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Fate and biodegradability of sulfonated aromatic amines.

Ten sulfonated aromatic amines were tested for their aerobic and anaerobic biodegradability and toxicity potential in a variety of environmental inocula. Of all the compounds tested, only two aminobenzenesulfonic acid (ABS) isomers, 2- and 4-ABS, were degraded. The observed degradation occurred only under aerobic conditions with inocula sources that were historically polluted with sulfonated aromatic amines. Bioreactor experiments, with non-sterile synthetic wastewater, confirmed the results from the aerobic batch degradation experiments. Both ABS isomers were degraded in long-term continuous experiment by a bioaugmented enrichment culture. The maximum degradation rate in the aerobic bioreactor was 1.6-1.8 g 1(-1) d(-1) for 2-ABS and a somewhat lower value for 4-ABS at hydraulic retention times (HRT) of 2.8-3.3 h. Evidence for extensive mineralization of 2- and 4-ABS was based on oxygen uptake and carbon dioxide production during the batch experiments and the high levels of chemical oxygen demand (COD) removal in the bioreactor. Furthermore, mineralization of the sulfonate group was demonstrated by high recovery of sulfate. The sulfonated aromatic amines did not show any toxic effects on the aerobic and anaerobic bacterial populations tested. The poor biodegradability of sulfonated aromatic amines indicated under the laboratory conditions of this study suggests that these compounds may not be adequately removed during biological wastewater treatment.

Aerobiosis↗

Studies on the binding of 1-anilino-8-naphthalene sulfonate to very low density and high density himan serum lipoproteins.

Very low density and high density lipoproteins have been isolated from human plasma and their interaction with 1-anilin0-8-naphthalene sulfonate has been studied under different conditions of pH and added salt. Intrinsic fluorescence of bound 1-anilino-8-naphthalene sulfonate was higher for high density lipoproteins then for very low density lipoproteins, but was unaffected by salt in both systems. Binding of 1-anilino-8-naphthalene sulfonate by both these lipoproteins was saturable and was higher in the presence of added NaCl or CaCl2, Ca2+ having a greater effect than Na+ in enhancing fluorescence. The binding data were analyzed by Scatchard plots; the number of binding sites and the affinity of 1-anilino-8-naphthalene sulfonate for the site increased with increasing salt concentration. Fluorescence pH curves were similar to those published for phospholipids. From these and previous observations it is suggested that the phospholipids probably represent the major binding sites for 1-anilino-8-naphthalene sulfonate.

Anilino Naphthalenesulfonates↗

Biological activity of leukotriene sulfones on respiratory tissues.

The biological activity of synthetic leukotriene C4, D4 and E4 sulfone has been determined in respiratory smooth muscle in vitro and in vivo. The sulfones of LTC4, LTD4 and LTE4 were potent contractile agonists on indomethacin-treated guinea pig tracheal chains with respective pD2-values of 8.2, 8.0 and 7.9. Contractions were submaximal (75-85% of the cholinergic maximum), slow in onset, prolonged in duration, slowly reversed by washing (compared to acetylcholine or histamine) and were partially reversed by 2 muM FPL-55712. The sulfones of LTC4, LTD4 and LTE4 also contracted indomethacin-treated guinea pig parenchyma (respective pD2's of 7.9 8.2 and 7.8) and rat parenchyma (respective pD2's of 7.1, 7.2 and 7.2) but were inactive on rat trachea (0.01-2.0 muM). When administered intravenously to anaesthetized guinea pigs, the sulfones of LTD4, LTE4 and to a lesser degree LTC4 (respective ED50's - 0.5; 2.0 and 4.6 microgram/kg) elicited dose-dependent increases in inflation pressure which were antagonized by FPL-55712 and indomethacin. Leukotriene C4, D4 and E4 sulfones display a qualitatively similar profile of biological activity to that of their corresponding sulfides.

Animals↗

Sulfonate-sulfur assimilation by yeasts resembles that of bacteria.

Three sulfonates were tested for their ability to serve as nutrients for Hansenula wingei, Rhodotorula glutinis, Trigonopsis variabilis and Saccharomyces cerevisiae. Cysteate, taurine and isethionate, under aerobic conditions, could be utilized as sources of sulfur, although in some instances final cell yields were less than those obtained with an equimolar amount of sulfate-sulfur. Sulfonate assimilation by S. cerevisiae resembled that of bacteria (reported earlier by us) in several aspects: first, sulfate-S was used in preference to that of sulfonate, when both were present; second, mutants unable to use sulfate as a source of sulfur because of deficiencies in ATP sulfurylase, adenylylsulfate kinase (APS kinase) or PAPS reductase were able to utilize sulfonates; and third, mutants deficient in sulfite reductase were unable to utilize sulfonates.

Aerobiosis↗

Biological activities of phthalocyanines--XV. Radiolabeling of the differently sulfonated 67Ga-phthalocyanines for photodynamic therapy and tumor imaging.

Phthalocyanines have been advanced as photosensitizers for the photodynamic therapy of cancer and selectively sulfonated derivatives have shown promise as tumor imaging agents. In order to study the effect of the degree of sulfonation on their biodistribution pattern, we prepared a series of sulfophthalocyanines (PcS) labeled with 67Ga. Direct chelation of metal free phthalocyanines with 67Ga gave chelates which demetallated on further purification whereas condensation of 67Ga with phthalic acid precursors, following purification and fractionation on Sep-Pak C18 cartridges, gave stable products. The distribution pattern of the [67Ga]GaPcS among human plasma proteins was strongly affected by the degree of sulfonation of the PcS. The lower sulfonated GaPcS showed significant binding to the various lipoprotein fractions whereas increased sulfonation favored association to albumin. The use of the 67Ga allowed for the validation of spectrophotometric quantification of GaPcS in biological samples and confirmed the in vivo stability of the radiolabeled complex.

Blood Proteins↗

Separation of rutin nona(H-) and deca(H-) sulfonate sodium by ion-pairing reversed-phase liquid chromatography.

Ion-pairing reversed-phase liquid chromatography (RPLC) was used to separate two polysulfonates, rutin nona(H-) sulfonate sodium and rutin deca(H-) sulfonate sodium, which have very similar chemical structures. The final product always contained both of them when one of the compounds was synthesized. Baseline separation was achieved on a C8-bonded silica column at ambient temperature. The eluent was acetonitrile-15 mM phosphate buffer solution containing 20 mM TBA (pH 6.0) (46:54, v/v). The calibration plot was linear in the concentration range 0.5-200 microg ml(-1) for both analytes. The limits of detection (LODs; 254 nm) were 0.03 microg ml(1-) for rutin nona(H-) sulfonate sodium and 0.04 microg ml(-1) for rutin deca(H-) sulfonate sodium. Three batches of rutin deca(H-) sulfonate sodium were analyzed using the assay; the results showed that the analytical performance is really satisfactory.

Chromatography, Liquid↗

Sulfonation of environmental estrogens by zebrafish cytosolic sulfotransferases.

Environmental estrogen-like chemicals are increasingly recognized as a potential hazardous factor for wildlife as well as humans. We have recently embarked on developing a zebrafish model for investigating the role of sulfonation in the metabolism and adverse functioning of environmental estrogens. Here, we report on a systematic investigation of the sulfonation of representative environmental estrogens (bisphenol A, 4-n-octylphenol, 4-n-nolylphenol, diethylstilbestrol, and 17 alpha-ethynylestradiol) by zebrafish cytosolic sulfotransferases (STs). Of the seven enzymes tested, four zebrafish STs (designated ZF ST #2, ZF ST #3, ZF ST #4, and ZF DHEA ST) exhibited differential sulfonating activities toward the five environmental estrogens tested, with ZF ST #3 being more highly active than the other three. It was further demonstrated that bisphenol A, 4-n-octylphenol, and 4-n-nonylphenol exerted concentration-dependent inhibition of the sulfonation of 17 beta-estradiol, implying a potential role of these environmental estrogens in interfering with the sulfonation, and possibly homeostasis, of endogenous estrogens. Kinetic studies revealed that the mechanism underlying the inhibition by bisphenol A or 4-n-nonylphenol to be of the competitive type.

Animals↗

Synthesis of sulfonated amino-polysaccharides having anti-HIV and blood anticoagulant activities.

Sulfonated 3-amino-3-deoxy-(1-->6)-alpha-D-allopyranans were synthesized to elucidate the relationship between structure and such specific biological activities as anti-HIV and blood anticoagulant activities. Ring-opening copolymerization of 1,6-anhydro-3-azido-2,4-di-O-benzyl-3-deoxy-beta-D-allopyranose 1 with 1,6-anhydro- 2,3,4-tri-O-benzyl-beta-D-allopyranose 2 with PF5 catalyst gave copolymers having various proportions of the 1 unit. 13C NMR spectroscopy showed the resulting copolymers to have alpha-(1-->6)-stereoregularity, and the monomer reactivity ratios were calculated to be r1 = 0.92 and r2 = 1.11 by the Kelen-Tüdös method. Reduction of the azido groups and subsequent debenzylation of the copolymers afforded new amino-polysaccharides consisting of 3-amino-3-deoxy-allose and allose units. Sulfonation of 3-amino-3-deoxy-(1-->6)-alpha-D-allopyranan and copolysaccharides consisting of 3-amino-allose and allose or glucose units was performed with piperidine-N-sulfonic acid to give polysaccharides containing sulfoamido and sulfonate groups in good yields. The sulfoamido-copolysaccharides containing of 3-amino-3-deoxy-allose and glucose units exhibited high anti-HIV activities manifested by the 50% protecting concentration (EC50) of 0.2-0.5 mg/mL and low cytotoxicity shown by a 50% cytotoxic concentration (CC50) of > 1000 micrograms/mL. The sulfoamido-copolysaccharides containing 3-amino-allose and allose units had somewhat lower anti-HIV activities (EC50 = 0.8-0.9 microgram/mL) and slightly higher cytotoxicities (CC50 = 740-797 micrograms/mL). In addition, it was found that the blood anti-coagulant activity increased, with increasing proportion of the amino-allose unit, from 30 to 58 unit/mg (standard dextran sulfate, 22.7 unit/mg). These results suggest that the sulfonated 3-amino-3-deoxyallose unit plays important roles on both anti-HIV and blood anticoagulant activities.

Animals↗

Variation in the Mode of Coordination of Aryl Sulfonates to Zirconocene in the Solid State.

The solid-state structures of three zirconocene aryl sulfonates were determined. In Cp(2)Zr(OSO(2)C(6)H(5))(2) (1), one of the sulfonate ligands is monodentate, the other bidentate coordinated. Cp(2)Zr(OSO(2)-4-C(6)H(4)Cl)(2) (2) and Cp(2)Zr(OSO(2)-3,4-C(6)H(3)Cl(2))(2) (3) are dimers of pentacoordinated zirconocenes with two monodentate sulfonates and a double bridge of &mgr;-O,&mgr;-O'-sulfonates. A possible explanation for the formation of the solid-state structures is offered in terms of differences in electron density of the sulfonate oxygen atoms. 1: C(22)H(20)O(6)S(2)Zr, a = 8.062(2) Å, b = 14.502(3) Å, c = 19.623(4) Å, alpha = 90.91(1) degrees, beta = 101.78(1) degrees, gamma = 106.00(2) degrees, triclinic, P&onemacr;, Z = 4. 2: C(22)H(18)Cl(2)O(6)S(2)Zr, a = 7.9669(8) Å, b = 11.0816(12) Å, c = 13.4056(10) Å, alpha = 79.944(7) degrees, beta = 75.009(7) degrees, gamma = 84.647(9) degrees, triclinic, P&onemacr;, Z = 2. 3: C(22)H(16)Cl(4)O(6)S(2)Zr, a = 7.7574(7) Å, b = 12.1124(12) Å, c = 13.4613(11) Å, alpha = 85.343(7) degrees, beta = 76.653(6) degrees, gamma = 79.880(8) degrees, triclinic, P&onemacr;, Z = 2.

Journal Article↗

Studies of the condensation of sulfones with ketones and aldehydes.

[reaction: see text] The condensation of ketones or aldehydes with sulfones was shown to give a variety of products. Condensation of 2-methylcyclohexanone with dimethyl sulfone using potassium t-butoxide as base gave useful yields of 1,2-dimethylenecyclohexane. Under the same conditions, cycloheptanone, 3-methyl-2-butanone, and 2-butanone were converted to dienes. Remarkably, these reaction conditions converted acetophenone into p-terphenyl (10%) and (E)-1,4-diphenyl-3-penten-1-one (44%). Propiophenone was converted to 2'-methyl-p-terphenyl (61%). Using alpha-tetralone produced 1-methynaphthalene and naphthalene. No reaction took place with beta-tetralone. Using diethyl sulfone with alpha-tetralone lead to pure naphthalene. Condensation of isobutyraldehyde and dimethyl sulfone using potassium t-butoxide gave isoprene in low yield. Using benzaldehyde and benzyl phenyl sulfone in N,N-dimethylacetamide gave 1,2-diphenyl-1-phenylsulfonylethylene, N,N-dimethylcinnamide, and a complex condensation product. Only 1,2-diphenyl-1-phenylsulfonylethylene was obtained when the solvent was THF.

Journal Article↗

Calorimetric and computational study of 1,4-dithiacyclohexane 1,1-dioxide (1,4-dithiane sulfone).

This work reports the enthalpies of formation in the condensed and gas state of 1,4-dithiacyclohexane 1,1-dioxide (1,4-dithiane sulfone, 5), derived from the enthalpy of combustion in oxygen, measured by a rotating bomb calorimeter and the variation of vapor pressures with temperatures determined by the Knudsen effusion technique. The theoretically estimated enthalpy of formation was calculated from high-level ab initio molecular orbital calculations at the G2(MP2) level. The theoretical calculations appear to be in very good agreement with experiment. A comparison of the conversion of thiane sulfone 3 to 1,3-dithiane sulfone 4 and 1,4-dithiane sulfone 5 clearly shows the 1,3 isomer to be 6.7 kJ mol(-1) less stable, probably owing to diminished electrostatic repulsion between the sulfur heteroatoms in 1,4-sulfone 5.

Calorimetry↗

Hydration of sulfonated polyimide membranes. II. Water uptake and hydration mechanisms of protonated homopolymer and block copolymers.

The hydration of sulfonated polyimide membranes in their protonated form is probed by infrared spectrometry using a recently described method. The membranes considered are the homopolymer, made of identical sulfonated repeat units, and two block copolymers composed of these units plus similar ones with no sulfonic groups in two different proportions. The experiments consist of registering series of spectra of these membranes at various hygrometries of the surrounding atmosphere. The quantitative analysis of the evolution of these spectra allows one to measure precisely the water uptake and to define in terms of chemical reactions the various hydration mechanisms that are active at a definite value of the hygrometry. It shows how the dried homopolymer significantly differs from the two dried block copolymers: in the homopolymer, a good proportion of SO(3)H groups that represent 83% of sulfonate groups, cannot establish H-bonds on C=O groups that are in a relatively small number. As a consequence, all coexisting SO(3)(-) groups are H-bonded to single H(3)O(+) cations with no extra H(2)O molecules. In both dried block copolymers, each SO(3)H group (60% of the sulfonate groups) establishes H-bonds on C=O groups that are in a sufficiently great number. These H-bonds stabilize these SO(3)H groups, and coexisting SO(3)(-) groups are H-bonded to cations that are found in the form of H(5)O(2)(+) or H(7)O(3)(+) that contain several H(2)O molecules. When the hygrometry increases, these differences get less marked but can be precisely defined.

Journal Article↗

Oxidative addition of Pd0 to Ar-SO2R bonds: heck-type reactions of sulfones.

[reaction: see text] Phenyl vinyl sulfones and sulfoxides react with Pd(OAc)(2) to form styryl sulfoxides and sulfones according to the first Mizoroki-Heck reaction reported for these thio derivatives. Only sulfones are able to react by using catalytic amounts of Pd (up to 1 mol %) in the presence of Ag(2)CO(3). 1,2-Diphenylsulfonyl ethenes, alkynylphenyl sulfones, and other sulfones, less prone to act as acceptors in the Heck-type reactions, can transfer the aryl group to alkyl acrylates forming cinnamic esters.

Journal Article↗

Benzo[a]pyrene bay-region sulfonates, a novel class of reactive intermediates.

The mutagenicity of 7r,8t-dihydroxy-9t,10t-epoxy-7,8,9,10-tetrahydrobenzo[a]pyrene (anti-BPDE) toward Salmonella typhimurium strain TA98 is enhanced by over 1.5-fold by the addition of 1-10 mM sulfite to the incubations. Sulfite itself is neither mutagenic nor toxic to the bacteria under these conditions. Analysis of anti-BPDE-derived products from these bacterial incubations demonstrates that, in addition to the expected hydrolysis products of the epoxide, novel more polar metabolites are produced. These same more polar compounds are produced by the addition of anti-BPDE to buffered aqueous solutions of sulfite. The major product of this reaction has been characterized by UV/visible and fluorescence spectroscopy, NI-FAB mass spectrometry, and proton NMR spectroscopy and is identified as 7,8,9-trihydroxy-7,8,9,10-tetrahydrobenzo[a]pyrene-10-sulfonate (BPT-10-sulfonate). This derivative is formed by the nucleophilic addition of sulfite to the 9,10-oxirane ring of anti-BPDE. This product is easily differentiated both spectrally and chromatographically from the isomeric 7,8,10-trihydroxy-7,8,9,10-tetrahydrobenzo[a]pyrene-9-sulfonate reported from the attack of the sulfite anion radical on the activated aliphatic double bond of 7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene (BP-7,8-diol) [Curtis et al. (1988) Carcinogenesis 9, 2015]. The nucleophilic trapping of diol epoxides by water or thiols is assumed to represent a detoxication of this class of mutagen. In contrast, the extensive conversion of anti-BPDE to BPT-10-sulfonate in the bacterial incubations correlates with a marked enhancement of resultant mutagenicity. Further support for a key role of BPT-10 sulfonate in the enhancement of anti-BPDE mutagenicity is provided by our findings on the reactivity of this compounds.(ABSTRACT TRUNCATED AT 250 WORDS)

7,8-Dihydro-7,8-dihydroxybenzo(a)pyrene 9,10-oxide↗

Superoxide converts indigo carmine to isatin sulfonic acid: implications for the hypothesis that neutrophils produce ozone.

Recently, it was proposed that neutrophils generate ozone (Wentworth, P. J., McDunn, J. E., Wentworth, A. D., Takeuchi, C., Nieva, J., Jones, T., Bautista, C., Ruedi, J. M., Gutierrez, A., Janda, K. D., Babior, B. M., Eschenmoser, A., and Lerner, R. A. (2002) Science 298, 2195-2199; Babior, B. M., Takeuchi, C., Ruedi, J., Gutierrez, A., and Wentworth, P. J. (2003) Proc. Natl. Acad. Sci. U. S. A. 100, 3031-3034). Evidence for the proposal was based largely on the chemistry of ozone reacting with indigo carmine to produce isatin sulfonic acid. In this investigation, we have examined the specificity of this reaction and whether it can be used as unequivocal evidence of ozone production by neutrophils. Stimulated neutrophils promoted the loss of indigo carmine and formation of isatin sulfonic acid in a reaction that was completely inhibited by superoxide dismutase. Methionine, which scavenges ozone, singlet oxygen, and hypochlorous acid, had no effect on the reaction. Neither did catalase or azide, which scavenge hydrogen peroxide and inhibit myeloperoxidase, respectively. From these results, it is apparent that superoxide was responsible for bleaching indigo carmine. Superoxide generated using xanthine oxidase and acetaldehyde also converted indigo carmine to isatin sulfonic acid in a reaction that was completely inhibited by superoxide dismutase and unaffected by catalase. When the xanthine oxidase reaction was carried out in H(2)(18)O, the proportion of (18)O incorporated into the isatin sulfonic acid was the same as that found for ozone. Thus, reactions of ozone and superoxide with indigo carmine are indistinguishable with respect to isatin sulfonic acid formation. We conclude that bleaching of indigo carmine cannot be used to invoke ozone production by neutrophils. Studies using indigo carmine to implicate ozone in other biological processes should also be interpreted with caution.

Chromatography, High Pressure Liquid↗

Efficacy of the cation exchange resin, sodium polystyrene sulfonate, to decrease iron absorption.

BACKGROUND: Iron is not bound by charcoal; therefore, a method of binding iron in the gastrointestinal tract to prevent absorption in iron overdose is needed. This study investigated the efficacy and safety of sodium polystyrene sulfonate to prevent absorption of iron in human volunteers. METHODS: Six adult volunteers completed this prospective crossover trial. Following an oral dose of elemental iron 10 mg/kg, each subject received sodium polystyrene sulfonate 30 g or water as control. Baseline and serial serum iron samples were drawn to determine pharmacokinetic parameters. RESULTS: A trend toward increased time to peak following sodium polystyrene sulfonate compared to the control arm (5.7 vs 3.6 hours) was observed but was not statistically significant (p = 0.517). A trend toward smaller area-under-the-curve for the sodium polystyrene sulfonate was evident but was not statistically significant (p = 0.77). Iron concentration increased on average 298 mcg/dL and 370 mcg/dL above baseline in the treatment and control arms (p = 0.44). Sodium polystyrene sulfonate is not an effective method of decontamination for iron overdose.

Administration, Oral↗

Metabolism of sodium 3 alpha,7 alpha-dihydroxy-5 beta-cholane-24-sulfonate in hamsters.

Metabolism of sodium 3 alpha,7 alpha-dihydroxy-5 beta-cholane-24-sulfonate, the sulfonate derivative of chenodeoxycholic acid, was studied in hamsters. In bile fistula hamsters, the sulfonate analogue was efficiently absorbed from the ileum and secreted rapidly into the bile without any modification such as conjugation. However, absorption from the jejunum was smaller than that observed for the ileum. After oral administration, the sulfonate analogue of chenodeoxycholic acid was recovered quantitatively in the feces as the unchanged form in contrast to simultaneously administered chenodeoxycholic acid, which was entirely converted to lithocholic acid during its passage through the intestinal tract. These results demonstrate that the sulfonate analogue is absorbed mainly from the ileum by active transport, enters the enterohepatic circulation like the endogenous conjugated bile acids, and completely resists bacterial degradation.

Animals↗

In vivo photodynamic effects of phthalocyanines in a skin-fold observation chamber model: role of central metal ion and degree of sulfonation.

Six sulfonated metallophthalocyanines, chelated with either aluminum or zinc and sulfonated to different degrees, were studied in vivo for their photodynamic activity in a rat skin-fold chamber model. The chamber, located on the back of female WAG/Rij rats, contained a syngeneic mammary carcinoma implanted into a layer of subcutaneous tissue. Twenty-four hours after intravenous administration of 2.5 mumol/kg of one of the dyes, the chambers received a treatment light dose of 600 J/cm2 with monochromatic light of 675 nm at a power density of 100 mW/cm2. During light delivery and up to a period of 7 days after treatment, vascular effects of tumor and normal tissue were scored. Tumor cell viability was determined by histology and by reimplantation of the chamber contents into the skin of the same animal, either 2 h after treatment or after the 7 day observation period. Vascular effects of both tumor and subcutaneous tissue were strongest with dyes with the lowest degree of sulfonation and decreased with increasing degree of sulfonation. Tumor regrowth did not occur with aluminum phthalocyanine mono- and disulfonate and with zinc phthalocyanine monosulfonate. With the protocol that was used, complete necrosis without recovery was only observed when reimplantation took place at the end of the 7 day follow-up period. Reimplantation 2 h after treatment always resulted in tumor regrowth. At this interval, the presence of viable tumor cells was confirmed histologically. In general tumor tissue vasculature was more susceptible to photodynamic damage than vasculature of the normal tissue. The effect on the circulation of both tumor and normal tissue increased with decreasing degree of sulfonation.(ABSTRACT TRUNCATED AT 250 WORDS)

Animals↗