Vesicle lipid bilayers have been employed as templates to modulate the product distribution in a dynamic covalent library of Michael adducts formed by mixing a Michael acceptor with thiols. In methanol solution, all possible Michael adducts were obtained in similar amounts. Addition of vesicles to the dynamic covalent library led to the formation of a single major product. The equilibrium constants for formation of the Michael adducts are similar for all of the thiols used in this experiment, and the effect of the vesicles on the composition of the library is attributed to the differential partitioning of the library members between the lipid bilayer and the aqueous solution. The results provide a quantitative approach for exploiting dynamic covalent chemistry within lipid bilayers.To date the majority of diene carboxylation processes afford the α,δ-dicarboxylated product, the selective mono-carboxylation of dienes is a significant challenge and the major product reported under transition metal catalysis arises from carboxylation at the α-carbon. Herein we report a new electrosynthetic approach, that does not rely on a sacrificial electrode, the reported method allows unprecedented direct access to carboxylic acids derived from dienes at the δ-position. In addition, the α,δ-dicarboxylic acid or the α,δ-reduced alkene can be easily accessed by simple modification of the reaction conditions.Despite the proven ability to form supramolecular assemblies via coordination to copper halides, organometallic building blocks based on four-membered cyclo-P4 ligands find only very rare application in supramolecular chemistry. To date, only three types of supramolecular aggregates were obtained based on the polyphosphorus end-deck complexes CpRTa(CO)2(η4-P4) (1a CpR = Cp''; 1b CpR = Cp'''), with none of them, however, possessing a guest-accessible void. To achieve this target, the use of silver salts of the weakly coordinating anion SbF6 - was investigated as to their self-assembly in the absence and in the presence of the template molecule P3Se4. The two-component self-assembly of the building block 1a and the coinage-metal salt AgSbF6 leads to the formation of 1D or 3D coordination polymers. However, when the template-driven self-assembly was attempted in the presence of an aliphatic dinitrile, the unprecedented barrel-like supramolecular host-guest assembly P3Se4@[(Cp''Ta(CO)2(η4-P4))Ag8]8+ of 2.49 nm in size was formed. Moreover, cyclo-P4-based supramolecules are connected in a 2D coordination network by dinitrile linkers. The obtained compounds were characterised by mass-spectrometry, 1H and 31P NMR spectroscopy and X-ray structure analysis.The continuing interest in nanoscale research has spurred the development of nanosensors for liquid phase measurements. These include nanopore-based sensors typically employed for detecting nanoscale objects, such as nanoparticles, vesicles and biomolecules, and electrochemical nanosensors suitable for identification and quantitative analysis of redox active molecules. In this Perspective, we discuss conductive nanopipettes (CNP) that can combine the advantages of single entity sensitivity of nanopore detection with high selectivity and capacity for quantitative analysis offered by electrochemical sensors. Additionally, the small physical size and needle-like shape of a CNP enables its use as a tip in the scanning electrochemical microscope (SECM), thus, facilitating precise positioning and localized measurements in biological systems.Molecular assemblers were proposed by K. Eric Drexler in 1986, based on the ideas of R. Feynman. In his (quite lurid) book "Engines of Creation The Coming Era of Nanotechnology" and follow-up publications Drexler proposes molecular machines capable of positioning reactive molecules with atomic precision and to build larger, more sophisticated structures via mechanosynthesis.  https://www.selleckchem.com/products/CHIR-258.html  These imaginative visions started a hot controversy. The debate culminated in a cover story of Chemical & Engineering News in 2003 (ref. 1) with the key question "Are molecular assemblers - devices capable of positioning atoms and molecules for precisely defined reactions - possible?" with Drexler as the proponent and Nobelist Richard E. Smalley being the opponent. Smalley raised two major objections the "fat fingers" and the "sticky fingers" problem. To grab and guide each individual atom the assembler must have many nano-fingers. Smalley argued that there is just not enough room in the nanometer-sized reaction region to accommodate all the fingers of all the manipulators necessary to have complete control of the chemistry. The sticky finger issue arises from the problem that …"the atoms of the manipulator hands will adhere to the atom that is being moved. So it will often be impossible to release the building block in precisely the right spot." Smalley concludes that the fat and the sticky finger problems are fundamental and cannot be avoided. While some of the statements of E. Drexler are bold and probably not very realistic, his ideas are inspiring and might be a good starting point to assess on how far laboratory chemistry has advanced towards real "molecular assemblers" within the last two decades.A hydroxamate transfer reaction between metal complexes has been investigated by a combination of experimental and theoretical studies. A hydroxamate-bound cobalt(ii) complex bearing a tetradentate macrocyclic ligand, [CoII(TBDAP)(CH3C(-NHO)O)]+ (1), is prepared by the reduction of a hydroximatocobalt(iii) complex with a biological reductant. Alternatively, 1 is accessible via a synthetic route for the reaction between the cobalt(ii) complex and acetohydroxamic acid in the presence of a base. 1 was isolated and characterized by various physicochemical methods, including UV-vis, IR, ESI-MS, and X-ray crystallography. The hydroxamate transfer reactivity of 1 was examined with a zinc complex, which was followed by UV-vis and ESI-MS. Kinetic and activation parameter data suggest that the hydroxamate transfer reaction occurs via a bimolecular mechanism, which is also supported by DFT calculations. Moreover, 1 is able to inhibit the activity against a zinc enzyme, i.e., matrix metalloproteinase-9. Our overall investigations of the hydroxamate transfer using the synthetic model system provide considerable insight into the final step involved in the inhibition of zinc-containing enzymes.