Design, synthesis, characterization, luminescence and non-linear optical (NLO) properties of multinuclear platinum(II) alkynyl complexes

A series of luminescent multinuclear platinum(II) alkynyl complexes containing triethynylbenzene or 1,4-bis(3,5-diethynylphenyl)buta-1,3-diyne as cores has been successfully synthesized and characterized. The electronic absorption, emission, nanosecond transient absorption and electrochemical properties of these complexes have been reported. These complexes show long-lived emissions in degassed benzene solution and in alcoholic glass at 77 K. Moreover, they are found to exhibit two-photon absorption (2PA) and two-photon induced luminescence (TPIL) properties, and their two-photon absorption cross-sections have been determined to be 6-191 GM upon excitation at 720 nm. Through a systematic comparison, it has been found that tetra- and hexanuclear platinum(II) complexes show better 2PA and TPIL properties than their di- and trinuclear counterparts.     

Counting Simsun Permutations by Descents

We count in the present work simsun permutations of length n by their number of descents. Properties studied include the recurrence relation and real-rootedness of the generating function of the number of n-simsun permutations with k descents. By means of generating function arguments, we show that the descent number is equidistributed over n-simsun permutations and n-André permutations. We also compute the mean and variance of the random variable X _n taking values the descent number of random n-simsun permutations, and deduce that the distribution of descents over random simsun permutations of length n satisfies a central and a local limit theorem as n ?? +???.     

Optimizing departure times in vehicle routes

Most solution methods for the vehicle routing problem with time windows (VRPTW) develop routes from the earliest feasible departure time. In practice, however, temporary traffic congestion make such solutions non-optimal with respect to minimizing the total duty time. Furthermore, the VRPTW does not account for driving hours regulations, which restrict the available travel time for truck drivers. To deal with these problems, we consider the vehicle departure time optimization (VDO) problem as a post-processing of a VRPTW. We propose an ILP formulation that minimizes the total duty time. The results of a case study indicate that duty time reductions of 15% can be achieved. Furthermore, computational experiments on VRPTW benchmarks indicate that ignoring traffic congestion or driving hours regulations leads to practically infeasible solutions. Therefore, new vehicle routing methods should be developed that account for these common restrictions. We propose an integrated approach based on classical insertion heuristics.     

Gold-catalyzed cycloisomerizations of 1-(2-(tosylamino)phenyl)prop-2-yn-1-ols to 1H-indole-2-carbaldehydes and (E)-2-(iodomethylene)indolin-3-ols

A method to prepare 1H-indole-2-carbaldehydes and (E)-2-(iodomethylene)indolin-3-ols by gold(I)-catalyzed cycloisomerization of 1-(2-(tosylamino)phenyl)prop-2-yn-1-ols with N-iodosuccinimide (NIS) is reported. The reactions were shown to be operationally simplistic and proceed efficiently for a wide variety of substrates, affording the corresponding products in good to excellent yields (70-99%). The mechanism is suggested to involve activation of the alkyne moiety of the substrate by the gold(I) catalyst. This triggers intramolecular addition of the tethered aniline moiety to give a vinyl gold intermediate, which undergoes iododeauration with NIS to give the (E)-2-(iodomethylene)indolin-3-ol adduct. Subsequent 1,3-allylic alcohol isomerization (1,3-AAI) followed by formylation of this vinyl iodide intermediate then gives the 1H-indole-2-carbaldehyde.     

Effect of epoxy and filler concentrations on curing behaviour of isotropic conductive adhesives

Isotropic conductive adhesives (ICAs) are considered as the most promising replacement to lead-based solders due to relatively low melting point, simple processing and fine pitch capability. The study reports on the effect of volume fractions of silver flakes and particles on the curing reaction of ICAs. In addition, the thermal behavior of ICAs formulated with two types of polymeric adhesives: diglycidylether of bisphenol-A (DGEBA) and polyurethane (PU) was also investigated in this work. The increase in silver flakes concentration seem to reduce the melting temperature of the DEGBA and PU-based ICAs, which could be due to retardation of cross-linking of polymers due to silver flakes acting as barrier within the polymer matrix. In addition, the formulation of ICAs containing silver flakes and particles yielded a much higher reaction compared to conventional ICAs. The study showed that use of polyurethane (PU) as opposed to conventional Diglycidylether of bisphenol-A (DGEBA) showed a more stable system.     

Atomic carbon adsorption on Ni nanoclusters: a DFT study

Atomic carbon is a key intermediate interacting with transition metal clusters during the growth of carbon nanotube (CNT). Present density functional calculations studied the initial carbon adsorption on four Ni nanoclusters (N₁₃, N₁₅, N₃₈, and N₅₅). Our results show that carbon atoms preferentially adsorb on high-coordination sites, and carbon adsorption energies are larger on smaller Ni clusters. Ni cluster reconstruction plays an important role in creating more stable subsurface adsorption sites. The migration of adsorbed carbon atom on the surface threefold hollow site into the underlying interstitial subsurface positions is thermodynamically and kinetically feasible. The results indicate that the investigation of CNT growth mechanism should include both surface and subsurface carbon atoms, coupled with surface reconstruction of Ni nanoclusters.     

Graphs whose critical groups have larger rank

The critical group C(G) of a graph G is a refinement of the number of spanning trees of the graph and is closely connected with the Laplacian matrix. Let r(G) be the minimum number of generators (i.e., the rank) of the group C(G) and β(G) be the number of independent cycles of G. In this paper, some forbidden induced subgraphs are given for r(G) = n − 3 and all graphs with r(G) = β(G) = n − 3 are characterized.     

Predicting XAFS scattering path cumulants and XAFS spectra for metals (Cu,Ni, Fe,Ti, Au) using molecular dynamics simulations

The ability of molecular dynamics (MD) simulations to support the analysis of X‐ray absorption fine‐structure (XAFS) data for metals is evaluated. The low‐order cumulants (ΔR, σ², C₃) for XAFS scattering paths are calculated for the metals Cu, Ni, Fe, Ti and Au at 300 K using 28 interatomic potentials of the embedded‐atom method type. The MD cumulant predictions were evaluated within a cumulant expansion XAFS fitting model, using global (path‐independent) scaling factors. Direct simulations of the corresponding XAFS spectra, χ(R), are also performed using MD configurational data in combination with the FEFFab initio code. The cumulant scaling parameters compensate for differences between the real and effective scattering path distributions, and for any errors that might exist in the MD predictions and in the experimental data. The fitted value of ΔR is susceptible to experimental errors and inadvertent lattice thermal expansion in the simulation crystallites. The unadjusted predictions of σ² vary in accuracy, but do not show a consistent bias for any metal except Au, for which all potentials overestimate σ². The unadjusted C₃ predictions produced by different potentials display only order‐of‐magnitude consistency. The accuracy of direct simulations of χ(R) for a given metal varies among the different potentials. For each of the metals Cu, Ni, Fe and Ti, one or more of the tested potentials was found to provide a reasonable simulation of χ(R). However, none of the potentials tested for Au was sufficiently accurate for this purpose.     

Bioprinting of Collagen: Considerations,Potentials, and Applications

Collagen is the most abundant extracellular matrix protein that is widely used in tissue engineering (TE). There is little research done on printing pure collagen. To understand the bottlenecks in printing pure collagen, it is imperative to understand collagen from a bottom‐up approach. Here it is aimed to provide a comprehensive overview of collagen printing, where collagen assembly in vivo and the various sources of collagen available for TE application are first understood. Next, the current printing technologies and strategy for printing collagen‐based materials are highlighted. Considerations and key challenges faced in collagen printing are identified. Finally, the key research areas that would enhance the functionality of printed collagen are presented.