Group 7 carbonyl complexes of a PNN-heteroscorpionate ligand.

A series of rhenium and manganese carbonyl complexes of a heteroscorpionate ligand with an atypical NP-donor set has been prepared to better understand their electronic and CO releasing properties. Thus, the ligand, pzTTP, with an ,-bis(pyrazol-1-yl)tolyl group decorated with an -situated di(-tolyl)phosphanyl reacts with carbonyl group 17 reagents to give [-(κNP-pzTTP)Re(CO)Br], 1, and [-(κNP-pzTTP)M(CO)](OTf = OSCF), 2-M (M = Re, Mn), if care is taken during the preparation of the manganeses derivative. When heated in CHCN, 2-Mn slowly transforms to [,-(κNP-pzTTP)Mn(CO)(NCCH)](OTf), 3-Mn.

The role of unit cohesion and perceived resilience in substance use disorder.

Soldiers have high rates of substance use disorders (SUD), often in the aftermath of stressors experienced during military deployments. There are several factors that protect against SUD. For example, individual factors like perceived resilience and group factors such as unit cohesion may make someone less likely to abuse substances.

Preferential crystallization of (±)-pinenyllithium·TMEDA.

(±)-Pinenyllithium·TMEDA or (tetramethylethylenediamine-κN,N')(η-6,6-dimethyl-2-methylenebicyclo[3.1.1]heptyl)lithium, [Li(CH)(CHN)], is readily prepared from β-pinene, butyllithium and TMEDA, and the racemic material preferentially crystallizes even from 96:4 (92% ee) mixtures of (-)- and (+)-β-pinene, respectively.

The effectiveness of cognitive behavioral therapy for insomnia on sleep outcomes in the context of pain among older adult veterans.

Background: Cognitive behavioral therapy for insomnia (CBT-I) is the gold-standard treatment for insomnia disorder in adults. Compared to young adults, older adults have increased risk for the development of conditions associated with chronic pain, which may impact the efficacy of CBT-I in improving insomnia symptoms in older adults. This study evaluated the effect of participant-rated pain on sleep-related outcomes of a supervised, non-clinician administered CBT-I program in older adult patients with chronic insomnia disorder.

Efficient Synthesis of Thiazole-Fused Bisnoralcohol Derivatives as Potential Therapeutic Agents.

Thiazole derivatives are known for a wide range of therapeutic properties. Bisnoralcohol is an inexpensive natural product obtained by the biodegradation of sterols. This article describes an efficient synthesis of a library of thiazole-fused bisnoralcohol derivatives.

Associations of humor, morale, and unit cohesion on posttraumatic stress disorder symptoms.

Military personnel experience many stressors during deployments that can lead to symptoms of posttraumatic stress disorder (PTSD). However, not all military personnel who are exposed to deployment stressors develop PTSD symptoms. Recent research has explored factors that contribute to military personnel resilience, a multifaceted and multidetermined construct, as a means to mitigate and prevent PTSD symptoms.

Photocatalytic Hydrogen Production with A Molecular Cobalt Complex in Alkaline Aqueous Solutions.

The thermodynamic favorability of an alkaline solution for the oxidation of water suggests the need for developing hydrogen evolution reaction (HER) catalysts that can function in basic aqueous solutions so that both of the half reactions in overall water splitting can occur in mutually compatible solutions. Although photocatalytic HERs have been reported mostly in acidic solutions and a few at basic pHs in mixed organic aqueous solutions, visible-light driven HER catalyzed by molecular metal complexes in purely alkaline aqueous solutions remains largely unexplored. Here, we report a new cobalt complex with a tetrapyridylamine ligand that catalyzes photolytic HER with turnover number up to 218 000 in purely aqueous solutions at pH 9.

Domino Reaction Protocol to Synthesize Benzothiophene-Derived Chemical Entities as Potential Therapeutic Agents.

An efficient synthesis of 3-amino-2-formyl-functionalized benzothiophenes by a domino reaction protocol and their use to synthesize a library of novel scaffolds have been reported. Reactions of ketones and 1,3-diones with these amino aldehyde derivatives formed a series of benzothieno[3,2-]pyridine and 3,4-dihydro-2-benzothiopheno[3,2-]quinolin-1-one, respectively. A plausible mechanism for the formation of fused pyridine derivatives by the Friedlander reaction has been elucidated by density functional theory (DFT) calculations.

Pain in your day? Get sleep treatment anyway! The role of pain in insomnia treatment efficacy in women veterans.

Insomnia and pain disorders are among the most common conditions affecting United States adults and veterans, and their comorbidity can cause detrimental effects to quality of life among other factors. Cognitive behavioural therapy for insomnia and related behavioural therapies are recommended treatments for insomnia, but chronic pain may hinder treatment benefit. Prior research has not addressed how pain impacts the effects of behavioural insomnia treatment in United States women veterans.

A non-inferiority randomized controlled trial comparing behavioral sleep interventions in women veterans: An examination of pain outcomes.

Objective: Insomnia is known to exacerbate pain symptoms. The purpose of the present study was to compare the secondary effects of cognitive behavioral therapy for insomnia (CBTI) against a novel treatment for insomnia called acceptance and behavioral changes for insomnia (ABC-I) among individuals with comorbid pain. Differences in the potential mechanisms through which these treatments impact pain were also examined.

Novel treatment based on acceptance and commitment therapy versus cognitive behavioral therapy for insomnia: A randomized comparative effectiveness trial in women veterans.

Objective: This randomized comparative effectiveness trial evaluated a novel insomnia treatment using acceptance and commitment therapy (ACT) among women veterans. Participants received either the acceptance and the behavioral changes to treat insomnia (ABC-I) or cognitive behavioral therapy for insomnia (CBT-I). The primary objectives were to determine whether ABC-I was noninferior to CBT-I in improving sleep and to test whether ABC-I resulted in higher treatment completion and adherence versus CBT-I.

Perceived care partner burden at 1-year post-injury and associations with emotional awareness, functioning, and empathy after TBI: A TBI model systems study.

Background: People with traumatic brain injury (TBI) can lack awareness of their own emotions and often have problems with emotion dysregulation, affective disorders, and empathy deficits. These impairments are known to impact psychosocial behaviors and may contribute to the burden experienced by care partners of individuals with TBI.

Objective: To examine the associations of emotional awareness, emotional functioning, and empathy among participants with TBI with care partner burden.

Mindfulness attenuates the impact of worry on late-life cognitive function.

Worry has been shown to have a negative impact on many aspects of neurocognitive performance. Interestingly, research indicates mindfulness both improves aspects of cognitive ability and reduces worry symptoms. Yet, the impact of mindfulness on the relationship between worry and cognition has yet to be explored.

Amphiphilicity in Oxygen Atom Transfer Reactions of Oxobis(iminoxolene)osmium Complexes.

Oxobis(iminoxolene)osmium(VI) compounds (ap)OsO (ap = 2-(4-RCHN)-4,6-BuCHO) are readily deoxygenated by phosphines and phosphites to give five-coordinate (ap)Os(PR') or six-coordinate (ap)Os(PR'). Structural data indicate that this net two-electron reduction is accompanied by apparent oxidation of the iminoxolene ligands due to their greater ability to engage in π donation to the reduced deoxy form of the osmium complex. In (ap)Os(PR'), the HOMO is a ligand-based combination of the iminoxolene redox-active orbitals, while the LUMO is a highly covalent metal-iminoxolene π* orbital.

High-valent osmium iminoxolene complexes.

2-(Arylamino)-4,6-di-tert-butylphenols containing 4-substituted phenyl groups (RapH2) react with oxobis(ethylene glycolato)osmium(vi) in acetone to give square pyramidal bis(amidophenoxide)oxoosmium(vi) complexes. A mono-amidophenoxide complex is observed as an intermediate in these reactions. Reactions in dichloromethane yield the diolate (Hap)2Os(OCH2CH2O).

Molybdenum(vi) tris(amidophenoxide) complexes.

Tris(2-(arylamido)-4,6-di-tert-butylphenoxo)molybdenum(vi) complexes (ap)Mo can be prepared either from (cycloheptatriene)Mo(CO) and the N-aryliminoquinone, or from MoO(acac) and the aminophenol. In contrast to all other reported unconstrained transition metal tris(amidophenoxide) complexes, the molybdenum complexes show a facial geometry in the solid state. In solution, the fac isomer predominates, though a small amount of mer isomer is detectable at room temperature.