Interaction of cationic liposomes with cell membrane models

The colloidal dispersion stability of nano-sized graphene sheets in supercritical fluid (SCF) media is very important for developing SCF-based exfoliation and dispersion technologies for stabilization and solubilization of graphenes. We carried out molecular dynamics simulations to elucidate the stability mechanism of graphene in supercritical CO(2) (scCO(2)). The potential of mean force (PMF) between two graphene nanosheets in scCO(2) was simulated, and the effect of scCO(2) density and temperature on the PMF behavior has been investigated. The simulation results demonstrate that there exists a free energy barrier between graphenes in the scCO(2) fluid, possibly obstructing the aggregation of graphenes. The single-layer confined CO(2) molecules between the graphene sheets can induce a dominating repulsion interaction between graphene sheets. At higher scCO(2) fluid density, there are more confined CO(2) molecules within the interplate regions, resulting in a stronger repulsive free energy barrier. The effect of temperature on the PMF is relatively minor. The scCO(2) solvent structure shows layered confined arrangement in the interfacial region near the graphene nanosheets, which is correlated well with the PMF profile curve.     

Supramolecular chirality transfer to large random aggregates of porphyrins

Chirality is rapidly induced in a fractal aggregate of the porphyrin t-CuPagg by addition of α-helical poly-glutamate. These results demonstrate a facile transfer of chirality via noncovalent interactions to preformed supramolecular assemblies grown in the absence of a chiral template.     

A molecular dynamics study of structure, stability and fragmentation patterns of sodium bis(2-ethylhexyl)sulfosuccinate positively charged aggregates in vacuo

Positively charged supramolecular aggregates formed in vacuo by n AOTNa (sodium bis(2-ethylhexyl)sulfosuccinate) molecules and n(c) additional sodium ions, i.e. [AOT(n)Na(n+n(c))](n(c)), have been investigated by molecular dynamics (MD) simulations for n = 1-20 and n(c) = 0-5. Statistical analysis of physical quantities like gyration radii, atomic B-factors and moment of inertia tensors provides detailed information on their structural and dynamical properties. Even for n(c) = 5, all stable aggregates show a reverse micelle-like structure with an internal solid-like core including sodium counterions and surfactant polar heads surrounded by an external layer consisting of the surfactant alkyl chains. Moreover, the aggregate shapes may be approximated by rather flat and elongated ellipsoids whose longer axis increases with n and n(c). The fragmentation patterns of a number of these aggregates have also been examined and have been found to markedly depend on the aggregate charge state. In one particular case, for which experimental findings are available in the literature, a good agreement is found with the present fragmentation data.     

HMGB1–Carbenoxolone Interactions: Dynamics Insights from Combined Nuclear Magnetic Resonance and Molecular Dynamics

The interplay of protein dynamics and molecular recognition is of fundamental importance in biological processes. Atomic‐resolution insights into these phenomena may provide new opportunities for drug discovery. Herein, we have combined NMR relaxation experiments and residual dipolar coupling (RDC) measurements with molecular dynamics (MD) simulations to study the effects of the anti‐inflammatory drug carbenoxolone (CBNX) on the conformational properties and on the internal dynamics of a subdomain (box A) of high‐mobility group B protein (HMGB1). ¹⁵N relaxation data show that CBNX binding enhances the fast pico‐ to nanosecond motions of a loop and partially removes the internal motional anisotropy of the first two helices of box A. Dipolar wave analysis of amide RDC data shows that ligand binding induces helical distortions. In parallel, increased mobility of the loop upon ligand binding is highlighted by the essential dynamics analysis (EDA) of MD simulations. Moreover, simulations detect two possible orientations for CBNX, which induces two possible conformations of helix H3, one being similar to the free form and the second one causing a partial helical distortion. Finally, we introduce a new approach for the analysis of the internal coordination of protein residues that is consistent with experimental data and allows us to pinpoint which substructures of box A are dynamically affected by CBNX. The observations reported here may be useful for understanding the role of protein dynamics in binding at atomic resolution.     

Advanced Materials in Cultural Heritage Conservation

Cultural Heritage is a crucial socioeconomic resource; yet, recurring degradation processes endanger its preservation. Serendipitous approaches in restoration practice need to be replaced by systematically addressing conservation issues through the development of advanced materials for the preservation of the artifacts. In the last few decades, materials and colloid science have provided valid solutions to counteract degradation, and we report here the main highlights in the formulation and application of materials and methodologies for the cleaning, protection and consolidation of works of art. Several types of artifacts are addressed, from murals to canvas paintings, metal objects, and paper artworks, comprising both classic and modern/contemporary art. Systems, such as nanoparticles, gels, nanostructured cleaning fluids, composites, and other functional materials, are reviewed. Future perspectives are also commented, outlining open issues and trends in this challenging and exciting field.     

Preparation and physical properties of novel nonionic surfactants and their grafting copolymers with linear low density polyethylene (LLDPE)

Three nonionic surfactants, S1, S2, and S3 and their acrylates, AS1, AS2, and AS3, were synthesized with poly(ethylene oxide) and diols such as glycol, 1,6‐hexanediol, and 1,10‐decanediol as the main starting materials. Their chemical structures were characterized by means of Fourier transform infrared (FTIR) spectroscopy and ¹H NMR. The surface activity and surface tension (γ) of S1, S2, and S3 were evaluated by a drop weight method. The surface tension was found to decrease with the length of the lipophilic spacer in the molecular chains (γ_S1 < γ_S2 < γ_S3). AS1, AS2, and AS3 were adopted as functionalizing monomers and grafted onto linear low density polyethylene (LLDPE) with a melt reactive extrusion procedure. The graft degrees of LLDPE were determined by FTIR. Three grafted LLDPE samples with grafting degrees of 1.16% (AS1), 0.82% (AS2), and 0.71% (AS3) were prepared. Thermal and rheological properties of grafted LLDPE samples were studied with differential scanning calorimetry and a rotational rheometer. Crystallization rates of grafted LLDPE were faster than that of plain LLDPE at a given crystallization temperature because graft chains could act as nucleating agents. The isothermal crystallization behavior of grafted LLDPE was in accordance with the Avrami model only in the first stage, and deviated from the model with an increase in the crystallization time. Shear thinning at high shear rates and shear thickening at low shear rates were observed for the grafted LLDPE. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 314–322, 2005     

On some abstract variable domain hyperbolic differential equations

The Cauchy problem is studied for a class of linear abstract differential equations of hyperbolic type with variable domain. Existence and uniqueness results are proved for (suitably defined) weak solutions. Some applications to P.D.E. are also given: they concern linear hyperbolic equations either in non-cylindrical regions or with mixed variable lateral conditions.This work was supported in part by the M.U.R.S.T. (Italy), through 60% and 40% research funds, and by the «G.N.AF.A. of the C.N.R.» (Italy).     

Conformational effects on circular dichroism in the photoelectron angular distribution.

The B-spline density-functional method has been applied to the conformers of the (1R, 2R)-1,2-dibromo-1,2-dichloro-1,2-difluoroethane molecule. The cross section, asymmetry, and dichroic parameters relative to core and valence orbitals, which do not change their nature along the conformational curve, have been systematically studied. While the cross section and the asymmetry parameter are weakly affected, the dichroic parameter appears to be rather sensitive to the particular conformer of the molecule, suggesting that this dynamical property could be a useful tool for conformational analysis. The computational method has also been applied to methyl rotation in methyloxirane. Unexpected and dramatic sensitivity of the dichroic-parameter profile to the methyl rotation, both in the core and valence states, has been found. Boltzmann averaging over the conformers reproduces quite closely the profiles previously obtained for the minimum-energy conformation, which is in good agreement with the experimental results.     

Regioselective reductive demethoxylation of 3,4,5-trimethoxystilbenes

Selective removal of the 4-methoxy group of 3,4,5-trimethoxystilbenes was performed under electron transfer conditions from Na metal in THF. Careful control of reaction conditions and quenching procedure allowed the synthesis of either (E)-3,5-dimethoxystilbenes or 3,5-dimethoxybibenzyls.