Lignin from Annual Plants as Raw Material Source for Flavors and Basic Chemicals

The enzymatic conversion of lignins, possibly in combination with electrochemical oxidation, makes aromatics such as syringol, guaiacol, vanillin and catechol available in the qualities required by the fragrance industry. The lignins were obtained by soda digestion from wheat straw and Miscanthus, characterized and then converted with laccases. The overall yield amounted up to 9 wt % with a product spectrum confined to four substances. Catechol was the major product, with a fraction of ≈75 %. It can easily be isolated by extraction with acetone.     

High-Throughput Experimentation in Oxidation Catalysis

High-throughput experimentation in catalysis comprises the following components: (i) automated high-throughput synthesis, (ii) testing in Stage I and Stage II, for which to some extent novel assays are necessary, (iii) data handling and experimental design tools, and (iv) robotics. This contribution covers these topics, using examples from the research of the authors, but also from the literature, in order to illustrate the problems and opportunities associated with high-throughput experimentation in catalysis, focusing particularly on heterogeneous catalysis.     

Silphinene Sesquiterpenes as Model Insect Antifeedants

Silphinene sesquiterpenes are established chrysomelid antifeedants. In this work, nine silphinene analogs, 11-acetoxy-5-angeloyloxysilphinen-3-one (1), 11-acetoxy-5-tigloyloxysilphinen-3-one (2), 11-acetoxy-5-iso- butyryloxysilphinen-3-one (3), 11-hydroxy-5-angeloyloxysilphinen-3-one (4), 11,5-dihydroxysilphinen-3-one (5), 11,5-diacetoxysilphinen-3-one (6), 5,11-diisobutyryloxysilphinen-3-one (7), silphinen-3,5,11-trione (8), and O-methyl-5-epicantabrenolic acid methyl ester (10), and a presilphiperfolane sesquiterpene (9) were tested against several divergent insect species, including the lepidopteran Spodoptera littoralis, the chrysomelid Leptinotarsa decemlineata, and five aphid species, and their antifeedant effects were compared with those of picrotoxinin, a GABA-antagonist, and thymol, an allosteric modulator for insect GABA receptors. All insects tested responded to at least one silphinene analog and/or GABA antagonist. Compound 3 and thymol were effective antifeedants against all species tested except S. littoralis, with varying potencies according to their feeding ecologies. The toxicity of these compounds was species-dependent and did not correlate with their antifeedant effect.     

DEPOSITION OF A FINE POWDER IN HORIZONTAL PIPELINES AND BENDS

The deposition of a very fine powder in a horizontal, lean-phase pneumatic conveying conduit containing a 90° bend has been studied experimentally. The total deposition and the deposition pattern were studied as a function of superficial gas velocity, solids loading and bend geometry: one sharp and three smooth bends of different radii of curvature were used. Most deposition was seen in the sharp bend, while in the smooth bends the deposition did not vary much with radius of curvature. The deposition decreased significantly with increasing superficial gas velocity. The experimental results were compared with CFD simulations of the flow field. The observations are consistent with the notion of deposition in regions with low near-wall gas velocity, indicating that models for deposition should be sought in considerations of the deposit stability for this type of system.     

Solubility of Si3N4 in Liquid SiO2

The nitrogen solubility in the SiO₂-rich liquid in the metastable binary SiO₂-Si₃N₄ system has been determined by analytical TEM to be 1%–4% of N/(O + N) at 1973–2223 K. Analysis of the near edge structure of the electron energy loss peak indicates that nitrogen is incorporated into the silicate network rather than being present as molecular N₂. A regular solution model with a positive enthalpy of mixing for the liquid was used to match the data for the metastable solubility of N in the presence of crystalline Si₃N₄ and to adjust the computed phase diagram. The solubility of Si₃N₄ in fused SiO₂ is far less than reported in liquid silicates also containing Al, Mg, and/or Y. Apparently, these cations act as modifiers that break anion bridges in the silicate network and, thereby, allow further incorporation of Si₃N₄ without prohibitive amounts of network cross-linking. Finally, indications emerged regarding the diffuse nature of the Si₃N₄-SiO₂ interface that leads to amorphous regions of higher N content.     

A conversation on VB vs MO theory: a never-ending rivalry?

Quantum mechanics has provided chemistry with two general theories, valence bond (VB) theory and molecular orbital (MO) theory. The two theories were developed at about the same time, but quickly diverged into rival schools that have competed, sometimes fervently, on charting the mental map and epistemology of chemistry. Three practitioners of MO and VB theory talk - fighting a little, trying to understand - of the past and present of these two approaches to describing bonding in molecules.     

Dissolution of softwood kraft pulps by direct derivatization in lithium chloride/N,N‐dimethylacetamide

A method for the characterization of the molar mass distributions (MMDs) of softwood kraft pulps dissolved in 0.5% lithium chloride (LiCl)/N,N‐dimethylacetamide (DMAc) by size exclusion chromatography is presented. The method is based on derivatization with ethyl isocyanate and the dissolution of samples in 8% LiCl/DMAc. In this study, the derivatization of hardwood kraft pulps did not influence the MMD. In the case of softwood pulps, however, the derivatization decreased the proportion of the high‐molecular‐mass material and increased the proportion of the low‐molecular‐mass material, which resulted in a distribution similar to the MMD of a hardwood kraft pulp. The results suggest that associations between hemicellulose and cellulose in the softwood kraft pulp were ruptured during derivatization. This led to a more correct estimation of the MMD of derivatized softwood kraft pulps than obtained by the dissolution of nonderivatized samples. This new method offers several advantages over derivatization with phenyl isocyanate: a precipitation step is not necessary, it is possible to follow the lignin distribution in the samples, and the method allows very high levels of dissolution of softwood kraft pulps up to a κ number of around 50. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 424–431, 2004     

Artificial Light Regulation of an Allosteric Bienzyme Complex by a Photosensitive Ligand

The artificial regulation of proteins by light is an emerging subdiscipline of synthetic biology. Here, we used this concept to photocontrol both catalysis and allostery within the heterodimeric enzyme complex imidazole glycerol phosphate synthase (ImGP‐S). ImGP‐S consists of the cyclase subunit HisF and the glutaminase subunit HisH, which is allosterically stimulated by substrate binding to HisF. We show that a light‐sensitive diarylethene (1,2‐dithienylethene, DTE)‐based competitive inhibitor in its ring‐open state binds with low micromolar affinity to the cyclase subunit and displaces its substrate from the active site. As a consequence, catalysis by HisF and allosteric stimulation of HisH are impaired. Following UV‐light irradiation, the DTE ligand adopts its ring‐closed state and loses affinity for HisF, restoring activity and allostery. Our approach allows for the switching of ImGP‐S activity and allostery during catalysis and appears to be generally applicable for the light regulation of other multienzyme complexes.     

Combined TPS, XPS, EXAFS, and NO-TPD study of the sulfiding of Mo/Al2O3

The sulfiding of Mo/Al₂O₃ in H₂S/Ar versus in H₂S/H₂ has been studied by temperature-programmed sulfiding (TPS), X-ray photon electron spectroscopy (XPS), extended X-ray absorption fine structure (EXAFS), and temperature-programmed desorption of NO (NO-TPD). All the applied techniques agree on the sulfur content in the sulfided catalysts and the findings are in accord with a model for the H₂S production reaction. The nucleation and growth of well-ordered MoS₂ clusters are probed by XPS during sulfiding with and without the presence of hydrogen. The resulting dispersion of the MoS₂ phase is evaluated on the basis of XPS, EXAFS, and NO-TPD, and is found to be highest when the sulfiding occurs in the presence of hydrogen.