Designing Heterogeneous Catalysts by Incorporating Enzyme-Like Functionalities into MOFs

Everyone who works within the field of catalysis draws inspiration from the amazing functionality of nature’s catalysts, the enzymes. It is particularly the mild conditions that these catalysts are able to operate at and the selectivity that they demonstrate that make these materials dream targets for scientists involved in the art of synthesizing homogeneous and heterogeneous industrial catalysts. But enzymes also have their weak points; in particular their low thermal stability and their often too slow reaction rates for an economical industrial process are problems that have to be overcome. The obvious solution would be to copy the catalytic active center into a robust open framework. A key property of an enzyme is its selectivity; this property is partly regulated by steric constraints surrounding the catalytically active site. The microporous zeolite based catalysts in some cases show impressive selectivity based on the geometrical constraints imposed by the size and shape of the regular channels in these crystalline silicate and alumino-phosphate based structures, and enzyme-like properties have been claimed but the pure inorganic nature of the selective internal surface in these materials makes it impossible to mimic many important enzymatic properties. The new generation of microporous materials, Metal Organic Frameworks (MOFs) are hybrids of organic and inorganic structures. This dualistic nature offers an unprecedented flexibility in the possibility to incorporate both organic and metallic functional groups into the ordered crystalline lattice and thereby opening up for a much greater possibility to copy structural motifs known from enzymes into much simpler but also more stable open structures. Several groups are working on development of new catalysts by this approach. Here we will illustrate this approach with structures that mimic anhydrase and C–H activation.     

Thermomechanical properties of copper–carbon nanofibre composites prepared by spark plasma sintering and hot pressing

Several types of carbon nanofibres (CNF) were coated with a uniform and dense copper layer by electroless copper deposition. The coated fibres were then sintered by two different methods, spark plasma sintering (SPS) and hot pressing (HP). The Cu coating thickness was varied so that different volume fraction of fibres was achieved in the produced composites. In some cases, the CNF were pre-coated with Cr for the improvement the Cu adhesion on CNF. The results show that the dispersion of the CNF into the Cu matrix is independent of the sintering method used. On the contrary, the dispersion is directly related to the efficiency of the Cu coating, which is tightly connected to the CNF type. Overall, strong variations of the thermal conductivity (TC) of the composites were observed (20–200 W/mK) as a function of CNF type, CNF volume fraction and Cr content, while the coefficient of thermal expansion (CTE) in all cases was found to be considerably lower than Cu (9.9–11.3 ppm/K). The results show a good potential for SPS to be used to process this type of materials, since the SPS samples show better properties than HP samples even though they have a higher porosity, in applications where moderate TC and low CTE are required.     

Phase-based multidimensional volume registration

We present a method for accurate image registration and motion compensation in multidimensional signals, such as two-dimensional (2-D) X-ray images and three-dimensional (3-D) computed tomography/magnetic resonance imaging volumes. The method is based on phase from quadrature filters, which makes it robust to noise and temporal intensity variations. The method is equally applicable to signals of two, three or higher number of dimensions. We use parametric models, e.g., affine models, finite elements or local affine models with global regularization. Experimental results show high accuracy for 2-D and 3-D motion compensation.     

Snowmobile fatalities aspects on preventive measures from a 25-year review

During October 1973 through May 1998, 157 snowmobile fatalities were autopsied in Northern Sweden, including 131 riders, 15 passengers, six occupants with unknown position and five victims pulled by a snowmobile. Most fatalities occurred during March and April (41%), on weekends/holidays (75%), between 18:00 and 02:00 h (59%), during darkness (63%), in clear weather (84%) and at leisure time (94%). The median age was 39 years and 92% were men. The most common causes of death were blunt trauma (53%) and drowning (38%). A total of 64% were inebriated by alcohol, with a mean blood alcohol concentration of 1.7 g/l. More inebriated victims were found during weekends/holidays than on weekdays (75 vs. 51%) and during nighttime than during daytime (92 vs. 52). Driving into water was the most common event (38%) followed by collisions with immobile objects (20%). Alcohol and speeding were the most common contributors to the crashes, while flotation snowmobile suit and helmet use were considered to be the most important injury prevention factors.     

Biosynthesis of new divinyl ether oxylipins in Ranunculus plants

[1-¹⁴C]Linolenic acid was incubated with homogenates of leaves from the aquatic plants Ranunculus lingua (greater spearwort) or R. peltatus (pond water-crowfoot). Analysis by reversed-phase high-performance liquid radiochromatography demonstrated the formation of a new divinyl ether FA, i.e., 12-[1′(E), 3′(Z)-hexadienyloxy]-9(Z), 11(Z)-dodecadienoic acid [11(Z)-etherolenic acid] as well as a smaller proportion of ω5(Z)-etherolenic acid previously identified in terrestrial Ranunculus plants. The same divinyl ethers were formed upon incubation of 13(S)-hydroperoxy-9(Z), 11(E), 15(Z)-octadecatrienoic acid, a lipoxygenase metabolite of linolenic acid, whereas the isomeric hydroperoxide, 9(S)-hydroperoxy-10(E), 12(Z), 15(Z)-octadecatrienoic acid, was not converted into divinyl ethers in R. lingua or R. peltatus. Incubation of [1-¹⁴C]linoleic acid or 13(S)-hydroperoxy-9(Z), 11(E)-octadecadienoic acid produced the divinyl ether 12-[1′(E)-hexenyloxy]-9(Z), 11(Z)-dodecadienoic acid [11(Z)-etheroleic acid] and a smaller amount of ω5(Z)-etheroleic acid. The experiments demonstrated the existence in R. lingua and R. peltatus of a divinyl ether synthase distinct from those previously encountered in higher plants and algae.     

Quantification of aroma vapours sorbed in polyethene films using supercritical carbon dioxide

Extraction with supercritical carbon dioxide was used to quantity the amounts of seven different aroma vapours sorbed in polyethene films. The method was found to completely extract all aroma compounds from the films. The solution of aroma compounds in the polymer films decreased with increasing polymer density. Monoterpenes were always completely sorbed in the films, whereas aldehydes and ketones had a much lower affinity for the films. The sulphur-containing compound, thiophene, was difficult to analyse due to its adsorption on metal surfaces.     

Quantifying unfrozen water in frozen soil by high-field 2H NMR

To understand wintertime controls of biogeochemical processes in high latitude soils it is essential to distinguish between direct temperature effects and the effects of changes in water availability mediated by freezing. Efforts to separate these controls are hampered by a lack of adequate methods to determine the proportion of unfrozen water. In this study we present a high-field 2H2O NMR method for quantifying unfrozen water content in frozen soil. The experimental material consisted of the humic layer of a boreal spruce forest soil mixed with varying proportions of quartz sand and humidified with deuterium-enriched water. The relative standard deviation of unfrozen water content (measured as NMR signal integral) was less than 2% for repeated measurements on a given sample and 3.5% among all samples, based on a total of 16 measurements. As compared to 1H NMR, this 2H NMR method was found to be superior for several reasons: it is less sensitive to field inhomogeneity and paramagnetic impurities, it gives a bigger line shape difference between the ice and liquid signal, it shows a sharper response to water fusion, and it excludes the possibility of hydrogen in the organic material interfering with the measurement.     

Detection of phosphorylated peptides in proteomic analyses using microfluidic compact disk technology

A compact disk (CD)-based microfluidic method for selective detection of phosphopeptides by mass spectrometry is described. It combines immobilized metal affinity chromatography (IMAC) and enzymatic dephosphorylation. Phosphoproteins are digested with trypsin and processed on the CD using nanoliter scale IMAC with and without subsequent in situ alkaline phosphatase treatment. This is followed by on-CD matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. Dephosphorylation of the IMAC-enriched peptides allows selective phosphopeptide detection based on the differential mass maps generated (mass shifts of 80 Da or multiples of 80 Da). The CD contains 96 microstructures, each with a 16 nL IMAC microfluidic column. Movement of liquid is controlled by differential spinning of the disk. Up to 48 samples are distributed onto the CD in two equal sets. One set is for phosphopeptide enrichment only, the other for identical phosphopeptide enrichment but combined with in situ dephosphorylation. Peptides are eluted from the columns directly into MALDI target areas, still on the CD, using a solvent containing the MALDI matrix. After crystallization, the CD is inserted into a MALDI mass spectrometer for analysis down to the femtomole level. The average success rate in phosphopeptide detection is over 90%. Applied to noncharacterized samples, the method identified two novel phosphorylation sites, Thr 735 and Ser 737, in the ligand-binding domain of the human mineralocorticoid receptor.     

Die Verteilung von Zink zwischen Ferrit und Austenit und die Thermodynamik des Zweistoffsystems Eisen—Zink

Verfahren zur Herstellung sehr reiner Eisen-Zink-Legierungen. Ermittlung der Sättigungsgehalte an Zink im Ferrit und Austenit mit Hilfe der Mikrosonde. Berechnungen zur Beschreibung der thermodynamischen Eigenschaften des zinklegierten paramagnetischen Ferrits und des zinklegierten Austenits unter Zuhilfenahme von thermodynamischen Werten aus dem Schrifttum. Berechnung des Gleichgewichts Austenit/Ferrit, Festlegung der γ-Schleife des Zustandsschaubildes und Vergleich mit den ermittelten Werten. Berechnung der Löslichkeit der Γ-Phase im α-Eisen mit Hilfe der bereits bekannten Thermodynamik der α-Phase. Berechnung einer metastabilen Mischungslücke und deren Spinodale im Ferrit.     

Biosynthesis of prostaglandin E1 by human seminal vesicles

[1-¹⁴C] 8,11,14-Eicosatrienoic acid was converted into prostaglandin E₁ when incubated with a homogenate of human seminal vesicles. No conversion could be detected with homogenates of human prostate or testis.