Aromatic Sulfonates Research Articles

Polymer electrolyte membranes based on poly(arylene ether sulfone) with pendant perfluorosulfonic acid

Poly(arylene ether sulfone)-based ionomers with sulfonate groups of varying acidity (perfluoroalkyl sulfonate, aryl sulfonate and alkyl sulfonate) were synthesized via borylation of aromatic C–H bonds and Suzuki coupling with sulfonated phenyl bromides. Properties of the ionomers, such as thermal stability, water uptake, ion exchange capacity, morphology and proton conductivity, were analyzed with respect to the effect of the sulfonate group. Superacidic fluoroalkyl sulfonated ionomers displayed much higher conductivity at low relative humidity than less acidic aryl and alkyl sulfonated ionomers in spite of their lower ion exchange capacities. The water uptake of the membranes correlated with their IEC, regardless of the acid group identity. The membranes with fluoroalkyl and alkyl sulfonate groups had similar hydration numbers as a function of RH, but the hydration number of the aromatic sulfonate sample was greater than the other polymers. Ionic domain structure analysis by atomic force microscopy, transmission electron microscopy and small-angle X-ray scattering revealed that all of the aromatic ionomers in this study had a small, disorganized phase structure. These results demonstrate that the primary influence on the proton conductivity of these randomly sulfonated copolymers is the acid strength while the nanoscale domain structure plays a secondary role in the low RH proton transport.

Shifts in soil bacterial communities associated with the potato rhizosphere in response to aromatic sulfonate amendments

Desulfonation is an important process in the sulfur cycle, through which organic sulfur compounds are mineralized, releasing S. Desulfonating bacteria are known to respond to inorganic S soil amendments. However, the extent to which these communities shift as a response to the addition of organic sulfur in the soil remains elusive. Here, we investigated how amendments of soil with inorganic or organic sulfur compounds influence the bacterial communities associated with potato, in a microcosm experiment. The soil was amended with two doses of linear alkylbenzene sulfonate (LAS), here used as a model aromatic sulfonate compound, or with sulfate. Degradation of LAS was observed already at the young plant stage, as in all treatments 10- to 50-fold reductions of the initial (background) LAS concentrations were noted. Quantitative PCR analyses showed no significant effects of treatment on the bacterial abundances, which tended to increase from the young plant to the flowering stages of plant development. The bacterial community structures, determined via PCR-DGGE, were strongly affected by the presence of plants. This rhizosphere effect became more apparent at the flowering stages. Both the bacterial and β-proteobacterial community structures were affected by the presence of LAS, but dose-related effects were not observed. LAS also caused significant changes in the community structures, as compared to those in inorganic sulfate amended soil. Sulfate did not influence the bacterial community structures and only affected the β-proteobacterial ones at the flowering stage. Surprisingly, the presence of LAS did not exert any significant effect on the abundance of the Variovorax asfA gene, although clone libraries revealed a dominance of Variovorax types in the rhizosphere, especially in the high-level LAS treatment. Our results suggest that rhizosphere communities are key players in LAS degradation in soils, and that desulfonator Variovorax spp. plays a minor role in the mineralization of aromatic sulfonates in soil cropped with potato.

Metabolic characteristics of the species Variovorax paradoxus

This review outlines information about the Gram-negative, aerobic bacterium Variovorax paradoxus. The genomes of these species have G+C contents of 66.5-69.4 mol%, and the cells form yellow colonies. Some strains of V. paradoxus are facultative lithoautotrophic, others are chemoorganotrophic. Many of them are associated with important catabolic processes including the degradation of toxic and/or complex chemical compounds. The degradation pathways or other skills related to the following compounds, respectively, are described in this review: sulfolane, 3-sulfolene, 2-mercaptosuccinic acid, 3,3'-thiodipropionic acid, aromatic sulfonates, alkanesulfonates, amino acids and other sulfur sources, polychlorinated biphenyls, dimethyl terephthalate, linuron, 2,4-dinitrotoluene, homovanillate, veratraldehyde, 2,4-dichlorophenoxyacetic acid, anthracene, poly(3-hydroxybutyrate), chitin, cellulose, humic acids, metal-EDTA complexes, yttrium, rare earth elements, As(III), trichloroethylene, capsaicin, 3-nitrotyrosine, acyl-homoserine lactones, 1-aminocyclopropane-1-carboxylate, methyl tert-butyl ether, geosmin, and 2-methylisoborneol. Strains of V. paradoxus are also engaged in mutually beneficial interactions with other plant and bacterial species in various ecosystems. This species comprises probably promising strains for bioremediation and other biotechnical applications. Lately, the complete genomes of strains S110 and EPS have been sequenced for further investigations.

Characterization and multi-mode liquid chromatographic application of 4-propylaminomethyl benzoic acid bonded silica—A zwitterionic stationary phase

4-Propylaminomethyl benzoic acid bonded silica (4-PAMBA-silica) was synthesized by reacting aminopropyl modified silica with 4-carboxybenzaldehyde and reducing the resulting Schiff base with sodium cyanoborohydride in situ. The structure of this bonded phase was confirmed by 13C cross polarization magic angle spinning (13C CP MAS) NMR. Elemental analysis indicated a coupling efficiency of about 79%. Chromatographic characterization of a 4-PAMBA-silica stationary phase revealed that at a mobile phase pH of 3.0, basic compounds were unresolved and co-eluted near the void volume, while aromatic sulfonates were retained and were well-resolved. By contrast, at a mobile phase pH of 7.0, the aromatic sulfonates were unresolved and eluted at the void volume, while basic compounds were retained and were well-resolved. To further understand the chromatographic retention mechanism the retention factors for a series of cationic and anionic compounds were measured at pH 7.0 and 3.0 as a function of the charge and concentration of competing ions in the mobile phase. A plot of the logarithm of the retention factor versus the logarithm of the eluent ion concentration was linear with a negative slope that is equal to the ratio of effective charges of the solutes and the eluent ions. This indicates that an ion exchange mechanism contributes to the separation of both cations and anions at pH 7.0 and pH 3.0, respectively. The increase in retention of alkanoic acids with their number of carbons at a mobile phase pH of 7.0 and exclusion of alkanoic acids at a mobile phase pH of 3.0 suggests that an ion exclusion mode and hydrophobic interaction mode are also operational with 4-PAMBA-silica. The amino acids, l-arginine, l-phenylalanine, and l-tyrosine were retained and well-resolved with a mobile phase containing a high concentration of organic solvent. This behavior was further studied by measuring the retention factors of polar and charged compounds as a function of the organic solvent content in the aqueous mobile phase. An increase in retention with decreasing water content in the mobile phase was observed, consistent with a hydrophilic interaction liquid chromatographic (HILIC) mode of separation.

Evaluation of the thermal effect on separation selectivity in anion-exchange processes using superheated water ion-exchange chromatography

The thermal effect on retention and separation selectivity of inorganic anions and aromatic sulfonate ions in anion-exchange chromatography is studied on a quaternized styrene-divinylbenzene copolymer anion-exchange column in the temperature range of 40-120 °C using superheated water chromatography. The selectivity coefficient for a pair of identically charged anions approaches unity as temperature increases provided the ions have the same effective size, such that the retention of an analyte ion decreases with an increase in temperature when the analyte ion has stronger affinity for the ion-exchanger than that of the eluent counterion, whereas it increases when it has weaker affinity. The change in anion-exchange selectivity with temperature observed with superheated water chromatography has been discussed on the basis of the effect of temperature on hydration of the ions. At elevated temperatures, especially in superheated water, the electrostatic interaction or association of the ions with the fixed ion in the resin phase becomes a predominant factor resulting in a different separation selectivity from that obtained at ambient temperature.

Ultrasonically Assisted Synthesis of Aromatic Sulfonic Acids under Vilsmeier Haack Conditions in Acetonitrile Medium

Sulfonation of aromatic compounds (Phenols, Anilines) is triggered by Vilsmeier Haack (VH) reagent (DMF/POCl3) or (DMF/SOCl2) in the presence of NaHSO3 under Sonication and conventional stirred conditions at room temperature. The reactions afforded corresponding Sulfonic acid derivatives in very good yields. The results obtained under Sonication were enhanced when compared with the yields of the conventional method.

Electrophilic Aromatic Sulfonation with SO3: Concerted or Classic SEAr Mechanism?

The electrophilic sulfonation of several arenes with SO(3) was examined by electronic structure computations at the M06-2X/6-311+G(2d,2p) and SCS-MP2/6-311+G(2d,2p) levels of theory. In contrast to the usual interpretations, the results provide clear evidence that in nonpolar media and in the absence of catalysts the mechanism of aromatic sulfonation with a single SO(3) is concerted and does not involve the conventionally depicted 1:1 σ complex (Wheland) intermediate. Moreover, the computed activation energy for the 1:1 process is unrealistically high; barriers for alternative 2:1 mechanisms involving attack by two SO(3) molecules are 12-20 kcal/mol lower! A direct 2:1 sulfonation mechanism, involving a single essential transition state, but no Wheland type intermediate, is preferred generally at MP2 as well as at M06-2X in isolation (gas phase) or in noncomplexing solvents (such as CCl(4) or CFCl(3)). However, in polar, higher dielectric SO(3)-complexing media, M06-2X favors an S(E)Ar mechanism for the 2:1 reaction involving a Wheland-type arene-(SO(3))(2) dimer intermediate. The reaction is slower in complexing solvents, since the association energy, e.g., with nitromethane, must be overcome. But, in accord with the experimental kinetics (second-order in SO(3)), attack by two sulfur trioxide molecules is still favored energetically over reaction with a single SO(3) in CH(3)NO(2). The theoretical results also reproduce the experimental reactivity and regioselectivity trends for benzene, toluene, and naphthalene sulfonation accurately.

Sorption of Aromatic Ionizable Organic Compounds to Montmorillonites Modified by Hexadecyltrimethyl Ammonium and Polydiallyldimethyl Ammonium

Environmental residues of aromatic ionizable organic compounds (AIOCs) have received considerable attention due to their potential human health and ecological risks. The main objective of this study was to investigate the key factors and mechanisms controlling sorption of a series of anionic and zwitterionic AIOCs (two aromatic sulfonates, 4-methyl-2,6-dinitrophenol, tetracycline, sulfamethoxazole, and tannic acid) to montmorillonites modified with hexadecyltrimethyl ammonium (HDTMA) and polydiallyldimethyl ammonium (PDADMA). Compared with naphthalene (a nonpolar and nonionic solute), all AIOCs showed stronger sorption (the sorbent-to-solution distribution coefficient was in the order of 10-10 L kg) to the two organoclays in spite of the much lower hydrophobicity, indicating the predominance of electrostatic interaction in sorption. The proposed electrostatic mechanism of the tested AIOCs was supported by the pH dependency of sorption to the two organoclays. The two organoclays manifested weaker sorption affinity but faster sorption kinetics for bulky AIOCs than commercial activated carbon, resulting from the high accessibility of sorption sites in the open, ordered clay interlayer. The findings of this study highlight the potential of using HDTMA- and PDADMA-exchanged montmorillonites as effective sorbents for AIOCs in water and wastewater treatments.

Synthesis, spectral, and thermal characterization of photoreactive epoxy resin containing cycloalkanone moiety in the main chain

AbstractDual functional epoxy resins were synthesized by solution polycondensation of 2,6‐bis(4‐hydroxy‐3‐methoxy benzylidene)cyclohexanone and 2,5‐bis(4‐hydroxy‐3‐methoxy benzylidene)cyclopentanone with epichlorohydrin. The synthesized epoxy resins were characterized systematically for their structure by UV, Fourier transform infrared (FTIR), 1H NMR, and 13C NMR spectroscopic techniques. Thermal characterization of synthesized epoxy resins was carried out by thermogravimetric analysis, and differential scanning calorimetry (DSC) under nitrogen atmosphere. The self extinguishing property of synthesized oligomers was studied by determining limiting oxygen index (LOI) values using Van Krevelen's equation. X‐ray analysis showed that the epoxy resins containing cyclopentanone have higher degree of crystallinity. The photoreactive property of the synthesized epoxy resins in solution and film states was investigated by UV–Vis spectroscopy. The photocross‐linking proceeds through the dimerization of olefinic chromophore present in the main chain of the oligomer via 2π + 2π cycloaddition reaction. The influence of photoacid generator on the rate of photocross‐linking of epoxy resin was studied by FTIR. UV irradiation of the epoxy resin in presence of photoacid generator produces aromatic sulfonium cation radicals and aromatic radicals which initiate the cationic ring‐opening polymerization of oxirane ring. The photoreactivity studies of the oligomers by FTIR and DSC indicated the presence of dual functionality in the synthesized epoxy resins. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Synthesis of poly(vinylidene fluoride)‐b‐poly(styrene sulfonate) block copolymers by controlled radical polymerizations

AbstractBlock copolymers based on poly(vinylidene fluoride), PVDF, and a series of poly(aromatic sulfonate) sequences were synthesized from controlled radical polymerizations (CRPs). According to the aromatic monomers, appropriate techniques of CRP were chosen: either iodine transfer polymerization (ITP) or atom transfer radical polymerization (ATRP) from PVDF‐I macromolecular chain transfer agents (CTAs) or PVDF‐CCl3 macroinitiator, respectively. These precursors were produced either by ITP of VDF with C6F13I or by radical telomerization of VDF with chloroform, respectively. Poly(vinylidene fluoride)‐b‐poly(sodium styrene sulfonate), PVDF‐b‐PSSS, block copolymers were produced from both techniques via a direct polymerization of sodium styrene sulfonate (SSS) monomer or an indirect way with the use of styrene sulfonate ethyl ester (SSE) as a protected monomer. Although the reaction led to block copolymers, the kinetics of ITP of SSS showed that PVDF‐I macromolecular CTAs were not totally efficient because a limitation of the CTA consumption (56%) was observed. This was probably explained by both the low activity of the CTA (that contained inefficient PVDF‐CF2CH2I) and a fast propagation rate of the monomer. That behavior was also noted in the ITP of SSE. On the other hand, ATRP of SSS initiated by PVDF‐CCl3 was more controlled up to 50% of conversion leading to PVDF‐b‐PSSS block copolymer with an average number molar mass of 6000 g·mol−1. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

A new approach for generic screening and quantitation of potential genotoxic alkylation compounds by pre-column derivatization and LC-MS/MS analysis

A generic LC-MS/MS method was developed for the analysis of potentially genotoxic alkyl halides. A broad selection of alkyl halides were derivatized using 4-dimethylaminopyridine in acetonitrile. The reaction conditions for derivatization, i.e., solvent, reaction time, temperature and concentration of alkyl halide, active pharmaceutical ingredient (API), and reagent, were optimized for sensitivity and robustness. The interference of the matrix and the API and the presence of water on the derivatization reaction were investigated for a model drug product (paracetamol/caffeine tablets). Hydrophilic interaction liquid chromatography was used to allow a quantitative determination of the derivatives by tandem mass spectrometry. The derivatization reaction was shown to be selective for alkyl halides, although some reactivity was also observed for an aromatic sulfonate, which is also genotoxic. Even though differences in reaction efficiencies have been observed, the enhanced sensitivity obtained by the derivatization allows the majority of the alkyl halides to be detected by MS/MS at relevant levels for genotoxic impurity evaluation, i.e., 10 mg kg(-1). Another key advantage is that for the majority of derivatives, reagent-related fragments are produced, which allows low-level screening for alkyl halides. Highly specific MS detection can be performed using neutral loss and precursor ion scan experiments. The applicability of a generic screening method will make the genotox evaluation less dependent on the quality of assessments based on predictions only, and it will provide essential information during the development of new chemical entities. In addition to screening, target analysis in the low milligrams per kilogram range can be performed. A similar response of the derivatized compounds was obtained in the range of 1-100 mg kg(-1) with a reproducibility better than 10%, which is sufficient for the determination of alkyl halides in APIs and drug products.

ChemInform Abstract: Aromatic Sulfonation. Part 114. Sulfonation of Anisole, Phenol, Toluene and Related Alkyl and Alkoxy Derivatives with SO3. The Influence of the Solvent System on the Reactivity and the Sulfonic Acid Product Distribution.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Effect of intercalated aromatic sulfonates on uptake of aromatic compounds from aqueous solutions by modified Mg–Al layered double hydroxide

In this study, we utilized Mg–Al layered double hydroxide (Mg–Al LDH) modified by intercalation with three aromatic sulfonates—2,7-naphthalene disulfonate (2,7-NDS 2−), benzenesulfonate (BS −), and benzenedisulfonate (BDS 2−)—for the uptake of two aromatics—1,3-dinitrobenzene (DNB) and anisole (AS)—from aqueous solution and determined the effect of the aromatic sulfonates on the uptake of these aromatics. We found that the electron-rich aromatic ring of the intercalated aromatic sulfonates such as 2,7-NDS 2− undergoes strong π– π stacking interactions with the electron-poorer benzene ring of DNB in aqueous solution, and these interactions result in a higher uptake of DNB by the modified Mg–Al LDHs. In contrast, the electron-poor aromatic ring of the aromatic sulfonates such as BDS 2− undergoes weak π– π stacking interactions with the electron-poorer benzene ring of DNB, and these interactions result in a lower uptake of DNB by the modified Mg–Al LDHs.

Synthesis of tricyclic and tetracyclic sultones by Pd-catalyzed intramolecular cyclization

A new efficient synthesis of aromatic six-membered ring sultones by the implementation of ligand-free Pd-catalyzed intramolecular cyclization of aromatic sulfonates derived from various bromo phenols and naphthols is described.

Electrochemically modulated liquid chromatography using a boron-doped diamond particle stationary phase

This paper reports on preliminary tests of the performance of boron-doped diamond powder (BDDP) as a stationary phase in electrochemically modulated liquid chromatography (EMLC). EMLC manipulates retention through changes in the potential applied ( E appl) to a conductive packing. Porous graphitic carbon (PGC) has routinely been utilized as a material in EMLC separations. Herein the utility of BDDP as a stationary phase in EMLC was investigated and its stability, both compositionally and microstructurally, relative to PGC was compared. The results show that BDDP is stable over a wide range of E appl values (i.e., −1.2 to +1.2 V vs. Ag/AgCl, sat’d NaCl). The data also reveal that electrostatics play a key role in the adsorption of the aromatic sulfonates on the BDDP stationary phase, and that these analytes are more weakly retained in comparison to the PGC support. The potential for this methodology to provide a means to advance the understanding of molecular adsorption and retention mechanisms on carbonaceous materials is briefly discussed.

Efficient Removal of Aromatic Sulfonates from Wastewater by a Recyclable Polymer: 2-Naphthalene Sulfonate as a Representative Pollutant

As a family of hydrophobic ionizable organic compounds, aromatic sulfonates can be present at high levels in industrial wastewaters. They tend to exist as anions over a wide range of pH and cannot be effectively trapped by conventional adsorbents. In the current study, a recyclable acrylic ester polymer (NDA-801) was synthesized for effective removal of aromatic sulfonates from wastewater of high acidity (e.g., pH < 1) and inorganic salts (e.g., approximately 5-10% Na2SO4 in mass), for which sodium 2-naphthalene sulfonate (2-NS) was chosen as a representative target contaminant 2-NS uptake onto NDA-801 increased with the increasing acidity of the solution. The zeta potential of NDA-801 measured at different pH levels as well as batch 2-NS adsorption from methanol/water binary systems demonstrated the favorable roles of electrostatic and hydrophobic interaction in 2-NS adsorption. As compared to a granular activated carbon GAC-1, NDA-801 exhibited much higher removal efficiency and capacity of 2-NS in fixed-bed adsorption. Moreover, the exhausted NDA-801 beads by 2-NS can be completely regenerated by water wash for repeated use, which is more economically desirable than by other regenerants, such as NaOH solution. Continuous column adsorption-regeneration cycles indicated negligible capacity loss of NDA-801 during operation and further validated its feasibility for potential application in associated wastewater treatment.

Preparative purification of 4-hydroxy-1-naphthalenesulfonic acid sodium salt by high-speed counter-current chromatography

Among the many applications of 4-hydroxy-1-naphthalenesulfonic acid sodium salt (HNSA, CAS No. 6099-57-6) is its use as a common intermediate in the manufacture of dyes used as color additives. In order to develop an HPLC method to analyze HNSA in such additives, it was necessary to obtain pure HNSA as a reference material. This compound is only commercially available in “technical” or “practical” grade (∼70–85% purity). Unsatisfactory results were encountered during the attempts to eliminate impurities using published preparative purification methods. The current work demonstrates the successful application of high-speed counter-current chromatography (HSCCC) to the preparative purification of “practical” grade HNSA. The purifications of 0.55 g and 1.00 g portions were achieved by using a solvent system that consisted of n-butanol/water (1:1), acidified with 0.2% trifluoroacetic acid. In contrast to the procedure involved in previous HSCCC separations of aromatic sulfonates, it was not necessary to add a ligand and a retainer to the solvent system for these separations. The resulting yields were 320 mg and 485 mg of HNSA, respectively, of over 99% purity. Elemental analysis, HPLC (at 240 nm), UV and high-resolution MS analyses confirmed the identity and purity of the HNSA obtained.

Removal of aromatic sulfonates from aqueous media by aminated polymeric sorbents: Concentration-dependent selectivity and the application

Sorption of aromatic sulfonates onto two aminated polystyrene sorbents with different pore structures (M-101 and D-301) was investigated for optimization of their potential application in chemical wastewater treatment. Sodium benzenesulfonate (BS), sodium 2-naphthalene sulfonate (2-NS) and disodium 2,6-naphthalene disulfonate (2,6-NDS) were selected as reference solutes and sodium sulfate was as a competitive inorganic salt. Sorption selectivity of both sorbents is dependent upon the concentration levels of aromatic sulfonates in solution coexisting with sodium sulfate at a high level. However, both sorbents exhibit different characters. D-301 presents more favorable sorption for the solutes at relatively high levels (e.g., higher than 5 mM for BS, 0.7 mM for 2-NS and 0.05 mM for 2,6-NS), while M-101 removes aromatic sulfonates more completely when the solute concentration kept at relatively low levels. Based on the experimental results, we proposed an integral process of sorption onto D-301 followed by secondary-sorption onto M-101 to remove aromatic sulfonates from industrial wastewater completely and economically. Furthermore, the satisfactory performance revealed from large-scale application further demonstrated the feasibility of extending this process to dispose of other associated chemical wastewaters.

Study of the factors determining the mobility of ions in the polypyrrole films doped with aromatic sulfonate anions

The electrochemical redox behavior of the polypyrrole (PPy) films doped with benzenesulfonate (BS), p-toluenesulfonate ( pTS) and naphtalene-1,5-disulfonate (NDS) was investigated by cyclic voltammetry, the chemical composition of the films was determined by XDS, the surface morphology was characterized by AFM, and the interactions between pyrrole oligomers and the anions were modeled with quantum chemical methods. It is the first detailed comparative study of the properties of these interesting systems with two complementing interactions (electrostatic and aromatic stacking). It was shown than these relatively similar aromatic sulfonate anions have rather different behavior in PPy films. The results showed that the redoxactivity of polypyrrole films doped with sulfonate ions increases in the sequence pTS < BS < NDS. The comparison of voltammograms measured in the presence of different anions with PPy films synthesized in the same solution show that the PPy/ pTS films have the most densely packed and the PPy/NDS films the least densely packed structure of the three. The mobility of ions in these films is mainly determined by the packing of the films, which in turn partly depends on the interactions between the dopant-anion and polymer chains.

Electrooxidation of Catechols in the Presence of Sulfite: Presentation of a Facile and Green Method for Aromatic Sulfonation

Electrooxidation of Catechols in the Presence of Sulfite: Presentation of a Facile and Green Method for Aromatic Sulfonation