Arvometallien liuospuhdistus jatkuvatoimisella ioninvaihdolla

Työn tarkoituksena oli tutkia arvometalleja sisältävän liuoksen puhdistamista jat-kuvatoimisella ioninvaihdolla. Teoriaosassa käsitellään ioninvaihdon periaate, sekä jatkuvatoimisen ioninvaihdon laiteratkaisuja ristivirta- ja vastavirtasysteemeissä. Lopuksi esitellään Simuloidun liikkuvapedin (SMB) virtausnopeuksien laske-miseksi käytettävä kolmiomenetelmä. Kokeellisen osan tarkoituksena on demonstroida laboratorioon rakennetun jatku-vatoimisen ioninvaihtimen, Simuloidun liikkuvapedin, käyttö arvometallia sisäl-tävän liuoksen puhdistamiseksi kahdenarvoisista metalli-ioneista. Kokeissa käy-tettiin hopeaa sisältävää NaCl-liuosta, josta pyrittiin puhdistamaan Mg2+, Ca2+, Pb2+ ja Zn2+-ionit ekstraktina. Laitteistolla suoritettiin kolme ajoa, joista kaksi edusti vastavirtasysteemiä ja yksi ristivirtasysteemiä. Ensimmäisessä vastavirta-ajossa sekä ekstrakti että raffinaattin erottuva hopealiuos tulivat puhtaina. Toisessa vastavirta-ajossa pyrittiin parantamaan tuottavuutta nostamalla syötön virtausnopeutta, jolloin raffinaatin puhtaus kärsi Pb2+ ja Mg2+-ionien kulkeutuessa liuosfaasin mukana raffinaattiin. Ristivirta-ajossa vain yksi kolmesta raffinaatista saavutti 100 % puhtauden. Kokeet osoittivat, että Mg2+, Ca2+, Pb2+ ja Zn2+-ionien erottaminen hopeaionista on mahdollista käyttämällämme SMB-laitteistolla. Tuottavuuden parantaminen syötön virtausnopeutta nostamalla kuitenkin heikentää puhtautta. Cross-flow-systeemin erilleenkytkettyjen kolonnien ansioista painehäviö on pienempi, mikä mahdollistaa korkeammat virtausnopeudet, mikäli ei vaadita 100 % puhtautta.

Siirtomaasodasta sisäisen turvallisuuden operaatioon : Sir Robert Thompsonin periaatteet Britannian operaatioissa Malaijilla ja Pohjois-Irlannissa

Sir Robert Thompson määritti vuonna 1966 julkaistussa kirjassaan Defeating Communist Insurgency viisi vastakumoukselliselle sodankäynnille keskeistä periaatetta, jotka ovat: - Hallituksella tulee olla selkeä poliittinen tavoite. - Hallituksen täytyy toimia lainmukaisesti. - Hallituksella pitää olla kaikille toimijoilleen yhteinen yleissuunnitelma ja suunnittelu. - Hallituksen tulee asettaa painopiste poliittisen kumouksellisuuden, ei sissien voittamiseen. - Kumouksellisen sodan ollessa sissisodan vaiheessa, hallituksen tulee turvata ensimmäisenä omat tukialueensa Thompsonin periaatteet pohjautuvat hänen kokemuksiinsa Malaijin kriisin aikana 1948 – 60 ja ne siirtyivät osaksi ensimmäisiä brittiläisiä vastakumouksellisen sodankäynnin ohjesääntöjä, jotka julkaistiin vuonna 1969. Samana vuonna alkoi Pohjois-Irlannin konflikti (1969 – 98). Tutkimuksen tavoitteena on selvittää miten Thompsonin periaatteita toteutettiin ne pääosin synnyttäneessä Malaijin kriisissä ja Pohjois-Irlannin konfliktissa. Tutkimuskysymyksiä ovat: Mitä Thompsonin periaatteet tarkoittavat ja miten ne ovat ilmenneet brittiläisessä ohjesääntökirjallisuudessa? Mikä periaatteiden toteutuksessa yhdisti Malaijin ja Pohjois-Irlannin konflikteja? Mitä eroja periaatteiden toteuttamisessa oli konfliktien välillä? Mitkä tekijät aiheuttivat keskeiset erot periaatteiden toteuttamisessa konfliktien välillä?Tutkimuksen käytetty lähdemateriaali koostuu täysin laadullisesta aineistosta. Tutkimusmenetelmänä on käytetty laadullista, teorialähtöistä sisällönanalyysiä Eri lähteitä vertailemalla tehtyä analyysiä on ohjannut Thompsonin määrittämien periaatteiden kehys. Malaijin ja Pohjois-Irlannin konflikteista saatua analysoitua tietoa on verrattu keskenään käyttäen teoriakehystä, ja näin on pyritty löytämään yhtäläisyyksiä ja eroja Thompsonin periaatteiden toteuttamisessa konfliktien välillä. Tutkimuksen kannalta keskeisiä lähdeteoksia ovat: Sir Robert Thompson: Defeating Communist Insurgency, David McKittrick ja David McVea: Making Sense of the Troubles, Magne Haugseng: The Tightening Grip: Northern Ireland – The Military and 35 Years of Terror. Tutkimuksen kannalta keskeisiä lähdeasiakirjoja ovat Britannian asevoimien Pohjois-Irlannin konfliktista kirjoittama tutkimusraportti Operation Banner - An Analysis of Military Operations in Northern Ireland ja Riley Sunderlandin RAND-tutkimuslaitokselle vuonna 1964 laatimat Malaiji-raportit. Keskeisin ohjesääntölähde oli Britannian asevoimien vuosina 1969 – 70 julkaisema kolmiosainen vastakumouksellisen sodankäynnin ohjesääntö Land Operations Volume III Counter Revolutionary Operations. Tutkimuksessa havaittiin, että Britannian hallituksella oli molemmissa operaatioissa selkeät tavoitteet. Molemmissa operaatioissa hätätilavaltuudet laadittiin mahdollistamaan asevoimille ja poliisille laajat toimivaltuudet. Tästä huolimatta molemmissa operaatioissa tapahtui turvallisuusjoukkojen väärinkäytöksiä. Pohjois-Irlannin väärinkäytöksiä on tuotu selkeämmin esille PIRA:n propagandan ja tiedotusvälineiden läsnäolon takia. Kummassakaan operaatiossa ei ole ollut yhtä selkeää suunnitelmaa, vaan sarja erilaisia suunnitelmia. Malaijilla kaikkien toimijoiden yhteinen suunnittelu toimi koska sitä varten luotiin organisaatiorakenne. Pohjois-Irlannissa yhteisen suunnittelun periaatetta ei toteutettu poliitikkojen haluttomuuden takia. Sekä Malaijilla että Pohjois-Irlannissa toiminnan kohdentaminen kumouksellisuuteen toteutettiin häiritsemällä kumouksellisen vastustajan huoltoa. Malaijilla kumouksellisuuden oikeutusta heikennettiin myös muilla keinoilla kuten yhteiskunnallisia oloja kehittämällä sekä käynnistämällä Malaijin itsenäistymiskehitys. Kummassakaan operaatiossa hallituksen tukialueet eivät olleet vakavasti uhattuna. Keskeinen erottava tekijä operaatioiden välillä johtui tapahtumapaikasta ja – ajasta. Vastustajana PIRA oli kehittyneempi ja se kykeni muuttamaan toimintaansa vastaamaan muutoksia turvallisuusjoukkojen toiminnassa.

Hydrometallurgical recovery of valuable metals from secondary raw materials

Wastes and side streams in the mining industry and different anthropogenic wastes often contain valuable metals in such concentrations their recovery may be economically viable. These raw materials are collectively called secondary raw materials. The recovery of metals from these materials is also environmentally favorable, since many of the metals, for example heavy metals, are hazardous to the environment. This has been noticed in legislative bodies, and strict regulations for handling both mining and anthropogenic wastes have been developed, mainly in the last decade. In the mining and metallurgy industry, important secondary raw materials include, for example, steelmaking dusts (recoverable metals e.g. Zn and Mo), zinc plant residues (Ag, Au, Ga, Ge, In) and waste slurry from Bayer process alumina production (Ga, REE, Ti, V). From anthropogenic wastes, waste electrical and electronic equipment (WEEE), among them LCD screens and fluorescent lamps, are clearly the most important from a metals recovery point of view. Metals that are commonly recovered from WEEE include, for example, Ag, Au, Cu, Pd and Pt. In LCD screens indium, and in fluorescent lamps, REEs, are possible target metals. Hydrometallurgical processing routes are highly suitable for the treatment of complex and/or low grade raw materials, as secondary raw materials often are. These solid or liquid raw materials often contain large amounts of base metals, for example. Thus, in order to recover valuable metals, with small concentrations, highly selective separation methods, such as hydrometallurgical routes, are needed. In addition, hydrometallurgical processes are also seen as more environmental friendly, and they have lower energy consumption, when compared to pyrometallurgical processes. In this thesis, solvent extraction and ion exchange are the most important hydrometallurgical separation methods studied. Solvent extraction is a mainstream unit operation in the metallurgical industry for all kinds of metals, but for ion exchange, practical applications are not as widespread. However, ion exchange is known to be particularly suitable for dilute feed solutions and complex separation tasks, which makes it a viable option, especially for processing secondary raw materials. Recovering valuable metals was studied with five different raw materials, which included liquid and solid side streams from metallurgical industries and WEEE. Recovery of high purity (99.7%) In, from LCD screens, was achieved by leaching with H2SO4, extracting In and Sn to D2EHPA, and selectively stripping In to HCl. In was also concentrated in the solvent extraction stage from 44 mg/L to 6.5 g/L. Ge was recovered as a side product from two different base metal process liquors with Nmethylglucamine functional chelating ion exchange resin (IRA-743). Based on equilibrium and dynamic modeling, a mechanism for this moderately complex adsorption process was suggested. Eu and Y were leached with high yields (91 and 83%) by 2 M H2SO4 from a fluorescent lamp precipitate of waste treatment plant. The waste also contained significant amounts of other REEs such as Gd and Tb, but these were not leached with common mineral acids in ambient conditions. Zn was selectively leached over Fe from steelmaking dusts with a controlled acidic leaching method, in which the pH did not go below, but was held close as possible to, 3. Mo was also present in the other studied dust, and was leached with pure water more effectively than with the acidic methods. Good yield and selectivity in the solvent extraction of Zn was achieved by D2EHPA. However, Fe needs to be eliminated in advance, either by the controlled leaching method or, for example, by precipitation. 100% Pure Mo/Cr product was achieved with quaternary ammonium salt (Aliquat 336) directly from the water leachate, without pH adjustment (pH 13.7). A Mo/Cr mixture was also obtained from H2SO4 leachates with hydroxyoxime LIX 84-I and trioctylamine (TOA), but the purities were 70% at most. However with Aliquat 336, again an over 99% pure mixture was obtained. High selectivity for Mo over Cr was not achieved with any of the studied reagents. Ag-NaCl solution was purified from divalent impurity metals by aminomethylphosphonium functional Lewatit TP-260 ion exchange resin. A novel preconditioning method, named controlled partial neutralization, with conjugate bases of weak organic acids, was used to control the pH in the column to avoid capacity losses or precipitations. Counter-current SMB was shown to be a better process configuration than either batch column operation or the cross-current operation conventionally used in the metallurgical industry. The raw materials used in this thesis were also evaluated from an economic point of view, and the precipitate from a waste fluorescent lamp treatment process was clearly shown to be the most promising.

Subshifts with Simple Cellular Automata

A subshift is a set of in nite one- or two-way sequences over a xed nite set, de ned by a set of forbidden patterns. In this thesis, we study subshifts in the topological setting, where the natural morphisms between them are ones de ned by a (spatially uniform) local rule. Endomorphisms of subshifts are called cellular automata, and we call the set of cellular automata on a subshift its endomorphism monoid. It is known that the set of all sequences (the full shift) allows cellular automata with complex dynamical and computational properties. We are interested in subshifts that do not support such cellular automata. In particular, we study countable subshifts, minimal subshifts and subshifts with additional universal algebraic structure that cellular automata need to respect, and investigate certain criteria of `simplicity' of the endomorphism monoid, for each of them. In the case of countable subshifts, we concentrate on countable so c shifts, that is, countable subshifts de ned by a nite state automaton. We develop some general tools for studying cellular automata on such subshifts, and show that nilpotency and periodicity of cellular automata are decidable properties, and positive expansivity is impossible. Nevertheless, we also prove various undecidability results, by simulating counter machines with cellular automata. We prove that minimal subshifts generated by primitive Pisot substitutions only support virtually cyclic automorphism groups, and give an example of a Toeplitz subshift whose automorphism group is not nitely generated. In the algebraic setting, we study the centralizers of CA, and group and lattice homomorphic CA. In particular, we obtain results about centralizers of symbol permutations and bipermutive CA, and their connections with group structures.

Studies in selectivity of lipases in preparation of cyanohydrins, sugar conjugates and secondary alcohols

Biocatalysis can be applied in organic synthetic chemistry to counter challenges posed by increased demands towards chemo-, regio- and stereoselectivity, not forgetting the need for greener chemistry. During the last 30 years, biocatalysis with the use of enzymes as chiral catalysts has become more common in chemistry laboratories and industrial processes. In this thesis, the use of lipases as versatile biocatalysts in the acylation of alcohols is examined both in the light of literature examples and four original publications. In the first part of the work presented in this thesis lipases were utilized in two examples concerning secondary alcohols. First, the kinetic resolution of heterocyclic aromatic secondary alcohols through transesterification was thoroughly examined including the studies of competing hydrolysis and esterification reactions. In another example, lipases were utilized in the formation of a dynamic systemic resolution (DSR) process which in turn was used as a developmental tool in the optimization of the dynamic kinetic resolution (DKR) of five heterocyclic aromatic cyanohydrins in one pot for the preparation of cyanohydrin esters as single enantiomers. In the second part of the work, the regio- and stereoselectivity of lipases was used to form sugar conjugates of glyceric and β-amino acids. The primary hydroxyl groups of methyl α-D-galacto-, -gluco- and -mannopyranosides were now acylated trough lipasecatalyzed transesterification and enantioselective lipase-catalyzed ring-opening of β- lactams, respectively.

Rikottujen ikkunoiden nollatoleranssi. Tutkimus New Yorkin rikoksentorjunnan uuskonservatiivi-mallista Suomessa

Väitöskirja on kriminologista kontrollin ja rikoksentorjunnan tutkimusta sekä poliisitutkimusta. Kohteena on ympäri maailmaa levinnyt nollatoleranssiksi kutsuttu järjestyspoliisistrategia. Strategiaa kokeiltiin vuosituhannen vaihteessa vuoden kestäneessä järjestyksenvalvonnan hankkeessa Tampereella. Vaikka kyseessä oli kokeilu, niin tutkimuksessa osoitetaan toimintatavan olleen ja olevan pitkälti kiinteä osa perinteistä suomalaisen järjestyspoliisin toimintaperiaatetta. Artikkeliväitöskirja sisältää viisi vuosina 1998–2005 julkaistua kirjoitusta. Kokoavan yhteenvetoartikkelin tutkimusongelmat ovat seuraavat: Millaisia ovat Yhdysvaltojen ja Suomen järjestyspoliisitoiminnan nollatoleranssien mekanismien, kontekstien ja vaikutusten keskeiset erot ja yhtäläisyydet? Millainen on Tampereen nollatoleranssikokeilu ja New Yorkin rikottujen ikkunoiden nollatoleranssi rikoksentorjunnan arvioinnin ja moraalisäätelyn esimerkkeinä? Tampereen kokeilun prosessi- ja vaikuttavuusarviointitutkimus koostaa tutkimuksen empiirisen aineiston. Hankkeen alku- ja loppumittauksena toimi lomakekysely tamperelaisille (2 x n2000). Lisäksi analyysissä käytettiin kansalaiskyselyn uhrikyselyä, poliisin rikos- ja päivystyskeskustilastoja, Tilastokeskuksen tilastoja, hankkeen suoritelomakkeita sekä rangaistusvaatimus- ja rikesakkolomakkeita sekä kouluterveystutkimuksia. Tampereen poliiseille tehtiin lomakekysely ja teemahaastatteluja. Sosiaali-, nuoriso- ja vapaaehtoistyöntekijöitä sekä yli viisikymmentä tamperelaista nuorta sekä kymmenkunta tamperelaista aikuista haastateltiin. Yhdysvaltojen osalta nojaudutaan verrattain suureen määrään julkaistua korkeatasoista ja ajankohtaista kriminologista tutkimusta. New Yorkiin ja Yhdysvaltoihin sovelletussa hallintavalta- ja moraalisäätelyanalyysissa rikotut ikkunat -teoria osoittautuu uuskonservatiiviseksi moraaliprojektiksi, joka opastaa kaupunkeja hankkimaan itselleen oikeuden tiukkaan järjestyksenvalvontaan. Aiemmin sen oli estänyt kansalaisoikeusmyönteinen lakien tulkinta. New Yorkissa ja Tampereella syntyi useita kielteisiä sivu- ja vastavaikutuksia, kuten ongelmien siirtymistä (displacement). Tämä on yksi keskeinen tulos tilannetorjunnan ja kontrollin tehostamisen ja kohdistamisen hankkeissa. Tulokset haastavat arvioimaan kriittisesti, ovatko kaikki lapsiin ja nuoriin kohdistuvat varhaisen puuttumisen hankkeet seuraustensa perusteella oikeutettuja.

Apua Kekkoselle vai kansainvälisen politiikan sivutuote? Noottikriisin suomalainen kuva

Tutkimus käsittelee noottikriisin suomalaista kuvaa. Noottikriisi on saanut nimensä Neuvostoliiton Suomelle 30.10.1961 antamasta nootista, jonka mukaan Länsi-Saksan aseellinen varustautuminen aiheutti sellaisen sotilaallisen uhkan, että vuoden 1948 yya-sopimuksen mukaiset sotilaalliset konsultaatiot olivat perusteltuja. Presidentti Urho Kekkonen ja pääministeri Nikita Hruštšov sopivat kuitenkin runsaan kolmen viikon kuluttua, ettei niitä pidetä. Noottikriisi on ollut hyvin kiistanalainen. Eniten on erimielisyyttä aiheuttanut nootin motiivi. Siksi tämän tutkimuksen pääaiheena ovat sen tulkinnat suomalaisten kirjoittamissa painetuissa teksteissä nootin jättämisen jälkeisestä päivästä vuoteen 2013. Erimielisyys johtuu pääasiassa käsityksestä, että noottia ei lähetetty Länsi-Saksan aiheuttaman uhkan takia vaan Kekkosen auttamiseksi vuoden 1962 presidentinvaaleissa. Tätä tulkintaa yksinään tai yhdistettynä yhteen tai useampaa muuhun tekijään on myös kannatettu eniten. Kekkonenkin ilmaisi päiväkirjassaan, että tarkoituksena oli hänen tukemisensa. Julkisuudessa hän ei kuitenkaan sanonut koskaan niin eksplisiittisesti. Erityinen piirre ovat vaihtelut huomattavan monen akateemisenkin kirjoittajan tulkinnoissa. Sama koskee sanomalehtiä. Monet nimesivät jälkeenpäin nootin tarkoitukseksi Kekkosen auttamisen, vaikka olivat aluksi kirjoittaneet jotain muuta. Ilmiö paljastaa että sanomalehdet harjoittivat heti nootin saapumisen jälkeen itsesensuuria.

The duality of tactical thought : a study of how Swedish land forces' commanders view tactics in irregular warfare

This is a sociological study of the views of officers in the Swedish Army and its Amphibious Forces on tactics in Irregular Warfare (IW), in particular, Counterinsurgency (COIN). IW comprises struggles, where the military weaker part uses an indirect approach with smaller units and integrates the civilian and military dimensions in a violence spectrum including subversion, terrorism, Guerrilla Warfare and infantry actions. IW is the main armed warfare style in insurgencies. COIN is the combined political, military, economic, social and legal actions in counter insurgencies. Data has been collected by means of interviews with almost all (n =43) officers, who were either commanding battalions or rifle and manoeuvre companies while undergoing training for general warfare and international operations. The main theoretical and methodological inspiration is the traditional one for research on social fields, inaugurated by the French sociologist Pierre Bourdieu. The statistical technique used is Multiple Correspondence Analysis. As a background and context base, an inquiry inspired by the Begriffsgechichte (Conceptual History) tradition explores the genesis and development of understandings of the term Irregular Warfare. The research question is outlined as; “how can contemporary Swedish military thought on tactics in Irregular Warfare be characterized using descriptive patterns, mapped in relation to background factors and normative standards? The most significant findings are that there are two main opposing notions separating the officers’ views on tactics in Irregular Warfare: (1) a focus on larger, combat oriented and collectively operating military units versus smaller and larger, more intelligence oriented and dispersed operating units, and (2) a focus on military tasks and kinetic effects versus military and civilian tasks as well as “soft” effects. The distribution of these views can be presented as a two-dimensional space structured by the two axes. This space represents four categories of tactics, partly diverging from normative military standards for Counterinsurgency. This social space of standpoints shows different structural tendencies for background factors of social and cultural character, particularly dominant concerning military backgrounds, international mission experiences and civilian education. Compared to military standards for Counterinsurgency, the two tactical types characterized by a Regular Warfare mind-set stands out as counter-normative. Signs of creative thought on military practice and theory, as well as a still persistent Regular Warfare doxa are apparent. Power struggles might thus develop, effecting the transformation to a broadened warfare culture with an enhanced focus also on Irregular Warfare. The result does not support research results arguing for a convergence of military thought in the European transformation of Armed Forces. The main argument goes beyond tactics and suggests sociological analysis on reciprocal effects regarding strategy, operational art, tactics as well as leadership, concerning the mind-set and preferences for Regular, Irregular and Hybrid Warfare.

Efficacy, safety, quality control, marketing and regulatory guidelines for herbal medicines (phytotherapeutic agents)

This review highlights the current advances in knowledge about the safety, efficacy, quality control, marketing and regulatory aspects of botanical medicines. Phytotherapeutic agents are standardized herbal preparations consisting of complex mixtures of one or more plants which contain as active ingredients plant parts or plant material in the crude or processed state. A marked growth in the worldwide phytotherapeutic market has occurred over the last 15 years. For the European and USA markets alone, this will reach about $7 billion and $5 billion per annum, respectively, in 1999, and has thus attracted the interest of most large pharmaceutical companies. Insufficient data exist for most plants to guarantee their quality, efficacy and safety. The idea that herbal drugs are safe and free from side effects is false. Plants contain hundreds of constituents and some of them are very toxic, such as the most cytotoxic anti-cancer plant-derived drugs, digitalis and the pyrrolizidine alkaloids, etc. However, the adverse effects of phytotherapeutic agents are less frequent compared with synthetic drugs, but well-controlled clinical trials have now confirmed that such effects really exist. Several regulatory models for herbal medicines are currently available including prescription drugs, over-the-counter substances, traditional medicines and dietary supplements. Harmonization and improvement in the processes of regulation is needed, and the general tendency is to perpetuate the German Commission E experience, which combines scientific studies and traditional knowledge (monographs). Finally, the trend in the domestication, production and biotechnological studies and genetic improvement of medicinal plants, instead of the use of plants harvested in the wild, will offer great advantages, since it will be possible to obtain uniform and high quality raw materials which are fundamental to the efficacy and safety of herbal drugs.

Retinol-induced changes in the phosphorylation levels of histones and high mobility group proteins from Sertoli cells

Chromatin proteins play a role in the organization and functions of DNA. Covalent modifications of nuclear proteins modulate their interactions with DNA sequences and are probably one of the multiple factors involved in the process of switch on/off transcriptionally active regions of DNA. Histones and high mobility group proteins (HMG) are subject to many covalent modifications that may modulate their capacity to bind to DNA. We investigated the changes induced in the phosphorylation pattern of cultured Wistar rat Sertoli cell histones and high mobility group protein subfamilies exposed to 7 µM retinol for up to 48 h. In each experiment, 6 h before the end of the retinol treatment each culture flask received 370 KBq/ml [32P]-phosphate. The histone and HMGs were isolated as previously described [Moreira et al. Medical Science Research (1994) 22: 783-784]. The total protein obtained by either method was quantified and electrophoresed as described by Spiker [Analytical Biochemistry (1980) 108: 263-265]. The gels were stained with Coomassie brilliant blue R-250 and the stained bands were cut and dissolved in 0.5 ml 30% H2O2 at 60oC for 12 h. The vials were chilled and 5.0 ml scintillation liquid was added. The radioactivity in each vial was determined with a liquid scintillation counter. Retinol treatment significantly changed the pattern of each subfamily of histone and high mobility group proteins.

Advanced analysis and design methods for preparative chromatographic separation processes

Preparative liquid chromatography is one of the most selective separation techniques in the fine chemical, pharmaceutical, and food industries. Several process concepts have been developed and applied for improving the performance of classical batch chromatography. The most powerful approaches include various single-column recycling schemes, counter-current and cross-current multi-column setups, and hybrid processes where chromatography is coupled with other unit operations such as crystallization, chemical reactor, and/or solvent removal unit. To fully utilize the potential of stand-alone and integrated chromatographic processes, efficient methods for selecting the best process alternative as well as optimal operating conditions are needed. In this thesis, a unified method is developed for analysis and design of the following singlecolumn fixed bed processes and corresponding cross-current schemes: (1) batch chromatography, (2) batch chromatography with an integrated solvent removal unit, (3) mixed-recycle steady state recycling chromatography (SSR), and (4) mixed-recycle steady state recycling chromatography with solvent removal from fresh feed, recycle fraction, or column feed (SSR–SR). The method is based on the equilibrium theory of chromatography with an assumption of negligible mass transfer resistance and axial dispersion. The design criteria are given in general, dimensionless form that is formally analogous to that applied widely in the so called triangle theory of counter-current multi-column chromatography. Analytical design equations are derived for binary systems that follow competitive Langmuir adsorption isotherm model. For this purpose, the existing analytic solution of the ideal model of chromatography for binary Langmuir mixtures is completed by deriving missing explicit equations for the height and location of the pure first component shock in the case of a small feed pulse. It is thus shown that the entire chromatographic cycle at the column outlet can be expressed in closed-form. The developed design method allows predicting the feasible range of operating parameters that lead to desired product purities. It can be applied for the calculation of first estimates of optimal operating conditions, the analysis of process robustness, and the early-stage evaluation of different process alternatives. The design method is utilized to analyse the possibility to enhance the performance of conventional SSR chromatography by integrating it with a solvent removal unit. It is shown that the amount of fresh feed processed during a chromatographic cycle and thus the productivity of SSR process can be improved by removing solvent. The maximum solvent removal capacity depends on the location of the solvent removal unit and the physical solvent removal constraints, such as solubility, viscosity, and/or osmotic pressure limits. Usually, the most flexible option is to remove solvent from the column feed. Applicability of the equilibrium design for real, non-ideal separation problems is evaluated by means of numerical simulations. Due to assumption of infinite column efficiency, the developed design method is most applicable for high performance systems where thermodynamic effects are predominant, while significant deviations are observed under highly non-ideal conditions. The findings based on the equilibrium theory are applied to develop a shortcut approach for the design of chromatographic separation processes under strongly non-ideal conditions with significant dispersive effects. The method is based on a simple procedure applied to a single conventional chromatogram. Applicability of the approach for the design of batch and counter-current simulated moving bed processes is evaluated with case studies. It is shown that the shortcut approach works the better the higher the column efficiency and the lower the purity constraints are.

Pupil size following dark adaptation in patients with retinitis pigmentosa

According to the equivalent light hypothesis, molecular defects in the photoreceptor lead to a continuous activation of the photoreceptor cascade in a manner equivalent to real light. The consequences in diseases such as retinitis pigmentosa (RP) are as disruptive to the cells as real light. Two forms of the equivalent light hypothesis can be distinguished: strong - mutations in rhodopsin or other cascade proteins in some forms of RP continuously excite the visual phototransduction cascade; weak - disruption of outer segments in all patients with RP eliminates circulating dark current and blocks neurotransmitter release in a manner similar to real light. Both forms of the equivalent light hypothesis predict that pupils of patients with RP will be constricted like those of normal subjects in the light. The purpose of this study was to test the equivalent light hypothesis by determining whether steady-state pupil diameter following full dark adaptation is abnormally small in any of a sample of patients with RP. Thirty-five patients with RP and 15 normal subjects were tested. Direct steady-state pupillometric measures were obtained from one eye in a full-field dome after 45 min of dark adaptation by videotaping the pupil with an infrared camera. Mean pupil diameter in the dark was comparable (t = -0.15, P = 0.88) between patients with RP (6.85 ± 0.58 mm) and normal subjects (6.82 ± 0.76 mm). The results of the present study are clearly counter to the prediction of the second (weaker) form of the equivalent light hypothesis.

Role of Tamm-Horsfall protein and uromodulin in calcium oxalate crystallization

One of the defenses against nephrolithiasis is provided by macromolecules that modulate the nucleation, growth, aggregation and retention of crystals in the kidneys. The aim of the present study was to determine the behavior of two of these proteins, Tamm-Horsfall and uromodulin, in calcium oxalate crystallization in vitro. We studied a group of 10 male stone formers who had formed at least one kidney stone composed of calcium oxalate. They were classified as having idiopathic nephrolithiasis and had no well-known metabolic risk factors involved in kidney stone pathogenesis. Ten normal men were used as controls, as was a group consisting of five normal women and another consisting of five pregnant women. Crystallization was induced by a fixed supersaturation of calcium oxalate and measured with a Coulter Counter. All findings were confirmed by light and scanning electron microscopy. The number of particulate material deposited from patients with Tamm-Horsfall protein was higher than that of the controls (P<0.001). However, Tamm-Horsfall protein decreased the particle diameter of the stone formers when analyzed by the mode of the volume distribution curve (P<0.002) (5.64 ± 0.55 µm compared to 11.41 ± 0.48 µm of uromodulin; 15.94 ± 3.93 µm and 12.45 ± 0.97 µm of normal men Tamm-Horsfall protein and uromodulin, respectively; 8.17 ± 1.57 µm and 9.82 ± 0.95 µm of normal women Tamm-Horsfall protein and uromodulin, respectively; 12.17 ± 1.41 µm and 12.99 ± 0.51 µm of pregnant Tamm-Horsfall protein and uromodulin, respectively). Uromodulin produced fewer particles than Tamm-Horsfall protein in all groups. Nonetheless, the total volume of the crystals produced by uromodulin was higher than that produced by Tamm-Horsfall protein. Our results indicate a different effect of Tamm-Horsfall protein and uromodulin. This dual behavior suggests different functions. Tamm-Horsfall protein may act on nucleation and inhibit crystal aggregation, while uromodulin may promote aggregation of calcium oxalate crystals.

Adaptive Dynamics of Resource Specialization

Ecological specialization in resource utilization has various facades ranging from nutritional resources via host use of parasites or phytophagous insects to local adaptation in different habitats. Therefore, the evolution of specialization affects the evolution of most other traits, which makes it one of the core issues in the theory of evolution. Hence, the evolution of specialization has gained enormous amounts of research interest, starting already from Darwin’s Origin of species in 1859. Vast majority of the theoretical studies has, however, focused on the mathematically most simple case with well-mixed populations and equilibrium dynamics. This thesis explores the possibilities to extend the evolutionary analysis of resource usage to spatially heterogeneous metapopulation models and to models with non-equilibrium dynamics. These extensions are enabled by the recent advances in the field of adaptive dynamics, which allows for a mechanistic derivation of the invasion-fitness function based on the ecological dynamics. In the evolutionary analyses, special focus is set to the case with two substitutable renewable resources. In this case, the most striking questions are, whether a generalist species is able to coexist with the two specialist species, and can such trimorphic coexistence be attained through natural selection starting from a monomorphic population. This is shown possible both due to spatial heterogeneity and due to non-equilibrium dynamics. In addition, it is shown that chaotic dynamics may sometimes inflict evolutionary suicide or cyclic evolutionary dynamics. Moreover, the relations between various ecological parameters and evolutionary dynamics are investigated. Especially, the relation between specialization and dispersal propensity turns out to be counter-intuitively non-monotonous. This observation served as inspiration to the analysis of joint evolution of dispersal and specialization, which may provide the most natural explanation to the observed coexistence of specialist and generalist species.