Patterns of breath support in projection of the singing voice

Recordings of the rib cage and abdominal motions and acoustic output were obtained from five professional opera singers during performance of an aria recorded with two levels of voice projection. The condition of greater projection resulted in a significant increase in the acoustic power in the frequency band 2-4 kHz, relative to the power in the 0-2 kHz band, and a decrease in the mean expiratory flow, implying a move to more efficient vocalization with the greater projection. Also, the condition of greater projection resulted in a larger rib cage, particularly in the lateral dimension, but only a small decrease in the abdominal lateral dimension, suggesting that the greater abdominal support required for a larger projection is obtained by increased activation of abdominal muscles acting medially.     

Performance Anxiety: Loss of the Spoken Edge

The study aimed to assess whether a specific training program in vocal and physical skills could reduce the level of perceived performance anxiety. Eighteen undergraduate performing arts students were divided into two even groups. The experimental group experienced 10 two-hour sessions in a specialized vocal and physical skills training program. The control group received the same number of sessions in text analysis by the same teacher. Ten weeks after the training period, both groups were videotaped delivering a short speech of general interest. The videotaped material was assessed by four judges, using a visual analog scale (VAS). Perceptual variables considered were eight vocal and physical features: physical ease, physical presence, effective gesture use, effective eye contact, correct breath use, suitable pace, vocal variety, speech clarity, and one performance feature: perceived performance anxiety. Results indicated that the particular vocal and physical skills training program used showed positive results in effectively reducing the level of perceived performance anxiety. The experimental group scored significantly higher on each of the eight vocal and physical features and significantly lower on the perceived anxiety feature than the control group. This research has implications for those affected by performance anxiety in vocal presentation.     

Evaluating the solvation properties of functionalized ionic liquids with varied cation/anion composition using the solvation parameter model

Ionic liquids (ILs) are promising gas chromatography (GC) stationary phases due to their high thermal stability, negligible vapor pressure, and ability to solvate a broad range of analytes. The tunability of ILs allows for structure modification in pursuit of enhanced separation selectivity and control of analyte elution order. In this study, the solvation parameter model is used to characterize the solvation interactions of fifteen ILs containing various cationic functional groups (i.e., dimethylamino, hydroxyl, and ether) and cation types paired with various counter anions, namely, tris(pentafluoroethyl)trifluorophosphate (FAP(-)), bis[(trifluoromethyl)sulfonyl]imide (NTf(2)(-)), thiocyanate (SCN(-)), tricyanomethide (C(CN)(3)(-)), tetracyanoborate (B(CN)(4)(-)), and bis[oxalate(2-)]borate (BOB(-)). The presence of functional groups affected the hydrogen bond basicity, hydrogen bond acidity, as well as dispersion interactions of the resulting ILs, while the change of cation type yielded modest influence on the dipolarity. The switch of counter anions in unfunctionalized ILs produced compounds with higher dipolarity and hydrogen bond basicity. The dipolarity and hydrogen bond basicity of ILs possessing cyano-containing anions appeared to be inversely proportional to the cyano content of the anion. The modification of IL structure resulted in a significant effect on the retention behavior as well as separation selectivity for many solutes, including reversed elution orders of some analytes. This study provides one of the most comprehensive examinations up-to-date on the relation between IL structure and the resulting solvation characteristics and gives tremendous insight into choosing suitable ILs as GC stationary phases for solute specific separations.     

The relationship between measured vibrato characteristics and perception in Western operatic singing

This study examined the association between acoustic and perceptual data related to vibrato in Western operatic singing using recordings of performances by internationally famous opera singers. Three related studies were conducted. Study 1 used commercial recordings of the same five singers and the same cadenza examined by Siegwart and Scherer(1), measured vibrato rate and extent in each singer's performance of the cadenza and tested possible associations between these vibrato attributes and judges' preference for singers. Studies 2 and 3, using recordings of different internationally famous singers and a different cadenza, measured vibrato onset, rate, and extent in each singer's performance of the cadenza, required judges to rank the singers in order of personal preference, to identify the emotion expressed, and to assess the degree of success in communicating emotion achieved by the singer. The findings showed that the perception of the singers' vibrato did not always agree with acoustic measurements. However, a comparison of the acoustic measurements with the preference and emotion judgments suggest that some elements of vibrato may affect listeners' perception of the voice, their preference for a particular singer, and assist the communication of emotion between singer and audience.     

Permanganate ion oxidations X. Kinetics and mechanisms of the initial stage in the oxidation of 4-hydroxy-2-pyrimidinethiols

Permanganate ion rapidly oxidizes the thiol group in 2-thiouracils (2,3-dihydro-2-thioxo-4(1H)-pyrimidinones, 4-hydroxy-2-pyrimidinethiols) to the corresponding uracil-2-sulfonates in phosphate-buffered solutions. The oxidations, which are first order in oxidant and first order in reductants, are characterized by relatively small energies of activation (E_a ? 4.3–6.7kcal/mol) and relatively large negative entropies of activation (ΔS? = ?24.9–?34.4 eu). The relative rates of oxidation of 2-thiouracil (2), 6-methyl- (4), 6-n-propyl- (6), 1,6-dimethyl-(8), and 3,6-dimethyl-2-thiouracil (9) are 1.00:1.23:0.98:7.32:2.54. The rate of oxidation of 1,3,6-trimethyl-2-thiouracil (12) is several orders of magnitude slower than that of the other thiouracils. Although the thiol group or thiolate anion is probably involved in the rate-determining step, several other possible mechanisms are also considered.     

Book Reviews

Structural Chemistry -     

THE EFFECTS OF PHOTODYNAMIC THERAPY USING DIFFERENTLY SUBSTITUTED ZINC PHTHALOCYANINES ON VESSEL CONSTRICTION, VESSEL LEAKAGE AND TUMOR RESPONSE

Abstract— The effects of four different zinc phthalocyanines were studied during and after photodynamic therapy (PDT). Measurements of vessel constriction, vessel leakage, tumor interstitial pressure, eicosanoid release, and tumor response of chondrosarcoma were made in Sprague-Dawley rats. Animals were injected intravenously with 1 μmol/ kg of mono-, di-, or tetrasulfonated zinc phthalocyanine, or 1 μmol/kg of a zinc phthalocyanine substituted with four tertiary butyl groups. Tissues were exposed to 400 J/cm² 670 nm light 24 h after photosensitizer injection. An additional group of animals was given indomethacin before treatment. The use of the monosulfonated and tertiary butyl substituted zinc phthalocyanines in PDT caused the release of specific eicosanoids, caused vessel constriction, and induced venule leakage and increases in tumor interstitial pressure. Tumor cures of 27% and 7% were observed. Photodynamic therapy using the disulfonated zinc phthalocyanine did not induce vessel constriction or the release ofeicosanoids, however; tumor cure was 43%. The use of thc tetrasulfonated zinc phthalocyanine caused intermediate effects between the mono- and disulfonated compounds. The administration of indornethacin to animals completely inhibited the effects of PDT using the monosulfonated compound but had minimal effects on treatment using the disulfonated compound. This suggests that the monosulfonated and disulfonated compounds act by different mechanisms of destruction.     

Triplex-Mediated, in vitro Targeting of Psoralen Photoadducts within the Genome of a Transgenic Mouse

Abstract— Light-activated psoralens can covalently modify DNA and are widely used to study nucleic acid secondary structure and mutagenesis. Sequence specificity can be added to the photoaddition reaction by attaching the psoralen to an oligonucleotide designed to recognize a double-stranded DNA binding site through formation of a triple helix. We have previously used this strategy to study targeted psoralen modification of a triplex binding site within the bacterial supF gene carried in viral genomes. In the present work we report the targeting of psoralen photoadducts in vitro to a specific site in the genome of a transgenic mouse. Both 10 base and 16 base oligonucleotide-psoralen conjugates were capable of sequence-specific modification of genomic mouse DNA, while a truncated 8 base conjugate was not. Light activation was necessary, and a dose dependence was demonstrated for target site modification and mutagenesis. The 10 base conjugate rapidly found its target, with sequence-specific binding occurring after just 10 min incubation in the presence of mouse DNA. The ability to target psoralen photoadducts within mammalian genomes may prove useful in the study of chromatin structure and DNA repair. Moreover, this work may lead to potential in vivo applications of targeted psoralen modification.     

Molecular dynamics simulations on the effects of diameter and chirality on hydrogen adsorption in single walled carbon nanotubes

We present systematic molecular dynamics simulation studies of hydrogen storage in single walled carbon nanotubes of various diameters and chiralities using a recently developed curvature-dependent force field. Our main objective is to address the following fundamental issues: 1. For a given H2 loading and nanotube type, what is the H2 distribution in the nanotube bundle? 2. For a given nanotube type, what is the maximal loading (H2 coverage)? 3. What is the diameter range and chirality for which H2 adsorption is most energetically favorable? Our simulation results suggest strong dependence of H2 adsorption energies on the nanotube diameter but less dependence on the chirality. Substantial lattice expansion upon H2 adsorption was found. The average adsorption energy increases with the lowering of nanotube diameter (higher curvature) and decreases with higher H2 loading. The calculated H2 vibrational power spectra and radial distribution functions indicate a strong attractive interaction between H2 and nanotube walls. The calculated diffusion coefficients are much higher than what has been reported for H2 in microporous materials such as zeolites, indicating that diffusivity does not present a problem for hydrogen storage in carbon nanotubes.     

High temperature gas chromatography of trimethylsilyl derivatives of alcohol ethoxylates and ethoxysulfates

Conversion of ethoxylated alcohols to trimethylsilyl derivatives and subsequent high temperature gas chromatography allowed for the determination of alkyl chain distribution, mole average degree of ethoxylation and weight percent distribution of several commercial mixtures. Repetitive derivatizations and analyses of a mixture with a vendor specified mole average degree of ethoxylation of 3.0 (Neodol 23-3), yielded an experimental result of 2.93 ± 0.05 (n = 6). Mixtures with different alkyl chain distributions and higher degrees of ethoxylation provided similar accuracy. Extension of the method to the analysis of ethoxylated alcohol sulfate raw materials and ethoxylated alcohol sulfates in dishwashing liquids is discussed.