Response characteristics of optical sensors for oxygen: models based on a distribution in tau(o) or kappa(q)

The features of two popular models used to describe the observed response characteristics of typical oxygen optical sensors based on luminescence quenching are examined critically. The models are the 'two-site' and 'Gaussian distribution in natural lifetime, tau(o),' models. These models are used to characterise the response features of typical optical oxygen sensors; features which include: downward curving Stern-Volmer plots and increasingly non-first order luminescence decay kinetics with increasing partial pressures of oxygen, pO(2). Neither model appears able to unite these latter features, let alone the observed disparate array of response features exhibited by the myriad optical oxygen sensors reported in the literature, and still maintain any level of physical plausibility. A model based on a Gaussian distribution in quenching rate constant, k(q), is developed and, although flawed by a limited breadth in distribution, rho, does produce Stern-Volmer plots which would cover the range in curvature seen with real optical oxygen sensors. A new 'log-Gaussian distribution in tau(o) or k(q)' model is introduced which has the advantage over a Gaussian distribution model of placing no limitation on the value of rho. Work on a 'log-Gaussian distribution in tau(o)' model reveals that the Stern-Volmer quenching plots would show little degree in curvature, even at large rho values and the luminescence decays would become increasingly first order with increasing pO(2). In fact, with real optical oxygen sensors, the opposite is observed and thus the model appears of little value. In contrast, a 'log-Gaussian distribution in k(o)' model does produce the trends observed with real optical oxygen sensors; although it is technically restricted in use to those in which the kinetics of luminescence decay are good first order in the absence of oxygen. The latter model gives a good fit to the major response features of sensors which show the latter feature, most notably the [Ru(dpp)(3)(2+)(Ph4B-)(2)] in cellulose optical oxygen sensors. The scope of a log-Gaussian model for further expansion and, therefore, application to optical oxygen sensors, by combining both a log-Gaussian distribution in k(o) with one in tau(o) is briefly discussed.

Effect of plasticizer viscosity on the sensitivity of an [RU(bpy)(3)(2+)(Ph4B-)(2)]-based optical oxygen sensor

The quenching of the electronically-excited, lumophoric state of [Ru(bpy)(3)(2+)(Ph4B-)(2)] by oxygen is studied in a wide variety of neat plasticizers. The Stern-Volmer constant, K-SV, is found to be inversely dependent upon the viscosity of the quenching medium, although the natural lifetime of the electronically excited state of [RU(bPY)(3)(2+)(Ph4B-)(2)] is largely independent of medium. The least viscous of the plasticizers tested, triethyl phosphate, did not, however, produce highly sensitive optical oxygen sensors when used to plasticize [RU(bPY)(3)(2+)(Ph4B-)(2)]-containing cellulose acetate butyrate (CAB) and poly(methyl methacrylate) (PMMA) films, Instead, the compatibility of the polymer-plasticizer combination, as measured by the difference in the values of the solubility parameter of the two, appears to be a major factor in determining the overall oxygen sensitivity of the thin plastic films. For highly compatible polymer-plasticizer combinations, the plasticizer with the lowest viscosity produces films of the highest oxygen sensitivity. This situation arises because in the film the quenching process is partly diffusion-controlled and, as a result, the quenching rate constant is inversely proportional to the effective viscosity of the reaction medium.

Use of luminescent gold compounds in the design of thin-film oxygen sensors

The use of two gold compounds incorporated into thin plastic films as luminescence quenching oxygen sensors is described. The films are sensitive both to gaseous oxygen and to oxygen dissolved in nonaqueous media such as ethanol. The luminescence quenching of these sensors by oxygen obeys the Stern-Volmer equation and Stern-Volmer constants of 5.35 x 10(-3) and 0.9 x 10(-3) Torr(-1) are found, respectively, for the two dyes in a polystyrene polymer matrix. The sensitivity of the films is strongly influenced by the nature of the polymer matrix, and greatest sensitivity was found in systems based an the polymers polystyrene or cellulose acetate butyrate. Sensitivity was not found to be temperature dependent though raising the temperature hom 15 to 50 degrees C did result in a slight decrease in emission intensity and a hypsochromic shift in the emission wavelength. The rate of response and recovery of the sensors can be increased either by decreasing film thickness or by increasing the operating temperature. The operational and storage stability of these films is generally good though exposure to light should be avoided as one of the dyes tends to undergo photobleaching probably due to a photoinduced ligand substitution reaction.

The Type IIb SN 2008ax: spectral and light curve evolution

We present spectroscopy and photometry of the He-rich supernova (SN) 2008ax. The early-time spectra show prominent P-Cygni H lines, which decrease with time and disappear completely about 2 months after the explosion. In the same period He I lines become the most prominent spectral features. SN 2008ax displays the ordinary spectral evolution of a Type IIb supernova. A stringent pre-discovery limit constrains the time of the shock breakout of SN 2008ax to within only a few hours. Its light curve, which peaks in the B band about 20 d after the explosion, strongly resembles that of other He-rich core-collapse supernovae. The observed evolution of SN 2008ax is consistent with the explosion of a young Wolf-Rayet (of WNL type) star, which had retained a thin, low-mass shell of its original H envelope. The overall characteristics of SN 2008ax are reminiscent of those of SN 1993J, except for a likely smaller H mass. This may account for the findings that the progenitor of SN 2008ax was a WNL star and not a K supergiant as in the case of SN 1993J, that a prominent early-time peak is missing in the light curve of SN 2008ax, and that H alpha is observed at higher velocities in SN 2008ax than in SN 1993J.

A whole-genome massively parallel sequencing analysis of BRCA1 mutant oestrogen receptor-negative and -positive breast cancers

BRCA1 encodes a tumour suppressor protein that plays pivotal roles in homologous recombination (HR) DNA repair, cell-cycle checkpoints, and transcriptional regulation. BRCA1 germline mutations confer a high risk of early-onset breast and ovarian cancer. In more than 80% of cases, tumours arising in BRCA1 germline mutation carriers are oestrogen receptor (ER)-negative; however, up to 15% are ER-positive. It has been suggested that BRCA1 ER-positive breast cancers constitute sporadic cancers arising in the context of a BRCA1 germline mutation rather than being causally related to BRCA1 loss-of-function. Whole-genome massively parallel sequencing of ER-positive and ER-negative BRCA1 breast cancers, and their respective germline DNAs, was used to characterize the genetic landscape of BRCA1 cancers at base-pair resolution. Only BRCA1 germline mutations, somatic loss of the wild-type allele, and TP53 somatic mutations were recurrently found in the index cases. BRCA1 breast cancers displayed a mutational signature consistent with that caused by lack of HR DNA repair in both ER-positive and ER-negative cases. Sequencing analysis of independent cohorts of hereditary BRCA1 and sporadic non-BRCA1 breast cancers for the presence of recurrent pathogenic mutations and/or homozygous deletions found in the index cases revealed that DAPK3, TMEM135, KIAA1797, PDE4D, and GATA4 are potential additional drivers of breast cancers. This study demonstrates that BRCA1 pathogenic germline mutations coupled with somatic loss of the wild-type allele are not sufficient for hereditary breast cancers to display an ER-negative phenotype, and has led to the identification of three potential novel breast cancer genes (ie DAPK3, TMEM135, and GATA4).

The synthesis and chemistry of formylphosphonate

New methods of synthesis and reactions of formylphosphonate have been investigated. Attempts to deprotect the corresponding diethyl acetal with Ti-IV halides led instead to the formation of halo(ethoxy)methylphosphonates which undergo substitution reactions with a wide range of nucleophiles. The products of reactions of formylphosphonate with bifunctional nucleophiles are determined in most cases by Baldwin's Roles, while the imines derived from formylphosphonate undergo Diels-Alder reactions only in those cases which carry a strongly electron-withdrawing N-substituent.

Morphological study of the uncommon rectus sterni muscle in German cadavers

Objective: The present investigation has been designed to study the incidence of the rectus stern muscle in German human cadavers dissected in the Kingdom of Saudi Arabia, trying to find a postulation for the development of such muscle when present. Design: Gross dissection of 130 cadavers, of both sexes, was performed throughout a period of 10 years. Setting: Department of Anatomy College of Medicine, King Faisal University, Dammam, Saudi Arabia. Intervention: Investigation of the origin and insertion of the rectus sterni and measurements of its length and width. Results: Two adult cadavers, one of each sex, had shown well-developed bilateral rectus stern muscles. All muscles identified were parasternal in position, being superficial to the medial portion of the pectoralis major muscle. Minor morphological differences were observed among the four muscle masses concerning their length, breadth, origin and insertion. Conclusion: The current study has determined the incidence of the rectus sterni muscle, in German cadavers to be 1.54% per bodies examined compared to 4% in cadavers from Saudis. Such a frequency is compared to that reported in different geographic populations. The rectus sterni muscle is innervated by the anterior cutaneous branches of the intercostal nerves. The description of the rectus sterni muscle and its incidence determined in the present study, might be of a great help for clinicians radiographing or tackling the pectoral region.

European Cystic Fibrosis Society Standards of Care: Quality Management in cystic fibrosis

Since the earliest days of cystic fibrosis (CF) treatment, patient data have been recorded and reviewed in order to identify the factors that lead to more favourable outcomes. Large data repositories, such as the US Cystic Fibrosis Registry, which was established in the 1960s, enabled successful treatments and patient outcomes to be recognized and improvement programmes to be implemented in specialist CF centres. Over the past decades, the greater volumes of data becoming available through Centre databases and patient registries led to the possibility of making comparisons between different therapies, approaches to care and indeed data recording. The quality of care for individuals with CF has become a focus at several levels: patient, centre, regional, national and international. This paper reviews the quality management and improvement issues at each of these levels with particular reference to indicators of health, the role of CF Centres, regional networks, national health policy, and international data registration and comparisons. 

Reva Siegel and the Role of Religion in Constructing the Meaning of ‘Human Dignity

The “religious understanding” of dignity is a topic of considerable complexity and is the subject of extensive scholarship. In this paper, I consider understandings of dignity that are currently under discussion in Roman Catholic circles, not least because Catholic discussions of dignity are often seen as influential in public policy and legal interpretation, directly and indirectly. I shall focus on one relatively neglected issue in legal scholarship: how scholars go about the task of identifying what a particular religion’s understanding of human dignity involves.
To illustrate the methodological problems that such an enterprise raises, I shall take one attempt by a scholar writing in the field of secular legal scholarship to describe Catholic understandings of dignity in the context of abortion and same-sex marriage. The discussion is that of Reva Siegel, an academic lawyer at Yale University; her recent analysis of differing understandings of dignity illustrates some of the issues that arise when the secular scholarly community addresses religious understandings of dignity.

Mögliche neue Strukturen im Ortsnetz und ihre minimale Länge

Auch für das Teilnehmeranschlußnetz werden neben dem heute üblichen „Sternnetz" neuerdings „Ring-" und „Verzweigungsnetze" genannt, und es wird die Frage diskutiert, ob damit geringere Kosten zu erwarten sind. Mit Begriffen der Graphentheorie werden hier z.B. die Strukturen Stern, Ring, Baum definiert. Ein gedachtes Ortsnetz wird dann in quadratische Bereiche mit der Seitenlänge l und mit M Teilnehmern aufgeteilt. Für verschiedene Strukturen des Leiternetzes in der Teilnehmerebene werden die Mindestlängen der Leiter und der Kabelkanäle berechnet. Unter anderem zeigt sich, daß unabhängig von der Struktur des Leiternetzes die Kabelkanäle, ein dominierender Kostenanteil in der Teilnehmerebene, praktisch gleich lang sind, nämlich l/M^0,5 je Teilnehmer.

CarolFest 2010, December 7, 2010

Concert program for CarolFest 2010, December 7, 2010

O feminino na obra de Uanhenga Xitu

Interessa-nos para este artigo perscrutar as representações da vida social em narrativas do escritor angolano Uanhenga Xitu, mormente no que diz respeito à personagem feminina e ao papel da mulher nas sociedades tradicionais angolanas. Nas narrativas cujas ações se passam no interior de Angola, as representações sociais da mulher revelam um modus vivendi diferenciado daquele experimentado por mulheres que migram para a capital, Luanda, espaço em que a noção de vida comunitária, tão significativa nas sociedades tradicionais, perde seu significado. Os trabalhos lá executados, por exemplo, serão em favor do colono, como os dos empregados domésticos, e não para a coletividade. Já nos espaços interiores, mais distantes da mão pesada do colonizador, as representações da vida social dos angolanos são mais expressivas e essa diferenciação revela que a migração do campo para a cidade, no caso de um país dominado pela colonização, metaforiza o abandono de um tipo de (con)vivência social em favor de outro. Como a política colonial portuguesa foi assimilacionista, essa migração será sinônimo de busca de adesão ao modus vivendi do outro, muitas vezes para sofrer menos os efeitos da dominação. Para essa discussão, não é por livre escolha que se tratará das personagens femininas na obra de Xitu, posto que as mulheres em seus textos ganham vez e voz para a expressão do proprium angolano, como se o autor as quisesse homenagear em sinal do reconhecimento de sua importância na construção e preservação da memória, que é capaz de criar laços identitários entre as milenares gerações passadas e as futuras, como esboçaremos (Esta reflexão teve origem no estudo desenvolvido no doutoramento, intitulado Entre dois contares: o espaço da tradição na escrita de Uanhenga Xitu, defendida em 1996 na FFLCH-USP, e orientada pela Dra. Maria Aparecida Santilli, falecida em março de 2008).

Sistema de visão para aterragem automática de UAV

Dissertação para obtenção do grau de Mestre em Engenharia Electrotécnica Ramo de Automação e Electrónica Industrial

The dynamics of interfaces: Seven authors in search of encounters across levels of description of an event involving a mother, father, and baby

The interfaces between the intrapsychic, interactional, and intergenerational domains are a new frontier. As a pilot, we exposed ourselves to a complex but controllable situation as viewed by people whose main interest is in one of the three interfaces; we also fully integrated the subjects in the team, to learn about their subjective perspectives and to provide them with an enriching experience. We started with a brief "triadification" sequence (i.e., moving from a "two plus one" to a "three together" family organization). Considering this sequence as representing at a micro level many larger family transitions, we proceeded with a microanalytic interview, a psychodynamic investigation, and a family interview. As expected, larger patterns of correspondences are emerging. Central questions under debate are: What are the most appropriate units at each level of description and what are their articulations between these levels? What is the status of "triadification"? Les interfaces entre les domaines intrapsychiques, interactionnels et intergénérationnels représentent une nouvelle frontiére. A titre exploratoire, nous nous sommes exposés à une situation complexe mais contrǒlable ainsi que le voient ceux dont I'intérět principal se porte sur l'une de ces trois interfaces. Nous avons aussi entièrement intégré les sujets dans l'équipe, de facon à comprendre leur perspective subjective et à leur offrir une expérience enrichissante. Nous avons commencé avec une brève séquence de "triadification," c'est-à-dire passer d'une organisation familiale "deux plus un" à Ltne organisation familiale "trois (add sentenc)ensemble." Considérant cette séquence comme representative à un niveau microscopique de transitions familiales bien plus larges, nous avons procedé à l'entretien microanalytique, à une enquěte psychodynamique et à un entretien familial. Comme prévu, de grands patterns de correspondances émergent. Les questions essentielles sur lesquelles portent le débat sont: quelles les unités les plus appropiées à chaque niveau de description et quelles sont les articulations entre ces niveaux? Quel est le statut de la "triadification"?

Hematopoietic stem cell transplantation in Switzerland: a comprehensive quality control report on centre effect.

Interest groups advocate centre-specific outcome data as a useful tool for patients in choosing a hospital for their treatment and for decision-making by politicians and the insurance industry. Haematopoietic stem cell transplantation (HSCT) requires significant infrastructure and represents a cost-intensive procedure. It therefore qualifies as a prime target for such a policy. We made use of the comprehensive database of the Swiss Blood Stem Cells Transplant Group (SBST) to evaluate potential use of mortality rates. Nine institutions reported a total of 4717 HSCT - 1427 allogeneic (30.3%), 3290 autologous (69.7%) - in 3808 patients between the years 1997 and 2008. Data were analysed for survival- and transplantation-related mortality (TRM) at day 100 and at 5 years. The data showed marked and significant differences between centres in unadjusted analyses. These differences were absent or marginal when the results were adjusted for disease, year of transplant and the EBMT risk score (a score incorporating patient age, disease stage, time interval between diagnosis and transplantation, and, for allogeneic transplants, donor type and donor-recipient gender combination) in a multivariable analysis. These data indicate comparable quality among centres in Switzerland. They show that comparison of crude centre-specific outcome data without adjustment for the patient mix may be misleading. Mandatory data collection and systematic review of all cases within a comprehensive quality management system might, in contrast, serve as a model to ascertain the quality of other cost-intensive therapies in Switzerland.