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81.
Novel palladium catalysed two- and three-component thermal (conventional heating and microwave) cascade processes are described involving allenylation of an aryl iodide to generate a (π-allyl)palladium species, which are intercepted (inter- or intramolecularly) by a carbon or nitrogen nucleophile followed by intramolecular Michael addition to afford carbo- and heterocycles in good yields. 相似文献
82.
83.
Trevitt AJ Soorkia S Savee JD Selby TS Osborn DL Taatjes CA Leone SR 《The journal of physical chemistry. A》2011,115(46):13467-13473
The gas-phase CN + propene reaction is investigated using synchrotron photoionization mass spectrometry (SPIMS) over the 9.8-11.5 eV photon energy range. Experiments are conducted at room temperature in 4 Torr of He buffer gas. The CN + propene addition reaction produces two distinct product mass channels, C(3)H(3)N and C(4)H(5)N, corresponding to CH(3) and H elimination, respectively. The CH(3) and H elimination channels are measured to have branching fractions of 0.59 ± 0.15 and 0.41 ± 0.10, respectively. The absolute photoionization cross sections between 9.8 and 11.5 eV are measured for the three considered H-elimination coproducts: 1-, 2-, and 3-cyanopropene. Based on fits using the experimentally measured photoionization spectra for the C(4)H(5)N mass channel and contrary to the previous study (Int. J. Mass. Spectrom.2009, 280, 113-118), where it was concluded that 3-cyanopropene was not a significant product, the new data suggests 3-cyanopropene is produced in significant quantity along with 1-cyanopropene, with isomer branching fractions from this mass channel of 0.50 ± 0.12 and 0.50 ± 0.24, respectively. However, similarities between the 1-, 2-, and 3-cyanopropene photoionization spectra make an unequivocal assignment difficult based solely on photoionization spectra. The CN + CH(2)CHCD(3) reaction is studied and shows, in addition to the H-elimination product signal, a D-elimination product channel (m/z 69, consistent with CH(2)CHCD(2)CN), providing further evidence for the formation of the 3-cyanopropene reaction product. 相似文献
84.
85.
Steven Bielamowicz MD Sheila V. Stager Andrea Badillo Alexis Godlewski 《Journal of voice》2002,16(1):117-123
Both unilateral and bilateral thyroarytenoid muscle injections of Botox provide effective management of voice symptoms in patients with adductor spasmodic dysphonia; however, the preferred injection technique has not been established. In this study, 16 patients were treated with unilateral injections (72 injections total) and 33 patients were managed with bilateral injections (133 injections total). Individual assignments to injection type were based on treatment previously received and dose was adjusted according to the patient's previous treatment response. An optimal treatment included a benefit lasting 3 months or more with side effects lasting 2 weeks or less. Compared to patients receiving bilateral injections, those receiving unilateral injections more frequently noted a benefit of 3 months or more (p = 0.03), side effects of 2 weeks or less duration (p = 0.03), as well as both a 3-month benefit and a 2-week or less side effect (p = 0.0004). Injection type had no effect on optimal Botox dosing with repeat injections. Successive unilateral injections at the same dose were more likely (p = 0.012) than successive bilateral injections to produce the same or longer duration of benefit. We conclude that a unilateral injection routine has a more optimal and consistent treatment effect/side effect profile. 相似文献
86.
Yolanda D. Heman-Ackah MD Deirdre D. Michael George S. Goding Jr. 《Journal of voice》2002,16(1):20-27
Traditional measures of dysphonia vary in their reliability and in their correlations with perceptions of grade. Measurements of cepstral peak prominence (CPP) have been shown to correlate well with perceptions of breathiness. Because it is a measure of periodicity, CPP should also predict roughness. The ability of CPP and other acoustic measures to predict overall dysphonia and the subcategories of breathiness and roughness in pathological voice samples is explored. Preoperative and postoperative speech samples from 19 patients with unilateral recurrent laryngeal nerve paralysis who underwent operative intervention were analyzed by trained listeners and by measures of smoothed CPP (CPPS), noise-to-harmonic ratio (NHR), amplitude perturbation quotient (APQ), relative average perturbation (RAP), and smoothed pitch perturbation quotient (sPPQ). The data were analyzed with bivariate Pearson correlation statistics. Grade of dysphonia and breathiness ratings correlated better with measurements of CPPS than with the other measures. CPPS from samples of connected speech (CPPS-s) best predicted overall dysphonia. None of the measures were useful in predicting roughness. 相似文献
87.
Jane Yang Nicole Maronian Victoria Reyes Pat Waugh Teresa Brentnall Allen Hillel MD 《Journal of voice》2002,16(2):278-282
Laryngeal and other otolaryngologic manifestations of Crohn's disease are uncommon and may be subtle. Crohn's disease is a well-known inflammatory bowel disease of unknown etiology marked by relapsing and remitting granulomatous inflammation of the alimentary tract. Extraintestinal manifestations of Crohn's disease may appear anytime during the course of the disease process and may be the initial symptom. Findings are nonspecific, primarily edema and ulcerations, and may be confused with a multitude of other disease processes. Awareness of these manifestations in the head and neck will prevent misdiagnosis or a delay in diagnosis. 相似文献
88.
Kyung Sook Kim MD. Shakilur Rahman Manwoo Lee Guinyun Kim Pham Duc Khue Nguyen Van Do Moo-Hyun Cho In Soo Ko Won Namkung H. Naik Tae-Ik Ro 《Journal of Radioanalytical and Nuclear Chemistry》2011,287(3):869-877
We measured the isomeric yield ratios for the photonuclear reactions of 93Nb(??,4n)89m,gNb and natMo(??,xnp)95m,gNb by using the activation method. The high-purity 93Nb and natMo metallic foils in disc shape were irradiated with uncollimated bremsstrahlung beams of 50-, 60-, and 70-MeV generated from an electron linear accelerator in Pohang Accelerator Laboratory. The induced activities in the irradiated foils were measured by the high-resolution ??-ray spectrometry with a calibrated high-purity Germanium (HPGe) detector coupled to a PC-based 4?K multichannel analyzer. The reaction 93Nb(??,4n)89m,gNb was studied for the first time which has no comparable literature data. The result of 95m,gNb isomeric pair was measured based on (??,p), (??,np), and (??,2np) reactions which is the first measurement at the intermediate energy region of 50?C70-MeV with a natMo target. 相似文献
89.
Meloni G Selby TM Goulay F Leone SR Osborn DL Taatjes CA 《Journal of the American Chemical Society》2007,129(45):14019-14025
The photoionization of 1-alkenylperoxy radicals, which are peroxy radicals where the OO moiety is bonded to an sp2-hybridized carbon, is studied by experimental and computational methods and compared to the similar alkylperoxy systems. Quantum chemical calculations are presented for the ionization energy and cation stability of several alkenylperoxy radicals. Experimental measurements of 1-cyclopentenylperoxy (1-c-C5H7OO) and propargylperoxy (CH2=C=CHOO) photoionization are presented as examples. These radicals are produced by reaction of an excess of O2 with pulsed-photolytically produced alkenyl radicals. The kinetic behavior of the products confirms the formation of the alkenylperoxy radicals. Electronic structure calculations are employed to give structural parameters and energetics that are used in a Franck-Condon (FC) spectral simulation of the photoionization efficiency (PIE) curves. The calculations also serve to identify the isomeric species probed by the experiment. Adiabatic ionization energies (AIEs) of 1-c-C5H7OO (8.70 +/- 0.05 eV) and CH2=C=CHOO (9.32 +/- 0.05 eV) are derived from fits to the experimental PIE curves. From the fitted FC simulation superimposed on the experimental PIE curves, the splitting between the ground state singlet and excited triplet cation electronic states is also derived for 1-c-C5H7OO (0.76 +/- 0.05 eV) and CH2=C=CHOO (0.80 +/- 0.15 eV). The combination of the AIE(CH2=C=CHOO) and the propargyl heat of formation provides Delta f H(0)(o) (CH2=C=CHOO+) of (1162 +/- 8) kJ mol-1. From Delta f H(0)(o) (CH2=C=CHOO+) and Delta f H (0)(o) (C3H3+) it is also possible to extract the bond energy D(0)(o)(C3H3+-OO) of 19 kJ mol-1 (0.20 eV). Finally, from consideration of the relevant molecular orbitals, the ionization behavior of alkyl- and alkenylperoxy radicals can be generalized with a simple rule: Alkylperoxy radicals dissociatively ionize, with the exception of methylperoxy, whereas alkenylperoxy radicals have stable singlet ground electronic state cations. 相似文献
90.
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. 相似文献