Axial Imidazole Distortion Effects on the Catalytic and Binding Properties of Chelated Deuterohemin Complexes

The effect of strain in the axial coordination of imidazole to the heme has been studied in the chelate complexes deuterohemin-histidine (DH-His) and deuterohemin-alanylhistidine (DH-AlaHis). Molecular mechanics calculations indicate that three types of distortion of the axial ligand occur in DH-His, due to the relatively short length of the arm carrying the donor group: tilting off-axis, tipping, and inclination of the imidazole plane with respect to the axial Fe-N bond. The effects of tilting (Deltagamma approximately 10 degrees ) and inclination of the imidazole ring (Deltadelta approximately 17 degrees ) are dominant, while tipping is small and is probably of little importance here. By contrast, the axial imidazole coordination is normal in DH-AlaHis and other computed deuterohemin-dipeptide or -tripeptide complexes where histidine is the terminal residue, the only exception being DH-ProHis, where the rigidity of the proline ring reduces the flexibility of the chelating arm. The distortion in the axial iron-imidazole bond in DH-His has profound and negative influence on the binding and catalytic properties of this complex compared to DH-AlaHis. The former complex binds more weakly carbon monoxide, in its reduced form, and imidazole, in its oxidized form, than the latter. The catalytic efficiency in peroxidative oxidations is also reduced in DH-His with respect to DH-AlaHis. The activity of the latter complex is similar to that of microperoxidase-11, the peptide fragment incorporating the heme that results from hydrolytic cleavage of cytochrome c.     

Mechanism of Formation of Peroxocarbonates RhOOC(O)O(Cl)(P)(3) and Their Reactivity as Oxygen Transfer Agents Mimicking Monooxygenases. The First Evidence of CO(2) Insertion into the O-O Bond of Rh(eta(2)-O(2)) Complexes

Extended labeling experiments have shown that formation of rhodium peroxocarbonate from CO(2) and [RhCl(eta(2)-O(2))(P)(3)] (P is PEt(2)Ph or PEtPh(2)) proceeds through O-O bond cleavage and CO(2) insertion. O-transfer to ancillary phosphine ligand to give R(3)P=O selectively (>85%) involves the Rh-linked O atom of the peroxo group of RhCl(CO(4))(P)(3).     

Human mobility and COVID-19 initial dynamics

Nonlinear Dynamics - Countries in Europe took different mobility containment measures to curb the spread of COVID-19. The European Commission asked mobile network operators to share on a...     

Alignment and aggregation effects in suspensions of spheres in non-Newtonian media

Summary Photographs are presented which demonstrate the alignment and aggregation effects in suspensions of spheres in viscoelastic media. Pictures were taken from plane shear flows between two glass plates. The spheres line up in flow direction and come into contact. If the spheres touch, the rotation ceases. This alignment and association was also observed and photographed in elongational and in pipe flow.The alignment process could be related to normal stresses. A further observation is that the ratio of the first normal stress difference to the shear stress is the determining parameter.Practical aspects are mentioned.

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Zusammenfassung Ausrichtungs- und Aggregationseffekte in Kugelsuspensionen mit viskoelastischer Suspensionsflüssigkeit werden aufgezeigt. Bei einem Teil der Bilder handelt es sich um Mikroaufnahmen von ebenen Schichtenströmungen zwischen zwei Glasplatten. Die Kugeln richten sich in Strömungsrichtung aus und kommen einander näher. Bei Berührung verschwindet die Rotationsgeschwindigkeit der Kugeln. Diese Ausrichtung und Anlagerung wird auch in der Dehn- und Rohrströmung beobachtet.Der Orientierungsvorgang ist ein Normalspannungseffekt. Nicht die absolute Höhe der ersten Normalspannungsdifferenz, sondern das Verhältnis der ersten Normalspannungsdifferenz zur Schubspannung ist der wesentliche Parameter.Auf praktische Folgerungen wird kurz hingewiesen.

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With 7 figures in 11 details     

Spatial Estimates for the Constrained Anisotropic Elastic Cylinder

This paper establishes spatial estimates in a prismatic (semi-infinite) cylinder occupied by an anisotropic homogeneous linear elastic material, whose elasticity tensor is strongly elliptic. The cylinder is maintained in equilibrium under zero body force, zero displacement on the lateral boundary and pointwise specified displacement over the base. The other plane end is subject to zero displacement (when the cylinder is finite, say). The limiting case of a semi-infinite cylinder is also considered and zero displacement on the remote end (at large distance) is not assumed in this case. A first approach is developed by considering two mean-square cross-sectional measures of the displacement vector whose spatial evolution with respect to the axial variable is studied by means of a technique based on a second-order differential inequality. Conditions on the elastic constants are derived that show the cross-sectional measures exhibit alternative behaviour and in particular for the semi-infinite cylinder that there is either at least exponential growth or at most exponential decay. A second approach considers cross-sectional integrals involving the displacement and its gradient and furnishes information upon the spatial evolution, without restricting the range of strongly elliptic elastic constants. Such models are principally based upon a first-order differential inequality as well as on one of second order. The general results are explicitly presented for transversely isotropic materials and graphically illustrated for a cortical bone.     

Patient-specific finite element analysis of popliteal stenting

Nitinol self-expanding stents are used for the endovascular management of peripheral artery diseases of the popliteal artery, which is located behind the knee joint. Unfortunately, the complex kinematics of the artery during the leg flexion leads to severe loading conditions, favouring the mechanical failure of the stent, calling for a specific biomechanical analysis. For this reason, in the present study we reconstruct by medical image analysis the patient-specific popliteal kinematics during leg flexion, which is subsequently exploited to compute the mechanical response of a stent model, virtually implanted in the artery by structural finite element analysis (FEA). The medical image analysis indicates a non-uniform configuration change of the artery during the leg flexion, leading to an increase of the vessel curvature above the knee. The computed mechanical response of the stent reflects the non-uniform configuration change of the artery as after the flexion the average stress is higher in the part of the stent located above the knee. Although the proposed analysis is limited to a case-study, it shows the capability of patient-specific FEA simulations to compute the mechanical response of a stent model subjected to the complex and severe loading conditions of the popliteal artery during leg flexion.     

Development and Validation of Hierarchical Models for the Design of Engine Control Strategies

The development of mathematical models for the design of controlstrategies for spark ignition automotive engines is described. The objectiveof the models, used for both simulation and optimization analysis, is theprediction of the effects of control strategies on fuel consumption andemissions of a vehicle over arbitrary driving cycles. In order to achievethe best compromise between precision, experimental costs, computationaltime and flexibility, a mixed modelling approach is used, withphenomenological and input-output models integrated within a hierarchicalsystem.Mean value models have been used to describe the most significant dynamiceffects: (i) air flow. (ii) two phases fuel flow in the intake manifold, and(iii) thermal flow in the cylinder walls. Stochastic effects due to sensorsand actuators can be also predicted.Two-zone and multizone thermodynamic models for the prediction ofpressure cycle sub-models for engine emissions (HC, CO, andNO _x and mechanical losses have been developed. Experimentaldesign techniques are also under development to optimize the interactionsbetween experimental analysis and models. Most of the models have beenintegrated in a computer code, used by a major automotive supplier.     

Thermal stresses in plane elasticity: Numerical solutions based only on harmonic functions

Summary A theoretical treatment is outlined allowing solution of thermal stress problems in plane elasticity by using only numerical methods suited to solving — in 2 D — the Laplace equation. Only one type of element matrix (supposing for the sake of simplicity F.E.M.s are used) and only one mesh would thus be required, both for the determination of the thermal field and of the displacement/stress field. The numerical solutions required in the plane domain of interest entail, consequently, only one variable per node in place of two. Even if numerous unit solutions are required in order to impose arbitrary boundary conditions, this reduction of nodal variables allows to spend less computation time in solving linear systems, at least for problems of a certain extent.

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Sommario Si delinea una tecnica che permette di risolvere i problemi di coazioni termiche in elasticità piana facendo uso solo di metodi numerici atti a risolvere l'equazione di Laplace. Un solo tipo di matrice degli elementi (nel caso si usi una formulazione a E. F.) e una sola reticolazione sono pertanto richiesti tanto per il problema termico come per quello elastico. Ne consegue altresì il vantaggio che le soluzioni numeriche richieste nel dominio di interesse cornportano una sola variabile per nodo, anzichè due; anche tenuto conto che sono richieste numerose soluzioni unitarie per poter imporre condizioni al contorno comunque definite, ne deriva per problemi di una certa ampiezza una riduzione del tempo di calcolo speso nella soluzione di sistemi.

     

Rayleigh Surface Waves on a Kelvin-Voigt Viscoelastic Half-Space

In this paper we consider the propagation of Rayleigh surface waves in an exponentially graded half-space made of an isotropic Kelvin-Voigt viscoelastic material. Here we take into account the effect of the viscoelastic dissipation energy upon the corresponding wave solutions. As a consequence we introduce the damped in time wave solutions and then we treat the Rayleigh surface wave problem in terms of such solutions. The explicit form of the secular equation is obtained in terms of the wave speed and the viscoelastic inhomogeneous profile. Furthermore, we use numerical methods and computations to solve the secular equation for some special homogeneous materials. The results sustain the idea, existent in literature on the argument, that there is possible to have more than one surface wave for the Rayleigh wave problem.