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Electrochemical titrations of thiosulfate, sulfite, dichromate and permanganate using dual microband electrodes.

Applications of titration using dual gold microband electrodes in generator-collector mode are presented. The main advantage is that the method dispenses with the need for accurate volume measurements and reagent preparation: rather than balancing of molar amounts, the fluxes of analyte and titrant are balanced instead. The titrant is generated electrochemically and the end-point is detected amperometrically by the appearance of a current due to the presence of the titrant at the other band. The aim is to show the versatility and capability of the method that employs disposable mass-produced electrodes and uses pulsed motion of the electrode before a measurement to renew the boundary conditions. The titration of ascorbic acid (vitamin C) with ferricyanide, which has been a model system, was extended to the determination of thiosulfate and sulfite with iodine and the determination of dichromate and permanganate with iron(II). The accuracy, limited by the present fabrication reproducibility of the disposable electrodes, is +/- 10%. The results demonstrate that the method is effective even with a very simple set-up, and the actual time needed for common titrations is significantly decreased. These examples demonstrate a comprehensive basis for further development and applications, including standard titrations in industry.

Calibration↗

Successful treatment of calciphylaxis with intravenous sodium thiosulfate.

Calciphylaxis is a dreaded complication of renal failure characterized by nodular subcutaneous calcification and painful tissue necrosis often leading to ulceration, secondary infection, and high mortality rates. The case of a woman receiving continuous ambulatory peritoneal dialysis who had a typical clinical presentation of calciphylaxis confirmed by x-ray and technetium scan findings is described. After nonresponse to conventional therapy, treatment with intravenous sodium thiosulfate 3 times weekly was begun, and she had rapid and dramatic relief of signs and symptoms and improvement of technetium scans. Prolonged treatment was well tolerated without serious side effects and accompanied by continued clinical improvement.

Aged↗

Circadian and ultradian (12 h) rhythms of hepatic thiosulfate sulfurtransferase (rhodanese) activity in mice during the first two months of life.

Thiosulfate sulfurtransferase (TST) is an important 'enzyme of protection,' that accelerates the detoxification of cyanide, converting it into thiocyanate. The TST physiological rhythm was investigated at wks 2, 4, and 8 of post-natal development (PND) in the mouse. The results revealed a statistically significant gender-related difference, with the highest activity in females, at all the documented PND stages. In the second week of PND (pre-weaning time), the circadian rhythm of the enzyme activity was associated with ultradian components. The prominent circadian rhythm (tau=24 h) peaked at the beginning of the light span, more precisely approximately 3 HALO (Hours After Light Onset). A week after weaning (wk 4 of PND), an impairment of the rhythm, with the peak shifted toward the second half of photophase, was recorded. Four to 6 wks later, about wk 8 of PND, the circadian rhythm pattern was stabilized, with its peak then located at the beginning of the dark span (13 HALO). The obtained results showed a 12 h phase-shift of the circadian TST peak time during PND, suggesting that the rhythm stabilization is age-dependent.

Activity Cycles↗

Acute cyanide intoxication treated with a combination of hydroxycobalamin, sodium nitrite, and sodium thiosulfate.

An 80-year-old diabetic patient was admitted to the hospital because of sudden unconsciousness and severe metabolic acidosis. His son reported the possibility of cyanide poisoning. Clinical data and the detection of cyanide in blood and gastric material confirmed this possibility. Supportive therapy and the following antidotes--sodium nitrite two doses 300 mg i.v., sodium thiosulfate 3 g i.v., and hydroxocobalamin 4 g in 24 hours--were administered immediately and the patient completely recovered in 48 hours. Our observations suggest that timely and appropriate use of antidotes for cyanide intoxication may prevent death, even in aged diabetic patients.

Acidosis↗

Effect of sodium thiosulfate on the pharmacokinetics and toxicity of cisplatin.

Concurrent administration of sodium thiosulfate (STS) can protect against the nephrotoxic effects of even very-high-dose cisplatin (CDDP) (i.e., 270 mg/m2 given intraperitoneally). The effect of STS on the pharmacology and toxicity of CDDP was investigated in patients receiving at each treatment 90 mg of CDDP/m2 intraperitoneally, with STS given concurrently on alternate cycles by the intravenous route. The patients received a total of 38 courses of therapy, 21 without STS and 17 with STS. STS reduced the total exposure to diethyldithiocarbamate-reactive CDDP for the peritoneal cavity and plasma by 36% and 25%, respectively. When given alone, CDDP caused a statistically significant acute reduction in creatinine clearance levels; this reduction was less evident when STS was given. We conclude that, whereas STS does reduce systemic exposure, the magnitude of this effect was not sufficient to account for the ability of STS to protect against high-dose CDDP.

Cisplatin↗

Rhodanese (thiosulfate: cyanide sulfurtransferase) in the digestive tract of chicken at different stages of development.

This study was undertaken to investigate the relationships between stage of embryonic development and early posthatch growth and the level of rhodanese (thiosulfate:cyanide sulfurtransferase) activity in different regions of the digestive tract and liver of chickens. The embryos were studied at 14, 17, and 20 d and chickens were 1, 2, and 3 wk old. All tissues studied contained rhodanese. The highest specific activity of rhodanese was present in the liver followed by the proventriculus (P < 0.05). The lowest level was in the esophagus. The level of rhodanese was found to increase with age in the proventriculus and duodenum. The highest rhodanese activity in 3-wk-old chickens was in the proventriculus followed by the liver. These results are discussed in terms of the role of different sections of the digestive tract of the chicken in cyanide metabolism.

Aging↗

Cisplatin combined with tiopronin or sodium thiosulfate: cytotoxicity in vitro and antitumor activity in vivo.

We have previously reported that the thiol compound tiopronin protects rat kidneys in vitro against the toxic activity of cisplatin. The influence of tiopronin and sodium thiosulfate (STS) on the cytotoxicity of cisplatin has been investigated on P388 leukemic cells in vitro after 3 days. The combination has also been investigated in vivo in BDF1 mice bearing a P388 s.c. tumor. In contrast to STS, tiopronin did not significantly reduce the cytotoxic activity of cisplatin in vitro and nor did it affect the uptake of platinum (cisplatin-derived), binding to DNA or the percentage of interstrand cross-links (%ISCL) formation. The co-administration of cisplatin (4 mg/kg) and tiopronin (150 and 300 mg/kg) to BDF1 female mice bearing a s.c. P388 tumor produced a significant reduction in tumor growth similar to that of a single 6 mg/kg dose of cisplatin. Interestingly, pre-incubation in vitro of either tiopronin or STS for 2 h with the species formed from cisplatin by hydrolysis demonstrated their ability in inhibiting the cytotoxicity of these reactive platinum products. These results indicate that tiopronin does not reduce the cytotoxicity of cisplatin in vitro, as STS does. This may be, at least partly, because of a different effect of the two thiol compounds on the cellular uptake and binding of platinum to DNA. Notably, tiopronin substantially reduced tumor growth in mice treated with a non-toxic dose of cisplatin (p < or = 0.0277), suggesting some positive influence of this thiol compound on the antitumor properties of cisplatin. The ability of tiopronin to protect in vitro against the cytotoxicity of the aquation products of cisplatin may be related to its nephroprotective effect.

Animals↗

Desulfonispora thiosulfatigenes gen. nov., sp. nov., a taurine-fermenting, thiosulfate-producing anaerobic bacterium.

Strain GKNTAUT has been described as a bacterium able to ferment the organosulfonate taurine (2-aminoethanesulfonate) quantitatively to acetate, ammonia and thiosulfate, an unusual metabolic product. This novel fermentation has now also been observed in four independent isolates from two continents. All five organisms were strictly anaerobic, Gram-positive, motile, spore-forming bacteria. Enrichments with isethionate (2-hydroxyethanesulfonate) and cysteate (2-amino-3-sulfopropionate), in contrast, yielded bacteria that disproportionated the sulfonate to sulfate and sulfide. The phylogenetic location of the taurine fermenters was analysed on the basis of 16S rDNA sequences. Strain GKNTAUT (= DSM 11270T = ATCC 700533T) is described as the type strain of a new genus and species, for which the name Desulfonispora thiosulfatigenes gen. nov., sp. nov. is proposed.

Anaerobiosis↗

Garciella nitratireducens gen. nov., sp. nov., an anaerobic, thermophilic, nitrate- and thiosulfate-reducing bacterium isolated from an oilfield separator in the Gulf of Mexico.

A novel Gram-positive, anaerobic and thermophilic bacterium, strain MET79(T), was isolated from an oil well located in the Gulf of Mexico. Cells were straight rods, motile by a subpolar flagellum. Spores were formed in old cultures. Inner gas vacuoles swelled the cells when exposed to air. The optimum growth conditions were 55 degrees C, pH 7.5 and 1 % NaCl. Yeast extract was required for growth. Strain MET79(T) fermented several sugars, some organic acids and Casamino acids. Glucose was fermented into lactate, acetate, butyrate, H(2) and CO(2). Strain MET79(T) reduced thiosulfate to hydrogen sulfide and nitrate to ammonium. The DNA G+C content was 30.9 mol%. The closest phylogenetic relative of strain MET79(T) was Caloranaerobacter azorensis (88.7 % 16S rDNA sequence similarity). As strain MET79(T) (=DSM 15102(T)=CIP 107615(T)) was physiologically and phylogenetically different from its closest relatives, it is assigned as the type strain of a novel species of a new genus, Garciella nitratireducens gen. nov., sp. nov.

Anaerobiosis↗

Sulfurivirga caldicuralii gen. nov., sp. nov., a novel microaerobic, thermophilic, thiosulfate-oxidizing chemolithoautotroph, isolated from a shallow marine hydrothermal system occurring in a coral reef, Japan.

Novel thermophilic bacteria, designated strains VW1 and MM1(T), were isolated from hydrothermal fluid and microbial mat samples, respectively, collected from a shallow marine hydrothermal system (water depth 22 m) occurring in coral reefs off Taketomi Island, Okinawa, Japan. Cells of the two novel strains were motile rods with a single polar flagellum in the exponential growth phase. In a medium that included elemental sulfur, cells of the two strains became non-motile with oval to spherical cell shapes. For both strains, growth occurred at between 30 and 60 degrees C (optimum temperature of 50-55 degrees C; 60-80 min doubling time) and between pH 5.5 and 7.1 (optimum pH 6.0). The isolates were microaerobic chemolithoautotrophs capable of using thiosulfate or tetrathionate as the sole energy source, O(2) as the sole electron acceptor and CO(2) as the sole carbon source. Organic substrates, such as yeast extract and tryptone, inhibited growth of both strains. The G+C contents of genomic DNA were 51.3 and 49.5 mol% for strains VW1 and MM1(T), respectively. Phylogenetic analysis based on 16S rRNA gene sequences indicated that the two strains were closely related to each other (99.9 % sequence similarity) and were distantly related to other previously described genera within the Gammaproteobacteria. The novel isolates could also be differentiated from other gammaproteobacterial genera on the basis of their physiological properties. It is suggested that the novel isolates represent the type species of a new genus, for which the name Sulfurivirga caldicuralii gen. nov., sp. nov. (type strain MM1(T)=JCM 13439(T)=DSM 17737(T)) is proposed.

Animals↗

Percutaneous absorption of gold sodium thiosulfate used for patch testing.

Contact allergy to gold has been shown to be correlated to wearing of golden jewellery as well as to the presence of dental gold. The prerequisite for sensitization and elicitation of an allergic contact dermatitis to gold is ionization and percutaneous absorption of the allergen. The present study was undertaken with the aim to demonstrate gold in blood after an occlusive patch testing with gold sodium thiosulfate (GSTS). Patients were patch tested with GSTS 0.5, 2.0 and 5.0% in petrolatum. Venous blood was sampled before testing as well as on day 3 (D3) or day 7 (D7). Blood gold levels were analysed by inductively coupled plasma mass spectrometry. In all 66 patients, the blood level of gold was significantly higher in the 2nd blood sample than in the 1st (median 0.34 versus 0.03 micro g/l). The increase was similar in patients allergic and not allergic to gold. There was no difference between gold levels on D3 and on D7 after epicutaneous application. Presumably, other allergens may also be taken up in blood during patch testing.

Adult↗

Gold trichloride and gold sodium thiosulfate as markers of contact allergy to gold.

The usefulness of a trivalent gold salt, gold trichloride (GTC), was evaluated as a marker of contact allergy to gold. Patients patch test-positive or patch test-negative to gold sodium thiosulfate (GSTS), 13 subjects of each, were patch tested with dilution series of GTC and equimolar concentrations of GSTS. In order to avoid false-positive and false-negative test reactions, the salts were buffered and placed on polypropene chambers. Allergic reactions were registered in 9/13 gold-allergic patients with GSTS and in 2/13 with GTC. The sum of positive reactions was 18 with GSTS and 5 with GTC. Irritant reactions were none with GSTS and 2 with GTC in the gold-allergic patients. It is concluded that GTC can elicit positive patch test reactions in patients with gold allergy but to a lesser degree when compared with GSTS. Thus, GTC cannot be recommended in patch testing, and GSTS is still the test agent of choice.

Aged↗

Contact allergies to nickel sulfate, gold sodium thiosulfate and palladium chloride in patients claiming side-effects from dental alloy components.

397 patients claiming various subjective symptoms related to dental restoration materials have been tested for the presence of metal allergy. The resultant data have been compared with the corresponding allergies of eczematous patients. The frequency difference of metal allergy in the dental group is statistically significant or close to significance for nickel sulfate, potassium dichromate, cobalt chloride, palladium chloride and gold sodium thiosulfate. The findings suggest that the dental patient group represents a subgroup with a high frequency of metal allergy.

Adolescent↗

Contact allergy to gold sodium thiosulfate.

100 consecutive patients routinely attending the contact dermatitis clinic were patched tested to gold sodium thiosulfate (GST). 13 patients had a positive patch test to GST, 11 of whom were female, and 12 had pierced ears. There was no correlation with any other substance in the European standard series, although there was a high incidence of nickel sensitivity in all patients (33%). Eczema on the ring fingers and neck was significantly more common in the group positive to GST. 1/2 of the patients with a positive response to GST had symptoms that they felt could be attributed to gold allergy.

Adult↗

Protection against cisplatin-induced toxicities by N-acetylcysteine and sodium thiosulfate as assessed at the molecular, cellular, and in vivo levels.

Cisplatin (CDDP) is a common, highly toxic chemotherapeutic agent. This study investigates chemoprotective effects of N-acetylcysteine (NAC) and sodium thiosulfate (STS) on in vitro and in vivo CDDP toxicities. For ototoxicity studies, CDDP (6 mg/kg) was administered to rats via a retrograde carotid artery infusion. Auditory brainstem response thresholds at 4 to 20 kHz were tested before and 7 days post-treatment. STS (8 g/m(2) i.v.) was administered at 4, 8, or 12 h after CDDP. For nephrotoxicity studies, rats were treated with CDDP intraperitoneally (10 mg/kg) before or after NAC (400 mg/kg) or STS (8 g/m(2)), and blood urea nitrogen (BUN) and creatinine concentrations were measured after 3 days. In vitro cytotoxicity and chemoprotection in human tumor cell lines were assessed by cell viability and immunoblotting assays. Rats treated with STS 4 h after CDDP exhibited no hearing change. The STS 8-h group had less otoprotection, whereas 12-h rats had ototoxicity. CDDP induced high BUN and creatinine, corresponding to renal tubule toxicities. All NAC-treated animals showed normal BUN and reduced creatinine levels compared with CDDP alone and no histopathological evidence of nephrotoxicity. Delayed STS treatment was not consistently protective against nephrotoxicity. STS administration fully protected against the in vitro cytotoxic and apoptotic effects of CDDP if added within 2 h of CDDP, but chemoprotection decreased if STS administration was 4 h, and was minimal by 6 h, after CDDP. Thus, the chemoprotection route and timing of administration can be manipulated to maintain CDDP antitumor efficacy while protecting against toxicities.

Acetylcysteine↗

Whole-genome transcriptional analysis of chemolithoautotrophic thiosulfate oxidation by Thiobacillus denitrificans under aerobic versus denitrifying conditions.

Thiobacillus denitrificans is one of the few known obligate chemolithoautotrophic bacteria capable of energetically coupling thiosulfate oxidation to denitrification as well as aerobic respiration. As very little is known about the differential expression of genes associated with key chemolithoautotrophic functions (such as sulfur compound oxidation and CO2 fixation) under aerobic versus denitrifying conditions, we conducted whole-genome, cDNA microarray studies to explore this topic systematically. The microarrays identified 277 genes (approximately 10% of the genome) as differentially expressed using RMA (robust multiarray average) statistical analysis and a twofold cutoff. Genes upregulated (ca. 6- to 150-fold) under aerobic conditions included a cluster of genes associated with iron acquisition (e.g., siderophore-related genes), a cluster of cytochrome cbb3 oxidase genes, cbbL and cbbS (encoding the large and small subunits of form I ribulose 1,5-bisphosphate carboxylase/oxygenase, or RubisCO), and multiple molecular chaperone genes. Genes upregulated (ca. 4- to 95-fold) under denitrifying conditions included nar, nir, and nor genes (associated, respectively, with nitrate reductase, nitrite reductase, and nitric oxide reductase, which catalyze successive steps of denitrification), cbbM (encoding form II RubisCO), and genes involved with sulfur compound oxidation (including two physically separated but highly similar copies of sulfide:quinone oxidoreductase and of dsrC, associated with dissimilatory sulfite reductase). Among genes associated with denitrification, relative expression levels (i.e., degree of upregulation with nitrate) tended to decrease in the order nar > nir > nor > nos. Reverse transcription-quantitative PCR analysis was used to validate these trends.

Adaptation, Physiological↗