The viscoelastic and flow properties of aqueous Laponite/TEMPO-oxidized nanofibrillated cellulose (TEMPO-NFC) systems are investigated with the aim to study the effect of content and proportion of both components on the properties. Both Laponite and TEMPO-NFC aqueous dispersions can find numerous applications in different fields (from industrial to biomedical one) due to their structural and rheological properties. The most important effects of blending are observed at low Laponite fractions, also with qualitative changes in the shape of the flow curves and mechanical spectra. Positive synergistic effects are ascribed to the interpenetration and electrostatic interactions between TEMPO-NFC fibrils and Laponite nanodisks. These mechanisms are more effective in Laponite-poor blends when a minority of clay nanoparticles and its aggregated forms are distributed within the nanocellulose matrix, acting as bridging agents between polymer nanofibrils. The synergistic effects are compared to those observed for Laponite blends with a nonionic biopolymer, scleroglucan.

The study concerns the development of rheological properties of aqueous TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl)-oxidized nanofibrillated cellulose (NFC) suspensions prepared from a commercially available TEMPO-NFC powder. Ageing of hydrogels with concentrations from 1 to 3 wt% of TEMPO-NFC was investigated by monitoring shear flow and linear viscoelastic properties after different days from sample preparation. For quantitative representation of the results time dependencies of zero shear viscosity and storage modulus are given. The increase of rheological parameters is described by a sigmoidal mathematical model. By superposition of individual data sets master curves displaying reduced values of the most significant parameters are constructed, showing the effect of ageing kinetics. The reduced storage modulus and zero-shear viscosity values increase for 2 and 3 decades, respectively, before reaching final values. Obtained results are useful for several applications of nanocellulose hydrogels, especially for those, where pumping, mixing, coating or injecting is necessary. For example, in biomedical field, a less viscous suspension can be injected to the spot of interest, where the final gel properties are developed.

Viscosupplementation is an intra-articular symptomatic treatment of mild osteoarthritis in synovial joints. It normally consists of single or repeated injections of hyaluronan- based fluids, aimed to restore desirable viscoelastic behavior of the synovial fluid and thus recreate the intra-articular joint homeostasis. Recently, a novel viscosupplement based on amidated carboxymethylcellulose has been developed by blending the soluble polymer (CMCAp) with its crosslinked derivative (CMCAg) in appropriate proportions and concentrations in order to ensure an optimal combination of flow behavior and viscoelastic properties. The present work is concerned with the rheological monitoring of the crosslinking reaction performed at 25 °C by starting from aqueous CMCAp solutions in order to describe the time evolution of the linear viscoelastic moduli occurring along the whole gelation process and to individuate how the polymer concentration affects the mechanical response at the sol-gel transition and the fractal dimension of the incipient polymeric network.

Both Laponite and scleroglucan can find several applications in various fields (from industrial to biomedical one) in virtue of their peculiar features and rheological properties displayed in aqueous phases. Structural states of Laponite dispersions strongly depend on concentration and ionic strength. When attractive and repulsive interparticle interactions are so effective that they lead to arrested states (attractive gel or repulsive glass), the rheological behavior of the dispersion undergoes a sharp transition, from quasi-Newtonian to markedly shear thinning and viscoelastic. Conversely, scleroglucan solutions gradually change to weak gels with increasing polymer concentration. The present work is concerned with aqueous Laponite-scleroglucan mixed systems, obtained according to different preparation modes, and is aimed at examining how much the content and proportion of both components affect the viscoelastic and flow properties of the mixed system.

Viscosupplement is an intra-articular symptomatic treatment of mild osteoarthritis. The treatment involves the injection of high-molecular-weight hyaluronan (HA), and especially of cross-linked HA to restore the lubricating and cushioning properties of the synovial fluid.This work involves the development of a novel viscosupplementation fluid based on amidated carboxymethylcellulose and obtained by blending the soluble polymer with its crosslinked derivative. Rheological analyses carried out under both oscillatory and continuous shear provided a rationale to assess the viscosupplement formulation and the production process. The hydrogel fraction content and the total polymer concentration can be properly selected in order to ensure an optimal combination of flowability and viscoelastic properties.

This paper focuses on the micro- and nano-topological organization of a hydrogel, constituted by a mixture of bacterial cellulose and acrylic acid, and intended for biomedical applications. The presence of acrylic acid promotes the formation of two interpenetrated continuous phases: the primary "pores phase" (PP) containing only water and the secondary "polymeric network phase" (PNP) constituted by the polymeric network swollen by the water. Low field Nuclear Magnetic Resonance (LF NMR), rheology, Scanning Electron Microscopy (SEM) and release tests were used to determine the characteristics of the two phases. In particular, we found that this system is a strong hydrogel constituted by 81% (v/v) of PP phase the remaining part being occupied by the PNP phase. Pores diameters span in the range 10-100 μm, the majority of them (85%) falling in the range 30-90 μm. The high PP phase tortuosity indicates that big pores are not directly connected to each other, but their connection is realized by a series of interconnected small pores that rend the drug path tortuous. The PNP is characterized by a polymer volume fraction around 0.73 while mesh size is around 3 nm. The theoretical interpretation of the experimental data coming from the techniques panel adopted, yielded to the micro- and nano-organization of our hydrogel.

I. De Simone, N. Coceani, R. Farra, S. M. Fiorentino, G. Grassi, R. Lapasin, D. Hasa, B. Perissutti, M. Grassi, and D. Voinovich Department of Chemical and Pharmaceutical Sciences, University of Trieste, Piazzale Europa 1, I-34127, Trieste, Italy Department of Engineering and Architercture, Piazzale Europa, I-34127, Trieste, Italy Department of Life Sciences, Cattinara University Hospital, Strada di Fiume 447, I-34149, Trieste, Italy

To set an approach for the future territorial planning, the Geological Survey of Friuli Venezia Giulia Region, through the researchers of Trieste University, started a program of debris-flow risk analysis using Flo-2D software as tool to delimit the hazardous areas. In the present paper, as a case study, a debris flow, called Fella sx, occurring in a torrent catchment was analyzed. The choice was due to the abundance of information about past events, inundated areas, rain fall, geology and to its representativeness. An initial back-analysis investigation identified a couple of representative rheological parameters. Riverbed samples were collected, sieve analyses were performed and rheological tests were carried out on the fraction finer than 0.063 mm using a rotationally controlled stress rehometer equipped with the serrated parallel plate geometry. The shear dependent behaviour was examined at different concentrations ranging from 33 to 48%, by weight. Viscosity data treatment was performed to determine the most suitable rheological model to provide the best approximation of the debris-flow behaviour. The rheological parameters, derived from experimental data, were used and compared with those obtained through the back-analysis and with the real inundated area. Data obtained through rheological analysis are useful in constructing scenarios of future events where no data for back-analysis are available.

Microencapsulation is a powerful technique commonly used for the protection of a wide range of biomolecules (small molecules and protein) and cells of bacterial, yeast and animal origin. In this work, solutions of mixed biopolymers are investigated as excipients for the formulation of a model system. The influence of the different components is studied from the viscoelastic behaviour of the starting solutions to the thermal characterisation of the gel beads therefrom produced. Rheological characterisation displays an almost regular trend for the several combination of solutes and for the frequency dependence, but some peculiarities emerge when both the model protein lysozyme and the cosolvent ethanol are present in the mixture; for the latter system a delayed melting behaviour of water appears in the gel beads. Changes in the temperature dependence of water evaporation from the beads are taken as an evidence of the rate of release from the beads.

Coronary restenosis consists of the partial/total re-occlusion of the artery lumen following percutaneous transluminal angioplasty (PTCA). In order to match this pathology, PTCA is followed by the implantation of rigid scaffolds (stent or coated stent) aimed to contrast the most important mechanical (coronary wall elastic recoil and late remodelling) and biological (smooth muscle cells iper-proliferation) factors leading to restenosis. In the light of the clinical problems recently arisen about the use of traditional coated stents, this paper proposes a theoretical study to comprehend the release kinetics of novel anti-proliferative drugs, i.e. nucleic acid based drugs (NABD), complexed with the proper delivery agent (DA). The release of NABD-DA is supposed to occur from a double gel layer adhering to coronary wall and embedding the stent. The proposed mathematical model assumes that diffusion, convection and cellular internalisation/metabolism are the leading mechanisms ruling drug spreading in the coronary wall. In addition, stent void fraction, positioning (totally embedded or totally out of the coronary wall) and continuous or discontinuous character of the gel layer are other three important model parameters. In order to generalise the results, stent geometry is idealised as a series of not connected, equally spaced, rings positioned in the stented zone. In correspondence of stent strut, drug transport cannot occur. The most important outcomes of this study are that, in the usual void fraction range (0.7-0.9), stent presence does not sensibly affect NABD-DA release kinetics. In addition, whereas stent positioning in the continuous gel configuration (totally embedded or totally out of coronary wall) is not very important, in the discontinuous case, it becomes relevant. Finally, this study evidences that a proper mixture of NABD complexed with different (in dimensions and kind) DA can ensure an almost constant NABD coronary concentration for several months, as requested by clinical observations.

AimTo study the solubility of perfluorohexyloctane (F6H8) in silicone oil (polydimethylsiloxane (PDMS) 1000) and to measure the viscosity and the specific gravity of the mixture obtained (heavy silicone oil or HSO tamponade) to define the ideal ratio of these components.MethodsThe solubility diagram of the mixture was obtained with the turbidimetric method, indicating the miscibility of F6H8 and silicone oil 1000 at all the useful temperatures. The viscosity was measured in steady shear conditions by using a controlled stress rheometer (Haake RS150) and a double cone/plate (DC 60/4) system, both at 25 and 37 degrees C for different volume per cent compositions of the mixture. The specific gravity was measured at 37 degrees C using a digital densimeter.ResultsA mixture of F6H8 30 v% and PDMS 70 v% was found to be transparent and stable at all the useful temperatures. By combining these proportions of the two substances, a resultant density of 1.06 g/cm(3) was obtained. The viscosity of the 30% F6H8 mixture was 203 mPa.s at 25 degrees C and 163 mPa.s at 37 degrees C respectively.ConclusionsThe ideal F6H8 and silicone oil mixture can be obtained combining 30% of F6H8 with 70% of silicone oil 1000. This mixture seems to have rheological properties useful for its use as an alternative intraocular heavy tamponade.Eye (2008) 22, 1082-1088; doi:10.1038/eye.2008.144; published online 6 June 2008.

The phase separation of paraffinic solids from crude oil constitutes a major operating issue for the petroleum industry, in view of the fact that the association of wax crystals into a disordered spanning network can lead to severe flow assurance problems. Although the presence of water in crude oil is quite common, its impact on waxy crude oil gelation and rheology has not received much more attention in the literature.

The delivery of short nucleic acid molecules (NAM), complexed with liposomes, to diseased vessel walls is dramatically limited by blood wash. We thus started investigations to study the possibility of embedding NAM/liposome complexes into a novel polymeric blend focusing attention on their effects on the rheological properties of the selected polymeric blend. Two different liposomes, able to transduce NAM efficiently into vascular smooth muscle cells, were embedded into a thermosensitive alginate/pluronic polymeric blend. Liposome particles, with and without NAM, were characterized for their sizes, superficial charges, morphologies and initial delivery studies performed in vitro. Whereas both liposomes with and without NAM do not substantially affect the final polymeric blend properties, NAM presence differentially influences the structuring process. This behavior is attributed both to particle sizes and superficial charge, with this last parameter appearing more relevant. Moreover, the presence of the polymeric blend substantially retards the delivery of NAM/liposome to vascular smooth muscle cells. In conclusion, our results indicate that both types of liposome/NAM complexes are suitable for the development of a delivery system for NAM-liposome complexes to vessel walls.

Porous biomaterials composed of highly purified collagen and solubilised elastin were prepared by freezing and lyophilisation and studied by subcutaneous implantation in young Sprague Dawley rats. The scaffolds, containing depots of soluble elastin, showed no calcification in this sensitive calcification model, in contrast to scaffolds containing insoluble elastin fibres. Scaffolds induced the formation of blood vessels and promoted elastic fibre synthesis as was shown with specific antibodies.

Rheological and erosion studies regarding a liposome-containing polymeric blend that is propaedeutic to its use in paving techniques in tubular organs, such as blood vessels, are reported. Attention is focused on an aqueous polymeric blend composed of Pluronic (PF127) and alginate (Protanal LF 10/60) because both polymers, when dissolved in water at a sufficiently high concentration, are subjected to different structural mechanisms, which are driven by temperature increase and addition of bivalent cations, respectively, and both result in marked viscoelastic and plastic properties. After proving the compatibility between PF127 and alginate, we show that the structural transition temperature of the blend, T(ST), can be properly modulated. In particular, we found that T(ST) for an aqueous solution of pure Pluronic 20% w/w is about 21 degrees C and that even slight reductions in polymer concentration result in considerable T(ST) decrease. The addition of salts or alginate (provided as Na-alginate) provokes a substantial decrease of T(ST) and thus the alginate concentration in the blend should not exceed 1% w/w. In addition, liposomes slow down the structural transition but do not substantially affect the rheological properties of the system in the final state at higher temperatures, thus showing that they can be added to the polymeric blend without significant effects. Finally, erosion tests show that after contact with a source of bivalent cations, the polymeric blend containing PF127 and alginate shows an erosion resistance neatly improved with respect to the simple structured Pluronic system having the same polymer concentration. As a whole, all these results constitute the basis for future potential applications of the considered polymeric blend in tubular organs such as blood vessels.

Hydroxyapatite (HA) is an interesting ceramic material for orthopedic applications, in particular for implant operations and bone regeneration, owing to its bioactivity and biocompatibility with the surrounding tissues. Even if different shaping processes can be used in order to obtain porous ceramic bodies with optimal final properties, the sponge impregnation method with aqueous HA dispersions is particularly suitable to achieve an appropriate macroporosity to bone regeneration. As for conventional slip or tape casting, the rheological behavior of HA suspensions must be properly fitted to process conditions and controlled through a satisfactory stabilization of the disperse phase, i.e., through an appropriate dispersant dosage and an accurate homogenization of dispersed powder. In the present work, HA powders with different crystallinity degree were used to prepare aqueous dispersions with different contents of solids and dispersant (ammonium polyacrylate). The specific surface area of HA powders is very high, and then special attention must be dedicated to the dispersant selection and the dispersion process since the rheology of HA suspensions is strongly influenced by the structural conditions of the disperse phase. Even small differences in dispersant concentration can lead to dramatic changes in the rheological properties also at relatively low values of solids volume concentration. Above a critical concentration, the viscosity drop associated with the apparently plastic behavior is confined within a very narrow stress range, a neat transition is observed in the linear viscoelastic properties, and the time‐dependent effects induced by the shear history become quite important and crucial for the experimental characterization.