Alveolar type II epithelial cell FASN maintains lipid homeostasis in experimental COPD.

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.

The elastic response of graphene oxide gels as a crumpling phenomenon.

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.

Balancing connectivity with function in silver(i) networks of pyridyltriazole (tzpa) ligands results in the formation of a metallogel.

A new flexible and divergent 1,2,3-triazol-4-yl-picolinamide (tzpa) ligand 2 and the half-equivalent model ligand 1, 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 of tzpa ligand 1 with AgCF3SO3 resulted in the formation of a 1D coordination polymer, binding in a bidentate fashion through the pyridyl and triazole nitrogen atoms of the tzpa binding site and a pendant pyridyl nitrogen atom of an adjacent ligand. Doubling the number of metal binding sites in ligand 2, while retaining the same metal binding domain, gives rise to the formation of a supramolecular metallogel on reaction with AgBF4 at 5 wt% in MeCN, possessing self-healing properties.

Fiber Reinforced Cartilage ECM Functionalized Bioinks for Functional Cartilage Tissue Engineering.

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-ß3 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.

Water-soluble, neutral 3,5-diformyl-BODIPY with extended fluorescence lifetime in a self-healable chitosan hydrogel.

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.

A resilient and luminescent stimuli-responsive hydrogel from a heterotopic 1,8-naphthalimide-derived ligand.

A heterotopic naphthalimide ligand N-(4-picolyl)-4-(4'-carboxyphenoxy)-1,8-naphthalimide HL is utilised for the formation of self-assembled soft materials. In the presence of K+ ions, L- forms a robust photoluminescent hydrogel 1 which is reversible under thermal, mechanical or chemical stimuli.

Sensitive electromechanical sensors using viscoelastic graphene-polymer nanocomposites.

Despite its widespread use in nanocomposites, the effect of embedding graphene in highly viscoelastic polymer matrices is not well understood. We added graphene to a lightly cross-linked polysilicone, often encountered as Silly Putty, changing its electromechanical properties substantially. The resulting nanocomposites display unusual electromechanical behavior, such as postdeformation temporal relaxation of electrical resistance and nonmonotonic changes in resistivity with strain. These phenomena are associated with the mobility of the nanosheets in the low-viscosity polymer matrix. By considering both the connectivity and mobility of the nanosheets, we developed a quantitative model that completely describes the electromechanical properties. These nanocomposites are sensitive electromechanical sensors with gauge factors >500 that can measure pulse, blood pressure, and even the impact associated with the footsteps of a small spider.

Self-assembly formation of a healable lanthanide luminescent supramolecular metallogel from 2,6-bis(1,2,3-triazol-4-yl)pyridine (btp) ligands.

The synthesis of five new 2,6-bis(1,2,3-triazol-4-yl)pyridine (btp) ligands is described: the self-assembly behaviour of the tri-methyl ester, 1, with Eu(III) showed the formation of a luminescent 1:3 Eu : btp complex, Eu13, which was studied in solution and in the solid state; while the tri-carboxylic acid, 2, formed a hydrogel and its corresponding complex Eu23, gave rise to a strongly red luminescent healable metallogel.

Effect of tetraalkylammonium cations on gas coalescence at a hydrogen-evolving microelectrode.

Hydrogen gas evolution at the surface of a microelectrode may result in periodic release of single bubbles larger than the electrode diameter. Bubbles often grow by incorporating smaller bubbles that coalesce with them. To explore the coalescence, we investigate how a series of six tetralkylammonium cations (TXA(+)), where the number of carbons on the alkyl chain varies from 1 to 6, affects the oscillatory behavior of the gas-evolving microcathode. Different concentrations of TXA(+) bromide salts ranging from a few micromolar up to 1 M were added in the acid electrolyte. The frequency of bubble release and the transition from periodic to aperiodic release are related to the inhibition of bubble coalescence and gas streaming. The concentration range where this transition occurs depends strongly on the cation hydrophobicity and it ranges from very small values for the hydrophobic cations to over 1 M for the most hydrophilic one. For some of the TXA(+) cations, the transition shows a smooth increase in release frequency before switching completely to bubble-stream behavior, while for others the transition is abrupt. A smooth increase in the gas oscillator frequency with concentration indicates that the adsorption of TXA(+) cations on the bubble surface is mass transport-limited. The inhibition of bubble coalescence by the smallest cations is electrochemically driven, facilitated by specific interactions established between the ions and the electrode surface.

Structure of marginally jammed polydisperse packings of frictionless spheres.

We model the packing structure of a marginally jammed bulk ensemble of polydisperse spheres. To this end we expand on the granocentric model [Clusel et al., Nature (London) 460, 611 (2009)], explicitly taking into account rattlers. This leads to a relationship between the characteristic parameters of the packing, such as the mean number of neighbors and the fraction of rattlers, and the radial distribution function g(r). We find excellent agreement between the model predictions for g(r) and packing simulations, as well as experiments on jammed emulsion droplets. The observed quantitative agreement opens the path towards a full structural characterization of jammed particle systems for imaging and scattering experiments.

Yielding and flow of highly concentrated, few-layer graphene suspensions.

For a wide range of applications of graphene suspensions, a thorough understanding of their rheological properties is crucial. We probe the microstructure of dense suspensions of micron-sized, few-layer, defect-free graphene platelets by measuring their viscoelastic properties at various concentrations up to 39 mg ml(-1). We propose a model to relate the yield strain to the mesh size of the microstructure as a function of volume fraction ϕ. From the yield stress measurements we infer the typical bond energy (≈20 kBT) and ϕ dependence of the bond number density. These results allow us to express the steady shear viscosity for Peclet number Pe < 10 in terms of the platelet dimensions, bond energy and ϕ using a relaxation ansatz.

Healable luminescent self-assembly supramolecular metallogels possessing lanthanide (Eu/Tb) dependent rheological and morphological properties.

Herein we present the use of lanthanide directed self-assembly formation (Ln(III) = Eu(III), Tb(III)) in the generation of luminescent supramolecular polymers, that when swelled with methanol give rise to self-healing supramolecular gels. These were analyzed by using luminescent and (1)H NMR titrations studies, allowing for the identification of the various species involved in the subsequent Ln(III)-gel formation. These highly luminescent gels could be mixed to give a variety of luminescent colors depending on their Eu(III):Tb(III) stoichiometric ratios. Imaging and rheological studies showed that these gels prepared using only Eu(III) or only Tb(III) have different morphological and rheological properties, that are also different from those determined upon forming gels by mixing of Eu(III) and Tb(III) gels. Hence, our results demonstrate for the first time the crucial role the lanthanide ions play in the supramolecular polymerization process, which is in principle a host-guest interaction, and consequently in the self-healing properties of the corresponding gels, which are dictated by the same host-guest interactions.

Bubble formation at a gas-evolving microelectrode.

The electrolytic production of gas bubbles involves three steps--nucleation, growth, and detachment. Here the growth of hydrogen bubbles and their detachment from a platinum microelectrode of diameter 125 µm are studied using high-speed photography and overpotential frequency spectrum (noise) analysis. The periodic release of large <800 µm bubbles--gas oscillator behavior--was often observed, with a corresponding periodic oscillation of the overpotential which is reflected as a main peak and a series of harmonics in the power spectral density. The release frequency is inversely correlated with the bubble size and hydrogen production rate. When the coalescence of bubbles at the electrode surface is inhibited, either chemically with a surfactant or ethylene glycol or hydrodynamically by magnetically induced convection, swarms of small ∼50 µm bubbles are released in an aperiodic stream. The abrupt transition from periodic to aperiodic release occurs when the surface tension falls below 70 mN m(-1). Hydrogen bubble growth is also studied on a transparent platinum thin-film electrode, where the bubble coalescence can be observed directly. It leaves sessile droplets of electrolyte within the footprint of the growing bubble, showing that the growth involves scavenging smaller bubbles from solution due to hydrogen generated directly at the electrode. A possible role of nanobubbles in the lift-off process is discussed.

Flow in linearly sheared two-dimensional foams: From bubble to bulk scale.

We probe the flow of two-dimensional (2D) foams, consisting of a monolayer of bubbles sandwiched between a liquid bath and glass plate, as a function of driving rate, packing fraction, and degree of disorder. First, we find that bidisperse, disordered foams exhibit strongly rate-dependent and inhomogeneous (shear-banded) velocity profiles, while monodisperse ordered foams are also shear banded but essentially rate independent. Second, we adapt a simple model [E. Janiaud, D. Weaire, and S. Hutzler, Phys. Rev. Lett. 97, 038302 (2006)] based on balancing the averaged drag forces between the bubbles and the top plate F[over ]_{bw} and the averaged bubble-bubble drag forces F[over ]_{bb} by assuming that F[over ]_{bw} approximately v;{2/3} and F[over ]_{bb} approximately ( partial differential_{y}v);{beta} , where v and ( partial differential_{y}v) denote average bubble velocities and gradients. This model captures the observed rate-dependent flows for beta approximately 0.36 , and the rate independent flows for beta approximately 0.67 . Third, we perform independent rheological measurements of F[over ]_{bw} and F[over ]_{bb} , both for ordered and disordered systems, and find these to be fully consistent with the forms assumed in the simple model. Disorder thus leads to a modified effective exponent beta . Fourth, we vary the packing fraction phi of the foam over a substantial range and find that the flow profiles become increasingly shear banded when the foam is made wetter. Surprisingly, the model describes flow profiles and rate dependence over the whole range of packing fractions with the same power-law exponents-only a dimensionless number k that measures the ratio of the prefactors of the viscous drag laws is seen to vary with packing fraction. We find that k approximately (phi-phi_{c});{-1} , where phi_{c} approximately 0.84 corresponds to the 2D jamming density, and suggest that this scaling follows from the geometry of the deformed facets between bubbles in contact. Overall, our work shows that the presence of disorder qualitatively changes the effective bubble-bubble drag forces and suggests a route to rationalize aspects of the ubiquitous Herschel-Bulkley (power-law) rheology observed in a wide range of disordered materials.

High-speed tracking of rupture and clustering in freely falling granular streams.

Thin streams of liquid commonly break up into characteristic droplet patterns owing to the surface-tension-driven Plateau-Rayleigh instability. Very similar patterns are observed when initially uniform streams of dry granular material break up into clusters of grains, even though flows of macroscopic particles are considered to lack surface tension. Recent studies on freely falling granular streams tracked fluctuations in the stream profile, but the clustering mechanism remained unresolved because the full evolution of the instability could not be observed. Here we demonstrate that the cluster formation is driven by minute, nanoNewton cohesive forces that arise from a combination of van der Waals interactions and capillary bridges between nanometre-scale surface asperities. Our experiments involve high-speed video imaging of the granular stream in the co-moving frame, control over the properties of the grain surfaces and the use of atomic force microscopy to measure grain-grain interactions. The cohesive forces that we measure correspond to an equivalent surface tension five orders of magnitude below that of ordinary liquids. We find that the shapes of these weakly cohesive, non-thermal clusters of macroscopic particles closely resemble droplets resulting from thermally induced rupture of liquid nanojets.

Rate dependence and role of disorder in linearly sheared two-dimensional foams.

The shear flow of two-dimensional foams is probed as a function of shear rate and disorder. Disordered, bidisperse foams exhibit strongly shear rate dependent velocity profiles. This behavior is captured quantitatively in a simple model based on the balance of the time-averaged drag forces in the system, which are found to exhibit power-law scaling with the foam velocity and strain rate. Disorder makes the scaling of the bulk drag forces different from that of the local interbubble drag forces, which we evidence by rheometrical measurements. In monodisperse, ordered foams, rate independent velocity profiles are found, which lends further credibility to this picture.

Three-dimensional shear in granular flow.

The evolution of granular shear flow is investigated as a function of height in a split-bottom Couette cell. Using particle tracking, magnetic-resonance imaging, and large-scale simulations, we find a transition in the nature of the shear as a characteristic height H* is exceeded. Below H* there is a central stationary core; above H* we observe the onset of additional axial shear associated with torsional failure. Radial and axial shear profiles are qualitatively different: the radial extent is wide and increases with height, while the axial width remains narrow and fixed.

Clustering instability in a freely falling granular jet.

This paper investigates a clustering instability of a freely falling granular jet composed of 100 microm glass spheres. The granular flow out of a circular nozzle starts out spatially uniform and then, further downstream, breaks up into well-defined clusters. An optical method is used that measures inhomogeneities in the flow in order to quantify the growth of the clusters. The role of air is investigated in this phenomenon by changing the ambient air pressure down to 1/5000th atm. Clustering is observed down to the lowest pressure and the presence of air leads to larger clusters but does not initiate the cluster formation. The analysis shows that the cluster size is set by fluctuations on the order of the size of the particles at the nozzle.

Effect of air on granular size separation in a vibrated granular bed.

Using high-speed video and magnetic resonance imaging (MRI) we study the motion of a large sphere in a vertically vibrated bed of smaller grains. As previously reported we find a nonmonotonic density dependence of the rise and sink time of the large sphere. We show that air drag causes relative motion between the intruder and the bed during the shaking cycle and is ultimately responsible for the observed density dependence of the risetime. We investigate in detail how the motion of the intruder sphere is influenced by size of the background particles, initial vertical position in the bed, ambient pressure, and convection. We explain our results in the framework of a simple model and find quantitative agreement in key aspects with numerical simulations to the model equations.