Ferrocenium Boronic Acid Catalyzed Deoxygenative Coupling of Alcohols with Carbon- and Nitrogen-Based Borate and Silane Nucleophiles.

A boronic acid catalyzed carbon-carbon and carbon-nitrogen bond-forming reaction for the functionalization of various π-activated alcohols has been developed. Ferrocenium boronic acid hexafluoroantimonate salt was identified as an effective catalyst in the direct deoxygenative coupling of alcohols with a variety of potassium trifluoroborate and organosilane nucleophiles. In a comparison between these two classes of nucleophiles, the use of organosilanes leads to higher reaction yields, increased diversity of the alcohol substrate scope, and high / selectivity.

Blood pressure-associated emotional dampening and risky behavior: Elevated resting blood pressure predicts risky simulated driving in women.

Elevated resting blood pressure (BP) is associated with dampened responses to emotionally meaningful stimuli. This BP-associated emotional dampening may also influence threat appraisal and, hence, motivation to avoid risk. The present study was designed to determine if resting BP is associated with risky driving behavior assessed in a high fidelity driving simulator.

Physical Activity Promotion for Persons Experiencing Disability: The Importance of Interdisciplinary Research and Practice.

This paper examines the need for interdisciplinary knowledge in the formation of public health models for health-promoting physical activity (PA) for people experiencing disability. PA promotion for people experiencing disability is a multifaceted endeavor and requires navigating a multitude of complicated and interactive factors. Both disability and health are multifaceted constructs and the relationship between PA and health is embedded within a complicated web of interactive influences.

Blood Pressure, Emotional Dampening, and Risk Behavior: Implications for Hypertension Development.

Objective: Elevated resting blood pressure (BP) is associated with risk for hypertension and emotional dampening, including reduced responses to emotionally meaningful stimuli. Perception of threat is a critical motivator in avoidance of risky health-damaging behavior. We hypothesize that BP-associated dampening of threat appraisal may increase risk-taking behavior.

Exploring the relationship between frontal asymmetry and emotional dampening.

Cardiovascular emotional dampening is the term used to describe the inverse relationship between resting blood pressure and emotional responsivity which extends from normotensive to hypertensive ranges. Little is known about its underlying physiological mechanisms, but it is thought to involve some disruption in emotion processing. One area that has yet to be explored in the literature is the relationship between emotional dampening and frontal asymmetry, a psychophysiological indicator for motivational direction and emotional valence bias.

Prediction of energy expenditure during walking in adults with down syndrome.

Background: When developing walking programmes for improving health in adults with Down syndrome (DS), physical activity professionals are in need of an equation for predicting energy expenditure. We therefore developed and cross-validated an equation for predicting the rate of oxygen uptake (VO ; an index of energy expenditure) for adults with and without DS.

Method: A total of 469 VO observations during walking across different speeds were available from 54 adults with DS and 61 adults without DS.

G-CSF Receptor Blockade Ameliorates Arthritic Pain and Disease.

G-CSF or CSF-3, originally defined as a regulator of granulocyte lineage development via its cell surface receptor (G-CSFR), can play a role in inflammation, and hence in many pathologies, due to its effects on mature lineage populations. Given this, and because pain is an extremely important arthritis symptom, the efficacy of an anti-G-CSFR mAb for arthritic pain and disease was compared with that of a neutrophil-depleting mAb, anti-Ly6G, in both adaptive and innate immune-mediated murine models. Pain and disease were ameliorated in Ag-induced arthritis, zymosan-induced arthritis, and methylated BSA/IL-1 arthritis by both prophylactic and therapeutic anti-G-CSFR mAb treatment, whereas only prophylactic anti-Ly6G mAb treatment was effective.

Carrots, Not Sticks: Adverse Impact and Wellness Programs.

Objective: The purpose of this study was to determine if wellness programs are likely to produce an adverse impact in various protected groups and to determine what features of the program may contribute to adverse impact.

Methods: Using a nationally representative sample of US adults, we examined the proportions of protected groups that would be expected to encounter adverse impact using various health factors such as weight, blood pressure, and cholesterol levels.

Results: The results of this study indicate that disincentive-based programs pose a high risk of differentially selecting protected groups into program categories.

Resting blood pressure differentially predicts time course in a tonic pain experiment.

Resting blood pressure (BP) shows a negative relationship with pain sensitivity (BP-related hypoalgesia). In chronic pain conditions, this relationship is inverted. The precise mechanisms responsible for the inversion are unknown.

Subclinical Posttraumatic Stress Disorder Symptoms: Relationships with Blood Pressure, Hostility, and Sleep.

The purpose of this study was to examine the relationships among subclinical PTSD symptoms, blood pressure, and several variables linked to both frank PTSD and the basic psychobiological adaptation to stress. The authors recruited a sample of 91 healthy, young men and women between 18 and 35 years. We examined links among subclinical posttraumatic stress disorder symptoms, blood pressure, sleep quality, and hostility.

Auditory Attention and Comprehension During a Simulated Night Shift: Effects of Task Characteristics.

Objective: The current study investigated performance on a dual auditory task during a simulated night shift.

Background: Night shifts and sleep deprivation negatively affect performance on vigilance-based tasks, but less is known about the effects on complex tasks. Because language processing is necessary for successful work performance, it is important to understand how it is affected by night work and sleep deprivation.

Unsymmetrical Diarylmethanes by Ferroceniumboronic Acid Catalyzed Direct Friedel-Crafts Reactions with Deactivated Benzylic Alcohols: Enhanced Reactivity due to Ion-Pairing Effects.

The development of general and more atom-economical catalytic processes for Friedel-Crafts alkylations of unactivated arenes is an important objective of interest for the production of pharmaceuticals and commodity chemicals. Ferroceniumboronic acid hexafluoroantimonate salt (1) was identified as a superior air- and moisture-tolerant catalyst for direct Friedel-Crafts alkylations of a variety of slightly activated and neutral arenes with stable and readily available primary and secondary benzylic alcohols. Compared to the use of classical metal-catalyzed alkylations with toxic benzylic halides, this methodology employs exceptionally mild conditions to provide a wide variety of unsymmetrical diarylmethanes and other 1,1-diarylalkane products in high yield with good to high regioselectivity.

A surprising substituent effect provides a superior boronic acid catalyst for mild and metal-free direct Friedel-Crafts alkylations and prenylations of neutral arenes.

The development of more general and efficient catalytic processes for Friedel-Crafts alkylations is an important objective of interest toward the production of pharmaceuticals and commodity chemicals. Herein, 2,3,4,5-tetrafluorophenylboronic acid was identified as a potent air- and moisture-tolerant metal-free catalyst that significantly improves the scope of direct Friedel-Crafts alkylations of a variety of slightly activated and neutral arenes, including polyarenes, with allylic and benzylic alcohols. This method also provides a simple alternative for the direct installation of prenyl units commonly found in naturally occurring arenes.

Transition-metal-free access to primary anilines from boronic acids and a common (+)NH2 equivalent.

Diversely substituted anilines are prepared by treatment of functionalized arylboronic acids with a common, inexpensive source of electrophilic nitrogen (H2N-OSO3H, HSA) under basic aqueous conditions. Electron-rich substrates are found to be the most reactive by this method. However, even moderately electron-poor substrates are well tolerated under the room temperature conditions.

Highly enantioselective (-)-sparteine-mediated lateral metalation-functionalization of remote silyl protected ortho-ethyl N,N-dialkyl aryl O-carbamates.

We report the enantioselective, lateral deprotonation of ortho-protected or functionalized tertiary N,N-dialkyl aryl O-carbamates 5-7 (Scheme 2 ) and meta-protected carbamates 14, 15, and 20 (Schemes 5 and 7 ) by s-BuLi/(-)-sparteine and subsequent quench with a variety of electrophiles to give products 11-13 and 16, 17, and 21 in yields up to 96% and enantiomeric ratios up to 99:1. The influence of organolithium reagents, ratio of organolithium/(-)-sparteine pair versus N,N-dialkyl aryl O-carbamate starting materials, temperature, solvents, electrophiles, substituents located ortho or meta to the O-carbamate moiety, and O-carbamate N-substituents was investigated. The identical absolute configuration of the stereogenic center of the major enantiomers of the products, as established by single-crystal X-ray analysis for substrates (S)-11c, (S)-19, and (S)-21a, provides evidence for a consistent stereochemical course in the enantioselective deprotonation.

Gait characteristics of adults with Down syndrome explain their greater metabolic rate during walking.

The altered gait patterns of adults with Down syndrome (DS) may contribute to their higher net metabolic rate (net-MR) during walking than adults without DS, leading to mobility limitations. This study examined the extent to which gait characteristics explain differences in net-MR during walking between adults with and without DS. Fifteen adults with DS (27 ± 8 years) and 15 adults without DS (28 ± 6 years) completed two testing sessions in which expiratory gases and kinematic data were collected, respectively, during treadmill walking.

Validity evidence for self-report with assistance to measure physical activity behavior in adults with intellectual disabilities.

Self-reported physical activity (PA) behavior with assistance from a secondary source has previously been used with adults with an intellectual disability (ID). Limited evidence of reliability and validity have been provided for this approach. This study examined evidence of convergent (CV) and discriminant (DV) validity for self-report with assistance from a secondary source as a measure of PA in adults with ID.

Emotional dampening in persons with elevated blood pressure: affect dysregulation and risk for hypertension.

Background: Persons with higher blood pressure have emotional dampening in some contexts. This may reflect interactive changes in central nervous system control of affect and autonomic function in the early stages of hypertension development.

Purpose: The purpose of this study is to determine the independence of cardiovascular emotional dampening from alexithymia to better understand the role of affect dysregulation in blood pressure elevations.

The ambiguous role of the paraeducator in the general physical education environment.

The use of paraeducators has increased as a main mechanism to include more students with disabilities in the public schools in the U.S. Although the utilization of paraeducators is intended to be a supportive service delivery option, many concerns and challenges have resulted.

Effects of estrogen and opioid blockade on blood pressure reactivity to stress in postmenopausal women.

Estrogen may influence coronary heart disease risk in women through the effects of endogenous opioids on autonomic control of blood pressure. In a randomized, placebo-controlled trial, we examined the combined effects of estrogen and the opioid antagonist, naltrexone, on blood pressure responses to psychological stress in 42 postmenopausal women. After 3 months of estrogen or estrogen plus progestin (hormone replacement therapy; n = 27) or placebo replacement, participants completed a mental arithmetic task after administration of .

Decreased Cognitive/CNS Function in Young Adults at Risk for Hypertension: Effects of Sleep Deprivation.

Hypertension has been linked to impaired cognitive/CNS function, and some of these changes may precede development of frank essential hypertension. The stress and fatigue of sleep deprivation may exacerbate these cognitive changes in young adults at risk. We hypothesize that individuals at risk for hypertension will show significant declines in cognitive function during a night of sleep deprivation.

Cardiovascular-emotional dampening: the relationship between blood pressure and recognition of emotion.

Objective: Persons with elevated blood pressure (BP) show dampened emotional responses to affect-laden stimuli. We sought to further examine cardiovascular-emotional dampening by examination of the relationship between resting hemodynamic measures and recognition of emotion in an African American community-based sample.

Methods: Participants were 106 African American men and women (55 women; mean age = 52.

Removal of interference from fetal MEG by frequency dependent subtraction.

Fetal magnetoencephalography (fMEG) recordings are contaminated by maternal and fetal magnetocardiography (MCG) signals and by other biological and environmental interference. Currently, all methods for the attenuation of these signals are based on a time-domain approach. We have developed and tested a frequency dependent procedure for removal of MCG and other interference from the fMEG recordings.

Mild and tunable benzoic acid catalysts for rearrangement reactions of allylic alcohols.

An efficient and simple catalytic method for the isomerization of readily prepared allylic alcohols is described. We focus particularly on cyclic examples and the synthesis of unusual enyne and dienols. The benzoic acid catalysts employed are commercially available and very inexpensive and can be tuned for reactivity and substrate sensitivity.