Total Synthesis of an Exceptional Brominated 4‐Pyrone Derivative of Algal Origin: An Exercise in Gold Catalysis and Alkyne Metathesis

A concise approach to the algal metabolite 1 is described, which also determines the previously unknown stereostructure of this natural product. Compound 1 is distinguished by a rare brominated 4‐pyrone nucleus linked as a ketene–acetal to a polyunsaturated macrocyclic scaffold comprising an extra homoallylic bromide entity. The synthesis of 1 is based on the elaboration and selective functionalization of the linear precursor 23 endowed with no less than six different sites of unsaturation including the highly enolized oxo‐alkanoate function. Key to success was the formation of the 2‐alkoxy‐4‐pyrone ring by a novel gold‐catalyzed transformation which engages only the acetylenic β‐ketoester substructure of 23 but leaves all other π‐bonds untouched. The synthesis was completed by a ring‐closing alkyne metathesis to forge the signature cycloalkyne motif of 1 followed by selective bromination of the ketene–acetal site in the resulting product 27 without touching the skipped diene–yne substructure resident within the macrocyclic tether.     

Structure of a Reactive Gold Carbenoid

A formal gold‐for‐chromium transmetalation allowed the gold carbenoid species [Cy₃PAuCAr₂]NTf₂ ( 11 ) (Ar=pMeOC₆H₄‐) to be obtained in crystalline form. The structure in the solid state suggests that there is only little back donation of electron density from gold to the carbene center of 11 and hence very modest Au? C double‐bond character; rather, it is the organic ligand framework that is responsible for stabilizing this species by resonance delocalization of the accumulated positive charge. Because 11 is capable of cyclopropanating p‐methoxystyrene even at low temperature, the discussion of its structure is deemed relevant for a better understanding of the mechanisms of π‐acid catalysis in general.     

An approach for optimization of loading cycles of hydraulic mining excavators

The present paper describes an optimization multi-stage approach for computing the optimal loading cycle of a heavy weight excavator along a predefined trajectory under dynamic constraints such as maximal ensuing forces, accelerations, and maximal allowed hydraulic power. The approach involves the use of splines of 3rd and 5th order for smooth interpolation of the spatial trajectory up to the level of linear and angular accelerations, as well as an SQP optimization routine to find the optimal end-effector motion law along the trajectory, which finally leads to strokes and pressures at the hydraulic actuators as a function of time. The approach can also be extended to other multi-body systems following a predetermined trajectory. The solution scheme can be included in a more general optimization routine aiming to optimize the trajectory itself. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Sensitivity of erythemally effective UV irradiance and daily exposure to temporal variability in total ozone

The provision of information to the public about current levels of the erythemally effective UV radiation is an important issue in health care. The quality of promoted values is therefore of special importance. The atmospheric parameter which affects the erythemally effective UV radiation under clear sky most is the total ozone content of the atmosphere. In this paper we examined the sensitivity of the erythemally effective irradiance and daily radiant exposure to the temporal variability of total ozone on time scales from 1 to 15 days. The results show that the sensitivity is highest for the first 24 h. Larger time scales do not exhibit a similar influence. Total ozone measurements of the previous day may already cause uncertainties higher than 0.5 UV index (UVI) independent of the geolocation. For comparison, a temporal persistence of 15 days may cause uncertainties of 1.2 UVI at 50°N, 1 UVI at 30°S and less than 1 UVI at the equator. The results of this study allow finding the necessary temporal resolution of total ozone values when a certain accuracy for the UVI or for the purpose of sun protection is required. The results are compared with those of two preceding studies where we quantified the influence of measurement uncertainties and spatial total ozone variability to the erythemally effective irradiance at noon and to the daily dose. We conclude that temporal variability of total ozone is the most critical issue, but also measurement uncertainties do have a noticeable influence on the erythemally effective radiation.     

Two-dimensional fluorescence difference gel electrophoresis for comparison of affinity and non-affinity based downstream processing of recombinant monoclonal antibody

Although Staphylococcus Protein A (SpA) affinity chromatography is the state of the art capture step for antibody purification, non-affinity methods are more economical. We used two-dimensional fluorescence difference gel electrophoresis (2-D DIGE) to evaluate the purification of a recombinant IgG₁ antibody from cultured cells, with two different processes: (1) SpA capture followed by cation-exchange chromatography (CEX); and (2) CEX capture, followed by anion exchanger, then hydrophobic interaction chromatography. Efficiencies were similar in sodium dodecylsulphate polyacrylamide gel electrophoresis and size-exclusion chromatography; however, 2-D DIGE revealed higher efficiency with SpA than with CEX capture. Thus, 2-D DIGE is a valuable tool for downstream process development.