Unexpected XPS Binding Energy Observations Further Highlighted by DFT Calculations of Ruthenocene-Containing [Ir(ppy)(RCOCHCORc)] Complexes: Cytotoxicity and Crystal Structure of [Ir(ppy)(FcCOCHCORc)].

The series of iridium(III) complexes, [Ir(ppy)(RCOCHCOR')], with R = CH and R' = CH (), Rc (), and Fc (), as well as R = Rc and R' = Rc () or Fc (), and R = R' = Fc (), ppy = 2-phenylpyridinyl, Fc = Fe(η-CH)(η-CH), and Rc = Ru(η-CH)(η-CH), has been investigated by single-crystal X-ray crystallography and X-ray photoelectron spectroscopy (XPS) supplemented by DFT calculations. Here, in the range of 3.74 ≤ Σχ ≤ 4.

Bacterial vaginosis-driven changes in vaginal T cell phenotypes and their implications for HIV susceptibility.

Bacterial vaginosis (BV) is a dysbiosis of the vaginal microbiome that is prevalent in reproductive-age women worldwide. Adverse outcomes associated with BV include an increased risk of sexually acquired Human Immunodeficiency Virus (HIV), yet the immunological mechanisms underlying this association are not well understood. To investigate BV driven changes to cervicovaginal tract (CVT) and circulating T cell phenotypes, participants with or without BV provided vaginal tract (VT) and ectocervical (CX) tissue biopsies and peripheral blood mononuclear cells (PBMC).

Regulatory T cells restrict immunity and pathology in distal tissue sites following a localized infection.

Regulatory T cells (Tregs) are well-known to mediate peripheral tolerance at homeostasis, and there is a growing appreciation for their role in modulating infectious disease immunity. Following acute and chronic infections, Tregs can restrict pathogen-specific T cell responses to limit immunopathology. However, it is unclear if Tregs mediate control of pathology and immunity in distal tissue sites during localized infections.

Unique immune profiles in collaborative cross mice linked to survival and viral clearance upon infection.

The response to infection is generally heterogeneous and diverse, with some individuals remaining asymptomatic while others present with severe disease or a diverse range of symptoms. Here, we address the role of host genetics on immune phenotypes and clinical outcomes following viral infection by studying genetically diverse mice from the Collaborative Cross (CC), allowing for use of a small animal model with controlled genetic diversity while maintaining genetic replicates. We demonstrate variation by deeply profiling a broad range of innate and adaptive immune cell phenotypes at steady-state in 63 genetically distinct CC mouse strains and link baseline immune signatures with virologic and clinical disease outcomes following infection of mice with herpes simplex virus 2 (HSV-2) or severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2).

Using Geometric Morphometric Analysis of Magnetic Resonance Imaging to Assess the Anatomy of the Eustachian Tube in Children with and without Otitis Media.

Otitis media (OM) is among the most common of childhood illnesses. It has long been hypothesized that children under age two are predisposed to OM due to differences in the anatomy of the Eustachian tube (ET), including the angle of the ET. OM in later childhood is less common but does occur, begging the question, are there shape differences in the ET that persist underlying later occurrences of OM? To answer this question, a novel method, which applied geometric and morphometric shape analysis to landmarks obtained from MRI data, was used.

CT Imaging of Eustachian Tube Balloon Dilation: Method Development on Cadaver Heads.

: To develop a methodology for the measurement of balloon dilation (BD) effects on Eustachian Tube (ET) structure using Computerized Tomography (CT) images. : The BD of the ET was performed on three cadaver heads (five ears) through the nasopharyngeal orifice. The axial CT images of the temporal bones were obtained before dilation, while an inflated balloon was in the lumen of ET, and after balloon removal in each ear.

Tubomanometry in measurement of velopharyngeal closure: A pilot study.

Objective: To investigate the differences in velum closure pattern in people with and without a history of middle ear disease using intranasal pressure curves recorded with the tubomanometer, a Eustachian tube (ET) testing device.

Study Design: Case control study.

Setting: Tertiary referral center.

Dissecting eustachian tube dysfunction: From phenotypes to endotypes.

Objective: A broad spectrum of complaints, symptoms and manifestations has been assigned to Eustachian tube (ET) dysfunction (ETD). While such presentations may manifest as ETD phenotypes, underlying mechanisms are defined as endotypes. Our goal is to develop a diagnostic approach to differentiate the endotypes and guide clinicians in the workup and selection of treatments targeting the mechanism of ETD.

Memory T cells possess an innate-like function in local protection from mucosal infection.

Mucosal infections pose a significant global health burden. Antigen-specific tissue-resident T cells are critical to maintaining barrier immunity. Previous studies in the context of systemic infection suggest that memory CD8+ T cells may also provide innate-like protection against antigenically unrelated pathogens independent of T cell receptor engagement.

Ferrocene-Bearing Dodecylphthalocyanines: Synthesis, Spectroscopic and Electrochemical Behavior.

Ferrocenylbutoxy-bearing dodecylated phthalocyanines, MPc(CH)(OCHFc) with M = 2H (compound series and ) or Zn (compound series , and ), ≤ 8 and ≤ 4, were synthesized through either metal-free statistical condensation between 3,6-bis(dodecyl)phthalonitrile, , and 4- (), or 3-(4'-ferrocenylbutoxy)phthalonitrile, , or a zinc template statistical condensation between 4,5-bis(dodecyl)phthalonitrile, , and in the presence of anhydrous zinc acetate, or by zinc insertion into metal-free phthalocyanines. Compounds were designed to have eight nonperipheral dodecyl substituents, six nonperipheral dodecyl, either one peripheral or one nonperipheral 4'-ferrocenylbutoxy substituent, four nonperipheral dodecyl and two peripheral 4'-ferrocenylbutoxy substituents, or four peripheral 4'-ferrocenylbutoxy substituents. The compound having six peripheral dodecyl and one peripheral 4'-ferrocenylbutoxy substituents was also synthesized.

Lymphatic anomalies during lifetime in patients with Noonan syndrome: Retrospective cohort study.

Noonan syndrome (NS) has been associated with an increased risk of lymphatic anomalies, with an estimated prevalence of 20%. The prevalence of lymphatic anomalies seems to differ between pathogenic variants. Therefore, this study aims to describe the clinical presentation, prevalence and genotype-phenotype correlations of lymphatic anomalies during life in patients with NS.

Octakis(dodecyl)phthalocyanines: Influence of Peripheral versus Non-Peripheral Substitution on Synthetic Routes, Spectroscopy and Electrochemical Behaviour.

Non-peripherally octakis-substituted phthalocyanines (Pc's), MPc(CH) with M = 2H () or Zn (), as well as peripherally octakis-substituted phthalocyanines (Pc's) with M = Zn (), Mg () and 2H (), were synthesized by cyclotetramerization of 3,6- () or 4,5-bis(dodecyl)phthalonitrile (), template cyclotetramerization of precursor phthalonitriles in the presence of Zn or Mg, metal insertion into metal-free phthalocyanines, and removal of Mg or Zn from the phthalocyaninato coordination cavity. The more effective synthetic route towards Pc was demetalation of . Pc's were more soluble than Pc's.

Correlation of Regulatory T Cell Numbers with Disease Tolerance upon Virus Infection.

The goal of a successful immune response is to clear the pathogen while sparing host tissues from damage associated with pathogen replication and active immunity. Regulatory T cells (Treg) have been implicated in maintaining this balance as they contribute both to the organization of immune responses as well as restriction of inflammation and immune activation to limit immunopathology. To determine if Treg abundance prior to pathogen encounter can be used to predict the success of an antiviral immune response, we used genetically diverse mice from the collaborative cross infected with West Nile virus (WNV).

Baseline T cell immune phenotypes predict virologic and disease control upon SARS-CoV infection in Collaborative Cross mice.

The COVID-19 pandemic has revealed that infection with SARS-CoV-2 can result in a wide range of clinical outcomes in humans. An incomplete understanding of immune correlates of protection represents a major barrier to the design of vaccines and therapeutic approaches to prevent infection or limit disease. This deficit is largely due to the lack of prospectively collected, pre-infection samples from individuals that go on to become infected with SARS-CoV-2.

Silica Nanopowder Supported Frustrated Lewis Pairs for CO Capture and Conversion to Formic Acid.

Treatment of hydroxylated silica nanopowders and allyl-functionalized silica nanopowders with 3-(diphenylborano)- or 3-bis(pentafluorophenylborano)propyltrimethoxysilane or 2-(diphenylphosphino)- or 2-(dicyclohexylphosphino)ethyltriethoxysilane generates silica nanopowder supported Lewis acids and silica nanopowder supported Lewis bases . These surfaces were characterized by C, B, and P cross-polarization magic angle spinning nuclear magnetic resonance (CP MAS NMR), X-ray photoelectron spectroscopy (XPS), and attenuated total reflection Fourier transform infrared (ATR FTIR). When is combined with solution-phase Lewis bases PR (R = CF, CH, mesityl), six associated silica nanopowder supported frustrated Lewis pairs (FLPs) are formed.

Synthesis, Characterization, and Electrochemistry of Diferrocenyl β-Diketones, -Diketonates, and Pyrazoles.

The synthesis of FcC(O)CH(R)C(O)Fc (Fc = Fe(η-CH)(η-CH); R = H, ; Bu, ; CHCH(OCHCH)OMe, ), [M(κ,'-FcC(O)CHC(O)Fc)] (M = Ti, = 3, ; M = Fe, = 3, ; M = BF, = 1, ), and 1-R'-3,5-Fc-CHN (R' = H, ; Me, ; Ph, ) is discussed. The solid-state structures of , , , , , , and ([TiCl(κ,'-PhC(O)CHC(O)Ph)]) show that and exist in their β-diketo form. Compound crystallizes as a tetramer based on a hydrogen bond pattern, including one central water molecule.

Baseline T cell immune phenotypes predict virologic and disease control upon SARS-CoV infection.

Unlabelled: The COVID-19 pandemic has revealed that infection with SARS-CoV-2 can result in a wide range of clinical outcomes in humans, from asymptomatic or mild disease to severe disease that can require mechanical ventilation. An incomplete understanding of immune correlates of protection represents a major barrier to the design of vaccines and therapeutic approaches to prevent infection or limit disease. This deficit is largely due to the lack of prospectively collected, pre-infection samples from indiviuals that go on to become infected with SARS-CoV-2.

A Kinetic Study of the Electron-Transfer Reactions of Nickel(III,II) Tripeptide Complexes with Cyano Complexes of Molybdenum, Tungsten, and Iron.

Experimentally measured rate constants, , for the reductions of [Ni(III)tripeptides(HO)] with Fe(CN), Mo(CN), and W(CN) are 10 to 10 times faster than the calculated rate constants with the Marcus theory for outer-sphere electron-transfer processes, , even when work terms are considered. This gives rise to a kinetic advantage of / = 10-10, which is consistent with an inner-sphere electron-transfer mechanism via a bridged intermediate. In addition, values are nearly independent of the electrochemical driving force of the reactions.

Change in Eustachian Tube Function With Balloon Dilation in Adults With Ventilation Tubes.

Objective: Assess the changes in Eustachian tube (ET) function (ETF) with balloon dilation of Eustachian tube (BDET).

Study Design: Prospective cohort for repeated testing measures.

Setting: Clinical research center.

The PRIDE Study: Evaluation of online methods of data collection.

Background: Large birth cohort studies are extremely valuable in assessing associations between early life exposures and long-term outcomes. Establishing new birth cohorts is challenging due to declining participation rates. Online methods of data collection may increase feasibility, but have not been evaluated thoroughly.

Synthesis, Spectroscopy and Electrochemistry in Relation to DFT Computed Energies of Ferrocene- and Ruthenocene-Containing -Diketonato Iridium(III) Heteroleptic Complexes. Structure of [(2-Pyridylphenyl)Ir(RcCOCHCOCH].

A series of new ferrocene- and ruthenocene-containing iridium(III) heteroleptic complexes of the type [(ppy)Ir(RCOCHCOR')], with ppy = 2-pyridylphenyl, R = Fc = Fe(η-CH)(η-CH) and R' = CH () or Fc (), as well as R = Rc = Ru(η-CH)(η-CH) and R' = CH (), Rc () or Fc () was synthesized the reaction of appropriate metallocene-containing -diketonato ligands with [(ppy)(-Cl)Ir]. The single crystal structure of (monoclinic, P2/n, Z = 4) is described. Complexes - absorb light strongly in the region 280-480 nm the metallocenyl -diketonato substituents quench phosphorescence in -.

Immune Predictors of Mortality After Ribonucleic Acid Virus Infection.

Background: Virus infections result in a range of clinical outcomes for the host, from asymptomatic to severe or even lethal disease. Despite global efforts to prevent and treat virus infections to limit morbidity and mortality, the continued emergence and re-emergence of new outbreaks as well as common infections such as influenza persist as a health threat. Challenges to the prevention of severe disease after virus infection include both a paucity of protective vaccines as well as the early identification of individuals with the highest risk that may require supportive treatment.

Regulatory T cells limit unconventional memory to preserve the capacity to mount protective CD8 memory responses to pathogens.

Immunological memory exists so that following infection an expanded population of pathogen-specific lymphocytes can rapidly and efficiently control infection in the case of reexposure. However, in the case of CD8+ T lymphocytes, a population of unconventional CD44+CD122+ virtual memory T cells (T) has been described that possesses many, though not all, features of "true memory" T cells, without the requirement of first encountering cognate antigen. Here, we demonstrate a role for regulatory T cell-mediated restraint of T at least in part through limiting IL-15 -presentation by CD11b+ dendritic cells.

Immune Correlates of Protection From West Nile Virus Neuroinvasion and Disease.

Background: A challenge to the design of improved therapeutic agents and prevention strategies for neuroinvasive infection and associated disease is the lack of known natural immune correlates of protection. A relevant model to study such correlates is offered by the Collaborative Cross (CC), a panel of recombinant inbred mouse strains that exhibit a range of disease manifestations upon infection.

Methods: We performed an extensive screen of CC-F1 lines infected with West Nile virus (WNV), including comprehensive immunophenotyping, to identify groups of lines that exhibited viral neuroinvasion or neuroinvasion with disease and lines that remained free of WNV neuroinvasion and disease.

Eustachian Tube Function in Adults with Ventilation Tubes Inserted for Otitis Media with Effusion.

Objective: To investigate the eustachian tube (ET) function (ETF) in adults with ventilation tube (VT) inserted for the treatment of chronic otitis media with effusion (COME).

Materials And Methods: A total of 17 subjects with at least one VT were enrolled. A detailed history was obtained, and risk factors were assessed with questionnaires.