The photolysis of Benzoic acid in the gas phase

The vapor phase photolysis of benzoic acid has been investigated in a flow system at temperatures ranging from 110° to 305°C, pressures from approximately 0.06 to 1.73 torr, and at various incident light intensities. The main identified products are carbon dioxide and benzene, and the minor identified products are carbon monoxide together with much smaller amounts of hydrogen. -- At 150° and 205° the rate of formation of carbon dioxide is directly proportional to the light intensity absorbed. For a constant incident light intensity, the rate of carbon dioxide formation was found to be independent of the benzoic acid concentration at pressures from 0.29 to 1.73 torr. The rate of formation of carbon dioxide increases with temperature and the activation energy is 3.5 ± 0.4 kcal mole⁻¹. -- A mechanism for carbon dioxide formation is suggested in which reaction occurs from a vibrationally excited ground state molecule, C₆H₅COOH', originating from the initially formed singlet state, C₆H₅COOH*, by internal conversion. The phenyl radical so formed initiates a free radical chain reaction. -- C₆H₅COOH + h v → C₆H₅COOH* -- C₆H₅COOH* → C₆H₅COOH' -- C₆H₅COOH' + M → C₆H₅COOH + M -- C₆H₅COOH' → C₆H₅ + COOH -> C₆H₅ + C₆H₅COOH → C₆H₅ + C₆H₆COO -- C₆H₅COO → C₆H₅ + CO₂ -- C₆H₅ + Wall →

Interactions between innexins UNC-7 and UNC-9 mediate electrical synapse specificity in the Caenorhabditis elegans locomotory nervous system

<p>Abstract</p> <p>Background</p> <p>Approximately 10% of <it>Caenorhabditis elegans </it>nervous system synapses are electrical, that is, gap junctions composed of innexins. The locomotory nervous system consists of several pairs of interneurons and three major classes of motor neurons, all with stereotypical patterns of connectivity that include gap junctions. Mutations in the two innexin genes <it>unc-7 </it>and <it>unc-9 </it>result in identical uncoordinated movement phenotypes, and their respective gene products were investigated for their contribution to electrical synapse connectivity.</p> <p>Results</p> <p><it>unc-7 </it>encodes three innexin isoforms. Two of these, UNC-7S and UNC-7SR, are functionally equivalent and play an essential role in coordinated locomotion. UNC-7S and UNC-7SR are widely expressed and co-localize extensively with green fluorescent protein-tagged innexin UNC-9 in the ventral and dorsal nerve cords. A subset of UNC-7S/SR expression visualizes gap junctions formed between the AVB forward command interneurons and their B class motor neuron partners. Experiments indicate that expression of UNC-7S/SR in AVB and expression of UNC-9 in B motor neurons is necessary for these gap junctions to form. In <it>Xenopus </it>oocyte pairs, both UNC-7S and UNC-9 form homomeric gap junctions, and together they form heterotypic channels. <it>Xenopus </it>oocyte studies and co-localization studies in <it>C. elegans </it>suggest that UNC-7S and UNC-9 do not heteromerize in the same hemichannel, leading to the model that hemichannels in AVB:B motor neuron gap junctions are homomeric and heterotypic.</p> <p>Conclusion</p> <p>UNC-7S and UNC-9 are widely expressed and contribute to a large number of the gap junctions identified in the locomotory nervous system. Proper AVB:B gap junction formation requires UNC-7S expression in AVB interneurons and UNC-9 expression in B motor neurons. More broadly, this illustrates that innexin identity is critical for electrical synapse specificity, but differential (compartmentalized) innexin expression cannot account for all of the specificity seen in <it>C. elegans</it>, and other factors must influence the determination of synaptic partners.</p

LKB1 is essential for the proliferation of T-cell progenitors and mature peripheral T cells

The serine/threonine kinase LKB1 has a conserved role in Drosophila and nematodes to co-ordinate cell metabolism. During T lymphocyte development in the thymus, progenitors need to synchronize increased metabolism with the onset of proliferation and differentiation to ensure that they can meet the energy requirements for development. The present study explores the role of LKB1 in this process and shows that loss of LKB1 prevents thymocyte differentiation and the production of peripheral T lymphocytes. We find that LKB1 is required for several key metabolic processes in T-cell progenitors. For example, LKB1 controls expression of CD98, a key subunit of the l-system aa transporter and is also required for the pre-TCR to induce and sustain the regulated phosphorylation of the ribosomal S6 subunit, a key regulator of protein synthesis. In the absence of LKB1 TCR-β-selected thymocytes failed to proliferate and did not survive. LBK1 was also required for survival and proliferation of peripheral T cells. These data thus reveal a conserved and essential role for LKB1 in the proliferative responses of both thymocytes and mature T cells

Deeply Virtual Compton Scattering on nucleons and nuclei in generalized vector meson dominance model

We consider Deeply Virtual Compton Scattering (DVCS) on nucleons and nuclei in the framework of generalized vector meson dominance (GVMD) model. We demonstrate that the GVMD model provides a good description of the HERA data on the dependence of the proton DVCS cross section on Q^2, W (at Q^2=4 GeV^2) and t. At Q^2 = 8 GeV^2, the soft W-behavior of the GVMD model somewhat underestimates the W-dependence of the DVCS cross section due to the hard contribution not present in the GVMD model. We estimate 1/Q^2 power-suppressed corrections to the DVCS amplitude and the DVCS cross section and find them large. We also make predictions for the nuclear DVCS amplitude and cross section in the kinematics of the future Electron-Ion Collider. We predict significant nuclear shadowing, which matches well predictions of the leading-twist nuclear shadowing in DIS on nuclei.Comment: 25 pages, 9 figures, 1 tabl

Validation of the Work Observation Method By Activity Timing (WOMBAT) method of conducting time-motion observations in critical care settings: an observational study

<p>Abstract</p> <p>Background</p> <p>Electronic documentation handling may facilitate information flows in health care settings to support better coordination of care among Health Care Providers (HCPs), but evidence is limited. Methods that accurately depict changes to the workflows of HCPs are needed to assess whether the introduction of a Critical Care clinical Information System (CCIS) to two Intensive Care Units (ICUs) represents a positive step for patient care. To evaluate a previously described method of quantifying amounts of time spent and interruptions encountered by HCPs working in two ICUs.</p> <p>Methods</p> <p>Observers used PDAs running the Work Observation Method By Activity Timing (WOMBAT) software to record the tasks performed by HCPs in advance of the introduction of a Critical Care clinical Information System (CCIS) to quantify amounts of time spent on tasks and interruptions encountered by HCPs in ICUs.</p> <p>Results</p> <p>We report the percentages of time spent on each task category, and the rates of interruptions observed for physicians, nurses, respiratory therapists, and unit clerks. Compared with previously published data from Australian hospital wards, interdisciplinary information sharing and communication in ICUs explain higher proportions of time spent on professional communication and documentation by nurses and physicians, as well as more frequent interruptions which are often followed by professional communication tasks.</p> <p>Conclusions</p> <p>Critical care workloads include requirements for timely information sharing and communication and explain the differences we observed between the two datasets. The data presented here further validate the WOMBAT method, and support plans to compare workflows before and after the introduction of electronic documentation methods in ICUs.</p

Structure of RapA, a Swi2/Snf2 Protein that Recycles RNA Polymerase During Transcription

SummaryRapA, as abundant as σ70 in the cell, is an RNA polymerase (RNAP)-associated Swi2/Snf2 protein with ATPase activity. It stimulates RNAP recycling during transcription. We report a structure of RapA that is also a full-length structure for the entire Swi2/Snf2 family. RapA contains seven domains, two of which exhibit novel protein folds. Our model of RapA in complex with ATP and double-stranded DNA (dsDNA) suggests that RapA may bind to and translocate on dsDNA. Our kinetic template-switching assay shows that RapA facilitates the release of sequestered RNAP from a posttranscrption/posttermination complex for transcription reinitiation. Our in vitro competition experiment indicates that RapA binds to core RNAP only but is readily displaceable by σ70. RapA is likely another general transcription factor, the structure of which provides a framework for future studies of this bacterial Swi2/Snf2 protein and its important roles in RNAP recycling during transcription

Selective Hybridization of a Terpyridine-Based Molecule with a Noble Metal

The electronic properties of metal-molecule interfaces can in principle be controlled by molecular design and self-assembly, yielding great potential for future nano- and optoelectronic technologies. However, the coupling between molecular orbitals and the electronic states of the surface can significantly influence molecular states. In particular, molecules designed to create metal-organic self-assembled networks have functional groups that by necessity are designed to interact strongly with metals. Here, we investigate the adsorption interactions of a terpyridine (tpy)-based molecule on a noble metal, Ag(111), by low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS) together with density functional theory (DFT) calculations. By comparing the local density of states (DOS) information gained from STS for the molecule on the bare Ag(111) surface with that of the molecule decoupled from the underlying metal by a NaCl bilayer, we find that tpy-localized orbitals hybridize strongly with the metal substrate. Meanwhile, those related to the phenyl rings that link the two terminal tpy groups are less influenced by the interaction with the surface. The selective hybridization of the tpy groups provides an example of strong, orbital-specific electronic coupling between a functional group and a noble-metal surface, which may alter the intended balance of interactions and resulting electronic behavior of the molecule-metal interface

Rapid Estimation of Damage to Tall Buildings Using Near Real‐Time Earthquake and Archived Structural Simulations

This article outlines a new approach to rapidly estimate the damage to tall buildings immediately following a large earthquake. The preevent groundwork involves the creation of a database of structural responses to a suite of idealized ground‐motion waveforms. The postevent action involves (1) rapid generation of an earthquake source model, (2) near real‐time simulation of the earthquake using a regional spectral‐element model of the earth and computing synthetic seismograms at tall building sites, and (3) estimation of tall building response (and damage) by determining the best‐fitting idealized waveforms to the synthetically generated ground motion at the site and directly extracting structural response metrics from the database. Here, ground‐velocity waveforms are parameterized using sawtoothlike wave trains with a characteristic period (T), amplitude (peak ground velocity, PGV), and duration (number of cycles, N). The proof‐of‐concept is established using the case study of one tall building model. Nonlinear analyses are performed on the model subjected to the idealized wave trains, with T varying from 0.5 s to 6.0 s, PGV varying from 0.125  m/s, and N varying from 1 to 5. Databases of peak transient and residual interstory drift ratios (IDR), and permanent roof drift are created. We demonstrate the effectiveness of the rapid response approach by applying it to synthetic waveforms from a simulated 1857‐like magnitude 7.9 San Andreas earthquake. The peak IDR, a key measure of structural performance, is predicted well enough for emergency response decision making

Influence of a knot on the strength of a polymer strand

Many experiments have been done to determine the relative strength of different knots, and these show that the break in a knotted rope almost invariably occurs at a point just outside the `entrance' to the knot. The influence of knots on the properties of polymers has become of great interest, in part because of their effect on mechanical properties. Knot theory applied to the topology of macromolecules indicates that the simple trefoil or `overhand' knot is likely to be present with high probability in any long polymer strand. Fragments of DNA have been observed to contain such knots in experiments and computer simulations. Here we use {\it ab initio} computational methods to investigate the effect of a trefoil knot on the breaking strength of a polymer strand. We find that the knot weakens the strand significantly, and that, like a knotted rope, it breaks under tension at the entrance to the knot.Comment: 3 pages, 4 figure