We report the results of an experimental and theoretical study of the electronic and structural properties of a key eumelanin precursor-5,6,-dihydroxyindole-2-carboxylic acid (DHICA)-and its dimeric forms. We have used optical spectroscopy to follow the oxidative polymerization of DHICA to eumelanin and observe red shifting and broadening of the absorption spectrum as the reaction proceeds. First principles density functional theory calculations indicate that DHICA oligomers (possible reaction products of oxidative polymerization) have the gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital red-shifted gaps with respect to the monomer. Furthermore, different bonding configurations (leading to oligomers with different structures) produce a range of gaps. These experimental and theoretical results lend support to the chemical disorder model where the broadband monotonic absorption characteristic of all melanins is a consequence of the superposition of a large number of nonhomogeneously broadened Gaussian transitions associated with each of the components of a melanin ensemble. These results suggest that the traditional model of eumelanin as an amorphous organic semiconductor is not required to explain its optical properties and should be thoroughly reexamined. These results have significant implications for our understanding of the physics, chemistry, and biological function of these important biological macromolecules. Indeed, one may speculate that the robust functionality of melanins in vitro is a direct consequence of its heterogeneity, i.e., chemical disorder is a "low cost" natural resource in these systems.
The three-dimensional branched nature of dendritic macromolecules provides many potential sites per molecule for the complexation of metal ions. Therefore, dendrimers may act as hosts for metals with coordination potentially occurring at the periphery, the interior, or both. To understand further the complexation of dendrimers with metal ions EXAFS experiments were carried out. In this work, the interaction of amine-terminated polyamido(amine), PAMAM, dendrimer with copper(II) ions determined by EXAFS is reported. It was found that a model consisting of the copper(II) ion forming five- and six-membered rings by chelating with the primary amine, amide, and tertiary amine nitrogen donors of the PAMAM dendrimer could describe the experimental EXAFS data well. Corroborative evidence for binding to amide nitrogen donors comes from the broadening of NMR resonances of a copper(II)−PAMAM mixture revealing the presence of paramagnetic copper(II) ions at these sites. The significance of the results presented in this paper is that copper(II) ions form complexes within the dendrimer structure and not just at the periphery. The current study may have implications for the use of PAMAM dendrimers as effective ligands in sensing systems.
Introduction: Many infectious diseases display seasonal variation corresponding with particular conditions. In orthopaedics a growing body of evidence has identified surges in postoperative infection rates during higher temperature periods. The aim of this research was to collate and synthesize the current literature on this topic. Methods: A systematic review and meta-analysis was performed using five databases (PubMed, Embase, CINAHL, Web of Science and Central (Cochrane)). Study quality was assessed using the Grading of Recommendations Assessment, Development and Evaluation method. Odds ratios (ORs) were calculated from monthly infection rates and a pooled OR was generated using the DerSimonian and Lairds method. A protocol for this review was registered with the National Institute for Health Research International Prospective Register of Systematic Reviews (CRD42017081871). Results: Eighteen studies analysing over 19 000 cases of orthopaedic related infection met inclusion criteria. Data on 6620 cases and 9035 controls from 12 studies were included for meta-analysis. The pooled OR indicated an overall increased odds of post-operative infection for patients undergoing orthopaedic procedures during warmer periods of the year (pooled OR 1.16, 95% confidence interval 1.04-1.30). Conclusion: A small but significantly increased odds of post-operative infection may exist for orthopaedic patients who undergo procedures during higher temperature periods. It is hypothesized that this effect is geographically dependent and confounded by meteorological factors, local cultural variables and hospital staffing cycles.
Mercury(II) in the title compound, [Hg(C4H13N3)2](SCN)2, is six‐coordinated with two diethylenetriamine (dien) ligands in a sym‐facial configuration. The complex cation has a twofold axis of symmetry, and the secondary amine groups are in trans positions.
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