NANOPARTICLES OF TUNGSTEN AS LOW-COST MONOMETALLIC CATALYST FOR SELECTIVE HYDROGENATION OF 3-HEXYNE

Low-cost tungsten monometallic catalysts containing variable amounts of metal (4.5, 7.1 and 8.5%W) were prepared by impregnating alumina with ammonium metatungstate as an inexpensive precursor. The catalysts were characterized using ICP, XPS, XRD, TPR and hydrogen chemisorption. These techniques revealed mainly WO3-Al2O3 (W6+) species on the surface. The effects of the content of W nanoparticles and reaction temperature on activity and selectivity for the partial hydrogenation of 3-hexyne, a non-terminal alkyne, were assessed under moderate conditions of temperature and pressure. The monometallic catalysts prepared were found to be active and stereoselective for the production of (Z )-3-hexene, had the following order: 7.1WN/A > 8.5 WN/A ≥ 4.5 WN/A. Additionally, the performance of the synthesized xWN/A catalysts exhibited high sensitivity to temperature variation. In all cases, the maximum 3-hexyne total conversion and selectivity was achieved at 323 K. The performance of the catalysts was considered to be a consequence of two phenomena: a) the electronic effects, related to the high charge of W (+6), causing an intensive dipole moment in the hydrogen molecule (van der Waals forces) and leading to heterolytic bond rupture; the H+ and H- species generated approach a 3-hexyne adsorbate molecule and cause heterolytic rupture of the C≡C bond into C- = C+; and b) steric effects related to the high concentration of WO3 on 8.5WN/A that block the Al2O3 support. Catalyst deactivation was detected, starting at about 50 min of reaction time. Electrodeficient W6+ species are responsible for the formation of green oil at the surface level, blocking pores and active sites of the catalyst, particularly at low reaction temperatures (293 and 303 K). The resulting best catalyst, 7.1WN/A, has low fabrication cost and high selectivity for (Z )-3-hexene (94%) at 323 K. This selectivity is comparable to that of the classical and more expensive industrial Lindlar catalyst (5 wt% Pd). The alumina supported tungsten catalysts are low-cost potential replacements for the Lindlar industrial catalyst. These catalysts could also be used for preparing bimetallic W-Pd catalysts for selective hydrogenation of terminal and non-terminal alkynes.

USE OF A LOW-COST TEMPLATE-FREE ZSM-5 FOR ATMOSPHERIC PETROLEUM RESIDUE PYROLYSIS

To understand the physicochemical properties and catalytic activity during the pyrolysis of atmospheric petroleum residue, a template-free ZSM-5 zeolite was synthesized using a direct method without additional seeds or an organic structure director and compared with conventionally synthesized ZSM-5. The crystallinities of the two zeolites were evaluated by XRD and FTIR and were quite similar; however, structural analyses using SEM and argon physisorption revealed that the zeolites diverged in particle diameter and in the external surface area of the micropores. The synthesis procedure without a template incorporated additional aluminum into the crystalline network, according to ICP-AES and TPD NH3 experiments. The catalytic pyrolysis performed over the template-free ZSM-5 generated results comparable to those for pyrolysis performed over the conventional ZSM-5 according to its hydrocarbon distribution. The selectivity to aromatics compounds was exactly the same for both ZSM-5 zeolites, and these values stand out compared to thermal pyrolysis. The template-free ZSM-5 produced 20% of light hydrocarbons (C4-C6), where such compounds are olefins and paraffins of great interest to the petrochemical industry. Therefore, template-free ZSM-5 is promising for industrial use due to its lowered synthesis time, low-cost and significant distribution to light hydrocarbons.

LOW COST ANALYZER FOR THE DETERMINATION OF PHOSPHORUS BASED ON OPEN-SOURCE HARDWARE AND PULSED FLOWS

The need for automated analyzers for industrial and environmental samples has triggered the research for new and cost-effective strategies of automation and control of analytical systems. The widespread availability of open-source hardware together with novel analytical methods based on pulsed flows have opened the possibility of implementing standalone automated analytical systems at low cost. Among the areas that can benefit from this approach are the analysis of industrial products and effluents and environmental analysis. In this work, a multi-pumping flow system is proposed for the determination of phosphorus in effluents and polluted water samples. The system employs photometric detection based on the formation of molybdovanadophosphoric acid, and the fluidic circuit is built using three solenoid micropumps. The detection is implemented with a low cost LED-photodiode photometric detection system and the whole system is controlled by an open-source Arduino Uno microcontroller board. The optimization of the timing to ensure the color development and the pumping cycle is discussed for the proposed implementation. Experimental results to evaluate the system behavior are presented verifying a linear relationship between the relative absorbance and the phosphorus concentrations for levels as high as 50 mg L-1.

Total Cost of Ownership - Elinkaarilaskennan sovellus

Ostotapahtumassa kiinnitetään usein huomiota hintaan, mutta hankintapäätökseen vaikuttavat myös muutkin kustannukset. Ongelman asiassa aiheuttaa kokonaiskustannusvaikutuksien arvioinnin ja mittauksen haasteellisuus, sekä kunnollisen raportointijärjestelmän puuttuminen. Hankinnan kokonaiskustannusten selvittäminen pitkällä aikavälillä on kuitenkin tärkeää, koska hankintojen osuus yritysten liikevaihdoista on jatkuvassa kasvussa. Työn tarkoituksena oli tarkastella Total cost of ownershipia, eli TCO:ta, elinkaarilaskennan sovellusta. Tarkastelun aluksi työlle luotiin teoreettinen pohja käyttäen hyväksi kirjallisuutta, artikkeleita sekä www-dokumentteja. Teoriaosuus rakentui kustannuslaskennan osalta kustannusten tunnistamisesta, jakamisesta ja kohdistamisesta. TCO:sta luotiin mahdollisimman laaja-alainen teoreettinen kuvaus. Seuraavaksi työssä käsiteltiin TCO:n soveltamista sen perinteisimpiin käyttökohteisiin: taloudellisesti merkittäviin hankintoihin, ulkoistamispäätöksiin, hinnoitteluun sekä toimittajien suorituskyvyn seurantaan ja analysointiin. TCO:n soveltamista käsittelevä osuus päätettiin kotimaisilla esimerkeillä TCO:n soveltamisesta IT-hankintojen apuvälineenä. Työ päätettiin käymällä läpi työtä tehdessä kypsyneet ajatukset sekä johtopäätökset.

Supply chain cost saving potential analysis

Target of this study was to examine the current supply chain with focus on external part and identify the cost potential areas which lie there. The goal was to evaluate the cost save potential and give estimate what would be required in order to realise it. Base data related to study was searched and examined with using company’s enterprise resource planning system. In case feasible two types of scenarios were built in order to describe the scale of save potential. First scenario was theoretical and achieving it would require further investments and second scenario was realistic approach where more limitations were taken into account. The results clearly show that there is high save potential in supply chain costs linked to balance between internal and external operations. Realising of it would require at least minor investments as current internal capacity is not on a level to fully absorb the additional volumes which are needed in order to realise the potential. This study can be used as a basis when starting new projects related to investment needs.

Cost evaluation process for competitors' products

A company’s capability to map out its cost position compared to other market players is important for competitive decision making. One aspect of cost position is direct product cost that illustrates the cost efficiency of a company’s product designs. If a company can evaluate and compare its own and other market players’ direct product costs, it can implement better decisions in product development and management, manufacturing, sourcing, etc. The main objective of this thesis was to develop a cost evaluation process for competitors’ products. This objective includes a process description and an analysis tool for cost evaluations. Additionally, process implementation is discussed as well. The main result of this thesis was a process description consisting of a sixteen steps process and an Excel based analysis tool. Since literature was quite limited in this field, the solution proposal was combined from many different theoretical concepts. It includes influences from reverse engineering, product cost assessment, benchmarking and cost based decision making. This solution proposal will lead to more systematic and standardized cost position analyses and result in better cost transparency in decision making.

AU COMMENCEMENT ÉTAIT LA MÉTAPHORE: UNE INTUITION PRÉCOCE DE NIETZSCHE SUR LA PRIMAUTÉ DE LA MÉTAPHORE COMME MATRICE COGNITIVE

RÉSUMÉ Cette étude met en perspective le précédent constitué par les travaux précoces du jeune Nietzsche où ce dernier fait valoir la force structurante de la métaphore comme matrice des facultés cognitives. Nous offrons d’abord une brève esquisse des postulats et des acquis des grammaires cognitives associées aux travaux d’Eleanor Rosch, ensuite de George Lakoff et Mark Johnson, ainsi qu’à la notion d’inscription corporelle de l’esprit développée par Francesco Varela. Cet exercice sert de propédeutique à une série de lectures tangentes mobilisant divers angles d’approche appelés à faciliter noter évaluation des contributions de Nietzsche au domaine de la cognition. Les travaux examinés nous situent dans la période contemporaine de la publication de son premier grand ouvrage, La naissance de la tragédie (1872) : les notes pour le cours intitulé Présentation de la rhétorique ancienne (Darstellung der antiken Rhetorik), prononcé au semestre d’hiver 1872-1873 à l’Université de Bâle, ensuite ses Theoretische Studien, datant de l’été 1873, avec un renvoi aux développements plus tardifs dans le Gai Savoir (1882). La thèse de Nietzsche peut être résumée comme suit : tous les éléments de l’appareil catégorial et du régime conceptuel à l’aide desquels nous appréhendons la réalité, a fortiori la notion de vérité qui en est le garant, sont le « précipité » ou le résidu d’un faisceau de métaphores qui constituent la force structurante des facultés cognitives. Si chez Kant nous n’avons accès qu’aux phénomènes et non au noumène, chez Nietzsche nous n’avons affaire qu’à des perspectives ou des points de vues alors que la réalité nous est monnayée sous forme de vérités qui sont des fictions ou des métaphores usées. Il ressort de cet examen que le tropisme endogène de la langue constitue une force majeure dans l’implémentation d’une conceptualité qui a la vertu d’oblitérer sa préhistoire et de se ménager un statut qui est incessamment implosé par le reflux de l’imagination créatrice nourrie par la force métaphorique qui répond à une impulsion foncière que Nietzsche associe à une « force artiste » (Kunstkraft) qui tend à démultiplier les perspectives dont la généalogie se conjugue à l’exponentiel.

Physiological cost of induced resistance in cotton plants at different nitrogen levels

Resistance induction through the use of chemical inducers often results in physiological costs to the plant. In this study, induced resistance in cotton plants was evaluated with regard to physiological costs in a cultivar susceptible to Colletotrichum gossypii var. cephalosporioides (CNPA GO 2002 - 7997). Plants were cultivated in substrates with two levels of nitrogen and received two applications of acibenzolar-S-methyl (ASM), jasmonic acid (JA) and Agro-Mos® (AM) disease resistance inducers. Plant height (H), internodal length (IL), shoot fresh weight (SFW), root fresh weight (RFW), shoot dry weight (SDW) and root dry weight (RDW) were evaluated. The activity of the phenylalanine ammonia lyase (PAL) and peroxidase (POX) was also determined. The plants treated with ASM presented high physiological costs with an accentuated reduction in H, SFW and SDW, whereas those treated with JA exhibited a significant increase in SDW, and did not significantly differ from H and IL. In the potting mix supplemented with nitrogen, all inducers differed from the control treatment regarding to internodal length, whereas only ASM and AM presented a significant difference between one another in the potting mix without the addition of nitrogen. Significant correlations (P=0.05) were found for most of the variables analyzed, with greater correlations observed between SFW and SDW (0.94); IL and H (0.74); SFW and H (0.70); and SDW and H (0.70). ASM induced the least amount of PAL activity, significantly differing from the remaining treatments. Greater POX activity was observed in ASM, which significantly differed from the control. AM and JA, however, presented lower activity than the control with regard to these enzymes, and it was not possible to confirm induction resistance in these two treatments.

Verbal learning in mild cognitive impairment and alzheimer's disease : behavioural and neural approaches

The main focus of the present thesis was at verbal episodic memory processes that are particularly vulnerable to preclinical and clinical Alzheimer’s disease (AD). Here these processes were studied by a word learning paradigm, cutting across the domains of memory and language learning studies. Moreover, the differentiation between normal aging, mild cognitive impairment (MCI) and AD was studied by the cognitive screening test CERAD. In study I, the aim was to examine how patients with amnestic MCI differ from healthy controls in the different CERAD subtests. Also, the sensitivity and specificity of the CERAD screening test to MCI and AD was examined, as previous studies on the sensitivity and specificity of the CERAD have not included MCI patients. The results indicated that MCI is characterized by an encoding deficit, as shown by the overall worse performance on the CERAD Wordlist learning test compared with controls. As a screening test, CERAD was not very sensitive to MCI. In study II, verbal learning and forgetting in amnestic MCI, AD and healthy elderly controls was investigated with an experimental word learning paradigm, where names of 40 unfamiliar objects (mainly archaic tools) were trained with or without semantic support. The object names were trained during a 4-day long period and a follow-up was conducted one week, 4 weeks and 8 weeks after the training period. Manipulation of semantic support was included in the paradigm because it was hypothesized that semantic support might have some beneficial effects in the present learning task especially for the MCI group, as semantic memory is quite well preserved in MCI in contrast to episodic memory. We found that word learning was significantly impaired in MCI and AD patients, whereas forgetting patterns were similar across groups. Semantic support showed a beneficial effect on object name retrieval in the MCI group 8 weeks after training, indicating that the MCI patients’ preserved semantic memory abilities compensated for their impaired episodic memory. The MCI group performed equally well as the controls in the tasks tapping incidental learning and recognition memory, whereas the AD group showed impairment. Both the MCI and the AD group benefited less from phonological cueing than the controls. Our findings indicate that acquisition is compromised in both MCI and AD, whereas long13 term retention is not affected to the same extent. Incidental learning and recognition memory seem to be well preserved in MCI. In studies III and IV, the neural correlates of naming newly learned objects were examined in healthy elderly subjects and in amnestic MCI patients by means of positron emission tomography (PET) right after the training period. The naming of newly learned objects by healthy elderly subjects recruited a left-lateralized network, including frontotemporal regions and the cerebellum, which was more extensive than the one related to the naming of familiar objects (study III). Semantic support showed no effects on the PET results for the healthy subjects. The observed activation increases may reflect lexicalsemantic and lexical-phonological retrieval, as well as more general associative memory mechanisms. In study IV, compared to the controls, the MCI patients showed increased anterior cingulate activation when naming newly learned objects that had been learned without semantic support. This suggests a recruitment of additional executive and attentional resources in the MCI group.

Cognitive Functions After Traumatic Brain Injury. A 30-year Follow-up Study

Many cognitive deficits after TBI (traumatic brain injury) are well known, such as memory and concentration problems, as well as reduced information-processing speed. What happens to patients and cognitive functioning after immediate recovery is poorly known. Cognitive functioning is flexible and may be influenced by genetic, psychological and environmental factors decades after TBI. The general aim of this thesis was to describe the long-term cognitive course after TBI, to find variables that may contribute to it, and how the cognitive functions after TBI are associated with specific medical factors and reduced survival. The original study group consisted of 192 patients with TBI who were originally assessed with the Mild Deterioration Battery (MDB) on average two years after the injury, during the years 1966 – 1972. During a 30-year follow-up, we studied the risks for reduced survival, and the mortality of the patients was compared with the general population using the Standardized Mortality Ratio (SMR). Sixty-one patients were re-assessed during 1998-2000. These patients were evaluated with the MDB, computerized testing, and with various other neuropsychological methods for attention and executive functions. Apolipoprotein-E (ApoE) genotyping and magnetic resonance imaging (MRI) based on volumetric analysis of the hippocampus and lateral ventricles were performed. Depressive symptoms were evaluated with the short form of the Beck depression inventory. The cognitive performance at follow-up was compared with a control group that was similar to the study group in regard to age and education. The cognitive outcome of the patients with TBI varied after three decades. The majority of the patients showed a decline in their cognitive level, the rest either improved or stayed at the same level. Male gender and higher age at injury were significant risk factors for the decline. Whereas most cognitive domains declined during the follow-up, semantic memory behaved in the opposite way, showing recovery after TBI. In the follow-up assessment, the memory decline and impairments in the set-shifting domain of executive functions were associated with MRI-volumetric measures, whereas reduction in information-processing speed was not associated with the MRI measures. The presence of local contusions was only weakly associated with cognitive functions. Only few cognitive methods for attention were capable of discriminating TBI patients with and without depressive symptoms. On the other hand, most complex attentional tests were sensitive enough to discriminate TBI patients (non-depressive) from controls. This means that complex attention functions, mediated by the frontal lobes, are relatively independent of depressive symptoms post-TBI. The presence of ApoE4 was associated with different kinds of memory processes including verbal and visual episodic memory, semantic memory and verbal working memory, depending on the length of time since TBI. Many other cognitive processes were not affected by the presence of ApoE4. Age at injury and poor vocational outcome were independent risk factors for reduced survival in the multivariate analysis. Late mortality was higher among younger subjects (age < 40 years at death) compared with the general population which should be borne in mind when assessing the need for rehabilitation services and long-term follow-up after TBI.

Mild Cognitive Impairment and Early Detection of Alzheimer`s Disease. A Positron Emission Tomography Study

Alzheimer`s disease (AD) is characterised neuropathologically by the presence of extracellular amyloid plaques, intraneuronal neurofibrillary tangles, and cerebral neuronal loss. The pathological changes in AD are believed to start even decades before clinical symptoms are detectable. AD gradually affects episodic memory, cognition, behaviour and the ability to perform everyday activities. Mild cognitive impairment (MCI) represents a transitional state between normal aging and dementia disorders, especially AD. The predictive accuracy of the current and commonly used MCI criteria devide this disorder into amnestic (aMCI) and non-amnestic (naMCI) MCI. It seems that many individuals with aMCI tend to convert to AD. However many MCI individuals will remain stable and some may even recover. At present, the principal drugs for the treatment of AD provide only symptomatic and palliative benefits. Safe and effective mechanism-based therapies are needed for this devastating neurodegenerative disease of later life. In conjunction with the development of new therapeutic drugs, tools for early detection of AD would be important. In future one of the challenges will be to detect at an early stage these MCI individuals who will convert to AD. Methods which can predict which MCI subjects will convert to AD will be much more important if the new drug candidates prove to have disease-arresting or even disease–slowing effects. These types of drugs are likely to have the best efficacy if administered in the early or even in the presymptomatic phase of the disease when the synaptic and neuronal loss has not become too widespread. There is no clinical method to determine with certainly which MCI individuals will progress to AD. However there are several methods which have been suggested as predictors of conversion to AD, e.g. increased [11C] PIB uptake, hippocampal atrophy in MRI, low CSF A beta 42 level, high CSF tau-protein level, apolipoprotein E (APOE) ε4 allele and impairment in episodic memory and executive functions. In the present study subjects with MCI appear to have significantly higher [¹¹C] PIB uptake vs healthy elderly in several brain areas including frontal cortex, the posterior cingulate, the parietal and lateral temporal cortices, putamen and caudate. Also results from this PET study indicate that over time, MCI subjects who display increased [¹¹C] PIB uptake appear to be significantly more likely to convert to AD than MCI subjects with negative [¹¹C] PIB retention. Also hippocampal atrophy seems to increase in MCI individuals clearly during the conversion to AD. In this study [¹¹C] PIB uptake increases early and changes relatively little during the AD process whereas there is progressive hippocampal atrophy during the disease. In addition to increased [¹¹C] PIB retention and hippocampal atrophy, the status of APOE ε4 allele might contribute to the conversion from MCI to AD.

Viestintä ravitsemusosaamisen kehittämisessä Case:Sairaalan ateriaprosessi

Tutkielman tarkoituksena oli tutkia viestinnän merkitystä osaamisen kehittämisessä. Tavoitteena oli tutkia, miten viestintä edistää ravitsemusosaamisen kehittämistä sairaalan ateriaprosessissa. Tutkimuksessa etsittiin vastausta kysymyksiin, mitkä ovat ravitsemusosaamisen kehittämisen ja viestinnän tavoitteet, millä työyhteisöviestinnän foorumeilla uuden ravitsemushoitosuosituksen ja ravitsemushoidon strategian edellyttämiä muutoksia käsitellään ja millaisia työssä oppimisen prosesseja näillä foorumeilla on tunnistettavissa. Empirian näkökulmasta tutkimusta voidaan kuvata tapaustutkimukseksi. Tapauksena on sairaalan ateriaprosessi. Tutkimuksen valmistelevana aineistona käytettiin uutta ravitsemushoitosuositusta (Nuutinen ym. 2010), jota täydennettiin haastatteluaineistolla. Tutkimuksessa ovat edustettuina hoitotyön, ruokapalvelun ja ravitsemushoidon asiantuntemuksen näkökulmat sairaalasta sekä ammatti- ja aikuisopistosta. Tutkimusmenetelmänä käytettiin teemahaastatteluja. Haastattelut nauhoitettiin ja litteroitiin tekstimuotoon. Aineisto analysoitiin teemakortiston ja teemoittelun avulla. Tutkimuksen tulokset osoittavat, että ravitsemusosaamisen kehittämisen tavoitteena on uuden ravitsemushoitosuosituksen ja ravitsemushoidon strategian edellyttämien muutosten toteuttaminen sairaalan ravitsemushoidon prosesseissa ja tuotteissa. Ravitsemusosaamisen kehittämisen tavoitteena on tässä yhteydessä ateriaprosessin ja ruokapalvelun tuotteiden eli ruokavalioiden kehittäminen. Ravitsemushoidon kehittämisen tarkoituksena on asiakkaiden toipumisen, elämänlaadun ja hyvinvoinnin edistäminen sekä terveydenhuollon kustannusten säästäminen. Viestinnällä on tärkeä merkitys ravitsemusosaamisen kehittämisessä. Viestinnän avulla edistetään yksilöllistä ja yhteistä eli tiimioppimista vuorovaikutuksen kautta. Ruokapalvelu- ja hoitohenkilöstön sekä ravitsemushoidon asiantuntijoiden välinen vuoropuhelu nähdään tärkeänä ravitsemusosaamisen kehittämisessä. Vuoropuhelun avulla vahvistetaan ravitsemushoitoon liittyvää tietopohjaa ja yhteistä käsitteistöä. Tavoitteena on yhteisen kielen ja toimintamallin luominen ravitsemushoidon kehittämiseen. Ravitsemushoitosuosituksen ja ravitsemushoidon strategian edellyttämiä muutoksia käsitellään ulkoisissa ja sisäisissä verkostoissa esimerkiksi ravitsemus-yhdyshenkilöverkoston tapaamisissa, moniammatillisissa työryhmissä, henkilöstö- ja oppisopimuskoulutuksissa sekä työfoorumilla eli fyysisessä työtilassa ja hyödyntäen viestintäteknologiaa. Hoitotyön, ruokapalvelun ja ravitsemushoidon asiantuntijoilla/opettajilla on tärkeä rooli ravitsemusosaamisen kehittämiseen liittyvässä työssä oppimisen ohjaamisessa. Ravitsemusosaamisen kehittämisessä on tunnistettavissa sosiaalisia, reflektiivisiä, kognitiivisia ja operationaalisia työssä oppimisen prosesseja. Sosiaalisia prosesseja ovat työkokemusten vaihdanta ja reflektiivisiä niiden arviointi. Kognitiivisten prosessien tarkoitus on tiedonhankinta ja prosessointi, jolloin yhdistetään kokemustietoa sekä uutta ravitsemustieteellistä tietoa. Tavoitteena on yhteisen kielen ja toimintamallin luominen, jota kokeillaan käytännössä. Operationaalisia prosesseja ovat fyysisessä työtilassa tapahtuva kokeilemalla, tekemällä ja soveltamalla oppiminen, jolloin uutta toimintamallia esimerkiksi vajaaravitsemuksen seulontaa, ateriatilausta tai reseptiikkaa kokeillaan käytännössä. Johtopäätöksenä voidaan todeta, että sairaalassa on omaksuttu oppivan organisaation periaatteita ravitsemusosaamisen kehittämisessä. Ravitsemusosaamisen kehittäminen on yhteydessä muutokseen, strategiaan, prosessien ja tuotteiden kehittämiseen. Viestinnän avulla edistetään ravitsemushoitosuosituksen ja ravitsemushoidon strategian edellyttämien muutosten toteuttamista sairaalan ateriaprosessissa ja ruokavalioissa. Hoito- ja ruokapalveluhenkilöstön sekä ravitsemushoidon asiantuntijoiden välisen vuoropuhelun tavoitteena on yhteisen kielen ja toimintamallin luominen ravitsemushoidon kehittämiseen. Tutkimus palvelee ravitsemusosaamisen kehittämistä sairaalan ateriaprosessissa. Tutkimuksen tuloksia on mahdollista käyttää vertailuoppimismateriaalina terveydenhuollon organisaatioissa ja verkostoissa.