The interest in functional supramolecular systems for the design of innovative materials and technologies, able to fundamentally change the world, is growing at a high pace. The huge array of publications that appeared in recent years in the global literature calls for systematization of the structural trends inherent in the formation of these systems revealed at different molecular platforms and practically useful properties they exhibit. The attention is concentrated on the topics related to functional supramolecular systems that are actively explored in institutes and universities of Russia in the last 10–15 years, such as the chemistry of host–guest complexes, crystal engineering, self-assembly and self-organization in solutions and at interfaces, biomimetics and molecular machines and devices.The bibliography includes 1714 references.
The mechanism that guides the formation of exceptionally preserved fossils with soft tissues variously displayed is a paramount challenge to paleontology. The key question for exceptional preservation is the nature of the slowdown of decay and acceleration of soft tissue mineralization. Here we report the experimental formation of subfossils of the brine shrimpArtemia salina(Crustacea, Branchiopoda), which were produced during 14 months of aging in a kaolinite clay sediment. EDS/SEM elemental analyses showed that the subfossils were preserved as thin clay-organic replicas that displayed fine anatomical details. Decomposition in the clay-colloidal solution established highly heterogeneous acidic conditions, with the lowest pH typically found in the vicinity of the buried organisms, and visually manifested in patchy coloration of the sediment. Elevated acidity is likely what ultimately slowed the decay. An acidic environment increases the rate of clay destruction and, consequently, the diffusion rate decline. As a result, the acidic products quickly accumulate around a buried body; this in turn inhibits bacterial proliferation, accelerates the acidic hydrolysis of clay and, accordingly, the release of tanning and mineralizing agents. The subfossils remained stable under experimental high pressure and temperature. These model subfossils exhibit features that are typical of some Lagerstätten fossils preserved in fine-grained sediments.
Fabrication of metal–organic frameworks (MOFs) as films on surfaces is a challenging and actively developed field in the context of potential applications of surface-integrated MOFs (SURMOFs) in sensing, catalysis and molecular electronics. Herein, we report a method for the preparation of composites of graphene oxide (GO) and zinc tetracarboxyphenyl porphyrin SURMOFs, which are potentially useful as synergetic catalysts on planar solid supports. The SURMOF films were assembled via layer-by-layer coordination of zinc porphyrins with ZnAc2 clusters on the ultrathin surface coatings of GO. We found that non-covalent adsorption of zinc acetate on the GO films is essential for anchoring porphyrin molecules in the growth-initiating template layer. UV-vis spectroscopy provided evidence for a stepwise assembly of the deposited SURMOF films. By using a combination of X-ray diffraction, scanning electron microscopy and atomic force microscopy methods, we show that the resulting GO-associated SURMOFs exhibit a leaflet-like planar morphology with out-of-plane periodicity. Because of the influence of the well-defined surface geometry, the molecular organization in thin SURMOFs is different from that of synthetic bulk materials with a similar composition. The results of BET method measurements suggest that the fabricated SURMOF films have exceptionally large surface areas and adsorption capacities. Our results provide a basis for new types of composite SURMOF structures using GO surface coatings as growth-guiding scaffolds for metal–organic coordination networks integrated with various solid supports.