Non-symmetric cysteine stapling in native peptides and proteins.

Stapling rigidifies peptides through covalent linkages between amino acids. We introduce 2-chloromethyl-6-cyanopyridine for non-symmetric stapling of N-terminal and internal cysteines. This biocompatible method produces diverse peptide macrocycles with enhanced affinity, stability and inhibitory potency.

Stabilisation of the [SiH] Anion within a Supramolecular Assembly.

The hypercoordinate [SiH] anion is not stable in solution. Here, we report the room temperature, solution stable molecular [SiH] complex, [{KCa(NON)(OEt)}][SiH] (NON=4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethyl-xanthene)), where the [SiH] anion is stabilised within a supramolecular assembly that mimics the solid-state environment of the anion in the lattice of KSiH. Solution-state reactivity of the complex towards carbon monoxide, benzaldehyde, azobenzene and acetonitrile is reported, yielding a range of reduction and C-C coupled products.

Liquid-Metal-Enabled Mechanical-Energy-Induced CO Conversion.

A green carbon capture and conversion technology offering scalability and economic viability for mitigating CO emissions is reported. The technology uses suspensions of gallium liquid metal to reduce CO into carbonaceous solid products and O at near room temperature. The nonpolar nature of the liquid gallium interface allows the solid products to instantaneously exfoliate, hence keeping active sites accessible.

Liquid-Metal-Templated Synthesis of 2D Graphitic Materials at Room Temperature.

Room-temperature synthesis of 2D graphitic materials (2D-GMs) remains an elusive aim, especially with electrochemical means. Here, it is shown that liquid metals render this possible as they offer catalytic activity and an ultrasmooth templating interface that promotes Frank-van der Merwe regime growth, while allowing facile exfoliation due to the absence of interfacial forces as a nonpolar liquid. The 2D-GMs are formed at low onset potential and can be in situ doped depending on the choice of organic precursors and the electrochemical set-up.

The Leaf Essential Oil of Eugenia reinwardtiana Growing in Australia.

The leaf essential oils of the two chemotypes of Eugenia reinwardtiana (Blume) DC growing in Australia have been investigated. Chemotype 1, isolated in 0.2% yield, w/w, dry weight, contained major amounts of α-pinene (10-26%), limonene (1-15%), β-caryophyllene (0.

Observation of a tungsten alkane σ-complex showing selective binding of methyl groups using FTIR and NMR spectroscopies.

The alkane σ-complex (HEB)W(CO)(2)(pentane) (HEB = η(6)-hexaethylbenzene) is produced from the UV photolysis of (HEB)W(CO)(3) in alkane solvents at low temperature. IR and (1)H and (13)C NMR spectroscopic data are reported, representing the first NMR data for a group 6 alkane complex. Only binding of the methyl functionality of the pentane ligand was observed in (HEB)W(CO)(2)(pentane).

Insight into binding of alkanes to transition metals from NMR spectroscopy of isomeric pentane and isotopically labeled alkane complexes.

Alkane complexes of the type Cp'Re(CO)2(alkane) (Cp' = cyclopentadienyl or (isopropyl)cyclopentadienyl; alkane = isotopomers of n-pentane and cyclopentane) have been characterized using NMR spectroscopy following photolysis of Cp'Re(CO)3 in the appropriate alkane at 163-193 K. In the case of n-pentane, three different complexes are observed corresponding to binding of the three different types of carbon in this alkane. ROESY NMR experiments indicate that these isomeric complexes are slowly interconverting intramolecularly at 173 K.

Characterization of an organometallic xenon complex using NMR and IR spectroscopy.

Photolysis of Re(iPrCp)(CO)2(PF3) in liquid or supercritical Xe yields two new compounds [Re(iPrCp)(CO)2Xe and Re(iPrCp)(CO)(PF3)Xe]. Re(iPrCp)(CO)(PF3)Xe has been characterized by NMR and IR spectroscopies. The compound is an organometallic Xe complex that has been characterized by using NMR spectroscopy and is shown to be longer-lived than other organometallic Xe complexes by IR spectroscopy.