Density functional based simulations of proton permeation of graphene and hexagonal boron nitride.

Using density functional theory, we study proton permeation through graphene and hexagonal boron nitride. We consider several factors influencing the barriers for permeation, including structural optimization, the role of the solvent, surface curvature and proton transport through hydrogenated samples. Furthermore, we discuss the ground state charge transfer from the membrane to the proton and the strong tendency for bond formation. If the process is assumed to be slow we find that none of these effects lead to a satisfactory answer to the observed discrepancies between theory and experiment.

Correction: Energetics, barriers and vibrational spectra of partially and fully hydrogenated hexagonal boron nitride.

Correction for 'Energetics, barriers and vibrational spectra of partially and fully hydrogenated hexagonal boron nitride' by J. M. H. Kroes et al., Phys. Chem. Chem. Phys., 2016, 18, 19359-19367.

Chirality-Dependent Transmission of Spin Waves through Domain Walls.

Spin-wave technology (magnonics) has the potential to further reduce the size and energy consumption of information-processing devices. In the submicrometer regime (exchange spin waves), topological defects such as domain walls may constitute active elements to manipulate spin waves and perform logic operations. We predict that spin waves that pass through a domain wall in an ultrathin perpendicular-anisotropy film experience a phase shift that depends on the orientation of the domain wall (chirality). The effect, which is absent in bulk materials, originates from the interfacial Dzyaloshinskii-Moriya interaction and can be interpreted as a geometric phase. We demonstrate analytically and by means of micromagnetic simulations that the phase shift is strong enough to switch between constructive and destructive interference. The two chirality states of the domain wall may serve as a memory bit or spin-wave switch in magnonic devices.

Scaling Behavior and Strain Dependence of In-Plane Elastic Properties of Graphene.

We show by atomistic simulations that, in the thermodynamic limit, the in-plane elastic moduli of graphene at finite temperature vanish with system size L as a power law L(-η(u)) with η(u)≃0.325, in agreement with the membrane theory. We provide explicit expressions for the size and strain dependence of graphene's elastic moduli, allowing comparison to experimental data. Our results explain the recently experimentally observed increase of the Young modulus by more than a factor of 2 for a tensile strain of only a few per mill. The difference of a factor of 2 between the measured asymptotic value of the Young modulus for tensilely strained systems and the value from ab initio calculations remains, however, unsolved. We also discuss the asymptotic behavior of the Poisson ratio, for which our simulations disagree with the predictions of the self-consistent screening approximation.

Energetics, barriers and vibrational spectra of partially and fully hydrogenated hexagonal boron nitride.

We study hydrogen chemisorption at full coverage and low concentrations on hexagonal boron nitride (h-BN). Chemisorption trends reveal the complex nature of hydrogenation. Barriers for diffusion are found to be significantly altered by the presence of additional H atoms. Moreover, the presence of a Stone-Wales defect may dramatically enhance the bond strength of H to the h-BN surface. These findings provide new insights to understand and characterize hydrogenated boron nitride.

Effect of Structural Relaxation on the Electronic Structure of Graphene on Hexagonal Boron Nitride.

We performed calculations of electronic, optical, and transport properties of graphene on hexagonal boron nitride with realistic moiré patterns. The latter are produced by structural relaxation using a fully atomistic model. This relaxation turns out to be crucially important for electronic properties. We describe experimentally observed features such as additional Dirac points and the "Hofstadter butterfly" structure of energy levels in a magnetic field. We find that the electronic structure is sensitive to many-body renormalization of the local energy gap.

Motion of domain walls and the dynamics of kinks in the magnetic Peierls potential.

We study the dynamics of magnetic domain walls in the Peierls potential due to the discreteness of the crystal lattice. The propagation of a narrow domain wall (comparable to the lattice parameter) under the effect of a magnetic field proceeds through the formation of kinks in its profile. We predict that, despite the discreteness of the system, such kinks can behave like sine-Gordon solitons in thin films of materials such as yttrium iron garnets, and we derive general conditions for other materials. In our simulations, we also observe long-lived breathers. We provide analytical expressions for the effective mass and limiting velocity of the kink in excellent agreement with our numerical results.

Moiré patterns as a probe of interplanar interactions for graphene on h-BN.

By atomistic modeling of moiré patterns of graphene on a substrate with a small lattice mismatch, we find qualitatively different strain distributions for small and large misorientation angles, corresponding to the commensurate-incommensurate transition recently observed in graphene on hexagonal BN. We find that the ratio of C-N and C-B interactions is the main parameter determining the different bond lengths in the center and edges of the moiré pattern. Agreement with experimental data is obtained only by assuming that the C-B interactions are at least twice weaker than the C-N interactions. The correspondence between the strain distribution in the nanoscale moiré pattern and the potential energy surface at the atomic scale found in our calculations makes the moiré pattern a tool to study details of dispersive forces in van der Waals heterostructures.

Nanoscopic friction under electrochemical control.

We propose a theoretical model of friction under electrochemical conditions focusing on the interaction of a force microscope tip with adsorbed polar molecules whose orientation depends on the applied electric field. We demonstrate that the dependence of friction force on the electric field is determined by the interplay of two channels of energy dissipation: (i) the rotation of dipoles and (ii) slips of the tip over potential barriers. We suggest a promising strategy to achieve a strong dependence of nanoscopic friction on the external field based on the competition between long-range electrostatic interactions and short-range chemical interactions between tip and adsorbed polar molecules.

Non-spherical shapes of capsules within a fourth-order curvature model.

We minimize a discrete version of the fourth-order curvature-based Landau free energy by extending Brakke's Surface Evolver. This model predicts spherical as well as non-spherical shapes with dimples, bumps and ridges to be the energy minimizers. Our results suggest that the buckling and faceting transitions, usually associated with crystalline matter, can also be an intrinsic property of non-crystalline membranes.

Is pizza sutable to type 1 diabetes? A real life identification of best compromise between taste and low glycemic index in patients on insulin pump.

Opposed to whole wheat (WWP), traditional pizza (TP) is loved by patients with type 1 diabetes mellitus (T1DM) despite causing hyperglycemia. 50 well-trained T1DM patients had higher glucose levels after TP than after WWP or mixed flour pizza, which however was tasty, digestible and metabolically appropriate to break diet monotony.

Topological defects and shape of aromatic self-assembled vesicles.

We show that the stacking of flat aromatic molecules on a curved surface results in topological defects. We consider, as an example, spherical vesicles, self-assembled from molecules with 5- and 6-thiophene cores. We predict that the symmetry of the molecules influences the number of topological defects and the resulting equilibrium shape.

Topological instabilities of spherical vesicles.

Within the framework of the Helfrich elastic theory of membranes and of differential geometry, we study the relative stability of spherical vesicles and double bubbles. We find that not only temperature but also magnetic fields can induce topological transformations between spherical vesicles and double bubbles and provide a phase diagram for the equilibrium shapes.

Relating chaos to deterministic diffusion of a molecule adsorbed on a surface.

Chaotic internal degrees of freedom of a molecule can act as noise and affect the diffusion of the molecule on a substrate. A separation of timescales between the fast internal dynamics and the slow motion of the centre of mass on the substrate makes it possible to directly link chaos to diffusion. We discuss the conditions under which this is possible, and show that in simple atomistic models with pair-wise harmonic potentials, strong chaos can arise through the geometry. Using molecular dynamics simulations, we demonstrate that a realistic model of benzene is indeed chaotic, and that the internal chaos affects the diffusion on a graphite substrate.

Theoretical study of the nucleation/growth process of carbon clusters under pressure.

We used molecular dynamics and the empirical potential for carbon LCBOPII to simulate the nucleation/growth process of carbon clusters both in vacuum and under pressure. In vacuum, our results show that the growth process is homogeneous and yields mainly sp(2) structures such as fullerenes. We used an argon gas and Lennard-Jones potentials to mimic the high pressures and temperatures reached during the detonation of carbon-rich explosives. We found that these extreme thermodynamic conditions do not affect substantially the topologies of the clusters formed in the process. However, our estimation of the growth rates under pressure are in much better agreement with the values estimated experimentally than our vacuum simulations. The formation of sp(3) carbon was negligible both in vacuum and under pressure which suggests that larger simulation times and cluster sizes are needed to allow the nucleation of nanodiamonds.

[Laparoscopic hysterectomy and urological lesions: risk analysis based on current literature and preventive strategies]. / Isterectomia laparoscopica e lesioni urologiche: analisi del rischio alla luce della letteratura corrente e strategie di prevenzione.

The aim of the paper is to discuss possible urological complications related to laparoscopic hysterectomy and to focus on the most effective strategies to get their occurrence reduced. A review of the literature concerning the safety of the procedure was conducted, comparing laparoscopic hysterectomy (LH) with abdominal hysterectomy (AH) and vaginal hysterectomy (VH) in terms of urological complications during surgery. The possible effect of the "learning curve" on the frequency of this kind of complications was evaluated. The effect of the "learning curve" has been shown by large observational studies where the number of urological complications occurring during LH seems to diminish as the ability in performing this surgical procedure increases. Also the great variability existing between different centres was highlighted showing that the spreading in case of urological complications varies between 0.4% and 4%. The lesions of the bladder roof are not specific for LH while they are commonly associated with AH, although their rate of occurrence is far higher in the LH group when compared with AH (2% vs 0.8%). Little difference seems to exist between VH and LH regarding this specific lesion (1.6 vs 1.2). Ureteral lesions occur with a frequency of 1.2% in the LH and 0.2% in case of an hysterectomy performed by the abdominal route whereas current data show that these lesions are very rare in those women undergoing VH. The present study stresses the importance of intraoperative diagnosis of urological lesions and gives some practical tips to avoid them providing also a brief description of some procedural aspects of LH as performed at our institution.

Skin denervation does not alter cortical potentials to surface concentric electrode stimulation: A comparison with laser evoked potentials and contact heat evoked potentials.

BACKGROUND: In the neurophysiological assessment of patients with neuropathic pain, laser evoked potentials (LEPs), contact heat evoked potentials (CHEPs) and the evoked potentials by the intraepidermal electrical stimulation via concentric needle electrode are widely agreed as nociceptive specific responses; conversely, the nociceptive specificity of evoked potentials by surface concentric electrode (SE-PREPs) is still debated. METHODS: In this neurophysiological study we aimed at verifying the nociceptive specificity of SE-PREPs. We recorded LEPs, CHEPs and SE-PREPs in eleven healthy participants, before and after epidermal denervation produced by prolonged capsaicin application. We also used skin biopsy to verify the capsaicin-induced nociceptive nerve fibre loss in the epidermis. RESULTS: We found that whereas LEPs and CHEPs were suppressed after capsaicin-induced epidermal denervation, the surface concentric electrode stimulation of the same denervated skin area yielded unchanged SE-PREPs. CONCLUSION: The suppression of LEPs and CHEPs after nociceptive nerve fibre loss in the epidermis indicates that these techniques are selectively mediated by nociceptive system. Conversely, the lack of SE-PREP changes suggests that SE-PREPs do not provide selective information on nociceptive system function. SIGNIFICANCE: Capsaicin-induced epidermal denervation abolishes laser evoked potentials (LEPs) and contact heat evoked potentials (CHEPs), but leaves unaffected pain-related evoked potentials by surface concentric electrode (SE-PREPs). These findings suggest that unlike LEPs and CHEPs, SE-PREPs are not selectively mediated by nociceptive system.

A pain in the skin. Regenerating nerve sprouts are distinctly associated with ongoing burning pain in patients with diabetes.

BACKGROUNDS: Patients with diabetic polyneuropathy commonly suffer from ongoing burning pain and dynamic mechanical allodynia. In this clinical and skin biopsy study, we aimed at assessing how intraepidermal regenerating nerve sprouts are associated with these two types of pain. METHODS: We consecutively enrolled 85 patients with diabetic polyneuropathy. All patients underwent skin biopsy at the distal leg. Intraepidermal nerve fibres were immunostained with the anti-protein gene product 9.5 (PGP9.5) to quantify all intraepidermal nerve fibres, and the growth-associated protein 43 (GAP43) to quantify regenerating nerve sprouts. RESULTS: We found that the GAP43-stained intraepidermal nerve fibre density and the ratio GAP43/PGP9.5 were significantly higher in patients with ongoing burning pain than in those without. The area of receiver operating characteristic (ROC) curve for the ratio GAP43/PGP9.5 was 0.74 and yielded a sensitivity and specificity for identifying ongoing burning pain of 72% and 71%, respectively. Conversely, although the density of PGP9.5 and GAP43 intraepidermal nerve fibre was higher in patients with dynamic mechanical allodynia than in those without, this difference was statistically weak and the ROC curve analysis of skin biopsy variables for this type of pain failed to reach the statistical significance. CONCLUSION: Our clinical and skin biopsy study showed that ongoing burning pain was strongly associated with regenerating sprouts, as assessed with GAP43 immunostaining. This finding improves our understanding on the mechanisms underlying neuropathic pain in patients with diabetic polyneuropathy and suggests that the GAP43/PGP 9.5 ratio might be used as an objective marker for ongoing burning pain due to regenerating sprouts. SIGNIFICANCE: Our skin biopsy study showing that regenerating sprouts, as assessed with GAP43-staining, were strongly associated with ongoing burning pain, improves our knowledge on the mechanisms underlying neuropathic pain in patients with diabetes.

Influence of latent heat and thermal diffusion on the growth of nematic liquid crystal nuclei.

The growth of nematic liquid crystal nuclei from an isotropic melt follows a power law behavior with exponent n found experimentally to vary between 1/2 for low quench depths, up to 1 for high quench depths. This behavior has been attributed to the competition between curvature and free energy. We show that curvature cannot account for the low quench depth behavior of the nucleus growth, and attribute this behavior to the diffusion of latent heat. We use a multiscale approach to solve the Landau-Ginzburg order parameter evolution equation coupled to a diffusive heat equation, and discuss this behavior for material parameters experimentally measured for the liquid crystal 8CB.

Solvent-driven formation of bolaamphiphilic vesicles.

We show that a spontaneous bending of single-layer bolaamphiphiles results from the frustration due to the competition between core-core and tail-solvent interactions. We find that spherical vesicles are stable under rather general assumptions on these interactions described within the Flory-Huggins theory. We consider also the deformation of the vesicles in an external magnetic field that has been recently experimentally observed.