Emission from the working and counter electrodes under co-reactant electrochemiluminescence conditions

We present a new approach to explore the potential-dependent multi-colour co-reactant electrochemiluminescence (ECL) from multiple luminophores. The potentials at both the working and counter electrodes, the current between these electrodes, and the emission over cyclic voltammetric scans were simultaneously measured for the ECL reaction of Ir(ppy)₃ and either [Ru(bpy)₃]²⁺ or [Ir(df-ppy)₂(ptb)]⁺, with tri-n-propylamine as the co-reactant. The counter electrode potential was monitored by adding a differential electrometer module to the potentiostat. Plotting the data against the applied working electrode potential and against time provided complementary depictions of their relationships. Photographs of the ECL at the surface of the two electrodes were taken to confirm the source of the emissions. This provided a new understanding of these multifaceted ECL systems, including the nature of the counter electrode potential and the possibility of eliciting ECL at this electrode, a mechanism-based rationalisation of the interactions of different metal-complex luminophores, and a previously unknown ECL pathway for the Ir(ppy)₃ complex at negative potentials that was observed even in the absence of the co-reactant.

Exploration of potential-dependent, multi-colour co-reactant electrochemiluminescence from multiple luminophores at the working and counter electrodes reveals new pathways to emission.     

Photoelectron spectroscopy and electronic structure calculations of d1 vanadocene compounds with chelated dithiolate ligands: implications for pyranopterin Mo/W enzymes

Gas-phase photoelectron spectroscopy and density functional theory have been used to investigate the electronic structures of open-shell bent vanadocene compounds with chelating dithiolate ligands, which are minimum molecular models of the active sites of pyranopterin Mo/W enzymes. The compounds Cp2V(dithiolate) [where dithiolate is 1,2-ethenedithiolate (S2C2H2) or 1,2-benzenedithiolate (bdt), and Cp is cyclopentadienyl] provide access to a 17-electron, d1 electron configuration at the metal center. Comparison with previously studied Cp2M(dithiolate) complexes, where M is Ti and Mo (respectively d0 and d2 electron configurations), allows evaluation of d0, d1, and d2 electronic configurations of the metal center that are analogues for the metal oxidation states present throughout the catalytic cycle of these enzymes. A "dithiolate-folding effect" that involves an interaction between the vanadium d orbitals and sulfur p orbitals is shown to stabilize the d1 metal center, allowing the d1 electron configuration and geometry to act as a low-energy electron pathway intermediate between the d0 and d2 electron configurations of the enzyme.     

The non-centrosymmetric borate oxides, MBi2B2O7 (M=Ca, Sr)

Two novel noncentrosymmetric borates oxides, MBi₂B₂O₇ or MBi₂O(BO₃)₂ (MCa, Sr), have been synthesized by solid-state reactions in air at temperatures in the 600-700 °C range. Their crystal structures have been determined ab initio and refined using powder neutron diffraction data. CaBi₂B₂O₇ crystallizes in the orthorhombic Pna2₁ space group with a=8.9371(5) Å, b=5.4771(3) Å, c=12.5912(7) Å, Z=4, R_wp=0.118, χ²=2.30. SrBi₂B₂O₇ crystallizes in the hexagonal P6₃ space group with a=9.1404(4) Å, c=13.0808(6) Å, Z=6, R_wp=0.115, χ²=4.15. Large displacement parameters suggest the presence of disorder in SrBi₂B₂O₇ as also revealed by diffuse 2×a superstructure reflections in electron diffraction patterns. Both structures are built of identical (001) neutral layers of corner-sharing BO₃ triangles and MO₆ trigonal prisms forming six-membered rings in which Bi₂O groups are located. Adjacent layers are stacked in a staggered configuration and connected through weak Bi-O bonds. A moderate efficiency for second harmonic generation (SHG) has been measured for a powder sample of CaBi₂B₂O₇ (d_eff=2d_eff(KDP)).     

Measurement of the X‐ray mass attenuation coefficients of silver in the 5–20 keV range

The X‐ray mass attenuation coefficients of silver were measured in the energy range 5–20 keV with an accuracy of 0.01–0.2% on a relative scale down to 5.3 keV, and of 0.09–1.22% on an absolute scale to 5.0 keV. This analysis confirms that with careful choice of foil thickness and careful correction for systematics, especially including harmonic contents at lower energies, the X‐ray attenuation of high‐Z elements can be measured with high accuracy even at low X‐ray energies (<6 keV). This is the first high‐accuracy measurement of X‐ray mass attenuation coefficients of silver in the low energy range, indicating the possibility of obtaining high‐accuracy X‐ray absorption fine structure down to the L₁ edge (3.8 keV) of silver. Comparison of results reported here with an earlier data set optimized for higher energies confirms accuracy to within one standard error of each data set collected and analysed using the principles of the X‐ray extended‐range technique (XERT). Comparison with theory shows a slow divergence towards lower energies in this region away from absorption edges. The methodology developed can be used for the XAFS analysis of compounds and solutions to investigate structural features, bonding and coordination chemistry.     

Validity and Reliability of the Reflux Symptom Index (RSI)

Laryngopharyngeal reflux (LPR) is present in up to 50% of patients with voice disorders. Currently, there is no validated instrument that documents symptom severity in LPR. We developed the reflux symptom index (RSI), a self-administered nine-item outcomes instrument for LPR. The purpose of this investigation was to evaluate the psychometric properties of the RSI. For validity assessment, 25 patients with LPR were evaluated prospectively before and six months after b.i.d. treatment with proton pump inhibitors (PPI). Each patient completed the RSI as well as the 30-item voice handicap index (VHI). For reliability assessment, the study patients were given the RSI on two separate occasions before the initiation of treatment. Normative RSI data were derived from 25 age-matched and gender-matched controls taken from an existing database of asymptomatic individuals without any evidence of LPR. The mean RSI (+/- standard deviation) of patients with LPR improved from 21.2 (+/- 10.7) to 12.8 (+/- 10.0), and the mean VHI improved from 52.2 (+/- 24.7) to 41.5 (+/- 25.0) after 6 months of therapy (p = 0.001 and 0.065, respectively). Of the three VHI subscales (emotional, physical, functional), only the functional subscale improved significantly (p = 0.037). Patients who experienced a five point or better improvement in RSI were 11 times more likely to experience a five-point improvement in VHI (95% confidence interval = 1.7, 76.8). For reliability assessment, the first and second pretreatment RSIs were 19.9 (+/- 11.1) and 20.9 (+/- 9.6), respectively (correlation coefficient = 0.81, p < 0.001). The single-item correlation coefficients ranged from 0.41 to 0.91 (p < 0.05 for all items). The mean pretreatment RSI in patients with LPR was significantly higher than controls (21.2 versus 11.6; p < 0.001). The mean RSI of patients with LPR after 6 months of PPI therapy approached that of asymptomatic controls (p > 0.05). The RSI is easily administered, highly reproducible, and exhibits excellent construct and criterion-based validity.     

Fibronectin: An Interesting Vocal Fold Protein

A great deal of information is accruing regarding the function of the extracellular matrix. Once thought to be simply a structural entity to surround cells, it is now known to do much more. Fibronectin in particular has received specific attention. Fibronectin is a ubiquitous glycoprotein found most abundantly in the extracellular matrix of regenerating, healing, and embryonic tissue. Vast evidence supports the fact that fibronectin participates in many diverse functions throughout the body that are relevant to vocal fold biology. This article introduces the structure of fibronectin and its isoforms and provides an introduction to some of the many functions it plays. It also reviews the evidence about fibronectin's place in vocal folds and vocal fold pathology. It discusses fibronectin's presence in vocal nodules, vocal polyps, vocal scarring, and Reinke's edema, and reviews the data on its role in mucosal wave impairment. Lastly, it discusses preliminary microarray data that show gene expression for fibronectin to be upregulated in true vocal folds when compared to false vocal folds.     

Short-Term Therapeutic Trial of Proton Pump Inhibitors in Suspected Extraesophageal Reflux

Pharyngoesophageal gastric acid reflux is thought to initiate chronic posterior laryngitis. The gold standard for measuring gastric reflux is dual-channel 24-hour pH monitoring. This is a time-consuming, inconvenient, expensive method that is not available in all areas. New therapeutic regimes that make use of proton pump inhibitors (PPIs) have proven to be therapeutically efficient for control of acid reflux. Twenty-four consecutive patients with chronic voice disorders and signs of posterior laryngitis were selected for therapy. Twenty-four hour pH monitoring was performed independently before the therapy. The trial therapy consisted of all patients receiving pantoprazole, 40 mg once daily for 6 weeks. Immediately following the therapy a statistically significant (p < 0.05) improvement was observed in all patients. This improvement was analyzed retrospectively by comparison with the results of 24-hour pH monitoring. In 71% of the patients the 24-hour pH-monitoring gave a positive result showing a high number of patients with extraesophageal reflux in our study group. Patients with positive results of pH-monitoring responded in a statistically significant manner (p < 0.05) to the pantoprazole therapy, whereas those patients without detected reflux did not. A 3-month follow-up of the patients with a positive result of the pH-monitoring confirmed the improvement. No patients reported adverse effects. A 6-week treatment with pantoprazole can be clinically justified. It helps to save time and reduce costs, allows for selection of reflux-negative patients for alternative therapy, and may prevent inadequate treatment of patients with false-negative pH monitoring. Twenty-four hour pH monitoring is still recommended for patients unresponsive to this trial therapy.     

Pulsed‐laser polymerization‐gel permeation chromatographic determination of the propagation‐rate coefficient for the methyl acrylate dimer: A sterically hindered monomer

The methyl acrylate dimer (MAD) is a sterically hindered macromonomer, and the propagating radical can fragment to an unsaturated end group. The propagation‐rate coefficient (k_p) for MAD was obtained by pulsed‐laser polymerization (PLP). The Mark–Houwink–Sakaruda parameters required for the analysis of the molecular weight distributions (MWDs) were obtained by multiple‐detector gel permeation chromatography (GPC) with on‐line viscometry. The small radical created by the fragmentation results in a short‐chain polymer that means the MWD may no longer be given by that expected for “ideal” PLP conditions; simulations suggest that the degree of polymerization required for “ideal” PLP conditions can be obtained from the primary point of inflection provided the GPC traces also show a clear secondary inflection point (radicals terminated by the second, rather than the first, pulse subsequent to initiation). Over the temperature range of 40–75 °C, the data can be best fitted by k_p/dm³ mol^?1 s^?1 = 10^6.1 exp(?29.5 kJ mol^?1), with a moderately large joint confidence interval for the Arrhenius parameters. The data are consistent with an increased activation energy and reduced frequency factor as compared with acrylate or methacrylate; both of these changes can be ascribed to hindrance. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3902–3915, 2001     

Electrophysiologic monitoring of the recurrent laryngeal nerves may not predict bilateral vocal fold immobility after thyroid surgery

Two cases of bilateral vocal fold immobility (VFI) after identification and preservation of the recurrent laryngeal nerves (RLNs) required tracheotomy until vocal fold recovery. The first patient underwent thyroid surgery without preoperative or postoperative evaluation of the vocal folds, administration of postoperative intravenous steroids, or electrophysiologic monitoring of the RLNs, whereas the second patient underwent a thyroid procedure in which all of the aforementioned were executed. Preoperative and postoperative clinical evaluation of the RLNs is strongly suggested in patients undergoing thyroid surgery, especially revision surgery. Patients potentially undergoing total thyroidectomy should be counseled about the remote chance of airway obstruction and should be properly selected for this operation. Subclinical stretching of the RLNs or ischemia from the endotracheal tube cuff can result in unilateral VFI, and rarely bilateral VFI, requiring reintubation, tracheotomy, or vocal fold lateralization. Electrophysiologic monitoring may not always predict bilateral VFI.