Low-molecular-weight gels are currently a hugely important class of materials that are attracting significant interest. These gels are formed when small molecules self-assemble into one-dimensional structures that entangle and cross-link to form a network that is capable of immobilizing the solvent. Here, we critically discuss the current state of the art and highlight two key areas where we believe there is significant untapped potential. The first is the observation that the properties of the gels are highly process dependent, which means that it is possible to access materials with very different properties from a single gelator. Second, using multiple gelators offers the opportunity to prepare materials with a high degree of information content and with a wider range of properties. We aim to spark thought and discussion on these aspects. INTRODUCTIONLow-molecular-weight gels (LMWGs), or supramolecular gels, are a fascinating and useful class of material. The gels arise from the self-assembly of small molecules into long, anisotropic structures, most commonly fibers. [1][2][3][4][5] At a sufficiently high concentration, these fibers entangle or otherwise form cross-links, leading to the network that is able to immobilize the solvent through surface tension and capillary forces. 1,2 These gels differ from permanently covalently cross-linked polymer gels because the cross-linking can be reversed by the input of energy, for example, by heating. 6 LMWGs have been around for many years but are receiving considerable current interest. 4 They are also used in industrial products, 7 although this seems rarely discussed in the academic literature.In addition to the industrial applications, many recent advances and uses are being described. [8][9][10][11][12] The specific self-assembly leading to gel formation can be exploited. For example, the fiber formation is a result of molecular stacking, meaning that the self-assembly leads to aggregates that can be suitable for optoelectronic applications. 13,14 The ready reversibility of gelation can be exploited, for example, to release cells from gels on demand in a manner that does not lead to cell death. 15 Ready gel formation by a simple trigger can also be used to allow easy and efficient gel loading. [16][17][18] Unsurprisingly, therefore, there is significant interest in these materials ( Figure 1). This is a fascinating area and in many ways holds attention because of the difficulties in probing and understanding the gels. The gels arise from assembly across many length scales, and understanding all of these is difficult. At the molecular level, the molecules must interact in a manner that leads to the formation of suitable aggregates that can eventually entangle. Thus, one-dimensional growth must be favored. From this perspective, it is very frustrating that it is often extremely difficult to predict whether a molecule will form a gel or not; indeed, gelation has been described as an empirical science. 4 Structurally similar small molecules can exhibitThe Bigger Pict...

Multicomponent supramolecular systems could be used to prepare exciting new functional materials, but it is often challenging to control the assembly across multiple length scales. Here we report a simple approach to forming patterned, spatially resolved multicomponent supramolecular hydrogels. A multicomponent gel is first formed from two low-molecular-weight gelators and consists of two types of fibre, each formed by only one gelator. One type of fibre in this 'self-sorted network' is then removed selectively by a light-triggered gel-to-sol transition. We show that the remaining network has the same mechanical properties as it would have done if it initially formed alone. The selective irradiation of sections of the gel through a mask leads to the formation of patterned multicomponent networks, in which either one or two networks can be present at a particular position with a high degree of spatial control.

Metal-organic frameworks (MOFs) are crystalline synthetic porous materials formed by binding organic linkers to metal nodes: they can be either rigid 1,2 or flexible. 3 Zeolites and rigid MOFs have widespread applications in sorption, separation and catalysis that arise from their ability to control the arrangement and chemistry of guests in their pores via the shape and functionality of the internal surface defined by their chemistry and structure. 4,5 Their structures correspond to an energy landscape with a single, albeit highly functional, energy minimum. In contrast, proteins function by navigating between multiple metastable structures using bond rotations of the polypeptide, 6,7 where each structure lies in one of the minima of a conformational energy landscape and can be selected according to the chemistry of the molecules interacting with the protein. These structural changes are realised through the mechanisms of conformational selection (where a higher energy minimum characteristic of the protein is stabilised by small molecule binding), and induced fit (where a small molecule imposes a structure on the protein that is not a minimum in the absence of that molecule). 8 Here we show that rotation about covalent bonds in a peptide linker can change a flexible MOF to afford nine distinct crystal structures, revealing a conformational energy landscape characterised by multiple structural minima. The uptake of small molecule guests by the MOF can be chemically triggered by inducing peptide conformational change. This change transforms the material from a minimum on the landscape that is inactive for guest sorption to an active one. Chemical control of the conformation of a flexible organic linker offers a route to modify the pore geometry and internal surface chemistry and thus the function of open-framework materials. Flexible MOF structures 9,10 can be rearranged in the presence of guests through mechanical mechanisms such as the repositioning of a rigid linker about an inorganic unit 11-13 or the relative displacement of two rigid networks, 14 opening a range of routes to control function 15 that are not accessible to rigid frameworks with their single structural minimum (Figure 1). Similar phenomena have been observed in the host-guest chemistry of interlocked cage molecules. 16-18 Alternatively, rotations about bonds involving sp 3 carbons 19-25 allow MOF to access different structures. For example, low energy conformational changes of dipeptide Gly-X linkers produce open and closed forms of Zn(Gly-X)2 frameworks. 26,27 The greater chemical diversity and more complex conformational space of higher order oligopeptides offer MOF with multiple open structures (Figure 1). This could allow interaction with molecules in the pores to select a specific structure for a defined function from the resulting energy landscape. That structure would be accessed through the single bond rotation pathway used by proteins (Figure 1). The tripeptide glycine-glycine-L-histidine (GGH) affords a three-dimensional chiral MOF Zn...

Addition of divalent cations to a solution of a naphthalene-diphenylalanine that forms worm-like micelles at high pH results in the formation of a rigid, self-supporting hydrogel.

Linear poly(p‐phenylene)s are modestly active UV photocatalysts for hydrogen production in the presence of a sacrificial electron donor. Introduction of planarized fluorene, carbazole, dibenzo[b,d]thiophene or dibenzo[b,d]thiophene sulfone units greatly enhances the H2 evolution rate. The most active dibenzo[b,d]thiophene sulfone co‐polymer has a UV photocatalytic activity that rivals TiO2, but is much more active under visible light. The dibenzo[b,d]thiophene sulfone co‐polymer has an apparent quantum yield of 2.3 % at 420 nm, as compared to 0.1 % for platinized commercial pristine carbon nitride.

Selectively fluorinated aromatic compounds are of interest in many sectors. Of the methodologies used for their formation, halogen exchange is the only industrial rival to the diazonium based routes. Although many compounds can be formed by halogen exchange, the formation of metafluorinated species by this route is difficult. One possible method for overcoming this is fluorodenitration. Although traditionally plagued by side reactions, recent reports suggest that, with careful control of the reaction conditions, fluorodenitration could well provide a viable industrial alternative for the formation of selectively fluorinated aromatic compounds.

A number of Fmoc amino acids can be effective low molecular weight hydrogelators. The type of gel formed depends on the amino acid used and, in the case of FmocF, the final pH of the system. The single crystal structure of two of the gelators (FmocF and FmocY) have been determined and the data compared to the fibre X-ray diffraction data. FmocF, which forms metastable gels, crystallises easily and the data for the fibre phase and crystal phase are relatively similar. For FmocF, the fibre axis in b is consistent with the hydrogen bonding repeat distances and the diffraction pattern calculated from the single crystal structure is a good match with the experimental fibre X-ray diffraction data. On the other hand, there are significant differences between the crystalline phase determined and the fibre phase for FmocY. The packing of FmocY within the crystal structure is created by interactions between the planar Fmoc groups, whilst it is clear that hydrogen bonding drives the self-assembly into fibrillar structures within the gels. This shows that understanding the packing in gel phase by analogy to isolated crystal structures has the potential to lead to erroneous conclusions. CrystEngCommThis journal is

Iron oxide nanoparticles (IONPs, sometimes called superparamagnetic iron oxide nanoparticles or SPIONs) have already shown promising results for in vivo cell tracking using magnetic resonance imaging (MRI). To fully exploit the potential of these materials as contrast agents, there is still a need for a greater understanding of how they react to physiological conditions. A key aspect is the specific nature of the surface coating, which can affect important properties of the IONPs such as colloidal stability, toxicity, magnetism and labelling efficiency. Polymers are widely used as coatings for IONPs as they can increase colloidal stability in hydrophilic conditions, as well as protect the iron oxide core from degradation. In this tutorial review, we will examine the design and synthesis approaches currently being employed to produce polymer coated IONPs as cell tracking agents, and what considerations must be made. We will also give some perspective on the challenges and limitations that remain for polymer coated IONPs as MRI contrast agents for stem cell tracking.