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.     

Polymer-supported bisBINOL ligands for the immobilization of multicomponent asymmetric catalysts

[reaction: see text] Polymer-supported bisBINOL ligands were successfully utilized for the immobilization of multicomponent asymmetric catalysts. The polymer-supported Al-Li-bis(binaphthoxide) (ALB) catalyst was more effective than the dendrimer-supported ALB in the Michael reaction of 2-cyclohexen-1-one with dibenzyl malonate affording the adduct in 91% yield with 96% ee. The polymer was also effective for the immobilization of a mu-oxodititanium complex that promoted carbonyl-ene reaction of ethyl glyoxalate with alpha-methyl styrene to provide the adduct with up to 98% ee.     

Near-infrared emissions with widely different widths in two kinds of Er-doped oxide glasses with high refractive indices and low phonon energies

Er³⁺-doped alkali-barium-bismuth-tellurite (LKBBT) and alkali-barium-bismuth-gallate (LKBBG) glasses with high refractive indices and low phonon energies have been designed, fabricated, characterized and compared. Intense 1.53 μm emissions with widely different widths in the two kinds of glasses were observed and recorded under 980 nm diode laser excitation. The full-widths at half-maximum of the 1.53 μm emission bands in LKBBT and LKBBG glasses are 58 and 40 nm, and the lifetimes of them were measured to be 3.21 and 3.97 ms, respectively. The quantum efficiencies for the ⁴I_13/2 level in both glasses are almost 100%. The 1.53 μm broad and narrow emissions with high spontaneous emission probabilities and large emission cross-sections indicate that Er³⁺-doped LKBBT and LKBBG glasses are suitable materials in developing broadband optical amplifier and infrared laser, respectively.     

Preparation of co‐polymethyl(alkoxy)siloxanes by acid‐catalyzed controlled hydrolytic copolycondensation of methyl(trialkoxy)silane and tetraalkoxysilane

Polymethyl(alkoxy)siloxane copolymers, poly(MTES‐co‐TEOS), and poly(MTMS‐co‐TMOS), are prepared by acid‐catalyzed controlled hydrolytic co‐polycondensation of methyl(trialkoxy)silane MeSi(OR)₃ (R = Et (MTES) and Me (MTMS)) and tetra‐alkoxysilane Si(OR)₄ (R = Et (TEOS) and Me (TMOS)), respectively. The products are purified by fractional precipitation to provide polymethyl(alkoxy)siloxane copolymers with molecular weight 1000–10,000 (poly(MTES‐co‐TEOS)) or 1700–100,000 (poly(MTMS‐co‐TMOS)) that are stable to self‐condensation. These polymers are soluble in common organic solvents except for hexane, and form flexible and transparent free‐standing films with a tensile strength of 4.0–10.0 MPa. The structure of the polymethyl(alkoxy)siloxane copolymers is thought to be a random or a block co‐polymer. They are found to provide coating films with an adhesive strength up to 10, a refractive index of 1.36–1.40, and a dielectric constant of 3.5–3.6. The products also show better weathering stability than polyethoxysiloxane due to the hydrolytic polycondensation of TEOS. Field emission‐scanning electron micrography analysis reveals that coating films are composed of a micro‐phase separated structure. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4732–4741     

Effect of the chemical species of arsenic on sensitivity in graphite furnace atomic absorption spectrometry.

The sensitivity of graphite furnace atomic absorption spectrometry (GFAAS) to arsenobetaine (AB) was 1.3-times higher than to inorganic As. In order to understand the mechanism underlying this observation, the atomization processes for both chemical species were investigated in terms of the enthalpy change (DeltaH) during the atomization process in GFAAS. The enthalpy change of AB was slightly lower than that of inorganic As, which suggested that AB was atomized more efficiently than was inorganic As. Moreover, it was observed that some co-existing organic materials enhanced the analytical sensitivity of inorganic As. The sensitivity difference between inorganic As and AB depended upon the mechanisms of their atomization processes.     

Thermodynamic properties of ethanol solution of chiral camphors and its derivatives

Enthalpies of mixing and the densities of ethanol solution of R- and S-enantiomers of camphor, 10-camphorsulfonamide, 10-camphorsulfonic acid, camphorquinone, and 10-camphorsulfonyl chloride have been measured for a wide range of mole fractions of heterochiral components at 298.15 K. Enthalpies of mixing were exothermic for all concentrations and heterochiral solutions were more stable than each of the homochiral solutions. Enthalpic stabilization of mixing of heterochiral solutions was increased with a decreasing concentration of all the camphor derivatives measured. The sequence of enthalpic stabilization on mixing was 10-camphorsulfonyl chloride, 10-camphorsulfonic acid, 10-camphorsulfonamide, camphor, and camphorquinone. Apparent molar volumes were determined and excess volumes of mixing of heterochiral solutions were small and negative. Enthalpic stabilizations were found to be dependent on dipole–dipole interaction between solutes and solvents.     

Investigation of individual micrometer-size Kosa particle with on-site combination of electron microscope and synchrotron X-ray microscope.

The Kosa (yellow sand) aerosol affects the global environment as well as human health because it migrates from the interior of China to other areas, absorbing various atmospheric elements. Investigation into individual Kosa aerosol particles, which are submicroscopic to several tens of micrometers in diameter, is required to resolving the issue. We installed a scanning electron microscope (SEM) equipped with an energy dispersive X-ray spectrometer (EDX) on a synchrotron radiation (SR) beam line and introduced the SR beam into the SEM chamber for combinatorial application of SEM-EDX and SR X-ray fluorescence (SR-XRF) spectrometry to individual particles. It should be noted that detailed topographic observation by SEM and sensitive elemental analysis by SR-XRF, both crucial for individual particle measurement but which previously had to be carried out separately, were jointly performed inside the SEM chamber in this setup. Here, we show that SR-XRF results, in conjunction with SEM images, contributed toward resolving individual particle dispositions. Atmospheric sulfur primarily adheres to calcium in the aerosol particles and the particle surface roughens as a consequence of the chemical reaction between the two elements.