Thermodynamic investigations on shape selective separation behaviors of poly(4-vinylpyridine)-grafted silica for polycyclic aromatic hydrocarbons in both normal-phase and reversed-phase high-performance liquid chromatography

With the successful implementation of poly(4-vinylpyridine)-grafted silica prepared by grafting-from approach (GF-VP(n)) as a stationary phase for the separation of polycyclic aromatic hydrocarbons (PAHs) in normal-phase HPLC, this paper describes the chromatographic retention behaviors of PAHs with GF-VP(n) in reversed-phase HPLC. Significantly higher retention factor along with enhanced shape selectivity were observed with GF-VP(n). Thermodynamic study on the retention behaviors of PAHs with GF-VP(n) in normal-phase and reversed-phase HPLC revealed that retention of PAHs was exothermic in both phases. Furthermore, higher entropic contribution was observed in reversed-phase HPLC compared to normal-phase HPLC.     

Unexpected one-pot synthesis of new polycyclic coumarin[4,3-c]pyridine derivatives via a tandem hetero-Diels-Alder and 1,3-dipolar cycloaddition reaction

O-Methyl-4-coumarincarbaldehyde oxime reacted as an azadiene with electron-deficient and electron-rich dienophiles to give, via one-step hetero-Diels-Alder cycloaddition reactions, the corresponding 5H-coumarin[4,3-c]pyridin-5-ones. When excess of the dienophile was used, fused azatetracyclo derivatives were also formed via a tandem Diels-Alder and 1,3-dipolar cycloaddition reaction of the dienophile to an azomethine ylide formed by the intermediate 2,3-dihydro-5H-coumarin[4,3-c]pyridine-5-one. The regio- and stereoselectivities of the new compounds correspond well with spectroscopic (2D NMR) and theoretical data. A possible mechanistic scheme is provided.     

Dynamical Instability Causes the Demise of a Supercooled Tetrahedral Liquid

We investigate the relaxation mechanism of a supercooled tetrahedral liquid at its limit of stability using isothermal isobaric (NPT) Monte Carlo simulations. In similarity with systems which are far from equilibrium but near the onset of jamming (O’Hern et al. in Phys Rev Lett 93:165702, 2004), we find that the relaxation is characterized by two time-scales: the decay of long-wavelength (slow) fluctuations of potential energy is controlled by the slope \([\partial (G/N)/\partial \phi ]\) of the Gibbs free energy (G) at a unique value of per particle potential energy \(\phi = \phi _{{\tiny mid}}\). The short-wavelength (fast) fluctuations are controlled by the bath temperature T. The relaxation of the supercooled liquid is initiated with a dynamical crossover after which the potential energy fluctuations are biased towards values progressively lesser than \(\phi _{{\tiny mid}}\). The dynamical crossover leads to the change of time-scale, i.e., the decay of long-wavelength potential energy fluctuations (intermediate stage of relaxation). Because of the condition [\(\partial ^2 (G/N)/\partial \phi ^2 = 0\)] at \(\phi = \phi _{{\tiny mid}}\), the slope \([\partial (G/N)/\partial \phi ]\) has a unique value and governs the intermediate stage of relaxation, which ends just after the crossover. In the subsequent stage, there is a relatively rapid crystallization due to lack of long-wavelength fluctuations and the instability at \(\phi _{{\tiny mid}}\), i.e., the condition that G decreases as configurations with potential energies lower than \(\phi _{{\tiny mid}}\) are accessed. The dynamical crossover point and the associated change in the time-scale of fluctuations is found to be consistent with the previous studies.     

Solitons in One‐Dimensional Lattices with a Flat Band

We investigate the spectral properties of a quasi‐one‐dimensional lattice in two possible dimerisation configurations. Both configurations are characterised by the same lattice topology and the identical spectra containing a flat band at zero energy. We find that, one of the dimerised configuration has similar symmetry to a one‐dimensional chain proposed by Su‐Schrieffer‐Heeger for studying solitons in conjugated polymers. Whereas, the other dimerised configuration only shows non‐trivial topological properties in the presence of chiral‐symmetry breaking adiabatic pumping.     

A Geometrically Exact Incremental Variational Formulation for Phase Field Models in Micromagnetics

Magnetic materials have been finding increasingly wide areas of application. We focus here on the continuum modeling of such materials and present an incremental variational principle for a dissipative micro-magneto-elastic model. It describes the quasi-static evolution of both magnetically as well as mechanically driven magnetic domains, which also incorporates the surrounding free space. Furthermore, the algorithmic preservation of the geometrical nature of the variables is an important challenge from the numerical perspective and to this end we present a novel FE discretization whereby the geometric property of the magnetization director is pointwise exactly preserved by nonlinear rotational updates at the nodes. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Rapid and Direct Conversion of Graphite Crystals into High‐Yielding,Good‐Quality Graphene by Supercritical Fluid Exfoliation

Graphene has attracted a great deal of attention in recent years due to its unusual electronic, mechanical, and thermal properties. Exploiting graphene properties in a variety of applications requires a chemical approach for the large‐scale production of high‐quality, processable graphene sheets (GS), which has remained an unanswered challenge. Herein, we report a rapid one‐pot supercritical fluid (SCF) exfoliation process for the production of high‐quality, large‐scale, and processable graphene for technological applications. Direct high‐yield conversion of graphite crystals to GS is possible under SCF conditions because of the high diffusivity and solvating power of SCFs, such as ethanol, N‐methyl‐pyrrolidone (NMP), and DMF. For the first time, we report a one‐pot direct conversion of graphite crystals to a high yield of graphene sheets in which about 90–95 % of the exfoliated sheets are <8 layers with approximately 6–10 % monolayers and the remaining 5–10 % are ≥10 layers.     

Modification of microstructure of the surface and the bulk in ion-irradiated membrane studied using positron annihilation spectroscopy

The effect of ion irradiation and etching on the microstructure of polyethyleneterephthalate (PET) membrane has been studied using positron annihilation spectroscopy. PET membrane of 25 μm thickness was irradiated by 100 MeV ³⁵Cl beam (7×10⁷ ions/cm²) and then etched with NaOH for 45 min. The modification in the microstructure at the surface of the membrane was probed by depth-dependent Doppler-broadened S-parameter and positronium 3γ–2γ annihilation ratio using a slow positron beam, while the free volume properties in the bulk of the membrane were studied using the conventional positron lifetime technique. Positron annihilation parameters were found to be very sensitive to the microstructural changes occurring in the polymer at such a low fluence. It was observed that on ion-irradiation, the surface of the membrane is modified in a different way than the bulk. While the ion-irradiation produces large fraction of excess free volumes at the surface of the membrane due to chain scission, the free volumes are reduced in the bulk of the membrane due to cross-linking. FTIR and XRD measurements were also carried out to investigate the changes occurring in the chemical structure and crystallinity of the polymer samples on ion-irradiation and etching.     

A Stochastic Perturbation of Inviscid Flows

We prove existence and regularity of the stochastic flows used in the stochastic Lagrangian formulation of the incompressible Navier-Stokes equations (with periodic boundary conditions), and consequently obtain a C ^k,α local existence result for the Navier-Stokes equations. Our estimates are independent of viscosity, allowing us to consider the inviscid limit. We show that as ν → 0, solutions of the stochastic Lagrangian formulation (with periodic boundary conditions) converge to solutions of the Euler equations at the rate of .     

Bs-Bs mixing in grand unified models

We study Bs-Bs mixing in supersymmetry grand unified SO(10), SU(5) models where the mixings among the second and third generation squarks arise due to the existence of flavor violating sources in the Dirac and Majorana couplings which are responsible for neutrino mixings. We find that when the branching ratio of tau-->mugamma decay is enhanced to be around the current experimental bound, Bs-Bs mixing may also contain large contribution from supersymmetry in the SO(10) boundary condition. Consequently, the phase of Bs-Bs mixing is large (especially for small tanbeta and large scalar mass m0) and can be tested by measuring CP asymmetries of Bs decay modes.