Rhenium oxo complexes of a chelating diyne ligand. Synthesis and study of the kinetics of protonation

A series of oxo complexes, Re(O)X(diyne) (X = I, Me, Et), have been prepared from 2,7-nonadiyne and Re(O)I(3)(PPh(3))(2). Addition of B(C(6)F(5))(3) to Re(O)I(2,7-nonadiyne) (5) results in coordination of the oxo ligand to the boron. The protonation of Re(O)(X)(2-butyne)(2) and Re(O)(X)(2,7-nonadiyne)(2) with a variety of acids has been examined. With 5 and HBF(4)/Et(2)O, the ultimate product was [Re(CH(3)CN)(3)(I)(2,7-nonadiyne)](2+) (7). The conversion of 5 to 7 changes the conformation of the diyne ligand from a "chair" to a "boat" and shifts its propargylic protons considerably downfield in the (1)H NMR. The kinetics of the protonation of Re(O)I(2,7-nonadiyne) (5) by CF(3)SO(3)H in CH(3)CN have been monitored by visible spectroscopy, in a stopped-flow apparatus, and by low temperature (1)H NMR. Two second-order rate constants, presumably successive protonations, were observed in the stopped-flow, k(1) = 11.9 M(-)(1) s(-)(1) and k(2) = 3.8 M(-)(1) s(-)(1). Low temperature (1)H NMR spectroscopy indicated that the resulting solution contained a mixture of two doubly protonated intermediates X and Y, each of which slowly formed the product 7 via an acid-independent process.     

Synthesis and X-ray crystal structure of a five-coordinate d8 complex: [Pt((Me2NN)(PMe2)(PPh2))2Cl][Cl]

C₃₆H₅₀Cl₂N₆P₄Pt·2 MeCN,2, triclinic P¯1,a=11.720(2),b=12.153(2),c=16.196(3),=76.74(1),=84.90(1),=88.13(1),Z=2,R=0.051,Rw=0.051. Interaction of Me₂NN(PMe₂)(PPh₂),1, with Pt(COD)Cl₂, COD=1,5 cyclooctadiene, in THF yields the title compound,2, in quantitative yield. Compound2 was characterized spectroscopically as well as via an X-ray diffraction study.     

Behavioral Characteristics of Children With Vocal Fold Nodules

Vocal fold nodules (VNs) in children are benign, bilateral lesions occurring on the mid-membranous vocal folds. Repetitive phonotraumatic behavior leading to chronic vocal fold injury and repair is frequently cited as the primary etiology; however, specific behavioral characteristics may predispose some children toward intense and potentially phonotraumatic voice use, thereby contributing secondarily to VN formation. The purpose of this case-control study was to determine whether children with VNs possess unique behavioral characteristics that may predispose them to VN development. Parents of 26 children with VNs (20 boys, 6 girls, mean age=7.2 years, SD=2.5 years), and 29 vocally normal, medical controls (22 boys, 7 girls, mean age=6.7 years, SD=2.4), completed the Childhood Behavior Checklist (CBCL/4-18, Achenbach, 1991), a standardized parent-rating scale with strong psychometric properties. No significant between-group differences were detected on any of the behavior problem syndrome scales. Group differences approached significance for the individual items "screams a lot" and "teases a lot" (VN group > Controls). The VN group scored significantly higher than the controls on the "Social Scale," a compilation of positive ratings of the child's social activity, frequency of contacts with friends, behavior with others, and behavior by themselves. Observed outcomes were consistent with previous characterizations of children with VN as "outgoing" or "extroverted" but were not consistent with other claims that this population may be at risk for "aggressive," "attentional," or "impulsive" behavior problems.     

Economy of effort in different speaking conditions. I. A preliminary study of intersubject differences and modeling issues

This study explores the hypothesis that clear speech is produced with greater "articulatory effort" than normal speech. Kinematic and acoustic data were gathered from seven subjects as they pronounced multiple repetitions of utterances in different speaking conditions, including normal, fast, clear, and slow. Data were analyzed within a framework based on a dynamical model of single-axis frictionless movements, in which peak movement speed is used as a relative measure of articulatory effort (Nelson, 1983). There were differences in peak movement speed, distance and duration among the conditions and among the speakers. Three speakers produced the "clear" condition utterances with movements that had larger distances and durations than those for "normal" utterances. Analyses of the data within a peak speed, distance, duration "performance space" indicated increased effort (reflected in greater peak speed) in the clear condition for the three speakers, in support of the hypothesis. The remaining four speakers used other combinations of parameters to produce the clear condition. The validity of the simple dynamical model for analyzing these complex movements was considered by examining several additional parameters. Some movement characteristics differed from those required for the model-based analysis, presumably because the articulators are complicated structurally and interact with one another mechanically. More refined tests of control strategies for different speaking styles will depend on future analyses of more complicated movements with more realistic models.     

Validation of subgradient optimization

The “relaxation” procedure introduced by Held and Karp for approximately solving a large linear programming problem related to the traveling-salesman problem is refined and studied experimentally on several classes of specially structured large-scale linear programming problems, and results on the use of the procedure for obtaining exact solutions are given. It is concluded that the method shows promise for large-scale linear programming