Synthetic Receptors Based on Abiotic Cyclo(pseudo)peptides

Work on the use of cyclic peptides or pseudopeptides as synthetic receptors started even before the field of supramolecular chemistry was firmly established. Research initially focused on the development of synthetic ionophores and involved the use of macrocycles with a repeating sequence of subunits along the ring to facilitate the correlation between structure, conformation, and binding properties. Later, nonnatural amino acids as building blocks were also considered. With growing research in this area, cyclopeptides and related macrocycles developed into an important and structurally diverse receptor family. This review provides an overview of these developments, starting from the early years. The presented systems are classified according to characteristic structural elements present along the ring. Wherever possible, structural aspects are correlated with binding properties to illustrate how natural or nonnatural amino acids affect binding properties

Optical detection of di- and triphosphate anions with mixed monolayer-protected gold nanoparticles containing zinc(II)–dipicolylamine complexes

Gold nanoparticles covered with a mixture of ligands of which one type contains solubilizing triethylene glycol residues and the other peripheral zinc(II)–dipicolylamine (DPA) complexes allowed the optical detection of hydrogenphosphate, diphosphate, and triphosphate anions in water/methanol 1:2 (v/v). These anions caused the bright red solutions of the nanoparticles to change their color because of nanoparticle aggregation followed by precipitation, whereas halides or oxoanions such as sulfate, nitrate, or carbonate produced no effect. The sensitivity of phosphate sensing depended on the nature of the anion, with diphosphate and triphosphate inducing visual changes at significantly lower concentrations than hydrogenphosphate. In addition, the sensing sensitivity was also affected by the ratio of the ligands on the nanoparticle surface, decreasing as the number of immobilized zinc(II)–dipicolylamine groups increased. A nanoparticle containing a 9:1 ratio of the solubilizing and the anion-binding ligand showed a color change at diphosphate and triphosphate concentrations as low as 10 μmol/L, for example, and precipitated at slightly higher concentrations. Hydrogenphosphate induced a nanoparticle precipitation only at a concentration of ca. 400 μmol/L, at which the precipitates formed in the presence of diphosphates and triphosphates redissolved. A nanoparticle containing fewer binding sites was more sensitive, while increasing the relative number of zinc(II)–dipicolylamine complexes beyond 25% had a negative impact on the limit of detection and the optical response. Transmission electron microscopy provided evidence that the changes of the nanoparticle properties observed in the presence of the phosphates were due to a nanoparticle crosslinking, consistent with the preferred binding mode of zinc(II)–dipicolylamine complexes with phosphate anions which involves binding of the anion between two metal centers. This work thus provided information on how the behavior of mixed monolayer-protected gold nanoparticles is affected by multivalent interactions, at the same time introducing a method to assess whether certain biologically relevant anions are present in an aqueous solution within a specific concentration range

Correction : Functionalisable acyclic cucurbiturils

The authors regret that in the introduction an important reference was omitted that reported another strategy to access functionalised acyclic cucurbiturils. The additional reference is given below. The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers

Transmembrane fluoride transport: direct measurement and selectivity studies

Fluoride has been overlooked as a target in the development of synthetic anion transporters despite natural fluoride transport channels being recently discovered. In this paper we report the direct measurement of fluoride bilayer transport facilitated by a series of strapped calix[4]pyrroles and show that these compounds facilitate transport via an electrogenic mechanism (determined using valinomycin and monensin coupled transport assays and an additional osmotic response assay). An HPTS transport assay was used to quantify this electrogenic process and assess the interference of naturally occurring fatty acids with the transport process and Cl- over H+/OH- transport selectivity

Surface exposure ages imply multiple low-amplitude Pleistocene variations in East Antarctic Ice Sheet, Ricker Hills, Victoria Land

One of the major issues in (palaeo-) climatology is the response of Antarctic ice sheets to global climate changes. Antarctic ice volume has varied in the past but the extent and timing of these fluctuations are not well known. In this study, we address the question of amplitude and timing of past Antarctic ice level changes by surface exposure dating using in situ produced cosmogenic nuclides (10Be and 21Ne). The study area lies in the Ricker Hills, a nunatak at the boundary of the East Antarctic Ice Sheet in southern Victoria Land. By determining exposure ages of erratic boulders from glacial drifts we directly date East Antarctic Ice Sheet variations. Erosion-corrected neon and beryllium exposure ages indicate that a major ice advance reaching elevations of about 500m above present ice levels occurred between 1.125 and 1.375 million years before present. Subsequent ice fluctuations were of lesser extent but timing is difficult as all erratic boulders from related deposits show complex exposure histories. Sample-specific erosion rates were on the order of 20-45cmMa-1 for a quartzite and 10-65cmMa-1 for a sandstone boulder and imply that the modern cold, arid climate has persisted since at least the early Pleistocen

Chirality Sensing of Terpenes, Steroids, Amino Acids, Peptides and Drugs with Acyclic Cucurbit[n]urils and Molecular Tweezers

Achiral chromophoric hosts, i.e. acyclic cucurbit[ n ]urils and molecular tweezers, were found to respond with characteristic Circular Dichroism (CD) spectra to the presence of micromolar concentrations of chiral hydrocarbons, terpenes, steroids, amino acids and their derivates, and drugs in water. In favourable cases, this allows for analyte identification or for reaction monitoring

Arctic Ocean evidence for late Quaternary initiation of northern Eurasian ice sheets

A high-resolution multiparameter stratigraphy allows the identification of late Quaternary glacial and interglacial cycles in a central Arctic Ocean sediment core. Distinct sandy layers in the upper part of the otherwise fine-grained sediment core from the Lomonosov Ridge (lat 87.5°N) correlate to four major glacials since ca. 0.7 Ma. The composition of these ice-rafted terrigenous sediments points to a glaciated northern Siberia as the main source. In contrast, lithic carbonates derived from North America are also present in older sediments and indicate a northern North American glaciation since at least 2.8 Ma. We conclude that large-scale northern Siberian glaciation began much later than other Northern Hemisphere ice sheets

Arctic Ocean evidence for late Quaternary initiation of northern Eurasian ice sheets

A high-resolution multiparameter stratigraphy allows the identification of late Quaternary glacial and interglacial cycles in a central Arctic Ocean sediment core. Distinct sandy layers in the upper part of the otherwise fine-grained sediment core from the Lomonosov Ridge (lat 87.5°N) correlate to four major glacials since ca. 0.7 Ma. The composition of these ice-rafted terrigenous sediments points to a glaciated northern Siberia as the main source. In contrast, lithic carbonates derived from North America are also present in older sediments and indicate a northern North American glaciation since at least 2.8 Ma. We conclude that large-scale northern Siberian glaciation began much later than other Northern Hemisphere ice sheets