Asymmetric additions to dienes catalysed by a dithiophosphoric acid.

Chiral Brønsted acids (proton donors) have been shown to facilitate a broad range of asymmetric chemical transformations under catalytic conditions without requiring additional toxic or expensive metals. Although the catalysts developed thus far are remarkably effective at activating polarized functional groups, it is not clear whether organic Brønsted acids can be used to catalyse highly enantioselective transformations of unactivated carbon-carbon multiple bonds. This deficiency persists despite the fact that racemic acid-catalysed Markovnikov additions to alkenes are well known chemical transformations. Here we show that chiral dithiophosphoric acids can catalyse the intramolecular hydroamination and hydroarylation of dienes and allenes to generate heterocyclic products in exceptional yield and enantiomeric excess. We present a mechanistic hypothesis that involves the addition of the acid catalyst to the diene, followed by nucleophilic displacement of the resulting dithiophosphate intermediate; we also report mass spectroscopic and deuterium labelling studies in support of the proposed mechanism. The catalysts and concepts revealed in this study should prove applicable to other asymmetric functionalizations of unsaturated systems

The changing motivations of students' use of lecture podcasts across a semester: an extended theory of planned behaviour approach

We extended the previous work of Moss, O’Connor and White, to include a measure of group norms within the theory of planned behaviour (TPB), to examine the influences on students’ decisions to use lecture podcasts as part of their learning. Participants (N = 90) completed the extended TPB predictors before semester began (Time 1) and mid-semester (Time 2) and reported on their podcast use at mid-semester (Time 2) and end of semester (Time 3). We found that attitudes and perceived social pressures were important in informing intentions at both time points. At Time 1, perceptions of control over performing the behaviour and, at Time 2, perceptions of whether podcast use was normative among fellow students (group norms) also predicted intended podcast use. Intentions to use podcasting predicted self-reported use at both Time 2 and Time 3. These results provide important applied information for educators to encourage student use of novel on-line educational tools

Non-Invasive Imaging of Coronary Artery Disease — The Expanding Role of Coronary Computed Tomographic Angiography in the Management of Low- to Intermediate-Risk Patients and Dealing with Intermediate Stenosis

Non-invasive anatomic imaging modalities play a crucial role in the diagnosis of coronary artery disease (CAD), particularly in the case of the symptomatic patient presenting in the emergency department

C4: The New Hampshire Spherulitic Rhyolites: Rocks of Importance to Prehistoric Native Americans

Guidebook for field trips in Western Maine and Northern New Hampshire: New England Intercollegiate Geological Conference, p. 305-316

River Otter, Lontra canadensis, Food Habits in the Missouri Ozarks

The reintroduction of River Otters (Lontra canadensis) between 1982 and 1992 resulted in widespread occurrence of the species throughout the Missouri Ozarks. This study examined otter diets from the vicinity of two Ozark streams in relation to seasonal and spatial trends. Otter scats (N = 4750) were collected and analyzed from the Osage Fork River and Big Piney River during the summer and winter seasons of 2001 and 2002. During the winter (January-March), fish occurred in 86% of the samples. During the summer (June–August), occurrence of fish dropped to approximately 15% for both rivers. Seven families of fish were identified in the diets, with Centrarchidae being most common regardless of river or season. Within the Centrarchidae, the genus Lepomis (mostly Longear Sunfish, Lepomis megalotis) was most common, with Micropterus (mostly Smallmouth Bass, Micropterus dolomieu) and Rock Bass (Ambloplites rupestris) also well represented. The mean age of Ambloplites consumed (mean = 3.3 years) was consistently older than that of either Micropterus (mean = 2.54 years) or Lepomis (mean = 2.78 years). Crayfish were recovered from a mean of 85.2% of scats in the winter and 99% in the summer. Smaller fish and crayfish were more common from the upper reaches of the streams while larger fish were prevalent in the lower reaches

A Knock-In Mouse Model for the R120G Mutation of αB-Crystallin Recapitulates Human Hereditary Myopathy and Cataracts

An autosomal dominant missense mutation in αB-crystallin (αB-R120G) causes cataracts and desmin-related myopathy, but the underlying mechanisms are unknown. Here, we report the development of an αB-R120G crystallin knock-in mouse model of these disorders. Knock-in αB-R120G mice were generated and analyzed with slit lamp imaging, gel permeation chromatography, immunofluorescence, immunoprecipitation, histology, and muscle strength assays. Wild-type, age-matched mice were used as controls for all studies. Both heterozygous and homozygous mutant mice developed myopathy. Moreover, homozygous mutant mice were significantly weaker than wild-type control littermates at 6 months of age. Cataract severity increased with age and mutant gene dosage. The total mass, precipitation, and interaction with the intermediate filament protein vimentin, as well as light scattering of αB-crystallin, also increased in mutant lenses. In skeletal muscle, αB-R120G co-aggregated with desmin, became detergent insoluble, and was ubiquitinated in heterozygous and homozygous mutant mice. These data suggest that the cataract and myopathy pathologies in αB-R120G knock-in mice share common mechanisms, including increased insolubility of αB-crystallin and co-aggregation of αB-crystallin with intermediate filament proteins. These knock-in αB-R120G mice are a valuable model of the developmental and molecular biological mechanisms that underlie the pathophysiology of human hereditary cataracts and myopathy

Bioinspired thermosensitive hydrogel as a vitreous substitute: Synthesis, properties, and progress of animal studies

In many vitreal diseases, the surgeon removes the natural vitreous and replaces it with silicone oils, gases, or balanced salt solutions to fill the eyeball and hold the retina in position. However, these materials are often associated with complications and have properties that differ from natural vitreous. Herein, we report an extension of our previous work on the synthesis of a biomimetic hydrogel that is composed of thiolated gellan as an analogue of type II collagen and poly(methacrylamide-co-methacrylate-co-bis(methacryloyl)cystamine), a polyelectrolyte, as an analogue of hyaluronic acid. This thermosensitive hydrogel can be injected into the eye as a viscous solution at 45 °C. It then forms a physical gel in situ when it reaches body temperature, and later forms disulfide covalent crosslinks. In this article, we evaluated two different formulations of the biomimetic hydrogels for their physical, mechanical, and optical properties, and we determined their biocompatibility with several cell lines. Finally, we report on the progress of the four-month preclinical evaluation of our bio-inspired vitreous substitute in comparison to silicone oil or a balanced salt solution. We assessed the eyes with a slit-lamp examination, intraocular pressure measurements, electroretinography, and optical coherence tomography. Preliminary results are very encouraging for the continuing evaluation of our bio-inspired hydrogel in clinical trials