The chemiluminescent peroxyoxalate system: state of the art almost 50 years from its discovery

Almost fifty years after the discovery of the peroxyoxalate reaction by E. A. Chandross in the early nineteen sixties, this review article intends to give a general overview on mechanistic aspects of this system and to describe the principles of its analytical application. After a short general introduction on the principles of chemiluminescence and the history of peroxyoxalate discovery, mechanistic aspects of high-energy intermediate formation, its structure and its reaction with an activator in the peroxyoxalate system are discussed. Finally, analytical applications of peroxyoxalate chemiluminescence are exemplified using representative recent examples, including oxalic acid detection in biological samples.

A general threshold stress hybrid hazard model for lifetime data

In this paper we propose a hybrid hazard regression model with threshold stress which includes the proportional hazards and the accelerated failure time models as particular cases. To express the behavior of lifetimes the generalized-gamma distribution is assumed and an inverse power law model with a threshold stress is considered. For parameter estimation we develop a sampling-based posterior inference procedure based on Markov Chain Monte Carlo techniques. We assume proper but vague priors for the parameters of interest. A simulation study investigates the frequentist properties of the proposed estimators obtained under the assumption of vague priors. Further, some discussions on model selection criteria are given. The methodology is illustrated on simulated and real lifetime data set.

INVESTIGATING THE PRESENCE OF THE HISTORY OF SCIENCE IN UNIVERSITY GENERAL CHEMISTRY TEXTBOOKS

INVESTIGATING THE PRESENCE OF THE HISTORY OF SCIENCE IN UNIVERSITY GENERAL CHEMISTRY TEXTBOOKS. This paper aims at analyzing the history of science content of three general chemistry textbooks used in Brazilian universities: the translations of Kotz and Treichel's Chemistry & Chemical Reactivity, Atkins and Jones's Chemical Principles, and Garritz and Chamizo's Quimica. Results revealed different trends for the inclusion of history of science in chemistry teaching. Katz & Treichel and Atkins & Jones used history mainly as curiosity and ornament. Garritz & Chamizo adopted the historical approach as one of the organizing axis of their textbook. Nevertheless, the historical content of the three textbooks may be criticized from current historiographical standpoint.

A general framework for multi-compartmental analysis of drug chemotherapy dynamics in human immunodeficiency virus type-1 infected individuals

An optimal control strategy for the highly active antiretroviral therapy associated to the acquired immunodeficiency syndrome should be designed regarding a comprehensive analysis of the drug chemotherapy behavior in the host tissues, from major viral replication sites to viral sanctuary compartments. Such approach is critical in order to efficiently explore synergistic, competitive and prohibitive relationships among drugs and, hence, therapy costs and side-effect minimization. In this paper, a novel mathematical model for HIV-1 drug chemotherapy dynamics in distinct host anatomic compartments is proposed and theoretically evaluated on fifteen conventional anti-retroviral drugs. Rather than interdependence between drug type and its concentration profile in a host tissue, simulated results suggest that such profile is importantly correlated with the host tissue under consideration. Furthermore, the drug accumulative dynamics are drastically affected by low patient compliance with pharmacotherapy, even when a single dose lacks. (C) 2012 Elsevier Inc. All rights reserved.

Underlying Event measurements in pp collisions at root s=0.9 and 7 TeV with the ALICE experiment at the LHC

We present measurements of Underlying Event observables in pp collisions at root s = 0 : 9 and 7 TeV. The analysis is performed as a function of the highest charged-particle transverse momentum p(T),L-T in the event. Different regions are defined with respect to the azimuthal direction of the leading (highest transverse momentum) track: Toward, Transverse and Away. The Toward and Away regions collect the fragmentation products of the hardest partonic interaction. The Transverse region is expected to be most sensitive to the Underlying Event activity. The study is performed with charged particles above three different p(T) thresholds: 0.15, 0.5 and 1.0 GeV/c. In the Transverse region we observe an increase in the multiplicity of a factor 2-3 between the lower and higher collision energies, depending on the track p(T) threshold considered. Data are compared to PYTHIA 6.4, PYTHIA 8.1 and PHOJET. On average, all models considered underestimate the multiplicity and summed p(T) in the Transverse region by about 10-30%.

The functional role of ascending nociceptive control in defensive behavior

Ascending nociceptive control is a novel spino-striato-rostral ventral medulla pain modulation pathway that mediates heterosegmental pain-induced analgesia, i.e., noxious stimulus-induced antinociception. In this study, we used the dorsal immobility response in rats as a model of the defensive responses. We demonstrated that the activation of ascending nociceptive control by peripheral noxious stimulation and spinal AMPA and mGluR1 receptor blockade significantly potentiated the duration of the dorsal immobility response in rats via an opioid-dependent mechanism in the nucleus accumbens. These results demonstrated the functional role of ascending nociceptive control in the modulation of defensive responses and spinal glutamatergic receptors in the dorsal immobility response. The immobility response is an antipredator behavior that reflects the underlying state of fear, and ascending nociceptive control may modulate fear. (c) 2012 Elsevier B.V. All rights reserved.

Fracture and resistance-curve behavior in hybrid natural fiber and polypropylene fiber reinforced composites

This article presents the results of a combined experimental and theoretical study of fracture and resistance-curve behavior of hybrid natural fiber- and synthetic polymer fiber-reinforced composites that are being developed for potential applications in affordable housing. Fracture and resistance-curve behavior are studied using single-edge notched bend specimens. The sisal fibers used were examined using atomic force microscopy for fiber bundle structures. The underlying crack/microstructure interactions and fracture mechanisms are elucidated via in situ optical microscopy and ex-situ environmental scanning microscopy techniques. The observed crack bridging mechanisms are modeled using small and large scale bridging concepts. The implications of the results are then discussed for the design of eco-friendly building materials that are reinforced with natural and polypropylene fibers.

SINGULARLY PERTURBED DISCOUNTED MARKOV CONTROL PROCESSES IN A GENERAL STATE SPACE

This paper studies the asymptotic optimality of discrete-time Markov decision processes (MDPs) with general state space and action space and having weak and strong interactions. By using a similar approach as developed by Liu, Zhang, and Yin [Appl. Math. Optim., 44 (2001), pp. 105-129], the idea in this paper is to consider an MDP with general state and action spaces and to reduce the dimension of the state space by considering an averaged model. This formulation is often described by introducing a small parameter epsilon > 0 in the definition of the transition kernel, leading to a singularly perturbed Markov model with two time scales. Our objective is twofold. First it is shown that the value function of the control problem for the perturbed system converges to the value function of a limit averaged control problem as epsilon goes to zero. In the second part of the paper, it is proved that a feedback control policy for the original control problem defined by using an optimal feedback policy for the limit problem is asymptotically optimal. Our work extends existing results of the literature in the following two directions: the underlying MDP is defined on general state and action spaces and we do not impose strong conditions on the recurrence structure of the MDP such as Doeblin's condition.

Impact of maternal mild hyperglycemia on maternal care and offspring development and behavior of Wistar rats

The aim of the present study was to evaluate the effect of maternal mild hyperglycemia on maternal behavior, as well as the development, behavior, reproductive function, and glucose tolerance of the offspring. At birth, litters were assigned either to Control (subcutaneous (sc)-citrate buffer) or STZ groups (streptozotocin (STZ)-100 mg/kg-sc.). On PND 90 both STZ-treated and Control female rats were mated. Glucose tolerance tests (GTT) and insulin tolerance tests (ITT) were performed during pregnancy. Pregnancy duration, litter size and sex ratio were assessed. Newborns were classified according to birth weight as small (SPA), adequate (APA), or large for pregnancy age (LPA). Maternal behavior was analyzed on PND 5 and 10. Offspring body weight, length, and anogenital distance were measured and general activity was assessed in the open field. Sexual behavior was tested in both male and female offspring. Levels of reproductive hormones and estrous cycle duration were evaluated in female offspring. Female offspring were mated and both a GTT and ITT performed during pregnancy. Neonatal STZ administration caused mild hyperglycemia during pregnancy and changed some aspects of maternal care. The hyperglycemic intrauterine milieu impaired physical development and increased immobility in the open field in the offspring although the latter effect appeared at different ages for males (adulthood) and females (infancy). There was no impairment in the sexual behavior of either male or female offspring. As adults, female offspring of STZ-treated mothers did not show glucose intolerance during pregnancy. Thus, offspring of female rats that show mild hyperglycemia in pregnancy have fewer behavioral and developmental impairments than previously reported in the offspring of severely diabetic dams suggesting that the degree of impairment is directly related to the mother glycemic intensity. (C) 2012 Elsevier Inc. All rights reserved.

First principles calculations for vacancies and antisites in PbSe and PbTe: bulk and nanowire.

The energetic stability and the electronic properties of vacancies (VX) and antisites (XY) in PbSe and PbTe are investigated. PbSe and PbTe are narrow band gap semiconductors and have the potential to be used in infrared detectors, laser, and diodes. They are also of special interest for thermoelectric devices (TE). The calculations are based in the Density Functional Theory (DFT) and the General Gradient Approximation (GGA) for the exchange-correlation term, as implemented in the VASP code. The core and valence electrons are described by the Projected Augmented Wave (PAW) and the Plane Wave (PW) methods, respectively. The defects are studied in the bulk and nanowire (NW) system. Our results show that intrinsec defects (vacancies and antisites) in PbTe have lower formation energies in the NW as compared to the bulk and present a trend in migrate to the surface of the NW. For the PbSe we obtain similar results when compare the formation energy for the bulk and NW. However, the Pb vacancy and the antisites are more stable in the core of the NW. The intrinsec defects are shallow defects for the bulk system. For both PbSe and PbTe VPb is a shallow acceptor defect and VSe and VT e are shallow donor defects for the PbSe and PbTe, respectively. Similar electronic properties are observed for the antisites. For the Pb in the anion site we obtain an n-type semiconductor for both PbSe and PbTe, SeP b is a p-type for the PbSe, and T eP b is a n-type for PbTe. Due the quantum con¯nement effects present in the NW (the band gap open), these defects have different electronic properties for the NW as compared to the bulk. Now these defects give rise to electronic levels in the band gap of the PbTe NW and the VT e present a metallic character. For the PbSe NW a p-type and a n-type semiconductor is obtained for the VP b and P bSe, respectively. On the other hand, deep electronic levels are present in the band gap for the VSe and SePb. These results show that due an enhanced in the electronic density of states (DOS) near the Fermi energy, the defective PbSe and PbTe are candidates for efficient TE devices.

Universal behavior of the Shannon mutual information of critical quantum chains

We consider the Shannon mutual information of subsystems of critical quantum chains in their ground states. Our results indicate a universal leading behavior for large subsystem sizes. Moreover, as happens with the entanglement entropy, its finite-size behavior yields the conformal anomaly c of the underlying conformal field theory governing the long-distance physics of the quantum chain. We study analytically a chain of coupled harmonic oscillators and numerically the Q-state Potts models (Q = 2, 3, and 4), the XXZ quantum chain, and the spin-1 Fateev-Zamolodchikov model. The Shannon mutual information is a quantity easily computed, and our results indicate that for relatively small lattice sizes, its finite-size behavior already detects the universality class of quantum critical behavior.