Mechanism of amine catalyzed isomerization of itaconic anhydride to citraconic anhydride: Citraconamic acid formation

The amine catalyzed isomerization of itaconic to citraconic anhydride has been investigated. Studies show that the rate of isomerization is dependent on the base strength and solvent media. Triethylamine causes complete isomerization within 5 min at room temperature in acetone or chloroform solvent, whereas aromatic tertiary amines such as pyridine and N,N-dimethylaniline require time perods as long as 23h at room temperature for almost complete isomerization. In the presence of aniline no isomerization occures even under acetone reflux conditions over a 24 h period. For the preparation of citraconamic acids from itaconic anhydrides and aliphatic diamines nuclear magnetic resonance and infrared spectroscopic evidence is presented to support the reaction path of initial isomerization of itaconic anhydride to citraconic anhydride followed by amine attack on the anhydride to form the corresponding cis-citraconamic acids. The mechanism of isomerization of itaconic to citraconic acids is proposed.     

From Stochastics to Complexity in Models of Economic Instability

Sixty years ago, the leading lights of the economics profession chose to model economic fluctuations as if they were caused by stochastic disturbances to an underlying stable, heavily damped system, in the mistaken belief that a mathematically unstable system does not fluctuate; it just breaks down. A perceptive minority instead concluded that the fundamental relations in economics must be nonlinear. It is shown that a single sector model with nonlinear behavior by workers, capitalists and the government generates a chaotic explanation for the most extreme of economic fluctuations, a Great Depression. A multi-sectoral model of a stylized economy confirms the judgment that economics is fundamentally a nonlinear discipline, by establishing that the input-output nature of production generates substantive nonlinearities, even when linear behavioral functions are assumed.     

Effect of Motif‐Programmed Artificial Proteins on the Calcium Uptake in a Synthetic Hydrogel

Motif‐programmed artificial proteins with mineralization‐related activity were covalently immobilized onto the surface of a hydrogel, poly(2‐hydroxyethyl methacrylate) (PHEMA). We investigated the influence of assaying conditions upon the ability of three selected proteins (PS64, PS382 and PS458) to modulate calcification in vitro. A long‐term assay measuring the real amount of calcium phosphate phase in the protein‐modified PHEMA showed that all proteins enhanced the uptake of calcium by the hydrogel. For PS382 and PS458, this is a behaviour opposite to that displayed when the same proteins were tested in a free state by a rapid solution assay. Such difference may be attributed to a restricted mobility of the proteins due to immobilization.

     

Facile assembly of a Cu9 amido complex: a new tripodal ligand design that promotes transition metal cluster formation

A tripodal amido ligand with a central non-chelating phosphorus donor allows for the facile assembly of a pentane soluble organometallic copper cluster with a central copper atom surrounded by a nonplanar chain of eight copper atoms and two terminal amido-copper bonds.     

Growth of nanosized MnAs/Si(111) magnetoelectronic heterostructures and their magnetooptical study

Thin (6–12 nm) epitaxial MnAs films were MBE-grown on Si(111) substrates under different technological conditions. The films feature essentially different surface morphology. This manifests itself in the formation, on the silicon surface, of hexagonal-shaped crystallites, whose dimensions vary depending on the growth conditions. The volume and surface magnetic properties of the films were studied using the magnetooptical Kerr effect and optical second harmonic generation. The Kerr effect was found to scale linearly with the effective thickness of the magnetic layer. The thickness of the magnetically disordered transition layer formed near the interface with the substrate was estimated. The surface and volume hysteresis properties of the films were found to be different. A contribution to the second-harmonic intensity was observed which is an odd function of magnetization. This effect originates from the interference of the magnetic and nonmagnetic contributions to the nonlinear polarization.     

The hydrodechlorination of chloroaromatic and unsaturated chloroaliphatic compounds using a nickel boride reagent

A nickel boride reagent, prepared in situ by the reaction of nickel chloride with sodium borohydride, has been used to hydrodechlorinate and hydrogenate chloroaromatic compounds. The same reagent can also dechlorinate chloro-olefinic compounds but chloroalkanes do not react. The reactions can be sustained by addition of hydrogen gas and the ratio of the aromatic to aliphatic hydrocarbons produced can be varied by addition of sodium hydroxide to the reaction mixture and by the duration of the reaction. The reactivity of polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), chlorobenzene and tetrachloroethylene have been studied. Capillary gas chromatography was used to follow the course of reactions and gas chromatography-mass spectroscopy (GC–MS) was used for product identification.