Stereocontrolled total synthesis of (+)-vincristine

An efficient total synthesis of (+)-vincristine has been accomplished through a stereoselective coupling of demethylvindoline and the eleven-membered carbomethoxyverbanamine presursor. Demethylvindoline was prepared by oxidation of 17-hydroxy-11-methoxytabersonine, followed by regioselective acetylation with mixed anhydride method. Although an initial attempt of coupling by using demethylvindoline formamide was not successful and resulted in recovery of the starting compounds, the reaction using demethylvindoline took place smoothly to furnish the desired bisindole product with the correct stereochemistry at C18′. After formation of the piperidine ring by sequential removal of the protective groups and intramolecular nucleophilic cyclization, the total synthesis of vincristine was completed by formylation of N1

An artificial metalloenzyme biosensor can detect ethylene gas in fruits and Arabidopsis leaves

© 2019, The Author(s). Enzyme biosensors are useful tools that can monitor rapid changes in metabolite levels in real-time. However, current approaches are largely constrained to metabolites within a limited chemical space. With the rising development of artificial metalloenzymes (ArM), a unique opportunity exists to design biosensors from the ground-up for metabolites that are difficult to detect using current technologies. Here we present the design and development of the ArM ethylene probe (AEP), where an albumin scaffold is used to solubilize and protect a quenched ruthenium catalyst. In the presence of the phytohormone ethylene, cross metathesis can occur to produce fluorescence. The probe can be used to detect both exogenous- and endogenous-induced changes to ethylene biosynthesis in fruits and leaves. Overall, this work represents an example of an ArM biosensor, designed specifically for the spatial and temporal detection of a biological metabolite previously not accessible using enzyme biosensors

An artificial metalloenzyme biosensor can detect ethylene gas in fruits and Arabidopsis leaves

© 2019, The Author(s). Enzyme biosensors are useful tools that can monitor rapid changes in metabolite levels in real-time. However, current approaches are largely constrained to metabolites within a limited chemical space. With the rising development of artificial metalloenzymes (ArM), a unique opportunity exists to design biosensors from the ground-up for metabolites that are difficult to detect using current technologies. Here we present the design and development of the ArM ethylene probe (AEP), where an albumin scaffold is used to solubilize and protect a quenched ruthenium catalyst. In the presence of the phytohormone ethylene, cross metathesis can occur to produce fluorescence. The probe can be used to detect both exogenous- and endogenous-induced changes to ethylene biosynthesis in fruits and leaves. Overall, this work represents an example of an ArM biosensor, designed specifically for the spatial and temporal detection of a biological metabolite previously not accessible using enzyme biosensors

Evaluation of a Threshold-Based Model of the Elevated-Temperature Fatique of Impact-Damaged γ-TiAl

Step-loading fatigue tests have been conducted on two γ-TiAl alloys with differing microstructures following quasi-static indentations intended to simulate assembly-related impact damage to low-pressure turbine blades. Fatigue tests were conducted at 600 °C using computer-controlled servohydraulic loading at a frequency of 20 Hz. Reasonably good agreement was achieved between the fatigue data and calculated fatigue strength based on the fatigue threshold and measured impact severity. In certain cases, the fatigue threshold model fails to completely describe the data. These discrepancies may be related to residual stresses, variations in crack-shape morphology, and small-crack effects. Residual stresses could not be directly measured, given the small size of the damage zones. However, a comparison of fatigue threshold approximations based on a through-thickness crack geometry and a corner-crack geometry suggests that these two models may represent the upper and lower bounds of the actual fatigue behavior. In addition, the behavior of small cracks was examined by modeling the stress-lifetime response of lightly damaged specimens of the duplex alloy. This effort indicates the need for small-crack fatigue threshold values when designing fatigue-critical γ-TiAl components