Incubation period in the 2,2,4,4‐tetramethyl‐1‐piperidinyloxy‐mediated thermal autopolymerization of styrene: Kinetics and simulations

Mechanisms and simulations of the induction period and the initial polymerization stages in the nitroxide‐mediated autopolymerization of styrene are discussed. At 120–125 °C and moderate 2,2,4,4‐tetramethyl‐1‐piperidinyloxy (TEMPO) concentrations (0.02–0.08 M), the main source of radicals is the hydrogen abstraction of the Mayo dimer by TEMPO [with the kinetic constant of hydrogen abstraction (k_h)]. At higher TEMPO concentrations ([N?] > 0.1 M), this reaction is still dominant, but radical generation by the direct attack against styrene by TEMPO, with kinetic constant of addition k_ad, also becomes relevant. From previous experimental data and simulations, initial estimates of k_h ≈ 1 and k_ad ≈ 6 × 10^?7 L mol^?1 s^?1 are obtained at 125 °C. From the induction period to the polymerization regime, there is an abrupt change in the dominant mechanism generating radicals because of the sudden decrease in the nitroxide radicals. Under induction‐period conditions, the simulations confirm the validity of the quasi‐steady‐state assumption (QSSA) for the Mayo dimer in this regime; however, after the induction period, the QSSA for the dimer is not valid, and this brings into question the scientific basis of the well‐known expression k_th[M]³ (where [M] is the monomer concentration and k_th is the kinetic constant of autoinitiation) for the autoinitiation rate in styrene polymerization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6962‐6979, 2006     

A complex containing three different kinds of Ru—N bonds: ethoxydinitronitrosyl(N,N,N′,N′‐tetramethylethylenediamine‐κ2N,N′)ruthenium(II)

The octahedral title compound, [Ru(C₂H₅O)(NO)(NO₂)₂(C₆H₁₆N₂)], crystallizes in the rhombohedral space group P3₁ with an ethoxy ligand axially coordinated trans to the nitro­syl ligand. The Ru^II ion is equatorially coordinated by a tetramethylethylenediamine group acting as a bidentate ligand, and to two nitro moieties whose planes are tilted with respect to the mean equatorial plane. Each nitro­gen ligand bonded to the metallic centre has a different hybridization state.     

Disseminating a warning message to evacuate: A simulation study of the behaviour of neighbours

Large-scale evacuations are a recurring theme on news channels, whether in response to major natural or manmade disasters. The role of warning dissemination is a key part in the success of such large-scale evacuations and its inadequacy in certain cases has been a ‘primary contribution to deaths and injuries’ (Hayden et al., 2007). Along with technology-driven ‘official warning channels’ (e.g. sirens, mass media), the role of unofficial channel (e.g. neighbours, personal contacts, volunteer wardens) has proven to be significant in warning the public of the need to evacuate. Although post-evacuation studies identify the behaviours of evacuees as disseminators of the warning message, there has not been a detailed study that quantifies the effects of such behaviour on the warning message dissemination. This paper develops an Agent-Based Simulation (ABS) model of multiple agents (evacuee households) in a hypothetical community to investigate the impact of behaviour as an unofficial channel on the overall warning dissemination. Parameters studied include the percentage of people who warn their neighbours, the efficiency of different official warning channels, and delay time to warn neighbours. Even with a low proportion of people willing to warn their neighbour, the results showed considerable impact on the overall warning dissemination.     

A Process to Produce Penicillin G Acylase by Surface-Adhesion Fermentation Using <Emphasis Type="Italic">Mucor griseocyanus</Emphasis> to Obtain 6-Aminopenicillanic Acid by Penicillin G Hydrolysis

The production of extracellular and mycelia-associated penicillin G acylase (maPGA) with Mucor griseocyanus H/55.1.1 by surface-adhesion fermentation using Opuntia imbricata, a cactus, as a natural immobilization support was studied. Enzyme activity to form 6-aminopencillanic acid (6-APA) from penicillin G was assayed spectrophotometrically. The penicillin G hydrolysis to 6-APA was evaluated at six different times using PGA samples recovered from the skim milk medium at five different incubation times. Additionally, the effect of varying the penicillin G substrate concentration level on the PGA enzyme activity was also studied. The maximum reaction rate, V _max, and the Michaelis constant, K _M, were determined using the Michaelis–Menten model. The maximum levels for maPGA and extracellular activity were found to be 2,126.50 international unit per liter (IU/l; equal to 997.83 IU/g of support) at 48 h and 755.33 IU/l at 60 h, respectively. Kinetics of biomass production for total biomass showed a maximum growth at 60 h of 3.36 and 2.55 g/l (equal to 0.012 g of biomass per gram of support) for the immobilized M. griseocyanus biomass. The maPGA was employed for the hydrolysis of penicillin G to obtain 6-APA in a batch reactor. The highest quantity of 6-APA obtained was 226.16 mg/l after 40-min reaction. The effect of substrate concentration on maPGA activity was evaluated at different concentrations of penicillin G (0–10 mM). K _M and V _max were determined to be 3.0 × 10⁻³ M and 4.4 × 10⁻³ mM/min, respectively.     

Systematic study of horizontal gauge theories

We analyze all the possible continuous horizontal gauge groups G _H in relation with their possibility to explain m _b ? m _t. We assume that the only effective fermionic degrees of freedom correspond to the known fermions but allow the possibility of adding a right handed neutrino to each family. We assume that the Higgs fields which generate masses for these fermions, trough renormalizable Yukawa couplings, transform as an irreducible representation of SU(3)_c ? SU(2)_L ? U(1)_Y ? G_H. Under these assumptions we find two U(1)_H or U(1) _H1 ? U(1) _H2 models free of anomalies and able to guarantee that only the top has a renormalizable mass-generating Yukawa coupling.     

On the Nitroxide Quasi‐Equilibrium in the Alkoxyamine‐Mediated Radical Polymerization of Styrene

Summary: The range of validity of two popular versions of the nitroxide quasi‐equilibrium (NQE) approximation used in the theory of kinetics of alkoxyamine mediated styrene polymerization, are systematically tested by simulation comparing the approximate and exact solutions of the equations describing the system. The validity of the different versions of the NQE approximation is analyzed in terms of the relative magnitude of (dN/dt)/(dP/dt). The approximation with a rigorous NQE, k_c[P][N] = k_d[P N], where P, N and P N are living, nitroxide radicals and dormant species respectively, with kinetic constants k_c and k_d, is found valid only for small values of the equilibrium constant K (10⁻¹¹–10⁻¹² mol · L⁻¹) and its validity is found to depend strongly of the value of K. On the other hand, the relaxed NQE approximation of Fischer and Fukuda, k_c[P][N] = k_d[P N]₀ was found to be remarkably good up to values of K around 10⁻⁸ mol · L⁻¹. This upper bound is numerically found to be 2–3 orders of magnitude smaller than the theoretical one given by Fischer. The relaxed NQE is a better one due to the fact that it never completely neglects dN/dt. It is found that the difference between these approximations lies essentially in the number of significant figures taken for the approximation; still this subtle difference results in dramatic changes in the predicted course of the reaction. Some results confirm previous findings, but a deeper understanding of the physico‐chemical phenomena and their mathematical representation and another viewpoint of the theory is offered. Additionally, experiments and simulations indicate that polymerization rate data alone are not reliable to estimate the value of K, as recently suggested.

Validity of the rigorous nitroxide quasi‐equilibrium assumption as a function of the nitroxide equilibrium constant.     

Is U(1)H a good family symmetry?

We analyze U(1)_H as a horizontal symmetry and its possibilities to explain the known elementary-fermion masses. We find that only two candidates, in the context of SU(3)_c ? SU(2)_L ? U(1)_Y ? U(1)_H nonsuper-symmetric, are able to fit the experimental result m_b«m_t. identity, but it is a common prejudice to assume that the appropriate family symmetry may explain this fact as a consequence of (i) and (ii). In what follows we will enlarge the SM gauge group with an extra U(1)_H horizontal local gauge symmetry (the simplest multi-family continuous symmetry we can think of). We then show that the structure SU(3)_c ? SU(2)_L ? U(1)_Y ? U(1)_H by itself is able to explain (ii), and that the simplest supersymmetric (SUSY) extension of this model without a μ-term can not cope with (ii).     

Family unification inSU(6) L ⊗U(1) Y

Electroweak and horizontal interactions are unified with the groupSU(6) _L U(1) _Y for three generations. The horizontal gauge group suggested from low energy phenomenology isSU(2) _H . This model does not contain exotic quarks, but exotic leptons are needed in order to make it anomaly-free. The breaking of the symmetry gives, in a natural way, heavy masses for exotic leptons and a BCS mass matrix for the up quarks, which implies that at tree level only the top quark gets a mass of orderM _W . The see-saw mechanism generates tiny masses for the three known neutrinos. The remaining of the known fermion masses are light, because they can be generated only as radiative corrections.     

Disaster preparedness in humanitarian logistics: A collaborative approach for resource management in floods

The logistical deployment of resources to provide relief to disaster victims and the appropriate planning of these activities are critical to reduce the suffering caused. Disaster management attracts many organisations working alongside each other and sharing resources to cope with an emergency. Consequently, successful operations rely heavily on the collaboration of different organisations. Despite this, there is little research considering the appropriate management of resources from multiple organisations, and none optimising the number of actors required to avoid shortages or convergence.This research introduces a disaster preparedness system based on a combination of multi-objective optimisation and geographical information systems to aid multi-organisational decision-making. A cartographic model is used to avoid the selection of floodable facilities, informing a bi-objective optimisation model used to determine the location of emergency facilities, stock prepositioning, resource allocation and relief distribution, along with the number of actors required to perform these activities.The real conditions of the flood of 2013 in Acapulco, Mexico, provided evidence of the inability of any single organisation to cope with the situation independently. Moreover, data collected showed the unavailability of enough resources to manage a disaster of that magnitude at the time. The results highlighted that the number of government organisations deployed to handle the situation was excessive, leading to high cost without achieving the best possible level of satisfaction. The system proposed showed the potential to achieve better performance in terms of cost and level of service than the approach currently employed by the authorities.