A low molecular weight hydrogel with unusual gel aging

We describe a dipeptide hydrogel with unusual aging characteristics. Over time, a transformation from a turbid gel to a transparent gel occurs which is initiated from the air–water interface. Here, we investigate this transition and discuss the implications of this aging on the bulk properties of the gel

Photoresponsive gelators

Low molecular weight gels can be responsive to a range of external stimuli. The use of light as an external stimulus to modify gels is of particular interest for a number of reasons. Light is a non-invasive trigger. For example, using light it is possible to spatially target a specific area of the gel leading to patterned gel surfaces. Here, we review the different approaches that have been used to form low molecular weight gels that respond to ligh

Probing the self-assembled structures and pKa of hydrogels using electrochemical methods

The surface chemistry of the aggregated structures that form the scaffold in self-assembled hydrogels - their charge, hydrophobicity and ion-binding dynamics - play an important role in determining the gel properties and the gel’s suitability for specific applications. However, there are limited methods available for the study of this surface chemistry. Here, we show that electrochemical techniques can be used to measure the surface chemical properties of the self-assembled aggregates structures and also to determine the pKa of the gelators. We also provide a method to quickly determine whether a functionalised-dipeptide will form either a gel or not. This method has scope for use in use in high-throughput screening and further complex pH-triggered self-assembled gelation systems

Controlling the assembly and properties of low-molecular-weight hydrogelators

Low-molecular-weight gels are formed by the self-assembly of small molecules into fibrous networks that can immobilize a significant amount of solvent. Here, we focus on our work with a specific class of gelator, the functionalized dipeptide. We discuss the current state of the art in the area, focusing on how these materials can be controlled. We also highlight interesting and unusual observations and unanswered questions in the field

Flapping Tail Membrane in Bats Produces Potentially Important Thrust during Horizontal Takeoffs and Very Slow Flight

Historically, studies concerning bat flight have focused primarily on the wings. By analyzing high-speed video taken on 48 individuals of five species of vespertilionid bats, we show that the capacity to flap the tail-membrane (uropatagium) in order to generate thrust and lift during takeoffs and minimal-speed flight (<1 m s−1) was largely underestimated. Indeed, bats flapped the tail-membrane by extensive dorso-ventral fanning motions covering as much as 135 degrees of arc consistent with thrust generation by air displacement. The degree of dorsal extension of the tail-membrane, and thus the potential amount of thrust generated during platform launches, was significantly correlated with body mass (P = 0.02). Adduction of the hind limbs during upstrokes collapsed the tail-membrane thereby reducing its surface area and minimizing negative lift forces. Abduction of the hind limbs during the downstroke fully expanded the tail-membrane as it was swept ventrally. The flapping kinematics of the tail-membrane is thus consistent with expectations for an airfoil. Timing offsets between the wings and tail-membrane during downstrokes was as much as 50%, suggesting that the tail-membrane was providing thrust and perhaps lift when the wings were retracting through the upstoke phase of the wing-beat cycle. The extent to which the tail-membrane was used during takeoffs differed significantly among four vespertilionid species (P = 0.01) and aligned with predictions derived from bat ecomorphology. The extensive fanning motion of the tail membrane by vespertilionid bats has not been reported for other flying vertebrates

Mechanoresponsive self‐assembled perylene bisimide films

In this work, self-assembled amino-acid appended perylene bisimides (PBIs) have been studied that when processed into thin films change their resistivity in response to being bent. The PBIs assemble into structures in water and form thin films upon drying. These normally delicate thin films can be tolerant to bending, depending on the aggregates they form. Furthermore, the films then reversibly change their resistivity in response to this mechanical stimulus. This change is proportional to the degree of bending of the film giving them the potential to be used quantitatively to measure mechanical movement, such as in wearable devices

Aligning self-assembled perylene bisimides in a magnetic field

Photoconductive self-assembled 1D structures can be formed by perylene bisimides. These structures are generally randomly orientated, limiting their applications as conductive wires. Here, we show that magnetic fields can be used to create highly aligned, directionally-dependent thin films. This approach leads to well-aligned structures over large areas

Creating transient gradients in supramolecular hydrogels

The self‐assembly of low molecular weight gelators in water usually produces homogeneous hydrogels. However, homogeneous gels are not always desired. Using a photoacid generator, it is shown how to form gels with a transient gradient in stiffness, proved using cavitation and bulk rheology. Small‐angle neutron scattering is used to show that the gels formed by photoacid are the result of the same structures as when using a conventional pH trigger. Patterned gels can also be formed, again with transient differences in stiffness

Health-seeking behaviour, diagnostics and transmission dynamics in the control of visceral leishmaniasis in the Indian subcontinent

Countries in the Indian subcontinent have committed to reducing the incidence of kala-azar, a clinical manifestation of visceral leishmaniasis, to below 1 in 10,000 by 2020. We address the role of timing of use and accuracy of diagnostics in kala-azar control and elimination. We use empirical data on health-seeking behaviour and health-system performance from the Indian state of Bihar, Bangladesh and Nepal to parameterize a mathematical model. Diagnosis of cases is key to case management, control and surveillance. Treatment of cases prevents onward transmission, and we show that the differences in time to diagnosis in these three settings explain the observed differences in incidence. Shortening the time from health-care seeking to diagnosis is likely to lead to dramatic reductions in incidence in Bihar, bringing the incidence down to the levels seen in Bangladesh and Nepal. The results emphasize the importance of maintaining population and health-system awareness, particularly as transmission and disease incidence decline. We explore the possibility of diagnosing patients before the onset of clinical kala-azar (before 14 days fever), and show that this could have a marked impact on incidence, even for a moderately sensitive test. However, limited specificity (that results in false positives) is a major barrier to such a strategy. Diagnostic tests of high specificity used at an early stage of active infection, even if sensitivity is only moderate, could have a key role in the control of kala-azar, and prevent its resurgence when paired with the passive health-care system and tests of high sensitivity, such as the test for rK39 antibody response

Controlling And Understanding Single And Multicomponent Supramolecular Gels

Supramolecular gels can be prepared by the self-assembly of small molecules into fibrous structures. The properties of the resulting gels depend on how the gels are formed, such that gels with very different properties can be prepared from a single gelator if different gelation methods are used. We have been working to understand this, and for example can prepare gels that can or cannot be 3D-printed from the same gelator by varying gelation method. Here, we will focus on explaining the design rules. As specific examples, we will discuss how varying the chirality of our dipeptide-based gelators can be used to control the self-assembled aggregates, leading to differences in the final gels. We will also show how our understanding can be expanded to multicomponent systems, where each component gelator can form gels alone. In these mixed systems, we can control assembly such that self-sorted multicomponent gels are formed. We will show how such systems can be characterised to prove this assembly and how this approach can be used to prepare gels with controlled and specific properties