Observations of tetrel bonding between sp3-carbon and THF

We report the direct observation of tetrel bonding interactions between sp³-carbons of the supramolecular synthon 3,3-dimethyl-tetracyanocyclopropane (1) and tetrahydrofuran in the gas and crystalline phase. The intermolecular contact is established via σ-holes and is driven mainly by electrostatic forces. The complex manifests distinct binding geometries when captured in the crystalline phase and in the gas phase. We elucidate these binding trends using complementary gas phase quantum chemical calculations and find a total binding energy of −11.2 kcal mol⁻¹ for the adduct. Our observations pave the way for novel strategies to engineer sp³-C centred non-covalent bonding schemes for supramolecular chemistry.

sp³-C⋯THF tetrel bonding was observed in the crystalline state and in the gas phase. Density functional calculations revealed interaction energies up to −11.2 kcal mol⁻¹ and showed that these adducts are held together mainly by electrostatics.     

A novel method to quantify the amount of surfactant at the oil/water interface and to determine total interfacial area of emulsions

We present a methodology to quantitatively determine the fraction of sodium dodecyl sulfate (SDS) that partitions to the oil/water interface in oil-in-water macroemulsions and calculate the total interfacial area (TIA) through the novel use of filtration through nanoporous membranes. Ultrafiltration was carried out in centrifuge tubes having nanoporous filters with a 30,000 molecular weight cutoff (MWCO), so that emulsion droplets would not pass through, and only SDS (as monomers and micelles) that is in the bulk water phase (i.e., not at the interface) could pass through. The concentration of SDS in the filtrate was determined and used to calculate the TIA for each system. The mean droplet diameter of the emulsions was measured by light scattering. We analyzed the effects of total SDS concentration and oil chain length on the amount of SDS that partitions to the interface, the TIA, and the droplet diameter. The results showed that partitioning of SDS to the oil/water interface increases with increasing total SDS concentration in emulsion systems (i.e., the more SDS we add to the bulk solution, the more SDS partitions to the oil/water interface). However, the surface-to-bulk partition coefficient (i.e., the SDS concentration at the interface divided by the SDS concentration in the aqueous phase) remains the same over the entire concentration range (8-200 mM). The results showed a chain-length compatibility effect in that the minimum amount of SDS partitioned to the interface for C(12) oil. The droplet size measurements revealed a maximum size of droplets for C(12) oil. Penetration of oil molecules into SDS film at the interface has been proposed to account for the maximum droplet size and minimum partitioning of SDS at the oil/water interface for C(12) oil+SDS emulsion system. The TIA, as determined from our ultrafiltration method, was consistently two orders of magnitude greater than that calculated from the droplet size measured by light scattering. Possible explanations for this disparity are discussed.     

Molding block copolymer micelles: a framework for molding of discrete objects on surfaces

Soft lithography based on photocurable perfluoropolyether (PFPE) was used to mold and replicate poly(styrene-b-isoprene) block-copolymer micelles within a broad range of shapes and sizes including spheres, cylinders, and torroids. These physically assembled nanoparticles were first formed in a selective solvent for one block then deposited onto substrates having various surface energies in an effort to minimize the deformation of the micelles due to attractive surface forces. The successful molding of these delicate nanoparticles underscores two advantages of PFPE as a molding material. First, it allows one to minimize particle deformation due to adsorption by using low energy substrates. Second, PFPE is not miscible with the organic micelles and thus prevents their dissociation. For spherical PS-b-PI micelles, a threshold value of the substrate surface energy for the mold to lift-off cleanly, that is, the particles remain adhered to the substrate after mold removal was determined to be around gamma congruent with 54 mJ/m2. For substrates with higher surface energies (>54 mJ/m2), the micelles undergo flattening which increase the contact area and thus facilitate molding, although at the expense of particle deformation. The results are consistent with theoretical predictions of a molding range for substrate surface energies, which depends on the size, shape, and mechanical properties of the particles. In a similar fashion, cylindrical PS-b-PI micelles remain on the substrate at surface energies gamma>or=54 mJ/m2 after a mold removal. However, cylindrical micelles behaved differently at lower surface energies. These micelles ruptured due to their inability to slide on the surfaces during mold lift-off. Thus, the successful molding of extended objects is attainable only when the particle is adsorbed on higher energy substrates where deformation can still be kept at a minimum by using stronger materials such as carbon nanotubes for the master.     

Models of unidirectional propagation in heterogeneous excitable media

Two differential equation models of excitable media (threshold and recovery kinetics) with solutions that exhibit unidirectional propagation are presented. It is shown that unidirectional propagation in heterogeneous excitable media with non-oscillatory kinetics can be initiated from homogeneous initial data. Simulations on a reaction-diffusion model with FitzHugh-Nagumo kinetics and spatially heterogeneous parameters yields a rotating wave on a one-dimensional circular spatial domain. An ordinary differential equation model with four semi-coupled excitable cells and heterogeneous parameters is analyzed to determine a critical parameter region over which unidirectional propagation may occur.     

Gapless color-flavor-locked quark matter

In neutral cold quark matter that is so dense that the strange quark mass Ms is unimportant, all three quark flavors pair in a color-flavor locked (CFL) pattern, and all nine fermionic quasiparticles have a gap Delta (or 2Delta). We argue that, as the density decreases (or Ms increases), there is a quantum phase transition (at M(2s/mu approximately 2Delta) to a new "gapless CFL phase" in which only seven quasiparticles have a gap. There is still an unbroken U(1)(Q) gluon/photon, but, unlike CFL, gapless CFL is a Q conductor with gapless (charged) quasiquarks and a nonzero electron density at zero temperature, so its low energy effective theory and astrophysical properties are qualitatively new. At the transition, the dispersion relations of both gapless quasiparticles are quadratic, but for larger M2s/mu, one becomes conventionally linear while the other remains quadratic, up to tiny corrections.     

The elastic and inelastic scattering of intermediate energy protons on deuterium at small momentum transfer

The differential cross sections for the elastic and inelastic scattering of protons on deuterium have been measured for scattering angles less than 14° at 198.5, 297.6 and 456.6 MeV. These quantities were determined relative to dσ / dΩ for pp elastic scattering with a precision of typically 2%. The range of excitation energies for the (p, p') reaction was chosen to emphasize the region near the np threshold dominated by the final-state interaction in the ¹S₀ channel. Particular attention was given to the dependence on excitation energy of the spectra at 198.5 MeV to examine the sensitivity to the ¹S₀ scattering length, a_np In this paper all data are compared with a new, detailed formulation of a simple model of the reaction mechanism based on the impulse approximation. The experimental results differ from the predictions by typically 10% and the differential cross sections exhibit a sensitivity to the intermediate-energy nucleon-nucleon amplitudes. If the impulse approximation is used to estimate a_np from the data at 198.5 MeV a value of − 24.7 ± 0.4 fm is obtained.     

Creatine kinase B deficient neurons exhibit an increased fraction of motile mitochondria

Background  

Neurons require an elaborate system of intracellular transport to distribute cargo throughout axonal and dendritic projections. Active anterograde and retrograde transport of mitochondria serves in local energy distribution, but at the same time also requires input of ATP. Here we studied whether brain-type creatine kinase (CK-B), a key enzyme for high-energy phosphoryl transfer between ATP and CrP in brain, has an intermediary role in the reciprocal coordination between mitochondrial motility and energy distribution. Therefore, we analysed the impact of brain-type creatine kinase (CK-B) deficiency on transport activity and velocity of mitochondria in primary murine neurons and made a comparison to the fate of amyloid precursor protein (APP) cargo in these cells, using live cell imaging.     

Partial information decomposition as a spatiotemporal filter

Understanding the mechanisms of distributed computation in cellular automata requires techniques for characterizing the emergent structures that underlie information processing in such systems. Recently, techniques from information theory have been brought to bear on this problem. Building on this work, we utilize the new technique of partial information decomposition to show that previous information-theoretic measures can confound distinct sources of information. We then propose a new set of filters and demonstrate that they more cleanly separate out the background domains, particles, and collisions that are typically associated with information storage, transfer, and modification in cellular automata.