Blue light promotes zero-valent sulfur production in a deep-sea bacterium.

Increasing evidence has shown that light exists in a diverse range of deep-sea environments. We unexpectedly found that blue light is necessary to produce excess zero-valent sulfur (ZVS) in Erythrobacter flavus 21-3, a bacterium that has been recently isolated from a deep-sea cold seep. E. flavus 21-3 is able to convert thiosulfate to ZVS using a novel thiosulfate oxidation pathway comprising a thiosulfate dehydrogenase (TsdA) and a thiosulfohydrolase (SoxB). Using proteomic, bacterial two-hybrid and heterologous expression assays, we found that the light-oxygen-voltage histidine kinase LOV-1477 responds to blue light and activates the diguanylate cyclase DGC-2902 to produce c-di-GMP. Subsequently, the PilZ domain-containing protein mPilZ-1753 binds to c-di-GMP and activates TsdA through direct interaction. Finally, Raman spectroscopy and gene knockout results verified that TsdA and two SoxB homologs cooperate to regulate ZVS production. As ZVS is an energy source for E. flavus 21-3, we propose that deep-sea blue light provides E. flavus 21-3 with a selective advantage in the cold seep, suggesting a previously unappreciated relationship between light-sensing pathways and sulfur metabolism in a deep-sea microorganism.

Acidity of persulfides and its modulation by the protein environments in sulfide quinone oxidoreductase and thiosulfate sulfurtransferase.

Persulfides (RSSH/RSS-) participate in sulfur metabolism and are proposed to transduce hydrogen sulfide (H2S) signaling. Their biochemical properties are poorly understood. Herein, we studied the acidity and nucleophilicity of several low molecular weight persulfides using the alkylating agent, monobromobimane. The different persulfides presented similar pKa values (4.6-6.3) and pH-independent rate constants (3.2-9.0 × 103 M-1 s-1), indicating that the substituents in persulfides affect properties to a lesser extent than in thiols because of the larger distance to the outer sulfur. The persulfides had higher reactivity with monobromobimane than analogous thiols and putative thiols with the same pKa, providing evidence for the alpha effect (enhanced nucleophilicity by the presence of a contiguous atom with high electron density). Additionally, we investigated two enzymes from the human mitochondrial H2S oxidation pathway that form catalytic persulfide intermediates, sulfide quinone oxidoreductase and thiosulfate sulfurtransferase (TST, rhodanese). The pH dependence of the activities of both enzymes was measured using sulfite and/or cyanide as sulfur acceptors. The TST half-reactions were also studied by stopped-flow fluorescence spectroscopy. Both persulfidated enzymes relied on protonated groups for reaction with the acceptors. Persulfidated sulfide quinone oxidoreductase appeared to have a pKa of 7.8 ± 0.2. Persulfidated TST presented a pKa of 9.38 ± 0.04, probably due to a critical active site residue rather than the persulfide itself. The TST thiol reacted in the anionic state with thiosulfate, with an apparent pKa of 6.5 ± 0.1. Overall, our study contributes to a fundamental understanding of persulfide properties and their modulation by protein environments.

Listeria monocytogenes utilizes glutathione and limited inorganic sulfur compounds as sources of essential cysteine.

Listeria monocytogenes (Lm) is a Gram-positive facultative intracellular pathogen that leads a biphasic lifecycle, transitioning its metabolism and selectively inducing virulence genes when it encounters mammalian hosts. Virulence gene expression is controlled by the master virulence regulator PrfA, which is allosterically activated by the host- and bacterially derived glutathione (GSH). The amino acid cysteine is the rate-limiting substrate for GSH synthesis in bacteria and is essential for bacterial growth. Unlike many bacteria, Lm is auxotrophic for cysteine and must import exogenous cysteine for growth and virulence. GSH is enriched in the host cytoplasm, and previous work suggests that Lm utilizes exogenous GSH for PrfA activation. Despite these observations, the import mechanism(s) for GSH remains elusive. Analysis of known GSH importers predicted a homologous importer in Lm comprised of the Ctp ABC transporter and the OppDF ATPases of the Opp oligopeptide importer. Here, we demonstrated that the Ctp complex is a high-affinity GSH/GSSG importer that is required for Lm growth at physiologically relevant concentrations. Furthermore, we demonstrated that OppDF is required for GSH/GSSG import in an Opp-independent manner. These data support a model where Ctp and OppDF form a unique complex for GSH/GSSG import that supports growth and pathogenesis. In addition, we show that Lm utilizes the inorganic sulfur sources thiosulfate and H2S for growth in a CysK-dependent manner in the absence of other cysteine sources. These findings suggest a pathoadaptive role for partial cysteine auxotrophy in Lm, where locally high GSH/GSSG or inorganic sulfur concentrations may signal arrival to distinct host niches.

Sodium thiosulfate does not protect ovarian reserve from cisplatin-induced gonadotoxicity†.

Cisplatin, a platinum-containing alkylating agent, is used in the treatment of various tumors owing to its potent antitumor activity. However, it causes permanent and adverse effects, particularly hearing loss and depletion of ovarian reserve. Until recently, there were no clinically available protective agents to mitigate the adverse side effects of cisplatin-induced cytotoxicity. In 2022, sodium thiosulfate (STS) was approved by the Food and Drug Administration for mitigating hearing loss in children and adolescents undergoing cisplatin treatment. Consequently, our investigation aimed to determine if STS could protect ovarian reserve against cisplatin-induced gonadotoxicity. In an ex vivo culture, the cisplatin-only group exhibited a loss of primordial follicles, while post-STS administration after cisplatin exposure effectively protected primordial follicles. However, when post-STS was administrated either 6 or 4 h after cisplatin exposure, it did not confer protection against cisplatin-induced gonadotoxicity in postnatal day 7 or adolescent mouse models. Immunofluorescence assays using γH2AX and cPARP revealed that oocytes within primordial follicles exhibited DNA damage after cisplatin exposure, irrespective of post-STS administration. This underscores the rapid and heightened sensitivity of oocytes to gonadotoxicity. In addition, oocytes demonstrated an increased expression of pCHK2 rather than pERK, suggesting that the pathway leading to oocyte death differs from the pathway observed in the inner ear cell death following cisplatin exposure. These results imply that while the administration of STS after cisplatin is highly beneficial in preventing hearing loss, it does not confer a protective effect on the ovaries in mouse models.

Differences in nonoxidative sulfur metabolism between normal human breast MCF-12A and adenocarcinoma MCF-7 cell lines.

Recent studies have revealed the role of endogenous hydrogen sulfide (H2S) in the development of breast cancer. The capacity of cells to generate H2S and the activity and expression of the main enzymes (cystathionine beta synthase; CBS, cystathionase γ-lyase; CGL, 3-mercaptopyruvate sulfurtransferase; MPST and thiosulfate sulfurtransferase; TST) involved in H2S metabolism were analyzed using an in vitro model of a non-tumourigenic breast cell line (MCF-12A) and a human breast adenocarcinoma cell line (MCF-7). In both cell lines, MPST, CGL, and TST expression was confirmed at the mRNA (RT-PCR) and the protein (Western Blot) level, while CBS expression was detected only in MCF-7 cells. Elevated levels of GSH, sulfane sulfur and increased CBS and TST activity were presented in the MCF-7 compared to the MCF-12A cells. It appears that cysteine might be mainly a substrate for GSH synthesis in breast adenocarcinoma. Increased capacity of the cells to generate H2S was shown for MCF-12A compared to MCF-7 cell line. Results suggest an important function of CBS in H2S metabolism in breast adenocarcinoma. The presented work may contribute to further research on new therapeutic possibilities for breast cancer - one of the most frequently diagnosed types of cancer among women.

Sodium thiosulfate: A donor or carrier signaling molecule for hydrogen sulfide?

Sodium thiosulfate has been used for decades in the treatment of calciphylaxis and cyanide detoxification, and has recently shown initial therapeutic promise in critical diseases such as neuronal ischemia, diabetes mellitus, heart failure and acute lung injury. However, the precise mechanism of sodium thiosulfate remains incompletely defined and sometimes contradictory. Although sodium thiosulfate has been widely accepted as a donor of hydrogen sulfide (H2S), emerging findings suggest that it is the executive signaling molecule for H2S and that its effects may not be dependent on H2S. This article presents an overview of the current understanding of sodium thiosulfate, including its synthesis, biological characteristics, and clinical applications of sodium thiosulfate, as well as the underlying mechanisms in vivo. We also discussed the interplay of sodium thiosulfate and H2S. Our review highlights sodium thiosulfate as a key player in sulfide signaling with the broad clinical potential for the future.

A retrospective review of outcomes after hyperbaric oxygen therapy for the treatment of calciphylaxis.

BACKGROUND: Calciphylaxis is a thrombotic vasculopathy characterized by painful necrotic ulcerations. There are no Food and Drug Administration approved therapies despite high mortality. OBJECTIVE: To compare mortality and wound healing outcomes in patients treated with hyperbaric oxygen therapy (HBOT) in addition to intravenous sodium thiosulfate (IV STS) versus patients who received IV STS only. Findings were stratified by dialysis status and modality. METHODS: 93 patients were included, with 57 patients in the control group (IV STS) and 36 patients in the treatment group (HBOT + IV STS). Mortality data were analyzed with traditional survival analyses and Cox proportional hazard models. Longitudinal wound outcomes were analyzed with mixed effects modeling. RESULTS: Univariate survival analyses showed that full HBOT treatment was associated with significantly (P = .016) longer survival time. Increasing number of HBOT sessions was associated with improved mortality outcomes, with 1, 5, 10 and 20 sessions yielding decreasing hazard ratios. There was also a significant (P = .042) positive association between increasing number of HBOT sessions and increased wound score. LIMITATIONS: Data collection was retrospective. CONCLUSION: HBOT may have a role in the treatment of calciphylaxis with benefits demonstrated in both mortality and wound healing. Larger prospective studies are needed to identify which patients would most benefit from this intervention.

Meta-Phenylenediamine-Derived Silver-Containing Nanoporous Hyper-Cross-Linked Polymer: An Innovative Fluorescence Probe for S2O32- ion Detection in Aqueous Media.

The meta-phenylenediamine polymer, when hyper-cross-linked, exhibits a minimal fluorescence intensity. However, the introduction of silver ions induces a significant increase in intensity, attributed to the plasmonic effect. This heightened intensity is selectively increased more upon the addition of thiosulfate ions. Capitalizing on this property, a fluorescence probe was developed. The correlation between fluorescence intensity reduction and S2O32- concentration follows a linear and consistent pattern. The precursor's response to diverse anions such as SO42-, CO32-, HPO42-, Cr2O72-, F-, Cl-, Br-, I-, H2PO4-, CH3COO-, NO3-, ClO-, and HCO3- was also examined. Under optimal conditions, the probe exhibited a linear range of 0.5-3 µM with a detection limit of 0.01 µM. Its effectiveness was demonstrated in measuring thiosulfate concentrations in aqueous media.

Comparative efficacy of sodium thiosulfate, bisphosphonates, and cinacalcet for the treatment of vascular calcification in patients with haemodialysis: a systematic review and network meta-analysis.

BACKGROUND: Up to now, there is no unequivocal intervention to mitigate vascular calcification (VC) in patients with hemodialysis. This network meta-analysis aimed to systematically evaluate the clinical efficacy of sodium thiosulfate, bisphosphonates, and cinacalcet in treating vascular calcification. METHODS: A comprehensive study search was performed using PubMed, Web of Science, the Cochrane Library, EMBASE and China National Knowledge Internet (CNKI) to collect randomized controlled trials (RCTs) of sodium thiosulfate, bisphosphonates, and cinacalcet for vascular calcification among hemodialysis patients. Then, network meta-analysis was conducted using Stata 17.0 software. RESULTS: In total, eleven RCTs including 1083 patients were qualified for this meta-analysis. We found that cinacalcet (SMD - 0.59; 95% CI [-0.95, -0.24]) had significant benefit on vascular calcification compared with conventional therapy, while sodium thiosulfate or bisphosphonates did not show such efficiency. Furthermore, as for ranking the efficacy assessment, cinacalcet possessed the highest surface under the cumulative ranking curve (SUCRA) value (88.5%) of lessening vascular calcification and was superior to sodium thiosulfate (50.4%) and bisphosphonates (55.4%). Thus, above results suggested that cinacalcet might be the most promising drug for vascular calcification treatment in hemodialysis patients. Mechanistically, our findings illustrated that cinacalcet reduced serum calcium (SMD - 1.20; 95% CI [-2.08, - 0.33]) and showed the tendency in maintaining the balance of intact Parathyroid Hormone (iPTH) level. CONCLUSIONS: This network meta-analysis indicated that cinacalcet appear to be more effective than sodium thiosulfate and bisphosphonates in mitigating vascular calcification through decreasing serum calcium and iPTH. And cinacalcet might be a reasonable option for hemodialysis patients with VC in clinical practice. SYSTEMATIC REVIEW REGISTRATION: [ http://www.crd.york.ac.uk/PROSPERO ], identifier [CRD42022379965].

Enhancing the bioreduction and interaction of arsenic and iron by thiosulfate in groundwater.

Thiosulfate influences the bioreduction and migration transformation of arsenic (As) and iron (Fe) in groundwater environments. The aim of this study was to investigate the impact of microbially-mediated sulfur cycling on the bioreduction and interaction of As and Fe. Microcosm experiments were conducted, including bioreduction of thiosulfate, As(V), and Fe(III) by Citrobacter sp. JH012-1, as well as the influence of thiosulfate input at different initial arsenate concentrations on the bioreduction of As(V) and Fe(III). The results demonstrate that Citrobacter sp. JH012-1 exhibited strong reduction capabilities for thiosulfate, As(V), and Fe(III). Improving thiosulfate level promoted the bioreduction of Fe(III) and As(V). When 0, 0.1, 0.5, and 1 mM thiosulfate were added, Fe(III) was completely reduced within 9 days, 3 days, 1 day, and 0.5 days, simultaneously, 72.8%, 82.2%, 85.5%, and 90.0% of As(V) were reduced, respectively. The products of As(III) binding with sulfide are controlled by the ratio of As-S. When the initial arsenate concentration was 0.025 mM, the addition of thiosulfate resulted in the accumulation of soluble thioarsenite. However, when the initial arsenate level increased to 1 mM, precipitates of orpiment or realgar were formed. In the presence of both arsenic and iron, As(V) significantly inhibits the bioreduction of Fe(III). Under the concentrations of 0, 0.025, and 1 mM As(V), the reduction rates of Fe(III) were 100%, 91%, and 83%, respectively. In this scenario, the sulfide produced by thiosulfate reduction tends to bind with Fe(II) rather than As(III). Therefore, the competition of arsenic-iron and thiosulfate concentration should be considered to study the impact of thiosulfate on arsenic and iron migration and transformation in groundwater.

Evaluating the Effects of Kidney Preservation at 10 °C with Hemopure and Sodium Thiosulfate in a Rat Model of Syngeneic Orthotopic Kidney Transplantation.

Kidney transplantation is preferred for end-stage renal disease. The current gold standard for kidney preservation is static cold storage (SCS) at 4 °C. However, SCS contributes to renal graft damage through ischemia-reperfusion injury (IRI). We previously reported renal graft protection after SCS with a hydrogen sulfide donor, sodium thiosulfate (STS), at 4 °C. Therefore, this study aims to investigate whether SCS at 10 °C with STS and Hemopure (blood substitute), will provide similar protection. Using in vitro model of IRI, we subjected rat renal proximal tubular epithelial cells to hypoxia-reoxygenation for 24 h at 10 °C with or without STS and measured cell viability. In vivo, we preserved 36 donor kidneys of Lewis rats for 24 h in a preservation solution at 10 °C supplemented with STS, Hemopure, or both followed by transplantation. Tissue damage and recipient graft function parameters, including serum creatinine, blood urea nitrogen, urine osmolality, and glomerular filtration rate (GFR), were evaluated. STS-treated proximal tubular epithelial cells exhibited enhanced viability at 10 °C compared with untreated control cells (p < 0.05). Also, STS and Hemopure improved renal graft function compared with control grafts (p < 0.05) in the early time period after the transplant, but long-term function did not reach significance. Overall, renal graft preservation at 10 °C with STS and Hemopure supplementation has the potential to enhance graft function and reduce kidney damage, suggesting a novel approach to reducing IRI and post-transplant complications.

Highly Efficient and Selective Extraction of Gold from Thiosulfate Leaching Solution Using Functionalized Dicationic Ionic Liquids.

Thiosulfate leaching has been regarded as a promising alternative to cyanidation, but it still faces the challenge of the recovery of low content of gold from high concentrations of thiosulfate solutions. Liquid-liquid extraction is a method to address this issue but is still limited by the use of volatile and toxic organic solvents. To overcome this limitation, this work synthesized some functionalized dicationic ionic liquids (DILs) to serve as extraction solvents for the recovery of the gold-thiosulfate complex, [Au(S2O3)2]3-, from thiosulfate solutions. Experimental results indicated that the DILs showed higher extraction rates toward [Au(S2O3)2]3- compared with their monocationic-based counterparts, likely due to the stronger electrostatic interaction between the dications of the ILs and [Au(S2O3)2]3-. The transfer of [Au(S2O3)2]3- from the water phase to the IL phase was identified as an anion exchange and endothermic process. The rate of extraction was limited by the anion exchange process occurring at the IL-water interface. The extraction ability of ILs highly depended on the type of anion; specifically, the ILs with anions that had strong hydrogen-bonding ability exhibited high extraction ability toward [Au(S2O3)2]3-. Finally, DILs proved effective in the recovery of [Au(S2O3)2]3- from an actual gold leaching solution and exhibited high selectivity toward coexisting ions, indicating their potential as environmentally friendly solvents for gold recovery.

Influence of the Use of Irrigation Solution Inhibitors in Improving Dentine Adhesion: A Systematic Review and Meta-Analysis.

INTRODUCTION: This systematic review examined the effect of neutralizing agents on bond strength after irrigation with sodium hypochlorite and their existing protocols in literature. METHODS: This present study adhered to the PRISMA guidelines and was registered at PROSPERO. Five electronic databases were searched (sept-2020/jan-2021) in English, Spanish, and Portuguese, without any restrictions on publication date. Cases reports, editorials and literature reviews were not included. The risk of bias was assessed using the Cochrane Collaboration tool. From the initial 7,147 studies, 2,745 were removed as duplicates and 4,382 were excluded after a title/abstract screen. RESULTS: Seventeen in vitro studies were included. The results showed that the higher the concentration of sodium hypochlorite, the lower the bond strength at dentine/restoration interface (p⟨0.01). Among the studies, sodium ascorbate was the most widely used neutralizer and showed the most significant results in increasing bond strength (p⟨0.01). The bond strength values were found to increase with longer application time of the neutralizing substances (p⟨0.01). CONCLUSIONS: The use of sodium ascorbate as a neutralizing agent can reverse the negative effects of the sodium hypochlorite and improve the bond strength between dentine and resin cement, however, it isn't possible to determine the best protocol for use.

Sodium thiosulfate ameliorates atopic dermatitis via inhibiting the activation of NLRP3 inflammasome.

Atopic dermatitis (AD) is a common disease with a considerable impact on the patient's quality of life and limited treatment options. Sodium thiosulfate (STS) is a traditional medicine used in the rescue of cyanide poisoning, and some pruritus dermatosis. However, the exact efficacy and mechanism of its application on AD are not clear. In this work, comparing to other traditional therapy, STS was found to effectively improve the severity of skin lesions and the quality of life in AD patients with a dose-dependent manner. Mechanically, STS downregulated the expression of IL-4, IL-13, IgE in the serum of AD patients, as well as reduce the concentration of eosinophils. Furthermore, in the AD-like mice model triggered by ovalbumin (OVA) and calcitriol, STS was found to reduce the epidermal thickness, scratching times, and the infiltration of dermal inflammatory cells in AD mice, as well as the reactive oxygen species (ROS) production and the expression levels of inflammatory cytokines in the skin tissue. In HacaT cells, STS inhibited the accumulation of ROS and activation of NLRP3 inflammasome and its downstream IL-1ß expression. Therefore, this study revealed that STS plays an important therapeutic role in AD, and the mechanism may be that STS inhibits the activation of NLRP3 inflammasome and the subsequent release of inflammatory cytokines. Thus, the role of STS in treating AD was clarified and the possible molecular mechanism was revealed.

Calciphylaxis and Kidney Disease: A Review.

Calciphylaxis is a life-threatening complication most often associated with chronic kidney disease that occurs as a result of the deposition of calcium in dermal and adipose microvasculature. However, this condition may also be seen in patients with acute kidney injury. The high morbidity and mortality rates associated with calciphylaxis highlight the importance to correctly diagnose and treat this condition. However, calciphylaxis remains a diagnosis that may be clinically challenging to make. Here, we review the literature on uremic calciphylaxis with a focus on its pathophysiology, clinical presentation, advances in diagnostic tools, and treatment strategies. We also discuss the unique histopathological features of calciphylaxis and contrast it with those of other forms of general vessel calcification. This review emphasizes the need for multidisciplinary collaboration including nephrology, dermatology, and palliative care to ultimately provide the best possible care to patients with calciphylaxis.

Bulb growth potential is independent of leaf longevity for the spring ephemeral Erythronium americanum Ker-Gawl.

Growth in most spring ephemerals is decreased under warmer temperatures. Although photosynthetic activities are improved at warmer temperatures, leaves senesce earlier, which prevents the bulb from reaching a larger size. A longer leaf life duration during a warm spring, therefore, may improve bulb mass. We tested this hypothesis by modulating leaf life span of Erythronium americanum through the application of Promalin® (PRO; cytokinins and gibberellins) that prolonged or silver thiosulfate (STS) that reduced leaf duration. Gas exchange and chlorophyll fluorescence were measured along with leaf and bulb carbohydrate concentrations. Plants were also pulse labelled with 13CO2 to monitor sugar transport to the bulb. Lower photosynthetic rates and shorter leaf life span of STS plants reduced the amount of carbon that they assimilated during the season, resulting in a smaller bulb compared with control plants. PRO plants maintained their photosynthetic rates for a longer period than control plants, yet final bulb biomass did not differ between them. We conclude that seasonal growth for E. americanum is not limited by leaf life duration under warm growing conditions, but rather by limited sink growth capacity. Under global warming, spring geophytes might be at risk of being reduced in size and, eventually, reproducing less frequently.

Revisiting the TCNQF4 0/1-/2- Catalysis Mechanism for the [Fe(CN)6 ]3-/4- -S2 O3 2- /S4 O6 2- Redox Reaction.

Published data suggest that sparingly soluble metal complexes of TCNQF n 1 - ${{\rm{TCNQF}}_{\rm{n}}^{{\rm{1 - }}} }$ , where n=0, 1, 2, 4, can act as heterogeneous catalysts for the kinetically very slow [ Fe ( CN ) 6 ]​ 3 - / 4 - ${{\rm{[Fe(CN)}}_{\rm{6}} {\rm{]}}^{{\rm{3 - /4 - }}} }$ - S 2 O 3 2 - ${{\rm{S}}_{\rm{2}} {\rm{O}}_{\rm{3}}^{{\rm{2 - }}} }$ / S 4 O 6 2 - ${{\rm{S}}_{\rm{4}} {\rm{O}}_{\rm{6}}^{{\rm{2 - }}} }$ reaction in aqueous solution. This study shows that the coordination polymer CuTCNQF 4 ${{\rm{CuTCNQF}}_{\rm{4}} }$ , participates as a homogeneous catalyst via an extremely small concentration of dissolved TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ . This finding suggests that the generally accepted mechanism of catalysis by TCNQF 4 ${{\rm{TCNQF}}_{\rm{4}} }$ based solids needs to be revisited to ascertain the role of homogeneous pathways. In the present study, UV-visible spectrophotometry was used to examine the catalysis of the aqueous redox reaction of [ Fe ( CN ) 6 ]​ 3 - ${{\rm{[Fe(CN)}}_{\rm{6}} {\rm{]}}^{{\rm{3 - }}} }$ (1.0 mM) with S 2 O 3 2 - ${{\rm{S}}_{\rm{2}} {\rm{O}}_{\rm{3}}^{{\rm{2 - }}} }$ (100 mM) in the presence of (i) a precursor catalyst, TCNQF 4 0 ${{\rm{TCNQF}}_{\rm{4}}^{\rm{0}} }$ ; (ii) the catalyst, TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ , as the water soluble Li+ salt; and (iii) CuTCNQF 4 ${{\rm{CuTCNQF}}_{\rm{4}} }$ . A homogeneous reaction scheme that utilises the TCNQF 4 1 - / 2 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - /2 - }}} }$ couple is provided. In the case of TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ derived from highly soluble LiTCNQF 4 ${{\rm{LiTCNQF}}_{\rm{4}} }$ , quantitative conversion of 1.0 mM S 2 O 3 2 - ${{\rm{S}}_{\rm{2}} {\rm{O}}_{\rm{3}}^{{\rm{2 - }}} }$ to 0.50 mM S 4 O 6 2 - ${{\rm{S}}_{\rm{4}} {\rm{O}}_{\rm{6}}^{{\rm{2 - }}} }$ occurs with complete reduction of [ Fe ( CN ) 6 ]​ 3 - ${{\rm{[Fe(CN)}}_{\rm{6}} {\rm{]}}^{{\rm{3 - }}} }$ to [ Fe ( CN ) 6 ]​ 4 - ${{\rm{[Fe(CN)}}_{\rm{6}} {\rm{]}}^{{\rm{4 - }}} }$ being rapidly accelerated by sub-micomolar concentrations of TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ . TCNQF 4 2 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{2 - }}} }$ generated in the catalytic cycle, reacts with [ Fe ( CN ) 6 ]​ 3 - ${{\rm{[Fe(CN)}}_{\rm{6}} {\rm{]}}^{{\rm{3 - }}} }$ to reform TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ and produce [ Fe ( CN ) 6 ]​ 4 - ${{\rm{[Fe(CN)}}_{\rm{6}} {\rm{]}}^{{\rm{4 - }}} }$ . Along with the rapid catalytic reaction, the sluggish competing reaction between TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ and S 2 O 3 2 - ${{\rm{S}}_{\rm{2}} {\rm{O}}_{\rm{3}}^{{\rm{2 - }}} }$ occurs to give TCNQF 4 2 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{2 - }}} }$ , which is protonated to HTCNQF 4 1 - ${{\rm{\;HTCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ , along with a trace amount of S 4 O 6 2 - ${{\rm{S}}_{\rm{4}} {\rm{O}}_{\rm{6}}^{{\rm{2 - }}} }$ . On addition of the precursor catalyst, TCNQF 4 0 ${{\rm{TCNQF}}_{\rm{4}}^{\rm{0}} }$ , rapid reduction with S 2 O 3 2 - ${{\rm{S}}_{\rm{2}} {\rm{O}}_{\rm{3}}^{{\rm{2 - }}} }$ occurs to form TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ - the active catalyst. CuTCNQF 4 ${{\rm{CuTCNQF}}_{\rm{4}} }$ added to water is shown to be sufficiently soluble to provide adequate TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ to act as the catalyst for the [ Fe ( CN ) 6 ]​ 3 - / 4 - ${{\rm{[Fe(CN)}}_{\rm{6}} {\rm{]}}^{{\rm{3 - /4 - }}} }$ - S 2 O 3 2 - ${{\rm{S}}_{\rm{2}} {\rm{O}}_{\rm{3}}^{{\rm{2 - }}} }$ / S 4 O 6 2 - ${{\rm{S}}_{\rm{4}} {\rm{O}}_{\rm{6}}^{{\rm{2 - }}} }$ reaction.

Reevaluation of sodium thiosulfate otoprotection using the consensus International Society of Paediatric Oncology Ototoxicity Scale: A report from the Children's Oncology Group study ACCL0431.

In two randomized trials (Children's Oncology Group ACCL0431 and International Childhood Liver Tumour Strategy Group SIOPEL-6), sodium thiosulfate (STS) demonstrated efficacy in preventing cisplatin-induced hearing loss (CIHL). However, the measures used in those trials have been superseded by the consensus International Society of Paediatric Oncology (SIOP) Ototoxicity Scale. To provide benchmark data for STS efficacy when using this contemporary scale, we reanalyzed ACCL0431 hearing outcomes with the SIOP scale and using multiple timepoints. Compared to the control arm, STS significantly reduced CIHL when assessed by the SIOP scale across these different approaches. These results provide critical data to inform treatment discussions and support future potential trial designs comparing otoprotectants.

Performance, comparison and utilization of reduced sulfur (-2) compounds (S2-, FeS and SCN-) in autotrophic denitrification process by thiosulfate-driven autotrophic denitrifier.

The coexistence of reduced sulfur (-2) compounds (S2-, FeS and SCN-) are found in some industrial wastewaters due to pre-treatment of Fe(II) salts. These compounds as electron donors have attracted increasing interest in autotrophic denitrification process. However, the difference of their functions still remain unknown, which limit efficient utilization in autotrophic denitrification process. The study aimed to investigate and compare utilization behavior of these reduced sulfur (-2) compounds in autotrophic denitrification process activated by thiosulfate-driven autotrophic denitrifiers (TAD). Results showed that the best denitrification performance was observed in SCN-; while the reduction of nitrate was significantly inhibited in S2- system and the efficient accumulation of nitrite was observed in FeS system with cycle experiments continuing. Additionally, intermediates containing sulfur were produced rarely in SCN- system. However, the utilization of SCN- was limited obviously in comparison with S2- in coexistence systems. Moreover, the presence of S2- increased the accumulation peak of nitrite in coexistence systems. The biological results indicated that the TAD utilized rapidly these sulfur (-2) compounds, in which genus of Thiobacillus, Magnetospirillum and Azoarcus might play main roles. Moreover, Cupriavidus might also participate in sulfur oxidation in SCN- system. In conclusion, these might be attributed to the characteristics of sulfur (-2) compounds including the toxicity, solubility and reaction process. These findings provide theoretical basis for regulation and utilization of these reduced sulfur (-2) compounds in autotrophic denitrification process.

Sailing between scylla and charybdis-anticoagulation dilemma in a patient with calciphylaxis and mechanical cardiac valve replacement: a case report and literature review.

Calciphylaxis is a rare and life-threatening condition in patients with end-stage kidney disease (ESKD). In this case report, we reported a 72-year-old female who had undergone aortic and mitral mechanical valve replacement 22 years ago due to rheumatic aortic and mitral stenosis. Following the valve replacement, she initiated warfarin treatment. Five years ago, she received a diagnosis of uremia and has since been undergoing regular hemodialysis. Ten months prior to her current admission, she experienced excruciating pain and was diagnosed with calciphylaxis. Additionally, an electrocardiogram revealed atrial fibrillation, while echocardiography indicated that the aortic and mitral mechanical valves were appropriately positioned, with normal perivalvular surroundings and good valve leaflet activity. No noticeable thrombosis was observed in the left atrium or left atrial appendage. Color Doppler imaging showed moderate stenosis in the lower extremity arteries, with no venous thromboembolism present. Extensive eggshell-like calcification within the arterial media was detected. The patient was managed with regular hemodialysis, symptomatic treatments (including anticoagulation and analgesia), and sodium thiosulfate. Unfortunately, symptomatic management provided limited relief, and during the one-month follow-up period, the patient passed away due to septic shock. Currently, there is insufficient conclusive evidence regarding alternative influential anticoagulants or appropriate prosthetic valve selection. For individuals with ESKD receiving maintenance hemodialysis, early identification, diagnosis, and treatment of calciphylaxis are of paramount importance.