Structure of Metallathiacycles: Planar vs Nonplanar Geometries. A Theoretical and Experimental Investigation

Since the previously reported results of Fenske-Hall molecular orbital calculations suggested that the bent metallacycle geometries observed in transition-metal-inserted thiophene complexes do not result from electronic properties, molecular mechanics calculations were employed to explore how steric factors could influence ring geometries. These calculations have identified steric factors responsible for the observed ring deformations in (C 5 Me 5 )Rh(PMe 3 )(η 2 -C,S-2,5-Me 2 C 4 H 2 S) and benzothiophene and dibenzothiophene analogs. The results of the molecular mechanics calculations have been supported by X-ray structural characterization of the products formed via insertion of the reactive 16-electron metal fragment [(C 5 Me 5 )Rh(PMe 3 )] into the C-S bonds of unsubstituted thiophene, benzothiophene, and dibenzothiophene. The parent thiophene complex, unlike the previously reported ringsubstituted analog (and as predicted by the molecular mechanics calculations) is found to adopt a planar six-membered ring structure. The benzothiophene insertion product shows a moderate degree of bending of the metallathiacycle, whereas the dibenzothiophene molecule is strongly bent

High Spatial Resolution Commercial Satellite Imaging Product Characterization

NASA Stennis Space Center's Remote Sensing group has been characterizing privately owned high spatial resolution multispectral imaging systems, such as IKONOS, QuickBird, and OrbView-3. Natural and man made targets were used for spatial resolution, radiometric, and geopositional characterizations. Higher spatial resolution also presents significant adjacency effects for accurate reliable radiometry

Development of an Interoperable GNSS Space Service Volume

Global Navigation Satellite Systems (GNSS), now routinely used for navigation by spacecraft in low Earth orbit, are being used increasingly by high-altitude users in geostationary orbit and high eccentric orbits as well, near to and above the GNSS constellations themselves. Available signals in these regimes are very limited for any single GNSS constellation due to the weak signal strength, the blockage of signals by the Earth, and the limited number of satellites. But with the recent development of multiple GNSS constellations and ongoing upgrades to existing constellations, multi-GNSS signal availability is set to improve significantly. This will only be achieved if these signals are designed to be interoperable and are clearly documented and supported. All satellite navigation constellation providers are working together through the United Nations International Committee on GNSS (ICG) to establish an interoperable multi-GNSS Space Service Volume (SSV) for the benefit of all GNSS space users. The multi-GNSS SSV represents a common set of baseline definitions and assumptions for high-altitude service in space, documents the service provided by each constellation, and provides a framework for continued support for space users. This paper provides an overview of the GNSS SSV concept, development, status, and achievements within the ICG. It describes the final adopted definition and performance characteristics of the GNSS SSV, as well as the numerous benefits and use cases enabled by this development. Extensive technical analysis was also performed to illustrate these benefits in terms of signal availability, both on a global scale, and for multiple distinct mission types. This analysis is summarized here and presented in detail in a companion paper by Enderle, et al

PPI-Delayed Diagnosis of Gastrinoma: Oncologic Victim of Pharmacologic Success

Functional neuroendocrine tumors are often low-grade malignant neoplasms that can be cured by surgery if detected early, and such detection may in turn be accelerated by the recognition of neuropeptide hypersecretion syndromes. Uniquely, however, relief of peptic symptoms induced by hypergastrinemia is now available from acid-suppressive drugs such as proton-pump inhibitors (PPIs). Here we describe a clinical case in which time to diagnosis from the onset of peptic symptoms was delayed more than 10 years, in part reflecting symptom masking by continuous prescription of the PPI omeprazole. We propose diagnostic criteria for this under-recognized new clinical syndrome, and recommend that physicians routinely measure serum gastrin levels in persistent cases of PPI-dependent dyspepsia unassociated with H. pylori

IL28B genetic variations are associated with high sustained virological response (SVR) of interferon-α plus ribavirin therapy in Taiwanese chronic HCV infection

Chronic hepatitis C virus (HCV) infection patients exhibit different sustained virological responses (SVRs) following the treatment with pegylated interferon-α (IFN-α) and ribavirin. Genome-wide association studies consistently linked SVR of IFN-α-based therapy to the IL28B single-nucleotide polymorphisms (SNPs) on chromosome 19q.13 in various populations. This study was undertaken to investigate the association of IL28B SNPs with SVR in a cohort of Taiwanese chronic HCV patients. Ten SNPs of IL28B were genotyped in 728 chronic HCV patients and 960 healthy controls. Genotype distributions, allele frequencies and haplotypes were tested for SVR and susceptibility in Taiwanese chronic HCV patients. Non-genotype 1 infection (adjusted P=3.3 × 10−12, odds ratio (OR) 0.179; 95% confidence interval (CI): 0.110–0.290) and low HCV viral load (<400 000 IU ml–1) (adjusted P=3.5 × 10−9, OR 0.299; 95% CI: 0.200–0.446) were two major factors identified for high SVR. Notably, eight IL28B SNPs including previously described disease-associated SNPs (Trend test P=0.005) were significantly associated with SVR. Our data indicate that IL28B polymorphisms are the essential contributing factors for high SVR in Taiwanese chronic HCV patients. Combination of virus genotyping and host genetic data may be used to select the optimal treatment regimes in IFN-based therapy

Relational Contracting, Repeated Negotiations, and Hold-Up

We propose a unified framework to study relational contracting and hold-up problems in infinite horizon stochastic games. We first illustrate that with respect to long run decisions, the common formulation of relational contracts as Pareto-optimal public perfect equilibria is in stark contrast to fundamental assumptions of hold-up models. We develop a model in which relational contracts are repeatedly newly negotiated during relationships. Negotiations take place with positive probability and cause bygones to be bygones. Traditional relational contracting and hold-up formulations are nested as opposite corner cases. Allowing for intermediate cases yields very intuitive results and sheds light on many plausible trade-offs that do not arise in these corner cases. We establish a general existence result and a tractable characterization for stochastic games in which money can be transferred. This paper formulates a theory of relational contracting in dynamic games. A crucial feature is that existing relational contracts can depreciate and ensuing negotiations then treat previous informal agreements as bygones. The model nests the traditional formulation of relational contracts as Pareto-optimal equilibria as a special case. In repeated games both formulations are always mathematically equivalent. We provide ample illustrations that in dynamic games the traditional formulation is restrictive in so far that it rules out by assumption many plausible hold-up problems - even for small discount factors. Our model provides a framework that naturally unifies the analysis of relational contracting and hold-up problems