Onset of coupled atmosphere-ocean oxygenation 2.3 billion years ago.

The initial rise of molecular oxygen (O2) shortly after the Archaean-Proterozoic transition 2.5 billion years ago was more complex than the single step-change once envisioned. Sulfur mass-independent fractionation records suggest that the rise of atmospheric O2 was oscillatory, with multiple returns to an anoxic state until perhaps 2.2 billion years ago1-3. Yet few constraints exist for contemporaneous marine oxygenation dynamics, precluding a holistic understanding of planetary oxygenation. Here we report thallium (Tl) isotope ratio and redox-sensitive element data for marine shales from the Transvaal Supergroup, South Africa. Synchronous with sulfur isotope evidence of atmospheric oxygenation in the same shales3, we found lower authigenic 205Tl/203Tl ratios indicative of widespread manganese oxide burial on an oxygenated seafloor and higher redox-sensitive element abundances consistent with expanded oxygenated waters. Both signatures disappear when the sulfur isotope data indicate a brief return to an anoxic atmospheric state. Our data connect recently identified atmospheric O2 dynamics on early Earth with the marine realm, marking an important turning point in Earth's redox history away from heterogeneous and highly localized 'oasis'-style oxygenation.

Mechanisms of Uptake and Translocation of Thallium in Brassica Vegetables: An X-ray Fluorescence Microspectroscopic Investigation.

Most nonoccupational human exposure to thallium (Tl) occurs via consumption of contaminated food crops. Brassica cultivars are common crops that can accumulate more than 500 µg Tl g-1. Knowledge of Tl uptake and translocation mechanisms in Brassica cultivars is fundamental to developing methods to inhibit Tl uptake or conversely for potential use in phytoremediation of polluted soils. Brassica cultivars (25 in total) were subjected to Tl dosing to screen for Tl accumulation. Seven high Tl-accumulating varieties were selected for follow-up Tl dosing experiments. The highest Tl accumulating Brassica cultivars were analyzed by synchrotron-based micro-X-ray fluorescence to investigate the Tl distribution and synchrotron-based X-ray absorption near-edge structure spectroscopy (XANES) to unravel Tl chemical speciation. The cultivars exhibited different Tl tolerance and accumulation patterns with some reaching up to 8300 µg Tl g-1. The translocation factors for all the cultivars were >1 with Brassica oleracea var. acephala (kale) having the highest translocation factor of 167. In this cultivar, Tl is preferentially localized in the venules toward the apex and along the foliar margins and in minute hot spots in the leaf blade. This study revealed through scanning electron microscopy and X-ray fluorescence analysis that highly Tl-enriched crystals occur in the stoma openings of the leaves. The finding is further validated by XANES spectra that show that Tl(I) dominates in the aqueous as well as in the solid form. The high accumulation of Tl in these Brassica crops has important implications for food safety and results of this study help to understand the mechanisms of Tl uptake and translocation in these crops.

MnFe2O4-biochar decreases bioavailable fractions of thallium in highly acidic soils from pyrite mining area.

The prevalence of toxic element thallium (Tl) in soils is of increasing concern as a hidden hazard in agricultural systems and food chains. In the present work, pure biochar (as a comparison) and jacobsite (MnFe2O4)-biochar composite (MFBC) were evaluated for their immobilization effects in Tl-polluted agricultural soils (Tl: ∼10 mg/kg). Overall, MFBC exhibited an efficient effect on Tl immobilization, and the effect was strengthened with the increase of amendment ratio. After being amended by MFBC for 15 and 30 days, the labile fraction of Tl in soil decreased from 1.55 to 0.97 mg/kg, and from 1.51 to 0.88 mg/kg, respectively. In addition, pH (3.05) of the highly acidic soil increased to a maximum of 3.97 after the immobilization process. Since the weak acid extractable and oxidizable Tl were the preponderantly mitigated fractions and displayed a negative correlation with pH, it can be inferred that pH may serve as one of the most critical factors in regulating the Tl immobilization process in MFBC-amended acidic soils. This study indicated a great potential of jacobsite-biochar amendment in stabilization and immobilization of Tl in highly acidic and Tl-polluted agricultural soils; and it would bring considerable environmental benefit to these Tl-contaminated sites whose occurrence has significantly increased in recent decades near the pyrite or other sulfide ore mining and smelting area elsewhere.

[Determination of 24 elements migration in Yixing clay pottery by inductively coupled plasma mass spectrometry].

OBJECTIVE: To establish an analytical method for determining the migration of 24 elements in Yixing clay pottery in 4% acetic acid simulated solution by inductively coupled plasma mass spectrometry. METHODS: Four types of Yixing clay pottery, including Yixing clay teapot, Yixing clay kettle, Yixing clay pot, and Yixing clay electric stew pot, were immersed in 4% acetic acid as a food simulant for testing. The migration amount of 24 elements in the migration solution was determined using inductively coupled plasma mass spectrometry. RESULTS: Lithium, magnesium, aluminum, iron, and barium elements with a mass concentration of 1000 µg/L; Lead, cadmium, total arsenic, chromium, nickel, copper, vanadium, manganese, antimony, tin, zinc, cobalt, molybdenum, silver, beryllium, thallium, titanium, and strontium elements within 100 µg/L there was a linear relationship within, the r value was between 0.998 739 and 0.999 989. Total mercury at 5.0 µg/L, there was a linear relationship within, the r value of 0.995 056. The detection limit of the elements measured by this method was between 0.5 and 45.0 µg/L, the recovery rate was 80.6%-108.9%, and the relative standard deviation was 1.0%-4.8%(n=6). A total of 32 samples of four types of Yixing clay pottery sold on the market, including teapots, boiling kettles, casseroles, and electric stewing pots, were tested. It was found that the migration of 16 elements, including beryllium, titanium, chromium, nickel, cobalt, zinc, silver, cadmium, antimony, total mercury, thallium, tin, copper, total arsenic, molybdenum, and lead, were lower than the quantitative limit. The element with the highest migration volume teapot was aluminum, magnesium, and barium; The kettle was aluminum and magnesium; Casserole was aluminum, magnesium, and lithium; The electric stew pot was aluminum. CONCLUSION: This method is easy to operate and has high accuracy, providing an effective and feasible detection method for the determination and evaluation of element migration in Yixing clay pottery.

Microbial diversity in paddy rhizospheric soils around a large industrial thallium-containing sulfide utilization zone.

Thallium (Tl) is a rare and extremely toxic metal whose toxicity is significantly higher than cadmium (Cd), lead (Pb) and antimony (Sb). The extensive utilization of Tl-bearing minerals, such as mining activities, has led to severe Tl pollution in a variety of natural settings, while little is known to date about its effect on the microbial diversity in paddy soils. Also, the geochemical behavior of Tl in the periodical alterations between dry and wet conditions of paddy soils remains largely unknown. Herein, the sequential extraction method and 16S rRNA gene sequence analysis were adopted to analyze Tl's migration and transformation behavior and the microbial diversity in the paddy soils with different pollution levels. The results indicated that Tl was mainly concentrated in reducible fraction, which is different from other types of soils, and may be closely attributed to the abundance of Fe-Mn (hydr)oxides in the paddy rhizospheric soils. Further analysis revealed that pH, total S, Pb, Sb, Tl and Cd were the dominant environmental factors, and the enrichment level of these potentially toxic metal(loid)s (PTMs) exerted obvious impacts on the diversity and abundance of microorganism in the rhizospheric soils, and regulating microbial community. The geochemical fractionation of Tl was closely correlated to soil microorganisms such as Fe reducing bacteria (Geothrix) and sulfate reducing bacteria (Anaerolinea), playing a critical role in Tl geochemical cycle through redox reaction. Hence, further study on microorganisms of paddy rhizospheric soils is of great significance to the countermeasures for remediating Tl-polluted paddy fields and protect the health of residents.

Correlation of heavy metals' exposure with the prevalence of coronary heart disease among US adults: findings of the US NHANES from 2003 to 2018.

We sought to explore the association between heavy metal exposure and coronary heart disease (CHD) based on data from the US National Health and Nutrition Examination Survey (NHANES, 2003-2018). In the analyses, participants were all aged > 20 and had participated in heavy metal sub-tests with valid CHD status. The Mann-Kendall test was employed to assess the trends in heavy metals' exposure and the trends in CHD prevalence over 16 years. Spearman's rank correlation coefficient and a logistics regression (LR) model were used to estimate the association between heavy metals and CHD prevalence. 42,749 participants were included in our analyses, 1802 of whom had a CHD diagnosis. Total arsenic, dimethylarsonic acid, monomethylarsonic acid, barium, cadmium, lead, and antimony in urine, and cadmium, lead, and total mercury in blood all showed a substantial decreasing exposure level tendency over the 16 years (all Pfor trend < 0.05). CHD prevalence varied from 3.53 to 5.23% between 2003 and 2018. The correlation between 15 heavy metals and CHD ranges from - 0.238 to 0.910. There was also a significant positive correlation between total arsenic, monomethylarsonic acid, and thallium in urine and CHD by data release cycles (all P < 0.05). The cesium in urine showed a negative correlation with CHD (P < 0.05). We found that exposure trends of total arsenic, dimethylarsonic acid, monomethylarsonic acid, barium, cadmium, lead, and antimony in urine and blood decreased. CHD prevalence fluctuated, however. Moreover, total arsenic, monomethylarsonic acid, and thallium in urine all showed positive relationships with CHD, while cesium in urine showed a negative relationship with CHD.

Highly inhibited transport of dissolved thallium(I) in manganese oxide-coated sand: Chemical condition effects and retention mechanisms.

Thallium contamination in water can cause great danger to the environment. In this study, we synthesized manganese oxide-coated sand (MOCS) and investigated the transport and retention behaviors of Tl(I) in MOCS under different conditions. Characterization methods combined with a two-site nonequilibrium transport model were applied to explore the retention mechanisms. The results showed that Tl(I) mobility was strongly inhibited in MOCS media, and the retention capacity calculated from the fitted model was 510.41 mg/g under neutral conditions. The retention process included adsorption and oxidative precipitation by the manganese oxides coated on the sand surface. Cotransport with the same concentration of Mn(II) led to halving Tl(I) retention due to competition for reactive sites. Enhanced Tl(I) retention was observed under alkaline conditions, as increasing pH promoted electronegativity on the media surface. Moreover, the competitive cation Ca2+ significantly weakened Tl(I) retention by occupying adsorption sites. These findings provide new insights into understanding Tl(I) transport behavior in water-saturated porous media and suggest that manganese oxide-coated sand can be a cost-effective filter media for treating Tl-contaminated water.

Pedogeochemical distribution of gallium, indium and thallium, their potential availability and associated risk in highly-weathered soil profiles of Taiwan.

Gallium (Ga), indium (In), and thallium (Tl) are emerging soil contaminants. Profile distribution of total content and available form as well as assessing the contamination degree of these elements in highly-weathered soils have not been studied. Consequently, the aim of this study was to determine the distribution of total (HF-digestion) and available (EDTA-extracted form) content of Ga, In, and Tl in eleven soil profiles collected from aged fluvial materials on the Quaternary terraces representing highly-weathered soils (Ultisols and Oxisols) in Taiwan as affected by soil properties. We also assessed the soils contamination degree using indices including enrichment factor (EF), geo-accumulation index (Igeo), and pollution loading index (PLI). The total element content varied from 9460 to 2340 µg kg-1 for Ga, 4.77-37.1 µg kg-1 for In, and from 55.7 to 206 µg kg-1 for Tl. The elements showed different profile distribution in the soils. Soil contamination degree was low in all profiles according to the Igeo and PLI values, but the contamination degree according to the EF was severe for Ga and minor or moderate for In in selected horizons of some profiles. The median content of EDTA-extracted Ga, In, and Tl accounted for 24.0, 8.70, and 5.1% of the total content, respectively. The available Ga and Tl can be predicted by a function of total element and clay using multivariate linear regression analysis. The available In was not able to be predicted by a significant fit of the regression with total In and the studied soil properties, and thus we require more assessment approaches of In availability for the soils in the future.

Thallium isotopes reveal protracted anoxia during the Toarcian (Early Jurassic) associated with volcanism, carbon burial, and mass extinction.

For this study, we generated thallium (Tl) isotope records from two anoxic basins to track the earliest changes in global bottom water oxygen contents over the Toarcian Oceanic Anoxic Event (T-OAE; ∼183 Ma) of the Early Jurassic. The T-OAE, like other Mesozoic OAEs, has been interpreted as an expansion of marine oxygen depletion based on indirect methods such as organic-rich facies, carbon isotope excursions, and biological turnover. Our Tl isotope data, however, reveal explicit evidence for earlier global marine deoxygenation of ocean water, some 600 ka before the classically defined T-OAE. This antecedent deoxygenation occurs at the Pliensbachian/Toarcian boundary and is coeval with the onset of initial large igneous province (LIP) volcanism and the initiation of a marine mass extinction. Thallium isotopes are also perturbed during the T-OAE interval, as defined by carbon isotopes, reflecting a second deoxygenation event that coincides with the acme of elevated marine mass extinctions and the main phase of LIP volcanism. This suggests that the duration of widespread anoxic bottom waters was at least 1 million years in duration and spanned early to middle Toarcian time. Thus, the Tl data reveal a more nuanced record of marine oxygen depletion and its links to biological change during a period of climatic warming in Earth's past and highlight the role of oxygen depletion on past biological evolution.

Migration characteristics of heavy metals in the weathering process of exposed argillaceous sandstone in a mercury-thallium mining area.

Lanmuchang mercury-thallium mine, a typical polymetallic mine is located in southwestern Guizhou, China, is the most serious and typical area resulted from multi-metal contamination (Tl, Hg, As, and Sb). After the mercury-thallium mining, a large area of surrounding rocks such as argillaceous sandstone with high contents of Tl, Hg, As, and Sb is exposed to air. Weathering caused the argillaceous sandstone to form different weathering layers, including the grey-black external layer, the brown-yellow middle layer and the gray-white inner layer, and the external layer was enriched with higher heavy metals. However, the reason of heavy metal migration and transformation in argillaceous sandstone caused by weathering is unclear. The objective of this paper was to investigate the migration, transformation and release characteristics of Tl, Hg, As, and Sb in argillaceous sandstone during the weathering. The results indicated that weathering not only promoted an acidic oxidation environment in argillaceous sandstone, but also increased its specific surface area, pore volume and hydrophilicity, which are beneficial to the permeability of oxygen and etching liquids during the process of weathering and leaching. Meanwhile, weathering led to the transformation or decomposition of hydrophilic groups, such as -OH and -CË­O in the grey-black external layer of argillaceous sandstone, resulting in the further release of heavy metals bound to these groups. The concentration of Tl, Hg, As, and Sb in the leaching solution of argillaceous sandstone represented a positive correlation with that of Fe, Ca, Mg at different levels, indicating that Tl, Hg, As, and Sb were released with the dissolution of Fe, Ca and Mg during weathering and leaching. In summary, these results indicated that weathering caused the dissolution and migration of heavy metals in the argillaceous sandstone. Tl, Hg, As, and Sb migrated from the grey-white inner layer to the grey-black external layer and partially adsorbed by free alumina (Ald), jarosite and Ca-bearing minerals, showing enrichment phenomena, partially released into the environment, causing environmental pollution.

Method Validation for Determination of Thallium by Inductively Coupled Plasma Mass Spectrometry and Monitoring of Various Foods in South Korea.

Thallium (Tl) is a rare element and one of the most harmful metals. This study validated an analytical method for determining Tl in foods by inductively coupled plasma mass spectrometry (ICP-MS) based on food matrices and calories. For six representative foods, the method's correlation coefficient (R2) was above 0.999, and the method limit of detection (MLOD) was 0.0070-0.0498 µg kg-1, with accuracy ranging from 82.06% to 119.81% and precision within 10%. We investigated 304 various foods in the South Korean market, including agricultural, fishery, livestock, and processed foods. Tl above the MLOD level was detected in 148 samples and was less than 10 µg kg-1 in 98% of the samples. Comparing the Tl concentrations among food groups revealed that fisheries and animal products had higher Tl contents than cereals and vegetables. Tl exposure via food intake did not exceed the health guidance level.

Secondary Sulfate Minerals from Pyrite Oxidation in Lanmuchang Hg-Tl Deposit, Southwest Guizhou Province, China: Geochemistry and Environmental Significance.

Thallium (Tl) is a highly toxic trace metal posing a significant threat to human health. Tl pollution in soils and chronic Tl poisoning related to Tl-rich sulfides weathering in the Lanmuchang mine of southwest Guizhou province, China, have been intensively studied in recent years. And yet, there are few studies on the role of secondary sulfate minerals associated with Tl mobility in this area. The sulfate minerals were characterized by XRD and SEM-EDS. The concentrations of Tl and other elements were determined by ICP-MS. The results show that sulfate minerals are predominantly melanterite, halotrichite, and fibroferrite. The average contents of Tl in rock, sulfate minerals, and soil samples were 156.4, 0.11, and 72.1 µg g-1, respectively. This study suggests that Tl in the mineralized rocks entered soils by pyrite oxidation with less scavenged of the sulfate minerals. The dissolution of the ferric sulfate minerals accelerates pyrite oxidation and maintains soil acidity, and this likely enhances Tl mobility from soil to crops.

Releasing Characteristics and Biological Toxicity of the Heavy Metals from Waste of Mercury-Thalliummine in Southwest Guizhou of China.

In this paper, the releasing characteristics and biological toxicity of Tl, Hg, As and Sb in waste of Lanmuchang mercury-thallium mine were studied. The results indicated that strong acidity can significantly promote the release of Tl from waste. With the increase of pH, the release of Sb grew steadily, while Hg and As showed a trend of first increasing and then decreasing. Fe2(SO4)3 contributed less to the release of As and Sb than to that of Hg and Tl. FeCl3 significantly inhibited the release of As, Sb and Tl. In the leaching experiments of litter and root exudates, the lixiviums appeared neutral, and the litter and root exudates solution significantly reduced the release of Tl, and showed less toxicity to luminescent bacteria. However, they promoted the release of Hg, As and Sb at different levels.

Persistent thallium contamination in river sediments, source apportionment and environmental implications.

The adverse impacts of detrimental thallium (Tl) contamination are of increasing concerns to sustainable development. Herein, the contents, distributions and sources of Tl and potential toxic elements (PTEs) (Pb, As, Cr, Cu, Ni, Co, Sb, Cd and U) were investigated in sediments collected in Gaofeng River, which has been contaminated by long-term mining activities, located in Yunfu City, Southern China. Results indicated that excessive Tl levels were found in sediments (1.80-16.70 mg/kg). Sequential extraction procedure indicated that despite a large amount of Tl entrapped in residual fraction, a significant level of Tl (0.28-2.34 mg/kg) still exhibited in geochemically labile fractions, which was easy for Tl mobilization and availability. Pb isotope tracing method further confirmed that the pyrite exploitations may be the prime contaminated contributor (47-76%) to these sediments. These findings highlight that it is essential to establish more effective measures for Tl contamination control and call for engineered remediation countermeasures towards polluted river sediments.

Distribution, accumulation, and potential risks of heavy metals in soil and tea leaves from geologically different plantations.

Risk assessment regarding heavy metals in tea is crucial to ensure the health of tea customers. However, the effects of geological difference on distribution of heavy metals in soils and their accumulation in tea leaves remain unclear. This study aimed to estimate the impacts of geological difference on distribution of cadmium (Cd), lead (Pb), thallium (Tl), mercury (Hg), arsenic (As), antimony (Sb), chromium (Cr), nickel (Ni), and manganese (Mn) in soils and their accumulation in tea leaves, and further evaluate their health risks. 22 soils and corresponding young tea leaves (YTL) and old tea leaves (OTL), from geologically different plantations, were sampled and analyzed. Results showed that heavy metals concentrations in soils, derived from Permian limestone and Cambrian weakly mineralized dolomite, were obviously greater than those from Silurian clastic rock. The geological difference controlled the distribution of soil heavy metals to a large extent. Contents of Cd, Tl, and Mn in tea leaves mainly depended on their contents in soils. Soil Hg, Pb, As, and Sb contents may not be the only influencing factors for their respective accumulation in tea leaves. More attentions should be paid to soil acidification of tea plantations to ensure the tea quality security. Target hazard quotients (THQ) of Cd, Pb, Tl, Hg, As, Sb, Cr, and Ni and hazard index (HI) via tea intake were below one, indicating no human health risk. The non-mineralized Silurian area was less at risk of heavy metals accumulation in tea leaves than the Cambrian metallogenic belt and the Permian Cd-enriched zone. This study could provide an important basis to understand and mitigate the potential risks of heavy metals in tea.

Microbial diversity response in thallium polluted riverbank soils of the Lanmuchang.

Thallium (Tl) is a toxic element, but little is known about microbial communities' response to TI mobilization and sequestration. Here, we characterize the microbial communities and their feedbacks to Tl-pollution in riverbank soils to understand the distribution of microbial metal tolerance. These soils have been affected by pollution sourced from a Tl-rich mineralized area in Lanmuchang, Guizhou, China. In all studied soil samples, Proteobacteria, Acidobacteria, and Actinobacteria were revealed relatively in higher abundance at the phylum level. The results indicated that a number of microbial communities including Gemmatimonadetes, and Actinobacteria were correlated with total Tl, suggesting potential roles of these microbes to Tl tolerance. The patterns of phylogenetic beta-diversity in studied samples showed a high diversity of the microbial community in soils with high Tl concentrations. Sequence analysis of microbial community indicated that most of the environmental parameters in soils were associated with the major phylogenetic groups such as Gemmobacteria, Bryobacteria, Proteobacteria, Actinobacteria, Firmicutes, and Rhodobacteria. Some species of microbes, Nocardioides (genus), Actinomycetales (Order), Ralstonia (phyla) and Sphingomonas (genus) might are tolerant of Tl. These results provide direction to the microbial communities in the presence of elevated Tl concentration in Lanmuchang and shed light on bioremediation of Tl polluted locations.

In Situ Measurement of Thallium in Natural Waters by a Technique Based on Diffusive Gradients in Thin Films Containing a δ-MnO2 Gel Layer.

Thallium (Tl) has been identified as a priority contaminant because of its severe toxic effects. Exact measurement of Tl is a challenge because it is difficult to avoid altering the element's chemical speciation during sampling, transport, and storage. In situ measurement may be a good choice. Based on the in situ technique of diffusive gradients in thin films (DGT), new DGT devices equipped with novel laboratory-synthesized manganese oxide (δ-MnO2) binding gels were developed and systematically validated for the measurement of Tl, including Tl(I) and Tl(III) species, in water. Comparison between Chelex binding gel and δ-MnO2 gel on the uptake kinetics of Tl demonstrated that δ-MnO2 binding gels could adsorb Tl rapidly and effectively. Removal of Tl from the δ-MnO2 gels was achieved by use of 1 mol·L-1 oxalic acid, yielding elution efficiencies of 1.0 for Tl(I) and 0.86 for TI(III). Theoretical responses from DGT devices loaded with δ-MnO2 gel (δ-MnO2-DGT) were obtained irrespective of pH (4-9) and ionic strength (0.1-200 mmol·L-1 NaNO3). δ-MnO2-DGT showed good potential for long-term monitoring of Tl due to its high adsorption capacity of 27.1 µg·cm-2 and the stable performance of δ-MnO2 binding gel kept in solution, containing only 10 mmol·L-1 NaNO3, for at least 117 days. Field deployment trials confirmed that δ-MnO2-DGT can accurately measure the time-averaged concentrations of Tl in fluvial watercourses. In summary, the newly developed δ-MnO2-DGT technique shows potential for environmental monitoring and biogeochemical investigation of Tl in waters.

Ratiometric Phosphorescent Probe for Thallium in Serum, Water, and Soil Samples Based on Long-Lived, Spectrally Resolved, Mn-Doped ZnSe Quantum Dots and Carbon Dots.

Thallium (Tl) is an extremely toxic heavy metal and exists in very low concentrations in the environment, but its sensing is largely underexplored as compared to its neighboring elements in the periodic table (especially mercury and lead). In this work, we developed a ratiometric phosphorescent nanoprobe for thallium detection based on Mn-doped ZnSe quantum dots (QDs) and water-soluble carbon dots (C-dots). Upon excitation with 360 nm, Mn-doped ZnSe QDs and C-dots can emit long-lived and spectrally resolved phosphorescence at 580 and 440 nm, respectively. In the presence of thallium, the phosphorescence emission from Mn-doped ZnSe QDs could be selectively quenched, while that from C-dots retained unchanged. Therefore, a ratiometric phosphorescent probe was thus developed, which can eliminate the potential influence from both background fluorescence and other analyte-independent external environment factors. Several other heavy metal ions caused interferences to thallium detection but could be efficiently masked with EDTA. The proposed method offered a detection limit of 1 µg/L, which is among the most sensitive probes ever reported. Successful application of this method for thallium detection in biological serum as well as in environmental water and soil samples was demonstrated.

Rhodol-based thallium sensors for cellular imaging of potassium channel activity.

Thallium (Tl+) flux assays enable imaging of potassium (K+) channel activity in cells and tissues by exploiting the permeability of K+ channels to Tl+ coupled with a fluorescent Tl+ sensitive dye. Common Tl+ sensing dyes utilize fluorescein as the fluorophore though fluorescein exhibits certain undesirable properties in these assays including short excitation wavelengths and pH sensitivity. To overcome these drawbacks, the replacement of fluorescein with rhodols was investigated. A library of 13 rhodol-based Tl+ sensors was synthesized and their properties and performance in Tl+ flux assays evaluated. The dimethyl rhodol Tl+ sensor emerged as the best of the series and performed comparably to fluorescein-based sensors while demonstrating greater pH tolerance in the physiological range and excitation and emission spectra 30 nm red-shifted from fluorescein.