Lancifodilactone G : insights about an unusually stable enol

From quantum mechanics calculations we confirm that the naturally occurring enol lancifodilactone G is stable over the keto form (by 2.6 kcal/mol in water), the only known stable aliphatic enol (devoid of conjugated or bulky aromatics and lacking a 1,3-diketone structural motif known to stabilize enols). We determine architectural elements responsible for the enol stabilization and find a mechanism for keto-enol conversion in solution. In addition, we correct previously reported computational results that were performed on the misinterpreted structure demonstrating that the enol form of this natural product is more stable than previously thought

Lessons Learned from Efforts at Institutional Change: Case Studies of Six OCEPT Institutions

As one part of a multifaceted evaluation of the Oregon Collaborative for Excellence in the Preparation of Teachers (OCEPT), a case study approach was used to enable a deeper understanding of how a diverse group of six institutions attempted to achieve OCEPT goals and to learn more about factors that facilitated or hindered their efforts. Multiple sources of data were used, with heavy reliance on a series of on-site interviews. The analytical framework included a depth and pervasiveness typology of institutional change and a view of change as encompassing meaning, organization, and effects. While goals and accomplishment levels, as well as the depth and pervasiveness of change. varied across the six institutions, OCEPT-influenced changes most likely to be sustained included: new kinds and levels of faculty collaboration; peer-led teaching and learning approaches, and attention to evidence that these approaches positively affect student course performance; increased faculty awareness of their role in teacher recruitment, with related changes in classroom practices; and, continued strengthening of access to infomiation and academic advising for those preparing to become teachers. These institutions, however, did not make significant progress on one major goal of the project—to increase the numbers of underrepresented groups interested in teaching careers. Change was affected by the compatibility of OCEPT goals with institutional and faculty culture, as well as by local collaborative leadership, the size and complexity of the institution, the presence of boundary spanners, and how OCEPT resources were used

Redundant actuator development program

Two concepts of redundant secondary actuator mechanization, applicable to future advanced flight control systems, were studied to quantitatively assess their design applicability to an AST. The two actuator concepts, a four-channel, force summed system and a three-channel, active/standby system have been developed and evaluated through analysis, analog computer simulation, and piloted motion simulation. The quantitative comparison of the two concepts indicates that the force summed concept better meet performance requirements, although the active/standby is superior in other respects. Both concepts are viable candidates for advanced control application dependent on the specific performance requirements

Comparing Complex Fitness Surfaces: Among-Population Variation in Mutual Sexual Selection in Drosophila serrata

The problem of synchronization of metacommunities is investigated in this article with reference to a rather general model composed of a chaotic environmental compartment driving a biological compartment. Synchronization in the absence of dispersal (i.e., the so-called Moran effect) is first discussed and shown to occur only when there is no biochaos. In other words, if the biological compartment is reinforcing environmental chaos, dispersal must be strictly above a specified threshold in order to synchronize population dynamics. Moreover, this threshold can be easily determined from the model by computing a special Lyapunov exponent. The application to prey-predator metacommunities points out the influence of frequency and coherence of the environmental noise on synchronization and agrees with all experimental studies performed on the subject

Genetic Constraints and the Evolution of Display Trait Sexual Dimorphism by Natural and Sexual Selection.

The evolution of sexual dimorphism involves an interaction between sex-specific selection and a breakdown of genetic constraints that arise because the two sexes share a genome. We examined genetic constraints and the effect of sex-specific selection on a suite of sexually dimorphic display traits in Drosophila serrata. Sexual dimorphism varied among nine natural populations covering a substantial portion of the species range. Quantitative genetic analyses showed that intersexual genetic correlations were high because of autosomal genetic variance but that the inclusion of X-linked effects reduced genetic correlations substantially, indicating that sex linkage may be an important mechanism by which intersexual genetic constraints are reduced in this species. We then explored the potential for both natural and sexual selection to influence these traits, using a 12-generation laboratory experiment in which we altered the opportunities for each process as flies adapted to a novel environment. Sexual dimorphism evolved, with natural selection reducing sexual dimorphism, whereas sexual selection tended to increase it overall. To this extent, our results are consistent with the hypothesis that sexual selection favors evolutionary divergence of the sexes. However, sex-specific responses to natural and sexual selection contrasted with the classic model because sexual selection affected females rather than males

Reconstructing the trajectory of the August 1680 hurricane from contemporary records

This paper draws on a range of contemporary documentary evidence from the New and Old Worlds as well as from the oceanic regions to reconstruct the trajectory and intensity of an Atlantic hurricane from August 1680. In doing so, it offers the example of one of the earliest and most comprehensive hurricane reconstructions thus far attempted. The source material includes evidence from land-based observers and some of the earliest examples of instrumental barometric data from the Caribbean and from Europe; importantly, it also calls on the written accounts offered in ships' logbooks from various parts of the Atlantic. The latter provide the opportunity of tracking the system across the otherwise data-deficient areas of the North Atlantic as it recurved toward Europe. The findings are of intrinsic interest in documenting a notable historical event. They also offer a methodological model of how such a variety of documentary sources can be drawn together and used to identify, track, and reconstruct such events from the distant past and thereby improve the chronology of hurricanes and make more reliable our interpretation of their changing frequencies

Microwave Assisted Synthesis of Py-Im Polyamides

Microwave synthesis was utilized to rapidly build Py-Im polyamides in high yields and purity using Boc-protection chemistry on Kaiser oxime resin. A representative polyamide targeting the 5′-WGWWCW-3′ (W = A or T) subset of the consensus Androgen and Glucocorticoid Response Elements was synthesized in 56% yield after 20 linear steps and HPLC purification. It was confirmed by Mosher amide derivatization of the polyamide that a chiral α-amino acid does not racemize after several additional coupling steps

Characterization and Solubilization of Pyrrole–Imidazole Polyamide Aggregates

To optimize the biological activity of pyrrole–imidazole polyamide DNA-binding molecules, we characterized the aggregation propensity of these compounds through dynamic light scattering and fractional solubility analysis. Nearly all studied polyamides were found to form measurable particles 50–500 nm in size under biologically relevant conditions, while HPLC-based analyses revealed solubility trends in both core sequences and peripheral substituents that did not correlate with overall ionic charge. The solubility of both hairpin and cyclic polyamides was increased upon addition of carbohydrate solubilizing agents, in particular, 2-hydroxypropyl-β-cyclodextrin (HpβCD). In mice, the use of HpβCD allowed for improved injection conditions and subsequent investigations of the availability of polyamides in mouse plasma to human cells. The results of these studies will influence the further design of Py-Im polyamides and facilitate their study in animal models

Australian long-term care personnel's knowledge and attitudes regarding palliative care for people with advanced dementia.

This study aimed to describe Australian long-term care (LTC) personnel's knowledge and attitudes concerning palliative care for residents with advanced dementia, and explore relationships with LTC facility/personnel characteristics. An analysis was undertaken of baseline data from a cluster randomised controlled trial of facilitated family case conferencing for improving palliative care of LTC residents with advanced dementia (the 'IDEAL Study'). Participants included any LTC personnel directly involved in residents' care. Knowledge and attitudes concerning palliative care for people with advanced dementia were measured using the questionnaire on Palliative Care for Advanced Dementia. Univariate and multivariate analyses explored relationships between personnel knowledge/attitudes and facility/personnel characteristics. Of 307 personnel in the IDEAL Study, 290 (94.5%) from 19/20 LTCFs provided sufficient data for inclusion. Participants included 9 (2.8%) nurse managers, 59 (20.5%) registered nurses, 25 (8.7%) enrolled nurses, 187 (64.9%) assistants in nursing/personal care assistants and 9 (3.1%) care service employees. In multivariate analyses, a facility policy not to rotate personnel through dementia units was the only variable associated with more favourable overall personnel knowledge and attitudes. Other variables associated with favourable knowledge were a designation of nursing manager or registered or enrolled nurse, and having a preferred language of English. Other variables associated with favourable attitudes were tertiary level of education and greater experience in dementia care. Like previous international research, this study found Australian LTC personnel knowledge and attitudes regarding palliative care for people with advanced dementia to be associated with both facility and personnel characteristics. Future longitudinal research is needed to better understand the relationships between knowledge and attitudes, as well as between these attributes and quality of care

Potentially Inappropriate Prescribing in Australian Nursing Home Residents with Advanced Dementia: A Substudy of the IDEAL Study

© 2018, Mary Ann Liebert, Inc. Background: Prescribing medications for nursing home residents with advanced dementia should focus on optimizing function and comfort, reducing unnecessary harms and aligning care goals with a palliative approach. Objective: The aim of the study was to estimate the proportion of Australian nursing home residents with advanced dementia receiving potentially inappropriate medications, and identify those most commonly prescribed and factors associated with their use. Design: Data were collected through retrospective audit of medication charts. Setting/Subjects: Two hundred eighteen nursing home residents with advanced dementia from 20 nursing homes participated in a cluster-randomized controlled trial of case conferencing (the IDEAL Study) from June 2013 to December 2014. Measurements: Inappropriate drug use was defined as medications classified as "never appropriate" by the Palliative Excellence in Alzheimer Care Efforts (PEACE) program criteria. Generalized linear mixed models were used to identify variables predicting use of "never" appropriate medications. Results: Over a quarter (n = 65, 30%) of residents received at least one medication classed as "never" appropriate, the most common being lipid-lowering agents (n = 38, 17.4%), antiplatelet agents (n = 18, 8.3%), and acetylcholinesterase inhibitors (n = 16, 7.3%). Residents who had been at the nursing home for ≤10 months (odds ratio [OR] 5.60, 95% confidence interval [CI] 1.74-18.06) and 11-21 months (OR 5.41, 95% CI 1.67-17.75) had significantly greater odds of receiving a never appropriate medication compared with residents who had been at the nursing home for >5 years. Conclusions: Use of potentially inappropriate medications in Australian nursing home residents with advanced dementia is common. A greater understanding of the rationale that underpins prescribing of medications is required