Palladium(ii)-catalysed tandem cyclisation of electron-deficient aromatic enynes

A novel palladium(ii) catalysed tandem cyclisation of substituted 2-alkenylphenyl alkynones gives substituted 2-vinyl indenones and 6,5,6-fused tricyclic lactone skeletons (pyrones), in one-pot. Wagner-Meerwein-like rearrangements were observed which occur preferentially to conventional chloride-mediated chloropalladations of enynes.     

Ground- and triplet excited-state properties correlation: a computational CASSCF/CASPT2 approach based on the photodissociation of allylsilanes

Excited-state properties, although extremely useful, are hardly accessible. One indirect way would be to derive them from relationships to ground-state properties which are usually more readily available. Herewith, we present quantitative correlations between triplet excited-state (T?) properties (bond dissociation energy, D?(T?), homolytic activation energy, E(a)(T?), and rate constant, k(r)) and the ground-state bond dissociation energy (D?), taking as an example the photodissociation of the C-Si bond of simple substituted allylsilanes CH?=CHC(R1R2)-SiH? (R1 and R2 = H, Me, and Et). By applying the complete-active-space self-consistent field CASSCF(6,6) and CASPT2(6,6) quantum chemical methodologies, we have found that the consecutive introduction of Me/Et groups has little effect on the geometry and energy of the T? state; however, it reduces the magnitudes of D?, D?(T?) and E(a)(T?). Moreover, these energetic parameters have been plotted giving good linear correlations: D?(T?) = α? + β? · D?, E(a)(T?) = α? + β? · D?(T?), and E(a)(T?) = α? + β? · D? (α and β being constants), while k(r) correlates very well to E(a)(T?). The key factor behind these useful correlations is the validity of the Evans-Polanyi-Semenov relation (second equation) and its extended form (third equation) applied for excited systems. Additionally, the unexpectedly high values obtained for E(a)(T?) demonstrate a new application of the principle of nonperfect synchronization (PNS) in excited-state chemistry issues.     

A microstructural flow-induced crystallization model for film blowing: validation with experimental data

The two-phase microstructural/constitutive model for film blowing of Doufas and McHugh (D-M) (J Rheol 45:1085–1104, 2001a) is validated against online film data of a linear low-density polyethylene (LLDPE) at a variety of processing conditions. The D-M model includes the effects of thermal and flow-induced (enhanced) crystallization (FIC) coupled with the rheological response of both the melt and semicrystalline phases under fabrication conditions. The model predictions of bubble radius, velocity, and crystallinity profiles are in quantitative agreement with available experimental data over a wide range of blow-up ratios (BUR), take-up ratios (TUR), and bubble cooling rates using the same set of material/model parameters. The model naturally predicts the location of the frost line as a consequence of system stiffening due to crystallization overcoming the pitfalls of traditional modeling approaches that impose it as an artificial boundary condition. For a wide range of processing conditions, it is found that key film mechanical properties including elongation to break, yield stress, tensile modulus, and tear strength correlate well with predicted locked-in extensional stresses and molecular orientation at the frost line enabling development of quantitative structure-process-properties relationships that are useful in product and process development. The D-M model for film blowing is physics-based including elements of molecular rheology (polymer kinetic theory), suspension, and nucleation theories as well as irreversible thermodynamics principles, yet being tractable for continuum-based numerical simulations with practical industrial applicability. The FIC enhancement factor of the model is shown to be proportional to $\exp \left (\lambda _{\text {eff},\textnormal {w}}^{2} -1\right )$ , where λ _eff,w is a molecular chain stretch ratio of the whole chain and proportional to exp (λ ² ? 1), where λ is the stretch ratio of the remaining (uncrystallized) amorphous chain, consistent with fundamental kinetic Monte Carlo simulations of flow-induced nucleation of Graham and Olmsted (Phys Rev Lett 103:115702-1–115702-4, 2009).     

The effect of spiroadamantane substitution on the conformational preferences of N-Me pyrrolidine and N-Me piperidine: a description based on dynamic NMR spectroscopy and ab initio correlated calculations

Dynamic NMR spectroscopy and ab initio correlated calculations revealed that the attachment of a spiroadamantane entity at the C-2 position of N-methylpyrrolidine or N-methylpiperidine induces a severe steric crowding around nitrogen, which changes the conformational space of the heterocycle resulting in: (a) the complete destabilization of the N-Me(eq) conformer in spiranic structures; in contrast the N-Me(eq) conformer corresponds to the global minimum in N-methylpyrrolidine or N-methylpiperidine. The spiroadamantane structure raises the energy of the equatorial conformer because of the severe van der Waals repulsion between the N-Me(eq) group and adamantane C-H bonds. (b) The interconversion between the only populated enantiomeric N-Me(ax) conformers ax→[eq]→ax′; the interconversion eq→ax between N-Me(eq) and N-Me(ax) conformers, which are both populated, is observed in N-methylpyrrolidine or N-methylpiperidine. (c) The raising of ring and nitrogen inversion barriers ax→ts by ∼4-6 kcal mol⁻¹. The dynamic NMR study provides evidence that the most important process required for the enantiomerization between the axial N-Me conformers in spiropiperidine 4 and spiropyrrolidine 5 are different, i.e., a nitrogen inversion in 5 (9.10 kcal mol⁻¹) and a ring inversion in 4 (15.2 kcal mol⁻¹). While an enantiomerization interconverts N-Me axial conformers in spiropiperidine 5 and spiropyrrolidine 4, substitution of the pyrrolidine ring of 5 with a C-Me group effects a diastereomerization between two N-Me axial conformers and reduces effectively the nitrogen inversion barrier according to the protonation experiments and the calculations. In general, all the calculations levels used, i.e., the MM3, B3LYP/6-31+G^∗∗ and MP2/6-311++G^∗∗//B3LYP/6-31+G^∗∗, predict correctly the different stability of the local minima; however only MP2/6-311++G^∗∗//B3LYP/6-31+G^∗∗ was found to be reliable for the calculation of the nitrogen inversion barriers.     

Synthesis and electrochemical characterization of nitrogen-doped and nitrogen–phosphorus-doped multi-walled carbon nanotubes

Nitrogen-doped and nitrogen–phosphorus-doped multi-walled carbon nanotubes (N-MWCNTs and N–P-MWCNTs, respectively) were fabricated by chemical vapor deposition and characterized using scanning electron microscopy and transmission electron microscopy in combination with energy dispersive X-ray spectroscopy and Raman spectroscopy. The electrochemical response of N-MWCNTs and N–P-MWCNTs towards ferrocyanide/ferricyanide was initially studied. The findings exhibit weakening of electrochemical response and sensitivity of nanotubes with phosphorus doping, and thus, within the composite films tested, those consist exclusively of N-MWCNTs exhibit the greatest electrocatalytic activity. N–P-MWCNT film was further applied for individual electrochemical analysis of ascorbic acid (AA), uric acid (UA), and dopamine (DA), and lower limits of detections of 11.6, 7.8, and 1.9 μM were estimated, respectively. The findings demonstrate that AA does not interfere with UA, but considerable interference of AA in analysis of DA was observed. Thus, the simultaneous analysis of AA, UA, and DA on N–P-MWCNTs appears to be restricted.     

Adjoint optimization of natural convection problems: differentially heated cavity

Optimization of natural convection-driven flows may provide significant improvements to the performance of cooling devices, but a theoretical investigation of such flows has been rarely done. The present paper illustrates an efficient gradient-based optimization method for analyzing such systems. We consider numerically the natural convection-driven flow in a differentially heated cavity with three Prandtl numbers (\(Pr=0.15{-}7\)) at super-critical conditions. All results and implementations were done with the spectral element code Nek5000. The flow is analyzed using linear direct and adjoint computations about a nonlinear base flow, extracting in particular optimal initial conditions using power iteration and the solution of the full adjoint direct eigenproblem. The cost function for both temperature and velocity is based on the kinetic energy and the concept of entransy, which yields a quadratic functional. Results are presented as a function of Prandtl number, time horizons and weights between kinetic energy and entransy. In particular, it is shown that the maximum transient growth is achieved at time horizons on the order of 5 time units for all cases, whereas for larger time horizons the adjoint mode is recovered as optimal initial condition. For smaller time horizons, the influence of the weights leads either to a concentric temperature distribution or to an initial condition pattern that opposes the mean shear and grows according to the Orr mechanism. For specific cases, it could also been shown that the computation of optimal initial conditions leads to a degenerate problem, with a potential loss of symmetry. In these situations, it turns out that any initial condition lying in a specific span of the eigenfunctions will yield exactly the same transient amplification. As a consequence, the power iteration converges very slowly and fails to extract all possible optimal initial conditions. According to the authors’ knowledge, this behavior is illustrated here for the first time.     

The effect of boundary conditions on guided wave propagation in two-dimensional models of healing bone

Guided wave propagation has recently drawn significant interest in the ultrasonic characterization of bone. In this work, we present a two-dimensional computational study of ultrasound propagation in healing bones aiming at monitoring the fracture healing process. In particular, we address the effect of fluid loading boundary conditions on the characteristics of guided wave propagation, using both time and time-frequency (t-f) signal analysis techniques, for three study cases. In the first case, the bone was assumed immersed in blood which occupied the semi-infinite spaces of the upper and lower surfaces of the plate. In the second case, the bone model was assumed to have the upper surface loaded by a 2mm thick layer of blood and the lower surface loaded by a semi-infinite fluid with properties close to those of bone marrow. The third case, involves a three-layer model in which the upper surface of the plate was again loaded by a layer of blood, whereas the lower surface was loaded by a 2mm layer of a fluid which simulated bone marrow. The callus tissue was modeled as an inhomogeneous material and fracture healing was simulated as a three-stage process. The results clearly indicate that the application of realistic boundary conditions has a significant effect on the dispersion of guided waves when compared to simplified models in which the bone's surfaces are assumed free.     

Nonlinear Finite Element Analysis of γ-Graphyne Structures under Shearing

In this study, a nonlinear, spring-based finite element approach is employed in order to predict the nonlinear mechanical response of graphyne structures under shear loading. Based on Morse potential functions, suitable nonlinear spring finite elements are formulated simulating the interatomic interactions of different graphyne types. Specifically, the four well-known types of γ-graphyne, i.e., graphyne-1 also known as graphyne, graphyne-2 also known as graphdiyne, graphyne-3, and graphyne-4 rectangular sheets are numerically investigated applying appropriate boundary conditions representing shear load. The obtained finite element analysis results are employed to calculate the in-plane shear stress–strain behaviour, as well as the corresponding mechanical properties as shear modulus and shear strength. Comparisons of the present graphyne shearing response predictions with other corresponding estimations are performed to validate the present research results.     

Higher-order aggregate networks in the analysis of temporal networks: path structures and centralities

Despite recent advances in the study of temporal networks, the analysis of time-stampednetwork data is still a fundamental challenge. In particular, recent studies have shownthat correlations in the ordering of links crucially alter causaltopologies of temporal networks, thus invalidating analyses based on static,time-aggregated representations of time-stamped data. These findings not only highlight animportant dimension of complexity in temporal networks, but also call for newnetwork-analytic methods suitable to analyze complex systems with time-varying topologies.Addressing this open challenge, here we introduce a novel framework for the study ofpath-based centralities in temporal networks. Studying betweenness,closeness and reach centrality, we first show than an application of these measures totime-aggregated, static representations of temporal networks yields misleading resultsabout the actual importance of nodes. To overcome this problem, we define path-basedcentralities in higher-order aggregate networks, a recently proposedgeneralization of the commonly used static representation of time-stamped data. Using dataon six empirical temporal networks, we show that the resulting higher-order measuresbetter capture the true, temporal centralities of nodes. Our resultsdemonstrate that higher-order aggregate networks constitute a powerful abstraction, withbroad perspectives for the design of new, computationally efficient data mining techniquesfor time-stamped relational data.