VCD to determine absolute configuration of natural product molecules: secolignans from Peperomia blanda

The absolute configuration and solution-state conformers of three peperomin-type secolignans isolated from Peperomia blanda (Piperaceae) are unambiguously determined by using vibrational circular dichroism (VCD) spectroscopy associated with density functional theory (DFT) calculations. Advantages of VCD over the electronic form of CD for the analysis of diastereomers are also discussed. This work extends our growing knowledge about secondary metabolites within the Piperaceae family species while providing a definitive and straightforward method to assess the absolute stereochemistry of secolignans.

The effect of adding features on product attractiveness: the role of product perceived congruity

Technological progress has been enabling companies to add disparate features to their existing products. This research investigates the effect of adding more features on consumers’ evaluation of the product, by examining in particular the role of the congruity of the features added with the base product as a variable the moderates the effect of increasing the number of features. Grounding on schema-congruity theory, I propose that the cognitive elaboration associated with the product congruity of the features added explains consumers’ evaluation as the number of new features increases. In particular, it is shown that consumers perceive a benefit from increasing the number of features only when these features are congruent with the product. The underlying mechanisms that explains this finding predicts that when the number of incongruent features increases the cognitive resources necessary to elaborate such incongruities increase and consumers are not willing to spend such resources. However, I further show that when encouraged to consider the new features thoughtfully, consumers do seem able to infer value from increasing the number of moderately incongruent features. Nonetheless, this finding does not apply for those new features that are extremely incongruent with the product. Further evidence for consumers’ ability to resolve the moderate incongruity associated with adding more features is also shown, by studying the moderating role of temporal construal. I propose that consumers perceive an increase in product evaluation as the number of moderately incongruent features increases when consumers consider purchasing the product in the distant future, whereas such an increase is not predicted for the near future scenario. I verify these effect in three experimental studies. Theoretical and managerial implications, and possible avenues of future research are also suggested.

Three essays in industrial organization

This dissertation comprises three essays on the topic of industrial organization. The first essay considers how different intellectual property systems can affect the incentives to invest in R&D when innovation is cumulative. I introduce a distinction between plain and sophisticated technological knowledge, which plays a crucial role in determining how different appropriability rules affect the incentives to innovate. I argue that the positive effect of weak intellectual property regimes on the sharing of intermediate technological knowledge vanishes when technological knowledge is sophisticated, as is likely to be the case in many high tech industries. The second essay analyzes a two-sided market for news where advertisers may pay a media outlet to conceal negative information on the quality of their own product (paying positive to avoid negative) and/or to disclose negative information on the quality of their competitors products (paying positive to go negative). It is shown that whether advertisers have negative consequences on the accuracy of media reports or not, ultimately depends on the extent of correlation among advertisers products. The third essay considers the role of social learning in the diffusion of a new technology. A population of agents can choose between two risky technologies: an old one for which they know the expected outcome, and a new one for which they have only a prior. Different environments are confronted. In the benchmark case agents are isolated and can perform costly experiments to infer the quality of the new technology. In the other cases agents are settled in a network and can observe the outcomes of neighbors. We observe that in expectations the quality of the new technology may be overestimated when there is a network spread of information.

Three-dimensional joint kinematics of swimming using body-worn inertial and magnetic sensors

Wearable inertial and magnetic measurements units (IMMU) are an important tool for underwater motion analysis because they are swimmer-centric, they require only simple measurement set-up and they provide the performance results very quickly. In order to estimate 3D joint kinematics during motion, protocols were developed to transpose the IMMU orientation estimation to a biomechanical model. The aim of the thesis was to validate a protocol originally propositioned to estimate the joint angles of the upper limbs during one-degree-of-freedom movements in dry settings and herein modified to perform 3D kinematics analysis of shoulders, elbows and wrists during swimming. Eight high-level swimmers were assessed in the laboratory by means of an IMMU while simulating the front crawl and breaststroke movements. A stereo-photogrammetric system (SPS) was used as reference. The joint angles (in degrees) of the shoulders (flexion-extension, abduction-adduction and internal-external rotation), the elbows (flexion-extension and pronation-supination), and the wrists (flexion-extension and radial-ulnar deviation) were estimated with the two systems and compared by means of root mean square errors (RMSE), relative RMSE, Pearson’s product-moment coefficient correlation (R) and coefficient of multiple correlation (CMC). Subsequently, the athletes were assessed during pool swimming trials through the IMMU. Considering both swim styles and all joint degrees of freedom modeled, the comparison between the IMMU and the SPS showed median values of RMSE lower than 8°, representing 10% of overall joint range of motion, high median values of CMC (0.97) and R (0.96). These findings suggest that the protocol accurately estimated the 3D orientation of the shoulders, elbows and wrists joint during swimming with accuracy adequate for the purposes of research. In conclusion, the proposed method to evaluate the 3D joint kinematics through IMMU was revealed to be a useful tool for both sport and clinical contexts.

Brand formative design - development and assessment of product design from a future, brand and consumer perspective

With this dissertation research we investigate intersections between design and marketing and in this respect, which factors do contribute that a product design becomes brand formative. We have developed a Brand Formative Design (BFD) framework, which investigates individual design features in a holistic, comparable, brand relevant, and consumer specific context. We discuss what kinds of characteristics contribute to BFD but also illuminate how they should be applied and examine: rnA holistic framework leading to Brand Formative Design. Identification and assessment of BFD Drivers. The dissection of products into three Distinctive Design Levels. The detection of surprising design preferences. The appropriate degree of scheme deviation with evolutionary design. Simulated BFD development processes with three different products and the integration of consumers. Future oriented objectification, comparability and assessment of design. Recommendations for the management of design in a brand specific context. Design is a product feature, which contributes significantly to the success of products. However, the development of new design contains challenges. Design can hardly be objectified; many people have an opinion concerning the attractiveness of new products but cannot formulate their future preferences. Product design is widely developed based on intuition, which can be difficult for the management of design. Here the concept of Brand Formative Design can provide a framework which contributes to structure, objectify, develop and assess new evolutionary design in brand and future relevant contexts, but also integrates consumers and their preferences without restricting creativity too much.

Phenotype-genotype correlation in eight Polish patients with inherited Factor XIII deficiency: identification of three novel mutations

Inherited factor XIII (FXIII) deficiency is known as one of the most rare blood coagulation disorder in humans. In the present study, phenotype and genotype of eight FXIII deficient Polish patients from five unrelated families were compared. The patients presented with a severe phenotype demonstrated by a high incidence of intracerebral haemorrhages (seven of eight patients), haemarthrosis (six patients) and bleeding due to trauma (five patients). Introduction of regular substitution with FXIII concentrate prevented spontaneous bleeding in seven patients. In all patients, mutations within the F13A gene have been identified revealing four missense mutations (Arg77Cys, Arg260Cys, Ala378Pro, Gly420Ser), one nonsense mutation (Arg661X), one splice site mutation (IVS5-1 G>A) and one small deletion (c.499-512del). One homozygous large deletion involving exon 15 was detected by failure of PCR product. The corresponding mutations resulted in severely reduced FXIII activity and FXIII A-subunit antigen concentration, while FXIII B-subunit antigen remained normal or mildly decreased. Structural analysis demonstrated that the novel Ala378Pro mutation may cause a disruption of the FXIII catalytic triad leading to a non-functional protein which presumably undergoes premature degradation. In conclusion, the severe phenotype with high incidence of intracranial bleeding and haemarthrosis was in accordance with laboratory findings on FXIII and with severe molecular defects of the F13A gene.

Presence in a Three-Dimensional Test Environment: Benefit or Threat to Market Research?

In market research, the adoption of interactive virtual reality-techniques could be expected to contain many advantages: artificial lab environments could be designed in a more realistic manner and the consideration of “time to the market”-factors could be improved. On the other hand, with an increasing degree of presence and the notional attendance in a simulated test environment, the market research task could fall prey to the tensing virtual reality adventure. In the following study a 3D-technique is empirically tested for its usability in market research. It will be shown that the interactive 3D-simulation is not biased by the immersion it generates and provides considerably better test results than 2D-stimuli do.

Tropical cyclone-related socio-economic losses in the western North Pacific region

The western North Pacific (WNP) is the area of the world most frequently affected by tropical cyclones (TCs). However, little is known about the socio-economic impacts of TCs in this region, probably because of the limited relevant loss data. Here, loss data from Munich RE's NatCatSERVICE database is used, a high-quality and widely consulted database of natural disasters. In the country-level loss normalisation technique we apply, the original loss data are normalised to present-day exposure levels by using the respective country's nominal gross domestic product at purchasing power parity as a proxy for wealth. The main focus of our study is on the question of whether the decadal-scale TC variability observed in the Northwest Pacific region in recent decades can be shown to manifest itself economically in an associated variability in losses. It is shown that since 1980 the frequency of TC-related loss events in the WNP exhibited, apart from seasonal and interannual variations, interdecadal variability with a period of about 22 yr – driven primarily by corresponding variations of Northwest Pacific TCs. Compared to the long-term mean, the number of loss events was found to be higher (lower) by 14% (9%) in the positive (negative) phase of the decadal-scale WNP TC frequency variability. This was identified for the period 1980–2008 by applying a wavelet analysis technique. It was also possible to demonstrate the same low-frequency variability in normalised direct economic losses from TCs in the WNP region. The identification of possible physical mechanisms responsible for the observed decadal-scale Northwest Pacific TC variability will be the subject of future research, even if suggestions have already been made in earlier studies.

Air-Sea Interactions During the Passage of a Winter Storm Over the Gulf Stream: A Three-Dimensional Coupled Atmosphere-Ocean Model Study

A three-dimensional, regional coupled atmosphere-ocean model with full physics is developed to study air-sea interactions during winter storms off the U. S. east coast. Because of the scarcity of open ocean observations, models such as this offer valuable opportunities to investigate how oceanic forcing drives atmospheric circulation and vice versa. The study presented here considers conditions of strong atmospheric forcing (high wind speeds) and strong oceanic forcing (significant sea surface temperature (SST) gradients). A simulated atmospheric cyclone evolves in a manner consistent with Eta reanalysis, and the simulated air-sea heat and momentum exchanges strongly affect the circulations in both the atmosphere and the ocean. For the simulated cyclone of 19-20 January 1998, maximum ocean-to-atmosphere heat fluxes first appear over the Gulf Stream in the South Atlantic Bight, and this results in rapid deepening of the cyclone off the Carolina coast. As the cyclone moves eastward, the heat flux maximum shifts into the region near Cape Hatteras and later northeast of Hatteras, where it enhances the wind locally. The oceanic response to the atmospheric forcing is closely related to the wind direction. Southerly and southwesterly winds tend to strengthen surface currents in the Gulf Stream, whereas northeasterly winds weaken the surface currents in the Gulf Stream and generate southwestward flows on the shelf. The oceanic feedback to the atmosphere moderates the cyclone strength. Compared with a simulation in which the oceanic model always passes the initial SST to the atmospheric model, the coupled simulation in which the oceanic model passes the evolving SST to the atmospheric model produces higher ocean-to-atmosphere heat flux near Gulf Stream meander troughs. This is due to wind-driven lateral shifts of the stream, which in turn enhance the local northeasterly winds. Away from the Gulf Stream the coupled simulation produces surface winds that are 5 similar to 10% weaker. Differences in the surface ocean currents between these two experiments are significant on the shelf and in the open ocean.

Three essays on prices and selection

Competitive Market Segmentation Abstract In a two-firm model where each firm sells a high-quality and a low-quality version of a product, customers differ with respect to their brand preferences and their attitudes towards quality. We show that the standard result of quality-independent markups crucially depends on the assumption that the customers' valuation of quality is identical across firms. Once we relax this assumption, competition across qualities leads to second-degree price discrimination. We find that markups on low-quality products are higher if consuming a low-quality product involves a firm-specific disutility. Likewise, markups on high-quality products are higher if consuming a high-quality product creates a firm-specific surplus. Selection upon Wage Posting Abstract We discuss a model of a job market where firms announce salaries. Thereupon, they decide through the evaluation of a productivity test whether to hire applicants. Candidates for a job are locked in once they have applied at a given employer. Hence, such a market exhibits a specific form of the bargain-then-ripoff principle. With a single firm, the outcome is efficient. Under competition, what might be called "positive selection" leads to market failure. Thus our model provides a rationale for very small employment probabilities in some sectors. Exclusivity Clauses: Enhancing Competition, Raising Prices Abstract In a setting where retailers and suppliers compete for each other by offering binding contracts, exclusivity clauses serve as a competitive device. As a result of these clauses, firms addressed by contracts only accept the most favorable deal. Thus the contract-issuing parties have to squeeze their final customers and transfer the surplus within the vertical supply chain. We elaborate to what extent the resulting allocation depends on the sequence of play and discuss the implications of a ban on exclusivity clauses.

A stratigraphic framework for abrupt climatic changes during the Last Glacial period based on three synchronized Greenland ice-core records: refining and extending the INTIMATE event stratigraphy

Due to their outstanding resolution and well-constrained chronologies, Greenland ice-core records provide a master record of past climatic changes throughout the Last Interglacial–Glacial cycle in the North Atlantic region. As part of the INTIMATE (INTegration of Ice-core, MArine and TErrestrial records) project, protocols have been proposed to ensure consistent and robust correlation between different records of past climate. A key element of these protocols has been the formal definition and ordinal numbering of the sequence of Greenland Stadials (GS) and Greenland Interstadials (GI) within the most recent glacial period. The GS and GI periods are the Greenland expressions of the characteristic Dansgaard–Oeschger events that represent cold and warm phases of the North Atlantic region, respectively. We present here a more detailed and extended GS/GI template for the whole of the Last Glacial period. It is based on a synchronization of the NGRIP, GRIP, and GISP2 ice-core records that allows the parallel analysis of all three records on a common time scale. The boundaries of the GS and GI periods are defined based on a combination of stable-oxygen isotope ratios of the ice (δ18O, reflecting mainly local temperature) and calcium ion concentrations (reflecting mainly atmospheric dust loading) measured in the ice. The data not only resolve the well-known sequence of Dansgaard–Oeschger events that were first defined and numbered in the ice-core records more than two decades ago, but also better resolve a number of short-lived climatic oscillations, some defined here for the first time. Using this revised scheme, we propose a consistent approach for discriminating and naming all the significant abrupt climatic events of the Last Glacial period that are represented in the Greenland ice records. The final product constitutes an extended and better resolved Greenland stratotype sequence, against which other proxy records can be compared and correlated. It also provides a more secure basis for investigating the dynamics and fundamental causes of these climatic perturbations.

Feasible Dose Reduction in Routine Chest Computed Tomography Maintaining Constant Image Quality Using the Last Three Scanner Generations: From Filtered Back Projection to Sinogram-affirmed Iterative Reconstruction and Impact of the Novel Fully Integrated Detector Design Minimizing Electronic Noise

OBJECTIVE The aim of the present study was to evaluate a dose reduction in contrast-enhanced chest computed tomography (CT) by comparing the three latest generations of Siemens CT scanners used in clinical practice. We analyzed the amount of radiation used with filtered back projection (FBP) and an iterative reconstruction (IR) algorithm to yield the same image quality. Furthermore, the influence on the radiation dose of the most recent integrated circuit detector (ICD; Stellar detector, Siemens Healthcare, Erlangen, Germany) was investigated. MATERIALS AND METHODS 136 Patients were included. Scan parameters were set to a thorax routine: SOMATOM Sensation 64 (FBP), SOMATOM Definition Flash (IR), and SOMATOM Definition Edge (ICD and IR). Tube current was set constantly to the reference level of 100 mA automated tube current modulation using reference milliamperes. Care kV was used on the Flash and Edge scanner, while tube potential was individually selected between 100 and 140 kVp by the medical technologists at the SOMATOM Sensation. Quality assessment was performed on soft-tissue kernel reconstruction. Dose was represented by the dose length product. RESULTS Dose-length product (DLP) with FBP for the average chest CT was 308 mGy*cm ± 99.6. In contrast, the DLP for the chest CT with IR algorithm was 196.8 mGy*cm ± 68.8 (P = 0.0001). Further decline in dose can be noted with IR and the ICD: DLP: 166.4 mGy*cm ± 54.5 (P = 0.033). The dose reduction compared to FBP was 36.1% with IR and 45.6% with IR/ICD. Signal-to-noise ratio (SNR) was favorable in the aorta, bone, and soft tissue for IR/ICD in combination compared to FBP (the P values ranged from 0.003 to 0.048). Overall contrast-to-noise ratio (CNR) improved with declining DLP. CONCLUSION The most recent technical developments, namely IR in combination with integrated circuit detectors, can significantly lower radiation dose in chest CT examinations.

Editorial genesis: From comparing texts (product) to interpreting rewritings (process)

In literary genetics, “editorial genetics” deals with the “public life” of texts, whereas the writing process is affected by edition and diffusion. Editorial genetics frequently has to deal with cases of “editorial rewriting”: in the literary domain for example, authors frequently modify previously published works, so that several versions may co-exist. We are especially interested in Balzac’s La Bourse (translated in English as The Purse) since we know three authorized versions of this specific work.By comparing different texts associated with a single work, the literary geneticist is facing different products that are themselves the result of a writing process. However, different specificities should be outlined: (1) the writing process does not leave any trace: we just have access to different products/texts and (2) since the texts we compare seem to be achieved, differences must be referred, not to programmatic or temporary linguistic structures, but to the reconfiguration of a pre-existing textuality.Do such products still reflect the processes that have given birth to them? Does the comparison between two texts considered as variations of a same text give access to this transformation’s processes? After describing the objects of this particular textual comparison and the terminology that permits to give an account of such phenomenon, this contribution suggests to express these questions differently, as a matter of poetics of transitions between texts, or, further digging, an hermeneutics of the transition between texts.

Delivery of the p67 sporozoite antigen of Theileria parva by using recombinant Salmonella dublin: secretion of the product enhances specific antibody responses in cattle

The p67 sporozoite antigen of Theileria parva has been fused to the C-terminal secretion signal of Escherichia coli hemolysin and expressed in secreted form by attenuated Salmonella dublin aroA strain SL5631. The recombinant p67 antigen was detected in the supernatant of transformed bacterial cultures. Immunization trials in cattle revealed that SL5631 secreting the antigen provoked a 10-fold-higher antibody response to p67 than recombinant SL5631 expressing but not secreting p67. Immunized calves were challenged with a 80% lethal dose of T. parva sporozoites and monitored for the development of infection. Two of three calves immunized intramuscularly with the p67-secreting SL5631 strain were found to be protected, whereas only one of three animals immunized with the nonsecreting p67-expressing SL5631 strain was protected. This is the first demonstration that complete eukaryotic antigens fused to the C-terminal portion of E. coli hemolysin can be exported from attenuated Salmonella strains and that such exported antigens can protect cattle against subsequent parasite challenge.

Global distributions of pteropods (Gymnosomata, Thecosomata, Pseudothecosomata) abundance and biomass - Gridded data product (NetCDF) - Contribution to the MAREDAT World Ocean Atlas of Plankton Functional Types

Pteropods are a group of holoplanktonic gastropods for which global biomass distribution patterns remain poorly resolved. The aim of this study was to collect and synthesize existing pteropod (Gymnosomata, Thecosomata and Pseudothecosomata) abundance and biomass data, in order to evaluate the global distribution of pteropod carbon biomass, with a particular emphasis on its seasonal, temporal and vertical patterns. We collected 25 902 data points from several online databases and a number of scientific articles. The biomass data has been gridded onto a 360 x 180° grid, with a vertical resolution of 33 WOA depth levels. Data has been converted to NetCDF format. Data were collected between 1951-2010, with sampling depths ranging from 0-1000 m. Pteropod biomass data was either extracted directly or derived through converting abundance to biomass with pteropod specific length to weight conversions. In the Northern Hemisphere (NH) the data were distributed evenly throughout the year, whereas sampling in the Southern Hemisphere was biased towards the austral summer months. 86% of all biomass values were located in the NH, most (42%) within the latitudinal band of 30-50° N. The range of global biomass values spanned over three orders of magnitude, with a mean and median biomass concentration of 8.2 mg C l-1 (SD = 61.4) and 0.25 mg C l-1, respectively for all data points, and with a mean of 9.1 mg C l-1 (SD = 64.8) and a median of 0.25 mg C l-1 for non-zero biomass values. The highest mean and median biomass concentrations were located in the NH between 40-50° S (mean biomass: 68.8 mg C l-1 (SD = 213.4) median biomass: 2.5 mg C l-1) while, in the SH, they were within the 70-80° S latitudinal band (mean: 10.5 mg C l-1 (SD = 38.8) and median: 0.2 mg C l-1). Biomass values were lowest in the equatorial regions. A broad range of biomass concentrations was observed at all depths, with the biomass peak located in the surface layer (0-25 m) and values generally decreasing with depth. However, biomass peaks were located at different depths in different ocean basins: 0-25 m depth in the N Atlantic, 50-100 m in the Pacific, 100-200 m in the Arctic, 200-500 m in the Brazilian region and >500 m in the Indo-Pacific region. Biomass in the NH was relatively invariant over the seasonal cycle, but more seasonally variable in the SH. The collected database provides a valuable tool for modellers for the study of ecosystem processes and global biogeochemical cycles.