We have studied the molecular properties of water in physically and chemically cross-linked gelatin hydrogels by FTIR-spectroscopy, NMR relaxation, and diffusivity and broadband dielectric spectroscopy, which are sensitive to dynamical properties of water, being a structural marker of polymer network. All experiments demonstrated definite reinforcement of the hydrogel net structure and an increase in the amount of hydrate water. FTIR experiments have shown that the chemical cross-linking of gelatin molecules initiates an increase in the collagen-like triple helices “strength”, as a result of infused restriction on protein molecular mobility. The “strengthening” of protein chains hinders the mobility of protein fragments, introducing complex modifications into the structural properties of water which are remained practically unchanged up to up to 30–40 °C.
The main object of this work was to characterize the structure and properties of laboratory-made fish gelatin from cod skin in comparison with known commercial gelatins of fish and mammalian origin. This is one way we can contribute to the World Food Program and characterize foodstuff resources from alternative natural sources. Our research was based on the combination of an expanded set of complementary physical–chemical methods to study the similarities and distinctions of hydrogels from traditional and novel gelatin sources from underused marine resources. In this work, we have compared the morphology, supramolecular structure and colloid properties of two commercial (mammalian and fish) gelatins with gelatin we extracted from cold-water cod skin in laboratory conditions. The obtained results are novel, showing that our laboratory-produced fish gelatin is much closer to the mammalian one in terms of such parameters as thermal stability and strength of structural network under temperature alterations. Especially interesting are our experimental observations comparing both fish gelatins: it was shown that the laboratory-extracted cod gelatin is essentially more thermally stable compared to its commercial analogue, being even closer in its rheological properties to the mammalian one.
Controlling the permittivity of dielectric composites is critical for numerous applications dealing with matter/electromagnetic radiation interaction. In this study, we have prepared polymer composites, based on a silicone elastomer matrix and Tuball carbon nanotubes (CNT) via a simple preparation procedure. The as-prepared composites demonstrated record-high dielectric permittivity both in the low-frequency range (102–107 Hz) and in the X-band (8.2–12.4 GHz), significantly exceeding the literature data for such types of composite materials at similar CNT content. Thus, with the 2 wt% filler loading, the permittivity values reach 360 at 106 Hz and >26 in the entire X-band. In similar literature, even the use of conductive polymer hosts and various highly conductive additives had not resulted in such high permittivity values. We attribute this phenomenon to specific structural features of the used Tuball nanotubes, namely their length and ability to form in the polymer matrix percolating network in the form of neuron-shaped clusters. The low cost and large production volumes of Tuball nanotubes, as well as the ease of the composite preparation procedure open the doors for production of cost-efficient, low weight and flexible composites with superior high permittivity.
Relaxation behavior of water confined in reverse micelles under temperature-induced micelle clustering is undertaken using broadband dielectric spectroscopy in frequency range 1 Hz–20 GHz. All microemulsion systems with sufficiently noticeable micelle water pool (water/surfactant molar ratio W > 10) depict three relaxation processes, in low, high and microwave frequencies, anchoring with relaxation of shell (bound) water, orientation of surfactant anions at water-surfactant interface and relaxation of bulk water confined in reverse micelles. The analysis of dielectric relaxation processes in AOT-based w/o microemulsions under temperature induced clustering of reverse micelles were made according to structural information obtained in NMR and conductometry experiments. The “wait and switch” relaxation mechanism was applied for the explanation of results for water in the bound and bulk states under spatial limitation in reverse micelles. It was shown that surfactant layer predominantly influences the bound water. The properties of water close to AOT interface are determined by strong interactions between water and ionic AOT molecules, which perturb water H-bonding network. The decrease in micelle size causes a weakening of hydrogen bonds, deformation of its steric network and reduction in co-operative relaxation effects.
Polymers from norbornenes are of interest for applications in opto- and microelectronic (low dielectric materials, photoresists, OLEDs). Norbornenes with ester motifs are among the most readily available norbornene derivatives. However, little is known about dielectric properties and the gas-transport of polynorbornenes from such monomers. Herein, we synthesized a new metathesis polymer from exo-5-norbornenecarboxylic acid and 1,1′-bi-2-naphthol. The designed monomer was obtained via a two-step procedure in a good yield. This norbornene derivative with a rigid and a bulky binaphthyl group was successfully polymerized over the 1st generation Grubbs catalyst, affording high-molecular-weight products (Mw ≤ 1.5·106) in yields of 94–98%. The polymer is amorphous and glassy (Tg = 161 °C), and it shows good thermal stability. Unlike most, polyNBi is a classic low-permeable glassy polymer. The selectivity of polyNBi was higher than that of polyNB. Being less permeable than polyNB, polyNBi unexpectedly showed a lower value of dielectric permittivity (2.7 for polyNBi vs. 5.0 for polyNB). Therefore, the molecular design of polynorbornenes has great potential to obtain polymers with desired properties in a wide range of required characteristics. Further tuning of the gas separation efficiency can be achieved by attaching an appropriate substituent to the ester and aryl group.