Preparation of Industrially Important Hydroxy Acids and Diacids from 2,2-Disubstituted Propane-1,3-Diols and Linear Primary Diols by Green Chemistry Methods

Environmentally benign and economical methods for the preparation of industrially important hydroxy acids and diacids were developed. The carboxylic acids, used in polyesters, alkyd resins, and polyamides, were obtained by the oxidation of the corresponding alcohols with hydrogen peroxide or air catalyzed by sodium tungstate or supported noble metals. These oxidations were carried out using water as a solvent. The alcohols are also a useful alternative to the conventional reactants, hydroxyaldehydes and cycloalkanes. The oxidation of 2,2-disubstituted propane-1,3-diols with hydrogen peroxide catalyzed by sodium tungstate afforded 2,2-disubstituted 3-hydroxypropanoic acids and 1,1-disubstituted ethane-1,2-diols as products. A computational study of the Baeyer-Villiger rearrangement of the intermediate 2,2-disubstituted 3-hydroxypropanals gave in-depth data of the mechanism of the reaction. Linear primary diols having chain length of at least six carbons were easily oxidized with hydrogen peroxide to linear dicarboxylic acids catalyzed by sodium tungstate. The Pt/C catalyzed air oxidation of 2,2-disubstituted propane-1,3-diols and linear primary diols afforded the highest yield of the corresponding hydroxy acids, while the Pt, Bi/C catalyzed oxidation of the diols afforded the highest yield of the corresponding diacids. The mechanism of the promoted oxidation was best described by the ensemble effect, and by the formation of a complex of the hydroxy and the carboxy groups of the hydroxy acids with bismuth atoms. The Pt, Bi/C catalyzed air oxidation of 2-substituted 2-hydroxymethylpropane-1,3-diols gave 2-substituted malonic acids by the decarboxylation of the corresponding triacids. Activated carbon was the best support and bismuth the most efficient promoter in the air oxidation of 2,2-dialkylpropane-1,3-diols to diacids. In oxidations carried out in organic solvents barium sulfate could be a valuable alternative to activated carbon as a non-flammable support. In the Pt/C catalyzed air oxidation of 2,2-disubstituted propane-1,3-diols to 2,2-disubstituted 3-hydroxypropanoic acids the small size of the 2-substituents enhanced the rate of the oxidation. When the potential of platinum of the catalyst was not controlled, the highest yield of the diacids in the Pt, Bi/C catalyzed air oxidation of 2,2-dialkylpropane-1,3-diols was obtained in the regime of mass transfer. The most favorable pH of the reaction mixture of the promoted oxidation was 10. The reaction temperature of 40°C prevented the decarboxylation of the diacids.

Alternate pathways of the early secretory route in yeast

The diversity of functions of eukaryotic cells is preserved by enclosing different enzymatic activities into membrane-bound organelles. Separation of exocytic proteins from those which remain in the endoplasmic reticulum (ER) casts the foundation for correct compartmentalization. The secretory pathway, starting from the ER membrane, operates by the aid of cytosolic coat proteins (COPs). In anterograde transport, polymerization of the COPII coat on the ER membrane is essential for the ER exit of proteins. Polymerization of the COPI coatomer on the cis-Golgi membrane functions for the retrieval of proteins from the Golgi for repeated use in the ER. The COPII coat is formed by essential proteins; Sec13/31p and Sec23/24p have been thought to be indispensable for the ER exit of all exocytic proteins. However, we found that functional Sec13p was not required for the ER exit of yeast endogenous glycoprotein Hsp150 in the yeast Saccharomyces cerevisiae. Hsp150 turned out to be an ATP phosphatase. ATP hydrolysis by a Walker motif located in the C-terminal domain of Hsp150 was an active mediator for the Sec13p and Sec24p independent ER exit. Our results suggest that in yeast cells a fast track transport route operates in parallel with the previously described cisternal maturation route of the Golgi. The fast track is used by Hsp150 with the aid of its C-terminal ATPase activity at the ER-exit. Hsp150 is matured with a half time of less than one minute. The cisternal maturation track is several-fold slower and used by other exocytic proteins studied so far. Operative COPI coat is needed for ER exit by a subset of proteins but not by Hsp150. We located a second active determinant to the Hsp150 polypeptide s N-terminal portion that guided also heterologous fusion proteins out of the ER in COPII coated vesicles under non-functional COPI conditions for several hours. Our data indicate that ER exit is a selective, receptor-mediated event, not a bulk flow. Furthermore, it suggests the existence of another retrieval pathway for essential reusable components, besides the COPI-operated retrotransport route. Additional experiments suggest that activation of the COPI primer, ADP ribosylation factor (ARF), is essential also for Hsp150 transport. Moreover, it seemed that a subset of proteins directly needed activated ARF in the anterograde transport to complete the ER exit. Our results indicate that coat structures and transport routes are more variable than it has been imagined.

Seasonal fluctuations in blue-green algae, especially in heterocystous species in polluted coastal waters off Helsinki city, in the northern part of the Gulf of Finland

Tiivistelmä

Victims of the White War or Rebellions of the Green Revolution? Bolivian Indigenous Women Prisoners' Position in the "War on Drugs" Explored through a Criminological Gaze

Tässä tutkielmassa tarkastellaan Bolivialaisten naisvankien (alkuperäisväestön) ja globaalin huumesodan ("War on Drugs") välistä yhteyttä. Keskustelu sijoitetaan laajemmin kokan viljelyn politiikkaan ja alkuperäisväestön kulttuuriin. Kokaa viljeleviä köyhiä maalaisia, joista huomattava osa on naisia, on vangittu Boliviassa kiihtyvää tahtia viime vuosikymmeninä. Moni naisista on kokan tuotannossa ja kaupassa mukana, sillä se on monesti ainoa keino taloudelliseen selviämiseen. Yleisesti ottaen naisvangit ja naisrikolliset ovat marginaalinen ilmiö. Kansainvälisesti tarkasteltuna naisvankien suhteellinen osuus koko vankilaväestöstä on noin 5,2 % (keskiarvo). Boliviassa osuus on vaihdellut 6,1 %:n ja 17,1 %:n välillä vuosina 2000-2008. Naisvankien määrä yleisesti ottaen on ollut rajussa kasvussa, suurin syy naisten vangitsemiseen on huumausaineisiin liittyvät rikokset. Näyttää myös siltä että vähemmistöt ja etnisen taustan omaavat henkilöt ovat yliedustettuina vankilaväestössä. Bolivia seuraa tätä kansainvälistä trendiä. Tämä tutkielma on rajattu kysymyksiin Bolivian intiaaniperäisten naisten osuudesta maan huumerikollisuudessa, sekä heidän suhteellisen korkeaa vangitsemisastetta selittäviin yhteiskunnallisiin tekijöihin. Kysymykset sukupuolesta, etnisyydestä ja kokan viljelyn politiikasta ovat keskiössä. Yleisiä kriminologisia teorioita peilataan kriittisesti suhteessa aineistoon ja Bolivian kontekstiin. Huumesodan ja Bolivian ankaran huumelainsäädännön seurauksista keskustellaan kriittisesti, sekä pohditaan köyhän alkuperäisväestön massavangitsemisen tarpeellisuutta. Tutkimuskysymykseni ovat: mitkä tekijät selittävät kohtuullisen korkean intiaaniperäisten naisvankien määrän Boliviassa, ja mikä on heidän asemansa globaalissa huumesodassa? Tutkielmassa on analysoitu kvantitatiivista ja kvalitatiivista aineistoa. Päälähteenä on ollut Bolivian tilastokeskuksen tuottamat rikostilastot. Tutkielman tärkeimpänä löydöksenä voidaan pitää havaintoa, että vastoin tiettyjä olettamuksia, intiaaniperäiset naiset ovat hyvinkin aktiivisia perinteisesti miehisiksi käsitetyillä aloilla kuten rikollisuudessa ja politiikassa. Tutkielmassa osoitetaan myös, että pidätysten määrät ovat moninkertaistuneet muutamassa vuosikymmenessä. Koska kokan viljelyssä on kyse pääasiallisesti taloudellisesta toimeentulosta, tämä tutkielma kysyy, onko hengissä pysyminen rikos?