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(2016)Hydrogels are promising biomaterials for tissue engineering. Concerning hydrogels chemical structures, the hydrogen bonding towards water makes them hydrophilic compounds. Hydrogels contain 95% ~ 99% water as the swelling agent and have the characteristics of extracellular matrix. Therefore, they are suitable for cell growth and appropriate for forming cell culture. Hydrogels can mimic the cell microenvironments and promote cell differentiation by interactions with cells. Cells can get oxygen, nutrients exchange as well as removal of metabolic waste to live. Hydrogels can be categorized into natural hydrogels, synthetic hydrogels and hybrid hydrogels by sources. Agarose, Collagen and Calcium alginate are the most popular natural hydrogels. Polyethylene (glycol) and its derivative Polyethylene (glycol) Diacrylate (PEGDA) are indispensable synthetic hydrogels. In this thesis, hydrogels are studied for their chemical structure, physical and mechanical properties and gel formation. Typical hydrogels, i.e. agarose, polyethylene (glycol) diacrylate (PEGDA), collagen and calcium alginate, are reviewed for their methodology of formation, mechanical properties and applications. Since hydrogel is a solid containing a given amount of water, it has viscoelasticity. Rheology test mechanism is described for viscoelastic materials. Micropatterning methods of hydrogels are investigated in variety of approaches. How the patterned surfaces affect cell behaviour is discussed in our literature review. From the experimental results, agarose and polyethylene (glycol) diacrylate are successfully fabricated and their micropatterned hydrogels show promising properties. In addition, impact of mechanical properties, such as water diffusion in hydrogels, how temperatures influence hydrogel structures and durability of the structures storage are investigated. Hydrogel viscoelasticities are measured by rheometer. Hydrogels are also tested in chips and cell wells for future cell growth study. Finally, this research has successfully fabricated the 3D micropatterned hydrogels for cell culture.
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(2020)The geochemical regolith data gathered from Dzhumba, a gold prospect in eastern Kazakhstan, was analyzed using factor analysis and then integrated into ArcGIS as spatial data. Principal axis factoring method was used for factor extraction combined with varimax orthogonal rotation and Kaiser normalization. Five clear factors were extracted from the data set of 47 elements in 3942 regolith samples. Kriging interpolation was used to generate spatial data surfaces from factor scores. The generated factors are composed of the geochemical associations in the raw data, and represent the underlying geological processes and formations of the area. The fourth factor generated represents gold mineralization with As, Sb, Au, Zr, Sc, Mn, Mo, Cu, K and Ni being the elements that are positively loaded onto factor 4. Therefore, single element maps of these elements have been produced alongside the factor maps in order to examine factor 4 more intensely. Also maps about structural geology and alteration in the Dzhumba project area have been produced in order to give better understanding of the factor maps. The data suggests that the deposit type is an orogenic gold deposit. Other factors created interesting results as well, and they gave information about the different geological units of the area. Factor 1 represents granitic rocks by their feldspar and trace element content, factor 2 represents black shales with possible mafic rock constituents, factor 3 represents a sulfide rich mafic mineral group or graphitic rocks that are most likely black shales and factor 5 possibly represents calcite alteration. Factor 4 is the main interest of this study. The most intense loadings for factor 4 are in Brigadnoe, Svistun and Dzhumba with a small peak in Belyi. Single element map for gold mostly corresponds to factor 4 for Svistun and Dzhumba, but Brigadnoe is represented with a small peak. However, gold has a major presence in Fedor-Ivanovskoe, which is absent from factor 4. Further exploration in Fedor-Ivanovskoe could be performed in order to clarify if this is due to an unrelated gold-only deposit or some other event. Possible future exploration in the area could benefit from factor 4 results, using As and Sb, or a combination of As, Sb, Zr, Sc, Mn, Mo, Cu, K and Ni as pathfinders for possible gold occurrences.
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(2023)Context: An abundance of research on the productivity of software development teams and developers exists identifying many factors and their effects in different contexts and concerning different aspects of productivity. Objective: This thesis aims to collect and analyse existing recent research results of factors that are related to or directly influence the productivity of teams or developers, how they influence it in different contexts and briefly summarise the metrics used in recent studies to measure productivity. Method: The method selected to reach for these aims was to conduct a systematic literature review on relevant studies published between 2017 and 2022. Altogether, 48 studies were selected and analysed during the review. Results: The metrics used by the reviewed studies for measuring productivity range from time used for completing a task to self-evaluated productivity to the amount of commits contributed. Some of these are used by multiple studies and many by only one or a few and measure productivity from different angles. Various factors were found and these range from team size to experienced emotion to working from home during the COVID-19 pandemic. The relationships found between these factors and some aspects of the productivity of developers and teams range from positive to negative and sometimes both depending on the context and the productivity metric in question. Conclusions: While many relationships were found between various factors and the productivity of software developers and development teams in this review, these do not cover all possible factors, relationships or measurable productivity aspects in all possible contexts. Additionally, one should keep in mind that most of the found relationships do not imply causality.
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(2020)The use of machine learning and algorithms in decision making processes in our every day lifehas been growing rapidly. The uses range from bank loans and taxation to criminal sentencesand child care decisions. Because of the possible high importance of such decisions, we need tomake sure that the algorithms used are as unbiased as possible.The purpose of this thesis is to provide an overview of the possible biases in algorithm assisteddecision making, how these biases affect the decision making process, and go through someproposes on how to tackle these biases. Some of the proposed solutions are more technical,including algorithms and different ways to filter bias from the machine learning phase. Othersolutions are more societal and legal and address the things we need to take into account whendeciding what can be done to reduce bias by legislation or by enlightening people on the issuesof data mining and big data.
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(2017)The aim of this study is to find out about away trips that Finnish ice hockey supporters make within Finland. The idea is also to find out if destination cities of the trips could better benefit from traveling hockey fans. The study aims at finding the basic frame by which the fan organizations choose their destinations, the motives of those who participate and visitors' perceptions of services available at the destination ice halls. Both qualitative and quantitative methods are used. Not many earlier studies about the topic exist. Literature about sport tourism concentrates mostly on people doing the sports themselves. Academic literature about sport fans, in turn, is usually about the psychological side of fandom. Several studies of Finnish ice hockey fans exist though. Also their point of view is often psychological. Many of Finnish studies are also only thesis-level works. Because of lack of earlier research about the topic, this work can be seen as a baseline research. Fan organizations choose their travel destinations mostly based on game schedule. Trips are mainly made to games played on Saturdays. On other days of the week the destination should be within a short distance. Distance to destination isn't very important on Saturdays unless the destination is very far away. Visiting fans don't spend much time at the destination city on a regular trip. Usually the fans enter the ice hall straight after stepping out of the bus and return soon after the game. However, overnight trips might interest the fans especially if the destination is far away. Previous experience about destinations also affects the choices fan organizations make. Most important reasons for participating in a trip are especially seeing the favorite team play and supporting the team. Traveling itself as a process isn't an important factor while making the decision to travel yet there could be interest to go on overnight trips more often than fans currently do. Also company affects travel decisions as people prefer going to games with friends or acquaintances. SM-Liiga ice halls seem to have all the different service types away trippers need. There's not much demand on a variety of services as visiting fans mostly buy just drinks of food. Supply of these services is good but visitors are less happy with quality, variety and price of the products sold. An important factor for game experience are the seating arrangements at the ice hall. They were found to correlate with happiness with overall game experience. Ice halls are considered safe and security works well. All in all visiting fans are happier with the service they receive at the ice halls than with the services itself. To improve their service in the eyes of visiting fans, the hosts should pay attention to variety of food and drinks and offer visitors seats that are suitable for their needs. Host organizations and local stakeholders could benefit from offering visiting fans moderately priced packages that could include for example transportation, game ticket, a meal and accommodation or some of these services. This way they could get visitors spend more money at the destination city and at the same time income would spread to a larger number of stakeholders.
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(2018)Minimum-cost minimum path cover is a graph-theoretic problem with an application in gene sequencing problems in bioinformatics. This thesis studies decomposing graphs as a preprocessing step for solving the minimum-cost minimum path cover problem. By decomposing graphs, we mean splitting graphs into smaller pieces. When the graph is split along the maximum anti-chains of the graph, the solution for the minimum-cost minimum path cover problem can be computed independently in the small pieces. In the end all the partial solutions are joined together to form the solution for the original graph. As a part of our decomposition pipeline, we will introduce a novel way to solve the unweighted minimum path cover problem and with that algorithm, we will also obtain a new time/space tradeoff for reachability queries in directed acyclic graphs. This thesis also includes an experimental section, where an example implementation of the decomposition is tested on randomly generated graphs. On the test graphs we do not really get a speedup with the decomposition compared to solving the same instances without the decomposition. However, from the experiments we get some insight on the parameters that affect the decomposition's performance and how the implementation could be improved.
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(2022)The objective of the shortest common superstring problem is to find a string of minimum length that contains all keywords in the given input as substrings. Shortest common superstrings have many applications in the fields of data compression and bioinformatics. For example, a common superstring can be seen as a compressed form of the keywords it is generated from. Since the shortest common superstring problem is NP-hard, we focus on the approximation algorithms that implement a so-called greed heuristic. It turns out that the actual shortest common superstring is not always needed. Instead, it is often enough to find an approximate solution of sufficient quality. We provide an implementation of the Ukkonen's linear time algorithm for the greedy heuristic. The practical performance of this implementation is measured by comparing it to another implementation of the same heuristic. We also hypothesize that shortest common superstrings can be potentially used to improve the compression ratio of the Relative Lempel-Ziv data compression algorithm. This hypothesis is examined and shown to be valid.
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(2024)Ultra-low frequency (ULF) waves in the Pc4-Pc5, 2 – 25 mHz range have been observed to accelerate trapped 1 – 10 MeV electrons in the Earth’s radiation belts. This acceleration can lead to particle losses and injections that occur on timescales comparable to the particle drift periods. Current models rely on diffusion equations written in terms of Fokker-Planck equations and are not suitable for describing fast temporal variations in the distribution function. This thesis is a study of fast transport of equatorially trapped electrons in the radiation belts. We look at solutions for the time evolution of the linear part of the perturbed distribution function using both analytical and numerical methods. Based on this work we build a simple model of fast transport in the radiation belts using a spectral PDE framework called Dedalus. The resulting program is a computationally inexpensive, simple approach to modelling drift-periodic signatures on fast timescales. In this study we investigate the behavior of the distribution function in three systems: a simple system without a wave term, and systems with a single non-resonant and resonant ULF wave. The wave solutions are evaluated with magnetic field perturbations of different magnitudes. The Earth’s magnetic field is modelled with the Mead field. The numerical solution of the perturbed differential equation is studied for relativistic equatorially trapped electrons. Phase-mixing is found to happen regardless of field fluctuations or resonance. The non-resonant wave solution shows time-delayed, spatially localized structures in the equatorial plane forming in the presence of large magnetic field fluctuations. These transients are also seen in the analytical solution and provide a new theoretical explanation for the ubiquitous observation of drift echoes in the inner and outer radiation belts of the Earth (Li et al., 2024).
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(2021)This master’s thesis is an ethnographic study about everyday urban encounters and social interaction. It explores how residents in the suburban housing estate of Kontula in East Helsinki negotiate social and cultural difference in their everyday lives. The study focuses on the semi-public spaces of the local shopping centre and examines residents’ capacity to live with difference. The study contributes to a multi-vocal and historically informed understanding of the processes that shape the social landscapes of a socially mixed and multi-ethnic neighbourhood. The study is based on fieldwork carried out in two phases between August 2019 and February 2020. The study applies anthropological methods of participant observation and qualitative interviews. The eleven research participants are adults between the ages of 30 and 71 who live in the neighbourhood and have extensive personal experience of the shopping centre. Although the interviews were a crucial aspect of the meaning-making process, the study relies primarily on participant observation in constructing an interpretation and analysis of social interaction at an intimate scale. In order to contextualise everyday encounters at the shopping centre, this thesis assesses how Kontula, as a stigmatised territory in the urban margins, encapsulates a complex interplay between moral claims of a “good” and “bad” neighbourhood. While some residents confirm negative stereotypes about the shopping centre and bring attention to local social problems and issues of unsafety, others downplay these problems and instead emphasise how tolerant and sociable the shopping centre is. Observations of stigmatised territories reveal how the participation of marginalised individuals and ethnic minorities at the shopping centre challenges the processes and discourses that constitute them as objects of fear and nuisance. The concepts of conviviality and cosmopolitan canopies are used to analyse local social interactions. The analysis suggests that the capacity to live with difference is enabled by ordinary meeting places, such as pubs and cafés, where residents come into regular social contact and engage with diverse individuals and groups. While the maintenance of ethnic boundaries remains salient in the way residents negotiate the social landscapes, these ordinary spaces of encounter situationally reconfigure categories of “us” and “them” and thus expand local meanings of who belongs. The analysis concludes that the contested meanings of belonging and the everyday negotiation of difference are attributes of an open multi-ethnic society coming to terms with difference and change. The analysis suggests that an equal right to participate and interact in shared urban spaces, rather than community consensus, is the hallmark of a society’s capacity to live with difference.
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(Helsingin yliopistoHelsingfors universitetUniversity of Helsinki, 2010)Sea-surface wind observations of previous generation scatterometers have been successfully assimilated into Numerical Weather Prediction (NWP) models. Impact studies conducted with these assimilation implementations have shown a distinct improvement to model analysis and forecast accuracies. The Advanced Scatterometer (ASCAT), flown on Metop-A, offers an improved sea-surface wind accuracy and better data coverage when compared to the previous generation scatterometers. Five individual case studies are carried out. The effect of including ASCAT data into High Resolution Limited Area Model (HIRLAM) assimilation system (4D-Var) is tested to be neutral-positive for situations with general flow direction from the Atlantic Ocean. For northerly flow regimes the effect is negative. This is later discussed to be caused by problems involving modeling northern flows, and also due to the lack of a suitable verification method. Suggestions and an example of an improved verification method is presented later on. A closer examination of a polar low evolution is also shown. It is found that the ASCAT assimilation scheme improves forecast of the initial evolution of the polar low, but the model advects the strong low pressure centre too fast eastward. Finally, the flaws of the implementation are found small and implementing the ASCAT assimilation scheme into the operational HIRLAM suite is feasible, but longer time period validation is still required.
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(2020)Federated learning is a method to train a machine learning model on multiple remote datasets without the need to gather the data from the remote sites to a central location. In healthcare, gathering the data from different hospitals into a central location can be a difficult and time-consuming task, due to privacy concerns and regulations regarding the use of sensitive data, making federated learning an attractive alternative to more traditional methods. This thesis adapted an existing federated gradient boosting model and developed a new federated random forest model and applied them to mortality prediction in intensive care units. The results were then compared to the centralized counterparts of the models. The results showed that while the federated models did not perform as well as the centralized models on a similar sized dataset, the federated random forest model can achieve superior performance when trained on multiple hospitals' data compared to centralized models trained on a single hospital. In scenarios where the centralized models had data from multiple hospitals the federated models could not perform as well as the centralized models. It was also found that the performance of the centralized models could not be improved with further federated training. In addition to practical advantages such as possibility of parallel or asynchronous training without modifications to the algorithm, the federated random forest performed better in all scenarios compared to the federated gradient boosting. The performance of the federated random forest was also found to be more consistent over different scenarios than the performance of federated gradient boosting, which was highly dependent on factors such as the order with the hospitals were traversed.
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(2018)X-ray computed tomography is an imaging method where the inner structure of an object is reconstructed from X-ray images taken from multiple directions around the object. When measurements from only a few measurement directions are available, the problem becomes severely ill-posed and requires regularization. This involves choosing a regularizer with desirable properties, as well as a value for the regularization parameter. In this thesis, sparsity promoting regularization with respect to the Haar wavelet basis is considered. The resulting minimization problem is solved using the iterative soft thresholding algorithm (ISTA). For the selection of the regularization parameter, it is assumed that an a priori known level of sparsity is available. The regularization parameter is then varied on each iteration of the algorithm so that the resulting reconstruction has the desired level of sparsity. This is achieved using variants of proportional-integral-derivative (PID) controllers. PID controllers require tuning to guarantee that the desired sparsity level is achieved. We study how different tunings affect the reconstruction process, and experiment with two adaptive variants of PID controllers: an adaptive integral controller, and a neural network based PID controller. The two adaptive methods are compared to each other, and additionally the adaptive integral controlled ISTA is compared to two classical reconstruction methods: filtered back projection and Tikhonov regularization. Computations are performed using both real and simulated X-ray data, with varying amounts of available measurement directions. The integral control is shown to be crucial for the regularization parameter selection while the proportional and derivative terms can be of use if additional control is required. Of the two adaptive variants, the adaptive integral control performs better with respect to all measured figures of merit. The adaptive integral controlled ISTA also outperforms the classical reconstruction methods both in terms of relative error and visual inspection when only a few measurement directions are available. The results indicate that variants of the PID controllers are effective for sparsity based regularization parameter selection. Adaptive variants are very end user friendly, avoiding the manual tuning of parameters. This makes it easier to use sparsity promoting regularization in real life applications. The PID control allows the regularization parameter to be selected during the iteration, thus making the overall reconstruction process relatively fast.
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(2017)The carnivoran fauna in East Africa has changed drastically over the last seven million years. Turnover in the fauna affected taxonomic composition during the Miocene-Pliocene boundary, as well as led to both reduced species richness and functional richness from 3 Ma ago onwards until the modern fauna was in place. The objective of this thesis was to examine how the niche space in the East African carnivore guild has changed over time by making inferences on the feeding ecology of individual taxa from two sites located in the Turkana Basin, a major depository of vertebrate fossils in northern Kenya. The first site, Lothagam, covers the time slice 7.4–5.3 Ma ago, whereas the second site, Koobi Fora, covers the time slice 3.4–1.38 Ma ago. An ecomorphological analysis was performed, which included dental ratios, body mass estimates and jaw measurements of carnivorans, as well as body mass estimates of some of their potential prey animals (bovids). The carnivorans were assigned to four different dietary specializations based on their dental ratios: hypercarnivore, bone-cracking hypercarnivore, mesocarnivore and hypocarnivore. Individual taxa were also identified as small-prey or large-prey specialists based on their body mass estimates and jaw depth. According to the results, the carnivore guild of Lothagam was mostly composed of hypercarnivores along with some mesocarnivores that were trending towards hypercarnivory. There is a notable absence of hypocarnivores and bone-cracking hypercarnivores in the Lothagam sample. The carnivorans of Koobi Fora displayed more variation in the dental ratios between individual taxa. Compared to the Lothagam guild, the Koobi Fora guild also included advanced bone-cracking hypercarnivores, as well as large hypocarnivores that are absent from East Africa today. The changes in the dietary specializations of individual Koobi Fora taxa were accompanied by an overall increase in body size, which coincided to some extent with an increase in prey size, at least with bovids. The results indicate that some of the extinct members of the carnivore guild became more ecologically specialized during the Plio-Pleistocene, which probably made them more vulnerable to extinction than the more generalized taxa during changing environmental conditions.
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(2021)Työssäni tutkin mahdollisuutta käyttää akustista ajankääntömenetelmää (time-reversal) teollisen ultraäänipuhdistimen puhdistustehon kohdentamiseen. Akustisella ajankääntömenetelmällä pystytään kohdistamaan painekenttä takaisin alkuperäiseen pisteeseen, tallentamalla ko. pisteestä lähetetyt painesignaalit akustisilla antureilla (etusuunta) ja lähettämällä ne takaisin ajassa käännettyinä (takasuunta). Tässä työssä tutkitun kohdentamismenetelmän perusteena toimii elementtimenetelmällä toteutettu simulaatiomalli, jossa sekä ultraäänipuhdistin, että puhdistettava järjestelmä oli mallinnettu tarkasti. Simulaatiomallin avulla voitiin puhdistettavasta alueesta valita mielivaltainen piste johon halutaan kohdentaa puhdistustehoa. Simuloidun etusuuntaisen ajon tuloksena tuotetut signaalit tuotiin ulos mallista ja takasuuntainen ajo suoritettiin kokeellisessa ympäristössä käyttäen simuloituja signaaleja. Työssä esitetään vertailu simuloidun ja kokeellisen ajankääntömenetelmään perustuvan kohdentamisen tuloksista ja osoitetaan, että simuloiduilla signaaleilla on mahdollista kohdentaa akustista tehoa ennalta valittuun mielivaltaiseen pisteeseen. Lisäksi työssä esitetään analyysi anturien määrän vaikutuksesta kohdentamiskykyyn, tarkastellaan ultraäänipuhdistimen avaruudellista kohdentamiskykyä sekä vahvistetaan simulaatioissa tehdyn lineaarisen oletuksen paikkansapitävyys.
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(2022)Nonlinear acoustic and electric effects for the purposes of fluid and fluid-fluid interface manipulation find many applications in the literature. Some examples include: electrospinning, electrospraying, ultrasonic sonoreactors, acoustic drop sampling and microfluidic particle manipulation via acoustic streaming. Ultrasound-enhanced electrospinning (USES) is one application in which both an acoustic and an electric field deform the surface of an aqueous polymer solution in order to achieve electrospinning of nanofibers. In this thesis, the nonlinear physics involved in USES are reviewed and applied to a finite element method based model of the system. This work builds on my previous publication on acoustic fountain formation and subsequent electrostatic deformation of a liquid-air interface in USES by also considering the effects of acoustic streaming. Results for acoustic streaming near a liquid-air interface in a case where the acoustic field is also focused around the interface are studied with simulations and compared against experiments. The results display an intricate balance of the shape and strength of the acoustic streaming field as the liquid-air interface simultaneously deforms. This even leads to situations where the streaming field could completely change direction. Finally, simulation predictions for acoustic streaming, fountain formation and electrostatic deformation of liquid-air interface in the USES set-up in its standard configuration are given. This simulation predicts a very weak acoustic streaming field and a smaller contribution from the electric field, compared to the acoustic field, on the interface forces. This implies that in the simulated configuration, the electric field serves more as force to pull the acoustic fountain a bit more in order for the acoustic field to find its new balance and exert an even stronger force than it was able to by itself. The simulation also indicates that for the robust and reproducible operation of USES, and possibly for the resulting nanofibers, one needs to have precise control of the process parameters, acoustic field and surface level, due to the complex nature of the fountain formation.
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(2018)Northern and high-altitude environments are expected to change dramatically due to climate change which strongly affects vegetation. Regarding to this, there has been interest on investigating how climatic factors affect vegetation distribution. One of the widely used methods to study species environment relationship is spatial species distribution modelling, in which the aim is to estimate suitable niches for species. However, only a few comprehensive distribution predictions for whole species groups have been made at a fine resolution and covering large extents. In the case of arctic-alpine plants Fennoscandia offers a good research area in terms of northern location, variable topography and wide climatic gradients. In this thesis the aim was to discover how climate affects the distribution and species richness patterns of arctic-alpine vascular plants. Relationship between arctic-alpine vegetation and climate was investigated by producing distribution predictions for each species based on important climatic variables and topography. Species data included observations from national species portals of Sweden and Norway, as well as field observations from three test regions Kevo, Northwestern-Lapland and Rastigaissa. The explanatory variables used were efficient temperature sum, water balance, minimum temperature of the coldest month and relative height. The species distribution predictions were produced using a 1 km2 grid covering whole Fennoscandia. Four different modelling methods (GAM, GLM, GBM, RF) were used and the predictions done with two different data sets. First the models were calibrated using only the observations from species portals, and the predictions were evaluated at the Lapland´s test regions. On the second modelling round the whole data was used in model calibration. From the modelling results both individual species distributions and the distribution of the whole vegetation group were investigated, as well as the relative importance of the explanatory variables. Then individual species distribution predictions were combined to visualize and study arctic-alpine species richness and its hotspots. Distribution of arctic-alpine vegetation was affected most by efficient temperature sum and minimum temperature of the coldest month. However, the relative importance of the variables varied for different species. Also the differences in the calibration data affected the results. Mainly species´ predicted distributions are located on areas where growing season is short and winter temperatures are low, even though there was some variation in the responses caused by the latter variable. Temperature variables were also significant in explaining species richness and its hotspots. It was shown that species richness focuses to the coldest areas and benefits from a bigger topography gradient. The results of this thesis show that climate defines both the distribution and the richness of arctic-alpine vegetation in Fennoscandia. However, resolution of one square kilometer does not fully capture the heterogeneity of the arctic-alpine area since temperature and moisture conditions vary greatly locally, for example depending on snow cover. Research on different scales is still needed to understand complicated species environment relationships.
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(2015)Ligniinin ja sen johdannaisten erottaminen biomassasta on noussut biojalostamoissa tärkeään rooliin, kun biomateriaalien käyttöä pyritään tehostaman. Suurta mielenkiintoa näissä yhdisteissä herättää erityisesti se, että yhdisteet pystyvät toimimaan antioksidantteina eli estämään haitallisten happi- ja typpiradikaalien reaktioita elävissä organismeissa. Ligniini on luonnon toiseksi yleisin fenolinen polymeeri. Se koostuu hapettuneista fenyylipropeeni monomeereista, jotka linkittyvät erilaisiin aryylieettereihin. Lehtipuissa, kuten koivuissa, linkittyminen aryylieettereihin tapahtuu suurimmaksi osaksi β-O-4 sidoksella. Havupuissa, kuten kuusessa, tämä on vähäisempää. Kirjallisuuskatsauksessa tarkastellaan aluksi biojalostamoita ja niiden toimintaa, jonka jälkeen tarkastellaan tarkemmin vapaiden radikaalien muodostumista organismien sisällä ja minkälaisia vaikutuksia niillä siellä on. Tämän lisäksi perehdytään solun sisäisiin antioksidantteihin, kuten superoksididismutaasiin, katalaasiin ja glutationiin ja siihen kuinka ne toimivat sekä kineettisiin antioksidantteihin eli kehoon ulkopuolelta tuleviin antioksidantteihin ja niiden toimintaan. Näihin kuuluvat biomassasta saatavat useat fenoliset yhdisteet, karotenoidit flavonoidit ja askorbiinihappo. Antioksidatiivisuuden mittaamiseen perehdytään katsauksen loppuosiossa. Antioksidatiivisuutta voidaan mitata DPPH (di(fenyyli)-(2,4,6-trinitrofenyyli)iminoatsanium) ja ABTS+ (2,2-atsinobis-(3-etyylibentsothiatsoliini-6-sulfonihappo)) radikaalien avulla sekä mm. ORAC- ja FRAP-menetelmillä. Tutkielman kokeellisessa osuudessa tutkittiin yhteensä 21 fenolisen yhdisteen ja kanelihapon antioksidatiivisuutta UV-Vis-spektorofotometrialla, käyttäen DPPH-radikaalia. Tämän lisäksi valmistettiin ligniinin polymeerirakenteessa esiintyvää dibentsodioksosiinia (DBDO) ja tutkittiin onnistuisiko DBDO:n linkitys koniferyylialkoholin kanssa entyysmikatalyyttisissä reaktio-olosuhteissa. Tulosten mukaan, linkittyminen näiden kahden välillä ei välttämättä tapahdu ollenkaan. Tarkempi analyysi saataisiin, jos näytteestä mitattaisiin sen massaspektri. Tällöin saataisiin enemmän informaatiota reaktiossa muodostuvasta tuotteista ja nähtäisiin millainen molekyylijakauma tuotteille tulisi. Antioksidatiivisuusmittauksissa selvisi, että tehokkaimmin vapaata radikaalia sieppasivat yhdisteet, joiden rakenteessa oli yksi tai useampi fenolinen hydroksyyliryhmä, konjugoituneita kaksoissidoksia tai syringyyliryhmä.
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(Helsingin yliopistoUniversity of HelsinkiHelsingfors universitet, 2007)Tässä kirjallisuuskatsauksessa perehdyttiin ensisijaisesti puuvartisten- ja ruohokasvien soluseinien fenyylipropanoidien ja ferulahappojen biosynteesiin ja kytkeytymisreaktioihin. Fenyylipropanoidireitti alkaa fenyylialaniinista ja johtaa monien prekursoreiden kuten lignaanien, flavonoidien, salisyylihappojen ja ligniiniprekursoreiden syntymiseen. Tutkielmassa keskityttiin ligniiniprekursoreiden muodostumiseen ja erityisesti sen biosynteesireitin välituotteen, ferulahapon hapetettuihin kytkeytymisreaktioihin kasvien soluseinillä. Fenyylipropanoiditutkimuksen lähtökohtana on jo vuosia ollut selvittää biosynteesireittejä ja menetelmiä, joiden avulla ligniini saadaan kasvin soluseinältä liukenemaan ja hiilihydraatti otettua talteen. Eräs tapa tunnistaa näitä hajoamistapahtumia on tutkia fenyylipropanoidien kytkentöjen muodostumista. Tässä pro gradu -tutkielmassa fenyylipropanoidireitin välituotteiden entsyymien säätelyä tarkasteltiin luonnonvaraisissa ja geneettisesti muunnelluissa kasveissa. Bieosynteesireitti selkeytyi paljon. Lisäksi siirtogeenisillä kasveilla havaittiin kokonaan uusia kytkentöjä ja rakenteita. Eräillä geeniyhdistelmillä voitiin lisätä tuntuvasti hiilihydraattimäärää samalla kun ligniinin kokonaismäärä väheni. Näin arveltiin voitavan kasvattaa biomassan määrää puukasveilla. Ferulahapot dehydrogenoituvat entsymaattisesti hapettavissa olosuhteissa fenoksiradikaaleiksi, jotka reagoivat edelleen muodostaen toisen radikaalimonomeerin tai -polymeerin kanssa kytkentöjä. Soluseinä tuottaa radikaalireaktioissa tarvitsemansa hapettimet ja entsyymit, vetyperoksidin ja peroksidaasin itse. Ferulahapon monomeerit ja dimeerit muodostavat esterisidoksia soluseinän hemiselluloosan kanssa. Näin syntyneet ferulaattidimeerit ja -trimeerit muodostivat ristikytkentöjä hiilihydraattien ja ligniinin välille sekä yhden tai useamman polysakkaridiketjun välille. Ferulahappojen katsottiin olevan lignifioitumisen aloituskohtia soluseinillä ja yhdistävän kaksi suurta polymeerista verkkorakennetta toisiinsa. Myös soluseinän hiilihydraattien koostumuksen havaittiin vaikuttavan muodostuvien kytkentöjen rakenteeseen. Lopuksi tarkasteltiin vielä ferulahapon antioksidatiivisia ominaisuuksia. Todettiin ligniinin ja ferulahapon määrän korreloivan soluseinän peroksidaasi- ja vetyperoksidimäärän kanssa. Kaveissa monet taudinaiheuttajat, vioittuneet kasvin osat sekä UV-säteily lisäsivät peroksidaasien tuotantoa ja edelleen ferulahappojen määrää. Fenoksiradikaalina ferulahappo kykeni eliminoimaan vetyperoksidin haitallisten happiradikaalien vaikutuksia pelkistämällä ne hapettuen itse radikaalisessa kytkeytymisreaktiossa. Tämä johti mielenkiintoisiin tulevaisuuden näkymiin ferulahaposta funktionaalisena elintarvikkeena, lääkeaineena sekä kosmeettisena valmisteena.
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(2020)Pierre de Fermat and Bernard Frénicle de Bessy discussed in their 1640 correspondence on magic squares. Frénicle did not appreciate Fermat’s contributions and it seems they have not been fully recognized even later. We will in this thesis look over their correspondence and study carefully every one of the ten "magic objects"by Fermat - nine squares and one cube. Through the ages, many methods have been developed to build magic squares, yet the one with which Fermat builds his even order magic squares, appears original even today. Fermat had related but slightly different method for odd order and even order squares. The idea behind odd order method was thoroughly explained later(without any reference to Fermat) by Frénicle as we point out here too. The even order method contains an original idea which we call "idea of self-supporting blocks". It is strongly based on the use of basic square as a starting point in construction process of magic square. After adopting this idea from Fermat, we use it first to provide an order 22 reconstruction for Fermat’s incomplete order 12 core of the full square. In the latter part of our work we show how this idea can be generalized for odd order squares as well. We demonstrate how it can be applied to build magic squares of any size, ordinary magic squares and bordered ones as well. Then the idea is applied to perfect magic cubes of orders divisible by 8. Frénicle presented in his letter as a challenge to Fermat a problem of magic squares with empty cells. It appears Fermat did not have time to respond to this challenge though he expressed he intended to. We will show how he might have done that. His method provides all the tools needed.
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(2019)Tutkielmassa perehdytään Fermat’n pieneen lauseeseen ja sen todistuksiin. Fermat’n pientä lausetta tarkastellaan myös alkulukutestauksen näkökulmasta. Loppupuolella määritellään Eulerin φ-funktio ja esitetään Eulerin lause. Eulerin lauseen käytännöllisyyttä tarkastellaan jakojäännösten selvittämisessä. Tutkielman johdanto on pieni katsaus Pierre de Fermat’n ja Leonhard Eulerin elämään. Johdannossa käsitellään myös Fermat’n pienen lauseen sekä Eulerin lauseen historiaa. Tutkielmassa on käytetty useita lukuteoreettisia käsitteitä, jotka määritellään heti johdannon jälkeen luvussa Tutkielmassa käytettyjä määritelmiä. Tutkielma esittää Fermat’n pienen lauseen kolmessa eri muodossa, jotka kaikki ovat keskenään ekvivalentteja. Lauseen käyttöä havainnollistetaan myös muutamalla esimerkillä. Luvussa Fermat’n pienen lauseen todistuksia kyseinen lause todistetaan ensin suoraviivaisesti ja sen jälkeen induktiolla. Lopuksi lausetta havainnollistetaan kuvitellun helminauhan avulla. Tutkielma osoittaa, että Fermat’n pieni lause toteutuu millä tahansa alkuluvulla p. Fermat’n pienen lauseen toteutuminen jollain luvulla ei kuitenkaan yksin riitä osoittamaan lukua alkuluvuksi. Otsikon Pseudoalkuluvut alla käsitellään lukuja, jotka eivät ole alkulukuja, mutta joilla Fermat’n pieni lause toteutuu. Jotta voitaisiin varmistua, että luku on alkuluku, E. Lucas kehitti 1800-luvun loppupuolella alkulukutestin, joka hyödyntää Fermat’n pientä lausetta. Testi on esitetty, todistettu ja sitä on havainnollistettu esimerkein kohdassa Lucas-Lehmer alkulukutesti. Testin todistukseen vaaditaan muutamia aputuloksia, jotka on esitetty ennen varsinaista testiä. Tutkielma määrittelee Eulerin φ-funktion ja havainnollistaa sen käyttöä esimerkillä. Tämän jälkeen tutkielmassa johdetaan kaava, jonka avulla φ-funktion arvon voi kätevästi laskea. Kaavan johtamista varten on todistettu muutama aputulos. Kaavan käytöstä on esimerkki. Tutkielmassa käsitellään Eulerin lause. Heti määritelmän jälkeen Eulerin lauseella ratkaistaan jakojäännöksiä. Sitten Eulerin lause todistetaan ensin induktion ja binomikaavan avulla ja sitten redusoidun jäännösluokkasysteemin avulla. Ennen kumpaakin todistusta esitellään ja todistetaan todistuksissa käytettäviä aputuloksia. Lopuksi tutkielma käsittelee suurten potenssien jakojäännösten ratkaisemista Eulerin lauseen ja binäärijärjestelmän avulla.
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