Environmental effects on electron spin relaxation in N@C60

We examine environmental effects of surrounding nuclear spins on the electron spin relaxation of the N@C60 molecule (which consists of a nitrogen atom at the centre of a fullerene cage). Using dilute solutions of N@C60 in regular and deuterated toluene, we observe and model the effect of translational diffusion of nuclear spins of the solvent molecules on the N@C60 electron spin relaxation times. We also study spin relaxation in frozen solutions of N@C60 in CS2, to which small quantities of a glassing agent, S2Cl2 are added. At low temperatures, spin relaxation is caused by spectral diffusion of surrounding nuclear 35Cl and 37Cl spins in the S2Cl2, but nevertheless, at 20 K, T2 times as long as 0.23 ms are observed.Comment: 7 pages, 6 figure

Vermicious thermo-responsive Pickering emulsifiers

Thermo-responsive vermicious (or worm-like) diblock copolymer nanoparticles prepared directly in n-dodecane via polymerisation-induced self-assembly (PISA) were used to stabilise water-in-oil Pickering emulsions. Mean droplet diameters could be tuned from 8 to 117 μm by varying the worm copolymer concentration and the water volume fraction and very high worm adsorption efficiencies (∼100%) could be obtained below a certain critical copolymer concentration (∼0.50%). Heating a worm dispersion up to 150 °C led to a worm-to-sphere transition, which proved to be irreversible if conducted at sufficiently low copolymer concentration. This affords a rare opportunity to directly compare the Pickering emulsifier performance of chemically identical worms and spheres. It is found that the former nanoparticles are markedly more efficient, since worm-stabilised water droplets are always smaller than the equivalent sphere-stabilised droplets prepared under identical conditions. Moreover, the latter emulsions are appreciably flocculated, whereas the former emulsions proved to be stable. SAXS studies indicate that the mean thickness of the adsorbed worm layer surrounding the water droplets is comparable to that of the worm cross-section diameter determined for non-adsorbed worms dispersed in the continuous phase. Thus the adsorbed worms form a monolayer shell around the water droplets, rather than ill-defined multilayers. Under certain conditions, demulsification occurs on heating as a result of a partial worm-to-sphere morphological transition

Stabilizing bubble and droplet interfaces using dipeptide hydrogels

Hydrophobic dipeptide molecules can be used to create interfacial films covering bubbles and droplets made from a range of oils. At high pH, the dipeptide molecules form micelles which transform into a hydrogel of fibres in response to the addition of salt. We characterize the properties of the hydrogel for two different salt (MgSO4) concentrations and then we use these gels to stabilize interfaces. Under high shear, the hydrogel is disrupted and will reform around bubbles or droplets. Here, we reveal that at low dipeptide concentration, the gel is too weak to prevent ripening of the bubbles; this then reduces the long-term stability of the foam. Under the same conditions, emulsions prepared from some oils are highly stable. We examine the wetting properties of the oil droplets at a hydrogel surface as a guide to the resulting emulsions

Sucrose Monoester Micelles Size Determined by Fluorescence Correlation Spectroscopy (FCS)

One of the several uses of sucrose detergents, as well as other micelle forming detergents, is the solubilization of different membrane proteins. Accurate knowledge of the micelle properties, including size and shape, are needed to optimize the surfactant conditions for protein purification and membrane characterization. We synthesized sucrose esters having different numbers of methylene subunits on the substituent to correlate the number of methylene groups with the size of the corresponding micelles. We used Fluorescence Correlation Spectroscopy (FCS) and two photon excitation to determine the translational D of the micelles and calculate their corresponding hydrodynamic radius, Rh. As a fluorescent probe we used LAURDAN (6-dodecanoyl-2-dimethylaminonaphthalene), a dye highly fluorescent when integrated in the micelle and non-fluorescent in aqueous media. We found a linear correlation between the size of the tail and the hydrodynamic radius of the micelle for the series of detergents measured

Equation of state of surface-adsorbing colloids

We have developed a simulation model to describe particle adsorption to and desorption from liquid interfaces. Using this model we formulate a closed interfacial equation of state for repulsive elastic spheres. The effect of a long-range attractive interaction is introduced by perturbation theory, and the effect a short-range attraction is studied using direct simulation. Based on our model predictions we conclude that for polymeric particles the surface pressure cannot be modelled directly by inert particles that interact via some effective potential. Internal degrees of freedom within gel particles are all-important. Consequently, the surface pressure of a fully packed layer is not proportional to kT/d^2, where d is the particle diameter; but proportional to kT/dm^2, where dm is the size of the molecular units that make up the particle. This increases the surface pressure and modulus by some four orders of magnitude. For short range interaction we study the dynamic behaviour, and find fractal-like structures at low concentrations. At intermediate coverage an irregular structure is formed that resembles a spinodal system. This system freezes, which arrests the spinodal structure. At high surface coverage the simulations show poly-crystalline domains. For dilute systems, the strength of the surface layers is determined by simulated compression and expansion. We find a power law for the surface pressure (Pi ~ Gamma^10+/-0.5), which is related to the (fractal) structure of the adsorbed network. The power law is consistent with surface percolation.Comment: 12 pages, pdf onl

Photoconductive Hybrid Films via Directional Self‐Assembly of C 60 on Aligned Carbon Nanotubes

Hybrid nanostructured materials can exhibit different properties than their constituent components, and can enable decoupled engineering of energy conversion and transport functions. Novel means of building hybrid assemblies of crystalline C 60 and carbon nanotubes (CNTs) are presented, wherein aligned CNT films direct the crystallization and orientation of C 60 rods from solution. In these hybrid films, the C 60 rods are oriented parallel to the direction of the CNTs throughout the thickness of the film. High‐resolution imaging shows that the crystals incorporate CNTs during growth, yet grazing‐incidence X‐ray diffraction (GIXD) shows that the crystal structure of the C 60 rods is not perturbed by the CNTs. Growth kinetics of the C 60 rods are enhanced 8‐fold on CNTs compared to bare Si, emphasizing the importance of the aligned, porous morphology of the CNT films as well as the selective surface interactions between C 60 and CNTs. Finally, it is shown how hybrid C 60 –CNT films can be integrated electrically and employed as UV detectors with a high photoconductive gain and a responsivity of 10 5 A W −1 at low biases (± 0.5 V). The finding that CNTs can induce rapid, directional crystallization of molecules from solution may have broader implications to the science and applications of crystal growth, such as for inorganic nanocrystals, proteins, and synthetic polymers. Aligned carbon nanotube (CNT) films cause rapid, directional crystallization of C 60 rods from solution, resulting in hybrid structures where the C 60 rods incorporate CNTs during growth and are oriented parallel to the direction of the CNTs. The hybrid sheets are integrated electrically and employed as UV detectors with high photoconductive gain (responsivity as high as 10 5 A W −1 at low biases (±0.5 V)).Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/90059/1/adfm_201102393_sm_suppl.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/90059/2/577_ftp.pd

PI3Kγ inhibition circumvents inflammation and vascular leak in SARS-CoV-2 and other infections

Virulent infectious agents such as severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and methicillin-resistant Staphylococcus aureus (MRSA) induce tissue damage that recruits neutrophils, monocyte, and macrophages, leading to T cell exhaustion, fibrosis, vascular leak, epithelial cell depletion, and fatal organ damage. Neutrophils, monocytes, and macrophages recruited to pathogen-infected lungs, including SARS-CoV-2-infected lungs, express phosphatidylinositol 3-kinase gamma (PI3Kγ), a signaling protein that coordinates both granulocyte and monocyte trafficking to diseased tissues and immune-suppressive, profibrotic transcription in myeloid cells. PI3Kγ deletion and inhibition with the clinical PI3Kγ inhibitor eganelisib promoted survival in models of infectious diseases, including SARS-CoV-2 and MRSA, by suppressing inflammation, vascular leak, organ damage, and cytokine storm. These results demonstrate essential roles for PI3Kγ in inflammatory lung disease and support the potential use of PI3Kγ inhibitors to suppress inflammation in severe infectious diseases

Polymerization-Induced Self-Assembly of Block Copolymer Nano-objects via RAFT Aqueous Dispersion Polymerization

In this Perspective, we discuss the recent development of polymerization-induced self-assembly mediated by reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization. This approach has quickly become a powerful and versatile technique for the synthesis of a wide range of bespoke organic diblock copolymer nano-objects of controllable size, morphology, and surface functionality. Given its potential scalability, such environmentally-friendly formulations are expected to offer many potential applications, such as novel Pickering emulsifiers, efficient microencapsulation vehicles, and sterilizable thermo-responsive hydrogels for the cost-effective long-term storage of mammalian cells

Self-shaping of oil droplets via the formation of intermediate rotator phases upon cooling.

Revealing the chemical and physical mechanisms underlying symmetry breaking and shape transformations is key to understanding morphogenesis. If we are to synthesize artificial structures with similar control and complexity to biological systems, we need energy- and material-efficient bottom-up processes to create building blocks of various shapes that can further assemble into hierarchical structures. Lithographic top-down processing allows a high level of structural control in microparticle production but at the expense of limited productivity. Conversely, bottom-up particle syntheses have higher material and energy efficiency, but are more limited in the shapes achievable. Linear hydrocarbons are known to pass through a series of metastable plastic rotator phases before freezing. Here we show that by using appropriate cooling protocols, we can harness these phase transitions to control the deformation of liquid hydrocarbon droplets and then freeze them into solid particles, permanently preserving their shape. Upon cooling, the droplets spontaneously break their shape symmetry several times, morphing through a series of complex regular shapes owing to the internal phase-transition processes. In this way we produce particles including micrometre-sized octahedra, various polygonal platelets, O-shapes, and fibres of submicrometre diameter, which can be selectively frozen into the corresponding solid particles. This mechanism offers insights into achieving complex morphogenesis from a system with a minimal number of molecular components.European Research Council (Grant ID: EMATTER 280078), European networks COST MP 1106 and 1305 and the capacity building project BeyondEverest of the European Commission (Grant ID: 286205)This is the author accepted manuscript. The final version is available from Nature Publishing Group via http://dx.doi.org/10.1038/nature1618