Light-gated binding in double-motorized porphyrin cages

Molecular motors change conformation under the influence of light and when attached to host molecules they may find applications as sensors and switchable catalysts. Here we present a porphyrin macrocyclic host functionalized with two motor appendages for future catalytic applications. The compound is formed as a mixture of six stereoisomers (three sets of enantiomers), which have been separated by (chiral) chromatography. 1H NMR and chiral spectroscopy revealed that in one set of diastereomers the two motors interact with the cavity of the host (bound-bound), whereas in a second set one interacts and the other one does not (bound-loose). In the third set both motors do not interact with the host compound (loose-loose). The motorized hosts bind guest molecules in the order: (loose-loose) > (bound-loose) > (bound-bound). They can be switched with light to pseudo-identical diastereomers, leading to orthogonal behavior in the light-gated binding of guest molecules. Whereas the photo-isomerization of the diastereomer set loose-loose significantly lowers the binding affinity for viologen guests, the opposite is true for the diastereomer set bound-bound, i.e. the binding affinity increases. For the diastereomer set bound-loose no influence on guest binding is observed as the effect of photoisomerization on the motors is cancelled out.

Taphonomy of a Panopea Ménard de la Groye, 1807 shell bed from the Pisco Formation (Miocene, Peru)

Invertebrate taphonomy can provide significant information about the post-mortem processes that affected the fossil record. In the East Pisco Basin of southern Peru, a Panopea Ménard de la Groye, 1807 shell bed was found in the upper Miocene strata of the Pisco Formation, hinting at a peculiar biostratinomic and diagenetic history. This bed contains abundant invertebrate fossil molds cemented by dolomite. The specimens of the deep infaunal bivalve, Panopea sp., occur together with bivalves representative of shallow infaunal species (Trachycardium sp. and Dosinia ponderosa [Gray, 1838]) and balanid barnacles, which are sessile encrusters. The Panopea specimens host compound molds evidencing an abundant encrusting fauna, including serpulids, ?foraminifera, bryozoans, and barnacles that colonized the inner surfaces of the valves before their final burial. We hypothesize that short-term, storm-related processes exhumed the living bivalves, resulting in a sedimentological concentration of relatively well-preserved shells. After the death of the exhumed bivalves, the inner surfaces of the articulated Panopea shells, representing hard-substratal, sheltered environments on an otherwise unstable sandy seafloor (i.e., “benthic islands”), were colonized by different encrusting organisms. Following the final burial, dolomite precipitated, cementing the sediment infill of the valves. Lastly, a decrease of pH occurred at the sulfate reduction-methanogenesis boundary, inducing the dissolution of the shell carbonate.

Transmembrane Fluoride Transport by a Cyclic Azapeptide With Two β-Turns

Diverse classes of anion transporters have been developed, most of which focus on the transmembrane chloride transport due to its significance in living systems. Fluoride transport has, to some extent, been overlooked despite the importance of fluoride channels in bacterial survival. Here, we report the design and synthesis of a cyclic azapeptide (a peptide-based N-amidothiourea, 1), as a transporter for fluoride transportation through a confined cavity that encapsulates fluoride, together with acyclic control compounds, the analogs 2 and 3. Cyclic receptor 1 exhibits more stable β-turn structures than the control compounds 2 and 3 and affords a confined cavity containing multiple inner –NH protons that serve as hydrogen bond donors to bind anions. It is noteworthy that the cyclic receptor 1 shows the capacity to selectively transport fluoride across a lipid bilayer on the basis of the osmotic and fluoride ion-selective electrode (ISE) assays, during which an electrogenic anion transport mechanism is found operative, whereas no transmembrane transport activity was found with 2 and 3, despite the fact that 2 and 3 are also able to bind fluoride via the thiourea moieties. These results demonstrate that the encapsulation of an anionic guest within a cyclic host compound is key to enhancing the anion transport activity and selectivity.

Layered supramolecular network of cyclodextrin triplet with azobenzene-grafting polyoxometalate for dye degradation and partner-enhancement

A tri-β-cyclodextrin-armed host compound is synthesized to construct layered supramolecular network co-assembly with a doubly azobenzene-decorated polyoxometalate cluster through host-guest interaction. The porous hybrid assembly displays automatic degradation of selective...

Design and synthesis of a bis-macrocyclic host and guests as building blocks for small molecular knots

The thread–link–cut (TLC) approach has previously shown promise as a novel method to synthesize molecular knots. The modular second-generation approach to small trefoil knots described herein involves electrostatic interactions between an electron-rich bis-macrocyclic host compound and electron-deficient guests in the threading step. The bis-macrocyclic host was synthesized in eight steps and 6.6% overall yield. Ammonium and pyridinium guests were synthesized in 4–5 steps. The TLC knot-forming sequence was carried out and produced a product with the expected molecular weight, but, unfortunately, further characterization did not produce conclusive results regarding the topology of the product.

Non-porous organic crystals and their interaction with guest molecules from the gas phase

Some organic molecules encapsulate solvents upon crystallization. One class of compounds that shows a high propensity to form such crystalline solvates are tetraaryladamantanes (TAAs). Recently, tetrakis(dialkoxyphenyl)-adamantanes have been shown to encapsulate a wide range of guest molecules in their crystals, and to stabilize the guest molecules against undesired reactions. The term ‘encapsulating organic crystals’ (EnOCs) has been coined for these species. In this work, we studied the behavior of three TAAs upon exposition to different guest molecules by means of sorption technique. We firstly measured the vapor adsorption/desorption isotherms with water, tetrahydrofuran and toluene, and secondly, we studied the uptake of methane on dry and wet TAAs. Uptake of methane beyond one molar equivalent was detected for wet crystals, even though the materials showed a lack of porosity. Thus far, such behavior, which we ascribe to methane hydrate formation, had been described for porous non-crystalline materials or crystals with detectable porosity, not for non-porous organic crystals. Our results show that TAA crystals have interesting properties beyond the formation of conventional solvates. Gas-containing organic crystals may find application as reservoirs for gases that are difficult to encapsulate or are slow to form crystalline hydrates in the absence of a host compound. Wet tetraaryladamantane crystals take up methane in form of methane hydrate structure I, even though they appear non-porous to argon.

Synthesis and crystal structure of 2,4,6,8-tetrakis(3,5-di-tert-butylphenoxy)pyrimido[5,4-d]pyrimidine: expansion of the Piedfort concept

The title host compound, C62H84N4O4, designed to self-assemble to form a new type of extended core Piedfort unit reminiscent of an eight-legged spider host, forms a number of crystalline inclusion compounds favouring oxygen-containing guest molecules. We have established the presence of this unit in the unsolvated molecular crystal at 100 K, which is monoclinic, space group P21/n, with Z = 8. The new Piedfort unit is chiral and its core structure closely approximates to D 2 symmetry, with both enantiomers present in the crystal. Rather than being superposed with a staggered arrangement of nitrogen atoms, the rings are rotated by an angle of approximately 45° with respect to each other, and the shortest contact between them is 3.181 (2) Å. The compound's significant inclusion properties may be taken to suggest the participation of an extended Piedfort unit in the microcrystalline adducts formed. The presence of such a dimeric host unit in the clathrates has, however, not yet been established because of the current lack of suitable single crystals for X-ray analysis.