Estudo da influência da natureza de reticulantes e aditivos orgânicos sobre o comportamento de géis de quitosana

The physical-chemical process of swelling in water-based gel of natural polymers is investigated with the purpose of applying these systems to biomedical materials for controlled release of drugs. In this work we develop a study about the sol-gel transition of solutions of chitosan in the presence of formaldehyde and glutaraldehyde like crosslinking agents and we have determined the effect of many aditives in the time of gelification from the elaborated sistems. The phisical-chemistry process of swelling of the formed gels was evaluated in function of the degree of crosslinking of the incorporated aditives and the pH. Gelling times of chitosan solutions were obtained using viscosimetric measurement, in the pre-gel state, as well as condutivity ones.The results obtained suggest that component concentration modifies the kinetic profile of the transition and the swelling behavior. Regarding H+ content, the gels were highly susceptible to swelling in acidic conditions, which characterize this system as pH - sensitive.

An update on EMU sovereign yield spread drivers in times of crisis: A panel data analysis

We empirically investigate the determinants of EMU sovereign bond yield spreads with respect to the German bund. Using panel data techniques, we examine the role of a wide set of potential drivers. To our knowledge, this paper presents one of the most exhaustive compilations of the variables used in the literature to study the behaviour of sovereign yield spreads and, in particular, to gauge the effect on these spreads of changes in market sentiment and risk aversion. We use a sample of both central and peripheral countries from January 1999 to December 2012 and assess whether there were significant changes after the outbreak of the euro area debt crisis. Our results suggest that the rise in sovereign risk in central countries can only be partially explained by the evolution of local macroeconomic variables in those countries.

An update on EMU sovereign yield spread drivers in times of crisis: A panel data analysis

We empirically investigate the determinants of EMU sovereign bond yield spreads with respect to the German bund. Using panel data techniques, we examine the role of a wide set of potential drivers. To our knowledge, this paper presents one of the most exhaustive compilations of the variables used in the literature to study the behaviour of sovereign yield spreads and, in particular, to gauge the effect on these spreads of changes in market sentiment and risk aversion. We use a sample of both central and peripheral countries from January 1999 to December 2012 and assess whether there were significant changes after the outbreak of the euro area debt crisis. Our results suggest that the rise in sovereign risk in central countries can only be partially explained by the evolution of local macroeconomic variables in those countries.

Highly functional binding surface for miniaturised solid-phase immunoassays. - A spot story -

Several bioaffinity assays are based on the detection of an analyte which is bound on a solid substrate via biochemical interaction. These so called solid phase assays are based on the adhesion of the primary binding partner on a solid surface, which then binds the analyte to be detected. In this thesis work a novel solid phase based assay technology, known as spot technology, was developed. The spot technology is based on combination of high-capacity solid phases, concentrated in a spot format, utilising modified streptavidin molecules and recombinant antibody fragments. The reduction of the solid phase binding surface to a size of a spot enabled denser binding of the target molecules, providing improved signal intensities and signal-to-background ratio when applied in different solid phase immunoassays. Streptavidin-biotin interactions are commonly utilised in numerous different bioaffinity assays and the ultimate nature of streptavidin to bind biotin is among the strongest non-covalent interaction reported between two biomolecules. In this study native core streptavidin was chemically modified to provide polymerised streptavidin molecules with altered adsorption properties. These streptavidin conjugates, when coated onto polystyrene surface, provided enhanced biotin binding capacity and surface stability when compared to a reference coating constructed with native streptavidin. Furthermore, the combination of chemically modified streptavidin, sitespecifically biotinylated antibody fragments and the spot coating technology provided highly dense solid phase coating with improved binding properties. The performance of the spot assay technology was further demonstrated in different immunoassay configurations. Human thyroid stimulating hormone (TSH) and human cardiac troponin I (cTnI) were used as model analytes to show the applicability of the highly sensitive spot-based solid-phase immunoassay for detection of very low levels of analytes. It was demonstrated that the spot technology provided an assay concept with enhanced sensitivity and short turn-around times, characteristics that are highly suitable for point-of-care applications.

Use of the Optical Cantilever Microphone in Photoacoustic Spectroscopy

A novel cantilever pressure sensor was developed in the Department of Physics at the University of Turku in order to solve the sensitivity problems which are encountered when condenser microphones are used in photoacoustic spectroscopy. The cantilever pressure sensor, combined with a laser interferometer for the measurement of the cantilever movements, proved to be highly sensitive. The original aim of this work was to integrate the sensor in a photoacoustic gas detector working in a differential measurement scheme. The integration was made successfully into three prototypes. In addition, the cantilever was also integrated in the photoacoustic FTIR measurement schemes of gas-, liquid-, and solid-phase samples. A theoretical model for the signal generation in each measurement scheme was created and the optimal celldesign discussed. The sensitivity and selectivity of the differential method were evaluated when a blackbody radiator and a mechanical chopper were used with CO₂, CH4, CO, and C2H4 gases. The detection limits were in the sub-ppm level for all four gases with only a 1.3 second integration time and the cross interference was well below one percent for all gas combinations other than those between hydrocarbons. Sensitivity with other infrared sources was compared using ethylene as an example gas. In the comparison of sensitivity with different infrared sources the electrically modulated blackbody radiator gave a 35 times higher and the CO2-laser a 100 times lower detection limit than the blackbody radiator with a mechanical chopper. As a conclusion, the differential system is well suited to rapid single gas measurements. Gas-phase photoacoustic FTIR spectroscopy gives the best performance, when several components have to be analyzed simultaneously from multicomponent samples. Multicomponent measurements were demonstrated with a sample that contained different concentrations of CO₂, H₂O, CO, and four different hydrocarbons. It required an approximately 10 times longer measurement time to achieve the same detection limit for a single gas as with the differential system. The properties of the photoacoustic FTIR spectroscopy were also compared to conventional transmission FTIR spectroscopy by simulations. Solid- and liquid-phase photoacoustic FTIR spectroscopy has several advantages compared to other techniques and therefore it also has a great variety of applications. A comparison of the signal-to-noise ratio between photoacoustic cells with a cantilever microphone and a condenser microphone was done with standard carbon black, polyethene, and sunflower oil samples. The cell with the cantilever microphone proved to have a 5-10 times higher signal-to-noise ratio than the reference detector, depending on the sample. Cantilever enhanced photoacoustics will be an effective tool for gas detection and analysis of solid- and liquid-phase samples. The preliminary prototypes gave good results in all three measurement schemes that were studied. According to simulations, there are possibilities for further enhancement of the sensitivity, as well as other properties, of each system.

Lukion opettajien ääni - Aineenopettajien käsityksiä muutoksista ja visioista lukiossa

Tulevaisuusorientaatio on tullut entistä tärkeämmäksi myös koulumaailmassa johtuen yhteiskunnassa nopeasti eteen tulevista muutoksista. On myös esitetty epäilyjä, että tulevaisuuteen reagoimisessa heikoin tilanne olisikin juuri kuntatason päätöksenteossa. Ymmärrys ja tieto opettajan työstä nimenomaan opettajan omasta perspektiivistä tarkasteltuna mahdollistavat lähtökohdan ja edellytykset todelliselle koulun uudistamiselle. Peruskysymys, johon tässä tutkimuksessa etsittiin vastausta oli: Millaisia ovat lukion aineenopettajien käsitykset lukion muutosprosesseista ja miten he visioivat oman lukionsa ja yleensä lukioiden tulevaisuutta? Aineiston keruu osui ajankohtaan, joka oli hyvin otollinen tulevaisuuden tarkasteluun, sillä uusi opetussuunnitelma otettiin käyttöön kaikissa Suomen lukioissa viimeistään lukuvuonna 2005-2006. Tutkimuksessa oli mukana kaksi hyvin erilaista lukiota Länsi-Suomen läänistä eli pieni maaseudun lukio ja hyvin suuri kaupunkilukio. Tutkimusaineiston keruu eteni kaksivaiheisesti: informoitu kysely ja teemahaastattelu. Tutkimusjoukon suuruus oli yhteensä 20, joista puolet oli miehiä ja puolet naisia. Aineenopettajien käsityksiä muutoksista ja visioista tutkittiin fenomenografisen tutkimusotteen avulla. Fenomenografiassa kiinnostuksen kohteena ovat ihmisten erilaiset käsitykset todellisuudesta ja näin saatava ymmärrys tavoista, joilla ihmiset kokevat tilanteita ja maailmaa. Organisaation muutosprosesseja voidaan kutsua myös oppimiseksi. Tutkimuksen oppivan organisaation näkökulmat perustuivat juuri yhteistyössä tapahtuvaan yhteisen toiminnan kehittämiseen. Aineenopettajien käsityksiä työyhteisöstään tarkasteltiin seuraavista oppivan organisaatiomallin näkökulmista: vuorovaikutus, päätöksenteko sekä rehtorin ja aineenopettajan rooli ja asema työyhteisössä. Aineenopettajien keskeisimmät käsitykset muutoksista lukiossa viime vuosina kohdistuivat aineenopettajan ammattirooliin ja lukio-opiskelijaan sekä opiskelijalta vaadittaviin lukio-opintoihin. Muutokset ammattiroolissa korostavat tutkimustulosten perusteella aineenopettajilta vaadittavia muitakin kuin opetettavien aineiden hallintataitoja. Suoranaista ammattitaidon puutetta opettajat kokivat varsinkin ryhmänohjaustehtävien yhteydessä, osittain myös uusien oppimisympäristöjen, esimerkiksi verkkopedagogisten taitojen, yhteydessä. Opettajien lisäkoulutuksen tarve koetaan konkreettisena, mutta sekä koulutusten sisältöihin, järjestelyihin ja ajankohtiin että koulun sijais- ym. järjestelyihin kaivattaisiin parannuksia. Verrattuna aikaisempiin tutkimuksiin näyttäisi siltä, että luokaton lukio on saanut opettajat enenevässä määrin huolestumaan opiskelijoiden syrjäytymisriskistä ja hyvinvoinnista. Opiskelijoiden syrjäytymisriskin kasvu lukio-opintojen aikana nouseekin yhdeksi lukion pessimistiseksi skenaarioksi. Muista pessimistisistä skenaarioista lukiolle, jotka saattoi johtaa tutkimustuloksista, voidaan mainita työyhteisön demokratiavajeen syveneminen sekä opetussuunnitelmasisältöjen ja ylioppilastutkintovaatimusten välisen kuilun syveneminen. Aineenopettajien käsitykset oman lukionsa visioista olivat sisällöiltään pääosin välineellisiä ja ne kohdentuivat kaikki opiskelijoihin. Esimerkiksi työyhteisöllisiä kehittämisajatuksia ei visioissa ilmennyt. Myöskään visioinnin dynaamisuus ei aineistossa korostunut. Aineenopettajien käsitykset visioiden arvopohjasta heijastivat perinteistä suomalaista arvomaailmaa eli itsekuria, velvollisuudentuntoa, kuuliaisuutta esivaltaa kohtaan ja perinteisten arvojen kunnioittamista. Sen sijaan antiikista perityviä Sokrateen edustamia keskustelua ja auktoriteettien kyseenalaistamista ei arvoissa ilmennyt, eikä myöskään uusliberalistista individualismia. Käsitykset visioiden synnystä näyttävät parhaiten selittävän opettajan muita käsityksiä liittyen visioon, visiointiin ja työyhteisöllisiin vaikutusmahdollisuuksiin sekä opettajan tulevaisuusorientoitumiseen.. Käsitykset vision syntytaustasta voidaan jakaa seuraaviin pää- ja alakategorioihin: 1. auktoriteettikeskeinen visiointi: johdon linjaus tai valtakunnallinen linjaus, 2. yhteisökeskeinen visiointi: yhteisöllinen linjaus tai toiminnallinen linjaus ja 3. yksilökeskeinen visiointi. Pessimistisimmiksi eli vähiten tulevaisuusorientoituneiksi opettajiksi työyhteisössä osoittautuivat ne opettajat, jotka pitivät oman lukionsa visiota koulun johdon sanelemana. Monet teoriat oppivasta organisaatiosta korostavat johtajuuden merkitystä työyhteisöä kehitettäessä. Johtajuuden merkitys nousi tämänkin tutkimuksen aineistosta keskeisesti esiin. Pyrkimystä kohti oppivaa organisaatiota opettajien puheista löytyy paljonkin, esimerkkeinä viittaukset johtajuuden ja vuorovaikutustapojen kehittämistarpeisiin. Sen sijaan opettajien puheet omista työyhteisöllisistä kehittymistarpeistaan, ns. alaistaidot, jäivät vähäisiksi. Tutkimustuloksista on luotu sovellusmalli kouluyhteisöjen visioinnin ja muun kehittämistyön tueksi.

Efeito do polietilenoglicol e da albumina na imobilização de lipase microbiana e na catálise em meio orgânico

Poly (ethylene) glycol (PEG) and bovine serum albumin (BSA), as additive agents, were used to enhance the activity of immobilized microbial lipase in organic solvent. Controlled pore silica (CPS) was selected as matrix and different immobilization procedures were evaluated: directly lipase binding on CPS and simultaneous addition of lipase and additive agent on the same support. The highest coupling yield (59.6%) was attained when the immobilization procedure was performed at lipase loading of 150 U/g support in the presence of PEG-1.500. This immobilized system was used in esterification reactions under repeated batch cycles and the biocatalyst half-life was found to increase 2.7 times when compared with the control.

Model for interevent times with long tails and multifractality in human communications: An application to financial trading

Social, technological, and economic time series are divided by events which are usually assumed to be random, albeit with some hierarchical structure. It is well known that the interevent statistics observed in these contexts differs from the Poissonian profile by being long-tailed distributed with resting and active periods interwoven. Understanding mechanisms generating consistent statistics has therefore become a central issue. The approach we present is taken from the continuous-time random-walk formalism and represents an analytical alternative to models of nontrivial priority that have been recently proposed. Our analysis also goes one step further by looking at the multifractal structure of the interevent times of human decisions. We here analyze the intertransaction time intervals of several financial markets. We observe that empirical data describe a subtle multifractal behavior. Our model explains this structure by taking the pausing-time density in the form of a superstatistics where the integral kernel quantifies the heterogeneous nature of the executed tasks. A stretched exponential kernel provides a multifractal profile valid for a certain limited range. A suggested heuristic analytical profile is capable of covering a broader region.

La importancia de las emociones en los períodos sensibles del desarrollo = The importance of emotions in sensitive developmental periods

Investigaciones recientes sugieren que en la adolescencia tienen lugar importantes cambios en la estructura,bioquímica y fisiología del cerebro que podrían explicar la dificultad que experimentan los adolescentes en elcontrol de sus emociones así como también otros rasgos de su comportamiento inestable. En este artículo presentamosalgunas investigaciones que establecen, asimismo, una correlación entre las reorganizaciones cerebrales quetienen lugar en el primer año de vida con signos de irritabilidad y desazón emocional que muestra el bebédurante este periodo. En ambos casos la dificultad de controlar los impulsos emocionales es susceptible de afectarla relación de los padres con el niño o joven. Discutimos la posible relevancia de esta coincidencia dentro de unaperspectiva evolucionista así como la posible vulnerabilidad de estos períodos. Finalmente, apuntamos la necesidadde una teoría integradora del desarrollo humano y ofrecemos algunos puntos de debate

A sensitive and robust lc-ms/ms method with monolithic column and electrospray ionization for the quantitation of efavirenz in human plasma: application to a bioequivalence study

An LC-MS/MS method has been developed for the determination of efavirenz (EFZ) in human plasma using hydrochlorothiazide as internal standard (I.S.). An ESI negative mode with multiple reaction-monitoring was used monitoring the transitions m/z 313.88→69.24 (EFZ) and 296.02→204.76 (I.S.). Samples were extracted using liquid-liquid extraction. The total run time was 2.0 min. The separation was achieved with HPLC-RP using a monolithic column. The assay was linear in the concentration range of 100 - 5000 ng mL-1. The mean recovery was 83%. Intra- and inter-day precision were < 9.5% and < 8.9%, respectively and accuracy was in the range ± 8.33%. The method was successfully applied to a bioequivalence study.

Simple and sensitive spectrophotometric methods for the analysis of mesalamine in bulk and tablet dosage forms

Three simple, sensitive, economical and reproducible spectrophotometric methods (A, B and C) are described for determination of mesalamine in pure drug as well as in tablet dosage forms. Method A is based on the reduction of tungstate and/or molybdate in Folin Ciocalteu's reagent; method B describes the reaction between the diazotized drug and α-naphthol and method C is based on the reaction of the drug with vanillin, in acidic medium. Under optimum conditions, mesalamine could be quantified in the concentration ranges, 1-30, 1-15 and 2-30 µg mL-1 by method A, B and C, respectively. All the methods have been applied to the determination of mesalamine in tablet dosage forms. Results of analysis are validated statistically.

The contributions of Henri Victor Regnault in the context of organic chemistry of the first half of the nineteenth century

A very little known aspect of the scientific career of Regnault is his contribution to the emerging organic chemistry in the first half of the nineteenth century. The purpose of this article is not only to describe two of his most important researches in this field, as were the discovery of two series of halogenated derivates of certain organic compounds and the precise identification of some of the then recently discovered alkaloids, but also the main features that identified his research method. With the involvement in these subjects, Regnault unintentionally positioned himself in the midst of some of the polemics about the classification of organic compounds that characterized this age of science.

Sensitive method for determination of piplartine, an alkaloid amide from Piper species, in rat plasma samples by liquid chromatography-tandem mass spectrometry

Piplartine (PPTN) is an alkaloid amide found in Piper species that presents different activities. PPTN determination in rat plasma is necessary to better understand its biological effects. The aim of this study was to develop a sensitive LC-MS/MS method for the determination of PPTN in rat plasma. The performance criteria for linearity, sensitivity, precision, accuracy, recovery, and stability have been assessed and were within the recommended guidelines. The validated method proved to be suitable in a pilot study of PPTN kinetic disposition in rat plasma after a single intraperitoneal dose, and represents an appropriate tool to further pharmacokinetic studies.

RAPID AND SENSITIVE DETERMINATION OF PALLADIUM USING HOMOGENEOUS LIQUID-LIQUID MICROEXTRACTION VIA FLOTATION ASSISTANCE FOLLOWED BY GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROMETRY

A method for the determination of trace amounts of palladium was developed using homogeneous liquid-liquid microextraction via flotation assistance (HLLME-FA) followed by graphite furnace atomic absorption spectrometry (GFAAS). Ammonium pyrrolidine dithiocarbamate (APDC) was used as a complexing agent. This was applied to determine palladium in three types of water samples. In this study, a special extraction cell was designed to facilitate collection of the low-density solvent extraction. No centrifugation was required in this procedure. The water sample solution was added to the extraction cell which contained an appropriate mixture of extraction and homogeneous solvents. By using air flotation, the organic solvent was collected at the conical part of the designed cell. Parameters affecting extraction efficiency were investigated and optimized. Under the optimum conditions, the calibration graph was linear in the range of 1.0-200 µg L-1 with a limit of detection of 0.3 µg L-1. The performance of the method was evaluated for the extraction and determination of palladium in water samples and satisfactory results were obtained. In order to verify the accuracy of the approach, the standard addition method was applied for the determination of palladium in spiked synthetic samples and satisfactory results were obtained.