Thallium(I) Tropolonates: Synthesis, Structure, Spectral Characteristics, and Antimicrobial Activity Compared to Lead(II) and Bismuth(III) Analogues.

Synthesis, single-crystal X-ray determination diffraction and FT-IR, NMR (1H, 13C, 19F and 205Tl), 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.

Separation of Radionuclides from Spent Decontamination Fluids via Adsorption onto Titanium Dioxide Nanotubes after Photocatalytic Degradation.

A one-step process combining the photocatalytic degradation of radionuclide complexes and the adsorption of liberated radionuclides on titanium dioxide nanotubes was developed and tested for the purification of aqueous waste produced from chemical decontamination of nuclear power plant circuit components. Among the tested forms of TiO2, only nanotubes exhibit both high photocatalytic activity and sorption ability, which support their application in a one-step purification process. The obtained results indicate that the photocatalytic degradation of complexes followed by the sorption of the radionuclides onto TiO2 nanotubes offers a promising route for treating spent decontamination fluids.

1,2-Benzenedithiol and Toluene-3,4-dithiol Arsenic(III) Complexes-Synthesis, Structure, Spectroscopic Characterization and Toxicological Studies.

A new group of arsenic(III) complexes with bidentate S,S-donor ligands, 1,2-benzenedithiol (Ph(SH)2) and toluene-3,4-dithiol (MePh(SH)2), were synthesized. The use of arsenic(III) iodide and bromide promoted the formation of neutral complexes (1-4) with the general formula AsX(LS2) (X = I or Br, L = MePh or Ph). The crystal structures of these compounds were determined using single-crystal X-ray diffraction (scXRD). Unlike other arsenic(III) complexes, AsBr(PhS2) complex (2) was found to crystallize with a rare 13 molecules in the asymmetric unit. The compounds were also characterized by conventional physico-chemical techniques (Fourier transform infrared (FT-IR) spectroscopy, ultraviolet-visible (UV-Vis) spectroscopy, nuclear magnetic resonance (NMR), high-performance liquid chromatography (HPLC), elemental analysis (EA) and electrospray ionization-mass spectrometry (ESI-MS)). The results from structural and spectroscopic studies were supported by DFT calculations using the B3LYP/LANL2DZ and (or) 6-31+G(d,p) approaches. The cytotoxicity of these complexes was estimated for human acute promyelocytic leukemia cell line (NB4). They exhibited remarkable cytotoxicities after 48 h of treatment with IC50 equal to about 10 µM and 40 µM for complexes with 1,2-benzenedithiolato and toluene-3,4-dithiolato ligand, respectively. Their toxicity was lower than that of commonly used chemotherapeutic As2O3 (IC50 = 1.4 µM).

211At labeled substance P (5-11) as potential radiopharmaceutical for glioma treatment.

INTRODUCTION: The purposes of the present work were to label substance P (5-11) with 211At using a rhodium(III) complex with a bifunctional ligand-2-(1,5,9,13-tetrathiacyclohexadecan-3-yloxy)acetic acid ([16aneS4]-COOH) and to assess the in vitro stability and toxicity of the obtained radiobioconjugate. METHODS: Two approaches were evaluated to obtain 131I/211At-Rh[16aneS4]-SP5-11 radiobioconjugates, based on 2-step and 1-step syntheses. In the first method 131I/211At-Rh[16aneS4]-COOH complexes were obtained that required further coupling to a biomolecule. In the second approach, the bioconjugate [16aneS4]-SP5-11 was synthesized and further labeled with 131I and 211At through the utilization of a Rh(III) metal cation bridge. The synthesized compounds were analyzed by HPLC, TLC and paper electrophoresis. RESULTS: The 131I/211At-Rh[16aneS4]-COOH complexes were obtained in high yield and possessed good stability in PBS and CSF. Preliminary studies on coupling of 131I-Rh[16aneS4]-COOH to substance P (5-11) in 2-step synthesis showed that this procedure was too long with respect to 211At half-life, prompting us to improve it by finally using a 1-step synthesis. This strategy not only shortened the labeling time, but also increased final yield of 131I/211At-Rh[16aneS4]-SP5-11 radiobioconjugates. The stability of both compounds in PBS and CSF was high. Toxicity studies with the 211At-Rh[16aneS4]-SP5-11 demonstrated that radiobioconjugate significantly reduced T98G cell viability in a dose dependent manner reaching 20% of survival at the highest radioactivity 1200kBq/mL. CONCLUSIONS: The radiobioconjugate 211At-Rh[16aneS4]-SP5-11 revealed its potential in killing glioma T98G cells during in vitro studies; therefore further animal studies to are required to determine its in vivo stability and treatment potential in normal and xenografted mice.

Stability and in vivo behavior of Rh[16aneS4-diol]211 at complex: a potential precursor for astatine radiopharmaceuticals.

INTRODUCTION: The heavy halogen (211)At is of great interest for targeted radiotherapy because it decays by the emission of short-range, high-energy α-particles. However, many astatine compounds that have been synthesized are unstable in vivo, providing motivation for seeking other (211)At labeling strategies. One relatively unexplored approach is to utilize prosthetic groups based on astatinated rhodium (III) complex stabilized with a tetrathioether macrocyclic ligand - Rh[16aneS(4)-diol](211)At. The purpose of the current study was to evaluate the in vitro and in vivo stability of this complex in comparison to its iodine analog - Rh[16aneS(4)-diol](131)I. METHODS: Rh[16aneS(4)-diol](211)At and Rh[16aneS(4)-diol](131)I complexes were synthesized and purified by HPLC. The stability of both complexes was evaluated in vitro by incubation in phosphate-buffered saline (PBS) and human serum at different temperatures. The in vivo behavior of the two radiohalogenated complexes was assessed by a paired-label biodistribution study in normal Balb/c mice. RESULTS: Both complexes were synthesized in high yield and purity. Almost no degradation was observed for Rh[16aneS(4)-diol](131)I in PBS over a 72 h incubation. The astatinated analog exhibited good stability in PBS over 14 h. A slow decline in the percentage of intact complex was observed for both tracers in human serum. In the biodistribution study, retention of (211)At in most tissues was higher than that of (131)I at all time points, especially in spleen and lungs. Renal clearance of Rh[16aneS(4)-diol](211)At and Rh[16aneS(4)-diol](131)I predominated, with 84.1 ± 2.3% and 94.6 ± 0.9% of injected dose excreted via the urine at 4 h. CONCLUSIONS: The Rh[16aneS(4)-diol](211)At complex might be useful for constructing prosthetic groups for the astatination of biomolecules and further studies are planned to evaluate this possibility.

Adsorption of 137Cs on titanium ferrocyanide and transformation of the sorbent to lithium titanate: a new method for long term immobilization of 137Cs.

Dynamic adsorption of radiocesium on titanium ferrocyanide grains from reactor coolant simulating solution containing salts at moderate concentrations has been investigated. Effective decontamination of the neutral solutions has been achieved, in the amounts of a more than 20 thousand bed volumes. After adsorption the titanium ferrocyanide was transferred to titanates and calcined at 900 °C. The leaching test of the obtained lithium titanates indicates that the loaded adsorbent can serve as an effective primary barrier in nuclear waste repositories.

2-Hy-droxy-7-nitro-cyclo-hepta-2,4,6-trien-1-one.

The title compound, also known as 7-nitro-tropolone, C7H5NO4, exists in the crystalline state as the 2-hy-droxy-7-nitro-cyclo-hepta-2,4,6-trien-1-one tautomer and not as 2-hy-droxy-3-nitro-cyclo-hepta-2,4,6-trien-1-one. The dihedral angle between the ring and the nitro group is 70.3 (2)°. In the crystal, neighbouring mol-ecules are linked into dimers by a pair of O-H⋯O hydrogen bonds. In addition, the crystal is stabilized by O⋯π [3.4039 (14) Å] and O⋯O [3.073 (2) Å] inter-actions.

catena-Poly[(µ(3)-2-hy-droxy-4-isopropyl-cyclo-hepta-2,4,6-trien-1-onato)(µ(2)-2-hy-droxy-4-isopropyl-cyclo-hepta-2,4,6-trien-1-onato)lead(II)].

In the title compound, [Pb(C(10)H(11)O(2))(2)](n) or [Pb(hino)(2)](n), the lead(II) ion is chelated by two hinokitiolate ligands in a distorted square-pyramidal configuration, with Pb-O bond lengths in the range 2.327 (6)-2.479 (9) Å. The 6s(2) lone electron pair of the lead(II) ion becomes stereochemically active and is directed towards the apex of this pyramid. The crystal structure of the title compound consists of chains formed by the bis-(hinokitiolato)lead(II) mol-ecules situated along the twofold screw axis. The coordination sphere around the lead(II) ion is completed by three additional O atoms, at 2.625 (7), 3.016 (8) and 3.064 (8) Å, from the two neighbouring Pb(hino)(2) units. Both isopropyl groups are rotationally disordered.