Real-time monitoring of solid-phase peptide synthesis using a variable bed glow reactor

On-resin aggregation and incomplete amide bond formation are major challenges for solid-phase peptide synthesis that are difficult to be monitored in real-time. Incorporation of a pressure-based variable bed flow reactor into an automated solid-phase peptide synthesizer permitted real-time monitoring of resin swelling to determine amino acid coupling efficiency and on-resin aggregation

Spectroscopy of 26^{26}F

The structure of the weakly-bound $^{26}_{\;\;9}$F$_{17}$ odd-odd nucleus, produced from $^{27,28}$Na nuclei, has been investigated at GANIL by means of the in-beam $\gamma$-ray spectroscopy technique. A single $\gamma$-line is observed at 657(7) keV in $^{26}_{9}$F which has been ascribed to the decay of the excited J=$2^+$ state to the J=1$^+$ ground state. The possible presence of intruder negative parity states in $^{26}$F is also discussed.Comment: 3 pages, 1 figure, accepted for publication in Physical Review

Chronotype and environmental light exposure in a student population

In humans and most other species, changes in the intensity and duration of light provide a critical set of signals for the synchronisation of the circadian system to the astronomical day. The timing of activity within the 24 h day defines an individual’s chronotype, i.e. morning, intermediate or evening type. The aim of this study was to investigate the associations between environmental light exposure, due to geographical location, on the chronotype of university students. Over 6 000 university students from cities in the Northern Hemisphere (Oxford, Munich and Groningen) and Southern Hemisphere (Perth, Melbourne and Auckland) completed the Munich ChronoType Questionnaire. In parallel, light measures (daily irradiance, timing of sunrise and sunset) were compiled from satellite or ground stations at each of these locations. Our data shows that later mid-sleep point on free days (corrected for oversleep on weekends MFSsc) is associated with (i) residing further from the equator, (ii) a later sunset, (iii) spending more time outside and (iv) waking from sleep significantly after sunrise. However, surprisingly, MSFscdid not correlate with daily light intensity at the different geographical locations. Although these findings appear to contradict earlier studies suggesting that in the wider population increased light exposure is associated with an earlier chronotype, our findings are derived exclusively from a student population aged between 17 and 26 years. We therefore suggest that the age and occupation of our population increase the likelihood that these individuals will experience relatively little light exposure in the morning whilst encountering more light exposure later in the day, when light has a delaying effect upon the circadian system

A one-dimensional lattice model for a quantum mechanical free particle

Two types of particles, A and B with their corresponding antiparticles, are defined in a one dimensional cyclic lattice with an odd number of sites. In each step of time evolution, each particle acts as a source for the polarization field of the other type of particle with nonlocal action but with an effect decreasing with the distance: A -->...\bar{B} B \bar{B} B \bar{B} ... ; B --> A \bar{A} A \bar{A} A ... . It is shown that the combined distribution of these particles obeys the time evolution of a free particle as given by quantum mechanics.Comment: 8 pages. Revte

Linking goniometer measurements to hyperspectral and multi-sensor imagery for retrieval of beach properties and coastal characterization

In June 2011, a multi-sensor airborne remote sensing campaign was flown at the Virginia Coast Reserve Long Term Ecological Research site with coordinated ground and water calibration and validation (cal/val) measurements. Remote sensing imagery acquired during the ten day exercise included hyperspectral imagery (CASI-1500), topographic LiDAR, and thermal infra-red imagery, all simultaneously from the same aircraft. Airborne synthetic aperture radar (SAR) data acquisition for a smaller subset of sites occurred in September 2011 (VCR\u2711). Focus areas for VCR\u2711 were properties of beaches and tidal flats and barrier island vegetation and, in the water column, shallow water bathymetry. On land, cal/val emphasized tidal flat and beach grain size distributions, density, moisture content, and other geotechnical properties such as shear and bearing strength (dynamic deflection modulus), which were related to hyperspectral BRDF measurements taken with the new NRL Goniometer for Outdoor Portable Hyperspectral Earth Reflectance (GOPHER). This builds on our earlier work at this site in 2007 related to beach properties and shallow water bathymetry. A priority for VCR\u2711 was to collect and model relationships between hyperspectral imagery, acquired from the aircraft at a variety of different phase angles, and geotechnical properties of beaches and tidal flats. One aspect of this effort was a demonstration that sand density differences are observable and consistent in reflectance spectra from GOPHER data, in CASI hyperspectral imagery, as well as in hyperspectral goniometer measurements conducted in our laboratory after VCR\u2711

Reactivity of Biarylazacyclooctynones in Copper-Free Click Chemistry

The 1,3-dipolar cycloaddition of cyclooctynes with azides, also called "copper-free click chemistry", is a bioorthogonal reaction with widespread applications in biological discovery. The kinetics of this reaction are of paramount importance for studies of dynamic processes, particularly in living subjects. Here we performed a systematic analysis of the effects of strain and electronics on the reactivity of cyclooctynes with azides through both experimental measurements and computational studies using a density functional theory (DFT) distortion/interaction transition state model. In particular, we focused on biarylazacyclooctynone (BARAC) because it reacts with azides faster than any other reported cyclooctyne and its modular synthesis facilitated rapid access to analogues. We found that substituents on BARAC's aryl rings can alter the calculated transition state interaction energy of the cycloaddition through electronic effects or the calculated distortion energy through steric effects. Experimental data confirmed that electronic perturbation of BARAC's aryl rings has a modest effect on reaction rate, whereas steric hindrance in the transition state can significantly retard the reaction. Drawing on these results, we analyzed the relationship between alkyne bond angles, which we determined using X-ray crystallography, and reactivity, quantified by experimental second-order rate constants, for a range of cyclooctynes. Our results suggest a correlation between decreased alkyne bond angle and increased cyclooctyne reactivity. Finally, we obtained structural and computational data that revealed the relationship between the conformation of BARAC's central lactam and compound reactivity. Collectively, these results indicate that the distortion/interaction model combined with bond angle analysis will enable predictions of cyclooctyne reactivity and the rational design of new reagents for copper-free click chemistry

Coulomb excitation of 73Ga

The B(E2; Ii -> If) values for transitions in 71Ga and 73Ga were deduced from a Coulomb excitation experiment at the safe energy of 2.95 MeV/nucleon using post-accelerated beams of 71,73Ga at the REX-ISOLDE on-line isotope mass separator facility. The emitted gamma rays were detected by the MINIBALL-detector array and B(E2; Ii->If) values were obtained from the yields normalized to the known strength of the 2+ -> 0+ transition in the 120Sn target. The comparison of these new results with the data of less neutron-rich gallium isotopes shows a shift of the E2 collectivity towards lower excitation energy when adding neutrons beyond N = 40. This supports conclusions from previous studies of the gallium isotopes which indicated a structural change in this isotopical chain between N = 40 and N = 42. Combined with recent measurements from collinear laser spectroscopy showing a 1/2- spin and parity for the ground state, the extracted results revealed evidence for a 1/2-; 3/2- doublet near the ground state in 73 31Ga42 differing by at most 0.8 keV in energy

Comparison of baroreflex sensitivity with a fall and rise in blood pressure induced by the Valsalva manoeuvre

Abstract The baroreflex plays a key role in human BP (blood pressure) regulation. Its efferent limb consists of a vagal and a sympathetic component. The Valsalva manoeuvre is widely used to quantify vagal baroreflex function [BRS_vagal (vagal baroreflex sensitivity)], but most studies have focused on the R-R interval response to BP decrement, even though the subsequent response to an increment in BP is important and different. In the present study, we sought to evaluate whether BRS_vagal can be determined from BRSvagal inc (BRS_vagal derived from the rise in BP during phases III-IV of the Valsalva manoeuvre), to assess the association between BRSvagal inc and BRSvagal dec (BRS_vagal derived from the preceeding BP decrement) and to validate BRSvagal inc as an index of autonomic function. We studied patients with severe autonomic failure (n = 49, 25 female), mild autonomic failure (n = 25, 11 female) and matched normal controls (n = 29, 15 female). BRSvagal inc and BRSvagal dec were calculated as the regression slope of R-R interval and systolic BP during phases III-IV and the early phase II of the Valsalva manoeuvre respectively, and compared these with other autonomic indices across the groups. BRSvagal inc was calculated in all subjects and correlated highly with BRSvagal dec (r = 0.72, P < 0.001). BRSvagal inc also correlated significantly with BP changes during phases II and IV of the Valsalva manoeuvre and sympathetic barosensitivity. BRSvagal inc was significantly different between the groups, being highest in the controls and lowest in patients with severe autonomic failure. In conclusion, vagal BRS, determined by relating R-R interval with the BP increase following phase III, is a valuable autonomic index, provides additional information about vagal baroreflex function and reflects overall severity of autonomic failure

Associations between number of consecutive night shifts and impairment of neurobehavioral performance during a subsequent simulated night shift

Objective: This study aimed to investigate sleep and circadian phase in the relationships between neurobehavioral performance and the number of consecutive shifts worked. Methods: Thirty-four shift workers [20 men, mean age 31.8 (SD 10.9) years] worked 2–7 consecutive night shifts immediately prior to a laboratory-based, simulated night shift. For 7 days prior, participants worked their usual shift sequence, and sleep was assessed with logs and actigraphy. Participants completed a 10-minute auditory psychomotor vigilance task (PVT) at the start (~21:00 hours) and end (~07:00 hours) of the simulated night shift. Mean reaction times (RT), number of lapses and RT distribution was compared between those who worked 2–3 consecutive night shifts versus those who worked 4–7 shifts. Results: Following 4–7 shifts, night shift workers had significantly longer mean RT at the start and end of shift, compared to those who worked 2–3 shifts. The slowest and fastest 10% RT were significantly slower at the start, but not end, of shift among participants who worked 4–7 nights. Those working 4–7 nights also demonstrated a broader RT distribution at the start and end of shift and had significantly slower RT based on cumulative distribution analysis (5th, 25th, 50th, 75th percentiles at the start of shift; 75th percentile at the end of shift). No group differences in sleep parameters were found for 7 days and 24 hours prior to the simulated night shift. Conclusion: A greater number of consecutive night shifts has a negative impact on neurobehavioral performance, likely due to cognitive slowing.M Magee, TL Sletten, SA Ferguson, RR Grunstein, C Anderson, DJ Kennaway, SW Lockley, SMW Rajaratna