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Allchar (North Macedonia) mining area is known for anomalous background Tl concentrations. In this study, we combine accurate detection of Tl stable isotope ratios with data on mineralogy/speciation and chemical extraction of Tl in Tl-contaminated Technosol profiles. We demonstrate that Tl in the studied soils varies significantly in both concentration (500 mg/kg-18 g/kg) and isotopic composition (-1.6 and +3.2 of ε 205 Tl, a ∼0.5‰ spread), which is due to changes in the phase chemistry and/or mineralogy of Tl. Moreover, the observed 205 Tl/ 203 Tl ratios do not reflect the extent to which individual soils undergo Tl isotopic fractionation during mineral weathering and soil formation. Clearly, they reflect the initial isotopic signal(s) of the primary ore or ore minerals, and thus, the general history or type of their genesis. As the Tl carriers, various types of Tl-Me-arsenates, mixtures of jarosite and dorallcharite and minor Mn-oxides predominated. We revealed intense adsorption of Tl by the identified Mn-oxides (≤6.7 at.%). It is hypothesized that these phases are of key importance in the fractionation of Tl isotopes, meaning at this type of secondary oxide-soil solution interface. However, model studies involving primary/secondary components (sulfides, sulfates, oxides and arsenates) are required to understand the mechanisms that may lead to post-depositional Tl isotopic redistribution in soils, as well as Tl isotope systematics in mining wastes in general., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

As trace levels of thallium (Tl) in water are lethal to humans and ecosystems, it is essential to exploit advanced technologies for efficient Tl removal. In response to this concern, an innovative composite membrane was developed, incorporating polytetrafluoroethylene (PTFE) and featuring a dual-support system with polydopamine (PDA) and polyethyleneimine (PEI), along with bimetallic Prussian blue analogues (Co@Fe-PBAs) as co-supports. The composite membrane exhibited an exceptional Tl + -adsorption capacity (q m ) of 186.1 mg g -1 when utilized for the treatment of water containing low concentration of Tl + (0.5 mg⋅L -1 ). Transmission electron microscopy displayed the obvious Tl + mapping inside the special hollow Co@Fe-PBAs crystals, demonstrating the deep intercalation of Tl + via ion exchange and diffusion. The Tl + -adsorption capability of the composite membrane was not greatly affected by coexisting Na + , Ca 2+ and Mg 2+ as well as the tricky K + , indicating the excellent anti-interference. Co-doped PBAs enhanced ion exchange and intercalation of the composite membrane with Tl + leading to excellent Tl + removal efficiency. The composite membrane could efficiently remove Tl + from thallium-contaminated river water to meet the USEPA standard. This study provides a cost-effective membrane-based solution for efficient Tl + removal from Tl + -containing wastewater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Prussian blue is known for its high affinity for thallium and other univalent metal cations and has been used as a treatment for radiocaesium and thallium/radiothallium poisoning. While Prussian blue nanoparticles (PBNPs) show potential for binding radioactive thallium for further use in nuclear medicine applications, the inclusion mechanism remains elusive. Understanding the interaction between PBNPs and 201 Tl is essential for identifying the physicochemical and radiochemical properties required for optimal in vivo performance. In this work, we evaluated the binding mechanism between Tl and PBNPs with different coatings and core shapes. Combining PBNPs with [ 201 Tl] thallium(I) chloride provided high radiolabelling yields and radiochemical stabilities under physiological conditions. Comprehensive characterisation by different X-ray techniques confirmed that Tl ions are located in the interstitial sites within the crystal structure, maintaining the integrity of the iron (Fe) 4p electronic distribution and inducing local modifications in the nearby C-N ligands. Additionally, this inclusion does not impact the core or the shell of the nanoparticles but does alter their ionic composition. The PB ionic network undergoes significant changes, with a substantial drop in K + content, confirming that Tl + ions replace K + and occupy additional spaces within the crystal structure. These results open new opportunities in nuclear medicine applications with 201 Tl-PBNPs where the size, shape and composition of the particles can be specifically tuned depending on the desired biological properties without affecting the radiochemical performance as a vehicle for 201 Tl.

Thallium (Tl) as a prominent priority contaminant in aquatic environment necessitates rigorous regulation. However, limited horizon devotes the impact of selective oxidation on the process of thallium purification. In this study, selective active radical of singlet oxygen ( 1 O 2 ) was continually generated for Tl(Ⅰ) oxidation accomplished with efficient Tl(Ⅲ) immobilization using iron-driven copper oxide (CuFe)/peroxymonosulfate (PMS). Fe-doping changed the active center of electronic structure for enhancing the catalytic and adsorptive reactivities, and installed magnetism for solid-liquid separation. Rapid reaction rate (0.253 min -1 ) coupled with vigorous elimination efficiency (98.32%) relied on electrostatic attraction, surface complexation, and H-bond interaction. EPR and XPS analyses demonstrated that the synergistic effects of ≡ Cu(Ⅰ)/≡Cu(Ⅱ) and ≡ Fe(Ⅲ)/≡Fe(Ⅱ) redounded to the sustained generation of 1 O 2 through the pathway of PMS → •O 2 - → 1 O 2 , and 1 O 2 exploited an advantage to selectively oxidize Tl(Ⅰ) to Tl(Ⅲ). 3D isosurface cubic charts revealed that the immobilizing ability of Tl(Ⅲ) hydrate for CuFe was notably superior to that of Tl(Ⅲ) hydrate for CuO and Tl(Ⅰ) hydrate for CuO/CuFe, which further attested surface reactivity promoted stable immobilization form. This work develops the continuous generation of 1 O 2 and stable immobilization with the goal of efficiently cleansing Tl-containing wastewater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The initial rise of molecular oxygen (O 2 ) 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 O 2 was oscillatory, with multiple returns to an anoxic state until perhaps 2.2 billion years ago 1-3 . 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 shales 3 , we found lower authigenic 205 Tl/ 203 Tl 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 O 2 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., (© 2024. The Author(s), under exclusive licence to Springer Nature Limited.)

Ion channels are essential proteins for all organisms. Electrophysiology is a useful and commonly employed method to study ion channels, however there is a need for operationally simpler, cost-effective and higher throughput techniques to study ion channel functions in their native environments. Fluorescent ion indicators, such as Fluo-4 and Thallos, have been used for decades to study ion channel activity by measuring the flux of ions through channels of interest. In this work, we present ION Thallos-HTL, a thallium indicator that can be localized using HaloTag technology. This novel indicator enables specific labeling of cells and intracellular compartments in live cells and responds to changes in thallium concentration within these environments. We demonstrate the utility of ION Thallos-HTL by conducting a thallium flux assay using high-throughput instrumentation in a mixed cell population where some cells are expressing HaloTag and some are not.

Three gallium(III)- and thallium(III)-containing polyoxopalladates (POPs) have been synthesized and structurally characterized in the solid state and in solution, namely, the phosphate-capped 12-palladate nanocubes [XPd 12 O 8 (PO 4 ) 8 ] 13- (X = Ga III , GaPd 12 P 8 ; X = Tl III , TlPd 12 P 8 ) and the 23-palladate double-cube [Tl 2 III Pd 23 P 14 O 70 (OH) 2 ] 20- ( Tl 2 Pd 23 P 14 ). The cuboid POPs, GaPd 12 P 8 and TlPd 12 P 8 , are solution stable as verified by the respective 31 P, 71 Ga, and 205 Tl nuclear magnetic resonance (NMR) spectra. Of prime interest, the spin-spin coupling schemes allowed for an intimate study of the solution behavior of the Tl III -containing POPs via a combination of 31 P and 205 Tl NMR, including the stoichiometry of the major fragments of Tl 2 Pd 23 P 14 . Moreover, biological studies demonstrated the antitumor and antiviral activity of GaPd 12 P 8 and TlPd 12 P 8 , which were validated to be as efficient as cis -platinum against human melanoma and acute promyelocytic leukemia cells. Furthermore, GaPd 12 P 8 and TlPd 12 P 8 exerted inhibitory activity against two herpetic viruses, HSV-2 and HCMV, in a dose-response manner.

To overcome the temperature effect of NaI(Tl) detectors for energy spectrometry without additional hardware, a new correction method was put forward based on pulse deconvolution, trapezoidal shaping and amplitude correction, named DTSAC. To verify this method, actual pulses from a NaI(Tl)-PMT detector were measured at various temperatures from -20 °C to 50 °C. Pulse processing and spectrum synthesis showed that the position drift of the 137 Cs 662 keV peak was less than 3 keV, and the corresponding resolution at 662 keV of the sum spectra ranged from 6.91% to 10.60% with the trapezoidal width set from 1000 ns to 100 ns. The DTSAC method corrects the temperature effect via pulse processing, and needs no reference peak, reference spectrum or additional circuits. The method solves the problem of correction of pulse shape and pulse amplitude at the same time, and can be used even at a high counting rate.

Objective: The present study is aimed to enhance the efficacy of Insoluble Prussian blue (PB) in the stomach. PB formulation was developed comprising of PB in combination with pH modifying agents particularly magnesium hydroxide, calcium carbonate, sodium carbonate, and sodium bicarbonate. pH profile and the binding efficacy of the final formulation was evaluated in simulated gastric fluid (SGF)., Methods: The capsule formulation was optimized with desired in vitro characteristics. The final formulations (FF1-FF4) were evaluated for drug release, pH profile, and binding efficacy for thallium (Tl). The stability studies were performed in terms of drug assay, Fourier-transformed infrared (FTIR) spectroscopy and Thermo-gravimetric analysis (TGA). The in vivo study was performed in rats to determine the removal efficacy of optimized formulation (FF4) for Tl., Results: The PB formulation consisting of optimized PB granules and pH modifying agents showed a significant increase in the binding efficacy for Tl in SGF at an equilibrium time of 24 h. The Maximum Binding Capacity (MBC) of FF1-FF4 was found to be higher than commercially available Radiogardase ® -Cs capsules and PB granules alone in SGF. The blood Tl level in rats treated with FF4 showed three-fold decreases in the level of Tl in the blood ( C max ) and Area under Curve (AUC) as compared to the control., Conclusion: The results revealed that the developed oral PB formulation has a significantly higher efficiency of binding Tl at the acidic pH of the stomach thereby reducing its absorption into the systemic circulation. Thus, the optimized formulation of PB with pH-modifying agents is a better drug for prophylactic use in thallium ingestion.

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Thallium (Tl) is a rare earth element increasingly being used in high-technology manufacturing. It is also an emerging pollutant with high exposure and toxicity risks to aquatic ecosystems. Tl exists in the environment in a monovalent [thallous, Tl(I)] or trivalent [thallic, Tl(III)] state. Currently, the stability of the two Tl species in natural water is uncertain and the toxicity in algae and daphnia are inconsistent due to lack of robust characterization of Tl species and matrix effects, while studies with fish are sparse. In this study, larvae of medaka fish (Oryzias latipes) were dosed with environmentally relevant concentrations of Tl(I) or Tl(III) spiked into synthetic and natural river water for 7 days to observe the toxic effects of two Tl species on fish. The transformation of Tl(I) and Tl(III) in water was analyzed by high performance liquid chromatography coupled with inductively coupled plasma and mass spectrometry. Analytical and toxicity results showed that Tl(I) is more stable presenting higher mortality and bioconcentration in medaka than Tl(III) in different water matrices. Tl(I)-induced LC 50 and body burden in treated fish were highly correlated with its competitive ion, potassium (K), especially in waters containing medium K levels. This study provides reliable evidence regarding the stability and toxicity of Tl(I) and Tl(III) as well as the interaction of aqueous K versus Tl(I) in fish. Such information is useful for justifying water-quality guidelines and ecological risks of Tl pollution in natural water ecosystems., (Copyright © 2022. Published by Elsevier B.V.)

Synthesis, single-crystal X-ray determination diffraction and FT-IR, NMR ( 1 H, 13 C, 19 F and 205 Tl), UV-vis, and luminescence spectra characteristics were described for series of thallium(I) compounds: thallium(I) triflate (Tl(OTf)), 1:1 co-crystals of thallium(I) triflate and tropolone (Htrop), Tl(OTf)·Htrop, as well as simple thallium(I) chelates: Tl(trop) ( 1 ), Tl(5-metrop) ( 2 ), Tl(hino) ( 3 ), with Htrop, 5-methyltropolone (5-meHtrop), 4-isopropyltropolone (hinokitiol, Hhino), respectively, and additionally more complex {Tl@[Tl(hino)] 6 }(OTf) ( 4 ) compound. Comparison of their antimicrobial activity with selected lead(II) and bismuth(III) analogs and free ligands showed that only bismuth(III) complexes demonstrated significant antimicrobial activity, from two- to fivefold larger than the free ligands.

Among transition and non-transition metals, thallium is a unique case of an element which, despite its known toxicity, provides interesting challenges through its biology and chemistry linked to diagnosis of human pathophysiologies. Poised to investigate in-depth the structural and electronic aspects of thallium involvement in physiological processes, the synthetic exploration of aqueous binary systems of Tl(I) with physiological binders from the family of hydroxycarboxylic acids (glycolic, lactic, mandelic and citric acid) was pursued in a pH-specific fashion. The isolated crystalline coordination polymers, emerging from that effort, were physicochemically characterized through elemental analysis, FT-IR, ESI-MS, 1 H-/ 13 C-NMR, and X-ray crystallography. The coordination environment of thallium in each molecular Tl(I) assembly, along with lattice dimensionality (2D3D), reflects the contributions of the ligands, collectively exemplifying interactions probed into though BVS and Hirshfeld surface analysis. The results portray a well-defined solid-state and solution profile for all species investigated, thereby providing the basis for their subsequent selection into in vitro biological studies involving the (patho)physiological cell lines 3T3-L1, Saos-2, C2C12, and MCF-7. Biotoxicity profiles, encompassing cell viability, morphology, and cell growth support clearly a concentration-, time-, and cell tissue-specific behavior for the chosen Tl(I) compounds in a structure-specific fashion. Collectively, the chemical experimental data support the biological results in formulating a structure-specific behavior for Tl(I)-hydroxycarboxylato species with respect to biotoxicity mechanisms in a (patho)physiological environment. The accrued knowledge stands as the foreground for further investigation into the relevant biological chemistry of Tl(I) and molecular technologies targeting its sequestration and removal from cellular media., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Three novel Tl(III) complexes (C1), (C2) and (C3) were synthesized using the one-pot reactions of pyridine dicarboxylic acid derivatives, 2-aminobenzimidazole and/or 4-aminopyridine, and also thallium(III) nitrate trihydrate metal salt. The structure of all three complexes was determined by the single-crystal X-ray diffraction. C1 and C2 were realized to be isostructural with disordered square anti-prismatic geometry and for C3 arrangement of the distorted tricapped triangular prism was proposed. Cyclic voltammetry measurements on the complexes exhibited that formal potential values are more positive for C1 (E 0 ' 0.109 V) and C3 (E 0 ' 0.244 V) compared to C2 (E 0 ' -0.051 V), versus Ag/AgCl under argon. Moreover, cytotoxicity of the compounds was evaluated in vitro against two cancer cell lines including a human melanoma (A375), a human colon adenocarcinoma (HT29), and also one normal cell human foreskin fibroblast (HFF). The selective and potent cytotoxicity effect was exhibited by C1 and C3 on cancer cell lines. The apoptosis through a caspase-dependent mitochondrion pathway was confirmed by ROS production, MMP reduction, p53 activation, Bax up-regulation, and Bcl-2 down-regulation, cytochrome c release, procaspase-9, and 3 expression, for A375 cells treated to C1 and C3. According to similar cellular uptake of the complexes in A375 cell line, the generation of ROS was considered as an effective agent to justify the inhibition effect C1 and C3 on mentioned cells. Furthermore, arresting the cell cycle in the G2-M phase and inducing apoptosis were indicated by these two complexes., (© 2021. The Author(s).)

Background: A gamma probe is a handheld device used for intraoperative interventions following interstitial injection of a radiotracer to locate regional lymph nodes through the external detection of radiation. This work reports on the design and performance evaluation of a novel fully integrated gamma probe (GammaPen), recently developed by our group., Materials and Methods: GammaPen is an all-in-one pocket gamma probe with low weight and adequate dimensions, consisting of a detector, a control unit and output all together. The detector module consists of a cylindrical Thallium-activated Cesium Iodide [CsI (Tl)] crystal optically coupled to a Silicon photomultiplier (SiPM), shielded using Tungsten housing on side and back faces. The electronics of the probe consists of two small boards to handle signal processing and analog peak detection tasks. A number of parameters, including probe sensitivity in air/water, spatial resolution in air/water, angular resolution in air/water, and side and back shielding effectiveness, were measured to evaluate the performance of the probe based on NEMA NU3-2004 standards., Results: The sensitivity of the probe in air at distances of 10, 30, and 50 mm is 18784, 3500, and 1575 cps/MBq. The sensitivity in scattering medium was also measured at distances of 10, 30, and 50 mm as 17,680, 3050, and 1104 cps/MBq. The spatial and angular resolutions in scattering medium were 47 mm and 87 degree at 30 mm distance from the probe, while they were 40 mm and 77 degree in air. The detector shielding effectiveness and leakage sensitivity are 99.91% and 0.09%, respectively., Conclusion: The performance characterization showed that GammaPen can be used effectively for sentinel lymph node localization. The probe was successfully used in several surgical interventions by an experienced surgeon confirming its suitability in a clinical setting.

Assessing the position of the Bragg peak (BP) in hadron radiotherapy utilizing prompt-gamma imaging (PGI) presents many challenges in terms of detector physics. Gamma detectors with the capability of extracting the best energy, timing, and spatial information from each gamma interaction, as well as with high detection efficiency and count rate performance, are needed for this application. In this work we present the characterization of a pixel Čerenkov charge induction (CCI) thallium bromide (TlBr) detector in terms of energy and and electron drift time for its potential use in PGI. The CCI TlBr detector had dimensions of 4 × 4 × 5 mm 3 and one of its electrodes was segmented in pixels with 1.7 mm pitch. A silicon photomultiplier (SiPM) was optically coupled to one of the faces of the TlBr slab to read out the Čerenkov light promptly emitted after the interaction of a gamma ray. The detector was operated stand-alone and the 1.275 prompt gammas from a 22 Na radioactive source were used for the study. The electron drift time was obtained by combining the Čerenkov and charge induction signals and then used as a measure of the depth of interaction. The electron mobility in TlBr was estimated as ∼27 cm 2 V -1 s -1 . Energy resolutions between 3.4% and 4.0% at 1.275 MeV were obtained after depth-correction. These values improved to 3.0%-3.3% when events with drift times of 3-6 μs were selected. These results show the potential of pixel CCI TlBr detectors to resolve gamma interactions in the detector with mm-like accuracy in 3D and with excellent energy resolution. Previous studies with CCI TlBr devices have shown a timing resolution of <400 ps full width at half maximum when detecting 511 keV gamma rays, therefore, the timing accuracy is expected to improve with the increased energy of the gamma rays in PGI. While other important detector characteristics such as count rate capability remain to be studied, results from this work combined with other preliminary data show pixel CCI detectors can simultaneously provide excellent energy, timing, and spatial resolution performance and are a very promising option for PGI in hadron therapy.

Seeking to enrich the yet less explored field of scorpionate complexes bearing antioxidant properties, we, here, report on the synthesis, characterization and assessment of the antioxidant activity of new complexes derived from three scorpionate ligands. The interaction between the scorpionate ligands thallium(I) hydrotris(5-methyl-indazolyl)borate (TlTp 4Bo,5Me ), thallium(I) hydrotris(4,5-dihydro-2H-benzo[g]indazolyl)borate (TlTp a ) and potassium hydrotris(3- tert -butyl- pyrazolyl)borate (KTp t Bu ), and metal(II) chlorides, in dichloromethane at room temperature, produced a new family of complexes having the stoichiometric formula [M(Tp 4Bo,5Me ) 2 ] (M = Cu, 1 ; Zn, 4 ; Cd, 7 ), [M(Tp a ) 2 ] (M = Cu, 2 ; Zn, 5 ; Cd, 8 ), [Cu(Hpz t Bu ) 3 Cl 2 ] ( 3 ), [Zn(Tp tBu )Cl] ( 6 ) and [Cd(Bp t Bu )(Hpz t Bu )Cl] ( 9 ). The obtained metal complexes were characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance and elemental analysis, highlighting the total and partial hydrolysis of the scorpionate ligand Tp t Bu during the synthesis of the Cu(II) complex 3 and the Cd(II) complex 9 , respectively. An assessment of the antioxidant activity of the obtained metal complexes was performed through both enzymatic and non-enzymatic assays against 1,1-diphenyl-2-picryl- hydrazyl (DPPH · ), 2,2'-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS + · ), hydroxyl (HO · ), nitric oxide (NO · ), superoxide (O 2 - ) and peroxide (OOH · ) radicals. In particular, the complex [Cu(Tp a ) 2 ]⋅0.5H 2 O ( 2 ) exhibited significant antioxidant activity, as good and specific activity against superoxide (O 2 -· ), (IC50 values equal to 5.6 ± 0.2 μM) and might be identified as auspicious SOD-mimics (SOD = superoxide dismutase).

Although compounds of the formula AMoO 2 F 3 (A = K, Rb, Cs, NH 4 , Tl) have been known for decades, crystal structures have only been reported for CsMoO 2 F 3 and NH 4 MoO 2 F 3 . The three compounds (Rb/NH 4 /Tl)MoO 2 F 3 are isostructural and crystallize in the centrosymmetric space group C 2 /c (No. 15). The compounds contain the MoO 2 F 3 - anionic chain, composed of corner-sharing MoO 2 F 4 octahedra, with Mo 6+ coordinated by two cis bridging fluoride anions that are trans to terminal oxide anions. The MoO 2 F 3 - chain has a very unusual and complex chain structure; a single chain contains alternating zigzag and helical sections. These helical regions alternate in chirality along the chain, and thus the chains exhibit periodic tendril perversion. To the best of the authors' knowledge, no other materials with a similar chain structure have been reported. On the other hand, KMoO 2 F 3 is noncentrosymmetric and chiral, crystallizing in the enantiomorphic space group P 2 1 2 1 2 1 (No. 19). KMoO 2 F 3 also contains the MoO 2 F 3 - anionic chain. However, the chain is helical, with only one enantiomer present, resulting in a chiral, noncentrosymmetric structure.

Adding chelating agents is a critical technique of heavy metal activation for enhancing phytoextraction through the formation of soluble metal complexes which will be more readily available for extraction. The preliminary, dynamic, equilibrium activation experiments and speciation analysis of Pb, Cd and Tl in contaminated red soils were used to select six chelates with relatively good activation performance from nine chelates, and the effects of dosage and pH on the heavy metals activation were studied systematically. Results showed that the activation of Pb, Cd and Tl by chelates reached equilibrium within 2 h, and the activation process showed three stages. Under neutral conditions, chelates had better activation performance on Pb- and Cd-contaminated soils. Except for S,S-ethylenediamine disuccinic acid (S,S-EDDS) and citric acid (CA), the maximum equilibrium activation effect (MEAE) of ethylenediaminetetraacetic acid (EDTA), N,N-bis (carboxymethyl) glutamic acid (GLDA), diethylenetriaminepentaacetic acid (DTPA) and aminotriacetic acid (NTA) was over 81%. The MEAE of Tl-contaminated soil was less than 15%. The decreasing order of the dosage of chelating agents corresponding to MEAE for three types of contaminated soils was Pb-, Cd- and Tl-contaminated soil, relating to the forms of heavy metals, the stability constants of metal-chelates and the activation of non-target elements Fe in red soil. Under acidic conditions, the activation efficiencies of chelates decreased to differing degrees in Pb- and Cd-contaminated soils, whereas the activation efficiencies of chelating agents in Tl-contaminated soils were slightly enhanced.

The development of efficient and regenerable adsorbent coupled with advanced oxidation for enhanced thallium (Tl) removal has been a recent focus on wastewater treatment. In this study, a magnetite-based biochar derived from watermelon rinds was synthesized and used as a sustainable adsorbent and catalyst for hypochlorite oxidation and removal of Tl(I) from wastewater. The addition of hypochlorite substantially enhanced the Tl(I) removal under normal pH range (6-9). Maximum Tl adsorption capacity of 1123 mg/g was achieved, which is 12.3% higher than the highest value previously reported. The magnetic biochar can be regenerated using 0.1 mol/L HNO 3 solution for elution in only 5 min, with a Tl desorption efficiency of 78.9%. The Tl removal efficiency was constantly higher than 98.5% during five consecutive recycle tests, indicating the effective reuse performance of the adsorbent. Oxidation, surface precipitation, pore retention and surface complexation were the main mechanisms for Tl(I) removal. The re-dissolution of Tl compounds and ion exchange of Tl cations with proton were the main mechanisms for adsorbent regeneration. Given the fast oxidation rate, high adsorption capacity, steady reusability and facile separability, this magnetic biochar-hypochlorite technique is a promising means for Tl(I) removal from wastewater. The catalytic hypochlorite oxidation induced by the magnetic biochar has also great potential to the effective removal of other pollutants., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Enriched levels of thallium (Tl) in the environment are not only derived from anthropogenic sources but also have potential natural origins owing to Tl-rich sulphide mineralization. However, little is known regarding the geochemical fractionations of Tl in contaminated soils from geogenic sources. This study aims to reveal the Tl geochemical fractionations in different types of soils from a large-scale independent Tl mine in southwestern China, via a modified Institute for Reference Materials and Measurement (IRMM) sequential extraction (four-step) scheme. The results revealed that a large percentage of Tl was related to the labile portions (including reducible, weak-acid-exchangeable, and oxidizable fraction) of the soils (68.8-367 mg kg -1 ). Further analyses by Scanning Transmission Electron Microscopy-Energy Dispersive X-ray Spectrometer (STEM-EDS) found that Tl mainly existed in the Fe-containing minerals (such as jarosite and hematite) with fine particles (∼1 μm). These results highlight that, apart from the anthropogenically induced Tl pollution, the naturally occurring Tl contamination in soils may also pose significant risks to human health and ecological safety. Owing to the relatively high mobility and bioavailability of Tl in the labile fractions, it is important to understand geochemical fractionations of this element for alleviating Tl pollution and effective management of naturally occurring Tl contaminated soils., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

One of the authors (O.K.) stayed in the area located ~110 km south from the Fukushima Daiichi Nuclear Power Plant during the arrival of radioactive plumes released into the environment due to the accident in March 2011 in Japan. A previous study determined his 131I thyroid content using an NaI(Tl) spectrometer. The one remaining issue was to investigate the measurement error due to inevitable differences in the configuration (e.g. the thyroid shape and volume) between the physical phantom employed for calibration of the spectrometer and the real subject. In the present study, Monte Carlo simulations for the thyroid measurements were performed using the Monte Carlo N-Particle (MNCP) code to investigate discrepancies in peak efficiencies of the spectrometer between the personalised voxel phantom created from O.K.'s magnetic resonance images and the several typical/reference phantoms that exist. As a result, the peak efficiencies for the Oak Ridge Institute of Nuclear Studies (ORINS) phantom were found to be comparable to those for the reference voxel phantoms reproducing realistic human anatomy (the Adult Male phantom and the Japanese Male phantom). The peak efficiency for the personalised phantom, on the other hand, was fairly close to that of the other physical phantom (the Transfer phantom) actually used for the calibration of the spectrometer, suggesting that the 131I thyroid content determined for him in the previous study was sufficiently accurate. The discrepancies of peak efficiencies at the primal photon energy of 131I (365 keV) among the different phantoms were improved by extending the distance between the neck and the spectrometer; however, the appropriate measurement geometry in an actual situation will depend on the primary purpose of the measurements and should be determined accordingly., (© The Author(s) 2019. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

In this study, the full energy peak count rates to radioactivity conversion factors of 3″Ø × 3″ NaI(Tl) and 2″Ø × 2″ LaBr3(Ce) detectors for radioactivity analysis in the soil were determined on site using a semi-empirical method with point-like gamma-ray sources. To validate the conversion factors derived for the detectors, in-situ gamma-ray measurements were performed in wide open fields with almost flat surface and compared with the sampling analysis for the radioactivity of U-series, Th-series, and 40K in the soil. As a result, radioactivity concentrations of 40K, 208Tl and 214Bi by in-situ and laboratory measurements agreed well with each other within 5%, and the MDAs for artificial radionuclides were estimated under the condition of fresh deposition considering a radiation emergency situation., (© The Author(s) 2019. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

Analysis of the content of As, Cd and Tl accompanying Zn-Pb ores was performed using soil material sampled around the zinc-works in Miasteczko Śląskie. It was found that the total content of As, Cd and Tl was considerably higher than the values recorded at the same sites 20 years earlier. This clearly confirms considerable pollution of the environment which continues despite pro-ecological actions taken by the zinc-works. The analysis of the spatial distribution of pollution revealed that the zinc-works itself is no longer the main source of contamination as was the case in 1998. Instead, in 2018 the main sources of As, Cd and Tl emissions were the erosion and deflation processes in old, unprotected mining and industrial waste dumps located near the zinc-works. The most polluted soil layers are the top layers in the soil profile. The content of As, Cd and Tl determined in them was 10 times greater than in the deep layers. There was also a positive change in environmental conditions, which occurred over the preceding 20 years, namely an increase in the content of sparingly soluble fractions, fractions bound with organic matter, and residual fractions. It was also found that depending on the geochemical background and readily mobile fraction values used in the calculations, there is still very high contamination and very high ecological risk with respect to As, Cd and Tl after 20 years. However, when using the quantity of phytoavailable elements as well as the quantity of cations on ion exchange positions and bound to carbonates to calculate the risk assessment code, the analysis showed that environmental conditions improved., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Thallium as a highly toxic metal element has been listed as one of priority drinking water contaminants. In this study, manganese oxide nanoparticles were synthesized through a simple hydrothermal method and applied for the removal of thallium(I). The adsorbent was composed of numerous needle-like nanorods and had an average volume diameter of 230 nm after heat-drying procedure. The crystal form of adsorbent was determined as α-MnO 2 . The adsorbent exhibited a much faster adsorption rate than most of previously reported adsorbent, achieving over 66.4% of equilibrium adsorption capacity in the first 10 min. The adsorption process was found to be highly affected by solution pH and higher than 100 mg/g of adsorption capacity could be obtained in a wide pH range of 6.0-10.0. The isotherm study indicated that the adsorption of Tl(I) on the adsorbent was favorable and governed by a chemisorption process, with the maximum adsorption capacity of 505.5 mg/g at pH 7.0. The adsorption process was confirmed to be thermodynamically spontaneous and endothermic. The presence of Na + , K + , Mg 2+ , Ca 2+ , and Cu 2+ cations had certain negative effects on the uptake of Tl(I). Based on the batch experiments and XPS analysis, the deprotonated hydroxyl groups that bonded to manganese atoms worked as the binding sites for the effective removal of Tl(I) ions and no redox reaction occurred during the adsorption process.

TREK2 (KCNK10, K 2P 10.1) is a two-pore domain potassium (K2P) channel and a potential target for the treatment of pain. Like the majority of the K2P superfamily, there is currently a lack of useful pharmacological tools to study TREK2. Here we present a strategy for identifying novel TREK2 activators. A cell-based thallium flux assay was developed and used to screen a library of drug-like molecules, from which we identified the CysLT1 antagonist Pranlukast as a novel activator of TREK2. This compound was selective for TREK2 versus TREK1 and showed no activity at TRAAK. Pranlukast was also screened against other members of the K2P superfamily. Several close analogues of Pranlukast and other CysLT1 antagonists were also tested for their ability to activate K2P channels. Consistent with previous work, structure activity relationships showed that subtle structural changes to these analogues completely attenuated the activation of TREK2, whereas for TREK1, analogues moved from activators to inhibitors. Pranlukast's activity was also confirmed using whole-cell patch clamp electrophysiology. Studies using mutant forms of TREK2 suggest Pranlukast does not bind in the K2P modulator pocket or the BL-1249 binding site. Pranlukast therefore represents a novel tool by which to study the mechanism of TREK2 activation., (Copyright © 2019 The Authors. Published by Elsevier Inc. All rights reserved.)

Because of its high toxicity, thallium (Tl) causes environmental pollution even at very low concentrations. Despite its extremely high environmental risk, limited information about Tl removal from water is present on the literature. This work focused on the use of an eco-friendly and low-cost Ilex paraguariensis (yerba mate) biowaste to remove Tl from environmental water samples. Raw (YM) and L-cysteine chemically modified yerba mate (YM@LC) were used. The effect of pH and biosorbent concentration on the biosorption capacity was studied using an experimental design. The optimal experimental conditions were as follows: YM concentration 0.25 g L -1 , pH 6.0, and YM@LC concentration 0.25 g L -1 , pH 4.0. Kinetic studies yielded data that were in accordance with pseudo-second-order model. Equilibrium studies were also developed and indicated that the most appropriate model was that of Sips, with a maximum capacity of biosorption at 328 K of 333.4 mg g -1 for YM and 384.4 mg g -1 for YM@LC. The thermodynamic evaluation exhibited an endothermic, spontaneous, and favorable biosorption for both biosorbents. YM and YM@LC showed significant potential for Tl removal from environmental water samples.

There has been a long-standing discussion in the scientific literature on the thallium (Tl) binding capacity of ferric hexacyanoferrate (insoluble) and potassium hexacyanoferrate (soluble) forms of Prussian blue (PB). The literature sometime suggests that the soluble form of PB should be used to treat thallium poisoning, instead of the FDA approved insoluble form of PB. The literature debate is further complicated by the lack of fundamental characterization data such as critical quality attributes (CQAs) that clearly define the analog forms. The purpose of this study is to compare, the binding capacity of soluble and insoluble PB analogs with the same CQAs (particle size/distribution and water content). Water content and particle size/particle distribution were determined by TGA, and solid-state laser diffraction particle sizing. Thallium binding studies were conducted at physiological pH to determine the maximal binding capacity (MBC) at equilibrium. Multiple linear regression and principal component analysis was also used for multivariate data analysis. Results indicate that insoluble and soluble analogs, with similar quality attributes, have nearly identical, MBC binding capacities of (441.5 mg/g) for insoluble vs soluble (458.4 mg/g). However, when both analog forms with different CQAs such as water, particle size were compared, results indicated significantly higher or lower thallium binding levels. In conclusion, it is essential that the FDA approved iron form with well-defined CQAs is used to treat thallium poisoning and radioactive thallium metal contamination for consistent therapeutic outcomes., (Published by Elsevier B.V.)

Experiments were performed with 30 11 cm × 42.5 cm × 5.5 cm NaI(Tl) detectors to better understand their positional response. Spectra were collected using 0.02 to 0.15 MBq point sources of Am, Cs, Co, and Ba positioned on lines parallel and perpendicular to the long axis of the crystal along both the narrow and wide detector faces as well as at different distances from them. A greater density of positions was sampled at the ends of the detector, and repeated measurements were made to examine potential gain drifts during the experiment. Spectroscopic peak counts, spectroscopic pulse heights, and net counts were analyzed. Empirical equations were fit to the aforementioned data for each specific source energy as a function of source position. In addition, a Monte Carlo radiation transport code was used to simulate the expected positionally variable response based solely upon radiation absorption. The simulated radiation transport efficiency functions were compared to the experimental data. The effects of the geometric radiation efficiency, the attenuation and scattering of emitted light within the scintillation crystal, and combined effects such as nonuniformity of the photomultiplier tube, photocathode response, and crystal irregularities were then distinguished. Functions describing each effect were derived. The results suggest potential new corrections to data obtained with large scintillation detectors as well as a novel approach to partial positional gamma-ray detection with minimal collimation, given that the energy resolution is within reason for particular photopeaks.

Thallium bromide (TlBr) is a semiconductor material and, simultaneously, a good Cerenkov radiator. The performance of a TlBr detector that integrates two different readouts, the charge induction readout and the detection of Cerenkov light, was evaluated. A TlBr detector with dimensions of 4  ×  4  ×  5 mm 3 , with a monolithic cathode and an anode segmented into strips, was manufactured. One of the bare and polished 4  ×  4 mm 2 faces of the detector was coupled to a silicon photomultiplier (SiPM) to read out the Cerenkov light. Simultaneous timing and energy resolutions of  <400 ps full width at half maximum (FWHM) and ~8.5% at 511 keV were measured using the Cerenkov detection and charge induction readouts, respectively. A coincidence time resolution of 330 ps was obtained when selecting Cerenkov events with amplitudes above 70 mV. The combination of both readouts showed the potential to resolve the depth-of-interaction (DOI) positioning, based on the improvement of energy resolution when selecting events with similar electron drift times. This manuscript sets the stage for a new family of semiconductor detectors that combine charge induction readout with the Cerenkov light detection. Such detectors can provide, simultaneously, outstanding timing, energy, and spatial resolution, and will be an excellent fit for applications that require the detection of high-energy gamma photons with high timing accuracy, such as time-of-flight positron emission tomography (TOF-PET) and prompt gamma imaging (PGI) to assess the particle range in hadron therapy.

We studied thallium (Tl) isotope fractionation in white mustard grown hydroponically at different Tl doses. Thallium isotope signatures in plants indicated preferential incorporation of the light 203 Tl isotope during Tl uptake from the nutrient solution. Negative isotope fractionation was even more pronounced in dependence on how much the available Tl pool decreased. This finding corresponds to the concept of isotope overprinting related to a high contamination level in the growing media (solution or soil). Regarding Tl translocation in plants, we observed a large Tl isotope shift with an enrichment in the heavy 205 Tl isotope in the shoots relative to the roots in treatments with low/moderate solution Tl concentrations (0.01/0.05 mg Tl/L), with the corresponding α 205/203 Tl fractionation factors of ˜1.007 and 1.003, respectively. This finding is probably a consequence of specific (plant) reactions of Tl replacing K in its cycle. The formation of the S-coordinated Tl(I) complexes, potentially affecting both Tl accumulation and Tl isotope fractionation in plants, however, was not proven in our plants, since we did not have indication for that on the basis of X-ray absorption spectroscopy, suggesting that Tl was mainly present as free/hydrated Tl + ion or chemically bound to O-containing functional groups., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Chelators including DTPA (diethylene triamine pentaacetic acid) and oxalic acid were selected for inducing phytoextraction of heavy metals (HMs) from Pb-, Tl-, and Pb-Tl- contaminated soil, in which heavy metals leakage was highly remarkable. Results showed that compared with the control group without chelating agent under planting conditions, the extraction efficiency (i.e., uptake coefficient) of Pb, Tl increased by 86%, 43% from Pb-Tl- contaminated soil in the presence of oxalic acid, and there was no significant change in heavy metal leakage under rainfall conditions. It was the best phytoremediation scheme in this work. Under rainfall conditions, the HMs concentration in the leachate showed a linear decreasing trend. Acid rain promoted the leakage of heavy metals, and the average leached amount of Tl increased by 1.47 times under acid rain conditions. However, for Pb, DTPA was the main influencing factor, followed by acid rain.

Thallium (Tl) is a very toxic heavy metal. As a part of ongoing investigations, the mobility, sources and fate of Tl were investigated for sediments from a watershed in the northern part of the Pearl River, South China, whose catchment has been seriously impacted by large-scale PbZn smelting activities onshore. A wide dispersion of severe Tl contamination was observed throughout the depth profiles. A modified IRMM (Institute for Reference Materials and Measurements, Europe) sequential extraction procedure of a selected depth profile uncovered an exceptionally high enrichment of Tl in geochemically-mobile fractions (i.e., weak-acid-exchangeable, reducible and oxidizable fractions), on average 5.94 ± 2.19 mg/kg (74.6% ± 5.1% of the total Tl content) not only in the surface sediments but also in deep sediments. The proximal quantitative source apportionment using Pb isotopic fingerprinting technique indicated that a majority (80%-90%) of Tl contamination along the depth profiles is anthropogenically derived from the PbZn smelting wastes. The results highlight the pivotal role of smelting activities in discharging huge amounts of geochemically-mobile Tl to the sediments down to approximately 1 m in length, which is quantitatively evidenced by Pb isotopic tracing technique. Lead isotopes combined with distribution of Tl and Pb contents identified a potential marker for a point source from the PbZn smelter in the river catchment, which also provides a theoretical framework for source apportionment of metal contamination in a larger river/marine system and in other sulfide mining/smelting areas likewise., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Thallium (Tl) and its compounds are non-essential and highly toxic for living organisms, even at low concentrations. In this paper, we analyzed the presence and geochemical distribution of Tl in different mining-metallurgical and sediment samples collected from several mining zones of Mexico. A modified BCR sequential extraction procedure was also applied to the samples to investigate the geochemical behavior and potential environmental risk of Tl according to types of ore deposit and mineral processing method applied. Results revealed the presence of Tl in the majority of the mining-metallurgical samples, with labile concentrations reaching up to values of 184.4 mg kg -1 , well above the environmental standards. A comparison of Tl partitioning in different samples showed that Tl was usually found associated with labile fractions instead of entrapped in the environmentally-passive residual fraction. Specifically, high levels of Tl were extracted from the exchangeable/acid-extractable and poorly-crystalline reducible fractions, suggesting its association with both soluble and amorphous Fe-Mn oxyhydroxides, respectively. Besides, Tl was also frequently found associated with the crystalline reducible fraction, presumably bonded to manganese oxides and jarosite-like minerals. Lastly, little amounts of Tl were extracted from the oxidizable fraction. Considering the fractionation of Tl in these mining-metallurgical samples, they may pose a significant environmental hazard. This study provides useful insights into the potential sources of Tl pollution in Mexico and emphasizes the need for further research to determine the extent of its impact and to develop effective remediation protocols to protect the environment from Tl toxicity., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Cytosolic distributions of nonessential metals Cd and Tl and seven essential elements among compounds of different molecular masses were studied in the liver of brown trout (Salmo trutta) from the karstic Krka River in Croatia. Analyses were done by size exclusion high performance liquid chromatography and high resolution inductively coupled plasma mass spectrometry. Common feature of Cd and Tl, as highly toxic elements, was their distribution within only two narrow peaks. The increase of cytosolic Cd concentrations was reflected in marked increase of Cd elution within low molecular mass peak (maximum at ∼15 kDa), presumably containing metallothioneins (MTs), which indicated successful Cd detoxification in brown trout liver under studied exposure conditions. Contrary, the increase of cytosolic Tl concentrations was reflected in marked increase of Tl elution within high molecular mass peak (maximum at 140 kDa), which probably indicated incomplete Tl detoxification. Common feature of the majority of studied essential elements was their distribution within more peaks, often broad and not well resolved, which is consistent with their numerous physiological functions. Among observed associations of essential metals/nonmetal to proteins, the following could be singled out: Cu and Zn association to MTs, Fe association to storage protein ferritin, and Se association to compounds of very low molecular masses (<5 kDa). The obtained results present the first step towards identification of metal-binding compounds in hepatic cytosol of brown trout, and thus a significant contribution to better understanding of metal fate in the liver of that important bioindicator species., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

In order to investigate the release of aluminium ions from food contact materials, three different types of uncoated aluminium menu trays for single use were tested with the foodstuffs sauerkraut juice, apple sauce and tomato puree, as well as with the food simulants 5 g/L citric acid solution and artificial tap water. To mimic a consumer relevant exposure scenario, the aluminium trays were studied using time and temperature gradients according to the Cook & Chill method, also taking into account storage time at elevated temperatures during the delivery period. The release of aluminium was found to exceed the specific release limit (SRL) of 5 mg aluminium per kilogram of food specified by the Council of Europe by up to six times. Furthermore, a release of thallium was also detected unexpectedly. Kinetic studies showed a comparable behaviour in the release of aluminium, manganese and vanadium as components of the aluminium alloy itself. In contrast, thallium could be identified as a surface contaminant or impurity because of an entirely different kinetic curve. Kinetic studies also allowed activation energy calculations. Additional camping saucepans were tested as an article for repeated use. In three subsequent release experiments with citric acid (5 g/L), artificial tap water and tomato puree as benchmark foodstuffs, the results were comparable to those of the uncoated wrought alloy aluminium trays., Competing Interests: The authors have declared that no competing interests exist.

Thallium bromide (TlBr) is a promising semiconductor detector material for positron emission tomography (PET) because it can offer very good energy resolution and 3D segmentation capabilities, and it also provides detection efficiency surpassing that of commonly used scintillators. Energy, timing, and spatial resolution were measured for thin (<1 mm) TlBr detectors. The energy and timing resolution were measured simultaneously for the same planar 0.87 mm-thick TlBr device. An energy resolution of (6.4  ±  1.3)% at 511 keV was achieved at  -400 V bias voltage and at room temperature. A timing resolution of (27.8  ±  4.1) ns FWHM was achieved for the same operating conditions when appropriate energy gating was applied. The intrinsic spatial resolution was measured to be 0.9 mm FWHM for a TlBr detector with metallic strip contacts of 0.5 mm pitch. As material properties improve, higher bias voltage should improve timing performance. A stack of thin detectors with finely segmented readout can create a modular detector with excellent energy and spatial resolution for PET applications.

Although thallium (Tl) is a highly toxic element, little information is available on the environmental risks of Tl in agricultural soils with intensive practices, particularly nearby mining sites. Therefore, we investigated the potential release of Tl in acidic soils with intensive cultivation nearby a waste copper mining site from southern China based on its level and chemical fractions as well as simulated release under artificial acid rain. Results showed that the average Tl content was 1.31 mg/kg in the studied area, which significantly exceeds the permissible thallium value of 1 mg/kg for agricultural soil in China. Some vertical increases of soil Tl from different land uses indicate the potential transport of Tl downward to groundwater. High positive correlations between surficial soil Tl and rubidium (Rb) and copper (Cu) indicated that Tl has the lithophile and chalcophile behavior. Tl in soils is mainly entrapped in residual fraction. The exchangeable fraction of Tl in agricultural soils was less than undisturbed natural soils and copper mined soils. Additionally, the percentage of Tl release from undisturbed natural soils and soils of copper ore area was more than that from agricultural soils in simulated acid rain. Furthermore, the releases of Tl from the soils increased with the acidity of artificial acid rain. Thus, more attention must be paid to land management of this similar area to avoid the risk of Tl impact on human health.

In SPECT/CT systems x-ray and γ-ray imaging is performed sequentially. Simultaneous acquisition may have advantages, for instance in interventional settings. However, this may expose a gamma camera to relatively high x-ray doses and deteriorate its functioning. We studied the NaI(Tl) response to x-ray pulses with a photodiode, PMT and gamma camera, respectively. First, we exposed a NaI(Tl)-photodiode assembly to x-ray pulses to investigate potential crystal afterglow. Next, we exposed a NaI(Tl)-PMT assembly to 10 ms LED pulses (mimicking x-ray pulses) and measured the response to flashing LED probe-pulses (mimicking γ-pulses). We then exposed the assembly to x-ray pulses, with detector entrance doses of up to 9 nGy/pulse, and analysed the response for γ-pulse variations. Finally, we studied the response of a Siemens Diacam gamma camera to γ-rays while exposed to x-ray pulses. X-ray exposure of the crystal, read out with a photodiode, revealed 15% afterglow fraction after 3 ms. The NaI(Tl)-PMT assembly showed disturbances up to 10 ms after 10 ms LED exposure. After x-ray exposure however, responses showed elevated baselines, with 60 ms decay-time. Both for x-ray and LED exposure and after baseline subtraction, probe-pulse analysis revealed disturbed pulse height measurements shortly after exposure. X-ray exposure of the Diacam corroborated the elementary experiments. Up to 50 ms after an x-ray pulse, no events are registered, followed by apparent energy elevations up to 100 ms after exposure. Limiting the dose to 0.02 nGy/pulse prevents detrimental effects. Conventional gamma cameras exhibit substantial dead-time and mis-registration of photon energies up to 100 ms after intense x-ray pulses. This is due PMT limitations and due to afterglow in the crystal. Using PMTs with modified circuitry, we show that deteriorative afterglow effects can be reduced without noticeable effects on the PMT performance, up to x-ray pulse doses of 1 nGy.

Gamma ray spectroscopy enables the identification of radioactive sources, and, with proper calibration, their activities. In use since the 1950s, NaI(Tl) spectroscopic systems remain popular due to their affordability and high detection efficiency. The crystals and accompanying electronics may vary, and there are practical choices necessary to produce the best possible spectra for a given application or correctly interpret system performance. An overview of the scintillation mechanism as well as the common features of a gamma ray spectrum are presented in this paper. This includes a discussion of the impacts of the size and shape of detector crystals on the spectrum and counting efficiency. A description of supporting electronics is included along with techniques for arranging and optimizing them. Coaxial cables become part of the circuit and can degrade the detector signal if they have mismatched impedance or excessive length. A discussion is included of tradeoffs involved in selecting combinations of individual electronics components for NaI(Tl) spectroscopic applications. Lastly, a comprehensive energy calibration procedure is provided. This paper thus serves as a tutorial on several practical aspects of a NaI(Tl) gamma ray spectroscopy system.

Thallium (Tl) is a toxic heavy metal that causes oxidative stress both in vitro and in vivo. In this work, we evaluated the production of oxygen (ROS)- and nitrogen (RNS)-reactive species in adherent PC12 (PC12adh) cells exposed for 0.5-6 h to Tl(I) or Tl(III) (10-100 µM). In this system, Tl(I) induced mostly H 2 O 2 generation while Tl(III) induced H 2 O 2 and ONOO ·- generation. Both cations enhanced iNOS expression and activity, and decreased CuZnSOD expression but without affecting its activity. Tl(I) increased MnSOD expression and activity but Tl(III) decreased them. NADPH oxidase (NOX) activity remained unaffected throughout the period assessed. Oxidant levels returned to baseline values after 6 h of incubation, suggesting a response of the antioxidant defense system to the oxidative insult imposed by the cations. Tl also affected the glutathione-dependent system: while Tl(III) increased glutathione peroxidase (GPx) expression and activity, Tl(I) and Tl(III) decreased glutathione reductase (GR) expression. However, GR activity was mildly enhanced by Tl(III). Finally, thioredoxin-dependent system was evaluated. Only Tl(I) increased 2-Cys peroxiredoxins (2-Cys Prx) expression, although both cations increased their activity. Tl(I) increased cytosolic thioredoxin reductase (TrxR1) and decreased mitochondrial (TrxR2) expression. Tl(III) had a biphasic effect on TrxR1 expression and slightly increased TrxR2 expression. Despite of this, both cations increased total TrxR activity. Obtained results suggest that in Tl(I)-exposed PC12adh cells, there is an early response to oxidative stress mainly by GSH-dependent system while in Tl(III)-treated cells both GSH- and Trx-dependent systems are involved.

The family of inward rectifying potassium channels (Kir channels) plays crucial roles in the regulation of heart rhythms, renal excretion, insulin release, and neuronal activity. Their dysfunction has been attributed to numerous diseases such as cardiac arrhythmia, kidney failure and electrolyte imbalance, diabetes mellitus, epilepsy, retinal degeneration, and other neuronal disorders. We have recently demonstrated that the melanocortin-4 receptor (MC4R), a Gα s -coupled GPCR, regulates Kir7.1 activity through a mechanism independent of Gα s and cAMP. In contrast to the many other members of the Kir channel family, less is known about the biophysical properties, regulation, and physiological functions of Kir7.1. In addition to using conventional patch clamp techniques, we have employed a high-throughput Tl + flux assay to further investigate the kinetics of MC4R-Kir7.1 signaling in vitro. Here, we discuss the employment of the Tl + flux assay to study MC4R -mediated regulation of Kir7.1 activity and to screen compounds for drug discovery.

Monovalent cation channels are critically important for physiological processes ranging from the control of neuronal excitability to the maintenance of solute balance. Mutations in these channels are associated with a multiplicity of diseases and monovalent cation channel-modulating drugs are used as therapeutics. Techniques that allow the measurement of the activity of these ion channels are useful for exploring their many biological roles as well as enabling the discovery and characterization of ion channel modulators for the purposes of drug discovery. Although there are numerous techniques for measuring the activity of monovalent cation channels, the thallium flux assay technique is a widely used fluorescence-based approach. Described herein is a method for using the thallium-flux technique for detecting and quantifying the activity of small-molecule potassium channel modulators in 384-well plates.

Thallium (Tl) is highly toxic to mammals and relevant pollution cases are increasing world-widely. Convenient and efficient method for the removal of trace Tl from contaminated source water is imperative. Here, the removal of trace Tl by K 2 FeO 4 [Fe(VI)] was investigated for the first time, with the exploration of reaction mechanisms. Six different types of water treatment agents (powdered activated carbon, Al 2 (SO 4 ) 3 , FeCl 3 , δ-MnO 2 , MnO 2 nano-particles, and K 2 FeO 4 ) were used for the removal of Tl in spiked river water, and K 2 FeO 4 showed excellent removal performance. Over 92% of Tl (1 μg/L) was removed within 5 min by applying 2.5 mg/L of K 2 FeO 4 (pH 7.0, 20 °C). XPS analysis revealed that in the reaction of Tl(I) with K 2 FeO 4 , Tl(I) was oxidized to Tl(III), and removed by the K 2 FeO 4 reduced ferric particles. The removal of Tl by in situ formed and ex situ formed ferric particle was examined respectively, and the results revealed that the removal of trace Tl could be attributed to the combination of adsorption and coprecipitation processes. The hydrodynamic size of the reduced particle from K 2 FeO 4 ranged from 10 nm to 100 nm, and its surface was negatively charged under neutral pH condition. These factors were conducive for the efficient removal of Tl by K 2 FeO 4 . The effects of solution pH, coexisting ions (Na + , Ca 2+ , and HCO 3 - ), humic acid, solution temperature, and reductive environment on the removal and desorption of Tl were investigated, and the elimination of Tl in polluted river water and reservoir water was performed. These results suggest that K 2 FeO 4 could be an efficient and convenient agent on trace Tl removal., (Copyright © 2017. Published by Elsevier Ltd.)

Medical X-ray imaging procedures require digital flat detectors operating at low doses to reduce radiation health risks. Solution-processed organic-inorganic hybrid perovskites have characteristics that make them good candidates for the photoconductive layer of such sensitive detectors. However, such detectors have not yet been built on thin-film transistor arrays because it has been difficult to prepare thick perovskite films (more than a few hundred micrometres) over large areas (a detector is typically 50 centimetres by 50 centimetres). We report here an all-solution-based (in contrast to conventional vacuum processing) synthetic route to producing printable polycrystalline perovskites with sharply faceted large grains having morphologies and optoelectronic properties comparable to those of single crystals. High sensitivities of up to 11 microcoulombs per air KERMA of milligray per square centimetre (μC mGy air -1 cm -2 ) are achieved under irradiation with a 100-kilovolt bremsstrahlung source, which are at least one order of magnitude higher than the sensitivities achieved with currently used amorphous selenium or thallium-doped cesium iodide detectors. We demonstrate X-ray imaging in a conventional thin-film transistor substrate by embedding an 830-micrometre-thick perovskite film and an additional two interlayers of polymer/perovskite composites to provide conformal interfaces between perovskite films and electrodes that control dark currents and temporal charge carrier transportation. Such an all-solution-based perovskite detector could enable low-dose X-ray imaging, and could also be used in photoconductive devices for radiation imaging, sensing and energy harvesting.

Three computational methods (M06-2X/Def2-TZVP, B3PW91/Def2-TZVP and B3LYP/LANL2DZ+dp) were used to study the effect of substitution on the potential energy surfaces of RTl≡PR (R = F, OH, H, CH₃, SiH₃, SiMe(Si t Bu₃)₂, Si i PrDis₂, Tbt (=C₆H₂-2,4,6-(CH(SiMe₃)₂)₃), and Ar* (=C₆H₃-2,6-(C₆H₂-2, 4,6- i -Pr₃)₂)). The theoretical results show that these triply bonded RTl≡PR compounds have a preference for a bent geometry (i.e., ∠R⎼Tl⎼P ≈ 180° and ∠Tl⎼P⎼R ≈ 120°). Two valence bond models are used to interpret the bonding character of the Tl≡P triple bond. One is model [I], which is best described as TlP. This interprets the bonding conditions for RTl≡PR molecules that feature small ligands. The other is model [II], which is best represented as TlP. This explains the bonding character of RTl≡PR molecules that feature large substituents. Irrespective of the types of substituents used for the RTl≡PR species, the theoretical investigations (based on the natural bond orbital, the natural resonance theory, and the charge decomposition analysis) demonstrate that their Tl≡P triple bonds are very weak. However, the theoretical results predict that only bulkier substituents greatly stabilize the triply bonded RTl≡PR species, from the kinetic viewpoint., Competing Interests: The authors declare no conflict of interest.

To our knowledge, this is the first work to mechanistically study the impact of the redox potential (E H ) and principal factors, such as pH, iron (Fe), manganese (Mn), dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), chlorides (Cl - ) and sulfates (SO 4 2- ), on the release dynamics of thallium (Tl) in periodically flooded soil. We simulated flooding using an automated biogeochemical microcosm system that allows for systematical control of pre-defined redox windows. The E H value was increased mechanistically at intervals of approximately 100 mV from reducing (-211 mV) to oxidizing (475 mV) conditions. Soluble Tl levels (0.02-0.28 μg L -1 ) increased significantly with increases in E H (r = 0.80, p < 0.01, n = 30). Thallium mobilization was found to be related to several simultaneous processes involving the gradual oxidation of Tl-bearing sulfides, reductive dissolution of Fe-Mn oxides and desorption from mineral sorbents. Manganese oxides did not appear to have a considerable effect on Tl retention under oxidizing conditions. Before conducting the microcosm experiment, Tl geochemical fractionation was assessed using the modified BCR sequential extraction procedure. The BCR revealed a majority of Tl in the residual fraction (77.7%), followed by reducible (13.3%) and oxidizable fractions (5.9%). By generating high levels of Tl toxicity at low doses, Tl released under oxidizing conditions may pose an environmental threat. In the future, similar studies should be conducted on various soils along with a determination of the Tl species and monitoring of the Tl content in plants to achieve more detailed insight into soluble Tl behavior., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

N -(Benzothiazol-2-yl)-4-chlorobenzenesulphonamide (NBTCS) was synthesized by condensation reaction of 4-chlorobenzenesulphonyl chloride and 2-aminobenzothiazole in acetone under reflux. Neodymium(III) and thallium(III) complexes of the ligand were also synthesized. Both ligand and metal complexes were characterized using UV-Vis, IR, ¹H- and 13 C-NMR spectroscopies, elemental analysis and molar conductance measurement. IR studies revealed that the ligand is tridentate and coordinates to the metal ions through nitrogen and oxygen atoms of the sulphonamide group and nitrogen atom attached to benzothiazole ring. The neodymium(III) complex displays a coordination number of eight while thallium(III) complex displays a coordination number of six. The ligand and its complexes were screened in vitro for their antibacterial activities against Escherichia coli strains ( E. coli 6 and E. coli 13 ), Proteus species, Staphylococcus aureus and Pseudomonas aeruginosa using the agar well diffusion technique. The synthesized compounds were found to be more active against the microorganisms screened relative to ciprofloxacin, gentamicin and co-trimoxazole.

The FLUKA code was implemented to simulate pulse-height spectra of a NaI(Tl) detector (excluding its resolution), considering radioactive sources of naturally occurring and artificial radionuclides present in the marine environment. For this purpose, a user-defined routine was developed for the proper simulation of the emitted γ-rays. The results were compared with simulations performed using the MCNP-CP code. The comparison of the recorded counts in the full-energy peaks, for the high intensity (emission probability >15%) emitted γ-rays for each radionuclide, yielded a satisfactory agreement (calculated ratios from 0.93 ± 0.05 to 1.07 ± 0.02) in all the studied cases., (Copyright © 2016 Elsevier Ltd. All rights reserved.)