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Recently, diimine Re(i) tricarbonyl complexes have attracted great interest due to their promising cytotoxic effects. Here, we compare the cytotoxicity and cellular uptake of two Re(i) compounds fac-[(Re(CO)3(bpy)(H2O)](CF3SO3) (1) and Na(fac-[(Re(CO)3(bpy)(S2O3)])·H2O (bpy = 2,2'-bipyridine) (2). The Re-thiosulfate complex in 2 was characterized in two solvated crystal structures {Na(fac-[Re(CO)3(bpy)(S2O3)])·1.75H2O·C2H5OH}4 (2 + 0.75H2O + C2H5OH)4 and (fac-[Re(CO)3(bpy)(H2O)]) (fac-[Re(CO)3(bpy)(S2O3)])·4H2O (3). The cytotoxicity of 1 and 2 was tested in the MDA-MB-231 breast cancer cell line and compared with that of cisplatin. The cellular localization of the Re(i) complexes was investigated using synchrotron-based X-ray fluorescence microscopy (XFM). The results show that replacement of the aqua ligand with thiosulfate renders the complex less toxic most likely by distrupting its cellular entry. Therefore, thiosulfate could potentially have a similar chemoprotective effect against diimine fac-Re(CO)3 complexes as it has against cisplatin.

In this work, we developed a novel, label-free, colorimetric sensor for Pb(2+) detection based on the acceleration of gold leaching by graphene oxide (GO) at room temperature. Gold nanoparticles (AuNPs) can be dissolved in a thiosulfate (S2O3(2-)) aqueous environment in the presence of oxygen; however, the leaching rate is very slow due to the high activation energy (27.99 kJ mol(-1)). In order to enhance the reaction rate, some accelerators should be added. In comparison with the traditional accelerators (metal ions or middle ligands), we found that GO could efficiently accelerate the gold leaching reaction. Kinetic data demonstrate that the dissolution rate of gold in the Pb(2+)-S2O3(2-)-GO system is 5 times faster than that without GO at room temperature. In addition, the effects of surface modification and the nanoparticle size on the etching of AuNPs were investigated. Based on the GO-accelerated concentration-dependent colour changes of AuNPs, a colorimetric sensor for Pb(2+) detection was developed with a linear range from 0.1 to 20 μM and the limit of detection (LOD) was evaluated to be 0.05 μM. This colorimetric assay is simple, low-cost, label-free, and has numerous potential applications in the field of environmental chemistry.

We studied the kinetics of reactions of cob(I)alamin and cob(I)inamide with thiosulfate, sulfite, and dithionite by UV-Visible (UV-Vis) and stopped-flow spectroscopy. We found that the two Co(I) species were oxidized by these sulfur-containing compounds to Co(II) forms: oxidation by excess thiosulfate leads to penta-coordinate complexes and oxidation by excess sulfite or dithionite leads to hexa-coordinate Co(II)-SO2(-) complexes. The net scheme involves transfer of three electrons in the case of oxidation by thiosulfate and one electron for oxidation by sulfite and dithionite. On the basis of kinetic data, the nature of the reactive oxidants was suggested, i.e., HS2O3(-) (for oxidation by thiosulfate), S2O5(2-), HSO3(-), and aquated SO2 (for oxidation by sulfite), and S2O4(2-) and SO2(-) (for oxidation by dithionite). No difference was observed in kinetics with cob(i)alamin or cob(i)inamide as reductants.

A simple, rapid colorimetric detection method for Pb(2+) in aqueous solution has been developed by using sodium thiosulfate (Na2S2O3) and hexadecyl trimethyl ammonium bromide (CTAB) modified gold nanoparticles (Au NPs). Na2S2O3 was added into the Au NP solution and thiosulfate ions (S2O3(2-)) were adsorbed on the surface of the Au NPs due to electrostatic interactions. Au atoms on the surface of the Au NPs were then oxidized to Au(i) by the O2 that existed in the solution in presence of thiosulfate. The addition of Pb(2+) (the final concentration was lower than 10 μM), accelerated the leaching of the Au NPs, and Pb-Au alloys also formed on the surface of the Au NPs. There was an obvious decrease in the surface plasmon resonance (SPR) absorption of the Au NPs. The lowest concentration for Pb(2+) that could be detected by the naked eye was 0.1 μM and using UV-vis spectroscopy was 40 nM. This is lower than the lead toxic level defined by the US Environmental Protection Agency (US EPA), which is 75 nM. In this method, CTAB, as a stabilizing agent for Au NPs, can accelerate the adsorption of S2O3(2-) on the surface of the Au NPs, which shortened the detection time to within 30 min. Moreover, this detection method is simple, cheap and environmentally friendly.

Five new thiosulfate based inorganic-organic hybrid open-framework compounds have been synthesized employing mild reaction conditions. Of the five compounds, [Na(2)(H(2)O)(8)][Cd(C(10)H(8)N(2))(S(2)O(3))(2)].2H(2)O, I and [Cd(2)(C(10)H(8)N(2))(2)(HS(2)O(3))(2)(S(2)O(3))(2)][(C(10)H(9)N(2))(2)(C(10)H(8)N(2))(2)].8H(2)O, II have one-dimensional (1D) structures and [Cd(C(10)H(8)N(2))(H(2)O)(2)(S(2)O(3))].2H(2)O, III, [Cd(2)(C(10)H(8)N(2))(3)(S(2)O(3))(2)], IV and [Cd(2)(C(10)H(8)N(2))(2.5)(S(2)O(3))(2)], V have three-dimensional (3D) structures. The 1D structures are somewhat related, formed by the bonding between tetrahedral Cd centers (CdN(2)S(2)) and 4,4'-bipyridine (bpy) units. The inter-chain spaces are occupied by the hanging thiosulfate units in both the cases along with Na(H(2)O)(6) chains in I and free bpy units in II. The three 3D structures have one-dimensional cadmium thiosulfate chains linked by bpy units. Interpenetration has been observed in all the 3D structures. The 3D structures appear to be related and can be derived from fgs net. Transformation studies on the 1D compound, [Na(2)(H(2)O)(8)][Cd(C(10)H(8)N(2))(S(2)O(3))(2)].2H(2)O, I, indicated a facile formation of [Cd(C(10)H(8)N(2))(H(2)O)(2)(S(2)O(3))].2H(2)O, III. Prolonged heating of I gave rise to a 3D cadmium sulfate phase, [Cd(2)(C(10)H(8)N(2))(2)(H(2)O)(3)(SO(4))(2)].2H(2)O, VI. Compound VI has one-dimensional cadmium sulfate chains formed by six-membered rings connected by bpy units to form a 3D structure, which appears to resemble the topological arrangement of III. Transformation studies of III indicates the formation of IV and V, and at a higher temperature a new 3D cadmium sulfate, [Cd(C(10)H(8)N(2))(SO(4))], VII. Compound VII has a 4 x 4 grid cadmium sulfate layers pillared by bpy units. All the compounds were characterized by PXRD, TGA, IR and UV-visible studies. Preliminary studies on the possible use of the 3D compounds (III-VII) in heterogeneous cyanosilylation of imines appear to be promising.