Dynamics of proteins encapsulated in silica sol-gel glasses studied with IR vibrational echo spectroscopy

Spectrally resolved infrared stimulated vibrational echo spectroscopy is used to measure the fast dynamics of heme-bound CO in carbonmonoxy-myoglobin (MbCO) and -hemoglobin (HbCO) embedded in silica sol-gel glasses. On the time scale of approximately 100 fs to several picoseconds, the vibrational dephasing of the heme-bound CO is measurably slower for both MbCO and HbCO relative to that of aqueous protein solutions. The fast structural dynamics of MbCO, as sensed by the heme-bound CO, are influenced more by the sol-gel environment than those of HbCO. Longer time scale structural dynamics (tens of picoseconds), as measured by the extent of spectral diffusion, are the same for both proteins encapsulated in sol-gel glasses compared to that in aqueous solutions. A comparison of the sol-gel experimental results to viscosity-dependent vibrational echo data taken on various mixtures of water and fructose shows that the sol-gel-encapsulated MbCO exhibits dynamics that are the equivalent of the protein in a solution that is nearly 20 times more viscous than bulk water. In contrast, the HbCO dephasing in the sol-gel reflects only a 2-fold increase in viscosity. Attempts to alter the encapsulating pore size by varying the molar ratio of silane precursor to water (R value) used to prepare the sol-gel glasses were found to have no effect on the fast or steady-state spectroscopic results. The vibrational echo data are discussed in the context of solvent confinement and protein-pore wall interactions to provide insights into the influence of a confined environment on the fast structural dynamics experienced by a biomolecule.     

Confinement or the nature of the interface? Dynamics of nanoscopic water

The dynamics of water confined in two different types of reverse micelles are studied using ultrafast infrared pump-probe spectroscopy of the hydroxyl OD stretch of HOD in H2O. Reverse micelles of the surfactant Aerosol-OT (ionic head group) in isooctane and the surfactant Igepal CO 520 (nonionic head group) in 50/50 wt % cyclohexane/hexane are prepared to have the same diameter water nanopools. Measurements of the IR spectra and vibrational lifetimes show that the identity of the surfactant head groups affects the local environment experienced by the water molecules inside the reverse micelles. The orientational dynamics (time-dependent anisotropy), which is a measure of the hydrogen bond network rearrangement, are very similar for the confined water in the two types of reverse micelles. The results demonstrate that confinement by an interface to form a nanoscopic water pool is a primary factor governing the dynamics of nanoscopic water rather than the presence of charged groups at the interface.     

Vibrational echo experiments on red blood cells: Comparison of the dynamics of cytoplasmic and aqueous hemoglobin

Ultrafast spectrally resolved stimulated vibrational echo experiments measure the dephasing of the CO stretching mode of hemoglobin-CO (Hb-CO) inside living human erythrocytes (red blood cells). A method is presented to overcome the adverse impact on the vibrational echo signal from the strong light scattering caused by the cells. The results are compared to experiments on Hb-CO aqueous solutions. It is demonstrated that the dynamics of the protein as sensed by the CO ligand are the same inside the erythrocytes and in aqueous solution, but differences in the absorption spectra show that the cell affects the protein's potential energy surface.     

Inversion formulas for the reznitskaya transform and stability of lipschitz type in determination of initial heat distribution

In the Reznitskaya transform combining the solutions of some general linear partial differential equations of hyperbolic type and parabolic type, isometrical identities and inversion formulas are established. Furthermore, stability of Lipschitz type in the determination of initial heat distribution is given as an application.     

Comparison between homotopy analysis method and optimal homotopy asymptotic method for nth‐order integro‐differential equation

This paper presents general framework for solving the nth‐order integro‐differential equation using homotopy analysis method (HAM) and optimal homotopy asymptotic method (OHAM). OHAM is parameter free and can provide better accuracy over the HAM at the same order of approximation. Furthermore, in OHAM the convergence region can be easily adjusted and controlled. Comparison, via two examples, between our solution using HAM and OHAM and the exact solution shows that the HAM and the OHAM are effective and accurate in solving the nth‐order integro‐differential equation. Copyright © 2011 John Wiley & Sons, Ltd.     

Bilateral Mixed Laryngoceles: Simultaneous Strobovideolaryngoscopy and External Video Examination

A music medicine practice affords a unique opportunity to diagnose and treat laryngeal music performers. Strobovideolaryngoscopic (SVL) and external video examination of the voice professional or brass instrument player may focus on the vocal folds, yet abnormalities of the supraglottis, neck, and thorax should be appreciated and documented. Laryngoceles are uncommon laryngeal disorders but may occur in up to 5% of benign laryngeal lesions. While many laryngoceles are asymptomatic, they may cause a cough, hoarseness, stridor, sore throat, pain, snoring, or globus sensation. In particular, musicians who play brass instruments are at high risk for laryngocele development. We highlight two patients with symptomatic laryngoceles to present anatomical, historical, classification, epidemiological, diagnostic, and management considerations.     

Bilateral Vocal Fold Posterior Glottic/Subglottic Stenotic Web Resected with Contact Tip Nd-YAG Laser

The standard treatment for respiratory failure remains endotracheal intubation, with periods of 22 or more days being commonplace. Posterior glottic stenotic web formation, from scarring in the posterior interarytenoid area, may occur after endotracheal intubation, thermal, corrosive, or direct surgical injury. A commonly used classification system for posterior glottic stenosis divides the occurrence into four types. Type I involves an interarytenoid scar band between the vocal folds that is anterior and separate from the posterior interarytenoid mucosa. Type II stenosis involves scarring of the mucosa or musculature of the posterior interarytenoid area. Types III and IV involve unilateral and bilateral cricoarytenoid joint fixation, respectively. Strobovideolaryngoscopy (SVL), rigid and flexible fiberoptic bronchoscopy, electromyography (EMG), radiologic imaging of the neck, larynx, and trachea as well as pulmonary function tests, including flow volume loops, provide important objective measurements of upper airway obstruction. A representative case of a professional voice user who suffered a Type II posterior glottic stenosis is presented. The treatment utilized a specific contact-tip neodymium-yttrium aluminum garnet (Nd-YAG) laser delivery system to achieve precise cutting, vaporization, and coagulation simultaneously, returning tactile touch technique to the airway/voice surgeon. Completely successful restoration of voice and airway have been maintained for 2 1/2 years postoperatively.     

Botulinum Toxin Type B for Treatment of Spasmodic Dysphonia: A Case Report

Although treatment with botulinum toxin type A (BTXA) has become the standard of care for most patients with laryngeal dystonia, its use is limited by the development of resistance to the toxin in some patients. Botulinum toxin type B (BTXB) has been found to be safe and effective in the treatment of cervical dystonia, but it has not been used previously to treat spasmodic dysphonia. Our experience with BTXB in a patient who developed resistance to BTXA suggests that BTXB may be safe and effective for the treatment of laryngeal dystonia, as well.