Synthesis, Characterization, Absorption Properties, and Electronic Structures of Paddlewheel-Type Dirhodium(II) Tetra-μ-(<i>n</i>-naphthoate) Complexes: An Experimental and Theoretical Study

The reactions of [Rh2(O2CCH3)4(OH2)2] with n-naphthalenecarboxylic acids (n = 1: 1-HNC, n = 2: 2-HNC) afford the dirhodium tetra-&#956;-(n-naphthoate) complexes [Rh2(1-NC)4] (1) and [Rh2(2-NC)4] (2), respectively. Single crystal X-ray diffraction analyses of [1(OCMe2)2] and [2(OCMe2)2], which were obtained by recrystallization from acetone (OCMe2) solutions of 1 and 2, reveal that the dirhodium cores are coordinated by four equatorially bridging naphthoate ligands and two axial OCMe2 ligands. Density functional theory (DFT) calculation confirmed that (i) the single Rh&#8315;Rh bond is formed between the two Rh ions and (ii) the electronic structures between two Rh ions in [1(OCMe2)2] and [2(OCMe2)2] are best described as &#960;4&#948;2&#963;2&#948;*2&#960;*4 and &#948;2&#960;4&#963;2&#948;*2&#960;*4, respectively. Time-dependent DFT (TDDFT) calculations clarify the absorption band characters of [1(OCMe2)2] and [2(OCMe2)2]; the former shows the bands due to d&#8315;d and metal&#8315;to&#8315;metal-ligand charge transfer (MMLCT) excitations in the visible light region, whereas the latter shows the bands due to only d&#8315;d excitations in the same region. The electrochemical properties and thermal stabilities of [1(OCMe2)2] and [2(OCMe2)2] were also investigated in this study

Coordination-Induced Self-Assembly of a Heteroleptic Paddlewheel-Type Dirhodium Complex

A novel heteroleptic paddlewheel-type dirhodium (Rh2) complex [Rh2(O2CCH3)3(PABC)] (1; PABC = para-aminobenzenecarboxylate), which has an amino group as a potential donor site for coordination with the metal ion, was synthesized and characterized by 1H NMR, ESI-TOF-MS, infrared spectra, and elemental analysis. The slow evaporation of N,N-dimethylformamide (DMF)-dissolved 1 produces the purple-colored crystalline polymeric species [Rh2(O2CCH3)3 (PABC)(DMF)]n (1P). Single-crystal and powder X-ray diffraction analyses, as well as thermo-gravimetric analysis, clarified that 1P formed a one-dimensional polymeric structure, in which the two axial sites of the Rh2 ion in 1P are coordinated by a DMF molecule and an amino group of the PABC ligand of the neighboring molecule 1, by coordination-induced self-assembly (polymerization) with an Rh-amino bond. The reversible structural change (self-assembly and disassembly transformations) between the discrete species [Rh2(O2CCH3)3(PABC)(DMF)2] (1D; green solution) and the polymeric species 1P (purple solid) was accompanied by a color change, which easily occurred by the dissolution and evaporation procedures with DMF

In-hospital blood collection increases the rate of indeterminate results in interferon-gamma release assays

Background: The interferon (IFN)-γ release assay (IGRA) has recently been established as a method to evaluate the infection status of tuberculosis instead of the tuberculin skin test. However, indeterminate results can create challenges to interpretation. The IGRA has been available in Japan since 2005, including the recently launched QuantiFERON-TB Gold Plus (QFT-plus) assay. Objectives: The aim of this study was to investigate the clinical features and predictors of indeterminate results by the QFT-plus test in routine practice. Methods: This was a cross-sectional study of 1258 patients. Multivariate logistic regression models were employed to investigate the clinical factors related to indeterminate results by the QFT-plus. Results: Overall, 91.8% of results were found to be conclusive and 8.2% were indeterminate. The QFT-plus indeterminate results were predominantly due to a low level of IFN-γ production by mitogens. Multivariate analysis indicated that an indeterminate result was significantly associated with age, sex, corticosteroid use, autoimmune disease, and inpatient setting. Conclusion: Certain types of individuals are at higher risk of an indeterminate IGRA result. The QFT-plus test for hospitalized patients should be avoided as much as possible, and it is better to perform the test for those patients in outpatient settings

A novel highly quantitative and reproducible assay for the detection of anti-SARS-CoV-2 IgG and IgM antibodies

The quantitative range and reproducibility of current serological tests for severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2) are not optimized. Herein, we developed a diagnostic test that detects SARS-CoV-2 IgG and IgM with high quantitativeness and reproducibility and low interference. The system was based on the high-sensitivity chemiluminescence enzyme immunoassay (HISCL) platform and detects IgG and IgM specific to SARS-CoV-2 spike and nucleocapsid proteins. Quantification accuracy and reproducibility were evaluated using serially diluted samples from 60 SARS-CoV-2-infected patients. Assay performance was evaluated using serum samples from the SARS-CoV-2-infected patients and 500 SARS-CoV-2-negative serum samples collected before the emergence of SARS-CoV-2. The system showed high quantification accuracy (range, 102), high reproducibility (within 5%), and no cross-reaction between SARS1- and MERS-S proteins. Detection accuracy was 98.3% and 93.3% for IgG and IgM against spike proteins and 100% and 71.7% for IgG and IgM against nucleocapsid proteins, respectively. Mean antibody levels were &gt; 10 times that in negative samples upon admission and &gt; 100 times that at convalescent periods. Clinical severity upon admission was not correlated with IgG or IgM levels. This highly quantitative, reproducible assay system with high clinical performance may help analyze temporal serological/immunological profiles of SARS-CoV-2 infection and SARS-CoV-2 vaccine effectiveness

Osteopontin Deficiency Accelerates Spontaneous Colitis in Mice with Disrupted Gut Microbiota and Macrophage Phagocytic Activity - Fig 2

<p>(<b>A</b>) Enhanced <i>OPN</i> mRNA synthesis in the colonic tissues of IL-10 KO mice. Representative images of FISH for <i>OPN</i> mRNA in the rectal tissues from WT, IL-10 KO, and OPN/IL-10 DKO mice at 4 weeks of age. Scale bar = 100 μm. (<b>B</b>) Enhanced <i>OPN</i> expression localized to the colonic epithelial cells. Representative images of FISH for <i>OPN</i> mRNA (red) and immunofluorescent staining for E-cadherin (green) in the rectal tissues from IL-10 KO mice at 4 weeks of age. Scale bar = 100 μm.</p

Gut microbiome-derived metabolites modulate intestinal epithelial cell damage and mitigate graft-versus-host disease

The effect of alterations in intestinal microbiota on microbial metabolites and on disease processes such as graft-versus-host disease (GVHD) is not known. Here we carried out an unbiased analysis to identify previously unidentified alterations in gastrointestinal microbiota-derived short-chain fatty acids (SCFAs) after allogeneic bone marrow transplant (allo-BMT). Alterations in the amount of only one SCFA, butyrate, were observed only in the intestinal tissue. The reduced butyrate in CD326 + intestinal epithelial cells (IECs) after allo-BMT resulted in decreased histone acetylation, which was restored after local administration of exogenous butyrate. Butyrate restoration improved IEC junctional integrity, decreased apoptosis and mitigated GVHD. Furthermore, alteration of the indigenous microbiota with 17 rationally selected strains of high butyrate-producing Clostridia also decreased GVHD. These data demonstrate a heretofore unrecognized role of microbial metabolites and suggest that local and specific alteration of microbial metabolites has direct salutary effects on GVHD target tissues and can mitigate disease severity