NMR analysis of lignins in CAD-deficient plants. Part 1. Incorporation of hydroxycinnamaldehydes and hydroxybenzaldehydes into lignins

Peroxidase/H2O2-mediated radical coupling of 4-hydroxycinnamaldehydes produces 8-O-4-, 8-5-, and 8-8-coupled dehydrodimers as has been documented earlier, as well as the 5-5-coupled dehydrodimer. The 8-5-dehydrodimer is however produced kinetically in its cyclic phenylcoumaran form at neutral pH. Synthetic polymers produced from mixtures of hydroxycinnamaldehydes and normal monolignols provide the next level of complexity. Spectral data from dimers, oligomers, and synthetic polymers have allowed a more substantive assignment of aldehyde components in lignins isolated from a CAD-deficient pine mutant and an antisense-CAD-downregulated transgenic tobacco. CAD-deficient pine lignin shows enhanced levels of the typical benzaldehyde and cinnamaldehyde end-groups, along with evidence for two types of 8-O-4-coupled coniferaldehyde units. The CAD-downregulated tobacco also has higher levels of hydroxycinnamaldehyde and hydroxybenzaldehyde (mainly syringaldehyde) incorporation, but the analogous two types of 8-O-4-coupled products are the dominant features. 8-8-Coupled units are also clearly evident. There is clear evidence for coupling of hydroxycinnamaldehydes to each other and then incorporation into the lignin, as well as for the incorporation of hydroxycinnamaldehyde monomers into the growing lignin polymer. Coniferaldehyde and sinapaldehyde (as well as vanillin and syringaldehyde) co-polymerize with the traditional monolignols into lignins and do so at enhanced levels when CAD-deficiency has an impact on the normal monolignol production. The implication is that, particularly in angiosperms, the aldehydes behave like the traditional monolignols and should probably be regarded as authentic lignin monomers in normal and CAD-deficient plants.     

Hydrofluoroarylation of alkynes with fluoroarenes

A combination of Ni(cod)(2) and PCyp(3) is found to be an effective catalyst for chemoselective activation of the C-H bond of fluoroarenes over C-F bonds followed by insertion of alkynes to allow direct alkenylation of the electron-deficient arenes. The characteristics of the reactions are: a C-H bond ortho to a fluorine substituent is selectively activated; the reactivity of fluorobenzenes is roughly proportional to the number of fluorine atoms. The reaction conditions tolerate a broad range of both alkynes and fluoroarenes containing both electron-withdrawing and -donating groups, thus allowing efficient synthesis of a variety of substituted ethenes containing a fluoroaryl motif in high regio- and stereoselective manners. Mechanistic studies including both labeling experiments and stoichiometric reactions reveal that oxidative addition of C-H bonds in fluoroarenes to nickel(0) is kinetically highly facile whereas that of C-F bonds is thermodynamically favoured.     

Role of Ti 3d carriers in mediating the ferromagnetism of Co∶TiO2 anatase thin films

We study the surface and bulk electronic structure of the room-temperature ferromagnet Co∶TiO(2) anatase films using soft- and hard-x-ray photoemission spectroscopy with probe sensitivities of ～1 and ～10 nm, respectively. We obtain direct evidence of metallic Ti(3+) states in the bulk, which get suppressed to give a surface semiconductor, thus indicating the difference in electronic structure between surface and bulk. X-ray absorption and resonant photoemission spectroscopy reveal Ti(3+) electrons at the Fermi level (E(F)) and high-spin Co(2+) electrons occurring away from E(F). The results show the importance of the charge neutrality condition: Co(2+)+V(O)(2-)+2Ti(4+)?Co(2+)+2Ti(3+) (V(O) is oxygen vacancy), which gives rise to the elusive Ti 3d carriers mediating ferromagnetism via the Co 3d-O 2p-Ti 3d exchange interaction pathway of the occupied orbitals.     

Fabrication of marker area to align TEM tomographic tilt series of rod-shaped specimens

In this study, we present a new method for placing markers for alignment of tomographic tilt-series of rod-shaped specimen before 3D reconstructions. By this method, markers (gold nanoparticles) were placed only on the carbon layer (referred to as the "marker area") deposited for protecting the specimen surface against ion beam irradiation; this placement was achieved by vacuum evaporation of gold with the help of a mask fabricated adjacent to the specimen. Experimental results showed that the use of the proposed method facilitates the identification of the markers in the alignment process, because the image of the marker area consists of simple high-contrast images of the gold nanoparticles on the carbon layer. The performance of the proposed method was successfully verified experimentally by applying it to a high-density Au/SiO? nanocomposite material as a test specimen.     

Polarity determination of wurtzite-type crystals using hard x-ray photoelectron diffraction

The surface structure of a single-crystal ZnO wafer was studied by angle-resolved x-ray photoelectron spectroscopy (ARXPS) using synchrotron radiation. As a result, well-defined x-ray photoelectron diffraction (XPD) patterns were obtained for the (0001) and (000$\overline{1}$) polar surfaces using the photoemission from the Zn 2p_3/2 and O 1s core levels. The XPD patterns were indexed assuming forward scattering of photoelectrons by neighboring ions. Further, the XPD patterns for the (0001) and (000$\overline{1}$) surfaces were different from each other, indicating the possibility for using the XPD technique for polarity determination.