Koboltin ja nikkelin poisto sinkkisulfaattiliuoksesta ioninvaihdolla

Työssä tutkittiin kahden silikapohjaisen erotusmateriaalin soveltuvuutta nikkelin ja koboltin poistoon sinkkisulfaattiliuoksista. Suurin osa kokeista tehtiin ioninvaihtimella, jonka funktionaalinen ryhmä on iminodietikkahappo. Vertailuerotusmateriaalin toiminta perustui adsorptioon. Liuoksina käytettiin sekä autenttista prosessiliuosta että synteettistä ZnSO4-liousta. Ioninvaihtimen kestävyyskokeissa selvisi, että tutkittu ioninvaihdin kestää hyvin sekä 60 oC lämpötilan että happamia olosuhteita. Emäksisissä liuoksissa silikarunko ei kestä. Jo 0,1 M NaOH-liuos liuottaa merkittävästi hartsia vuorokauden aikana. Vaihtimen vetyionikapasiteetiksi saatiin titrauksella 2,3 mekv/g. Tasapainokokeilla saatiin selville, että ioninvaihdin on selektiivinen nikkelille sinkin suhteen ja että selektiivisyys kasvaa liuoksen pH:n laskiessa. Koboltille ioninvaihdin ei ole selektiivinen sinkin suhteen. Mikäli sinkin pitoisuus on tuhansia kertoja nikkelin pitoisuutta suurempi, ei ioninvaihtimen Ni-selektiivisyys riitä myöskään nikkelille. Synteettisillä ZnSO4-liuoksilla tehtyjen kolonnikokeiden perusteella havaittiin, että tutkitulla ioninvaihtimella voidaan laimeista ZnSO4-liuoksista poistaa nikkeliä selektiivisesti. Nikkelin eluointi onnistui helposti 1 M H2SO4:lla. Vertailukokeen perusteella oli ioninvaihtimen Ni/Zn-selektiivisyys referenssiadsorbentin Ni/Zn-selektiivisyyttä pienempi. Ioninvaihtokolonnin mallintaminen ei onnistunut riittävän hyvin kuvaamaan ioninvaihtimessa tapahtuvaa samanaikaista ioninvaihtoa ja adsorptiota. Sen sijaan kun kolonnissa oli vertailumateriaalina käytetty adsorbentti, saatiin kolonnikokeiden tulokset mallilla hyvin ennustettua.

Characterization of the antioxidant capacity of natives fruits from the Brazilian Amazon Region

The objective of the present study was to characterize the chemistry and the antioxidant capacity in 8 species of native fruits from Amazonia. All the fruits were collected at full physiological and commercial maturity from properties located at: Boa Vista / RR, São Luiz do Anauá / RR, Manaus / AM, and Belém / PA. At the end of the experiment, the functional pattern for the camu-camu fruits showed that the total phenolic and ascorbic acid content and antioxidant assays were superior compared to the other samples. Despite the functional losses detected for the freeze-dried samples of the camu-camu fruit, all the other freeze-dried samples kept under -20ºC showed appropriate stability for long-term storage. In addition, it was also observed that fruit peel showed higher antioxidant activity than pulp or samples containing peel and pulp tissues in the same extract. When the ratio between the ORAC and total phenolic assays were observed, the uxi fruit demonstrated the highest antioxidant power compared to the other fruits studied, despite its relatively low levels of phenolic compound content and ORAC values. This means that there is a relevant contribution of these phenolic compounds to the antioxidant activity of uxi fruit.

Intrinsic ROS-production capacity of nanoparticles

Engineered nanomaterials (ENMs) exhibit special physicochemical properties and thus are finding their way into an increasing number of industries, enabling products with improved properties. Their increased use brings a greater likelihood of exposure to the nanoparticles (NPs) that could be released during the life cycle of nano-abled products. The field of nanotoxicology has emerged as a consequence of the development of these novel materials, and it has gained ever more attention due to the urgent need to gather information on exposure to them and to understand the potential hazards they engender. However, current studies on nanotoxicity tend to focus on pristine ENMs, and they use these toxicity results to generalize risk assessments on human exposure to NPs. ENMs released into the environment can interact with their surroundings, change characteristics and exhibit toxicity effects distinct from those of pristine ENMs. Furthermore, NPs' large surface areas provide extra-large potential interfaces, thus promoting more significant interactions between NPs and other co-existing species. In such processes, other species can attach to a NP's surface and modify its surface functionality, in addition to the toxicity in normally exhibits. One particular occupational health scenario involves NPs and low-volatile organic compounds (LVOC), a common type of pollutant existing around many potential sources of NPs. LVOC can coat a NP's surface and then dominate its toxicity. One important mechanism in nanotoxicology is the creation of reactive oxygen species (ROS) on a NP's surface; LVOC can modify the production of these ROS. In summary, nanotoxicity research should not be limited to the toxicity of pristine NPs, nor use their toxicity to evaluate the health effects of exposure to environmental NPs. Instead, the interactions which NPs have with other environmental species should also be considered and researched. The potential health effects of exposure to NPs should be derived from these real world NPs with characteristics modified by the environment and their distinct toxicity. Failure to suitably address toxicity results could lead to an inappropriate treatment of nano- release, affect the environment and public health and put a blemish on the development of sustainable nanotechnologies as a whole. The main objective of this thesis is to demonstrate a process for coating NP surfaces with LVOC using a well-controlled laboratory design and, with regard to these NPs' capacity to generate ROS, explore the consequences of changing particle toxicity. The dynamic coating system developed yielded stable and replicable coating performance, simulating an important realistic scenario. Clear changes in the size distribution of airborne NPs were observed using a scanning mobility particle sizer, were confirmed using both liquid nanotracking analyses and transmission electron microscopy (TEM) imaging, and were verified thanks to the LVOC coating. Coating thicknesses corresponded to the amount of coating material used and were controlled using the parameters of the LVOC generator. The capacity of pristine silver NPs (Ag NPs) to generate ROS was reduced when they were given a passive coating of inert paraffin: this coating blocked the reactive zones on the particle surfaces. In contrast, a coating of active reduced-anthraquinone contributed to redox reactions and generated ROS itself, despite the fact that ROS generation due to oxidation by Ag NPs themselves was quenched. Further objectives of this thesis included development of ROS methodology and the analysis of ROS case studies. Since the capacity of NPs to create ROS is an important effect in nanotoxicity, we attempted to refine and standardize the use of 2'7-dichlorodihydrofluorescin (DCFH) as a chemical tailored for the characterization of NPs' capacity for ROS generation. Previous studies had reported a wide variety of results, which were due to a number of insufficiently well controlled factors. We therefore cross-compared chemicals and concentrations, explored ways of dispersing NP samples in liquid solutions, identified sources of contradictions in the literature and investigated ways of reducing artificial results. The most robust results were obtained by sonicating an optimal sample of NPs in a DCFH-HRP solution made of 5,M DCFH and 0.5 unit/ml horseradish peroxidase (HRP). Our findings explained how the major reasons for previously conflicting results were the different experimental approaches used and the potential artifacts appearing when using high sample concentrations. Applying our advanced DCFH protocol with other physicochemical characterizations and biological analyses, we conducted several case studies, characterizing aerosols and NP samples. Exposure to aged brake wear dust engenders a risk of potential deleterious health effects in occupational scenarios. We performed microscopy and elemental analyses, as well as ROS measurements, with acellular and cellular DCFH assays. TEM images revealed samples to be heterogeneous mixtures with few particles in the nano-scale. Metallic and non-metallic elements were identified, primarily iron, carbon and oxygen. Moderate amounts of ROS were detected in the cell-free fluorescent tests; however, exposed cells were not dramatically activated. In addition to their highly aged state due to oxidation, the reason aged brake wear samples caused less oxidative stress than fresh brake wear samples may be because of their larger size and thus smaller relative reactive surface area. Other case studies involving welding fumes and differently charged NPs confirmed the performance of our DCFH assay and found ROS generation linked to varying characteristics, especially the surface functionality of the samples. Les nanomatériaux manufacturés (ENM) présentent des propriétés physico-chimiques particulières et ont donc trouvés des applications dans un nombre croissant de secteurs, permettant de réaliser des produits ayant des propriétés améliorées. Leur utilisation accrue engendre un plus grand risque pour les êtres humains d'être exposés à des nanoparticules (NP) qui sont libérées au long de leur cycle de vie. En conséquence, la nanotoxicologie a émergé et gagné de plus en plus d'attention dû à la nécessité de recueillir les renseignements nécessaires sur l'exposition et les risques associés à ces nouveaux matériaux. Cependant, les études actuelles sur la nanotoxicité ont tendance à se concentrer sur les ENM et utiliser ces résultats toxicologiques pour généraliser l'évaluation des risques sur l'exposition humaine aux NP. Les ENM libérés dans l'environnement peuvent interagir avec l'environnement, changeant leurs caractéristiques, et montrer des effets de toxicité distincts par rapport aux ENM originaux. Par ailleurs, la grande surface des NP fournit une grande interface avec l'extérieur, favorisant les interactions entre les NP et les autres espèces présentes. Dans ce processus, d'autres espèces peuvent s'attacher à la surface des NP et modifier leur fonctionnalité de surface ainsi que leur toxicité. Un scénario d'exposition professionnel particulier implique à la fois des NP et des composés organiques peu volatils (LVOC), un type commun de polluant associé à de nombreuses sources de NP. Les LVOC peuvent se déposer sur la surface des NP et donc dominer la toxicité globale de la particule. Un mécanisme important en nanotoxicologie est la création d'espèces réactives d'oxygène (ROS) sur la surface des particules, et les LVOC peuvent modifier cette production de ROS. En résumé, la recherche en nanotoxicité ne devrait pas être limitée à la toxicité des ENM originaux, ni utiliser leur toxicité pour évaluer les effets sur la santé de l'exposition aux NP de l'environnement; mais les interactions que les NP ont avec d'autres espèces environnementales doivent être envisagées et étudiées. Les effets possibles sur la santé de l'exposition aux NP devraient être dérivés de ces NP aux caractéristiques modifiées et à la toxicité distincte. L'utilisation de résultats de toxicité inappropriés peut conduire à une mauvaise prise en charge de l'exposition aux NP, de détériorer l'environnement et la santé publique et d'entraver le développement durable des industries de la nanotechnologie dans leur ensemble. L'objectif principal de cette thèse est de démontrer le processus de déposition des LVOC sur la surface des NP en utilisant un environnement de laboratoire bien contrôlé et d'explorer les conséquences du changement de toxicité des particules sur leur capacité à générer des ROS. Le système de déposition dynamique développé a abouti à des performances de revêtement stables et reproductibles, en simulant des scénarios réalistes importants. Des changements clairs dans la distribution de taille des NP en suspension ont été observés par spectrométrie de mobilité électrique des particules, confirmé à la fois par la méthode dite liquid nanotracking analysis et par microscopie électronique à transmission (MET), et a été vérifié comme provenant du revêtement par LVOC. La correspondance entre l'épaisseur de revêtement et la quantité de matériau de revêtement disponible a été démontré et a pu être contrôlé par les paramètres du générateur de LVOC. La génération de ROS dû aux NP d'argent (Ag NP) a été diminuée par un revêtement passif de paraffine inerte bloquant les zones réactives à la surface des particules. Au contraire, le revêtement actif d'anthraquinone réduit a contribué aux réactions redox et a généré des ROS, même lorsque la production de ROS par oxydation des Ag NP avec l'oxygène a été désactivé. Les objectifs associés comprennent le développement de la méthodologie et des études de cas spécifique aux ROS. Etant donné que la capacité des NP à générer des ROS contribue grandement à la nanotoxicité, nous avons tenté de définir un standard pour l'utilisation de 27- dichlorodihydrofluorescine (DCFH) adapté pour caractériser la génération de ROS par les NP. Des etudes antérieures ont rapporté une grande variété de résultats différents, ce qui était dû à un contrôle insuffisant des plusieurs facteurs. Nous avons donc comparé les produits chimiques et les concentrations utilisés, exploré les moyens de dispersion des échantillons HP en solution liquide, investigué les sources de conflits identifiées dans les littératures et étudié les moyens de réduire les résultats artificiels. De très bon résultats ont été obtenus par sonication d'une quantité optimale d'échantillons de NP en solution dans du DCFH-HRP, fait de 5 nM de DCFH et de 0,5 unité/ml de Peroxydase de raifort (HRP). Notre étude a démontré que les principales raisons causant les conflits entre les études précédemment conduites dans la littérature étaient dues aux différentes approches expérimentales et à des artefacts potentiels dus à des concentrations élevées de NP dans les échantillons. Utilisant notre protocole DCFH avancé avec d'autres caractérisations physico-chimiques et analyses biologiques, nous avons mené plusieurs études de cas, caractérisant les échantillons d'aérosols et les NP. La vielle poussière de frein en particulier présente un risque élevé d'exposition dans les scénarios professionnels, avec des effets potentiels néfastes sur la santé. Nous avons effectué des analyses d'éléments et de microscopie ainsi que la mesure de ROS avec DCFH cellulaire et acellulaire. Les résultats de MET ont révélé que les échantillons se présentent sous la forme de mélanges de particules hétérogènes, desquels une faible proportion se trouve dans l'échelle nano. Des éléments métalliques et non métalliques ont été identifiés, principalement du fer, du carbone et de l'oxygène. Une quantité modérée de ROS a été détectée dans le test fluorescent acellulaire; cependant les cellules exposées n'ont pas été très fortement activées. La raison pour laquelle les échantillons de vielle poussière de frein causent un stress oxydatif inférieur par rapport à la poussière de frein nouvelle peut-être à cause de leur plus grande taille engendrant une surface réactive proportionnellement plus petite, ainsi que leur état d'oxydation avancé diminuant la réactivité. D'autres études de cas sur les fumées de soudage et sur des NP différemment chargées ont confirmé la performance de notre test DCFH et ont trouvé que la génération de ROS est liée à certaines caractéristiques, notamment la fonctionnalité de surface des échantillons.

Oxygen adsorption on clean and oxygen precovered Cu(100)

Kuparipinnan hapettumisen alkuvaiheet ovat vielä nykyisin tutkijoille epäselviä. Kuitenkin, jotta hapettumisprosessia voitaisiin säädellä, on sangen tärkeää ymmärtää mistä varsinainen hapettuminen lähtee liikkeelle ja mitkä ovat hapettumisen seuraavat vaiheet. Tähän kysymykseen haetaan vastauksia tässä työssä käyttäen puhtaasti teoreettisia menetelmiä pinnan käsittelyssä. Aikaisempien teoreettisten ja kokeellisten tutkimusten välillä on pieni ristiriita liittyen hapen tarttumistodennäköisyyteen. Teoreettisten tutkimusten mukaan happi ei puhtaalle pinnalle tullessaan näe potentiaalivallia, mutta kokeelliset tutkimukset osoittavat sellaisen kuitenkin olevan. Tuohon ristiriitaan pureudutaan käyttäen aikaisemmista laskuista poikkeavaa kvanttimekaaniseen molekyylidynamiikkaan perustuvaa lähestymistapaa. Työssä havaitaan, että aikaisemmin yleisesti käytetty menetelmä hukkaa huomattavan määrän tietoa ja siten tutkijat eivät voi ainoastaan tyytyä tarkastelemaan kyseisellä menetelmällä saatuja tuloksia. Kuparipinnalle havaittiin, että korkeilla molekyylin kineettisen energian arvolla aikaisemmin suoritetut laskut hajottavista trajektoreista pitävät paikkansa, mutta matalilla kineettisen energian arvoilla molekyyli kohtaa erittäin voimakkaan ``steering'' vaikutuksen ja trajektorit joiden piti olla hajottavia johtavatkin molekulaariseen adsorptioon. Kun hapen konsentraatio pinnalla on suurempi kuin 0.5 ML, pinta rekonstruoituu. Myös rekonstruktion jälkeistä pintaa on tutkittu samanlaisilla menetelmillä kuin puhdasta pintaa. Rekonstruoituneelle pinnalle ei löydetty hajottavia trajektoreita ja havaittiin, että hapelle annetun kineettisen energian matalilla arvoilla myös tässä tapauksessa on erittäin voimakas ``steering'' vaikutus.

The Human Mesenchymal Stromal Cell-Derived Osteocyte Capacity to Modulate Dendritic Cell Functions Is Strictly Dependent on the Culture System.

In vitro differentiation of mesenchymal stromal cells (MSC) into osteocytes (human differentiated osteogenic cells, hDOC) before implantation has been proposed to optimize bone regeneration. However, a deep characterization of the immunological properties of DOC, including their effect on dendritic cell (DC) function, is not available. DOC can be used either as cellular suspension (detached, Det-DOC) or as adherent cells implanted on scaffolds (adherent, Adh-DOC). By mimicking in vitro these two different routes of administration, we show that both Det-DOC and Adh-DOC can modulate DC functions. Specifically, the weak downregulation of CD80 and CD86 caused by Det-DOC on DC surface results in a weak modulation of DC functions, which indeed retain a high capacity to induce T-cell proliferation and to generate CD4(+)CD25(+)Foxp3(+) T cells. Moreover, Det-DOC enhance the DC capacity to differentiate CD4(+)CD161(+)CD196(+) Th17-cells by upregulating IL-6 secretion. Conversely, Adh-DOC strongly suppress DC functions by a profound downregulation of CD80 and CD86 on DC as well as by the inhibition of TGF-β production. In conclusion, we demonstrate that different types of DOC cell preparation may have a different impact on the modulation of the host immune system. This finding may have relevant implications for the design of cell-based tissue-engineering strategies.

Anti-MPER antibodies with heterogeneous neutralization capacity are detectable in most untreated HIV-1 infected individuals

Background The MPER region of the HIV-1 envelope glycoprotein gp41 is targeted by broadly neutralizing antibodies. However, the localization of this epitope in a hydrophobic environment seems to hamper the elicitation of these antibodies in HIV infected individuals. We have quantified and characterized anti-MPER antibodies by ELISA and by flow cytometry using a collection of mini gp41-derived proteins expressed on the surface of 293T cells. Longitudinal plasma samples from 35 HIV-1 infected individuals were assayed for MPER recognition and MPER-dependent neutralizing capacity using HIV-2 viruses engrafted with HIV-1 MPER sequences. Results Miniproteins devoid of the cysteine loop of gp41 exposed the MPER on 293T cell membrane. Anti-MPER antibodies were identified in most individuals and were stable when analyzed in longitudinal samples. The magnitude of the responses was strongly correlated with the global response to the HIV-1 envelope glycoprotein, suggesting no specific limitation for anti-MPER antibodies. Peptide mapping showed poor recognition of the C-terminal MPER moiety and a wide presence of antibodies against the 2F5 epitope. However, antibody titers failed to correlate with 2F5-blocking activity and, more importantly, with the specific neutralization of HIV-2 chimeric viruses bearing the HIV-1 MPER sequence; suggesting a strong functional heterogeneity in anti-MPER humoral responses. Conclusions Anti-MPER antibodies can be detected in the vast majority of HIV-1 infected individuals and are generated in the context of the global anti-Env response. However, the neutralizing capacity is heterogeneous suggesting that eliciting neutralizing anti-MPER antibodies by immunization might require refinement of immunogens to skip nonneutralizing responses.

Assessing an Adolescent's Capacity for Autonomous Decision-Making in Clinical Care.

The purpose of this article is to provide policy guidance on how to assess the capacity of minor adolescents for autonomous decision-making without a third party authorization, in the field of clinical care. In June 2014, a two-day meeting gathered 20 professionals from all continents, working in the field of adolescent medicine, neurosciences, developmental and clinical psychology, sociology, ethics, and law. Formal presentations and discussions were based on a literature search and the participants' experience. The assessment of adolescent decision-making capacity includes the following: (1) a review of the legal context consistent with the principles of the Convention on the Rights of the Child; (2) an empathetic relationship between the adolescent and the health care professional/team; (3) the respect of the adolescent's developmental stage and capacities; (4) the inclusion, if relevant, of relatives, peers, teachers, or social and mental health providers with the adolescent's consent; (5) the control of coercion and other social forces that influence decision-making; and (6) a deliberative stepwise appraisal of the adolescent's decision-making process. This stepwise approach, already used among adults with psychiatric disorders, includes understanding the different facets of the given situation, reasoning on the involved issues, appreciating the outcomes linked with the decision(s), and expressing a choice. Contextual and psychosocial factors play pivotal roles in the assessment of adolescents' decision-making capacity. The evaluation must be guided by a well-established procedure, and health professionals should be trained accordingly. These proposals are the first to have been developed by a multicultural, multidisciplinary expert panel.

Adsorption energy and spin state of first-row transition metals adsorbed on MgO(100)

Slab and cluster model spin-polarized calculations have been carried out to study various properties of isolated first-row transition metal atoms adsorbed on the anionic sites of the regular MgO(100) surface. The calculated adsorption energies follow the trend of the metal cohesive energies, indicating that the changes in the metal-support and metal-metal interactions along the series are dominated by atomic properties. In all cases, except for Ni at the generalized gradient approximation level, the number of unpaired electron is maintained as in the isolated metal atom. The energy required to change the atomic state from high to low spin has been computed using the PW91 and B3LYP density-functional-theory-based methods. PW91 fails to predict the proper ground state of V and Ni, but the results for the isolated and adsorbed atom are consistent within the method. B3LYP properly predicts the ground state of all first-row transition atom the high- to low-spin transition considered is comparable to experiment. In all cases, the interaction with the surface results in a reduced high- to low-spin transition energy.

Characterization and genetic mapping of eceriferum-ym (cer-ym), a cutin deficient barley mutant with impaired leaf water retention capacity.

The cuticle covers the aerial parts of land plants, where it serves many important functions, including water retention. Here, a recessive cuticle mutant, eceriferum-ym (cer-ym), of Hordeum vulgare L. (barley) showed abnormally glossy spikes, sheaths, and leaves. The cer-ym mutant plant detached from its root system was hypersensitive to desiccation treatment compared with wild type plants, and detached leaves of mutant lost 41.8% of their initial weight after 1 h of dehydration under laboratory conditions, while that of the wild type plants lost only 7.1%. Stomata function was not affected by the mutation, but the mutant leaves showed increased cuticular permeability to water, suggesting a defective leaf cuticle, which was confirmed by toluidine blue staining. The mutant leaves showed a substantial reduction in the amounts of the major cutin monomers and a slight increase in the main wax component, suggesting that the enhanced cuticle permeability was a consequence of cutin deficiency. cer-ym was mapped within a 0.8 cM interval between EST marker AK370363 and AK251484, a pericentromeric region on chromosome 4H. The results indicate that the desiccation sensitivity of cer-ym is caused by a defect in leaf cutin, and that cer-ym is located in a chromosome 4H pericentromeric region.

Streptavidin - A Versatile Binding Protein for Solid-Phase Immunoassays

Streptavidin, a tetrameric protein secreted by Streptomyces avidinii, binds tightly to a small growth factor biotin. One of the numerous applications of this high-affinity system comprises the streptavidin-coated surfaces of bioanalytical assays which serve as universal binders for straightforward immobilization of any biotinylated molecule. Proteins can be immobilized with a lower risk of denaturation using streptavidin-biotin technology in contrast to direct passive adsorption. The purpose of this study was to characterize the properties and effects of streptavidin-coated binding surfaces on the performance of solid-phase immunoassays and to investigate the contributions of surface modifications. Various characterization tools and methods established in the study enabled the convenient monitoring and binding capacity determination of streptavidin-coated surfaces. The schematic modeling of the monolayer surface and the quantification of adsorbed streptavidin disclosed the possibilities and the limits of passive adsorption. The defined yield of 250 ng/cm² represented approximately 65 % coverage compared with a modelled complete monolayer, which is consistent with theoretical surface models. Modifications such as polymerization and chemical activation of streptavidin resulted in a close to 10-fold increase in the biotin-binding densities of the surface compared with the regular streptavidin coating. In addition, the stability of the surface against leaching was improved by chemical modification. The increased binding densities and capacities enabled wider high-end dynamic ranges in the solid-phase immunoassays, especially when using the fragments of the capture antibodies instead of intact antibodies for the binding of the antigen. The binding capacity of the streptavidin surface was not, by definition, predictive of the low-end performance of the immunoassays nor the assay sensitivity. Other features such as non-specific binding, variation and leaching turned out to be more relevant. The immunoassays that use a direct surface readout measurement of time-resolved fluorescence from a washed surface are dependent on the density of the labeled antibodies in a defined area on the surface. The binding surface was condensed into a spot by coating streptavidin in liquid droplets into special microtiter wells holding a small circular indentation at the bottom. The condensed binding area enabled a denser packing of the labeled antibodies on the surface. This resulted in a 5 - 6-fold increase in the signal-to-background ratios and an equivalent improvement in the detection limits of the solid-phase immunoassays. This work proved that the properties of the streptavidin-coated surfaces can be modified and that the defined properties of the streptavidin-based immunocapture surfaces contribute to the performance of heterogeneous immunoassays.

Evolution of Ba and Role of Absorptive Capacity in Collaboration between MNCs and Chinese Universities in China

During the recent years, collaboration with Chinese universities has aroused growing interest among multinational companies (MNCs). Cross-cultural university-industry (U-I) collaboration creates various challenges in collaborative knowledge creation and innovation due to the differences e.g. between university and company motivation, objectives and activities. Also different values, norms, and means of actions result often in collisions and misunderstandings. This thesis examines the establishment of the relationships and the evolution of the collaboration between MNCs and Chinese universities. Empirical findings underscore that the partners in collaboration are required to possess research interest as well as capability to acquire, assimilate and exploit new external knowledge. Time and communication have a critical role in the evolution of the collaboration. In China the personal relationships, guanxi, play an important role. Collaborative knowledge creation requires a platform, Ba, which enables the creation of common understanding, commitment, trust and mutual respect. Empirical data has been collected through interviewing company experts and academe of Chinese universities from ICT and forest industries as well as attending panel discussions and meetings with the experts from the field of study.

Germaniumin talteenotto ioninvaihtohartseilla

Työssä tutkittiin laboratorio-olosuhteissa germaniumin talteenottoa happamista hydrometallurgisista sulfaattiliuoksista käyttäen kaupallisia ioninvaihtohartseja. Germaniumin talteenottoa tutkittiin sekä tasapaino- että kolonnikokein syöttöliuoksista joiden pH oli alueella 0,8–3,0. Tutkituista hartseista parhaiten germanium voitiin erottaa käyttäen emäsmuotoista N-metyyli-D-glukamiini-tyyppistä ioninvaihtohartsia (esim. Rohm & Haasin IRA-743). Germaniumille määritettiin adsorptioisotermit tasapainokokein sekä emäs- että happomuotoisilla hartseilla. Adsorptioisotermien perusteella parhaiten germa-niumia adsorboi emäsmuotoinen IRA-743-hartsi kun liuoksen alku-pH oli tutkitun alueen korkein. Lämpötilassa 25 °C kapasiteetti oli 114 mg Ge/g. Tasapainokokein määritettiin emäsmuotoisilla hartseilla germaniumin lisäksi myös kuparia ja kobolttia sisältävillä liuoksilla Ge:n jakaantumisvakiot sekä erotustekijät Ge/Cu ja Ge/Co. Havaittiin, että IRA-743:lla alku-pH:ssa 3,0 Ge:n jakaantumisvakiot sekä erotustekijät Ge/Cu ja Ge/Co olivat selvästi suuremmat kuin muilla tutkituilla hartseilla. Arseenin, nikkelin, sinkin ja rauta(III):n adsorboitumista emäsmuotoiseen IRA-743:een tutkittiin monimetallisella liuoksella syöttöliuoksen pH:n ollessa alueella 1,4–3,6. Kokeissa havaittiin, että hartsi adsorboi hieman Ni:a ja Zn:a tasapaino-pH:n ollessa yli 5,5. Arseenia ei tutkitulla pH-alueella havaittu adsorboituvan. Lisäksi huomattiin, että rauta alkaa saostua pH:n ollessa hieman alle kolme. Kolonnikokeissa havaittiin, että emäsmuotoinen IRA-743-hartsi toimii hyvin germaniumin talteenotossa myös kolonnissa. Pelkästään germaniumia ja kobolttia sisältäneellä liuoksella hartsin dynaamiseksi kapasiteetiksi saatiin 54 mg Ge/g. Germaniumin eluointi IRA-743:sta onnistui parhaiten 0,5 M H2SO4:lla. Kolonnikokeita IRA-743:lla ajettiin myös monimetallisilla liuoksilla, mutta silloin havaittiin hartsin kapasiteetin pienenevän hartsin myrkyttymisen takia.