Assessing the Character of the CF Ligand from the Electrochemical and Photophysical Properties of [Ni(CF)(NN)] Complexes.

Organonickel complexes containing α-diimine ligands [Ni(CF)(NN)] (NN = 2,2'-bipyridine (bpy), 2,9-dimethyl-1,10-phenanthroline (dmphen), 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen), dipyrido[3,2-:2',3'-]phenazine (dppz), 1,4-bis(isopropyl)-1,4-diazabutadiene (Pr-DAB), and 1,4-bis(2,6-dimethylphenyl)-1,4-diazabutadiene (Xyl-DAB) were prepared and studied structurally, spectroscopically, and electrochemically. Their molecular structures from single-crystal X-ray diffraction show near-perfect square planar Ni(II) coordination except in the case of dmphen. Primary reversible electrochemical reductions in the range from -1 to -2 V vs ferrocene/ferrocenium couple lead to mainly diimine-localized radical anion complexes, while secondary reductions in the range from -2 to -2.

Enhanced luminescence properties through heavy ancillary ligands in [Pt(C^N^C)(L)] complexes, L = AsPh and SbPh.

In the frame of our research aiming to develop efficient triplet-emitting materials, we are exploring the concept of introducing additional heavy atoms into cyclometalated transition metal complexes to enhance intersystem-crossing (ISC) and thus triplet emission through increased spin-orbit coupling (SOC). In an in-depth proof-of-principle study we investigated the double cyclometalated Pt(II) complexes [Pt(C^N^C)(PnPh)] (HC^N^CH = 2,6-diphenyl-pyridine (Hdpp) or dibenzoacridine (Hdba); Pn = pnictogen atoms P, As, Sb, or Bi) through a combined experimental and theoretical approach. The derivatives containing Pn = P, As, and Sb were synthesised and characterised comprehensively using single crystal X-ray diffraction (scXRD), UV-vis absorption and emission spectroscopy, transient absorption (TA) spectroscopy and cyclic voltammetry (CV).

Rhenium Tricarbonyl Complexes of Azodicarboxylate Ligands.

The excellent π-accepting azodicarboxylic esters adcOR (R = Et, Pr, Bu, Bn (CH-CH) and Ph) and the piperidinyl amide derivative adcpip were used as bridging chelate ligands in dinuclear Re(CO) complexes [{Re(CO)Cl}(µ-adcOR)] and [{Re(CO)Cl}(µ-adcpip)]. From the adcpip ligand the mononuclear derivatives [Re(CO)Cl(adcpip)] and [Re(CO)(PPh)(µ-adcpip)]Cl were also obtained. Optimised geometries from density functional theory (DFT) calculations show and isomers for the dinuclear -Re(CO) complexes at slightly different energies but they were not distinguishable from experimental IR or UV-Vis absorption spectroscopy.

Triplet Emitting C^N^C Cyclometalated Dibenzo[c,h]Acridine Pt(II) Complexes.

In a series of Pt(II) complexes [Pt(dba)(L)] containing the very rigid, dianionic, bis-cyclometalating, tridentate C^N^C2− heterocyclic ligand dba2− (H2dba = dibenzo[c,h]acridine), the coligand (ancillary ligand) L = dmso, PPh3, CNtBu and Me2Imd (N,N’-dimethylimidazolydene) was varied in order to improve its luminescence properties. Beginning with the previously reported dmso complex, we synthesized the PPh3, CNtBu and Me2Imd derivatives and characterized them by elemental analysis, 1H (and 31P) NMR spectroscopy and MS. Cyclic voltammetry showed partially reversible reduction waves ranging between −1.

Examining dietary self-talk content and context for discretionary snacking behaviour: a qualitative interview study.

Consuming discretionary snack foods high in calories, salt, sugar or fat in between regular meals can have a negative impact on weight management and health. Despite the intention to refrain from discretionary snacking, individuals often report feeling tempted by snack foods. A cognitive process to resolve food choice related tension may be dietary self-talk which is one's inner speech around dietary choice.

Photoluminescence of Ni(II), Pd(II), and Pt(II) Complexes [M(Medpb)Cl] Obtained from C‒H Activation of 1,5-Di(2-pyridyl)-2,4-dimethylbenzene (MedpbH).

The three complexes [M(Medpb)Cl] (M = Ni, Pd, Pt) containing the tridentate ,,-cyclometalating 3,5-dimethyl-1,5-dipyridyl-phenide ligand (Medpb) were synthesised using a base-assisted C‒H activation method. Oxidation potentials from cyclic voltammetry increased along the series Pt < Ni < Pd from 0.15 to 0.

Ni, Pd, and Pt complexes of a tetradentate dianionic thiosemicarbazone-based O^N^N^S ligand.

New tetradentate phenolate O^N^N^S thiosemicarbazone (TSC) ligands and their Ni(ii), Pd(ii) and Pt(ii) complexes were studied. The diamagnetic and square planar configured orange or red complexes show reversible reductive electrochemistry and in part reversible oxidative electrochemistry at very moderate potentials. DFT calculations show essentially pyridyl-imine centred lowest unoccupied molecular orbitals (LUMO) while the highest occupied molecular orbitals (HOMO) receive contributions from the phenolate moiety, the metal d orbitals and the TSC thiolate atom in keeping with UV-vis spectroelectrochemistry.

Mitochondrial Metabolism in Astrocytes Regulates Brain Bioenergetics, Neurotransmission and Redox Balance.

In the brain, mitochondrial metabolism has been largely associated with energy production, and its dysfunction is linked to neuronal cell loss. However, the functional role of mitochondria in glial cells has been poorly studied. Recent reports have demonstrated unequivocally that astrocytes do not require mitochondria to meet their bioenergetics demands.

The Complete Care Model and Glycemic Control in California State Prisons.

Since integrating the chronic care theory in 2008 and the complete care model (CCM) in 2015, the California Department of Corrections and Rehabilitation (CDCR) has seen steady improvement in health care-related mortality. However, comparing glycated hemoglobin (HbA1c) levels for the 2 years pre- and the 2 years post-CCM shows the glycemic control for diabetes patients has not significantly changed. Findings suggest that additional components of the theory will need to be incorporated into the CCM to achieve CDCR's progressive goal of 90% of their diabetes patients having HbA1c levels less than 8%.

Evaluating the immediate effect of forearm and wrist orthoses on pain and function in individuals with lateral elbow tendinopathy: A systematic review.

Background: Lateral elbow tendinopathy is associated with pain during gripping, with forearm/wrist orthoses prescribed for treatment.

Objectives: To investigate the immediate effects of forearm and/or wrist orthoses on outcome measures of pain and function in individuals with lateral elbow tendinopathy.

Design: Systematic review METHODS: Four electronic databases were searched to identify randomised controlled trials reporting the immediate effects of forearm and/or wrist orthoses on pain and function in individuals with lateral elbow tendinopathy.

Shotgun metagenomic analysis of microbial communities from the Loxahatchee nature preserve in the Florida Everglades.

Background: Currently, much is unknown about the taxonomic diversity and the mechanisms of methane metabolism in the Florida Everglades ecosystem. The Loxahatchee National Wildlife Refuge is a section of the Florida Everglades that is almost entirely unstudied in regard to taxonomic profiling. This short report analyzes the metagenome of soil samples from this Refuge to investigate the predominant taxa, as well as the abundance of genes involved in environmentally significant metabolic pathways related to methane production (nitrogen fixation and dissimilatory sulfite reduction).

Survival Mechanisms and Xenobiotic Susceptibility of Keratinocytes Exposed to Metal-Derived Nanoparticles.

Metal-derived nanoparticles (Mt-NPs) are increasingly used in cosmetology due to their ultraviolet shielding (titanium dioxide [TiO]), antioxidant (cerium dioxide [CeO]), and biocidal (silver [Ag]) properties. In the absence of overt toxicity (i.e.

Assessing the generality and durability of interview-informed functional analyses and treatment.

Due to the limited research demonstrating socially valid outcomes of function-based treatments in ecologically relevant environments (Santiago, Hanley, Moore, & Jin, 2016), we replicated and extended the effects of the interview-informed functional analysis and skill-based treatment procedure described by Hanley, Jin, Vanselow, and Hanratty (2014) with two children diagnosed with autism in a home setting. The assessment and treatment was implemented by a home-based service provider and treatment was extended to the participants' parents. Following the interview-informed functional analyses, we taught the participants functional communication responses and to engage in less-preferred activities when functional communication outcomes were delayed.

Mitochondrial dysfunction in glial cells: Implications for neuronal homeostasis and survival.

Mitochondrial dysfunction is central to the pathogenesis of neurological disorders. Neurons rely on oxidative phosphorylation to meet their energy requirements and thus alterations in mitochondrial function are linked to energy failure and neuronal cell death. Furthermore, in neurons, dysfunctional mitochondria are reported to increase the steady-state levels of reactive oxygen species derived from the leakage of electrons from the electron transport chain.

Genomic epidemiology of multidrug-resistant Mycobacterium tuberculosis during transcontinental spread.

The transcontinental spread of multidrug-resistant (MDR) tuberculosis is poorly characterized in molecular epidemiologic studies. We used genomic sequencing to understand the establishment and dispersion of MDR Mycobacterium tuberculosis within a group of immigrants to the United States. We used a genomic epidemiology approach to study a genotypically matched (by spoligotype, IS6110 restriction fragment length polymorphism, and mycobacterial interspersed repetitive units-variable number of tandem repeat signature) lineage 2/Beijing MDR strain implicated in an outbreak of tuberculosis among refugees in Thailand and consecutive cases within California.

Beijing sublineages of Mycobacterium tuberculosis differ in pathogenicity in the guinea pig.

The Beijing family of Mycobacterium tuberculosis strains is part of lineage 2 (also known as the East Asian lineage). In clinical studies, we have observed that isolates from the sublineage RD207 of lineage 2 were more readily transmitted among humans. To investigate the basis for this difference, we tested representative strains with the characteristic Beijing spoligotype from four of the five sublineages of lineage 2 in the guinea pig model and subjected these strains to comparative whole-genome sequencing.