Bufadienolides. 8. 12(13→14)abeo skeletal rearrangements

Several methods were developed for converting isodigitoxigenin (2a) into methyl acetals 4b and 4c. Of these, methanolysis (followed by acetylation) of isodigitoxigenin in the presence of p-toluenesulfonic acid proved most useful. Each isomer reached an equilibrium corresponding to ca. 3:1 acetal 4c to 4b within 15 min in benzene containing p-toluenesulfonic acid. Addition of dihydropyran to the equilibrium mixture resulted in excellent conversion into vinyl ether 5a. Heating either acetal 4b or 4c in benzene containing p-toluenesulfonic acid led to a skeletal rearrangement culminating in formation of C-norcardenolide 6. In addition to results of physical measurements, the structure of spiran 6 was confirmed by degradation to methyl ketone 8. Similar rearrangement of isodigitoxigenin gave spiran 9 accompanied by C-norcardenolide 6. Treating lactone 9 with p-toluenesulfonic acid in methanol-water provided acetals 10a and 10b, which on further contact with p-toluenesulfonic acid in refluxing benzene gave lactone 9 and cardenolide 6. Evidence underlying the stereochemical assignments noted for structures 4, 9, and 10 was also discussed.

Structure of abnormal products isolated from the isomerization of 7-methoxychromano3,4-disoxazole - A novel synthesis of one of the products

A one-step synthesis of (IIb), an isomerization product of 7-methoxychromano3,4-disoxazole, from (III) is reported.

Impact of cosmic inhomogeneities on SNe observations

We study the impact of cosmic inhomogeneities on the interpretation of SNe observations. We build an inhomogeneous universe model that can confront supernova data and yet is reasonably well compatible with the Copernican Principle. Our model combines a relatively small local void, that gives apparent acceleration at low redshifts, with a meatball model that gives sizeable lensing (dimming) at high redshifts. Together these two elements, which focus on different effects of voids on the data, allow the model to mimic the concordance model.

Growth of ionization currents in dry air at high values of E/N

Uniform field steady-state ionization currents were measured in dry air as a function of N at constant E/N (E is the electric field strength and N the gas number density) and constant electrode separation d for 14·13 × 10-16 less-than-or-eq, slant E/N less-than-or-eq, slant 282·5 × 10-16 V cm2. Uniform field sparking potentials were also measured for Nd range 1·24 × 1016 less-than-or-eq, slant Nd less-than-or-eq, slant 245 × 1016 cm-2. The ratio of the Townsend primary ionization coefficient α to N, α/N, was found to depend on E/N only. The secondary coefficients were also evaluated for aluminium and gold-plated electrodes for the above range of E/N. Measurements of the sparking potentials showed that Paschen's law is not obeyed in air at values of Nd near and below the Paschen minimum.

The ratio of diffusion coefficient to mobility for slow electrons in dry air

Using Huxley's solution of the diffusion equation for electron-attaching gases, the ratio of diffusion coefficient D to mobility μ for electrons in dry air was measured over the range 3·06 × 10-17

Perspektiv på språkprocessering

Automatisk språkprocessering har efter mer än ett halvt sekel av forskning blivit ett mycket viktigt område inom datavetenskapen. Flera vetenskapligt viktiga problem har lösts och praktiska applikationer har nått programvarumarknaden. Disambiguering av ord innebär att hitta rätt betydelse för ett mångtydigt ord. Sammanhanget, de omkringliggande orden och kunskap om ämnesområdet är faktorer som kan användas för att disambiguera ett ord. Automatisk sammanfattning innebär att förkorta en text utan att den relevanta informationen går förlorad. Relevanta meningar kan plockas ur texten, eller så kan en ny, kortare text genereras på basen av fakta i den ursprungliga texten. Avhandlingen ger en allmän översikt och kort historik av språkprocesseringen och jämför några metoder för disambiguering av ord och automatisk sammanfattning. Problemområdenas likheter och skillnader lyfts fram och metodernas ställning inom datavetenskapen belyses.

Cystatin C, a measure of renal function, as prognostic risk marker in acute heart failure : Studies on the cardiorenal syndrome

Acute heart failure (AHF) is a complex syndrome associated with exceptionally high mortality. Still, characteristics and prognostic factors of contemporary AHF patients have been inadequately studied. Kidney function has emerged as a very powerful prognostic risk factor in cardiovascular disease. This is believed to be the consequence of an interaction between the heart and kidneys, also termed the cardiorenal syndrome, the mechanisms of which are not fully understood. Renal insufficiency is common in heart failure and of particular interest for predicting outcome in AHF. Cystatin C (CysC) is a marker of glomerular filtration rate with properties making it a prospective alternative to the currently used measure creatinine for assessment of renal function. The aim of this thesis is to characterize a representative cohort of patients hospitalized for AHF and to identify risk factors for poor outcome in AHF. In particular, the role of CysC as a marker of renal function is evaluated, including examination of the value of CysC as a predictor of mortality in AHF. The FINN-AKVA (Finnish Acute Heart Failure) study is a national prospective multicenter study conducted to investigate the clinical presentation, aetiology and treatment of, as well as concomitant diseases and outcome in, AHF. Patients hospitalized for AHF were enrolled in the FINN-AKVA study, and mortality was followed for 12 months. The mean age of patients with AHF is 75 years and they frequently have both cardiovascular and non-cardiovascular co-morbidities. The mortality after hospitalization for AHF is high, rising to 27% by 12 months. The present study shows that renal dysfunction is very common in AHF. CysC detects impaired renal function in forty percent of patients. Renal function, measured by CysC, is one of the strongest predictors of mortality independently of other prognostic risk markers, such as age, gender, co-morbidities and systolic blood pressure on admission. Moreover, in patients with normal creatinine values, elevated CysC is associated with a marked increase in mortality. Acute kidney injury, defined as an increase in CysC within 48 hours of hospital admission, occurs in a significant proportion of patients and is associated with increased short- and mid-term mortality. The results suggest that CysC can be used for risk stratification in AHF. Markers of inflammation are elevated both in heart failure and in chronic kidney disease, and inflammation is one of the mechanisms thought to mediate heart-kidney interactions in the cardiorenal syndrome. Inflammatory cytokines such as interleukin-6 (IL-6) and tumor necrosis factor-alpha (TNF-α) correlate very differently to markers of cardiac stress and renal function. In particular, TNF-α showed a robust correlation to CysC, but was not associated with levels of NT-proBNP, a marker of hemodynamic cardiac stress. Compared to CysC, the inflammatory markers were not strongly related to mortality in AHF. In conclusion, patients with AHF are elderly with multiple co-morbidities, and renal dysfunction is very common. CysC demonstrates good diagnostic properties both in identifying impaired renal function and acute kidney injury in patients with AHF. CysC, as a measure of renal function, is also a powerful prognostic marker in AHF. CysC shows promise as a marker for assessment of kidney function and risk stratification in patients hospitalized for AHF.

Steroids and related natural products. VIII. Synthesis of oxasteroids

Peroxydisulfuric acid oxidation of testosterone propionate, progesterone, and cholest-4-en-3-one has been shown to yield 3-oxo-17β-hydroxy-4-oxa-5α-androstane (I, after saponification), 3,20-dioxo-4-oxa-5α-pregnane (V) and 3-oxo-4-oxa-5α-cholestane (VII) respectively. Boron trifluoride etherate-lithium aluminum hydride reduction of δ-lactones I, V, and VII led to the corresponding tetrahydropyran derivatives (IIb, VIa, and VIII). Similar reduction of 3β-hydroxy-17-oxo-17a-oxa-D-homo-5α-androstane (XI) gave 3β-hydroxy-17a-oxa-D-homo-5α-androstane (XIIa). Diborane-boron trifluoride etherate was also found to reduce lactones to cyclic ethers, while reduction with diborane gave hemiacetals. Evidence in support of the structures and stereochemistry assigned to the lactones and their unusual reduction products has been summarized. A tentative mechanism is proposed for lactone → ether reduction employing diborane-boron trifluoride etherate.

Steroids and related natural products. VII. Boron trifluoride etherate-lithium aluminum hydride reduction of smilagenin acetate

Reduction of smilagenin acetate (Va) using a boron trifluoride etherate-lithium aluminum hydride reagent, followed by hydrogen peroxide oxidation and acetylation, was found to yield: 3β-ethoxysmilagenin (Vb), 3β-ethoxydihydrosmilagenin acetate (VIa), dihydrosmilagenin diacetate (VIb), and a complex mixture of partially acetylated products. Similar reaction conditions were employed to convert dihydrodiosgenin (II) to dihydrochlorogenin (III). Boron trifluoride etherate-lithium aluminum hydride reduction of 3β-acetoxy-5α-cholestane and 3β-acetoxy-5α-lanostane (VIIIa) was shown to yield the corresponding 3β-ethoxy (e.g., VIIIb) derivatives.

Vaggvisor i Kvevlax : Språkliga strukturer och konstruktioner

Lullabies in Kvevlax. Linguistic structures and constructions. The study is a linguistic analysis of constructions that shape the texts used in lullabies in Kvevlax in Ostrobothnia in Finland. The empirical goal is to identify linguistic constructions in traditional lullabies that make use of the dialect of the region. The theoretical goal was to test the usability of Construction Grammar (CxG) in analyses of this type of material, and to further develop the formal description of Construction Grammar in such a way as to make it possible to analyze all kinds of linguistically complex texts. The material that I collected in the 1960s comprises approximately 600 lullabies and concomitant interviews with the singers on the use of lullabies. In 1991 I collected additional material in Kvevlax. The number of informants is close to 250. Supplementary material covering the Swedish-language regions in Finland was compiled from the archives of the Society of Swedish Literature in Finland. The first part of the study is mainly based on traditional grammar and gives general information about the language and the structures used in the lullabies. In the detailed study of the Kvevlax lullabies in the latter part of the study I use a version of Construction Grammar intended for the linguistic analysis of usage-based texts. The analysis focuses on the most salient constructions in the lullabies. The study shows that Construction Grammar as a method has more general applicability than traditional linguistic methods. The study identifies important constructions, including elements typical of this genre, that structure the text in different variants of the same lullabies. In addition, CxG made it possible to study pragmatic aspects of the interactional, cultural and contextual language that is used in communication with small children. The constructions found in lullabies are also used in language in general. In addition to being able to give detailed linguistic descriptions of the texts, Construction Grammar can also explain the multidimensionality of language and the variations in the texts. The use of CxG made it possible to show that variations are not random but follow prototypical linguistic patterns, constructions. Constructions are thus found to be linguistic resources with built-in variation potentials.

Long-range synthon Aufbau modules (LSAM) in crystal structures: systematic changes in C6H6-nFn (0 <= n <= 6) fluorobenzenes

We discuss the assembly of a three-dimensional molecular crystal in terms of short-range supramolecular synthons that spontaneously organize themselves according to Aufbau principles into long-range geometries characteristic of the molecules themselves. For this purpose we have examined the systematic changes in the known crystal structures of a family of fluorobenzenes, C6H6-nFn, where 0 <= n <= 6. Crystal assembly is initiated by forming long-range synthon Aufbau modules (LSAM) that carry the imprint of the synthons. For example, when 1 <= n <= 5 the short-range synthons use H center dot center dot center dot F interactions to form the LSAMs. In the n = 0 and n = 6 compounds, the synthons are H center dot center dot center dot C and F center dot center dot center dot C interactions, respectively. The LSAMs are usually one-dimensional. In this study we show that these 1D LSAMs assemble into 2D quasi-hexagonal close-packed layers. The 3D crystal structure is obtained from the various kinds of close-packing known for these 2D layers. The final stages of this 1D -> 2D -> 3D assembly seem to be more influenced by the packing of LSAMs than by any other factor. In these final stages, there may not be so much influence exerted by the stronger short-range synthons. We discuss the evolution of these fluorobenzene crystal structures in terms of putative LSAMs and the purely geometric relationships between the n and (6 - n) compounds that can thus be expected. Such particle-hole pairs show structural similarities. Our discussion is quantified by the interpretation of intermolecular distances in terms of atomic sizes and with qualitative predictions of magnetic model systems.

Long-range synthon Aufbau modules (LSAM) in crystal structures: systematic changes in C6H6-nFn (0 <= n <= 6) fluorobenzenes

We discuss the assembly of a three-dimensional molecular crystal in terms of short-range supramolecular synthons that spontaneously organize themselves according to Aufbau principles into long-range geometries characteristic of the molecules themselves. For this purpose we have examined the systematic changes in the known crystal structures of a family of fluorobenzenes, C6H6-nFn, where 0 <= n <= 6. Crystal assembly is initiated by forming long-range synthon Aufbau modules (LSAM) that carry the imprint of the synthons. For example, when 1 <= n <= 5 the short-range synthons use H center dot center dot center dot F interactions to form the LSAMs. In the n = 0 and n = 6 compounds, the synthons are H center dot center dot center dot C and F center dot center dot center dot C interactions, respectively. The LSAMs are usually one-dimensional. In this study we show that these 1D LSAMs assemble into 2D quasi-hexagonal close-packed layers. The 3D crystal structure is obtained from the various kinds of close-packing known for these 2D layers. The final stages of this 1D -> 2D -> 3D assembly seem to be more influenced by the packing of LSAMs than by any other factor. In these final stages, there may not be so much influence exerted by the stronger short-range synthons. We discuss the evolution of these fluorobenzene crystal structures in terms of putative LSAMs and the purely geometric relationships between the n and (6 - n) compounds that can thus be expected. Such particle-hole pairs show structural similarities. Our discussion is quantified by the interpretation of intermolecular distances in terms of atomic sizes and with qualitative predictions of magnetic model systems.

Rättsekonomisk analys av revisors skadeståndsansvar i Norden

Revisorn utför ekonomisk kontroll inom sitt uppdrag. Ett vållande av ekonomisk skada när revisorn utför uppdraget innebär att han kan åläggas skadeståndsansvar. På senare tid har revisors vållande vid ekonomisk kontroll prövats av de högsta rättsinstanserna i de nordiska länderna. De högsta rättsinstanserna tenderar att gå långt i sina bedömningar om revisors vållande av ekonomisk skada. De ställer ofta aktsamhetskravet högt då de ålägger revisorerna skadeståndsansvar. I avhandlingen testas revisors skadeståndsansvar enligt en i undersökningen uppbyggd ekonomisk modell. Målsättningen är att vållanderegeln skall leda till ekonomisk effektivitet. Ekonomisk effektivitet prövas genom att en ekonomisk avvägning mellan nyttan och kostnaden med att företa skadeförebyggande åtgärder görs. I den ekonomiska analysen beskrivs revisors vållande i termer av revisors bristande omsorg, medan revisors grova vållande beskrivs som uppenbar försummelse. För undersökningen utgör det nordiska rättsfallsmaterialet ett material där strukturen är likadan, vilket gör det möjligt att pröva ekonomisk effektivitet. Resultatet av den ekonomiska analysen visar att ersättning för förmögenhetsskador inte skall utgöra den egentliga målsättningen. För att kunna begränsa omfattningen av revisors ersättningsansvar så att det ur en samhällsekonomisk synvinkel är ekonomiskt effektivt, bör det formuleras en snäv bedömningsgrund för revisors bristande omsorg. Den ekonomiska analysen påvisar att revisorerna vid bristande omsorg bör åläggas ett administrativt ansvar i form av disciplinära åtgärder. Revisorer skall åläggas skadeståndsansvar endast vid uppenbar försummelse. Genom uppenbar försummelse underlåter revisorerna att förebygga uppenbar förutsebar skada och åsidosätter sitt professionsansvar på ett medvetet sätt.

Den anonyma seniorkonsumenten identifieras: Om identitetsskapande processer i en marknadsföringskontext

Marknadsföringen till äldre konsumenter har länge varit en grå zon. Konsumtionsvilja och penningstyrka är två sätt att beskriva dagens äldre konsument, och i avhandlingen bildar dessa omdömen och många andra beskrivningar fem diskurser som har benämnts senior, radikal, förlängd ungdom, hedonist och lyx och själfull och erfaren. Diskurserna baserar sig på analysen av intervjuer med reklambyråer och tidskrifter riktade till marknadsförare. Diskurserna är exempel på hur man bygger upp en identitet för den äldre konsumenten i marknadsföringens värld. Identiteterna erbjuder möjligheter till ett mångsidigare åldrande men de kan också skapa nya stereotyper. Resultaten i avhandlingen visar hur vår språkanvändning och vårt sätt att avbilda människor påverkar kategoriseringen och stereotypiseringen av dem. Avhandlingen erbjuder ett sätt att lära sig bemöta den äldre konsumenten, och egentligen vilken konsument som helst, med en så dynamisk uppfattning om denna som möjligt. Tidigare har marknadsförare främst utgått från konsumentens kronologiska ålder och diskussionen har kretsat kring när någon kan klassas som en äldre konsument. Att försöka bestämma när någon är gammal eller äldre utesluter det faktum att ålder skapas och återskapas i vårt sätt att tala om den. I denna skapelseprocess spelar marknadsförarens handlingar en viktig roll. Om ålder enbart ses som ett slags åldersgräns påtvingas vi färdiga kategorier och stereotyper som både stämplar och begränsar. Avhandlingen inför begreppet kulturell ålder där kulturens olika processer som skapar en åldersidentitet för konsumenten poängteras. Åldrande är en pågående, självuppfyllande process som ständigt omformas, definieras och förstärks av de bilder som finns runt omkring oss och sättet att tala om det (språk och representation). När vi känner till de ideologiska skiftningarna kan vi skapa en mera dynamisk kommunikation med konsumenten. Vi förstår också bättre vår roll vid uppkomsten av stereotyper och andra rigida konstruktioner. Avhandlingen har utnyttjat diskursanalytiska begrepp i kombination med ett kultursynsätt. Kombinationen kan utnyttjas då man analyserar sättet att konstruera identiteten hos olika konsumentgrupper i marknadernas olika dialoger. Därför borde man inte fråga ”Hur gammal är den äldre konsumenten?” utan ”Hur åldras konsumenten?”.