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 9.0. Density functional theory (DFT) calculations suggested a modified electron transfer (E)-proton transfer (C)-electron transfer (E)-proton transfer (C) (mod-ECEC) pathway for hydrogen production from the protonation of CoII-H species. The remarkable catalytic activity resulting from subtle structural changes of the ligand scaffold highlights the importance of studying structure-function relationships in molecular catalyst design. Our present work significantly advances the development of a molecular metal catalyst for visible-light driven HER in more challenging alkaline aqueous solutions that holds substantial promise in solar-driven water-splitting systems.

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. Using data from a comparative effectiveness clinical trial of two insomnia behavioural treatments (both including sleep restriction, stimulus control, and sleep hygiene education), we examined the impact of pain severity and pain interference on sleep improvements from baseline to post-treatment and 3-month follow-up. We found no significant moderation effects of pain severity or interference in the relationship between treatment phase and sleep outcomes. Findings highlight opportunities for using behavioural sleep interventions in patients, particularly women veterans, with comorbid pain and insomnia, and highlight areas for future research.

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-b]pyridine and 3,4-dihydro-2H-benzothiopheno[3,2-b]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. Furthermore, hydrazones were obtained by reacting the aldehyde functional group of benzothiophenes with different hydrazine derivatives. Preliminary screening of these compounds against several bacterial strains and cancer cell lines led to the discovery of several hit molecules. Hydrazone and benzothieno[3,2-b]pyridine derivatives are potent cytotoxic and antibacterial agents, respectively. One of the potent compounds effected ∼97% growth inhibition of the LOX IMVI cell line at 10 µM concentration.

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. However, there is little research on the differential influence of these resilience factors on SUD over and above deployment stressors. In this study, we examined the relative effects of perceived resilience, unit cohesion, and deployment stressors on SUD in a sample of 21,449 active duty and reserve soldiers from the U.S. Army (primarily White and male, mean age = 28.66, SD = 7.41) using structural equation modeling. We found that unit cohesion (ß = -.17) and perceived resilience (ß = -.16) had negative effects on SUD over and above deployment stressors. The study findings clarify research on resilience to SUD and have implications for addressing substance use in the military, specifically regarding the importance of building unit cohesion.

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. Much of this research has focused on the effects of individual-level factors (e.g., use of coping strategies like humor, the morale of individual unit members), with some research focusing on unit-level factors (e.g., the cohesiveness of a unit). However, there is little research exploring how these factors relate to each other in mitigating or reducing PTSD symptoms. In this study, we examined the association between deployment stressors, perceived unit cohesion, morale, humor, and PTSD symptoms in a sample of 20,901 active-duty military personnel using structural equation modeling. Results indicated that perceived unit cohesion, humor, and morale were positively associated with each other and negatively associated with PTSD symptoms over and above the effect of deployment stressors. These findings highlight the influence of resilience factors on PTSD symptoms beyond their substantial overlap and have implications for future research as well as the potential development of interventions for military personnel.

Vanadyl as a Spectroscopic Probe of Tunable Ligand Donor Strength in Bimetallic Complexes.

Incorporation of secondary metal ions into heterobimetallic complexes has emerged as an attractive strategy for rational tuning of compounds' properties and reactivity, but direct solution-phase spectroscopic interrogation of tuning effects has received less attention than it deserves. Here, we report the assembly and study of a series of heterobimetallic complexes containing the vanadyl ion, [VO]2+, paired with monovalent cations (Cs+, Rb+, K+, Na+, and Li+) and a divalent cation (Ca2+). These complexes, which can be isolated in pure form or generated in situ from a common monometallic vanadyl-containing precursor, enable experimental spectroscopic and electrochemical quantification of the influence of the incorporated cations on the properties of the vanadyl moiety. The data reveal systematic shifts in the V-O stretching frequency, isotropic hyperfine coupling constant for the vanadium center, and V(V)/V(IV) reduction potential in the complexes. These shifts can be interpreted as charge density effects parametrized through the Lewis acidities of the cations, suggesting broad potential for the vanadyl ion to serve as a spectroscopic probe in multimetallic species.

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

Objectives: 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. Based on research discussed herein, we hypothesize that those with higher levels of dispositional mindfulness will have better cognitive performance than those with lower levels of dispositional mindfulness, regardless of worry level. The present study investigated the potential moderating influence of mindfulness on the relationship between worry and cognitive performance.Methods: The sample included 113 older veterans who were screened at the VA Palo Alto Health Care System in Palo Alto, CA. Cognitive domains of interest included learning and memory, processing speed, attention, working memory, and executive function. Mindfulness was assessed with the Five Facet Mindfulness Questionnaire (FFMQ), and worry symptoms were assessed using the Penn State Worry Questionnaire (PSWQ). Hypotheses were tested with multiple regression analyses using the Hayes (2003) PROCESS macro.Results: Contrary to what was hypothesized, only mindful awareness significantly moderated the relationship between worry and processing speed.Conclusion: This finding has important implications for introducing mindfulness techniques into older adults' routines to decrease worry and mitigate its negative effects on processing speed.

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

Oxobis(iminoxolene)osmium(VI) compounds (Rap)2OsO (Rap = 2-(4-RC6H4N)-4,6-tBu2C6H2O) are readily deoxygenated by phosphines and phosphites to give five-coordinate (Rap)2Os(PR'3) or six-coordinate (Rap)2Os(PR'3)2. 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 (Rap)2Os(PR'3)2, the HOMO is a ligand-based combination of the iminoxolene redox-active orbitals, while the LUMO is a highly covalent metal-iminoxolene π* orbital. In the trans isomer, the HOMO is required to be ligand-localized by symmetry, while in the cis isomer, the ligands adopt a conformation that minimizes metal-ligand π* interactions in the HOMO. Kinetic studies indicate that the deoxygenations involve the rate-determining attack of the phosphorus(III) reagent on the five-coordinate oxo complexes. Varying the substituents of the aryl groups on the iminoxolene ligands or on the triarylphosphines has little effect on the rate of oxygen atom transfer, with the best correlation shown between oxygen atom transfer rates and the HOMO-LUMO gap of the oxo complexes. This suggests that the osmium oxo group shows a balance between electrophilic and nucleophilic character in its oxygen atom transfer reactions with phosphorus(III) reagents.

Preferential crystallization of (±)-pinenyllithium·TMEDA.

(±)-Pinenyllithium·TMEDA or (tetramethylethylenediamine-κ2N,N')(η3-6,6-dimethyl-2-methylenebicyclo[3.1.1]heptyl)lithium, [Li(C10H15)(C6H16N2)], is readily prepared from ß-pinene, butyllithium and TMEDA, and the racemic material preferentially crystallizes even from 96:4 (92% ee) mixtures of (-)- and (+)-ß-pinene, respectively. The structure is monomeric, with the geminal-dimethyl bridge of the bicyclic structure shielding one face of the allyl system, restricting the lithium to the opposite face and preventing the Li-allyl-Li aggregation observed with some other allyllithium systems. The symmetry of the allyl system, bond lengths, bond angles and out-of-plane deviations are compared to existing structures. In addition, a much older structure of this complex is compared to this very recent one.

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. These novel compounds have been studied for their antineoplastic and antibacterial properties, which led to the discovery of hit compounds with therapeutic potential. The antibacterial compound is noncytotoxic and nonhemolytic against cancer cell lines and sheep red blood cells, respectively. Several of the antineoplastic compounds showed activity against human cancer cell lines with growth inhibition at submicromolar concentration.

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. METHODS: Secondary analysis was conducted using data from a randomized controlled trial among 106 community-dwelling older adult veterans (N = 106; mean age 72.1 years, 96% male, 78.3% White, 6.6% Hispanic, 5.7% African American) with chronic (≥3 months) insomnia disorder. Participants engaged in five sessions of manual-based CBT-I in individual or group format within one Department of Veterans Affairs healthcare system, provided by non-clinician "sleep coaches" who had weekly telephone supervision by behavioral sleep medicine specialists. Insomnia symptoms (Insomnia Severity Index), perceived sleep quality (Pittsburgh Sleep Quality Index), fatigue (Flinder's Fatigue Scale), daytime sleepiness (Epworth Sleepiness Scale), and perceived pain severity (items from the Geriatric Pain Measure) were assessed at 4 time points: baseline, one-week posttreatment, 6-month follow-up, and 12-month follow-up. Mixed effects models with time invariant and time varying predictors were employed for analyses. RESULTS: CBT-I improved insomnia symptoms, perceived sleep quality, fatigue, and daytime sleepiness among older veterans with chronic insomnia. Participant-reported pain was associated with greater improvements in insomnia symptoms following CBT-I. Pain did not affect improvements in other sleep-related outcomes (-0.38 ≤ b ≤ 0.07, p > 0.05). Between-subjects differences in pain, but not within-subject changes in pain over time, appeared to play a central role in insomnia symptom improvement at posttreatment, with individuals with higher-than-average pain showing greater insomnia symptom improvement (ISI score reduction; -0.32 ≤ b ≤ -0.28, p ≤ 0.005). CONCLUSIONS: Pain did not meaningfully hinder the effects of CBT-I on sleep outcomes. Among older veterans with chronic insomnia disorder, individuals with higher pain exhibited slightly greater improvement in insomnia than those with lower levels of pain. These findings suggest that experiencing pain does not impair treatment response and should not preclude older adults with insomnia from being offered 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. METHOD: This multisite, cross-sectional, observational study used data from 90 dyads (participants with TBI and their care partner) 1-year post-injury. Participants with TBI completed the Difficulty with Emotional Regulation Scale (DERS; Awareness, Clarity, Goals, Impulse, Nonacceptance, and Strategies subscales); PTSD Checklist-Civilian Version; NIH Toolbox Anger-Affect, Hostility and Aggression Subdomains; PHQ-9; GAD-7; and the Interpersonal Reactivity Index (empathic concern and perspective taking subscales). Care partners completed the Zarit Burden Inventory (ZBI) and provided demographic information. RESULTS: Care partners were predominately female (77%), and most were either a spouse/partner (55.2%) or parent (34.4%). In an unadjusted model that included assessments of emotional awareness, emotional functioning, and empathy of the participant with TBI, the DERS-Awareness and NIH-Hostility subscales accounted for a significant amount of variance associated with care partner burden. These findings persisted after adjusting for care partner age, relationship, education, and the functional status of the participant with TBI (ß= 0.493 and ß= 0.328, respectively). CONCLUSION: These findings suggest that high levels of hostility and low emotional self-awareness can significantly affect the burden felt by TBI care partners.

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. METHODS: Data consisted of a secondary analysis from a randomized comparative effectiveness trial of CBT-I and ABC-I among women veterans with insomnia and comorbid pain. Pain outcomes, beliefs about sleep, and psychological flexibility were assessed at baseline, post-treatment, and at three-months follow-up. RESULTS: At baseline, 93 women veterans reported comorbid insomnia and pain (mean age = 46.7; 33.3% Black, 24.7% Hispanic/Latina). Both CBT-I (n = 48) and ABC-I (n = 45) were associated with decreased pain intensity (p < .001, Cohen's d = 0.41-0.67) and pain interference (p < .001, Cohen's d = 0.71-0.77) at post-treatment and three-months follow-up, with results indicating that ABC-I was non-inferior to CBT-I for pain improvement. Both conditions were associated with greater psychological flexibility post-treatment, and CBT-I resulted in larger reductions in dysfunctional beliefs about sleep (p = .01, Cohen's d = 0.59). CONCLUSION: CBT-I and ABC-I both had positive secondary effects on pain with ABC-I being non-inferior to CBT-I with respect to its impact on pain. The mechanisms of change associated with these treatments may differ with CBT-I leading to greater reductions in dysfunctional beliefs. Hybrid treatments which incorporate an acceptance and commitment approach to both insomnia and pain warrant further examination.

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. METHOD: One hundred forty-nine women veterans with insomnia disorder (Mage = 48.0 years) received ABC-I or CBT-I. The main sleep outcomes were Insomnia Severity Index (ISI), Pittsburgh Sleep Quality Index (PSQI), and sleep efficiency (SE) by actigraphy (objective) and sleep diary (subjective). Measures were collected at baseline, immediate posttreatment, and 3-month posttreatment follow-up. Treatment completion and adherence were assessed during the interventions. RESULTS: Both interventions improved all sleep outcomes from baseline to immediate posttreatment and 3-month posttreatment follow-up. At immediate posttreatment, ABC-I was statically noninferior for sleep diary SE and objective SE, but noninferiority was not statistically confirmed for ISI or PSQI total scores. At 3-month posttreatment follow-up, ABC-I was noninferior for all four of the key outcome variables. There was not a statistically significant difference between the number of participants who discontinued CBT-I (11%) versus ABC-I (18%; p = .248) before completing treatment. ABC-I was superior to CBT-I for some adherence metrics. CONCLUSIONS: Overall, ABC-I was similar in effectiveness compared to CBT-I for the treatment of insomnia and may improve adherence to some behavioral elements of treatment. (PsycInfo Database Record (c) 2023 APA, all rights reserved).

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). Both the glycolate and oxo complex are converted to the corresponding cis-dichloride complex on treatment with chlorotrimethylsilane. The novel bis(aminophenol) ligand EganH4, containing an ethylene glycol dianthranilate bridge, forms the chelated bis(amidophenoxide) complex (Egan)OsO, where the two nitrogen atoms of the tetradentate ligand bind in the trans positions of the square pyramid. Structural and spectroscopic features of the complexes are described well by an osmium(vi)-amidophenoxide formulation, with the amount of π donation from ligand to metal increasing markedly as the co-ligands change from oxo to diolate to dichloride. In the oxo-bis(amidophenoxides), the symmetry of the ligand π orbitals results in only one effective π donor interaction, splitting the energy of the two osmium-oxo π* orbitals and rendering the osmium-oxo bonding appreciably anisotropic.

Molybdenum(vi) tris(amidophenoxide) complexes.

Tris(2-(arylamido)-4,6-di-tert-butylphenoxo)molybdenum(vi) complexes (Rap)3Mo can be prepared either from (cycloheptatriene)Mo(CO)3 and the N-aryliminoquinone, or from MoO2(acac)2 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. At elevated temperature the two species interconvert through Rây-Dutt trigonal twists, which are faster than Bailar twists in this system, presumably because of steric effects of the N-aryl groups. Substituents on the N-aryl ring shift the fac/mer equilibrium of the complex, with more electron-withdrawing substituents generally increasing the proportion of the mer isomer. The preference for fac over mer geometry is thus suggested to be due to enhanced π bonding in the fac isomer. In contrast to analogous catecholate complexes, the tris(amidophenoxide) complexes are not Lewis acidic and are inert to nucleophilic oxidants such as amine-N-oxides.