Identifying aspirin polymorphs from combined DFT-based crystal structure prediction and solid-state NMR

A combined experimental and computational approach was used to distinguish between different polymorphs of the pharmaceutical drug aspirin. This method involves the use of ab initio random structure searching (AIRSS), a density functional theory (DFT)-based crystal structure prediction method for the high-accuracy prediction of polymorphic structures, with DFT calculations of nuclear magnetic resonance (NMR) parameters and solid-state NMR experiments at natural abundance. AIRSS was used to predict the crystal structures of form-I and form-II of aspirin. The root-mean-square deviation between experimental and calculated ¹H chemical shifts was used to identify form-I as the polymorph present in the experimental sample, the selection being successful despite the large similarities between the molecular environments in the crystals of the two polymorphs.     

Physicochemical properties and bio-interfacial interactions of surface modified PDLLA-PAMAM linear dendritic block copolymers

Here, we demonstrate the applicability of self-assembling linear-dendritic block copolymers (LDBCs) and their nanoaggregates possessing varied surfaces as therapeutic nanocarriers. These LDBCs are comprised of a hydrophobic, linear polyester chemically coupled to a hydrophilic dendron polyamidoamine (PAMAM)—the latter of which acts as the surface of the self-assembled nanoaggregate in aqueous media. To better understand how surface charge density affects the overall operability of these nanomaterials, we modified the nanoaggregate surface to yield cationic (NH₃⁺), neutral (OH), and anionic (COO⁻) surfaces. The effect of these modifications on the physicochemical properties (i.e., size, morphology, and surface charge density), colloidal stability, and cellular uptake mechanism of the polymeric nanocarrier were investigated. This comparative study demonstrates the viability of nanoaggregates formed from PDLLA-PAMAM LDBCs to serve as nanocarriers for applications in drug delivery.     

A high‐resolution scheme for low Mach number flows

A method for computing low Mach number flows using high‐resolution interpolation and difference formulas, within the framework of the Marker and Cell (MAC) scheme, is presented. This increases the range of wavenumbers that are properly resolved on a given grid so that a sufficiently accurate solution can be obtained without extensive grid refinement. Results using this scheme are presented for three problems. The first is the two‐dimensional Taylor–Green flow which has a closed form solution. The second is the evolution of perturbations to constant‐density, plane channel flow for which linear stability solutions are known. The third is the oscillatory instability of a variable density plane jet. In this case, unless the sharp density gradients are resolved, the calculations would breakdown. Under‐resolved calculations gave solutions containing vortices which grew in place rather than being convected out. With the present scheme, regular oscillations of this instability were obtained and vortices were convected out regularly. Stable computations were possible over a wider range of sensitive parameters such as density ratio and co‐flow velocity ratio. Copyright © 2004 John Wiley Sons, Ltd.     

Orders of Indescribable Sets

We extract some properties of Mahlo’s operation and show that some other very natural operations share these properties. The weakly compact sets form a similar hierarchy as the stationary sets. The height of this hierarchy is a large cardinal property connected to saturation properties of the weakly compact ideal.     

Spin-transfer switching in MgO magnetic tunnel junction nanostructures

Spin-transfer driven switching was observed in MgO based magnetic tunnelling junctions (MTJ) with tunnelling magnetoresistance ratio of up to 160% and the average intrinsic switching current density (J_c0) down to 2 MA/cm², which are the best known results reported in spin-transfer switched MTJ nanostructures. Based on a comparison of results both from MgO and AlO_x MTJs, further switching current decrease via MgO dual structures with two pinned layers is discussed.     

Deacetalisation-bicyclisation routes to novel polycyclic heterocycles using stannous chloride dihydrate

The stannous chloride dihydrate-mediated deprotection-bicyclisation of a range of amides possessing a pendant acetal group is reported. These mild reaction conditions have been used to prepare a number of ring-fused heterocyclic compounds, some in enantiomerically pure form, which should be of interest both in their own right and as building blocks for the production of more complex target molecules.     

Property (<Emphasis Type="Italic">T</Emphasis>) and rigidity for actions on Banach spaces

We study property (T) and the fixed-point property for actions on L ^p and other Banach spaces. We show that property (T) holds when L ² is replaced by L ^p (and even a subspace/quotient of L ^p ), and that in fact it is independent of 1≤p<∞. We show that the fixed-point property for L ^p follows from property (T) when 1<p< 2+ε. For simple Lie groups and their lattices, we prove that the fixed-point property for L ^p holds for any 1< p<∞ if and only if the rank is at least two. Finally, we obtain a superrigidity result for actions of irreducible lattices in products of general groups on superreflexive spaces. Bader partially supported by ISF grant 100146; Furman partially supported by NSF grants DMS-0094245 and DMS-0604611; Gelander partially supported by NSF grant DMS-0404557 and BSF grant 2004010; Monod partially supported by FNS (CH) and NSF (US).     

Viscoelastic properties of nanostructured natural rubber/polystyrene interpenetrating polymer networks

The effects of the blend ratio and initiating system on the viscoelastic properties of nanostructured natural rubber/polystyrene‐based interpenetrating polymer networks (IPNs) were investigated in the temperature range of ?80 to 150 °C. The studies were carried out at different frequencies (100, 50, 10, 1, and 0.1 Hz), and their effects on the damping and storage and loss moduli were analyzed. In all cases, tan δ and the storage and loss moduli showed two distinct transitions corresponding to natural rubber and polystyrene phases, which indicated that the system was not miscible on the molecular level. However, a slight inward shift was observed in the IPNs, with respect to the glass‐transition temperatures (T_g's) of the virgin polymers, showing a certain degree of miscibility or intermixing between the two phases. When the frequency increased from 0.1 to 100 Hz, the T_g values showed a positive shift in all cases. In a comparison of the three initiating systems (dicumyl peroxide, benzoyl peroxide, and azobisisobutyronitrile), the dicumyl peroxide system showed the highest modulus. The morphology of the IPNs was analyzed with transmission electron microscopy. The micrographs indicated that the system was nanostructured. An attempt was made to relate the viscoelastic behavior to the morphology of the IPNs. Various models, such as the series, parallel, Halpin–Tsai, Kerner, Coran, Takayanagi, and Davies models, were used to model the viscoelastic data. The area under the linear loss modulus curve was larger than that obtained by group contribution analysis; this showed that the damping was influenced by the phase morphology, dual‐phase continuity, and crosslinking of the phases. Finally, the homogeneity of the system was further evaluated with Cole–Cole analysis. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1680–1696, 2003     

A Genetic Algorithm for Solving a Capacitated p-Median Problem

Facility-location problems have several applications, such as telecommunications, industrial transportation and distribution. One of the most well-known facility-location problems is the p-median problem. This work addresses an application of the capacitated p-median problem to a real-world problem. We propose a genetic algorithm (GA) to solve the capacitated p-median problem. The proposed GA uses not only conventional genetic operators, but also a new heuristic “hypermutation” operator suggested in this work. The proposed GA is compared with a tabu search algorithm.