Spectrophotometric determination of diclofenac in pharmaceutical preparations assisted by microwave oven

In this work, an effective and low-cost method for the determination of sodium or potassium diclofenac is proposed in its pure form and in their pharmaceutical preparations. The method is based on the reaction between diclofenac and tetrachloro-p-benzoquinone (p-chloranil), in methanol medium. This reaction was accelerated by irradiating of reactional mixture with microwave energy (1100 W) during 27 seconds, producing a charge transfer complex with a maximum absorption at 535 nm. The optimal reaction conditions values such as reagent concentration, heating time and stability of the reaction product were determined. Beer's law is obeyed in a concentration range from of 1.25x10-4 to 2.00x10-3 mol l-1 with a correlation coefficient of 0.9993 and molar absorptivity of 0.49 x10³ l mol-1 cm-1. The limit of detection (LOD) was 1.35x10-5 mol l-1 and the limit of quantification (LOQ) was 4.49x10-5 mol l-1. In the presence of the common excipients, such as glucose, lactose, talc, starch, magnesium stearate, sodium sulphite, titanium dioxide, polyethyleneglycol, polyvinylpirrolidone, mannitol and benzilic alcohol no interferences were observed. The analytical results obtained by applying the proposed method compare very favorably with those given by the United States Pharmacopeia standard procedure. Recoveries of diclofenac from various pharmaceutical preparations were within 95.9% to 103.3%, with standard deviations ranging from 0.2% to 1.8%.

Spectrophotometric determination of lansoprazole in pharmaceuticals using bromate-bromide mixture based on redox and complexation reactions

Two sensitive spectrophotometric methods are described for the determination of lansoprazole (LPZ) in bulk drug and in capsule formulation. The methods are based on the oxidation of lansoprazole by insitu generated bromine followed by determination of unreacted bromine by two different reaction schemes. In one procedure (method A), the residual bromine is treated with excess of iron (II), and the resulting iron (III) is complexed with thiocyanate and measured at 470 nm. The second approach (method B) involves treating the unreacted bromine with a measured excess of iron (II) and remaining iron (II) is complexed with orthophenanthroline at a raised pH, and measured at 510 nm. In both methods, the amount of bromine reacted corresponds to the amount of LPZ. The experimental conditions were optimized. In method A, the absorbance is found to decrease linearly with the concentration of LPZ (r = -0.9986) where as in the method B a linear increase in absorbance occurs (r = 0.9986) The systems obey Beer's law for 0.5-4.0 and 0.5-6.0 µg mL-1 for method A and method B, respectively. The calculated molar absorptivity values are 3.97µ10(4) and 3.07µ10(4) L mol-1cm-1 for method A and method B, respectively, and the corresponding Sandell sensitivity values are 0.0039 and 0.0013 µg cm-2. The limit of detection (LOD) and quantification (LOQ) are also reported for both methods. Intra-day and inter-day precision, and accuracy of the methods were established as per the current ICH guidelines. The methods were successfully applied to the determination of LPZ in capsules and the results tallied well with the label claim and the results were statistically compared with those of a reference method by applying the Student's t-test and F-test. No interference was observed from the concomitant substances normally added to capsules. The accuracy and validity of the methods were further ascertained by performing recovery experiments via standard-addition method.

Cerimetric determination of simvastatin in pharmaceuticals based on redox and complex formation reactions

Two sensitive spectrophotometric methods are described for the determination of simvastatin (SMT) in bulk drug and in tablets. The methods are based on the oxidation of SMT by a measured excess of cerium (IV) in acid medium followed by determination of unreacted oxidant by two different reaction schemes. In one procedure (method A), the residual cerium (IV) is reacted with a fixed concentration of ferroin and the increase in absorbance is measured at 510 nm. The second approach (method B) involves the reduction of the unreacted cerium (IV) with a fixed quantity of iron (II), and the resulting iron (III) is complexed with thiocyanate and the absorbance measured at 470 nm. In both methods, the amount of cerium (IV) reacted corresponds to SMT concentration. The experimental conditions for both methods were optimized. In method A, the absorbance is found to increase linearly with SMT concentration (r = 0.9995) whereas in method B, the same decreased (r = -0.9943). The systems obey Beer's law for 0.6-7.5 and 0.5-5.0 µg mL-1 for method A and method B, respectively. The calculated molar absorptivity values are 2.7 X 10(4) and 1.06 X 10(5) Lmol-1 cm-1, respectively; and the corresponding sandel sensitivity values are 0.0153 and 0.0039µg cm-2, respectively. The limit of detection (LOD) and quantification (LOQ) are reported for both methods. Intra-day and inter-day precision, and accuracy of the methods were established as per the current ICH guidelines. The methods were successfully applied to the determination of SMT in tablets and the results were statistically compared with those of the reference method by applying the Student's t-test and F-test. No interference was observed from the common excipients added to tablets. The accuracy and validity of the methods were further ascertained by performing recovery experiments via standard addition procedure.

Spectrophotometric determination of ofloxacin in pharmaceuticals and human urine

Three simple and sensitive spectrophotometric methods are described for the determination of ofloxacin (OFX) in pharmaceuticals and in spiked human urine. First and second methods are based on the measurement of absorbance of OFX in 0.1 M HCl at 293 nm (method A) and 0.1 M NaOH at 287 nm, respectively. The third method is based on the measurement of 2:1 complex formed between OFX and iron(III) in H2SO4 medium, the complex peaking at 420 nm (method C). The optimum conditions for all the three methods are optimized. Beer's law is obeyed over the ranges 0.63-12.5 using method A and method B, and 10-120 µg mL-1 using method C. The apparent molar absorptivity values are calculated to be 3.5 × 10(4), 2.76 × 10(4) and 2.51 × 10³ L mol-1cm-1 for method A, method B and method C, respectively. The Sandell sensitivity, limit of detection (LOD) and limit quantification (LOQ) values are also reported. All the methods were validated in accordance with current ICH guidelines. The developed methods were employed with high degree of precision and accuracy for the estimation of total drug content in commercial tablet formulations of DOX. The results obtained from human spiked urine are satisfactory and recovery values are in the range 95.5-106.6%.

Potentiometric and conductimetric studies of chemical equilibria for pyridoxine hydrochloride in aqueous solutions: simple experimental determination of pKa values and analytical applications to pharmaceutical analysis

The combination of two low-cost classical procedures based on titrimetric techniques is presented for the determination of pyridoxine hydrochloride in pharmaceuticals samples. Initially some experiments were carried out aiming to determine both pKa1 and pKa2 values, being those compared to values of literature and theoretical procedures. Commercial samples containing pyridoxine hydrochloride were electrochemically analysed by exploiting their acid-base and precipitation reactions. Potentiometric titrations accomplished the reaction between the ionizable hydrogens present in pyridoxine hydrochloride, being NaOH used as titrant; while the conductimetric method was based on the chemical precipitation between the chloride of pyridoxine hydrochloride molecule and Ag+ ions from de silver nitrate, changing the conductivity of the solution. Both methods were applied to the same commercial samples leading to concordant results when compared by statistical tests (95 and 98% confidence levels). Recoveries ranging from 99.0 to 108.1% were observed, showing no significant interference on the results.

Distribution and role of macrophytes in coastal lagoons : implications of critical shifts

Crossroads, crucibles and refuges are three words that may describe natural coastal lagoon environments. The words refer to the complex mix of marine and terrestrial influences, prolonged dilution due to the semi-enclosed nature and the function of a habitat for highly diverse plant and animal communities, some of which are endangered. To attain a realistic picture of the present situation, high vulnerability to anthropogenic impact should be added to the description. As the sea floor in coastal lagoons is usually entirely photic, macrophyte primary production is accentuated compared with open sea environments. There is, however, a lack of proper knowledge on the importance of vegetation for the general functioning of coastal lagoon ecosystems. The aim of this thesis is to assess the role of macrophyte diversity, cover and species identity over temporal and spatial scales for lagoon functions, and to determine which steering factors primarily restrict the qualitative and quantitative composition of vegetation in coastal lagoons. The results are linked to patterns of related trophic levels and the indicative potential of vegetation for assessment of general conditions in coastal lagoons is evaluated. This thesis includes five field studies conducted in flads and glo-flads in the brackish water northern Baltic Sea. Flads and glo-flads are defined as a Baltic variety of coastal lagoons, which due to an inlet threshold and post-glacial landuplift slowly will be isolated from the open sea. This process shrinks inlet size, increases exposure and water retention, and is called habitat isolation. The studied coastal lagoons are situated in the archipelago areas of the eastern coast of Sweden, the Åland Islands and the south-west mainland of Finland, where land-uplift amounts to ca. 5 mm/ per year. Out of 400 evaluated sites, a total of 70 lagoons varying in inlet size, archipelago position and anthropogenic influence to cover for essential environmental variation were chosen for further inventory. Vegetation composition, cover and richness were measured together with several hydrographic and morphometric variables in the lagoons both seasonally and inter-annually to cover for general regional, local and temporal patterns influencing lagoon and vegetation development. On smaller species-level scale, the effects of macrophyte species identity and richness for the fish habitat function were studied by examining the influence of plant interaction on juvenile fish diversity. Thus, the active election of plant monoand polycultures by fish and the diversity of fish in the respective culture were examined and related to plant height and water depth. The lagoons and vegetation composition were found to experience a regime shift initiated by increased habitat isolation along with land-uplift. Vegetation composition altered, richness decreased and cover increased forming a less isolated and more isolated regime, named the vascular plant regime and charophyte regime, respectively according to the dominant vegetation. As total phosphorus in the water, turbidity and the impact of regional influences decreased in parallel, the dominance of charophytes and increasing cover seemed to buffer and stabilize conditions in the charophyte regime and indicated an increased functional role of vegetation for the lagoon ecosystem. The regime pattern was unaffected by geographical differences, while strong anthropogenic impact seemed to distort the pattern due to loss of especially Chara tomentosa L. in the charophyte regime. The regimes were further found unperturbed by short-time temporal fluctuations. In fact the seasonal and inter-annual dynamics reinforced the functional difference between the regimes by the increasing role of vegetation along habitat isolation and the resemblance to lake environments for the charophyte regime. For instance, greater total phosphorus and chlorophyll a concentrations in the water in the beginning of the season in the charophyte regime compared with the vascular plant regime presented a steeper reduction to even lower values than in the vascular plant regime along the season. Despite a regional importance and positive relationship of macrophyte diversity in relation to trophic diversity, species identity was underlined in the results of this thesis, especially with decreasing spatial scale. This result was supported partly by the increased role of charophytes in the functioning of the charophyte regime, but even more explicitly by the species-specific preference of juvenile fish for tall macrophyte monocultures. On a smaller species-level scale, tall plant species in monoculture seemed to be able to increase their length, indicating that negative selection forms preferred habitat structures, which increase fish diversity. This negative relationship between plant and fish diversity suggest a shift in diversity patterns among trohic levels on smaller scale. Thus, as diversity patterns seem complex and diverge among spatial scales, it might be ambiguous to extend the understanding of diversity relationships from one trophic level to the other. All together, the regime shift described here presents similarities to the regime development in marine lagoon environments and shallow lakes subjected to nutrient enrichment. However, due to nutrient buffering by vegetation with increased isolation and water retention as a consequence of the inlet threshold, the development seems opposite to the course along an eutrophication gradient described in marine lagoons lacking an inlet threshold, where the role of vegetation decreases. Thus, the results imply devastating consequences of inlet dredging (decreasing isolation) in terms of vegetation loss and nutrient release, and call for increased conservational supervision. Especially the red listed charophytes would suffer negatively from such interference and the consequences are likely to also deteriorate juvenile fish production. The fact that a new species to Finland, Chara connivens Salzm. Ex. Braun 1835 was discovered during this study further indicates a potential of the lagoons serving as refuges for rare species.

Ympäristönäkökohtien huomioiminen asumisen läheisyyteen sijoitettavassa maanpäällisessä kivilinjassa

Työn tavoitteena oli selvittää, miten asutuksen läheisyydessä sijaitsevasta kivilinjasta aiheutuvat merkittävät ympäristövaikutukset muuttuvat, kun kivilinja siirretään kallion sisältä maan pinnalle. Kivilinjan aiheuttamia merkittäviä ympäristövaikutuksia ovat erityisesti melu ja pöly. Lisäksi työssä tarkasteltiin toiminnan muutoksesta aiheutuvia vaikutuksia kasvillisuuteen ja eläimistöön, liikennevirtoihin sekä pinta- ja pohjavesiin. Työssä tarkasteltiin myös uuden kivilinjan vaikutuksia yrityksen sisäisiin ympäristönäkökohtiin, kuten työolosuhteiden hallintaan. Työssä laskettiin äänitaso lähimmässä häiriintyvässä kohteessa uuden kivilinjan rakentamisen jälkeen. Äänitaso ei todennäköisesti uuden kivilinjan käyttöönoton myötä tule ylittämään ympäristöluvassa asetettuja raja-arvoja. Kasvillisuuteen ja eläimistöön uudella kivilinjalla voi olla sekä positiivisia että negatiivisia vaikutuksia. Vesistövaikutukset eivät todennäköisesti tule olemaan merkittäviä. Alueen liikennevirtoihin tulee uuden kivilinjan käyttöönoton myötä muutoksia. Ajettavien kilometrien määrä vähenee noin 18 000 kilometriä. Erityisesti prosessin loppupään ajokilometrit vähenevät huomattavasti.

Pienloistelamppujen johtuvat RF-häiriöt verrattuna CISPR 15 - standardin raja-arvoihin

Hehkulamput tullaan kieltämään Euroopan Unionin alueella vuoden 2016 syyskuuhun mennessä. Hehkulamput korvataan suurimmaksi osaksi pienloistelampuilla, jotka omaavat hehkulamppuihin verrattuna paremman hyötysuhteen. Pienloistelamput aiheuttavat kuitenkin häiriöitä niitä syöttävään sähköverkkoon. Tässä kandidaatin työssä mitattiin 15 erilaisen pienloistelampun aiheuttamat johtuvat RF-taajuiset häiriöt. Tuloksia verrattiin CISPR 15 – standardissa esitettyihin raja-arvoihin, joita pienloistelamppujen tulisi noudattaa. Mittaukset suoritettiin käyttämällä CISPR 16 –standardin kanssa yhteensopivaa mittavastaanotinta (Rohde & Schwarz ESHS30) sekä myöskin CISPR 16 yhteensopivaa keinoverkkoa (Rohde & Schwarz ESH2Z5). Lamput mitattiin CISPR 15 –standardin mukaisesti, muutamia poikkeuksia lukuun ottamatta. Lamppuja ei mitattu käyttämällä CISPR 15 –standardissa vaadittua lampun pidintä. Eikä lamppuja myöskään esikäytetty ollenkaan. Lukuun ottamatta yhtä pienloistelamppua, kaikki jäivät raja-arvon alapuolelle. Rajan ylittäneen lampun tulos tosin mahtuu mittavastaanottimen mittavirheeseen. Joten kyseessä ei ollut suuren suuri ylitys. Muiden tutkittujen pienloistelamppujen johtuvat RF-häiriöt ovat hyväksyttävällä tasolla ja ne tuskin tulevat aiheuttamaan ongelmia.

Lujasta rakenneteräksestä tehdyn rakenteen vikasietoisuuden määritys

Tässä työssä tutkittiin Ruukin valmistamista lujista Optim 700 MC Plus sekä Optim 700 QL teräksistä tehtyjen hitsattujen palkkirakenteiden vikasietoisuutta sekä murtumiskäyttäytymistä laboratoriossa suoritettujen täyden mittakaavan kokeiden avulla. Koerakenteet suunniteltiin siten, että rakenteen kylmämuovauksen sekä hitsauksen vaikutukset yhdessä rakenteen geometrian vaikutuksen kanssa heikentävät rakenteen murtumissitkeyttä rakenteeseen tehdyn teräväkärkisen alkusärön tasossa. Suunnitellussa koesarjassa varioidaan testauslämpötilan lisäksi hitsauksen lämmöntuontia sekä koerakenteeseen tehtävän alkusärön kokoa. Tässä työssä tavoitteena oli yleisesti esittää menettely hitsatun säröllisen teräsrakenteen kestävyyden arviointia varten. Optim 700 MC Plus teräksestä tehdyn koerakenteen käyttäytymistä tutkittiin laskennallisesti murtumismekaniikan avulla. Laadittujen FEM - mallien avulla laskettiin rakenteen murtumisparametrien arvot kummallekin tutkittavalle teräkselle. Optim 700 MC Plus materiaalista valmistetuille koerakenteen säröalueen rakennedetaljia vastaavalle koekappaleille suoritettiin murtumissitkeyskokeita. Murtumissitkeyskokeista saatujen tulosten avulla pystyttiin kuvaamaan täyden mittakaavan koerakenteessa olevan särön murtumiskäyttäytymistä mitoitusmenetelmissä. Koerakenteelle laskettiin tässä työssä kriittisen särökoon ja sitä vastaavan kuorman arvot perustuen rakenteen oletettuun hauraaseen, epästabiiliin sitkeään sekä plastiseen murtumiskäyttäytymiseen. Tässä työssä testattiin molemmista tutkittavista materiaaleista valmistetut täyden mittakaavan koerakenteet -40 °C lämpötilassa. Molemmat testatut rakenteet käyttäytyvät mitattujen siirtymätulosten perusteella melko hauraasti. Optim 700 MC Plus materiaalille saatujen laskentatulosten voidaan todeta testatun koekappaleen perusteella soveltuvan hauraasti käyttäytyvän rakenteen mitoitukseen.

Applying organizational core values in everyday delivery work - case Accenture

The purpose of this thesis is to study organizational core values and their application in practice. With the help of literature, the thesis discusses the implementation of core values and the benefits that companies can gain by doing it successfully. Also, ways in which companies can improve their values’ application to their everyday work are presented. The case company’s value implementation is evaluated through a survey research conducted on their employees. The true power of values lies in their application, and therefore, core values should be the basis for all organizational behavior, integrated into everything a company does. Applying values in practice is an ongoing process and companies should continuously work towards creating a more value-based organizational culture. If a company does this effectively, they will most likely become more successful with stakeholders as well as financially. Companies looking to turn their values into actions should start with a self-assessment. Employee surveys are effective in assessing the current level of value implementation, since employees have valuable, first-hand information regarding the situations and behaviors they face in their everyday work. After the self-assessment, things like management commitment, communication, training, and support are key success factors in value implementation.

Reglering och förvaltning av produktions- och slaktdjurs välbefinnande : en offentligrättslig undersökning

Djur och djurskyddet hör till ett rättsligt regleringsområde som inte varit föremål för omfattande rättsvetenskaplig forskning i vårt land även om intresset för djurs välbefinnande ökat både i samhället och inom EU. Avhandlingen har avfattats som en artikelavhandling och är en offentligrättslig studie om djurskyddslagstiftningen och förvaltningen av djurskyddsärenden i Finland. Tematiken har behandlats både ur djurens och djurens ägares eller innehavares synvinkel med utgångspunkt i djurskyddslagstiftningen och förvaltningen av djurskyddsärenden i Finland. Forskningen är fokuserad huvudsakligen på skyddet av och välbefinnandet hos produktions- och slaktdjur även om bland annat de begrepp som granskas också berör andra djurkategorier. De övergripande frågeställningarna i avhandlingen är två. För det första, vad är det som avses med djurs välbefinnande och skydd i regleringen av djurskyddet och för det andra, hur realiseras dessa i djurskyddsmyndigheternas förvaltningsverksamhet? I forskningen presenteras och diskuteras bland annat en ny begreppskonstruktion: djurs rättsliga välbefinnande. Den empiriska delen i avhandlingen omfattar förvaltningsverksamheten inom området av djurskydd under åren 1996–2006. Sammanlagt 10468 dokument som upprättats av djurskyddsmyndigheten i samband med verkställandet av djurskyddsövervakning ingår i undersökningen. Forskningen utmynnar i en åtgärdsförteckning med förslag till utvecklingen av området för djurskydd.

Democracy begins at home : parenting, empathy, and adolescents' support for democratic values

Bakgrund Demokratiska samhällen är sårbara och historiskt sett sällsynta. Förutsättningarna för en fungerande demokrati innefattar mer än formella institutioner eller enbart frånvaron av diktatorer och extremgrupper. För att en regim skall fungera enligt demokratiska principer behövs medborgare som stöder demokratiska värden. Därför är det av vikt att förstå de processer som får individer att känna tilltro till demokratiska värden. Trots att man kan anta att stöd för sådana värderingar utvecklas som ett resultat av social inlärning är de konkreta omständigheterna som leder till ett dylikt lärande mindre uppenbara. Den klassiska litteraturen beträffande politisk socialisation lyfte fram föräldrarna som avgörande för de ungas medborgerliga fostran, men i moderna samhällen har föräldrarna sällan som en uttalad målsättning att försöka påverka sina barns nuvarande eller framtida politiska preferenser. Den föreliggande studiens mål var att fördjupa diskursen kring politisk socialisation gen om att analysera föräldraskapets betydelse för demokratiska värderingar hos ungdomar. Metod Den föreliggande studien utgick från två slumpmässiga urval. Det ena omfattade 1341 studerande, 17 år gamla, inom andra stadiets utbildning i tre regioner i Finland (södra, syd-västra och västra) och det andra 678 studerande, 16 år gamla vid studiens inledande, från den flamländska delen av Belgien. Studien innefattade frågeformulär som besvarades under skoltid. Resultat De centrala resultaten från studien kan sammanfattas i fyra punkter. För det första kunde empatiskt tänkande konstateras vara en god förklarande variabel för ungdomars demokratiska värderingar (Artikel 1). För det andra gav studien stöd för antagandet att stödjande föräldraskap är av betydelse för utvecklingen av empati under ungdomsåren (Artikel 2). För det tredje utvärderades empati, i relation till andra betydelsefulla variabler, som förklarande variabel för demokratiska värderingar (Artikel 3). För det fjärde gav den föreliggande studien bevis för att demokratiskt föräldraskap, både direkt och indirekt, är relaterat till demokratiska värderingar hos ungdomar. Sammanfattning Sammanfattningsvis visade den föreliggande studien hur föräldraskap både direkt och indirekt kan påverka demokratiska värderingar hos ungdomar och hur dessa resultat kunde användas för demokratisk samhällsfostran.

Energy demand in citrus production under varied operational efficiency values

Citrus orchards are very important in Brazil, especially in São Paulo State, where occupy an area of 600,000 ha approximately. To identify sustainability degree of citrus production system, an energy analysis allows evaluating efficiency of direct and indirect applied inputs. Thus, this study aimed to evaluate citrus production system under energetic point of view, in which invested energy is paid back with citrus production; being compared within three scenarios for operational field efficiency. As result, by sensitivity analysis was determined that fuel was the main energy demander, followed by pesticides and fertilizers. In operational work capacity analysis, all combinations between efficiency (minimum, typical and maximum) and yield levels became positive in the seventh year, except for the combination minimum efficiency and 10 % less yield, positive in the eighth year. The best combination (maximum efficiency and 10 % more yield) has promoted investment payoff around the sixth and seventh year. By this study, it is possible to determine the total energy demand to produce citrus and indentify the applied inputs that need more attention by the decision-makers. Labor and seedlings can be ommited for further studies with citrus, since they were irrelevant. Management of agricultural machinery may pose an important role on decreasing environmental impact of citrus production.

Dry months in the agricultural region of Ribeirão Preto, state of São Paulo-Brazil: an study based on the extreme value theory

The application of the Extreme Value Theory (EVT) to model the probability of occurrence of extreme low Standardized Precipitation Index (SPI) values leads to an increase of the knowledge related to the occurrence of extreme dry months. This sort of analysis can be carried out by means of two approaches: the block maxima (BM; associated with the General Extreme Value distribution) and the peaks-over-threshold (POT; associated with the Generalized Pareto distribution). Each of these procedures has its own advantages and drawbacks. Thus, the main goal of this study is to compare the performance of BM and POT in characterizing the probability of occurrence of extreme dry SPI values obtained from the weather station of Ribeirão Preto-SP (1937-2012). According to the goodness-of-fit tests, both BM and POT can be used to assess the probability of occurrence of the aforementioned extreme dry SPI monthly values. However, the scalar measures of accuracy and the return level plots indicate that POT provides the best fit distribution. The study also indicated that the uncertainties in the parameters estimates of a probabilistic model should be taken into account when the probability associated with a severe/extreme dry event is under analysis.