Liquid-like and solid-like acetonitrile intercalated into graphite oxide as studied by the spin probe technique.

The molecular mobility of acetonitrile intercalated into the inter-plane space of graphite oxide was studied using the spin probe technique. It was revealed that two types of intercalated substance - liquid-like and solid-like - are simultaneously present in between the oxidized graphene planes, and their ratio depends on temperature. The micro-viscosity of liquid-like intercalated acetonitrile was found to be higher than that of bulk acetonitrile and depends on the amount of intercalated liquid.

Glass-like behavior of intercalated organic solvents in graphite oxide detected by spin-probe EPR.

Membranes based on graphite oxide (GO) are promising materials for the separation of polar liquids and gases. Understanding the properties of solvents immersed in GO is important for the development of various technological applications. Here, the molecular motions of the TEMPO nitroxide spin probe in acetonitrile intercalated into the GO inter-plane space were studied using electron paramagnetic resonance (EPR), including its pulsed version, and electron spin echo (ESE). For a sample containing 75% acetonitrile relative to equilibrium sorption at room temperature, ESE-detected stochastic librations were observed for TEMPO molecules above 135 K. Since these librations are an inherent property of molecular glasses, this fact indicates that intercalated acetonitrile forms a two-dimensional glass state. Above 225 K, an acceleration of stochastic librations was observed, indicating the manifestation of a glass-like dynamical cross-over. Continuous wave (CW) EPR spectra of TEMPO showed the absence of overall tumbling motions in the entire investigated temperature range of up to 340 K, indicating that the intercalated acetonitrile does not behave as a bulk liquid (the melting point of acetonitrile is 229 K). Dynamical librations of TEMPO molecules detected by CW EPR were found to accelerate above 240 K.

Mobility of liquids intercalated into the interplane space of graphite oxide as revealed by a combination of 19F NMR, 1H NMR and EPR spin probe methods.

A combination of 19F and 1H NMR with the Carr-Purcell-Meiboom-Gill (CPMG) pulse sequence was used to examine the mobility of liquids in the interplane space of graphite oxide (GO) for the first time. The proposed approach allows for the reduction of NMR signals from immobile hydrogen-containing groups on the surface of GO and for monitoring of the molecular mobility of intercalated liquids. The mobile fractions of H2O, CH3CN and CF3CH2OH were detected inside the corresponding swollen GO samples. For H2O, the amount of mobile liquid showed a peculiar temperature dependence where a certain portion survived well below 273 K. The sensitivity of the proposed 1H NMR + CPMG procedure is also compared to the sensitivity of the EPR nitroxide spin probe method.

First Iridium(IV) Chloride-Dimethyl Sulfoxide Complex [H(dmso)2][IrCl5(dmso-κO)]: Synthesis and Structure along with Novel Polymorph Modifications of [H(dmso)2][trans-IrCl4(dmso-κS)2] and [H(dmso)][trans-IrCl4(dmso-κS)2].

As evidenced by UV-Vis and EPR spectroscopies, the reaction of H2IrCl6·6H2O or Na2[IrCl6]·nH2O with DMSO results in a slow reduction of Ir(IV) avoiding the formation of Ir(IV) dimethyl sulfoxide complexes in measurable quantities. More specifically, we successfully isolated and solved the crystal structure of a sodium hexachloridoiridate(III), Na3[IrCl6]·2H2O, as a product of Na2[IrCl6]·nH2O reduction in an acetone solution. Furthermore, it was shown that [IrCl5(Me2CO)]- species is gradually formed in an acetone solution of H2IrCl6·6H2O upon storage. The reaction of DMSO with aged acetone solution of H2IrCl6·6H2O dominated by [IrCl5(Me2CO)]- affords a novel iridium(IV) chloride-dimethyl sulfoxide salt [H(dmso)2][IrCl5(dmso-κO)] (1). The compound was characterized by various spectroscopies (IR, EPR, UV-Vis) and X-ray diffraction techniques applied both to single-crystal and polycrystalline powder. The DMSO ligand is coordinated to the iridium site via the oxygen atom. New polymorph modifications of known iridium(III) complexes [H(dmso)2][trans-IrCl4(dmso-κS)2] and [H(dmso)][trans-IrCl4(dmso-κS)2] were isolated and structurally elucidated as byproducts of the above reaction.

Novel Orientation-Sensitive Spin Probes for Graphene Oxide Membranes Study.

Spin probe EPR spectroscopy is currently the only method to quantitatively report on the orientational ordering of graphene oxide membranes. This technique is based on the analysis of EPR spectra of a membrane containing stable radicals sorbed on oxidized graphene planes. The efficiency of the method depends on the spin probe structure; therefore, it is important to find stable paramagnetic substances that are most sensitive to the alignment of graphene oxide membranes. In the present work, three novel stable nitroxide radicals containing aromatic fragments with two nitrogen atoms were tested as spin probes to study graphene oxide membranes. The spin-Hamiltonian parameters of the radicals in graphite oxide powder and orientational order parameters of the probes inside graphene oxide membrane were determined. The sensitivity of one of these radicals to membrane orientational ordering was found to be higher than for any of spin probes used previously. A likely reason for this higher sensitivity is the presence of heteroatoms which can facilitate interaction between paramagnetic molecules and oxygen-containing groups on the inner surface of the membrane. The new high-sensitivity spin probe may significantly increase the potential of EPR spectroscopy for studying the internal structure of graphene oxide membranes.

Evaluation and Characterization of Ultrathin Poly(3-hydroxybutyrate) Fibers Loaded with Tetraphenylporphyrin and Its Complexes with Fe(III) and Sn(IV).

The effect of small additions (1-5 wt.%) of tetraphenylporphyrin (TPP) and its complexes with Fe (III) and Sn (IV) on the structure and properties of ultrathin fibers based on poly(3-hydroxybutyrate) (PHB) has been studied. A comprehensive study of biopolymer compositions included X-ray diffraction (XRD), differential scanning calorimetry (DSC), spin probe electron paramagnetic resonance method (EPR), and scanning electron microscopy (SEM). It was demonstrated that the addition of these dopants to the PHB fibers modifies their morphology, crystallinity and segmental dynamics in the amorphous regions. The annealing at 140 °C affects crystallinity and molecular mobility in the amorphous regions of the fibers, however the observed changes exhibit multidirectional behavior, depending on the type of porphyrin and its concentration in the fiber. Fibers exposure to an aqueous medium at 70 °C causes a nonlinear change in the enthalpy of melting and challenging nature of a change of the molecular dynamics.

New Insight into the Mechanism of Drug Release from Poly(d,l-lactide) Film by Electron Paramagnetic Resonance.

A novel approach based on convolution of the electron paramagnetic resonance (EPR) spectra was used for quantitative study of the release kinetics of paramagnetic dopants from poly(d,l-lactide) films. A non-monotonic dependence of the release rate on time was reliably recorded. The release regularities were compared with the dynamics of polymer structure changes determined by EPR, SEM, and optic microscopy. The data obtained allow for the conclusion that the main factor governing dopant release is the formation of pores connected with the surface. In contrast, the contribution of the dopant diffusion through the polymer matrix is negligible. The dopant release can be divided into two phases: release through surface pores, which are partially closed with time, and release through pores initially formed inside the polymer matrix due to autocatalytic hydrolysis of the polymer and gradually connected to the surface of the sample. For some time, these processes co-occur. The mathematical model of the release kinetics based on pore formation is presented, describing the kinetics of release of various dopants from the polymer films of different thicknesses.

Determination of orientation distribution function of anisotropic paramagnetic species by analysis of ESR spectra angular dependence.

A method has been developed to determine orientation distribution function (ODF) of anisotropic paramagnetic species by analysis of the angular dependence of the ESR spectra. The method is based on computational spectra simulation. The ODF is represented as an expansion in terms of orthonormal functions. The expansion coefficients are determined through minimization of discrepancies between simulated spectra and experimental ones. By means of the suggested method we have determined the orientation distribution functions for radical probe 2,2,6,6-tetramethyl-4-ol-piperidinooxyl in 4-n-amyl-4'-cyanobiphenyl aligned by magnetic field and 2-septadecyl-2,3,4,5,5-pentamethylimidazolidine in polyethylene stretched films. In each case, thermal evolution of the ODF has been investigated.

Rotational and translational diffusion of spin probes in room-temperature ionic liquids.

We have studied the rotational and translational diffusion of the spin probe 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPOL) in five imidazolium-based room-temperature ionic liquids (RTILs) and glycerol by means of X-band electron paramagnetic resonance (EPR) spectroscopy. Rotational correlation times and rate constants of intermolecular spin exchange have been determined by analysis of the EPR line shape at various temperatures and spin probe concentrations. The model of isotropic rotational diffusion cannot account for all spectral features of TEMPOL in all RTILs. In highly viscous RTILs, the rotational mobility of TEMPOL differs for different molecular axes. The translational diffusion coefficients have been calculated from spin exchange rate constants. To this end, line shape contributions stemming from Heisenberg exchange and from the electron-electron dipolar interaction have been separated based on their distinct temperature dependences. While the Debye-Stokes-Einstein law is found to apply for the rotational correlation times in all solvents studied, the dependence of the translational diffusion coefficients on the Stokes parameter T/η is nonlinear; i.e., deviations from the Stokes-Einstein law are observed. The effective activation energies of rotational diffusion are significantly larger than the corresponding values for translational motion. Effects of the identity of the RTIL cations and anions on the activation energies are discussed.