Regio- and stereoselectivity of oxidative coupling reactions of phenols : Spirodienones as construction units in lignin

Dimeric phenolic compounds lignans and dilignols form in the so-called oxidative coupling reaction of phenols. Enzymes such as peroxidases and lac-cases catalyze the reaction using hydrogen peroxide or oxygen respectively as oxidant generating phenoxy radicals which couple together according to certain rules. In this thesis, the effects of the structures of starting materials mono-lignols and the effects of reaction conditions such as pH and solvent system on this coupling mechanism and on its regio- and stereoselectivity have been studied. After the primary coupling of two phenoxy radicals a very reactive quinone me-thide intermediate is formed. This intermediate reacts quickly with a suitable nucleophile which can be, for example, an intramolecular hydroxyl group or another nucleophile such as water, methanol, or a phenolic compound in the reaction system. This reaction is catalyzed by acids. After the nucleophilic addi-tion to the quinone methide, other hydrolytic reactions, rearrangements, and elimination reactions occur leading finally to stable dimeric structures called lignans or dilignols. Similar reactions occur also in the so-called lignification process when monolignol (or dilignol) reacts with the growing lignin polymer. New kinds of structures have been observed in this thesis. The dimeric com-pounds with so-called spirodienone structure have been observed to form both in the dehydrodimerization of methyl sinapate and in the beta-1-type cross-coupling reaction of two different monolignols. This beta-1-type dilignol with a spirodienone structure was the first synthetized and published dilignol model compound, and at present, it has been observed to exist as a fundamental construction unit in lignins. The enantioselectivity of the oxidative coupling reaction was also studied for obtaining enantiopure lignans and dilignols. A rather good enantioselectivity was obtained in the oxidative coupling reaction of two monolignols with chiral auxiliary substituents using peroxidase/H2O2 as an oxidation system. This observation was published as one of the first enantioselective oxidative coupling reaction of phenols. Pure enantiomers of lignans were also obtained by using chiral cryogenic chromatography as a chiral resolution technique. This technique was shown to be an alternative route to prepare enantiopure lignans or lignin model compounds in a preparative scale.

Locality and order-invariant logics

Malli on logiikassa käytetty abstraktio monille matemaattisille objekteille. Esimerkiksi verkot, ryhmät ja metriset avaruudet ovat malleja. Äärellisten mallien teoria on logiikan osa-alue, jossa tarkastellaan logiikkojen, formaalien kielten, ilmaisuvoimaa malleissa, joiden alkioiden lukumäärä on äärellinen. Rajoittuminen äärellisiin malleihin mahdollistaa tulosten soveltamisen teoreettisessa tietojenkäsittelytieteessä, jonka näkökulmasta logiikan kaavoja voidaan ajatella ohjelmina ja äärellisiä malleja niiden syötteinä. Lokaalisuus tarkoittaa logiikan kyvyttömyyttä erottaa toisistaan malleja, joiden paikalliset piirteet vastaavat toisiaan. Väitöskirjassa tarkastellaan useita lokaalisuuden muotoja ja niiden säilymistä logiikkoja yhdistellessä. Kehitettyjä työkaluja apuna käyttäen osoitetaan, että Gaifman- ja Hanf-lokaalisuudeksi kutsuttujen varianttien välissä on lokaalisuuskäsitteiden hierarkia, jonka eri tasot voidaan erottaa toisistaan kasvavaa dimensiota olevissa hiloissa. Toisaalta osoitetaan, että lokaalisuuskäsitteet eivät eroa toisistaan, kun rajoitutaan tarkastelemaan äärellisiä puita. Järjestysinvariantit logiikat ovat kieliä, joissa on käytössä sisäänrakennettu järjestysrelaatio, mutta sitä on käytettävä siten, etteivät kaavojen ilmaisemat asiat riipu valitusta järjestyksestä. Määritelmää voi motivoida tietojenkäsittelyn näkökulmasta: vaikka ohjelman syötteen tietojen järjestyksellä ei olisi odotetun tuloksen kannalta merkitystä, on syöte tietokoneen muistissa aina jossakin järjestyksessä, jota ohjelma voi laskennassaan hyödyntää. Väitöskirjassa tutkitaan minkälaisia lokaalisuuden muotoja järjestysinvariantit ensimmäisen kertaluvun predikaattilogiikan laajennukset yksipaikkaisilla kvanttoreilla voivat toteuttaa. Tuloksia sovelletaan tarkastelemalla, milloin sisäänrakennettu järjestys lisää logiikan ilmaisuvoimaa äärellisissä puissa.

A Probabilistic Approach to the Primary Visual Cortex

What can the statistical structure of natural images teach us about the human brain? Even though the visual cortex is one of the most studied parts of the brain, surprisingly little is known about how exactly images are processed to leave us with a coherent percept of the world around us, so we can recognize a friend or drive on a crowded street without any effort. By constructing probabilistic models of natural images, the goal of this thesis is to understand the structure of the stimulus that is the raison d etre for the visual system. Following the hypothesis that the optimal processing has to be matched to the structure of that stimulus, we attempt to derive computational principles, features that the visual system should compute, and properties that cells in the visual system should have. Starting from machine learning techniques such as principal component analysis and independent component analysis we construct a variety of sta- tistical models to discover structure in natural images that can be linked to receptive field properties of neurons in primary visual cortex such as simple and complex cells. We show that by representing images with phase invariant, complex cell-like units, a better statistical description of the vi- sual environment is obtained than with linear simple cell units, and that complex cell pooling can be learned by estimating both layers of a two-layer model of natural images. We investigate how a simplified model of the processing in the retina, where adaptation and contrast normalization take place, is connected to the nat- ural stimulus statistics. Analyzing the effect that retinal gain control has on later cortical processing, we propose a novel method to perform gain control in a data-driven way. Finally we show how models like those pre- sented here can be extended to capture whole visual scenes rather than just small image patches. By using a Markov random field approach we can model images of arbitrary size, while still being able to estimate the model parameters from the data.

Kohti leikkaussalin tuloksellista toiminnanohjausta

Background: The aging population is placing increasing demands on surgical services, simultaneously with a decreasing supply of professional labor and a worsening economic situation. Under growing financial constraints, successful operating room management will be one of the key issues in the struggle for technical efficiency. This study focused on several issues affecting operating room efficiency. Materials and methods: The current formal operating room management in Finland and the use of performance metrics and information systems used to support this management were explored using a postal survey. We also studied the feasibility of a wireless patient tracking system as a tool for managing the process. The reliability of the system as well as the accuracy and precision of its automatically recorded time stamps were analyzed. The benefits of a separate anesthesia induction room in a prospective setting were compared with the traditional way of working, where anesthesia is induced in the operating room. Using computer simulation, several models of parallel processing for the operating room were compared with the traditional model with respect to cost-efficiency. Moreover, international differences in operating room times for two common procedures, laparoscopic cholecystectomy and open lung lobectomy, were investigated. Results: The managerial structure of Finnish operating units was not clearly defined. Operating room management information systems were found to be out-of-date, offering little support to online evaluation of the care process. Only about half of the information systems provided information in real time. Operating room performance was most often measured by the number of procedures in a time unit, operating room utilization, and turnover time. The wireless patient tracking system was found to be feasible for hospital use. Automatic documentation of the system facilitated patient flow management by increasing process transparency via more available and accurate data, while lessening work for staff. Any parallel work flow model was more cost-efficient than the traditional way of performing anesthesia induction in the operating room. Mean operating times for two common procedures differed by 50% among eight hospitals in different countries. Conclusions: The structure of daily operative management of an operating room warrants redefinition. Performance measures as well as information systems require updating. Parallel work flows are more cost-efficient than the traditional induction-in-room model.

Benchmarking Scientific Journals from the Submitting Author’s Viewpoint

Authors of scholarly papers to a large extent base the decision on where to submit their manuscripts on the prestige of journals, taking little account of other possible factors. Information concerning such factors is in fact often not available. This paper argues for the establishment of methods for benchmarking scientific journals, taking into account a wider range of journal performance parameters than is currently available. A model for how prospective authors determine the value of submitting to a particular journal is presented. The model includes eight factors that influence an author’s decision and 21 other underlying factors. The model is a qualitative one. The method proposes to benchmark groups of journals by application of the factors. Initial testing of the method has been undertaken in one discipline.

Knowledge Transfer within Western Multinationals' Subsidiary Units in China and Finland - The Impact of Headquarter Control Mechanisms, Subsidiary Location and Social Capital (summary section only)

It is suggested that the ability and practices of how the multinational corporation (MNC) manages knowledge transfer among its geographically dispersed subsidiary units are crucial for the building and development of firm competitive advantage. However, cross-border transfer of valuable organizational knowledge is likely to be problematic and laborious, especially within diversified and differentiated MNCs. Using data collected from 164 western multinational companies’ subsidiary units located in China and Finland, this study aims to investigate cross-border knowledge transfer within the MNC. It explores a number of factors that influence the transfer of knowledge among units in the differentiated MNC. The study consists of five individual papers. Paper 1 investigates a range of organizational mechanisms that may positively influence a subsidiary’s propensity to undertake knowledge transfers to other parts of the corporation. Paper 2 explores the impact of subsidiary location on the motivational dispositions of knowledge receiving units to value and accept knowledge from subsidiaries located in economically less advanced countries. Paper 3 examines the influence of social capital variables on knowledge transfer in dyadic relationships between foreign-owned subsidiaries and their sister and patent units. Paper 4 provides some initial insights into potentially different effects of trust and shared vision in intra-organizational vs. inter-organizational relationships. Using a case study setting, Paper 5 explores means and mechanisms used in transferring human resource management practices to Western MNCs’ business units in China from a cultural perspective. The results of the study show that MNC management through choices regarding organizational controls can encourage and enhance corporate-internal knowledge transfer. It also finds evidence that more knowledge is transferred from subsidiaries located in an industrialized country (e.g., Finland) than subsidiaries located in a developing country (e.g., China). While the study has highlighted the importance of social capital in promoting knowledge transfer, it has also uncovered some new findings that the effect of trust and shared vision may be contingent upon different contexts. Finally, in Paper 5, a number of mechanisms used in transferring selected HRM practices and competences to the Chinese business units have been identified. The findings suggest that cultural differences should be taken into consideration in the choice and use of different transfer mechanisms.

Hedging Options with Different Time Units in the Pricing Models

This study examined the effects of the Greeks of the options and the trading results of delta hedging strategies, with three different time units or option-pricing models. These time units were calendar time, trading time and continuous time using discrete approximation (CTDA) time. The CTDA time model is a pricing model, that among others accounts for intraday and weekend, patterns in volatility. For the CTDA time model some additional theta measures, which were believed to be usable in trading, were developed. The study appears to verify that there were differences in the Greeks with different time units. It also revealed that these differences influence the delta hedging of options or portfolios. Although it is difficult to say anything about which is the most usable of the different time models, as this much depends on the traders view of the passing of time, different market conditions and different portfolios, the CTDA time model can be viewed as an attractive alternative.