Investigations of the Effect of the Non-Manganese Metal in Heterometallic-Oxido Cluster Models of the Oxygen Evolving Complex of Photosystem II: Lanthanides as Substitutes for Calcium

We report the syntheses and electrochemical properties of nine new clusters ([LLnMn^(IV)_(3)O_4(OAc)_3(DMF)_n]^+ (Ln = La^3+, Ce^3+, Nd^3+, Eu^3+, Gd^3+, Tb^3+, Dy^3+, Yb^3+, and Lu^3+, n = 2 or 3)) supported by a ligand (L^3–) based on a 1,3,5-triarylbenzene motif appended with alkoxide and pyridine donors. All complexes were obtained by metal substitution of Ca2+ with lanthanides upon treatment of previously reported LMn_3CaO_4(OAc)_3(THF) with Ln(OTf)_3. Structural characterization confirmed that the clusters contain the [LnMn_3O_4] cubane motif. The effect of the redox-inactive centers on the electronic properties of the Mn_3O_4 cores was investigated by cyclic voltammetry. A linear correlation between the redox potential of the cluster and the ionic radii or pKa of the lanthanide metal ion was observed. Chemical reduction of the LMn^(IV)_3GdO_4(OAc)_3(DMF)2 cluster with decamethylferrocene, resulted in the formation of LGdMn^(IV)_2Mn^(III)O_4(OAc)_3(DMF)_2, a rare example of mixed-valence [MMn_3O_4] cubane. The lanthanide-coordinated ligands can be substituted with other donors, including water, the biological substrate

Molecular population genetics and gene expression analysis of duplicated CBF genes of Arabidopsis thaliana

<p>Abstract</p> <p>Background</p> <p><it>CBF/DREB </it>duplicate genes are widely distributed in higher plants and encode transcriptional factors, or CBFs, which bind a DNA regulatory element and impart responsiveness to low temperatures and dehydration.</p> <p>Results</p> <p>We explored patterns of genetic variations of <it>CBF1, -2</it>, and -<it>3 </it>from 34 accessions of <it>Arabidopsis thaliana</it>. Molecular population genetic analyses of these genes indicated that <it>CBF2 </it>has much reduced nucleotide diversity in the transcriptional unit and promoter, suggesting that <it>CBF2 </it>has been subjected to a recent adaptive sweep, which agrees with reports of a regulatory protein of <it>CBF2</it>. Investigating the ratios of K_a/K_sbetween all paired <it>CBF </it>paralogus genes, high conservation of the AP2 domain was observed, and the major divergence of proteins was the result of relaxation in two regions within the transcriptional activation domain which was under positive selection after <it>CBF </it>duplication. With respect to the level of <it>CBF </it>gene expression, several mutated nucleotides in the promoters of <it>CBF3 </it>and <it>-1 </it>of specific ecotypes might be responsible for its consistently low expression.</p> <p>Conclusion</p> <p>We concluded from our data that important evolutionary changes in <it>CBF1, -2</it>, and -<it>3 </it>may have primarily occurred at the level of gene regulation as well as in protein function.</p

Effect of the Mn Oxidation State on Single-Molecule-Magnet Properties: Mn^(III) vs Mn^(IV) in Biologically Inspired DyMn_3O_4 Cubanes

Inspired by the ferromagnetic coupling in the cubane model CaMn^(IV)_3O_4 of the oxygen-evolving complex of photosystem II, 3d–4f mixed-metal DyMn_3O_4 clusters were prepared for investigation of the magnetic properties. For comparison, YMn^(IV)_3O_4 and YMn^(IV)_2Mn^(III)O_4 clusters were investigated as well and showed ferromagnetic interactions, like the calcium analogue. DyMn^(IV)_3O_4 displays single-molecule-magnet properties, while the one-electron-reduced species (DyMn^(IV)_2Mn^(III)O_4) does not, despite the presence of a Mn^(III) center with higher spin and single-ion anisotropy

Epidemiology of acute otitis media among young children: A multiple database study in Taiwan

Background/PurposeAcute otitis media (AOM) is a common complication of upper respiratory tract infection (URTI) among children. The purpose of this study was to evaluate the epidemiology of AOM among young children in Taiwan, including the age incidence and seasonality by combining multiple databases.MethodsTwo country-based questionnaire survey studies had been conducted to evaluate the experience of otitis media (OM) among young children: one in 2007 and the other between 2005 and 2010. The number of OM cases (5% of population younger than 7 years) in 2005 and annual visiting rates for URTI from 2005 to 2010 obtained from the National Health Insurance Research Database of Taiwan were collected and comprised the third database. The fourth database comprised ambulatory visits of children with OM to a medical center in central Taiwan between 2005 and 2010.ResultsData from a total of 1099 questionnaires were entered into Database I in 2007, and data from 9705 questionnaires between 2005 and 2010 comprised Database II. There were 86,702 children (younger than 7 years, representing 5% of the whole population for this age group) retrieved from Database III in 2007, and 5,904 cases of OM in children between 2005 and 2010 in a hospital. In Database I, 7.46% children experienced at least one episode of AOM compared with 9.21% in Database II for children aged 5 years and younger. In Database III, 13.2% children younger than 7 years had AOM in 2005. The peak season of AOM among children was from March to May (Databases III and IV).ConclusionAOM was thought to be a very common disease among children; however, this comparative analysis showed that the overall prevalence of AOM among children younger than 5 years was only 20%, much lower than in other countries. AOM was more prevalent during the spring season, and still was similarly common after age 2 years

Toward Models for the Full Oxygen-Evolving Complex of Photosystem II by Ligand Coordination To Lower the Symmetry of the Mn_3CaO_4 Cubane: Demonstration That Electronic Effects Facilitate Binding of a Fifth Metal

Synthetic model compounds have been targeted to benchmark and better understand the electronic structure, geometry, spectroscopy, and reactivity of the oxygen-evolving complex (OEC) of photosystem II, a low-symmetry Mn_4CaO_n cluster. Herein, low-symmetry Mn^(IV)_3GdO_4 and Mn^(IV_)3CaO_4 cubanes are synthesized in a rational, stepwise fashion through desymmetrization by ligand substitution, causing significant cubane distortions. As a result of increased electron richness and desymmetrization, a specific μ_3-oxo moiety of the Mn_3CaO_4 unit becomes more basic allowing for selective protonation. Coordination of a fifth metal ion, Ag+, to the same site gives a Mn_3CaAgO_4 cluster that models the topology of the OEC by displaying both a cubane motif and a “dangler” transition metal. The present synthetic strategy provides a rational roadmap for accessing more accurate models of the biological catalyst

Soluble tumor endothelial marker 1 in heart failure with reduced ejection fraction: A pilot study

BackgroundTumor endothelial marker 1 (TEM1/CD248) is a transmembrane protein that expresses in mesenchymal lineage derived cells during embryogenesis and becomes undetectable in normal adults after birth. Re-expression of TEM1 is found in organ fibrosis, wound healing and cardiac remodeling indicating its potential role in heart failure (HF). The purpose of this study is to explore the role of soluble TEM1 (sTEM1) in patients with HF with reduced ejection fraction.MethodsWe examined endomyocardial biopsy specimens from three HF patients and blood samples from 48 patients admitted for acute decompensated HF (age 72 years, men 61.7%). The expression of TEM1 in cardiac tissue and concentrations of sTEM1 in plasma were evaluated. Cultured rat cardiomyocytes (H9c2) and human cardiac fibroblasts (HCF) were stimulated with hypoxia or transforming growth factor beta (TGF-β) to observe the release of sTEM1 into culture media. The conditioned media of hypoxia-stimulated H9c2 cells was harvested and added into cultured cardiac fibroblast to evaluate its biological effect.ResultsImmunofluorescence study of biopsy specimens from three HF patients showed TEM1 expression in cardiomyocytes and cardiac fibroblasts. The plasma level of sTEM1 was significantly higher in patients (0.90 ± 0.23 vs. 0.33 ± 0.10 ng/mL, p = 0.032) with LVEF ≤ 35% compared with those with LVEF 36–49%. The sTEM1 levels had correlations with HF biomarkers of cardiac fibrosis, including growth differentiation factor-15 (GDF-15) and galectin-3. There was a significant increase in sTEM1 levels in the cultured media of H9c2 and HCF after being stressed with hypoxia or TGF-β. The conditioned media derived from hypoxia-stimulated H9c2 cells significantly increased cell proliferation of cardiac fibroblasts. This effect was partially reversed by anti-TEM1 antibody.ConclusionThis pilot study demonstrated that cardiac TEM1 expression was upregulated in HF. The levels of sTEM1 were significantly higher in HF patients with LVEF ≤ 35% and correlated with other biomarkers of cardiac fibrosis. In vitro study proved that functional sTEM1 was released into cultured media after stressing cardiomyocytes and HCF

Ferroelectric Control of the Conduction at the LaAlO 3 /SrTiO 3 Hetero-interface

Abstract The LaAlO 3 /SrTiO 3 (LAO/STO) interface serves as a model system in which a highly mobile quasi-twodimensional electron gas (2DEG) forms between two band insulator

Nickel(I) Monomers and Dimers with Cyclopentadienyl and Indenyl Ligands

The reaction of (μ-Cl)_2Ni_2(NHC)_2 (NHC=1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene (IPr) or 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene (SIPr)) with either one equivalent of sodium cyclopentadienyl (NaCp) or lithium indenyl (LiInd) results in the formation of diamagnetic NHC supported Ni^I dimers of the form (μ-Cp)(μ-Cl)Ni_2(NHC)_2 (NHC=IPr (1 a) or SIPr (1 b); Cp=C_5H_5) or (μ-Ind)(μ-Cl)Ni_2(NHC)_2 (NHC=IPr (2 a) or SIPr (2 b); Ind=C_7H_9), which contain bridging Cp and indenyl ligands. The corresponding reaction between two equivalents of NaCp or LiInd and (μ-Cl)_2Ni_2(NHC)_2 (NHC=IPr or SIPr) generates unusual 17 valence electron NiI monomers of the form (η5-Cp)Ni(NHC) (NHC=IPr (3 a) or SIPr (3 b)) or (η5-Ind)Ni(NHC) (NHC=IPr (4 a) or SIPr (4 b)), which have nonlinear geometries. A combination of DFT calculations and NBO analysis suggests that the NiI monomers are more strongly stabilized by the Cp ligand than by the indenyl ligand, which is consistent with experimental results. These calculations also show that the monomers have a lone unpaired-single-electron in their valence shell, which is the reason for the nonlinear structures. At room temperature the Cp bridged dimer (μ-Cp)(μ-Cl)Ni_2(NHC)_2 undergoes homolytic cleavage of the Ni[BOND]Ni bond and is in equilibrium with (η^5-Cp)Ni(NHC) and (μ-Cl)_2Ni_2(NHC)_2. There is no evidence that this equilibrium occurs for (μ-Ind)(μ-Cl)Ni_2(NHC)_2. DFT calculations suggest that a thermally accessible triplet state facilitates the homolytic dissociation of the Cp bridged dimers, whereas for bridging indenyl species this excited triplet state is significantly higher in energy. In stoichiometric reactions, the Ni^I monomers (η^5-Cp)Ni(NHC) or (η^5-Ind)Ni(NHC) undergo both oxidative and reductive processes with mild reagents. Furthermore, they are rare examples of active NiI precatalysts for the Suzuki–Miyaura reaction. Complexes 1 a, 2 b, 3 a, 4 a and 4 b have been characterized by X-ray crystallography

AA9int: SNP interaction pattern search using non-hierarchical additive model set.

MOTIVATION: The use of single nucleotide polymorphism (SNP) interactions to predict complex diseases is getting more attention during the past decade, but related statistical methods are still immature. We previously proposed the SNP Interaction Pattern Identifier (SIPI) approach to evaluate 45 SNP interaction patterns/patterns. SIPI is statistically powerful but suffers from a large computation burden. For large-scale studies, it is necessary to use a powerful and computation-efficient method. The objective of this study is to develop an evidence-based mini-version of SIPI as the screening tool or solitary use and to evaluate the impact of inheritance mode and model structure on detecting SNP-SNP interactions. RESULTS: We tested two candidate approaches: the 'Five-Full' and 'AA9int' method. The Five-Full approach is composed of the five full interaction models considering three inheritance modes (additive, dominant and recessive). The AA9int approach is composed of nine interaction models by considering non-hierarchical model structure and the additive mode. Our simulation results show that AA9int has similar statistical power compared to SIPI and is superior to the Five-Full approach, and the impact of the non-hierarchical model structure is greater than that of the inheritance mode in detecting SNP-SNP interactions. In summary, it is recommended that AA9int is a powerful tool to be used either alone or as the screening stage of a two-stage approach (AA9int+SIPI) for detecting SNP-SNP interactions in large-scale studies. AVAILABILITY AND IMPLEMENTATION: The 'AA9int' and 'parAA9int' functions (standard and parallel computing version) are added in the SIPI R package, which is freely available at https://linhuiyi.github.io/LinHY_Software/. SUPPLEMENTARY INFORMATION: Supplementary data are available at Bioinformatics online