Obtaining Kinetic Parameters by Modulated Thermogravimetry

A new technique, called modulated thermogravimetry, is introduced as a tool for obtaining continuous kinetic information for decomposition and volatilization reactions. The approach makes use of an oscillatory temperature program to obtain kinetic parameters during a mass loss. MTGA™ may be used under quasi-isothermal conditions to observe a single mass loss or may be combined with linear heating rate or Hi-Res™ controlled rate thermogravimetry to scan from one mass loss region to another. Results obtained are in agreement with those obtained by other kinetic methods. This revised version was published online in July 2006 with corrections to the Cover Date.     

Hydroxylamido(1-)-O,N-Komplexe des Molybdäns(VI) mit terminalen Oxo-, Sulfido- und Selenido-Liganden Die Kristallstrukturen von [MoO2(C5H10NO)2] und von [MoS2(C5H10NO)2]

Hydroxylamido(1-)-O,N Complexes of Molybdenum(VI) Containing Terminal Oxo, Sulfido, and Selenido Ligands. Crystal Structures of [MoO₂(C₅H₁₀NO)₂] and of [MoS₂(C₅H₁₀NO)₂] Molecular complexes of cis-dioxo-bis(hydroxylamido(1-)-O,N)molybdenum(VI) containing O,N-coordinated, N,N-substituted hydroxylamine ligands react with H₂S in toluene substituting one or both terminal oxo groups yielding cis-oxosulfido- and cis-disulfido-bis (hydroxylamido(1-)-O,N) molybdenum complexes, respectively. With H₂Se the corresponding cis-oxoselenido complexes are formed. The crystal structures of the two title compounds containing piperidine-N-oxide as ligands are described: The cis-disulfido complex crystallizes tetragonal in the space group D—I 4 2 m with four formula units per unit cell; the corresponding cis-dioxo complex crystallizes orthorhombic (D—P 2₁2₁2₁; Z = 4). The ¹H—nmr spectra and the UV-visible absorption spectra are reported.     

Radical cyclization cascade involving ynamides: an original access to nitrogen-containing heterocycles

A radical cascade involving a 5-exo-dig cyclization followed by a 6-endo-trig radical trapping transforms ynamides into heterogeneous polycyclic compounds in good yields. This leads interestingly to the formation of isoindols, isoindolinones, and pyridoisoindolones. [reaction: see text]     

Transient behavior of a nonequilibrium plasma formed by merged beams

A low density, low temperature plasma formed by two merged beams of electrons and ions at near zero relative velocity is studied by solving a set of time-dependent rate equations. In particular, we investigate the role played by the radiative recombination (RR) and three-body recombination (TBR) on the population of excited states during the initial stage of plasma rearrangement and relaxation. It is found in the case of hydrogenic plasmas that low-lying states are filled predominantly by RR, while high Rydberg states are populated mainly by TBR. As the plasma further relaxes, the collisional excitation and de-excitation, and radiative decays become important, filling the median excited states. The dependence of the TBR and RR rates on ionic chargeZ is discussed to extend the result to plasmas of highZ ions.     

Monolayers as models for supported catalysts: zirconium phosphonate films containing manganese(III) porphyrins

Organized monolayer films of a manganese tetraphenylporphyrin have been prepared and used as supported oxidation catalysts. Manganese 5,10,15,20-tetrakis(tetrafluorophenyl-4'-octadecyloxyphosphonic acid) porphyrin (1) has been immobilized as a monolayer film by a combination of Langmuir-Blodgett (LB) and self-assembled monolayer techniques that use zirconium phosphonate linkages to bind the molecule to the surface. Analysis by FTIR, XPS, UV-vis and polarized optical spectroscopy show that the films consist of noninteracting molecules effectively anchored and oriented nearly parallel to the surface. The monolayer films are stable to the solvent and temperature conditions needed to explore organic oxidations. The activity of films of 1 toward the epoxidation of cyclooctene using iodosylbenzene as the oxidant was compared to that of Manganese 5,10,15,20-tetrakis(pentafluorophenyl) porphyrin (2) and 1 under equivalent homogeneous conditions. The immobilized porphyrin 1 shows an enhanced activity relative to either homogeneous reaction. The main difference between 1 and 2 is the four alkyl phosphonate arms in 1 designed to incorporate the porphyrin within the films. The increased activity of immobilized 1 is a combination of the porphyrin structure, which prohibits the formation of mu-oxo dimers even in solution, and a change in conformation when anchored to the surface. The study demonstrates that careful monolayer studies can provide useful models for the design and study of supported molecular catalyst systems.     

Rapid biomass analysis

New, rapid, and inexpensive methods that monitor the chemical composition of corn stover and corn stover-derived samples are a key element to enabling the commercialization of processes that convert stover to fuels and chemicals. These new techniques combine near infrared (NIR) spectroscopy and projection to latent structures (PLS) multivariate analysis to allow the compositional analysis of hundreds of samples in 1 d at a cost of about $10 each. The new NIR/PLS rapid analysis methods can also be used to support a variety of research projects that would have been too costly to pursue by traditional methods.