Some novel halogenated phenazine derivatives

3-Amino-10-aryl-2-arylimino-2,10-dihydrophenazines 1 undergo iodination in the 4-position of the phenazine nucleus yielding compounds which are identical with those obtained by oxidation of appropriate N-aryl-o-phenylenediamines with sodium iodate in the presence of acid. Bromination also takes place in this position but a second bromine atom enters the para-position of the arylimino moiety. The isomeric 10-aryl-3-aryl-amino-2,10-dihydro-2-iminophenazines 2 yield unstable iodo-derivatives but undergo bromination in the 1-and 4-position of the phenazine nucléus and in the ortho- and para-positions of the arylamino substituent. Preliminary chlorination experiments indicate that the substitution pattern is analogous to that established for the brominated products. The removal of bromine and iodine from the phenazine ring by reaction with a primary or secondary amine and their replacement by hydrogen rather than by the amine residue is also recorded.     

Rheological properties of nanopowder alumina coated with adsorbed fatty acids

The rheological properties of a nanosized alumina powder coated with fatty acid steric stabilizers of varying chain length were investigated. The storage and loss moduli of the complex modulus were measured to characterize the behavior of the flocculated systems. As chain length increased, there was a transition from an elastic response to fluid behavior. However, the fluid system developed elastic characteristics at relatively low volume fractions of 22%. The length of the steric barrier required to produce the fluid dispersion was estimated to be approximately 2 nm and correlates with attractive interactions on the order of the system thermal energy. Moreover, in the flocculated systems, the storage modulus was found to be higher than reported previously in the literature. These higher values were related to the additional attractive forces due to van der Waals attractions between the hydrocarbon tails of the adsorbed fatty acid layers.     

In situ tissue pathology from spatially encoded mass spectrometry classifiers visualized in real time through augmented reality

Integration between a hand-held mass spectrometry desorption probe based on picosecond infrared laser technology (PIRL-MS) and an optical surgical tracking system demonstrates in situ tissue pathology from point-sampled mass spectrometry data. Spatially encoded pathology classifications are displayed at the site of laser sampling as color-coded pixels in an augmented reality video feed of the surgical field of view. This is enabled by two-way communication between surgical navigation and mass spectrometry data analysis platforms through a custom-built interface. Performance of the system was evaluated using murine models of human cancers sampled in situ in the presence of body fluids with a technical pixel error of 1.0 ± 0.2 mm, suggesting a 84% or 92% (excluding one outlier) cancer type classification rate across different molecular models that distinguish cell-lines of each class of breast, brain, head and neck murine models. Further, through end-point immunohistochemical staining for DNA damage, cell death and neuronal viability, spatially encoded PIRL-MS sampling is shown to produce classifiable mass spectral data from living murine brain tissue, with levels of neuronal damage that are comparable to those induced by a surgical scalpel. This highlights the potential of spatially encoded PIRL-MS analysis for in vivo use during neurosurgical applications of cancer type determination or point-sampling in vivo tissue during tumor bed examination to assess cancer removal. The interface developed herein for the analysis and the display of spatially encoded PIRL-MS data can be adapted to other hand-held mass spectrometry analysis probes currently available.

Integration between a hand-held mass spectrometry desorption probe based on picosecond infrared laser technology (PIRL-MS) and an optical surgical tracking system demonstrates in situ tissue pathology from point-sampled mass spectrometry data.     

Polymerization of MMA by oscillating zirconocene catalysts, diastereomeric zirconocene mixtures, and diastereospecific metallocene pairs

Characteristics of methyl methacrylate (MMA) polymerization using oscillating zirconocene catalysts, (2-Ph-Ind)₂ZrX₂ (X = Cl, 1; X = Me, 2), mixtures of rac- and meso-zirconocene diastereomers, (SBI)ZrMe₂ [3, SBI = Me₂Si(Ind)₂] and (EBI)ZrMe₂ [4, EBI = C₂H₄(Ind)₂], as well as diastereospecific metallocene pairs, rac-4/Cp₂ZrMe₂ (5) and rac-4/CGCTiMe₂ [6, CGC = Me₂Si(Me₄C₅)(t-BuN)], are reported. MMA polymerization using the chloride catalyst precursor 1 activated with a large excess of the modified methyl aluminoxane is sluggish, uncontrolled, and produces atactic PMMA. On the other hand, the polymerization by a 2/1 ratio of 2/B(C₆F₅)₃ or 2/Ph₃CB(C₆F₅)₄ is controlled and produces syndiotactic PMMA. Mixtures of diastereomeric ansa-zirconocenes 3 or 4 containing various rac/meso ratios, when activated with B(C₆F₅)₃, yield bimodal PMMA; this behavior is attributed to the meso-diastereomer that, in its pure form, affords bimodal, syndio-rich atactic PMMA. For MMA polymerization using diastereospecific metallocene pairs, rac-4/5 and rac-4/6, the isospecific catalyst site dominates the polymerization events under the conditions employed in this study, and the aspecific and syndiospecific sites are largely nonproductive, thereby forming only highly isotactic PMMA.     

Generalizations of a Theorem of Datko and Pazy

This note gives necessary and sufficient conditions for exponential stability of semigroups of linear operators in Banach spaces. Generalizations of a well-known result due to Datko, Pazy and Neerven are obtained for the case of semigroups of operators that are not strongly continuous.     

Organotransition-Metal-Mediated Borane-Cage Expansion

Attempts were made to synthesize dinuclear Group 6 metal complexes of the arachno -octahydrotriborate anion. Specifically, the dimer [CpW(CO) 3 ] 2 (Cp = m 5 -C 5 H 5 ) was employed as the metal reagent. However, the formation of dinuclear metallaborane complexes did not ensue. Rather, clean, rapid, systematic borane-cage expansion was observed. The [B 3 H 8 ] m cluster was quantitatively converted to B 5 H 9 ,[B 9 H 14 ] m , or [B 11 H 14 ] m , or both, depending on reaction conditions. Refluxing a 1:1 mixture of [B 3 H 8 ] m and [CpW(CO) 3 ] 2 in toluene or dioxane lead to the rapid, quantitative conversion of [B 3 H 8 ] m to B 5 H 9 . However, refluxing a 2:1 mixture of [B 3 H 8 ] m and [CpW(CO) 3 ] 2 in the same solvents yielded [B 9 H 14 ] m and [B 11 H 14 ] m as the primary products; when glyme was the solvent, only [B 9 H 14 ] m was observed, even after prolonged heating.