Desenvolvimento e aplicação de método GC-MS/MS para análise simultânea de 17 HPAs em material particulado atmosférico

Os hidrocarbonetos policíclicos aromáticos (HPAs) estão associados ao aumento da incidência de diversos tipos de cânceres no homem. Essas moléculas são formadas principalmente na queima incompleta de matéria orgânica, sendo encontradas em todos os compartimentos ambientais. Órgãos regulamentadores das áreas ambiental e de saúde ocupacional consideram 17 HPAs como contaminantes atmosféricos prioritários. Este trabalho apresenta um método para análise simultânea destes HPAs utilizando-se a cromatografia a gás acoplada à espectrometria de massas operando no modo tandem (GC-MS/MS). Os limites de detecção e quantificação do método mostraram-se até 5 vezes inferiores aos obtidos no método GC-MS (SCAN). O método mostrou-se seletivo para análise de HPAs em extratos de amostras de material particulado atmosférico. Uma análise comparativa de dois sistemas de solventes (diclorometano/metanol 4:1 v/v e hexano/acetona 1:1 v/v) para a extração de HPAs, utilizando amostras de material particulado atmosférico, revelou que ambas as misturas de solventes possuem poder de extração semelhante. Os resultados sugerem que é possível realizar extração de HPAs de material particulado atmosférico em ultra-som com a mistura hexano/acetona (1:1), que é menos tóxica em relação à mistura diclorometano/metanol (4:1), bastante utilizada nestas análises, sem perdas significativas na exatidão do método.

Spot-test identification and rapid quantitative sequential analysis of dipyrone

A qualitative spot-test and tandem quantitative analysis of dipyrone in the bulk drug and in pharmaceutical preparations is proposed. The formation of a reddish-violet color indicates a positive result. In sequence a quantitative procedure can be performed in the same flask. The quantitative results obtained were statistically compared with those obtained with the method indicated by the Brazilian Pharmacopoeia, using the Student's t and the F tests. Considering the concentration in a 100 µL aliquot, the qualitative visual limit of detection is about 5×10-6 g; instrumental LOD ≅ 1.4×10-4 mol L-1 ; LOQ ≅ 4.5×10-4 mol L-1.

Työntömastotrukkien tuotannon optimointi

Tutkimuksessa luodaan Tuko Logistics Oy:n työntömastotrukkien toimintaa opti-moivia toimintaehdotuksia varastonohjausjärjestelmästä saatavan työntömastotruk-kidatan pohjalta. Tutkimus on toteutettu haastattelututkimuksena ja käyttäen apuna tieteellisiä julkaisuja. Tehtävien lomittamistutkimuksen ja loogiseen päättelyn tulok-sena on luotu kaksi toimintaehdotusta: A ja B. Toimintaehdotusten vaikutuksia van-haan järjestelmään verrataan mittareilla, joista osa on tehty jonoteorian jonomallien laskukaavojen pohjalta. Mittareita ovat: tehdyt tehtävät tunnissa, tuottamattoman ajon suhde tuottavaan, normaalitehtäväjonon pituus ja normaalitehtäväjonon koko-naisodotusaika. Toimintaehdotus B osoittautuu tehokkaammaksi ehdotukseksi, mutta Toimintaehdotus A:lla voi varmistaa tehtävien riittämisen työntömastotrukeille. Tut-kimuksessa ehdotetaan myös muita työntömastotrukkien toimintaa optimoivia muu-toksia, jotka voidaan ottaa käyttöön jokaisessa toimintamallissa.

Advanced orbital pipe welding

Since the introduction of automatic orbital welding in pipeline application in 1961, significant improvements have been obtained in orbital pipe welding systems. Requirement of more productive welding systems for pipeline application forces manufacturers to innovate new advanced systems and welding processes for orbital welding method. Various methods have been used to make welding process adaptive, such as visual sensing, passive visual sensing, real-time intelligent control, scan welding technique, multi laser vision sensor, thermal scanning, adaptive image processing, neural network model, machine vision, and optical sensing. Numerous studies are reviewed and discussed in this Master’s thesis and based on a wide range of experiments which already have been accomplished by different researches the vision sensor are reported to be the best choice for adaptive orbital pipe welding system. Also, in this study the most welding processes as well as the most pipe variations welded by orbital welding systems mainly for oil and gas pipeline applications are explained. The welding results show that Gas Metal Arc Welding (GMAW) and its variants like Surface Tension Transfer (STT) and modified short circuit are the most preferred processes in the welding of root pass and can be replaced to the Gas Tungsten Arc Welding (GTAW) in many applications. Furthermore, dual-tandem gas metal arc welding technique is currently considered the most efficient method in the welding of fill pass. Orbital GTAW process mostly is applied for applications ranging from single run welding of thin walled stainless tubes to multi run welding of thick walled pipes. Flux cored arc welding process is faster process with higher deposition rate and recently this process is getting more popular in pipe welding applications. Also, combination of gas metal arc welding and Nd:YAG laser has shown acceptable results in girth welding of land pipelines for oil and gas industry. This Master’s thesis can be implemented as a guideline in welding of pipes and tubes to achieve higher quality and efficiency. Also, this research can be used as a base material for future investigations to supplement present finding.

The Structural Basis for inorganic Pyrophosphatase Catalysis and Regulation

Inorganic pyrophosphatases (PPases) are essential enzymes for every living cell. PPases provide the necessary thermodynamic pull for many biosynthetic reactions by hydrolyzing pyrophosphate. There are two types of PPases: integral membrane-bound and soluble enzymes. The latter type is divided into two non-homologous protein families, I and II. Family I PPases are present in all kingdoms of life, whereas family II PPases are only found in prokaryotes, including archae. Family I PPases, particularly that from Saccharomyces cerevisiae, are among the most extensively characterized phosphoryl transfer enzymes. In the present study, we have solved the structures of wild-type and seven active site variants of S. cerevisiae PPase bound to its natural metal cofactor, magnesium ion. These structures have facilitated derivation of the complete enzyme reaction scheme for PPase, fulfilling structures of all the reaction intermediates. The main focus in this study was on a novel subfamily of family II PPases (CBSPPase) containing a large insert formed by two CBS domains and a DRTGG domain within the catalytic domain. The CBS domain (named after cystathionine beta-synthase in which it was initially identified) usually occurs as tandem pairs with two or four copies in many proteins in all kingdoms of life. The structure formed by a pair of CBS domains is also known as a Bateman domain. CBS domains function as regulatory units, with adenylate ligands as the main effectors. The DRTGG domain (designated based on its most conserved residues) occurs less frequently and only in prokaryotes. Often, the domain co-exists with CBS domains, but its function remains unknown. The key objective of the current study was to explore the structural rearrangements in the CBS domains induced by regulatory adenylate ligands and their functional consequences. Two CBS-PPases were investigated, one from Clostridium perfringens (cpCBS-PPase) containing both CBS and DRTGG domains in its regulatory region and the other from Moorella thermoacetica (mt CBS-PPase) lacking the DRTGG domain. We additionally constructed a separate regulatory region of cpCBS-PPase (cpCBS). Both full-length enzymes and cpCBS formed homodimers. Two structures of the regulatory region of cpCBS-PPase complexed with the inhibitor, AMP, and activator, diadenosine tetraphosphate, were solved. The structures were significantly different, providing information on the structural pathway from bound adenylates to the interface between the regulatory and catalytic parts. To our knowledge, these are the first reported structures of a regulated CBS enzyme, which reveal large conformational changes upon regulator binding. The activator-bound structure was more open, consistent with the different thermostabilities of the activator- and inhibitor-bound forms of cpCBS-PPase. The results of the functional studies on wild-type and variant CBS-PPases provide support for inferences made on the basis of structural analyses. Moreover, these findings indicate that CBS-PPase activity is highly sensitive to adenine nucleotide distribution between AMP, ADP and ATP, and hence to the energy level of the cell. CBS-PPase activity is markedly inhibited at low energy levels, allowing PPi energy to be used for cell survival instead of being converted into heat.

Matkailun tuhat kärjessä?

Kirjallisuusarvostelu

Suomalaisen demokratian historialliset ulottuvuudet

Kirjallisuusarvostelu

Suomalaisen demokratia-analyysin taloustieteellisestä perustasta

Kirjallisuusarvostelu

Kapearailotekniikan käyttö jauhekaarihitsauksessa

Diplomityössä tavoitteena oli tutkia kapearailojauhekaaritekniikan soveltuvuutta konepajakäyttöön ja sen vaikutusta hitsauksen tuottavuuteen sekä hitsin mekaanisiin ominaisuuksiin. Työ tehtiin vertailukokeilla, jossa koehitsaukset suoritettiin eri aineenpaksuuksille siten, että jokaiselle tutkimuksen kohteena olleelle materiaalille tehtiin yksi hitsaus käytössä olevalla jauhekaaritekniikalla, jolloin saatiin vertailukohde, johon uutta kapearailotekniikkaa verrattiin. Tulokset osoittivat, että kapearailotekniikalla 1 palko/palkokerros aineenpaksuudeltaan Pl. 60 mm koekappale saatiin hitsattua n. 39 % nopeammin verrattuna perinteiseen tandem -hitsaukseen. Kyseisellä aineenpaksuudella lisäainelangan kulutus oli n. 41 % ja jauheen kulutus n. 71 % pienempi verrattuna perinteiseen X- railohitsaukseen tandem -menetelmällä. Lisäksi tuli esille, että ”palkoa palonpäälle” -tekniikka on kapearailotekniikoista tehokkain, sillä 2 palkoa/palkokerros menetelmässä railon leveyttä jouduttiin leventämään, jolloin kapearailotekniikan pieni railotilavuus menetettiin. Lisäaineen kulutus tälläkin menetelmällä jäi pienemmäksi verrattuna X- railohitsaukseen. Ennalta pelättyä kuonan irtoamisongelmaa ei kapearailohitsauksessa havaittu, vaan kuona irtosi ongelmitta railon kyljistä. Lisäksi kapearailotekniikalla hitsattujen hitsien lujuudet olivat vertailukelpoiset tandem- ja yksilankamenetelmällä hitsattujen hitsien kanssa.

Ulkomaalaislupaprosessin läpäisyaikojen hallinta poliisilaitoksella

Tämä diplomityö käsittelee Lappeenrannan teknillisen yliopiston ja Etelä- Karjalan poliisilaitoksen yhteistä kehitysprojektia, jonka tavoitteena oli tuottaa käytäntöön vietävissä oleva kehittämissuunnitelma ulkomaalaislupa-asioiden läpäisyaikojen hallintaan. Kehitysalueita on pyritty löytämään poliisilaitoksen henkilöstön haastatteluilla ja prosessianalyyseilla. Työ sisältää teoriaosion määräaikahallinnasta, yleiskatsauksen ulkomaalaislupa-asioista Suomessa sekä selvityksen ulkomaalaislupa-asioiden tilanteesta Etelä-Karjalan poliisilaitoksella. Työssä muodostettiin kolme kehittämisteemaa: seurannan kehittäminen, prosessien ja työtapojen kehittäminen ja yhteistyön kehittäminen. Tärkein kehittämistoimi oli Excel-pohjaisen seurantajärjestelmän suunnittelu, rakentaminen ja käyttöönottaminen. Seurantajärjestelmää voidaan hyödyntää tehtävien päivittäisessä ohjauksessa, määräaikatavoitteiden toteutumisen seurannassa sekä tilannekuvan ylläpitämisessä. Tavoitetilanteessa seurantajärjestelmän avulla hallitaan tilannetta siten, että hallitsemattomia hakemusruuhkia ei synny. Hankkeesta saatuja kokemuksia tehtäväjonojen hallinnasta ja suorituskyvyn mittaamisesta voidaan ajatella hyödynnettävän myös muissa prosesseissa.

Absence of intestinal colonization by vancomycin-resistant enterococci in nonhuman primates

The animal reservoirs of vancomycin-resistant enterococci (VRE) have important role in the epidemiology of the bacteria and resistant genes. The present work searched fecal samples taken off nonhuman primates for the presence of VRE. Resistance profiles, virulence traits, and genetic variability among enterococci isolates were also analyzed. The samples included Capuchin monkeys (Cebus apella, n=28) and Common marmoset (Callithrix penicillata, n=37) housed in the Primate Center of the University of Brasília, Brazil. Most individuals were captive monkeys from the Central-West and South-East regions of Brazil (n=48). We collected rectal swabs and carried out selective isolation followed by multiplex Polymerase Chain Reaction (PCR) to identify species and resistance genes. No vanA or vanB-containing enterococci were found. The carriage rates ranged from 1.5% for the VanC-type E. casseliflavus and E. gallinarum until 12.3% (n=8) for Enterococcus faecalis. All E. faecalis isolates showed susceptibility to vancomycin, teicoplanin, ampicillin, gentamicin, and streptomycin. The virulence genes ace and esp were prevalent (100.0%, 87.5%). Multilocus variable number of tandem repeats (MLVA) revealed diversity in the number of repeats among E. faecalis isolates and targets, which was higher for espC, efa5, and efa6. We identified six different MLVA genotypes that were divergent from those described in human beings. Also, they were clustered into two genogroups that showed host-specificity for the species Cebus apella or Callithrix penicillata. In conclusion, no vanA- or vanB-containing enterococci were found colonizing those primate individuals. This finding suggested that the primate individuals investigated in our study are not directly involved in the epidemiological chain of high-level vancomycin-resistant genes vanA or vanB in Brazil. Our study also showed that E. faecalis isolated from nonhuman primates carry virulence traits and have ability to spread their lineages among different individuals.

Experimental poisoning by Baccharis megapotamica var. weirii in buffalo

Five male 6-8 month-old Murrah buffalo calves were orally dosed with the fresh aerial parts of Baccharis megapotamica var. weirii at doses of 1, 3, 4, 5 and 10g/kg body weight (bw) (~1-10mg macrocyclic trichothecenes/kg/bw). The B. megapotamica used for the experiment was harvested on a farm where a recent spontaneous outbreak of poisoning caused by such plant had occurred. Clinical signs appeared 4-20 hours and 4 buffaloes died 18-49 hours after the ingestion of the plant. Clinical signs were apathy, anorexia, and watery diarrhea, fever, colic, drooling, muscle tremors, restlessness, laborious breathing and ruminal atony, and dehydration. The most consistent gross findings were restricted to the gastrointestinal (GI) tract consisted of varying degrees of edema and reddening of the mucosa of the forestomach. Histopathological findings consisted of varying degrees of necrosis of the epithelial lining of the forestomach and of lymphocytes within lymphoid organs and aggregates. Fibrin thrombi were consistently found in sub-mucosal vessels of the forestomach and in the lumen of hepatic sinusoids. It is suggested that dehydration, septicemia and disseminated intravascular coagulation participate in the pathogenesis of the intoxication and play a role as a cause of death. A subsample of B. megapotamica var. weirii was frozen-dried and ground and analyzed using UHPLC (Ultra High Performance Liquid Chromatography) with high resolution Time of Flight mass spectrometry and tandem mass spectrometry, it was shown that the plant material contained at least 51 different macrocyclic trichothecenes at a total level of 1.1-1.2mg/g. About 15-20% of the total trichothecenes contents was found to be monosaccharide conjugates, with two thirds of these being glucose conjugates and one third constituted by six aldopentose conjugates (probably xylose), which has never been reported in the literature.

Infant Colic Crying and Gastrointestinal Tract – Causes, Consequences and Cure

Despite over 50 years of investigation, the precise cause of infant colic crying remains unresolved and the long-term consequences unrevealed, and an effective treatment is lacking. Indeed, a more profound understanding of the complex nature of infants’ excessive crying is needed. The purpose of this series of studies was to investigate the association between gut microbiota composition and infant crying, to evaluate the impact of colic crying on children’s later health and to study the possibilities of treating and preventing excessive crying with pro- and prebiotics. The material comprised three on-going, prospective randomized controlled trials of the probiotic Lactobacillus rhamnosus GG (ATCC 53103, LGG) or a mixture of prebiotics administered in early infancy. The study populations consisted of term infants (n=89), preterm infants (n=94) and term colic infants (n=30). Early crying was found to be inversely associated with the number of Bifidobacterium and Lactobacillus. Furthermore, at the age of 13 years functional gastrointestinal disorders (FGID) were manifested more frequently among children with previous colic crying than in those without. In preterm infants pro- and prebiotic supplementation during the first months of life reduced the frequency of excessive crying when compared to placebo. In parallel, probiotic LGG in tandem with a cow’s milk elimination diet and behavioral counseling reduced the daily crying amount among term colic infants when compared to placebo. In conclusion, the composition of the gut microbiota is associated with infant crying and colic, and probiotic LGG might provide a safe and effective treatment or preventive option to alleviate excessive crying in early infancy in term and preterm infants. Furthermore, early colic crying might be associated with the later development of FGID.

Dinâmica e variabilidade espacial de plantas daninhas em sistemas de mobilização do solo em sorgo forrageiro

O mapeamento e a caracterização da distribuição espacial de plantas daninhas por meio da agricultura de precisão, associada a levantamentos fitossociológicos, têm sido utilizados no controle localizado da infestação. O presente trabalho avaliou a incidência e a dinâmica de plantas daninhas, além da distribuição espacial em distintos sistemas de mobilização do solo, na cultura do sorgo forrageiro. O experimento foi conduzido em Petrolina-PE. Os tratamentos constaram de quatro sistemas de mobilização do solo: sem preparo primário, grade tandem mais arado de aivecas, grade off-set de discos de 0,61 m e grade tandem mais escarificador. A coleta de dados ocorreu na cultura do sorgo forrageiro aos 110 dias após emergência, em uma área retangular de 20 x 12 m (240 m²) com malha regular de 4 x 3 m, referenciadas em coordenadas x e y. A caracterização fitossociológica foi realizada pela avaliação da densidade, frequência, abundância, dominância e índice de valor de importância das espécies, e a variabilidade espacial, por meio da geoestatística com a construção de mapas de isolinhas. Cenchrus echinatus teve maior incidência e índice de valor de importância. O mapeamento de plantas daninhas tem relevância para a aplicação de métodos de controle, principalmente quando aliado ao levantamento fitossociológico.