Surface supramolecular organization of a terbium(III) double-decker complex on graphite and its single molecule magnet behavior

The two-dimensional self-assembly of a terbium(III) double-decker phthalocyanine on highly oriented pyrolitic graphite (HOPG) was studied by atomic force microscopy (AFM), and it was shown that it forms highly regular rectangular two-dimensional nanocrystals on the surface, that are aligned with the graphite symmetry axes, in which the molecules are organized in a rectangular lattice as shown by scanning tunneling microscopy. Molecular dynamics simulations were run in order to model the behavior of a collection of the double-decker complexes on HOPG. The results were in excellent agreement with the experiment, showing that-after diffusion on the graphite surface-the molecules self-assemble into nanoscopic islands which align preferentially along the three main graphite axes. These low dimension assemblies of independent magnetic centers are only one molecule thick (as shown by AFM) and are therefore very interesting nanoscopic magnetic objects, in which all of the molecules are in interaction with the graphite substrate and might therefore be affected by it. The magnetic properties of these self-assembled bar-shaped islands on HOPG were studied by X-ray magnetic circular dichroism, confirming that the compounds maintain their properties as single-molecule magnets when they are in close interaction with the graphite surface.     

On the impossibility of defining adhesive hard spheres as sticky limit of a hard-sphere-Yukawa potential

For fluids of molecules with short-ranged hard-sphere-Yukawa (HSY) interactions, it is proven that the Noro-Frenkel "extended law of corresponding states" cannot be applied down to the vanishing attraction range, since the exact HSY second virial coefficient diverges in such a limit. It is also shown that, besides Baxter's original approach, a fully correct alternative definition of "adhesive hard spheres" can be obtained by taking the vanishing-range-limit (sticky limit) not of a Yukawa tail, as is commonly done, but of a slightly different potential with a logarithmic-Yukawa attraction.     

A relax-and-cut framework for Gomory mixed-integer cuts

Gomory mixed-integer cuts (GMICs) are widely used in modern branch-and-cut codes for the solution of mixed-integer programs. Typically, GMICs are iteratively generated from the optimal basis of the current linear programming (LP) relaxation, and immediately added to the LP before the next round of cuts is generated. Unfortunately, this approach is prone to instability. In this paper we analyze a different scheme for the generation of rank-1 GMICs read from a basis of the original LP—the one before the addition of any cut. We adopt a relax-and-cut approach where the generated GMICs are not added to the current LP, but immediately relaxed in a Lagrangian fashion. Various elaborations of the basic idea are presented, that lead to very fast—yet accurate—variants of the basic scheme. Very encouraging computational results are presented, with a comparison with alternative techniques from the literature also aimed at improving the GMIC quality. We also show how our method can be integrated with other cut generators, and successfully used in a cut-and-branch enumerative framework.     

Two-wavelength lidar inversion algorithm for determination of aerosol extinction-to-backscatter ratio and its application to CALIPSO lidar measurements

A modified two-wavelength lidar inversion algorithm is proposed to aid in the retrieval of aerosol extinction-to-backscatter ratios (lidar ratio) as well as backscatter coefficients and extinction color ratios from simultaneous two-wavelength elastic backscatter lidar measurements. To demonstrate the feasibility of the algorithm, both the Raman method and the two-wavelength method have been applied to the ground-based measurements at 355 and 532 nm; moreover, it has been applied to the data acquired by the Cloud Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO) lidar, and to the simultaneous ground-based lidar measurements carried out at Napoli (southern Italy, 40.838 °N, 14.183 °E, 118 m above sea level). Three cases of Saharan dust transport towards Europe have been considered. From the comparison, it can be found that the values of lidar ratio and backscatter coefficient retrieved by the modified two-wavelength algorithm are in good agreement with those obtained by the Raman method. Moreover the retrieved mean values of the lidar ratios and color ratios are in agreement with those reported by other authors.     

A Nuclear Magnetic Resonance study of the reversible denaturation of hydrated lysozyme

The understanding of the physical processes that occur below the threshold of protein thermal denaturation is of fundamental importance. In this thermal region proteins undergo a reversible folding/unfolding process whose evolution depends upon temperature and time. When the kinetics of the folding is altered, the specific biological activity of the protein is altered as well and aggregation phenomena usually intervene. The most important role in driving these processes is played by the solvent and water is certainly the solvent par excellence. It is well known that proteins become biologically active with no less than a water monolayer covering their surface. The knowledge of the physical properties of this monolayer is of basic importance to prevent folding alterations. We present a proton Nuclear Magnetic Resonance study at very high resolution of the thermodynamic properties of lysozyme hydration water as a function of temperature and time in the thermal region of the reversible denaturation.     

1H NMR and Calorimetric Studies of the Inclusion of Trimethylammonium Cations into Water Soluble Calixresorcinarenes

Abstract

The complexation of tetramethylammonium (TEMA), benzyltrimethylammonium (BTMA), p-nitrobenzyltrimethylammonium (BTMAN) and N, N, N-trimethylanilinium (TMA) by the tetrasulphonate derivative of the resorcinol cyclic tetramer (1), was studied in aqueous solution by ¹H NMR and calorimetry. Host 1 specifically recognizes the—N⁺ (CH₃)₃ group of TEMA, BTMA and BTMAN, whereas it binds TMA unselectively; TMA is included both via the charged group and the aromatic moiety. The binding constants of all four guests with 1, as determined by both ¹H NMR and calorimetric titrations, show that all inclusion processes are almost equally stabilised.

ΔHΔ and ΔSΔ values, determined by direct calorimetry, reveal specific interactions that are not expressed in the ΔGΔ terms and indicate that we are dealing with “non-classical hydrophobic effects”. The effects of the structural, conformational and electronic properties of the guests on the forces driving the inclusion processes are discussed.     

Purely linear response of the quantum Hall current to space-adiabatic perturbations

Letters in Mathematical Physics - We provide an algorithm that factorizes one-dimensional quantum walks on an arbitrary but fixed cell structure into a protocol of two basic operations: a fixed...     

Graphs of maps between manifolds in trace spaces and with vanishing mean oscillation

We give a positive answer to a question raised by Alberti in connection with a recent result by Brezis and Nguyen. We show the existence of currents associated with graphs of maps in trace spaces that have vanishing mean oscillation. The degree of such maps may be written in terms of these currents, of which we give some structure properties. We also deal with relevant examples.     

New heterocyclic systems derived from pyridine: new substrates for the investigation of the azide/tetrazole equilibrium

By exploiting the reactivity of 7-alkyl-3-chloro-4-cyano-1-hydrazino-5,6,7,8-tetrahydro-2,7-naphthyridines 5 some 7-alkyl-1-azido-3-chloro-4-cyano-5,6,7,8-tetrahydro-2,7-naphthyridines 6 were synthesized. Looking at their chemical properties we have ascertained that in these compounds the azide/tetrazole equilibrium is completely shifted towards the azido form (both in solid state and in solution). Their behaviour with some amines was tested as well. Moreover by exploiting the reactivity of the chlorine and of the nitrile group we have fused on the pyridine system two new rings (pyrazole or thiophene), thus obtaining previously unknown heterocyclic systems (10 and 11). Interestingly, in these new systems, the position of the above equilibrium is reversed.     

Label‐Free Photoelectrochemical Detection of Double‐Stranded HIV DNA by Means of a Metallointercalator‐Functionalized Electrogenerated Polymer

The design of photoactive functionalized electrodes for the sensitive transduction of double‐stranded DNA hybridization is reported. Multifunctional complex [Ru(bpy‐pyrrole)₂(dppn)]²⁺ (bpy‐pyrrole=4‐methyl‐4′‐butylpyrrole‐2,2′‐bipyridine, dppn=benzo[i]dipyrido[3,2‐a:2′,3′‐c]phenazine) exhibiting photosensitive, DNA‐intercalating, and electropolymerizable properties was synthesized and characterized. The pyrrole groups undergo oxidative electropolymerization on planar electrodes forming a metallopolymer layer on the electrode. Thanks to the photoelectrochemical and intercalating properties of the immobilized Ru^II complex, the binding of a double‐stranded HIV DNA target was photoelectrochemically detected on planar electrodes. Photocurrent generation through visible irradiation was correlated to the interaction between double‐stranded DNA and the metallointercalator polymer. These interactions were well fitted by using a Langmuir isotherm, which allowed a dissociation constant of 2×10⁶ L mol^?1 to be estimated. The low detection limit of 1 fmol L^?1 and sensitivity of 0.01 units per decade demonstrate excellent suitability of these modified electrodes for detection of duplex DNA.