Topology optimization of composite hyperelastic material using SPIMFO-method

Meccanica - Fiber reinforced materials are used in assorted engineering application and for this reason, new additive manufacturing technologies have been developed for this type of materials. With...     

Electrochemical reduction of monothiobenzils in the presence of aroyl chlorides. First synthesis of (Z)-α-benzoyloxy-β-benzoylthiostilbenes

The first method for the synthesis of the title compounds has been established involving a stereoselective electrochemical diacylation process. The cathodic reductions of monothiobenzils in an aprotic medium, under constant potential, in the presence of twofold molecular amounts of aroyl chlorides provide previously unknown (Z)-α-benzoyloxy-β-benzoythiostilbenes in high to quantitative yields.     

High performance liquid chromatographic separation of polar and non-polar chlorophyll pigments from algae using a wide pore polymeric octadecylsilica column

A method employing a wide pore polymeric reversed phase column has been developed for the separation of most of the chlorophylls and related compounds previously described as occurring in marine microalgae. The high selectivity toward molecular shape of this kind of stationary phase has enabled compounds of very similar structure, such as chlorophylls c₁, c₂ and Mg-divinylpheoporphyrin a₅ monomethyl ester, and chlorophyll a and the phytol-substituted chlorophyll c-like pigments, which commonly coelute on monomeric bonded phases, to be resolved in a single run. Some of these pigments, formerly thought to be a single compound, have, in fact, been demonstrated to be groups of two or more. The method has been successfully applied to both algal cultures and natural sea water samples. When visible light absorbance detection was used, the method proved suitable for separation of various carotenoids.     

Semicarbazones and thiosemicarbazones,XII: Crystal structure of salicylaldehyde semicarbazone

Summary The crystal and molecular structure of salicylaldehyde semicarbazone was obtained by single crystal X-ray diffraction. The O atom of the semicarbazone fragment isanti to the N atom of the hydrazinic group. The distribution of bond lengths in the semicarbazone fragment indicates delocalization of the -electrons. The crystal structure is stabilized by intra- and intermolecular hydrogen bonds.

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Semicarbazone und Thiosemicarbazone, 12. Mitt.: Die Kristallstruktur des Salicylaldehyd-Semicarbazons

Zusammenfassung Die Kristallstruktur und die molekulare Struktur des Salicylaldehyd-Semicarbazons wurde über Einkristall-Röntgenstreuung ermittelt. Das O-Atom des Semicarbazonteils stehtanti zum N-Atom der Hydrazin-Gruppierung. Die Bindungslängen in der Semicarbazoneinheit zeigen eine Delokalisierung der -Elektronen an. Die Geometrie der Verbindung wird durch stabilisierende intra- und intermolekulare Wasserstoffbrückenbindungen bestimmt.

     

Rheological behavior and structural interpretation of waxy crude oil gels

A waxy crude oil which gels below a threshold temperature has been investigated under static and dynamic conditions, using a combination of rheological methods, optical microscopy, and DSC. Particular attention is given in this work to the influence of the mechanical history on gel strength and to describing the time-dependent rheological behavior. The gels display a strong dependence of the yield stress and moduli on the shear history, cooling rate, and stress loading rate. Of particular interest is the partial recovery of the gel structure after application of small stress or strain (much smaller than the critical values needed for flow onset) during cooling, which can be used to reduce the ultimate strength of the crude oil gel formed below the pour point. A second focus of this study is to further develop the physical interpretation of the mechanism by which wax crystallization produces gelation. Gelation of the waxy crude oil studied is suggested to be the result of the association between wax crystals, which produces an extended network structure, and it is shown that the system displays features common to attractive colloidal gels, for one of which, fumed silica (Aerosil 200) in paraffin oil, rheological data are reported. The colloidal gel model provides a simple and economical basis for explaining the response of the gelled oil to various mechanical perturbations and constitutes a fruitful basis from which to develop technologies for controlling the gelation phenomenon, as suggested by the rheological results reported.     

Characterization of a peptide affinity support that binds selectively to staphylococcal enterotoxin B

The influences of mass transfer and adsorption-desorption kinetics on the binding of staphylococcal enterotoxin B (SEB) to an affinity resin with the peptide ligand, Tyr-Tyr-Trp-Leu-His-His (YYWLHH) have been studied. The bed and particle porosities, the axial dispersion coefficient and the pore diffusivity were measured using pulse experiments under unretained conditions. Adsorption isotherms for SEB on YYWLHH resins with peptide densities in the range from 6 to 220 micromol/g were measured and fitted to a bi-Langmuir equation. At peptide densities below 9 micromol/g and above 50 micromol/g, dissociation constants were lower (2 x 10(-3) to 7 x 10(-3) mol/m3), and binding capacities were larger (43-47 mg SEB/g). In the range from 9 to 50 micromol/g dissociation constants were larger (13 x 10(-3) to 24 x 10(-3) mol/m3) and capacities were lower (33-37 mg SEB/g). These observations are consistent with a transition from single point attachment of the protein to the ligand at low peptide densities to multipoint attachment at high peptide densities. The general rate (GR) model of chromatography was used to fit experimental breakthrough curves under retained conditions to determine the intrinsic rate constants for adsorption, which varied from 0.13 to 0.50 m3 mol(-1) s(-1), and exhibited no clear trend with increasing peptide density. An analysis of the number of transfer units for the various mass transfer steps in the column indicated that film mass transfer, pore diffusion (POR) and the kinetics of adsorption can all play an important role in the overall rate of adsorption, with the intrinsic adsorption step apparently being the rate determining step at peptide densities below 50 micromol/g.     

Characterization of the pores in hydrous ferric oxide aggregates formed by freezing and thawing

Hydrous ferric oxides (HFO) are efficient sorbents for inorganic and organic pollutants and therefore have great potentials in environmental science and engineering applications. Freezing and thawing of HFO suspensions leads to the formation of dense HFO aggregates. It facilitates the handling and increases the drying rate of HFO. In this study, we used a combination of pycnometry, gas adsorption (N(2) gas, water vapor), and small-angle neutron scattering (SANS) to characterize the porosity and pore size distribution of dense HFO aggregates formed by freezing dialyzed HFO suspensions at -25 degrees C and thawing them at room temperature. The crystallinity of the HFO, which was a 2-line ferrihydrite, was not affected by this treatment. Wet sieving and laser diffraction analysis showed that the dense HFO aggregates had a unimodal size distribution with an average diameter of 235+/-35 microm. Increasing the freezing rate by cooling with liquid N(2) (-196 degrees C) resulted in much smaller aggregates with an average diameter of 20 microm. Adding NaNO(3) electrolyte to the HFO suspensions prior to freezing also resulted in the formation of smaller aggregates. The dense HFO aggregates formed at -25 degrees C had a porosity of 0.73+/-0.02 ll(-1). SANS revealed a unimodal size distribution of pores, with an average pore diameter of 2.0 nm. The diameter of the HFO crystallites was estimated by transmission electron microscopy to be 1.9+/-0.5 nm. Geometrical considerations taking into account the unit particle and average pore size suggest that the crystallites retain 1-2 layers of hydration water during the coagulation induced by freezing. Analysis by N(2) gas adsorption showed that drying the dense HFO aggregates induced a reduction in porosity by about 25% and shifted the pore size distribution to smaller diameters. Rewetting during water vapor adsorption did not induce significant changes of the aggregate structure. The specific surface area of the dry HFO aggregates was between 320 and 380 m(2)g(-1).     

Glycosylidene Carbenes. Part 23. Regioselective glycosidation of deoxy- and fluorodeoxy-myo-inositol derivatives

To demonstrate the relevance of the kinetic acidity of individual OH groups for the regioselectivity of glycosylation by glycosylidene carbenes, we compared the glycosylation by 1 of the known triol 2 with the glycosylation of the diol D - 3 and the fluorodiol L - 4 . Deoxygenation with Bu₃SnH of the phenoxythiocarbonyl derivative of 5 (Scheme 1) or the carbonothioate 6 gave the racemic alcohol (±)- 7 . The enantiomers were separated via the allophanates 9a and 9b , and desilylated to the deoxydiols D - and L - 3 , respectively. The assignment of their absolute configuration is based upon the CD spectra of the bis(4-bromobenzoates) D - and L - 10 . The (+)-(R)-1-phenylethylcarbamates 13a and 13b (Scheme 2) were prepared from the fluoroinositol (±)- 11 via (±)- 4 and the silyl ether (±)- 12 and separated by chromatography. The absolute configuration of 13a was established by X-ray analysis. Decarbamoylation of 13a ( → L - 12 ) and desilylation afforded the fluorodiol L - 4 . The H-bonds of D - 3 and L - 4 in chlorinated solvents and in dioxane were studied by IR and ¹H-NMR spectroscopy (Fig. 2). In both diols, HO? C(2) forms an intramolecular, bifurcated H-bond. There is an intramolecular H-bond between HO? C(6) and F in solutions of L - 4 in CH₂Cl₂, but not in 1,4-dioxane; the solubility of L - 4 in CH₂Cl₂ is too low to permit a meaningful glycosidation in this solvent. Glycosidation of D - 3 in dioxane by the carbene derived from 1 (Scheme 3) followed by acetylation gave predominantly the pseudodisaccharides 18/19 (38%), derived from glycosidation of the axial OH group besides the pseudodisaccharides 16 / 17 (13%) and the epoxides 20 / 21 (7%), derived from protonation of the carbene by the equatorial OH group. Similarly, the reaction of L - 4 with 1 (Scheme 4) led to the pseudodisaccharides 28 / 29 (46%) and 26 / 27 (14%), derived from deprotonation of the axial and equatorial OH groups, respectively. Formation of the epoxides involved deprotonation of the intramolecularly H-bonded tautomer, followed by intramolecular alkylation, elimination, and substitution (Scheme 4). The regio- and diastereoselectivities of the glycosidation correlate with the H-bonds in the starting diols.     

Computational studies of the 3-Dimensional structure of cyclopenta polycyclic aromatic hydrocarbons containing a gulf region

Recently, some cyclopenta-fused polyaromatic hydrocarbons, an environmentally relevant subclass of chemicals, have been shown to have carcinogenic activity in animals. It has been suggested that benz[l] aceanthrylene ( I ), an active member of this subclass with a gulf region, has a trans dihydrodiol metabolite that is nonplanar and has two distinct spatial configurations. We have used MMP 2(85) and AM 1 to investigate the three-dimensional structure of this dihydrodiol and other similar derivatives of ( I ) and have found that although ( I ) is somewhat nonplanar the relevant derivatives are all nearly planar. Further, we have computed potential functions for the bending of the angular ring in the gulf region using MMP 2(85), AM 1, and ab initio computed energies for AM 1 spatial configurations and find that these molecules all have only a single potential minimum. We have performed the same calculations for benzo[c]phenanthren and its 1,12 dimethyl derivative, molecules with a similar gulf region for which crystallographic data exists. In agreement with that data, we find that two distinct spatial configurations exist separated by significant barries. The differences between the results generated by the three different methods of computation will be discussed.     

Agro-industrial waste enzymes: Perspectives in circular economy

According to the Food and Agriculture Organization of the United Nations, approximately 1.3 billion tons of food is wasted each year, equivalent to approximately one-third of world production. Agri-food wastes are the source of proteins, carbohydrates, lipids, and other essential minerals that have been exploited for value-added products by the development of biorefineries and sustainable business as important elements of circular economies. The innovation and materialization of these types of processes, including the use of disruptive technologies on microbial bioconversion and enzyme technology, such as nanotechnology, metabolic engineering, and multi-omics platforms, increase the perspectives on the waste valorization process. Lignocellulolytic enzymes, pectinases, and proteases are mainly used as catalyzers on agri-food waste treatment, and their production in house might be the trend in near future for agro-industrial countries. Another way to transform the agri-food wastes is via aerobic or anaerobic microbial process from fungal or bacterial cultures; these processes are the key to produce waste enzymes.