Radical Annulation Strategy to Chiral Pupukeanones: Total Synthesis of (+)-10-ex&l(- Naphthyl)pupukean-9-onea nd (+)-lO-exo-l(- Naphthyl)-5-epipupukean-9-ones1

Intramolecular alkylation reaction of the bromoenone 12, obtained from S-carvone in three steps, furnished the bicyclo[2.2.2]octenone 13. Contrary to the anticipated radical annulation reaction, the bicyclic bromides 14 and 15, obtained from the enone 13, generated exclusively the cyclopropane product 18 via a 3-exo-trig radical cyclization on reaction with nBu3SnH and AIBN, even in the presence of a large excess of a radicophile. On the other hand, bromoenone 24, synthesized from R-carvone via S-naphthylcarvone 21, underwent radical annulation reaction in the presence of radicophiles to furnish the isotwistanes 25-28 in a regio- and stereospecific manner. Hydrogenation of the olefin 34, obtained from the diketone 27 via a regiospecific Wittig reaction, furnished the naphthyl-5-epipupukean-9-one 33, whereas stereoselective hydrogenation of the enone 36, prepared from the keto ester 25 via a Grignard reaction and dehydration sequence, generated the naphthylpupukeanone 32.

Biomarkers in acute respiratory failure

Acute respiratory failure (ARF) is the most common type of organ failure leading to the need for intensive care. It is often secondary to acute lung injury (ALI) and its more severe form, acute respiratory distress syndrome (ARDS). ARF, and especially ALI and ARDS, cause increased morbidity, and mortality rates remain high (up to 40%). These disorders are characterised by inflammatory reaction and tissue damage. In some cases, inflammation continues and leads to an overwhelming repair process with ongoing fibrosis, accompanied by organ dysfunction and eventually a loss of function. Measuring the magnitude of the inflammation, and the repair process, would theoretically offer information concerning outcome. Early identification of patients whose disease process is likely to proceed unfavourably, would help clinicians to optimise their treatment. The aim of this study was to evaluate the epidemiology of ARF, its treatment, and outcome in Finland, with special interest in biomarkers, and their value in the prediction of mortality. Altogether, 958 adult patients treated with ventilatory support were prospectively included in this study during an eight week period in 2007 in 25 intensive care units. Plasma aminoterminal pro-brain natriuretic peptide (NT-pro-BNP) was assessed in 602 patients, and plasma cell-free DNA in 580 patients, to evaluate their prognostic value in ARF. Markers of collagen metabolism were studied in longitudinal serum samples in 68 patients in order to evaluate their evolution in ARF and the association to multiple organ dysfunction (MOD). Ventilatory support was used in 39% of all ICU patients. The estimated incidence of ARF was 149.5/100 000 per year. Median tidal volumes used were higher than recommended. Overall mortality at 90 days was 31%. Plasma NT-pro-BNP and cell-free DNA were highly increased in the majority of patients. Both markers were independent predictors of 90-day mortality, but their discriminative power was at most moderate when used separately. The mortality was highest in those patients, in whom both biomarkers were over their separate cut-off values. Thus, combined use of these biomarkers may increase their clinical value in the mortality prediction. The markers of collagen metabolism changed significantly over time in surviving patients. None of these markers did associate with MOD in these patients.

Heraproteiinivalmisteen vaikutus laihdutukseen ja laihdutustuloksen pysyvyyteen ylipainoisilla aikuisilla

Johdanto: Lihavuus on maailmalaajuisesti merkittävä kansanterveydellinen ja –taloudellinen ongelma. Lihavuuden ehkäisemiseksi ja epidemian leviämisen hillitsemiseksi on tärkeää tuntea lihavuuteen vaikuttavat tekijät. Yksittäisistä ruoka-aineista maidon käytön on havaittu monissa epidemiologisissa ja kokeellisissa tutkimuksissa olevan yhteydessä alhaisempaan painoon, ehkäisevän lihomista ja edistävän laihtumista. Maidon sisältämistä yhdisteistä kalsiumin vaikutuksia on tutkittu eniten. Myös heraproteiinin on esitetty olevan yksi mahdollinen painoon vaikuttava komponentti, ja näyttöä tästä on saatu eläinkokeista. Tavoitteet: Tutkimuksessa tavoitteena oli selvittää, vaikuttaako päivittäin nautittu heraproteiinia sisältävä välipalajuoma laihtumiseen tai saavutetun laihdutustuloksen pysyvyyteen ylipainoisilla aikuisilla. Aineisto ja menetelmät: Tutkimus toteutettiin osana Valio Oy:n OMPPU2-tutkimusta, joka oli satunnaistettu, lumekontrolloitu ja kaksoissokkoutettu kahden rinnakkaisen ryhmän tutkimus. Tutkimus alkoi rekrytoinneilla alkuvuodesta 2010, joissa tutkimukseen valittiin 105 ylipainoista (BMI 27–35), tervettä, 20–50-vuotiasta naista ja miestä. Tutkimushenkilöt satunnaistettiin tutkimus- ja verrokkiryhmiin, ja molemmat ryhmät nauttivat tutkimusvalmisteensa päivittäin hedelmätäysmehuun sekoitettuna (tutkimusryhmä heraproteiinijauheen ja verrokkiryhmä maltodekstriinijauheen). Tutkimus koostui kahdesta jaksosta: viiden kuukauden laihdutusjaksosta ja tätä seuranneesta kolmen kuukauden painonhallintajaksosta. Tutkimuskäynneillä tutkimuksen alussa, laihdutusjakson lopussa ja painonhallintajakson lopussa mitattiin tutkimushenkilöiden paino ja vyötärönympärys sekä määritettiin kehonkoostumus bioimpedanssilaitteella. Tutkimushenkilöiden ruoankäyttö ja ravinnonsaanti laskettiin samoissa aikapisteissä kerättyjen kolmen päivän ruokapäiväkirjojen perusteella. Tutkimushenkilöitä, joilla tutkimusvalmisteen käyttö oli alle 50 %, ei otettu huomioon tilastoanalyyseissä. Tilastollinen analyysi tehtiin käyttäen kahden riippumattoman otoksen t-testiä ja kaksisuuntaista parittaista t-testiä normaalijakautuneilla muuttujilla, ja Mann-Whitneyn U-testiä ja Wilcoxonin ttestiä ei-normaalijakautuneilla muuttujilla. Tutkimusvalmisteen ja painonmuutosten välinen korrelaatio laskettiin käyttäen Pearsonin korrelaatiokertoimia. Tulokset on ilmaistu keskiarvoina (keskihajonta). Tulokset: Molemmat ryhmät laihtuivat laihdutusjakson aikana. Heraproteiiniryhmässä painonpudotus oli 2,4 (3,8) kg (p=0,002) ja verrokkiryhmässä 3,4 (4,1) kg (p<0,001). Ryhmien välinen ero ei ollut merkitsevä. Rasvamassa väheni verrokkiryhmässä 2,4 (3,8) kg (p<0,001), mikä oli viiteellisesti enemmän (p=0,054) kuin heraproteiiniryhmässä 1,1 (3,1) kg (p=0,129). Rasvaprosentti ja viskeraalirasvan määrä pienenivät verrokkiryhmässä heraproteiiniryhmää enemmän (p<0,025). Vyötärönympärys pieneni heraproteiiniryhmässä 1,9 (3,0) cm (p=0,001) ja verrokkiryhmässä 3,8 (3,8) cm (p<0,001) ryhmien välisen eron ollessa merkitsevä (p=0,017). Maltodekstriinin käyttö korreloi käänteisesti painonmuutosten kanssa laihdutusjaksolla (r=-0,389, p=0,013). Painonhallintajaksolla painossa ei tapahtunut merkitseviä muutoksia kummassakaan ryhmässä. Heraproteiinin käytön ja painonmuutosten välisestä negatiivisesta korrelaatiosta oli viitteitä tällä jaksolla (r=-0,344, p=0,063). Kun tarkasteltiin koko tutkimuksen aikana tapahtuneita muutoksia (laihdutusjakson alusta painonhallintajakson loppuun), ei ryhmien välillä ollut merkitseviä eroja painon tai kehonkoostumuksen muutoksissa. Energiansaanti väheni molemmissa ryhmissä merkitsevästi laihdutusjakson aikana (p<0,01), mutta muutos ei eronnut ryhmien välillä. Ravintoaineista rasvan saanti väheni (p<0,001) ja C-vitamiinin saanti lisääntyi (p<0,001) molemmissa ryhmissä laihdutusjaksolla. Alkoholin saanti väheni verrokkiryhmässä (p=0,017). Proteiinin saanti lisääntyi heraproteiiniryhmässä merkitsevästi enemmän kuin verrokkiryhmässä (p=0,002). Painonhallintajaksolla energiansaanti ei muuttunut kummassakaan ryhmässä laihdutusjakson loppuun verrattuna. Fyysisessä aktiivisuudessa tutkimuksen aikana ei ollut eroa ryhmien välillä. Johtopäätökset: Heraproteiinin ei havaittu tehostavan laihdutusta maltodekstriiniin verrattuna tässä tutkimuksessa. Sen sijaan maltodekstriiniä nauttineessa ryhmässä rasvaprosentti ja erityisesti vatsan alueen rasva pienenivät heraproteiiniryhmää enemmän laihdutusjaksolla. Tulos oli lähes täysin vastakkainen tutkimushypoteesin kanssa, eikä vaikuttaisi selittyvän eroilla energiansaannissa tai fyysisessä aktiivisuudessa. Tämä tutkimus ei siis tue olettamusta, että heraproteiini osana laihdutusruokavaliota auttaisi laihdutuksessa. Painonhallintajaksolla heraproteiinin ja painonmuutosten välinen lähes merkitsevä käänteinen korrelaatio saattaa viitata heraproteiinin merkitykseen painonhallinnassa. Vapaasti elävien ihmisten kohdalla sekoittavia tekijöitä on kuitenkin vaikea vakioida, mikä vaikeuttaa johtopäätösten tekemistä.

Dietary habits and obesity: the role of emotional and cognitive factors

In post-industrialised societies, food is more plentiful, accessible and palatable than ever before and technological development has reduced the need for physical activity. Consequently, the prevalence of obesity is increasing, which is problematic as obesity is related to a number of diseases. Various psychological and social factors have an important influence on dietary habits and the development of obesity in the current food-rich and sedentary environments. The present study concentrates on the associations of emotional and cognitive factors with dietary intake and obesity as well as on the role these factors play in socioeconomic disparities in diet. Many people cognitively restrict their food intake to prevent weight gain or to lose weight, but research on whether restrained eating is a useful weight control strategy has produced conflicting findings. With respect to emotional factors, the evidence is accumulating that depressive symptoms are related to less healthy dietary intake and obesity, but the mechanisms explaining these associations remain unclear. Furthermore, it is not fully understood why socioeconomically disadvantaged individuals tend to have unhealthier dietary habits and the motives underlying food choices (e.g., price and health) could be relevant in this respect. The specific aims of the study were to examine 1) whether obesity status and dieting history moderate the associations of restrained eating with overeating tendencies, self-control and obesity indicators; 2) whether the associations of depressive symptoms with unhealthier dietary intake and obesity are attributable to a tendency for emotional eating and a low level of physical activity self-efficacy; and 3) whether the absolute or relative importance of food choice motives (health, pleasure, convenience, price, familiarity and ethicality) contribute to the socioeconomic disparities in dietary habits. The study was based on a large population-based sample of Finnish adults: the participants were men (N=2325) and women (N=2699) aged 25-74 who took part in the DILGOM (Dietary, Lifestyle and Genetic Determinants of Obesity and Metabolic Syndrome) sub-study of the National FINRISK Study 2007. The participants weight, height, waist circumference and body fat percentage were measured in a health examination. Psychological eating styles (the Three-Factor Eating Questionnaire-R18), food choice motives (a shortened version of the Food Choice Questionnaire), depressive symptoms (the Center for Epidemiological Studies Depression Scale) and self-control (the Brief Self-Control Scale) were measured with pre-existing questionnaires. A validated food frequency questionnaire was used to assess the average consumption of sweet and non-sweet energy-dense foods and vegetables/fruit. Self-reported total years of education and gross household income were used as indicators of socioeconomic position. The results indicated that 1) restrained eating was related to a lower body mass index, waist circumference, emotional eating and uncontrolled eating, and to a higher self-control in obese participants and current/past dieters. In contrast, the associations were the opposite in normal weight individuals and those who had never dieted. Thus, restrained eating may be related to better weight control among obese individuals and those with dieting experiences, while among others it may function as an indicator of problems with eating and an attempt to solve them. 2) Emotional eating and depressive symptoms were both related to less healthy dietary intake, and the greater consumption of energy-dense sweet foods among participants with elevated depressive symptoms was attributable to the susceptibility for emotional eating. In addition, emotional eating and physical activity self-efficacy were both important in explaining the positive association between depressive symptoms and obesity. 3) The lower vegetable/fruit intake and higher energy-dense food intake among individuals with a low socioeconomic position were partly explained by the higher priority they placed on price and familiarity and the lower priority they gave to health motives in their daily food choices. In conclusion, although policy interventions to change the obesogenic nature of the current environment are definitely needed, knowledge of the factors that hinder or facilitate people s ability to cope with the food-rich environment is also necessary. This study implies that more emphasis should be placed on various psychological and social factors in weight control programmes and interventions.

Chiral Synthons from Carvone. Part 10. Synthesis of (+)-(1S,3S,4S,7S, 8R)-5,7-Dimethyl-10-oxatetracyclo-(5.3.0.03,5,04,8)decan-9-one.

Degradation of the tolyl group in the tricyclic ketone 1b followed by stereospecific reduction of the resultant ketoester (6) furnishes the title compound (4) containing a new tetracyclic framework, establishing the stereochemistry of the aryl group in 1.

On kuhnels 9-vertex complex projective plane

We present an elementary combinatorial proof of the existence and uniqueness of the 9-vertex triangulation of C P2. The original proof of existence, due to Kuhnel, as well as the original proof of uniqueness, due to Kuhnel and Lassmann, were based on extensive computer search. Recently Arnoux and Marin have used cohomology theory to present a computer-free proof. Our proof has the advantage of displaying a canonical copy of the affine plane over the three-element field inside this complex in terms of which the entire complex has a very neat and short description. This explicates the full automorphism group of the Kuhnel complex as a subgroup of the automorphism group of this affine plane. Our method also brings out the rich combinatorial structure inside this complex.

Enantioselective Synthesis of Possible Diastereomers of Heptadeca-1-ene-4,6-diyne-3,8,9,10-tetrol; Putative Structure of a Conjugated Diyne Natural Product Isolated from Hydrocotyle leucocephala

Enantioselective synthesis of possible diastereomers of heptadeca-1-ene-4,6-diyne-3,8,9,10-tetrol, a structure proposed for the natural product isolated from Hydrocotyle leucocephala is accomplished. The reported spectral data of the natural product did not match those of any of the isomers that were synthesized and established that the structure proposed for the natural product is not correct and requires revision.

Structure of 9[alpha],19-dihydroxy-4-androstene-3,17-dione

C19H26O4, M(r) = 318.41, orthorhombic, P2(1)2(1)2(1), a = 10.591 (1), b = 11.133 (1), c = 13.657 (2) angstrom, V = 1610.29 angstrom 3, Z = 4, D(m) (flotation in KI) = 1.301, D(x) = 1.313 g cm-3, Mo K-alpha, lambda = 0.7107 angstrom, mu = 0.85 cm-1, F(000) = 688, T = 293 K, R = 0.057 for 1253 significant reflections. The A ring is disordered with atoms C(2) and O(19) occupying two possible sites. The molecules are held together by a hydrogen bond [O(9)...O(17) = 2.89 angstrom].

Intramolecular Reactivity - Keto Participation in the Hydrolysis of N-Methyl-N-(9-Oxobicyclo[3.3.1]Nonan-2-Alpha-YL) Morpholinium Iodide, and A Cannizzaro-Type Reaction of 3-(2-Oxocyclohexyl)Propanal

Mechanistic studies of two intramolecular processes, nucleophilic displacement of N-methylmorpholinium in N-methyl-N-{9-oxobicyclo[3,3,1]nonan-2 alpha-yl}morpholinium iodide, anchimerically assisted by keto carbonyl, and a Cannizzaro-type reaction of 3-(2-oxocyclohexyl)propanal, occurring via axial hydride transfer onto the cyclohexanone, are reported.

Pressure-induced charge transfer in lanthanum nickel ferrate (LaNi0.5Fe0.5O3) and analogies to composition-driven charge transfer in dilanthanum cuprate (La2CuO4): an infrared study

A reversible pressure-induced phase transition in lanthanum nickel ferrate (LaNi0.5Fe0.5O3) manifests itself in the infrared spectrum of the transition metal-oxygen stretching (nu(TM-O)) modes by the emergence of new peaks at pressures greater than similar to 1.4 x 10(9) Pa. Analogies to this transition are made by considering charge transfer in dilanthanum cuprate (La2CuO4) and its modification by partial substitution of copper ions by chromium ions.

Stereospecific solid-state NaBH4-promoted reduction of 1-methylpentacyclo[5.4.0.0(2,6).0(3,10).0(5,9)]undecane-8,11-dione

NaBH4 reduction of a cage dione proceeds in a stereospecific fashion to give the endo,endo-diol. This reactivity is related to the crystal structure.

LiSr1.65 square 0.35B1.3B ' O-1.7(9) (B = Ti, Zr; B ' = Nb, Ta): New lithium ion conductors based on the perovskite structure

We describe the design and synthesis of new lithium ion conductors with the formula, LiSr(1.65)rectangle(0.35)B(1.3)B'O-1.7(9) (rectangle = vacancy; B = Ti, Zr; B' = Nb, Ta), on the basis of a systematic consideration of the composition-structure-property correlations in the well-known lithium-ion conductor, La-(2/3-x)Li(3x)rectangle((1/3)-2x)TiO3 (I), as well as the perovskite oxides in Li-A-B,B'-O (A = Ca, Sr, Ba; B = Ti, Zr; B' = Nb, Ta) systems. A high lithium-ion conductivity of ca. 0.12 S/cm at 360 degrees C is exhibited by LiSr(1.65)rectangle(0.35)Ti(1.3)Ta(1.7)O(9) (III) and LiSr(1.65)rectangle(0.35)Zr(1.3)Ta(1.7)O(9) (IV), of which the latter containing stable Zr(IV) and Ta(V) oxidation states is likely to be a candidate electrolyte material for all-solid-state lithium battery application. More importantly, we believe the approach described here could be extended to synthesize newer, possibly better, lithium ion conductors.

Structure of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecyl 1,10-ditosylate by X-ray crystallography and F-19-NMR spectroscopy

2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecyl 1,10-ditosylate and its precursors were synthesized and characterized by H-1- and F-19-NMR spectroscopic methods and X-ray crystallography. These compounds are building blocks for the syntheses of the surfactants containing polyperfluoromethylene spacer. The molecule has extended all-trans conformation with molecular symmetry (1) over bar (C-i). There is a reasonably strong C-H ... O interaction in the crystal and there are two F ... F intermolecular contact distances less than the sum of van der Waals radii. (C) 1999 Elsevier Science B.V. All rights reserved.

An enantiospecific approach to 8,9-seco-C-aromatic taxanes

An enantiospecific approach to functionalised C-aromatic-8,9-seco-taxanes starting from the readily available monoterpene (R)-carvone is described.