Nondiffusive weak localization in two-dimensional systems with spin-orbit splitting of the spectrum

The effect of spin splitting caused by structural asymmetry (Rashba’s contribution) and bulk asymmetry (Dresselhaus’s contribution) on the magnetoconductance of two-dimensional structures with high mobility of charge carriers is studied. The theory of weak localization with regard to both of the contributions is developed. The theory is valid in the entire region of classically low magnetic fields for arbitrary relations between the frequencies of spin precession and elastic collisions. The suppression of the correction for antilocalization is demonstrated in the case of equal contributions of structural anisotropy and bulk anisotropy to the spin splitting. The effect of the contribution, cubic in the wave vector, to the spin splitting on the quantum magnetoresistance is studied.     

Nanostructured polymer blends: Synthesis and structure

Nanostructured polymer blends prepared via anionic ring opening polymerizations of cyclic monomers in the presence of a pre-made polymer melt exhibit a number of special properties over traditional polymer blends and homopolymers. Here, we report on a simple and versatile method of in situ polymerization of macrocyclic carbonates in the presence of a maleic anhydride polypropylene (mPP) matrix and a surface-active compatibilizer (i.e. PC grafted onto a mPP backbone generated in situ) to yield a micro- and nanostructured polymer blends consisting of a polycarbonate (PC) minor phase, and a polypropylene (PP) major phase. By varying the processing conditions and concentration of the macrocyclic carbonate it was possible to reduce the size of the PC dispersions to an average minor diameter of 150 nm. NMR and TEM characterizations indicate that the PC dispersions do not influence crystal content in the PP phase. Overall, the results point to a simple strategy and versatile route to new polymeric materials with enhanced benefits.     

Synthesis and Study of Ion Adsorption and Fluorescent Properties of Silica-Grafted Bis(crownazo)methine

A ketocyanine ligand containing two N-aza-15-crown-5 residues has been synthesized and covalently anchored to a silica substrate through an azomethine link. The ligand formation and molecular structure have been determined by combining spectral data and molecular simulations. Preferential adsorption of rare-earth metals from aqueous solutions to the modified surface has been noticed. In the case of lanthanum, the adsorption is accompanied by significant fluorescence enhancement, which allows this system to be used as a sensor for La³⁺ ion.     

Critical Infrastructure in the Face of a Predatory Future: Preparing for Untoward Surprise

The editors of this special issue asked Todd LaPorte to reflect on the issues that emerge from the discussions in this special issue and, more in general, from the discussions that have proliferated in the wake of recent crises and disasters. In his contribution, Professor LaPorte contemplates what political leaders can do to prepare for catastrophic surprises. A crucial initiative, he argues, would be the initiation of a public discussion about the level of distress that a society is willing to accept in the pursuit of efficient, reliable critical infrastructures.     

Molecular basis of resistance to HIV-1 protease inhibition: a plausible hypothesis

The binding thermodynamics of the HIV-1 protease inhibitor acetyl pepstatin and the substrate Val-Ser-Gln-Asn-Tyr-Pro-Ile-Val-Gln, corresponding to one of the cleavage sites in the gag, gag-pol polyproteins, have been measured by direct microcalorimetric analysis. The results indicate that the binding of the peptide substrate or peptide inhibitor is entropically driven; i.e., it is characterized by an unfavorable enthalpy and a favorable entropy change, in agreement with a structure-based thermodynamic analysis based upon an empirical parameterization of the energetics. Dissection of the binding enthalpy indicates that the intrinsic interactions are favorable and that the unfavorable enthalpy originates from the energy cost of rearranging the flap region in the protease molecule. In addition, the binding is coupled to a negative heat capacity change. The dominant binding force is the increase in solvent entropy that accompanies the burial of a significant hydrophobic surface. Comparison of the binding energetics obtained for the substrate with that obtained for synthetic nonpeptide inhibitors indicates that the major difference is in the magnitude of the conformational entropy change. In solution, the peptide substrate has a higher flexibility than the synthetic inhibitors and therefore suffers a higher conformational entropy loss upon binding. This higher entropy loss accounts for the lower binding affinity of the substrate. On the other hand, due to its higher flexibility, the peptide substrate is more amenable to adapt to backbone rearrangements or subtle conformational changes induced by mutations in the protease. The synthetic inhibitors are less flexible, and their capacity to adapt is more restricted. The expected result is a more pronounced effect of mutations on the binding affinity of the synthetic inhibitors. On the basis of the thermodynamic differences in the mode of binding of substrate and synthetic inhibitors, it appears that a key factor to understanding resistance is given by the relative balance of the different forces that contribute to the binding free energy and, in particular, the balance between conformational and solvation entropy.