The Role of Radical Bridges in Polynuclear Single-Molecule Magnets

Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs.     

General coordinate invariance and conformal invariance in nonrelativistic physics: Unitary Fermi gas

We show that the Lagrangian for interacting nonrelativistic particles can be coupled to an external gauge field and metric tensor in a way that exhibits a nonrelativistic version of general coordinate invariance. We explore the consequences of this invariance on the example of the degenerate Fermi gas at infinite scattering length, where conformal invariance also plays an important role. We find the most general effective Lagrangian consistent with both general coordinate and conformal invariance to leading and next-to-leading orders in the momentum expansion. At the leading order the Lagrangian contains one phenomenological constant and reproduces the results of the Thomas-Fermi theory and superfluid hydrodynamics. At the next-to-leading order there are two additional constants. We express various physical quantities through these constants.     

Rheological and physical properties of aliphatic hyperbranched polyesters

The effects of the size (pseudo‐generation number) and nature of end groups on physical and rheological properties were investigated for a series of hyperbranched polyesters based on an ethoxylated pentaerythritol core and 2,2‐bis‐(hydroxymethyl)propionic acid repeat units. The observed linear dependence of the melt viscosity on the molar mass in the high pseudo‐generation‐number limit indicated that entanglement effects were substantially absent. Moreover, the marked influence of end capping of the end groups on the physical and rheological properties suggested that intermolecular interactions were dominated by contacts between the outer shells of the molecules, in which the end groups were assumed to be concentrated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1218–1225, 2004     

Electrospinning of ultrafine cellulose acetate fibers: Studies of a new solvent system and deacetylation of ultrafine cellulose acetate fibers

Electrospinning of cellulose acetate (CA) in a new solvent system and the deacetylation of the resulting ultrafine CA fibers were investigated. Ultrafine CA fibers (∼2.3 μm) were successfully prepared via electrospinning of CA in a mixed solvent of acetone/water at water contents of 10–15 wt %, and more ultrafine CA fibers (0.46 μm) were produced under basic pH conditions. Ultrafine cellulose fibers were regenerated from the homogeneous deacetylation of ultrafine CA fibers in KOH/ethanol. It was very rapid and completed within 20 min. The crystal structure, thermal properties, and morphology of ultrafine CA fibers were changed according to the degree of deacetylation, finally to those of pure cellulose, but the nonwoven fibrous mat structure was maintained. The activation energy for the deacetylation of ultrafine CA fibers was 10.3 kcal/mol. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 5–11, 2004     

On the Existence of Solutions to Vector Quasivariational Inequalities and Quasicomplementarity Problems with Applications Break to Traffic Network Equilibria

For vector quasivariational inequalities involving multifunctions in topological vector spaces, an existence result is obtained without a monotonicity assumption and with a convergence assumption weaker than semicontinuity. A new type of quasivariational inequality is proposed. Applications to quasicomplementarity problems and traffic network equilibria are considered. In particular, definitions of weak and strong Wardrop equilibria are introduced for the case of multivalued cost functions.     

Random oscillations in the Van der Pol system under the action of a broadband random process

We construct the second approximation for random oscillations described by the Van der Pol equation which are under the action of a broadband random process. Translated from Ukrainskii Matematicheskii Zhurnal, Vol. 50, No. 11, pp. 1517–1521, November, 1998.     

Surface and interfacial properties of PVDF/acrylic copolymer blends before and after UV exposure

Morphological and chemical properties of both the surface and interface of poly(vinylidene fluoride)/poly(methyl methacrylate)-co-poly(ethyl acrylate) (PVDF/PMMA-co-PEA) blend films have been investigated before and after the samples were exposed to ultraviolet (UV) irradiation using a xenon arc lamp at 50 °C and 9% relative humidity (RH) for 7 months. Surface and interfacial morphologies were studied by atomic force microscopy (AFM). Chemical composition information was obtained by confocal Raman microscopy, attenuated total reflection-FTIR spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and contact angle measurements. Results show an enrichment of the PVDF material at the air surface, while the acrylic copolymer enriches the interface. Blends having greater than 50% mass fraction of PVDF show little change in the surface morphology after UV exposure for 7 months. However, for a lower PVDF content, blends exhibit significant degradation of PMMA-co-PEA copolymer and a much rougher surface after UV exposure. Microstructural changes in the PVDF spherulites are also observed after UV degradation. It is found that the surface and interfacial morphologies are correlated with the chemical properties.     

Direct measurement of fluid velocity gradients at a wall by PIV image processing with stereo reconstruction

Velocity gradient is typically estimated in Particle Image Velocimetry (PIV) by differentiating a measured velocity field, which amplifies noise in the measured velocities. If gradients near a boundary are sought, such noise is usually greater than in bulk fluid, because of small tracer displacement, uncertainty in the effective positions of velocity vectors, intense deformation of tracer patterns, and laser reflection. We consider here a modified form of the Particle Image Distortion (PID) method todirectly calculate velocity gradients at a fixed wall, and refer it as “PIV/IG” (“Interface Gradiometry”). Results from synthetic 2D PIV images suggest our method achieves higher SNR and accuracy than velocity differentiation. Also, we have developed a procedure to reconstruct three-dimensional velocity gradient at a fixed wall the two non-zero components from PIV/IG data obtained in stereo views; these equations simplify considerably thanks to the no-slip condition. Experimental data from the bottom wall of turbulent open channel flow appear to suffer from a form of pixel locking. As with standard PIV, this underlines the importance of adequate tracer diameter in the images, sufficient seeding density, and of dynamic range of the camera sensor.