Stereospecific solid-state NaBH4-promoted reduction of 1-methylpentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-dione

NaBH₄ reduction of a cage dione proceeds in a stereospecific fashion to give theendo,endo-diol. This reactivity is related to the crystal structure.     

Time-resolved synchrotron X-ray study of crystalline phase transition in poly(aryl ether ketone ketone) containing alternated terephthalic/isophthalic moieties

Unique crystallization and melting behavior in poly(aryl ether ketone ketone) containing alternated terephthalic and isophthalic moieties were studied by time-resolved synchrotron x-ray methods. Recently, this material has been shown to exhibit three polymorphs (forms I, II, and III). In this work, we further investigated their distinctive thermal properties and found that form I is the dominating and the most thermally stable phase while form II is favored by fast nucleation conditions and is the least stable phase. On the other hand, form III represents a minor intermediate phase that usually coexists with form I and can be transferred from form II and to form I. Structural and morphological changes in form I have been followed by simultaneous wide-angle x-ray diffraction (WAXD)/small-angle x-ray scattering (SAXS) measurements during cold- or melt-crystallization and subsequent melting. In all cases, a larger dimensional change was found in the crystallographic a-axis than the b-axis during heating and cooling. This may be due to the greater lateral stress variation with respect to temperature along the a direction of the primary lamellae which is induced by either the formation of secondary lamellae or the preferential chain-folding direction in poly(aryl ether ketone ketone)s. During the phase transitions of form II ← III in the cold-crystallized specimen and form III ← I in the melt-crystallized samples, lamellar variables (long period, lamellar thickness, and invariant) obtained from SAXS remain almost constant. This indicates that the density distribution in the long spacing is independent of the melting in form II or III. For melt-crystallization, the corresponding changes in unit-cell dimensions and lamellar morphology during the annealing-induced low endotherm are most consistent with the argument that these changes are due to the melting of thin lamellar population. © 1995 John Wiley & Sons, Inc.     

The Jacobian and the Ginzburg-Landau energy

We study the Ginzburg-Landau functional for , where U is a bounded, open subset of . We show that if a sequence of functions satisfies , then their Jacobians are precompact in the dual of for every . Moreover, any limiting measure is a sum of point masses. We also characterize the -limit of the functionals , in terms of the function space B2V introduced by the authors in [16,17]: we show that I(u) is finite if and only if , and for is equal to the total variation of the Jacobian measure Ju. When the domain U has dimension greater than two, we prove if then the Jacobians are again precompact in for all , and moreover we show that any limiting measure must be integer multiplicity rectifiable. We also show that the total variation of the Jacobian measure is a lower bound for the limit of the Ginzburg-Landau functional. Received: 15 December 2000 / Accepted: 23 January 2001 / Published online: 25 June 2001     

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.     

Directed metalation/ligand coupling approach to the enantioselective synthesis of 1,1′-binaphthyls

Introduction of a 2-isopropoxycarbonyl or 2-NN-dimethylcarbamoyl group into homochiral 1-p-tolyl- or 1-t-butyl-sulfinylnaphthalenes, via directed metalation reaction, followed by ligand coupling reaction with 1-naphthylmagnesium bromide, furnished atropisomeric 1,1′-binaphthyls in 82–95% enantiomeric excess (e.e.).     

Miscible blends of modified poly(aryl ether ketones) with aromatic polyimides

The phase behavior of binary blends of poly(ether ether ketone) (PEEK), sulfonated PEEK, and sulfamidated PEEK with aromatic polyimides is reported. PEEK was determined to be immiscible with a poly(amide imide) (TORLON 4000T). Blends of sulfonated and sulfamidated PEEK with this poly(amide imide), however, are reported here to be miscible in all proportions. Blends of sulfonated PEEK and a poly(ether imide) (ULTEM 1000) are also reported to be miscible. Spectroscopic investigations of the intermolecular interactions suggest that formation of electron donoracceptor complexes between the sulfonated/sulfamidated phenylene rings of the PEEKs and the n-phenylene units of the polyimides are responsible for this miscibility. © 1993 John Wiley & Sons, Inc.     

Identifying sets of key players in a social network

A procedure is described for finding sets of key players in a social network. A key assumption is that the optimal selection of key players depends on what they are needed for. Accordingly, two generic goals are articulated, called KPP-POS and KPP-NEG. KPP-POS is defined as the identification of key players for the purpose of optimally diffusing something through the network by using the key players as seeds. KPP-NEG is defined as the identification of key players for the purpose of disrupting or fragmenting the network by removing the key nodes. It is found that off-the-shelf centrality measures are not optimal for solving either generic problem, and therefore new measures are presented. Stephen P. Borgatti is Professor of Organization Studies at the Carroll School of Management, Boston College. His research is focused on social networks, social cognition and knowledge management. He is also interested in the application of social network analysis to the solution of managerial problems.     

Control of the block copolymer morphology in templated epoxy thermosets

It has been found that by the addition of low concentrations of an amphiphilic block copolymer to an epoxy resin, novel disordered morphologies can be formed and preserved through curing. This article will focus on characterizing the influence of the block copolymer and casting solvent on the templated morphology achieved in the thermoset sample. The ultimate goal of this work is to determine the parameters that would control the microphase morphology produced. Epoxy resins blended with a series of amphiphilic block copolymers based on hydrogenated polyisoprene (polyethylene-alt-propylene or PEP) and polyethylene oxide (PEO), specifically, were investigated. In this article, the cure-induced order–order phase transition from the spherical to wormlike micelle morphology will also be discussed. It is proposed that the formation of the wormlike micelle structure from the spherical micelle structure is similar to the phase transition behavior that occurs in dilute block copolymer solutions as a function of the influence of the solvent on micelle morphology. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3338–3348, 2007