Convenient preparation of 5-ethynyl-octaethylporphyrin free base and zinc complex

A method leading to the preparation of the free base or zinc meso-ethynyl functionalized octaethylporphyrin has been developed, which will open the access to various meso-ethynyl metalloporphyrins.     

A new, fast and efficient synthesis of 3-aryl indenones: intramolecular cyclization of 1,3-diarylpropynones in superacids

1,3-Diarylpropynones were cleanly converted to the corresponding 3-arylindenones in various superacidic media. This new, simple, one-pot reaction proved to be efficient (yields up to 95%) and very fast (reaction time less than 30 min).     

Markovian Solutions of Inviscid Burgers Equation

For solutions of (inviscid, forceless, one dimensional) Burgers equation with random initial condition, it is heuristically shown that a stationary Feller–Markov property (with respect to the space variable) at some time is conserved at later times, and an evolution equation is derived for the infinitesimal generator. Previously known explicit solutions such as Frachebourg–Martin's (white noise initial velocity) and Carraro–Duchon's Lévy process intrinsic-statistical solutions (including Brownian initial velocity) are recovered as special cases.     

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     

Conversations on mind, matter, and mathematics

Conclusion  The debate between Jean-Pierre Changeux and Alain Connes is one of the most, interesting to take place in recent years. It re-frames in a very up-to-date context a whole series of traditional and difficult questions from the standpoint of the knowledge and experience of two of the leading protagonists of contemporary science. To the choice presented by the neurobiologist between a Platonist ontology and a neurocognitive psychology of mathematical activity, the mathematician replies with a conception that is objective (neither ontological nor psychological) of the thoroughly consistent universe of mathematical idealities. It is indeed in this three-sided arena that the major difficulties play themselves out. One of the great virtues of the book is to cast a spotlight on this confrontation.     

On the global structure of crystalline surfaces

We bound the number of plane segments in a crystalline minimal surface S in terms of its Euler characteristic, the number of line segments in its boundary, and a factor determined by the Wulff shapeW of its surface energy function. A major technique in the proofs is to quantize the Gauss map ofS based on the Gauss map ofW. One thereby bounds the number of positive-curvature corners and the interior complexity ofS. The support of the National Science Foundation and the Air Force Office of Scientific Research and the hospitality of Stanford University, where this paper was extensively rewritten, are gratefully acknowledged.     

Inherited LU-factorizations of matrices

Various types of LU-factorizations for nonsingular matrices, where L is a lower triangular matrix and U is an upper triangular matrix, are defined and characterized. These types of LU-factorizations are extended to the general m × n case. The more general conditions are considered in the light of the structures of [C.R. Johnson, D.D. Olesky, P. Van den Driessche, Inherited matrix entries: LU factorizations, SIAM J. Matrix Anal. Appl. 10 (1989) 99-104]. Applications to graphs and adjacency matrices are investigated. Conditions for the product of a lower and an upper triangular matrix to be the zero matrix are also obtained.     

Magnetic-Field-Dependent Electronic Relaxation of Gd3+ in Aqueous Solutions of the Complexes [Gd(H2O)8]3+, [Gd(propane-1,3-diamine-N,N,N′,N′-tetraacetate)(H2O)2]−, and [Gd(N,N′-bis[(N-methylcarbamoyl)methyl]-3-azapentane-1,5-diamine-3,N,N′-triacetate)(H2O)] of interest in magnetic-resonance imaging

EPR Spectra have been measured for aqueous solutions of a series of Gd³⁺ complexes at variable temperature and a range of magnetic fields; S-band (0.14 T), X-band (0.34 T), Q-band (1.2 T), and 2-mm-band (5.0 T). The major contribution to the observed line widths is magnetic-field-dependent and is interpreted as being due to the modulation of the zero-field splitting produced by distortion of the complexes from perfect symmetry. The transverse and longitudinal relaxation matrices for an ⁸S ion with such an interaction have been calculated using Redfield theory with vector-coupling methods, and diagonalised numerically to obtain relaxation rates and intensities for the degenerate transitions which contribute to the multiplet. The observed line width, which is inversely proportional to the magnetic field at low temperatures, is best described by the intensity-weighted mean transverse relaxation time for the four transitions with non-zero intensity. A least-squares fit of the data yields the square of the zero-field splitting tensor, Δ², and a correlation time, τ_v, with activation energy, E_v. The physical significance of these parameters and the extent of validity of the theoretical approach are considered. The parameters are used to predict the magnetic-field dependence of the longitudinal and transverse electronic relaxation times, which are discussed in the context of their relevance to ¹H-NMR relaxivity.     

A diffusion approximation result for two parameter processes

Summary We consider a one-dimensional linear wave equation with a small mean zero dissipative field and with the boundary condition imposed by the so-called Goursat problem. In order to observe the effect of the randomness on the solution we perform a space-time rescaling and we rewrite the problem in a diffusion approximation form for two parameter processes. We prove that the solution converges in distribution toward the solution of a two-parameter stochastic differential equation which we identify. The diffusion approximation results for oneparameter processes are well known and well understood. In fact, the solution of the one-parameter analog of the problem we consider here is immediate. Unfortunately, the situation is much more complicated for two-parameter processes and we believe that our result is the first one of its kind.Partially supported by ONR N00014-91-J-1010