Roofed polyquinanes: synthesis and electronic structure

Starting from readily available norbornenobenzoquinone 7 and employing a photothermal metathesis reaction as the main strategy, novel "roofed" polyquinane bisenones 3 and 13 have been synthesized. Among these, the former is potentially serviceable for further elaboration to dodecahedrane 1. Catalytic hydrogenation of 3 provided the dione 12, which fully inscribes the circumference of dodecahedrane sphere. The "roofed" C-16-bisenone 3 has been successfully annulated to C19-bisenone 24 and C19-trisenone 26 by employing the Greene methodology and Pauson-Khand reaction, respectively. The molecular structures of 3 and 13 were computed using molecular mechanics and semiempirical MO methods. The nonbonded distances between the double bonds vary strongly with the method employed. The interactions between the pi-MO's were, therefore, probed by means of photoelectron (PE) spectroscopy. Comparison with the PE spectra of a series of model systems with increasing complexity enabled an unambiguous assignment of the observed peaks. The symmetric and antisymmetric combinations of the pi-MO's of the enone moieties of 3 and 13 show large splittings, characteristic of propano-bridged systems in which through-space and through-bond effects act in concert.

Oestrogen-induced synthesis of thiamin-binding protein in immature chicks. Kinetics of induction, hormonal specificity and modulation

A specific radioimmunoassay procedure was developed to monitor the plasma concentrations of thiamin-binding protein, a minor yolk constituent of the chicken egg. By using this sensitive assay, the kinetics of oestrogen-induced elaboration of this specific protein in immature chicks was investigated. After a single injection of the steroid hormone, with an initial lag period of 4–5h the thiamin-binding protein rapidly accumulated in the plasma, attaining peak concentrations around 75h and declining thereafter. A 4-fold amplification of the response was noticed during the secondary stimulation, and this increased to 9-fold during the tertiary stimulation with the steroid hormone. The magnitude of the response was dependent on the hormone dose, and the initial latent period and the duration of the ascending phase of induction were unchanged for the hormonal doses tested during both the primary and secondary stimulations. The circulatory half-life of the protein was 6h as calculated from the measurement of the rate of disappearance of the exogenously administered 125I-labelled protein. Simultaneous administration of progesterone, dihydrotestosterone or corticosterone did not alter the pattern of induction. On the other hand, hyperthyroidism markedly decreased the oestrogenic response, whereas propylthiouracil-induced hypothyroidism had the opposite effect. The anti-oestrogen E- and Z-clomiphene citrates, administered 30min before oestrogen, effectively blocked the hormonal induction. a-Amanitin and cycloheximide administered along with or shortly after the sex steroid severely curtailed the protein elaboration. A comparison of the kinetics of induction of thiamin- and riboflavin-binding proteins by oestrogen revealed that, beneath an apparent similarity, a clear-cut difference exists between the two vitamin-binding proteins, particularly with regard to hormonal dose-dependent sensitivity of induction and the half-life in circulation. The steroid-mediated elaboration of the two yolk proteins thus appears to be not strictly co-ordinated, despite several common regulatory features underlying their induction.

The Role of Electronic Word of Mouth in Shaping Consumer Attitudes

The purpose of this research was to investigate the role of electronic word of mouth (eWOM) in shaping consumer attitudes towards various products and services with concentration on the consumer attitude change. eWOM has long been proven to play an important role in influencing consumer attitudes and has been researched from a variety of perspectives. This study attempts to look deeper into the process of consumer attitude change by applying as the central theory of the study the Elaboration Likelihood Model of Persuasion by Petty and Cacioppo. In the processes of examining the background academic and empirical research the Internet and Web 2.0 are closely depicted in order to understand how throughout the past centuries technology allowed the rise of various mediums where consumers can not only share their opinions online about products and services but also communicate with other consumers. Manuel Castel’s Internet Galaxy, Gildin’s, Carl and Noland’s, Hennig-Thurau, Gwinner, Walsh and Gremler’s researches on eWOM are the central works that helped to shape both the theoretical and empirical parts of this study. The mixed method approach was chosen as a research method for this study. An online survey was conducted via the Surveymonkey.com platform and eight qualitative in-depth interviews were conducted. The results of the study show that central route queues as text quality and text argumentativeness are more prominent among the research subjects and the peripheral route queues: source credibility and source expertise did not show considerable significance. Also more experience and participation consumers have with user-rating websites and applications more inclined they are to elaborate on the central route cues and are more likely to search for opinions that they consider rational and credible. Also these respondents are less inclined to search for ratings that confirm their existing beliefs about products or services. Less experience/participation they have about eWOM more likely they are to search for reviews confirmatory to their own.

Formal total synthesis of (+)-didemniserinolipid B

The formal total synthesis of (+)-didemniserinolipid B, a marine tunicate possessing a 6,8-dioxabicyclo3.2.1]octane framework, was accomplished starting from L-(+)-tartaric acid. The key transformations in the synthesis include the elaboration of a gamma-hydroxy-amide readily obtained by desymmetrization of tartaric acid bis-amide via the controlled addition of a Grignard reagent followed by stereoselective reduction of the resulting ketone. (C) 2010 Elsevier Ltd. All rights reserved.

Cardiac remodeling in Drosophila arises from changes in actin gene expression and from a contribution of lymph gland-like cells to the heart musculature

Understanding the basis of normal heart remodeling can provide insight into the plasticity of the cardiac state, and into the potential for treating diseased tissue. In Drosophila, the adult heart arises during metamorphosis from a series of events, that include the remodeling of an existing cardiac tube, the elaboration of new inflow tracts, and the addition of a layer of longitudinal muscle fibers. We have identified genes active in all these three processes, and studied their expression in order to characterize in greater detail normal cardiac remodeling. Using a Transglutaminase-lacZ transgenic line, that is expressed in the inflow tracts of the larval and adult heart, we confirm the existence of five inflow tracts in the adult structure. In addition, expression of the Actin87E actin gene is initiated in the remodeling cardiac tube, but not in the longitudinal fibers, and we have identified an Act87E promoter fragment that recapitulates this switch in expression. We also establish that the longitudinal fibers are multinucleated, characterizing these cells as specialized skeletal muscles. Furthermore, we have defined the origin of the longitudinal fibers, as a subset of lymph gland cells associated with the larval dorsal vessel. These studies underline the myriad contributors to the formation of the adult Drosophila heart, and provide new molecular insights into the development of this complex organ. (C) 2011 Elsevier Ireland Ltd. All rights reserved.

Enantioselective total synthesis of iso-cladospolide B, cladospolide C and cladospolide B from tartaric acid

The enantioselective synthesis of the natural products cladospolide B, cladospolide C, and iso-cladospolide B has been accomplished from tartaric acid. Key reactions in the synthetic sequence include the elaboration of a gamma-hydroxy amide derived from tartaric acid via alkene cross metathesis, Yamaguchi lactonization, and ring closing metathesis. (C) 2011 Elsevier Ltd. All rights reserved.

Enantiodivergent total synthesis of microcarpalide from L-tartaric acid

Stereoselective approach for the synthesis of both enantiomers of bio-active decanolactone microcarpalide is described from L-tartaric acid. The synthesis of the key intermediates en route to the natural product is achieved from L-tartaric acid involving the elaboration of gamma-hydroxy amide derived from tartaric acid and ring opening of an epoxide derived from tartaric acid. (C) 2011 Elsevier Ltd. All rights reserved.

Total Synthesis of (-)-Anamarine

Total synthesis of polyhydroxy delta-pyranone natural product (-)-anamarine is accomplished from D-(-)-tartaric acid. The main feature of the synthesis is the utility of hitherto unexplored beta-keto phosphonate derived from tartaric acid amide and further elaboration involving stereoselective reduction.

Total synthesis of panaxytriol and panaxydiol

The enantioselective total synthesis of the diyne containing natural products panaxytriol and (3S,10R)-panaxydiol from L-tartaric acid is reported. Key steps in the synthesis include the elaboration of a gamma-hydroxy amide derived from tartaric acid to the required alkyne and the formation of the desired diyne unit by a Cadiot-Chodkiewicz coupling. (C) 2011 Elsevier Ltd. All rights reserved.

Total synthesis of (-)-ent-pachastrissamine (ent-Jaspine B)

The total synthesis of the enantiomer of the tetrahydrofuran containing natural product Jaspine B is reported. The key reactions in the synthesis include formation of the tetrahydrofuran unit by an acid mediated Williamson etherification and a subsequent elaboration with an olefin cross metathesis reaction. (C) 2011 Elsevier Ltd. All rights reserved.

Total synthesis of (+)-anamarine

An enantiospecific total synthesis of polyhydroxy delta-pyrone natural product (+)-anamarine is accomplished. The main features of the synthesis include the stereoselective reduction of the ketone obtained by the desymmetrization of the bis-dimethyl amide of tartaric acid and further elaboration involving asymmetric Brown's allylation and ring closing metathesis. (C) 2014 Elsevier Ltd. All rights reserved.

Enantiospecific Formal Total Synthesis of Iriomoteolide 3a

A formal total synthesis of the marine macrolide iriomoteolide3a is described. Salient features of the synthesis include the elaboration of a -keto phosphonate derived from D-(-)-tartaric acid and the extension of a chiral butyrolactone derived from L-glutamic acid. Ring-closing metathesis is employed to construct the macrolactone core of the natural product.

Proto-alphabetic inscriptions from the Wadi Arabah

Abstract: Three early West Semitic inscriptions from the Arabah valley are studied here, all of them apparently connected with the Egyptian copper-mining activity in the region, notably at Timna, in the period of the Ramessides. The most striking detail in these texts is a sign corresponding to an Egyptian hieroglyph (N6B ) which depicts two serpents guarding the sun-disc, and another with one serpent (N6 , ); these never appear on conventional tables of early alphabetic letters; this leads to a critical reappraisal of current identifications of the original picture-signs, and elaboration of a new system of interpreting early Canaanite inscriptions, involving recognition that the signs could sometimes stand for whole words and could also be used as rebuses.

Translatio materiae : adopción de formas y géneros latinos en las colecciones hispánicas de milagros marianos

Resumen: Un tipo de literatura latina no narrativa, asimilable más bien al discurso doctrinal teológico y mariológico y, por otro lado, a la himnodia litúrgica, deja entrever su influencia en las colecciones ibéricas de milagros marianos en verso del siglo XIII, las Cantigas de Santa María de Alfonso X y los Milagros de Nuestra Señora de Gonzalo de Berceo. Las muy escasas menciones a fuentes en las Cantigas de Santa María no invalidan la evidencia de múltiples “citas” reconocibles. Así, por ejemplo, es posible encontrar himnos y antífonas explícitamente citados (Te Deum laudamus, Salve Regina, Ave Maris Stella, además de glosas al Ave María) y, más allá de estos, se perciben otros modos de inserción de la lírica himnódica en la narración de los milagros. Se propone, entonces, iluminar estos loci donde parece haber un texto aludido o “escondido”, para considerar sus diversos modos de traducción, adopción y reelaboración.

Magisterio-teología : relación, esquemas eclesiológicos y proceso evolutivo en el período de 1950-1975

Resumen: El artículo se propone analizar la relación entre el magisterio y los teólogos desde la especificidad de los esquemas eclesiológicos. Esta formalidad eclesiológica es animada por la conjetura de que en los momentos de relaciones conflictivas entre el magisterio y la teología, confluyen dos esquemas eclesiológicos diversos en los que alguno de los interlocutores asume funciones no propias dejando al otro en un espacio eclesial no acorde a sus especificidades. Después de un desarrollo histórico se pasa a una elaboración especulativa desde el análisis lingüístico del discurso teológico.