Direct Kinetic Observation of the Chemiexcitation Step in Peroxyoxalate Chemiluminescence

A high-energy intermediate in the peroxyoxalate reaction can be accumulated at room temperature under specific reaction conditions and in the absence of any reducing agent in up to micromolar concentrations. Bimolecular interaction of this intermediate, accumulated in the reaction of oxalyl chloride with hydrogen peroxide, with an activator (highly fluorescent aromatic hydrocarbons with low oxidation potential) added in delay shows unequivocally that this intermediate is responsible for chemiexcitation of the activator. Activation parameters for the unimolccular decomposition of this intermediate (Delta H(double dagger) = 11.2 kcal mol(-1); Delta S(double dagger) = -23.2 cal mol(-1) K(-1)) and for its bimolecular reaction with 9,10-diphenylanthracene (Delta H(double dagger) = 4.2 kcal mol(-1); Delta S(double dagger) = -26.9 cal mol(-1) K(-1)) show that this intermediate is much less stable than typical 1,2-dioxetanes and 1,2-dioxetanones and demonstrate its highly favored interaction with the activator. Therefore, it can be inferred that structural characterization of the high-energy intermediate in the presence of an activator must be highly improbable. The observed linear free-energy correlation between the catalytic rate constants and the oxidation potentials of several activators definitely confirms the occurrence of the chemically initiated electron-exchange luminescence (CIEEL) mechanism in the chemiexcitation step of the peroxyoxalate system.

First dynamic kinetic resolution of selenium-containing chiral amines catalyzed by palladium (Pd/BaSO(4)) and Candida antartica lipase (CAL-B)

An efficient method for chemoenzymatic dynamic kinetic resolution of selenium-containing chiral amines (organoselenium-1-phenylethanamines) has been developed, leading to the corresponding amides in excellent enantioselectivities and high isolated yields. This one-pot procedure employs two different types of catalysts: Pd on barium sulphate (Pd/BaSO(4)) as racemization catalyst and lipase (CAL-B) as the resolution catalyst. (C) 2009 Elsevier Ltd. All rights reserved.

Lipase-Catalyzed Highly Enantioselective Kinetic Resolution of Boron-Containing Chiral Alcohols

The first application of enzymes as catalysts to obtain optically pure boron compounds is described. The kinetic resolution of boron-containing chiral alcohols via enantioselective transesterification catalyzed by lipases was studied. Aromatic, allylic, and aliphatic secondary alcohols containing a boronate ester or boronic acid group were resolved by lipase from Candida antartica (CALB), and excellent E values (E > 200) and high enantiomeric excesses (up to >99%) of both remaining substrates and acetylated product were obtained.

Enzymatic kinetic resolution of organochalcogenides in supercritical CO(2)

1-(Phenylthio)-, 1-(phenylseleno)- and 1-(phenyltelluro)-propan-2-ol were efficiently resolved by CAL-B in sc-CO(2). (C) 2011 Elsevier Ltd. All rights reserved.

Kinetic resolution of iodophenylethanols by Candida antarctica lipase and their application for the synthesis of chiral biphenyl compounds

The kinetic resolution of (+/-)-iodophenylethanols was carried out using lipase from Candida antarctica and in some cases the enantiomeric excesses were high (up to >98%). Enantiomerically enriched (S)-iodophenylethanols produced by the enzymatic resolution process were used in the synthesis of chiral biphenyl compounds by the Suzuki reaction with good yields (63-65%). (C) 2010 Elsevier Ltd. All rights reserved.

Expression, purification and kinetic characterization of His-tagged glyceraldehyde-3-phosphate dehydrogenase from Trypanosoma cruzi

Trypanosomes are flagellated protozoa responsible for serious parasitic diseases that have been classified by the World Health Organization as tropical sicknesses of major importance. One important drug target receiving considerable attention is the enzyme glyceraldehyde-3-phosphate dehydrogenase from the protozoan parasite Trypanosoma cruzi, the causative agent of Chagas disease (T. cruzi Glyceraldehyde-3-phosphate dehydrogenase (TcGAPDH); EC 1.2.1.12). TcGAPDH is a key enzyme in the glycolytic pathway of T. cruzi and catalyzes the oxidative phosphorylation of D-glyceraldehyde-3-phosphate (G3P) to 1,3-bisphosphoglycerate (1,3-BPG) coupled to the reduction of oxidized nicotinamide adenine dinucleotide, (NAD(+)) to NADH, the reduced form. Herein, we describe the cloning of the T. cruzi gene for TcGAPDH into the pET-28a(+) vector, its expression as a tagged protein in Escherichia coli, purification and kinetic characterization. The His(6)-tagged TcGAPDH was purified by affinity chromatography. Enzyme activity assays for the recombinant His(6)-TcGAPDH were carried out spectrophotometrically to determine the kinetic parameters. The apparent Michaelis-Menten constant (K(M)(app)) determined for D-glyceraldehyde-3-phosphate and NAD(+) were 352 +/- 21 and 272 +/- 25 mu M, respectively, which were consistent with the values for the untagged enzyme reported in the literature. We have demonstrated by the use of Isothermal Titration Calorimetry (ITC) that this vector modification resulted in activity preserved for a higher period. We also report here the use of response surface methodology (RSM) to determine the region of optimal conditions for enzyme activity. A quadratic model was developed by RSM to describe the enzyme activity in terms of pH and temperature as independent variables. According to the RMS contour plots and variance analysis, the maximum enzyme activity was at 29.1 degrees C and pH 8.6. Above 37 degrees C, the enzyme activity starts to fall, which may be related to previous reports that the quaternary structure begins a process of disassembly. (C) 2010 Elsevier Inc. All rights reserved.

Attityd till att fullfölja nuvarande studier - En applikation av The Theory of Planned Behavior

För att förutsäga och förklara människors beteenden och intentioner har ”attityd” länge varit ett centralt begrepp inom socialpsykologin. En vanlig teori och modell för ändamålet är ”theory of planned behavior” (TpB), vilken säger att en individs beteende styrs av dess intention, som i sin tur är en funktion av den personliga attityden, det sociala trycket och den upplevda kontrollen att kunna genomföra aktuellt beteende. Syftet med föreliggande studie var att undersöka attityden och intentionen till att fullfölja nuvarande studier och göra en applikation av TpB-modellen via en Internetenkät riktad till studenter på Högskolan Dalarna (N = 1292). Hypotesen att ”den upplevda kontrollen” är den viktigaste direkta variabeln för intentionen kunde godtas, vilket kan antagas bero på beteendets karaktär. Diskussion förs också kring intentionens eventuella omvandling till verkligt beteende.

Vad påverkar föräldrars sätt att tillgodose barns behov av regelbundet umgänge? : En applikation på Theory of Planned Behaviour

Föreliggande undersökning var en attitydundersökning baserad på Theory of Planned Behaviour där attityd, subjektiv norm, upplevd kontroll samt intention anses kunna predicera beteende. Syftet med undersökningen är försöka ta reda på vilka faktorer som påverkar hur mycket tid man som förälder umgås med sina barn efter en separation eller skilsmässa eftersom många barn i den situationen förlorar kontakten med den ena föräldern. 36 försöksdeltagare besvarade ett frågeformulär bestående av 31 frågor och påståenden gällande umgänge. Resultaten visar att tiden man som förälder umgås med sina barn efter en skilsmässa beror på intention och upplevd kontroll. Intentionen förklaras av upplevd kontroll och dom förväntningar man upplever från omgivningen. Attityden hade endast liten betydelse i modellen.

Sociala faktorers inverkan på elevers intentioner till högre studier : En applikation av Theory of planned behavior

Denna studie grundar sig på en enkätundersökning av 59 gymnasieungdomars intentioner till att inom de närmaste 5 åren påbörja studier vid högskola eller universitet. Undersökningen är baserad på Theory of planned behavior och syftar till att testa teorins pålitlighet i att besvara vilken av de socialt betingade bakgrundsfaktorerna attityd, subjektiv norm och upplevd beteendekontroll som utgör den bästa prediktorn för undersökningsdeltagarnas intentioner. Därtill undersöks dessa faktorers samband med föräldrarnas utbildningsnivå. Theory of planned behavior visade sig vara ett reliabelt mätinstrument gällande studiens övriga frågor, där den upplevda beteendekontrollen och den subjektiva normen utgjorde signifikanta prediktorer gällande undersökningsdeltagarnas intentioner. Därtill påvisades samband mellan föräldrars utbildningsnivå och deltagarnas intentioner samt subjektiva norm. Författaren menar att studier likt denna ger ett värdefullt bidrag till det viktiga arbetet med att förverkliga den svenska skolans likvärdighetsmål.

Towards an epistemological theory of historical consciousness

This paper presents a theoretical analysis of the concept of historical consciousness. It argues that a focus on the epistemological problems of the concept can be a way of constructing a theory of the concept that both incorporates the diverse perspectives that exist in research about the concept and specifies how a historical consciousness can be developed in an individual.

Vector Theory of Spontaneous Lorentz Violation

Classical electromagnetism predicts two massless propagating modes, which are known as the two polarizations of the photon. On the other hand, if the Lorentz symmetry of classical electromagnetism is spontaneously broken, the new theory will still have two massless Nambu-Goldstone modes resembling the photon. If the Lorentz symmetry is broken by a bumblebee potential that allows for excitations out of the minimum, then massive modes arise. Furthermore, in curved spacetime, such massive modes will be created through a process other than the usual Higgs mechanism because of the dependence of the bumblebee potential on both the vector field and the metric tensor. Also, it is found that these massive modes do not propagate due to the extra constraints.