Path to achieving molecular dispersion in a dense reactive mixture

A uniform dispersion of reactants is necessary to achieve a complete reaction involving multicomponents. In this study, we have examined the role of plasticizer in the reaction of two seemingly unlikely reactants: a highly crystalline hexamethylenetetramine (HMTA) and a strongly hydrogen bonded phenol formaldehyde resin. By combining information from NMR, infrared spectroscopy and differential scanning calorimetry, we were able to determine the role of specific intermolecular interactions necessary for the plasticizer to dissolve the highly crystalline HMTA and to plasticize the phenol formaldehyde resin in this crosslinking reaction. The presence of the plasticizer increased the segmental mobility, disrupted the hydrogen bonded matrix, and freed the hydroxyl units, which further increased the solubility of the HMTA. Both the endothermic and exothermic transitions are accounted for in the calorimetric data obtained. For the first time, it is possible to obtain the effective molar ratio of each component needed to complete the crosslinking reaction efficiently. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1519–1526     

Bounds for rectilinear crossing numbers

A rectilinear drawing of a graph is one where each edge is drawn as a straight-line segment, and the rectilinear crossing number of a graph is the minimum number of crossings over all rectilinear drawings. We describe, for every integer k ≥ 4, a class of graphs of crossing number k, but unbounded rectilinear crossing number. This is best possible since the rectilinear crossing number is equal to the crossing number whenever the latter is at most 3. Further, if we consider drawings where each edge is drawn as a polygonal line segment with at most one break point, then the resulting crossing number is at most quadratic in the regular crossing number. © 1993 John Wiley & Sons, Inc.     

Carathéodory's method for a class of dynamic games

The method of equivalent variational methods, originally due to Carathéodory for free problems in the calculus of variations is extended to investigate feedback Nash equilibria for a class of n-person differential games. Both the finite-horizon and infinite-horizon cases are considered. Examples are given to illustrate the presented results.     

On the role of the interface charge in non-ideal metal–semiconductor contacts

The bias dependent interface charge is considered as the origin of the observed non-ideality in current–voltage and capacitance–voltage characteristics. Using the simplified model for the interface electronic structure based on defects interacting with the continuum of interface states, the microscopic origin of empirical parameters describing the bias dependent interface charge function is investigated. The results show that in non-ideal metal–semiconductor contacts the interface charge function depends on the interface disorder parameter, density of defects, barrier pinning parameter and the effective gap center. The theoretical predictions are tested against several sets of published experimental data on bias dependent ideality factor and excess capacitance in various metal–semicoductor systems.     

The efficacy of tilted axial MRI of the CNS

The angle between the straight axial plane and the orbito-meatal line was measured in 156 consecutive magnetic resonance examinations. Inconsistent head positioning caused this angle to vary by as much as 44 degrees. Careful positioning of the patient by the technologist can minimize this variability, leading potentially to improved image interpretation. To assess the merit of a standardized orientation for MR examinations of the head, straight axial and tilted axial MR scans were compared in 34 patients. The tilted images were obtained parallel to the orbito-meatal line and were found to be superior for visualization of the cerebellum. When correlative x-ray CTs are available or when an abnormality in the posterior fossa is suspected, tilted axial MR scans should be employed.     

The canalicular structure of compact bone in the rat at different ages.

Osteocytes communicate through a canalicular system that maintains the vitality and mineral metabolism of bone. Casting the vascular canals and canaliculi of compact bone with methacrylate and viewing them with scanning electron microscopy shows their extent and relationships. Confocal laser scanning microscopy of the same specimen before corrosion establishes the degree of calcification of the different tissue components. These methods were used to compare basal with alveolar compact bone in the rat mandible at different ages. Sections of the mandibular molar region were placed in a methacrylate resin. After polymerization and study with confocal microscopy, the organic matrix was removed. Juvenile rats had large irregular central vascular canals and lacunae that were more concentric in the basal than the alveolar bone. Cast lacunae were round, and the canaliculi from these lacunae were short and thick in both bones. Adult rats had regular concentrically arranged lacunae in the basal bone. Cast lacunae were ellipsoid and flatter in the basal bone than in the alveolar bone. The intercommunicating canaliculi were increased and canaliculi had more branching than the juvenile rats. The aged rats had fewer vascular canals, lacunae, and canaliculi and had osteoporotic changes. The cast lacunae were slender and flat especially in the basal bone. The porosity of the mandible became more pronounced in the alveolar than in the basal bone with aging. The canaliculi of mandibular compact bone thinned and developed extensive branching with adulthood but decreased in size and number with advanced age. Lacunae proceed from the large circular structures of youth to the flat forms of the aged. These studies show that the internal structure of compact bone changes with age and mirrors its functional state.     

The Ulam number of infinite graphs

The following is a conjecture of Ulam: In any partition of the integer lattice on the plane into uniformly bounded sets, there exists a set that is adjacent to at least six other sets. Two sets are adjacent if each contain a vertex of the same unit square. This problem is generalized as follows. Given any uniformly bounded partitionP of the vertex set of an infinite graphG with finite maximum degree, letP (G) denote the graph obtained by letting each set of the partition be a vertex ofP (G) where two vertices ofP (G) are adjacent if and only if the corresponding sets have an edge between them. The Ulam number ofG is defined as the minimum of the maximum degree ofP (G) where the minimum is taken over all uniformly bounded partitionsP. We have characterized the graphs with Ulam number 0, 1, and 2. Restricting the partitions of the vertex set to connected subsets, we obtain the connected Ulam number ofG. We have evaluated the connected Ulam numbers for several infinite graphs. For instance we have shown that the connected Ulam number is 4 ifG is an infinite grid graph. We have settled the Ulam conjecture for the connected case by proving that the connected Ulam number is 6 for an infinite triangular grid graph. The general Ulam conjecture is equivalent to proving that the Ulam number of the infinite triangular grid graph equals 6. We also describe some interesting geometric consequences of the Ulam number, mainly concerning good drawings of infinite graphs.     

On possible spin injection at non-ideal Schottky contacts

The role of the tunneling mechanisms in metal-disordered layer-semiconductor structure under spin injection at the interface is investigated. The non-ideal metal-semiconductor structure as prepared by ionized cluster beam deposition is considered, and it is shown that the depletion region of the semiconductor can be tailored to include a suitably heavily doped region near the interface. The tunneling is described within a simplified model in which the expression for the interface resistance of the metal-disordered layer-semiconductor structure is obtained. It is argued that in the case of ionized cluster beam deposited non-ideal Schottky structure a significant spin injection is achieved.     

Charge donation to and dearomatization of benzene attending complexation: DFT estimates of binding energies of TpMXO(L) with benzene, for Tp = hydridotris(pyrazolyl) borate, MXO = MoNO, ReCO, and WNO, and L = ammonia, N-methylimidazole, pyridine, phosphine, methyl isocyanide, and carbon monoxide

By density functional methods we characterize the bonding and charge distribution in complexes of benzene with dearomatizing agents tpReCO(L), tpMoNO(L), and tpWNO(L), where tp = hydrido Tris (pyrazolyl)borate), for a range of ligands L. Our LSDA and B3LYP density functional calculations use the Spartan LACVP+ basis and pseudopotential on Re, Mo, and W and 6-31G* on light atoms. The binding energy is strongly dependent on the nature of the ligand L, being greatest for L = ammonia and N-methylimidazole and weakest for CH3NC and CO. We find a correlation between strength of binding and electron transfer from the dearomatizing agents toward benzene. For the most strongly bound systems we find substantial (up to 500 millielectrons) charge transfer towards benzene, while for the most weakly bound systems charge is withdrawn from benzene. Structural details illustrate the ability of Re, Mo, and W species to dearomatize complexed benzene, which is extensive for all but the most weakly bound species with L = MeNC and CO. Re and W dearomatizing agents, which are computed and observed to form stable complexes with benzene, may be economic alternatives to osmium dearomatizing agents.