The design, construction, and operation of devices and machines at the molecular scale using the bottom-up approach captivates a lot of interest in nanoscience. Particularly intriguing are interlocked molecular architectures, which are ideal candidates for these aims. [n]Pseudorotaxanes, [n]rotaxanes, and [n]catenanes serve as versatile prototypes for constructing molecular machines because they can be engineered to execute a diverse range of functions, including mechanical-like movements in response to chemical, photochemical, or electrochemical stimuli. The study explores the synthesis and characterization of a two-station two-gate calix[6]arene-based [2]catenane. Building on prior work with calix[6]arene-based Mechanically Interlocked Molecules (MIMs), this research integrates two functional gates—an azobenzene unit and a stilbene unit —into a two-station “track” ring. The synthesis employed threading and capping strategies to prepare the precursor [2]rotaxane isomers 12(azo-up) and 12(azo-down). Challenges in the deprotection of TBS groups led to the adoption of a supramolecular-assisted approach for the direct synthesis of the desired pseudorotaxane. The final catenation reaction, using a trans-stilbene-based bisacyl chloride as the “clipping unit”, afforded the [2]catenane C3(azo-down) in 25% yield after purification. Mass spectrometry and NMR spectroscopy confirmed the successful synthesis and orientation of C3(azo-down).

Eleven calix[4]arene ligands, bearing zwitterionic α‐amino acids or charged ammonium or sulfonate/carboxylate groups, are synthesized and screened for the binding to the envelopes of three bacterial strain representatives of Gram‐positive, Gram‐negative, and mycobacteria. The binding is followed by on‐cell Saturation Transfer Difference Nuclear Magnetic Resonance (NMR) experiments directly on alive cells. While the anionic tetrasulfonatocalixarene does not bind to any bacterial strains significantly and the cationic calixarenes strongly bind to both Gram‐positive and Gram‐negative bacteria, the zwitterionic tetraprolino‐ and tetraphenylalaninocalix[4]arene show a remarkable selectivity for Gram‐negatives over Gram‐positives and mycobacteria. The tetraprolinocalixarene binds to the lipopolysaccharides extracted from two Gram‐negative bacteria (Pseudomonas putida or Escherichia coli), suggesting these biomacromolecules as possible targets in the recognition of their cell walls. The ligand binding epitope map demonstrates a deep involvement of the amino acids and calixarene aromatic nuclei in the interaction. In this study, for the first time, the ability of synthetic macrocycles to selectively recognize the envelope of Gram‐negative bacteria is highlighted, and the way to the chemical modifications of the ligand structure is paved to develop devices for the detection or treatment of bacterial infections, thus allowing to add another string to the bow for the fight against antimicrobial resistance.

The incorporation of three terdentate 2,6-bis-triazolyl-pyridine units on a calix[4]arene gives a preorganized lipophilic ligand with enhanced efficiency in binding trivalent actinides over lanthanides. Combined time-resolved laser-induced fluorescence spectroscopy, and 1D and 1H-15N HMQC NMR investigations allowed to propose the structures of the complexes and to provide insights into the actinide selectivity.

A highly selective palladium-catalyzed carbonylation of 2-alkynylanilines bearing an amide moiety to condensed six-membered het-erocyclic structures has been developed under mild conditions(room temperature and atmospheric pressure of CO).The carbonyla-tive protocol is also compatible with CO surrogates,such as benzene-1,3,5-triyl triformate(TFBen)or the newly developed ca-lix[6]arenes functionalized with six formate groups(CLX[6]CO),which are both capable to release CO in situ.A series of tricyclic fused heterocycles containing the important oxazino-quinolinone scaffold have been selectively obtained(only the 6-endo-dig cyclization mode has been observed)in good to excellent yields(up to 99％).

The host-guest interaction of a 1,3,5-trisaminocalix[6]arene receptor with N-methylisoquinolinium trifluoromethanesulfonate (Kass of 500 ± 30 M-1 in CD2Cl2) can be dissipatively driven by means of 2-cyano-2-(4'-chloro)phenylpropanoic acid used as a convenient chemical fuel. When the fuel is added to a dichloromethane solution containing the above complex, the host is induced to immediately release the guest in the bulk solution. Consumption of the fuel allows the guest to be re-uptaken by the host. The operation can be satisfactorily reiterated with four subsequent additions of fuel, producing four successive release-reuptake cycles. The percentage of the guest temporarily released in the bulk solution by the host and the time required for the reuptake process can be finely regulated by varying the quantities of added fuel.

Nitroaromatic explosives are the most common explosives, and their detection is important to public security, human health, and environmental protection. In particular, the detection of solid explosives through directly revealing the presence of their vapors in air would be desirable for compact and portable devices. In this study, amino-functionalized carbon nanotubes were used to produce resistive sensors to detect nitroaromatic explosives by interaction with their vapors. Devices formed by carbon nanotube networks working at room temperature revealed trinitrotoluene, one of the most common nitroaromatic explosives, and di-nitrotoluene-saturated vapors, with reaction and recovery times of a few and tens of seconds, respectively. This type of resistive device is particularly simple and may be easily combined with low-power electronics for preparing portable devices.

The temporal control (ON/OFF/ON) of the fluorescence of a dichloromethane/acetonitrile 1 : 1 solution of calixarene 3 decorated with two pyrenyl moieties at the upper rim is attained by the addition of CCl3CO2H used as a convenient chemical fuel.

The main goal of this project is to demonstrate the advantages of sensor integration on a remotely controlled robotic platform for increasing operator safety and improving the classification of explosive targets. This is accomplished by combining the imaging provided by radars and an optoelectronic sensor, a time-of-flight (ToF) depth camera. An additional aim is to demonstrate the operability and practicality of the system in a field with landmine simulants having plastic cases.