Characterization of the core-shell nanoparticles formed as soluble hydrogen-bonding interpolymer complexes at low pH

The formation of soluble hydrogen-bonding interpolymer complexes between poly(acrylic acid) (PAA) and poly(acrylic acid-co-2-acrylamido-2-methyl-1-propane sulfonic acid)-graft-poly(N,N-dimethylacrylamide) (P(AA-co-AMPSA)-g-PDMAM) at pH=2.0 was studied. A viscometric study showed that in semidilute solution a physical gel is formed due to the interconnection of the anionic P(AA-co-AMPSA) backbone of the graft copolymer, in a transient network, by means of the complexes formed between the PDMAM side chains of the graft copolymer and PAA. Dynamic and static light scattering measurements, in conjunction with small-angle neutron scattering measurements, suggest the formation of core-shell colloidal nanoparticles in dilute solution, comprised by an insoluble PAA/PDMAM core surrounded by an anionic P(AA-co-AMPSA) corona. Even if larger clusters are formed in semidilute solution, the size of the insoluble core remains practically stable. Atomic force microscopy performed under ambient conditions reveal that the particles collapse and flatten upon deposition on a substrate, with dimensions close to the ones of the dry hydrophobic core.     

Novel Monte Carlo scheme for systems with short-ranged interactions

We propose a Monte Carlo (MC) sampling algorithm to simulate systems of particles interacting via very short-ranged discontinuous potentials. Such models are often used to describe protein solutions or colloidal suspensions. Most normal MC algorithms fail for such systems because, at low temperatures, they tend to get trapped in local potential-energy local minima due to the short range of the pair potential. To circumvent this problem, we have devised a scheme that changes the construction of trial moves in such a way that the potential-energy difference between initial and final states drops out of the acceptance rule for the Monte Carlo trial moves. This approach allows us to simulate systems with short-ranged attraction under conditions that were unreachable up to now.     

Attraction of iodide ions by the free water surface, revealed by simulations with a polarizable force field based on Drude oscillators

Recent theoretical and experimental studies have shown that polarizable anions, such as iodide and bromide, preferentially accumulate close to the surface of electrolyte solutions. This finding is in sharp contrast to the previously prevailing idea that salts are dielectrically excluded from the free water surface and opens up new avenues for research in specific salt effects. In this work, we have verified the ability of a recently introduced polarizable water model, SWM4-DP, to reproduce this behavior, by simulations of a NaI/water slab, corresponding to a 1.2 M solution. The water and ion polarizabilities are modeled by classical Drude oscillator particles. As revealed by the simulations, a double layer is formed close to the free water surface, with the iodide ions located closer to the interface and the sodium ions at a neighboring, interior layer. Near the surface, all solution species acquire an induced dipole moment, that is perpendicular to the surface and points toward the exterior. The double charge layer causes ordering of water at a subsurface region. Simulations with a simpler system of a single iodide ion in a water slab show that the surface position is stabilized by induced charge interactions; in contrast, the charge-dipole interactions between the iodide permanent charge and the water permanent dipole moment favor the bulk position. Thus, the polarizabilities of ion and water are essential for explaining the increased preference of iodide for the air-water interface, in accordance with other studies.     

The total synthesis of coleophomones B, C, and D

Members of the coleophomone family of natural products all possess several intriguing and challenging architectural features, as well as exhibit unusual biological activity. They, therefore, constitute attractive targets for synthesis. In this Article, we describe the total synthesis of coleophomones B (2), C (3), and D (4). The highly strained and congested 11-membered macrocycle of coleophomones B (2) and C (3) was constructed using an impressive olefin metathesis reaction. Furthermore, both of the requisite geometric isomers of the Delta(16,17) within the macrocycle could be accessed from a common precursor, facilitating a divergence that lent the coleophomone B (2)/C (3) synthesis an unusually high degree of efficiency. The synthesis of coleophomone D (4) confirmed that it exists as a dynamic mixture of isomeric forms with a different aromatic substitution pattern from the other family members.     

Extended UNIQUAC model for thermodynamic modeling of CO2 absorption in aqueous alkanolamine solutions

The extended UNIQUAC model [K. Thomsen, P. Rasmussen, Chem. Eng. Sci. 54 (1999) 1787–1802] was applied to the thermodynamic representation of carbon dioxide absorption in aqueous monoethanolamine (MEA), methyldiethanolamine (MDEA) and varied strength mixtures of the two alkanolamines (MEA–MDEA). For these systems, altogether 13 interaction model parameters are adjusted. Out of these parameters, 11 are temperature dependent.     

On a posterior evaluation of a simple greedy method for set packing

We consider an approach for ex post evaluation of approximate solutions obtained by a well known simple greedy method for set packing. A performance bound is derived that is a function of the highest average reward per item over subsets as well as the number of allocated subsets and ground items. This a posterior bound can enable much revelation of optimality when the solution is near optimal. One of the advantages of the ex post analysis is that it does not require computing the optimal solution to the LP relaxation. The ex post bound will not be guaranteed to reveal substantial levels of optimality for all problem instances but can be a useful tool that is complementary to other traditional methods for ex post evaluation for the set packing problem.     

Incompressible surfaces in handlebodies and isotopies

It is shown that every properly embedded incompressible surface in a handlebody can be constructed by a canonical gluing process. A simple condition is given which asserts that the result of the gluing process is an incompressible surface. A new notion of isotopy is introduced in order to distinguish surfaces belonging to distinct isotopy classes. Several examples (known and new) are constructed.     

Application of Complexity Theory to an Information Processing Model in Science Education

The current work examines the role of working-memory capacity in problem solving in science education. It treats an information-processing model with tools of complexity theory. Nonlinear methods are used to correlate the subjects' achievement scores with working-memory capacity. Data have been taken from the achievement scores in simple organic-synthesis chemical problems. The subjects (N = 319) were in grade twelve (age 17–18). Problems of various Z-demands (that is the number of steps needed to solve the problem) from two to eight were used. Rank-order sequences of the subjects, according to their scores, were generated, and each score was then replaced by the value of subject's working memory capacity measured by the digit backward span test. Then the sequences were mapped onto a one-dimensional random walk model and when treated as dynamic flows were found to possess fractal geometry with characteristics depending on the Z-demand of the problem. The findings were interpreted using concepts from complexity theory, such as correlation exponents, fractal dimensions and entropy. The null hypothesis was tested with surrogate data.     

Valuing Asian options using the finite element method and duality techniques

The main objective of this paper is to develop an adaptive finite element method for computation of the values, and different sensitivity measures, of the Asian option with both fixed and floating strike. The pricing is based on Black–Scholes PDE-model and a method developed by Ve?e? where the resulting PDEs are of parabolic type in one spatial dimension and can be applied to both continuous and discrete Asian options. We propose using an adaptive finite element method which is based on a posteriori estimates of the error in desired quantities, which we derive using duality techniques. The a posteriori error estimates are tested and verified, and are used to calculate optimal meshes for each type of option. The use of adapted meshes gives superior accuracy and performance with less degrees of freedom than using uniform meshes. The suggested adaptive finite element method is stable, gives fast and accurate results, and can be applied to other types of options as well.