Hydrogen-Bonded and Halogen-Bonded: Orthogonal Interactions for the Chloride Anion of a Pyrazolium Salt

In the hydrochloride of a pyrazolyl-substituted acetylacetone, the chloride anion is hydrogen-bonded to the protonated pyrazolyl moiety. Equimolar co-crystallization with tetrafluorodiiodobenzene (TFDIB) leads to a supramolecular aggregate in which TFDIB is situated on a crystallographic center of inversion. The iodine atom in the asymmetric unit acts as halogen bond donor, and the chloride acceptor approaches the σ-hole of this TFDIB iodine subtending an almost linear halogen bond, with Cl···I = 3.1653(11) Å and Cl···I–C = 179.32(6)°. This contact is roughly orthogonal to the N–H···Cl hydrogen bond. An analysis of the electron density according to Bader’s Quantum Theory of Atoms in Molecules confirms bond critical points (bcps) for both short contacts, with ρbcp = 0.129 for the halogen and 0.321eÅ−3 for the hydrogen bond. Our halogen-bonded adduct represents the prototype for a future class of co-crystals with tunable electron density distribution about the σ-hole contact.

Effective Elimination and Biodegradation of Polycyclic Aromatic Hydrocarbons from Seawater through the Formation of Magnetic Microfibres

Supramolecular aggregates formed between polycyclic aromatic hydrocarbons and either naphthalene or perylene-derived diimides have been anchored in magnetite magnetic nanoparticles. The high affinity and stability of these aggregates allow them to capture and confine these extremely carcinogenic contaminants in a reduced space. In some cases, the high cohesion of these aggregates leads to the formation of magnetic microfibres of several microns in length, which can be isolated from the solution by the direct action of a magnet. Here we show a practical application of bioremediation aimed at the environmental decontamination of naphthalene, a very profuse contaminant, based on the uptake, sequestration, and acceleration of the biodegradation of the formed supramolecular aggregate, by the direct action of a bacterium of the lineage Roseobacter (biocompatible with nanostructured receptors and very widespread in marine environments) without providing more toxicity to the environment.

Fluorescence Enhancement by Calixarene Supramolecular Aggregate

We herein constructed supramolecular assemblies from guanidinocalixarenes and sulfonatocalixarenes by exploiting multiple salt bridge interactions. They encapsulate six different kinds of fluorescent dyes (both cationic and anionic), leading to a fluorescence enhancement that could not be achieved by either single calixarene. As such, this study advances the research on high-performance fluorophores.

Macromolecular Structure of a Commercial Humic Acid Sample

The molecular structure of a commercial sample of humic acids (HA) was investigated by membrane dialysis experiments (MD) and low-pressure size-exclusion chromatography (LP-SEC). MD showed that HA molecules were retained by dialysis membrane with a cut-off of 6–8 kDa, independently from HA concentration (15 or 150 mg L−1), NaHCO3 concentration (0.005–2.0 mol L−1), and from propan 2-ol (0–5 v/v %). SEC experiments at low pressure gave chromatograms with a broad peak, with an elution volume between those of the globular proteins bovine serum albumin (molecular weight = 66.5 kDa) and lysozyme from egg (molecular weight = 14.4 kDa). The pattern of the chromatogram did not vary with HA concentration, and second-run chromatograms of single eluted fractions showed relatively sharp peaks. From these data, we reveal that the commercial HA sample analysed has a macromolecular structure rather than being a supramolecular aggregate of relatively small molecules, as recently proposed for some samples of HA obtained from different sources.

A Novel Approach Based on Two-Dimensional Correlation Spectroscopy to Determine the Stoichiometric Ratio of Two Substances Involved in Intermolecular Interactions

A novel technique called AOSD@Job’s, combining asynchronous orthogonal sample design scheme (AOSD) with Job’s method, is proposed to estimate the stoichiometric ratio of two substances that form a supramolecular aggregate under intermolecular interactions. First, a mathematical analysis was performed along with the procedure of the AOSD@Job’s method. Then, the validity of the AOSD@Job’s method was manifested by computer simulation on two model systems. Finally, the AOSD@Job’s method was applied on two real chemical systems. The stoichiometric ratio between the coordination complex of Ni2+ and ethylenediaminetetraacetic acid disodium salt (EDTA) was estimated to be 1.0. Benzyl alcohol (BA) and β-cyclodextrin (β-CD) were determined to form a 1 : 1 host–guest complex. These values were consistent with the values reported in the literature. Compared with the traditional Job’s method, the AOSD@Job’s method has an evident advantage since it is still valid even if all the peaks of the supramolecular aggregate severely overlap with the peaks of the substances that form the aggregate.

Cu(ii)-Based binuclear compound for the application of photosensitive electronic devices

Binuclear Cu(ii)-acetylenedicarboxylate assembled through extensive hydrogen bonding and C–H⋯π interactions to make 3D supramolecular aggregate behaves as light sensing electronic device.