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.

Thermal Conductivity of Detonation Nanodiamond Hydrogels and Hydrosols by Direct Heat Flux Measurements.

The methodology and results of thermal conductivity measurements by the heat-flow technique for the detonation nanodiamond suspension gels, sols, and powders of several brands in the range of nanoparticle concentrations of 2-100% w/w are discussed. The conditions of assessing the thermal conductivity of the fluids and gels (a FOX 50 heat-flow meter) with the reproducibility (relative standard deviation) of 1% are proposed. The maximum increase of 13% was recorded for the nanodiamond gels (140 mg mL-1 or 4% v/v) of the RDDM brand, at 0.687 ± 0.005 W m-1 K-1. The thermal conductivity of the nanodiamond powders is estimated as 0.26 ± 0.03 and 0.35 ± 0.04 W m-1 K-1 for the RUDDM and RDDM brands, respectively. The thermal conductivity for the aqueous pastes containing 26% v/v RUDDM is 0.85 ± 0.04 W m-1 K-1. The dignities, shortcomings, and limitations of this approach are discussed and compared with the determining of the thermal conductivity with photothermal-lens spectrometry.

Green and rapid preparation of long-term stable aqueous dispersions of fullerenes and endohedral fullerenes: The pros and cons of an ultrasonic probe.

A green, scalable, and sustainable approach to prepare aqueous fullerene dispersions (AFD) C60, C70, endohedral metallofullerene Gd@C82, and their derivatives C60Cl6, C70Cl10, and supramolecular and ester-like derivatives, 10 fullerene species total, is proposed. For the first time, an immersed ultrasonic probe was used to preparing dispersions for pristine fullerenes without addends. Both ultrasound-assisted solvent-exchange and direct sonication techniques for AFD preparation using an immersed probe were tested. The average time for AFD preparation decreases 10-15 times compared to an ultrasound-bath-assisted technique, while final fullerene concentrations in AFDs remained at tens of ppm (up to 80 ppm). The aqueous dispersions showed long-term stability, a negatively charged surface with a zeta potential up to -32 mV with an average nanocluster diameter of no more than 180 nm. The total anionic and cationic compositions of samples were found by inductively coupled plasma atomic emission spectroscopy and chromatographic techniques. The highlights and challenges of using an ultrasound probe for AFD production are discussed.

Multilayered intercalation of 1-octanol into Brodie graphite oxide.

Multilayered intercalation of 1-octanol into the structure of Brodie graphite oxide (B-GO) was studied as a function of temperature and pressure. Reversible phase transition with the addition/removal of one layer of 1-octanol was found at 265 K by means of X-ray Diffraction (XRD) and Differential Scanning Calorimetry (DSC). The same transition was observed at ambient temperature upon a pressure increase above 0.6 GPa. This transition was interpreted as an incongruent melting of the low temperature/high pressure B-GO intercalated structure with five layers of 1-octanol parallel to GO sheets (L-solvate), resulting in the formation of a four-layered structure that is stable under ambient conditions (A-solvate). Vacuum heating allows the removal of 1-octanol from the A-solvate layer by layer, while distinct sets of (00l) reflections are observed for three-, two-, and one-layered solvate phases. Step by step removal of the 1-octanol layers results in changes of distance between graphene oxide planes by ∼4.5 Å. This experiment proved that both L- and A-solvates are structures with layers of 1-octanol parallel to GO planes. Unusual intercalation with up to five distinct layers of 1-octanol is remarkably different from the behaviour of small alcohol molecules (methanol and ethanol), which intercalate B-GO structure with only one layer under ambient conditions and a maximum of two layers at lower temperatures or higher pressures. The data presented in this study make it possible to rule out a change in the orientation of alcohol molecules from parallel to perpendicular to the GO planes, as suggested in the 1960s to explain larger expansion of the GO lattice due to swelling with larger alcohols.

Improving the dispersity of detonation nanodiamond: differential scanning calorimetry as a new method of controlling the aggregation state of nanodiamond powders.

Detonation nanodiamond (ND) is a suitable source material to produce unique samples consisting of almost uniform diamond nanocrystals (d = 3-5 nm). Such samples exist in the form of long stable aqueous dispersions with narrow size distribution of diamond particles. The material is finding ever increasing application in biomedicine. The major problem in producing monodispersed diamond colloids lies in the necessity of deagglomeration of detonation soot and/or removing of clusters formed by already isolated core particles in dry powders. To do this one must have an effective method to monitor the aggregation state or dispersity of powders and gels prior to the preparation of aqueous dispersions. In the absence of dispersity control at various stages of preparation the reproducibility of properties of existing ND materials is poor. In this paper we introduce differential scanning calorimetry (DSC) as a new tool capable to distinguish the state of aggregation in dry and wetted ND materials and to follow changes in this state under different types of treatment. Samples with identical X-ray diffraction patterns (XRD) and high resolution transmission electron microscopy (HRTEM) images gave visibly different DSC traces. Strong correlation was found between dynamic light scattering (DLS) data for colloids and DSC parameters for gels and powders of the same material. Based on DSC data we improved dispersity of existing ND materials and isolated samples with the best possible DSC parameters. These were true monodispersed easily dispersible fractions of ND particles with diameters of ca. 3 nm.

The first solid phase synthesis of pincer palladium complexes.

Both dimeric µ-chlorine bridged and monomeric bidentate Pd(II) complexes with SCN hybrid pincer-type ligands, bearing thiophosphoryl group and imine moiety of the benzothiazole ring as coordination arms, formed in the reaction with (PhCN)(2)PdCl(2) under kinetic control (20 °C, dichloromethane solution) were readily converted into the corresponding SCN pincer complexes via solid phase synthesis (neat, 200 °C, 15 min). The synthesis of pincer complexes can be performed also by heating (200 °C, 5 min) of a homogeneous mixture of the initial reactants, namely, the ligand and (PhCN)(2)PdCl(2), obtained by manual grinding in a mortar. The efficacy of solid phase approaches is comparable with the analogous synthesis in solutions under severe conditions.