Tuning the Regioselective Functionalization of Trifluoromethylated Dienes via Lanthanum-Mediated Single C−F Bond Activation

The development of new fluorine-containing building blocks and their efficient synthetic access is currently a challenging research field. Herein, the highly regio- and stereoselective addition of a large range of aldehydes onto trifluoromethylated benzofulvenes was achieved using a simple La/I₂/DIBAL-Cl system via a selective C−F bond activation process. This versatile methodology provided homodienyl alcohols bearing a terminal CF₂-alkene with potential further applications, as shown by the dehydration to the first benzofulvenes carrying a difluorovinyl group. In addition, for certain electron-poor aldehydes, unprecedented ipso substitution of the CF₃ group in a diene was observed, which, according to DFT studies, is related to the presence of the large, Lewis-acidic lanthanum metal.     

On classification and construction of algebraic Frobenius manifolds

We develop the theory of generalized bi-Hamiltonian reduction. Applying this theory to a suitable loop algebra we recover a generalized Drinfeld–Sokolov reduction. This gives a way to construct new examples of algebraic Frobenius manifolds.     

Frobenius manifolds from regular classical W-algebras

We obtain polynomial Frobenius manifolds from classical W-algebras associated to regular nilpotent elements in simple Lie algebras using the related opposite Cartan subalgebras.     

Exploiting quadrupolar interactions in the synthesis of the macrocyclic portion of longithorone C

2,3,4,5,6-Pentafluorobenzyl and 3,5-bistrifluoromethylbenzyl ester auxiliaries can enable difficult macrocyclizations to afford rigid all-carbon paracyclophanes. The effectiveness of these auxiliaries has been demonstrated in preparing the carbon skeleton of the macrocyclic natural product longithorone C.     

Extracellular electron transfer in microbial biocorrosion

Biocorrosion by microbial biofilms is also termed microbiologically influenced corrosion (MIC). For many decades in MIC research, people focused on corrosive metabolites. In the past decade, researchers started to apply bioenergetics to MIC science research. They realized that extracellular oxidation of a metal can supply electrons for microbial respiration, which causes MIC. Because these electrons must be transported to the cytoplasm via extracellular electron transfer (EET), this kind of MIC is called EET-MIC, which is different from metabolite-MIC (M-MIC). Advances have been made to decipher inward EET involved in MIC. Carbon source starvation and electron mediator acceleration have been used to study impact of EET on MIC. More recently, manipulations of electron mediator-related genes have been used to elucidate EET in MIC. EET in energy metabolism in microbiology and EET for MIC are intertwined. Well-established corrosion research tools, especially electrochemical methods that are highly sensitive, are useful for microbiologists to study EET.     

Bioenergetics and extracellular electron transfer in microbial fuel cells and microbial corrosion

Bioenergetics can be used to analyze the theoretical voltage output of a microbial fuel cell (MFC) and the thermodynamic driving force in microbiologically influenced corrosion (MIC). MFCs involve both inward and outward extracellular electron transfer (EET), whereas only inward EET is behind EET–MIC caused by an electroactive biofilm's harvest of energy from a metal. EET is often rate-limiting, and it is an important process in microbial energy metabolism. EET is critical to the understanding of MFCs and EET–MIC bioelectrochemical processes. Many advances have been made in the past decade on EET by MFC and MIC researchers. Gene manipulations have been used to improve EET in MFCs, leading to enhanced energy output. They have also been used to elucidate the EET processes for better understanding of EET–MIC, which aids in MIC analysis and decision-making of biocide treatment and its efficacy assessment. Researchers are starting to integrate EET knowledge from both fields.     

Array-based functional screening of heparin glycans

Array methodologies have become powerful tools for interrogation of glycan-protein interactions but have critically lacked the ability to generate cell response data. Here, we report the development of a slide-based array method exemplified by measurement of activation of fibroblast growth factor signaling by heparin saccharides. Heparan sulfate-deficient Swiss 3T3 cells were overlaid onto an aminosilane-coated slide surface onto which heparin saccharides had been spotted and immobilized. The cells were transiently stimulated with FGF2 and immunofluorescence measured to assess downstream ERK1/2 phosphorylation. Activation of this signaling pathway response was restricted to cells exposed to heparin saccharides competent to activate FGF2 signaling. Differential activation of the overlaid cells by different-sized heparin saccharides was demonstrated by quantitative measurement of fluorescence intensity. This "glycobioarray" platform has significant potential as a generic tool for functional glycomics screening.     

Development of perfluoroarene-arene interactions for macrocyclic en-yne metathesis and the total synthesis of macrocyclic natural products

Efficient direct en-yne metathesis of strained macrocyclic systems is possible using highly active Grubbs-Hoveyda second-generation catalyst and when exploiting fluoroarene-arene gearing interactions. These interactions are effective even under high reaction temperatures and in the presence of a competitive pi-rich solvent such as toluene. These results suggest that efficient pi-pi stacking or pi-lp interactions between auxiliaries containing pentafluorophenyl and 3,5-bis(trifluoromethyl)phenyl groups are responsible for the good yields of macrocyclization products. The 3,5-bis(trifluoromethyl)benzyl gearing elements provide higher yields and greater E-selectivity in the macrocyclic en-yne metathesis to form model paracyclophanes that could be applied toward the preparation of members of the longithorone family of natural products.