Matija Lovrak

The ratio between diffusion and reaction time scales determines the size of soft matter objects made through self-assembly-coupled reaction–diffusion.

We report a simple method for gluing polymer hydrogels together, based on supramolecular chemistry. The gluing is achieved by reactive self‐assembly of a low molecular weight gelator at the interface of the two polymer hydrogels. Formation and assembly of the hydrazine‐based gelator into fibers at the polymer gel interface leads to a greatly increased detachment stress.

Self-assembly provides access to a variety of molecular materials, yet spatial control over structure formation remains difficult to achieve. Here we show how reaction–diffusion (RD) can be coupled to a molecular self-assembly process to generate macroscopic free-standing objects with control over shape, size, and functionality. In RD, two or more reactants diffuse from different positions to give rise to spatially defined structures on reaction. We demonstrate that RD can be used to locally control formation and self-assembly of hydrazone molecular gelators from their non-assembling precursors, leading to soft, free-standing hydrogel objects with sizes ranging from several hundred micrometres up to centimeters. Different chemical functionalities and gradients can easily be integrated in the hydrogel objects by using different reactants. Our methodology, together with the vast range of organic reactions and self-assembling building blocks, provides a general approach towards the programmed fabrication of soft microscale objects with controlled functionality and shape.

Lipid deposition can be assessed with combined intravascular photoacoustic/ultrasound (IVPA/US) imaging. To date, the clinical translation of IVPA/US imaging has been stalled by a low imaging speed and catheter complexity. In this paper, we demonstrate imaging of lipid targets in swine coronary arteries in vivo, at a clinically useful frame rate of 20 s⁻¹. We confirmed image contrast for atherosclerotic plaque in human samples ex vivo. The system is on a mobile platform and provides real-time data visualization during acquisition. We achieved an IVPA signal-to-noise ratio of 20 dB. These data show that clinical translation of IVPA is possible in principle.

One often thinks of catalysts as chemical tools to accelerate a reaction or to have a reaction run under more benign conditions. As such, catalysis has a role to play in the chemical industry and in lab scale synthesis that is not to be underestimated. Still, the role of catalysis in living systems (cells, organisms) is much more extensive, ranging from the formation and breakdown of small molecules and biopolymers to controlling signal transduction cascades and feedback processes, motility, and mechanical action. Such phenomena are only recently starting to receive attention in synthetic materials and chemical systems. “Smart” soft materials could find many important applications ranging from personalized therapeutics to soft robotics to name but a few. Until recently, approaches to control the properties of such materials were largely dominated by thermodynamics, for instance, looking at phase behavior and interaction strength. However, kinetics plays a large role in determining the behavior of such soft materials, for instance, in the formation of kinetically trapped (metastable) states or the dynamics of component exchange. As catalysts can change the rate of a chemical reaction, catalysis could be used to control the formation, dynamics, and fate of supramolecular structures when the molecules making up these structures contain chemical bonds whose formation or exchange are susceptible to catalysis. In this Account, we describe our efforts to use synthetic catalysts to control the properties of supramolecular hydrogels. Building on the concept of synthesizing the assembling molecule in the self-assembly medium from nonassembling precursors, we will introduce the use of catalysis to change the kinetics of assembler formation and thereby the properties of the resulting material. In particular, we will focus on the synthesis of supramolecular hydrogels where the use of a catalyst provides access to gel materials with vastly different appearance and mechanical properties or controls localized gel formation and the growth of gel objects. As such, catalysis will be applied to create molecular materials that exist outside of chemical equilibrium. In all, using catalysts to control the properties of soft materials constitutes a new avenue for catalysis far beyond the traditional use in industrial and lab scale synthesis.

The method for the examination of gas/water interface electrokinetic behavior is developed. "Bubbling potential", i.e. the difference in the potential of the indicator electrode in the absence and presence of gas bubbles was measured. The indicator electrode is a reference electrode with the porous plug exposed to gas bubbles. The charged bubble in contact with the porous plug would affect the potential of the indicator electrode. However, electrodes, whose potential depends on the reversible interfacial reaction, would be relaxed due to the interfacial ionic equilibration and their potential will not be affected by the presence of bubbles. Measured Bubbling potentials are directly related to electrokinetic - potentials. The proposed method is fast, accurate and reproducible so that it can be used for the examination of gas/water interfaces in different conditions. The isoelectric point of argon bubbles in the aqueous NaCl solution was obtained as pHiep = 3.9 and pHiep = 3.4 at ionic strength of 10–3 and 10–2 mol dm–3, respectively. (doi: 10.5562/cca2235