Closed-shell interaction in silver and gold chlorides

Hartree-Fock and coupled-cluster calculations have been performed for cubic AgCl and for AuCl having a cubic or the observed structure with space group I4_1/amd. Cohesive energies and lattice constants are in excellent agreement with experiment for AgCl; for AuCl we find good agreement, and the experimental structure is correctly predicted to be lower in energy than the cubic one. Electron-correlation effects on lattice constants are very large, of up to 0.8 \AA for cubic AuCl. We especially discuss the strength of the closed-shell interactions, and for the first time a quantitative analysis of the so-called "aurophilic" Au(I)-Au(I) interaction is presented in solids.Comment: accepted by J. Chem. Phy

Covariant localizations in the torus and the phase observables

We describe all the localization observables of a quantum particle in a one-dimensional box in terms of sequences of unit vectors in a Hilbert space. An alternative representation in terms of positive semidefinite complex matrices is furnished and the commutative localizations are singled out. As a consequence, we also get a vector sequence characterization of the covariant phase observables.Comment: 16 pages, no figure, Latex2

The norm-1-property of a quantum observable

A normalized positive operator measure $X\mapsto E(X)$ has the norm-1-property if \no{E(X)}=1 whenever $E(X)\ne O$. This property reflects the fact that the measurement outcome probabilities for the values of such observables can be made arbitrary close to one with suitable state preparations. Some general implications of the norm-1-property are investigated. As case studies, localization observables, phase observables, and phase space observables are considered.Comment: 14 page

Development of predictive models for catalyst development

Abstract. This work was done as a part of the BioSPRINT project, which aims to improve biorefinery operations through process intensification and to replace fossil-based polymers with new bio-based products. The goal was to identify machine learned (ML) models that will accelerate the catalyst identification with high-throughput (HTP) screening methods, identify non-obvious formulations and allow catalyst tuning for different feedstock compositions. Maximum activity for conversion of complex sugar mixtures with optimal selectivity towards the key products of interest is desired. In the literature part of the thesis, ML was studied in general, where the focus was on different variable selection methods and modeling techniques, more specifically on data-driven modeling. Furthermore, modeling in catalysis was discussed with focus on ML in catalysis. Catalyst screening and selection, descriptor modeling and selection, and predictive modeling in catalysis were studied. In the experimental part, focus was on developing ML models that predict catalyst performance with relevant descriptors. Dataset for hydrogenation of 5-ethoxymethylfurfural with simple bimetal catalysts, including main metals and promoters, was used as ML model input with the addition of catalyst descriptors found in the literature. Four different responses were used in the experiments: selectivity and conversion with two different solvents. Methods used in the experimental part were discussed in detail, where data collection, preprocessing, variable selection, modeling and model validation were considered. Reference models without variable selection were first identified. Secondly, regularization algorithms were used to identify models. Finally, models with variable subsets obtained with regularization algorithms were identified. The effect of cross-validation was also studied. In general, good modeling results were obtained with boosted ensemble tree methods, support vector machine (SVM) methods and Gaussian process regression (GPR) methods. Lasso regression turned out to be the best variable selection method. Good results were obtained with the descriptors found in the literature. It was also shown, that fairly good results can be obtained with only two variables in the studied case. Promoter variables were not considered nearly as important as main metals with variable selection algorithms. Even though the modeling results were good, the variable selection methods were almost purely data-driven, and the actual relevance of the variables cannot be guaranteed. In the future work, optimization should be studied with the goal of finding catalysts that maximize catalyst performance values based on the model predictions. Also, extrapolation capabilities of the models need to be studied and improved. The studied methods can be easily implemented to other datasets. In the BioSPRINT project, experimental results related to the dehydration reaction of C5 and C6 sugars with simple metal catalysts will be obtained and used with the studied methods.Ennustavien mallien laatiminen katalyytin valmistuksen tehostamiseksi. Tiivistelmä. Tämä työ tehtiin osana BioSPRINT-projektia, jonka tavoitteena on kehittää biojalostamoiden toimintaa parantamalla niiden prosessitehokkuutta ja korvata fossiilipohjaiset polymeerit uusilla biopohjaisilla tuotteilla. Työn tavoitteena oli muodostaa koneoppimista hyödyntämällä mallit, jotka nopeuttavat optimaalisten katalyyttien löytämistä tehoseulonnan (high-throughput (HTP) screening) avulla, auttavat identifioimaan vaikeasti löydettäviä katalyyttiyhdistelmiä ja mahdollistavat katalyytin valinnan eri lähtöainekoostumuksilla. Tavoitteena on maksimoida monimutkaisten sokeriyhdisteiden konversio ja selektiivisyys halutuiksi tuotteiksi. Työn kirjallisuusosiossa perehdyttiin koneoppimiseen yleisellä tasolla, missä pääpaino oli muuttujanvalintamenetelmissä ja datapohjaisissa mallinnusmenetelmissä. Lisäksi kirjallisuusosassa tutkittiin mallinnuksen käyttöä katalyysissä, missä pääpaino oli koneoppimisen käytössä. Työssä tarkasteltiin myös katalyyttien seulontaa ja valintaa, laskennallisten muuttujien (deskriptorien) määrittelyä ja valintaa, sekä ennustavan mallinnuksen käyttöä katalyysissä. Kokeellisessa osiossa painopiste oli koneoppimista hyödyntävien mallien muodostuksessa, jotka ennustavat katalyyttien suorituskykyä oleellisilla deskriptoreilla. Data-aineistona käytettiin 5-etoksimetyylifurfuraalin hydrausreaktion tuloksia yksinkertaisilla kaksikomponenttisilla metallikatalyyteillä, jotka sisältävät päämetallin ja promoottorin. Data-aineistoa täydennettiin kirjallisuudesta löytyvillä katalyyttien deskriptoreilla ja käytettiin koneoppimista hyödyntävien mallien sisääntulona. Tutkimuksissa käytettiin neljää eri vastemuuttujaa: selektiivisyyttä ja konversiota kahdella eri liuottimella. Kokeellisessa osiossa käytetyt menetelmät käytiin läpi perusteellisesti huomioon ottaen data-aineiston keräämisen, esikäsittelyn, muuttujanvalinnan, mallinnuksen ja mallin validoinnin. Ensin referenssimallit identifioitiin. Tämän jälkeen regularisaatioalgoritmeilla suoritettiin mallinnus. Lopuksi mallinnus suoritettiin käyttämällä muuttujajoukkoja, jotka oli valittu käyttäen regularisaatioalgoritmeja. Myös ristivalidoinnin vaikutusta tutkittiin. Yleisesti hyvät mallinnustulokset saavutettiin boosted ensemble tree -tekniikalla, tukivektorikoneella ja Gaussian process -regressiolla. Lasso-menetelmä todettiin parhaaksi muuttujanvalinta-algoritmiksi. Hyvät tulokset saavutettiin kirjallisuudesta löytyvien deskriptorien avulla. Tutkimuksissa todettiin myös, että hyvät mallinnustulokset voidaan saavuttaa kyseisessä tutkimustapauksessa jopa vain kahdella muuttujalla. Päämetalleja kuvaavien muuttujien merkitsevyys todettiin paljon suuremmaksi kuin promoottorien vastaavien muuttujien. Saatavia mallinnustuloksia tarkasteltaessa täytyy huomioida, että muuttujanvalinta oli melkein täysin datapohjainen eikä muuttujien varsinaista merkitsevyyttä voida taata. Jatkossa mallien ennustuksia voidaan hyödyntää optimoinnissa, jossa tavoitteena on etsiä katalyyttiyhdistelmä, joka maksimoi katalyyttien suorituskyvyn. Myös mallin ekstrapolointikykyä täytyy tutkia ja kehittää. Tutkittavat menetelmät ovat helposti sovellettavissa myös muille samantyylisille data-aineistoille. BioSPRINT-projektista saadaan tulevaisuudessa käytettäväksi viisi- ja kuusihiilisten sokerien dehydraatioon perustuva data-aineisto yksinkertaisilla metallikatalyyteillä, jota tullaan käyttämään jatkotutkimuksissa

Validation of Tornio AP3 model based furnace control and grain size calculation

Abstract. Automation for annealing and pickling -line 3 was renewed in 2016, but the model-based control wasn’t good enough that production could rely on it, so doing modifications to the model was necessary. The goal was to get the model working so that automation could control furnaces mostly without input from line operators. Phenomena concerning grain size calculation in the automation system was studied theoretically to acquire sufficient information. The solving of problem was done by inspecting source code for programming errors, examining calculation log files and tables used by automation and finally measuring accuracy of the calculation both statistically and comparing calculated results with measured grain size from production trials. The accuracy was improved by modifying both grain size calculation and set-point calculation. Many changes were suggested for general parameters, grain specific grain growth parameters and source code. After these changes maximum grain size calculation error improved to 0,45 ASTM, but because of poor control of zone temperatures high accuracy in annealing can’t be done. The fixing of automations system is started, and it continues even when this thesis project is finished.Tiivistelmä. Hehkutus- ja peittauslinja 3:n automaatio uusittiin vuonna 2016, mutta uunien mallipohjainen ohjaus ei ollut riittävän hyvällä tasolla, jotta tuotannossa voitaisiin luottaa siihen. Tämän vuoksi mallin validointi oli tarpeellista. Tavoitteena oli saada malli toimimaan siten, että uuneja voitaisiin ohjata pääasiassa pelkästään automaatiolla ilman operaattoreiden panosta. Raekokolaskennan taustalla olevia ilmiöitä ja automaatiota tarkasteltiin kirjallisuuden pohjalta tietopohjan luomiseksi. Ongelmaa lähestyttiin tarkastelemalla lähdekoodia ohjelmointivirheiden osalta, seuraamalla laskennan lokitietoja, tarkastelemalla automaation käyttämiä taulukoita, hyödyntämällä tilastollista tietoa, sekä vertaamalla laskennan tuloksia tuotantokokeiden tuottamaan raekokoon. Laskennan tarkkuutta on mahdollista parantaa modifioimalla sekä raekoko-, että vyöhykkeiden asetusarvojen laskentaa. Laskentaan ehdotettiin useita parannuksia yleisiin parametreihin, laatukohtaisiin rakeenkasvuparametreihin ja lähdekoodiin. Näiden parannusten perusteella laskennan suurin virhe on 0,45 ASTM yksikköä. Tuotantolinjan heikon vyöhykelämpötilan hallinnan takia näidenkään muutosten jälkeen tarkkuutta vaativia hehkutuksia ei voida suorittaa. Automaation korjaus on aloitettu, mutta sitä ei ehditty viemään loppuun tämän projektin puitteissa

Cranberry-Lingonberry juice effect on gut and urinary tract microbiome

Abstract. Cranberry, Vaccinium oxycoccos, and lingonberry, Vaccinium vitis-idaea, have long been known to provide many health benefits as a source of nutrition. Similar to other berries, these traditional herbs contain flavonoids and vitamins, but also have a special benefit to prevent urinary tract infection (UTI). Previous studies have shown that A-type proanthocyanins (PAC) of cranberries may influence the adhesion of bacteria causing urinary tract infection. UTI pathogens originate from the gut and earlier studies have shown that there is a connection between urinary tract and gut microbiome UTI causing pathogens. However, the cranberry mechanism of action on the gut and urinary tract microbiome is not yet elucidated. This study aimed to investigate the Cranberry-Lingonberry juice (CLJ) effect on the gut and urinary tract bacterial communities. The hypothesis assumed that the metabolism of proanthocyanidins in the gut alters bacterial communities and reduces the amount of E. coli and possibly other proteobacteria in the urine. The research was done by examining urine and fecal samples from children with urinary tract infection for three (urine) to twelve (fecal samples) months. The samples were collected by Oulu University Hospital Child Health and Maternity Clinic from 77 patients who drank CLJ or flavonoid-free control juice in randomized trial. Total of 206 samples, including 40 urine and 166 fecal samples, were collected for study. DNA was extracted from samples using two different DNA extraction protocols of QIAGEN, USA and quantified using Nanodrop spectrophotometer. The bacterial 16S rRNA was amplified by using Polymerase chain reaction (PCR), which also attached unique barcodes for each sample. Agarose gel electrophoresis was used to ensure amplification of PCR. All amplified PCR products were prepared for sequencing by Ion Torrent next generation sequencing. The QIIME 2 next-generation microbiome bioinformatics platform was used to analyze the sequence data and metadata information. Greengenes 16S rRNA, Silva gene databases and Human oral microbiome database (HOMD) were used as alignment reference databases. Metadata information about sample material and collection time was used for grouping. The alpha and beta diversity, as well as differential abundances between treatments, were analyzed using QIIME 2 platform and R-statistical program. Compliance data was used to limit the data to patients who used more than 80% probability of CLJ or control juice in the second round of statistical analysis. Altogether 183 samples were amplified, of which 150 was fecal and 40 urine, for downstream analysis. From the samples, 18 different phyla and 511 genera were identified, most of them even at species level. Statistical analysis showed no significant differences in alpha- or beta diversity between CLJ and controls in any groups. Different abundances between treatment groups were found, but in the end none of them were statistically significant. By using HOMD-database, E. coli and other UTI-related species were identified from compliance 80% limited data. Statistical analyses showed a significant decrease of these bacteria in the urinary tract and gut microbiomes of CLJ group patients. In the future, chemical studies about microbial metabolism products could be done from the samples to get a more specific view about CLJ treatment effect on gut and microbial communities, and cranberry juice polyphenols effect on the body

Student co-operation between universities and companies:case Oulu

Abstract. This thesis focuses on university–industry collaboration, and especially on student co-operation between companies and universities. Student co-operation in this study covers all university–industry interactions that fundamentally relate to students. The thesis aims to find out the key aspects that play a role when companies engage in student co-operation with universities. Also, students’ perceptions of these collaborations are investigated. Additionally, the role of faculty personnel is looked into, as much of educational collaboration includes them, too. University of Oulu is used as a case university, but the topic itself is universal and the findings contribute to the existing literature of university–industry collaboration, either by confirming what is already known, or at times creating new knowledge. It must also be noted that the literature regarding student co-operation (instead of university–industry collaboration in general) is rather scarce, which adds to the significance of the results of this thesis, also (and especially) in the Finnish context. To achieve the goals of the research, eight companies that collaborate with University of Oulu were chosen and their representatives were interviewed. Data collection for the student and staff perspectives was done through qualitative surveys. During the analysis process, five themes emerged as key aspects of student co-operation. The themes are: recruiting, branding, communication, influence & learning, and social responsibility. Additionally, the role of student associations as well as the role of career days are important, as they act as major touchpoints between companies and students. Especially recruiting and branding are important motives for companies to engage in student co-operation. While students perceive these activities rather positively in general, the results reveal that there are areas of development companies may not be aware of. Also, the role of communication is crucial for the realization of collaboration. At the time of writing, most companies perceived that it is not on the level it needs to be. Many companies also emphasized the role of responsibility as an integral part of collaboration. This is an aspect much of prior research omits, and the emergence of it itself acts as one of the findings of the study

Design and implementation of a bi-directional visible light communication testbed

Abstract. This work defines a bi-directional visible light communication (VLC) testbed design and implementation process using Universal Software Radio Peripheral (USRP) software defined radios (SDR) and open-source software. The visible light communication design uses LED light sources for wireless communications purposes. The testbed combines light, infrared and radio frequencies as wireless media to be utilized in a hybrid wireless communication system. Bi-directional communication at 12.5 Mbps bit rate was successfully achieved and only limited by a sample rate of the USRP system. The achieved communication distance was in the range of 0.5 to 7 meters depending on the used optics. A TCP-IP communication and access to the Internet was also established by using light and infrared communication links. The Internet connection was also established by using power line communication for providing data to the lighting through the existing power line cables. The results in the work were obtained by using a GMSK modulation. Also, GFSK, QPSK, 8-PSK, 16-QAM and OFDM modulation were initially tested for future study.Kaksisuuntaisen näkyvän valon tiedonsiirtotestialustan suunnittelu ja toteutus. Tiivistelmä. Työssä suunnitellaan ja rakennetaan kaksisuuntainen kokeiluympäristö valon käyttöön langattomassa tiedonsiirrossa käyttäen ohjelmistoradioita ja avoimen lähdekoodin ohjelmistoja. Kokeiluympäristössä voidaan tutkia ja käyttää valon, Infrapunan ja radioaaltojen taajuusalueita tiedonsiirtoon. Valon tiedonsiirrossa käytetään valaistuskäyttöön suunniteltuja LED valaisimia sekä valaistukseen että tiedonsiirtoon. Työssä saavuttiin laitteiston näytteistystaajuuden rajoittama kaksisuuntainen 12,5 Mb/s tiedonsiirtonopeus ja käytetyn optiikan ominaisuuksista sekä tiedonsiirtonopeudesta riippuvainen tiedonsiirtoetäisyys 0,5–7 metriä. Järjestelmään ohjelmoitiin valo- ja infrapunalinkin avulla toimiva TCP-IP yhteys Internetiin. Internet yhteys valaisimelle onnistuttiin siirtämään myös käyttäen sähköverkon valmiita kaapelointeja. Työn tulokset saavuttiin käyttäen GMSK moduloitua signaalia. Myös GFSK, QPSK, 8-PSK, 16-QAM ja OFDM modulaatioiden toimivuus testattiin tutkimuksen jatkoa varten

Experimental verification of broadband cloaking using a volumetric cloak composed of periodically stacked cylindrical transmission-line networks

Cloaking using a volumetric structure composed of stacked two-dimensional transmission-line networks is verified with measurements. The measurements are done in a waveguide, in which an array of metallic cylinders is inserted causing a short-circuit in the waveguide. The metal cylinders are cloaked using a previously designed and simulated cloak that hides the cylinders and thus enables wave propagation inside the waveguide.Comment: 8 pages, 3 figure

Educational differences in all-cause mortality by marital status

Using life table measures, we compare educational differentials in all-cause mortality at ages 40 to 70 in Bulgaria to those in Finland and the United States. Specifically, we assess whether the relationship between education and mortality is modified by marital status. Although high education and being married are associated with lower mortality in all three countries, absolute educational differences tend to be smaller among married than unmarried individuals. Absolute differentials by education are largest for Bulgarian men, but in relative terms educational differences are smaller among Bulgarian men than in Finland and the U.S. Among women, Americans experience the largest education-mortality gradients in both relative and absolute terms. Our results indicate a particular need to tackle health hazards among poorly educated men in countries in transition.all-cause mortality, Bulgaria, educational differentials, Finland, life table measures, marital status, USA