SU-8-Based Microchips for Capillary Electrophoresis and Electrospray Ionization Mass Spectrometry

Miniaturization of analytical instrumentation is attracting growing interest in response to the explosive demand for rapid, yet sensitive analytical methods and low-cost, highly automated instruments for pharmaceutical and bioanalyses and environmental monitoring. Microfabrication technology in particular, has enabled fabrication of low-cost microdevices with a high degree of integrated functions, such as sample preparation, chemical reaction, separation, and detection, on a single microchip. These miniaturized total chemical analysis systems (microTAS or lab-on-a-chip) can also be arrayed for parallel analyses in order to accelerate the sample throughput. Other motivations include reduced sample consumption and waste production as well as increased speed of analysis. One of the most promising hyphenated techniques in analytical chemistry is the combination of a microfluidic separation chip and mass spectrometer (MS). In this work, the emerging polymer microfabrication techniques, ultraviolet lithography in particular, were exploited to develop a capillary electrophoresis (CE) separation chip which incorporates a monolithically integrated electrospray ionization (ESI) emitter for efficient coupling with MS. An epoxy photoresist SU-8 was adopted as structural material and characterized with respect to its physicochemical properties relevant to chip-based CE and ESI/MS, namely surface charge, surface interactions, heat transfer, and solvent compatibility. As a result, SU-8 was found to be a favorable material to substitute for the more commonly used glass and silicon in microfluidic applications. In addition, an infrared (IR) thermography was introduced as direct, non-intrusive method to examine the heat transfer and thermal gradients during microchip-CE. The IR data was validated through numerical modeling. The analytical performance of SU-8-based microchips was established for qualitative and quantitative CE-ESI/MS analysis of small drug compounds, peptides, and proteins. The CE separation efficiency was found to be similar to that of commercial glass microchips and conventional CE systems. Typical analysis times were only 30-90 s per sample indicating feasibility for high-throughput analysis. Moreover, a mass detection limit at the low-attomole level, as low as 10E+5 molecules, was achieved utilizing MS detection. The SU-8 microchips developed in this work could also be mass produced at low cost and with nearly identical performance from chip to chip. Until this work, the attempts to combine CE separation with ESI in a chip-based system, amenable to batch fabrication and capable of high, reproducible analytical performance, have not been successful. Thus, the CE-ESI chip developed in this work is a substantial step toward lab-on-a-chip technology.

Heated Nebulizer Microchips for Mass Spectrometry

Miniaturized analytical devices, such as heated nebulizer (HN) microchips studied in this work, are of increasing interest owing to benefits like faster operation, better performance, and lower cost relative to conventional systems. HN microchips are microfabricated devices that vaporize liquid and mix it with gas. They are used with low liquid flow rates, typically a few µL/min, and have previously been utilized as ion sources for mass spectrometry (MS). Conventional ion sources are seldom feasible at such low flow rates. In this work HN chips were developed further and new applications were introduced. First, a new method for thermal and fluidic characterization of the HN microchips was developed and used to study the chips. Thermal behavior of the chips was also studied by temperature measurements and infrared imaging. An HN chip was applied to the analysis of crude oil – an extremely complex sample – by microchip atmospheric pressure photoionization (APPI) high resolution mass spectrometry. With the chip, the sample flow rate could be reduced significantly without loss of performance and with greatly reduced contamination of the MS instrument. Thanks to its suitability to high temperature, microchip APPI provided efficient vaporization of nonvolatile compounds in crude oil. The first microchip version of sonic spray ionization (SSI) was presented. Ionization was achieved by applying only high (sonic) speed nebulizer gas to an HN microchip. SSI significantly broadens the range of analytes ionizable with the HN chips, from small stable molecules to labile biomolecules. The analytical performance of the microchip SSI source was confirmed to be acceptable. The HN microchips were also used to connect gas chromatography (GC) and capillary liquid chromatography (LC) to MS, using APPI for ionization. Microchip APPI allows efficient ionization of both polar and nonpolar compounds whereas with the most popular electrospray ionization (ESI) only polar and ionic molecules are ionized efficiently. The combination of GC with MS showed that, with HN microchips, GCs can easily be used with MS instruments designed for LC-MS. The presented analytical methods showed good performance. The first integrated LC–HN microchip was developed and presented. In a single microdevice, there were structures for a packed LC column and a heated nebulizer. Nonpolar and polar analytes were efficiently ionized by APPI. Ionization of nonpolar and polar analytes is not possible with previously presented chips for LC–MS since they rely on ESI. Preliminary quantitative performance of the new chip was evaluated and the chip was also demonstrated with optical detection. A new ambient ionization technique for mass spectrometry, desorption atmospheric pressure photoionization (DAPPI), was presented. The DAPPI technique is based on an HN microchip providing desorption of analytes from a surface. Photons from a photoionization lamp ionize the analytes via gas-phase chemical reactions, and the ions are directed into an MS. Rapid analysis of pharmaceuticals from tablets was successfully demonstrated as an application of DAPPI.

Death in the Bolivian High Plateau : Burials and Tiwanaku Society

My Ph.D. dissertation presents a multi-disciplinary analysis of the mortuary practices of the Tiwanaku culture of the Bolivian high plateau, situated at an altitude of c. 3800 m above sea level. The Tiwanaku State (c. AD 500-1150) was one of the most important pre-Inca civilisations of the South Central Andes. The book begins with a brief introductory chapter. In chapter 2 I discuss methodological and theoretical developments in archaeological mortuary studies from the late 1960s until the turn of the millennium. I am especially interested in the issue how archaeological burial data can be used to draw inferences on the social structure of prehistoric societies. Chapter 3 deals with the early historic sources written in the 16th and 17th centuries, following the Spanish Conquest of the Incas. In particular, I review information on how the Incas manifested status differences between and within social classes and what kinds of burial treatments they applied. In chapter 4 I compare the Inca case with 20th century ethnographic data on the Aymara Indians of the Bolivian high plateau. Even if Christianity has affected virtually every level of Aymara religion, surprisingly many traditional features can still be observed in present day Aymara mortuary ceremonies. The archaeological part of my book begins with chapter 5, which is an introduction into Tiwanaku archaeology. In the next chapter, I present an overview of previously reported Tiwanaku cemeteries and burials. Chapter 7 deals with my own excavations at the Late Tiwanaku/early post-Tiwanaku cemetery site of Tiraska, located on the south-eastern shore of Lake Titicaca. During the 1998, 2002, and 2003 field seasons, a total of 32 burials were investigated at Tiraska. The great majority of these were subterranean stone-lined tombs, each containing the skeletal remains of 1 individual and 1-2 ceramic vessels. Nine burials have been radiocarbon dated, the dates in question indicating that the cemetery was in use from the 10th until the 13th century AD. In chapter 8 I point out that considerable regional and/or ethnic differences can be noted between studied Tiwanaku cemetery sites. Because of the mentioned differences, and a general lack of securely dated burial contexts, I feel that at present we can do no better than to classify most studied Tiwanaku burials into three broad categories: (1) elite and/or priests, (2) "commoners", and (3) sacrificial victims and/or slaves and/or prisoners of war. On the basis of such indicators as monumental architecture and occupational specialisation we would expect to find considerable status-related differences in tomb size, grave goods, etc. among the Tiwanaku. Interestingly, however, such variation is rather modest, and the Tiwanaku seem to have been a lot less interested in expending considerable labour and resources in burial facilities than their pre-Columbian contemporaries of many parts of the Central Andes.

Developments and Microbiological applications in African foods: Emphasis on Nigerian Wara cheese

African indigenous foods have received limited research. Most of these indigenous foods are fermented and they form part of the rich nutritional culture of many groups in African countries. The industrialization and commercialisation of these indigenous African fermented foods should be preceded by a thorough scientific knowledge of their processing which can be vital in the elimination of hunger and poverty. This study highlighted emerging developments and the microbiology of cereal-based and cassava-based food products that constitute a major part of the human diet in most African countries. In addition, investigations were also carried out on the coagulant of the Calotropis procera plant used in traditional production of Nigerian Wara cheese and on the effects of adding a nisin producing Lactococcus lactis strain originating from human milk to Nigerian Wara cheese. Fermented cereal-based food such as ogi utilize popular African and readily available grains maize, millet or sorghum as substrates and is popular as a weaning diet in infants. In this study, the bulkiness caused by starch gelatinization was solved by amylase treatments in the investigation on cooked and fermented oat bran porridge. A similar treatment could reduce the viscosity of any cereal porridge. The properties of the Sodom apple leaves (Calotropis procera) extract in cheesemaking were studied. C. procera was affected by monovalent (K+ and Na+) and divalent (Mg2+ and Ca2+) cations during coagulation. The rennet strength of this coagulant was found to be 7 % compared to animal rennet at 35 °C. Increasing the incubation temperature to 70 °C increased the rennet strength 28-fold. The molecular weight of the partially purified protease was determined by SDS-PAGE and was confirmed by Zymography to be approximately 60 kilodaltons. The high proteolytic activity at 70 °C supported the suitability of the protease enzyme as a coagulant in future commercial production of Nigerian Wara cheese. It was also possible to extend the shelf life of Wara cheese by a nisin producing lactic acid bacteria Lactococcus lactis LAC309. The levels of nisin in both whey and curd fractions of Wara were investigated, results showed a 3 log reduction of toxicogenic Bacillus licheniformis spiked on Wara after 3 days. These studies are the first in Finland to promote the advancement of scientific knowledge in African foods. Recognizing these indigenous food products and an efficient transfer of technology from the developed countries to industrialize them are necessary towards a successful realization of the United Nations Millenium Development Program.

Extraction methods in soil phosphorus characterisation : Limitations and applications

The quantification and characterisation of soil phosphorus (P) is of agricultural and environmental importance and different extraction methods are widely used to asses the bioavailability of P and to characterize soil P reserves. However, the large variety of extractants, pre-treatments and sample preparation procedures complicate the comparison of published results. In order to improve our understanding of the behaviour and cycling of P in soil, it is crucial to know the scientific relevance of the methods used for various purposes. The knowledge of the factors affecting the analytical outcome is a prerequisite for justified interpretation of the results. The aim of this thesis was to study the effects of sample preparation procedures on soil P and to determine the dependence of the recovered P pool on the chemical nature of extractants. Sampling is a critical step in soil testing and sampling strategy is dependent on the land-use history and the purpose of sampling. This study revealed that pre-treatments changed soil properties and air-drying was found to affect soil P, particularly extractable organic P, by disrupting organic matter. This was evidenced by an increase in the water-extractable small-sized (<0.2 µm) P that, at least partly, took place at the expense of the large-sized (>0.2 µm) P. However, freezing induced only insignificant changes and thus, freezing can be taken to be a suitable method for storing soils from the boreal zone that naturally undergo periodic freezing. The results demonstrated that chemical nature of the extractant affects its sensitivity to detect changes in soil P solubility. Buffered extractants obscured the alterations in P solubility induced by pH changes; however, water extraction, though sensitive to physicochemical changes, can be used to reveal short term changes in soil P solubility. As for the organic P, the analysis was found to be sensitive to the sample preparation procedures: filtering may leave a large proportion of extractable organic P undetected, whereas the outcome of centrifugation was found to be affected by the ionic strength of the extractant. Widely used sequential fractionation procedures proved to be able to detect land-use -derived differences in the distribution of P among fractions of different solubilities. However, interpretation of the results from extraction experiments requires better understanding of the biogeochemical function of the recovered P fraction in the P cycle in differently managed soils under dissimilar climatic conditions.

Radical Enhanced Atomic Layer Deposition of Metals and Oxides

Atomic Layer Deposition (ALD) is a chemical, gas-phase thin film deposition method. It is known for its ability for accurate and precise thickness control, and uniform and conformal film growth. One area where ALD has not yet excelled is film deposition at low temperatures. Also deposition of metals, besides the noble metals, has proven to be quite challenging. To alleviate these limitations, more aggressive reactants are required. One such group of reactants are radicals, which may be formed by dissociating gases. Dissociation is most conveniently done with a plasma source. For example, dissociating molecular oxygen or hydrogen, oxygen or hydrogen radicals are generated. The use of radicals in ALD may surmount some of the above limitations: oxide film deposition at low temperatures may become feasible if oxygen radicals are used as they are highly reactive. Also, as hydrogen radicals are very effective reducing agents, they may be used to deposit metals. In this work, a plasma source was incorporated in an existing ALD reactor for radical generation, and the reactor was used to study five different Radical Enhanced ALD processes. The modifications to the existing reactor and the different possibilities during the modification process are discussed. The studied materials include two metals, copper and silver, and three oxides, aluminium oxide, titanium dioxide and tantalum oxide. The materials were characterized and their properties were compared to other variations of the same process, utilizing the same metal precursor, to understand what kind of effect the non-metal precursor has on the film properties and growth characteristics. Both metals were deposited successfully, and silver for the first time by ALD. The films had low resistivity and grew conformally in the ALD mode, demonstrating that the REALD of metals is true ALD. The oxide films had exceptionally high growth rates, and aluminium oxide grew at room temperature with low cycle times and resulted in good quality films. Both aluminium oxide and titanium dioxide were deposited on natural fibres without damaging the fibre. Tantalum oxide was also deposited successfully, with good electrical properties, but at slightly higher temperature than the other two oxides, due to the evaporation temperature required by the metal precursor. Overall, the ability of REALD to deposit metallic and oxide films with high quality at low temperatures was demonstrated.

Novel Organo-Noble-Gas Hydrides

Noble gases are mostly known as inert monatomic gases due to their limited reactivity with other elements. However, the first predictions of noble-gas compounds were suggested by Kossel in 1916, by von Antropoff in 1924, and by Pauling in 1930. It took many decades until the first noble-gas compound, XePtF6, was synthesized by Neil Bartlett in 1962. This was followed by gradual development of the field and many noble-gas compounds have been prepared. In 1995, a family of noble-gas hydride molecules was discovered at the University of Helsinki. These molecules have the general formula of HNgY, where H is a hydrogen atom, Ng is a noble-gas atom (Ar, Kr, or Xe), and Y is an electronegative fragment. The first molecular species made include HXeI, HXeBr, HXeCl, HKrCl and HXeH. Nowadays the total number of prepared HNgY molecules is 23 including both inorganic and organic compounds. The first and only neutral ground-state argon compound, HArF, was synthetized in 2000. Helium and neon are the only elements in the periodic table that do not form neutral, ground-state molecules. In this Thesis, experimental preparation of eight novel xenon- and krypton-containing organo-noble-gas hydrides made from acetylene (HCCH), diacetylene (HCCCCH) and cyanoacetylene (HCCCN) are presented. These novel species include the first organic krypton compound, HKrCCH, as well as the first noble-gas hydride molecule containing two Xe atoms, HXeCCXeH. Other new compounds are HXeCCH, HXeCC, HXeC4H, HKrC4H, HXeC3N, and HKrC3N. These molecules are prepared in noble-gas matrices (krypton or xenon) using ultraviolet photolysis of the precursor molecule and thermal mobilization of the photogenerated H atoms. The molecules were identified using infrared spectroscopy and ab initio calculations. The formation mechanisms of the organo-noble-gas molecules are studied and discussed in this context. The focus is to evidence experimentally the neutral formation mechanisms of HNgY molecules upon global mobility of H atoms. The formation of HXeCCXeH from another noble-gas compound (HXeCC) is demonstrated and discussed. Interactions with the surrounding matrix and molecular complexes of the HXeCCH molecule are studied. HXeCCH was prepared in argon and krypton solids in addition to a Xe matrix. The weak HXeCCH∙∙∙CO2 complex is prepared and identified. Preparation of the HXeCCH∙∙∙CO2 complex demonstrates an advanced approach to studies of HNgY complexes where the precursor complex (HCCH∙∙∙CO2) is obtained using photolysis of a larger molecule (propiolic acid).

Quorum sensing in the plant pathogen Erwinia carotovora subsp. carotovora

Erwinia carotovora subsp. carotovora (Ecc) is a Gram-negative enterobacterium that causes soft-rot in potato and other crops. The main virulence determinants, the extracellular plant cell wall -degrading enzymes (PCWDEs), lead to plant tissue maceration. In order to establish a successful infection the production of PCWDEs are controlled by a complex regulatory network, including both specific and global activators and repressors. One of the most important virulence regulation systems in Ecc is mediated by quorum sensing (QS), which is a population density -dependent cell-to-cell communication mechanism used by many Gram-negative bacteria. In these bacteria N-acylhomoserine lactones (AHSL), act as diffusible signaling molecules enabling communication between bacterial cells. The AHSLs are structurally diverse and differ in their acyl chain length. This gives the bacteria signaling specificity and enables the recognition and communication within its own species. In order to detect and respond to the AHSLs the bacteria use QS regulators, LuxR-type proteins. The aim of this study was to get a deeper understanding of the Ecc QS system. In the first part of the study we showed that even different strains of Ecc use different dialects and of physiological concentrations, only the cognate AHSL with the correct acyl chain is recognized as a signal that can switch on virulence genes. The molecular basis of the substrate specificity of the AHSL synthase ExpI was investigated in order to recognize the acyl chain length specificity determinants of distinct AHSL synthases. Several critical residues that define the size of the substrate-binding pocket were identified. We demonstrated that in the ExpISCC1 mutations M127T and F69L are sufficient to change the N-3-oxohexanoyl-L-homoserine lactone producing ExpISCC1 to an N-3-oxooctanoyl-L-homoserine lactone (3-oxo-C8-HSL) producing enzyme. In the second study the means of sensing specificity and response to the AHSL signaling molecule were investigated. We demonstrated that the AHSL receptor ExpR1 of Ecc strain SCC3193 has strict specificity for the cognate AHSL 3-oxo-C8-HSL. In addition we identified a second AHSL receptor ExpR2 with a novel property to sense AHSLs with different acyl chain lengths. In the absence of AHSLs ExpR1 and ExpR2 were found to act synergistically to repress the virulence gene expression. This repression was shown to be released by addition of AHSLs and appears to be largely mediated by the global negative regulator RsmA. In the third study random transposon mutagenesis was used to widen the knowledge of the Ecc QS regulon. Two new QS-controlled target genes, encoding a DNA-binding regulator Hor and a plant ferredoxin-like protein FerE, were identified. The QS control of the identified genes was executed by the QS regulators ExpR1 and ExpR2 and as expression of PCWDE genes mediated by the RsmA repressor. Hor was shown to contribute to bacterial virulence at least partly through its control of PCWDE production, while FerE was shown to contribute to oxidative stress tolerance and in planta fitness of the bacteria. In addition our results suggest that QS is central to the control of oxidative stress tolerance in Ecc. In conclusion, these results indicate that Ecc strain SCC3193 is able to react and respond both to the cognate AHSL signal and the signals produced by other bacterial species, in order to control a wide variety of functions in the plant pathogen Ecc.

Suomen metsäteollisuuden uusien mahdollisuuksien aluetaloudelliset vaikutukset

Biojalostamo lisäisi talouskasvua ja työllisyyttä Tutkimuksessa selvitettiin biojalostamotoiminnan aluetaloudellisia vaikutuksia Kymenlaakson ja Satakunnan maakuntiin. Biodieselin valmistus kohentaisi molemmilla alueilla talouskasvua yhteensä 3,0–3,5 prosenttiyksiköllä eli noin 200 miljoonalla eurolla vuoteen 2020 mennessä. Työllisyys paranisi Kymenlaaksossa 437 ja Satakunnassa 420 henkilötyövuodella. Biojalostamotoiminta näyttäisi tukevan työllisyyttä suhteellisesti vähemmän kuin talouskasvua johtuen alan pääomavaltaisuudesta. Kymenlaakso hyötyisi biojalostamosta hiukan enemmän kuin Satakunta johtuen aluetalouksien rakenteellisista eroista. Metsäteollisuuden menetyksiä voitaisiin kompensoida Kymenlaakso on kärsinyt metsäteollisuuden supistumisesta tähän asti suurimmat menetykset. Biojalostamon perustaminen Kymenlaaksoon voisi merkittävästi korvata paperin tuotannon laskusta aiheutuneita menetyksiä. Talouskasvun suhteen biojalostamo voisi korvata puolet menetyksistä. Työllisyysmenetyksistä biojalostamotoiminta pystyisi kompensoimaan noin neljäsosan. Tukien merkitystä biojalostamon aluetaloudellisiin vaikutuksiin selvitettiin tukityypeittäin ja -tasoittain. Sekä raaka-aine- että tuotantotukivaikutukset jäivät simuloinneissa vaatimattomiksi. Tukien tehottomuutta selittää niiden pienuus. Muut toimialat kärsivät biojalostamoalan tukemisesta, mikä vähentää tukien aluetaloudellista vaikuttavuutta. Toisaalta reaalimaailmassa tuet voivat olla ratkaisevassa asemassa bioenergia-alan käynnistyessä ja sen kehityksen alkumetreillä. Bioenergia-strategian mukainen kehitys tuottaisi tulosta Bioenergian käytön lisäämisen aluetaloudellista vaikuttavuutta tutkittiin Keski-Suomen maakuntaa koskevan tapaustutkimuksen avulla. Vaikutusten laskenta pohjautui maakunnan bioenergian käytön tavoitteiden mukaisiin määriin. Mikäli bioenergian käyttö kasvaisi Keski-Suomessa neljällä terawattitunnilla vuoteen 2015 mennessä, vaikutus talouskasvuun olisi yhteensä 0,5 prosenttiyksikköä eli 35 miljoonaa euroa. Maakunnan työllisyys paranisi yli 200 henkilötyövuodella. Todennäköisesti myönteisiä aluetalousvaikutuksia vahvistaisi vielä alueen energiaostoista johtuvien vuotojen väheneminen energiaomavaraisuuden kasvaessa. Keski-Suomelle voisi kertyä hyötyjä myös bioenergiateknologian alan laitevalmistuksen osaamisen lisääntymisen kautta. Biojalostamotoiminta on täysin uudenlaista toimintaa, joten tilastollista seurantatietoa tältä alalta ei ole käytettävissä. Julkisia teknis-taloudellisia selvityksiä biodieselin tuotannosta on saatavilla suhteellisen niukasti. Koska simuloinneista saadut tulokset perustuvat biojalostamolle oletettuun kustannusrakenteeseen, tuloksia on tästä syystä käsiteltävä vain suuntaa-antavina. Ruralia-instituutti suosittaa biojalostamotoiminnan aluetaloudellisten vaikutusten seuraamista ja laskelmien päivittämistä, kun tarkempaa tietoa biojalostamon tuotannon kustannuksista ja tuotteiden kysynnän rakenteesta on saatavilla. Biojalostamon kustannusrakenne. Biojalostamotoiminta kompensoisi noin puolet massa- ja paperiteollisuuden supistumisesta aiheutuneista talouskasvun menetyksistä Kymenlaaksossa.

Metallien jalostuksen ja metallituoteteollisuuden investointien aluetaloudelliset vaikutukset

Tutkimuksen tavoitteena oli selvittää vuoden 2008 lopulla alkaneen laman näkymistä Suomen metalliteollisuudessa. Tehtävänä oli arvioida missä määrin toimialan tuotanto ja investoinnit ovat muuttuneen laman myötä. Lisäksi tuli tarkastella näiden muutosten aluetaloudellisia vaikutuksia. Tutkimus kohdennettiin yhdeksään seutukuntaan: Helsinki, Jyväskylä, Kemi-Tornio, Pori, Raahe, Rauma, Tampere, Turku ja Vaasa. Näillä alueilla toimii merkittäviä alan yrityksiä ja metalliteollisuudella on huomattava vaikutus. Lähtötiedot kerättiin eLomake-kyselyllä, haastatteluin ja hyödyntämällä ETLA:n maakunnallista tuotantoennustetta. Laskelmat tehtiin seutukuntatasoisina vuosille 2009–2013 käyttäen Ruralia-instituutissa kehitettyä yleisen tasapainon RegFinDyn-aluemallia. Tutkimuksen on rahoittanut Työ- ja elinkeinoministeriö. Kyselyyn vastanneiden ja ETLA:n ennusteen mukainen seutukuntien metalliteollisuuden lamanäkemys ovat lähellä toisiaan ja tuottavat saman johtopäätöksen. Alan tuotannon menetyksillä on huomattava negatiivinen vaikutus seutukuntien talouskasvuun ja työllisyyteen. Alueellisen BKT:n muutos on lamavuosina välillä -1,5% (Helsinki) ja -18,0% (Raahe) normaalikehitykseen verrattuna kun kerroinvaikutuksetkin huomioidaan. Vaikutukset ovat suhteellisesti suurimmat seutukunnissa, jotka ovat pieniä ja joissa toimiala on erittäin merkittävä. Tällaisia seutukuntia ovat Kemi-Tornio ja Raahe. Negatiivinen vaikutus kokonaistuotantoon on merkittävä myös Jyväskylän, Rauman, Tampereen ja Turun seutukunnissa. Kokonaistuotannon lasku on pienin Helsingin ja Porin seutukunnissa. Vaasan seutukunnan metalliteollisuuden kehitystä voi taloustilanteeseen nähden pitää hyvänä. Metalliteollisuuden lähiajan vaikutus alueen talouskasvuun ja työllisyyteen on neutraali. Tuotannon menetykset veisivät yhdeksän seutukunnan metalliteollisuudesta yhteensä 3500 henkilötyövuotta kun muun talouden kompensoiva vaikutuskin huomioidaan. Eniten henkilötyövuosia, yli 700 menettäisi Raahen seutukunta. Myös Helsingin, Tampereen ja Turun seutukuntien työpaikkojen menetykset olisivat tuntuvat, 400–600. Tulokset heijastelevat seutukunnan vahvimpien metalliteollisuuden alatoimialojen tilannetta. Raahen ja Kemi-Tornion vahvin metalliteollisuuden toimiala on perusmetallien valmistus, jonka vientiä lama on tiputtanut erityisen rajusti. Vaasan seutukunnan muista parempaa tilannetta selittää ainakin osaksi seudun voimakas energiaklusteri. Kyselyn ja ETLA:n ennusteiden mukaiset tuotannon muutokset eivät tutkimuksen mukaan pitäisi johtaa niin suureen toimialan investointien laskuun kuin mitä kyselyn vastaukset ennakoivat. Kemi-Tornion ja Tampereen seutukunnissa investointien ennakoitiin laskevan 70%:lla lamavuosien aikana. Syynä äkkijarrutukseen lienee maailmantalouden suuri epävarmuus, rahoituksen saamisen kiristyminen sekä yritysten pyrkimys investointeja leikkaamalla vähentää riskejään ja parantaa taseitaan. Tulosten mukaan tehokas yritys olisi leikannut investointejaan paljon vähemmän, 5–10%:lla. Tulosten mukaan hintojen lasku eli deflaatio on seutukuntatasolla selvästi suurempaa kuin koko kansantalouden tasolla on laman aikana tähän mennessä koettu. Metalliteollisuudesta riippuvaisissa seutukunnissa kuluttajahinnat laskivat välillä 1,1% (Helsinki) ja 5,8% (Raahe). Deflaatio on tulosten mukaan kuitenkin vain tilapäinen ilmiö, mutta auttaa laman aikana ylläpitämään yksityistä kulutusta. Teknologiateollisuus ry:n äskettäin esitetty lamanäkemys on synkkä, metalliteollisuus toipuisi vain hitaasti lamasta. Kyselyyn vastanneet suurten yritysten edustajat olivat sitä vastoin suhteellisen toiveikkaita. Heidän arvionsa oli, että lama voisi taittua jo vuoden 2010 keväästä lähtien.

Hirsitaloteollisuuden kehityshaasteet

Pientalobarometri 2/2008 ennustaa omakotitalorakentamisen jatkavan laskuaan rakentamiskustannusten kasvamisesta, kaavoituksesta, tonttitarjonnasta ja talouden tilasta johtuen. Kustannusten odotetaan edelleen nousevan mm. energia­tehokkuuden kohentumisen myötä. Työ- ja elinkeinoministeriön Puutalojen ja rakennuspuusepäntuotteiden valmistus –toimialaraportissa 2008 oletetaan myös, että lämmöneristysvaatimukset ovat saattaneet lisätä massiivihirsitalojen kysyntää, koska uusien määräysten voimaantulon jälkeen niitä ei mahdollisesti enää tehdä. Kehityksen voidaan olettaa johtavan rakennusten koon ja varustetason järkevöittämiseen. Oma­koti­talorakentamisen tarpeeksi pientalobarometri laskee 20 000 asuntoaloitusta, mutta toimialaraportissa määrän arvioidaan vuonna 2008 jäävän 12 500 oma­kotitalon aloitukseen. Avaimet käteen –rakentaminen on kasvusuunnassa ja talo­paketit ovat kehittymässä selvemmiksi rakennusosakokonaisuuksiksi. Pientalobarometri kertoo suomalaisten toivovan yksilöllisyyttä. Talotehtaiden toimituksista yksilöllisiä suunnitteluratkaisuja on kolmannes ja tyyppimuunnoksia puolet. Valmisosatalojen osuus asunnoista on noin 68 % ja teollisen hirren osuus valmisosatalojen markkinoista on nyt kutakuinkin samoissa 10 % lukemissa kuin 20 vuotta sitten. Korkeimmillaan teollisen hirren osuus valmisosataloista kävi 17 % tasolla kymmenen vuotta sitten, vuosina 1995 ja 1996. Siporex-, betoni,- tiili- ja harkkotalojen osuus on noussut kahdessakymmenessä vuodessa 4 %:sta 12 %:iin ja precut-talojen osuus 2 %:sta 16 %:iin, kun taas puuelementtien osuus on laskenut 85 %:sta 62 %:iin. Talopaketin keskimääräinen kuluttajahinta on Toimialaraportin mukaan noin 83 000 euroa ja niitä valmistuu vuodessa alle 10 000. Talopakettimarkkinat ovat Pientalobarometrin mukaan vuonna 2008 hieman laskeneet vuosien 2006 ja 2007 huippulukemista alle 800 miljoonan euron. Teollisten hirsivalmistajien liikevaihto laski myös vuodesta 2007 alle 350 miljoonan. Toimialaraportin mukaan puutalojen valmistus työllistää vajaa 4000 henkeä 251 toimipaikassa (2006). Alan liikevaihto vuonna 2006 oli 812 miljoonaa euroa ja viennin arvo 178 miljoonaa euroa. Viennin kasvun todettiin riippuvan hirsitaloteollisuudesta. Viennin kannalta tärkeitä alueita ovat Keski-Eurooppa, Venäjä, Japani ja Pohjoismaat. Puutalojen vienti on Toimialaraportin mukaan kohonnut 90-luvun alun noin 30 miljoonasta yli 200 miljoonaan euroon, josta hirsitalojen viennin arvo ylittää 160 miljoonaa. Tutkimus- ja kehittämiskuluiksi arvioidaan puutalon valmistajilla 0–2 % tuotannon arvosta. Puutalojen mediaanikäyttökate oli Toimialaraportin mukaan vuonna 2006 noin 6 % kun teollisuuden vastaava luku on 10 %. Finnveran tilastointi hirsitalojen kustannusrakenteesta ja kannattavuudesta ei poikkea tästä, vaan hirsitalojen käyttökatteeksi ilmoitetaan 6,4 % ja kokonaistulokseksi 3,4 % vuonna 2007. Toimialaraportin mukaan teollisuuden omavaraisuusaste on noin 43 % kun taas puutaloteollisuuden omavaraisuusaste jää 26,5 %:iin ja hirsitalojen Finnveran mukaan 27,7 %:iin. Hirsitaloja valmistaa Toimialaraportin mukaan noin 150 yritystä. Alan kahden suurimman yrityksen osuus on lähes puolet koko alan liikevaihdosta.

Synthesis of Reduced Metabolites of Isoflavonoids, and their Enantiomeric Forms

Isoflavonoids are naturally occurring plant derived biochemicals, which act as phytoalexins. Isoflavonoids are of interest due to their estrogenic and other potential physiological properties, particularly in mammals that typically consume isoflavonoid rich nutrients such as soy and red clover. The literature review of this thesis mainly focuses on the reduced metabolites of hydroxy and/or methoxy substituted isoflavones with four groups: isoflavan-4-ols, isoflav-3-enes, isoflavans and α-methyldeoxybenzoins (1,2-diarylpropan-1-ones), which are all reduced metabolites of food derived isoflavones in mammals. Related isoflavan-4-ones are briefly discussed. Results of an extensive survey of the literature concerning the synthesis of polyhydroxy- or methoxysubstituted isoflavonoids and especially asymmetric approaches are discussed. The experimental section describes new synthetic methods to prepare polyphenolic reduced isoflavonoid structures such as isoflav-3-enes, isoflavan-4-ones, cis- and trans-isoflavan-4-ols, 1,2-diarylpropan-1-ones and isoflavans by various hydride reagents and hydrogenations. The specific reactivity differences of various hydride reagents toward isoflavonoids are discussed. The first enantioselective synthesis of natural (S)-(-)-equol and the opposite enantiomer (R)-(+)-equol is also described by the asymmetric iridium PHOX catalysed hydrogenation of isoflav-3-enes. Both of these equol enantiomers are found to possess biological activity in mammals due to estrogen receptor binding activity. The natural enantiomer prefers estrogen receptor β and the R-enantiomer prefers the estrogen receptor α. Also the precursor, isoflav-3-ene, is found to possess positive biological effects on mammals. In connection with the synthetic work, the (S)-(-)-equol was discovered from serum of ewes after isoflavone rich red clover feeding. The chiral HPLC method was developed to identify natural equol enantiomer for the first time in this species. The first synthesis of natural isoflavonoid (R)-(-)-angolensin and its enantiomer (S)-(+)-angolensin is desribed by the use of recyclable chiral auxiliaries (chiral pseudoephedrines). The method offers a general approach also to other natural polyphenolic 1,2-diarylpropan-1-ones and to further study isoflavonoid metabolism in human and other mammals. The absolute configurations of these new chiral isoflavonoid metabolites were determined by X-ray spectroscopy. Also thorough NMR and MS analysis of synthesised structures are presented.

Löydöstä muinaispuvuksi : arkeologisten tekstiilien ennallistaminen

From a find to an ancient costume - reconstruction of archaeological textiles Costume tells who we are. It warms and protects us, but also tells about our identity: gender, age, family, social group, work, religion and ethnicity. Textile fabrication, use and trade have been an important part of human civilization for more than 10 000 years. There are plenty of archaeological textile findings, but they are small, fragmentary and their interpretation requires special skills. Finnish textile findings from the younger Iron Age have already been studied for more than hundred years. They have also been used as a base for several reconstructions called muinaispuku , ancient costume. Thesis surveys the ancient costume reconstruction done in Finland and discusses the objectives of the reconstruction projects. The earlier reconstruction projects are seen as a part of the national project of constructing a glorious past for Finnish nationality, and the part women took in this project. Many earlier reconstructions are designed to be festive costumes for wealthy ladies. In the 1980s and 1990s many new ancient costume reconstructions were made, differing from their predecessors at the pattern of the skirt. They were also done following the principles of making a scientific reconstruction more closely. At the same time historical re-enactment and living history as a hobby have raised in popularity, and the use of ancient costumes is widening from festive occasions to re-enactment purposes. A hypothesis of the textile craft methods used in younger Iron Age Finland is introduced. Archaeological findings from Finland and neighboring countries, ethnological knowledge of textile crafts and experimental archaeology have been used as a basis for this proposition. The yarn was spinned with a spindle, the fabrics woven on a warp-weighted loom and dyed with natural colors. Bronze spiral applications and complicated tablet-woven bands have possibly been done by specialist craftswomen or -men. The knowledge of the techniques and results of experimenting and experimental archaeology gives a possibility to review the success of existing ancient costume reconstructions as scientific reconstructions. Only one costume reconstruction project, the Kaarina costume fabricated in Kurala Kylämäki museum, has been done using as authentic methods as possible. The use of ancient craft methods is time-consuming and expensive. This fact can be seen as one research result itself for it demonstrates how valuable the ancient textiles have been also in their time of use. In the costume reconstruction work, the skill of a craftswoman and her knowledge of ancient working methods is strongly underlined. Textile research is seen as a process, where examination of original textiles and reconstruction experiments discuss with each other. Reconstruction projects can give a lot both to the research of Finnish younger Iron Age and the popularization of archaeological knowledge. The reconstruction is never finished, and also the earlier reconstructions should be reviewed in the light of new findings.