesulfonic acid) in the 0.15 unit mM solution with poly(allylamine) gave a polymer complex membrane on a gold substrate in which one polymer layer was formed with a thickness of 1 nm. Properties including the proton conductivity of the membrane suggested possible applications of the polymer complex membrane.

A simple and effective way to enhanee fast‐atom bombardment mass spectra of sulfonic acids

AbstractA technique for the simplification of fast‐atom bombardment (FAB) spectra of polysulfonic acids, especially azo dyes complicated by sodium, is discussed. The sodium may be present as the sulfonate salt or the salt may be formed during FAB analysis from impurities present in the sample. The incorporated sodium as well as other impurities which may be present in commercial samples are removed by means of a simple cationic‐exchange‐resin procedure, yielding simplified and unambiguous FAB spectra of the sodium‐free material.

Alkylthioderivatives and sulfonic acids of fluoro naphthalines

Nucleophilic substitution of fluorine by thiolat anion in octafluoro naphthaline yielded the series of compounds C 10F 8−n(SR) n; (n = 1,2,4,5,6,8); (R = C 2H 5, i-C 3H 8; t-C 4H 9; C 6H 5CH 2). Reductive fragmentation by Na in HMPA converts Polyfluoropoly (alkylthio) naphthalenes into polymercapto naphthalenes, which on oxidation give a series of naphthalene polysulfonic acids C 10H 8−n(SO 3H) n; (n ≤ 6). ▪ Hydrogenation of C 10F 8−n(SR)n compounds on Raney nickel gives the corresponding C 10H nF 8−n compounds. These are new educts for the preporation of C 10H n(SR) 8−n; C 10H n(SH) 8−n and C 10H n(SO 3H) 8−n compounds.

Sulfonates from high molecular weight aromatic fractions from Romashkino petroleum

1. Mainly monosulfonic acids are obtained from the sulfonation of monocyclic aromatic hydrocarbons. Bi-cyclic aromatic hydrocarbons give a considerable amount of polysulfonated compounds on sulfonation with monohydrate (100% H2SO4). 2. On sulfonating fractions of bicyclic aromatic compounds with sulfur trioxide and monohydrate a certain amount of sulfones is formed, according to IR spectroscopy data. 3. Sulfonation of bicyclic hydrocarbons by sulfur trioxide in liquid sulfur dioxide enables the formation of the byproducts, polysulfonic acids and sulfones, to be avoided. 4. The sulfonates prepared from bicyclic hydrocarbons containing a considerable amount of sulfur derivatives, have an appreciably lower surface activity then the monocyclic sulfonates.

Sulfonation of 9-Aminophenanthrene

9-Aminophenanthrene (1) gave an aminophenanthrene sulfonic acid (3) almost free from the isomers upon baking its bisulfate under various conditions. An excellent yield (98%) was attained when the reaction was carried out at 220°C under 4 mmHg. The structure of (3) was determined to be 9-aminophenanthrene-3- sulfonic acid based on the facts that (3) was synthesized by ammonolysis of 9-bromophenanthrene -3-sulfonic acid (2) and that (2) was derived by the Sandmeyer reaction from (3). Direct sulfonation of (1) with concentrated sulfuric acid proceeded with great ease and gave a mixed product of monosulf onic acids and polysulf onic acids even when the reaction was conducted at a low temperature so as to retain the major portion of the (1) unreacted. Trials to separate the mixture into its components failed to succeed.