A comparison of spin relaxation and local motion between symmetrically and asymmetrically ring-substituted bisphenol units in dissolved polycarbonates

Carbon-13 and proton spin-lattice relaxation times were measured at two field strengths on solutions 10% by weight of two polycarbonates in C₂D₂Cl₄ from ?20 to +120°C. The first polycarbonate is an asymmetrically substituted form with one chlorine on one of the two phenylene aromatic rings of the bisphenol unit, whereas the second polycarbonate is symmetrically substituted with two chlorines on each of the two rings. The nuclear spin relaxation data are interpreted in terms of several local motions likely in these polymers. Segmental motion was described by the Hall–Helfand correlation function. Segmental motion in the monosubstituted polycarbonate is somewhat slower than in unsubstituted polycarbonate, whereas segmental motion in the tetrasubstituted polycarbonate is considerably slower. Phenylene ring rotation is observed in unsubstituted polycarbonate and in the monosubstituted polycarbonate above 40°C. Below 40°C in the monosubstituted species, and at all temperatures in the tetrasubstituted species, ring rotation is replaced by ring libration as the predominant motion contributing to spin lattice relaxation. In addition, the rotational motion of the two types of rings in the asymmetric monosubstituted form are very similar although not identical. The substituted ring is slightly less mobile than the rings of unsubstituted polycarbonate. This indicates a strong coupling of ring motion, although the coupling leads to less than synchronous motion. Methyl group rotation is present in both polymers and is little affected by the various structural modifications.     

Access to Paullone Analogues by Intramolecular Heck Reaction

The syntheses of paullone ( 1a ) and three paullone derivatives, including a sulfur analogue ( 2a ), a tricyclic derivative ( 2b ), and a ring‐enlarged variant ( 2c ), are described, Pd‐catalyzed intramolecular Heck reaction being the key step. The kinase‐inhibitory properties of the novel paullone analogues were investigated.     

A selective synthesis of 4‐bromo‐2‐furancarboxaldehyde and its pinacolborane derivative

A selective synthesis of ethylene acetal of 4‐bromo‐2‐furancarboxaldehyde ( 4 ) and its pinacolborane derivative ( 5 ) is described. The synthesis was carried out using 2‐furancarboxaldehyde ( 1 ) that was bromi‐nated to 4,5‐dibromo‐2‐furancarboxaldehyde ( 2 ) in an emulsion of aluminum chloride and methylene chloride. The product was isolated, protected as ethylene acetal, and selectively debrominated to the ethylene acetal of 4‐bromo‐2‐furancarboxaldehyde ( 4 ) in one step. This moiety was reacted with pinacolborane to give a reactive reagent of Suzuki coupling.     

Femtosecond dynamics of secondary radiation formation from quantum well excitons

The time-resolved secondary emission of resonantly created excitons in GaAs quantum wells is studied using femtosecond up-conversion spectroscopy. The behaviour of the rise and decay of the secondary emission and reflectivity in quantum wells is strongly dependent upon the disorder at the interfaces, the exciton density and the temperature. In the case of low densities and temperatures the emission is independent of the exciton density and rises quadratically in time, in excellent agreement with recent theory for Rayleigh scattering from two-dimensional excitons subjected to disorder. These rise times are compared directly with times measured by time-integrated four-wave mixing (FWM). The comparison of the dynamics displayed in time-resolved secondary radiation and time-integrated FWM provide a clear understanding of the coherence properties of QW excitons in the first few picoseconds after excitation. High-contrast oscillations that are due to quantum beats between the heavy- and light-hole 1s-states are seen. The visibility decay at very low densities is long ps and is related to the action of potential fluctuations on the scattering of heavy-hole and light-hole excitons.     

On the use of the Galerkin method for 3D numerical modelling of the general circulation: the South Atlantic eperiment

A linear three‐dimensional hydrodynamical numerical model, with the application of the Galerkin Method for the vertical dependence, is here presented. The spherical coordinate system is used, in order to allow large‐scale simulations. The equations and mathematical development of the model are shown in detail, together with the boundary and initial conditions, and the sequence of equations' solution. The model is applied to the South Atlantic Ocean, for estimating typical seasonal circulations, and the results are summarized in maps of currents at surface and 1000 m depth, and in transport values of the Brazil Current between 30°S and 40°S. Copyright © 2002 John Wiley & Sons, Ltd.     

Equivariant quantization on quotients of simple Lie groups by reductive subgroups of maximal rank

We consider a class of homogeneous manifolds including all semisimple coadjoint orbits. We describe manifolds of that class admitting deformation quantizations equivariant under the action ofG and the corresponding quantum group. We also classify Poisson brackets relating to such quantizations. Presented at the 11th Colloquium “Quantum Groups and Integrable Systems”, Prague, 20–22 June 2002.     

Flexural rigidity of a liquid surface

The energy of a mass of liquid is evaluated asymptotically in powers of the range of the intermolecular potential divided by a typical dimension of the liquid. The leading term is the internal energy, proportional to the liquid volume. The second term is the energy of surface tension, proportional to the area of the liquid surface. The third term is proportional to an integral over this surface of the square of the mean curvature of the surface minus one-third of its Gaussian curvature. This new term has exactly the form of the bending energy of a thin elastic plate. Comparing it with the bending energy yields expressions for the flexural rigidity and the Poisson ratio of the liquid surface. This flexural rigidity of the surface leads to new terms in the equation of equilibrium of the liquid surface, in addition to the usual surface tension terms.     

Equivalence of Toda-Hopf invariants

In this paper it is shown that various existing constructions of ‘Hopf invariant’ are equivalent to each other. In consequence one gets that the oneToda-Hopf invariant enjoys various properties. Both authors supported in part by the NSF.     

Crutch or Catalyst: Teachers' Beliefs and Practices Regarding Calculator use in Mathematics Instruction

This study investigated K‐12 teachers' beliefs and reported teaching practices regarding calculator use in their mathematics instruction. A survey was administered to more than 800 elementary, middle and high school teachers in a large metropolitan area to address the following questions: (a) what are the beliefs and practices of mathematics teachers regarding calculator use? and (b) how do these beliefs and practices differ among teachers in three grade bands? Factor analysis of 20 Likert scale items revealed four factors that accounted for 54% of the variance in the ratings. These factors were named Catalyst Beliefs, Teacher Knowledge, Crutch Beliefs, and Teacher Practices. Compared to elementary teachers, high school teachers were significantly higher in their perception of calculator use as a catalyst in mathematics instruction. However, the higher the grade level of the teacher, the higher the mean score on the perception that calculator use may be a way of getting answers without understanding mathematical processes. The mean scores for teachers in all three grade bands indicated agreement that students can learn mathematics through calculator use and using calculators in instruction will lead to better student understanding and make mathematics more interesting. The survey results shed light on teachers' self reported beliefs, knowledge, and practices in regard to consistency with elements of the National Council of Teachers of Mathematics Principles and Standards for School Mathematics (2000) technology principle and the NCTM use of technology position paper (2003). This study extended previous research on teachers' beliefs regarding calculator use in classrooms by examining and comparing the results of teacher surveys across three grade bands.