Palladium Bisphosphine Monoxide Complexes: Synthesis, Scope, Mechanism, and Catalytic Relevance.

Recent studies in transition metal catalysis employing chelating phosphines have suggested a role for partial ligand oxidation in formation of the catalytically active species, with potentially widespread relevance in a number of catalytic systems. We examine the internal redox reaction of Pd(bisphosphine)X (X = Cl, OAc, ) complexes to reveal previously underexplored aspects of bisphosphine monoxides (BPMOs), including evaluation of ligand structure and development of general reaction conditions to access a collection of structurally diverse BPMO precatalysts based on organopalladium oxidative addition complexes. In particular, a series of Pd(BPMO)(R)(X) (R = aryl, alkyl; X = I, Br) oxidative addition complexes bearing 24 different BPMO ligands were characterized by NMR and X-ray crystallography.

Limited carry-over effects of socioemotional manipulations on subsequent unrelated memory tasks.

Although age is typically associated with significant impairments in memory performance, several domains exist in which these impairments are reduced or even eliminated. These "pockets of preservation" in older adults' memory can be seen in tasks involving socioemotional processing and may be supported by distinct encoding or retrieval modes relative to neutral content. The current study examines whether engaging in socioemotional tasks prior to encoding or retrieval allows older adults to enter an encoding or retrieval mode that better supports memory performance.

The benefits of socioemotional learning strategies and video formats for older digital immigrants learning a novel smartphone application.

The need to continually learn and adjust to new technology can be an arduous demand, particularly for older adults who did not grow up with digital technology ("older digital immigrants" or ODIs). This study tests the efficacy of socioemotional learning strategies (i.e.

Individual Differences in Older Adult Frontal Lobe Function Relate to Memory and Neural Activity for Self-Relevant and Emotional Content.

Objectives: Older adults show memory benefits for self-relevant and emotional content, but there are individual differences in this effect. It has been debated whether processing of self-relevant and emotional information relies on similar processes to one another. We examined whether variation in frontal lobe (FL) function among older adults related similarly to the processing of self-relevant information as it did to emotional information, or whether these relations diverged.

Empathy, memory, and aging during the COVID-19 pandemic.

Recently, there has been increasing attention to the interaction between empathy and memory. During the COVID-19 pandemic, a period when empathy played a key role in people's behaviors, we assessed the relationship between empathy and memory. In this pre-registered report, we used memory accuracy for the number of COVID-19 cases as a measure of recent memory and examined its relationship with trait empathy.

Ru-Catalyzed Enantioselective Hydrogenation of 2-Pyridyl-Substituted Alkenes and Substrate-Mediated H/D Exchange.

A highly efficient and enantioselective asymmetric hydrogenation catalyzed by Ru-DTBM-segphos is reported for a broad range of pyridine-pyrroline tri-substituted alkenes. Kinetic, spectroscopic, and computational studies suggest that addition of H is rate-determining and that alkene insertion is the enantio-determining step. These studies also reveal an intriguing Ru-catalyzed H/D exchange process that is facilitated by the substrate at room temperature and low pressure where hydrogenation activity is suppressed.

Age-related differences in Default Mode Network resting-state functional connectivity but not gray matter volume relate to sacrificial moral decision-making and working memory performance.

Older adults make fewer utilitarian decisions than younger adults during sacrificial moral dilemmas, which are associated with age-related reductions in Default Mode Network resting-state functional connectivity. Decreases on tasks associated with fluid cognitive abilities, such as working memory capacity, are also associated with age-related Default Mode Network changes. Regions within this network demonstrate some of the greatest age-related gray matter atrophy.

Moral decision-making during the COVID-19 pandemic: Associations with age, negative affect, and negative memory.

The COVID-19 pandemic provided the opportunity to determine whether age-related differences in utilitarian moral decision-making during sacrificial moral dilemmas extend to non-sacrificial dilemmas in real-world settings. As affect and emotional memory are associated with moral and prosocial behaviors, we also sought to understand how these were associated with moral behaviors during the 2020 spring phase of the COVID-19 pandemic in the United States. Older age, higher negative affect, and greater reports of reflecting on negative aspects of the pandemic were associated with higher reported purchase of hard-to-find goods, while older age and higher negative affect alone were associated with higher reported purchase of hard-to-find medical supplies.

Distinct stress-related changes in intrinsic amygdala connectivity predict subsequent positive and negative memory performance.

Experiencing stress before an event can influence how that event is later remembered. In the current study, we examine how individual differences in one's physiological response to a stressor are related to changes to underlying brain states and memory performance. Specifically, we examined how changes in intrinsic amygdala connectivity relate to positive and negative memory performance as a function of stress response, defined as a change in cortisol.

Cobalt-electrocatalytic HAT for functionalization of unsaturated C-C bonds.

The study and application of transition metal hydrides (TMHs) has been an active area of chemical research since the early 1960s, for energy storage, through the reduction of protons to generate hydrogen, and for organic synthesis, for the functionalization of unsaturated C-C, C-O and C-N bonds. In the former instance, electrochemical means for driving such reactivity has been common place since the 1950s but the use of stoichiometric exogenous organic- and metal-based reductants to harness the power of TMHs in synthetic chemistry remains the norm. In particular, cobalt-based TMHs have found widespread use for the derivatization of olefins and alkynes in complex molecule construction, often by a net hydrogen atom transfer (HAT).

Kinetic and Thermodynamic Considerations in the Rh-Catalyzed Enantioselective Hydrogenation of 2-Pyridyl-Substituted Alkenes.

The mechanism of asymmetric hydrogenation of 2-pyridyl alkenes catalyzed by chiral Rh-phosphine complexes at ambient temperature is examined using kinetic, spectroscopic, and computational tools. The reaction proceeds with reversible substrate binding followed by rate-determining addition of hydrogen. Substrate binding occurs only through the pyridine nitrogen in contrast to other substrate classes exhibiting stronger substrate direction.

Real-world management of targeted therapies in chronic lymphocytic leukemia.

The advent of novel targeted therapies, including B-cell receptor (BCR) pathway and B-cell lymphoma 2 (BCL2) inhibitors, has substantially changed the treatment paradigm for chronic lymphocytic leukemia (CLL). Although targeted therapies have improved outcomes compared to traditional chemoimmunotherapy in the front-line and relapsed or refractory settings, they are associated with resistance mutations and suboptimal outcomes in certain high-risk patients. Additionally, targeted therapies are associated with drug interactions and unique adverse effect profiles which can be challenging for patients and clinicians to manage.

Cue-utilization in the imagination inflation effect paradigm in older adults with mild cognitive impairment.

Objective: We investigated the imagination inflation effect in healthy older adults and older adults with mild cognitive impairment (MCI) to determine whether an intervention can reduce susceptibility to these distortions, with implications for daily functioning.

Method: Fifty-seven older adults aged 69-90 participated. In Session 1, participants either: listened to an action statement being read, performed the action, or imagined performing the action.

Cognitive decline, socioemotional change, or both? How the science of aging can inform future research on sacrificial moral dilemmas.

Older adults comprise the fastest-growing population in the United States. By exercising their right to vote, guiding the value systems of future generations, and holding political office, they shape the moral context of society. It is therefore imperative that we understand older adults' capacity for moral decision-making.

Combined Experimental and Computational Mechanistic Investigation of the Palladium-Catalyzed Decarboxylative Cross-Coupling of Sodium Benzoates with Chloroarenes.

Reported herein is a mechanistic investigation into the palladium-catalyzed decarboxylative cross-coupling of sodium benzoates and chloroarenes. The reaction was found to be first-order in Pd. A minimal substituent effect was observed with respect to chloroarene, and the reaction was zero-order with respect to chloroarene.

Aging, Empathy, and Prosocial Behaviors During the COVID-19 Pandemic.

Objectives: Previous literature suggests age-related increases in prosociality. Does such an age-prosociality relationship occur during the coronavirus disease 2019 (COVID-19) pandemic, or might the pandemic-as a stressor that may differently influence young and older adults-create a boundary condition on the relationship? If so, can empathy, a well-known prosocial disposition, explain the age-prosociality relationship? This study investigated these questions and whether the target (distant others compared to close others) of prosocial behaviors differs by age.

Methods: Participants completed a series of surveys on dispositional empathy and prosocial behaviors for a study assessing their experiences during the COVID-19 pandemic.

An ERP investigation of age differences in the negativity bias for self-relevant and non-self-relevant stimuli.

As we age, we show increased attention and memory for positive versus negative information, and a key event-related potential (ERP) marker of emotion processing, the late positive potential (LPP), is sensitive to these changes. In young adults the emotion effect on the LPP is also quite sensitive to the self-relevance of stimuli. Here we investigated whether the shift toward positive stimuli with age would be magnified by self-relevance.

Slow oscillation-spindle coupling is negatively associated with emotional memory formation following stress.

Both stress and sleep enhance emotional memory. They also interact, with the largest effect of sleep on emotional memory being seen when stress occurs shortly before or after encoding. Slow wave sleep (SWS) is critical for long-term episodic memory, facilitated by the temporal coupling of slow oscillations and sleep spindles.

Tolerability and toxicity of pegaspargase in adults 40 years and older with acute lymphoblastic leukemia.

Pegaspargase is a modified version of asparaginase with prolonged asparagine depletion. It appears to be safe in adults <40 years old, but has a unique spectrum of toxicities, the risks of which appear to increase with age. The primary objective of this study was to evaluate pegaspargase tolerability and toxicity as assessed by evaluation of incidence and severity of adverse events.

Gold Catalyzed Decarboxylative Cross-Coupling of Iodoarenes.

This report details a decarboxylative cross-coupling of (hetero)aryl carboxylates with iodoarenes in the presence of a gold catalyst (>25 examples, up to 96% yield). This reaction is site specific, which overcomes prior limitations associated with gold catalyzed oxidative coupling reactions. The reactivity of the (hetero)aryl carboxylate correlates qualitatively to the field effect parameter ().

Three-dimensional printing versus conventional machining in the creation of a meatal urethral dilator: development and mechanical testing.

Background: Three-dimensional (3D) printing is a promising technology, but the limitations are often poorly understood. We compare different 3D printing methods with conventional machining techniques in manufacturing meatal urethral dilators which were recently removed from the Australian market.

Methods: A prototype dilator was 3D printed vertically orientated on a low-cost fused deposition modelling (FDM) 3D printer in polylactic acid (PLA) and acrylonitrile butadiene styrene (ABS).

Neural mechanisms supporting emotional and self-referential information processing and encoding in older and younger adults.

Emotion and self-referential information can both enhance memory, but whether they do so via common mechanisms across the adult lifespan remains underexplored. To address this gap, the current study directly compared, within the same fMRI paradigm, the encoding of emotionally salient and self-referential information in older adults and younger adults. Behavioral results replicated the typical patterns of better memory for emotional than neutral information and for self-referential than non-self-referential materials; these memory enhancements were present for younger and older adults.

Correlation of IL-6 secretion and hyponatremia with the use of CD19+ chimeric antigen receptor T-cells .

Background: Various studies have demonstrated that interleukin-6 (IL-6) activates the central magnocellular arginine vasopressin (AVP)-secreting neurons in the brain to produce non-osmotic, non-volume-mediated increases in AVP. The most common toxicity of CD19+ chimeric antigen receptor (CAR) T-cells is cytokine release syndrome, which is related to increased levels of IL-6. This study will evaluate the correlation of IL-6 levels with hyponatremia in patients receiving CD19+ CAR T-cells.

Interactive effects of stress reactivity and rapid eye movement sleep theta activity on emotional memory formation.

Sleep and stress independently enhance emotional memory consolidation. In particular, theta oscillations (4-7 Hz) during rapid eye movement (REM) sleep increase coherence in an emotional memory network (i.e.