Enzymes for energy: Recently, an elegant and efficient protein-engineering approach was proposed to create self-assembling enzyme arrays. This approach paves the way for efficient biofuel cells and for complex bioelectrocatalytic processes (general scheme shown; blue: enzyme, red: substrate, green: product).
The black mamba snake here illustrates the structure of mambaglin-1, a pain-relieving peptide found in its venom. Thick gray lines lines represent the four disulfide bonds linking Cys1–3, 2–4, 5–6, and 7–8. The N-terminus of the 57 amino acid peptide is at the head of the snake and the C-terminus at the tail. The peptide has potential as a pharmacological probe or drug lead. Image design by David Craik and drawing by Peta Harvey, University of Queensland.
A definite turn-on: Turning on fluorescence only where successful labeling is happening sounds as desirable as delivering a drug only where the drug target resides. New fluorogenic xanthene derivatives from the Bertozzi research group are getting us closer to “magic bullet” dyes (see picture).
No added solvent means no waste solvent or recycling costs. Understandably the chemical industry is interested in developing approaches to increase the product to solvent ratio in synthesis. In recent work various zeolites were prepared by grinding the dry materials and then heating to 180 °C, and this method could lead to significant savings in zeolite synthesis.
Discriminating against arsenate: Determination of the structure of periplasmic phosphate binding proteins at very high resolution provides the basis for understanding the high discrimination of bacteria against arsenate. The results complete our insight into earlier erroneous conclusions on the ability of certain bacteria to use arsenate instead of phosphate.
Fundamental aspects of chemically activated reactive intermediates can possibly be learned from the novel generation of arynes. The intramolecular [4+2] cycloaddition between a diyne and an (electronically activated) alkyne also provides a new route to generate arynes (see scheme).
Spot on! Cell-free protein expression on surfaces can be implemented in biosensors and in microfluidic devices like that shown in the picture. Proteins are generated and immobilized successively on separated spots in a microfluidic reactor. This approach opens up novel opportunities for basic and applied biomedical research.
The complex class of cobalamin-sensitive riboswitches use a “kissing loop” to regulate gene expression. The molecular details of the recognition and folding mode of this riboswitch have been revealed by recent X-ray structures. These insights, together with the identification of RNA polymerase pause sites during transcription, have resulted in a more complete understanding of the response mechanism. AdoCbl=adenosylcobalamin.
The migrations of different groups to the metal–carbene center of RhII-stabilized iminocarbenes that were derived from N-sulfonyl triazoles are discussed (see scheme). The reactivity of these Rh-iminocabenes can be tuned easily by variation of substituents on the parent triazole.
Two views: The mechanism of the conjugate addition of linear aldehydes to nitro olefins has been investigated by two research groups. In spite of extensive experimental data, important questions remain unanswered (see scheme; TMS=trimethylsilyl, En=enamine).
Activation à la carte: The direct arylation of heteroarenes was accomplished by employing aromatic esters as effective coupling partners under nickel catalysis (see scheme; Z=O, S). The key process implies an unconventional and unprecedent Ni-catalyzed decarbonylative coupling utilizing cost-efficient nickel catalysts.
Topologically stable magnetic screw-like nanostructures called skyrmions were designed by using the concept of topology and the guidance of theory. These particles in real space are found in non-centrosymmetric compounds such as MnSi. Skyrmions might have an enormous impact in the context of future spintronics applications.
Cross-linked: The concept of phenotypic screening with probes of fully functionalized small molecules (see picture) has recently been introduced. This approach significantly increases the efficiency and success of target identification after the screening campaign.
Less is more: Significant advancements have been made in recent years in the development of the E-selective, catalytic, functional-group-tolerant semihydrogenation of alkynes to E-alkenes through transition-metal catalysis (see scheme). For this type of catalysis, the use of mononuclear metal catalysts is superior to that of multinuclear metal catalysts.
All aglow: Both a fluorescent biosensor, composed of a circularly permuted yellow fluorescent protein (cpYFP), and a small-molecule fluorescent probe (1) for the detection of CO in living cells have been recently reported. Though different these novel probes were designed based on the unique binding ability of CO to transition-metal ions.
For commercial viability new technologies for the sustainable generation of energy should be simple and efficient. Photoelectrodes made of boron arsenide are the latest advance: they can be synthesized easily directly from the elements and convert sunlight into electric current.
“Ruth” helps iron! A novel method for the non-enzymatic dynamic kinetic resolution (DKR) of secondary aryl alcohols by the use of the planar chiral ferrocene derivative (+)-1 in combination with the ruthenium racemization catalyst 2 yields acetylated alcohols in high enantioselectivity and yield. This development opens opportunities for new developments in the field of non-enzymatic dynamic kinetic resolution.
Radically efficient: New and appealing enantioselective cyclizations leading to highly functionalized carbocycles and heterocycles have been reported (see scheme; TMS=trimethylsilyl). These methodologies, based on the cascade combination of radical and polar steps, provide alternatives to conventional methodologies.
Prochiral silanes: Recent work has demonstrated the powerful potential of enantioselective desymmetrization catalyzed by transition-metal complexes in the stereoselective formation of silicon-stereogenic silanes. These methods offer new possibilities for asymmetric synthesis of any functionalized chiral silanes that possess tetraorganosilicon stereocenters.
Good as gold: Gold hydrides were long considered unstable. In the past few years reports have appeared on not only the stable NHC gold(I) monohydride complex 1 (see structure; NHC=N-heterocyclic carbene) but also a dinuclear gold(I) hydride and most recently the gold(III) monohydride complex 2 with a C-N-C pincer ligand. One can expect new and important impulses for inorganic and organometallic chemistry and homogeneous gold catalysis.
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