Block copolymer nanoparticles of controlled sizes via ring‐opening metathesis polymerization

This article describes the formation and characterization of self‐assembled nanoparticles of controlled sizes based on amphiphilic block copolymers synthesized by ring‐opening metathesis polymerization. We synthesized a novel hydrophobic derivative of norbornene; this monomer could be polymerized using Grubbs' catalyst [Cl₂Ru(CHPh)(PCy₃)₂] forming polymers of controlled molecular weight. We synthesized amphiphilic block copolymers of controlled composition and showed that they assemble into nanoparticles of controlled size. The nanoparticles were characterized using dynamic light scattering and transmission electron microscopy. Tuning the composition of the block copolymer enables the tuning of the diameters of the nanoparticles in the 30‐ to 80‐nm range. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3352–3359, 2004     

On the Long-Time Behavior of the Quantum Fokker-Planck Equation

We analyze the long-time behavior of transport equations for a class of dissipative quantum systems with Fokker-planck type diffusion operator, subject to confining potentials of harmonic oscillator type. We establish the existence and uniqueness of a non-equilibrium steady state for the corresponding dynamics. Further, using a (classical) convex Sobolev inequality, we prove an optimal exponential rate of decay towards this state and additionally give precise dispersion estimates in those cases, where no stationary state exists.     

Finitely additive integration and local integration with respect to upper integrals

Summary We study the integration theory for general integral metrics when restricted to upper integrals q, finding improvements in the relation between the classes of the q-integrable and the q_l-integrable functions. We give new results and notions which lead to the desirable characterizations of q-integrable functions as q_l-integrable f with q(|f|) < ∞, and of q_l-integrable functions via the integrability of their upper truncations, under natural conditions which are fulfilled in most finitely additive integration theories.     

Self-similar solutions and large time asymptotics for the dissipative quasi-geostrophic equation

We analyze the well-posedness of the initial value problem for the dissipative quasi-geostrophic equations in the subcritical case. Mild solutions are obtained in several spaces with the right homogeneity to allow the existence of self-similar solutions. While the only small self-similar solution in the strong L^p{\cal L}^{p} space is the null solution, infinitely many self-similar solutions do exist in weak- L^p{\cal L}^{p} spaces and in a recently introduced [7] space of tempered distributions. The asymptotic stability of solutions is obtained in both spaces, and as a consequence, a criterion of self-similarity persistence at large times is obtained.     

Decay Rates in Probability Metrics Towards Homogeneous Cooling States for the Inelastic Maxwell Model

We quantify the long-time behavior of solutions to the nonlinear Boltzmann equation for spatially uniform freely cooling inelastic Maxwell molecules by means of the contraction property of a suitable metric in the set of probability measures. Existence, uniqueness, and precise estimates of overpopulated high energy tails of the self-similar profile proved in ref. 9 are revisited and derived from this new Liapunov functional. For general initial conditions the solutions of the Boltzmann equation are then proved to converge with computable rate as t → ∞ to the self-similar solution in this distance, which metrizes the weak convergence of measures. Moreover, we can relate this Fourier distance to the Euclidean Wasserstein distance or Tanaka functional proving also its exponential convergence towards the homogeneous cooling states. The findings are relevant in the understanding of the conjecture formulated by Ernst and Brito in refs. 15, 16, and complement and improve recent studies on the same problem of Bobylev and Cercignani⁽⁹⁾ and Bobylev, Cercignani and one of the authors.⁽¹¹⁾     

Single-sex Classes: Female Physics Students State Their Case

Since the passage of Title IX in 1972, gender equity has been addressed through means that reflect inclusion and integration by gender. Recent Supreme Court decisions such as the one deeming the Virginia Military Institute's admission policies to be unlawfully discriminatory against women suggest a reinforced and perhaps narrowed interpretation of appropriate means for attaining gender equity in public schools. This case and others also suggest that publicly funded single-sex programs may be in jeopardy. This study examines data collected from a girls-only physics class in a public coeducational high school. Interview and observation data from this class, as well as from a coeducational physics class taught by the same teacher, illustrate that the girls in the single-sex class made substantial gains in both academic achievement and in perceptions of themselves as competent learners of science.     

Theoretical study of anion carriers based on trifluoroacetophenone

Model calculations on anion carrier ligands related to trifluoroacetophenone were carried out using the semiempirical AM 1 method in order to investigate the factors involved in such anion-ligand complexation. The reaction of halogen derivatives of acetophenone with various nucleophiles such as water, carbonic acid, and bicarbonate anion was studied. By this means, the effect of various structural changes, such as variation of the ring substituents and variation of the degree and type of halogen atom substitution, could be determined. It is shown that in terms of relative stability, fluorine derivatives are preferable to chlorine derivatives for the binding of water and carbonic acid. Monosubstitution of a methoxy group in the ortho position of the trifluoroacetophenone ring also brought about stability in the case of the hydration reaction. An electron-withdrawing ester group in the para position on the trifluoroacetophenone ring brings about stabilization also.     

Comparison of the thermal behavior of three cellulose fibers mercerized or submitted to solar degradation

Comparison of Lyocell, modal and viscose fibers was performed by means of differential scanning calorimetry, thermogravimetry and scanning electron microscopy. Thermal analysis was performed in air atmosphere. Samples were mercerized (21.3 g 100 mL-1) or submitted to solar radiation (seven months). Solar degraded samples presents a higher thermal stability and are initially less degraded. Furthermore, Lyocell fiber is the most stable under thermal degradation conditions. Heating produces a reduction of the fiber diameter (about 50%). This revised version was published online in July 2006 with corrections to the Cover Date.     

Suzuki cross-coupling of solid-supported chloropyrimidines with arylboronic acids

The utility of the Suzuki cross-coupling to synthesize biaryl compounds is expanded herein to include reactions of resin-supported chloropyrimidines with boronic acids. In particular, an efficient method is described for the synthesis of a library of biaryl compounds from solid-supported chloropyrimidines. The Suzuki reaction was performed in an inert atmosphere using Pd(2)(dba)(3)/P(t-Bu)(3) as catalyst, spray-dried KF as base, and THF as solvent. The reaction was allowed to proceed overnight at 50 degrees C. Upon cleavage with acid, a library of 4-(substituted amino)-6-arylpyrimidines was obtained in moderate yield and high purity.     

Isomers of C20: an energy profile III

Semiempirical calculations, at the PM3 level provided within the Winmopac v2.0 software package, are used to geometrically optimize and determine the absolute energies (heats of formation) of a variety of C(20) isomers that are predicted to exist in and around the ring and cage isomers. Using the optimized Cartesian coordinates for the ring and the cage isomers, a saddle-point calculation was performed. The resulting energy profile, consisting of a series of peaks and valleys, is used as a starting point for the identification and location of fifteen additional isomers of C(20) that are predicted to be energetically stable, both via geometry optimizations and force constant analysis. These additional isomers were subsequently determined to lie adjacent to one another on the potential surface and establish a step-wise transformation between the ring and the cage. Transition-state optimization of the Cartesian coordinates at the saddle point between adjacent isomers was performed to quantify the energy of the transition state. The step-wise process from one isomer to another, which extends out over the three-dimensional surface, is predicted to require approximately 15% less energy than that of the direct, two-dimensional transformation predicted in the bowl-cage profile. However, the net atomic rearrangement for the step-wise process is about four times greater than that of the direct process. Although less in energy, the amount of atomic rearrangement in the step-wise process would make the occurrence of such a route prohibitive. Utilizing the direct distance separating the three primary isomers (ring, bowl, cage), the method of triangulation is performed to quantitatively position other C(20) structures on the potential surface, relative to the ring, bowl, and cage isomers.