The low molecular weight gelator (LMWG) 1 based on the tripodal benzene-1,3,5-tricarboxamide (BTA) motif, capped with terpyridine (tpy) units, was shown to form supramolecular gels with versatile functionalities such as self-healing, while the cross-linking of its fibers with d- and f-block metal ions led to modified photophysical properties, the obtained gels were additionally capable of extrusion.

Small structural changes to benzene-1,3,5-tricarboxamide (BTA) dictate its self-assembly behavior and morphological outcome. Functionalization with an a-amino acid close to the BTA core, which also possesses a terminal terpyridine (tpy) unit, led to a robust gel in the case of glycine, whereas monodisperse, solid micro- spheres formed in the case of alanine, phenylalanine, and leucine. The self-assembly pathways of the chiral and achiral BTAs are orthogonal and both microspheres and gel fibers independently assemble in the same medium. Further hierarchical self-assembly results upon addition of lanthanide ions (i.e., Eu(III) and Tb(III) that emit at long wavelengths with long excited-state lifetimes) that crosslink the microspheres through coordination, whereas coordination within the gel led to a change in morphology toward microspheres, as well as the formation of hierarchical superstructures. The chirality of the BTA influences helicity of the assembly and the resulting enantiomeric conformation around the lanthanides, evidenced by circularly polarized luminescence.

Understanding and predicting the spreading of droplets on solid surfaces is crucial in many applications such as inkjet printing, printed electronics and spray coating where the fluid is a suspension and in general non-Newtonian. However, many models that predict the maximum spreading diameter usually only apply to Newtonian fluids. Here we study experimentally and theoretically the maximum spreading diameter of graphene oxide suspension droplets impacting on a smooth surface for a wide range of concentrations and impact velocities of up to 6 g/l and 3 m/s, respectively. As the particle concentration increases the rheological behaviour changes from a viscous fluid to a shear-thinning yield stress fluid and the maximum spreading diameter decreases. The rheology for all concentrations is well described by a Herschel-Bulkley model that allows us to determine the characteristic viscosity during spreading. We use this viscosity to develop an energy balance model that takes into account the viscous dissipation and change in surface energies to find the maximum spread diameter for a given impact velocity. The model contains one non-dimensional parameter that encodes both the dynamic contact angle during spreading and the droplet shape at maximum spread. Our model is in good agreement with our data at all concentrations and agrees well with literature data on Newtonian fluids. Furthermore, the model gives the correct limits in the viscous and capillary regime and can be solved analytically for Newtonian fluids.

Nanoscience at times can seem out of reach to the developing world and the general public, with much of the equipment expensive and knowledge seemingly esoteric to nonexperts. Using only cheap, everyday household items, accessible research with real applications can be shown. Here, graphene suspensions were produced using pencil lead, tap water, kitchen appliances, soaps and coffee filters, with a children’s glue-based graphene nanocomposite for highly sensitive pulse measurements demonstrated.

Thin film networks of solution processed nanosheets show remarkable promise for use in a broad range of applications including strain sensors, energy storage, printed devices, textile electronics, and more. While it is known that their electronic properties rely heavily on their morphology, little is known of their mechanical nature, a glaring omission given the effect mechanical deformation has on the morphology of porous systems and the promise of mechanical post processing for tailored properties. Here, this work employs a recent advance in thin film mechanical testing called the Layer Compression Test to perform the first in situ analysis of printed nanosheet network compression. Due to the well-defined deformation geometry of this unique test, this work is able to explore the out-of-plane elastic, plastic, and creep deformation in these systems, extracting properties of elastic modulus, plastic yield, viscoelasticity, tensile failure and sheet bending vs. slippage under both out of plane uniaxial compression and tension. This work characterizes these for a range of networks of differing porosities and sheet sizes, for low and high compression, as well as the effect of chemical cross linking. This work explores graphene and MoS2 networks, from which the results can be extended to printed nanosheet networks as a whole.

Alveolar epithelial type II (AEC2) cells strictly regulate lipid metabolism to maintain surfactant synthesis. Loss of AEC2 cell function and surfactant production are implicated in the pathogenesis of the smoking-related lung disease chronic obstructive pulmonary disease (COPD). Whether smoking alters lipid synthesis in AEC2 cells and whether altering lipid metabolism in AEC2 cells contributes to COPD development are unclear. In this study, high-throughput lipidomic analysis revealed increased lipid biosynthesis in AEC2 cells isolated from mice chronically exposed to cigarette smoke (CS). Mice with a targeted deletion of the de novo lipogenesis enzyme, fatty acid synthase (FASN), in AEC2 cells (FasniΔAEC2) exposed to CS exhibited higher bronchoalveolar lavage fluid (BALF) neutrophils, higher BALF protein, and more severe airspace enlargement. FasniΔAEC2 mice exposed to CS had lower levels of key surfactant phospholipids but higher levels of BALF ether phospholipids, sphingomyelins, and polyunsaturated fatty acid–containing phospholipids, as well as increased BALF surface tension. FasniΔAEC2 mice exposed to CS also had higher levels of protective ferroptosis markers in the lung. These data suggest that AEC2 cell FASN modulates the response of the lung to smoke by regulating the composition of the surfactant phospholipidome.

Pendant droplets of water and paramagnetic solutions are studied in the presence of uniform and nonuniform magnetic fields produced by small permanent magnet arrays, both in static conditions and during dynamic pinch-off. Static measurements of the droplet shape are analyzed in terms of an apparent surface tension γapp or an effective density ρeff. The change of surface tension of deionized water in a uniform field of 450 mT is insignificant, 0.19 ± 0.21 mNm−1. Measurements on droplets of compensated zero-susceptibility solutions of Cu2+, Mn2+, and Dy3+, where the shape is unaffected by any magnetic body force, show changes of surface tension of about −1% in 500 mT. Magnetic field gradients of up to 100 T2 m−1 deform the droplets and lead to changes of ρeff that are negative for diamagnetic solutions (buoyancy effect) and positive for paramagnetic solutions. The droplet profile of strongly paramagnetic 0.1 molar DyCl3 solution is analyzed, treating the nonuniform vertical field gradient as a spatial variation of gravity. The influence of Maxwell stress on the droplet shape is discussed. In dynamic measurements, the droplet shape at pinch-off is recorded by high-speed photography and analyzed in terms of a relative change of dynamic surface tension in the presence of a magnetic field. The surface-tension-dependent prefactor of the scaling law that governs the pinch-off dynamics shows no difference for pure water or 0.11 M DyCl3 solutions in the field. The nonuniform field has no influence in the pinch-off region because the filament diameter is much less than the capillary length.

HYPOTHESIS:Ortho and para water are the two nuclear isomers where the hydrogen protons align to give a total nuclear spin of 1 or 0. The equilibrium ratio of 3:1 is established slowly in freshly evaporated water vapour while the isomers behave distinct gasses, with their own partial pressures. Magnetic-field-induced ortho ⟷ para transformations are expected to alter the evaporation rate. EXPERIMENT:Evaporation from beakers of deionized water and a 6 M solution of urea is monitored simultaneously for periods from 1 to 60 h with and without a 500 mT magnetic field, while logging the ambient temperature and humidity. Balances with the two beakers are shielded in the same Perspex container. Many runs have been conducted over a two-year period. FINDINGS:The evaporation rate of water is found to increase by 12 ± 7% of in the field but that of water with dissolved urea decreases by 28 ± 6%. Two effects are at play. One is dephasing of the Larmor precession of adjacent protons on a water molecule in a field gradient, which tends to equalize the isomer populations. The other is Lorentz stress on the moving charge dipole, which can increase the proportion of the ortho isomer. From analysis of the time and field dependence of the evaporation, we infer that the ortho fraction is 39 ± 1% in fresh vapour from water and 60 ± 5% in fresh vapour from urea.

The formation of bio-inspired healable lanthanide luminescent hydrogels is detailed. These materials are composed of K(I)-stabilized guanosine quadruplexes (G4) that were bio-conjugated to mannose-derived picolinic acid ligand 1 using boric acid chemistry (G4-1). The supramolecular self-assembly between G4-1 and europium (Eu(III)) was confirmed, including the use of time-gated luminescence spectroscopy. The most stable hydrogel was formed when the ratio between 1 and Eu(III) was 1:1, and this gel was found to retain a helical column. The obtained gel samples were further characterized using techniques, such as scanning electron microscopy (SEM), circular dichroism (CD), and luminescence spectroscopy. We demonstrate that a Eu(III)-centered circularly polarized luminescence (CPL) signal from guanosine hydrogels can be observed even via long-range interaction, whereas the rheology of these gels exhibits their healable properties.

The broad spectrum of chemical and electronic properties of 2D nanomaterials makes them attractive in a wide range of applications, especially in the context of printed electronics. Therefore, understanding the rheological properties of nanosheet suspensions is crucial for many additive manufacturing techniques. Here, we study the viscoelastic properties of aqueous suspensions of graphene oxide nanosheets. We show that in the gel phase, the magnitude of the elastic response and its scaling with volume fraction is independent of the lateral size of the particles and the interaction strength between them. We explain this behavior by modelling the elasticity of these gels as a crumpling phenomenon where the magnitude of the response is determined by the bending stiffness and thickness of the sheets. Due to their low bending stiffness these nanosheets crumple upon deformation and may therefore be considered soft colloids. Furthermore, we provide an explanation why the yield strain decreases with packing fraction for these gels.

Previous studies using Deionized (DI) water found that household plastic products used in food preparation and storage are a local and immediate source of extremely high quantities of microplastics (MPs) released directly into to the human body and the environment. However, DI water is rarely used outside of laboratories. Here, MP release from plastic products exposed to ordinary drinking water was studied. To facilitate this study, the concept of Synthetic drinking water (SDW) was introduced, which involved preparing water in accordance with the WHO standard but modified to mimic the composition of local Tap drinking water (TDW). It was found that the level of MP released from plastics exposed to TDW and SDW are very similar, demonstrating that SDW is an appropriate real-world reference standard to test MP release levels from plastic products. In contrast with the use of DI water, plastics exposed to hot (40-100 degrees C) SDW and TDW showed the progressive development of a Copper (II) oxide (CuO) passivation film due to the presence of Cu2+ ions in the water samples. Similar passivation films formed on 97% of all food grade plastics. Longitudinal studies of polypropylene products (kettles) exposed to boiling TDW during normal use resulted in the continuous growth of CuO passivation films that ultimately yielded a 99.8% reduction in MP release. Engineered reductions in MP release levels were observed following separate controlled exposures to SDW with elevated Cu2+ levels, yielding denser CuO passivation films. This study underscores the importance of reproducing real world conditions in microplastic studies and also the potential for nature-inspired engineered films to mitigate against the release of MPs and the possibility of sustainable MP-free products.

2D material hydrogels have recently sparked tremendous interest owing to their potential in diverse applications. However, research on the emerging 2D MXene hydrogels is still in its infancy. Herein, we show a universal 4D printing technology for manufacturing MXene hydrogels with customizable geometries, which suits a family of MXenes such as Nb 2 CT x , Ti 3 C 2 T x , and Mo 2 Ti 2 C 3 T x . The obtained MXene hydrogels offer 3D porous architectures, large specific surface areas, high electrical conductivities, and satisfying mechanical properties. Consequently, ultrahigh capacitance (3.32 F cm −2 (10 mV s −1 ) and 233 F g −1 (10 V s −1 )) and mass loading/thickness-independent rate capabilities are achieved. The further 4D-printed Ti 3 C 2 T x hydrogel micro-supercapacitors showcase great low-temperature tolerance (down to –20 °C) and deliver high energy and power densities up to 93 μWh cm −2 and 7 mW cm −2 , respectively, surpassing most state-of-the-art devices. This work brings new insights into MXene hydrogel manufacturing and expands the range of their potential applications.

Morpholine-substituted 1,8-naphthalimide fluorophores exhibit solvent and pH-dependent emission characteristics based on aggregation, and form robust chemically reversible metallogels.

The ongoing miniaturization of devices and development of wireless and implantable technologies demand electromagnetic interference (EMI)-shielding materials with customizability. Additive manufacturing of conductive polymer hydrogels with favorable conductivity and biocompatibility can offer new opportunities for EMI-shielding applications. However, simultaneously achieving high conductivity, design freedom, and shape fidelity in 3D printing of conductive polymer hydrogels is still very challenging. Here, an aqueous Ti3 C2 -MXene-functionalized poly(3,4-ethylenedioxythiophene):polystyrene sulfonate ink is developed for extrusion printing to create 3D objects with arbitrary geometries, and a freeze-thawing protocol is proposed to transform the printed objects directly into highly conductive and robust hydrogels with high shape fidelity on both the macro- and microscale. The as-obtained hydrogel exhibits a high conductivity of 1525.8 S m-1 at water content up to 96.6 wt% and also satisfactory mechanical properties with flexibility, stretchability, and fatigue resistance. Furthermore, the use of the printed hydrogel for customizable EMI-shielding applications is demonstrated. The proposed easy-to-manufacture approach, along with the highlighted superior properties, expands the potential of conductive polymer hydrogels in future customizable applications and represents a real breakthrough from the current state of the art.

Foam-forming has in the past predominantly been used to create two-dimensional sheet-like fibrous materials. Allowing the foam to drain freely and decay under gravity, rather than applying a vacuum to remove it rapidly, we can produce lightweight three-dimensional fibrous structures from cellulose fibres, of potential use for thermal and acoustic insulation. $$\mu$$ CT scanning of the fibrous materials enable us to determine both void size distributions and also distributions of fibre orientations. Through image analysis and uniaxial compression testing, we find that the orientation of the fibres, rather than the size of the voids, determine the compressive strength of the material. The fibrous samples display a layering of the fibres perpendicular to the direction of drainage of the precursor liquid foam. This leads to an anisotropy of the compressive behaviour of the samples. Varying the initial liquid fraction of the foam allows for tuning of the compressive strength. We show an increase in over seven times can be achieved for samples of the same density (13 kg.m-3).

A new flexible and divergent 1,2,3-triazol-4-yl-picolinamide (tzpa) ligand2and the half-equivalent model ligand1, both functionalised with pendant 3-pyridyl groups, are reported and their coordination behaviour with silver(i) ions is explored, both in the crystalline phase and through the formation of a supramolecular metallogel. The self-assembly oftzpaligand1with AgCF(3)SO(3)resulted in the formation of a 1D coordination polymer, binding in a bidentate fashion through the pyridyl and triazole nitrogen atoms of thetzpabinding site and a pendant pyridyl nitrogen atom of an adjacent ligand. Doubling the number of metal binding sites in ligand2, while retaining the same metal binding domain, gives rise to the formation of a supramolecular metallogel on reaction with AgBF(4)at 5 wt% in MeCN, possessing self-healing properties.

3,5-Diformyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (3,5-diformyl-BODIPY) can be used as an efficient biofunctional cross-linker to generate a new class of chitosan-based hydrogels with fluorescence resonance energy transfer (FRET) dynamics and good solubility in water. The hydrogel was fully characterized by FT-IR, UV-vis, fluorescence, FE-SEM, AFM, rheology and picosecond time-resolved spectroscopic techniques. The self-healing ability was demonstrated by rheological recovery and macroscopic and microscopic observations. The fluorescence lifetime was found to increase in aqueous solution of the BODIPY-chitosan hydrogel compared to the 3,5-diformyl-BODIPY monomer. Calculations based on experimental results such as red-shift and decreased intensity of the emission spectrum of highly dye-concentrated hydrogel in comparison to dilute hydrogels, together with changes in the fluorescence lifetime of the hydrogel at different concentration of dyes, suggest that the BDP-CS hydrogels fluorescence dynamics obey the Förster resonance energy transfer (FRET). Improvements in mechanical and photochemical properties and the acceptable values of BODIPY fluorescence lifetime in the hydrogel matrix indicate the utility of the newly synthesized hydrogels for biomedical applications.

Focal articular cartilage (AC) defects, if left untreated, can lead to debilitating diseases such as osteoarthritis. While several tissue engineering strategies have been developed to promote cartilage regeneration, it is still challenging to generate functional AC capable of sustaining high load-bearing environments. Here, a new class of cartilage extracellular matrix (cECM)-functionalized alginate bioink is developed for the bioprinting of cartilaginous tissues. The bioinks are 3D-printable, support mesenchymal stem cell (MSC) viability postprinting and robust chondrogenesis in vitro, with the highest levels of COLLII and ACAN expression observed in bioinks containing the highest concentration of cECM. Enhanced chondrogenesis in cECM-functionalized bioinks is also associated with progression along an endochondral-like pathway, as evident by increases in RUNX2 expression and calcium deposition in vitro. The bioinks loaded with MSCs and TGF-β3 are also found capable of supporting robust chondrogenesis, opening the possibility of using such bioinks for direct "print-and-implant" cartilage repair strategies. Finally, it is demonstrated that networks of 3D-printed polycaprolactone fibers with compressive modulus comparable to native AC can be used to mechanically reinforce these bioinks, with no loss in cell viability. It is envisioned that combinations of such biomaterials can be used in multiple-tool biofabrication strategies for the bioprinting of biomimetic cartilaginous implants.