Interactions of poly(dimethylsiloxane) with nanosilica and silica gel upon cooling-heating.

To control the properties of poly(dimethylsiloxane) (PDMS, Oxane 1000) as a bio-inert material, the characteristics of Oxane 1000 were compared for PDMS alone and interacting with silica gel Si-100 and nanosilica PS400. Low-temperature (1)H NMR spectroscopy, applied to static samples at 200-300 K, and differential scanning calorimetry (DSC) at 153-393 K were used to analyze the properties of PDMS and composites. The NMR study shows that liquid and solid-like fractions of PDMS co-exist over a broad temperature range. The cooling-heating cycles give hysteresis loops of intensity of (1)H NMR signals of methyl groups of a liquid fraction of PDMS vs. temperature depending on the silica type. The loop width differs for PDMS alone and bound to silicas, and the samples preheated at 420 K are characterized by much narrower loops. DSC measurements of the samples show a significant difference in the thermograms on the first and second DSC scans that depend on the silica type. For PDMS confined in pores of silica gel, 3D spatial structure of the polymers can be more ordered than that of PDMS located in thin layers at a surface of nanosilica. Therefore, both melting endotherms and crystallization exotherms are observed for PDMS/silica gel. However, for PDMS/nanosilica, both thermal features are much weaker and observed during only the first DSC scan.

[Clusters of nonsolvent water in partially destroyed Saccharomyces cerevisiae yeast cells].

The state of water in partially destroyed dry yeast cells has been studied using low-temperature 1H NMR spectroscopy. It has been shown that the residual water is in the form of clusters of strongly and weakly associated water (SAW and WAW, respectively). Three or more types of SAW different in the chemical shift values have been found. It has been established that the interfacial water poorly dissolves hydrochloric and trifluoroacetic acids as well as DMSO and CD3CN. Hydrochloric acid on a surface of biomaterials can be separated into HCl and water. This process is stabilized by polar co-solvents (DMSO and CD3CN) added to the CDCl3 dispersion medium.

Hydrated phosphorus oxyacids alone and adsorbed on nanosilica.

Low-temperature (1)Н NMR spectroscopy was used to study states of water bound to phosphoric and phosphonic acids (phosporus oxyacids, POA) alone or adsorbed onto nanosilica OX-50 (specific surface area S(BET)=52 m(2)/g) or A-300 (S(BET)=297 m(2)/g). Concentrated solutions or weakly hydrated solid POA or dried silica/POA powders placed in CCl(4) medium are characterized by different temperature dependences of the chemical shift of the proton resonance (δ(H)) because of partial dissociation of PO-H bonds strongly affected by water amounts and temperature. NMR cryoporometry results show that both small water clusters and nanodomains are present at the interfaces of hydrated solid POA and silica/POA powders. Quantum chemical calculations of the (1)H NMR spectra demonstrate the influence of POA/water cluster structure and dissociation of the PO-H bonds on the δ(H) values.

Comparative characterization of polymethylsiloxane hydrogel and silylated fumed silica and silica gel.

Polymethylsiloxane (PMS) hydrogel (C(PMS)=10 wt%, soft paste-like hydrogel), diluted aqueous suspensions, and dried/wetted xerogel (powder) were studied in comparison with suspensions and dry powders of unmodified and silylated nanosilicas and silica gels using (1)H NMR, thermally stimulated depolarization current (TSDC), quasielastic light scattering (QELS), rheometry, and adsorption methods. Nanosized primary PMS particles, which are softer and less dense than silica ones because of the presence of CH(3) groups attached to each Si atom and residual silanols, form soft secondary particles (soft paste-like hydrogel) that can be completely decomposed to nanoparticles with sizes smaller than 10 nm on sonication of the aqueous suspensions. Despite the soft character of the secondary particles, the aqueous suspensions of PMS are characterized by a higher viscosity (at concentration C(PMS)=3-5 wt%) than the suspension of fumed silica at a higher concentration. Three types of structured water are observed in dry PMS xerogel (adsorbed water of 3 wt%). These structures, characterized by the chemical shift of the proton resonance at delta(H) approximately 1.7,3.7, and 5 ppm, correspond to weakly associated but strongly bound water and to strongly associated but weakly or strongly bound waters, respectively. NMR cryoporometry and QELS results suggest that PMS is a mesoporous-macroporous material with the textural porosity caused by voids between primary particles forming aggregates and agglomerates of aggregates. PMS is characterized by a much smaller adsorption capacity with respect to proteins (gelatin, ovalbumin) than unmodified fumed silica A-300.