An expeditious synthesis of hexahydrobenzo[f]isochromenes and of hexahydrobenzo[f]isoquinoline via iodine-catalyzed Prins and aza-Prins cyclization

Homoallylic alcohols (primary, secondary, or tertiary containing an endocyclic or an exocyclic double bond) react with equimolar amounts of aldehydes (aliphatic or aromatic) and ketones (aliphatic) in the presence of 5 mol % of iodine. This Prins cyclization was used in the preparation of hexahydrobenzo[f]isochromenes and of a 4-hydroxy-tetrahydropyran, in 54-81% yield. The procedure is also efficient for an aza-Prins cyclization of a homoallylic sulfonamide and benzaldehyde, producing a hexahydrobenzo[f]isoquinoline. (C) 2009 Elsevier Ltd. All rights reserved.

Reactivity of Beer Bitter Acids Toward the 1-Hydroxyethyl Radical as Probed by Spin-Trapping Electron Paramagnetic Resonance (EPR) and Electrospray Ionization-Tandem Mass Spectrometry (ESI-MS/MS)

The iso-alpha-acids or isohumulones are the major contributors to the bitter taste of beer, and it is well-recognized that they are degraded during beer aging. In particular, the trans-isohumulones seem to be less stable than the cis-isohumulones. The major radical identified in beer is the 1-hydroxyethyl radical; however, the reactivity between this radical and the isohumulones has not been reported until now. Therefore, we studied the reactivity of isohumulones toward the 1-hydroxyethyl radical through a competitive kinetic approach. It was observed that both cis- and trans-isohumulones and dihydroisohumulones are decomposed in the presence of 1-hydroxyethyl radicals, while the reactivities are comparable. On the other hand, the tetrahydroisohumulones did not react with 1-hydroxyethyl radicals. The apparent second-order rate constants for the reactions between the 1-hydroxyethyl radical and these compounds were determined by electron paramagnetic resonance (EPR) spectroscopy and electrospray ionization-tandem mass spectrometry [ESI(+)-MS/MS]. It follows that degradation of beer bitter acids is highly influenced by the presence of 1-hydroxyethyl radicals. The reaction products were detected by liquid chromatography electrospray ionization-ion trap-tandem mass spectrometry (LC-ESI-IT-MS/MS), and the formation of oxidized derivatives of the isohumulones was confirmed. These data help to understand the mechanism of beer degradation upon aging.

Light-Induced Oxidation of Unsaturated Lipids as Sensitized by Flavins

Triplet-excited riboflavin ((3)RF*) was found by laser flash photolysis to be quenched by polyunsaturated fatty acid methyl esters in tert-butanol/water (7:3, v/v) in a second-order reaction with k similar to 3.0 x 10(5) L mol(-1) s(-1) at 25 degrees C for methyl linoleate and 3.1 x 10(6) L mol(-1) s(-1), with Delta H double dagger = 22.6 kJ mol(-1) and Delta S double dagger = -62.3 J K(-1) mol(-1), for methyl linolenate in acetonitrile/water (8:2, v/v). For methyl oleate, k was <10(4) L mol(-1) s(-1). For comparison, beta-casein was found to have a rate constant k similar to 4.9 x 10(8) L mol(-1) s(-1). Singlet-excited flavin was not quenched by the esters as evidenced by insensitivity of steady-state fluorescence to their presence. Density functional theory (DFT) calculations showed that electron transfer from unsaturated fatty acid esters to triplet-excited flavins is endergonic, while a formal hydrogen atom transfer is exergonic (Delta G(HAT)degrees = -114.3, -151.2, and -151.2 kJ mol(-1) for oleate, linoleate, and linolenate, respectively, in acetonitrile). The reaction is driven by acidity of the lipid cation radical for which a pK(a) similar to -0.12 was estimated by DFT calculations. Absence of electrochemical activity in acetonitrile during cyclic voltammetry up to 2.0 V versus NHE confirmed that Delta G(ET)degrees > 0 for electron transfer. Interaction of methyl esters with (3)RF* is considered as initiation of the radical chain, which is subsequently propagated by combination reactions with residual oxygen. In this respect, carbon-centered and alkoxyl radicals were detected using the spin trapping technique in combination with electron paramagnetic resonance spectroscopy. Moreover, quenching of 3RF* yields, directly or indirectly, radical species which are capable of initiating oxidation in unsaturated fatty acid methyl esters. Still, deactivation of triplet-excited flavins by lipid derivatives was slower than by proteins (factor up to 10(4)), which react preferentially by electron transfer. Depending on the reaction environment in biological systems (including food), protein radicals are expected to interfere in the mechanism of light-induced lipid oxidation.

Experimental Chemotherapy against Trypanosoma cruzi Infection Using Ruthenium Nitric Oxide Donors

The ruthenium NO donors of the group trans-[Ru(NO)(NH(3))(4)L](n+), where the ligand (L) is N-heterocyclic H(2)O, SO(3)(2 -), or triethyl phosphite, are able to lyse Trypanosoma cruzi in vitro and in vivo. Using half-maximal (50%) inhibitory concentrations against bloodstream trypomastigotes (IC(50)(try)) and cytotoxicity data on mammalian V-79 cells (IC(50)(V79)), the in vitro therapeutic indices (TIs) (IC(50)(V79)/IC(50)(try)) for these compounds were calculated. Compounds that exhibited an in vitro TI of >= 10 and trypanocidal activity against both epimastigotes and trypomastigotes with an IC(50)(try/epi) of <= 100 mu M were assayed in a mouse model for acute Chagas` disease, using two different routes (intraperitoneal and oral) for drug administration. A dose-effect relationship was observed, and from that, the ideal dose of 400 nmol/kg of body weight for both trans-[Ru(NO)(NH(3))(4)isn](BF(4))(3) (isn, isonicotinamide) and trans-[Ru(NO)(NH3) 4imN](BF4) 3 (imN, imidazole) and median (50%) effective doses (ED50) of 86 and 190 nmol/kg, respectively, were then calculated. Since the 50% lethal doses (LD(50)) for both compounds are higher than 125 mu mol/kg, the in vivo TIs (LD(50)/ED(50)) of the compounds are 1,453 for trans-[Ru(NO)(NH(3))(4)isn](BF(4))(3) and 658 for trans-[Ru(NO)(NH(3))(4)imN](BF(4))(3). Although these compounds exhibit a marked trypanocidal activity and are able to react with cysteine, they exhibit very low activity in T. cruzi -glycosomal glyceraldehyde-3-phosphate dehydrogenase tests, suggesting that this enzyme is not their target. The trans-[Ru(NO)(NH(3))(4)isn](BF(4))(3) and trans-[Ru(NO)(NH(3))(4)imN](BF(4))(3) compounds are able to eliminate amastigote nests in myocardium tissue at 400-nmol/kg doses and ensure the survival of all infected mice, thus opening a novel set of therapies to try against trypanosomatids.

Photodegradation of Folate Sensitized by Riboflavin

Folate is shown to react with singlet-excited state of riboflavin in a diffusion controlled reaction and with triplet-excited state of riboflavin in a somewhat slower reaction with (3)k(q) = 4.8 x 10(8) L mol(-1) s(-1) in aqueous phosphate buffer at pH 7.4, ionic strength of 0.2 mol L(-1), and 25 degrees C. Singlet quenching is assigned as photo-induced reductive electron transfer from ground state folate to singlet-excited riboflavin, while triplet quenching is assigned as one-electron transfer rather than hydrogen atom transfer from folate to triplet-excited riboflavin, as the reaction quantum yield, phi = 0.32, is hardly influenced by solvent change from water to deuterium oxide, phi = 0.37. Cyclic voltammetry showed an irreversible two-electron anodic process for folate, E = 1.14 V versus NHE at a scan-rate of 50 mV s(-1), which appears to be kinetically controlled by the heterogeneous electron transfer from the substrates to the electrode. Main products of folate photooxidation sensitized by riboflavin were pterin-6-carboxylic acid and p-aminobenzoyl-L-glutamic acid as shown by liquid chromatographic ion-trap mass spectrometry (LC-IT-MS).

Oxotechnetium(V) Complexes with a Novel Class of Tridentate Thiosemicarbazide Ligands

A novel tridentate thiosemicarbazide-type ligand class with an SNS donor set, H(2)L(1), was prepared by reactions of N-[N`,N`-dialkylamino(thiocarbonyl)]benzimidoyl chlorides with thiosemicarbazides. H(2)L(1) ligands readily react with (NBu(4))[TcOCl(4)] in MeOH under the formation of red oxotechnetium(V) complexes of composition [TcOCl(L(1))]. The monomeric, five-coordinate compounds are air-stable and bind (L(1))(2-) tridentate in the equatorial coordination sphere. The compounds represent the first examples of oxotechnetium(V) complexes with NS chelate-bonded thiosemicarbazones.

Barn och katastrofer : en systematisk litteraturstudie

Syftet med denna litteraturstudie var att belysa ämnet barn och katastrofer, som hur barn reagerar efter traumatiska händelser, hur de utvecklar Post- Traumatic Stress Disorder (PTSD), hur PTSD behandlas samt hur vårdpersonal kan hjälpa barn på bästa sätt. Studien var en systematisk litteraturstudie. Litteraturen söktes via Elin@dalarna, Pub Med och DOAJ. Sökord som användes för att få fram relevanta artiklar var: ”adaption”, ”care”, ”catastrophe”, ”children”, ”child”, ”disasters”, ”help”, ”natural disaster”, ”PTSD”, ”react”, ”trauma”. Dessa ord användes ett och ett samt i kombination med varandra. De vetenskapliga artiklarna som användes kvalitetsbedömdes med en kombinerad granskningsmall av Forsberg och Wengström (2003) samt Willman och Stoltz (2002) granskningsmallar för kvalitativa och kvantitativa studier. Denna granskning resulterade i ett urval av 16 vetenskapliga artiklar som var publicerade mellan1990 och 2006 och var skrivna på svenska eller engelska. Sökorden fanns med i artikelns titel eller abstract, samt att dess innehåll skulle besvara frågeställningarna som fanns. De studier som granskades i denna uppsats visade att barn reagerar väldigt olika beroende på deras sociala liv och levnadsstandard, samt hur svårt drabbade de blivit av naturkatastrofen. Barns första reaktioner efter en naturkatastrof var ofta ilska och aggressioner över det inträffade, barnen anklagade ofta sig själva för det inträffade. Barn som levde under sociala missförhållande, utan föräldrar, hem och vänner löpte högre risk att få symtom på PTSD, och det var vanligare att flickor fick symtom än pojkar. De vanligaste behandlingsmetoderna för symtom av PTSD var kognitiv beteendeterapi och läkemedel. Den viktigaste hjälpen för barn som upplevt en naturkatastrof var att hjälpa dem tillbaka till det vardagliga livet.

Study of ink mileage and print through

This report contains a study of ink mileage, show through and other mechanisms that are important inthe study of substrate printability. These mechanisms have an impact on how ink will react on paper.To develop a substrate that provides good ink mileage and less show through requires a closer studyof substrate characteristics.Substrates with different characteristics have been tested by a technique developed for this projectcalled modified ink mileage. Ink mileage is a method to determine how much ink that is required for acertain target density. Further tests on the same substrates have been done including print throughand surface roughness measurements.

Filmmusikens betydelse : En receptionsstudie om hur musik i film bidrar till förståelse

This essay is about film music and how people react in a study where the music and picture comes from two different genres that both has unique conventions, of how the “standard” music ought to be composed. The purpose of this essay is mainly to try and get an understanding of film music’s importance in the movies dramatic structure, and how people react when the conventions of music is broken and two genres are combined into one.The questions that are to be answered in this essay are: *how could music as a tool change the character of a film? *How does the participants, of this inquire, experience the film depending on what music they hear? *And what is it that the participants think that the music brings to the movies narration?The method of this survey is based on a number of participants that have responded on questions of how they experienced the movie, both with music and without. This study has shown that when music and picture, which comes from different genres, interact with each other it tends to create comical features and a sense of that the music has an advantage in terms of the genre that people feel that the film has.

La risa en los Chistes de Facebook

People tell jokes in order to amuse and produce laughter. It is possible to represent laughter in the cyberspace discourse by writing how it sounds or by using a representation of a facial expression formed by various combinations of keyboard characters called emoticon. Jokes are appreciated by both men and women in our society but is there any difference between the way they represent laughter in the cyberspace discourse? In this research, we use the qualitative and quantitative method. First, we analyze the mechanism of linguistic construction of five jokes and their types and techniques based on Freud’s theory about this subject. Then we present the reactions produced by the jokes found in a social network and focus in the written representation of the laughter. The results show us that more women than men react to the jokes by writing a comment. The most popular laughter used by both men and women in a Spanish social network is "jajajaja" and the emoticon "XD". We have also found that people use the international laughter "hahahaha" and more women than men use "jejeje" to represent laughter in the same network. Although each individual has a laughter style, the way people represent the laughter graphically in the cyberspace discourse is almost the same between men and women but it differs in the way they use them as a reaction to the type and technique of the joke.

Fri vilja eller tradition? : Prästrespektive i den prästerliga kulturen

The purpose of the study was to investigate, using data from the sacerdotal culture, t h espouses of five priests. The main questions were: How does the priestly calling affect thespouse? Do the spouses involve themselves with voluntary work? Do the spouses feel thecongregation have expectations? Do the female and male answers differ?The sacerdotal culture has consisted of several elements. The main element is the priest’scalling for his work. As far as the spouse is concerned within the congregation, the spouseshave been seen as necessary for voluntary work. The congregation has also expected thespouse to act in a certain way and to undertake certain tasks.How the five informants feel about and react to the sacerdotal culture is focus for this study.The study shows that the sacerdotal culture is still strong today and it is something that thespouses take into account. They can choose not to participate but that might involve, forinstance, having to live somewhere else. The study found that the calling affects the femaleinformants, but not so much the males. The amount of participation varies from spouse tospouse and is a matter of their own choice. Expectations can also vary and participation inthe congregation can create higher expectations.

Exploring 'Samoaness' in the Samoan language film The Orator (O Le Tulafale)

The Pacific nation of the Independent Samoa (formerly Western Samoa)  is not known for having a developed film industry.   In 2011, a Samoan languge film called The Orator (O le Tulafale) placed the spotlight on Samoa, its people, and the Samoan culture when it became the country’s first ever film to be accepted into major international film festivals such as the 68th Venice Film Festival.  Samoans the world over have embraced the film for its richness, compassion, and authenticity. Yet at times, the film portrays the Samoan culture as harsh and cruel.   Samoans are usually quick to criticise negative portrayals of their culture but the thousands of comments on the film’s official Facebook page show otherwise.  From April 2011 to March 2012, there were only 11 comments criticising the film on Facebook, and these criticisms were denounced as ‘un-Samoan’. This raised the question as to why Samoans did not react to the unflattering portrayals of their culture, but instead react against legitimate criticisms of the film.  By using Foucault’s concept of heterotopia and the Samoan narrative structure of fāgogo, a heterotopia space and a utopia space are created in which past memories confirming Samoan cultural identity and bonds to the culture are evoked and are (re)experienced by Samoans while viewing the film.  Thus the film’s ability to encourage this is what Samoans praise rather than the actual film.  

An Experimental Study of Submerged Entry Nozzles (SEN) Focusing on Decarburization and Clogging

The submerged entry nozzle (SEN) is used to transport the molten steel from a tundish to a mould. The main purpose of its usage is to prevent oxygen and nitrogen pick-up by molten steel from the gas. Furthermore, to achieve the desired flow conditions in the mould. Therefore, the SEN can be considered as a vital factor for a stable casting process and the steel quality. In addition, the steelmaking processes occur at high temperatures around 1873 K, so the interaction between the refractory materials of the SEN and molten steel is unavoidable. Therefore, the knowledge of the SEN behaviors during preheating and casting processes is necessary for the design of the steelmaking processes  The internal surfaces of modern SENs are coated with a glass/silicon powder layer to prevent the SEN graphite oxidation during preheating. The effects of the interaction between the coating layer and the SEN base refractory materials on clogging were studied. A large number of accretion samples formed inside alumina-graphite clogged SENs were examined using FEG-SEM-EDS and Feature analysis. The internal coated SENs were used for continuous casting of stainless steel grades alloyed with Rare Earth Metals (REM). The post-mortem study results clearly revealed the formation of a multi-layer accretion. A harmful effect of the SENs decarburization on the accretion thickness was also indicated. In addition, the results indicated a penetration of the formed alkaline-rich glaze into the alumina-graphite base refractory. More specifically, the alkaline-rich glaze reacts with graphite to form a carbon monoxide gas. Thereafter, dissociation of CO at the interface between SEN and molten metal takes place. This leads to reoxidation of dissolved alloying elements such as REM (Rare Earth Metal). This reoxidation forms the “In Situ” REM oxides at the interface between the SEN and the REM alloyed molten steel. Also, the interaction of the penetrated glaze with alumina in the SEN base refractory materials leads to the formation of a high-viscous alumina-rich glaze during the SEN preheating process. This, in turn, creates a very uneven surface at the SEN internal surface. Furthermore, these uneven areas react with dissolved REM in molten steel to form REM aluminates, REM silicates and REM alumina-silicates. The formation of the large “in-situ” REM oxides and the reaction of the REM alloying elements with the previously mentioned SEN´s uneven areas may provide a large REM-rich surface in contact with the primary inclusions in molten steel. This may facilitate the attraction and agglomeration of the primary REM oxide inclusions on the SEN internal surface and thereafter the clogging. The study revealed the disadvantages of the glass/silicon powder coating applications and the SEN decarburization. The decarburization behaviors of Al2O3-C, ZrO2-C and MgO-C refractory materials from a commercial Submerged Entry Nozzle (SEN), were also investigated for different gas atmospheres consisting of CO2, O2 and Ar. The gas ratio values were kept the same as it is in a propane combustion flue gas at different Air-Fuel-Ratio (AFR) values for both Air-Fuel and Oxygen-Fuel combustion systems. Laboratory experiments were carried out under nonisothermal conditions followed by isothermal heating. The decarburization ratio (α) values of all three refractory types were determined by measuring the real time weight losses of the samples. The results showed the higher decarburization ratio (α) values increasing for MgO-C refractory when changing the Air-Fuel combustion to Oxygen-Fuel combustion at the same AFR value. It substantiates the SEN preheating advantage at higher temperatures for shorter holding times compared to heating at lower temperatures during longer holding times for Al2O3-C samples. Diffusion models were proposed for estimation of the decarburization rate of an Al2O3-C refractory in the SEN. Two different methods were studied to prevent the SEN decarburization during preheating: The effect of an ZrSi2 antioxidant and the coexistence of an antioxidant additive and a (4B2O3 ·BaO) glass powder on carbon oxidation for non-isothermal and isothermal heating conditions in a controlled atmosphere. The coexistence of 8 wt% ZrSi2 and 15 wt% (4B2O3 ·BaO) glass powder of the total alumina-graphite refractory base materials, presented the most effective resistance to carbon oxidation. The 121% volume expansion due to the Zircon formation during heating and filling up the open pores by a (4B2O3 ·BaO) glaze during the green body sintering led to an excellent carbon oxidation resistance. The effects of the plasma spray-PVD coating of the Yttria Stabilized Zirconia (YSZ) powder on the carbon oxidation of the Al2O3-C coated samples were investigated. Trials were performed at non-isothermal heating conditions in a controlled atmosphere. Also, the applied temperature profile for the laboratory trials were defined based on the industrial preheating trials. The controlled atmospheres consisted of CO2, O2 and Ar. The thicknesses of the decarburized layers were measured and examined using light optic microscopy, FEG-SEM and EDS. A 250-290 μm YSZ coating is suggested to be an appropriate coating, as it provides both an even surface as well as prevention of the decarburization even during heating in air. In addition, the interactions between the YSZ coated alumina-graphite refractory base materials in contact with a cerium alloyed molten stainless steel were surveyed. The YSZ coating provided a total prevention of the alumina reduction by cerium. Therefore, the prevention of the first clogging product formed on the surface of the SEN refractory base materials. Therefore, the YSZ plasma-PVD coating can be recommended for coating of the hot surface of the commercial SENs.

Evolutionary Testing of Autonomous Software Agents

A system built in terms of autonomous agents may require even greater correctness assurance than one which is merely reacting to the immediate control of its users. Agents make substantial decisions for themselves, so thorough testing is an important consideration. However, autonomy also makes testing harder; by their nature, autonomous agents may react in different ways to the same inputs over time, because, for instance they have changeable goals and knowledge. For this reason, we argue that testing of autonomous agents requires a procedure that caters for a wide range of test case contexts, and that can search for the most demanding of these test cases, even when they are not apparent to the agents’ developers. In this paper, we address this problem, introducing and evaluating an approach to testing autonomous agents that uses evolutionary optimization to generate demanding test cases.

Estimating the Impact of Catastrophic Sea Level Rise in Maine

Maine's 3,500 miles of coastline is the longest coastline in the continental US. The goal of our study was to use GIS to estimate the impact future global sea level rise could potentially have on our state. We show the area of coastline and some of the economic and social impacts that would result from a rise of one meter and six meters. We used roads to estimate the impact on infrastructure and public building, including schools, libraries, hospitals, police and fire stations, as a measure of social impact. A sea level rise of six meters would result in a loss of over 650 km¬2 from coastal communities and cost the state of Maine over 3 million in repaving costs. Through our study, we hope coastal communities will be able to prepare for and react to the predicted changes in global sea level.