Mechanism-Guided Design of Robust Palladium Catalysts for Selective Aerobic Oxidation of Polyols.

The palladium complex [(L1)Pd(µ-OAc)]2[OTf]2 (L1 = neocuproine) is a selective catalyst for the aerobic oxidation of vicinal polyols to α-hydroxyketones, but competitive oxidation of the ligand methyl groups limits the turnover number and necessitates high Pd loadings. Replacement of the neocuproine ligand with 2,2'-biquinoline ligands was investigated as a strategy to improve catalyst performance and explore the relationship between ligand structure and reactivity. Evaluation of [(L2)Pd(µ-OAc)]2[OTf]2 (L2 = 2,2'-biquinoline) as a catalyst for aerobic alcohol oxidation revealed a threefold enhancement in turnover number relative to the neocuproine congener, but a much slower rate. Mechanistic studies indicated that the slow rates observed with L2 were a consequence of precipitation of an insoluble trinuclear palladium species─(L2Pd)3(µ-O)22+─formed during catalysis and characterized by high-resolution electrospray ionization mass spectrometry. Density functional theory was used to predict that a sterically modified biquinoline ligand, L3 = 7,7'-di-tert-butyl-2,2'-biquinoline, would disfavor the formation of the trinuclear (LPd)3(µ-O)22+ species. This design strategy was validated as catalytic aerobic oxidation with [(L3)Pd(µ-OAc)]2[OTf]2 is both robust and rapid, marrying the kinetics of the parent L1-supported system with the high aerobic turnover numbers of the L2-supported system. Changes in ligand structure were also found to modulate regioselectivity in the oxidation of complex glycoside substrates, providing new insights into structure-selectivity relationships with this class of catalysts.

"Is it us or is it me?": Family experiences of connectedness following a reflecting team intervention.

The present study examined family-wide versus individual perceptions of, and changes in, family connectedness in response to a one-time reflecting team (RT) intervention. Seventy-six families (N = 208 individuals), recruited during family therapy, completed family connectedness measures before and after the RT intervention. A subset of adults (n = 26) completed 1-week follow-up measures. Three-level (family, individual, time) multilevel models were used to partition sources of variance in connectedness while permitting different fixed and random effects for adults and minors. Results indicate that family connectedness is a characteristic of whole-families (34% of the variance), individuals (43%), and change over time (23%), including measurement error. Additionally, participants reported higher family connectedness after the RT. This study demonstrates the importance of considering family connectedness as a multilevel relationship construct that potentially changes in response to RT.

Effect of Redox Active Ligands on the Electrochemical Properties of Manganese Tricarbonyl Complexes.

The synthesis, structural characterization, and electrochemical behavior of the neutral Mn(azpy)(CO)3(Br) 4 (azpy = 2-phenylazopyridine) complex is reported and compared with its structural analogue Mn(bipy)(CO)3(Br) 1 (bipy = 2,2'-bipyridine). 4 exhibits reversible two-electron reduction at a mild potential (-0.93 V vs Fc+/0 in acetonitrile) in contrast to 1, which exhibits two sequential one-electron reductions at -1.68 V and -1.89 V vs Fc+/0 in acetonitrile. The key electronic structure differences between 1 and 4 that lead to disparate electrochemical properties are investigated using a combination of Mn-K-edge X-ray absorption spectroscopy (XAS), Mn-Kß X-ray emission spectroscopy (XES), and density functional theory (DFT) on 1, 4, their debrominated analogues, [Mn(L)(CO)3(CH3CN)][CF3SO3] (L = bipy 2, azpy 5), and two-electron reduced counterparts [Mn(bipy)(CO)3][K(18-crown-6)] 3 and [Mn(azpy)(CO)3][Cp2Co] 6. The results reveal differences in the distribution of electrons about the CO and bidentate ligands (bipy and azpy), particularly upon formation of the highly reduced, formally Mn(-1) species. The data show that the degree of ligand noninnocence and resulting redox-activity in Mn(L)(CO)3 type complexes impacts not only the reducing power of such systems, but the speciation of the reduced complexes via perturbation of the monomer-dimer equilibrium in the singly reduced Mn(0) state. This study highlights the role of redox-active ligands in tuning the reactivity of metal centers involved in electrocatalytic transformations.

Genome-wide association study in frontal fibrosing alopecia identifies four susceptibility loci including HLA-B*07:02.

Frontal fibrosing alopecia (FFA) is a recently described inflammatory and scarring type of hair loss affecting almost exclusively women. Despite a dramatic recent increase in incidence the aetiopathogenesis of FFA remains unknown. We undertake genome-wide association studies in females from a UK cohort, comprising 844 cases and 3,760 controls, a Spanish cohort of 172 cases and 385 controls, and perform statistical meta-analysis. We observe genome-wide significant association with FFA at four genomic loci: 2p22.2, 6p21.1, 8q24.22 and 15q2.1. Within the 6p21.1 locus, fine-mapping indicates that the association is driven by the HLA-B*07:02 allele. At 2p22.1, we implicate a putative causal missense variant in CYP1B1, encoding the homonymous xenobiotic- and hormone-processing enzyme. Transcriptomic analysis of affected scalp tissue highlights overrepresentation of transcripts encoding components of innate and adaptive immune response pathways. These findings provide insight into disease pathogenesis and characterise FFA as a genetically predisposed immuno-inflammatory disorder driven by HLA-B*07:02.

Looking into the One-way Mirror: A Pilot Study on the Impact of Reflecting Teams on Family Members.

Reflecting Teams (RTs) are an internationally recognized clinical consultation methodology, first developed by Tom Andersen in 1985. Over the last three decades, family therapists around the world have used RTs to enhance treatment. However, this innovation to family therapy practice is not well-standardized nor evaluated. The pilot study described in this article is an attempt to expand on the previous studies on RTs, and quantitatively examines RTs conducted with family therapy participants at a university medical center psychiatric institute. Preliminary analyses indicate that after participating in a single RT, family members may feel more hopeful, believe they can better support each other in times of stress, have more confidence in working together, and resolve conflicts. Additionally, the analyses suggest that family members may feel better understood and have more ideas about how to have a conversation with their family members, even though, after the RT, they may not view their family differently. These preliminary results suggest that further studies should explore the influence of RTs on family functioning.

Los "equipos reflexivos" (Reflecting Teams, RTs) son una metodología de consulta clínica reconocida a nivel internacional que fue desarrollada por primera vez por Tom Andersen en 1985 (Andersen, 1992). Durante las últimas tres décadas, los terapeutas familiares de todo el mundo han usado los equipos reflexivos para optimizar el tratamiento (p. ej.: Brownlee, Vis, & McKenna, 2009; Höger, Temme, Reiter, & Steiner, 1994). Sin embargo, esta innovación en la práctica de terapia familiar no está bien estandarizada ni evaluada. El estudio piloto descrito en este artículo es un intento de ampliar estudios previos sobre los equipos reflexivos y de analizar cuantitativamente los equipos reflexivos implementados con los participantes de una terapia familiar en un instituto psiquiátrico y un centro médico universitario. Los análisis preliminares indican que después de participar en un solo equipo reflexivo, los familiares pueden sentirse más optimistas, creer que pueden apoyarse mejor mutuamente en momentos de estrés, tener más confianza en trabajar juntos y resolver conflictos. Los integrantes de la familia también pueden sentirse mejor comprendidos y tener más ideas acerca de cómo conversar con sus familiares. Sin embargo, después del equipo reflexivo, es posible que no vean a su familia de forma diferente. Estos resultados preliminares sugieren que otros estudios deberían analizar la influencia de los equipos reflexivos en el funcionamiento familiar.

Student veterans with posttraumatic stress symptoms: Perceived preferences for on-campus psychoeducation.

OBJECTIVE: This investigation aimed to better understand perceived barriers to academic success and preferences for a veteran-specific psychosocial course among veterans with symptoms of posttraumatic stress (PTS). METHOD: Ninety-three veterans participated in this investigation as part of a larger study examining psychosocial functioning among veterans with PTS symptoms. Participants completed a self-report survey focused on perceived barriers to academic success and psychoeducational preferences related to health and well-being. RESULTS: Perceived barriers to academic success reported as most problematic were sleep difficulties, stress, depression, and financial concerns. Results indicated that veterans would be interested in attending an on-campus course focusing on these areas. CONCLUSIONS AND IMPLICATIONS FOR PRACTICE: These findings contribute to the understanding of student veterans with PTS symptoms' perceived needs and inform the development of campus programs for this population. (PsycINFO Database Record (c) 2018 APA, all rights reserved).

Control of clustering behavior in anionic cerium(iii) corrole complexes: from oligomers to monomers.

The first synthesis of anion capped cerium corrole complexes is reported. Unusual clustering of the lanthanide corrole units has been found and the degree of aggregation can be controlled by the choice of the capping ligand. A polymeric structure 1a, with the general formula [Cor-Ce(THF)-Cp-Na]n (Cor = 5,15-bis(2,4,6-trimethylphenyl)-10-(4 methoxyphenyl)-corrole, THF = tetrahydrofuran), is formed using sodium cyclopentadienide (NaCp) and a dimeric structure 2a, with the general formula [Cor-Ce-Tp]2, is formed when potassium tris(pyrazolyl)borate (KTp) is used. Encapsulation of the counter-cation leads to the isolation of the monomeric structures 1b and 2b, with the general formulas [AM(2.2.2-cryptand)][Cor-Cp-X] (AM = Na or K, X = Cp or Tp). The structural and spectroscopic properties of the complexes have been investigated.

Hydrogel-forming microneedle arrays exhibit antimicrobial properties: potential for enhanced patient safety.

We describe, for the first time, the microbial characterisation of hydrogel-forming polymeric microneedle arrays and the potential for passage of microorganisms into skin following microneedle penetration. Uniquely, we also present insights into the storage stability of these hydroscopic formulations, from physical and microbiological viewpoints, and examine clinical performance and safety in human volunteers. Experiments employing excised porcine skin and radiolabelled microorganisms showed that microorganisms can penetrate skin beyond the stratum corneum following microneedle puncture. Indeed, the numbers of microorganisms crossing the stratum corneum following microneedle puncture were greater than 105 cfu in each case. However, no microorganisms crossed the epidermal skin. When using a 21G hypodermic needle, more than 104 microorganisms penetrated into the viable tissue and 106 cfu of Candida albicans and Staphylococcus epidermidis completely crossed the epidermal skin in 24 h. The hydrogel-forming materials contained no microorganisms following de-moulding and exhibited no microbial growth during storage, while also maintaining their mechanical strength, apart from when stored at relative humidities of 86%. No microbial penetration through the swelling microneedles was detectable, while human volunteer studies confirmed that skin or systemic infection is highly unlikely when polymeric microneedles are used for transdermal drug delivery. Since no pharmacopoeial standards currently exist for microneedle-based products, the exact requirements for a proprietary product based on hydrogel-forming microneedles are at present unclear. However, we are currently working towards a comprehensive specification set for this microneedle system that may inform future developments in this regard.

Risk of exposure to eastern equine encephalomyelitis virus increases with the density of northern cardinals.

For a variety of infectious diseases, the richness of the community of potential host species has emerged as an important factor in pathogen transmission, whereby a higher richness of host species is associated with a lowered disease risk. The proposed mechanism driving this pattern is an increased likelihood in species-rich communities that infectious individuals will encounter dead-end hosts. Mosquito-borne pathogen systems potentially are exceptions to such "dilution effects" because mosquitoes vary their rates of use of vertebrate host species as bloodmeal sources relative to host availabilities. Such preferences may violate basic assumptions underlying the hypothesis of a dilution effect in pathogen systems. Here, we describe development of a model to predict exposure risk of sentinel chickens to eastern equine encephalitis virus (EEEV) in Walton County, Florida between 2009 and 2010 using avian species richness as well as densities of individual host species potentially important to EEEV transmission as candidate predictor variables. We found the highest support for the model that included the density of northern cardinals, a highly preferred host of mosquito vectors of EEEV, as a predictor variable. The highest-ranking model also included Culiseta melanura abundance as a predictor variable. These results suggest that mosquito preferences for vertebrate hosts influence pathogen transmission.