Cistromic Reprogramming of the Diurnal Glucocorticoid Hormone Response by High-Fat Diet.

The glucocorticoid receptor (GR) is a potent metabolic regulator and a major drug target. While GR is known to play integral roles in circadian biology, its rhythmic genomic actions have never been characterized. Here we mapped GR's chromatin occupancy in mouse livers throughout the day and night cycle. We show how GR partitions metabolic processes by time-dependent target gene regulation and controls circulating glucose and triglycerides differentially during feeding and fasting. Highlighting the dominant role GR plays in synchronizing circadian amplitudes, we find that the majority of oscillating genes are bound by and depend on GR. This rhythmic pattern is altered by high-fat diet in a ligand-independent manner. We find that the remodeling of oscillatory gene expression and postprandial GR binding results from a concomitant increase of STAT5 co-occupancy in obese mice. Altogether, our findings highlight GR's fundamental role in the rhythmic orchestration of hepatic metabolism.

ATV-Related Trauma in the Pediatric Population.

BACKGROUND: All-terrain vehicles (ATVs) are prevalent in Appalachia and cause significant morbidity and mortality in the pediatric population. This study investigated the injury types and severity in pediatric patients over a 15-year period. METHODS: A retrospective chart review was performed on pediatric ATV-related traumas presenting to our institution from 2005 to 2020. Patients were divided into 3 age groups (0-7, 8-12, and 13-17 y) to evaluate differences in accident demographics, hospitalization, Glasgow Coma Scale, Injury Severity Score, substance use, characterization of orthopaedic and nonorthopaedic injuries, and procedures performed. RESULTS: Inclusion criteria were met by 802 patients. Males represented 71.7% (n=575) and females 28.3% (n=227); the mean age was 12.4 years. The majority (88.5%, n=710) of patients admitted following their accident had a mean stay length of 3.3 days. Of admissions, intensive care unit admission was required by 23.8%, n=191 (mean stay 4.0 d). There were 7 fatalities. The vast majority of accidents occurred between May and September (79.2%, n=635). In patients with documented helmet status, 45% (n=271) were helmeted. Roughly half of all patients (n=393) sustained a fracture (excluding fractures to the head), 370 sustained an injury to the head/face, 129 sustained intra-abdominal/intra-thoracic injuries, and 29 sustained injuries to all 3 systems. The most common fractures involved the forearm (n=98), femur (n=65), and spine (n=59). The most common open fractures were the tibia (n=12), humerus (n=8), and forearm (n=8). The oldest group was more likely than the middle or younger groups to sustain spine ( P <0.0001), pelvis ( P =0.0001), hand ( P =0.0089), and foot ( P =0.0487) fractures. Ethanol testing was positive in 5.0% (n=25) of the oldest group and cannabinoids were present in 6.8% (n=34). The youngest group was significantly more likely to sustain a fracture of the humerus than the middle or older groups ( P <0.0001). Orthopaedic surgical management was required in 24.4% (n=196) of patients. CONCLUSIONS: Pediatric ATV accidents present a significant source of morbidity and mortality. Further intervention is necessary to minimize pediatric ATV injuries. LEVEL OF EVIDENCE: Level IV-Retrospective Case Series.

Sleep Outcomes From AWAKE-HF: A Randomized Clinical Trial of Sacubitril/Valsartan vs Enalapril in Patients With Heart Failure and Reduced Ejection Fraction.

BACKGROUND: Heart failure and sleep-disordered breathing have been increasingly recognized as co-occurring conditions. Their bidirectional relationship warrants investigation into whether heart failure therapy improves sleep and sleep-disordered breathing. We sought to explore the effect of treatment with sacubitril/valsartan on sleep-related endpoints from the AWAKE-HF study. METHODS AND RESULTS: AWAKE-HF was a randomized, double-blind study conducted in 23 centers in the United States. Study participants with heart failure with reduced rejection fraction and New York Heart Association class II or III symptoms were randomly assigned to receive treatment with either sacubitril/valsartan or enalapril. All endpoints were assessed at baseline and after 8 weeks of treatment. Portable sleep-monitoring equipment was used to measure the apnea-hypopnea index, including obstructive and central events. Total sleep time, wake after sleep onset and sleep efficiency were exploratory measures assessed using wrist actigraphy. THE RESULTS WERE AS FOLLOWS: 140 patients received treatment in the double-blind phase (sacubitril/valsartan, n = 70; enalapril, n = 70). At baseline, 39% and 40% of patients randomly assigned to receive sacubitril/valsartan or enalapril, respectively, presented with undiagnosed, untreated, moderate-to-severe sleep-disordered breathing (≥ 15 events/h), and nearly all had obstructive sleep apnea. After 8 weeks of treatment, the mean 4% apnea-hypopnea index changed minimally from 16.3/h to 15.2/h in the sacubitril/valsartan group and from 16.8/h to 17.6/h in the enalapril group. Mean total sleep time was long at baseline and decreased only slightly in both treatment groups at week 8 (-14 and -11 minutes for sacubitril/valsartan and enalapril, respectively), with small changes in wake after sleep onset and sleep efficiency in both groups. CONCLUSIONS: In a cohort of patients with heart failure with reduced rejection fraction who met prescribing guidelines for sacubitril/valsartan, one-third had undiagnosed moderate-to-severe obstructive sleep apnea. The addition of sacubitril/valsartan therapy did not significantly improve sleep-disordered breathing or sleep duration or efficiency. Patients who meet indications for treatment with sacubitril/valsartan should be evaluated for sleep-disordered breathing.

X-ray Crystal Structure of Thorium Tetrahydroborate, Th(BH4)4, and Computational Studies of An(BH4)4 (An = Th, U).

The crystal structure of Th(BH4)4 is described. Two of the four BH4- ions are terminal and tridentate (κ3), whereas the other two bridge between neighboring ThIV centers in a κ2,κ2 (i.e., bis-bidentate) fashion. Thus, each thorium center is bound to six BH4- groups by 14 Th-H bonds. The six boron atoms describe a distorted octahedron in which the κ3-BH4- ions are mutually cis; the 14 ligating hydrogen atoms define a highly distorted bicapped hexagonal antiprism. The thorium centers are linked into a polymer consisting of interconnected helical chains wound about 4-fold screw axes. The structures of An(BH4)4 (An = Th, U) were also investigated by DFT. The geometries of [An(BH4)6]2-, [An3(BH4)16]4-, and [An5(BH4)26]6- fragments of the polymeric structures were optimized at the B3LYP and/or PBE levels. Most calculated geometries are 14-coordinate and agree with the experimental structures, but isolated [Th(BH4)6]2- units are predicted to feature 16-coordinate ThIV centers.

Comparative Study of Natural Terpenoid Precursors in Reactive Plasmas for Thin Film Deposition.

If plasma polymer thin films are to be synthesised from sustainable and natural precursors of chemically heterogeneous composition, it is important to understand the extent to which this composition influences the mechanism of polymerisation. To this end, a well-studied monoterpene alcohol, terpinen-4-ol, has been targeted for a comparative study with the naturally occurring mix of terpenes (viz. Melaleuca alternifolia oil) from which it is commonly distilled. Positive ion mode mass spectra of both terpinen-4-ol and M. alternifolia oil showed a decrease in disparities between the type and abundance of cationic species formed in their respective plasma environments as applied plasma power was increased. Supplementary biological assay revealed the antibacterial action of both terpinen-4-ol and M. alternifolia derived coatings with respect to S. aureus bacteria, whilst cytocompatibility was demonstrated by comparable eukaryotic cell adhesion to both coatings. Elucidating the processes occurring within the reactive plasmas can enhance the economics of plasma polymer deposition by permitting use of the minimum power, time and precursor pre-processing required to control the extent of monomer fragmentation and fabricate a film of the desired thickness and functionality.

Effects of dietary nitrate supplementation on microvascular physiology at 4559 m altitude - A randomised controlled trial (Xtreme Alps).

Native highlanders (e.g. Sherpa) demonstrate remarkable hypoxic tolerance, possibly secondary to higher levels of circulating nitric oxide (NO) and increased microcirculatory blood flow. As part of the Xtreme Alps study (a randomised placebo-controlled trial of dietary nitrate supplementation under field conditions of hypobaric hypoxia), we investigated whether dietary supplementation with nitrate could improve NO availability and microvascular blood flow in lowlanders. Plasma measurements of nitrate, nitrite and nitroso species were performed together with measurements of sublingual (sidestream dark-field camera) and forearm blood flow (venous occlusion plethysmography) in 28 healthy adult volunteers resident at 4559 m for 1 week; half receiving a beetroot-based high-nitrate supplement and half receiving an identically-tasting low nitrate 'placebo'. Dietary supplementation increased plasma nitrate concentrations 4-fold compared to the placebo group, both at sea level (SL; 19.2 vs 76.9 µM) and at day 5 (D5) of high altitude (22.9 vs 84.3 µM, p < 0.001). Dietary nitrate supplementation also significantly increased both plasma nitrite (0.78 vs. 0.86 µM SL, 0.31 vs. 0.41 µM D5, p = 0.03) and total nitroso product (11.3 vs. 19.7 nM SL, 9.7 vs. 12.3 nM D5, p < 0.001) levels both at sea level and at 4559 m. However, plasma nitrite concentrations were more than 50% lower at 4559 m compared to sea level in both treatment groups. Despite these significant changes, dietary nitrate supplementation had no effect on any measured read-outs of sublingual or forearm blood flow, even when environmental hypoxia was experimentally reversed using supplemental oxygen. In conclusion, dietary nitrate supplementation does not improve microcirculatory function at 4559 m.

Land-use and climatic causes of environmental novelty in Wisconsin since 1890.

Multiple global change drivers are increasing the present and future novelty of environments and ecological communities. However, most assessments of environmental novelty have focused only on future climate and were conducted at scales too broad to be useful for land management or conservation. Here, using historical county-level data sets of agricultural land use, forest composition, and climate, we conduct a regional-scale assessment of environmental novelty for Wisconsin landscapes from ca. 1890 to 2012. Agricultural land-use data include six cropland types, livestock densities for four livestock species, and human populations. Forestry data comprise biomass-weighted relative abundances for 15 tree genera. Climate data comprise seasonal means for temperature and precipitation. We found that forestry and land use are the strongest cause of environmental novelty (NoveltyForest  = 3.66, NoveltyAg  = 2.83, NoveltyClimate  = 1.60, with Wisconsin's forests transformed by early 20th-century logging and its legacies and multiple waves of agricultural innovation and obsolescence. Climate change is the smallest contributor to contemporary novelty, with precipitation signals stronger than temperature. Magnitudes and causes of environmental novelty are strongly spatially patterned, with novelty in southern Wisconsin roughly twice that in northern Wisconsin. Forestry is the most important cause of novelty in the north, land use and climate change are jointly important in the southwestern Wisconsin, and land use and forest composition are most important in central and eastern Wisconsin. Areas of high regional novelty tend also to be areas of high local change, but local change has not pushed all counties beyond regional baselines. Seven counties serve as the best historical analogues for over one-half of contemporary Wisconsin counties (40/72), and so can offer useful historical counterparts for contemporary systems and help managers coordinate to tackle similar environmental challenges. Multi-dimensional environmental novelty analyses, like those presented here, can help identify the best historical analogues for contemporary ecosystems, places where new management rules and practices may be needed because novelty is already high, and the main causes of novelty. Separating regional novelty clearly from local change and measuring both across many dimensions and at multiple scales thus helps advance ecology and sustainability science alike.

Infrared Signature of the Cation-π Interaction between Calcite and Aromatic Hydrocarbons.

The cation-π interaction is proposed as an important mechanism for the adsorption of aromatic hydrocarbons having non-zero quadrupole moments by mineral surfaces. Direct evidence supporting such a mechanism is, however, limited. Using the model mineral calcite, we probe the cation-π interaction with adsorbed benzene, toluene, and ethylbenzene (BTE) molecules using attenuated total reflectance Fourier transform infrared spectroscopy. We show that the presence of calcite increases the energy required to excite the synchronized bending of aromatic C-H bonds of BTE molecules. The unique conformation of this vibrational mode indicates that the planar aromatic rings of BTE molecules are constrained in a tilted face-down position by the cation-π interaction, as further confirmed by density functional theory calculations. Our results suggest that the shift of the excitation energy of the aromatic C-H bending may be used as an infrared signature for the cation-π interaction occurring on mineral surfaces.

Treatment of an open medial tibiotalar dislocation with no associated fracture.

Tibiotalar dislocations without associated fractures are very uncommon in adults, and only a few studies have been published regarding this injury. More than 50% of these dislocations will be posteromedial, with a high incidence of open injuries, and 25% are pure posterior dislocations. In the present report, we discuss our experience and management of a medial tibiotalar dislocation with no associated fracture. In the present case, the patient was brought to the operating room on presentation to our facility and underwent irrigation and debridement with primary closure of his wound. He was immobilized postoperatively. The patient tolerated the operation well and did not sustain any postoperative complications. He was able to regain function of the injured extremity until he was lost to follow-up. Regarding treatment, the surgery should be speedy, gentle to the soft tissue, and with as little implanted material as possible. Although we do not advocate that our management and treatment of this injury become the standard, the present case provides a good example of some of the challenges often encountered when treating these injuries.

Assessing the role of biomarker feedback in a 12-week community weight management programme among overweight men: A pilot study.

BACKGROUND: The primary objective of this study was to examine the feasibility of recruitment, retention, and delivery of biomarker feedback among men partaking in Shape Up, a physical activity for health programme. Secondarily, it explored the potential effects of biomarker feedback on participants' adherence and motivation levels. METHODS: In this two-arm non-randomised pilot study, 46 men (mean±SD age 46.0±8.6 years) participating in the 12-week Shape Up programme were assigned to a control group or biomarker feedback group. Biomarker feedback consisted of 3 blood test panels: at baseline, 12 weeks, and 24 weeks (follow-up), each with a doctor's report. Both groups completed questionnaires (Short Active Lives Survey [SALS], Treatment Self-Regulation Questionnaire [TSRQ], and EQ-5D-5L) to gauge levels of motivation and engagement. The mean difference was calculated between baseline and programme end. Recruitment, retention, and attendance rates were determined. RESULTS: Mean recruitment (approach-to-consent), retention, and attendance rates were 96.3%, 92.3%, and 83.7% in the control group, and 85.2%, 86.2%, and 81.5% in the biomarker feedback group, respectively. Of biomarker feedback group participants, 86.4% attended their 12-week blood test and 45.5% attended their follow-up blood test. The mean 12-week differences (95% CI) for the control group and biomarker feedback group were 138.1 (2.7, 273.5) and 467.3 (249.4, 685.2) for active minutes per week, 0.2 (-0.8, 1.2) and 0.4 (0.0, 0.8) for autonomous TSRQ domains, 0.2 (-0.3, 0.8) and 0.8 (0.1, 1.4) for controlled TSRQ domains, and 19 (12.7, 26.5) and 27.2 (19.8, 34.6) for EQ-5D-5L scores, respectively. CONCLUSION: Biomarker feedback was well-received by participants and deemed feasible, with high recruitment and retention rates for the duration of the 12-week programme. Biomarker feedback may affect aspects of motivation but did not appear to influence adherence to the programme. Biomarker data may provide additional evidence of programme efficacy. Important design considerations are provided for definitive larger-scale trials.

Exploring Factors Influencing Patients' Embarrassment and Feelings of Imposition in Objective Structured Clinical Examination Interactions.

OBJECTIVE: To identify factors influencing patient responses in potentially sensitive situations that might lead to embarrassment (defined by politeness theory (PT) as positive face-threatening acts [FTAs]) or a sense of imposition (defined by PT as negative FTAs) during Objective Structured Clinical Examinations (OSCEs) and to assess the participant's ability to mitigate such situations. METHODS: Nineteen OSCE video recordings of 10 pharmacy trainees interacting with mock patients were examined using the PT framework. All relevant participants' speech acts were coded and quantified into type of FTAs and the mitigation strategies used. Patient (assessor) responses were classified then quantified into preferred responses (ie, quick response) vs unpreferred (ie, delayed or hesitant responses) using conversation analysis. The chi-square test was used to identify any association between relevant variables according to predefined hypotheses using SPSS version 27. RESULTS: A total of 848 FTAs were analyzed. Participants failed to meet patient face needs in 32.4% of positive FTAs, negative FTAs in 11.5% of negative FTAs, and 44.4% of positive and negative FTAs. Although patients disclosing information about any inappropriate lifestyle behavior (as per OSCE scripts) expressed these via unpreferred mannerisms, participants were less likely to provide patients with reassurance when patient face needs were challenged in this way (68.2% of these unpreferred responses were not given reassuring feedback) than when they were maintained. CONCLUSION: Improving educational programs to include the context of patient face needs and conversational strategies for properly dealing with highly sensitive situations was suggested as a way to equip trainees with the skills to effectively build rapport with patients.

A trigonal-prismatic hexanuclear technetium(II) bromide cluster: solid-state synthesis and crystallographic and electronic structure.

The compound Na{[Tc6Br12]2Br} has been obtained from the decomposition of TcBr4 under vacuum in a Pyrex ampule at 450 °C. The stoichiometry of the compound has been confirmed by energy-dispersive X-ray spectroscopy and its structure determined by single-crystal X-ray diffraction. The compound contains a trigonal-prismatic hexanuclear [Tc6Br12] cluster. The cluster is composed of two triangular Tc3Br6 units linked by multiple Tc-Tc bonds. In the Tc3Br6 unit, the average Tc-Tc distance [2.6845(5) Å] is characteristic of Tc-Tc single bonds, while the average Tc-Tc distance between the two triangular units [2.1735(5) Å] is characteristic of Tc≡Tc triple bonds. The electronic structure of the [Tc6Br12] cluster was studied by first-principles calculations, which confirm the presence of single and triple Tc-Tc bonds in the cluster.

An Applied Linguistics Study of How Students Prevent Embarrassments and Impositions During Interactive Examination OSCEs.

OBJECTIVE: To assess the effectiveness of politeness strategies used by pharmacy students to avoid embarrassing or imposing on others during objective structured clinical examinations. METHODS: A total of 19 objective structured clinical examinations video recordings of 10 students (participants) interacting with mock patients were examined using the framework of Politeness Theory (PT). All relevant participant acts (speech activities) were coded using PT into (1) type of face threatening acts (ie, potentially sensitive situations-as regarded by PT) and (2) politeness strategies used to mitigate them. Conversation Analysis was then used to examine the effectiveness of conversational strategies by judging the 'patient' responses to these strategies. RESULTS: Most acts had the potential to impact patients' negative face needs (ie, desire to act autonomously, eg, upon the practitioner making a request), positive face needs (ie, desire to be liked, eg, upon the practitioner making a diagnosis), or both. Despite applying a variety of positive politeness strategies (eg, avoiding disagreement, or expressing understanding) to prevent embarrassment to the patient, and negative politeness strategies (eg, being indirect, using hedging, or minimizing the imposition) to avoid directly imposing on them, "dispreferred responses" showed participants mostly focused on avoiding impositions, corresponding to what they have been taught, rather embarrassments. CONCLUSION: Participants were less aware that discussing sensitive topics could cause embarrassment to patients, with the potential to upset them. Developing teaching and evaluation methods to consider patients' face needs could help in assessing and improving pharmacy students' communication skills.

Differentiating between trivalent lanthanides and actinides.

The reactions of LnCl(3) with molten boric acid result in the formation of Ln[B(4)O(6)(OH)(2)Cl] (Ln = La-Nd), Ln(4)[B(18)O(25)(OH)(13)Cl(3)] (Ln = Sm, Eu), or Ln[B(6)O(9)(OH)(3)] (Ln = Y, Eu-Lu). The reactions of AnCl(3) (An = Pu, Am, Cm) with molten boric acid under the same conditions yield Pu[B(4)O(6)(OH)(2)Cl] and Pu(2)[B(13)O(19)(OH)(5)Cl(2)(H(2)O)(3)], Am[B(9)O(13)(OH)(4)]·H(2)O, or Cm(2)[B(14)O(20)(OH)(7)(H(2)O)(2)Cl]. These compounds possess three-dimensional network structures where rare earth borate layers are joined together by BO(3) and/or BO(4) groups. There is a shift from 10-coordinate Ln(3+) and An(3+) cations with capped triangular cupola geometries for the early members of both series to 9-coordinate hula-hoop geometries for the later elements. Cm(3+) is anomalous in that it contains both 9- and 10-coordinate metal ions. Despite these materials being synthesized under identical conditions, the two series do not parallel one another. Electronic structure calculations with multireference, CASSCF, and density functional theory (DFT) methods reveal the An 5f orbitals to be localized and predominately uninvolved in bonding. For the Pu(III) borates, a Pu 6p orbital is observed with delocalized electron density on basal oxygen atoms contrasting the Am(III) and Cm(III) borates, where a basal O 2p orbital delocalizes to the An 6d orbital. The electronic structure of the Ce(III) borate is similar to the Pu(III) complexes in that the Ce 4f orbital is localized and noninteracting, but the Ce 5p orbital shows no interaction with the coordinating ligands. Natural bond orbital and natural population analyses at the DFT level illustrate distinctive larger Pu 5f atomic occupancy relative to Am and Cm 5f, as well as unique involvement and occupancy of the An 6d orbitals.

Periodic trends in lanthanide and actinide phosphonates: discontinuity between plutonium and americium.

The hydrothermal reactions of trivalent lanthanide and actinide chlorides with 1,2-methylenediphosphonic acid (C1P2) in the presence of NaOH or NaNO(3) result in the crystallization of three structure types: RE[CH(2)(PO(3)H(0.5))(2)] (RE = La, Ce, Pr, Nd, Sm; Pu) (A type), NaRE(H(2)O)[CH(2)(PO(3))(2)] (RE = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy; Am) (B type), or NaLn[CH(2)(PO(3)H(0.5))(2)]·(H(2)O) (Ln = Yb and Lu) (C type). These crystals were analyzed using single crystal X-ray diffraction, and the structures were used directly for detailed bonding calculations. These phases form three-dimensional frameworks. In both A and B, the metal centers are found in REO(8) polyhedra as parts of edge-sharing chains or edge-sharing dimers, respectively. Polyhedron shape calculations reveal that A favors a D(2d) dodecahedron while B adopts a C(2v) geometry. In C, Yb and Lu only form isolated MO(6) octahedra. Such differences in terms of structure topology and coordination geometry are discussed in detail to reveal periodic deviations between the lanthanide and actinide series. Absorption spectra for the Pu(III) and Am(III) compounds are also reported. Electronic structure calculations with multireference methods, CASSCF, and density functional theory, DFT, reveal localization of the An 5f orbitals, but natural bond orbital and natural population analyses at the DFT level illustrate unique occupancy of the An 6d orbitals, as well as larger occupancy of the Pu 5f orbitals compared to the Am 5f orbitals.

Synthesis of a uranyl persulfide complex and quantum chemical studies of formation and topologies of hypothetical uranyl persulfide cage clusters.

The compound Na(4)[(UO(2))(S(2))(3)](CH(3)OH)(8) was synthesized at room temperature in an oxygen-free environment. It contains a rare example of the [(UO(2))(S(2))(3)](4-) complex in which a uranyl ion is coordinated by three bidentate persulfide groups. We examined the possible linkage of these units to form nanoscale cage clusters analogous to those formed from uranyl peroxide polyhedra. Quantum chemical calculations at the density functional and multiconfigurational wave function levels show that the uranyl-persulfide-uranyl, U-(S(2))-U, dihedral angles of model clusters are bent due to partial covalent interactions. We propose that this bent interaction will favor assembly of uranyl ions through persulfide bridges into curved structures, potentially similar to the family of nanoscale cage clusters built from uranyl peroxide polyhedra. However, the U-(S(2))-U dihedral angles predicted for several model structures may be too tight for them to self-assemble into cage clusters with fullerene topologies in the absence of other uranyl-ion bridges that adopt a flatter configuration. Assembly of species such as [(UO(2))(S(2))(SH)(4)](4-) or [(UO(2))(S(2))(C(2)O(4))(4)](4-) into fullerene topologies with ~60 vertices may be favored by use of large counterions.

Elucidation of tetraboric acid with a new borate fundamental building block in a chiral uranyl fluoroborate.

A new neutral borate species, H(2)B(4)O(7) (also known as tetraboric acid), with a one-dimensional chain structure, is found in the interlayer spacing in Rb(2)[(UO(2))(2)B(8)O(12)F(6)]·H(2)B(4)O(7) (RbUBOF-2) derived from boric acid flux reaction of uranyl(VI) nitrate with RbBF(4). This new form of tetraboric acid possesses a novel borate fundamental building block with the symbol 4Δ:<3Δ>Δ.

Uranium and thorium hydride complexes as multielectron reductants: a combined neutron diffraction and quantum chemical study.

The unusual uranium reaction system in which uranium(4+) and uranium(3+) hydrides interconvert by formal bimetallic reductive elimination and oxidative addition reactions, [(C(5)Me(5))(2)UH(2)](2) (1) ⇌ [(C(5)Me(5))(2)UH](2) (2) + H(2), was studied by employing multiconfigurational quantum chemical and density functional theory methods. 1 can act as a formal four-electron reductant, releasing H(2) gas as the byproduct of four H(2)/H(-) redox couples. The calculated structures for both reactants and products are in good agreement with the X-ray diffraction data on 2 and 1 and the neutron diffraction data on 1 obtained under H(2) pressure as part of this study. The interconversion of the uranium(4+) and uranium(3+) hydride species was calculated to be near thermoneutral (~-2 kcal/mol). Comparison with the unknown thorium analogue, [(C(5)Me(5))(2)ThH](2), shows that the thorium(4+) to thorium(3+) hydride interconversion reaction is endothermic by 26 kcal/mol.

Heats of formation of MHxCly (M = Si, P, As, Sb) compounds and main group fluorides from high level electronic structure calculations.

Atomization energies at 0 K and heats of formation at 0 and 298 K are predicted for the MH(x)Cl(y) compounds (M = Si, P, As, and Sb) and for a number of trivalent, tetravalent, and pentavalent fluorides (SbF(3), BiF(3), GeF(4), SnF(4), PbF(4), AsF(5), SbF(5)) from coupled cluster theory (CCSD(T)) calculations using correlation consistent basis sets and extrapolation to the complete basis set limit. Small-core, relativistic effective core potentials were used for the heavier elements (Ge, As, Sn, Sb, Pb, and Bi), including correlation of the outer core electrons. Additional scalar relativistic (for the lighter elements) and atomic spin-orbit corrections are included in order to achieve near chemical accuracy of ±1.5 kcal/mol. Vibrational zero point energies were computed from scaled harmonic frequencies at the second order Møller-Plesset perturbation theory (MP2) level where possible. Agreement between theory and the available experimental data is excellent. We present a revised heat of formation of the antimony atom in the gas phase. The calculated values will be of use in predicting the behavior of chemical vapor deposition systems.

The utility of Conversation Analysis versus Roter's Interaction Analysis System for studying communication in pharmacy settings: a scoping review.

OBJECTIVES: To compare the usefulness of the Roter Interaction Analysis System with Conversation Analysis (CA) for studying dynamic patient-pharmacist interactions within pharmacy practice. A scoping review was undertaken to identify all studies using Roter's method or CA to investigate patient-pharmacist interactions. The studies were then compared and contrasted for their methodological advantages and disadvantages. KEY FINDINGS: In total, 31 studies met the inclusion criteria. Roter's method is effective in briefly describing patient-pharmacist interactions and can be used to measure the effect of training courses without consuming too much time. CA, although a time-consuming undertaking, looks at very specific features and the sequence of conversations including the dynamics of two-way interactions and can therefore be used to identify the source of conflict or misunderstandings. A flowchart showing the usefulness of both methods is suggested to help other researchers select the appropriate method(s) for their own research. SUMMARY: Although both methods are effective for investigating patient-pharmacist interactions independently, using them sequentially could enable researchers to firstly identify how to make improvements (via CA), design relevant training and then investigate the impact of such training (via Roter's method) to enrich communications research.