Kapillaarielektroforeesin soveltaminen uuttofaasin koostumuksen analysointiin

Työn tarkoituksena oli löytää kapillaarielektroforeesimenetelmä (CE), joka soveltuisi metallien neste-nesteuutossa käytettävien orgaanisten uuttofaasien koostumuksen analysointiin. Kapillaarielektroforeesissa käytetyn elektrolyyttiliuoksen analyytti-kohtaista optimointia ei tässä työssä tehty, vaan liikkeelle lähdettiin fenoleille tarkoitetulla menetelmällä. Tarkasteltavia uuttoreagenssiryhmiä olivat hydroksi-oksiimit sekä fosfiinihappo- ja fosforihappopohjaiset reagenssit. Tutkittavia kaupallisia laimentimia olivat Orfom SX 11 ja Shellsol D70. Lisäksi tutkittiin kahta modifiointiainetta, TOPOa (tri-n-oktyylifosfiinioksidi) ja TXIB:tä (2,2,4-trimetyyli-1,3-pentaanidiolidi-isobutyraatti). Työssä tavoiteltiin kapillaarielektroforeesin hyötyjä erityisesti hydrometallurgisessa teollisuudessa. Suurimpana hyötynä ennakoitiin mahdollisuus analysoida suuria molekyylejä, kuten uuttoreagenssi-metallikomplekseja, joita ei pystytä analysoimaan kaasukromatografilla (GC). Näytteet voidaan myös analysoida ilman hidasta ja usein ei-kvantitatiivista derivatisointia. Kirjallisuudesta ei löytynyt aiempia artikkeleita CE:n soveltamisesta kyseisille aiheille. Kapillaarielektroforeesianalyyseissa pystyttiin esimerkiksi havaitsemaan hydroksi-oksiimin kuparikompleksi orgaanisessa faasissa. Seulonta-ajoissa yleisenä ongelmana oli kuitenkin tulosten heikko toistettavuus. Kapillaari-elektro-foreesi-menetelmä tarjoaa selvästi mahdollisuuksia tulevaisuudessa, mutta vielä sillä ei päästy luotettavaan toistoon sähkökentän häiriöiden ja elektrolyyttiliuoksen riittämättömän optimoinnin vuoksi. Lisäksi teollisissa olosuhteissa käytetyille autenttisille hydroksioksiimi- ja fosfiinihapponäytteille tehtiin perinteisiä kaasukromatografia-analyysejä, joiden perusteella voitiin nähdä uuttofaasin koostumuksen muuttuneen prosessissa. Hapettuminen sekä eri hydrolyysireaktiot ovat tärkeimmät syyt reagenssien ja laimentimien muuttumiselle. Näitä hajoamistuotteita ei tässä työssä onnistuttu analysoimaan kapillaarielektroforeesilla.

Recovery and refining of manganese as by-product from hydrometallurgical processes

The consumption of manganese is increasing, but huge amounts of manganese still end up in waste in hydrometallurgical processes. The recovery of manganese from multi-metal solutions at low concentrations may not be economical. In addition, poor iron control typically prevents the production of high purity manganese. Separation of iron from manganese can be done with chemical precipitation or solvent extraction methods. Combined carbonate precipitation with air oxidation is a feasible method to separate iron and manganese due to the fast kinetics, good controllability and economical reagents. In addition the leaching of manganese carbonate is easier and less acid consuming than that of hydroxide or sulfide precipitates. Selective iron removal with great efficiency from MnSO4 solution is achieved by combined oxygen or air oxidation and CaCO3 precipitation at pH > 5.8 and at a redox potential of > 200 mV. In order to avoid gypsum formation, soda ash should be used instead of limestone. In such case, however, extra attention needs to be paid on the reagents mole ratios in order to avoid manganese coprecipitation. After iron removal, pure MnSO4 solution was obtained by solvent extraction using organophosphorus reagents, di-(2-ethylhexyl)phosphoric acid (D2EHPA) and bis(2,4,4- trimethylpentyl)phosphinic acid (CYANEX 272). The Mn/Ca and Mn/Mg selectivities can be increased by decreasing the temperature from the commonly used temperatures (40 –60oC) to 5oC. The extraction order of D2EHPA (Ca before Mn) at low temperature remains unchanged but the lowering of temperature causes an increase in viscosity and slower phase separation. Of these regents, CYANEX 272 is selective for Mn over Ca and, therefore, it would be the better choice if there is Ca present in solution. A three-stage Mn extraction followed by a two-stage scrubbing and two-stage sulfuric acid stripping is an effective method of producing a very pure MnSO4 intermediate solution for further processing. From the intermediate MnSO4 some special Mn- products for ion exchange applications were synthesized and studied. Three types of octahedrally coordinated manganese oxide materials as an alternative final product for manganese were chosen for synthesis: layer structured Nabirnessite, tunnel structured Mg-todorokite and K-kryptomelane. As an alternative source of pure MnSO4 intermediate, kryptomelane was synthesized by using a synthetic hydrometallurgical tailings. The results show that the studied OMS materials adsorb selectively Cu, Ni, Cd and K in the presence of Ca and Mg. It was also found that the exchange rates were reasonably high due to the small particle dimensions. Materials are stable in the studied conditions and their maximum Cu uptake capacity was 1.3 mmol/g. Competitive uptake of metals and acid was studied using equilibrium, batch kinetic and fixed-bed measurements. The experimental data was correlated with a dynamic model, which also accounts for the dissolution of the framework manganese. Manganese oxide micro-crystals were also bound onto silica to prepare a composite material having a particle size large enough to be used in column separation experiments. The MnOx/SiO2 ratio was found to affect significantly the properties of the composite. The higher the ratio, the lower is the specific surface area, the pore volume and the pore size. On the other hand, higher amount of silica binder gives composites better mechanical properties. Birnesite and todorokite can be aggregated successfully with colloidal silica at pH 4 and with MnO2/SiO2 weight ratio of 0.7. The best gelation and drying temperature was 110oC and sufficiently strong composites were obtained by additional heat-treatment at 250oC for 2 h. The results show that silica–supported MnO2 materials can be utilized to separate copper from nickel and cadmium. The behavior of the composites can be explained reasonably well with the presented model and the parameters estimated from the data of the unsupported oxides. The metal uptake capacities of the prepared materials were quite small. For example, the final copper loading was 0.14 mmol/gMnO2. According to the results the special MnO2 materials are potential for a specific environmental application to uptake harmful metal ions.

Composition of Hawthorn (Crataegus spp.) Fruits and Leaves and emblic Leafflower (Phyllanthus emblica) Fruits

Hawthorn (Crataegus sp.) is widely distributed in the northern hemisphere (Asia, Europe and North America). It has been used as a medicinal material and food for hundreds of years both in Europe and in China. Clinical investigations and other research suggest that extracts of hawthorn fruits and leaves have multiple health effects including hypolipidaemic, anti-atherosclerotic, hypotensive, cardioprotective and blood vessel relaxing activities. Hawthorn fruit extracts have also displayed antioxidant and radical scavenging activities. Emblic leafflower fruit (Phyllanthus emblica) is widely used in Chinese and Indian traditional medicine. It has been found to have anti-cancer, hypoglycaemic and hypolipidaemic activities as well as cardioprotective effects and antioxidant activity. The fruit is currently used as a functional food targeted at obese people in China. Phenolic compounds, procyanidins (PCs), flavonols and C-glycosyl flavones in hawthorn and hydrolysable tannins in emblic leafflower fruits are considered among the major bioactive compounds in these berries. Moreover, hawthorn and emblic leafflower fruits are rich in vitamin C, triterpenoids, fruit acids, sugar alcohols and some other components with beneficial effects on the health of human beings. The aim of the thesis work was to characterise the major phenolic compounds in hawthorn fruits and leaves and emblic leafflower fruits as well as other components contributing to the nutritional profile and sensory properties of hawthorn fruits. Differences in the content and compositional profile of the major phenolic compounds, sugars, acids and sugar alcohols within various origins and species of hawthorn were also investigated. Acids, sugars and sugar alcohols in the fruits of different origins/cultivars belonging to three species (C. pinnatifida, C. brettschneideri and C. scabrifolia) of hawthorn were analysed by gas chromatography (GC-FID) and mass spectrometry (Publication I). Citric acid, quinic acid, malic acid, fructose, glucose, sorbitol and myo-inositol were found in all the subspecies. Sucrose was present only in C. scabrifolia and three cultivars of C. pinnatifida var. major. Forty-two phenolic compounds were identified/tentatively identified in fruits of C. pinnatifida var. major by polyamide column chromatography combined with high-performance liquid chromatograph-electrospray ionisation mass spectrometry (HPLC-ESI-MS) (Publication II). Ideain, chlorogenic acid, procyanidin (PC) B2, (-)-epicatechin, hyperoside and isoquercitrin were the major phenolic components identified. In addition, 35 phenolic compounds were tentatively identified based on UV and mass spectra. Eleven major phenolic compounds (hyperoside, isoquercitrin, chlorogenic acid, ideain, (-)-epicatechin, two PC dimers, three PC trimers and a PC dimer-hexoside) were quantified in the fruits of 22 cultivars/origins of three species of Chinese hawthorn by HPLC-ESI-MS with single ion recording function (SIR) (Publication III). The fruits of the hawthorn cultivars/origins investigated fell into two groups, one rich in sugars and flavonols, the other rich in acids and procyanidins. Based on the compositional features, different biological activities and sensory properties may be expected between cultivars/origins of the two groups. The results suggest that the contents of phenolic compounds, acids, sugars and sugar alcohols may be used as chemotaxonomic information distinguishing the hawthorn species from each other. Phenolic compounds in fruits and leaves of C. grayana and their changes during fruit ripening/harvesting were investigated using HPLC-UV-ESI-MS (Publication IV). (-)-Epicatechin, PC B2 and C1, hyperoside and a quercetin-pentoside were the major phenolic compounds in both fruits and leaves. Three C-glycosyl flavones (a luteolin-C-hexoside, a methyl luteolin-C-hexoside and an apigenin-C-hexoside) were present in leaves in abundance, but only at trace levels in fruits. Ideain and 5-O-caffeoylquinic acid were found in fruits only. Additionally, eleven phenolic compounds were identified/tentatively identified in both leaves and fruits (three B-type PC trimers, two B-type PC tetramers, a quercetin-rhamnosylhexoside, a quercetin-pentoside, a methoxykaempferol-methylpentosylhexoside, a quercetin-hexoside acetate, a methoxykaempferol-pentoside, chlorogenic acid and an unknown hydroxycinnamic acid derivative). The total content of phenolic compounds reached the highest level by the end of August in fruits and by the end of September in leaves. The compositional profiles of phenolic compounds in fruits and leaves of C. grayana were different from those of C. pinnatifida, C. brettschneideri, C. scabrifolia, C. pinnatifida. var. major, C. monogyna, C. laevigata and C. pentagyna. Phenolic compounds in emblic leafflower fruits were characterised by Sephadex LH-20 column chromatography combined with HPLC-ESI-MS (Publication V). A mucic acid gallate, three isomers of mucic acid lactone gallate, a galloylglucose, gallic acid, a digalloylglucose, putranjivain A, a galloyl-HHDP-glucose, elaeocarpusin and chebulagic acid represented the major phenolic compounds in fruits of emblic leafflower. In conclusion, results of this study significantly increase the current knowledge on the key bioactive and nutritional components of hawthorn and emblic leafflower fruits. These results provide important information for research on the mechanism responsible for the health benefits of these fruits.

Tartrate-Resistant Acid Phosphatase 5b: a Serum Marker of Bone Resorption

Bone is a physiologically dynamic tissue being constantly regenerated throughout life as a consequence of bone turnover by bone-resorbing osteoclasts and bone-forming osteoblasts. In certain bone diseases, such as osteoporosis, the imbalance in bone turnover leads to bone loss and increased fracture risk. Measurement of bone mineral density (BMD) predicts the risk of fracture, but also biochemical markers of bone metabolism have been suggested to be suitable for prediction of fractures and monitoring the efficacy of antiresorptive treatment. Tartrate-resistant acid phosphatase 5b (TRACP 5b) is an enzyme released from osteoclasts into the circulation, from where it can be detected kinetically or immunologically. Conventional assays for serum total TRACP were spectrophotometric and suffered from interference by other acid phosphatases and non-osteoclastic TRACP 5a isoform. Our aim was to develop novel immunoassays for osteoclastic TRACP 5b. Serum TRACP 5b levels were elevated in individuals with high bone turnover, such as children, postmenopausal women, patients with osteoporosis, Paget’s disease and breast cancer patients with bone metastases. As expected, hormone replacement therapy (HRT) in postmenopausal women decreased the levels of serum TRACP 5b. Surprisingly, the highest TRACP 5b levels were observed in individuals with rare autosomal dominant osteopetrosis type II (ADO2), which is characterized by high BMD and fracture risk with simultaneously elevated levels of deficient osteoclasts. In ADO2 patients, elevated levels of serum TRACP 5b were associated with high fracture frequency. It is likely that serum TRACP 5b reflects the number of inactive osteoclasts in ADO2. Similar results supporting the hypothesis that TRACP 5b would reflect the number of osteoclasts instead of their activity were observed with cultured osteoclasts and in animal models. Novel TRACP 5b immunoassays may prove to be of value either as independent or combinatory tools with other bone metabolic markers and BMD measurements in clinical practice and bone research.

Classification of acid sulphate soils of Finland according to Soil Taxonomy and the FAO/Unesco legend

Selostus: Suomen happamien sulfaattimaiden kansainvälinen luokittelu

The biotechnology of lactic acid bacteria with emphasis on applications in food safety and human health

Selostus: Terveyttä ja ruoan turvallisuutta edistävät maitohappobakteerien biotekniset sovellukset

Contribution of modern biotechnology of lactic acid bacteria to development of health-promoting foods

Selostus: Terveysvaikutteisten elintarvikkeiden tuottamista edesauttavat maitohappobakteerien molekyyligeneettiset tutkimukset

Effect of anionic salts in concentrate mixture on some blood and urine minerals, acid-base balance and feed intake of dry pregnant cows on grass silage based feeding with high calcium intake

Selostus: Kationi-anionitasapaino ummessaolevien lypsylehmien säilörehuruokinnassa kalsiumin saannin ollessa runsas

Effect of anionic salts in concentrate mixture and calcium intake on some blood and urine minerals, acid-base balance and feed intake of dry pregnant cows on grass silage based feeding

Selostus: Kationi-anionitasapaino ja kalsiumin saanti ummessaolevien lypsylehmien säilörehuruokinnassa

Effect of anionic salts in concentrate mixture and magnesium intake on some blood and urine minerals and acid-base balance of dry pregnant cows on grass silage based feeding

Selostus: Kationi-anionitasapaino ja magnesiumin saanti ummessaolevien lypsylehmien säilörehuruokinnassa

Use of inoculated lactic acid bacteria in fermenting sour cabbage

Selostus: Maitohappobakteerien hyödyntäminen hapankaalin fermentoinnissa

Changes in the contents of kaempherol, quercetin and L-ascorbic acid in sea buckthorn berries during maturation

Selostus: Tyrnin marjojen kamferoli-, kversetiini- ja L-askorbiinihappopitoisuuksien muutokset kypsymisen aikana

Phosphorus in Finnish soils in the 1900s with particular reference to the acid ammonium acetate soil test

Selostus: Suomen maaperän fosforin tutkiminen 1900-luvulla ja viljavuustutkimuksen kehittäminen

Apparent ileal amino acid digestibility and the nutritive value of the triticale cultivars Moreno and Ulrika for growing-finishing pigs

Selostus: Ruisvehnälajikkeiden Ulrika ja Moreno rehuarvo lihasikojen ruokinnassa