Two-dimensional J-spectra with absorption-mode lineshapes

Two-dimensional J-spectroscopy offers the possibility of a complete separation of chemical shifts and J-couplings. However, the usefulness of the experiment is considerably reduced by the fact that peaks in the spectra have the phase-twist lineshape. We present a simple new spectroscopic method for recording J-spectra in which the peaks are both in the absorption mode and retain their natural intensities, albeit at the cost of a considerable reduction in the signal-to-noise ratio. No special data-processing is required. The method is tested on quinine, and the steroid dehydroisoandrosterone.     

Observation of long-range orientational order in monolayers of polydisperse colloids

Polydisperse amorphous-silicon colloidal particles ranging from approximately 10 to 140 nm in diameter were evaporated onto carbon substrates. The particles formed close-packed monolayers in which each particle had 6-fold nearest-neighbor coordination characteristic of a hexagonal lattice yet completely lacked positional order. Orientational correlation functions were calculated for the particles and found to be constant throughout the aggregate, indicating the occurrence of long-range orientational order. Computer simulations revealed that the structural organization in this system resulted from capillary immersion forces that lead to a size separation as the particles deposit from the evaporating solvent onto the substrate.     

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.     

Study of spectroscopic characteristics of holmium-doped double sodium-yttrium fluoride crystals Na<Subscript>0.4</Subscript>Y<Subscript>0.6</Subscript>F<Subscript>2.2</Subscript>:Ho<Superscript>3+</Superscript>

We have grown crystals Na_0.4Y_0.6F_2.2:Ho³⁺ (NYF:Ho³⁺) by the Bridgman-Stockbarger method. The optical spectra and luminescence kinetics of NYF:Ho³⁺ crystals have been studied. Based on the analysis of low-temperature absorption spectra, we determine the structure of the Stark splitting of holmium levels in NYF:Ho³⁺ crystals. From absorption spectra examined at T = 300 K, we calculate absorption cross-section spectra and oscillator strengths of transitions from the ground state of holmium to excited multiplets. We show that the absorption spectra of NYF:Ho³⁺ crystals consist of broad bands that lie in the UV, visible, and near-IR ranges. The most intense bands are observed in the visible range, they correspond to transitions ⁵ I ₈ → (⁵ F ₁, ⁵ G ₆) and ⁵ I ₈ → (⁵ F ₄, ⁵ S ₂), and their maximal absorption cross sections are σ_abs^max (λ = 450.3 nm) = 1.16 × 10⁻²⁰ cm² and σ_abs^max (λ = 535.1 nm) = 0.9 × 10⁻²⁰ cm². The intensity parameters Ω _t have been calculated by the Judd-Ofelt method taking into account 10, 12, and 20 transitions from the ⁵ I ₈ ground state to excited multiplets. We show that, with an increasing number of transitions taken into account in the calculation, the parameters Ω _t somewhat increase. For 20 transitions, we have obtained the following intensity parameters: Ω₂ = 0.97 × 10⁻²⁰, Ω₄ = 1.74 × 10⁻²⁰, and Ω₆ = 1.15 × 10⁻²⁰ cm². With these parameters, we have calculated the probabilities of radiative transitions, the radiative lifetimes, and the branching ratios. The rates of multiphoton nonradiative transitions have been estimated. The luminescence decay kinetics from excited holmium levels ⁵ F ₃ (⁵ F ₄, ⁵ S ₂) and ⁵ F ₅ have been studied upon selective excitation in the range of 490 nm, and the lifetimes of these levels have been experimentally determined. We find that the calculated and experimental rates of radiative and nonradiative relaxation from excited holmium levels agree well with each other. We show that, upon pumping in the range of 490 nm, the multiplet (⁵ F ₄, ⁵ S ₂) is populated as a result of the radiative and nonradiative excitation relaxation from the ⁵ F ₃ level, while the lower-lying ⁵ F ₅ level is populated due to direct radiative transitions ⁵ F _{3, 2} → ⁵ F ₅, obviating the cascade scheme ⁵ F ₃ → (⁵ F ₄, ⁵ S ₂) ↝ ⁵ F ₅. We conclude that NYF:Ho³⁺ crystals are processable; admit doping by holmium in high concentrations (up to 100%); and, with respect to all their radiative characteristics, can be considered as potential active media for solid-state continuously tunable lasers in the IR and visible ranges.     

Harmful Substances on the Opera Stage: Possible Negative Effects on Singers'' Respiratory Tracts

Objective, quantitative information is lacking in the medical community about actual working conditions for professional singers onstage, and moreover, about which conditions are safe. Physicians, speech-language pathologists, and speech scientists focusing on laryngology should have relevant information about the opera as workplace and the medical sequelae of unhealthy environments. We describe five toxic substances to which singers presenting to our clinics were exposed while working professionally on the opera stage: (1) aromatic diisocyanates, (2) penicillium frequentans in cork granulate, (3) formaldehyde in cork granulate, (4) cobalt and aluminum (pigment components), and (5) quartz sand capable of entering the alveolae. Biological considerations and clinical data for some subjects suggest a direct causal link between the exposures and the patients' complaints and findings. Our observations suggest that whenever singers complain about deleterious conditions such as dry and hot onstage climate or suspicion of the presence of harmful substances, the specific conditions existing in the theater in question should be investigated. Harmful substances are not only poorly tolerated by singers, but also they should be preventable.     

Laryngeal and Vocal Changes During Vagus Nerve Stimulation in Epileptic Patients

Left vagus nerve stimulation (VNS) by means of an implanted electrode has proven to reduce seizure frequency in epileptic patients with medically refractory seizures. This technique is now widely applied over the world. Voice changes appear to be one of the major side effects. The morphodynamic changes in the larynx and the acoustic impacts have been analyzed in detail in 7 implanted patients. Basic vagus stimulation is well tolerated. Extra stimulation induces an adductory spasm of either the ipsilateral vocal fold or the vestibular fold. The result, when the patient phonates, consists of a slight increase of F0 as well as a moderate increase of random period perturbation, but there is no evidence for the occurrence of "bifurcations." Further, as the glottic closure remains sufficient, there is no increase in turbulent noise. The lack of increase in turbulent noise and the lack of "bifurcations" appears to clearly differentiate a spasmodic contraction of the vocal cord from a unilateral vocal fold paralysis.     

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.     

Combination of DQ and ZQ Coherences for Sensitive Through‐Bond NMR Correlation Experiments in Biosolids under Ultra‐Fast MAS

A double‐zero quantum (DZQ)‐refocused INADEQUATE experiment is introduced for J‐based NMR correlations under ultra‐fast (60 kHz) magic angle spinning (MAS). The experiment records two spectra in the same dataset, a double quantum–single quantum (DQ‐SQ) and zero quantum–single quantum (ZQ‐SQ) spectrum, whereby the corresponding signals appear at different chemical shifts in ω₁. Furthermore, the spin‐state selective excitation (S³E) J‐decoupling block is incorporated in place of the second refocusing echo of the INADEQUATE scheme, providing an additional gain in sensitivity and resolution. The two sub‐spectra acquired in this way can be treated separately by a shearing transformation, producing two diagonal‐free single quantum (SQ‐SQ)‐type spectra, which are subsequently recombined to give an additional sensitivity enhancement, thus offering an improvement greater than a factor of two as compared to the original refocused INADEQUATE experiment. The combined DZQ scheme retains transverse magnetization on the initially polarized (I) spin, which typically exhibits a longer transverse dephasing time (T₂′) than its through‐bond neighbour (S). By doing so, less magnetization is lost during the refocusing periods in the sequence to give even further gains in sensitivity for the J correlations. The experiment is demonstrated for the correlation between the carbonyl (CO) and alpha (CA) carbons in a microcrystalline sample of fully protonated, [¹⁵N,¹³C]‐labelled Cu^II, Zn^II superoxide dismutase, and its efficiency is discussed with respect to other J‐based schemes.     

Enantioseparation of chiral sulfonates by liquid chromatography and subcritical fluid chromatography

Tert‐butylcarbamoyl‐quinine and ‐quinidine weak anion‐exchange chiral stationary phases (Chiralpak® QN‐AX and QD‐AX) have been applied for the separation of sodium β‐ketosulfonates, such as sodium chalconesulfonates and derivatives thereof. The influence of type and amount of co‐ and counterions on retention and enantioresolution was investigated using polar organic mobile phases. Both columns exhibited remarkable enantiodiscrimination properties for the investigated test solutes, in which the quinidine‐based column showed better enantioselectivity and slightly stronger retention for all analytes compared to the quinine‐derived chiral stationary phase. With an optimized mobile phase (MeOH, 50 mM HOAc, 25 mM NH₃), 12 of 13 chiral sulfonates could be baseline separated within 8 min using the quinidine‐derivatized column. Furthermore, subcritical fluid chromatography (SubFC) mode with a CO₂‐based mobile phase using a buffered methanolic modifier was compared to HPLC. Generally, SubFC exhibited slightly inferior enantioselectivities and lower elution power but also provided unique baseline resolution for one compound.