Kaupan omat merkit päivittäistavarakaupan tuotevalikoimassa: tutkimus Ruokakeskon Pirkka-brändistä sekä sen roolista Forssan K-citymarketissa

Kaupan omat merkit pitävät markkinaosuuden kasvua yllä Euroopassa, olipa kyse sitten kehittyvistä vähittäiskaupan markkinoista Idässä tai vakiintuneimmista vähittäiskaupan alueista. Vähittäismyyjien omien merkkien osuus myytävistä tuotteista on yli 40 prosenttia monissa Euroopan maissa. Tämän tutkielman ensisijaisena tarkoituksena on tutkia kaupan omien merkkien roolia päivittäistavarakaupan tuotevalikoimassa. Tutkielman empiirisessä osiossa kaupan oman merkin roolia päivittäistavarakaupan tuotevalikoimassa havainnollistetaan Ruokakeskon Pirkka-tuotemerkin kautta. Tutkielman tarkoitusta lähestytään tarkentavien osakysymysten avulla. Teoriasta haetaan vastauksia kysymyksiin: 1. Millaisia kaupan omien merkkien tyyppejä tutkijat ovat tunnistaneet? 2. Millaisia markkinointistrategioita kaupalla niiden käyttöön liittyy? 3. Millaisia tavoitteita kauppa asettaa yleisesti omille merkeilleen? Empiirisen tutkimuksen avulla pyritään vastaamaan kysymyksiin: 1. Minkä tyyppinen kaupan oma merkki on Ruokakeskon Pirkka-brändi ja millainen on Pirkka-brändin markkinointistrategia? 2. Mitä tavoitteita Ruokakesko on Pirkka-brändilleen asettanut? 3. Vastaako ostokäyttäytyminen Ruokakeskon Pirkka-brändille asettamia tavoitteita? Tutkimusstrategiana on surveytutkimus sekä tapaustutkimus. Johtuen siitä, että kahdessa ensimmäisessä osakysymyksessä analyysiyksikkö on eri kuin kolmannessa osakysymyksessä käytetään tutkielmassa sekä laadullista että määrällistä tutkimusotetta. Kvalitatiivista sekä kvantitatiivista tutkimusotetta yhdistelemällä onnistutaan saamaan hyvä kokonaiskuva analyysiyksiköistä. Aineistoa kerättiin useammasta lähteestä. Päätutkimusmenetelmiä oli kaksi: kyselytutkimus sekä tutkimushaastattelu. Kyselytutkimuksen aineisto kerättiin Forssan K-citymarketissa asiakkailta kysymyslomakkeen avulla. Otannan kooksi muodostui 295 täytettyä kysymyslomaketta. Vastaukset analysoitiin IBM SPSS Statistics 20 tilasto-ohjelman avulla. Haastattelututkimus suoritettiin avoimena haastattelua. Ei ole täysin yksiselitteistä minkä tyyppinen kaupan oma merkki tai millainen rooli Ruokakeskon omalla merkillä Pirkalla on. Pirkka-brändille asetetut keskeisimmät tavoitteet ovat erilaistaa kilpailevista päivittäistavarakauppaketjuista, tarjota paremmat katteet sekä luoda kuvaa vähittäismyyjästä. Kuluttajat ostavat Pirkka-tuotteita pääasiallisesti hinnan takia.

Novel technology for preparation of optically active chemicals

Asymmetric synthesis using modified heterogeneous catalysts has gained lots of interest in the production of optically pure chemicals, such as pharmaceuticals, nutraceuticals, fragrances and agrochemicals. Heterogeneous modified catalysts capable of inducing high enantioselectivities are preferred in industrial scale due to their superior separation and handling properties. The topic has been intensively investigated both in industry and academia. The enantioselective hydrogenation of ethyl benzoylformate (EBF) to (R)-ethyl mandelate over (-)-cinchonidine (CD)-modified Pt/Al2O3 catalyst in a laboratory-scale semi-batch reactor was studied as a function of modifier concentration, reaction temperature, stirring rate and catalyst particle size. The main product was always (R)-ethyl mandelate while small amounts of (S)-ethyl mandelate were obtained as by product. The kinetic results showed higher enantioselectivity and lower initial rates approaching asymptotically to a constant value as the amount of modifier was increased. Additionally, catalyst deactivation due to presence of impurities in the feed was prominent in some cases; therefore activated carbon was used as a cleaning agent of the raw material to remove impurities prior to catalyst addition. Detailed characterizations methods (SEM, EDX, TPR, BET, chemisorption, particle size distribution) of the catalysts were carried out. Solvent effects were also studied in the semi-batch reactor. Solvents with dielectric constant (e) between 2 and 25 were applied. The enantiomeric excess (ee) increased with an increase of the dielectric coefficient up to a maximum followed by a nonlinear decrease. A kinetic model was proposed for the enantioselectivity dependence on the dielectric constant based on the Kirkwood treatment. The non-linear dependence of ee on (e) successfully described the variation of ee in different solvents. Systematic kinetic experiments were carried out in the semi-batch reactor. Toluene was used as a solvent. Based on these results, a kinetic model based on the assumption of different number of sites was developed. Density functional theory calculations were applied to study the energetics of the EBF adsorption on pure Pt(1 1 1). The hydrogenation rate constants were determined along with the adsorption parameters by non-linear regression analysis. A comparison between the model and the experimental data revealed a very good correspondence. Transient experiments in a fixed-bed reactor were also carried out in this work. The results demonstrated that continuous enantioselective hydrogenation of EBF in hexane/2-propanol 90/10 (v/v) is possible and that continuous feeding of (-)-cinchonidine is needed to maintain a high steady-state enantioselectivity. The catalyst showed a good stability and high enantioselectivity was achieved in the fixed-bed reactor. Chromatographic separation of (R)- and (S)-ethyl mandelate originating from the continuous reactor was investigated. A commercial column filled with a chiral resin was chosen as a perspective preparative-scale adsorbent. Since the adsorption equilibrium isotherms were linear within the entire investigated range of concentrations, they were determined by pulse experiments for the isomers present in a post-reaction mixture. Breakthrough curves were measured and described successfully by the dispersive plug flow model with a linear driving force approximation. The focus of this research project was the development of a new integrated production concept of optically active chemicals by combining heterogeneous catalysis and chromatographic separation technology. The proposed work is fundamental research in advanced process technology aiming to improve efficiency and enable clean and environmentally benign production of enantiomeric pure chemicals.

Biologia floral e fenologia reprodutiva do camu-camu (Myrciaria dubia (H.B.K.) McVaugh, Myrtaceae) no Estado Pará, Brasil

O camu-camu (Myrciaria dubia (H.B.K.) McVaugh, Myrtaceae) é uma fruteira nativa que ocorre nas margens de rios e lagos inundáveis da Amazônia, e está sendo domesticada visando o cultivo em terra firme. O alto teor de ácido ascórbico nos frutos, cerca de 2.800 mg.100g-1 de polpa, fortalece a demanda para consumo no país e exportação. No período de 1997 a 1998, investigou-se a biologia floral e fenologia reprodutiva do camu-camu, em plantios da Embrapa Amazônia Oriental, em Belém, e em áreas de ocorrência natural, em Santarém e Oriximiná, no Estado do Pará, norte do Brasil. Observações diretas sobre o comportamento dos visitantes foram acompanhadas da coleta de espécimens para identificação e registro fotográfico. M. dubia apresenta inflorescências com flores brancas, hermafroditas e poliândricas. A antese ocorre entre as 5:00 e 7:00 h. O pólen é seco e facilmente transportado pelo vento ou gravidade, sendo o principal recurso e atrativo floral. Os osmóforos estão localizados no cálice, corola, anteras e estigma. Constatou-se que a fenofase de floração foi do tipo "steady-state", sendo mais expressiva em março e a frutificação teve um pico no mês de julho. Observouse desfolha parcial em todas as plantas estudadas, principalmente em novembro. Os principais visitantes foram Nannotrigona punctata e Trigona pallens (Meliponinae) e pequenos besouros (Chrysomelidae). As abelhas sem ferrão foram consideradas os polinizadores legítimos.

O aumento em superfície em Adelia membranifolia (Müll. Arg.) Pax & K. Hoffm. e Peltophorum dubium (Spreng.) Taub., em resposta ao estresse por deficiência nutricional e alagamento do substrato

Foram estudadas as respostas plásticas em plântulas e plantas jovens de duas espécies arbóreas nativas, Adelia membranifolia (Müll. Arg.) Pax & K. Hoffm. (Euphorbiaceae) e Peltophorum dubium (Spreng.) Taub. (Leguminosae-Caesalpinoidae), submetidas ao alagamento do substrado associado ao déficit nutricional. Avaliou-se o acréscimo em superfície no módulo de expressão, definido como a região do eixo da plântula que, sob condições de estresse, sofre rediferenciação sendo considerada a hipertrofia lenticelar como a expressão morfogenética mais comum. Em A. membranifolia a associação do estresse nutricional e alagamento do substrato foi a condição mais restritiva tanto para o crescimento em altura e diâmetro do colo quanto para as expressões morfogenéticas. Já em P. dubium o estado nutricional foi mais restritivo que o alagamento para o crescimento do colo. Em geral, para ambas as espécies, plantas nutridas mantidas alagadas restabeleceram seu ritmo de crescimento a partir do terceiro mês de tratamento, além de expressarem respostas plásticas como a hipertrofia lenticelar e a formação de raízes adventícias. Quanto ao aumento em superfície, nos lotes desnutridos, verificou-se que em A. membranifolia de um total de 38% de superfície expressa, 12% corresponderam à hipertrofia lenticelar. Em P. dubium verificou-se as maiores variações de aumento em superfície expressa por hipertrofia lenticelar, elevando de 5% para 13%. Em geral a superfície modular nos lotes tratados foi o dobro em relação ao controle. É possível que o aumento em superfície, para algumas espécies, seja significativo como tendência ao aumento da estabilidade no desenvolvimento a partir de interações fisiológicas.

Lipase and omega-transaminase catalysis in preparation of alcohol and amine enantiomers

Enantiopure intermediates are of high value in drug synthesis. Biocatalysis alone or combined with chemical synthesis provides powerful tools to access enantiopure compounds. In biocatalysis, chemo-, regio- and enantioselectivity of enzymes are combined with their inherent environmentally benign nature. Enzymes can be applied in versatile chemical reactions with non-natural substrates under synthesis conditions. Immobilization of an enzyme is a crucial part of an efficient biocatalytic synthesis method. Successful immobilization enhances the catalytic performance of an enzyme and enables its reuse in successive reactions. This thesis demonstrates the feasibility of biocatalysis in the preparation of enantiopure secondary alcohols and primary amines. Viability and synthetic usability of the studied biocatalytic methods have been addressed throughout this thesis. Candida antarctica lipase B (CAL-B) catalyzed enantioselective O-acylation of racemic secondary alcohols was successfully incorporated with in situ racemization in the dynamic kinetic resolution, affording the (R)-esters in high yields and enantiopurities. Side reactions causing decrease in yield and enantiopurity were suppressed. CAL-B was also utilized in the solvent-free kinetic resolution of racemic primary amines. This method produced the enantiomers as (R)-amides and (S)-amines under ambient conditions. An in-house sol-gel entrapment increased the reusability of CAL-B. Arthrobacter sp. omega-transaminase was entrapped in sol-gel matrices to obtain a reusable catalyst for the preparation enantiopure primary amines in an aqueous medium. The obtained heterogeneous omega-transaminase catalyst enabled the enantiomeric enrichment of the racemic amines to their (S)-enantiomers. The synthetic usability of the sol-gel catalyst was demonstrated in five successive preparative kinetic resolutions.

Ouratea lancifolia R. G. Chacon & K. Yamam. (Ochnaceae), uma nova espécie do Cerrado, Brasil

A nova espécie Ouratea lancifolia R. G. Chacon & K. Yamam. é descrita. Ela compreende arbustos pequenos de savana gramíneo-lenhosa e se caracteriza pelas lâminas foliares lanceoladas de base cordada e margens serreadas. São apresentados descrição, ilustração e comentários ecológicos. São analisadas as diferenças em relação às duas espécies mais próximas, O. lanceolata (Pohl) Engl. e O. floribunda (A. St.-Hil.) Engl., também ocorrentes no bioma Cerrado.

Preparation and purification of Flavobacterium heparinum chondroitinases AC and B by hydrophobic interaction chromatography

Flavobacterium heparinum is a soil bacterium that produces several mucopolysaccharidases such as heparinase, heparitinases I and II, and chondroitinases AC, B, C and ABC. The purpose of the present study was to optimize the preparation of F. heparinum chondroitinases, which are very useful tools for the identification and structural characterization of chondroitin and dermatan sulfates. We observed that during the routine procedure for cell disruption (ultrasound, 100 kHz, 5 min) some of the chondroitinase B activity was lost. Using milder conditions (2 min), most of the chondroitinase B and AC protein was solubilized and the enzyme activities were preserved. Tryptic soy broth without glucose was the best culture medium both for bacterial growth and enzyme induction. Chondroitinases AC and B were separated from each other and also from glucuronidases and sulfatases by hydrophobic interaction chromatography on HP Phenyl-Sepharose. A rapid method for screening of the column fractions was also developed based on the metachromatic shift of the color of dimethylmethylene blue.

K-liitoksen epäkeskeisen tuennan aiheuttaman sekundäärisen momentin määritys

Työssä on tutkittu laboratoriokokeen ja elementtimenetelmän avulla eri geometrioiden vaikutusta sekundääriseen momentin syntymiseen K-liitoksella. Kokeen liitos on tehty S700-lujuusluokan Ruukin Optim 700 plus MH nelikulmaisista rakenneputkista (RHS). Elementtimalleissa on käytetty geometrista ja materiaalista epälineaarisuutta ennustamaan liitoksen muodonmuutoskykyä ja laskennallista kestävyyttä. Liitoksen elementtimalleissa muutettavia geometrioita ovat: vapaaväli, uumasauvan ja paarteen välinen kulma, paarteen seinämän paksuus, liitoksen eksentrisyys ja uumasauvan ja paarteen leveyden suhde. Laboratoriokokeen liitoksen vetouumasauvassa vaikuttava sekundäärisen momentin aiheuttama jännitys on noin 25 % vetouumasauvan myötörajasta. Suurin sekundäärinen momentti syntyy, kun vapaaväliä pienennetään ja uumasauvaa kavennetaan paarteeseen nähden. Eurocode 3:n mitoitusohjeita voidaan elementtimallien perusteella soveltaa tietyille geometrioille turvallisesti.

Pulsed electric field assisted sol-gel preparation of TiO2 particles and their photocatalytic properties

The objective of this thesis was to study the effect of pulsed electric field on the preparation of TiO2 nanoparticles via sol-gel method. The literature part deals with properties of different TiO2 crystal forms, principles of photocatalysis, sol-gel method and pulsed electric field processing. It was expected that the pulsed electric field would have an influence on crystallite size, specific surface area, polymorphism and photocatalytic activity of produced particles. TiO2 samples were prepared by using different frequencies and treatment times of pulsed electric field. The properties of produced TiO2 particles were examined X-ray diffraction (XRD), Raman spectroscopy and BET surface area analysis. The photocatalytic activities of produced TiO2 particles were determined by using them as photocatalysts for the degradation of formic acid under UVA-light. The photocatalytic activities of samples produced with sol-gel method were also compared with the commercial TiO2 powder Aeroxide® (Evonic Degussa GmbH). Pulsed electric field did not have an effect on the morphology of particles. Results from XRD and Raman analysis showed that all produced TiO2 samples were pure anatase. However, pulsed electric field did have an effect on crystallite size, specific surface area and photocatalytic activity of TiO2 particles. Generally, the crystallite sizes were smaller, specific surface areas larger and initial formic acid degradation rates higher for samples that were produced by applying the pulsed electric field. The higher photocatalytic activities were attributed to larger surface areas and smaller crystallite sizes. Though, with all of the TiO2 samples produced by the sol-gel method the initial formic acid degradation rates were significantly slower than with the commercial TiO2 powder.

Erythrocytes may contain a ouabain-insensitive K+-ATPase which plays a role in internal K+ balance

Erythrocytes are useful in evaluating K+ transport pathways involved in internal K+ balance. Several forms of H+,K+-ATPase have been described in nephron segments active in K+ transport. Furthermore, the activity of a ouabain-insensitive isoform of H+,K+-ATPase expressed in collecting duct cells may be modulated by acid-base status. Various assays were performed to determine if a ouabain-insensitive K+-ATPase is present in rat erythrocytes and, if so, whether it plays a role in internal K+ balance. Kinetic studies demonstrated that maximal stimulation of enzyme activity was achieved with 2.5 mM K+ at pH 7.4. Subsequent experiments were performed on erythrocyte membranes collected from animals submitted to varying degrees of K+ homeostasis: control rats, K+-depleted rats, K+-loaded rats, and rats rendered hyperkalemic due to acute renal failure. As observed in the collecting duct cell studies, there was a significant decrease in the activity of ouabain-insensitive K+-ATPase in the erythrocytes of both K+-loaded and metabolically alkalotic K+-depleted rats. However, this enzyme activity in erythrocyte membranes of rats with metabolic acidosis-related hyperkalemia was similar to that of control animals. This finding may be interpreted as resulting from two potentially modulating factors: the stimulating effect that metabolic acidosis has on K+-ATPase and the counteracting effect that hyperkalemia and uremia have on metabolic acidosis. In summary, we present evidence of a ouabain-insensitive K+-ATPase in erythrocytes, whose activity is modulated by acid-base status and K+ levels.

Tomato and garlic by gavage modulate 7,12-dimethylbenz[a]anthracene-induced genotoxicity and oxidative stress in mice

Chemoprotection by dietary agents is a promising strategy for cancer prevention. The aim of the present study was to evaluate the combined effect of tomato and garlic against 7,12-dimethylbenz- [a]anthracene (DMBA)-induced genetic damage and oxidative stress in 12-14-week-old male Swiss albino mice. The animals were randomized into experimental and control groups and divided into eight groups of five animals each. Group 1 animals were injected intraperitoneally with 35 mg/kg body weight DMBA suspended in peanut oil as a single dose. Groups 2-4 animals received tomato (500 mg/kg body weight), garlic (125 mg/kg body weight) and a combination of tomato and garlic for 5 days by gavage, respectively, followed by DMBA 1.5 h after the final feeding. The doses of tomato and garlic correspond to the average human daily consumption. Animals in groups 5, 6 and 7 received tomato alone, garlic alone and tomato + garlic combination, respectively, for 5 days. Group 8 animals received the same volume of water and served as control. The incidence of bone marrow micronuclei and the extent of lipid peroxidation and the concentrations of antioxidants glutathione, glutathione peroxidase and glutathione-S-transferase were measured in the liver, 48 h after DMBA exposure. Increased frequency of micronuclei and enhanced lipid peroxidation accompanied by compromised antioxidant defenses were observed in DMBA-treated animals. Although pretreatment with tomato or garlic significantly reduced the frequency of DMBA-induced bone marrow micronuclei, the combination of tomato and garlic exhibited more profound effect in inhibiting DMBA-induced genotoxicity and oxidative stress. We suggest that a broad spectrum of antimutagenic and anticlastogenic effects can be achieved through an effective combination of functional foods such as tomato and garlic.

A key role for Na+/K+-ATPase in the endothelium-dependent oscillatory activity of mouse small mesenteric arteries

Oscillatory contractile activity is an inherent property of blood vessels. Various cellular mechanisms have been proposed to contribute to oscillatory activity. Mouse small mesenteric arteries display a unique low frequency contractile oscillatory activity (1 cycle every 10-12 min) upon phenylephrine stimulation. Our objective was to identify mechanisms involved in this peculiar oscillatory activity. First-order mesenteric arteries were mounted in tissue baths for isometric force measurement. The oscillatory activity was observed only in vessels with endothelium, but it was not blocked by L-NAME (100 µM) or indomethacin (10 µM), ruling out the participation of nitric oxide and prostacyclin, respectively, in this phenomenon. Oscillatory activity was not observed in vessels contracted with K+ (90 mM) or after stimulation with phenylephrine plus 10 mM K+. Ouabain (1 to 10 µM, an Na+/K+-ATPase inhibitor), but not K+ channel antagonists [tetraethylammonium (100 µM, a nonselective K+ channel blocker), Tram-34 (10 µM, blocker of intermediate conductance K+ channels) or UCL-1684 (0.1 µM, a small conductance K+ channel blocker)], inhibited the oscillatory activity. The contractile activity was also abolished when experiments were performed at 20°C or in K+-free medium. Taken together, these results demonstrate that Na+/K+-ATPase is a potential source of these oscillations. The presence of α-1 and α-2 Na+/K+-ATPase isoforms was confirmed in murine mesenteric arteries by Western blot. Chronic infusion of mice with ouabain did not abolish oscillatory contraction, but up-regulated vascular Na+/K+-ATPase expression and increased blood pressure. Together, these observations suggest that the Na+/K+ pump plays a major role in the oscillatory activity of murine small mesenteric arteries.

Spectrum of K ras mutations in Pakistani colorectal cancer patients

The incidence of colorectal cancer (CRC) is increasing daily worldwide. Although different aspects of CRC have been studied in other parts of the world, relatively little or almost no information is available in Pakistan about different aspects of this disease at the molecular level. The present study was aimed at determining the frequency and prevalence of K ras gene mutations in Pakistani CRC patients. Tissue and blood samples of 150 CRC patients (64% male and 36% female) were used for PCR amplification of K ras and detection of mutations by denaturing gradient gel electrophoresis, restriction fragment length polymorphism analysis, and nucleotide sequencing. The K ras mutation frequency was found to be 13%, and the most prevalent mutations were found at codons 12 and 13. A novel mutation was also found at codon 31. The dominant mutation observed was a G to A transition. Female patients were more susceptible to K ras mutations, and these mutations were predominant in patients with a nonmetastatic stage of CRC. No significant differences in the prevalence of K ras mutations were observed for patient age, gender, or tumor type. It can be inferred from this study that Pakistani CRC patients have a lower frequency of K ras mutations compared to those observed in other parts of the world, and that K ras mutations seemed to be significantly associated with female patients.

Estudo químico de alimentos formulados à base de palmito Bactris gasipaes H.B.K. (pupunha) desidratado

O coração da palmeira Bactris gasipaes H.B.K. (pupunha) foi utilizado, sob forma desidratada, na formulação de uma sopa-creme para merenda escolar. Análises químicas do palmito e do coração da palmeira (açúcares redutores, lipídeos, proteínas totais, aminograma, fibras, calorias e minerais) foram feitas tanto na forma in natura como na forma processada, bem como na de sopa-creme. Não foram encontradas diferenças relevantes em relação a essas determinações, podendo-se ressaltar a boa qualidade aminoacídica do coração da palmeira.

Estabilidade de ácido ascórbico e antocianinas em néctar de camu-camu (Myrciaria dubia (H. B. K.) McVaugh)

O camu-camu é um fruto com notável potencial nutricional, pelo seu alto conteúdo em ácido ascórbico. Sendo assim, objetivou-se avaliar a estabilidade do ácido ascórbico e pigmentos presentes no néctar de camu-camu, armazenados sob diferentes condições de luminosidade e temperatura. Os frutos foram despolpados e avaliados quanto às características físico-químicas. O néctar, obtido a partir da polpa, foi acondicionado em garrafas PET e armazenado em temperatura ambiente e sob refrigeração na presença e ausência de luz, sendo avaliado por 120 dias quanto à estabilidade de ácido ascórbico e antocianinas. O teor de ácido ascórbico nos néctares armazenados sob luz não diferiu estatisticamente dos armazenados protegidos da luz (343,25 e 340,48 mg.100 g -1), respectivamente, nos armazenados sob refrigeração, e (330,48 e 333,56 mg.100 g -1) nos armazenados em temperatura ambiente. Constatou-se que esta vitamina em néctares armazenados por 120 dias em temperatura de refrigeração apresentou boa estabilidade, com perda de apenas 12 a 14%. Quanto às antocianinas, a temperatura ambiente contribuiu negativamente, ocasionando uma degradação mais acelerada, no entanto, a exposição à luz não teve efeito. Nestas condições experimentais, conclui-se que o fator luminosidade tem pouca influência sobre o ácido ascórbico e antocianinas no néctar de camu-camu, e que a temperatura ambiente de armazenamento é fator negativo na estabilidade destes pigmentos.