Methods of changing low molecular weight gel properties through gelation kinetics.

Low molecular weight gels continue to attract notable interest, with many potential applications. However, there are still significant gaps in our understanding of these systems and the correlation between the pre-gel and final gel states. The kinetics of the gelation process plays a crucial role in the bulk properties of the hydrogel and presents an opportunity to fine-tune these systems to meet the requirements of the chosen application. Therefore, it is possible to use a single gelator for multiple applications. This review discusses four ways to modify the pre-gelled structures before triggering gelation. Such modifications can enhance the material's intended performance, which may result in significant advancements in high-tech areas, such as drug delivery, cell culturing, electronics, and tissue engineering.

Atomic structures of naphthalene dipeptide micelles unravel mechanisms of assembly and gelation.

Peptide-based biopolymers have gained increasing attention due to their versatile applications. A naphthalene dipeptide (2NapFF) can form chirality-dependent tubular micelles, leading to supramolecular gels. The precise molecular arrangement within these micelles and the mechanism governing gelation have remained enigmatic. We determined, at near-atomic resolution, cryoelectron microscopy structures of the 2NapFF micelles LL-tube and LD-tube, generated by the stereoisomers (l,l)-2NapFF and (l,d)-2NapFF, respectively. The structures reveal that the fundamental packing of dipeptides is driven by the systematic π-π stacking of aromatic rings and that same-charge repulsion between the carbonyl groups is responsible for the stiffness of both tubes. The structural analysis elucidates how a single residue's altered chirality gives rise to markedly distinct tubular structures and sheds light on the mechanisms underlying the pH-dependent gelation of LL- and LD-tubes. The understanding of dipeptide packing and gelation mechanisms provides insights for the rational design of 2NapFF derivatives, enabling the modulation of micellar dimensions.

Tuning conductivity while maintaining mechanical properties in perylene bisimide hydrogels at physiological pH.

By using different salts as a method to achieve gelation of two different amino-acid-functionalised perylene bisimides, we were able to tune reduction potentials while maintaining the mechanical and optical properties of the system all at pH 7.4.

Application of quasi solid electrolytes in organic based electrochromic devices: A mini review.

The interest in all solid organic based electrochromic devices (ECDs) is on the increase. This is because these devices offer the applicability of electrochromic materials in products such as smart sensors, smart windows, flexible wearables and energy storage devices. The use of quasi-solid electrolytes for the construction of these ECDs is attractive because of their ease of preparation, availability, low cost, improve electrochromic performance, good ionic conductivity and prevention of leakages in ECDs. Hence, in this review, a detailed discussion is presented on the progress in the development of semi-solid electrolytes for ECDs fabrication. The preparation of the most common electrolytes that have been applied for organic based ECDs are summarized. Particular attention is given to efforts and strategies that have been adopted to improve the efficiency of quasi-solid electrolytes. Importantly, knowledge gaps that warrant further research are clearly identified and recommendations for future works are suggested. This review will be very beneficial for both established and new researchers in the field of electrochromic devices and material science.

Investigating multigelator systems across multiple length scales.

Preparation of multicomponent systems provides a method for changing the properties of low molecular weight gelator (LMWG)-based systems. Here we have prepared a variety of multicomponent systems where both components are N-functionalised dipeptide-based LMWGs that may either co-assemble or self-sort when mixed. We exemplify how varying the concentration ratio of the two components can be used to tune the properties of the multicomponent systems pre-gelation, during gelation and in the gel state using viscosity and rheology measurements, circular dichroism, NMR and small angle neutron scattering. We also investigate the effect of changing the chirality of a single component on the properties of these systems. While predicting the outcome of multicomponent assembly is a challenge, the preparation of a variety of systems allows us to probe the factors affecting their design. This work provides insights into how the properties of multicomponent systems composed of two gelators with the same basic structural design can be tuned by varying the chirality and the concentration ratio of the two components and considering the behaviour of the two components when alone.

Using Solution History to Control Hydrogel Properties of a Perylene Bisimide.

pH dependence on water soluble aggregates is well-known in the field of low molecular weight gelators (LMWGs), with different aggregates sometimes having very different properties depending on their final pH. This aggregation determines their applications and performance. Here, we investigate the pH dependence of perylene bisimide gels; initially solutions are formed at a high pH and gels form as the pH is decreased. We find it is not only the final pH but also the starting pH that can impact the resulting gel. We use small angle neutron scattering (SANS), rheology, 1 H NMR spectroscopy and absorption spectroscopy to examine the effect of starting pH on gelation kinetics and final gel properties. Adjusting the solution from pH 9 (where there are few or no aggregates) to pH 6 results in the formation of different worm-like micelles than the ones directly formed at pH 6, leading to again gels with different mechanical properties. This work highlights the importance of controlling the pH of solutions before gelation, but also opens up more possible morphologies and therefore more properties from the same molecule.

Photothermal Perylene Bisimide Hydrogels.

Gels formed using a perylene bisimide (PBI) as a low molecular weight gelator can show the photothermal effect. Formation of the PBI radical anion results in new absorption bands forming, meaning that subsequent irradiation with a wavelength of light overlapping with the new absorption band leads to heating of the gel. This approach can be used to heat the gel, as well as the surrounding milieu. We show how we can use electrochemical methods as well as multicomponent systems to form the radical anion without the need for UV light, and how we can use the photothermal effect to induce phase transitions in the solutions above the gels by exploiting photothermal behavior.

Process Dependent Complexity in Multicomponent Gels.

Mixing low molecular weight gelators (LMWGs) can be used to combine favorable properties of the individual components within a multifunctional gel. Such multicomponent systems are complex enough in themselves but the method of combining components is not commonly considered something to influence self-assembly. Herein, two multicomponent systems comprising of a naphthalene-based dipeptide hydrogelator and one of two modified naphthalene diimides (NDIs), one of which forms gels, and the other does not, are investigated. These systems are probed, examining the structures formed and their gel properties (when preparing a solution from either a mixed powder of both components or by mixing pre-formed solutions of each component) using rheology, small angle neutron scattering (SANS), and absorbance spectroscopy. It is found that by altering the method of preparation, it is can either induce self-sorting or co-assembly within the fibers formed that underpin the gel network.

Electrochemically Enhanced Delivery of Pemetrexed from Electroactive Hydrogels.

Electroactive hydrogels based on derivatives of polyethyleneglycol (PEG), chitosan and polypyrrole were prepared via a combination of photopolymerization and oxidative chemical polymerization, and optionally doped with anions (e.g., lignin, drugs, etc.). The products were analyzed with a variety of techniques, including: FT-IR, UV-Vis, 1H NMR (solution state), 13C NMR (solid state), XRD, TGA, SEM, swelling ratios and rheology. The conductive gels swell ca. 8 times less than the non-conductive gels due to the presence of the interpenetrating network (IPN) of polypyrrole and lignin. A rheological study showed that the non-conductive gels are soft (G' 0.35 kPa, G″ 0.02 kPa) with properties analogous to brain tissue, whereas the conductive gels are significantly stronger (G' 30 kPa, G″ 19 kPa) analogous to breast tissue due to the presence of the IPN of polypyrrole and lignin. The potential of these biomaterials to be used for biomedical applications was validated in vitro by cell culture studies (assessing adhesion and proliferation of fibroblasts) and drug delivery studies (electrochemically loading the FDA-approved chemotherapeutic pemetrexed and measuring passive and stimulated release); indeed, the application of electrical stimulus enhanced the release of PEM from gels by ca. 10-15% relative to the passive release control experiment for each application of electrical stimulation over a short period analogous to the duration of stimulation applied for electrochemotherapy. It is foreseeable that such materials could be integrated in electrochemotherapeutic medical devices, e.g., electrode arrays or plates currently used in the clinic.

Investigating Aggregation Using In Situ Electrochemistry and Small-Angle Neutron Scattering.

Using small-angle neutron scattering to investigate the aggregation of self-assembling molecules is well established. Some of these molecules are electrochemically useful, for example, in electrochromic devices. Electrochemistry can also be used in some cases to induce aggregation. Here, we describe an approach whereby electrochemistry can be directly carried out on a sample in the neutron beam, allowing us to monitor changes directly in situ. We exemplify with two examples but highlight that there are many other potential opportunities.

Managing research throughout COVID-19: Lived experiences of supramolecular chemists.

The international Women in Supramolecular Chemistry network believes that taking an area-specific approach effectively supports equality, diversity, and inclusion. Science lacks diversity, and this is intersectional. We share effects of coronavirus disease 2019 (COVID-19) by triangulating findings from an online survey, a collaborative autoethnography, and reflective group research meetings. We show how qualitative research with the community offers insights into challenges and supports individuals, and we demonstrate that research leaders have often taken responsibility for their teams' mental health and well-being at the cost of their own.

Mechanical Characterization of Multilayered Hydrogels: A Rheological Study for 3D-Printed Systems.

We describe rheological protocols to study layered and three-dimensional (3D)-printed gels. Our methods allow us to measure the properties at different depths and determine the contribution of each layer to the resulting combined properties of the gels. We show that there are differences when using different measuring systems for rheological measurement, which directly affects the resulting properties being measured. These methods allow us to measure the gel properties after printing, rather than having to rely on the assumption that there is no change in properties from a preprinted gel. We show that the rheological properties of fluorenylmethoxycarbonyl-diphenylalanine (FmocFF) gels are heavily influenced by the printing process.

An Area-Specific, International Community-Led Approach to Understanding and Addressing Equality, Diversity, and Inclusion Issues within Supramolecular Chemistry.

Diversity, equality, and inclusion (DEI/EDI) are pressing issues in chemistry and the natural sciences. In this Essay we share how an area-specific approach is "calling in" the community so that it can act to address EDI issues, and support those who are marginalised. Women In Supramolecular Chemistry (WISC) is an international network that aims to support equality, diversity, and inclusion within supramolecular chemistry. WISC has taken a field-specific approach using qualitative research methods with scientists to identify the support that is needed and the problems the supramolecular community needs to address. Herein, we present survey data from the community which highlight the barriers that are faced by those who take career breaks for any reason, a common example is maternity leave, and the importance of mentoring to aid progression post-PhD. In conclusion, we set out an interdisciplinary and creative approach to addressing EDI issues within supramolecular chemistry.

Water soluble organic electrochromic materials.

Organic materials in electrochromic device applications possess a number of advantages over transition metal oxides like WO3 such as ease of synthesis and tunability, flexibility, and derivability from renewable feedstocks. However, these advantages are offset by the need to use organic solvents in their processing which are often flammable and/or toxic. Therefore, it is of paramount importance to the longterm economic and environmental sustainability of organic electronics research to develop water soluble organic materials. Herein, we describe the advances made in developing water soluble organic electronic materials for electrochromic applications. We here classify electrochromic materials into two broad categories: those that transition between colourless and coloured states (Type I) and those that transition between differently coloured states (Type II). The methods by which organic electrochromes are made water soluble are described in detail along with their potential applications in order to promote research in water soluble organic electronic materials in general.

High-throughput characterisation of supramolecular gelation processes using a combination of optical density, fluorescence and UV-Vis absorption measurements.

Herein, we showcase the use of high-throughput microplate reader methodologies for the characterisation of supramolecular gels. We demonstrate how UV-Vis absorption, optical density and fluorescence measurements can selectively define gel fibre assembly/disassembly processes, casting a new light on the construction of these materials.