Hydrogen-atom Attack on Phenol and Toluene is \u3cem\u3eortho\u3c/em\u3e-directed

The reaction of H + phenol and H/D + toluene has been studied in a supersonic expansion after electric discharge. The (1 + 1′) resonance-enhanced multiphoton ionization (REMPI) spectra of the reaction products, at m/z = parent + 1, or parent + 2 amu, were measured by scanning the first (resonance) laser. The resulting spectra are highly structured. Ionization energies were measured by scanning the second (ionization) laser, while the first laser was tuned to a specific transition. Theoretical calculations, benchmarked to the well-studied H + benzene → cyclohexadienyl radical reaction, were performed. The spectrum arising from the reaction of H + phenol is attributed solely to the ortho-hydroxy-cyclohexadienyl radical, which was found in two conformers (syn and anti). Similarly, the reaction of H/D + toluene formed solely the ortho isomer. The preference for the ortho isomer at 100–200 K in the molecular beam is attributed to kinetic, not thermodynamic effects, caused by an entrance channel barrier that is ∼5 kJ mol−1 lower for ortho than for other isomers. Based on these results, we predict that the reaction of H + phenol and H + toluene should still favour the ortho isomer under elevated temperature conditions in the early stages of combustion (200–400 °C)

Examination of Post-Service Health-Related Quality of Life Among Rural and Urban Military Members of the Millennium Cohort Study

Little information exists on the health-related quality of life (HRQL) of U.S. veterans based on rural (versus urban) status, especially those in younger age groups, and whether deployment influences this outcome. We addressed these questions in the Millennium Cohort Study, a prospective investigation of U.S. military personnel assessed first in 2001 and then subsequently every three years via self-administered questionnaires. Participants separated from the military at the time of the most recent survey were eligible (n = 10,738). HRQL was assessed using the SF-36V Physical Component Summary (PCS) and Mental Component Summary (MCS) scores. Rural status was assigned from zip codes using the Rural-Urban Commuting Area classification. The mean age of participants was 35 years (SD = 8.98). Compared with urban dwellers, rural residents reported significantly lower unadjusted mean PCS (49.80 vs. 50.42) and MCS (49.97 vs. 50.81) scores, but differences became nonsignificant after covariate adjustment. No interaction was seen between deployment and rural status. Rural status is not independently associated with HRQL among recent U.S. veterans

ANALYSIS OF SWITCHGRASS CHARACTERISTICS USING NEAR INFRARED SPECTROSCOPY

Switchgrass varieties grown under various environments were investi-gated by dispersive and Fourier Transform Near-Infrared (NIR) spectro-meters. The collected NIR spectra were analyzed using multivariate approaches. More specifically, principal component analysis (PCA) and projection to latent structures (PLS) regression techniques were employed to classify and predict characteristics of the switchgrass samples. The multivariate results were compared to reflectance indices that are commonly used to study the physiological performance of plants. From near infrared spectra, discrimination between the two growth locations was successfully achieved by PCA. Separation based on the ecotype and the rate of fertilizer applied to the field was also possible by the multivariable analysis of the spectral data. For the classification/ discrimination of the switchgrass samples, the near infrared spectra collected by the dispersive and the Fourier Transform spectrometers provided similar results. From the two near infrared data sets robust models were developed to predict non-structural carbohydrates content and the rate of nitrogen applied to the field. However, the spectra collected by the dispersive spectrometer resulted in more accurate models for these samples

Adductor Strains in Athletes

Acute adductor injuries are a common occurrence in sport. The overall incidence of adductor strains across 25 college sports was 1.29 injuries per 1000 exposures, with men's soccer (3.15) and men's hockey (2.47) having the highest incidences. As with most muscle strains there is a high rate of recurrence for adductor strains; 18% in professional soccer and 24% in professional hockey. Effective treatment, with successful return to play, and avoidance of reinjury, can be achieved with a proper understanding of the anatomy, a thorough clinical exam yielding an accurate diagnosis, and an evidence-based treatment approach, including return to play progression

The optical spectrum of a large isolated polycyclic aromatic hydrocarbon: hexa-peri-hexabenzocoronene, C42H18

The first optical spectrum of an isolated polycyclic aromatic hydrocarbon large enough to survive the photophysical conditions of the interstellar medium is reported. Vibronic bands of the first electronic transition of the all benzenoid polycyclic aromatic hydrocarbon hexa-peri-hexabenzocoronene were observed in the 4080-4530 Angstrom range by resonant 2-color 2-photon ionization spectroscopy. The strongest feature at 4264 Angstrom is estimated to have an oscillator strength of f=1.4x10^-3, placing an upper limit on the interstellar abundance of this polycyclic aromatic hydrocarbon at 4x10^12 cm^-2, accounting for a maximum of ~0.02% of interstellar carbon. This study opens up the possibility to rigorously test neutral polycyclic aromatic hydrocarbons as carriers of the diffuse interstellar bands in the near future.Comment: 9 pages, 1 figure. Fixed a typo on the frequency of the 'b' ban

Effect of Six Weeks of Oral \u3ci\u3eEchinacea purpurea\u3c/i\u3e Supplementation On Nitric Oxide Production

Echinacea purpurea, a purple coneflower plant of the compositae family (Asteraceae), is native to North America and commonly used as an herbal supplement to enhance immune function. Echinacea purpurea has been shown to stimulate macrophage activity which is a known stimulator of nitric oxide (NO) production. Echinacea purpurea supplementation (8,000 mg·d-1) in untrained (42.5 ± 1.6 mL·kg-1·min-1) males was shown to elicit a 63% increase (p \u3c 0.05) in serum erythropoietin (EPO) following two weeks of supplementation. This is supported in part by earlier findings which indicated that four weeks of Echinacea purpurea supplementation demonstrated a non-significant increase in maximal oxygen uptake (VO2max). It is plausible that Echinacea-induced EPO production may stimulate physiological responses independent of and/or in addition to erythropoiesis. There is also evidence suggesting EPO has vasculo-protective effects including the activation of endothelial nitric oxide synthase (eNOS). Based on these findings, a proposed non-hematological response to the Echinacea-induced increase in EPO could be enhanced NO production. The purpose of this investigation was to determine whether six weeks of oral Echinacea purpurea supplementation augmented NO production as a result of an Echinacea-induced increase in EPO and/or Echinacea-induced macrophage activity

Laboratory Focus on Improving the Culture of Biosafety: Statewide Risk Assessment of Clinical Laboratories That Process Specimens for Microbiologic Analysis

The Wisconsin State Laboratory of Hygiene challenged Wisconsin laboratories to examine their biosafety practices and improve their culture of biosafety. One hundred three clinical and public health laboratories completed a questionnaire-based, microbiology-focused biosafety risk assessment. Greater than 96% of the respondents performed activities related to specimen processing, direct microscopic examination, and rapid nonmolecular testing, while approximately 60% performed culture interpretation. Although they are important to the assessment of risk, data specific to patient occupation, symptoms, and travel history were often unavailable to the laboratory and, therefore, less contributory to a microbiology-focused biosafety risk assessment than information on the specimen source and test requisition. Over 88% of the respondents complied with more than three-quarters of the mitigation control measures listed in the survey. Facility assessment revealed that subsets of laboratories that claim biosafety level 1, 2, or 3 status did not possess all of the biosafety elements considered minimally standard for their respective classifications. Many laboratories reported being able to quickly correct the minor deficiencies identified. Task assessment identified deficiencies that trended higher within the general (not microbiology-specific) laboratory for core activities, such as packaging and shipping, direct microscopic examination, and culture modalities solely involving screens for organism growth. For traditional microbiology departments, opportunities for improvement in the cultivation and management of highly infectious agents, such as acid-fast bacilli and systemic fungi, were revealed. These results derived from a survey of a large cohort of small- and large-scale laboratories suggest the necessity for continued microbiology-based understanding of biosafety practices, vigilance toward biosafety, and enforcement of biosafety practices throughout the laboratory setting

Potent Adjuvantic Activity of a CCR1-agonistic Bis-Quinoline

A bis-quinoline compound, (7-chloro-N-(4-(7-chloroquinolin-4-ylamino)butyl)quinolin-4-amine; RE-660) was found to have C-C chemokine receptor type 1 (CCR1)-agonistic properties.RE-660 displayed strong adjuvantic activity in mice when co-administered with bovine α-lactalbumin used as a model subunit protein antigen. RE-660 evoked a balanced Th1 (IgG2)/Th2 (IgG1) antibody profile, and the quality of antibodies elicited by the bis-quinoline was found to be superior to that evoked by glucopyranosyl lipid A by surface plasmon resonance experiments. No evidence of proinflammatory activity was observed in human blood ex vivo models. In preliminary acute toxicity studies, the compound was found to be of lower toxicity than chloroquine in mice, and was non-mutagenic in an Ames screen

Data Reduction Pipeline for the CHARIS Integral-Field Spectrograph I: Detector Readout Calibration and Data Cube Extraction

We present the data reduction pipeline for CHARIS, a high-contrast integral-field spectrograph for the Subaru Telescope. The pipeline constructs a ramp from the raw reads using the measured nonlinear pixel response, and reconstructs the data cube using one of three extraction algorithms: aperture photometry, optimal extraction, or $\chi^2$ fitting. We measure and apply both a detector flatfield and a lenslet flatfield and reconstruct the wavelength- and position-dependent lenslet point-spread function (PSF) from images taken with a tunable laser. We use these measured PSFs to implement a $\chi^2$-based extraction of the data cube, with typical residuals of ~5% due to imperfect models of the undersampled lenslet PSFs. The full two-dimensional residual of the $\chi^2$ extraction allows us to model and remove correlated read noise, dramatically improving CHARIS' performance. The $\chi^2$ extraction produces a data cube that has been deconvolved with the line-spread function, and never performs any interpolations of either the data or the individual lenslet spectra. The extracted data cube also includes uncertainties for each spatial and spectral measurement. CHARIS' software is parallelized, written in Python and Cython, and freely available on github with a separate documentation page. Astrometric and spectrophotometric calibrations of the data cubes and PSF subtraction will be treated in a forthcoming paper.Comment: 18 pages, 15 figures, 3 tables, replaced with JATIS accepted version (emulateapj formatted here). Software at https://github.com/PrincetonUniversity/charis-dep and documentation at http://princetonuniversity.github.io/charis-de

Structure-Activity Relationships in Toll-like Receptor 2-Agonists Leading to Simplified Monoacyl Lipopeptides

Toll-like receptor 2-agonistic lipopeptides typified by S-[2,3-bis(palmitoyloxy)-(2RS)-propyl]-R-cysteinyl-S-serine (PAM2CS) compounds are potential vaccine adjuvants. In continuation of previously reported structure-activity relationships on this chemotype, we have determined that at least one acyl group of optimal length (C16) and an appropriately orientated ester carbonyl group is essential for TLR2-agonistic activity. The spacing between one of the palmitoyl ester carbonyl and the thioether is crucial to allow for an important H-bond, which observed in the crystal structure of the lipopeptide:TLR2 complex; consequently, activity is lost in homologated compounds. Penicillamine-derived analogues are also inactive, likely due to unfavorable steric interactions with the carbonyl of Ser 12 in TLR2. The thioether in this chemotype can be replaced with a selenoether. Importantly, the thioglycerol motif can be dispensed with altogether, and can be replaced with a thioethanol bridge. These results have led to a structurally simpler, synthetically more accessible, and water-soluble analogue possessing strong TLR2-agonistic activities in human blood