Molecular dynamics simulation of the PEO sulfonic acid anion in water

Atomistic molecular modeling has been used to study the sulfonic acid anion of poly(ethylene oxide) (PEO sulfonic acid anion) in vacuum and a polymer electrolyte system consisting of the PEO sulfonic acid anion in water. The vibrational spectra of the molecules were simulated by the local mode method and found to be in good agreement with the experimental IR and Raman spectra. The structure of PEO sulfonic acid anion was studied in vacuum and water and compared to the structure of an isolated PEO sulfonic acid in vacuum. The simulated value for the root mean square end-to-end distance for the PEO sulfonic acid anion was 22 Å in vacuum and 12 Å in water. The root mean square radius of gyration of the PEO sulfonic acid anion was 8.4 Å in vacuum and 5.6 Å in water. The PEO sulfonic acid anion was randomly coiled in water and in an extended shape in vacuum.     

Effect of the sulfonic acid group on copolymers of aniline and toluidine with m‐aminobenzene sulfonic acid

This article describes the results of the preparation and characterization of self‐doped conducting copolymers of aniline and toluidine with m‐aminobenzene sulfonic acid. The copolymers have an intrinsic acid group that is capable of doping polyaniline. Spectroscopic, morphological, and electrical conductivity studies have provided insight into the structural and electronic properties of the copolymers. The differences in the properties of polyaniline and polytoluidine due to the sulfonic acid ring substituent on the phenyl ring are discussed. The scanning electron micrographs of the copolymers reveal regions of sharp‐edged, needle‐shaped structures, whereas the X‐ray diffraction patterns show that the copolymers are relatively more crystalline in nature. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4065–4076, 2002     

双活性磺酸基蔗渣木聚糖对羟基苯甲酸酯的合成及活性模拟

以蔗渣木聚糖(BX)为主要原料、氨基三磺酸钠为酯化剂,在一步酯化合成磺酸基蔗渣木聚糖酯的基础上,利用磺酸基蔗渣木聚糖酯和对羟基苯甲酸进行二步酯化反应,合成了磺酸基蔗渣木聚糖对羟基苯甲酸酯,并考察了反应条件对酯化反应的影响,通过单因素实验确定了第二步酯化反应较佳的合成工艺条件.蔗渣木聚糖酯化改性前后的样品分别用FT-IR,DG-DTG和XRD进行了表征,并对该双酯化衍生物的分子进行了优化与活性模拟.结果表明:FT-IR证明双酯化产物含有磺酸基团和对羟基苯甲酸酯基团,TG-DTG分析表明该双酯化衍生物的热稳定性提高,XRD说明发生双酯化改性后分子排列的规整性提高,结晶度增加;活性模拟实现了磺酸基蔗渣木聚糖对羟基苯甲酸酯与艾滋病毒的对接.     

An evaluation of some simple sulfonic acids as nonaqueous titrants

The simple aliphatic and aromatic sulfonic acids show evidence of possibilities as new titrants in a glacial acetic acid medium. Excellent precision is obtained in potentiometric titrations with both ethane- and methane sulfonic acids with a standard deviation of 0.2%. Benzenemonosulfonic and naphthalenesulfonic acids both give an average precision of 0.4%. In visual titrations with with crystal violet indicator, the color changes at the end-point are very sharp. The chief advantage of these acids as titrants lies in the fact that they dissolve readily in glacial acetic acid and can be titrated to give reproducible results with the glass-calomel electrode system. None of the sulfonic acids tested was as strong a titrant as perchloric acid, but, unlike perchloric acid, they did not form precipitates or gels in the titration with potassium acid phthalate.     

Mechanochemical degradation of aromatic sulfonic acids

Sulfonic acids and sulfonates are widely used as surfactants in various industrial processes. Although partial biodegradation occurs, their release in the environment has determined a widespread pollution problem due to their remarkable tendency towards accumulation. For this reason, various methodologies to effectively degrade sulfonic acids and sulfonates in real matrices are currently under investigation. In this study, we focused our attention on the mechanochemical degradation of the 1,5-naphthalene disulfonic acid using strongly reducing agents such as pure Mg and Ca metals. The mechanochemical processing induced either a gradual degradation of the organic compound or a combustion-like reaction depending upon the experimental conditions. A partial degradation of the sulfonic acid was observed as a result of gradual reactions. An almost complete removal of the pollutant was instead observed after combustion-like reactions.     

Effect of sulfonic acid containing mesogens on liquid-crystalline behavior of polysiloxane-based polymers

A series of liquid-crystalline polysiloxanes synthesized by cholest-5-en-3-ol (3beta)-10-undecenoate and 4'-octanoyloxy-biphenyl-4-yl 4-allyloxy-3-sulfo-benzoate were prepared in a one-step reaction with sulfonic acid group contents ranging between 0 and 2.73 wt %. All the polymers displayed smectic mesophases with a large temperature range for the mesophases. With an increase of sulfonic acid containing mesogens in the polymers, the temperature of the glass transition did not change greatly, while the temperature of the clear point decreased. The hydrogen-bonding mesogen aggregates in the domains disturb the liquid-crystalline molecular mobility and orientation, leading to a decrease in temperature from the mesophase to the isotropic transition. Unlike the polymers containing lower sulfonic acid mesogens, some polymers showed a dendritic texture of the SmB* phase, indicating that the sulfonic mesogens enhanced the rigid moieties of the supermolecular structure of the liquid-crystalline phases. All the polymers displayed sharp and strong peaks at low angles around 2theta approximately 2.6 degrees and broad peaks at wide angles around 2theta approximately 17 degrees in X-ray measurements. The intensity of the strong peak at low angles in the X-ray profiles decreased with an increase of sulfonic acid mesogens in the polymer systems.     

Synthesis, characterization and evaluation of sulfonic resins as catalysts

Ion-exchange resins have been often used as catalysts especially those based on styrene-divinylbenzene copolymers with sulfonic acid groups in the aromatic rings of polymer chains. That is due to the advantages of heterogenous catalysis over the homogeneous acid catalysis. Moreover, resin catalysts can often lead to high selectivity in organic reactions due to the matrix effects. Therefore, the study of copolymers synthesis conditions to determine the type of polymer structure produced as well as the characterization of sulfonic resins obtained thereof are of great interest. The current paper describes the synthesis, characterization and evaluation as catalysts of sulfonic resins derived from polymer supports synthesized by aqueous suspension polymerization of styrene and divinylbenzene. The reaction conditions were varied and polymer supports with different physical properties and morphological characteristics were obtained. The polymer supports were chemically modified by sulfonation. The resultant sulfonic resins had their catalyst activity evaluated in the esterification of acetic acid with n-butanol.     

Synthesis of polybenzimidazoles with sulfonic acid groups

2-Sulfoterephthalic acid (STA) and disulfoisophthalic acid (DSIA) were synthesized through the sulfonation and the oxidation of m- and p-xylene. The polycondensation reactions of STA and DSIA with aromatic tetraamines gave polybenzimidazoles which contained one or two sulfonic acid groups for each repeating unit. The polymer obtained was soluble in sulfuric acid, some organic solvents, and aqueous strong alkaline solution. The polymers were stable up to 400°C, but they gave polybenzimidazoles above 400°C by eliminating sulfonic acid groups, instead of ring closure.     

Thermal degradation studies of polystyrene sulfonic and polyacrylic carboxylic cationites

The thermal degradation of polyacrylic carboxylic and polystyrene sulfonic cationites was investigated using thermal analysis (TG) combined with Scanning Electron Microscopy (SEM). Fourier Transform Infrared Spectroscopy (FTIR) was used to characterize the resins degradation steps. The carboxylic cationite undergoes degradation through dehydration forming polyanhydrides, decomposition of polyanhydrides through decarboxylation with elimination of CO₂ and CO. The sulfonic cationite undergoes degradation through dehydration, followed by decomposition of sulfonic acid functional groups liberating SO₂. It was observed that strong acid (−SO₃H⁺) cationite shows small mass loss of 55%, as against 88% mass loss shown by low-acidity carboxylic cationite. The possible reason for small mass loss of sulfonic cationite is discussed. The text was submitted by the authors in English.     

Chemical force titrations of amine- and sulfonic acid-modified poly(dimethylsiloxane)

Chemical force titrations-measurements of the adhesive interaction between a pair of suitably chemically modified atomic force microscopy (AFM) tip and sample surfaces as a function of pH-have been carried out for various combinations of silanol, amine, carboxylic acid, and sulfonic acid functional groups on both tip and sample. The primary surface material studied was poly(dimethylsiloxane) (PDMS). Surface modification was carried out using a plasma oxidation process to form silanol sites; further modification with amine or sulfonic acid sites was carried out by reaction of the silanol sites with the appropriate trialkoxysilane derivative. AFM tips were also modified using trialkoxysilane compounds. In the cases of tip/sample combinations with the same functional group on each, surface pK(1/2) values could be determined. In several "mixed" tip/sample combinations, a peak appeared in the titration curve midway between the surface pK(1/2) values of the tip and sample, consistent with an ionic H-bonding model for the interactions. The amine/sulfonic acid pair showed more complex behavior; the amine-terminated tip/sulfonic acid-terminated PDMS surface force titration curve consisted of two peaks centered at pH 4 and pH 8. Reversing the tip/sample pair resulted in the peak positions being shifted upward by 1.0 pH unit. The peak appearing at lower pH is assigned to electrostatic interactions between the two oppositely charged surfaces, whereas the higher pH peak is believed to arise due to ionic H-bonding interactions. AFM images show the effects on surface patterning of amine- and sulfonic acid-modified PDMS surfaces that have undergone two different oxidation methods (air plasma oxidation and Tesla coil oxidation). The surface morphologies of freshly prepared and 24 h aged air plasma oxidized PDMS are also discussed in this study.     

Synthesis of new sulfonic acid-containing oligosaccharide mimetics of sialyl Lewis A

Two trisaccharides as new sulfonic acid mimetics of the sialyl Lewis A tetrasaccharide were synthesized. The natural sialic acid residue is replaced by a C-sulfonic acid moiety attached to position C-3′ of the lactosamine unit of the mimetics. The l-fucose unit was also replaced by a d-arabinose ring in one of the analogues. Formation of the sulfonic acid moiety on the trisaccharide level could be successfully achieved by means of introduction of an acetylthio moiety into the galactose skeleton and subsequent oxidation. The equatorial arrangement of the acetylthio group linked to C-3 of the galactose ring could be achieved by double nucleophilic substitution; efficient formation of the gulo-triflate derivatives required low-power microwave activation. Oxidation of the acetylthio group was carried out using Oxone in acetic acid.     

磺酸官能化的磁性核壳结构的纳米材料用于果糖脱水制备5-羟甲基糠醛(英)

通过反相微乳液法制备了以Fe₃O₄为核,磺酸官能化的硅基材料为壳层的磁性酸性催化剂.首先制备纳米Fe₃O₄磁核,然后涂层包覆苯基修饰的纳米级硅层,最后进行苯基磺化修饰,制得固体酸催化剂Fe₃O₄@Si/Ph-SO₃H.在果糖脱水制备5-羟甲基糠醛反应中,该催化剂表现出较好的催化活性,优于传统催化剂A-15,且与均相无机酸催化活性相当.当采用二甲基亚砜作溶剂,在110℃下反应3 h,果糖转化率达到99%,5-羟甲基糠醛收率为82%.另外,该催化剂经磁法回收后可多次重复使用.     

Fragmentation of protonated ions of peptides containing cysteine,cysteine sulfinic acid,and cysteine sulfonic acid

The oxidation of the sulfhydryl group in cysteine to sulfenic acid, sulfinic acid, and sulfonic acid in proteins is important in a number of enzymatic processes. In this study we examined the fragmentation of four peptides containing cysteine, cysteine sulfinic acid (Cys-SO(2)H), and cysteine sulfonic acid (Cys-SO(3)H) in an ion-trap mass spectrometer. Our results show that the presence of a Cys-SO(2)H in a peptide leads to preferential cleavage of the amide bond at the C-terminal side of the oxidized cysteine residue. The results are important for the determination of the site of the cysteine oxidation and might be useful for the sequencing of cysteine-containing peptides.     

Contribution of sulfonyl-aromatic and sulfonic acid-aromatic interactions in novel sulfonyl/sulfonic acid-embedded reversed phase materials

Two novel sulfonyl-embedded reversed phase materials with sulfonic acid moieties (SO(X)-RP) were prepared by a simple oxidation of two silica-based sulfur-embedded RP-phases (S-RP). The chromatographic behavior of the resultant sulfonyl/sulfonic acid-embedded phase C3-SO(2)-C18/SO(3)H and the sulfonyl-embedded phase C3-SO(2)-C14 e.c. (silanol endcapped) was extensively elucidated with a number of well-established as well as self-assembled column tests. These SO(X)-RP phases were also compared with their corresponding S-RP phases as well as with two commercial carbonyl-containing RP phases (CO-RP) with amide- and urea-embedding. The SO(X)-RP phases were found to exhibit exceptionally high planar recognition ability for polyaromatic analytes at comparable retention times to the investigated CO-RP phases and highly reduced retention compared to the parent, non-oxidized S-RP-materials. The results of this study suggest that the selectivity enhancement observed with the S-oxidized phases is due to sulfonyl-pi and sulfonic acid-pi interactions. Furthermore these novel SO(X)-RP phases proved to be fully applicable under 100% aqueous mobile-phase conditions making them a useful alternative to conventional RP as well as polar-embedded CO-RP phases.     

Interaction of aluminum polyhydroxochloride sol and poly(4-vinylbenzene sulfonic acid) sodium salt

The interaction of aluminum polyhydroxochloride sol and poly(4-vinylbenzene sulfonic acid) sodium salt is studied. It is found that, in dilute aqueous solutions at pH 4.6, aluminum polyhydroxochloride sol and poly(4-vinylbenzene sulfonic acid) sodium salt form insoluble polymer-colloid complexes of steady compositions. Potentiometric titration data show that the interaction between particles of aluminum polyhy-droxochloride sol and linear macromolecules of the polyelectrolyte occurs via salt bonds formed between unlikely charged groups on the surface of particles and units of the linear polyelectrolyte. The composition of the polymer-colloid complex is determined, and the degree of conversion for the reaction of aluminum poly-hydroxochloride sol and poly(4-vinylbenzene sulfonic acid) sodium salt is estimated. The influence of various polyelectrolytes on the stability of the polymer-colloid complex is studied.     

Negative fast atom bombardment ionization of aromatic sulfonic acids: unusual sample-matrix interaction

The most intense ion(s) in negative ion fast atom bombardment (FAB) mass spectra of 2- and 4-benzaldehyde sulfonic acid (BSA) in glycerol or 3-nitrobenzyl alcohol matrix corresponds to a covalent association of the analyte with one or two matrix molecules accompanied by the elimination of a molecule of water. The molecular ion [M - H](-), however, is of low abundance. The identity of the resulting ions [M + nA - H(2)O - H](-) (where M is the analyte and A is the matrix) was confirmed by exact mass measurement using the peak matching technique. These covalent matrix-analyte complexes were not observed when the sulfonic acid functionality in BSA was substituted with COOH, NO(2), and OH or when the sulfonic acid was in salt form. These observations indicate that the free sulfonic acid group in BSA is responsible for the covalent adduct formation. To our knowledge, analyte-matrix covalent association in negative ion FAB spectra of BSA has not been reported previously.     

Polyaniline doped with different sulfonic acids by in situ doping polymerization

Doped polyaniline (PANI) was synthesized by an “in situ doping polymerization” method in the presence of different sulfonic acids, such as methanesulfonic acid (MSA), p‐methylbenzene sulfonic acid (MBSA), β‐naphthalenesulfonic acid (β‐NSA), α‐naphthalenesulfonic acid (α‐NSA), 1,5‐naphthalenedisulfonic acid (1,5‐NSA), and 2,4‐dinitronaphol‐7‐sulfonate acid (NONSA). Morphology, solubility in m‐cresol, and electrical properties of the doped PANI were measured with the variation of the molecular structure of the selected sulfonic acids. Granular morphology was obtained when the sulfonic acids without a naphthalene ring, such as MSA and MBSA, were used. Regular tubular morphology was obtained only when β‐NSA was used. The tubular morphology can be modified by changing the substitutes, the number, and location of sulfo‐group(SOH) on the naphthalene ring. These results indicated that naphthalene ring in the selected sulfonic acids plays an important role in forming the tubular morphology of the doped PANI by the “in situ doping polymerization” method. All resulting PANI salts were soluble in m‐cresol, with the solubility depending on the molecular structure of the selected dopants. Room‐temperature conductivity for the doped PANI ranges from 10⁻¹ to 10⁰S/cm. Temperature dependence of conductivity shows a semiconductor behavior, and it can be expressed by one dimenson Variable Range Hopping (VRH) model. 1 © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1277–1284, 1999     

Purity testing of sulfonic acids of different chain length by capillary electrophoresis

Summary A CZE method has been developed for the purity testing of sulfonic acids. By use of an optimized electrolyte system, short analysis times and high resolution (R _S=2–4) can be achieved for inorganic anions and for alkyl sulfonic acids from methane-1- to decane-1-sulfonic acid. By use of indirect UV detection by-products of different sulfonic acids can be determined at the 2 m level, equivalent to 0.02%,w/w. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996     

Bi-functionalization of silica spheres with sulfonic and carboxylic groups via a co-condensation route

Silica spheres with uniform size of 230–250 nm were functionalized with sulfonic groups and bi-functionalized with carboxylic and sulfonic groups via a co-condensation route, by adding the organosilanes (3-(triethoxysilyl)mercaptopropyl and 4-(triethoxysilyl)butyronitrile) to a pre-hydrolized TEOS solution. The conversion of mercapto and cyano groups to, respectively, sulfonic and carboxylic groups was carried out by treating both the samples with nitric acid solution. The presence of alkyl-SO₃H and alkyl-COOH species at the silica surface in an approximate molar ratio of 1:1 was assessed by TG and NMR. FT-IR spectroscopy showed that both Brønsted acidic groups are accessible and give proton-transfer reaction to ammonia with the formation of ammonium ion. Sulfonic groups react irreversibly with ammonia at room temperature at variance with carboxylic groups which give a reversible proton-transfer, in agreement with the stronger Brønsted acidity of the former.     

Open-air and solvent-free ester condensation catalyzed by sulfonic acids

Ester condensation is one among the most fundamental organic transformations, and more environmentally benign alternatives to current esterification processes are needed. Under solvent-free and drying agent-free conditions, catalytic amounts of sulfonic acids promote ester condensation between an equimolar mixture of carboxylic acids and alcohols. In particular, p-toluenesulfonic acid (TsOH) and 10-camphorsulfonic acid (CSA), which have appropriate acidities, efficiently catalyze the ester condensation of secondary alcohols without their decomposition. Since the present protocol does not require solvents under simple open-air conditions, a large amount of esters can be synthesized in a rather small apparatus.