An analytical relation between entropy production and quantum Lyapunov exponents for Gaussian bipartite systems

We study and compare the information loss of a large class of Gaussian bipartite systems. It includes the usual Caldeira-Leggett-type model as well as Anosov models ( parametric oscillators, the inverted oscillator environment, etc), which exhibit instability, one of the most important characteristics of chaotic systems. We establish a rigorous connection between the quantum Lyapunov exponents and coherence loss, and show that in the case of unstable environments coherence loss is completely determined by the upper quantum Lyapunov exponent, a behavior which is more universal than that of the Caldeira-Leggett-type model.

Why Implementing History and Philosophy in School Science Education is a Challenge: An Analysis of Obstacles

Teaching and learning with history and philosophy of science (HPS) has been, and continues to be, supported by science educators. While science education standards documents in many countries also stress the importance of teaching and learning with HPS, the approach still suffers from ineffective implementation in school science teaching. In order to better understand this problem, an analysis of the obstacles of implementing HPS into classrooms was undertaken. The obstacles taken into account were structured in four groups: 1. culture of teaching physics, 2. teachers` skills, epistemological and didactical attitudes and beliefs, 3. institutional framework of science teaching, and 4. textbooks as fundamental didactical support. Implications for more effective implementation of HPS are presented, taking the social nature of educational systems into account.

Heteroscedastic controlled calibration model applied to analytical chemistry

In chemical analyses performed by laboratories, one faces the problem of determining the concentration of a chemical element in a sample. In practice, one deals with the problem using the so-called linear calibration model, which considers that the errors associated with the independent variables are negligible compared with the former variable. In this work, a new linear calibration model is proposed assuming that the independent variables are subject to heteroscedastic measurement errors. A simulation study is carried out in order to verify some properties of the estimators derived for the new model and it is also considered the usual calibration model to compare it with the new approach. Three applications are considered to verify the performance of the new approach. Copyright (C) 2010 John Wiley & Sons, Ltd.

Approaches for multicopper oxidases in the design of electrochemical sensors for analytical applications

We report an effective approach for the construction of a biomimetic sensor of multicopper oxidases by immobilizing a cyclic-tetrameric copper(II) species, containing the ligand (4-imidazolyl)ethylene-2-amino-1-ethylpyridine (apyhist), in the Nafion (R) membrane on a vitreous carbon electrode surface. This complex provides a tetranuclear arrangement of copper ions that allows an effective reduction of oxygen to water, in a catalytic cycle involving four electrons. The electrochemical reduction of oxygen was studied at pH 9.0 buffer solution by using cyclic voltammetry, chronoamperometry, rotating disk electrode voltammetry and scanning electrochemical microscopy techniques. The mediator shows good electrocatalytic ability for the reduction of O(2) at pH 9.0, with reduction of overpotential (350 mV) and increased current response in comparison with results obtained with a bare glassy carbon electrode. The heterogeneous rate constant (k(ME)`) for the reduction of O(2) at the modified electrode was determined by using a Koutecky-Levich plot. In addition, the charge transport rate through the coating and the apparent diffusion coefficient of O(2) into the modifier film were also evaluated. The overall process was found to be governed by the charge transport through the coating, occurring at the interface or at a finite layer at the electrode/coating interface. The proposed study opens up the way for the development of bioelectronic devices based on molecular recognition and self-organization. (C) 2010 Elsevier Ltd. All rights reserved.

Exploring Liquid Sequential Injection Chromatography To Teach Fundamentals of Separation Methods: A Very Fast Analytical Chemistry Experiment

Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP)

Development of an Analytical Methodology for Quantification of Strong Acid in Diesel Oil

Many factors can affect the quality of diesel oil, in particular the degradation processes that are directly related to some organosulfur compounds. During the degradation process, these compounds are oxidized into their corresponding sulfonic acids, generating a strong acid content during the process. p-Toluene sulfonic acid analysis was performed using the linear sweep voltammetry technique with a platinum ultramicroelectrode in aqueous solution containing 3 mol L(-1) potassium chloride. An extraction step was introduced prior to the voltammetric detection in order to avoid the adsorption of organic molecules, which inhibit the electrochemical response. The extraction step promoted the transference of sulfonic acid from the diesel oil to an aqueous phase. The method was accurate and reproducible, with detection and quantification limits of 5 ppm and 15 ppm, respectively. Recovery of sulfonic acid was around 90%.

Graphite-silicone rubber composite electrode: Preparation and possibilities of analytical application

Composite electrodes were prepared using graphite powder and silicone rubber in different compositions. The use of such hydrophopic materials interned to diminish the swallowing observed in other cases when the electrodes are used in aqueous solutions for a long time. The composite was characterized for the response reproducibility, ohmic resistance, thermal behavior and active area. The voltammetric response in relation to analytes with known voltammetric behavior was also evaluated, always in comparison with the glassy carbon. The 70% (graphite, w/w) composite electrode was used in the quantitative determination of hydroquinone (HQ) in a DPV procedure in which a detection limit of 5.1 x 10(-8) mol L-1 was observed. HQ was determined in a photographic developer sample with errors lower then 1% in relation to the label value. (c) 2007 Elsevier B.V. All rights reserved.

Analytical Potentialities of Carbon Nanotube/Silicone Rubber Composite Electrodes: Determination of Propranolol

A new composite electrode based on multiwall carbon nanotubes (MWCNT) and silicone-rubber (SR) was developed and applied to the determination of propranolol in pharmaceutical formulations. The effect of using MWCNT/graphite mixtures in different proportions was also investigated. Cyclic voltammetry and electrochemical impedance spectroscopy were used for electrochemical characterization of different electrode compositions. Propranolol was determined using MWCNT/SR 70% (m/m) electrodes with linear dynamic ranges up to 7.0 mu molL(-1) by differential pulse and up to 5.4 mu molL(-1) by square wave voltammetry, with LODs of 0.12 and 0.078 mu molL(-1), respectively. Analysis of commercial samples agreed with that obtained by the official spectrophotometric method. The electrode is mechanically robust and presented reproducible results and a long useful life.

Diagnostics for the Developing World: Microfluidic Paper-Based Analytical Devices

Microfluidic paper-based analytical devices (mu PADs) are a new class of point-of-care diagnostic devices that are inexpensive, easy to use, and designed specifically for use in developing countries. (To listen to a podcast about this feature, please go to the Analytical Chemistry multimedia page at pubs.acs.org/page/ancham/audio/index.html.)

On the molecular mass of the extracellular hemoglobin of Glossoscolex paulistus: Analytical ultracentrifugation reexamination

The giant extracellular hemoglobin of Glossoscolex paulistus (HbGp) is constituted by Subunits containing heme groups with molecular masses (M) in the range of 15 to 19 kDa, monomers of 16 kDa (d), and trimers of 51 to 52 kDa (abc) linked by nonheme structures named linkers of 24 to 32 kDa (L). HbGp is homologous to Lumbricus terrestris hemoglobin (HbLt). Several reports propose M of HbLt in the range of 3.6 to 4.4 MDa. Based on subunits M determined by mass spectrometry and assuming HbGp stoichiometry of 12(abcd)(3)L(3) (Vinogradov model) plus 144 heme groups, a Value of M for HbGp oligomer of 3560 kDa can be predicted. This Value is nearly 500 kDa higher than the unique HbGp M Value reported in the literature. In the current work, sedimentation velocity analytical ultracentrifugation (AUC) experiments were performed to obtain M for HbGp in oxy and cyano-met forms. s(20,w)(0), values of 58.1 +/- 0.2 S and 59.6 +/- 0.2 S, respectively, for the two oxidation forms were obtained. The ratio between sedimentation and diffusion coefficients supplied values for M of approximately 3600 100 and 3700 100 kDa for oxy and cyano-met HbGp forms, respectively. An independent determination of the partial specific volume, V(bar), for HbGp was performed based on density measurements, providing a value of 0.764 +/- 0.008, in excellent agreement with the estimates from SEDFIT software. Our results show total consistency between M obtained by AUC and recent partial characterization by mass spectrometry. Therefore, HbGp possesses M very close to that of HbLt, suggesting an oligomeric assembly in agreement with the Vinogradov model. (c) 2008 Elsevier Inc. All rights reserved.

Analytical Assessment of a Home Made Capillary Electrophoresis Equipment with Linear Charge Coupled Device for Visible Light Absorption Detection in the Determination of Food Dyes

The performance of modular home made capillary electrophoresis equipment with spectrophotometric detection, at a visible region by means of a miniaturized linear charge coupled device, was evaluated for the determination of four food dyes. This system presents a simple but efficient home made cell detection scheme. A computer program that converts the spectral data after each run into the electropherograms was developed to evaluate the analytical parameters. The dyes selected for analytical evaluation of the system were Brilliant Blue FCF, Fast Green FCF, Sunset Yellow FCF, and Amaranth. Separation was carried out in a 29cm length and 75 mu m I.D fused silica capillary, using 10mmolL-1 borate buffer at pH 9, with separation voltage of 7.5kV. The detection limits for the dyes were between 0.3 and 1.5mgL-1 and the method presented adequate linearity over the ranges studied, with correlation coefficients greater than 0.99. The method was applied for determination and quantification of these dyes in fruit juices and candies.

Comparison of the analytical performance of electrophoresis microchannels fabricated in PDMS, glass, and polyester-toner

This paper compares the analytical performance of microchannels fabricated in PDMS, glass, and polyester-toner for electrophoretic separations. Glass and PDMS chips were fabricated using well-established photolithographic and replica-molding procedures, respectively. PDMS channels were sealed against three different types of materials: native PDMS, plasma-oxidized PDMS, and glass. Polyester-toner chips were micromachined by a direct-printing process using an office laser printer. All microchannels were fabricated with similar dimensions according to the limitations of the direct-printing process (width/depth 150 mu m/12 mu m). LIF was employed for detection to rule out any losses in separation efficiency due to the detector configuration. Two fluorescent dyes, coumarin and fluorescein, were used as model analytes. Devices were evaluated for the following parameters related to electrophoretic separations: EOF, heat dissipation, injection reproducibility, separation efficiency, and adsorption to channel wall.

Vad händer med dialogen? : En studie av dialogisk interaktion mellan pedagog och barn i förskolan

The overall purpose of this study is to gain knowledge about dialogues in the setting of the preschool. The more in-depth purpose is to highlight what happens in dialogues between a teacher and a child when more children join the situation of interaction in which the dialogue is taking place. A further purpose is to attempt to understand what it is that influences change in the dialogue and what significance the actions of the teacher can have for this change. The study is based on several questions that concern interaction in preschools, who it is that initiates an increase in the number of participants in those situations that involve dialogue, and what happens with the dialogue when more children join and what causes the change in the dialogue. The study is based on video observations from a preschool; approximately 10 teachers and 50 children between the ages of one and six took part in the study. The situations that were observed and documented in video format were everyday activities (both indoor and outdoor) that were led at a nominal level by teachers. In total, 40 films were recorded. Film length was between one and 60 minutes. In 32 of the films, there was interaction between a teacher and several children, and 18 of these included dialogues between a teacher and several children. Dialogue is here given a specific significance and refers to the interaction that can be described in terms of presence, listening, reciprocity, and extending. This definition of dialogue derives from a combination of Martin Buber’s philosophy of dialogue and aspects of interaction that earlier research found to be significant for children’s learning. In two of the 18 films that showed dialogue, no other children became part of the situation of interaction; the remaining 16 films were transcribed; and both verbal and non-verbal events were made apparent in the transcriptions. Analyses of the recorded material and of the transcriptions were conducted using analytical terms borrowed from conversation analysis as well as the central term for this study dialogue.  The results demonstrate a complex practice and also demonstrate that dialogues in the sense given in this study take place between children and teachers. Situations of interaction also occur where dialogues take place in which a number of children join. It can be the child joining the situation of interaction who takes the initiative to an increased number of participants; however, it can also be the teacher or the child in the dialogue. The initial address can take place during a moment of transition in the interaction or at the same time as another participant is talking. The dialogue often changes when more children join the situation where the dialogue is taking place. The dialogue can end completely or be interrupted and resume. The results further demonstrate that the dialogue can continue without seemingly being affected by the fact that more children join. This happens when the child joining and the teacher in the dialogue interact in a non-verbal manner at the same time as the teacher is talking with the child in the dialogue. The dialogue can also be continued with more participants. Who takes the initiative, how the initial address occurs, and which content is given focus by the different participants are all factors that seem to affect what happens to the dialogue. How the teacher acts when more children join also appears to be significant in terms of what happens with the dialogue when more children join. In those situations where the teacher begins talking with a number of children about different subjects, the interaction ceases to be dialogic. When the teacher asks the joining child to wait, the dialogue is both interrupted and resumed, and on those occasions when the dialogue continues with more participants, the teacher listens to the joining child and the participants take turns speaking.

Dissonant Voices : Philosophy, Children's Literature, and Perfectionist Education

Dissonant Voices has a twofold aspiration. First, it is a philosophical treatment of everyday pedagogical interactions between children and their elders, between teachers and pupils. More specifically it is an exploration of the possibilities to go on with dissonant voices that interrupt established practices – our attunement – in behaviour, practice and thinking. Voices that are incomprehensible or expressions that are unacceptable, morally or otherwise. The text works on a tension between two inclinations: an inclination to wave off, discourage, or change an expression that is unacceptable or unintelligible; and an inclination to be tolerant and accept the dissonant expression as doing something worthwhile, but different. The second aspiration is a philosophical engagement with children’s literature. Reading children’s literature becomes a form of philosophising, a way to explore the complexity of a range of philosophical issues. This turn to literature marks a dissatisfaction with what philosophy can accomplish through argumentation and what philosophy can do with a particular and limited set of concepts for a subject, such as ethics. It is a way to go beyond philosophising as the founding of theories that justify particular responses. The philosophy of dissonance and children’s literature becomes a way to destabilise justifications of our established practices and ways of interacting. The philosophical investigations of dissonance are meant to make manifest the possibilities and risks of engaging in interactions beyond established agreement or attunements. Thinking of the dissonant voice as an expression beyond established practices calls for improvisation. Such improvisations become a perfectionist education where both the child and the elder, the teacher and the student, search for as yet unattained forms of interaction and take responsibility for every word and action of the interaction. The investigation goes through a number of picture books and novels for children such as Harry Potter, Garmann’s Summer, and books by Shaun Tan, Astrid Lindgren and Dr. Seuss as well narratives by J.R.R. Tolkien, Henrik Ibsen, Jane Austen and Henry David Thoreau. These works of fiction are read in conversation with philosophical works of, and inspired by, Ludwig Wittgenstein and Stanley Cavell, their moral perfectionism and ordinary language philosophy.

Perfectionist Philosophy as a (an Untaken) Way of Life

I am honored to respond to Paul Guyer’s elaboration on the role of examples of perfectionism in Cavell’s and Kant’s philosophies. Guyer’s appeal to Kant’s notion of freedom opens the way for suggestive readings of Cavell’s work on moral perfectionism but also, as I will show, for controversy. There are salient aspects of both Kant’s and Cavell’s philosophy that are crucial to understanding perfectionism and, let me call it, perfectionist education, that I wish to emphasize in response to Guyer. In responding to Guyer’s text, I shall do three things. First, I shall explain why I think it is misleading to speak of Cavell’s view that moral perfectionism is involved in a struggle to make oneself intelligible to oneself and others in terms of necessary and sufficient conditions for moral perfection. Rather, I will suggest that the constant work on oneself that is at the core of Cavell’s moral perfectionism is a constant work for intelligibility. Second, I shall recall a feature of Cavell’s perfectionism that Guyer does not explicitly speak of: the idea that perfectionism is a theme, “outlook or dimension of thought embodied and developed in a set of texts.” Or, as Cavell goes on to say, “there is a place in mind where good books are in conversation. … [W]hat they often talk about … is how they can be, or sound, so much better than the people that compose them.” This involves what I would call a perfectionist conception of the history of philosophy and the kinds of texts we take to belong to such history. Third, I shall sketch out how the struggle for intelligibility and a perfectionist view of engagement with texts and philosophy can lead to a view of philosophy as a form of education in itself. In concluding these three “criticisms,” I reach a position that I think is quite close to Guyer’s, but with a slightly shifted emphasis on what it means to read Kant and Cavell from a perfectionist point of view.