Cardiovascular responses to physical activity during work and leisure.

OBJECTIVES: Recent evidence suggests that occupational physical activity (OPA) is associated with adverse cardiovascular health, whereas leisure time physical activity is protective. This study explored explanatory physiological mechanisms. METHODS: Nineteen males (68% white, age=46.6±7.9 years, body mass index=27.9±5.1 kg/m2) with high self-reported OPA wore activity (ActiGraph and activPAL) and heart rate (HR) monitors for 7 days and an ambulatory blood pressure (BP) monitor on one workday and one non-workday. Mixed effects models compared cardiovascular variables (24-hour, nocturnal, waking and non-work time HR and BP) and nocturnal HR variability (HRV) on workdays versus non-workdays. Additional models examined associations of daily activity (steps, light physical activity (LPA) and moderate-to-vigorous physical activity (MVPA)) with cardiovascular variables. Workday by daily activity interactions were examined. RESULTS: 24-hour and waking HR and diastolic BP as well as non-work diastolic BP were significantly higher on workdays versus non-workdays (p<0.05 for all). However, no difference in systolic BP or nocturnal HR or BP was observed between work and non-workdays (p>0.05 for all). Low-frequency and high-frequency power indices of nocturnal HRV were lower on workdays (p<0.05 for both). Daily steps and LPA were positively associated with 24-hour and waking HR on work and non-workdays. Significant interactions suggested MVPA increases HR and lowers nocturnal HRV during workdays, with the opposite effect on non-workdays. CONCLUSIONS: Cardiovascular load was higher on workdays versus non-workdays with no compensatory hypotensive response following workdays. Daily MVPA may differentially affect ambulatory cardiovascular load and nocturnal HRV on workdays versus non-workdays, supporting the physical activity health paradox hypothesis.

Solvent Cage Effects: A Comparison of Geminate and Nongeminate Radical Cage Pair Combination Efficiencies.

This study measured and compared the combination efficiencies (FcP) of geminate radical cage pairs to nongeminate (collisional) radical cage pairs (Fc'). For the [Cp'(CO)3Mo·, ·Mo(CO)3Cp'] radical cage pair, Fc' was found to be smaller than FcP in solutions having the same viscosity. It is proposed that the difference in FcP and Fc' arises because the radicals in the collisional cage pair are less likely to have the correct orbital orientation for radical-radical combination to occur, whereas photochemically generated geminate cage pairs are more likely to have the correct orbital orientation. As predicted, FcP and Fc' both increase when the microviscosity of a solution increases.

Volar Cortical Integrity in Non-Operatively Treated Adult Distal Radius Fractures.

Background: We sought to independently validate published data that volar cortical integrity (VCI) is an independent predictor of maintenance of closed reduction in a series of non-surgically treated distal radius fractures, while simultaneously investigating previously reported predictors of instability. Our null hypothesis was that volar cortical integrity would not affect maintenance of reduction. Methods: Four hundred thirty-three adult distal radius fractures were screened from our Orthopedic database with 112 meeting inclusion criteria. Two groups were determined on the basis of maintenance of reduction (MOR) or loss of reduction (LOR) at 5-6 weeks post-reduction. Bivariate analysis was applied to previously published instability factors along with VCI. A forward stepwise logistic regression was then used to identify instability factors that, as a group, are most predictive of outcome. Results: Results of 112 patients were collected. Reduction was maintained in 62 patients (55.35%) at 5-6 weeks Biivariate analysis showed a statistically significant difference in volar cortical integrity between the 2 groups (80.6% MOR vs 59.2% LOR). Forward stepwise logistic regression analysis of subgroups revealed that post-reduction radial height and VCI were together statistically significant in the model. The presence of VCI, post-reduction radial height greater than or equal to ulnar neutral at the time of initial reduction resulted in a 67.8% successful MOR. Conclusions: We were able to confirm the importance of volar cortical integrity as a predictor of successful maintenance of reduction in non-surgically managed distal radius fractures. When combined with post-reduction radial height greater than or equal to ulnar neutral at the time of initial reduction, it showed a 67.8% MOR with non-operative management in our data-set.

Validation of the Shin Pain Scoring System: A Novel Approach for Determining Tibial Bone Stress Injuries.

BACKGROUND: The incidence of adolescent overuse injuries, including bone stress injuries (BSIs), is on the rise. The identification of a BSI in the early stages is key to successful treatment. The Shin Pain Scoring System (SPSS) was developed to aid clinicians in identifying patients with a BSI. HYPOTHESIS: The SPSS will correlate with magnetic resonance imaging (MRI) grading of a BSI in an adolescent population. STUDY DESIGN: Cohort study (diagnosis); Level of evidence, 2. METHODS: Enrolled in this study were 80 adolescent high school athletes between the ages of 13 and 18 years participating in a variety of sports with more than 1 week of atraumatic shin pain. The SPSS questionnaire was completed for each participant, and physical examination findings were recorded. Each question and physical examination item was allotted a point value, which totaled 29 points. Radiographs and MRI scans of both lower legs were obtained for each participant. The SPSS score was statistically analyzed using logistic regression, a classification matrix, and a 2 × 2 contingency table to evaluate validity and predictability. RESULTS: Logistic regression analysis of our data determined that 3 categories of SPSS scores provided the highest diagnostic value when compared with MRI grading based on the Fredericson classification (0-4). The SPSS correctly identified 43.5% of injuries for category 1 (MRI grades 0-1), 62.5% for category 2 (MRI grade 2), and 50.0% for category 3 (MRI grades 3-4). Overall, the SPSS correctly identified the degree of BSI in 54.4% of all tibias studied. Binary analysis for validity demonstrated a sensitivity of 96%, specificity of 26%, positive predictive value of 76%, and negative predictive value of 71% for the SPSS relative to the "gold standard" MRI results. CONCLUSION: The SPSS is a potentially valid method to identify tibial BSIs, given the sensitivity and negative and positive predictive values. It also provides helpful categorization to alert clinicians to the presence of a BSI and direct further diagnostics and/or interventions. The SPSS should be considered as an additional tool to use when evaluating adolescents with atraumatic tibial BSIs.

Multi-spectral image shift-estimation error calculations using simulated phenomenology.

Registration of multi-spectral imagery is a critical pre-processing step for applications such as image fusion, but phenomenological differences between spectral bands can lead to significant estimation errors. To develop credible requirements for multi-spectral imaging systems, it is critical to characterize errors, both algorithmic and fundamental, associated with estimating registration parameters; however, attempting to quantify error using archival data sets poses a number of problems. In this paper, we demonstrate the use of commercially available graphics software and available optical property measurements to create fully synthetic, multi-spectral imagery with high-fidelity representations of emissive and reflective phenomenology. We discuss and demonstrate techniques needed to quantify error for both area- and feature-based algorithms. We further show that such synthetic data sets can be used to quantify both the Fisher information and sample errors associated with estimation of the shift between images acquired in different spectral bands and, by extension, estimation of registration model parameters. With the flexibility offered by synthetic data, such characterization can be obtained for robust domains of image brightness, sensor parameters, and differences in image phenomenology.

Intrinsic bias in Fisher information calculations for multi-mode image registration.

To address the need for the analysis of image processing and optical requirements in multi-mode imaging systems, such as multi-spectral and polarimetric imagers, I have developed a Fisher information matrix to quantify errors in estimating the shift between images with non-transformational feature differences. If images of the same field have differences not attributable to a geometric transformation, as is common for images acquired using different spectral or polarization filters, uncertainty in estimating the parameters of the transformation will be increased by intrinsic bias, or bias inherent in the data itself, as opposed to bias originating in the estimation algorithm. The approach to shift-estimation error analysis described in this Letter accounts for intrinsic bias, has intuitively expected properties and, given planned system sensitivity and operating conditions, can be used with simulated multi-mode imagery to estimate image registration error and develop realistic requirements.

Airlight-imposed errors for space-object polarimetric observations from the ground.

We discuss and characterize how polarimetric sensing is contaminated by various "airlight" phenomena, as well as unpolarized light from the target, when space objects are observed with a ground-based telescope. Estimates of the polarization state are limited by unpolarized target light regardless of sensor technology or estimator algorithm, and increased target brightness actually degrades estimation of the S1, S2, and S3 Stokes parameters if the added light is unpolarized. Unpolarized airlight in the field of view has an identical degrading effect. Atmospheric scattering can significantly polarize airlight, so airlight polarization must be calibrated and subtracted from the estimated target polarization. We derive an expression for the mean-square Stokes estimation error when noisy, biased estimates for the airlight polarization state are subtracted from noisy, biased estimates of the target polarization state; this expression shows that target and airlight Stokes estimation noise and bias generally sum in the ms estimation error for airlight-calibrated target Stokes. While SNR for the estimate of a given Stokes parameter increases with the magnitude of that parameter, estimation bias also appears to be correlated with magnitude. We note that when the linear Stokes reference is not arbitrary, requiring a rotational transformation of the estimated Stokes vector, the SNRs of the S1 and S2 estimates vary with the rotation angle. Finally, we show that measured data can be used in numerical calculations described here to approximate the errors associated with Stokes estimation, with or without airlight calibration.

Radical Cage Effects: The Prediction of Radical Cage Pair Recombination Efficiencies Using Microviscosity Across a Range of Solvent Types.

This study reports a method for correlating the radical recombination efficiencies (FcP) of geminate radical cage pairs to the properties of the solvent. Although bulk viscosity (macroviscosity) is typically used to predict or interpret radical recombination efficiencies, the work reported here shows that microviscosity is a much better parameter. The use of microviscosity is valid over a range of different solvent system types, including nonpolar, aromatic, polar, and hydrogen bonding solvents. In addition, the relationship of FcP to microviscosity holds for solvent systems containing mixtures of these solvent types. The microviscosities of the solvent systems were straightforwardly determined by measuring the diffusion coefficient of an appropriate probe by NMR DOSY spectroscopy. By using solvent mixtures, selective solvation was shown to not affect the correlation between FcP and microviscosity. In addition, neither solvent polarity nor radical rotation affects the correlation between FcP and the microviscosity.

Enhancing Executive Function and Neural Health in Bipolar Disorder through Reasoning Training.

Cognitive deficits in executive function and memory among individuals with bipolar disorder (BD) are well-documented; however, only recently have efforts begun to address whether such cognitive deficits can be ameliorated through cognitive training. This pilot study examined the effects of a top-down, cognitive reasoning training program in adults with BD on both brain and cognitive measures. Twenty-seven participants (11 males, 16 females), aged 21-70 years old, completed the study. Participants completed neurocognitive testing and functional magnetic resonance imaging (fMRI) before and after training, consisting of 8 h (2 h/week) of training in small groups. The training delivered information processing strategies that were implemented and applicable to a variety of daily living contexts. Results indicated that participants showed significant gains in the primary outcome measure of complex abstraction, also referred to as gist reasoning, as well as in untrained domains of executive function and memory. We found a significant increase in resting cerebral blood flow (CBF) in left inferior frontal gyrus after cognitive training. We also found that resting CBF in the right frontal middle gyrus correlated positively with performance on the measure of complex abstraction. This feasibility study provides promising evidence that short-term reasoning training can enhance cognitive performance and brain health in adults with BD. These data motivate further efforts to explore adjuvant therapeutics to improve cognitive performance and underlying brain systems in bipolar, as well as other psychiatric disorders. Clinicaltrials.gov Identifier: NCT02843282, http://www.clinicaltrials.gov/ct2/show/NCT02843282.

Radical Cage Effects: Comparison of Solvent Bulk Viscosity and Microviscosity in Predicting the Recombination Efficiencies of Radical Cage Pairs.

This study reports the results of experiments that probed how solvents affect the recombination efficiency (FcP) of geminate radical cage pairs. The macroviscosity of solvents has traditionally been used to make quantitative predictions about FcP, but experiments reported here show that FcP varies dramatically for solvent systems with identical macroviscosities. Experiments show that FcP correlates with the solvent microviscosity: five different solvent systems (consisting of a solvent and a structurally similar viscogen) were examined, and FcP was the same for all five solvent systems at any particular microviscosity. The translational diffusion coefficient of the radicals (measured by DOSY) in the solvent system was used to define the microviscosity of the solvent system.

Safety and Tolerability of Stribild in the Southeast United States.

PURPOSE: The purpose of this study is to assess postmarketing safety and tolerability of Stribild (elvitegravir [EVG]/cobicistat [COBI]/tenofovir disoproxil fumarate [TDF]/emtricitabine [FTC]). METHODS: A retrospective, pharmacoepidemiologic study in 2 outpatient HIV clinics in the Southeast United States was conducted among adults receiving EVG/COBI/TDF/FTC. We evaluated incidence and treatment-related adverse events, including change in serum creatinine (SCr). RESULTS: Patients were primarily treatment experienced (n = 173, 60%), African American (n = 210, 73%), and males (n = 187, 65%). One hundred ninety-five (68%) patients had any increase in SCr, and 65 (23%) had an increase of ≥0.3 mg/dL. Mean SCr change from baseline to peak was 0.2 mg/dL. Being treatment experienced (odds ratio [OR] = 2.21, 95% confidence interval [CI]: 1.12-4.38) was associated with SCr ≥0.3 mg/dL, while body mass index ≥30 kg/m(2) (OR = 0.41, 95% CI: 0.18-0.93) was protective. Twenty (7%) patients discontinued therapy, 3 due to acute kidney injury. CONCLUSION: Our results demonstrate limited adverse events and low discontinuation rates associated with EVG/COBI/TDF/FTC.

Synthesis of tetraphosphine macrocycles using copper(i) templates.

The synthesis of phosphine macrocycles is a relatively underdeveloped area and no standard synthetic routes have emerged. Accordingly, two general synthetic routes to tetradentate phosphine macrocycles were investigated. Both routes use Cu(i) ions as template ions because, unlike other metals such as Pd(ii) and Pt(ii), the Cu(i) ions can be removed from the macrocyclic complex without degrading the macrocycle ligand. The first route involves the coupling of two bidentate secondary phosphines bonded to Cu(i) using 1,3-dibromopropane or 1,4-dibromobutane. Using this route, tetradentate phosphine macrocycles with either -(CH2)3OCH3 or Ph groups bonded to the P atoms were synthesized. Macrocycle phosphines containing the -(CH2)3OCH3 groups were investigated for their potential water-solubility, but experiments showed these phosphines were not water soluble. The second synthetic route involved the alkylation of an open-chain, mixed tertiary-secondary, tetradentate phosphine coordinated to Cu(i). Following formation of the macrocyclic ligand, the Cu(i) template was removed by reaction with aqueous KCN to yield the free macrocyclic phosphine. This route was demonstrated for the preparation of the macrocyclic phosphine ligand 1,5,9,13-tetraphenyl-1,5,9,13-tetraphosphacycloheptadecane. Following demetallation, this macrocyclic ligand was coordinated to Fe(ii) and Co(ii) to form the corresponding macrocyclic phosphine complexes.

Steric and Electronic Influences of Buchwald-Type Alkyl-JohnPhos Ligands.

The electron-donating and steric properties of Buchwald-type ligands ([1,1'-biphenyl-2-yl]dialkylphosphine; R-JohnPhos, where R = Me, Et, (i)Pr, Cy, (t)Bu) were determined. The π-acidity and σ-donating properties of the R-JohnPhos ligands were quantified using a Cotton-Kraihanzel analysis of the Cr(0)(CO)5(R-JohnPhos) complexes. Somewhat surprisingly, the σ-donating abilities of the R-JohnPhos ligands follow the trend (t)Bu-JohnPhos < Et-JohnPhos < (i)Pr-JohnPhos < Cy-JohnPhos ≪ Me-JohnPhos. This ordering is proposed to arise from competition between the intrinsic electron-donating ability of the R groups (Me < Et < (i)Pr ≈ Cy < (t)Bu) and steric interactions (front and back strain) that decrease the electron-donating ability of the phosphine. X-ray crystallographic data of 22 metal complexes (general forms: trans-Cr(0)(CO)4(PR3)2, Pd(0)(PR3)2(η(2)-dba), and trans-Pd(II)(Cl)2(PR3)2) were also analyzed to help explain the electronic trends measured for the R-JohnPhos ligands. The R-JohnPhos ligands are exceptionally sensitive to back strain in comparison to typical phosphines, and the strong σ-donating ability of the Methyl-JohnPhos ligand is attributed to its ability to avoid both front strain and back strain. Consequently, the -PMe2 moiety allows for very short phosphorus-metal bond distances. Because of the sterically dominating o-biphenyl and close phosphorus-metal bond distances, MeJPhos maintains a large overall steric profile that is actually larger than that of CyJPhos as measured by percent buried volume (%V(bur)). Overall, the -PMe2 moiety is a powerful way to incorporate strong σ-donation into "designer" phosphines while retaining other advantageous structural and reactivity properties.

AMP: A platform for managing and mining data in the treatment of Autism Spectrum Disorder.

We introduce AMP (Autism Management Platform), an integrated health care information system for capturing, analyzing, and managing data associated with the diagnosis and treatment of Autism Spectrum Disorder in children. AMP's mobile application simplifies the means by which parents, guardians, and clinicians can collect and share multimedia data with one another, facilitating communication and reducing data redundancy, while simplifying retrieval. Additionally, AMP provides an intelligent web interface and analytics platform which allow physicians and specialists to aggregate and mine patient data in real-time, as well as give relevant feedback to automatically learn data filtering preferences over time. Together AMP's mobile app, web client, and analytics engine implement a rich set of features that streamline the data collection and analysis process in the context of a secure and easy-to-use system so that data may be more effectively leveraged to guide treatment.

Cramér-Rao lower bound calculations for image registration using simulated phenomenology.

The Cramér-Rao lower bound (CRLB) is a valuable tool to quantify fundamental limits to estimation problems associated with imaging systems, and has been used previously to study image registration performance bounds. Most existing work, however, assumes constant-variance noise; for many applications, noise is signal-dependent. Further, linear filters applied after detection can potentially yield reduced registration error, but prior work has not treated the CRLB behavior caused by filter-imposed noise correlation. We have developed computational methods to efficiently generalize existing image registration CRLB calculations to account for the effect of both signal-dependent noise and linear filtering on the estimation of rigid-translation ("shift") parameters. Because effective use of the CRLB requires radiometrically realistic simulated imagery, we have also developed methods to exploit computer animation software and available optical properties databases to conveniently build and modify synthetic objects for radiometric image simulations using DIRSIG. In this paper, we present the generalized expressions for the rigid shift Fisher information matrix and discuss the properties of the associated CRLB. We discuss the methods used to synthesize object "sets" for use in DIRSIG, and then demonstrate the use of simulated imagery in the CRLB code to choose an error-minimizing filter and optimal integration time for an image-based tracker in the presence of random platform jitter.

Crystal structure of trans-dihydrido-bis[tris-(di-methyl-amino)-phosphane-κP]platinum(II).

The mol-ecule of the title compound, [PtH2(C6H18N3P)2], has a centrosymmetric square-planar structure in which the Pt(II) atom is bonded to two H and two P atoms in a mutually trans configuration. The Pt(II) atom sits on an inversion center and thus the asymmetric unit contains only half the mol-ecule. The Pt-P and Pt-H distances are 2.2574 (10) and 1.49 (7) Å, respectively.

The synthesis of heteroleptic phosphines.

Heteroleptic phosphines (R2PR(1)) are a class of essential ligands for inorganic and organometallic chemistry. However, the syntheses of these phosphines are often fraught with laborious synthetic hurdles. Consequently, a renewed interest in innovative synthetic methods to access heteroleptic phosphines is emerging. This Perspective presents an overview of modern synthetic approaches to heteroleptic phosphines as well as a discussion of the strengths and limitations of these synthetic methods. A major emphasis is placed on simple and direct routes to phosphines and significant synthetic innovations for P-C bond-forming reactions.

Homeotic function of Drosophila Bithorax-complex miRNAs mediates fertility by restricting multiple Hox genes and TALE cofactors in the CNS.

The Drosophila Bithorax complex (BX-C) Hox cluster contains a bidirectionally transcribed miRNA locus, and a deletion mutant (Δmir) lays no eggs and is completely sterile. We show these miRNAs are expressed and active in distinct spatial registers along the anterior-posterior axis in the CNS. Δmir larvae derepress a network of direct homeobox gene targets in the posterior ventral nerve cord (VNC), including BX-C genes and their TALE cofactors. These are phenotypically critical targets, because sterility of Δmir mutants was substantially rescued by heterozygosity of these genes. The posterior VNC contains Ilp7+ oviduct motoneurons, whose innervation and morphology are defective in Δmir females, and substantially rescued by heterozygosity of Δmir targets, especially within the BX-C. Collectively, we reveal (1) critical roles for Hox miRNAs that determine segment-specific expression of homeotic genes, which are not masked by transcriptional regulation; and (2) that BX-C miRNAs are essential for neural patterning and reproductive behavior.

Benzyl-tris-[2-(di-benzyl-amino)-eth-yl]ammonium iodide.

In the title quaternary ammonium salt, C55H61N4 (+)·I(-), all three N,N-di-benzyl-ethanamine, -(CH2)2N(CH2C6H5)2, groups have different conformations. The N-C-C-N torsion angles are significantly different [89.86 (13), 162.61 (10) and 175.70 (10)°] and the dihedral angles between the phenyl rings in these groups are different as well [58.21 (4), 43.73 (4) and 76.72 (5)°]. In the crystal, the I(-) anions fill empty spaces between the bulky cations. The cations and anions are linked by weak C-H⋯I inter-actions, forming a chain along [110].

The influence of student characteristics on the dependability of behavioral observation data.

Although generalizability theory has been used increasingly in recent years to investigate the dependability of behavioral estimates, many of these studies have relied on use of general education populations as opposed to those students who are most likely to be referred for assessment due to problematic classroom behavior (e.g., inattention, disruption). The current study investigated the degree to which differences exist in terms of the magnitude of both variance component estimates and dependability coefficients between students nominated by their teachers for Tier 2 interventions due to classroom behavior problems and a general classroom sample (i.e., including both nominated and non-nominated students). The academic engagement levels of 16 (8 nominated, 8 non-nominated) middle school students were measured by 4 trained observers using momentary time-sampling procedures. A series of G and D studies were then conducted to determine whether the 2 groups were similar in terms of the (a) distribution of rating variance and (b) number of observations needed to achieve an adequate level of dependability. Results suggested that the behavior of students in the teacher-nominated group fluctuated more across time and that roughly twice as many observations would therefore be required to yield similar levels of dependability compared with the combined group. These findings highlight the importance of constructing samples of students that are comparable to those students with whom the measurement method is likely to be applied when conducting psychometric investigations of behavioral assessment tools.