Catalytic enantioselective Diels-Alder reactions using titanium complexes of cis-N-sulfonyl-2-amino-1-indanols

A titanium complex derived from (1R, 2S)-N-(2,4,6-trimethylbenzenesulfonyl)-2-amino-1-indanol catalyzes the Diels-Alder reaction of 2-bromoacrolein and cyclopentadiene with 96.5:3.5 enantioselectivity. A new and efficient synthesis of 2-amino-1-indanol (6) contributes to the potential of this methodology.     

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.     

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.     

A rotating disc electrode study of oxygen reduction at platinised nickel and cobalt coatings

Platinized nickel and cobalt coatings, Pt(Ni) and Pt(Co), have been prepared on glassy carbon, GC, rotating disc electrode substrates by a two-step room temperature procedure that involved the electrodeposition of nickel and cobalt layers and their spontaneous partial replacement by platinum (“transmetalation”) when immersed into a chloroplatinic acid solution. By tuning the quantity of initially deposited nickel and cobalt, Pt(Ni) and Pt(Co) bimetallic coatings having a 26% atom Ni and 30% atom Co composition have been prepared. For both materials typical Pt surface electrochemistry was recorded during fast voltammetry in deaerated acid, pointing to the existence of a continuous Pt skin over a Pt–Ni and Pt–Co core. Oxygen reduction at the Pt(Ni)/GC and Pt(Co)/GC electrodes was studied by means of steady-state voltammetry at a rotating disc electrode and the construction of Tafel plots from corresponding voltammetric data. It was found that, when the initial potential of the voltammetric sweep allowed the formation of a complete Pt oxide monolayer, then oxygen reduction was hindered for low overpotentials at Pt(Ni) and Pt(Co), compared to pure bulk Pt. On the other hand, when the initial potential was less positive (thus leading to the formation of a fraction of surface oxide monolayer) the presence of Ni and Co enhanced the kinetics of oxygen reduction. The former behaviour is attributed to a decrease in oxide reduction ability of Pt in the presence of Ni and Co, while the latter to an increase in dissociative oxygen chemisorption due to Ni and Co.     

Photooxygenation of Furylalkylamines: Easy Access to Pyrrolizidine and Indolizidine Scaffolds

A highly adaptable method targeting the ubiquitous and very important pyrrolizidine and indolizidine scaffolds is presented. The general synthetic utility of the method is underscored by its application to the rapid and easy synthesis of five natural products starting from readily accessible alkylfuran precursors. These unprotected primary furylalkylamines are subjected to photooxygenation conditions, which initiate a complex cascade reaction sequence concluding with the production of high value motifs. This sequence can be tailored to need by varying the choice of both photosensitizer and base additive.