Radical-based C-C Bond-Forming Processes Enabled by the Photoexcitation of 4-Alkyl-1,4-dihydropyridines

We report herein that 4-alkyl-1,4-dihydropyridines (alkyl-DHPs) can directly reach an electronically excited state upon light absorption and trigger the generation of C(sp3)-centered radicals without the need for an external photocatalyst. Selective excitation with a violet-light-emitting diode turns alkyl-DHPs into strong reducing agents that can activate reagents via single-electron transfer manifolds while undergoing a homolytic cleavage to generate radicals. We used this photochemical dual-reactivity profile to trigger radical-based carbon-carbon bond-forming processes, including nickel catalyzed cross-coupling reactions

Comment on "Evolution of a Quasi-Stationary State"

Approximately forty years ago it was realized that the time development of decaying systems might not be precisely exponential. Rolf Winter (Phys. Rev. {\bf 123}, 1503 (1961)) analyzed the simplest nontrivial system - a particle tunneling out of a well formed by a wall and a delta-function. He calculated the probability current just outside the well and found irregular oscillations on a short time scale followed by an exponential decrease followed by more oscillations and finally by a decrease as a power of the time. We have reanalyzed this system, concentrating on the survival probability of the particle in the well rather than the probability current, and find a different short time behavior.Comment: 8 pages, 6 figures, RevTex

Mathematical model for a novel cryogenic flow sensor using fibre Bragg gratings

In this work, a mathematical model is presented for a newly developed cryogenic flow meter which is based on fibre Bragg grating (FBG) principle. The principle of operation is to use the viscous drag force induced by a flowing fluid on an optical fibre placed transverse to the flow. An optical fibre will have a 5 mm long grating element inscribed in it and will be placed so that the sensor is at the centre of the pipe. The fibre will act as the bluff body, while the FBG sensor will pick up the bending strain induced in the fibre due to the drag force. The amount of bending strain which can be measured as a shift in Bragg wavelength can be calibrated to provide the mass flow rate. Here a mathematical model is being presented to predict the operation of the sensor and to calculate the sensor characteristics so that the sensor design can be optimised. The sensor exhibits an exponential relationship between sensitivity and mass flow rate. It is also seen that the sensitivity depends greatly on the fluid properties such as density and viscosity

Some anisotropic universes in the presence of imperfect fluid coupling with spatial curvature

We consider Bianchi VI spacetime, which also can be reduced to Bianchi types VI0-V-III-I. We initially consider the most general form of the energy-momentum tensor which yields anisotropic stress and heat flow. We then derive an energy-momentum tensor that couples with the spatial curvature in a way so as to cancel out the terms that arise due to the spatial curvature in the evolution equations of the Einstein field equations. We obtain exact solutions for the universes indefinetly expanding with constant mean deceleration parameter. The solutions are beriefly discussed for each Bianchi type. The dynamics of the models and fluid are examined briefly, and the models that can approach to isotropy are determined. We conclude that even if the observed universe is almost isotropic, this does not necessarily imply the isotropy of the fluid (e.g., dark energy) affecting the evolution of the universe within the context of general relativity.Comment: 17 pages, no figures; to appear in International Journal of Theoretical Physics; in this version (which is more concise) an equation added, some references updated and adde

Flow characterisation for a validation study in high-speed aerodynamics

Validation studies are becoming increasingly relevant when investigating complex flow problems in high-speed aerodynamics. These investigations require calibration of numerical models with accurate data from the physical wind tunnel being studied. This paper presents the characterisation process for a joint experimental-computational study to investigate the streamwise corners of a Mach 2.5 channel flow. As well as checks of flow quality typically performed for phenomenological investigations, additional quantitative tests are conducted. The extra care to obtain high quality data and eliminate any systematic errors reveal useful information about the wind tunnel flow. Further important physical insights are gained from designing and conducting wind tunnel tests in conjunction with numerical simulations. Crucially, the close experimental-computational collaboration enabled the identification of secondary flows in the sidewall boundary-layers; these strongly influence the flow in the corner regions, the target of the validation study

MICROMEGAS chambers for hadronic calorimetry at a future linear collider

Prototypes of MICROMEGAS chambers, using bulk technology and analog readout, with 1x1cm2 readout segmentation have been built and tested. Measurements in Ar/iC4H10 (95/5) and Ar/CO2 (80/20) are reported. The dependency of the prototypes gas gain versus pressure, gas temperature and amplification gap thickness variations has been measured with an 55Fe source and a method for temperature and pressure correction of data is presented. A stack of four chambers has been tested in 200GeV/c and 7GeV/c muon and pion beams respectively. Measurements of response uniformity, detection efficiency and hit multiplicity are reported. A bulk MICROMEGAS prototype with embedded digital readout electronics has been assembled and tested. The chamber layout and first results are presented

Conditions for spontaneous homogenization of the Universe

The present-day Universe appears to be homogeneous on very large scales. Yet when the casual structure of the early Universe is considered, it becomes apparent that the early Universe must have been highly inhomogeneous. The current paradigm attempts to answer this problem by postulating the inflation mechanism However, inflation in order to start requires a homogeneous patch of at least the horizon size. This paper examines if dynamical processes of the early Universe could lead to homogenization. In the past similar studies seem to imply that the set of initial conditions that leads to homogenization is of measure zero. This essay proves contrary: a set of initial conditions for spontaneous homogenization of cosmological models can form a set of non-zero measure.Comment: 7 pages. Fifth Award in the 2010 Gravity Research Foundation essay competitio

Impact of predicted precipitation scenarios on multitrophic interactions

1. Predicted changes in the frequency and intensity of extreme rainfall events in the UK have the potential to disrupt terrestrial ecosystem function. However, responses of different trophic levels to these changes in rainfall patterns, and the underlying mechanisms, are not well characterised. 2. This study aimed to investigate how changes in both the quantity and frequency of rainfall events will affect the outcome of interactions between plants, insect herbivores (above- and below- ground) and natural enemies. 3. Hordeum vulgare L. plants were grown in controlled conditions and in the field, and subjected to three precipitation scenarios: ambient (based on a local 10 year average rainfall); continuous drought (40% reduction compared to ambient); drought/ deluge (40% reduction compared to ambient at a reduced frequency). The effects of these watering regimes and wireworm (Agriotes species) root herbivory on the performance of the plants, aphid herbivores above-ground (Sitobion avenae, Metapolophium dirhodum and Rhopalosiphum padi), and natural enemies of aphids including ladybirds (Harmonia axyridis) were assessed from measurements of plant growth, insect abundance and mass, and assays of feeding behaviour. 4. Continuous drought decreased plant biomass, whereas reducing the frequency of watering events did not affect plant biomass but did alter plant chemical composition. In controlled conditions, continuous drought ameliorated the negative impact of wireworms on plant biomass. 5. Compared to the ambient treatment, aphid mass was increased by 15% when feeding on plants subjected to drought/ deluge; and ladybirds were 66% heavier when feeding on these aphids but this did not affect ladybird prey choice. In field conditions, wireworms feeding below-ground reduced the number of shoot-feeding aphids under ambient and continuous drought conditions but not under drought/ deluge. 6. Predicted changes in both the frequency and intensity of precipitation events under climate change have the potential to limit plant growth, but reduce wireworm herbivory, while simultaneously promoting above-ground aphid numbers and mass, with these effects transferring to the third trophic level. Understanding the effect of future changes in precipitation on species interactions is critical for determining their potential impact on ecosystem functioning and constructing accurate predictions under global change scenarios

The influence of gene expression time delays on Gierer-Meinhardt pattern formation systems

There are numerous examples of morphogen gradients controlling long range signalling in developmental and cellular systems. The prospect of two such interacting morphogens instigating long range self-organisation in biological systems via a Turing bifurcation has been explored, postulated, or implicated in the context of numerous developmental processes. However, modelling investigations of cellular systems typically neglect the influence of gene expression on such dynamics, even though transcription and translation are observed to be important in morphogenetic systems. In particular, the influence of gene expression on a large class of Turing bifurcation models, namely those with pure kinetics such as the Gierer–Meinhardt system, is unexplored. Our investigations demonstrate that the behaviour of the Gierer–Meinhardt model profoundly changes on the inclusion of gene expression dynamics and is sensitive to the sub-cellular details of gene expression. Features such as concentration blow up, morphogen oscillations and radical sensitivities to the duration of gene expression are observed and, at best, severely restrict the possible parameter spaces for feasible biological behaviour. These results also indicate that the behaviour of Turing pattern formation systems on the inclusion of gene expression time delays may provide a means of distinguishing between possible forms of interaction kinetics. Finally, this study also emphasises that sub-cellular and gene expression dynamics should not be simply neglected in models of long range biological pattern formation via morphogens

Generation of Bianchi type V cosmological models with varying Λ\Lambda-term

Bianchi type V perfect fluid cosmological models are investigated with cosmological term $\Lambda$ varying with time. Using a generation technique (Camci {\it et al.}, 2001), it is shown that the Einstein's field equations are solvable for any arbitrary cosmic scale function. Solutions for particular forms of cosmic scale functions are also obtained. The cosmological constant is found to be decreasing function of time, which is supported by results from recent type Ia supernovae observations. Some physical aspects of the models are also discussed.Comment: 16 pages, 3 figures, submitted to CJ