Obtaining three-dimensional (3D) configurational information of surface organometallic complexes is a persistent challenge due to the low spatial sensitivity of most spectroscopic methods. We show that employing O-enriched supports enables highly informative multidimensional NMR experiments, including radial and vertical distance measurements, that can be used to elucidate site geometry.
View Article and Find Full Text PDFAmong commercial plastics, polyolefins are the most widely produced worldwide but have limited recyclability. Here, we report a chemical recycling route for the conversion of post-consumer high-density polyethylene (HDPE) into telechelic macromonomers suitable for circular reprocessing. Unsaturation was introduced into HDPE by catalytic dehydrogenation using an Ir-POCOP catalyst without an alkene acceptor.
View Article and Find Full Text PDFBackground: Merkel cell polyomavirus (MCPyV) is associated with the development of Merkel cell carcinoma (MCC). Antibody (MCPyV-Ab) titers may have prognostic implications. This study evaluated the impact of the presence or absence of MCPyV-Ab on the 2-year overall survival (OS) and disease-free survival (DFS) of MCC patients.
View Article and Find Full Text PDFLynch syndrome (LS) is a common genetic syndrome characterized by pathogenic mutations of DNA mismatch repair genes resulting in a hereditary predisposition to cancer. While typically associated with colonic and endometrial cancer, LS additionally influences the development of many other malignancies. The Amsterdam II and Revised Bethesda Guidelines are the established clinical criteria for diagnosing LS.
View Article and Find Full Text PDFCancer Rep (Hoboken)
February 2022
Background: MUTYH-associated polyposis is a rare disorder resulting from mutations involved in DNA mismatch repair. This results in an increased susceptibility to colonic adenomatosis and other cancers. Studies have examined the resulting frequency of extracolonic manifestations; however, these typically occur alone, concurrently, or temporally separate from an already diagnosed colorectal cancer in individuals with a biallelic mutation.
View Article and Find Full Text PDFIsocyanide coordination networks (CNs), which consist of multitopic isocyanide linker groups and transition-metal-based secondary building units (SBUs), are a promising class of organometallic framework materials for the inclusion of low-valent metal centers as primary structural components. Previously, it was demonstrated that the ditopic -terphenyl isocyanide ligand, [CNAr] (Ar = 2,6-(2,4,6-MeCH)CH), could provide single-metal node frameworks based on Cu(I) and Ni(0) centers. However, the relatively short linker length in [CNAr] precluded the formation of networks with significant porosity.
View Article and Find Full Text PDFBackground: Autogenous bone is frequently espoused as the gold standard material for cranioplasty procedures, yet alloplastic cranioplasty continues to persist in the search, presumably, for a simpler technique. Although short-term outcomes can be successful using foreign materials, long-term follow-up in these patients often demonstrates increased rates of failure because of exposure or late infection. Autogenous bone grafts, however, integrate and revascularize, and are thus more resistant to infection than alloplastic materials.
View Article and Find Full Text PDFA synthetic strategy featuring dicyanometalates [M(CN)] (M = Ag, Au) as N-coordinating ditopic linkers connecting partially blocked Fe centers has been employed to produce heterometallic hexanuclear complexes, which exhibit spin-crossover (SCO) behavior at the Fe sites. The reaction between tris(2-pyridylmethyl)amine (tpma)-capped Fe ions and [Ag(CN)] proceeded with partial decomposition of the dicyanoargentate and led to the formation of {[Fe(tpma)](μ-CN)[μ-Ag(CN)]}(ClO)·3HO (), in which both [Ag(CN)] and CN act as bridging ligands, and the opposite [Ag(CN)] bridges are engaged in a pronounced argentophilic d-d interaction. In an analogous synthesis, the more stable [Au(CN)] species remained intact and furnished the complex {[Fe(tpma)][μ-Au(CN)]} (), which features two Fe centers bridged by two [Au(CN)] dimers.
View Article and Find Full Text PDFA permanently porous, three-dimensional metal-organic material formed from zero-valent metal nodes is presented. Combination of ditopic m-terphenyl diisocyanide, [CNAr], and the d Ni(0) precursor Ni(COD), produces a porous metal-organic material featuring tetrahedral [Ni(CNAr)] structural sites. X-ray absorption spectroscopy provides firm evidence for the presence of Ni(0) centers, whereas gas-sorption and thermogravimetric analysis reveal the characteristics of a robust network with a microdomain N-adsorption profile.
View Article and Find Full Text PDFReactions of Fe(II) precursors with the tetradentate ligand S,S'-bis(2-pyridylmethyl)-1,2-thioethane (bpte) and monodentate NCE(-) coligands afforded mononuclear complexes [Fe(bpte)(NCE)2] (1, E = S; 2, E = Se; 3, E = BH3) that exhibit temperature-induced spin crossover (SCO). As the ligand field strength increases from NCS(-) to NCSe(-) to NCBH3(-), the SCO shifts to higher temperatures. Complex 1 exhibits only a partial (15%) conversion from the high-spin (HS) to the low-spin (LS) state, with an onset around 100 K.
View Article and Find Full Text PDFTwo Fe(II) complexes, {[(tpma)Fe(μ-CN)]4}X4 (X = ClO4(-) (1a), BF4(-) (1b); tpma = tris(2-pyridylmethyl)amine), were prepared by reacting the {Fe(tpma)}(2+) building block with (Bu4N)CN. The crystal structures of 1a and 1b feature a tetranuclear cation composed of cyanide-bridged Fe(II) ions, each capped with a tetradentate tpma ligand. The Fe4(μ-CN)4 core of the complex is strongly distorted, assuming a butterfly-like geometry.
View Article and Find Full Text PDFJ Child Adolesc Psychopharmacol
November 2015
Unlabelled: Screening tests for colon, cervical and breast cancer remain underutilized despite their proven effectiveness in reducing morbidity and mortality. Stone et al. concluded that cancer screening is most likely to improve when a health organization supports performance through organizational changes (OC) in staffing and clinical procedures.
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