Phase transitions for modified Erdős–Rényi processes

A fundamental and very well studied region of the Erdős–Rényi process is the phase transition at m∼n/2 edges in which a giant component suddenly appears. We examine the process beginning with an initial graph. We further examine the Bohman–Frieze process in which edges between isolated vertices are more likely. While the positions of the phase transitions vary, the three processes belong, roughly speaking, to the same universality class. In particular, the growth of the giant component in the barely supercritical region is linear in all cases.     

Real‐Time IR Study of Ultra‐Thin Film Photopolymerization of Liquid Porphyrin Monomer

By using an advanced polarization modulation infrared reflection adsorption spectroscopy (PM‐IRRAS) device it is possible to study the photopolymerization of an ultrathin layer of a porphyrin monomer in real time. The method can be compared with the indirect UV/Vis method previously introduced by our group. With PM‐IRRAS it is possible to analyze polymerization kinetics of photopolymerization at various temperatures to determine the activation energy of the reaction.

     

Characterization of G‐Quadruplex/Hairpin Transitions of RNAs by 19F NMR Spectroscopy

2′‐O‐[(4‐Trifluoromethyl‐triazol‐1‐yl)methyl] reporter groups have been incorporated into guanosine‐rich RNA models (including a known bistable Qd/Hp RNA and two G‐rich regions of mRNA of human prion protein, PrP) and applied for the ¹⁹F NMR spectroscopic characterization of plausible G‐quadruplex/hairpin (Qd/Hp) transitions in these RNA structures. For the synthesis of the CF₃‐labeled RNAs, phosphoramidite building blocks of 2′‐O‐[(4‐CF₃‐triazol‐1‐yl)methyl] nucleosides (cytidine, adenosine, and guanosine) were prepared and used as an integral part of the standard solid‐phase RNA synthesis. The obtained ¹⁹F NMR spectra supported the usual characterization data (obtained by UV‐ and CD‐melting profiles and by ¹H NMR spectra of the imino regions) and additionally gave more detailed information on the Qd/Hp transitions. The molar fractions of the secondary structural species (Qd, Hp) upon thermal denaturation and under varying ionic conditions could be determined from the intensities and shifts of the ¹⁹F NMR signals. For a well‐behaved Qd/Hp transition, thermodynamic parameters could be extracted.     

Antimony Complexes for Electrocatalysis: Activity of a Main-Group Element in Proton Reduction

Main-group complexes are shown to be viable electrocatalysts for the H₂-evolution reaction (HER) from acid. A series of antimony porphyrins with varying axial ligands were synthesized for electrocatalysis applications. The proton-reduction catalytic properties of TPSb(OH)₂ (TP=5,10,15,20-tetra(p-tolyl)porphyrin) with two axial hydroxy ligands were studied in detail, demonstrating catalytic H₂ production. Experiments, in conjunction with quantum chemistry calculations, show that the catalytic cycle is driven via the redox activity of both the porphyrin ligand and the Sb center. This study brings insight into main group catalysis and the role of redox-active ligands during catalysis.     

The protonation state of small carboxylic acids at the water surface from photoelectron spectroscopy

We report highly surface sensitive core-level photoelectron spectra of small carboxylic acids (formic, acetic and butyric acid) and their respective carboxylate conjugate base forms (formate, acetate and butyrate) in aqueous solution. The relative surface propensity of the carboxylic acids and carboxylates is obtained by monitoring their respective C1s signal intensities from a solution in which their bulk concentrations are equal. All the acids are found to be enriched at the surface relative to the corresponding carboxylates. By monitoring the PE signals of acetic acid and acetate as a function of total concentration, we find that the protonation of acetic acid is nearly complete in the interface layer. This is in agreement with literature surface tension data, from which it is inferred that the acids are enriched at the surface while (sodium) formate and acetate, but not butyrate, are depleted. For butyric acid, we conclude that the carboxylate form co-exists with the acid in the interface layer. The free energy cost of replacing an adsorbed butyric acid molecule with a butyrate ion at 1.0 M concentration is estimated to be >5 kJ mol(-1). By comparing concentration dependent surface excess data with the evolution of the corresponding photoemission signals it is furthermore possible to draw conclusions about how the distribution of molecules that contribute to the excess is altered with bulk concentration.     

A new device to study ex-vivo the effects of extracorporeal photochemotherapy on the immune system

Extracorporeal photochemotherapy (ECP) is a medical procedure effective in the treatment of several different T-cell mediated diseases such as cutaneous T-cell lymphoma and Graft-versus-Host Disease. During ECP treatment the patient's blood is processed by means of a cell separator to collect leukocytes (leukapheresis), mostly lymphocytes and monocytes, which are then incubated with the photoactive drug 8-methoxypsoralen (8-MOP), exposed to ultraviolet-A light (UV-A) and reinfused to the patient. It has been suggested that during ECP not only UV-A irradiation but also changes in the environmental condition may be relevant. Although ECP has been shown to have an in-vivo immunomodulatory effect, the mechanisms through which ECP exerts its effect remain elusive. One of the reasons for this incomplete knowledge is the absence of a reliable model for ECP. In order to investigate the effect of ECP on the peripheral immune system, we developed a new device which mimics the complete ECP cycle including blood transit through the cell separator. Peripheral blood samples (50ml) were obtained from volunteers and processed using a peristaltic pump. Peripheral blood mononuclear cells (PBMC) were then collected and treated with 8-MOP and UV-A under the same conditions used for the patients' therapy. Using this strategy we investigated 8-MOP, UV-A and their combined effect on the production of the pro-inflammatory cytokines interferon-gamma (IFN-gamma), interleukine-2 (IL-2) and tumor necrosis factor-alpha (TNF-alpha) in PBMC with and without polyclonal stimulation. We firstly demonstrated that our device does not affect total red and white blood cell counts. After 8-MOP and UV-A irradiation a significant decrease was observed in both activated CD4(+) and CD8(+) T lymphocytes producing IFN-gamma, IL-2 and TNF-alpha. Our findings are in line with those previously obtained in humans after complete ECP treatment, thus suggesting that our newly developed device is suitable for investigating the mechanism of action of ECP ex-vivo.     

Adsorption of organic probes on silica through Lewis interactions: a comparison of experimental results and quantum chemical calculations

The adsorption of organic probe molecules on a partly dehydroxylated silica (SiO(2)) surface has been studied in a non-aquatic and non-polar environment. These results were compared to, verified and explained by quantum chemical calculations on the same systems. Since the systems are water free and since the non-polar solvent cyclohexane is used in the experiments, the quantum chemical calculations are well comparable to the experimental results without any additional terms. The characterized surface was found to contain both Lewis acid and Lewis base sites and a good agreement between the experimentally determined and the calculated data was found.     

The phase transition in inhomogeneous random graphs

The “classical” random graph models, in particular G(n,p), are “homogeneous,” in the sense that the degrees (for example) tend to be concentrated around a typical value. Many graphs arising in the real world do not have this property, having, for example, power‐law degree distributions. Thus there has been a lot of recent interest in defining and studying “inhomogeneous” random graph models. One of the most studied properties of these new models is their “robustness”, or, equivalently, the “phase transition” as an edge density parameter is varied. For G(n,p), p = c/n, the phase transition at c = 1 has been a central topic in the study of random graphs for well over 40 years. Many of the new inhomogeneous models are rather complicated; although there are exceptions, in most cases precise questions such as determining exactly the critical point of the phase transition are approachable only when there is independence between the edges. Fortunately, some models studied have this property already, and others can be approximated by models with independence. Here we introduce a very general model of an inhomogeneous random graph with (conditional) independence between the edges, which scales so that the number of edges is linear in the number of vertices. This scaling corresponds to the p = c/n scaling for G(n,p) used to study the phase transition; also, it seems to be a property of many large real‐world graphs. Our model includes as special cases many models previously studied. We show that, under one very weak assumption (that the expected number of edges is “what it should be”), many properties of the model can be determined, in particular the critical point of the phase transition, and the size of the giant component above the transition. We do this by relating our random graphs to branching processes, which are much easier to analyze. We also consider other properties of the model, showing, for example, that when there is a giant component, it is “stable”: for a typical random graph, no matter how we add or delete o(n) edges, the size of the giant component does not change by more than o(n). © 2007 Wiley Periodicals, Inc. Random Struct. Alg., 31, 3–122, 2007