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A number of ten stable free mono-, di- and tri-radicals of the TEMPO nitroxide type were synthesized and characterized via physico-chemical methods (elemental analysis, MS, UV-Vis, IR, ESR, and X-ray, where appropriate). The design of the compounds was chosen such that supramolecular interaction could be gained via hydrogen-bonding or π–π interactions; therefore the compounds should contain amino- or urea-moieties, (nitro)aromatic rings, or a crown ether residue. The formation of inclusion complexes between these (poly)radicals and cucurbit[6]uril was studied via Electron Spin Resonance (ESR) spectroscopy. The binding constants were evaluated from the analysis of the rotational correlation time dependence on the concentration of cucurbit[6]uril. These constants are an order of magnitude lower than the values reported before for complexes of TEMPO derivatives with β-cyclodextrin. The complexation behaviour of cucurbit[6]uril was revealed in the ESR spectra of the nitroxides in the presence and in the absence of the host molecules, recorded at low temperatures. The experiments revealed that the mobilities of the nitroxides investigated are higher in the absence of the host molecule, a different behaviour compared with complexes with cyclodextrins. This behavior can be understood by taking into account the role played by the presence of salts necessary to ensure the solubility of cucurbit[6]uril in water.

The reactions of {Cr6} horseshoe chains {[nPr2NH2]3[Cr6F11(O2CtBu)10]}2, 1 and precursors of actinides and group IV metals led to a series of ring complexes [nPr2NH2][Cr7TiF6O2(O2CtBu)16], 2, [nPr2NH2][Cr6Ti2F5O3(O2CtBu)16], 3, [Cr6ThF7(O2CtBu)15 (Me2SO)], 4, [(nPr2NH2)2(Cr6Th2F12(O2CtBu)16)], 5 and [nPr2NH2][Cr6U2O2F8(O2CtBu)16(Me2SO)], 6. X-ray structure studies indicate that the {Cr6} chains maintain their structures in these complexes, acting as polydentate fluoride ligands. Their static magnetic properties were measured and fitted by isotropic exchange Hamiltonian. In accordance with 1, the magnetic exchanges between CrIII are antiferromagnetic, while the exchange interactions can be modified by the tetravalent metals. For compound 6, ferromagnetic exchanges JCr–U and JU–U are obtained. EPR spectra of compounds 2–5 were measured at Q band and were simulated. The spectrum of 2 has the same profile as {Cr7Cd} and {Cr7Zn} rings with a ground state S = 3/2. 3, 4 and 5 give similar EPR spectra with S = 0 ground states.

Low-molecular-weight organic gelators generate physical gels by the formation of three-dimensional fibrous network structures as a response to various physicochemical stimuli such as heat, light, ultrasound and chemical environments. Dibenzylidene sorbitol (DBS) represents a typical compound able to generate gels because of some prerequisite structural features: the presence of functional groups to form intermolecular hydrogen bonds and of aromatic groups to be involved in π–π interactions, or chirality. Herein, we present the synthesis of three derivatives of DBS-bearing carboxy groups attached to phenyl rings and the corresponding spin-labelled compounds. We studied the formation of physical gels resulting from self-assembly of DBS derivatives with the aim of highlighting the influence of the position of the carboxy group on the gel properties. These types of compounds can form gels in polar solvents (such as water, DMSO) by either temperature treatment or variation of the pH. In this study, the systems were investigated by rheological measurements, SEM analysis and EPR measurements. The results showed that the introduction of carboxy groups into the structure of DBS generates weaker gels compared with the parent gelator, DBS. The spin probes used in this study (spin-labelled DBS derivatives and 5-doxyl stearic acid) demonstrated that assembly of gelator molecules is a highly selective process. The two-component feature of EPR spectra of spin probes in gels is proof that EPR spectroscopy is sensitive to the non-homogeneity of these systems.

The formation of alginate gel from low molecular weight alginate and very low molecular weight alginate in the presence of divalent cations was investigated using Electron Paramagnetic Resonance (EPR) spectroscopy. The transition from sol to gel in the presence of divalent cations was monitored by the changes in the dynamics of spin labelled alginate. The immobilisation of the spin labelled alginate in the gel reflects the strength of interaction between the cation and alginate chain. Diffusion experiments showed that both the cation and alginate polyanion in the gel fibres can exchange with molecules in solution. In particular, we showed that dissolved alginate polyanions can replace alginates in the gel fibres, which can hence diffuse through the bulk of the gel. This illustrates the surprisingly highly dynamic nature of these gels and opens up the possibility of preparing multicomponent alginate gels via polyanion exchange process.

In this work, we present evidence on the suitability of spin probes to report on the thermal treatment of bovine serum albumin (BSA), in the temperature range 293-343 K, and indirectly monitor the release of sodium dodecyl sulfate (SDS) from its complex with BSA using a covalent gel with β-cyclodextrin (β-CD) in the network. The spin probes used, 5- and 7-doxyl-stearic acids (5-DSA, 7-DSA) or 4-(N,N'-dimethyl-N-hexadecyl)ammonium-2,2',6,6'-tetramethylpiperidine-1-oxyl iodide (CAT16), present similar, fatty acid-like structural features. Their continuous wave electron paramagnetic resonance (CW-EPR) spectra, however, reflect different dynamics when complexed with BSA: a restricted motion for 5-DSA, almost nonsensitive to the heating/cooling cycle, and a faster temperature-dependent dynamic motion for CAT16. Molecular docking allows us to rationalize these results by revealing the different binding modes of 5-DSA and CAT16. The EPR data on the temperature effect on BSA are supported by circular dichroism results projecting recovery, upon cooling, of the initial binding ability of BSA for samples heated to 323 K. The interactions occurring in BSA/SDS/β-CD systems are investigated by CW-EPR and FT-ESEEM spectroscopies. It is found that the covalent gel containing β-CD can efficiently remove SDS from the BSA/SDS complex. The gel is not permeable to BSA but it can encapsulate SDS, thus yielding the free protein in solution and allowing recovery of the native protein conformation. Collectively, the accrued knowledge supports potential applications in protein purification biotechnological processes.

The properties of a gel consisting of a covalent network formed by the reaction of isocyanate end-capped polyethylene glycol (PEG) with β-cyclodextrin, were investigated by EPR spectroscopy. Spin-labelled cyclodextrin was incorporated into the cross-link points of the gel and at the chain ends. The dynamics of the gel fibres as reported by the spin label, was found to be sensitive to the H-bonding ability of the solvent, density of cross-links and temperature. Addition of spin probes (e.g., TEMPO and adamantane-TEMPO) to the unlabelled gel made it possible to characterise the solvent pools in the gel. While TEMPO was uniformly distributed throughout the solvent pools, the adamantane derivative was located at the gel fibre-solvent pool interface; these two probes thus reported on the different locations in the solvent pools. At low temperature, the gels were shown to prevent ice crystallisation in the solvent pools resulting in the formation of supercooled water. Both probes showed that the water froze at ca. 250 K, thus suggesting that the properties of the supercooled water are uniform across the solvent pools.

Micellar to gel phase transition in the aqueous triblock copolymer F127 solutions occurs at higher temperatures in the presence of cyclodextrin and the temperature range corresponding to the gel phase is contracted. These features were observed by dynamic rheometry and the tube inversion method. We investigated further the behaviours of various molecular probes in Pluronic F127 solutions in the absence and in the presence of hydroxypropyl-β-cyclodextrin (HPB) as a function of temperature by continuous wave electron paramagnetic resonance (cw-EPR), Electron Spin Echo Envelope Modulation (ESEEM) and fluorescence spectroscopy, to correlate the observed macroscopic and microscopic changes. The use of molecular probes with different structural particularities allowed the targeting of different regions of F127 micelles which are inhomogeneous at the nanoscale level and the elucidation of the mode in which HPB influences the phase transition in such systems. Dansyl-TEMPO (DT), with a dual character (paramagnetic and fluorescent), spin labelled cyclodextrin (MTCYC), spin labelled Pluronics – L62NO and F127NO, dansyl β-CD (D-β-CD) and pyrene were employed as molecular probes. Both cw-EPR and fluorescence measurements revealed that molecular probes with a more hydrophobic character are more sensitive to phase transition occurring in the studied systems.