Dynamic glottal pressures in an excised hemilarynx model

During phonation, air pressures act upon the vocal folds to help maintain their oscillation. The air pressures vary dynamically along the medial surface of the vocal folds, although no live human or excised studies have shown how those pressure profiles vary in time. The purpose of this study was to examine time-dependent glottal pressure profiles using a canine hemilarynx approach. The larynx tissue was cut in the midsaggital plane from the top to about 5 mm below the vocal folds. The right half was replaced with a Plexiglas pane with imbedded pressure taps. Simultaneous recordings were made of glottal pressure signals, subglottal pressure, particle velocity, and average airflow at various levels of adduction. The data indicate that the pressures in the glottis (on the Plexiglas) vary both vertically and longitudinally throughout the phonatory cycle. Pressures vary most widely near the location of maximum vibratory amplitude, and can include negative pressures during a portion of the cycle. Pressures anterior and posterior to the maximum amplitude location may have less variation and may remain positive throughout the cycle, giving rise to a new concept called dynamic bidirectional pressure gradients in the glottis. This is an important concept that may relate strongly to tissue health as well as basic oscillatory mechanics.     

Development and validation of a LC method for the separation and determination of the anticancer‐active FeIII(4‐methoxy‐salophene) using the new second‐generation monolith

LC method with the newly introduced second‐generation monolithic silica RP‐18e column has been developed for the separation of Fe^III(salophene) and four methoxy‐substituted Fe^III(salophene) complexes. The method has been validated for the quantitation of Fe^III(4‐OMe‐salophene), a highly active anticancer substance in vitro, bound to serum albumin. Our routinely used high‐resolution continuum‐source atomic absorption spectroscopy method based on the determination of the central iron atom was unsuitable in this case because serum originally contains significant amounts of iron as revealed by a blank sample of serum albumin. The developed LC method depends on detecting the whole complex rather than the bound iron. Two morphologically different first‐ and second‐generation HPLC monolithic columns have been compared for this purpose. The newly introduced second‐generation monolithic silica column Chromolith® HighResolution RP‐18e column (100 × 4.6 mm, Merck) separated the mixture successful within 13 min. A mobile phase consisting of 25 mM phosphate buffer pH 3/methanol (60:40, v/v) was used at a flow rate of 1 mL/min. The dynamic linear working range of the calibration curve for Fe^III(4‐OMe‐salophene) was found to be between 1 and 200 μg/mL. Detection and quantitation limits were 0.3 and 1 μg/mL, respectively.     

Re-shaping the coffee ring

Not your cup of tea? "Coffee rings" of spherical colloidal particles are left behind after water droplets resting on surfaces have dried out. This controlled evaporation of colloidal solutions can be exploited to deposit material in regular patterns. It is now shown that if spherical colloids are replaced by slightly elongated ones, the coffee ring is not formed and is replaced by an even more uniform deposition.     

Ion mobility spectrometry of laser desorbed pesticides from fruit surfaces

The applicability of a technique combining laser desorption and ion mobility spectrometry for rapid detection of pesticides on fruit surfaces is explored. A selection of 20 fungicides, herbicides and insecticides with very different chemical and spectroscopic characteristics was used to study its features. For a variety of fruits the maximum tolerable laser irradiance was determined, at which no signals are generated by the clean surface. The spectra recorded for each substance on fruits were compared to those obtained for the same compound using laser desorption from a well defined surface. Furthermore, the influence of a dew layer on the sample was investigated. Limits of detection were estimated to be in the range of some tens of ng/kg for apples.     

Template-directed synthesis in 3'- and 5'-direction with reversible termination

Extending both ways: A method for DNA-templated synthesis on solid support is described. Controlled, stepwise chain extension was demonstrated both in the direction favored by nature (3'-extension; see scheme) and in the direction typical for conventional DNA synthesizers (5'-extension).     

A theoretical investigation of the relative stability of hydrated glycine and methylcarbamic acid--from water clusters to interstellar ices

We have theoretically investigated how the low-energy conformers of the neutral and the zwitterionic forms of glycine as well as methylcarbamic acid are stabilized by the presence water. The MP2/6-311++G(d,p) method was utilized to conduct calculations on glycine and methylcarbamic acid in both isolated clusters and in clusters embedded in the conductor-like polarizable continuum model (C-PCM), where the clusters explicitly contain between one and ten water molecules. The neutral forms of glycine and methylcarbamic acid were found to have similar hydration energies, whereas the neutral methylcarbamic acid was determined to be approximately 32 kJ mol(-1) more stable than the neutral glycine in the isolated clusters and 30 kJ mol(-1) more stable in the C-PCM embedded clusters. Both the number and strength of the hydrogen bonding interactions between water and the zwitterions drive the stability. This lowers the relative energy of the glycine zwitterion from 50 kJ mol(-1) above neutral glycine, when there are two water molecules in the clusters to 11 kJ mol(-1) below for the clusters containing ten water molecules. For the methylcarbamic acid clusters with two water molecules, the zwitterion is 51 kJ mol(-1) higher in energy than the neutral form, but it remains 13 kJ mol(-1) above the neutral methylcarbamic acid in the clusters containing ten water molecules. When the bulk water environment is simulated by the C-PCM calculations, we find both the methylcarbamic acid and glycine zwitterionic forms have similar energies at 20 kJ mol(-1) above the neutral methylcarbamic acid energy and 10 kJ mol(-1) lower than the neutral glycine energy. Although neither methylcarbamic acid nor glycine have been detected in the interstellar medium yet, our findings indicate that methylcarbamic acid is the more stable product from methylamine and carbon dioxide reactions in a water ice. This suggests that methylcarbamic acid likely plays a role in the intermediate steps if glycine is formed in the interstellar medium.     

Crossed beam reaction of phenyl and D5-phenyl radicals with propene and deuterated counterparts--competing atomic hydrogen and methyl loss pathways

We conducted the crossed molecular beams reactions of the phenyl and D5-phenyl radicals with propylene together with its partially deuterated reactants at collision energies of ~45 kJ mol(-1) under single collision conditions. The scattering dynamics were found to be indirect and were mainly dictated by an addition of the phenyl radical to the sterically accessible CH(2) unit of the propylene reactant. The resulting doublet radical isomerized to multiple C(9)H(11) intermediates, which were found to be long-lived, decomposing in competing methyl group loss and atomic hydrogen loss pathways with the methyl group loss leading to styrene (C(6)H(5)C(2)H(3)) and the atomic hydrogen loss forming C(9)H(10) isomers cis/trans 1-phenylpropene (CH(3)CHCHC(6)H(5)) and 3-phenylpropene (C(6)H(5)CH(2)C(2)H(3)). Fractions of the methyl versus hydrogen loss channels of 68 ± 16% : 32 ± 10% were derived experimentally, which agrees nicely with RRKM theory. As the collision energy rises to 200 kJmol(-1), the contribution of the methyl loss channel decreases sharply to typically 25%; the decreased importance of the methyl group loss channel was also demonstrated in previous crossed beam experiments conducted at elevated collision energies of 130-193 kJ mol(-1). The presented work highlights the interesting differences of the branching ratios with rising collision energies in the reaction dynamics of phenyl radicals with unsaturated hydrocarbons related to combustion processes. The facility of forming styrene, a common molecule found in combustion against the elusiveness of forming the cyclic indane molecule demonstrates the need to continue to explore the potential surfaces through the combinative single collision experiment and electronic structure calculations.     

The smallest stable fullerene, M@C28 (m = Ti, Zr, U): stabilization and growth from carbon vapor

The smallest fullerene to form in condensing carbon vapor has received considerable interest since the discovery of Buckminsterfullerene, C(60). Smaller fullerenes remain a largely unexplored class of all-carbon molecules that are predicted to exhibit fascinating properties due to the large degree of curvature and resulting highly pyramidalized carbon atoms in their structures. However, that curvature also renders the smallest fullerenes highly reactive, making them difficult to detect experimentally. Gas-phase attempts to investigate the smallest fullerene by stabilization through cage encapsulation of a metal have been hindered by the complexity of mass spectra that result from vaporization experiments which include non-fullerene clusters, empty cages, and metallofullerenes. We use high-resolution FT-ICR mass spectrometry to overcome that problem and investigate formation of the smallest fullerene by use of a pulsed laser vaporization cluster source. Here, we report that the C(28) fullerene stabilized by encapsulation with an appropriate metal forms directly from carbon vapor as the smallest fullerene under our conditions. Its stabilization is investigated, and we show that M@C(28) is formed by a bottom-up growth mechanism and is a precursor to larger metallofullerenes. In fact, it appears that the encapsulating metal species may catalyze or nucleate endohedral fullerene formation.     

Ruthenium(II) Photosensitizers of Tridentate Click‐Derived Cyclometalating Ligands: A Joint Experimental and Computational Study

A systematic series of heteroleptic bis(tridentate)ruthenium(II) complexes of click‐derived 1,3‐bis(1,2,3‐triazol‐4‐yl)benzene N^C^N‐coordinating ligands was synthesized, analyzed by single crystal X‐ray diffraction, investigated photophysically and electrochemically, and studied by computational methods. The presented comprehensive characterization allows a more detailed understanding of the radiationless deactivation mechanisms. Furthermore, we provide a fully optimized synthesis and systematic variations towards redox‐matched, broadly and intensely absorbing, cyclometalated ruthenium(II) complexes. Most of them show a weak room‐temperature emission and a prolonged excited‐state lifetime. They display a broad absorption up to 700 nm and high molar extinction coefficients up to 20 000 M ^?1 cm^?1 of the metal‐to‐ligand charge transfer bands, resulting in a black color. Thus, the complexes reveal great potential for dye‐sensitized solar‐cell applications.