NMR investigation and theoretical calculations of the effect of solvent on the conformational analysis of 4',7-di-hydroxy-8-prenylflavan

The NMR conformational study of 4',7-di-hydroxy-8-prenylflavan 1 was carried out in acetone-d6, DMSO-d6 and CDCl3 which enabled the proposition of three conformations, namely 1a, 1b and 1c, differing in the position of the prenyl group. Geometry optimizations performed using AM1 method showed that 1a (deltaHf = -86.2 kcal/mol) is as stable as 1b (deltaHf = -85.1 kcal/mol) and 1c (deltaHf = -85.4 kcal/mol). When the solvent was included, the calculations showed that the solute-solvent interactions could be explained either in the light of the electronic intermolecular delocalization or the electrostatic character between solute and solvent. Theoretical calculations (HF/6-31G*, deltaFT/BLYP/6-31G*, and deltaFT/B3LYP/6-31G*) showed that the combination of these types of interactions present in each solute-solvent system, dependent on the chemical properties of the solvent, lead to different spatial arrangements of the prenyl group, which in turn determined the conformation of 1.

Tuotannonohjauksen kehittäminen piensarjatuotannossa

Tämä diplomityö käsittelee teollisen yrityksen tuotannonohjauksen kehittämistä piensarjatuotannossa. Työn kohteena on ABB Oy:n Tuulivoimageneraattorit-tulosyksikkö, joka valmistaa vakiotuotteita asiakasohjautuvasti. Työssä esitellään aluksi tuotannon ja tuotannonohjauksen teoriaa. Lävitse käydään perusasioiden kuten määritelmien, tavoitteiden ja tehtävien lisäksi tuotannonohjausprosessia sekä tuotannonohjauksen tietotekniikkaa. Teorian jälkeisessä empiriaosuudessa esitellään työssä kehitettyjä keinoja tuotannonohjauksen parantamiseksi. Tutkimus on toteutettu teoreettisen ja empiirisen tutkimustyön avulla. Teoreettiseen tutkimustyöhön sisältyi suomalaisiin ja ulkomaalaisiin kirjallisuuslähteisiin perehtyminen. Empiirinen tutkimustyö suoritettiin itsenäisen ongelman ratkaisutyön avulla. Tämä sisälsi kehittämiskohteiden analysoinnin, tarkempien kehittämistarpeiden määrityksen sekä kokeilujen kautta tapahtuneen kehittämistyön. Tutkimuksen päätavoitteena oli selvittää, miten tuotannonohjauksen kehittämisellä voidaan parantaa kohteena olevan tulosyksikön tuottavuutta ja kannattavuutta. Päätavoitteen pohjalta muodostettiin kuusi osatavoitetta: toimitusvarmuuden parantaminen, kapasiteetin kuormitusasteen nostaminen, kapasiteetin suunnittelun kehittäminen, läpäisyaikojen lyhentäminen, uuden ERP-järjestelmän vaatimusmäärittely sekä tuotannonohjausprosessin määrittäminen. Työssä rakennettiin neljään ensiksi mainittuun osatavoitteeseen tietotekniset sovellukset, jotka mahdollistavat osatavoitteiden suunnittelun ja ohjaamisen. Sovelluksia varten kullekin tuotteelle määriteltiin esimerkiksi työnvaiheketjut läpäisyaikoineen, kuormitusryhmät, kuormitusryhmien kapasiteetit, tuotteiden kuormittavuudet sekä kriittiset työvälineet. Työ osoitti, että tietotekniikka auttaa suuresti tuotannonohjauksessa. Lisääntynyt läpinäkyvyys, parantunut tiedonkulku, simulointimahdollisuudet sekä graafinen esitystapa helpottavat erilaisten suunnitelmien teossa ja parantavat siten päätöksenteon laatua. Tietotekniikan hyväksikäytön pohjana toimii tuotannon perus- ja tapahtumatietojen kurinalainen päivitys. Tämän vuoksi tietojärjestelmistä kannattaa rakentaa mahdollisimman yksinkertaisia.

Kevyiden rakennemateriaalien soveltamismahdollisuudet metsäkoneissa

Asiakkaiden ympäristötietoisuus, metsäkoneille asetettavat korkeat vaatimukset ja kiristyvä kilpailu pakottavat metsäkoneiden valmistajat etsimään vaihtoehtoisia valmistusmateriaaleja, joita käyttämällä metsäkoneet kevenevät ja sitä kautta niiden ympäristökuormitukset ja käyttökustannukset alenevat ja kapasiteetti kasvaa. Metsäkoneiden rakenteiden keventämisessä alumiini on yksi varteenotettava vaihtoehto teräksen korvaajaksi, sillä alumiinin ominaisuus/paino -suhde on terästä parempi. Alumiinin käyttöä hitsatuissa rakenteissa ovat rajoittaneet sen korkea hinta ja melko huono väsymiskestävyys. Diplomityön tavoitteena on ollut selvittää mahdollisuuksia korvata metsäkoneiden rakenteista löytyviä teräksestä valmistettuja osia alumiinista valmistetuilla osilla. Diplomityön teoriaosassa on käsitelty rakenteiden keventämistä, metsäkoneille asetettavia vaatimuksia, alumiinien materiaaliominaisuuksia, alumiinirakenteiden valmistuksessa käytettäviä menetelmiä sekä alumiinirakenteiden suunnittelua. Lisäksi teoriaosassa on käsitelty komposiittien materiaaliominaisuuksia ja komposiittirakenteiden suunnittelua. Diplomityön kokeellisessa osassa on vertailtu nykyisiä rakennemateriaaleja ja alumiineja metsäkoneen eri osien rakennemateriaaleina osien vaatimusprofiileihin ja materiaalien ominaisuusprofiileihin perustuen. Vaatimusprofiilien perusteella on laadittu ominaisuusprofiilit alumiineille ja teräksille. Sovittamalla vaatimus- ja ominaisuusprofiilit yhteen arvoanalyysin avulla, metsäkoneista on etsitty mahdollisia kohteita, joissa nykyinen rakennemateriaali voitaisiin korvata alumiinilla. Tältä pohjalta metsäkoneista löytyi rakenteita, joissa alumiinin käyttö rakennemateriaalina teräksen sijaan olisi mahdollista. Diplomityö toimii hyvänä pohjana tutkittaessa mahdollisuuksia metsäkoneiden rakenteiden keventämiseksi.

Theoretical background for market emergence framework : Case: Electricity Distribution Industry

Both the competitive environment and the internal structure of an industrial organization are typically included in the processes which describe the strategic management processes of the firm, but less attention has been paid to the interdependence between these views. Therefore, this research focuses on explaining the particular conditions of an industry change, which lead managers to realign the firm in respect of its environment for generating competitive advantage. The research question that directs the development of the theoretical framework is: Why do firms outsource some of their functions? The three general stages of the analysis are related to the following research topics: (i) understanding forces that shape the industry, (ii) estimating the impacts of transforming customer preferences, rivalry, and changing capability bases on the relevance of existing assets and activities, and emergence of new business models, and (iii) developing optional structures for future value chains and understanding general boundaries for market emergence. The defined research setting contributes to the managerial research questions “Why do firms reorganize their value chains?”, “Why and how are decisions made?” Combining Transaction Cost Economics (TCE) and Resource-Based View (RBV) within an integrated framework makes it possible to evaluate the two dimensions of a company’s resources, namely the strategic value and transferability. The final decision of restructuring will be made based on an analysis of the actual business potential of the outsourcing, where benefits and risks are evaluated. The firm focuses on the risk of opportunism, hold-up problems, pricing, and opportunities to reach a complete contract, and finally on the direct benefits and risks for financial performance. The supplier analyzes the business potential of an activity outside the specific customer, the amount of customer-specific investments, the service provider’s competitive position, abilities to revenue gains in generic segments, and long-term dependence on the customer.

The communicative dimension of landscape. A theoretical and applied proposal

The fusion of knowledge, the interrelationship of disciplines and, finally, the interaction of learning fields, provides new challenges for an auto denominated global society. The contemporary value of landscape, linked to the patent commodification of culture, the commercial construction of identities, the triumph of inauthenticity, of the induced representation or the economy of symbolism, open up great prospects for studying the symbolic value of landscape. The rapprochement of geographical praxis to the study of space intangibles, linked to the discovery of emotional geographies, besides the growing interest of communicational sciences on the territorial discourse, allow us to envisage a communicative study of landscape based on a fusion of geographical and communicational knowledge. The balancing of the variables: geography, landscape, emotion and communication, enables the progress towards analysing the emotionalisation of space to discern its intangible value, which emerges from the application of different communication techniques.

An experimental and theoretical study of multiphase flow in a circulating fluidized bed

A systematic averaging procedure has been derived in order to obtain an integral form of conservation equations for dispersed multiphase flow, especially applicable to fluidized beds. A similar averaging method is applied further to formulate macroscopic integral equations, which can be used in one-dimensional and macroscopic multi dimensional models. Circulating fluid bed hydrodynamics has been studied experimentally and both macroscopic and microscopic flow profiles have been measured in a cold model. As an application of the theory, the one dimensional model has been used to study mass and momentum conservation of gas and solid in a circulating fluid bed. Axial solid mixing has also been modelled by the one dimensional model and mixing parameters have been evaluated.

Sales and Operations Planning Implementation

The master’s thesis focused on implementing a sales and operations planning process. The main objectives were to create planning methods and tools for the implementation. The ultimate goal of the process, beyond this master’s thesis, is to balance the supply of products with customer demand, with optimized profitability. The theoretical part focused on giving a thorough view on the sales and operations planning process. The basis for a monthly planning cycle was identified. Methods, tools, and metrics for demand forecasting and operations planning were also introduced. Based on the theoretical part, a method for forecasting, a forecast spreadsheet, and a forecast accuracy metric were designed. A spreadsheet tool and methods were also designed for the monthly planning of production volumes, capacity, and inventory. The implementation progress was reviewed for two product families for three months. The sales and operations planning process was able to successfully identify a demand peak for the product families. Suggestions for the future of sales and operations planning were also made.

El deporte como instrumento de desarrollo de la capacidad crítica de los adolescentes. Experiencias realizadas en cuatro centros de secundaria = Sport as a tool in the development of critical capacity of teenagers. Experiments carried out in four centres of Secondary education

In the article we resume four experiments of an interdisciplinary nature carried out in four different secondary education centres. The nexus of the union of these didactic proposals is that of looking at values in sport and the critical capacity of the students from distinct perspectives: violence, mass media, politics and gender and the treatment of body in our society

Antioxidant capacity of eugenol derivatives

Toxicity and antioxidant capacity of eugenol derivatives (E2 = 2-Methoxy-4-[1-propenylphenyl]acetate, E3 = 4-Allyl-2-methoxyphenylacetate, E4 = 4-Allyl-2-methoxy-4-nitrophenol, E5 = 5-Allyl-3-nitrobenzene-1,2-diol, E6 = 4-Allyl-2-methoxy-5-nitrophenyl acetate) were evaluated in order to determine the influence of the sustituents. E2-E6 were synthesized from eugenol (E1). E1 was extracted from cloves oil, and E2-E6 were obtained through acetylation and nitration reactions. Antioxidant capacity evaluated by DPPH (1, 1-Diphenyl-2-picrylhydrazil) and ORAC fluorescein demonstrated that E1 and E5 have a higher capacity and the minor toxicity evaluated by red blood cells haemolysis and the Artemia saline test. In accordance with our results, the compound's (E1-E5) use in the pharmaceutical, cosmetic and or food industries could be suggested.

Electrochemical and theoretical evaluation of the interaction between dna and amodiaquine: evidence of the guanine adduct formation

The electrochemical behavior of the interaction of amodiaquine with DNA on a carbon paste electrode was studied using voltametric techniques. In an acid medium, an electroactive adduct is formed when amodiaquine interacts with DNA. The anodic peak is dependent on pH, scan rate and the concentration of the pharmaceutical. Adduct formation is irreversible in nature, and preferentially occurs by interaction of the amodiaquine with the guanine group. Theoretical calculations for optimization of geometry, and DFT analyses and on the electrostatic potential map (EPM), were used in the investigation of adduct formation between amodiaquine and DNA.

Determination of polyphenol contents and antioxidant capacity of no-alcoholic red grape products (vitis labrusca) from conventional and organic crops

The polyphenol contents and antioxidant capacity of Brazilian red grape juices and wine vinegars were analyzed. Additionally, it was analyzed the human polyphenol absorption and acute effect in plasmatic oxidative metabolism biomarkers after juice ingestion. The organic Bordo grape juice (GBO) presented a higher level of trans-resveratrol, quercitin, rutin, gallic acid, caffeic acid and total flavonoids then other juices and vinegars as well as antioxidant capacity. The plasmatic polyphenol increased 27.2% after GBO juice ingestion. The results showed that juices and vinegars from Brazilian crops present similar chemical and functional properties described in studies performed in other countries.

Analysis of passion fruit rinds (Passiflora edulis): isoorientin quantification by HPTLC and evaluation of antioxidant (radical scavenging) capacity

The content of isoorientin in passion fruit rinds (Passiflora edulis fo. flavicarpa O. Degener) was determined by HPTLC (high performance thin layer chromatography) with densitometric analysis. The results revealed a higher amount of isoorientin in healthy rinds of P. edulis (92.275 ± 0.610 mg L-1) than in rinds with typical symptoms of PWV (Passion fruit Woodiness Virus) infection (28.931 ± 0.346 mg L-1). The HPTLC data, allied to assays of radical scavenging activity, suggest the potential of P. edulis rinds as a natural source of flavonoids or as a possible functional food.

Self-condensation of n-(N-propyl)butanimine: NMR and mass spectral analyses and investigation by theoretical calculation

The stability of N-propylbutanimine (1) was investigated under different experimental conditions. The acid-catalyzed self-condensation that produced the E-enimine (4) and Z-inimine (5) was studied by experimental analyses and theoretical calculations. Since the calculations for the energy of 5 indicated that it had a lower energy than 4, yet 4 was the principal product, the self-condensation of 1 must be kinetically controlled.

Highly improved chromium (III) uptake capacity in modified sugarcane bagasse using different chemical treatments

The present paper focuses on improving chromium (III) uptake capacity of sugarcane bagasse through its chemical modification with citric acid and/or sodium hydroxide. The chemical modifications were confirmed by infrared spectroscopy, with an evident peak observed at 1730 cm-1, attributed to carbonyl groups. Equilibrium was reached after 24 h, and the kinetics followed the pseudo-second-order model. The highest chromium (III) maximum adsorption capacity (MAC) value was found when using sugarcane bagasse modified with sodium hydroxide and citric acid (58.00 mg g-1) giving a MAC value about three times greater (20.34 mg g-1) than for raw sugarcane bagasse.

Theoretical investigation of electronic excitation transfer between chlorophylls in light-harvesting antenna of photosystem ii using quantum computers

The excitation energy transfer between chlorophylls in major and minor antenna complexes of photosystem II (PSII) was investigated using quantum Fourier transforms. These transforms have an important role in the efficiency of quantum algorithms of quantum computers. The equation 2n=N was used to make the connection between excitation energy transfers using quantum Fourier transform, where n is the number of qubits required for simulation of transfers and N is the number of chlorophylls in the antenna complexes.