Time resolved structural dynamics of butadiyne-linked porphyrin dimers

In this work the timescales and mechanisms associated with the structural dynamics of butadiyne-linked porphyrin dimers are investigated through time resolved narrowband pump / broadband probe transient absorption spectroscopy. Our results confirm previous findings that the broadening is partly due to a distribution of structures with different (dihedral) angular conformations. Comparison of measurements with excitations on the red and blue sides of the Q-band unravel the ground and excited state conformational re-equilibration timescales. Further comparison to a planarized dimer, through addition of a ligand, provide conclusive evidence for the twisting motion performed by the porphyrin dimer in solution

Study protocol: The Adherence and Intensification of Medications (AIM) study - a cluster randomized controlled effectiveness study

Abstract Background Many patients with diabetes have poor blood pressure (BP) control. Pharmacological therapy is the cornerstone of effective BP treatment, yet there are high rates both of poor medication adherence and failure to intensify medications. Successful medication management requires an effective partnership between providers who initiate and increase doses of effective medications and patients who adhere to the regimen. Methods In this cluster-randomized controlled effectiveness study, primary care teams within sites were randomized to a program led by a clinical pharmacist trained in motivational interviewing-based behavioral counseling approaches and authorized to make BP medication changes or to usual care. This study involved the collection of data during a 14-month intervention period in three Department of Veterans Affairs facilities and two Kaiser Permanente Northern California facilities. The clinical pharmacist was supported by clinical information systems that enabled proactive identification of, and outreach to, eligible patients identified on the basis of poor BP control and either medication refill gaps or lack of recent medication intensification. The primary outcome is the relative change in systolic blood pressure (SBP) measurements over time. Secondary outcomes are changes in Hemoglobin A1c, low-density lipoprotein cholesterol (LDL), medication adherence determined from pharmacy refill data, and medication intensification rates. Discussion Integration of the three intervention elements - proactive identification, adherence counseling and medication intensification - is essential to achieve optimal levels of control for high-risk patients. Testing the effectiveness of this intervention at the team level allows us to study the program as it would typically be implemented within a clinic setting, including how it integrates with other elements of care. Trial Registration The ClinicalTrials.gov registration number is NCT00495794.http://deepblue.lib.umich.edu/bitstream/2027.42/78258/1/1745-6215-11-95.xmlhttp://deepblue.lib.umich.edu/bitstream/2027.42/78258/2/1745-6215-11-95.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/78258/3/1745-6215-11-95-S1.DOCPeer Reviewe

3D Spectroscopic Observations of Star-Forming Dwarf Galaxies

We give an introduction into the observational technique of integral field or 3D spectroscopy. We discuss advantages and drawbacks of this type of observations and highlight a few science projects enabled by this method. In the second part we describe our 3D spectroscopic survey of Blue Compact Dwarf Galaxies. We show preliminary results from data taken with the VIMOS integral field unit and give an outlook on how automated spectral analysis and forthcoming instruments can provide a new view on star formation and associated processes in dwarf galaxies.Comment: To appear in the proceedings of the JENAM 2010 Symposium "Dwarf Galaxies: Keys to Galaxy Formation and Evolution" (Lisbon, 9-10 September 2010), P. Papaderos, S. Recchi, G. Hensler (eds.), Springer Verlag (2011), in pres

Modeling the organization of the WUSCHEL expression domain in the shoot apical meristem

Motivation: The above-ground tissues of higher plants are generated from a small region of cells situated at the plant apex called the shoot apical meristem. An important genetic control circuit modulating the size of the Arabidopsis thaliana meristem is a feed-back network between the CLAVATA3 and WUSCHEL genes. Although the expression patterns for these genes do not overlap, WUSCHEL activity is both necessary and sufficient (when expressed ectopically) for the induction of CLAVATA3 expression. However, upregulation of CLAVATA3 in conjunction with the receptor kinase CLAVATA1 results in the downregulation of WUSCHEL. Despite much work, experimental data for this network are incomplete and additional hypotheses are needed to explain the spatial locations and dynamics of these expression domains. Predictive mathematical models describing the system should provide a useful tool for investigating and discriminating among possible hypotheses, by determining which hypotheses best explain observed gene expression dynamics. Results: We are developing a method using in vivo live confocal microscopy to capture quantitative gene expression data and create templates for computational models. We present two models accounting for the organization of the WUSCHEL expression domain. Our preferred model uses a reaction-diffusion mechanism in which an activator induces WUSCHEL expression. This model is able to organize the WUSCHEL expression domain. In addition, the model predicts the dynamical reorganization seen in experiments where cells, including the WUSCHEL domain, are ablated, and it also predicts the spatial expansion of the WUSCHEL domain resulting from removal of the CLAVATA3 signal

Full characterization of vibrational coherence in a porphyrin chromophore by two-dimensional electronic spectroscopy

In this work we present experimental and calculated two-dimensional electronic spectra for a 5,15-bisalkynyl porphyrin chromophore. The lowest energy electronic Qy transition couples mainly to a single 380 cm–1 vibrational mode. The two-dimensional electronic spectra reveal diagonal and cross peaks which oscillate as a function of population time. We analyze both the amplitude and phase distribution of this main vibronic transition as a function of excitation and detection frequencies. Even though Feynman diagrams provide a good indication of where the amplitude of the oscillating components are located in the excitation-detection plane, other factors also affect this distribution. Specifically, the oscillation corresponding to each Feynman diagram is expected to have a phase that is a function of excitation and detection frequencies. Therefore, the overall phase of the experimentally observed oscillation will reflect this phase dependence. Another consequence is that the overall oscillation amplitude can show interference patterns resulting from overlapping contributions from neighboring Feynman diagrams. These observations are consistently reproduced through simulations based on third order perturbation theory coupled to a spectral density described by a Brownian oscillator model

COLA II - Radio and Spectroscopic Diagnostics of Nuclear Activity in Galaxies

We present optical spectroscopic observations of 93 galaxies taken from the infra-red selected COLA (Compact Objects in Low Power AGN) sample. The sample spans the range of far-IR luminosities from normal galaxies to LIRGs. Of the galaxies observed, 78 (84%) exhibit emission lines. Using a theoretically-based optical emission-line scheme we classify 15% of the emission-line galaxies as Seyferts, 77% as starbursts, and the rest are either borderline AGN/starburst or show ambiguous characteristics. We find little evidence for an increase in the fraction of AGN in the sample as a function of far-IR luminosity but our sample covers only a small range in infrared luminosity and thus a weak trend may be masked. As a whole the Seyfert galaxies exhibit a small, but significant, radio excess on the radio-FIR correlation compared to the galaxies classified as starbursts. Compact (<0.05'') radio cores are detected in 55% of the Seyfert galaxies, and these galaxies exhibit a significantly larger radio excess than the Seyfert galaxies in which cores were not detected. Our results indicate that there may be two distinct populations of Seyferts, ``radio-excess'' Seyferts, which exhibit extended radio structures and compact radio cores, and ``radio-quiet'' Seyferts, in which the majority of the radio emission can be attributed to star-formation in the host galaxy. No significant difference is seen between the IR and optical spectroscopic properties of Seyferts with and without radio cores. (Abridged)Comment: 24 pages, 4 figures, 6 tables. Accepted for publication in ApJ, February 200

Resolving vibrational from electronic coherences in two-dimensional electronic spectroscopy: The role of the laser spectrum

The observation of coherent quantum effects in photosynthetic light-harvesting complexes prompted the question whether quantum coherence could be exploited to improve the efficiency in new energy materials. The detailed characterization of coherent effects relies on sensitive methods such as two-dimensional electronic spectroscopy (2D-ES). However, the interpretation of the results produced by 2D-ES is challenging due to the many possible couplings present in complex molecular structures. In this work, we demonstrate how the laser spectral profile can induce electronic coherence-like signals in monomeric chromophores, potentially leading to data misinterpretation. We argue that the laser spectrum acts as a filter for certain coherence pathways and thus propose a general method to differentiate vibrational from electronic coherences