Protection Group Effects During α,γ‐Diol Lignin Stabilization Promote High‐Selectivity Monomer Production

Protection groups were introduced during biomass pretreatment to stabilize lignin's α,γ‐diol group during its extraction and prevent its condensation. Acetaldehyde and propionaldehyde stabilized the α,γ‐diol without any aromatic ring alkylation, which significantly increased final product selectivity. The subsequent hydrogenolysis catalyzed by Pd/C generated lignin monomers at near‐theoretical yields based on Klason lignin (48 % from birch, 20 % from spruce, 70 % from high‐syringyl transgenic poplar), and with high selectivity to a single 4‐n‐propanolsyringol product (80 %) in the case of the poplar. Unlike direct hydrogenation of native wood, hydrogenolysis of protected lignin with Ni/C also led to high selectivity to this single product (78 %), paving the way to high‐selectivity lignin upgrading with base metal catalysts. The use of extracted lignin facilitated valorization of polysaccharides, leading to high yields of all three major biomass polymers to a single major product.     

The application of optical coherence tomography to problems in polymer matrix composites

The Composites Group at the National Institute of Standards and Technology has found optical coherence tomography (OCT) to be a powerful tool for non-destructive characterization of polymer matrix composites. Composites often exhibit superior properties to traditional materials such as wood and metal. However, the barrier to their widespread infiltration into consumer markets is cost. Composites can be made more cost competitive by improved composite design, process optimization, and quality control. OCT provides a means of evaluating the three aforementioned areas. OCT is a very versatile technique that can be applied to a variety of problems in polymer composites such as: microstructure determination for permeability and mechanical property prediction, void, dry spot, and defect detection, and damage evaluation. Briefly, OCT uses a low coherence source such as a superluminescent diode laser with a fiber optic based Michelson interferometer. In this configuration, the composite is the fixed arm of the interferometer. Reflections from heterogeneities within the sample are mapped as a function of thickness for any one position. Volume information is generated by translating the sample on a motorized stage. Information about the location and size of a feature within the composite is obtained. In this work, the power of OCT for imaging composite microstructure and damage is presented. An example of permeability prediction using the composite microstructure imaged from OCT is demonstrated. The effect of image processing on the value of permeability is discussed. Using the same sample, OCT imaging of composite impact damage is compared to more traditional techniques, X-ray computed tomography and confocal microscopy.     

Effects of ultraviolet radiation, temperature and moisture on aging of coatings and sealants - A chemical and rheological study

Photodegradation of polymeric materials leads to significant modifications in both chemical properties and mechanical-rheological behaviors over time. Thus, it is important to characterize both properties to gain a better understanding of the durability of the materials. In this contribution, the chemorheological tools based upon Fourier transform infrared (FTIR) spectroscopy and dynamic mechanical thermal analysis (DMTA) were used to study the effects of temperature and moisture on photodegradation of a model sealant/coating system based upon a styrene-butadiene-styrene triblock copolymer. Specimens were exposed coincidentally to ultraviolet-visible radiation between 295 nm and 600 nm, and one of four different combinations of temperature and relative humidity (RH), i.e., (a) 30 °C and <1% RH, (b) 30 °C and 80% RH, (c) 55 °C and <1% RH, and (d) 55 °C and 80% RH. The rate of photodegradation was examined in terms of formation of oxidation species and evolution of mechanical-rheological data, including glass transition temperatures, moduli, and the number of effective crosslinked butadiene chains per unit volume per exposure time. Environmental exposure resulted in similar degradation modes for all four environments but the rate of photodegradation was found to depend strongly on temperature. Conversely, the role of moisture on photodegradation was not significant. The study shows that chemical modification can be directly related to the corresponding rheological modifications. In addition, the relative stability of styrene and butadiene against photodegradation as a function of temperature and moisture was compared.     

17O-NMR. of Enriched Acetic Acid,Glycine, Glutamic Acid and Aspartic Acid in Aqueous Solution. II. Relaxation Studies

The ¹⁷O-NMR. line widths of the enriched amino acids glycine, aspartic acid, glutamic acid and, for comparative reasons, acetic acid were measured in aqueous solution between pH 1 and 14. The ¹⁷O-NMR. line-width maxima of glycine at pH≈?11 and acetic acid at pH≈?5 are shown to arise from traces of paramagnetic metal ions. The increase in line width in case of glycine on going from the zwitterion 10 the cataion is attributed to an increase in the ¹⁷O-quadrupole coupling constant. No evidence for an intermolecular or intramolecular association of glycine in the zwitterionic form was found. When the paramagnetic impurities were eliminated by addition of EDTA, both the longitudinal and transverse relaxation times remained unchanged on deprotonation of the amino group. The overlapping of the α, β- and α, γ-carboxyl resonances of aspartic and glutamic acid, respectively, created difficulties for their line-width analysis.     

Suppression of nitric oxide production in mouse macrophages by soybean flavonoids accumulated in response to nitroprusside and fungal elicitation

Background

The anti-inflammatory properties of some flavonoids have been attributed to their ability to inhibit the production of NO by activated macrophages. Soybean cotyledons accumulate certain flavonoids following elicitation with an extract of the fungal pathogen Diaporthe phaseolorum f. sp. meridionalis (Dpm). Sodium nitroprusside (SNP), a nitric oxide donor, can substitute for Dpm in inducing flavonoid production. In this study, we investigated the effect of flavonoid-containing diffusates obtained from Dpm- and SNP-elicited soybean cotyledons on NO production by lipopolysaccharide (LPS)- and LPS plus interferon-γ (IFNγ)-activated murine macrophages.

Results

Significant inhibition of NO production, measured as nitrite formation, was observed when macrophages were activated in the presence of soybean diffusates from Dpm- or SNP-elicited cotyledons. This inhibition was dependent on the duration of exposure to the elicitor. Daidzein, genistein, luteolin and apigenin, the main flavonoids present in diffusates of elicited cotyledons, suppressed the NO production by LPS + IFNγ activated macrophages in a concentration-dependent manner, with IC₅₀ values of 81.4 μM, 34.5 μM, 38.6 μM and 10.4 μM respectively. For macrophages activated with LPS alone, the IC₅₀ values were 40.0 μM, 16.6 μM, 10.4 μM and 2.8 μM, respectively. Western blot analysis showed that iNOS expression was not affected by daidzein, was reduced by genistein, and was abolished by apigenin, luteolin and Dpm- and SNP-soybean diffusates at concentrations that significantly inhibited NO production by activated macrophages.

Conclusions

These results suggest that the suppressive effect of flavonoids on iNOS expression could account for the potent inhibitory effect of Dpm- and SNP-diffusates on NO production by activated macrophages. Since the physiological concentration of flavonoids in plants is normally low, the treatment of soybean tissues with SNP may provide a simple method for substantially increasing the concentration of metabolites that are beneficial for the treatment of chronic inflammatory diseases associated with NO production.

     

17O-NMR. of Enriched Acetic Acid,Glycine, Glutamic Acid and Aspartic Acid in Aqueous Solution. I. Chemical Shift Studies

The ¹⁷O-NMR. chemical shifts of the enriched amino acids glycine, aspartic acid and glutamic acid were measured in aqueous solution as a function of pH. High magnetic fields are necessary to resolve the α, β- and α, γ-carboxyl resonances of aspartic acid and glutamic acid, respectively. The chemical shifts of acetic acid were measured for comparative reasons. Ionization constants and titration shifts were obtained by nonlinear least-squares fits to one-proton titration curves. The average excitation energy approximation is discussed in terms of the observed changes in ¹⁷O-shielding on deprotonation. No intramolecular association between the α-amino group and the α-carboxyl group in the zwitterionic form is required to explain the high-frequency shift of the carboxylate ion. Also no indication of an intramolecular association between the α-amino group and the side-chain carboxyl groups of aspartic acid or glutamic acid was found.     

Evaluating aging of coatings and sealants: Mechanisms

Photodegradation mechanisms of a model coating/sealant system based upon styrene-butadiene-styrene triblock copolymer have been investigated. The model system was exposed to ultraviolet-visible radiation using an integrating sphere-based exposure chamber at 30 °C and <1% relative humidity. Chemical degradation was monitored by transmission Fourier transform infrared (FTIR) spectroscopy and changes in mechanical properties via dynamic mechanical thermal analysis (DMTA). It was found that cross-linking was the dominant degradation process, causing substantial increases in storage modulus and glass transition temperature of the butadiene units with increasing exposure. The styrene units were relatively stable as indicated by the lack of significant changes in the FTIR bands or in the glass transition temperature associated with the styrene units. The present study clearly has shown that chemorheological investigations provide useful tools to characterize the mechanisms of environmental attack of polymers. The ability to investigate both chemical and mechanical-rheological properties provides the opportunity to make modifications to the material and, hence, improve its chemical and mechanical-rheological properties.