Mild Bioconjugation Through the Oxidative Coupling of ortho‐Aminophenols and Anilines with Ferricyanide

Using a small‐molecule‐based screen, ferricyanide was identified as a mild and efficient oxidant for the coupling of anilines and o‐aminophenols on protein substrates. This reaction is compatible with thiols and 1,2‐diols, allowing its use in the creation of complex bioconjugates for use in biotechnology and materials applications.     

Fiber‐Based Flexible All‐Solid‐State Asymmetric Supercapacitors for Integrated Photodetecting System

Integrated nanodevices with the capability of storing energy are widely applicable and have thus been studied extensively. To meet the demand for flexible integrated devices, all‐solid‐state asymmetric supercapacitors that simultaneously realize energy storage and optoelectronic detection were fabricated by growing Co₃O₄ nanowires on nickel fibers, thus giving the positive electrode, and employing graphene as both the negative electrode and light‐sensitive material. The as‐assembled integrated systems were characterized by an improved energy storage, enhanced power density (at least by 1860 % enhanced) by improving the potential window from 0–0.6 V to 0—1.5 V, excellent photoresponse to white light, and superior flexibility of both the fiber‐based asymmetric supercapacitor and the photodetector. Such flexible integrated devices might be used in smart and self‐powered sensory, wearable, and portable electronics.     

Enzymatic Conversion of Flavonoids using Bacterial Chalcone Isomerase and Enoate Reductase

Flavonoids are a large group of plant secondary metabolites with a variety of biological properties and are therefore of interest to many scientists, as they can lead to industrially interesting intermediates. The anaerobic gut bacterium Eubacterium ramulus can catabolize flavonoids, but until now, the pathway has not been experimentally confirmed. In the present work, a chalcone isomerase (CHI) and an enoate reductase (ERED) could be identified through whole genome sequencing and gene motif search. These two enzymes were successfully cloned and expressed in Escherichia coli in their active form, even under aerobic conditions. The catabolic pathway of E. ramulus was confirmed by biotransformations of flavanones into dihydrochalcones. The engineered E. coli strain that expresses both enzymes was used for the conversion of several flavanones, underlining the applicability of this biocatalytic cascade reaction.     

Metal‐Free Deoxygenation of Carbohydrates

The conversion of readily available cellulosic biomass to valuable feedstocks and fuels is an attrative goal but a challenging transformation that requires the cleavage of multiple nonactivated C? O bonds. Herein, the Lewis acid trispentafluorophenylborane (B(C₆F₅)₃) is shown to catalyze the metal‐free hydrosilylative reduction of monosaccharides and polysaccharides to give hydrocarbons with reduced oxygen content. The choice of the silane reductant influences the degree of deoxygenation, with diethylsilane effecting the complete reduction to produce hexanes while tertiary silanes give partially deoxygenated tetraol and triol products.     

Serendipitous Discovery of a Potent Influenza Virus A Neuraminidase Inhibitor

We have previously reported a potent neuraminidase inhibitor that comprises a carbocyclic analogue of zanamivir in which the hydrophilic glycerol side chain is replaced by the hydrophobic 3‐pentyloxy group of oseltamivir. This hybrid inhibitor showed excellent inhibitory properties in the neuraminidase inhibition assay (K_i=0.46 nM ; K_{i (zanamivir)}=0.16 nM ) and in the viral replication inhibition assay in cell culture at 10^?8 M . As part of this lead optimization, we now report a novel spirolactam that shows comparable inhibitory activity in the cell culture assay to that of our lead compound at 10^?7 M . The compound was discovered serendipitously during the attempted synthesis of the isothiourea derivative of the original candidate. The X‐ray crystal structure of the spirolactam in complex with the N8 subtype neuraminidase offers insight into the mode of inhibition.     

Dehydrogenative Meyer–Schuster‐Like Rearrangement: A Gold‐Catalyzed Reaction Generating an Alkyne

Easily accessible propargylic esters are converted to the inverted alkynyl ketones in an oxidative gold‐catalyzed reaction. Gagosz’s catalyst in combination with PhI(OAc)₂ is the best system for this conversion and 18 examples with yields up to 80 % are reported. The results indicate that the triple bond in the product is formed by elimination from a vinylgold intermediate. In a formal sense the new conversion overall is a dehydrogenative Meyer–Schuster rearrangement.     

Quinones as Dienophiles in the Diels–Alder Reaction: History and Applications in Total Synthesis

In the canon of reactions available to the organic chemist engaged in total synthesis, the Diels–Alder reaction is among the most powerful and well understood. Its ability to rapidly generate molecular complexity through the simultaneous formation of two carbon? carbon bonds is almost unrivalled, and this is reflected in the great number of reported applications of this reaction. Historically, the use of quinones as dienophiles is highly significant, being the very first example investigated by Diels and Alder. Herein, we review the application of the Diels–Alder reaction of quinones in the total synthesis of natural products. The highlighted examples span some 60 years from the landmark syntheses of morphine (1952) and reserpine (1956) by Gates and Woodward, respectively, through to the present day examples, such as the tetracyclines.     

Mixed IR/Vis Two‐Dimensional Spectroscopy: Chemical Exchange beyond the Vibrational Lifetime and Sub‐ensemble Selective Photochemistry

Two‐dimensional exchange spectroscopy (2D EXSY) is a powerful method to study the interconversion (chemical exchange) of molecular species in equilibrium. This method has recently been realized in femtosecond 2D‐IR spectroscopy, dramatically increasing the time resolution. However, current implementations allow the EXSY signal (and therefore the chemical process of interest) only to be tracked during the lifetime (T₁) of the observed spectroscopic transition. This is a severe limitation, as typical vibrational T₁ are only a few ps. An IR/Vis pulse sequence is presented that overcomes this limit and makes the EXSY signal independent of T₁. The same pulse sequence allows to collect time‐resolved IR spectra after electronic excitation of a particular chemical species in a mixture of species with strongly overlapping UV/Vis spectra. Different photoreaction pathways and dynamics of coexisting isomers or of species involved in different intermolecular interactions can thus be revealed, even if the species cannot be isolated because they are in rapid equilibrium.     

Large Hexagonal Bi‐ and Trilayer Graphene Single Crystals with Varied Interlayer Rotations

Bi‐ and trilayer graphene have attracted intensive interest due to their rich electronic and optical properties, which are dependent on interlayer rotations. However, the synthesis of high‐quality large‐size bi‐ and trilayer graphene single crystals still remains a challenge. Here, the synthesis of 100 μm pyramid‐like hexagonal bi‐ and trilayer graphene single‐crystal domains on Cu foils using chemical vapor deposition is reported. The as‐produced graphene domains show almost exclusively either 0° or 30° interlayer rotations. Raman spectroscopy, transmission electron microscopy, and Fourier‐transformed infrared spectroscopy were used to demonstrate that bilayer graphene domains with 0° interlayer stacking angles were Bernal stacked. Based on first‐principle calculations, it is proposed that rotations originate from the graphene nucleation at the Cu step, which explains the origin of the interlayer rotations and agrees well with the experimental observations.     

Molecular Characterization of DNA Double Strand Breaks with Tip‐Enhanced Raman Scattering

DNA double strand breaks (DSBs) are deadly lesions that can lead to genetic defects and cell apoptosis. Techniques that directly detect DNA DSBs include scanning electron microscopy, atomic force microscopy (AFM), and fluorescence based approaches. While these techniques can be used to identify DSBs they provide no information on the molecular events occurring at the break. Tip‐enhanced Raman scattering (TERS) can provide molecular information from DNA at the nanoscale and in combination with AFM provides a new way to visualize and characterize the molecular structure of DSBs. DSBs result from cleavage at the 3’‐ and 5’‐bonds of deoxyribose upon exposure to UVC radiation based on the observation of P? O? H and methyl/methylene deformation modes enhanced in the TERS spectra. It is hypothesized that strand fragments are hydrogen‐terminated at the lesion, indicating the action of free radicals during photon exposure.