In Situ Infrared (FTIR) Study of the Mechanism of the Borohydride Oxidation Reaction on Smooth Pt Electrode

Although Pt has been thoroughly studied regarding its activity for the borohydride oxidation reaction (BOR), the BOR mechanism at Pt remains unclear: Depending on the applied potential, spontaneous BH(4)(-) hydrolysis can compete with the direct BOR. The goal of the present work is to provide more insight into the behavior of smooth Pt electrodes toward the BOR, by coupling in situ infrared reflectance spectroscopy with electrochemistry. The measurements were performed on a Pt electrode in 1 M NaOH/1 M NaBH(4), so as to detect the reaction intermediate species generated as a function of the applied potential. Several bands were monitored in the B-H ((v) over bar approximate to 1180, 1080, and 972 cm(-1)) and B-O ((v) over bar = 1325 and similar to 1425 cm(-1)) bond regions upon increased electrode polarization. These absorption bands, which appear sequentially and were already detected for similar measurements on Au electrodes, are assigned to BH(3), BH(2), and BO(2)(-) species. In light of these experimental data and previous results obtained in our group for Pt- or Au-based electrodes, possible initial elementary steps of the BOR on platinum electrodes are proposed and discussed according to the relevant literature data.

Atmospheric pressure photoionization mass spectrometry as a tool for the investigation of the hydrolysis reaction mechanisms of phosphite antioxidants

The hydrolysis reaction mechanism of phosphite antioxidants is investigated by liquid chromatography-mass spectrometry (LC/MS). The phosphites were chosen because they differed in chemical structure and phosphorus content. Dopant assisted-atmospheric pressure photoionization (DA-APPI) is chosen as the ion source for (lie ionization of the compounds. [it our previous work, DA-APPI was shown to offer an attractive alternative to atmospheric pressure chemical ionization (APCI) since it provided background-ion free mass spectra and higher sensitivity [M. Papanastasiou, et al., Polymer Degradation and Stability 91 (11) (2006) 2675-2682]. In positive ion mode, the molecules are generally detected in their protonated form. In negative ion mode, the phosphites are unstable and only fragment ions are observed: these however, are characteristic of each phosphite and may be used for the identification of the analytes in complex mixtures. The analytes under investigation are exposed to accelerated humid ageing conditions and their hydrolytic pathway and stability is investigated. Different substituents around the phosphorus atom are shown to have a significant effect on the stability of the phosphites, with phenol substituents producing very hydrolytically stable structures. Alkanox P24 and PEP-36 follow a similar hydrolytic pathway via the scission of the first and then the second P-O-phenol bonds, eventually leading to the formation of phenol, Phosphorous acid and pentaerythritol as end products. HP-10 exhibits a rather different Structure and the products detected suggest scission of either the P-O-hydrocarbon or one of the P-O-phenol bonds. A phenomenon similar to that of autocatalysis is observed for all phosphites and is attributed to the formation of dialkyl phosphites as intermediate products. (C) 2008 Elsevier B.V. All rights reserved.

Kinetics of autocatalytic acid hydrolysis of cellulose with crystalline and amorphous fractions

The acid hydrolysis of cellulose with crystalline and amorphous fractions is analyzed on the basis of autocatalytic model with a positive feedback of acid production from the degraded biopolymer. In the condition of low acid rate production compared with hydrolysis rate, both fraction of cellulose decrease exponentially with linear and cubic time dependence, and the normalized number of scissions per cellulose chain follows a sigmoid behavior with reaction time. The model predicts that self generated acidic compounds from cellulose accelerate the degradation of the biopolymer. However, if the acidic compounds produced are volatile species, then their release under low pressure will reduce the global rate of degradation of cellulose toward its intrinsic rate value determined by the residual acid catalyst present in the starting material.

Approximate solution of the autocatalytic hydrolysis of cellulose

Depolymerization of cellulose in homogeneous acidic medium is analyzed on the basis of autocatalytic model of hydrolysis with a positive feedback of acid production from the degraded biopolymer. The normalized number of scissions per cellulose chain, S(t)/nA degrees A = 1 - C(t)/C(0), follows a sigmoid behavior with reaction time t, and the cellulose concentration C(t) decreases exponentially with a linear and cubic time dependence, C(t) = C(0)exp[-at - bt (3)], where a and b are model parameters easier determined from data analysis.

Determination of amino acids by capillary electrophoresis-electrospray ionization-mass spectrometry: An evaluation of different protein hydrolysis procedures

In this work, a CE equipment, online hyphenated to an IT MS analyzer by a linear sheath liquid interface promoting ESI, was used to develop a method for quantitative determination of amino acids. Under appropriate conditions (BGE composition, 0.8% HCOOH, 20% CH(3)OH; sheath liquid composition, 0.8% HCOOH, 60% methanol; V(ESI), +4.50 W), analytical curves of all amino acids from 3 to 80 mg/L were recorded presenting acceptable linearity (r > 0.99). LODs in the range of 16-172 mu mol/L were obtained. BSA, a model protein, was submitted to different hydrolysis procedures (classical acid and basic, and catalyzed by the H(+) form of a cation exchanger resin) and its amino acid profiles determined. In general, the resin-mediated hydrolysis yields were overall similar or better than those obtained by classical acid or basic hydrolysis. The resulting experimental-to-theoretical BSA concentration ratios served as correction factors for the quantitation of amino acids in Brazil nut resin generated hydrolysates.

Hamiltonian constraint analysis of vector field theories with spontaneous Lorentz symmetry breaking

Recent investigations of various quantum-gravity theories have revealed a variety of possible mechanisms that lead to Lorentz violation. One of the more elegant of these mechanisms is known as Spontaneous Lorentz Symmetry Breaking (SLSB), where a vector or tensor field acquires a nonzero vacuum expectation value. As a consequence of this symmetry breaking, massless Nambu-Goldstone modes appear with properties similar to the photon in Electromagnetism. This thesis considers the most general class of vector field theories that exhibit spontaneous Lorentz violation-known as bumblebee models-and examines their candidacy as potential alternative explanations of E&M, offering the possibility that Einstein-Maxwell theory could emerge as a result of SLSB rather than of local U(1) gauge invariance. With this aim we employ Dirac's Hamiltonian Constraint Analysis procedure to examine the constraint structures and degrees of freedom inherent in three candidate bumblebee models, each with a different potential function, and compare these results to those of Electromagnetism. We find that none of these models share similar constraint structures to that of E&M, and that the number of degrees of freedom for each model exceeds that of Electromagnetism by at least two, pointing to the potential existence of massive modes or propagating ghost modes in the bumblebee theories.

Vector Theory of Spontaneous Lorentz Violation

Classical electromagnetism predicts two massless propagating modes, which are known as the two polarizations of the photon. On the other hand, if the Lorentz symmetry of classical electromagnetism is spontaneously broken, the new theory will still have two massless Nambu-Goldstone modes resembling the photon. If the Lorentz symmetry is broken by a bumblebee potential that allows for excitations out of the minimum, then massive modes arise. Furthermore, in curved spacetime, such massive modes will be created through a process other than the usual Higgs mechanism because of the dependence of the bumblebee potential on both the vector field and the metric tensor. Also, it is found that these massive modes do not propagate due to the extra constraints.

"Spontaneous overflow of powerful feelings" : romantic imagery in Mary Shelley's Frankstein

Romantic English literature – written at a time when prose fiction was predominantly a medium for sheer entertainment – is rooted in poetry. One or two novelists may exceptionally be granted the adjective “Romantic”, but Mary Shelley is not ranked among them. For centuries, her work has been restricted to that section in handbooks reserved for exotic Gothic literature. This thesis argues that literary criticism has failed to recognize Frankenstein’s obvious relation with the movement. The argument will be fostered by a brief look at such handbooks, and developed through the analysis of the imagery of the novel, so as to trace the Romantic elements there contained. The analysis relies mainly on the frame developed by Northrop Frye concerning the nature and function of imagery in literature. The concept of intertextuality will also be useful as a tool to account for the insertion of images in the novel, and for the novel’s insertion within the Romantic context. The work is divided into three parts. The first contextualizes the main issues set forth by Frankenstein, establishing connections with the life of the author and with the Romantic movement. The second exposes the theoretical basis on which the thesis is grounded. The last presents my reading of the novel’s web of images. In the end, I hope to validate the thesis proposed, that Frankenstein embodies the aesthetic and philosophical assessments of the English Romantic agenda, and therefore deserves to be situated in its due place in the English Literary canon as the legitimate representative of Romanticism in prose form.

Hudumia: a platform to support spontaneous volunteers' situational awareness, coordination and safety underemergency scenarios

Spontaneous volunteers always emerge under emergency scenarios and are vital to a successful community response, yet some uncertainty subsists around their role and its inherent acceptance by official entities under emergency scenarios. In our research we have identified that most of the spontaneous volunteers do have none or little support from official entities, hence they end up facing critical problems as situational awareness, safety instructions and guidance, motivation and group organization. We argue that official entities still play a crucial role and should change some of their behaviors regarding spontaneous volunteerism. We aim with this thesis to design a software architecture and a framework in order to implement a solution to support spontaneous volunteerism under emergency scenarios along with a set of guidelines for the design of open information management systems. Together with the collaboration from both citizens and emergency professionals we have been able to attain several important contributions, as the clear identification of the roles taken by both spontaneous volunteers and professionals, the importance of volunteerism in overall community response and the role which open collaborative information management systems have in the community volunteering efforts. These conclusions have directly supported the design guidelines of our software solution proposal. In what concerns to methodology, we first review literature on technologies support to emergencies and how spontaneous volunteers actually challenge these systems. Following, we have performed a field research where we have observed that the emerging of spontaneous volunteer’s efforts imposes new requirements for the design of such systems, which leaded to the creation of a cluster of design guidelines that supported our software solution proposal to address the volunteers’ requirements. Finally we have architected and developed an online open information management tool which has been evaluated via usability engineering methods, usability user tests and heuristic evaluations.

Post consumer pet depolymerization by acid hydrolysis

The reaction of post-consumer poly(ethylene terephthalate) with aqueous solutions of sulfuric acid 7.5M was investigated in terms of temperature, time and particle size. The reaction extent reached 80% in four days at 100 degrees C and 90% in 5 hours at 135 degrees C. TPA obtained was purified and considered in the same level of quality of the commercial one after tests of elemental analysis, particle size and color. It was concluded that the hydrolysis occurred preferentially at the chain ends and superficially, having as controller mechanism the acid diffusion into the polymer structure. The shrinking-core model can explain the reaction kinetics.

Modeling upper eyelid kinematics during spontaneous and reflex blinks

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Spontaneous Blinking in Patients With Graves' Upper Eyelid Retraction

Purpose: To describe spontaneous blink kinematics in Graves' upper eyelid retraction (UER).Methods: The magnetic search coil technique was used to record spontaneous blinks of 15 healthy subjects (aged 23-56 years, 15 eyelids) and 15 patients with Graves' UER (aged 22-62 years, 15 eyelids) during a 5-min period of video observation, and the signals were digitized at 200 Hz (12 bits). Overall, a total of 2,798 blinks were recorded for the controls and 1,860 for the patients. The distance between pupil center and upper eyelid margin in the primary position of gaze (MRD) was measured with the Image J software.Results: The blinking rate of patients was lower than that of control subjects, with a mean (+/-SEM) blinking rate (blinks/min) of 13.0 +/- 1.7 for patients and of 20.0 +/- 2.1 for the controls (t = 2.58, P = 0.016). There were no statistically significant differences in blink amplitude between controls (22.7 +/- 3.1 degrees) and Graves' patients (24.7 +/- 3.3 degrees). However, while only 22% of the blinks performed by controls were smaller than MRD, this rate was 78% for patients. In addition, in blinks larger than 25, patients showed lower down-phase velocity than controls.Conclusions: Patients with Graves' UER show reduced blinks rates and abnormal blink kinematics, which might be related to the development of exposure keratitis in this disease.

Spontaneous Interblink Time Distributions in Patients with Graves' Orbitopathy and Normal Subjects

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Intra-prostatic injection of botulinum toxin type A in treatment of dogs with spontaneous benign prostatic hyperplasia

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)