Phospholyl and Arsolyl Triple-Decker Sandwich Complexes of Europium(II) and Strontium(II).

To study the influence of heteroatoms on the photophysical properties of divalent Eu and Sr complexes, the synthesis of the phospholyl and arsolyl compounds [{(Dtp)(thf)M}2{µ-η8:η8-C8H8}] (M = EuII and SrII; Dtp = 3,4-dimethyl-2,5-bis(tert-butyl)phospholyl) and [{(Dtas)(thf)M}2{µ-η8:η8-C8H8}] (M = EuII and SrII; Dtas = 3,4-dimethyl-2,5-bis(tert-butyl)arsolyl) is reported. Organometallic compounds of divalent europium with P and As heterocyclic ligands have not been described previously. They were prepared by salt elimination reactions from potassium phospholyl or arsolyl, K2C8H8, and EuI2(thf)2 or SrI2. Photophysical properties were investigated alongside a reference cyclopentadienyl complex with a comparable structure. Critically, the influence of the heteroatom on the photoluminescence emission and excitation and quantum yields of the complexes is significant. Density functional theory calculations were performed to rationalize the ligand influences.

Synthesis, Structural Characterization, and Magnetic Properties of Lanthanide Arsolyl Sandwich Complexes.

A series of trivalent lanthanide sandwich complexes [(η5-C4R4As)Ln(η8-C8H8)] using three different arsolyl ligands are reported. The complexes were obtained via salt elimination reactions between potassium arsolyl salts and lanthanide precursors [LnI(COT)(THF)2] (Ln = Sm, Dy, Er; COT = η8-C8H8). The resulting compounds exhibit classical sandwich complex structures with one notable exception. Characterization was conducted in both the solid state using single-crystal X-ray diffraction and in solution for the Sm compounds using NMR spectroscopy. Furthermore, the magnetic properties of an Er complex were investigated, revealing distinctive single-molecule-magnet behavior characterized by an energy barrier of Ueff = 323.3 K. Theoretical calculations were employed to support and interpret the experimental findings, with a comparative analysis performed against previously reported complexes.

Diversity-Oriented Synthesis of [2.2]Paracyclophane-derived Fused Imidazo[1,2-a]heterocycles by Groebke-Blackburn-Bienaymé Reaction: Accessing Cyclophanyl Imidazole Ligands Library.

This report describes the synthesis of a [2.2]paracyclophane-derived annulated 3-amino-imidazole ligand library through a Groebke-Blackburn-Bienaymé three-component reaction (GBB-3CR) approach employing formyl-cyclophanes in combination with diverse aliphatic and aromatic isocyanides and heteroaromatic amidines. The GBB-3CR process gives access to skeletally-diverse cyclophanyl imidazole ligands, namely 3-amino-imidazo[1,2-a]pyridines and imidazo[1,2-a]pyrazines. Additionally, a one-pot protocol for the GBB-3CR by an in situ generation of cyclophanyl isocyanide is demonstrated. The products were analyzed by detailed spectroscopic techniques, and the cyclophanyl imidazo[1,2-a]pyridine was confirmed unambiguously by single-crystal X-Ray crystallography. The cyclophanyl imidazole ligands can be readily transformed to showcase their useful utility in preparing N,C-palladacycles through regioselective ortho-palladation.

Application of the Redox-Transmetalation Procedure to Access Divalent Lanthanide and Alkaline-Earth NHC Complexes*.

Divalent lanthanide and alkaline-earth complexes supported by N-heterocyclic carbene (NHC) ligands have been accessed by redox-transmetalation between air-stable NHC-AgI complexes and the corresponding metals. By using the small ligand 1,3-dimethylimidazol-2-ylidene (IMe), two series of isostructural complexes were obtained: the tetra-NHC complexes [LnI2 (IMe)4 ] (Ln=Eu and Sm) and the bis-NHC complexes [MI2 (IMe)2 (THF)2 ] (M=Yb, Ca and Sr). In the former, distortions in the NHC coordination were found to originate from intermolecular repulsions in the solid state. Application of the redox-transmetalation strategy with the bulkier 1,3-dimesitylimidazol-2-ylidene (IMes) ligand yielded [SrI2 (IMes)(THF)3 ], while using a similar procedure with Ca metal led to [CaI2 (THF)4 ] and uncoordinated IMes. DFT calculations were performed to rationalise the selective formation of the bis-NHC adduct in [SrI2 (IMe)2 (THF)2 ] and the tetra-NHC adduct in [SmI2 (IMe)4 ]. Since the results in the gas phase point towards preferential formation of the tetra-NHC complexes for both metal centres, the differences between both arrangements are a result of solid-state effects such as slightly different packing forces.

The effect of mindfulness meditation training on biological acute stress responses in generalized anxiety disorder.

Mindfulness-Based interventions have increased in popularity in psychiatry, but the impact of these treatments on disorder-relevant biomarkers would greatly enhance efficacy and mechanistic evidence. If Generalized Anxiety Disorder (GAD) is successfully treated, relevant biomarkers should change, supporting the impact of treatment and suggesting improved resilience to stress. Seventy adults with GAD were randomized to receive either Mindfulness-Based Stress Reduction (MBSR) or an attention control class; before and after, they underwent the Trier Social Stress Test (TSST). Area-Under-the-Curve (AUC) concentrations were calculated for adrenocorticotropic hormone (ACTH) and pro-inflammatory cytokines. MBSR participants had a significantly greater reduction in ACTH AUC compared to control participants. Similarly, the MBSR group had a greater reduction in inflammatory cytokines' AUC concentrations. We found larger reductions in stress markers for patients with GAD in the MBSR class compared to control; this provides the first combined hormonal and immunological evidence that MBSR may enhance resilience to stress.

Transcranial magnetic stimulation: A potential new treatment for depression associated with traumatic brain injury.

BACKGROUND: Each year, more than 1.7 million Americans suffer a traumatic brain injury (TBI) and the lifetime prevalence of major depressive disorder following TBI is between 25-50%. There are no validated established strategies to treat TBI depression. Repetitive transcranial magnetic stimulation (rTMS) is a novel putative treatment option for post-TBI depression, which, compared with standard pharmacological agents, may provide a more targeted treatment with fewer side-effects. However, TBI is associated with an increased risk of both early and late spontaneous seizures, a significant consideration in evaluating rTMS as a potential treatment for TBI depression. Whilst the risk of seizure from rTMS is low, underlying neuropathology may somewhat increase that risk. REVIEW: This review focuses on the safety aspects of rTMS in TBI patients. The authors review why low frequency rTMS might be less likely to trigger a seizure than high frequency rTMS and propose low frequency rTMS as a safer option in TBI patients. Because there is little data on the safety of rTMS in TBI, the authors also review the safety of rTMS in patients with other brain pathology. CONCLUSION: It is concluded that pilot safety and tolerability studies should be first conducted in persons with TBI and neuropsychiatric comorbidities. These results could be used to help design larger randomized controlled trials.

Telomere length and telomerase in a well-characterized sample of individuals with major depressive disorder compared to controls.

BACKGROUND: Leukocyte telomere length (LTL) is a marker of cellular turnover and oxidative stress. Studies suggest major depressive disorder (MDD) is associated with oxidative stress, but examinations of MDD and LTL have yielded mixed results, likely because of differences in measurement methods and unmeasured confounding. This study examined LTL and telomerase activity in 166 individuals with MDD compared to 166 age- and gender-matched matched controls free of any psychiatric disorder, using well-validated assays and clinical assessment methods, and controlling for a range of potential confounders. METHODS: Subjects aged 18 to 70 were evaluated by trained raters and provided blood for LTL and telomerase activity measurement. LTL was assayed using Southern blot and replicated with qPCR, and telomerase activity was assayed with a repeat amplification protocol using a commercial kit. RESULTS: There was no significant difference in telomere length for individuals with MDD [mean (SD)=9.1 (3.0)kbp] compared to controls [mean(SD)=8.9(2.5)kbp] measured by Southern blot (p=0.65) or by confirmatory qPCR (p=0.91) assays. Controlling for potential confounders did not alter the results. Telomerase activity did not differ by MDD diagnosis overall (p=0.40), but the effect of MDD was significantly modified by gender (t(299)=2.67, p=0.0079) even after controlling for potential confounders, with telomerase activity significantly greater only in males with MDD versus controls. CONCLUSION: Our well-characterized, well-powered examination of concurrently assessed telomere length and telomerase activity in individuals with clinically significant, chronic MDD and matched controls failed to provide strong evidence of an association of MDD with shorter LTL, while telomerase activity was higher in men with MDD [corrected].

Anxiety sensitivity in bereaved adults with and without complicated grief.

Complicated grief (CG) is a bereavement-specific syndrome chiefly characterized by symptoms of persistent separation distress. Physiological reactivity to reminders of the loss and repeated acute pangs or waves of severe anxiety and psychological pain are prominent features of CG. Fear of this grief-related physiological arousal may contribute to CG by increasing the distress associated with grief reactions and increasing the likelihood of maladaptive coping strategies and grief-related avoidance. Here, we examined anxiety sensitivity (AS; i.e., the fear of anxiety-related sensations) in two studies of bereaved adults with and without CG. In both studies, bereaved adults with CG exhibited elevated AS relative to those without CG. In study 2, AS was positively associated with CG symptom severity among those with CG. These findings are consistent with the possibility that AS contributes to the development or maintenance of CG symptoms.

Mindfulness-Oriented Recovery Enhancement for Alcohol Dependence: Therapeutic Mechanisms and Intervention Acceptability.

Mindfulness-based interventions may decrease addictive behaviors while promoting non-reactivity to stressors. This study employed qualitative methods to enhance understanding of mindfulness-related treatment effects. Study participants were eighteen alcohol dependent adults residing in a therapeutic community who had participated in a Mindfulness-Oriented Recovery Enhancement (MORE) intervention. Interviews were conducted to elicit participant narratives. Responses to open-ended questions were analyzed using a grounded theory approach and the method of constant comparison. Narrative accounts suggested that MORE enhanced self-awareness while helping clients to cope more effectively with emotional distress and addictive impulses. MORE appears to be acceptable to participants and feasible to implement within a residential treatment setting. Mindfulness training may assist marginalized persons recover from addiction.