Alcohol addition to acetonitrile activated by the [Re6(mu3-Se)8]2+ cluster core

The addition of methanol and ethanol to the previously reported cluster solvates [Re6(mu3-Se)8(PEt3)5(MeCN)](SbF6)2 and trans-[Re6(mu3-Se)8(PEt3)4(CH3CN)2][SbF6]2 afforded three cluster complexes with imino ester ligands: {Re6(mu3-Se)8(PEt3)5[HN=C(OCH3)(CH3)]}(SbF6)2, {Re6(mu3-Se)8(PEt3)5[HN=C(OCH2CH3)(CH3)]}{SbF6}2, and trans-{Re6(mu3-Se)8(PEt3)4[HN=C(OCH3)(CH3)]2}{SbF6}2. In all cases, predominant formation of the Z isomers was observed.     

Isomer-specific ultraviolet spectroscopy of m- and p-divinylbenzene

The ultraviolet spectroscopy of m- and p-divinylbenzene isomers (mDVB and pDVB) was studied by a combination of methods, including resonance-enhanced two-photon ionization (R2PI), laser-induced fluorescence (LIF), UV-UV hole-burning spectroscopy (UVHB), and single vibronic level fluorescence spectroscopy (SVLF). In mDVB, there are three low-energy conformations, cis-cis, cis-trans, and trans-trans whose S1 <-- S0 origins occur at 31,408, 31,856, and 32,164 cm(-1), respectively, as confirmed by UVHB spectroscopy. There are two possible conformations in pDVB, cis and trans. UVHB studies confirm the S1 <-- S0 origin of trans-pDVB occurs at 32,553 cm(-1), and the corresponding cis-pDVB origin is tentatively assigned to a transition at 32 621 cm(-1). SVLF studies were used to determine several of the vinyl torsional levels of the isomers of mDVB and pDVB. A two-dimensional flexible model was used to fit these levels in mDVB to a potential form and determine the barriers to isomerization.     

Photochemistry of benzylallene: ring-closing reactions to form naphthalene

Conformer-specific, vibrationally resolved electronic spectroscopy of benzylallene (4-phenyl-1,2-butadiene) is presented along with a detailed analysis of the products formed via its ultraviolet photoexcitation. Benzylallene is the minor product of the recombination of benzyl and propargyl radicals. The mass-selective resonant two-photon ionization spectrum of benzylallene was recorded under jet-cooled conditions, with its S(0)-S(1) origin at 37,483 cm(-1). UV-UV holeburning spectroscopy was used to show that only one conformer was present in the expansion. Rotational band contour analysis provided rotational constants and transition dipole moment direction consistent with a conformation in which the allene side chain is in the anti position, pointing away from the phenyl ring. The photochemistry of benzylallene was studied in a pump-probe geometry in which photoexcitation occurred by counter-propagating the expansion with a photoexcitation laser. The laser was timed to interact with the gas pulse in a short tube that extended the collisional region of the expansion. The products were cooled during expansion of the gas mixture into vacuum, before being interrogated using mass-selective resonant two-photon ionization. The UV-vis spectra of the photochemical products were compared to literature spectra for identification. Several wavelengths were chosen for photoexcitation, ranging from the S(0)-S(1) origin transition (266.79 nm) to 193 nm. Comparison of the product spectral intensities as a function of photoexcitation wavelength provides information on the wavelength dependence of the product yields. Photoexcitation at 266.79 nm yielded five products (benzyl radical, benzylallenyl radical, 1-phenyl-1,3-butadiene, 1,2-dihydronaphthalene, and naphthalene), with naphthalene and benzylallenyl radicals dominant. At 193 nm, the benzylallenyl radical signal was greatly reduced in intensity, while three additional C(10)H(8) isomeric products were observed. An extensive set of calculations of key stationary points on the ground state C(10)H(10) and C(10)H(9) potential energy surfaces were carried out at the DFT B3LYP/6-311G(d,p) level of theory. Mechanisms for formation of the observed products are proposed based on these potential energy surfaces, constrained by the results of cursory studies of the photochemistry of 1-phenyl-1,3-butadiene and 4-phenyl-1-butyne. A role for tunneling on the excited state surface in the formation of naphthalene is suggested by studies of partially deuterated benzylallene, which blocked naphthalene formation.     

Characterization of chronic vocal fold scarring in a rabbit model

The purpose of the current study was to assess the histologic and rheologic properties of the scarred vocal fold lamina propria during a chronic phase of wound repair in a rabbit model. Eighteen rabbit larynges were scarred using a procedure that involved stripping the vocal fold lamina propria down to the thyroarytenoid muscle, using 3-mm microforceps. The approximate dimension of injury to the vocal fold was 3 x 1.5 x 0.5 mm [length x width x depth]. At 6 months postoperatively, histologic analysis of the scarred and control lamina propria in eight of these rabbits was completed for collagen, procollagen, elastin, and hyaluronic acid. Compared with control samples, scarred tissue samples revealed fragmented and disorganized elastin fibers. Additionally, collagen was significantly increased, organized, and formed thick bundles in the scarred vocal fold lamina propria. Measurements of the viscoelastic shear properties of the scarred and control lamina propria in the remaining 10 rabbits revealed increased elastic shear modulus (G') in 8 of 10 scarred samples and increased dynamic viscosity (eta') in 9 of 10 scarred samples. Although rheologic differences were not statistically significant, they revealed that on average, scarred samples were stiffer and more viscous than the normal controls. Histologic data are interpreted as indicating that by 6 months postinjury, the scarred rabbit vocal fold has reached a mature phase of wound repair, characterized by an increased, organized, and thick bundle collagen matrix. Rheologic data are interpreted as providing support for the potential role of increased, thick bundle collagen, and a disorganized elastin network on shear stiffness and dynamic viscosity in the chronic vocal fold scar. Based on these results, a 6-month postoperative time frame is proposed for future studies of chronic vocal fold scarring using the rabbit animal model.     

Laryngeal Chondroma

Cartilaginous tumors of the larynx represent less than 1% of laryngeal tumors. Chondroma and "low-grade" chondrosarcoma are the most common; 70%-75% of these tumors arise on the endolaryngeal surface of the posterior lamina of the cricoid cartilage. The clinical presentation is varied and directly dependent on the size and location of the tumor; stridor, hoarseness, dyspnea, or a neck mass are common presenting signs. CT scanning in the axial plane is the mainstay of radiographic imaging due to its ability to show size, extent of the tumor, and invasion into surrounding structures. Surgical extirpation is the standard therapy with no role for radiation therapy or chemotherapy. Although significant recurrence rates have been reported, there is not a significant difference between initial conservative therapy followed by salvage therapy versus initial radical therapy.     

Prolonged Ulcerative Laryngitis

Acute and prolonged laryngitis commonly are diagnosed and treated by primary care physicians. These ailments come to the attention of the otolaryngologist when symptoms are prolonged despite treatment. Since the beginning of 1991, the senior authors (RTS, JRS) have recognized a clinical syndrome defined by prolonged hoarseness, prolonged laryngeal inflammation, and vocal fold ulceration. Patients are frequently young, nonsmokers, and nondrinkers who have had an upper respiratory infection prior to, or associated with, the onset of laryngeal symptomatology. Patients may be affected for up to 1 year despite aggressive medical therapy. This review of 14 patients highlights the features of this previously undescribed entity.     

Kinetic study of the CN radical reaction with 2-methylfuran

The gas phase reaction of the ground state cyano-radical (CN (X²∑⁺)) with 2-methylfuran (2-MF) is investigated in a quasi-static reaction cell at pressures ranging from 2.2 to 7.6 Torr and temperatures ranging from 304 to 440 K. The CN radicals are generated in their ground electronic state by pulsed laser photolysis of gaseous cyanogen iodide (ICN) at 266 nm. Their concentration is monitored as a function of reaction time using laser-induced fluorescence at 387.3 nm on the B²∑⁺ (ν′ = 0) ← X²∑⁺ (ν″ = 0) vibronic band. The reaction rate coefficient is found to be rapid and independent of pressure and temperature. Over the investigated temperature and pressure ranges, the rate coefficient is measured to be 2.83 (± 0.18) × 10⁻¹⁰ cm³ molecules s⁻¹. The enthalpies of the stationary points and transition states on the CN + 2-MF potential energy surface are calculated using the CBS-QB3 computational method. The kinetic results suggest the lack of a prereactive complex on the reaction entrance channel with either a very small or nonexistent entrance energy barrier. In addition, the potential energy surface calculations reveal only submerged barriers along the minimum energy path. Based on comparisons between previous CN reactions with unsaturated hydrocarbons, the most likely reaction pathway is CN addition onto one of the unsaturated carbons followed by either H or methyl elimination. The implications for the transformation of biomass-derived fuels in nitrogen-rich flames is discussed.