The transport of anions across cellular membranes is an important biological function governed by specialised proteins. In recent years, many small molecules have emerged that mimick the anion transport behaviour of these proteins, but only a few of these synthetic molecules also display the gating/switching behaviour seen in biological systems. A small series of thiosquaramides was synthesised and their pH-dependent chloride binding and anion transport behaviour was investigated using 1H NMR titrations, single crystal X-ray diffraction and a variety of vesicle-based techniques. Spectrophotometric titrations and DFT calculations revealed that the thiosquaramides are significantly more acidic than their oxosquaramide analogues, with pKa values between 4.0 and 9.0. This led to the observation that at pH 7.2 the anion transport ability of the thiosquaramides is fully switched OFF due to deprotonation of the receptor, but is completely switched ON at lower pH.
Abstract-Decades of research have repeatedly shown that people perform poorly at estimating and understanding conditional probabilities that are inherent in Bayesian reasoning problems. Yet in the medical domain, both physicians and patients make daily, life-critical judgments based on conditional probability. Although there have been a number of attempts to develop more effective ways to facilitate Bayesian reasoning, reports of these findings tend to be inconsistent and sometimes even contradictory. For instance, the reported accuracies for individuals being able to correctly estimate conditional probability range from 6% to 62%. In this work, we show that problem representation can significantly affect accuracies. By controlling the amount of information presented to the user, we demonstrate how text and visualization designs can increase overall accuracies to as high as 77%. Additionally, we found that for users with high spatial ability, our designs can further improve their accuracies to as high as 100%. By and large, our findings provide explanations for the inconsistent reports on accuracy in Bayesian reasoning tasks and show a significant improvement over existing methods. We believe that these findings can have immediate impact on risk communication in health-related fields.
A macrocyclic tetralactam host is threaded by a highly fluorescent squaraine dye that is flanked by two polyethyleneglycol (PEG) chains with nanomolar dissociation constants in water. Furthermore, the rates of bimolecular association are very fast with kon ~106–107 M−1s−1. The association is effective under cell culture conditions and produces large changes in dye optical properties including turn-on near-infrared fluorescence that can be imaged using cell microscopy. Association constants in water are ~1000 times higher than in organic solvents and strongly enthalpically favored at 27 °C. The threading rate is hardly affected by the length of the PEG chains that flank the squaraine dye. For example, macrocyle threading by a dye conjugate with two appended PEG2000 chains is only three times slower than threading by a conjugate with triethyleneglycol chains that are twenty times shorter. The results are a promising advance towards synthetic mimics of streptavidin/biotin.
A new squaraine rotaxane molecular shuttle exhibits high chemical stability and acts as a deep-red, fluorescent and colorimetric sensor for Cl À anion with reversible, ratiometric response. The molecular design encapsulates a dihydroxyl substituted squaraine dye inside an anthracene-containing tetralactam macrocycle and a "clicked capping" reaction was used to convert an appropriate pseudorotaxane precursor into a permanently interlocked rotaxane in high yield. Reversible binding of Cl À to the rotaxane in solution, or on the surface of prototype dipsticks, causes lateral displacement of the surrounding macrocycle away from the central squaraine station and a substantial 30-40 nm shift in the squaraine absorption/fluorescence maxima that can be easily detected by the naked eye. The collective attributes of intense absorption/emission and ratiometric response at deep-red wavelengths is a significant advance in optical Cl À sensor performance by an organic molecule.
Dynamic difficulty adjustments can be used in humancomputer systems in order to improve user engagement and performance. In this paper, we use functional near-infrared spectroscopy (fNIRS) to obtain passive brain sensing data and detect extended periods of boredom or overload. From these physiological signals, we can adapt a simulation in order to optimize workload in real-time, which allows the system to better fit the task to the user from moment to moment. To demonstrate this idea, we ran a laboratory study in which participants performed path planning for multiple unmanned aerial vehicles (UAVs) in a simulation. Based on their state, we varied the difficulty of the task by adding or removing UAVs and found that we were able to decrease errors by 35% over a baseline condition. Our results show that we can use fNIRS brain sensing to detect task difficulty in real-time and construct an interface that improves user performance through dynamic difficulty adjustment.
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