Terpenoid transformations over gold catalysts

Nowadays biomass transformation has a great potential for the synthesis of value-added compounds with a wide range of applications. Terpenoids, extracted from biomass, are inexpensive and renewable raw materials which often have a biological activity and are widely used as important organic platform molecules in the development of new medicines as well as in the synthesis of fine chemicals and intermediates. At the same time, special attention is devoted to the application of gold catalysts to fine chemical synthesis due to their outstanding activity and/or selectivity for transformations of complex organic compounds. Conversion of renewable terpenoids in the presence of gold nanoparticles is one of the new and promising directions in the transformation of biomass to valuable chemicals. In the doctoral thesis, different kinds of natural terpenoids, such as α-pinene, myrtenol and carvone were selected as starting materials. Gold catalysts were utilized for the promising routes of these compounds transformation. Investigation of selective α-pinene isomerization to camphene, which is an important step in an industrial process towards the synthesis of camphor as well as other valuable substrates for the pharmaceutical industry, was performed. A high activity of heterogeneous gold catalysts in the Wagner-Meerwein rearrangement was demonstrated for the first time. Gold on alumina carrier was found to reach the α-pinene isomerization conversion up to 99.9% and the selectivity of 60-80%, thus making this catalyst very promising from an industrial viewpoint. A detailed investigation of kinetic regularities including catalyst deactivation during the reaction was performed. The one-pot terpene alcohol amination, which is a promising approach to the synthesis of valuable complex amines having specific physiological properties, was investigated. The general regularities of the one-pot natural myrtenol amination in the presence of gold catalysts as well as a correlation between catalytic activity, catalyst redox treatment and the support nature were obtained. Catalytic activity and product distribution were shown to be strongly dependent on the support properties, namely acidity and basicity. The gold-zirconia (Au/ZrO2) catalyst pretreated under oxidizing atmosphere was observed to be rather active, resulting in the total conversion of myrtenol and the selectivity to the corresponding amine of about 53%. The reaction kinetics was modelled based on the mechanistic considerations with the catalyst deactivation step incorporated in the mechanism. Carvone hydrogenation over a gold catalyst was studied with the general idea of investigating both the activity of gold catalysts in competitive hydrogenation of different functional groups and developing an approach to the synthesis of valuable carvone derivatives. Gold was found to promote stereo- and chemoselective carvone hydrogenation to dihydrocarvone with a predominant formation of the trans-isomer, which generally is a novel synthetic method for an industrially valuable dihydrocarvone. The solvent effect on the catalytic activity as well as on the ratio between trans- and cis-dihydrocarvone was evaluated.

Bio-ethanol valorization towards C4s including 1-butanol over metal modified alumina and zeolite catalysts

Bio-ethanol has been used as a fuel additive in modern society aimed at reducing CO2-emissions and dependence on oil. However, ethanol is unsuitable as fuel supplement in higher proportions due to its physico-chemical properties. One option to counteract the negative effects is to upgrade ethanol in a continuous fixed bed reactor to more valuable C4 products such as 1-butanol providing chemical similarity with traditional gasoline components. Bio-ethanol based valorization products also have other end-uses than just fuel additives. E.g. 1-butanol and ethyl acetate are well characterised industrial solvents and platform chemicals providing greener alternatives. The modern approach is to apply heterogeneous catalysts in the investigated reactions. The research was concentrated on aluminium oxide (Al2O3) and zeolites that were used as catalysts and catalyst supports. The metals supported (Cu, Ni, Co) gave very different product profiles and, thus, a profound view of different catalyst preparation methods and characterisation techniques was necessary. Additionally, acidity and basicity of the catalyst surface have an important role in determining the product profile. It was observed that ordinary determination of acid strength was not enough to explain all the phenomena e.g. the reaction mechanism. One of the main findings of the thesis is based on the catalytically active site which originates from crystallite structure. As a consequence, the overall evaluation of different by-products and intermediates was carried out by combining the information. Further kinetic analysis was carried out on metal (Cu, Ni, Co) supported self-prepared alumina catalysts. The thesis gives information for further catalyst developments aimed to scale-up towards industrially feasible operations.

Design and validation of stateful composite RESTful web services

A web service is a software system that provides a machine-processable interface to the other machines over the network using different Internet protocols. They are being increasingly used in the industry in order to automate different tasks and offer services to a wider audience. The REST architectural style aims at producing scalable and extensible web services using technologies that play well with the existing tools and infrastructure of the web. It provides a uniform set of operation that can be used to invoke a CRUD interface (create, retrieve, update and delete) of a web service. The stateless behavior of the service interface requires that every request to a resource is independent of the previous ones facilitating scalability. Automated systems, e.g., hotel reservation systems, provide advanced scenarios for stateful services that require a certain sequence of requests that must be followed in order to fulfill the service goals. Designing and developing such services for advanced scenarios with REST constraints require rigorous approaches that are capable of creating web services that can be trusted for their behavior. Systems that can be trusted for their behavior can be termed as dependable systems. This thesis presents an integrated design, analysis and validation approach that facilitates the service developer to create dependable and stateful REST web services. The main contribution of this thesis is that we provide a novel model-driven methodology to design behavioral REST web service interfaces and their compositions. The behavioral interfaces provide information on what methods can be invoked on a service and the pre- and post-conditions of these methods. The methodology uses Unified Modeling Language (UML), as the modeling language, which has a wide user base and has mature tools that are continuously evolving. We have used UML class diagram and UML state machine diagram with additional design constraints to provide resource and behavioral models, respectively, for designing REST web service interfaces. These service design models serve as a specification document and the information presented in them have manifold applications. The service design models also contain information about the time and domain requirements of the service that can help in requirement traceability which is an important part of our approach. Requirement traceability helps in capturing faults in the design models and other elements of software development environment by tracing back and forth the unfulfilled requirements of the service. The information about service actors is also included in the design models which is required for authenticating the service requests by authorized actors since not all types of users have access to all the resources. In addition, following our design approach, the service developer can ensure that the designed web service interfaces will be REST compliant. The second contribution of this thesis is consistency analysis of the behavioral REST interfaces. To overcome the inconsistency problem and design errors in our service models, we have used semantic technologies. The REST interfaces are represented in web ontology language, OWL2, that can be part of the semantic web. These interfaces are used with OWL 2 reasoners to check unsatisfiable concepts which result in implementations that fail. This work is fully automated thanks to the implemented translation tool and the existing OWL 2 reasoners. The third contribution of this thesis is the verification and validation of REST web services. We have used model checking techniques with UPPAAL model checker for this purpose. The timed automata of UML based service design models are generated with our transformation tool that are verified for their basic characteristics like deadlock freedom, liveness, reachability and safety. The implementation of a web service is tested using a black-box testing approach. Test cases are generated from the UPPAAL timed automata and using the online testing tool, UPPAAL TRON, the service implementation is validated at runtime against its specifications. Requirement traceability is also addressed in our validation approach with which we can see what service goals are met and trace back the unfulfilled service goals to detect the faults in the design models. A final contribution of the thesis is an implementation of behavioral REST interfaces and service monitors from the service design models. The partial code generation tool creates code skeletons of REST web services with method pre and post-conditions. The preconditions of methods constrain the user to invoke the stateful REST service under the right conditions and the post condition constraint the service developer to implement the right functionality. The details of the methods can be manually inserted by the developer as required. We do not target complete automation because we focus only on the interface aspects of the web service. The applicability of the approach is demonstrated with a pedagogical example of a hotel room booking service and a relatively complex worked example of holiday booking service taken from the industrial context. The former example presents a simple explanation of the approach and the later worked example shows how stateful and timed web services offering complex scenarios and involving other web services can be constructed using our approach.

Through the looking glass: does our metadata make sense?

Esitys KDK-käytettävyystyöryhmän järjestämässä seminaarissa: Miten käyttäjien toiveet haastavat metatietokäytäntöjämme? / How users' expectations challenge our metadata practices? 30.9.2014.

Predicting variety composite means without diallel crossing

Prediction of variety composite means was shown to be feasible without diallel crossing the parental varieties. Thus, the predicted mean for a quantitative trait of a composite is given by: Yk = a1 sigmaVj + a2sigmaTj + a3 - a4, with coefficients a1 = (n - 2k)/k²(n - 2); a2 = 2n(k - 1)/k²(n - 2); a3 = n(k - 1)/k(n - 1)(n - 2); and a4 = n²(k - 1)/k(n - 1)(n - 2); summation is for j = 1 to k, where k is the size of the composite (number of parental varieties of a particular composite) and n is the total number of parent varieties. Vj is the mean of varieties and Tj is the mean of topcrosses (pool of varieties as tester), and and are the respective average values in the whole set. Yield data from a 7 x 7 variety diallel cross were used for the variety means and for the "simulated" topcross means to illustrate the proposed procedure. The proposed prediction procedure was as effective as the prediction based on Yk = - ( -)/k, where and refer to the mean of hybrids (F1) and parental varieties, respectively, in a variety diallel cross. It was also shown in the analysis of variance that the total sum of squares due to treatments (varieties and topcrosses) can be orthogonally partitioned following the reduced model Yjj’ = mu + ½(v j + v j’) + + h j+ h j’, thus making possible an F test for varieties, average heterosis and variety heterosis. Least square estimates of these effects are also given

Glass pipette-carbon fiber microelectrodes for evoked potential recordings

Current methods for recording field potentials with tungsten electrodes make it virtually impossible to use the same recording electrode also as a lesioning electrode, for example for histological confirmation of the recorded site, because the lesioning procedure usually wears off the tungsten tip. Therefore, the electrode would have to be replaced after each lesioning procedure, which is a very high cost solution to the problem. We present here a low cost, easy to make, high quality glass pipette-carbon fiber microelectrode that shows resistive, signal/noise and electrochemical coupling advantages over tungsten electrodes. Also, currently used carbon fiber microelectrodes often show problems with electrical continuity, especially regarding electrochemical applications using a carbon-powder/resin mixture, with consequent low performance, besides the inconvenience of handling such a mixture. We propose here a new method for manufacturing glass pipette-carbon fiber microelectrodes with several advantages when recording intracerebral field potentials

Portfolio Selection via Composite Measure Analysis: Evidence from the U.S. Stock Market

The aim of this research is to examine the pricing anomalies existing in the U.S. market during 1986 to 2011. The sample of stocks is divided into decile portfolios based on seven individual valuation ratios (E/P, B/P, S/P, EBIT/EV, EVITDA/EV, D/P, and CE/P) and price momentum to investigate the efficiency of individual valuation ratio and their combinations as portfolio formation criteria. This is the first time in financial literature when CE/P is employed as a constituent of composite value measure. The combinations are based on median scaled composite value measures and TOPSIS method. During the sample period value portfolios significantly outperform both the market portfolio and comparable glamour portfolios. The results show the highest return for the value portfolio that was based on the combination of S/P & CE/P ratios. The outcome of this research will increase the understanding on the suitability of different methodologies for portfolio selection. It will help managers to take advantage of the results of different methodologies in order to gain returns above the market.

Polysiloxane/PVA-glutaraldehyde hybrid composite as solid phase for immunodetections by ELISA

We developed an efficient method to prepare a hybrid inorganic-organic composite based on polyvinyl alcohol (PVA) and polysiloxane using the sol-gel disc technique. Antigen obtained from Yersinia pestis was covalently immobilized onto these discs with glutaraldehyde and used as solid phase in ELISA for antibody detection in serum of rabbits experimentally immunized with plague. Using 1.25 µg antigen per disc, a peroxidase conjugate dilution of 1:4,000 and a serum dilution of 1:200 were adequate for the establishment of the procedure. These values are similar to those used for PVA-glutaraldehyde discs, plasticized filter paper discs and the polyaniline-Dacron composite discs. This procedure is comparable to that which utilizes the adsorption of the antigen to conventional PVC plates, with the amount of antigen being one fourth that employed in conventional PVC plates (5 µg/well). In addition to the performance of the polysiloxane/PVA-glutaraldehyde disc as a matrix for immunodetection, its easy synthesis and low cost are additional advantages for commercial application.

The reliability of the Brazilian version of the Composite International Diagnostic Interview (CIDI 2.1)

The objective of the present study was to determine the reliability of the Brazilian version of the Composite International Diagnostic Interview 2.1 (CIDI 2.1) in clinical psychiatry. The CIDI 2.1 was translated into Portuguese using WHO guidelines and reliability was studied using the inter-rater reliability method. The study sample consisted of 186 subjects from psychiatric hospitals and clinics, primary care centers and community services. The interviewers consisted of a group of 13 lay and three non-lay interviewers submitted to the CIDI training. The average interview time was 2 h and 30 min. General reliability ranged from kappa 0.50 to 1. For lifetime diagnoses the reliability ranged from kappa 0.77 (Bipolar Affective Disorder) to 1 (Substance-Related Disorder, Alcohol-Related Disorder, Eating Disorders). Previous year reliability ranged from kappa 0.66 (Obsessive-Compulsive Disorder) to 1 (Dissociative Disorders, Maniac Disorders, Eating Disorders). The poorest reliability rate was found for Mild Depressive Episode (kappa = 0.50) during the previous year. Training proved to be a fundamental factor for maintaining good reliability. Technical knowledge of the questionnaire compensated for the lack of psychiatric knowledge of the lay personnel. Inter-rater reliability was good to excellent for persons in psychiatric practice.

Optical spectroscopy of organic material based on C60

The structure and optical properties of thin films based on C60 materials are studied. Reproducible vacuum method of thin fullerene films production with Cd impurity on Si, glass and mica surfaces is developed. Surface morphology of the films are investigated by AFM and SEM methods. The ab initio quantum - chemical calculations of the geometry, total energy and excited energy states of complex fullerene- cadmium telluride supramolecules are performed. Photoluminescence spectra of composite thin films based on C60 before and after X-ray irradiation were measured. The intensity of additional peaks is defined as the charge composition due to the type of substrate. These results are interpreted as an appearance of the dipole-allowed transitions in the fullerene excited singlet states spectrum cause of an interference with cadmium telluride. X-ray irradiated films were investigated, and additional peaks in photoluminescence spectra were detected. These peaks appear as a result of molecular complexes formation from C60CdTe mixture and dimerization of the films. Density functional B3LYP quantum-chemical calculations for C60CdTe, molecular complexes, (C60)2 and C120O dimers were performed to elucidate some experimental results.

Magnetization studies of polystyrene/multiwall carbon nanotube composite films

Lappeenranta University of Technology School of Technology Technical Physics Evgenii Zhukov MAGNETIZATION STUDIES OF POLYSTYRENE/MULTIWALL CARBON NANOTUBE COMPOSITE FILMS Master’s thesis 2015 55 pages, 41 pictures, 9 Tables. Examiners: Professor Erkki Lähderanta D.Sc. Ivan Zakharchuk Keywords: polystyrene, multi-walled carbon nanotubes, MWCNT, composite, magnetization, SQUID. In this thesis magnetic properties of polystyrene/multiwall carbon nanotube (MWCNT) composites are investigated with Quantum Design SQUID magnetometer (MPMS XL). The surface of the composite films is studied via BRUKER Multimode 8 Atomic Force Microscope, as well. The polystyrene/MWCNT composites have been prepared by the group of professor Okotrub (Physics Chemistry of Nanomaterials laboratory, Nikolaev Institute of Inorganic Chemistry, Russia). The composite films have been prepared by solution processing and stretching method. The approximate length and inner diameter of the MWCNTs used in fabrication are 260 μm and 10 nm, respectively. The content of MWCNTs is 1 and 2.5 contents percent (wt%) for studied samples. The stretching of the samples is 30% for samples with 1 and 2.5 wt% content, and one sample with 1 wt% loading of MWCNTs is 100% stretched. MWCNTs aligned perpendicular to a silicon substrate are used as a reference sample. The magnetization field dependencies of the samples exhibit hysteresis behavior. The values of saturation magnetization of composite films are much less compared to that of the reference sample. The saturation magnetization coercitivity field value drops with decrease of MWCNT content. At high magnetic fields strong presence of diamagnetism is observed. Measurements in magnetic field parallel and perpendicular to the composite plate display anisotropy with respect to the direction of stretching. Temperature dependences of magnetization for all samples display difference between zero-field cooled and field-cooled curves of magnetization. This divergence confirms the presence of magnetic interactions in the material. The atomic force microscopy study of the composites’ surfaces revealed that they are relatively smooth and the nanotubes are aligned with the axis of stretching to some extent. 

Operant serial feature-positive conditional discrimination with composite features and different topography responses

In a serial feature-positive conditional discrimination procedure the properties of a target stimulus A are defined by the presence or not of a feature stimulus X preceding it. In the present experiment, composite features preceded targets associated with two different topography operant responses (right and left bar pressing); matching and non-matching-to-sample arrangements were also used. Five water-deprived Wistar rats were trained in 6 different trials: X-R®Ar and X-L®Al, in which X and A were same modality visual stimuli and the reinforcement was contingent to pressing either the right (r) or left (l) bar that had the light on during the feature (matching-to-sample); Y-R®Bl and Y-L®Br, in which Y and B were same modality auditory stimuli and the reinforcement was contingent to pressing the bar that had the light off during the feature (non-matching-to-sample); A- and B- alone. After 100 training sessions, the animals were submitted to transfer tests with the targets used plus a new one (auditory click). Average percentages of stimuli with a response were measured. Acquisition occurred completely only for Y-L®Br+; however, complex associations were established along training. Transfer was not complete during the tests since concurrent effects of extinction and response generalization also occurred. Results suggest the use of both simple conditioning and configurational strategies, favoring the most recent theories of conditional discrimination learning. The implications of the use of complex arrangements for discussing these theories are considered.

Fiber-reinforced composite fixed dental prostheses: Studies of the materials used as pontics

Fiber-reinforced composite fixed dental prostheses – Studies of the materials used as pontics University of Turku, Faculty of Medicine, Institute of Dentistry, Department of Biomaterials Science, Finnish Doctoral Program in Oral Sciences – FINDOS, Annales Universitatis Turkuensis, Turku, Finland 2015 Fiber-reinforced composites (FRC), a non-metallic biomaterial, represent a suitable alternative in prosthetic dentistry when used as a component of fixed dental prostheses (FDPs). Some drawbacks have been identified in the clinical performance of FRC restorations, such as delamination of the veneering material and fracture of the pontic. Therefore, the current series of studies were performed to investigate the possibilities of enhancing the mechanical and physical properties of FRC FDPs by improving the materials used as pontics, to then heighten their longevity. Four experiments showed the importance of the pontic design and surface treatment in the performance of FRC FDPs. In the first, the load-bearing capacities of inlay-retained FRC FDPs with pontics of various materials and thicknesses were evaluated. Three different pontic materials were assessed with different FRC framework vertical positioning. Thicker pontics showed increased load-bearing capacities, especially ceramic pontics. A second study was completed investigating the influence of the chemical conditioning of the ridge-lap surface of acrylic resin denture teeth on their bonding to a composite resin. Increased shear bond strength demonstrated the positive influence of the pretreatment of the acrylic surfaces, indicating dissolution of the denture surfaces, and suggesting potential penetration of the monomer systems into the surface of denture teeth. A third study analyzed the penetration depth of different monomer systems on the acrylic resin denture teeth surfaces. The possibility of establishing a durable bond between acrylic pontics and FRC frameworks was demonstrated by the ability of monomers to penetrate the surface of acrylic resin denture teeth, measured by a confocal scanning type microscope. A fourth study was designed to evaluate the load-bearing capacities of FRC FDPs using the findings of the previous three studies. In this case, the performance of pre-shaped acrylic resin denture teeth used as pontics with different composite resins as filling materials was evaluated. The filling material influenced the load-bearing capacities, providing more durable FRC FDPs. It can be concluded that the mechanical and physical properties of FRC FDPs can be improved as has been shown in the development of this thesis. The improvements reported then might provide long lasting prosthetic solutions of this kind, positioning them as potentially permanent rehabilitation treatments. Key words: fiber-reinforced composite, fixed dental prostheses, inlay-retained bridges, adhesion, acrylic resin denture teeth, dental material.

Utilization of recycled mineral wool as filler in wood plastic composites

The impact of a recycled mineral wool filler on the various properties of wood plastic composites was studied and the critical factors affecting the formation of the properties were determined. An estimation of the volume of mineral wool fiber waste generated in the European Union between the years 2010-2020 was presented. Furthermore, the effect of fiber pre-treatment on the properties of the wood plastic composites were studied, and the environmental performance of a wood plastic composite containing recycled mineral fibers was assessed. The results showed that the volumes of construction and demolition waste and new mineral wool produced in the European Union are growing annually, and therefore also the volumes of recycled mineral wool waste generated are increasing. The study showed that the addition of recycled mineral wool into composites can enhance some of the mechanical properties and increase the moisture resistance properties of the composites notably. Recycled mineral wool as a filler in wood plastic composites can also improve the fire resistance properties of composites, but it does not protect the polymer matrix from pyrolysis. Fiber pre-treatment with silane solution improved some of the mechanical properties, but generally the use of maleated polypropylene as the coupling agent led to better mechanical and moisture resistance properties. The environmental performance of recycled mineral wool as the filler in wood plastic composites was superior compared to glass fibers. According to the findings, recycled mineral wool fibers can provide a technically and environmentally viable alternative to the traditional inorganic filler materials used in wood plastic composites.

Stability of volatile profile and sensory properties of passion fruit juice during storage in glass bottles

This study aimed at assessing the stability of passion fruit juice in glass bottles during a 120-day storage period, regarding its volatile compounds profile and sensory properties (aroma and flavor). Samples were obtained from a Brazilian tropical juice industry (Fortaleza, Brazil) and submitted to sensory and chromatographic analyses. The characteristic aroma and flavor of passion fruit were evaluated by a trained panel with a non-structured scale of 9 cm. The headspace volatile compounds were isolated from the product by suction and trapped in Porapak Q, analyzed through high-resolution gas chromatography and identified through gas chromatography-mass spectrometry (GC-MS). Twelve odoriferous compounds were monitored: ethyl butanoate, ethyl propanoate, 3-methyl-1-butanol, 3-methyl-2-butenol, (E)-3-hexenol, (Z)-3-hexenol, 3-methylbutyl acetate, benzaldehyde, ethyl hexanoate, hexyl acetate, limonene and furfural. The slight variations observed in the volatile profile were not enough to provoke significant changes in the characteristic aroma and flavor of the passion fruit juice.