Random, blocky and alternating ordering in supramolecular polymers of chemically bidisperse monomers

As a first step to understanding the role of molecular or chemical polydispersity in self-assembly, we put forward a coarse-grained model that describes the spontaneous formation of quasi-linear polymers in solutions containing two self-assembling species. Our theoretical framework is based on a two-component self-assembled Ising model in which the bidispersity is parameterized in terms of the strengths of the binding free energies that depend on the monomer species involved in the pairing interaction. Depending upon the relative values of the binding free energies involved, different morphologies of assemblies that include both components are formed, exhibiting paramagnetic-, ferromagnetic- or anti ferromagnetic-like order,i.e., random, blocky or alternating ordering of the two components in the assemblies. Analyzing the model for the case of ferromagnetic ordering, which is of most practical interest, we find that the transition from conditions of minimal assembly to those characterized by strong polymerization can be described by a critical concentration that depends on the concentration ratio of the two species. Interestingly, the distribution of monomers in the assemblies is different from that in the original distribution, i.e., the ratio of the concentrations of the two components put into the system. The monomers with a smaller binding free energy are more abundant in short assemblies and monomers with a larger binding affinity are more abundant in longer assemblies. Under certain conditions the two components congregate into separate supramolecular polymeric species and in that sense phase separate. We find strong deviations from the expected growth law for supramolecular polymers even for modest amounts of a second component, provided it is chemically sufficiently distinct from the main one.Comment: Submitted to Macromolecules, 6 figures. arXiv admin note: substantial text overlap with arXiv:1111.176

Functional Inequality in Latin America: News from the Twentieth Century

We report on a novel approach for the measurement of gas adsorption in microporous solids using X-ray computed tomography (CT) that we refer to as digital adsorption. Similar to conventional macroscopic methods, the proposed protocol combines observations with an inert and an adsorbing gas to produce equilibrium isotherms in terms of the truly measurable quantity in an adsorption experiment, namely the surface excess. Most significantly, X-ray CT allows probing the adsorption process in three dimensions, so as to build spatially-resolved adsorption isotherms with a resolution of approximately 10 mm3 within a fixed-bed column. Experiments have been carried out at 25 C and in the pressure range 1-30bar using CO2 on activated carbon, zeolite 13X and glass beads (as control material), and results are validated against literature data. A scaling approach was applied to analyze the whole population of measured adsorption isotherms (~7600), leading to single universal adsorption isotherm curves that are descriptive of all voxels for a given adsorbate-adsorbent system. By analyzing the adsorption heterogeneity at multiple length scales (1 mm3 to 1 cm3), packing heterogeneity was identified as the main contributor for the larger spatial variability in the adsorbed amount observed for the activated carbon rods as compared to zeolite pellets. We also show that this technique is readily applicable to a large spectrum of commercial porous solids, and that it can be further extended to weakly adsorbing materials with appropriate protocols that reduce measurement uncertainties. As such, the obtained results prove the feasibility of digital adsorption and highlight substantial opportunities for its wider use in the field of adsorptive characterization of porous solids

Self-assembly and characterization of small and monodisperse dye nanospheres in a protein cage

Phthalocyanines (Pc) are dyes in widespread use in materials science and nanotechnology, with numerous applications in medicine, photonics, electronics and energy conversion. With the aim to construct biohybrid materials, we here prepared and analyzed the structure of two Pc- loaded virus- like particles (VLP) with diameters of 20 and 28 nm (i.e., T = 1 and T= 3 icosahedral symmetries, respectively). Our cryoelectron microscopy (cryo- EM) studies show an unprecedented, very high level of Pc molecule organization within both VLP. We found thaT = 10 nm diameter nanospheres form inside the T = 1 VLP by self- assembly of supramolecular Pc stacks. Monodisperse, self- assembled organic dye nanospheres were not previously known, and are a consequence of capsid- imposed symmetry and size constraints. The Pc cargo also produces major changes in the protein cage structure and in the mechanical properties of the VLP. Pc- loaded VLP are potential photosensitizer/ carrier systems in photodynamic therapy (PDT), for which their mechanical behaviour must be characterized. Many optoelectronic applications of Pc dyes, on the other hand, are dependent on dye organization at the nanoscale level. Our multidisciplinary study thus opens the way towards nanomedical and nanotechnological uses of these functional molecules

The question of land access and the Spanish Land Reform of 1932

Spanish land reform, involving the break-up of the large southern estates, was a central issue during the first decades of the twentieth century, and justified for economic and political reasons. We employ new provincial data on landless workers, land prices and agrarian wages to consider if government intervention was needed because of the failure of the free action of markets to redistribute land. Our evidence shows that the relative number of landless workers decreased significantly from 1860 to 1930 before the approval of the 1932 Land Reform during the Second Republic (1931-36). This was due to two interrelated market forces: the falling ratio between land prices and rural wages, which made land cheaper for landless workers to rent and buy land plots, and structural change that drained rural population from the countryside. Given that shifts in factor prices were helping workers gain access to land, the economic arguments for reform by the 1930s remain unclea

Nanopore surface coating delivers nanopore size and shape through conductance-based sizing

The performance of nanopore single-molecule sensing elements depends intimately on their physical dimensions and surface chemical properties. These factors underpin the dependence of the nanopore ionic conductance on electrolyte concentration, yet the measured, or modeled, dependence only partially illuminates the details of geometry and surface chemistry. Using the electrolyte-dependent conductance data before and after selective surface functionalization of solid-state nanopores, however, introduces more degrees of freedom and improves the performance of conductance-based nanopore characterizations. Sets of representative nanopore profiles were used to generate conductance data, and the nanopore shape and exact dimensions were identified, through conductance alone, by orders-of-magnitude 3 reductions in the geometry optimization metrics. The optimization framework could similarly be used to evaluate the nanopore surface coating thickness

Introduction: new research in monetary history - A map

This handbook aims to provide a comprehensive (though obviously not exhaustive) picture of state-of-the-art international scholarship on the history of money and currency. The chapters of this handbook cover a wide selection of research topics. They span chronologically from antiquity to nowadays and are geographically stretched from Latin America to Asia, although most of them focus on Western Europe and the USA, as a large part of the existing research does. The authors of these chapters constitute, we hope, a balanced sample of various generations of scholars who contributed to what Barry Eichengreen defined as "the new monetary and financial history" – an approach that combines the analysis of monetary aggregates and policies with the structure and dynamics of the banking sector and financial markets. We have structured this handbook in ten broad thematic parts: the historical origins of money; money, coinage, and the state; trade, money markets, and international currencies; money and metals; monetary experiments; Asian monetary systems; exchange rate regimes; monetary integration; central banking and monetary policy; and aggregate price shocks. In this introduction, we offer for each part some historical context, a few key insights from the literature, and a brief analytical summary of each chapter. Our aim is to draw a map that hopefully will help readers to organize their journey through this very wide and diverse research area