A series of heterobimetallic lantern complexes with the central unit {PtM(SAc)4(NCS)} have been prepared and thoroughly characterized. The {Na(15C5)}[PtM(SAc)4(NCS)] series, 1 (Co), 2 (Ni), 3 (Zn), are discrete compounds in the solid state, whereas the {Na(12C4)2)}[PtM(SAc)4(NCS)] series, 4 (Co), 5 (Ni), 6 (Zn), and 7 (Mn), are ion-separated species. Compound 7 is the first {PtMn} lantern of any bridging ligand (carboxylate, amide, etc.). Monomeric 1-7 have M(2+), necessitating counter cations that have been prepared as {(15C5)Na}(+) and {(12C4)2Na}(+) variants, none of which form extended structures. In contrast, neutral [PtCr(tba)4(NCS)]∞ 8 forms a coordination polymer of {PtCr}(+) units linked by (NCS)(-) in a zigzag chain. All eight compounds have been thoroughly characterized and analyzed in comparison to a previously reported family of compounds. Crystal structures are presented for compounds 1-6 and 8, and solution magnetic susceptibility measurements are presented for compounds 1, 2, 4, 5, and 7. Further structural analysis of dimerized {PtM} units reinforces the empirical observation that greater charge density along the Pt-M vector leads to more Pt···Pt interactions in the solid state. Four structural classes, one new, of {MPt}···{PtM} units are presented. Solid state magnetic characterization of 8 reveals a ferromagnetic interaction in the {PtCr(NCS)} chain between the Cr centers of J/kB = 1.7(4) K.

Low-spin (S = 1/2) Ni(iii) cyclam complex salts can show SMM-type properties depending on the axial ligand donor atom identity.

The heterogeneous progression to the development of prostate cancer (PCa) has precluded effective early detection screens. Existing prostate cancer screening paradigms have relatively poor specificity for cancer relative to other prostate diseases, commonly benign prostatic hyperplasia (BPH). A method for discrimination of BPH, HGPIN, and PCa urine proteome was developed through testing 407 patient samples using matrix assisted laser desorption-mass spectrometry time of flight (MALDI-TOF). Urine samples were adsorbed to reverse phase resin, washed, and the eluant spotted directly for MALDI-TOF analysis of peptides. The processing resolved over 130 verifiable signals of a mass range of 1000-5000 m/z to suggest 71.2% specificity and 67.4% sensitivity in discriminating PCa vs. BPH. Comparing BPH and HGPIN resulted in 73.6% specificity and 69.2% sensitivity. Comparing PCa and HGPIN resulted in 80.8% specificity and 81.0% sensitivity. The high throughput, low-cost assay method developed is amenable for large patient numbers required for supporting biomarker identification.

We describe the structural and electronic impacts of modifying the bridging atom in a family of Co(ii) pincer complexes with the formula Co(t-Bu)PPyP(t-Bu)Br (Py = pyridine, E = CH, NH, and O for compounds 1-3, respectively). Structural characterization by single crystal X-ray diffraction indicates that compounds 1 and 3 are 5-coordinate complexes with both bromides bound to the Co(ii) ion, while compound 2 is square planar with one bromide in the outer coordination sphere. The reduction potentials of 1-3, characterized by cyclic voltammetry, are consistent with the increasing electron-withdrawing character of the pincer ligand as the linker (E) between the pyridine and phosphine arms becomes more electronegative. Magnetic property studies of compounds 1 and 2 confirm high- and low-spin behavior, respectively, through a broad temperature range. However, complex 3 features an unusual combination of high spin S = 3/2 Co(ii) and temperature dependent spin-crossover between S = 3/2 and S = 1/2 states. The different magnetic behaviors observed among the three CoBr pincer complexes reflects the importance of small ligand perturbations on overall coordination geometry and resulting spin state properties.