Comparison of yellow poplar pretreatment between NREL digester and sunds hydrolyzer

Single-stage cocurrent dilute acid pretreatments were carried out on yellow poplar (Liriodendron tulipifera) sawdust using an as-installed and short residence time modified pilot-scale Sunds hydrolyzer and a 4-L bench-scale NREL digester (steam explosion reactor). Pretreatment conditions for the Sunds hydrolyzer, installed in the NREL process development unit (PDU), which operates at 1 t/d (bone-dry t) feed rate, spanned the temperature range of 160 – 210°C, 0.1 – 1.0% (w/w) sulfuric acid, and 4-10-min residence times. The batch pretreatments of yellow poplar sawdust in the bench-scale digester were carried out at 210 and 230°C, 0.26% (w/w) sulfuric acid, and 1-, 3-, and 4-min residence times. The dilute acid prehydrolysis solubilized more than 90% of the hemicellulose, and increased the enzymatic digestibility of the cellulose that remained in the solids. Compositional analysis of the pretreated solids and liquors and mass balance data show that the two pretreatment devices had similar pretreatment performance.     

High-resolution electron microscopy of montmorillonite and montmorillonite/epoxy nanocomposites

With the use of high-resolution transmission electron microscopy the structure and morphology of montmorillonite (MMT), a material of current interest for use in polymer nanocomposites, was characterized. Using both imaging theory and experiment, the procedures needed to generate lattice images from MMT were established. These procedures involve careful control of the microscope's objective lens defocus to maximize contrast from features of a certain size, as well as limiting the total dose of electrons received by the sample. Direct images of the MMT lattice were obtained from neat Na+ MMT, organically modified MMT, and organically modified MMT/epoxy nanocomposites. The degree of crystallinity and turbostratic disorder were characterized using electron diffraction and high-resolution electron microscopy (HREM). Also, the extent of the MMT sheets to bend when processed into an epoxy matrix was directly visualized. A minimum radius of curvature tolerable for a single MMT sheet during bending deformation was estimated to be 15 nm, and from this value a critical failure strain of 0.033 was calculated. HREM can be used to improve the understanding of the structure of polymer nanocomposites at the nanometer-length scale.     

Efficient trapping of HNO by deoxymyoglobin

Nitrosyl hydride, HNO, also commonly termed nitroxyl, is a transient species that has been implicated in the biological activity of nitric oxide, NO. Herein, we report the first generation of a stable HNO-metal complex by direct trapping of free HNO. Deoxymyoglobin (Mb-Fe(II)) rapidly reacts with HNO produced from the decomposition of methylsulfonylhydroxylamine (MSHA) or Angeli's salt (AS) in aqueous solutions from pH 7 to pH 10, forming an adduct, Mb-HNO. The unique 1H NMR signal of the Fe-bound HNO at 14.8 ppm allows definitive proof of its formation. The generation of Mb-HNO and quantification of various myoglobin byproducts were accomplished by correlation of 1H NMR, UV-vis, and EPR spectroscopies. Typically, the maximum Mb-HNO yield obtained is 60-80%; competitive side reactions with byproducts as well as the further reactivity of the Mb-HNO decrease the overall yield. At pH 10, the observed rate of Mb-HNO generation by trapping HNO from MSHA is close to that for MSHA decomposition; kinetic simulations give a lower limit to the bimolecular rate of trapping as 1.4 x 10(4) M(-1) s(-1). The binding of HNO to deoxymyoglobin is rapid and essentially irreversible, which suggests that the biological activity of nitroxyl may be mediated by its reactivity with ferrous heme proteins such as myoglobin and hemoglobin.     

Ferromagnetic spin alignment in head-to-tail coupled oligo(1, 4-phenyleneethynylene)s and Oligo(1,4-phenylenevinylene)s bearing pendant p-phenylenediamine radical cations

The intramolecular and long-range ferromagnetic coupling between p-phenylenediamine radical cations in head-to-tail coupled oligo(1, 4-phenyleneethynylene)s and oligo(1,4-phenylenvinylene)s between neighbors and next-nearest neighbors is described. UV/vis/near-IR experiments show that the radical cations are localized in the pendant p-phenylenediamine units of the conjugated oligomers. The ESR spectra of these oligo(1,4-phenyleneethynylene) and oligo(1, 4-phenylenvinylene) di(radical cation)s are consistent with those of a triplet state. A linear behavior is observed for the doubly integrated ESR intensity of the DeltaM(s) = +/-1 and DeltaM(s) = +/-2 signals with the inverse temperature (I approximately 1/T), consistent with Curie's law. This behavior indicates a triplet ground-state diradical with a large triplet-singlet energy gap or possibly a degeneracy of singlet and triplet states.