A Pilot Survey of Vocal Health in Young Singers

The objective of this study was to determine the incidence of vocal problems in young choir singers and to correlate vocal problems with demographic and behavioral information. A questionnaire addressing vocal habits and hygiene was offered to 571 young choir singers, up to 25 years of age, who sing at least weekly; 129 (22.6%) responded. More than one-half of the respondents had experienced vocal difficulty, particularly older adolescents. Detrimental behaviors and circumstances surveyed were not reflective of the incidence of vocal difficulty, except for morning hoarseness, chronic fatigue, insomnia, and female gender after puberty. Voice care professionals should be aware that self-reported voice difficulties are common among young choral singers, especially postpubescent girls, and children with symptoms consistent with reflux (morning hoarseness) and emotional stress (insomnia). Laryngologists should communicate with choral conductors and singing teachers to enhance early identification and treatment of children with voice complaints, and to develop choral educational strategies that help decrease their incidence.     

HPLC isolation and NMR structure elucidation of the most prominent octabromo isomer in technical octabromo diphenyl ether

The major octabromo isomer of technical octabromo diphenyl ether mixture (technical octaBDE) DE-79 was isolated by RP-HPLC. Three serially coupled columns (each 250 mm long) enabled a good separation of the target compound from other congeners using 100% ACN as eluent. Approximately 100 microg of the target compound was isolated with a purity of >90% and investigated by MS for confirmation of the degree of bromination. 1H-NMR and 2-D 1H-13C correlation NMR spectra unequivocally clarified that the octaBDE in question is 2,2',3,3',4,4',6,6'-octabromodiphenyl ether (BDE 197). Based on annual production rates of technical BDE products (1999/2001), approximately 380 tons of BDE 197 were annually produced which, on the long term, may enter the environment. Compared with other individual BDE congeners, BDE 197 has the seventh highest application rate. Reductive debromination of BDE 197 can lead to four hepta-, 15 hexa-, 23 penta-, and 28 tetra-BDE isomers, respectively. This variety includes all known major BDEs of environmental concern (BDE 47, 85, 99, 100, 153, 154, and 183). The identification of BDE 197 in technical octaBDE DE-79 strongly suggests that research on the environmental fate of BDEs should include this key-BDE congener.     

The migrastatin family: discovery of potent cell migration inhibitors by chemical synthesis

The first asymmetric total synthesis of (+)-migrastatin (1), a macrolide natural product with anti-metastatic properties, has been accomplished. Our concise and flexible approach utilized a Lewis acid-catalyzed diene aldehyde condensation (LACDAC) to install the three contiguous stereocenters and the trisubstituted (Z)-alkene of migrastatin (2 + 3 --> 21). Construction of the two remaining stereocenters and incorporation of the glutarimide-containing side chain was achieved by an anti-selective aldol addition of propionyl oxazolidinone 28 to angelic aldehyde 27, followed by a Horner-Wadsworth-Emmons (HWE) coupling of 32 with glutarimide aldehyde 5. Finally, the assembly of the macrocycle was realized by a highly (E)-selective ring-closing metathesis (35 --> 37). Utilizing the power of diverted total synthesis (DTS), a series of otherwise inaccessible analogues was prepared and evaluated for their potential as tumor cell migration inhibitors in several in vitro assays. These studies revealed a dramatic increase in activity when the natural motif was considerably simplified, presenting macrolactones 45 and 48, as well as macrolactam 55, macroketone 60, and CF(3)-alcohol 71 as promising anti-metastatic agents.     

Einige Aspekte in der Zuordnungstheorie

Zusammenfassung Gegeben seien endliche MengenX, Y undZ X × Y, Z _x ={y¦(x,y) Z},Z _y ={x¦(x,y) Z}.Man nenntA X (bzw.B Y)zuordenbar, wenn es eine Injektion:A Y (bzw.: B X) mit(x) Z _x (bzw.(y) Z _y ) gibt, und (A, B) mit #A=#B > 0 einZuordnungspaar, wenn eine Bijektionf:A B mitf(x)Z _x B (bzw.f ^–1 (y) Z _y A) existiert. Die Bijektionf heißtZuordnungsplan fürA, B.In der vorliegenden Arbeit werden Fragen nach der Existenz von optimal zuordenbaren Mengen und optimalen Zuordnungspaaren behandelt, wenn man auf den MengenX undY Ordnungen vorgibt, wobei auch Nebenbedingungen berücksichtigt werden. In manchen Fällen lassen sich anhand der Beweise Zuordnungspläne oder ihre Berechnungsvorschrift explizit angeben.Zum Schluß werden die Aussagen an konkreten, dem Bereich der Wirtschaftswissenschaften entnommenen Beispielen erläutert.

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Summary LetX, Y be finite sets andZ X × Y, Z _x ={y¦(x,y) Z},Z _y ={x¦(x,y)Z}. A X (resp.B Y) is calledassignable if there is an injection: A Y (resp.: B X) with (x) Z _x (resp.(y) Z _y ), (A, B) with #A=#B > 0 anassigned pair if there is a bijection f:A B withf (x) Z _x B (resp.f ^–1(y) Z _y A). The bijectionf is called aplan forA andB.In this paper problems are discussed concerning the existence of optimal assignable sets and optimal assigned pairs ifX andY are totally ordered, additional constraints are also considered. In some cases the proofs give explicit constructions of plans. The results are illustrated by application to problems occurring in Operations Research.

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Diese Arbeit ist mit Unterstützung des Sonderforschungsbereiches 72 an der Universität Bonn entstanden.     

Characterization of the Reaction of Chloroacetaldehyde with Single and Double Stranded DNA

Chloroacetaldehyde reacts with viral M13mp18 single and double stranded DNA to form the highly fluorescent adducts, etheno-AMP and etheno-CMP.

Absorbance and fluorescence spectroscopy can be used to monitor and characterize these reactions. Both single and double stranded DNA showed increases in the absorbance following reaction with the aldehyde. The fluorescence also increased in these two groups and continued to rise with increasing time of incubation until a point of saturation was reached. The fluorescence of the double stranded moiety was considerably enhanced following reaction with the aldehyde while that of the single stranded population was not, making this method appropriate for the separation of small quantities of the two populations of DNA.