832 research outputs found
Pseudopotential Approaches to Ca, Sr and Ba Hybrides. Why are some Alkaline Earth MX Compounds Bent?
Quasirelativistic and nonrelativistic lo-valence-electronp seudopotentialsf or Ca, Sr, and Ba are presented. Results of calculations with 6s6p5d basis sets for MH, MH , and MH, are compared with all-electron and 2-valence-electron pseudopotential calculations with and , without core-polarization potentials. The lo-valence-electron pseudopotential approach agrees well with all-electron calculations. It circumvents problems for the 2-valence-electron pseudopotentials arising from an incomplete separation of valence and subvalence shells in polar molecular systems due to strongly contracted occupied (n - 1 )-d orbitals. All higherlevel calculations show SrH and BaII, to be bent with angles of - 140° and 120°, respectively, while CaH is linear with a flat potential-energy surface for the bending motion. The use of a core-polarization potential together with the 2-valence-electronp seudopotentiala pproach allows an investigation of the relative importance of core-polarization vs direct d-orbital bonding participation as reasons for the bent structures. The calculations strongly suggest that both contribute to the bending in SrH and BaII. Even at the Hartree-Fock level of theory lovalence- electronp seudopotentialc alculations given reasonablea nglesw hen the potentialenergy surface is not exceedingly flat, and only moderately contracted basis sets including both compact d functions and diffuse p functions are used. The effect of core-valence correlation and the importance off functions also are discussed
Localization of a 64-kDa phosphoprotein in the lumen between the outer and inner envelopes of pea chloroplasts
The identification and localization of a marker protein for the intermembrane space between the outer and inner chloroplast envelopes is described. This 64-kDa protein is very rapidly labeled by [Îł-32P]ATP at very low (30 nM) ATP concentrations and the phosphoryl group exhibits a high turnover rate. It was possible to establish the presence of the 64-kDa protein in this plastid compartment by using different chloroplast envelope separation and isolation techniques. In addition comparison of labeling kinetics by intact and hypotonically lysed pea chloroplasts support the localization of the 64-kDa protein in the intermembrane space. The 64-kDa protein was present and could be labeled in mixed envelope membranes isolated from hypotonically lysed plastids. Mixed envelope membranes incorporated high amounts of 32P from [Îł-32P]ATP into the 64-kDa protein, whereas separated outer and inner envelope membranes did not show significant phosphorylation of this protein. Water/Triton X-114 phase partitioning demonstrated that the 64-kDa protein is a hydrophilic polypeptide. These findings suggest that the 64-kDa protein is a soluble protein trapped in the space between the inner and outer envelope membranes. After sonication of mixed envelope membranes, the 64-kDa protein was no longer present in the membrane fraction, but could be found in the supernatant after a 110000 Ă g centrifugation
A preliminary model of work during initial examination and treatment planning appointments
Objective This study's objective was to formally describe the work process for charting and treatment planning in general dental practice to inform the design of a new clinical computing environment.Methods Using a process called contextual inquiry, researchers observed 23 comprehensive examination and treatment planning sessions during 14 visits to 12 general US dental offices. For each visit, field notes were analysed and reformulated as formalised models. Subsequently, each model type was consolidated across all offices and visits. Interruptions to the workflow, called breakdowns, were identified.Results Clinical work during dental examination and treatment planning appointments is a highly collaborative activity involving dentists, hygienists and assistants. Personnel with multiple overlapping roles complete complex multi-step tasks supported by a large and varied collection of equipment, artifacts and technology. Most of the breakdowns were related to technology which interrupted the workflow, caused rework and increased the number of steps in work processes.Conclusion Current dental software could be significantly improved with regard to its support for communication and collaboration, workflow, information design and presentation, information content, and data entry
Continuous symmetry of C60 fullerene and its derivatives
Conventionally, the Ih symmetry of fullerene C60 is accepted which is
supported by numerous calculations. However, this conclusion results from the
consideration of the molecule electron system, of its odd electrons in
particular, in a close-shell approximation without taking the electron spin
into account. Passing to the open-shell approximation has lead to both the
energy and the symmetry lowering up to Ci. Seemingly contradicting to a
high-symmetry pattern of experimental recording, particularly concerning the
molecule electronic spectra, the finding is considered in the current paper
from the continuous symmetry viewpoint. Exploiting both continuous symmetry
measure and continuous symmetry content, was shown that formal Ci symmetry of
the molecule is by 99.99% Ih. A similar continuous symmetry analysis of the
fullerene monoderivatives gives a reasonable explanation of a large variety of
their optical spectra patterns within the framework of the same C1 formal
symmetry exhibiting a strong stability of the C60 skeleton.Comment: 11 pages. 5 figures. 6 table
Biosynthesis of Mitochondrial Porin and Insertion into the Outer Mitochondrial Membrane of Neuruspora crassa
Mitochondrial porin, the major protein of the outer mitochondrial membrane is synthesized by free cytoplasmic polysomes. The apparent molecular weight of the porin synthesized in homologous or heterologous cell-free systems is the same as that of the mature porin. Transfer in vitro of mitochondrial porin from the cytosolic fraction into the outer membrane of mitochondria could be demonstrated. Before membrane insertion, mitochondrial porin is highly sensitive to added proteinase; afterwards it is strongly protected. Binding of the precursor form to mitochondria occurs at 4°C and appears to precede insertion into the membrane. Unlike transfer of many precursor proteins into or across the inner mitochondrial membrane, assembly of the porin is not dependent on an electrical potential across the inner membrane
Synthesis of Highly Substituted Adamantanones from Bicyclo[3.3.1]nonanes
Trifluoromethanesulfonic acid and other electrophiles promote formation of the adamantanone core from the readily accessible 1,5-dimethyl-3,7-dimethylenebicyclo[3.3.1]nonan-9-one 2. Because adamantyl cation 3 can be trapped by a range of nucleophiles, including aromatic and heteroaromatic rings, alcohol, nitriles, and halides, access to a wide variety of functionality at the newly formed tertiary position is provided
Bioheterojunction Effect on Fluorescence Origin and Efficiency Improvement of Firefly Chromophores
We propose the heterojunction effect in the analysis of the fluorescence
mechanism of the firefly chromophore. Following this analysis, and with respect
to the HOMO-LUMO gap alignment between the chromophore's functional fragments,
three main heterojunction types (I, II, and I*) are identified. Time-dependent
density-functional theory optical absorption calculations for the firefly
chromophore show that the strongest excitation appears in the deprotonated
anion state of the keto form. This can be explained by its high HOMO-LUMO
overlap due to strong bio-heterojunction confinement. It is also found that the
nitrogen atom in the thiazolyl rings, due to its larger electronegativity,
plays a key role in the emission process, its importance growing when HOMO and
LUMO overlap at its location. This principle is applied to enhance the
chromophore's fluorescence efficiency and to guide the functionalization of
molecular optoelectronic devices.Comment: 7 pages, 6 figure
Optoelectronic Properties of Carbon Nanorings: Excitonic Effects from Time-Dependent Density Functional Theory
The electronic structure and size-scaling of optoelectronic properties in
cycloparaphenylene carbon nanorings are investigated using time-dependent
density functional theory (TDDFT). The TDDFT calculations on these molecular
nanostructures indicate that the lowest excitation energy surprisingly becomes
larger as the carbon nanoring size is increased, in contradiction with typical
quantum confinement effects. In order to understand their unusual electronic
properties, I performed an extensive investigation of excitonic effects by
analyzing electron-hole transition density matrices and exciton binding
energies as a function of size in these nanoring systems. The transition
density matrices allow a global view of electronic coherence during an
electronic excitation, and the exciton binding energies give a quantitative
measure of electron-hole interaction energies in the nanorings. Based on
overall trends in exciton binding energies and their spatial delocalization, I
find that excitonic effects play a vital role in understanding the unique
photoinduced dynamics in these carbon nanoring systems.Comment: Accepted by the Journal of Physical Chemistry
In Situ NMR Spectroscopy of Supercapacitors: Insight into the Charge Storage Mechanism
Electrochemical capacitors, commonly known as supercapacitors, are important energy storage devices with high power capabilities and long cycle lives. Here we report the development and application of in situ nuclear magnetic resonance(NMR) methodologies to study changes at the electrodeâelectrolyte interface in working devices as they charge and discharge. For a supercapacitor comprising activated carbon electrodes and an organic electrolyte, NMR experiments carried out at different charge states allow quantification of the number of charge storing species and show that there are at least two distinct charge storage regimes. At cell voltages below 0.75 V, electrolyte anions are increasingly desorbed from the carbon micropores at the negative electrode, while at the positive electrode there is little change in the number of anions that are adsorbed as the voltage is increased. However, above a cell voltage of 0.75 V, dramatic increases in the amount of adsorbed anions in the positive electrode are observed while anions continue to be desorbed at the negative electrode. NMR experiments with simultaneous cyclic voltammetry show that supercapacitor charging causes marked changes to the local environments of charge storing species, with periodic changes of their chemical shift observed. NMR calculations on a model carbon fragment show that the addition and removal of electrons from a delocalized system should lead to considerable increases in the nucleus-independent chemical shift of nearby species, in agreement with our experimental observations
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