Using experimental and computational energy equilibration to understand hierarchical self-assembly of Fmoc-dipeptide amphiphiles

Despite progress, a fundamental understanding of the relationships between the molecular structure and self-assembly configuration of Fmoc-dipeptides is still in its infancy. In this work, we provide a combined experimental and computational approach that makes use of free energy equilibration of a number of related Fmoc-dipeptides to arrive at an atomistic model of Fmoc-threonine-phenylalanine-amide (Fmoc-TF-NH2) which forms twisted fibres. By using dynamic peptide libraries where closely related dipeptide sequences are dynamically exchanged to eventually favour the formation of the thermodynamically most stable configuration, the relative importance of C-terminus modifications (amide versus methyl ester) and contributions of aliphatic versus aromatic amino acids (phenylalanine F vs. leucine L) is determined (F > L and NH2 > OMe). The approach enables a comparative interpretation of spectroscopic data, which can then be used to aid the construction of the atomistic model of the most stable structure (Fmoc-TF-NH2). The comparison of the relative stabilities of the models using molecular dynamic simulations and the correlation with experimental data using dynamic peptide libraries and a range of spectroscopy methods (FTIR, CD, fluorescence) allow for the determination of the nanostructure with atomistic resolution. The final model obtained through this process is able to reproduce the experimentally observed formation of intertwining fibres for Fmoc-TF-NH2, providing information of the interactions involved in the hierarchical supramolecular self-assembly. The developed methodology and approach should be of general use for the characterization of supramolecular structures

Developing Student Skills to Actively Engage in Feedback Conversations: A Pilot Study

Purpose: Students often have passive or counterproductive responses to feedback. The aim of this pilot study was to evaluate a feedback training module containing online learning and live simulation. It was hypothesized that 1) student confidence in feedback skills would increase following the module, and 2) compared with a control group who undertook the module after their clinical placement, the feedback group who undertook the module before their placement would perform better on clinical placement on the sections of the Assessment of Physiotherapy Practice related to communication, but those related to clinical skills would not be affected. Methods: A convenience sample of all 68 students in the first of two years of a masters graduate-entry physiotherapy program in Australia was recruited for the study. The feedback group (N=46) received the module before their 5-week orthopaedic clinical placement, and the control group (N=22) received the module after their placement. The module included two-hours of online independent learning and three-hours of simulated learning activity. Students provided and received feedback and were facilitated in developing skills to explore the understandings and attitudes underlying behaviours. Results: All students rated the module as having a large impact on their feedback abilities. The increased confidence in feedback skills was significant for the feedback group. Compared with the control group and with the previous two cohorts undertaking the same placement, the feedback group had improved performance at the mid-point, but not at the end of their five week placement. Conclusions: A focussed feedback module, including a simulated learning activity, increased student confidence and was perceived by students as having a positive impact on their feedback skills. There was a positive impact of the module on student performance during but not at the end of their clinic placement. An incidental finding was the suggestion that a time gap between on-campus learning and the related clinical placement may have a detrimental effect on student performance

Thiazole-induced rigidification in substituted dithieno-tetrathiafulvalene : the effect of planarisation on charge transport properties

Two novel tetrathiafulvalene (TTF) containing compounds 1 and 2 have been synthesised via a four-fold Stille coupling between a tetrabromo-dithienoTTF 5 and stannylated thiophene 6 or thiazole 4. The optical and electrochemical properties of compounds 1 and 2 have been measured by UV-vis spectroscopy and cyclic voltammetry and the results compared with density functional theory (DFT) calculations to confirm the observed properties. Organic field effect transistor (OFET) devices fabricated from 1 and 2 demonstrated that the substitution of thiophene units for thiazoles was found to increase the observed charge transport, which is attributed to induced planarity through S-N interactions of adjacent thiazole nitrogen atoms and TTF sulfur atoms and better packing in the bulk

An ambipolar BODIPY derivative for a white exciplex OLED and cholesteric liquid crystal laser toward multifunctional devices

A new interface engineering method is demonstrated for the preparation of an efficient white organic light-emitting diode (WOLED) by embedding an ultrathin layer of the novel ambipolar red emissive compound 4,4-difluoro-2,6-di(4-hexylthiopen-2-yl)-1,3,5,7,8-pentamethyl-4-bora-3a,4a-diaza-s-indacene (bThBODIPY) in the exciplex formation region. The compound shows a hole and electron mobility of 3.3 × 10–4 and 2 × 10–4 cm2 V–1 s–1, respectively, at electric fields higher than 5.3 × 105 V cm–1. The resulting WOLED exhibited a maximum luminance of 6579 cd m–2 with CIE 1931 color coordinates (0.39; 0.35). The bThBODIPY dye is also demonstrated to be an effective laser dye for a cholesteric liquid crystal (ChLC) laser. New construction of the ChLC laser, by which a flat capillary with an optically isotropic dye solution is sandwiched between two dye-free ChLC cells, provides photonic lasing at a wavelength well matched with that of a dye-doped planar ChLC cell

Synthesis and properties of novel star-shaped oligofluorene conjugated systems with BODIPY cores

Star-shaped conjugated systems with varying oligofluorene arm length and substitution patterns of the central BODIPY core have been synthesised, leading to two families of compounds, T-B1-T-B4 and Y-B1-Y-B4, with T- and Y-shaped motifs, respectively. Thermal stability, cyclic voltammetry, absorption and photoluminescence spectroscopy of each member of these two families were studied in order to determine their suitability as emissive materials in photonic applications

Improving performance in golf: current research and implications from a clinical perspective

ABSTRACTGolf, a global sport enjoyed by people of all ages and abilities, involves relatively long periods of low intensity exercise interspersed with short bursts of high intensity activity. To meet the physical demands of full swing shots and the mental and physical demands of putting and walking the course, it is frequently recommended that golfers undertake golf-specific exercise programs. Biomechanics, motor learning, and motor control research has increased the understanding of the physical requirements of the game, and using this knowledge, exercise programs aimed at improving golf performance have been developed. However, while it is generally accepted that an exercise program can improve a golfer's physical measurements and some golf performance variables, translating the findings from research into clinical practice to optimise an individual golfer's performance remains challenging. This paper discusses how biomechanical and motor control research has informed current practice and discusses how emerging sophisticated tools and research designs may better assist golfers improve their performance

The Astropy Problem

The Astropy Project (http://astropy.org) is, in its own words, "a community effort to develop a single core package for Astronomy in Python and foster interoperability between Python astronomy packages." For five years this project has been managed, written, and operated as a grassroots, self-organized, almost entirely volunteer effort while the software is used by the majority of the astronomical community. Despite this, the project has always been and remains to this day effectively unfunded. Further, contributors receive little or no formal recognition for creating and supporting what is now critical software. This paper explores the problem in detail, outlines possible solutions to correct this, and presents a few suggestions on how to address the sustainability of general purpose astronomical software