Studies on heteroporphycene synthesis

Chapter one of this thesis gives an overview of light-matter interactions, organic photochemistry and two-photon absorption spectroscopy. Conceptual beginnings of the project are discussed and target compounds for synthesis are identified through computational studies. Chapter two, section one outlines the efforts to synthesise dioxaporphycene porphycene targets through crossed McMurry coupling reactions. Contained are novel crossed porphycene compounds as well as a newly discovered macrocycle containing both furan and sulfur functionality, the structure of which was characterised crystallographically. The crossed McMurry reaction is rationalised computationally, where we identify a key factor for a compatible cross-coupling partner. The efforts contained in this section have been published in the European Journal of Organic Chemistry. Chapter two, section two describes the substantial steps taken to synthesise a new carbazole structure as a precursor compound to porphycene macrocycles. The chapter contains key novel structures which led to the direct precursor target and discusses the synthetic methods used to reach the final structures. Chapter two, section three describes an alternative synthetic route towards porphycene macrocycles, via a stepped approach to build complex functionality from common starting materials. Chapter two, section four describes the contributions made towards the group project on intramolecular nitrofuran Diels-Alder reactions and the counter intuative rate enhancement observed by the introduction of the nitro-group. A computational study of the effect is contained and the effect is rationalised in the discussion. A summary of the research contained in this section has been published in the Journal of Organic Chemistry. Chapter three, contains experimental details of all the novel compounds produced in the research chapters along with details of synthetic improvements or alternative synthesis of known compounds

Formation of Low Mass Stars in Elliptical Galaxy Cooling Flows

X-ray emission from hot (T = 10^7 K) interstellar gas in massive elliptical galaxies indicates that 10^{10} M_sun has cooled over a Hubble time, but optical and radio evidence for this cold gas is lacking. We provide detailed theoretical support for the hypothesis that this gas has formed into low luminosity stars. Within several kpc of the galactic center, interstellar gas first cools to T = 10^4 K where it is heated by stellar UV and emits the observed diffuse optical line emission. This cooling occurs at a large number (10^6) of isolated sites. After less than a solar mass of gas has accumulated (10^{-6} M_sun/yr) at a typical cooling site, a neutral (HI or H_2) core develops in the HII cloud where gas temperatures drop to T = 15 K and the ionization level (from thermal X-rays) is very low (x = 10^{-6}). We show that the maximum mass of cores that become gravitationally unstable is only about 2 M_sun. No star can exceed this mass. Fragmentation of collapsing cores produces a population of low mass stars with a bottom-heavy IMF and radial orbits. Gravitational collapse and ambipolar diffusion are rapid. The total mass of star-forming (dust-free) HI or H_2 cores in a typical bright elliptical is only 10^6 M_sun, below current observational thresholds.Comment: 23 pages in AASTEX LaTeX with 8 figures; accepted by Astrophysical Journa

Coupled dark matter-dark energy in light of near Universe observations

Cosmological analysis based on currently available observations are unable to rule out a sizeable coupling among the dark energy and dark matter fluids. We explore a variety of coupled dark matter-dark energy models, which satisfy cosmic microwave background constraints, in light of low redshift and near universe observations. We illustrate the phenomenology of different classes of dark coupling models, paying particular attention in distinguishing between effects that appear only on the expansion history and those that appear in the growth of structure. We find that while a broad class of dark coupling models are effectively models where general relativity (GR) is modified --and thus can be probed by a combination of tests for the expansion history and the growth of structure--, there is a class of dark coupling models where gravity is still GR, but the growth of perturbations is, in principle modified. While this effect is small in the specific models we have considered, one should bear in mind that an inconsistency between reconstructed expansion history and growth may not uniquely indicate deviations from GR. Our low redshift constraints arise from cosmic velocities, redshift space distortions and dark matter abundance in galaxy voids. We find that current data constrain the dimensionless coupling to be |xi|<0.2, but prospects from forthcoming data are for a significant improvement. Future, precise measurements of the Hubble constant, combined with high-precision constraints on the growth of structure, could provide the key to rule out dark coupling models which survive other tests. We shall exploit as well weak equivalence principle violation arguments, which have the potential to highly disfavour a broad family of coupled models.Comment: 34 pages, 6 figures; changes to match published versio

Constraining stellar assembly and AGN feedback at the peak epoch of star formation

We study stellar assembly and feedback from active galactic nuclei (AGN) around the epoch of peak star formation (1<z<2), by comparing hydrodynamic simulations to rest-frame UV-optical galaxy colours from the Wide Field Camera 3 (WFC3) Early-Release Science (ERS) Programme. Our Adaptive Mesh Refinement simulations include metal-dependent radiative cooling, star formation, kinetic outflows due to supernova explosions, and feedback from supermassive black holes. Our model assumes that when gas accretes onto black holes, a fraction of the energy is used to form either thermal winds or sub-relativistic momentum-imparting collimated jets, depending on the accretion rate. We find that the predicted rest-frame UV-optical colours of galaxies in the model that includes AGN feedback is in broad agreement with the observed colours of the WFC3 ERS sample at 1<z<2. The predicted number of massive galaxies also matches well with observations in this redshift range. However, the massive galaxies are predicted to show higher levels of residual star formation activity than the observational estimates, suggesting the need for further suppression of star formation without significantly altering the stellar mass function. We discuss possible improvements, involving faster stellar assembly through enhanced star formation during galaxy mergers while star formation at the peak epoch is still modulated by the AGN feedback.Comment: 6 pages, 4 figures, accepted for publication in MNRAS Letter

Diabetes and Pre-Diabetes as Determined by Glycated Haemoglobin A1c and Glucose Levels in a Developing Southern Chinese Population

BACKGROUND: The American Diabetes Association and World Health Organization have recently adopted the HbA1c measurement as one method of diagnostic criteria for diabetes. The change in diagnostic criteria has important implications for diabetes treatment and prevention. We therefore investigate diabetes using HbA1c and glucose criteria together, and assess the prevalent trend in a developing southern Chinese population with 85 million residents. METHODS: A stratified multistage random sampling method was applied and a representative sample of 3590 residents 18 years of age or above was obtained in 2010. Each participant received a full medical check-up, including measurement of fasting plasma glucose, 2-hour post-load plasma glucose, and HbA1c. Information on history of diagnosis and treatment of diabetes was collected. The prevalence of diabetes obtained from the present survey was compared with the data from the survey in 2002. RESULTS: The prevalence of diabetes based on both glucose and HbA1c measurements was 21.7% (95% CI: 17.4%-26.1%) in 2010, which suggests that more than 1 in 5 adult residents were suffering from diabetes in this developing population. Only 12.9% (95% CI: 8.3%-17.6%) of diabetic residents were aware of their condition. The prevalence of pre-diabetes was 66.3% (95% CI: 62.7%-69.8%). The prevalence of diabetes and pre-diabetes which met all the three diagnostic thresholds (fast plasma glucose, 2 hour post-load plasma glucose, and HbA1c) was 3.1% and 5.2%, respectively. Diabetes and pre-diabetes as determined by HbA1c measurement had higher vascular risk than those determined by glucose levels. The prevalence of diabetes increased from 2.9% (95% CI: 2.0%-3.7%) in 2002 to 13.8% (95% CI: 10.2%-17.3%) in 2010 based on the same glucose criteria. CONCLUSIONS: Our results show that the diabetes epidemic is accelerating in China. The awareness of diabetes is extremely low. The glucose test and HbA1c measurement should be used together to increase detection of diabetes and pre-diabetes

The New Emerging Model for the Structure of Cooling Cores in Clusters of Galaxies

New X-ray observations with XMM-Newton show a lack of spectral evidence for large amounts of cooling and condensing gas in the centers of galaxy clusters believed to harbour strong cooling flows. The paper reexplores the cooling flow scenario in the light of the new observations. We explore the diagnostics of the temperature structure of cooling cores with XMM-spectroscopy, tests for intracluster X-ray absorption towards central AGN, the effect of metal abundance inhomogeneities, and the implications of high resolution images in the centers of clusters. We find no evidence of intrinsic absorption in the center of the cooling flows of M87 and the Perseus cluster. We further consider the effect of cluster rotation in cooling flow regions in the frame of cosmic structure evolution models. Also the heating of the core regions of clusters by jets from a central AGN is reconsidered. We find that the power of the AGN jets as estimated by their interaction effects with the intracluster medium in several examples is more then sufficient to heat the cooling flows and to reduce the mass deposition rates. We explore in more detail which requirements such a heating model has to fulfill to be consistent with all observations, point out the way such a model could be constructed, and argue that such model building seems to be successful. In summary it is argued that most observational evidence points towards much lower mass deposition rates than previously inferred in the central region of clusters thought to contain strong cooling flows.Comment: 19 pages, 14 figures, submitted to Astronomy and Astrophysic

The VIMOS VLT Deep Survey: Tracing the galaxy stellar mass assembly history over the last 8Gyr

We selected a mass-limited sample of 4048 objects from the VIMOS VLT Deep Survey in the redshift interval 0.5<z<1.3. We used the amplitude of the 4000 Balmer break (Dn4000) to separate the galaxy population and the EW[OII]3727 line as proxy for the star formation activity. We discuss to what extent stellar mass drives galaxy evolution, showing for the first time the interplay between stellar ages and stellar masses over the past 8Gyr. Low-mass galaxies have small Dn4000 and at increasing stellar mass, the galaxy distribution moves to higher Dn4000 values as observed in the local Universe. As cosmic time goes by, we witness an increasing abundance of massive spectroscopically ET systems at the expense of the LT systems. This spectral transformation is a process started at early epochs and continuing efficiently down to the local Universe. This is confirmed by the evolution of our type-dependent stellar mass function. The underlying stellar ages of LT galaxies apparently do not show evolution, likely as a result of a continuous formation of new stars. All star formation activity indicators consistently point towards a star formation history peaked in the past for massive galaxies, with little or no residual star formation taking place in the most recent epochs. The activity and efficiency of forming stars are mechanisms that depend on stellar mass, and the mass assembly becomes progressively less efficient in massive systems as time elapses. The concepts of star formation downsizing and mass assembly downsizing describe a single scenario that has a top-down evolutionary pattern. The role of (dry) merging events seems to be only marginal at z<1.3, as our estimated efficiency in stellar mass assembly can possibly account for the progressive accumulation of passively evolving galaxies.Comment: Accepted for pubblication in A&A, 14 pages, 5 figure

Study of B0(s)→K0Sh+h′− decays with first observation of B0s→K0SK±π∓ and B0s→K0Sπ+π−

A search for charmless three-body decays of B 0 and B0s mesons with a K0S meson in the final state is performed using the pp collision data, corresponding to an integrated luminosity of 1.0 fb−1, collected at a centre-of-mass energy of 7 TeV recorded by the LHCb experiment. Branching fractions of the B0(s)→K0Sh+h′− decay modes (h (′) = π, K), relative to the well measured B0→K0Sπ+π− decay, are obtained. First observation of the decay modes B0s→K0SK±π∓ and B0s→K0Sπ+π− and confirmation of the decay B0→K0SK±π∓ are reported. The following relative branching fraction measurements or limits are obtained B(B0→K0SK±π∓)B(B0→K0Sπ+π−)=0.128±0.017(stat.)±0.009(syst.), B(B0→K0SK+K−)B(B0→K0Sπ+π−)=0.385±0.031(stat.)±0.023(syst.), B(B0s→K0Sπ+π−)B(B0→K0Sπ+π−)=0.29±0.06(stat.)±0.03(syst.)±0.02(fs/fd), B(B0s→K0SK±π∓)B(B0→K0Sπ+π−)=1.48±0.12(stat.)±0.08(syst.)±0.12(fs/fd)B(B0s→K0SK+K−)B(B0→K0Sπ+π−)∈[0.004;0.068]at90%CL

Model-independent search for CP violation in D0→K−K+π−π+ and D0→π−π+π+π− decays

A search for CP violation in the phase-space structures of D0 and View the MathML source decays to the final states K−K+π−π+ and π−π+π+π− is presented. The search is carried out with a data set corresponding to an integrated luminosity of 1.0 fb−1 collected in 2011 by the LHCb experiment in pp collisions at a centre-of-mass energy of 7 TeV. For the K−K+π−π+ final state, the four-body phase space is divided into 32 bins, each bin with approximately 1800 decays. The p-value under the hypothesis of no CP violation is 9.1%, and in no bin is a CP asymmetry greater than 6.5% observed. The phase space of the π−π+π+π− final state is partitioned into 128 bins, each bin with approximately 2500 decays. The p-value under the hypothesis of no CP violation is 41%, and in no bin is a CP asymmetry greater than 5.5% observed. All results are consistent with the hypothesis of no CP violation at the current sensitivity