Ellagitannin chemistry. Evolution of a three-component coupling strategy for the synthesis of the dimeric ellagitannin coriariin A and a dimeric gallotannin analogue

The total synthesis of the dimeric ellagitannin coriariin A is reported. The key reaction to access the dimeric framework was realized early in the synthesis pathway via a bis acylation reaction of a dehydrodigalloyl diacid with 2 equiv of a glucopyranose trichloroacetimidate. The glucose rings were subsequently functionalized, culminating in a double oxidative cyclization to form stereoselectively both (S)-HHDP ester units. This bis acylation strategy was also employed to prepare a gallotannin analogue of coriariin A whose earlier synthesis by orthoquinone dimerization was plagued by yield-limiting side reactions.     

The lignol approach to biorefining of woody biomass to produce ethanol and chemicals

Processes that produce only ethanol from lignocellulosics display poor economics. This is generally overcome by constructing large facilities having satisfactory economies of scale, thus making financing onerous and hindering the development of suitable technologies. Lignol Innovations has developed a biorefining technology that employs an ethanol-based organosolv step to separate lignin, hemicellulose components, and extractives from the cellulosic fraction of woody biomass. The resultant cellulosic fraction is highly susceptible to enzymatic hydrolysis, generating very high yields of glucose (>90% in 12–24h) with typical enzyme loadings of 10–20 FPU (filter paper units)/g. This glucose is readily converted to ethanol, or possibly other sugar platform chemicals, either by sequential or simultaneous saccharification and fermentation. The liquor from the organosolv step is processed by well-established unit operations to recover lignin, furfural, xylose, acetic acid, and a lipophylic extractives fraction. The process ethanol is recovered and recycled back to the process. The resulting recycled process water is of a very high quality, low BOD₅, and suitable for overall system process closure. Significant benefits can be attained in greenhouse gas (GHG) emission reductions, as per the Kyoto Protocol. Revenues from the multiple products, particularly the lignin, ethanol and xylose fractions, ensure excellent economics for the process even in plants as small as 100 mtpd (metric tonnes per day) dry woody biomass input—a scale suitable for processing wood residues produced by a single large sawmill.     

Co-precipitation in some binary sulphate systems

Studies have been made of the distribution behaviour of tracers with alkaline earth sulphates, using the technique of precipitation from homogeneous solution. The co-precipitation of strontium with barium sulphate and of lead, lanthanum, and yttrium, separately, with barium sulphate, and with strontium sulphate, were investigated. Although there was qualitative correlation between the observed values of the distribution coefficient and the theoretical solubility product ratios for each of the binary systems studied, the divergence between theory and observation was so great that it seems unlikely that there is any quantitative correlation.     

The s-p bonded representatives of the prominent BaAl4 structure type: a case study on structural stability of polar intermetallic network structures

This work presents a detailed, combined experimental and theoretical study on the structural stability of s-p bonded compounds with the BaAl4 structure type (space group I4/mmm, Z = 2) as part of a broad program to investigate the complex questions of structure formation and atomic arrangements in polar intermetallics. From ab initio calculations employing pseudopotentials and a plane wave basis set, we extracted optimized structural parameters, binding energies, and the electronic structure of the systems AeX(III)4, AeX(II)2X(IV)2, AeX(II)2X(III)2 (Ae = Ca, Sr, Ba; X(II) = Mg, Zn; X(III) = Al, Ga; X(IV) = Si, Ge). For all systems we found a pronounced pseudo-gap in the density of states separating network X42- bonding from antibonding electronic states that coincides with the Fermi level for an electron count of 14 electrons per formula unit, the optimum value for stable BaAl4-type polar intermetallics. However, the synthesis and structural characterization (from X-ray single crystal and powder diffraction data) of the new compounds AeZn2-Al2+, AeZn2-deltaGa2+delta (Ae = Ca, Sr, Ba; delta = 0-0.2) and AeMg0.9Al3.1, AeMg1.7Ga2.3 (Ae = Sr, Ba) manifested that electron deficiency is rather frequent for BaAl4-type polar intermetallics. The site preference for different "X" elements in the ternary systems was quantified by calculating "coloring energies", which, for some systems, was strongly dependent on the size of the electropositive Ae component. The Ae2+ cations decisively influence the nearest neighbor distances in the encapsulating polyanionic networks X4(2-) and the structures of these networks are surprisingly flexible to the size of the Ae component without changing the overall bonding picture. A monoclinically distorted variant of the BaAl4 structure occurs when the cations become too small for matching the size of encapsulating X4(2-) cages. An even larger size mismatch leads to the formation of the EuIn4 structure type.     

Spectrophotometric determination of pentaerythritol tetranitrate (PETN) in waste water from lead styphnate primer plants

An accurate spectrophotometric method is proposed for the determination of pentaerythritol tetranitrate (PETN) in waste water from lead styphnate primer plants by use of phenoldisulphonic acid. The waste water is filtered through a sintered glass crucible and the PETN is determined in the filtrate and the residue. In the determination of PETN in the filtrate, sodium hydroxide is added and the PETN is extracted with methylene chloride (in alkaline solution, styphnate and TNT are not extracted). The methylene chloride solution is then evaporated to dryness, the residue is treated with a solution of phenoldisulphonic acid in sulphuric acid, water and ammonia are added, and the yellow colour is measured. In the determination of PETN in the residue, the PETN is dissolved in acetone, an aliquot of the acetone solution is treated with water and sodium hydroxide, the PETN is extracted with methylene chloride and the colour is developed as above. Various factors affecting the determination were investigated. The solubility of PETN in water was studied.     

Flow-through particles for the high-performance liquid chromatographic separation of biomolecules: perfusion chromatography

This paper reports a new technique for reducing resistance to stagnant mobile phase mass transfer without sacrificing high adsorbent capacity or necessitating extremely high pressure operation. The technique involves the flow of liquid through a porous chromatographic particle, and has thus been termed "perfusion chromatography". This is accomplished with 6000-8000 A pores which transect the particle. Data from electron microscopy, column efficiency, frontal analysis and theoretical modelling all suggest that mobile phase will flow through these large pores. In this manner, solutes enter the interior of the particles through a combination of convective and diffusional transport, with convection dominating for Peclet numbers greater than one. The implications of flow through particles on bandspreading, resolution and dynamic loading capacity are examined. It is shown that the rate of solute transport is strongly coupled to mobile phase velocity such that bandspreading, resolution of proteins and dynamic loading capacity are unaffected by increases in mobile phase velocity up to several thousand centimeters per hour. The surface area of this very large-pore diameter material is enhanced by using a network of smaller, 500-1500 A interconnecting pores between the throughpores. Scanning electron micrographs show that the pore network is continuous and that no point in the matrix is more than 5000-10,000 A from a through-pore. As a consequence, diffusional path lengths are minimized and the large porous particles take on the transport characteristics of much smaller particles but with a fraction of the pressure drop. Capacity and resolution studies show that these materials bind and separate an amount of protein equivalent to that of conventional high-performance liquid chromatography as well as low performance agarose-based media at greater than 10-100 times higher mobile phase velocity with no loss in resolution.