Discarge compilation from The Global River Discharge (RivDIS) Project

The Global River Discharge (RivDIS) data set contains monthly discharge measurements for 1018 stations located throughout the world. The period of record varies widely from station to station, with a mean of 21.5 years. These data were digitized from published UNESCO archives by Charles Voromarty, Balaze Fekete, and B.A. Tucker of the Complex Systems Research Center (CSRC) at the University of New Hampshire. River discharge is typically measured through the use of a rating curve that relates local water level height to discharge. This rating curve is used to estimate discharge from the observed water level. The rating curves are periodically rechecked and recalibrated through on-site measurement of discharge and river stage.

Studien über die Phenanthrensulfosäuren /

Arkiv f. kemi, mineral. o. geol., Bd. 4: Nr. 33.

Årsbok.

Supplements were issued and bound with the volumes for 1910, 1924, 1959.

Öfversigt af kongl. vetenskaps-akademiens forhandlingar.

Mode of access: Internet.

Arkiv för zoologi /

"The publication of Öfversigt af K. Vetenskaps-akademiens förhandlingar and Bihang til K. Svenska vetenskaps-akademiens handlingar ... will not be continued. A yearbook and four publications will be published instead. These four publications are named: Arkiv för matematik ... Arkiv för kemi ... Arkiv för botanik, Arkiv för zoologi."

Organohalogen contaminants in wildlife from the Yangtze River Delta : Development of methods and assessments of legacy and emerging persistent organic pollutants

Rapid economic development has occurred during the past few decades in China with the Yangtze River Delta (YRD) area as one of the most progressive areas. The urbanization, industrialization, agricultural and aquaculture activities result in extensive production and application of chemicals. Organohalogen contaminants (OHCs) have been widely used as i.e. pesticides, flame retardants and plasticizers. They are persistent, bioaccumulative and pose a potential threat to ecosystem and human health. However, limited research has been conducted in the YRD with respect to chemicals environmental exposure. The main objective of this thesis is to investigate the contamination level, distribution pattern and sources of OHCs in the YRD. Wildlife from different habitats are used to indicate the environmental pollution situation, and evaluate selected matrices for use in long term biomonitoring to determine the environmental stress the contamination may cause. In addition, a method is developed for dicofol analysis. Moreover, a specific effort is made to introduce statistic power analysis to assist in optimal sampling design. The thesis results show extensive contamination of OHCs in wildlife in the YRD. The occurrences of high concentrations of chlorinated paraffins (CPs) are reported in wildlife, in particular in terrestrial species, (i.e. short-tailed mamushi snake and peregrine falcon). Impurities and byproducts of pentachlorophenol products, i.e. polychlorinated diphenyl ethers (PCDEs) and hydroxylated polychlorinated diphenyl ethers (OH-PCDEs) are identified and reported for the first time in eggs from black-crowned night heron and whiskered tern. High concentrations of octachlorodibenzo-p-dioxin (OCDD) are determined in these samples. The toxic equivalents (TEQs) of polychlorinated dibenzo-p-dioxin (PCDDs) and polychlorinated dibenzofurans (PCDFs) are at mean levels of 300 and 520 pg TEQ g-1lw (WHO2005 TEQ) in eggs from the two bird species, respectively. This is two orders of magnitude higher than European Union (EU) regulation limit in chicken eggs. Also, a novel pattern of polychlorinated biphenyls (PCBs) with octa- to decaCBs, contributing to as much as 20% of total PCBs therein, are reported in birds. The legacy POPs shows a common characteristic with relatively high level of organochlorine pesticides (i.e. DDT, hexacyclohexanes (HCHs) and Mirex), indicating historic applications. In contrast, rather low concentrations are shown of industrial chemicals such as PCBs and polybrominated diphenyl ethers (PBDEs). A refined and improved analytical method is developed to separate dicofol from its major decomposition compound, 4,4’-dichlorobenzophenone. Hence dicofol is possible to assess as such. Statistic power analysis demonstrates that sampling of sedentary species should be consistently spread over a larger area to monitor temporal trends of contaminants in a robust manner. The results presented in this thesis show high CPs and OCDD concentrations in wildlife. The levels and patterns of OHCs in YRD differ from other well studied areas of the world. This is likely due to the extensive production and use of chemicals in the YRD. The results strongly signal the need of research biomonitoring programs that meet the current situation of the YRD. Such programs will contribute to the management of chemicals and environment in YRD, with the potential to grow into the human health sector, and to expand to China as a whole.

Catalytic reactions with palladium supported on mesocellular foam : Applications in hydrogenation, isomerization, and C-C bond forming reactions

The major part of this thesis concerns the development of catalytic methodologies based on palladium nanoparticles immobilized on aminopropyl-functionalized siliceous mesocellular foam (Pd0-AmP-MCF). The catalytic activity of the precursor to the nanocatalyst, PdII-AmP-MCF is also covered by this work. In the first part the application of Pd0-AmP-MCF in Suzuki-Miyaura cross-coupling reactions and transfer hydrogenation of alkenes under microwave irradiation is described. Excellent reactivity was observed and a broad range of substrates were tolerated for both transformations. The Pd0-AmP-MCF exhibited high recyclability as well as low metal leaching in both cases. The aim of the second part was to evaluate the catalytic efficiency of the closely related PdII-AmP-MCF for cycloisomerization of various acetylenic acids. The catalyst was able to promote formation of lactones under mild conditions using catalyst loadings of 0.3 - 0.5 mol% at temperatures of up to 50 oC in the presence of Et3N. By adding 1,4-benzoquinone to the reaction, the catalyst could be recycled four times without any observable decrease in the activity. The selective arylation of indoles at the C-2 position using Pd-AmP-MCF and symmetric diaryliodonium salts is presented in the third part. These studies revealed that Pd0-AmP-MCF was more effective than PdII-AmP-MCF for this transformation. Variously substituted indoles as well as diaryliodonium salts were tolerated, giving arylated indoles in high yields within 15 h at 20 - 50 oC in H2O. Only very small amounts of Pd leaching were observed and in this case the catalyst exhibited moderate recyclability. The final part of the thesis describes the selective hydrogenation of the C=C in different α,β-unsaturated systems. The double bond was efficiently hydrogenated in high yields both under batch and continuous-flow conditions. High recyclability and low metal leaching were observed in both cases.

Sustainable Catalysis : Rational Pd Loading on MIL-101Cr-NH2 for More Efficient and Recyclable Suzuki-Miyaura Reactions

Palladium nanoparticles have been immobilized into an amino-functionalized metal-organic framework (MOF), MIL-101Cr-NH2, to form Pd@MIL-101Cr-NH2. Four materials with different loadings of palladium have been prepared (denoted as 4-, 8-, 12-, and 16wt%Pd@MIL-101Cr-NH2). The effects of catalyst loading and the size and distribution of the Pd nanoparticles on the catalytic performance have been studied. The catalysts were characterized by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier-transform infrared (FTIR) spectroscopy, powder X-ray diffraction (PXRD), N-2-sorption isotherms, elemental analysis, and thermogravimetric analysis (TGA). To better characterize the palladium nanoparticles and their distribution in MIL-101Cr-NH2, electron tomography was employed to reconstruct the 3D volume of 8wt%Pd@MIL-101Cr-NH2 particles. The pair distribution functions (PDFs) of the samples were extracted from total scattering experiments using high-energy X-rays (60keV). The catalytic activity of the four MOF materials with different loadings of palladium nanoparticles was studied in the Suzuki-Miyaura cross-coupling reaction. The best catalytic performance was obtained with the MOF that contained 8wt% palladium nanoparticles. The metallic palladium nanoparticles were homogeneously distributed, with an average size of 2.6nm. Excellent yields were obtained for a wide scope of substrates under remarkably mild conditions (water, aerobic conditions, room temperature, catalyst loading as low as 0.15mol%). The material can be recycled at least 10times without alteration of its catalytic properties.

Catalytic Processes Mediated by Metal−Organic Frameworks : Reactivity and Mechanistic Studies

The present thesis describes the development of heterogeneous catalytic methodologies using metal−organic frameworks (MOFs) as porous matrices for supporting transition metal catalysts. A wide spectrum of chemical reactions is covered. Following the introductory section (Chapter 1), the results are divided between one descriptive part (Chapter 2) and four experimental parts (Chapters 3–6). Chapter 2 provides a detailed account of MOFs and their role in heterogeneous catalysis. Specific synthesis methods and characterization techniques that may be unfamiliar to organic chemists are illustrated based on examples from this work. Pd-catalyzed heterogeneous C−C coupling and C−H functionalization reactions are studied in Chapter 3, with focus on their practical utility. A vast functional group tolerance is reported, allowing access to substrates of relevance for the pharmaceutical industry. Issues concerning the recyclability of MOF-supported catalysts, leaching and operation under continuous flow are discussed in detail. The following chapter explores puzzling questions regarding the nature of the catalytically active species and the pathways of deactivation for Pd@MOF catalysts. These questions are addressed through detailed mechanistic investigations which include in situ XRD and XAS data acquisition. For this purpose a custom reaction cell is also described in Chapter 4. The scope of Pd@MOF-catalyzed reactions is expanded in Chapter 5. A strategy for boosting the thermal and chemical robustness of MOF crystals is presented. Pd@MOF catalysts are coated with a protecting SiO2 layer, which improves their mechanical properties without impeding diffusion. The resulting nanocomposite is better suited to withstand the harsh conditions of aerobic oxidation reactions. In this chapter, the influence of the nanoparticles’ geometry over the catalyst’s selectivity is also investigated. While Chapters 3–5 dealt with Pd-catalyzed processes, Chapter 6 introduces hybrid materials based on first-row transition metals. Their reactivity is explored towards light-driven water splitting. The heterogenization process leads to stabilized active sites, facilitating the spectroscopic probing of intermediates in the catalytic cycle.

Optimization of a steel plant utilizing converted biomass

Inom nära framtid kan det vara ekonomiskt lönsamt att investera i träbaserad biomassa-användning inom stålproduktion. En förutsättning är att biomassans bränsle-egenskaper förbättras genom en sorts förkolning, närmare sagt långsam pyrolysering. Som biomassakälla duger skogsrester och dylikt. Nyttan med att använda biomassa är att man reducerar fossila CO2-utsläpp och på så vis minskar på den globala uppvärmningen; detta kräver dock att återplantering görs för att fånga de frigjorda CO2-utsläppen som härstammar från biomassans skörd, transport, processering och förbränning. En investering i en pyrolyseringsanläggning integrerad i ett stålverk kan vara lönsam ifall utsläppskatten är över 20 € per ton CO2 då biomassakostnaden är 40 € per ton torr substans. Detta är dock inte fallet i dagens läge och i Finland är dessa avgifter beroende av politiska beslut på Europeisk nivå. Det kunde dock vara av politiskt intresse att stödja biomassa-användningen inom stålindustrin eftersom detta skulle skapa nya arbetsplatser såväl inom själva stålindustrin som inom skogsindustrin och möjligen även inom kemi-industrin, beroende på hur de resulterande pyrolysprodukterna (träkol, gas och bio-oljor) utnyttjas. Med tanke på att närmare en femtedel av alla CO2-utsläpp härstammande från industrin kommer från stålindustrin så är det uppenbart att mera miljövänligare alternativ kommer att krävas i framtiden. Lähitulevaisuudessa voi olla taloudellisesti kannattavaa käyttää puuperäistä biomassaa teräksen valmistuksessa. Tämä vaatii kuitenkin sen, että biomassa läpikäy eräänlaisen hiillostuksen, eli pyrolyysin, ja tässä tapauksessa, hitaan pyrolyysin. Biomassalähteeksi kelpaavat esimerkiksi hakkuujätteet ja muu puujäte. Hyöty biomassankäytöstä syntyy siitä, kun se osittain korvaa perinteisesti käytettyjä fossiilisia polttoaineita, jolloin fossiiliset hiilidioksidipäästöt vähenevät ja tällöin myös vaikutus ilmaston lämpenemiseen vähenee. Edellytyksenä on tietysti se, että uusia puita ja kasveja istutetaan, jotta biomassan keräyksestä, kuljetuksesta, käsittelystä sekä poltosta vapautunut hiilidioksidi saadaan jälleen talteen. Arvion mukaan pyrolyysiyksikön integroiminen terästehtaaseen tulee taloudellisesti kannattavaksi, kun hiilidioksidivero nousee yli 20 € per tonni, kun biomassan hinnaksi on arvioitu 40 € per tonni kuiva-ainesta. Kyseinen hintataso ei ole tällä hetkellä voimassa ja Suomen tilanne tässä asiassa on vahvasti kytköksissä Euroopan tasolla tehtäviin päätöksiin. Aihe voisi kuitenkin olla poliittisella tasolla kiinnostava ja taloudellisen tuen arvoista, koska biomassan käyttö loisi lisää työpaikkoja niin terästeollisuudessa kuin puuteollisuudessakin ja mahdollisesti myös kemianteollisuudessa, riippuen siitä miten erinäisiä pyrolyysituotteita (puuhiili, kaasu ja bio-öljy) hyödynnettäisiin. Ottaen huomioon, että terästeollisuus maailmanlaajuisesti vastaa noin viidesosasta kaikista teollisuudesta peräisin olevista hiilidioksidipäästöistä on päivänselvää, että ympäristöystävällisemmille vaihtoehdoille on tarvetta tulevaisuudessa.

Population pharmacokinetics and pharmacodynamics of lumefantrine in young Ugandan children treated with artemether-lumefantrine for uncomplicated malaria

Background. The pharmacokinetics and pharmacodynamics of lumefantrine, a component of the most widely used treatment for malaria, artemether-lumefantrine, has not been adequately characterized in young children. Methods. Capillary whole-blood lumefantrine concentration and treatment outcomes were determined in 105 Ugandan children, ages 6 months to 2 years, who were treated for 249 episodes of Plasmodium falciparum malaria with artemether-lumefantrine. Results. Population pharmacokinetics for lumefantrine used a 2-compartment open model with first-order absorption. Age had a significant positive correlation with bioavailability in a model that included allometric scaling. Children not receiving trimethoprim-sulfamethoxazole with capillary whole blood concentrations <200 ng/mL had a 3-fold higher hazard of 28-day recurrent parasitemia, compared with those with concentrations >200 ng/mL (P =. 0007). However, for children receiving trimethoprim-sulfamethoxazole, the risk of recurrent parasitemia did not differ significantly on the basis of this threshold. Day 3 concentrations were a stronger predictor of 28-day recurrence than day 7 concentrations. Conclusions. We demonstrate that age, in addition to weight, is a determinant of lumefantrine exposure, and in the absence of trimethoprim-sulfamethoxazole, lumefantrine exposure is a determinant of recurrent parasitemia. Exposure levels in children aged 6 months to 2 years was generally lower than levels published for older children and adults. Further refinement of artemether-lumefantrine dosing to improve exposure in infants and very young children may be warranted. © 2016 The Author.

Physicochemical characteristics of silica nanoparticles tailored for nanomedicine

Multifunktionella kiseldioxidnanopartiklar har en bred tillämpning inom nanomedicin. En attraktiv kombination är samtidig läkemedelstillförsel och spårning av nanopartiklarna, vilket är känt som ”teranostik”. Genom kontrollerad design av kiseldioxidnanopartiklarna kan terapi och diagnostik på detta sätt kombineras i samma partikel. För en lyckad användning av nanopartiklar inom nanomedicin måste deras fysikalisk-kemiska egenskaper vara välkontrollerade för att kunna förutspå deras beteende i biologiska system. I denna studie tillverkades kiseldioxidnanopartiklar med varierande storlek, form, yta och sammansättning med fokus på att utrusta nanopartiklarna med multifunktionalitet och på så sätt främja deras användning inom biomedicinska tillämpningar. Kiseldioxidnanopartiklar med sfäriska och stav-liknande former, porösa, icke-porösa och ihåliga strukturer tillverkades. De erhållna resultaten visade att nanopartiklarnas form har större inverkan på upptaget i celler jämfört med effekten av deras ytladdning. Nanopartiklarnas dispersionsstabilitet är en annan viktig aspekt för både diagnostiska och terapeutiska tillämpningar. Genom att ändra kiseldioxidnanopartiklarnas fysikalisk-kemiska ytegenskaper med ytfunktionalisering, bedömdes dispersionstabiliteten av nanopartiklarna. Nanopartiklarnas ytsammansättning justerades och skillnader i dispergerbarhet och dispersionsstabilitet undersöktes i biologiskt medium. Inom terapeutiska tillämpningar är målsökande läkemedelsfyllda nanopartiklar en lovande taktik som medför lägre läkemedelsdoser och minskar sidoeffekterna. I denna avhandling designades mesoporösa kiseldioxidnanopartiklar för användning som målsökande läkemedelsbärare. Dessa partiklar laddades med ett potentiellt anti-cancer läkemedel. En klart högre apoptotisk effekt kunde påvisas med de läkemedelsfyllda partiklarna jämfört med fri drog in vitro. En viktig egenskap för sådana multifunktionella nanopartiklar är också att kunna spåra dem under läkemedelsfrisättningen i biologisk miljö med olika bildåtergivningsmetoder. Detta kan uppnås genom att infoga en markör i kiseldioxidnätverket. Kiseldioxidnanopartiklarnas bildåtergivningsförmåga modifierades på olika sätt och inverkan på detekterbarheten analyserades med fluorescerande metoder och med magnetisk resonanstomografi. Denna avhandling lyfter fram de kritiska parametrarna vid syntes av kiseldioxidnanopartiklar för teranostiska tillämpningar. Olika metoder undersöktes för att erhålla skräddarsydda nanopartiklar. Detta arbete bidrar med en djup insikt i hur nanopartiklarnas fysikalisk-kemiska egenskaper påverkar deras beteende i biologisk miljö, och arbetet kan därför fungera som riktlinje för att designa säkra och effektiva nanomediciner.