Self-assembly, nematic phase formation and organocatalytic behaviour of a proline-functionalized lipopeptide

The self-assembly of the amphiphilic lipopeptide PAEPKI-C16 (P = proline, A = alanine, E = glutamic acid, K = lysine, I = isoleucine, C16 = hexadecyl) was investigated using a combination of spectroscopic, microscopic and scattering methods and compared to C16-IKPEAP with the same (reversed) peptide sequence and the alkyl chain positioned N-terminally and which lacks a free N-terminal proline residue. The catalytic activity of these peptides were then compared using a model aldol reaction system. For PAEPKI-C16, Cryo-TEM images showed the formation of micrometer length fibers, which by Small-angle X-ray scattering (SAXS) were found to have a radius of 2.5 - 2.6 nm. Spectroscopic analysis shows these fibers are built from -sheets. This behaviour is in complete contrast to that of C16-IKPEAP which forms spherical micelles with peptides in a disordered conformation [Hutchinson, J. A. et al. J. Phys. Chem. B 2019, 123, 613]. For PAEPKI-C16, the spontaneous alignment of fibers was observed upon increasing pH, which was accompanied by observed birefringence and anisotropy of SAXS patterns. This shows the formation of a nematic liquids and unprecedented nematic hydrogel formation was also observed these lipopeptides at sufficiently high concentrations. SAXS shows retention of an ultrafine (1.7 nm core radius) fibrillar network within the hydrogel. PAEPKI-C16 with free N-terminal proline shows enhanced anti:syn diastereoselectivity and better conversion compared to C16-IKPEAP. The cytotoxicity of PAEPKI-C16 was also lower than C16-IKPEAP for both fibroblast and cancer cell lines. These results highlight the sensitivity of lipopeptide properties to the presence of a free proline residue. The spontaneous nematic phase formation by PAEPKI-C16 points to the highly anisotropy of its ultrafine fibrillar structure and the formation of such a phase at low concentration in aqueous solution may be valuable for future applications

Sea otter effects on trophic structure of seagrass communities in southeast Alaska

Previous research in southeast Alaska on the effects of sea otters Enhydra lutris in seagrass Zostera marina communities identified many but not all of the trophic relationships that were predicted by a sea otter-mediated trophic cascade. To further resolve these trophic connections, we compared biomass, carbon (δ13C) and nitrogen (δ15N) stable isotope (SI), and fatty acid (FA) data from 16 taxa at 3 sites with high and 3 sites with low sea otter density (8.2 and 0.1 sea otters km−2, respectively). We found lower crab and clam biomass in the high sea otter region but did not detect a difference in biomass of other seagrass community taxa or the overall community isotopic niche space between sea otter regions. Only staghorn sculpin differed in δ13C between regions, and Fucus, sugar kelp, butter clams, dock shrimp, and shiner perch differed in δ15N. FA analysis indicated multivariate dissimilarity in 11 of the 15 conspecifics between sea otter regions. FA analysis found essential FAs, which consumers must obtain from their diet, including 20:5ω3 (EPA) and 22:6ω3 (DHA), were common in discriminating conspecifics between sea otter regions, suggesting differences in consumer diets. Further FA analysis indicated that many consumers rely on diverse diets, regardless of sea otter region, potentially buffering these consumers from sea otter-mediated changes to diet availability. While sea otters are major consumers in this system, further studies are needed to understand the mechanisms responsible for the differences in biomarkers between regions with and without sea ottersWe thank Tiffany Stephens, Maggie Shields, Melanie Borup, Ashely Bolwerk, Nicole LaRoche, Tom Bell, Michael Stekoll and the rest of the Apex Predators, Ecosystems and Community Sustainability (APECS) team and 26 Earthwatch volunteers for assistance in the field and laboratory. Special thanks to Reyn Yoshioka, Natalie Thompson, the Coastal Trophic Ecology Lab, and Oregon Institute of Marine Biology for their assistance with fatty acid extractions, Melissa Rhodes-Reese at University of Alaska Southeast for water nutrient analysis, and Matthew Rogers and NOAA Auke Bay Laboratories for assistance with stable isotope analyses. This study was funded by the National Science Foundation (NSF #1635716, #1600230 to G.L.E.), through the generous support of Earthwatch, and a 56 NSF Graduate Research Fellowship, a North Pacific Re - search Board Graduate Student Research Award, an American Fisheries Society Steven Berkeley Marine Conservation Fellowship, and a Lerner Gray Memorial Fund (to W.W.R). This study was completed in partial fulfillment of the requirements for W.W.R.’s PhD at the University of Alaska Fairbanks and we thank committee members Dr. Franz Mueter and Dr. Anne Beaudreau for their comments on this project and the manuscript. Finally, we thank the 3 anonymous reviewers whose comments greatly improved the manuscript. This study was conducted on the traditional lands and waters of the Alaska Native Tlingit and Haida peoples. We are grateful for our access to these spaces and benefited from conversations and support from the members of Tribal communities and governments.Ye

Polymorphism of asymmetric catalysts based on amphiphilic lipopeptides in solution

The self-assembly of model [P]RWG lipopeptides (P: L-proline, R: L-arginine, W: L-tryptophan, G: L-glycine), containing one or two aliphatic octadecyl (C18) chains in water and cyclohexanone/water solutions was examined. The self-assembly of mixtures of these RWG and PRWG lipopeptides was also investigated. These materials presented a similar critical aggregation concentration of ∼4.0 × 10−4 wt% and were characterized by unordered secondary structures with some β-sheet content. TEM and cryo-TEM revealed the presence of mainly nanotape structures with micelles observed for systems rich in PRWG(C18H37). Analysis of detailed SAXS form factor measurements revealed the presence of bilayers 3–4 nm thick while the PRWG(C18H37) micelles have a core radius of approximately 3 nm, and a shell thickness of 2 nm. For the cyclohexanone/water systems polymorphs containing cluster aggregates (with radius of 0.25 nm to 0.50 nm) and some elongated structures (with radius of 5.7 nm to 26.1 nm) were seen. Longer structures were formed with the increase of the proline-containing lipopeptide content. The catalytic activity of these peptides was assessed using a model nitro-aldol reaction. The concentration of water in the reaction system influenced the conversion, higher content promoted better efficiency for the water systems, but the opposite was observed for the cyclohexanone/water samples

'It's a Form of Freedom': The experiences of people with disabilities within equestrian sport

This paper explores the embodied, gendered experiences of disabled horse‐riders. Drawing on data from five in‐depth interviews with paradressage riders, the ways in which their involvement in elite disability sport impacts upon their sense of identity and confidence are explored, as well as the considerable health and social benefits that this involvement brings. Social models of disability are employed and the shortcomings of such models, when applied to disability sport, are highlighted. The data presented here demonstrates the necessity of seeing disability sport as an embodied experience and acknowledging the importance of impairment to the experiences of disabled athletes. Living within an impaired body is also a gendered experience and the implications of this when applied to elite disability sport are considered

Investigation of β-carotene–gelatin composite particles with a multiwavelength UV/vis detector for the analytical ultracentrifuge

A multiwavelength UV/vis detector for the analytical ultracentrifuge (MWL-AUC) has been developed recently. In this work, β-carotene–gelatin composite particles are investigated with MWL-AUC. Band centrifugation with a Vinograd cell is used to ensure maximum sample separation. Spectral changes of the system are observed in dependence of the sedimentation coefficient and are attributed to a previously unknown inhomogeneity of the β-carotene chemical composition with both H- and J-aggregates coexisting in a mixture. In addition, our data suggest that pure H- and J-aggregates exist in a particle while their relative concentrations in a mixture determine the color characteristics of the sample. The unique abilities and properties of MWL-AUC include sedimentation coefficient distributions for all possible wavelengths, full UV/vis spectra of each different species in the mixture and 3D movies of the sedimentation process. These properties significantly extend the scope of the analytical ultracentrifuge technique and show that complex biopolymer multicomponent mixtures can be resolved into their individual species

Independent and combined effects of physical activity and body mass index on the development of Type 2 Diabetes - a meta-analysis of 9 prospective cohort studies.

BACKGROUND: The aim of this harmonized meta-analysis was to examine the independent and combined effects of physical activity and BMI on the incidence of type 2 diabetes. METHODS: Our systematic literature review in 2011 identified 127 potentially relevant prospective studies of which 9 fulfilled the inclusion criteria (total N = 117,878, 56.2 % female, mean age = 50.0 years, range = 25-65 years). Measures of baseline physical activity (low, intermediate, high), BMI-category [BMI < 18.4 (underweight), 18.5-24.9 (normal weight), 25.0-29.9 (overweight), 30+ (obese)] and incident type 2 diabetes were harmonized across studies. The associations between physical activity, BMI and incident type 2 diabetes were analyzed using Cox regression with a standardized analysis protocol including adjustments for age, gender, educational level, and smoking. Hazard ratios from individual studies were combined in a random-effects meta-analysis. RESULTS: Mean follow-up time was 9.1 years. A total of 11,237 incident type 2 diabetes cases were recorded. In mutually adjusted models, being overweight or obese (compared with normal weight) and having low physical activity (compared with high physical activity) were associated with an increased risk of incident type 2 diabetes (hazard ratios 2.33, 95 % CI 1.95-2.78; 6.10, 95 % CI: 4.63-8.04, and 1.23, 95 % CI: 1.09-1.39, respectively). Individuals who were both obese and had low physical activity had 7.4-fold (95 % CI 3.47-15.89) increased risk of type 2 diabetes compared with normal weight, high physically active participants. CONCLUSIONS: This harmonized meta-analysis shows the importance of maintaining a healthy weight and being physically active in diabetes prevention

Performance of a fast fiber based UV/Vis multiwavelength detector for the analytical ultracentrifuge

The optical setup and the performance of a prototype UV/Vis multiwavelength analytical ultracentrifuge (MWL-AUC) is described and compared to the commercially available Optima XL-A from Beckman Coulter. Slight modifications have been made to the optical path of the MWL-AUC. With respect to wavelength accuracy and radial resolution, the new MWL-AUC is found to be comparable to the existing XL-A. Absorbance accuracy is dependent on the light intensity available at the detection wavelength as well as the intrinsic noise of the data. Measurements from single flashes of light are more noisy for the MWL-AUC, potentially due to the absence of flash-to-flash normalization in the current design. However, the possibility of both wavelength and scan averaging can compensate for this and still give much faster scan rates than the XL-A. Some further improvements of the existing design are suggested based on these findings

Measurement of polarisation observables in Ks0Σ+K^0_s\Sigma^+ photoproduction off the proton

The reaction $\gamma \, p \rightarrow K^0_S\,\Sigma^+$ is studied in the photon energy range from threshold. Linearly polarised photon beams from coherent bremsstrahlung enabled the first measurement of photon beam asymmetries in this reaction up to $E_\gamma = 2250$ MeV. In addition, the recoil hyperon polarisation was determined through the asymmetry in the weak decay $\Sigma^+ \rightarrow p \pi^0$ up to $E_\gamma = 1650$ MeV. The data are compared to partial wave analyses, and the possible impact on the interpretation of a recently observed cusp-like structure near the $K^*$ thresholds is discussed.Comment: 6 pages, 5 figures. References [8,9,10,11] which were not on the original submission are now include